WO2025156639A1 - Cut-resistant fiber and preparation method therefor - Google Patents

Cut-resistant fiber and preparation method therefor

Info

Publication number
WO2025156639A1
WO2025156639A1 PCT/CN2024/116564 CN2024116564W WO2025156639A1 WO 2025156639 A1 WO2025156639 A1 WO 2025156639A1 CN 2024116564 W CN2024116564 W CN 2024116564W WO 2025156639 A1 WO2025156639 A1 WO 2025156639A1
Authority
WO
WIPO (PCT)
Prior art keywords
fiber
cut
polyethylene
temperature
resistant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/CN2024/116564
Other languages
French (fr)
Chinese (zh)
Inventor
叶纯麟
张振飞
杨天慧
李建龙
张乐天
郭宁
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Research Institute of Chemical Industry SRICI
Original Assignee
Shanghai Research Institute of Chemical Industry SRICI
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Research Institute of Chemical Industry SRICI filed Critical Shanghai Research Institute of Chemical Industry SRICI
Priority to KR1020257026858A priority Critical patent/KR20250134125A/en
Priority to JP2025540982A priority patent/JP2026507416A/en
Publication of WO2025156639A1 publication Critical patent/WO2025156639A1/en
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/12Stretch-spinning methods
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00Treatment of filament-forming or like material
    • D01D1/04Melting filament-forming substances
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
    • D01D5/08Melt spinning methods
    • D01D5/082Melt spinning methods of mixed yarn
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00General methods for the manufacture of artificial filaments or the like
    • D01F1/02Addition of substances to the spinning solution or to the melt
    • D01F1/10Other agents for modifying properties
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/46Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins

