Modified TPEE material and preparation method thereof
By adding glass fiber and modified bamboo fiber to TPEE material to form a physical cross-linked network, the mechanical properties and long-term stability of TPEE material are solved, its performance under high temperature, high humidity and ultraviolet light is improved, and its application range is expanded.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- GANSU JINGKAIDA NEW MATERIALS CO LTD
- Filing Date
- 2026-03-05
- Publication Date
- 2026-04-21
AI Technical Summary
TPEE materials have defects in mechanical properties and long-term stability, including low modulus, insufficient wear resistance, creep, poor resistance to hot water hydrolysis, easy hydrolysis and UV degradation, which limit their application in high-end fields.
By adding glass fiber, modified bamboo fiber, maleic anhydride-grafted ethylene-octene copolymer, anti-hydrolysis stabilizer and lubricant, combined with alkali treatment and intercalated montmorillonite technology, a physical cross-linking network and mechanical interlocking are formed, thereby improving the mechanical properties and stability of the material.
It significantly improves the mechanical properties and long-term stability of TPEE materials, expands their application scenarios, and reduces the risk of performance degradation of materials under high temperature, high humidity and ultraviolet light.
Smart Images
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Abstract
Description
Technical Field
[0001] This invention relates to the field of material modification technology, and in particular to a modified TPEE material and its preparation method. Background Technology
[0002] While TPEE (thermoplastic polyester elastomer) is a common and widely used material with irreplaceable roles in automotive, electronics, medical, and industrial products, its mechanical properties and long-term stability still have significant defects, severely limiting its application effectiveness. Specifically, although TPEE has higher tensile strength and compressive modulus than polyurethane (TPU), its modulus under low strain conditions may be lower than other thermoplastic elastomers, making the products prone to deformation under load; although its abrasion resistance is comparable to TPU, it is still insufficient under high load or high-speed friction scenarios, easily leading to wear; although its fatigue resistance is excellent, under long-term high temperature or high stress, the material is prone to creep, resulting in decreased dimensional stability. Furthermore, TPEE also suffers from significant long-term stability issues: its tensile strength decreases significantly at high temperatures (above 120°C), affecting the reliability of high-temperature components; prolonged contact with strong acids, alkalis, or organic solvents may lead to hydrolysis or corrosion, resulting in material performance deterioration; it is prone to degradation under ultraviolet radiation, requiring the addition of UV-protective additives to delay aging; and it exhibits poor resistance to hot water hydrolysis, especially in high-temperature and high-humidity environments, where hydrolysis reactions easily occur, leading to material embrittlement and decreased fracture strength. These defects in mechanical properties and long-term stability not only increase the risk of product failure but may also pose safety hazards, limiting the application expansion of TPEE in high-end fields. Therefore, improving the mechanical strength of TPEE materials has become an urgent problem to be solved. Summary of the Invention
[0003] The purpose of this invention is to overcome the deficiencies in the prior art and provide a modified TPEE material and its preparation method.
[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a modified TPEE material, prepared from raw materials comprising the following parts by mass: 70-75 parts TPEE, 7-10 parts glass fiber, 6-10 parts maleic anhydride-grafted ethylene-octene copolymer, 8-15 parts modified bamboo fiber, 0.5-1 part hydrolysis stabilizer, and 0.5-1 part lubricant.
[0005] Preferably, the glass fiber has a diameter of 10~13μm and a length of 1~2mm.
[0006] Preferably, the method for preparing modified bamboo fiber includes the following steps: (1) Bamboo fiber is treated with alkali to obtain alkaline bamboo fiber; (2) Sodium-based montmorillonite, hexadecyltrimethylammonium bromide and water are mixed to obtain intercalated montmorillonite; (3) After the polyamide and intercalated montmorillonite are initially mixed, alkaline bamboo fiber is added for secondary mixing to obtain modified bamboo fiber.
