Heat-resistant toughened high-performance nylon composite material and preparation method thereof

Abstract

The invention discloses a heat-resistant and toughened high-performance nylon composite material, and discloses a preparation method of the heat-resistant and toughened high-performance nylon composite material, and the heat-resistant and toughened high-performance nylon composite material comprises the following raw materials by weight: 20-30 parts of nylon PA66; 15 to 25 parts of nylon PA6; 10 to 15 parts of nylon PA610; 3 to 8 parts of POE-G-MAH; 2 to 5 parts of SEBS-G-MAH (Styrene Ethylene Butylene 1 to 3 parts of EPDM-G-MAH (Ethylene-Propylene 0.05 to 0.15 part of a copper salt antioxidant; 0.1 to 0.3 part of a phosphite ester antioxidant; 0.1 to 0.2 part of a light stabilizer; 5 to 8 parts of glass fiber; 1-2 parts of a lubricant; 0.5 to 2 parts of a coupling agent; wherein the total content of the POE-G-MAH, the SEBS-G-MAH and the EPDM-G-MAH ranges from 8% to 20%. A PA66, PA6 and PA610 ternary nylon blending system is adopted, and the comprehensive heat resistance of the material is improved by utilizing the performance complementation of different nylons; three grafted elastomers, namely POE-G-MAH, SEBS-G-MAH and EPDM-G-MAH, are adopted, and the content of a total toughening agent is controlled to be 8-20%, so that the rigidity of the material is not influenced while the toughening effect is ensured.

Description

Technical Field

[0001] This invention relates to the field of nylon materials technology, and in particular to a heat-resistant and toughened high-performance nylon composite material and its preparation method. Background Technology

[0002] Nylon materials are widely used in automobiles, electronics, and machinery manufacturing due to their excellent mechanical properties, heat resistance, and chemical stability. However, traditional nylon materials are prone to thermo-oxidative aging at high temperatures, leading to performance degradation and limiting their application in high-temperature conditions.

[0003] Existing toughening and modification technologies for nylon materials mainly employ a single toughening agent system, which suffers from insufficient resistance to heat and oxygen aging and poor long-term stability. Summary of the Invention

[0004] This invention aims to at least solve one of the technical problems existing in the prior art. To this end, this invention proposes a heat-resistant and toughened high-performance nylon composite material that can increase toughness and heat resistance without affecting rigidity.

[0005] The present invention also proposes a high-performance nylon composite material B having the above-mentioned heat-resistant and toughened properties.

[0006] The heat-resistant and toughened high-performance nylon composite material according to a first aspect of the present invention comprises the following raw materials in parts by weight: nylon PA66: 20-30 parts; nylon PA6: 15-25 parts; nylon PA610: 10-15 parts; POE-G-MAH: 3-8 parts; SEBS-G-MAH: 2-5 parts; EPDM-G-MAH: 1-3 parts; copper salt antioxidant: 0.05-0.15 parts; phosphite antioxidant: 0.1-0.3 parts; light stabilizer: 0.1-0.2 parts; glass fiber: 5-8 parts; lubricant: 1-2 parts; coupling agent: 0.5-2 parts; wherein the total content of POE-G-MAH, SEBS-G-MAH and EPDM-G-MAH is 8%-20%.

[0007] The heat-resistant and toughened high-performance nylon composite material according to embodiments of the present invention has at least the following beneficial effects: It employs a ternary nylon blend system of PA66, PA6, and PA610, utilizing the complementary properties of different nylons to improve the overall heat resistance of the material; it uses three grafted elastomers—POE-G-MAH, SEBS-G-MAH, and EPDM-G-MAH—with the total toughening agent content controlled at 8%-20%, ensuring the toughening effect without affecting the rigidity of the material.

[0008] According to some embodiments of the present invention, the copper salt antioxidant is selected from one or more of cuprous iodide, cuprous bromide, and cuprous chloride.

[0009] According to some embodiments of the present invention, the phosphite antioxidant is selected from one or more of antioxidant 168, antioxidant 618, and antioxidant 626.

