Antistatic antibacterial ultra-high molecular weight polyethylene fiber and method for producing the same
By adding antistatic and antibacterial agents during the preparation of ultra-high molecular weight polyethylene fibers and employing specific swelling and multi-stage stretching methods, the problems of static electricity and antibacterial properties have been solved, thereby improving production efficiency and fiber performance.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- CHINA PETROLEUM & CHEMICAL CORP
- Filing Date
- 2024-12-30
- Publication Date
- 2026-06-30
Smart Images
Figure BDA0005219420810000071 
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of ultra-high molecular weight polyethylene fiber preparation, and specifically refers to an antistatic and antibacterial ultra-high molecular weight polyethylene fiber and its preparation method. Background Technology
[0002] Ultra-high molecular weight polyethylene fiber, abbreviated as UHMWPE fiber, is also known as high-strength, high-modulus polyethylene fiber. It, along with carbon fiber and aramid fiber, is considered one of the "world's three major high-tech fibers." UHMWPE fiber is the strongest and most resilient fiber in the world, currently boasting the highest specific strength and ballistic performance among industrialized fiber materials. It possesses numerous excellent properties, including ultra-high strength, ultra-high modulus, low density, wear resistance, low-temperature resistance, UV resistance, anti-shielding properties, good flexibility, high impact energy absorption, and resistance to strong acids, strong alkalis, and chemical corrosion.
[0003] However, it is prone to accumulating static electricity during processing and use, affecting production stability. In some cases, static electricity in fibers can even cause accidents such as fires and explosions, limiting its application in fields where static electricity is critical. Static electricity can also reduce the comfort of fabrics. Meanwhile, consumers now have increasingly higher demands for functional fibers, with antibacterial properties becoming a trend in fabric manufacturing. Therefore, endowing ultra-high molecular weight polyethylene fibers with antistatic and antibacterial functions is of great significance. Summary of the Invention
[0004] Therefore, the purpose of this invention is to provide an antistatic and antibacterial ultra-high molecular weight polyethylene fiber and its preparation method. The antistatic and antibacterial ultra-high molecular weight polyethylene fiber provided by this invention has the advantages of high strength and high modulus. Moreover, its preparation method eliminates static electricity in the ultra-high molecular weight polyethylene fiber during processing, reduces the occurrence of fiber breakage during processing, effectively improves production efficiency, and endows the fiber with antibacterial properties, thereby improving the product performance of the fiber.
[0005] Therefore, in a first aspect, the present invention provides a method for preparing antistatic and antibacterial ultra-high molecular weight polyethylene fiber, comprising the following steps:
[0006] S1, ultra-high molecular weight polyethylene, solvent, antioxidant, antistatic agent and antibacterial agent are swollen to obtain spinning solution;
[0007] S2, the spinning solution is extruded through a screw extruder to obtain gel fiber;
[0008] S3, through multi-stage stretching, yields antistatic and antibacterial ultra-high molecular weight polyethylene fiber;
[0009] The swelling conditions include: a swelling temperature of 80-100℃ and a swelling time of 1-4 hours; the total draw ratio of the multi-stage stretching is 10-18 times.
[0010] In the preparation of ultra-high molecular weight polyethylene (UHMWPE) fibers, while the addition of antistatic and antibacterial agents improves their antistatic and antibacterial properties, it significantly deteriorates their tensile strength and modulus, resulting in poor mechanical properties. To ensure that UHMWPE fibers simultaneously possess excellent antistatic and antibacterial properties, tensile strength, and modulus, the preparation method provided by this invention utilizes a spinning solution produced under specific swelling conditions combined with multi-stage drawing at a specific ratio. The resulting UHMWPE fibers not only effectively reduce the entanglement, spinning, and roller entanglement that previously occurred due to electrostatic effects, thus improving production efficiency, but also possess antistatic and antibacterial effects, while exhibiting significant advantages in tensile strength and modulus.
[0011] In some preferred embodiments of the present invention, the spinning solution comprises 3-10 parts by weight of ultra-high molecular weight polyethylene, 0.1-0.5 parts by weight of antioxidant, 0.1-2 parts by weight of antistatic agent, and 0.1-3 parts by weight of antibacterial agent; preferably, the content of antistatic agent in the spinning solution is 0.2-1 parts by weight; and / or, the content of antibacterial agent is 0.3-1.5 parts by weight.
