High-strength and high-toughness bio-based polymer melt-spun fiber and preparation method thereof

Abstract

The invention discloses a high-strength and high-toughness bio-based polymer melt-spun fiber and a preparation method thereof, and the method comprises the following steps: drying PA11, POE-g-MAH and MMT, uniformly mixing according to a ratio, granulating through a screw extruder, then carrying out melt extrusion, carrying out fiber drafting by using a traction winding machine with an adjustable rotating speed, and finally collecting the fiber through a fiber winding machine. According to the method, a maleic anhydride functional group on a POE-g-MAH molecular chain can chemically react with an amino group of PA11 to form strong interface bonding; mMT is used as a reinforcing phase, so that the rigidity, the strength and the thermal stability of the material are remarkably improved. And the composite material is prepared into high-performance fibers by virtue of granulation and melt spinning processes through process optimization. The fiber has excellent tensile strength and impact toughness, and can be widely applied to the fields of high-end spinning, industrial yarn ropes, safety protection, composite material reinforcement and the like.

Description

Technical Field

[0001] This invention belongs to the technical field of bio-based polymer melt-spun fibers, and relates to a high-strength, high-toughness bio-based melt-spun fiber and its preparation method. Background Technology

[0002] Traditional chemical fibers (such as polyester PET, nylon 6, and nylon 66) are entirely derived from non-renewable petroleum resources, imposing a heavy burden on the environment throughout their entire life cycle. Against this backdrop, bio-based composite materials have become an inevitable trend. The application of bio-based composite materials can reduce environmental pollution, achieve energy and resource conservation, and align with the current concept of green and sustainable development.

[0003] Nylon 11 (PA11) is a bio-based long-chain polyamide with excellent comprehensive properties, derived from castor oil. As a 100% bio-based high-performance polyamide, Nylon 11 (PA11) perfectly meets the requirements of green, low-carbon, and renewable energy. It retains the excellent mechanical properties and chemical stability of traditional nylon while possessing the green attributes of bio-based materials. It is renowned for its excellent flexibility, impact resistance, chemical corrosion resistance, low water absorption, and abrasion resistance, and is widely used in automotive fuel lines, flexible conduits, sports equipment, and high-end textile fibers. However, with the increasing demands on material performance in industrial applications, the limitations of pure nylon 11 in certain specific scenarios are becoming increasingly apparent. Its main drawback is its relatively low absolute tensile strength and flexural modulus, which limits its application in components requiring high rigidity and high load-bearing capacity (such as high-performance structural components and high-strength fibers). To overcome this shortcoming, reinforcing and toughening modification of nylon 11 has become a research hotspot. POE-g-MAH stands for maleic anhydride-grafted polyolefin elastomer. It is a functionalized polymer obtained by chemically grafting highly polar maleic anhydride (MAH) molecules onto the non-polar polyolefin elastomer (POE) backbone. MMT is an abbreviation for montmorillonite, a naturally occurring silicate mineral and a major component of bentonite. This invention proposes a method for obtaining high-strength and high-toughness fibers by improving the process of combining POE-g-MAH and MMT. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing high-strength and high-toughness bio-based polymer melt-spun fibers, which solves the problem that the absolute tensile strength and flexural modulus of pure PA11 are relatively low, and expands its application range in components requiring high rigidity and high load-bearing capacity (such as high-performance structural parts and high-strength fibers).

[0005] The present invention adopts the following technical solution: A method for preparing high-strength, high-toughness bio-based polymer melt-spun fibers includes the following steps: 1) After drying PA11 granules, POE-g-MAH and MMT, mix them according to different formulation ratios to ensure that POE-g-MAH and MMT are fully adhered to PA11 granules. 2) The resulting mixture is added to a screw extruder for melt blending and granulation; 3) After drying the obtained composite particles, they are placed in a melt spinning machine for spinning. After stretching treatment, the high-strength and high-toughness bio-based composite material is obtained.

[0006] Furthermore, the drying temperature is 60-80℃, and the drying time is 12 hours.