[0010] According to some embodiments of the present invention, the light stabilizer is selected from one or more of hindered amine light stabilizers, benzotriazole light stabilizers, and benzophenone light stabilizers.

[0011] According to some embodiments of the present invention, the lubricant is selected from one or more of zinc stearate, calcium stearate, and ethylene bis-stearamide.

[0012] According to some embodiments of the present invention, the coupling agent is selected from one or more of silane coupling agents KH550, KH560, and KH570.

[0013] According to a second aspect of the present invention, a method for preparing a heat-resistant and toughened high-performance nylon composite material according to a first aspect of the present invention comprises the following steps: Step 1: Weigh all raw materials according to their weight proportions, and dry the nylon resin at 80-100℃ for 4-6 hours; Step 2: Dry the nylon PA66, PA6, and PA610 resins in a hot air circulating drying oven at 80-100℃ for 4-6 hours, and preheat the glass fiber at 110-130℃ for 2-3 hours. Step 3: Add the dried nylon PA66, PA6, and PA610 resins to a high-speed mixer and mix at 50-60℃ for 2-3 minutes; Step 4: Add POE-G-MAH, SEBS-G-MAH, EPDM-G-MAH and other toughening agents in sequence, and continue mixing for 3-5 minutes; Step 5: Add copper salt antioxidant, phosphite antioxidant, light stabilizer, lubricant and coupling agent, and mix at 80-100℃ for 5-8 minutes; Step 6: Add the preheated glass fiber to the twin-screw extruder via a side-feeding device; Step 7: Cool the material extruded from the twin-screw extruder to 40-60℃; Step 8: Cut the material into pellets using underwater pelletizing or air-cooled pelletizing methods; Step 9: Dry the cut granules at 80-100℃ for 2-4 hours.

[0014] The preparation method according to the embodiments of the present invention has at least the following beneficial effects: using a ternary nylon blend system of PA66, PA6, and PA610, the complementary properties of different nylons are utilized to improve the overall heat resistance of the material; using three grafted elastomers, POE-G-MAH, SEBS-G-MAH, and EPDM-G-MAH, the total toughening agent content is controlled at 8%-20%, ensuring the toughening effect without affecting the rigidity of the material.

[0015] According to some embodiments of the present invention, the total mixing time of steps 3 to 4 is controlled to be 10-15 minutes.

[0016] According to some embodiments of the present invention, the moisture content of the material after step 9 is controlled to be below 0.05%.

[0017] According to some embodiments of the present invention, the moisture content of the nylon resin after drying in step 1 is controlled to be below 0.05%.

[0018] Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Detailed Implementation

[0019] The embodiments of the present invention are described in detail below, wherein the same or similar reference numerals denote the same or similar elements or elements having the same or similar functions throughout. The following embodiments are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention.

[0020] In the description of this invention, it should be understood that the orientation descriptions, such as up, down, front, back, left, right, etc., indicating the orientation or positional relationship, are based on the indicated orientation or positional relationship and are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation, and therefore should not be construed as a limitation of this invention.

[0021] In the description of this invention, "several" means one or more, "more than" means two or more, "greater than," "less than," and "exceeding" are understood to exclude the stated number, while "above," "below," and "within" are understood to include the stated number. The use of "first" and "second" in the description is merely for distinguishing technical features and should not be construed as indicating or implying relative importance, or implicitly indicating the number of indicated technical features, or implicitly indicating the order of the indicated technical features.

[0022] In the description of this invention, unless otherwise explicitly defined, terms such as "set up," "install," and "connect" should be interpreted broadly, and those skilled in the art can reasonably determine the specific meaning of the above terms in this invention in conjunction with the specific content of the technical solution.