[0007] Preferably, in step (1), the length of the bamboo fiber is 3-5 mm, and the alkali treatment reagent is sodium hydroxide solution with a concentration of 4-6%. The ratio of bamboo fiber to sodium hydroxide solution is 1g: 10~15mL; The alkali treatment temperature is 20~30℃, and the time is 6~12h.
[0008] Preferably, in step (2), the mass ratio of sodium montmorillonite, hexadecyltrimethylammonium bromide and water is 1:1~1.5:40~50; In step (2), the mixing temperature is 70~80℃, the rotation speed is 400~600rpm, and the time is 4~6h.
[0009] Preferably, in step (3), the mass ratio of polyamide, intercalated montmorillonite and alkaline bamboo fiber is 6~7:3~5:10~15; In step (3), the initial mixing temperature is 180~225℃; the time is 10~15min. In step (3), the temperature for the second mixing is 225~235℃ and the time is 10~15min.
[0010] Preferably, the hydrolysis stabilizer is one or more of N,N'-bis(2,6-diisopropylphenyl)carbodiimide, bisphenol A bisglycidyl ether, and polyethylene glycol diglycidyl ether. The lubricant comprises one or more of calcium stearate, paraffin wax, and polyethylene wax.
[0011] The present invention also provides a method for preparing the modified TPEE material, comprising the following steps: (a) TPEE, maleic anhydride-grafted ethylene-octene copolymer, hydrolysis stabilizer and lubricant are mixed to obtain a blend; (b) Glass fiber and modified bamboo fiber are added to the blend and mixed to obtain the modified TPEE material.
[0012] Preferably, the melting temperature of the mixture in step (a) is 200~220℃ and the time is 10~20min.
[0013] Preferably, the melting temperature of the mixture in step (b) is 210~230℃ and the time is 10~15min.
[0014] This invention provides a modified TPEE material, prepared from raw materials comprising the following parts by mass: 70-75 parts TPEE, 7-10 parts glass fiber, 6-10 parts maleic anhydride-grafted ethylene-octene copolymer, 8-15 parts modified bamboo fiber, 0.5-1 part hydrolysis stabilizer, and 0.5-1 part lubricant. In this invention, modified bamboo fiber plays a major role in reinforcing the TPEE material. Firstly, the bamboo fiber is alkali-treated. Under alkaline conditions, the surface resin is removed, increasing the specific surface area and roughness, and reducing polarity differences. Simultaneously, grooves, pits, and microfibrils are formed on the fiber surface, facilitating the penetration of polyamide into these defects after melting. After curing, mechanical interlocking is formed, significantly improving the overall integrity and mechanical properties. Similarly, the intercalation treatment of montmorillonite effectively expands the interlayer spacing, facilitating intercalation bonding of polyamide during blending. After the three raw materials are melt-mixed, under temperature and shear conditions, the amide in the polyamide adsorbs onto the montmorillonite layer. At this point, the montmorillonite increases in volume, forming a physical cross-linked network in the mixture. Simultaneously, the polyamide also combines with the alkali-treated bamboo fiber, thus binding the montmorillonite and bamboo fiber together. The fiber bears the load transfer and dispersion, while the montmorillonite becomes the connection point in the network, significantly ensuring the integrity of the material under stress. When the modified bamboo fiber and glass fiber are added together to TPEE material, the glass fiber acts as a force transmission bridge, dispersing the load; the modified bamboo fiber, as the skeleton material in the modified material, can effectively improve the mechanical properties of the material; at the same time, the maleic anhydride groups react with the hydroxyl and carboxyl groups in the TPEE material to form covalent bonds, firmly anchoring various raw materials; in the blending modification, various raw materials are evenly dispersed without accumulation, effectively improving the mechanical properties of the material.
[0015] The method provided by this invention is simple and reliable, has low process requirements and high efficiency, and is suitable for large-scale modification preparation. Detailed Implementation
[0016] This invention provides a modified TPEE material, prepared from raw materials comprising the following parts by mass: 70-75 parts TPEE, 7-10 parts glass fiber, 6-10 parts maleic anhydride-grafted ethylene-octene copolymer, 8-15 parts modified bamboo fiber, 0.5-1 part hydrolysis stabilizer, and 0.5-1 part lubricant.