[0007] Furthermore, the PA11 weight percentage is 80-100%, the POE-g-MAH weight percentage is 5-15%, and the MMT weight percentage is 3-5%. For example, the ratio can be PA11 / POE-g-MAH / MMT: 82 / 15 / 3, 80 / 15 / 5, 87 / 10 / 3, 92 / 5 / 3, 85 / 10 / 5, 90 / 5 / 5. More preferably, the PA11 weight percentage is 80-85%, the POE-g-MAH weight percentage is 10-15%, and the MMT weight percentage is 3-5%. Furthermore, the granulation temperature is 190-230℃.

[0008] Furthermore, during granulation, MMT and PA11 are first melt-blended to form a high-concentration masterbatch, and then the masterbatch is melt-blended again with POE-g-MAH to form a new masterbatch.

[0009] Furthermore, the spinning temperature during melt extrusion is 190-230℃, and the extrusion speed is 10-60mm / min.

[0010] Furthermore, the rotation speeds of the traction winding machine and the fiber winding machine are precisely controlled, with the speed of the first guide roller GR1, which first contacts the fiber, controlled to be 190-300 rpm, the speed of the second guide roller GR2, which is 190-300 rpm, and the collection winding speed controlled to be 150-300 rpm.

[0011] A high-strength, high-toughness bio-based polymer melt-spun fiber, prepared by the above method, has its strength effectively improved compared to pure PA11 fiber, while its toughness is also improved or maintained.

[0012] The beneficial effects of this invention are as follows: This invention yields a high-strength, high-toughness bio-based polymer melt-spun fiber and its preparation method. The resulting fiber achieves a synergistic improvement in strength and toughness. The process is simple, requiring no complex equipment or solvents, and the cost is controllable, making it highly suitable for large-scale industrial production. Using nylon 11 as the matrix aligns with sustainable development principles. Through high-performance modification, its application range is expanded, helping to replace more petroleum-based engineering plastics and reduce carbon footprint. Attached Figure Description

[0013] Figure 1 This is a production process diagram of polymer melt-spun fibers in this invention. Detailed Implementation

[0014] The present invention will be further described in detail below with reference to the accompanying drawings and specific examples. The production process adopted by the technical solution of the present invention is as follows: Figure 1 As shown.

[0015] Example 1 PA11 chips were dried at 80℃ for 12 hours and then melt-extruded using a screw extruder at an extrusion temperature of 220℃ and a melt extrusion speed of 30 mm / min. The speed of the first guide roller GR1 was 190 rpm, the speed of the second guide roller GR2 was 280 rpm, and the speed of the fiber winding machine was 300 rpm. The tensile strength was 3.5 cN / dtex, and the elongation at break was 889.95%.

[0016] Example 2 85% PA11 and 15% POE-g-MAH were mixed evenly and dried at 80℃ for 12 hours. The mixture was then fed into a screw extruder to produce composite granules. The temperatures of each section were 190℃, 210℃, and 230℃, respectively. The composite granules were dried at 80℃ for 12 hours and then melt-extruded through a screw extruder at an extrusion temperature of 220℃ and a melt extrusion speed of 30 mm / min. The speed of the first guide roller GR1 was 190 rpm, the speed of the second guide roller GR2 was 280 rpm, and the speed of the fiber winding machine was 300 rpm. The tensile strength decreased to 3.21 cN / dtex, while the elongation at break was improved compared to pure PA11 fiber.

[0017] Example 3 95% PA11 and 5% MMT were mixed evenly and dried at 80℃ for 12 hours. The mixture was then fed into a screw extruder to produce composite granules. The temperatures of each section were 190℃, 210℃, and 230℃, respectively. The composite granules were dried at 80℃ for 12 hours and then melt-extruded through a screw extruder at an extrusion temperature of 220℃ and a melt extrusion speed of 30 mm / min. The speed of the first guide roller GR1 was 1900 rpm, the speed of the second guide roller GR2 was 280 rpm, and the speed of the fiber winding machine was 300 rpm. The tensile strength increased to 4.5 cN / dtex, while the elongation at break decreased compared to pure PA11.