[0023] Example 1: High-performance nylon composite material is prepared by the following steps: Step 1: Weigh all raw materials according to their weight proportions, and dry the nylon resin at 80-100℃ for 4-6 hours; Step 2: Dry the nylon PA66, PA6, and PA610 resins in a hot air circulating drying oven at 80-100℃ for 4-6 hours, and preheat the glass fiber at 110-130℃ for 2-3 hours. Step 3: Add the dried nylon PA66, PA6, and PA610 resins to a high-speed mixer and mix at 50-60℃ for 2-3 minutes; Step 4: Add POE-G-MAH, SEBS-G-MAH, EPDM-G-MAH and other toughening agents in sequence, and continue mixing for 3-5 minutes; Step 5: Add copper salt antioxidant, phosphite antioxidant, light stabilizer, lubricant and coupling agent, and mix at 80-100℃ for 5-8 minutes; Step 6: Add the preheated glass fiber to the twin-screw extruder via a side-feeding device; Step 7: Cool the material extruded from the twin-screw extruder to 40-60℃; Step 8: Cut the material into pellets using underwater pelletizing or air-cooled pelletizing methods; Step 9: Dry the cut granules at 80-100℃ for 2-4 hours.

[0024] The composition includes: Nylon PA66: 20 parts; Nylon PA6: 25 parts; Nylon PA610: 15 parts; POE-G-MAH: 3 parts; SEBS-G-MAH: 5 parts; EPDM-G-MAH: 1 part; other toughening agents: 2 parts; copper salt antioxidant: 0.05 parts; phosphite antioxidant: 0.3 parts; light stabilizer: 0.1 parts; glass fiber: 5 parts; lubricant: 1 part; coupling agent: 0.5 parts.

[0025] Example 1: Resistance to heat and oxygen aging (heat aging conditions: 150℃, 1000 hours) Performance indicators before aging After aging retention rate Tensile strength 88 MPa 77 MPa 87.5% Bending strength 125 MPa 106 MPa 84.8% Cantilever beam impact strength <![CDATA[9.2 kJ / m 2 ]]> <![CDATA[5.2 kJ / m 2 ]]> 56.5% The heat distortion temperature of Example 1 is 185℃; in addition, as shown in the table above, the impact strength retention rate of Example 1 after aging at 150℃ for 1000h is 56.5%.

[0026] Example 2: High-performance nylon composite material is prepared by the following steps: Step 1: Weigh all raw materials according to their weight proportions, and dry the nylon resin at 80-100℃ for 4-6 hours; Step 2: Dry the nylon PA66, PA6, and PA610 resins in a hot air circulating drying oven at 80-100℃ for 4-6 hours, and preheat the glass fiber at 110-130℃ for 2-3 hours. Step 3: Add the dried nylon PA66, PA6, and PA610 resins to a high-speed mixer and mix at 50-60℃ for 2-3 minutes; Step 4: Add POE-G-MAH, SEBS-G-MAH, EPDM-G-MAH and other toughening agents in sequence, and continue mixing for 3-5 minutes; Step 5: Add copper salt antioxidant, phosphite antioxidant, light stabilizer, lubricant and coupling agent, and mix at 80-100℃ for 5-8 minutes; Step 6: Add the preheated glass fiber to the twin-screw extruder via a side-feeding device; Step 7: Cool the material extruded from the twin-screw extruder to 40-60℃; Step 8: Cut the material into pellets using underwater pelletizing or air-cooled pelletizing methods; Step 9: Dry the cut granules at 80-100℃ for 2-4 hours.

[0027] The composition includes: Nylon PA66: 30 parts; Nylon PA6: 15 parts; Nylon PA610: 10 parts; POE-G-MAH: 8 parts; SEBS-G-MAH: 2 parts; EPDM-G-MAH: 3 parts; other toughening agents: 4 parts; copper salt antioxidant: 0.15 parts; phosphite antioxidant: 0.1 parts; light stabilizer: 0.2 parts; glass fiber: 8 parts; lubricant: 2 parts; coupling agent: 2 parts.

[0028] Example 2: Resistance to heat and oxygen aging (heat aging conditions: 150℃, 1000 hours) Performance indicators before aging After aging retention rate Tensile strength 92 MPa 80 MPa 86.9% Bending strength 132 MPa 110 MPa 83.3% Cantilever beam impact strength <![CDATA[8.8 kJ / m 2 ]]> <![CDATA[5.1 kJ / m 2 ]]> 57.9% In Example 2, the heat distortion temperature was 188℃. Furthermore, as shown in the table above, the impact strength retention rate after aging at 150℃ for 1000 hours in Example 2 was 57.9%.