[0012] In some preferred embodiments of the present invention, the viscosity-average molecular weight of the ultra-high molecular weight polyethylene is 1 million to 8 million, preferably 4 million to 8 million.
[0013] In some preferred embodiments of the present invention, the ultra-high molecular weight polyethylene has a viscosity-average molecular weight of 4-8 million. By selecting ultra-high molecular weight polyethylene with a specific viscosity-average molecular weight, the present invention can further improve the mechanical properties of the resulting fibers.
[0014] In some preferred embodiments of the present invention, the solvent is selected from one or more of decahydronaphthalene, tetrahydronaphthalene, paraffin oil, white oil, xylene, and toluene.
[0015] In some preferred embodiments of the present invention, the antioxidant is selected from one or more of 2,6-di-tert-butyl-4-methylphenol, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid), octadecyl-3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate, calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonate monoethyl ester), 4,6-bis(octylthiomethyl)o-cresol, and tetrakis(2,4-di-tert-butylphenol)-4,4-biphenyl diphosphite.
[0016] In some preferred embodiments of the present invention, the antistatic agent is selected from one or more of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, octadecyl primary amine polyoxyethylene ether, octadecyl diethanolamine, and stearoyl trimethyl ammonium chloride.
[0017] In some preferred embodiments of the present invention, the antibacterial agent is a carbon nanotube loaded with silver and / or copper, wherein the carbon nanotube has a wall thickness of 2-4 nm, a diameter of 50-100 nm, a length of 500-1000 nm, and a silver and / or copper content of 1-20 wt%, preferably 5-15 wt%.
[0018] In some preferred embodiments of the present invention, the swelling conditions include: under stirring conditions, preferably, the stirring rate is 50-1000 r / min.
[0019] In some preferred embodiments of the present invention, the stirring rate is 400-800 r / min. At this stirring rate, the ultra-high molecular weight polyethylene raw material is more evenly dispersed in the solvent and swells more fully, ensuring more uniform feeding during the feeding process into the twin-screw extruder.
[0020] In some preferred embodiments of the present invention, the swelling conditions include: a swelling temperature of 90-100°C and a swelling time of 2-5 hours. Under these swelling conditions, the organic solvent can penetrate more fully into the interior of the ultra-high molecular weight polyethylene raw material, achieving more complete swelling, which is beneficial for molecular chain deorientation in subsequent processing, resulting in the production of fiber products with more uniform and better performance.
[0021] In some preferred embodiments of the present invention, in step S2, after the spinning solution is extruded by a screw extruder, the solvent in the intermediate product is removed by evaporation or extraction to obtain gel fiber.
[0022] In some preferred embodiments of the present invention, the evaporation is thermal evaporation. Preferably, the temperature of the thermal evaporation is 110-120°C, and the time is 2-8 minutes. Under the above-mentioned thermal evaporation conditions, the organic solvent can be volatilized more fully, resulting in fibers with lower solvent content. At the same time, the organic solvent can be recovered more efficiently, achieving the advantages of being green, clean, and low-cost.
[0023] In some preferred embodiments of the present invention, in step S3, the multi-stage drawing is a two-stage drawing, a three-stage drawing, a four-stage drawing, or a five-stage drawing.
[0024] In some preferred embodiments of the present invention, the multi-stage drawing is a three-stage drawing, wherein the first-stage drawing temperature is 138-145℃ with a draw ratio of 5-10 times; the second-stage drawing temperature is 140-148℃ with a draw ratio of 1.1-1.8 times; and the third-stage drawing temperature is 142-150℃ with a draw ratio of 1-1.5 times. Through multi-stage drawing under the above conditions, the mechanical properties of ultra-high molecular weight polyethylene fibers can be further improved.
[0025] In some preferred embodiments of the present invention, the total draw ratio of the multi-stage draw is 11-15 times.
[0026] Therefore, in a second aspect, the present invention provides an antistatic and antibacterial ultra-high molecular weight polyethylene fiber prepared by the above-described preparation method, having a breaking strength of 35-42 cN / dtex, a modulus of 1500-1700 cN / dtex, and a resistivity of 3.5 × 10⁻⁶. 7 -5.5×10 7 The antibacterial rate is 95%-99.99% (Ω·cm), preferably 98.95%-99.99%.