[0018] Example 4 82% PA11 and 3% MMT were mixed evenly and dried at 80℃ for 12 hours. The mixture was then fed into a screw extruder to produce composite granules at temperatures of 190℃, 210℃, and 230℃. The resulting composite granules were then mixed evenly with 15% POE-g-MAH and dried at 80℃ for 12 hours. This mixture was then fed into a screw extruder to produce new composite granules at temperatures of 190-230℃. The composite granules were dried at 80℃ for 12 hours and then melt-extruded through a screw extruder at an extrusion temperature of 220℃ and a melt extrusion speed of 30 mm / min. The speed of the first guide roller GR1 was 1900 rpm, the speed of the second guide roller GR2 was 280 rpm, and the fiber winding speed was 300 rpm. The tensile strength was 4.32 cN / dtex, and the elongation at break was not significantly different from that of pure PA11.

[0019] Example 5 80% PA11 and 5% MMT were mixed evenly and dried at 80℃ for 12 hours. The mixture was then fed into a screw extruder to produce composite granules at temperatures of 190℃, 210℃, and 230℃. The resulting composite granules were then mixed evenly with 15% POE-g-MAH and dried at 80℃ for 12 hours. This mixture was then fed into a screw extruder to produce new composite granules at temperatures of 190-230℃. The composite granules were dried at 80℃ for 12 hours and then melt-extruded through a screw extruder at an extrusion temperature of 220℃ and a melt extrusion speed of 30 mm / min. The speed of the first guide roller (GR1) was 1900 rpm, the speed of the second guide roller (GR2) was 280 rpm, and the fiber winding speed was 300 rpm. The tensile strength was 4.51 cN / dtex, and the elongation at break was slightly higher than that of pure PA11.

[0020] Example 6 87% PA11 and 3% MMT were mixed evenly and dried at 80℃ for 12 hours. The mixture was then fed into a screw extruder to produce composite granules at temperatures of 190℃, 210℃, and 230℃. The resulting composite granules were then mixed evenly with 10% POE-g-MAH and dried at 80℃ for 12 hours. This mixture was then fed into a screw extruder to produce new composite granules at temperatures of 190-230℃. The composite granules were dried at 80℃ for 12 hours and then melt-extruded through a screw extruder at an extrusion temperature of 220℃ and a melt extrusion speed of 30 mm / min. The speed of the first guide roller GR1 was 1900 rpm, the speed of the second guide roller GR2 was 280 rpm, and the fiber winding speed was 300 rpm. The tensile strength was 3.35 cN / dtex, and the elongation at break was not significantly different from that of pure PA11.

[0021] Example 7 92% PA11 and 3% MMT were mixed evenly and dried at 80°C for 12 hours. The mixture was then fed into a screw extruder to produce composite granules at temperatures of 190°C, 210°C, and 230°C. The resulting composite granules were then mixed evenly with 5% POE-g-MAH and dried at 80°C for 12 hours. The mixture was then fed into a screw extruder to produce new composite granules at temperatures of 190-230°C. The composite granules were dried at 80°C for 12 hours and then melt-extruded through a screw extruder at an extrusion temperature of 220°C and a melt extrusion speed of 30 mm / min. The speed of the first guide roller GR1 was 1900 rpm, the speed of the second guide roller GR2 was 280 rpm, and the speed of the fiber winding machine was 300 rpm. The tensile strength was 3.33 cN / dtex, and the elongation at break was lower than that of Example 6.

