A bio-based long carbon chain nylon alloy reinforcing material and a preparation method thereof

Abstract

The present application relates to a kind of bio-based long carbon chain nylon alloy reinforcing material and its preparation method, the bio-based long carbon chain nylon alloy reinforcing material is prepared from the following components by mass percentage: EPDM resin 10-15%, compatible agent 4-10%, carbon fiber 10-25%, lubricant 0.2-0.7%, antioxidant 0.2-1%, heat stabilizer 0.3-1.5%, PA610 high viscosity resin balance.The present application uses PA610 high viscosity resin and EPDM resin to form alloy material, with PA610 high viscosity resin as main base material, material melt strength is high, is beneficial to blow molding, but it is relatively hard, by the EPDM resin added can reduce material hardness, ensure the softness and comfort of product, also can improve the salt resistance of material PA610 by more than 40%, simultaneously, since the excellent low temperature performance of EPDM, can resist-70 DEG C low temperature, the cold resistance of PA610 is relatively poor, PA610 is added with EPDM, can ensure the normal use of product in cold environment for a long time.

Description

Technical Field

[0001] This invention relates to the field of polymer materials technology, and in particular to a bio-based long carbon chain nylon alloy reinforced material and its preparation method. Background Technology

[0002] Bio-based long-chain nylon materials are widely used in pipelines in transportation, electrical, and transmission industries due to their advantages such as bio-based monomer polymerization, low carbon footprint and environmental friendliness, relatively low water absorption, high mechanical properties, good self-lubricating properties, excellent fatigue resistance, good chemical solvent resistance, good low-temperature performance, and a balance of rigidity and flexibility. For pipeline components used in near-shore high-humidity and high-salt environments or in contact with de-icing agents, ordinary nylon has poor salt resistance and is prone to cracking within a short period. Long-chain nylon has good salt resistance, but its low-temperature resistance is insufficient. Furthermore, since most pipe fittings are irregularly shaped, blow molding has significant advantages over extrusion and injection molding, and its molding efficiency is higher. However, ordinary bio-based long-chain nylon materials have poor blow molding properties. Since these components are used in functional or thermal environments, excellent long-term thermal aging performance is required, which ordinary bio-based long-chain nylon materials cannot meet. Summary of the Invention

[0003] Based on this, the purpose of this invention is to provide a blow-molded, conductive, aging-resistant, and salt-corrosion-resistant bio-based long-chain carbon nylon alloy reinforced material and its preparation method, so as to solve the problems mentioned in the background art.

[0004] To achieve the above objectives, the present invention adopts the following technical solution.

[0005] The present invention provides a bio-based long carbon chain nylon alloy reinforced material, which is prepared from the following components in the following mass percentages: 10-15% EPDM resin, 4-10% compatibilizer, 10-25% carbon fiber, 0.2-0.7% lubricant, 0.2-1% antioxidant, 0.3-1.5% heat stabilizer, and the balance of PA610 high viscosity resin.

[0006] This invention uses PA610 high-viscosity resin and EPDM resin to form an alloy material. PA610 high-viscosity resin is the main base material. The material has high melt strength, which is beneficial for blow molding, but it is relatively hard. By adding EPDM resin, the hardness of the material can be reduced, ensuring the softness and comfort of the product. It can also improve the salt resistance of PA610 by more than 40%. At the same time, because EPDM has excellent low-temperature performance, it can withstand temperatures as low as -70℃. PA610 has relatively poor cold resistance. Adding EPDM to PA610 can ensure the normal use of the product in cold environments for a long time.

[0007] As a further improvement to the above-mentioned solution of the present invention, the EPDM resin is a blow-molded EPDM resin, and the flowability of the EPDM resin is less than 0.5 g / 10 min.

[0008] As a further improvement to the above-described scheme of the present invention, the compatibilizer is at least one of grafted PE, grafted PP and grafted POE.