[0017] In this invention, the mass fraction of TPEE is preferably 70.5 to 74.5 parts, more preferably 71 to 74 parts, and even more preferably 72 to 73 parts.
[0018] In this invention, the mass fraction of glass fiber is preferably 7.5 to 9.5 parts, more preferably 8 to 9 parts, and even more preferably 8.5 to 8.8 parts.
[0019] In this invention, the mass fraction of maleic anhydride-grafted ethylene-octene copolymer is preferably 6.5 to 9.5 parts, more preferably 7 to 9 parts, and even more preferably 7.5 to 8 parts.
[0020] In this invention, the modified bamboo fiber is preferably 9 to 14 parts by weight, more preferably 10 to 13 parts, and even more preferably 11 to 12 parts by weight.
[0021] In this invention, the mass fraction of the anti-hydrolysis stabilizer is preferably 0.55 to 0.95 parts, more preferably 0.6 to 0.9 parts, and even more preferably 0.7 to 0.8 parts.
[0022] In this invention, the mass fraction of the lubricant is preferably 0.55 to 0.95 parts, more preferably 0.6 to 0.9 parts, and even more preferably 0.7 to 0.8 parts.
[0023] In this invention, the diameter of the glass fiber is preferably 10-13 μm, more preferably 11-12 μm, and even more preferably 11.5-11.8 μm; the length is preferably 1-2 mm, more preferably 1.2-1.8 mm, and even more preferably 1.4-1.6 mm.
[0024] In this invention, the method for preparing modified bamboo fiber includes the following steps: (1) Bamboo fiber is treated with alkali to obtain alkaline bamboo fiber; (2) Sodium-based montmorillonite, hexadecyltrimethylammonium bromide and water are mixed to obtain intercalated montmorillonite; (3) After the polyamide and intercalated montmorillonite are initially mixed, alkaline bamboo fiber is added for secondary mixing to obtain modified bamboo fiber.
[0025] In this invention, the length of bamboo fiber in step (1) is preferably 3~5mm, more preferably 3.5~4.5mm, and even more preferably 3.8~4.2mm; the reagent for alkali treatment is preferably sodium hydroxide solution, and the concentration of sodium hydroxide solution is preferably 4~6%, more preferably 4.5~5.5%, and even more preferably 4.8~5.2%.
[0026] In this invention, the preferred ratio of bamboo fiber to sodium hydroxide solution is 1g:10~15mL, more preferably 1g:11~14mL, and even more preferably 1g:12~13mL.
[0027] In this invention, the alkali treatment temperature is preferably 20~30℃, more preferably 22~28℃, and even more preferably 24~26℃; the time is preferably 6~12h, more preferably 8~10h, and even more preferably 8.5~9h; after the alkali treatment, the bamboo fiber is washed with water until neutral, dried, and pulverized to obtain alkaline bamboo fiber; the length of the pulverized material is preferably ≤1mm, more preferably ≤0.8mm, and even more preferably ≤0.5mm.
[0028] In this invention, the mass ratio of sodium montmorillonite, hexadecyltrimethylammonium bromide and water in step (2) is preferably 1:1~1.5:40~50, more preferably 1:1.1~1.4:42~48, and even more preferably 1:1.2~1.3:44~46.
[0029] In this invention, the mixing temperature in step (2) is preferably 70~80℃, more preferably 72~78℃, and even more preferably 74~76℃; the rotation speed is preferably 400~600rpm, more preferably 450~550rpm, and even more preferably 480~520rpm; and the time is preferably 4~6h, more preferably 4.5~5.5h, and even more preferably 4.8~5.2h.