[0029] Example 3: High-performance nylon composite material is prepared by the following steps: Step 1: Weigh all raw materials according to their weight proportions, and dry the nylon resin at 80-100℃ for 4-6 hours; Step 2: Dry the nylon PA66, PA6, and PA610 resins in a hot air circulating drying oven at 80-100℃ for 4-6 hours, and preheat the glass fiber at 110-130℃ for 2-3 hours. Step 3: Add the dried nylon PA66, PA6, and PA610 resins to a high-speed mixer and mix at 50-60℃ for 2-3 minutes; Step 4: Add POE-G-MAH, SEBS-G-MAH, EPDM-G-MAH and other toughening agents in sequence, and continue mixing for 3-5 minutes; Step 5: Add copper salt antioxidant, phosphite antioxidant, light stabilizer, lubricant and coupling agent, and mix at 80-100℃ for 5-8 minutes; Step 6: Add the preheated glass fiber to the twin-screw extruder via a side-feeding device; Step 7: Cool the material extruded from the twin-screw extruder to 40-60℃; Step 8: Cut the material into pellets using underwater pelletizing or air-cooled pelletizing methods; Step 9: Dry the cut granules at 80-100℃ for 2-4 hours.

[0030] The composition includes: Nylon PA66: 25 parts; Nylon PA6: 20 parts; Nylon PA610: 12 parts; POE-G-MAH: 5 parts; SEBS-G-MAH: 3 parts; EPDM-G-MAH: 2 parts; other toughening agents: 3 parts; copper salt antioxidant: 0.1 parts; phosphite antioxidant: 0.2 parts; light stabilizer: 0.15 parts; glass fiber: 6 parts; lubricant: 1.5 parts; coupling agent: 1 part.

[0031] Example 3: Heat and oxygen aging resistance (heat aging conditions: 150℃, 1000 hours) Performance indicators before aging After aging retention rate Tensile strength 90 MPa 76 MPa 84.4% Bending strength 130 MPa 108 MPa 83.1% Cantilever beam impact strength <![CDATA[10 kJ / m 2 ]]> <![CDATA[5.2 kJ / m 2 ]]> 52.0% In Example 3, the heat distortion temperature was 186℃. Furthermore, as shown in the table above, the impact strength retention rate after aging at 150℃ for 1000 hours in Example 3 was 52%.

[0032] Traditional nylon materials typically retain less than 40% of their impact strength after aging at 150°C for 1000 hours. However, in Examples 1 to 3 above, the impact strength retention rate of the high-performance nylon composite materials reaches over 52%, and their heat distortion temperature is all above 180°C, demonstrating excellent heat resistance.

[0033] In summary, a ternary nylon blend system of PA66, PA6, and PA610 was adopted to improve the overall heat resistance of the material by utilizing the complementary properties of different nylons. Three grafted elastomers, POE-G-MAH, SEBS-G-MAH, and EPDM-G-MAH, were used, and the total toughening agent content was controlled at 8%-20% to ensure toughening effect without affecting the rigidity of the material.

[0034] As a further optimization of the above embodiments one to three and the remaining extended embodiments, the copper salt antioxidant is selected from one or more of cuprous iodide, cuprous bromide, and cuprous chloride.

[0035] In some embodiments, the phosphite antioxidant is selected from one or more of antioxidant 168, antioxidant 618, and antioxidant 626.

[0036] In some embodiments, the light stabilizer is selected from one or more of hindered amine light stabilizers, benzotriazole light stabilizers, and benzophenone light stabilizers.

[0037] In some embodiments, the lubricant is selected from one or more of zinc stearate, calcium stearate, and ethylene bis-stearamide.

[0038] In some embodiments, the coupling agent is selected from one or more of silane coupling agents KH550, KH560, and KH570.