[0009] As a further improvement to the above-mentioned solution of the present invention, the carbon fiber is short-cut carbon fiber, and the carbon fiber is at least one grade of carbon fiber selected from TC-35-12000, T-700, and SYT49S-12.

[0010] As a further improvement to the above-described solution of the present invention, the lubricant is at least one of PETS, OP wax, silicone, silicone oil and mesoamide.

[0011] As a further improvement of the above-described solution of the present invention, the antioxidant includes a primary antioxidant and a secondary antioxidant. The primary antioxidant is at least one of antioxidant 245, antioxidant 1010, antioxidant 1098, and antioxidant 9228, and the secondary antioxidant is at least one of antioxidant 168 and antioxidant 626.

[0012] As a further improvement to the above-mentioned scheme of the present invention, the heat stabilizer is at least one of the following: inorganic copper salt nylon heat stabilizer, organic copper salt nylon heat stabilizer, inorganic phosphate nylon heat stabilizer, aluminum silicate treated with titanate and dipentaerythritol (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate) compound heat stabilizer.

[0013] As a further improvement to the above-mentioned solution of the present invention, the colorant is at least one of nylon carrier aniline black masterbatch and PE carrier black masterbatch.

[0014] As a further improvement to the above-mentioned solution of the present invention, the relative viscosity of the PA610 high-viscosity resin is 5-6.

[0015] This invention proposes a method for preparing the aforementioned bio-based long-chain nylon alloy reinforced material, comprising the following steps:

[0016] Weigh each component according to the ratio, mix PA610 high viscosity resin, EPDM resin, compatibilizer and colorant evenly, then add lubricant, main antioxidant, auxiliary antioxidant and heat stabilizer and mix evenly to obtain a mixture.

[0017] The mixture is added to the main feed port of a twin-screw extruder, while carbon fibers are fed into the side feed port. After melting, extrusion, cooling, air drying, and pelletizing, a bio-based long carbon chain nylon alloy reinforced material is obtained.

[0018] The temperatures of the twin-screw extruder from the first zone to the die head are 215℃, 225℃, 230℃, 230℃, 230℃, 225℃, 220℃, 220℃, 220℃, 220℃, 220℃, and 230℃ respectively; the screw speed is 400 rpm, and the feeding speed is 25-30 rpm.

[0019] It should be noted that any range described in this invention includes the endpoint value, any value between the endpoint values, and any sub-range formed by the endpoint value or any value between the endpoint values.

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] 1. This invention uses PA610 high-viscosity resin and EPDM resin to form an alloy material. PA610 high-viscosity resin is the main base material. The material has high melt strength, which is beneficial for blow molding, but it is relatively hard. By adding EPDM resin, the hardness of the material can be reduced, ensuring the softness and comfort of the product. It can also improve the salt resistance of PA610 by more than 40%. At the same time, because EPDM has excellent low-temperature performance, it can withstand temperatures as low as -70℃. PA610 has relatively poor cold resistance. Adding EPDM to PA610 can ensure the normal use of the product in cold environments for a long time.

[0022] 2. Due to the poor compatibility between PA610 and EPDM, this invention improves the compatibility between PA610 high-viscosity resin and EPDM resin by adding a compatibilizer, thus meeting material performance requirements and improving salt resistance. By adding heat stabilizers and antioxidants, the product's 80% impact strength retention time at 120℃ can be increased from 600 hours to 2000 hours, which helps maintain long-term stable performance and ensures long-term use in high-salt environments. The addition of lubricants helps improve the product's appearance and reduce carbon fiber leakage. The addition of special colorants helps improve the product's appearance, avoids undesirable appearance caused by carbon fibers, and makes the product's color black, glossy, and uniform.