[0022] Example 8 85% PA11 and 5% MMT were mixed evenly and dried at 80℃ for 12 hours. The mixture was then fed into a screw extruder to produce composite granules at temperatures of 190℃, 210℃, and 230℃. The resulting composite granules were then mixed evenly with 10% POE-g-MAH and dried at 80℃ for 12 hours. This mixture was then fed into a screw extruder to produce new composite granules at temperatures of 190-230℃. The composite granules were dried at 80℃ for 12 hours and then melt-extruded through a screw extruder at an extrusion temperature of 220℃ and a melt extrusion speed of 30 mm / min. The speed of the first guide roller GR1 was 1900 rpm, the speed of the second guide roller GR2 was 280 rpm, and the fiber winding speed was 300 rpm. The tensile strength was 4.52 cN / dtex, and the elongation at break was not significantly different from that of pure PA11.

[0023] Example 9 90% PA11 and 5% MMT were mixed evenly and dried at 80℃ for 12 hours. The mixture was then fed into a screw extruder to produce composite granules at temperatures of 190℃, 210℃, and 230℃. The resulting composite granules were then mixed evenly with 5% POE-g-MAH and dried at 80℃ for 12 hours. The mixture was then fed into a screw extruder to produce new composite granules at temperatures of 190-230℃. The composite granules were dried at 80℃ for 12 hours and then melt-extruded through a screw extruder at an extrusion temperature of 220℃ and a melt extrusion speed of 30 mm / min. The speed of the first guide roller GR1 was 1900 rpm, the speed of the second guide roller GR2 was 280 rpm, and the speed of the fiber winding machine was 300 rpm. The tensile strength was 4.46 cN / dtex, and the elongation at break was lower than that of Example 8.

[0024] The above-described embodiments provide a detailed explanation of the preparation method of the present invention. It should be understood that these embodiments are only for illustrating the present invention and are not intended to limit the present invention. Any modifications, additions, or similar substitutions made within the scope of the principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method of making a high-strength, high-tenacity, bio-based, polymeric, melt-spun fiber, characterized by: The method comprises the following steps: 1) mixing PA11 particles, POE-g-MAH and MMT after drying, so that POE-g-MAH and MMT are fully attached to the PA11 particles; 2) adding the obtained mixture into a screw extruder for melt blending and granulation; 3) drying the prepared composite particles, and then putting them into a melt spinning machine for spinning, and then performing drawing treatment to obtain the high-strength and high-toughness bio-based composite fiber.

2. The method of making high strength, high tenacity, bio-based polymeric melt-spun fibers according to claim 1, characterized in that, The drying temperature is 60-80℃, and the time is 12h.

3. The method of making high strength, high tenacity, bio-based polymeric melt-spun fibers according to claim 1, characterized in that, The weight percentage of PA11 in step 1) is 80-100%, the weight percentage of POE-g-MAH is 5-15%, and the weight percentage of MMT is 3-5%.

4. The method of making high strength, high tenacity, bio-based polymeric melt-spun fibers according to claim 1, characterized in that, The weight percentage of PA11 in step 1) is 80-85%, the weight percentage of POE-g-MAH is 10-15%, and the weight percentage of MMT is 3-5%.

5. The method of making high strength, high tenacity, bio-based polymeric melt-spun fibers according to claim 1, characterized in that, The granulation temperature is 190-230℃.

6. The method of making high strength, high tenacity, bio-based polymeric melt-spun fibers according to claim 1, characterized in that, The MMT is first melt blended with PA11 to prepare a high-concentration master batch, and then the master batch is melt blended with POE-g-MAH to prepare a new master batch.

7. The method of making high strength, high tenacity, bio-based polymeric melt-spun fibers according to claim 1, wherein, The spinning temperature during melt extrusion is 190-230℃, and the extrusion speed is 10-60mm / min.

8. The method of making high strength, high tenacity, bio-based polymeric melt-spun fibers according to claim 1, characterized in that, The rotating speed of the drawing and winding machine and the fiber winding machine is precisely controlled, the speed GR1 of the first godet which first contacts the fiber is 190-300rmp, the speed GR2 of the second godet is 190-300rmp, and the winding speed of the collection is 150-300rmp.

9. A high strength, high tenacity bio-based polymer melt-spun fiber, characterized in that, The high-strength and high-toughness bio-based composite fiber is prepared by using the method according to any one of claims 1-8.

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