[0030] In this invention, drying is performed before step (3), wherein the moisture content of the polyamide is preferably ≤0.8%, more preferably ≤0.7%, and more preferably ≤0.6%; the drying temperature of the intercalated montmorillonite is preferably 70~90℃, more preferably 75~85℃, and more preferably 78~82℃; the drying time is preferably ≥5h, more preferably ≥8h, and more preferably ≥10h; the drying temperature of the alkaline bamboo fiber is preferably 50~70℃, more preferably 55~65℃, and more preferably 58~62℃; the drying time is preferably ≥5h, more preferably ≥8h, and more preferably ≥10h.
[0031] In this invention, the mass ratio of polyamide, intercalated montmorillonite and alkaline bamboo fiber in step (3) is preferably 6~7:3~5:10~15, more preferably 6.2~6.8:3.5~4.5:11~14, and even more preferably 6.4~6.6:3.8~4.2:12~13.
[0032] In this invention, the temperature of the initial mixing in step (3) is preferably 180~225℃, more preferably 185~220℃, and even more preferably 190~210℃; the time is preferably 10~15min, more preferably 11~14min, and even more preferably 12~13min.
[0033] In this invention, the temperature of the secondary mixing in step (3) is preferably 225~235℃, more preferably 226~234℃, and even more preferably 228~232℃; the time is preferably 10~15min, more preferably 11~14min, and even more preferably 12~13min; after the secondary mixing is completed, the modified bamboo fiber is obtained by extrusion granulation.
[0034] In this invention, the hydrolysis stabilizer is one or more of N,N'-bis(2,6-diisopropylphenyl)carbodiimide, bisphenol A diglycidyl ether, and polyethylene glycol diglycidyl ether.
[0035] In this invention, the lubricant comprises one or more of calcium stearate, paraffin wax, and polyethylene wax.
[0036] The present invention also provides a method for preparing the modified TPEE material, comprising the following steps: (a) TPEE, maleic anhydride-grafted ethylene-octene copolymer, hydrolysis stabilizer and lubricant are mixed to obtain a blend; (b) Glass fiber and modified bamboo fiber are added to the blend and mixed to obtain the modified TPEE material.
[0037] In this invention, the mixing in steps (a) and (b) is carried out in a twin-screw extruder. The melting temperature of the mixture in step (a) is preferably 200~220°C, more preferably 205~215°C, and even more preferably 208~210°C; the time is preferably 10~20 min, more preferably 12~18 min, and even more preferably 14~16 min.
[0038] In this invention, the melting temperature of the mixture in step (b) is preferably 210~230°C, more preferably 215~225°C, and even more preferably 218~220°C; the time is preferably 10~15 min, more preferably 11~14 min, and even more preferably 12~13 min.
[0039] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.
[0040] Example 1
[0041] The following raw materials are prepared: 72 parts TPEE, 8 parts glass fiber, 7 parts maleic anhydride-grafted ethylene-octene copolymer, 10 parts modified bamboo fiber, 0.8 parts hydrolysis stabilizer, and 0.8 parts lubricant.
[0042] In the above raw materials, the glass fiber has a diameter of 10 μm and a length of 1.3 mm. The modified bamboo fiber is prepared according to the following method: bamboo fiber with a length of 4 mm is placed in a 5% sodium hydroxide solution with a ratio of 1 g: 14 mL and treated with alkali at 25 °C for 8 h. After treatment, it is washed with water until neutral, dried, and pulverized to obtain alkaline bamboo fiber with a length ≤ 0.8 mm. The mass ratio of sodium montmorillonite, hexadecyltrimethylammonium bromide, and water is controlled at 1:1.4:45. The mixture is mixed at 75 °C and 500 rpm for 5 h to obtain intercalated montmorillonite. The water content of polyamide is dried to below 0.8%, and the intercalated montmorillonite is dried at 80 °C for 8 h. The alkaline bamboo fiber is dried at 60 °C for 5 h. The mass ratio of polyamide, intercalated montmorillonite, and alkaline bamboo fiber is controlled at 6.5:4:13. The mixture is mixed at 180 °C for 15 min and then at 230 °C for 15 min. After mixing, the mixture is extruded and granulated to obtain modified bamboo fiber. The hydrolysis stabilizer is N,N'-bis(2,6-diisopropylphenyl)carbodiimide; the lubricant is calcium stearate.