[0023] 3. This invention uses bio-based long-chain nylon PA610 high-viscosity resin as the base resin. Compared with conventional nylon, PA610 has low water absorption, good low-temperature resistance, and good resistance to ethylene glycol and salt. Furthermore, the monomers are derived from castor oil, making it more low-carbon and environmentally friendly, and more in line with the national policy of energy conservation and emission reduction. Detailed Implementation

[0024] To facilitate understanding of the present invention, a more comprehensive description will be given below with reference to specific embodiments. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a more thorough and complete understanding of the disclosure of the present invention.

[0025] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0026] The specific information of the raw materials used in the following examples and comparative examples is as follows:

[0027] The lubricant is a silicone masterbatch manufactured by Dow Corning, with the brand name MB50-008.

[0028] The main antioxidant is antioxidant 1098, manufactured by Tianjin Lialong, and its brand name is RIANOX 1098;

[0029] The auxiliary antioxidant is antioxidant 168, manufactured by Tianjin Lialong, and its brand name is RIANOX 168;

[0030] Heat stabilizer, manufactured by Brügmann, brand name H318;

[0031] Colorant, manufactured by Gaolai, brand name N1033;

[0032] PA610 high viscosity resin, manufactured by Shandong Dongchen, brand name PA610 high viscosity, relative viscosity is 5;

[0033] EPDM resin, manufactured by Mitsui Chemicals, brand name 2032PM;

[0034] Short-cut carbon fiber, manufactured by Zhongfu Shenying, grade SYT49S-12;

[0035] It is understood that the above raw materials and reagents are merely examples of some specific embodiments of the present invention, making the technical solution of the present invention clearer, and do not mean that the present invention can only use the above reagents. The specific scope shall be determined by the claims.

[0036] Example 1

[0037] This embodiment proposes a bio-based long carbon chain nylon alloy reinforced material, comprising the following raw materials by mass percentage: 63.25% PA610 high viscosity resin, 10% EPDM resin, 4% compatibilizer, 20% chopped carbon fiber, 0.3% lubricant, 0.15% primary antioxidant, 0.3% secondary antioxidant, 0.5% heat stabilizer, and 1.5% colorant.

[0038] The preparation method of the bio-based long carbon chain nylon alloy reinforced material in this embodiment includes the following steps:

[0039] (1) Drying treatment: First, dry the PA610 high viscosity resin at 80℃ for 6 hours for later use; then weigh each raw material according to the mass percentage.

[0040] (2) Mixing: Add the weighed PA610 high viscosity resin, EPDM resin, compatibilizer and colorant to a high-speed mixer and mix at high speed for 5 minutes. Then add the weighed lubricant, antioxidant and heat stabilizer and continue to mix at high speed for 5 minutes to obtain the mixture.

[0041] (3) Melt extrusion: The above mixture is added to the main feed port of the twin-screw extruder. While melt extruding, the weighed short-cut carbon fibers are fed into the side feed port for melt extrusion. The temperature of the twin-screw extruder from the first zone to the die head is 215℃, 225℃, 230℃, 230℃, 230℃, 225℃, 220℃, 220℃, 220℃, 220℃, 220℃, 230℃; the screw speed is 400 rpm, and the feed rate is 25-30 rpm.

[0042] (4) Extrusion pelletizing: The extruded material is cooled, dried, pelletized, passed through a vibrating screen, homogenized in a homogenizing tank and packaged to obtain the finished product, which is a blow-molded, conductive, aging-resistant and salt-corrosion-resistant bio-based long carbon chain nylon alloy reinforced material.

[0043] Example 2

[0044] This embodiment proposes a bio-based long carbon chain nylon alloy reinforced material, comprising the following raw materials by mass percentage: 58.25% PA610 high viscosity resin, 15% EPDM resin, 4% compatibilizer, 20% chopped carbon fiber, 0.3% lubricant, 0.15% primary antioxidant, 0.3% secondary antioxidant, 0.5% heat stabilizer, and 1.5% colorant.