[0027] The present invention has the following beneficial effects:
[0028] First, the preparation method provided by the present invention, by selecting a spinning solution produced under specific swelling conditions and combining it with multi-stage drawing at a specific ratio, produces ultra-high molecular weight polyethylene fibers that not only effectively reduce the entanglement, spinning, and roller entanglement that occurred in the past due to electrostatic effects, thus improving production efficiency, but also have antistatic and antibacterial effects, and at the same time have significant advantages in terms of breaking strength and modulus.
[0029] Secondly, the preparation method provided by the present invention preferably involves swelling ultra-high molecular weight polyethylene in a limited range of additives, allowing additives such as antistatic agents and antibacterial agents to penetrate into the polyethylene, eliminating static electricity during production and use, effectively reducing the entanglement, coiling, and roller entanglement that occurred in the past due to static electricity, improving production efficiency, and simultaneously imparting antibacterial and antistatic effects to the fiber, while also having significant advantages in terms of tensile strength and modulus. Detailed Implementation
[0030] The embodiments of the present invention will be described in detail below with reference to examples. However, those skilled in the art will understand that the following examples are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer are followed. Reagents or instruments whose manufacturers are not specified are all commercially available conventional products.
[0031] (I) Materials
[0032] The silver-containing carbon nanotubes have a wall thickness of 3 nm, a diameter of 80 nm, a length of 800 nm, and a silver content of 10 wt%.
[0033] The copper-containing carbon nanotubes have a wall thickness of 3 nm, a diameter of 80 nm, a length of 800 nm, and a copper content of 10 wt%.
[0034] (II) Test Methods
[0035] The tensile strength and modulus were measured according to GB / T 19975-2005, Test Method for Tensile Properties of High-Strength Fiber Filaments.
[0036] The method for measuring resistance is ASTM B193-2020;
[0037] The method for measuring the antibacterial rate is FZ / T 01021-1992.
[0038] Example 1
[0039] Ultra-high molecular weight polyethylene, solvent decahydronaphthalene, antioxidant, antistatic agent, and antibacterial agent were added to a swelling vessel and swelled under mechanical stirring at a rate of 500 r / min to obtain a spinning solution. The antibacterial agent was silver-containing carbon nanotubes with a wall thickness of 3 nm, a diameter of 80 nm, a length of 800 nm, and a silver content of 10 wt%.
[0040] The spinning solution is extruded through a screw extruder. After the solvent is heated to 115℃ and evaporated for 5 minutes, gel fibers are obtained. Through multi-stage drawing, antistatic and antibacterial ultra-high molecular weight polyethylene fibers are obtained. The screw extruder is divided into 9 heating zones, with the following specific operating temperatures: Zone 1 85℃, Zone 2 115℃, Zone 3 140℃, Zone 4 155℃, Zone 5 165℃, Zone 6 165℃, Zone 7 165℃, Zone 8 170℃, and Zone 9 170℃.
[0041] The multi-stage drawing process consists of three stages: the first stage drawing temperature is 140℃ with a draw ratio of 7.6; the second stage drawing temperature is 142℃ with a draw ratio of 1.5; and the third stage drawing temperature is 143℃ with a draw ratio of 1.05. The total draw ratio for the three stages is 11.97.
[0042] The components, dosages, and specific operating parameters are shown in Table 1 below, and the measurement results are shown in Table 2.
[0043] Example 2
[0044] The steps are the same as in Example 1. The components, dosages, and specific operating parameters are shown in Table 1 below, and the measurement results are shown in Table 2.
[0045] Example 3
[0046] The difference from Example 1 is that the number of polyethylene molecules and the multi-stage stretching steps, the components and their dosages, and the specific operating parameters are shown in Table 1 below, and the measurement results are shown in Table 2.
[0047] The multi-stage drawing process consists of three stages: the first stage drawing temperature is 140℃ with a draw ratio of 8.89; the second stage drawing temperature is 142℃ with a draw ratio of 1.5; and the third stage drawing temperature is 143℃ with a draw ratio of 1.05. The total draw ratio for the three stages is 14.
[0048] Examples 4-5
[0049] The steps are the same as in Example 1. The components, dosages, and specific operating parameters are shown in Table 1 below, and the measurement results are shown in Table 2.
[0050] Example 6
[0051] The steps are the same as in Example 1. The components, dosages, and specific operating parameters are shown in Table 1 below, and the measurement results are shown in Table 2.
[0052] Comparative Examples 1-5
[0053] The steps are the same as in Example 1. The components, dosages, and specific operating parameters are shown in Table 1 below, and the measurement results are shown in Table 2.