[0043] The preparation method of modified TPEE material is as follows: TPEE, maleic anhydride-grafted ethylene-octene copolymer, anti-hydrolysis stabilizer and lubricant are mixed and mixed at 210℃ for 15 min in a twin-screw extruder; then glass fiber and modified bamboo fiber are added to the blend and mixed for another 15 min to obtain modified TPEE material.
[0044] Example 2
[0045] The following raw materials are used: 70 parts TPEE, 10 parts glass fiber, 8.5 parts maleic anhydride-grafted ethylene-octene copolymer, 14 parts modified bamboo fiber, 1 part hydrolysis stabilizer, and 1 part lubricant.
[0046] In the above raw materials, the glass fiber has a diameter of 12 μm and a length of 1.5 mm. The modified bamboo fiber is prepared according to the following method: bamboo fiber with a length of 3.5 mm is placed in a 4% sodium hydroxide solution with a ratio of 1 g: 12 mL and treated with alkali at 25 °C for 10 h. After treatment, it is washed with water until neutral, dried, and pulverized to obtain alkaline bamboo fiber with a length ≤ 1 mm. The mass ratio of sodium montmorillonite, hexadecyltrimethylammonium bromide, and water is controlled at 1:1.1:50. The mixture is then mixed at 80 °C and 400 rpm for 4 h to obtain intercalated montmorillonite. The water content of polyamide is dried to below 0.7%, and the intercalated montmorillonite is dried at 70 °C for 5 h. The alkaline bamboo fiber is dried at 50 °C for 5 h. The mass ratio of polyamide, intercalated montmorillonite, and alkaline bamboo fiber is controlled at 7:3:10. The mixture is then mixed at 200 °C for 15 min and then at 225 °C for 10 min. After mixing, the mixture is extruded and granulated to obtain modified bamboo fiber. The hydrolysis stabilizer is bisphenol A diglycidyl ether; the lubricant is paraffin wax.
[0047] The preparation method of modified TPEE material is as follows: TPEE, maleic anhydride-grafted ethylene-octene copolymer, anti-hydrolysis stabilizer and lubricant are mixed and mixed in a twin-screw extruder at 200℃ for 10 min; then glass fiber and modified bamboo fiber are added to the blend and the temperature is controlled at 220℃ and mixed for another 15 min to obtain modified TPEE material.
[0048] Example 3
[0049] The following raw materials are used: 73 parts TPEE, 9 parts glass fiber, 6 parts maleic anhydride-grafted ethylene-octene copolymer, 9 parts modified bamboo fiber, 0.7 parts hydrolysis stabilizer, and 1 part lubricant.
[0050] In the above raw materials, the glass fiber has a diameter of 13 μm and a length of 1 mm. The modified bamboo fiber is prepared according to the following method: bamboo fiber with a length of 4 mm is placed in a 5.5% sodium hydroxide solution with a ratio of 1 g: 11 mL and treated with alkali at 30 °C for 8 h. After treatment, it is washed with water until neutral, dried, and pulverized to obtain alkaline bamboo fiber with a length ≤ 0.8 mm. The mass ratio of sodium montmorillonite, hexadecyltrimethylammonium bromide, and water is controlled at 1:1.4:50. The mixture is mixed at 70 °C and 600 rpm for 5 h to obtain intercalated montmorillonite. The water content of polyamide is dried to below 0.8%, and the intercalated montmorillonite is dried at 90 °C for 6 h. The alkaline bamboo fiber is dried at 60 °C for 8 h. The mass ratio of polyamide, intercalated montmorillonite, and alkaline bamboo fiber is controlled at 6.5:5:11. The mixture is mixed at 180 °C for 10 min and then at 230 °C for 15 min. After mixing, the modified bamboo fiber is obtained by extrusion granulation. The hydrolysis stabilizer is polyethylene glycol diglycidyl ether; the lubricant is polyethylene wax.