[0045] The preparation method of the bio-based long carbon chain nylon alloy reinforced material in this embodiment includes the following steps:

[0046] (1) Drying treatment: First, dry the PA610 high viscosity resin at 80℃ for 6 hours for later use; then weigh each raw material according to the mass percentage.

[0047] (2) Mixing: Add the weighed PA610 high viscosity resin, EPDM resin, compatibilizer and colorant to a high-speed mixer and mix at high speed for 5 minutes. Then add the weighed lubricant, antioxidant and heat stabilizer and continue to mix at high speed for 5 minutes to obtain the mixture.

[0048] (3) Melt extrusion: The above mixture is added to the main feed port of the twin-screw extruder. While melt extruding, the weighed short-cut carbon fibers are fed into the side feed port for melt extrusion. The temperature of the twin-screw extruder from the first zone to the die head is 215℃, 225℃, 230℃, 230℃, 230℃, 225℃, 220℃, 220℃, 220℃, 220℃, 220℃, 230℃; the screw speed is 400 rpm, and the feed rate is 25-30 rpm.

[0049] (4) Extrusion pelletizing: The extruded material is cooled, dried, pelletized, passed through a vibrating screen, homogenized in a homogenizing tank and packaged to obtain the finished product, which is a blow-molded, conductive, aging-resistant and salt-corrosion-resistant bio-based long carbon chain nylon alloy reinforced material.

[0050] Example 3

[0051] This embodiment proposes a bio-based long carbon chain nylon alloy reinforced material, comprising the following raw materials by mass percentage: 52.25% PA610 high viscosity resin, 15% EPDM resin, 10% compatibilizer, 20% chopped carbon fiber, 0.3% lubricant, 0.15% primary antioxidant, 0.3% secondary antioxidant, 0.5% heat stabilizer, and 1.5% colorant.

[0052] The preparation method of the bio-based long carbon chain nylon alloy reinforced material in this embodiment includes the following steps:

[0053] (1) Drying treatment: First, dry the PA610 high viscosity resin at 80℃ for 6 hours for later use; then weigh each raw material according to the mass percentage.

[0054] (2) Mixing: Add the weighed PA610 high viscosity resin, EPDM resin, compatibilizer and colorant to a high-speed mixer and mix at high speed for 5 minutes. Then add the weighed lubricant, antioxidant and heat stabilizer and continue to mix at high speed for 5 minutes to obtain the mixture.

[0055] (3) Melt extrusion: The above mixture is added to the main feed port of the twin-screw extruder. While melt extruding, the weighed short-cut carbon fibers are fed into the side feed port for melt extrusion. The temperature of the twin-screw extruder from the first zone to the die head is 215℃, 225℃, 230℃, 230℃, 230℃, 225℃, 220℃, 220℃, 220℃, 220℃, 220℃, 230℃; the screw speed is 400 rpm, and the feed rate is 25-30 rpm.

[0056] (4) Extrusion pelletizing: The extruded material is cooled, dried, pelletized, passed through a vibrating screen, homogenized in a homogenizing tank and packaged to obtain the finished product, which is a blow-molded, conductive, aging-resistant and salt-corrosion-resistant bio-based long carbon chain nylon alloy reinforced material.

[0057] Comparative Example 1

[0058] This comparative example presents a bio-based long-chain carbon nylon alloy reinforced material comprising the following raw materials by mass percentage: 67.25% PA610 high-viscosity resin, 6% EPDM resin, 4% compatibilizer, 20% chopped carbon fiber, 0.3% lubricant, 0.15% primary antioxidant, 0.3% secondary antioxidant, 0.5% heat stabilizer, and 1.5% colorant.

[0059] The preparation method of the bio-based long-chain carbon nylon alloy reinforced material in this comparative example includes the following steps:

[0060] (1) Drying treatment: First, dry the PA610 high viscosity resin at 80℃ for 6 hours for later use; then weigh each raw material according to the mass percentage.