[0039] As a further optimization of the above embodiments one to three and the remaining extended embodiments, in steps 3 to 4 of the preparation method, the total mixing time of steps 3 to 4 is controlled at 10-15 minutes.

[0040] In some embodiments, the moisture content of the material after step 9 is controlled to be below 0.05%.

[0041] In some embodiments, the moisture content of the nylon resin after drying in step 1 is controlled to be below 0.05%.

[0042] The embodiments of the present invention have been described in detail above. However, the present invention is not limited to the above embodiments. Within the scope of knowledge possessed by those skilled in the art, various changes can be made without departing from the spirit of the present invention.

Claims

1. A heat-resistant and toughened high-performance nylon composite material, characterized in that, The raw materials include the following parts by weight: Nylon PA66: 20-30 parts; Nylon PA6: 15-25 parts; Nylon PA610: 10-15 parts; POE-G-MAH: 3-8 parts; SEBS-G-MAH: 2-5 parts; EPDM-G-MAH: 1-3 parts; Copper salt antioxidant: 0.05-0.15 parts; Phosphite antioxidant: 0.1-0.3 parts; Light stabilizer: 0.1-0.2 parts; glass fiber: 5-8 parts; Lubricant: 1-2 parts; Coupling agent: 0.5-2 parts; wherein the total content of POE-G-MAH, SEBS-G-MAH and EPDM-G-MAH is 8%-20%.

2. The heat-resistant and toughened high-performance nylon composite material according to claim 1, characterized in that, The copper salt antioxidant is selected from one or more of cuprous iodide, cuprous bromide, and cuprous chloride.

3. The heat-resistant and toughened high-performance nylon composite material according to claim 1, characterized in that, The phosphite antioxidant is selected from one or more of antioxidant 168, antioxidant 618, and antioxidant 626.

4. The heat-resistant and toughened high-performance nylon composite material according to claim 1, characterized in that, The light stabilizer is selected from one or more of hindered amine light stabilizers, benzotriazole light stabilizers, and benzophenone light stabilizers.

5. The heat-resistant and toughened high-performance nylon composite material according to claim 1, characterized in that, The lubricant is selected from one or more of zinc stearate, calcium stearate, and ethylene bis-stearamide.

6. The heat-resistant and toughened high-performance nylon composite material according to claim 1, characterized in that, The coupling agent is selected from one or more of the silane coupling agents KH550, KH560, and KH570.

7. A preparation method for preparing the heat-resistant and toughened high-performance nylon composite material according to any one of claims 1-6, characterized in that, Includes the following steps: Step 1: Weigh all raw materials according to their weight proportions, and dry the nylon resin at 80-100℃ for 4-6 hours; Step 2: Dry the nylon PA66, PA6, and PA610 resins in a hot air circulating drying oven at 80-100℃ for 4-6 hours, and preheat the glass fiber at 110-130℃ for 2-3 hours. Step 3: Add the dried nylon PA66, PA6, and PA610 resins to a high-speed mixer and mix at 50-60℃ for 2-3 minutes; Step 4: Add POE-G-MAH, SEBS-G-MAH, EPDM-G-MAH and other toughening agents in sequence, and continue mixing for 3-5 minutes; Step 5: Add copper salt antioxidant, phosphite antioxidant, light stabilizer, lubricant and coupling agent, and mix at 80-100℃ for 5-8 minutes; Step 6: Add the preheated glass fiber to the twin-screw extruder via a side-feeding device; Step 7: Cool the material extruded from the twin-screw extruder to 40-60℃; Step 8: Cut the material into pellets using underwater pelletizing or air-cooled pelletizing methods; Step 9: Dry the cut granules at 80-100℃ for 2-4 hours.

8. The preparation method according to claim 7, characterized in that, The total mixing time for steps 3 to 4 should be controlled within 10-15 minutes.

9. The preparation method according to claim 7, characterized in that, The moisture content of the material after step 9 should be controlled below 0.05%.

10. The preparation method according to claim 7, characterized in that, The moisture content of the nylon resin after drying in step 1 is controlled to be below 0.05%.