[0054] Comparative Example 6
[0055] The difference from Example 1 is that it involves a multi-stage stretching process. The components, dosages, and specific operating parameters are shown in Table 1 below, and the measurement results are shown in Table 2.
[0056] The multi-stage drawing process consists of three stages: the first stage drawing temperature is 140℃ with a draw ratio of 5; the second stage drawing temperature is 142℃ with a draw ratio of 1.5; and the third stage drawing temperature is 143℃ with a draw ratio of 1.05. The total draw ratio for the three stages is 7.88.
[0057] Comparative Example 7
[0058] The difference from Example 1 is that it involves a multi-stage stretching process. The components, dosages, and specific operating parameters are shown in Table 1 below, and the measurement results are shown in Table 2.
[0059] The multi-stage drawing process consists of three stages: the first stage drawing temperature is 140℃ with a draw ratio of 12.7; the second stage drawing temperature is 142℃ with a draw ratio of 1.5; and the third stage drawing temperature is 143℃ with a draw ratio of 1.05. The total draw ratio for all three stages is 20.
[0060] Comparative Example 8
[0061] The antibacterial agent and antistatic agent were dispersed in decahydronaphthalene solvent and ultrasonically dispersed for 1 hour, then poured into a bath apparatus. The antibacterial agent was silver-containing carbon nanotubes with a wall thickness of 3 nm, a diameter of 80 nm, a length of 800 nm, and a silver content of 10 wt%.
[0062] Ultra-high molecular weight polyethylene, solvent decahydronaphthalene, and antioxidant are added to a swelling vessel and swelled under mechanical stirring at a rate of 500 r / min to obtain a spinning solution. The spinning solution is then extruded through a screw extruder, and the solvent is heated to 115°C and evaporated for 5 minutes to obtain gel fiber. After multi-stage stretching, the fiber is continuously coated with bath liquid through a guide roller after each stage of hot stretching, ultimately yielding antistatic and antibacterial ultra-high molecular weight polyethylene fiber.
[0063] The screw extruder is divided into nine heating zones, with the following specific operating temperatures: Zone 1 85℃, Zone 2 115℃, Zone 3 140℃, Zone 4 155℃, Zone 5 165℃, Zone 6 165℃, Zone 7 165℃, Zone 8 170℃, and Zone 9 170℃. The multi-stage drafting is a three-stage process: the first stage drafting temperature is 140℃ with a draft ratio of 7.6; the second stage drafting temperature is 142℃ with a draft ratio of 1.5; and the third stage drafting temperature is 143℃ with a draft ratio of 1.05. The total draft ratio for all three stages is 11.97.
[0064] The components, dosages, and specific operating parameters are shown in Table 1 below, and the measurement results are shown in Table 2.
[0065]
[0066]
[0067]
[0068] Table 2
[0069]
[0070] Based on the data in Tables 1-2, compared to Comparative Examples 1-3, the addition of antioxidants, antistatic agents, and antibacterial agents in Example 1 significantly improved the tensile strength, electrical resistance, and antibacterial rate of the obtained fibers.
[0071] According to the data in Table 1-2, the tensile strength and modulus of the fibers obtained after adding antioxidants, antistatic agents and antibacterial agents in Comparative Examples 4-7 decreased significantly. In Example 1, by adjusting the swelling conditions and the total draw ratio, the tensile strength and modulus of the fibers obtained were significantly improved.
[0072] According to the data in Table 1-2, Comparative Example 8, which added antistatic and antibacterial agents during the hot stretching process, had poor antistatic and antibacterial properties of the resulting fiber. Example 1, which added antistatic and antibacterial agents during the swelling process, significantly improved the antistatic and antibacterial properties of the resulting fiber.
[0073] In summary, the preparation method provided by this invention, through the selection of spinning solutions produced under specific swelling conditions and combined with multi-stage drawing at a specific ratio, yields ultra-high molecular weight polyethylene fibers. These fibers not only effectively reduce the entanglement, spinning, and roller entanglement that previously occurred due to electrostatic effects, thus improving production efficiency, but also have antistatic and antibacterial effects. Furthermore, they exhibit significant advantages in terms of breaking strength and modulus.
[0074] The above description of the embodiments is provided to enable those skilled in the art to understand and apply the present invention. It will be apparent to those skilled in the art that various modifications can be easily made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the embodiments described herein, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention. Adding other functional additives to the preparation components of the present invention to give the composite material corresponding properties is also protected by the present invention.