[0061] (2) Mixing: Add the weighed PA610 high viscosity resin, EPDM resin, compatibilizer and colorant to a high-speed mixer and mix at high speed for 5 minutes. Then add the weighed lubricant, antioxidant and heat stabilizer and continue to mix at high speed for 5 minutes to obtain the mixture.

[0062] (3) Melt extrusion: The above mixture is added to the main feed port of the twin-screw extruder. While melt extruding, the weighed short-cut carbon fibers are fed into the side feed port for melt extrusion. The temperature of the twin-screw extruder from the first zone to the die head is 215℃, 225℃, 230℃, 230℃, 230℃, 225℃, 220℃, 220℃, 220℃, 220℃, 220℃, 230℃; the screw speed is 400 rpm, and the feed rate is 25-30 rpm.

[0063] (4) Extrusion pelletizing: The extruded material is cooled, dried, pelletized, passed through a vibrating screen, homogenized in a homogenizing tank and packaged to obtain the finished product, which is a blow-molded, conductive, aging-resistant and salt-corrosion-resistant bio-based long carbon chain nylon alloy reinforced material.

[0064] Comparative Example 2

[0065] This comparative example presents a bio-based long-chain carbon nylon alloy reinforced material comprising the following raw materials by mass percentage: 47.25% PA610 high-viscosity resin, 20% EPDM resin, 10% compatibilizer, 20% chopped carbon fiber, 0.3% lubricant, 0.15% primary antioxidant, 0.3% secondary antioxidant, 0.5% heat stabilizer, and 1.5% colorant.

[0066] The preparation method of the bio-based long-chain carbon nylon alloy reinforced material in this comparative example includes the following steps:

[0067] (1) Drying treatment: First, dry the PA610 high viscosity resin at 80℃ for 6 hours for later use; then weigh each raw material according to the mass percentage.

[0068] (2) Mixing: Add the weighed PA610 high viscosity resin, EPDM resin, compatibilizer and colorant to a high-speed mixer and mix at high speed for 5 minutes. Then add the weighed lubricant, antioxidant and heat stabilizer and continue to mix at high speed for 5 minutes to obtain the mixture.

[0069] (3) Melt extrusion: The above mixture is added to the main feed port of the twin-screw extruder. While melt extruding, the weighed short-cut carbon fibers are fed into the side feed port for melt extrusion. The temperature of the twin-screw extruder from the first zone to the die head is 215℃, 225℃, 230℃, 230℃, 230℃, 225℃, 220℃, 220℃, 220℃, 220℃, 220℃, 230℃; the screw speed is 400 rpm, and the feed rate is 25-30 rpm.

[0070] (4) Extrusion pelletizing: The extruded material is cooled, dried, pelletized, passed through a vibrating screen, homogenized in a homogenizing tank and packaged to obtain the finished product, which is a blow-molded, conductive, aging-resistant and salt-corrosion-resistant bio-based long carbon chain nylon alloy reinforced material.

[0071] The amounts of each raw material used in Examples 1-3 and the comparative examples are shown in Table 1.

[0072] Table 1

[0073]

[0074] Test case

[0075] The performance of the bio-based long carbon chain nylon alloy reinforced materials prepared in Examples 1-3 and Comparative Examples 1-2 was tested. The performance test methods, conditions and test results are shown in Table 2.

[0076] Table 2

[0077]

[0078] The results in Table 2 show that:

[0079] 1. As can be seen from the results of Examples 1-3, the conductive reinforced alloy material composed of PA610 high viscosity resin and EPDM resin has no problems in conductive blow molding. Due to the addition of lubricant and special colorant, the appearance is good, no floating fibers are generated, and the inner wall is smooth without obvious bumps. The alloy material of Examples 1-3 has good impact performance, and after being soaked in 120°C, 2000H calcium chloride solution (0.2mol / L), the performance retention index is very good.