[0051] The preparation method of modified TPEE material is as follows: TPEE, maleic anhydride-grafted ethylene-octene copolymer, anti-hydrolysis stabilizer and lubricant are mixed and mixed in a twin-screw extruder at 210℃ for 15min; then glass fiber and modified bamboo fiber are added to the blend and the temperature is controlled at 220℃ and mixed for another 10min to obtain modified TPEE material.
[0052] The modified TPEE materials prepared in Examples 1-3 were subjected to performance tests, and the results are recorded in Table 1.
[0053] Table 1 Performance Test Results
[0054] As can be seen from Table 1, the modified TPEE material provided by this invention has excellent mechanical properties and significantly broadens its application scenarios.
[0055] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.
Claims
1. A modified TPEE material, characterized in that, It is prepared from raw materials comprising the following parts by mass: 70-75 parts TPEE, 7-10 parts glass fiber, 6-10 parts maleic anhydride-grafted ethylene-octene copolymer, 8-15 parts modified bamboo fiber, 0.5-1 part hydrolysis stabilizer, and 0.5-1 part lubricant.
2. The modified TPEE material as described in claim 1, characterized in that, The glass fibers have a diameter of 10~13μm and a length of 1~2mm.
3. The modified TPEE material as described in claim 2, characterized in that, The preparation method of modified bamboo fiber includes the following steps: (1) Bamboo fiber is treated with alkali to obtain alkaline bamboo fiber; (2) Sodium-based montmorillonite, hexadecyltrimethylammonium bromide and water are mixed to obtain intercalated montmorillonite; (3) After the polyamide and intercalated montmorillonite are initially mixed, alkaline bamboo fiber is added for secondary mixing to obtain modified bamboo fiber.
4. The modified TPEE material as described in claim 3, characterized in that, In step (1), the length of the bamboo fiber is 3-5 mm, and the reagent for alkali treatment is sodium hydroxide solution with a concentration of 4-6%. The ratio of bamboo fiber to sodium hydroxide solution is 1g: 10~15mL; The alkali treatment temperature is 20~30℃, and the time is 6~12h.
5. The modified TPEE material as described in claim 4, characterized in that, In step (2), the mass ratio of sodium montmorillonite, hexadecyltrimethylammonium bromide, and water is 1:1~1.5:40~50; In step (2), the mixing temperature is 70~80℃, the rotation speed is 400~600rpm, and the time is 4~6h.
6. The modified TPEE material as described in claim 5, characterized in that, In step (3), the mass ratio of polyamide, intercalated montmorillonite, and alkaline bamboo fiber is 6~7:3~5:10~15; In step (3), the initial mixing temperature is 180~225℃; the time is 10~15min. In step (3), the temperature for the second mixing is 225~235℃ and the time is 10~15min.
7. The modified TPEE material according to any one of claims 1 to 6, characterized in that, The hydrolysis stabilizer is one or more of N,N'-bis(2,6-diisopropylphenyl)carbodiimide, bisphenol A bisglycidyl ether, and polyethylene glycol diglycidyl ether. The lubricant comprises one or more of calcium stearate, paraffin wax, and polyethylene wax.
8. A method for preparing the modified TPEE material according to any one of claims 1 to 7, characterized in that, Includes the following steps: (a) TPEE, maleic anhydride-grafted ethylene-octene copolymer, hydrolysis stabilizer and lubricant are mixed to obtain a blend; (b) Glass fiber and modified bamboo fiber are added to the blend and mixed to obtain the modified TPEE material.
9. The method for preparing the modified TPEE material as described in claim 8, characterized in that, The melting temperature of the mixture in step (a) is 200~220℃ and the time is 10~20min.
10. The method for preparing the modified TPEE material as described in claim 9, characterized in that, In step (b), the melting temperature of the mixture is 210~230℃ and the time is 10~15min.