Claims
1. A method for producing an antistatic antibacterial ultrahigh molecular weight polyethylene fiber, characterized by, Includes the following steps: S1, ultra-high molecular weight polyethylene, solvent, antioxidant, antistatic agent and antibacterial agent are swollen to obtain spinning solution; S2, the spinning solution is extruded through a screw extruder to obtain gel fiber; S3, through multi-stage stretching, yields antistatic and antibacterial ultra-high molecular weight polyethylene fiber; The swelling conditions include: a swelling temperature of 80-100℃ and a swelling time of 1-4h; the total draw ratio of the multi-stage stretching is 10-18 times.
2. The production method according to claim 1, characterized by, The spinning solution contains 3-10 parts by weight of ultra-high molecular weight polyethylene, 0.1-0.5 parts by weight of antioxidant, 0.1-2 parts by weight of antistatic agent, and 0.1-3 parts by weight of antibacterial agent; preferably, the content of antistatic agent in the spinning solution is 0.2-1 parts by weight; and / or, the content of antibacterial agent is 0.3-1.5 parts by weight.
3. The production method according to claim 1 or 2, characterized by, The ultra-high molecular weight polyethylene has a viscosity-average molecular weight of 1 million to 8 million, preferably 4 million to 8 million; and / or The solvent is selected from one or more of decahydronaphthalene, tetrahydronaphthalene, paraffin oil, white oil, xylene, and toluene.
4. The production method according to any one of claims 1 to 3, characterized by, The antioxidant is selected from one or more of the following: 2,6-di-tert-butyl-4-methylphenol, tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, pentaerythritol tetrakis(3,5-di-tert-butyl-4-hydroxyhydrocinnamic acid), octadecyl-3,5-bis(1,1-dimethylethyl)-4-hydroxyphenylpropionate, calcium bis(3,5-di-tert-butyl-4-hydroxybenzylphosphonate monoethyl ester), 4,6-bis(octylthiomethyl)o-cresol, and tetrakis(2,4-di-tert-butylphenol)-4,4-biphenyl diphosphite.
5. The production method according to any one of claims 1 to 4, characterized by, The antistatic agent is selected from one or more of octadecyl dimethyl hydroxyethyl quaternary ammonium nitrate, octadecyl primary amine polyoxyethylene ether, octadecyl diethanolamine, and stearoyl trimethyl ammonium chloride.
6. The production method according to any one of claims 1 to 5, characterized by, The antibacterial agent is a carbon nanotube loaded with silver and / or copper. The carbon nanotube has a wall thickness of 2-4 nm, a diameter of 50-100 nm, a length of 500-1000 nm, and a silver and / or copper content of 1-20 wt%, preferably 5-15 wt%.
7. The production method according to any one of claims 1 to 6, characterized by, The swelling conditions include: under stirring conditions, preferably, the stirring rate is 50-1000 r / min, more preferably 400-800 r / min; and / or, the swelling temperature is 90-100℃, and the swelling time is 2-4 h.
8. The production method according to any one of claims 1 to 7, characterized by, In step S2, after the spinning solution is extruded by a screw extruder, the solvent in the intermediate product is removed by evaporation or extraction to obtain gel fiber; preferably, the evaporation is heating evaporation, more preferably, the heating evaporation temperature is 110-120℃ and the time is 2-8min.
9. The production method according to any one of claims 1 to 8, characterized by, In step S3, the multi-stage drawing is a two-stage drawing, a three-stage drawing, a four-stage drawing, or a five-stage drawing; preferably, the multi-stage drawing is a three-stage drawing, wherein the first-stage drawing temperature is 138-145℃ and the drawing ratio is 5-10 times; the second-stage drawing temperature is 140-148℃ and the drawing ratio is 1.1-1.8 times; the third-stage drawing temperature is 142-150℃ and the drawing ratio is 1-1.5 times, with a total drawing ratio of 10-18 times, preferably 11-15 times.
10. An antistatic antibacterial ultrahigh molecular weight polyethylene fiber produced by the production method according to any one of claims 1 to 9, characterized by, a breaking strength of 30-42 cN / dtex, preferably 35-42 cN / dtex, a modulus of 1200-1700 cN / dtex, preferably 1500-1700 cN / dtex, an electrical resistance of 3.5 x 10 7 -5.5 x 10 7 Ω-cm, a bacteriostatic rate of 95-99.99%, preferably 98.95-99.99%.