[0080] 2. As can be seen from the results of Examples 1-3, as the amount of EPDM increases, the tensile strength, flexural strength and flexural modulus decrease, while the elongation at break and impact strength gradually increase. After soaking in 120℃, 2000H calcium chloride solution (0.2mol / L), the impact performance is also well maintained.

[0081] 3. As can be seen from the results of Examples 1-3, the addition of compatibilizer helps to improve performance, mainly by improving resin compatibility and the compatibility between resin and short-cut carbon fiber.

[0082] 4. Compared with Examples 1-3, Comparative Example 1 has a lower EPDM content, which greatly affects the low-temperature performance of the material. The low-temperature impact is too low, which increases the risk of product failure in cold regions and fails to meet customer performance requirements, so it is not acceptable.

[0083] 5. Compared with Examples 1-3, Comparative Example 2 has too much EPDM, and the melt strength of the material is too low, causing the blown product to crack in the mold cavity and making molding difficult.

[0084] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0085] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A bio-based long-chain carbon nylon alloy reinforced material, characterized in that, It is prepared from the following components in the following mass percentages: 10-15% EPDM resin, 4-10% compatibilizer, 10-25% carbon fiber, 0.2-0.7% lubricant, 0.2-1% antioxidant, 0.3-1.5% heat stabilizer, and the balance of PA610 high-viscosity resin; the relative viscosity of the PA610 high-viscosity resin is 5-6.

2. The bio-based long-chain carbon nylon alloy reinforced material according to claim 1, characterized in that, The EPDM resin is a blow-molded EPDM resin, and the flowability of the EPDM resin is less than 0.5 g / 10 min.

3. The bio-based long-chain carbon nylon alloy reinforced material according to claim 1, characterized in that, The compatibilizer is at least one of grafted PE, grafted PP and grafted POE.

4. The bio-based long-chain carbon nylon alloy reinforced material according to claim 1, characterized in that, The carbon fiber is short-cut carbon fiber, and the carbon fiber is at least one grade of carbon fiber selected from TC-35-12000, T-700, and SYT49S-12.

5. The bio-based long-chain carbon nylon alloy reinforced material according to claim 1, characterized in that, The lubricant is at least one of PETS, OP wax, silicone, silicone oil, and erucamide.

6. The bio-based long-chain carbon nylon alloy reinforced material according to claim 1, characterized in that, The antioxidant includes a primary antioxidant and a secondary antioxidant. The primary antioxidant is at least one of antioxidant 245, antioxidant 1010, antioxidant 1098, and antioxidant 9228. The secondary antioxidant is at least one of antioxidant 168 and antioxidant 626.

7. The bio-based long-chain carbon nylon alloy reinforced material according to claim 1, characterized in that, The heat stabilizer is at least one of the following: inorganic copper salt nylon heat stabilizer, organic copper salt nylon heat stabilizer, inorganic phosphate nylon heat stabilizer, aluminum silicate treated with titanate and dipentaerythritol (3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate compound heat stabilizer.

8. A method for preparing a bio-based long-chain carbon nylon alloy reinforced material as described in any one of claims 1-7, characterized in that, Includes the following steps: Weigh each component according to the proportion, mix PA610 high viscosity resin, EPDM resin, compatibilizer and colorant evenly, then add lubricant, main antioxidant, auxiliary antioxidant and heat stabilizer and mix evenly to obtain a mixture. The mixture is added to the main feed port of a twin-screw extruder, while carbon fibers are fed into the side feed port. After melting, extrusion, cooling, air drying, and pelletizing, a bio-based long carbon chain nylon alloy reinforced material is obtained. The temperatures of the twin-screw extruder from the first zone to the die head are 215℃, 225℃, 230℃, 230℃, 230℃, 225℃, 220℃, 220℃, 220℃, 220℃, 220℃, and 230℃ respectively; the screw speed is 400 rpm, and the feeding speed is 25-30 rpm.

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