Definitions

  • the present invention relates to the technical field of polymer materials, in particular to a cut-resistant fiber and a preparation method thereof.
  • High-performance polyethylene fibers characterized by their lightweight, high strength, long service life, wear resistance, high strength, moisture resistance, and corrosion resistance, are widely used in towing ropes, load-bearing ropes, rescue ropes, and cut-resistant gloves.
  • the use of high-performance fibers has gradually increased in the cut-resistant field, such as civilian and police cut-resistant gloves and military clothing.
  • the demand for high-performance fibers with excellent cut-resistant properties is also increasing. Due to its low raw material cost and high strength and modulus, high-performance polyethylene fibers have gradually gained application in this field.
  • the first category includes methods disclosed in Chinese Patents CN200980146604, CN201410264678, International Application Publication No. WO2005/066401A1, and U.S. Patent No. 430577, in which high-molecular-weight polyethylene is first swelled and dissolved with a solvent and then extruded into polyethylene filaments. The filaments are then subjected to solvent extraction and drying to remove the solvent, and finally to multi-stage stretching to obtain high-strength and high-modulus polyethylene fibers.
  • This type of method can produce high-strength and high-modulus ultra-high molecular weight polyethylene fiber products, which have excellent mechanical properties and relatively good cut resistance.
  • the general cut resistance grade can reach EN388-2, making them the mainstream fiber raw material for cut-resistant products.
  • ultra-high molecular weight polyethylene fibers are difficult to process, have complex production processes, and are expensive. Problems such as solvent volatilization and recovery during the production process are difficult to resolve, resulting in a significant impact on the environment.
  • the cut resistance performance does not meet the requirements of products with high cut resistance requirements.
  • the second category primarily encompassing those disclosed in Chinese patents CN106149085A, CN107326462A, and CN108315833A, further enhances the properties of ultra-high molecular weight polyethylene (UHMWPE) spinning.
  • UHMWPE ultra-high molecular weight polyethylene
  • the main approach involves mixing nanomaterials and inorganic materials, such as graphene, nanosilica, carbon fiber, and glass fiber, into the UHMWPE raw material. This process then produces fiber products with high cut-resistant properties through a spinning process. While the fiber products produced by this method offer superior cut-resistant properties compared to UHMWPE fibers, the processing costs and complexity are extremely high.
  • the main challenge is the difficulty of uniformly dispersing the nanoscale inorganic materials in the solvent while also preventing agglomeration within the fiber product. This requires demanding modification procedures such as emulsification and grafting of the inorganic and nanomaterials. Furthermore, the solvents mixed with the nanomaterials and inorganic materials are difficult to recycle,
  • the third category mainly includes Chinese patents CN201780040580.9, CN201880081866.6, CN201080007173.6, etc., which use inorganic fibers and polyethylene fibers to mix and knit to form wear-resistant fiber products. After these fiber products are made into gloves or fabrics, the inorganic fibers are easy to pierce out, affecting the comfort, and the mixing cost is also relatively high.
  • the purpose of the present invention is to provide a cut-resistant fiber and a preparation method thereof in order to solve the above problems, thereby solving the problems of environmental pollution, high cost, and complicated steps caused by the preparation of traditional ultra-high molecular weight polyethylene fibers and their modification.
  • a first aspect of the present invention provides a method for preparing a cut-resistant fiber, comprising the following steps:
  • S1 surface treating the inorganic fiber material to improve the affinity of the inorganic fiber material to the polyethylene base material
  • the inorganic fiber comprises a mixture of one or more of carbon fiber, glass fiber, wollastonite fiber, and basalt fiber.
  • the aspect ratio of the inorganic fiber material is greater than 50.
  • the length of the inorganic fiber material ranges from 1 to 1500 ⁇ m, preferably from 300 to 1500 ⁇ m.
  • the diameter of the inorganic fiber material is 1-40 ⁇ m, preferably 5-25 ⁇ m.
  • the surface treatment is one or more of coupling agent treatment, surface chemical modification treatment, surface coating treatment, and plasma treatment.
  • the weight average molecular weight of the narrow molecular weight distribution polyethylene is between 150,000 and 1,000,000, and the molecular weight distribution is lower than 3.0.
  • the extrusion temperature of the twin-screw extruder is 160°C-240°C
  • the spinneret temperature is 180°C-250°C.
  • the temperature during high-ratio stretching is 60°C-150°C.
  • the cooling temperature is 5°C-40°C
  • the cooling medium is air or water.
  • the ratio of high-temperature multiple stretching is 5-20 times, and the temperature is 70°C-130°C.
  • a second aspect of the present invention provides a cut-resistant fiber obtained by the above preparation method.
  • the core concept of the present invention is:
  • the main reason why polyethylene melt spinning cannot currently form cut-resistant fibers is that the molecular weight of the fibers produced by melt spinning is relatively low. Low-molecular-weight polyethylene often has low wear resistance, which is detrimental to cut resistance.
  • the present invention uses polyethylene with a weight-average molecular weight greater than 100,000 to first improve the wear resistance of the polyethylene base material. At the same time, the polyethylene molecular chain structure with a narrow molecular weight distribution is adopted, with the polyethylene molecular weight distribution being less than 3.0, further reducing the effect of low molecular weight on slippage or untangling between molecular chains, thereby improving the wear resistance and cut resistance of the polyethylene base material.
  • the present invention not only improves the wear resistance of the polyethylene base material but also melt-blends an inorganic fiber material with a narrow molecular weight distribution polyethylene.
  • This invention leverages the high draw ratio of the narrow molecular weight distribution polyethylene melt. After the polyethylene melt is ejected from the spinneret, it is stretched at high speed, achieving a draw ratio of over 180 times. This fully orients the inorganic fiber material blended in the polyethylene melt, parallel to the fiber product's direction. This oriented inorganic fiber filler significantly enhances the fiber product's cut resistance.
  • This invention utilizes polyethylene raw materials with a reasonable molecular weight distribution and molecular weight range, and a targeted processing technology to uniformly disperse the inorganic fiber material within the polyethylene fiber and form an oriented structure, resulting in a polyethylene fiber product with cut-resistant properties.
  • the cut-resistant fiber products of this patent have the following advantages:
  • the inorganic fiber processing method is simple, which reduces the processing steps and reduces the processing cost.
  • the tensile properties test uses the methods and equipment in "ANSI/ISEA 2016" to test the cut resistance level of the finished yarn.
  • Glass fiber (length 600 ⁇ m, diameter 10 ⁇ m), silane coupling agent KH560, liquid paraffin, and polyethylene wax were placed in a high-speed mixer at a ratio of 6:2:1:1 and mixed at high speed. The temperature was controlled between 70°C and 90°C. The mixing was performed for 1 minute each time, followed by a 30-second pause. The total mixing time was about 10 minutes to obtain the treated glass fiber.
  • the raw materials are fed into a screw extruder for melt extrusion.
  • the temperature of the twin-screw from the feeding section to the discharge section is 145°C to 180°C, the speed is 90 rpm, and the aperture of the extrusion die is 0.5 mm.
  • the extruded raw fiber was stretched multiple times at 80°C and then wound up.
  • the stretching ratio was 400 times the extrusion rate.
  • the cooling temperature and medium after stretching were 20°C air.
  • the wound fiber was stretched multiple times again at high temperature.
  • the stretching ratio was 7 times and the hot tunnel temperature was 100°C.
  • the fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A5.
  • Carbon fibers 1000 ⁇ m in length and 7 ⁇ m in diameter
  • fluorine gas 0.7-0.8 MPa
  • the temperature was 150°C.
  • the reaction lasted for two hours to obtain surface-fluorinated carbon fibers.
  • Polyethylene with a weight average molecular weight of 150,000, Mw/Mn of 2.9, a thousand carbon methyl number of ⁇ 0.1, and a density of 0.948 g/ cm3 obtained by metallocene catalyst polymerization was blended with fluorinated carbon fiber, fluororubber, antioxidant 1010, and antioxidant PS802 in a ratio of 95:4.5:0.1:0.2:0.2 to obtain a carbon fiber/polyethylene blend, and the blending time was 3 minutes.
  • the carbon fiber/polyethylene blend was fed into a screw extruder for melt extrusion.
  • the twin-screw extruder had a temperature of 145°C to 190°C from the feed section to the discharge section, a rotation speed of 90 rpm, and an extrusion die aperture of 0.4 mm.
  • the extruded raw fiber was stretched multiple times at 60°C and then wound up.
  • the stretching ratio was 300 times the extrusion rate.
  • the cooling temperature and medium after stretching were 20°C water bath.
  • the wound fiber was stretched multiple times again at high temperature.
  • the stretching ratio was 8 times and the hot channel temperature was 110°C.
  • the fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A5.
  • Wollastonite fiber (length 300 ⁇ m, diameter 5 ⁇ m), titanate coupling agent JN-9, liquid paraffin, and polyethylene wax were placed in a high-speed mixer at a ratio of 6:2:1:1 and mixed at high speed. The temperature was controlled between 70°C and 90°C. The mixture was blended for 1 minute each time, then stopped for 30 seconds. The total mixing time was about 10 minutes to obtain the treated wollastonite fiber.
  • Polyethylene with a weight average molecular weight of 400,000, Mw/Mn of 2.9, a thousand carbon methyl number of ⁇ 0.1, and a density of 0.941 g/ cm3 obtained by metallocene catalyst polymerization was blended with treated wollastonite fiber, stearic acid, calcium stearate, and antioxidant 1010 in a ratio of 94:5, 0.3, 0.4, and 0.3 for 3 minutes to obtain a raw material.
  • the raw materials were fed into a screw extruder for melt extrusion.
  • the temperature of the twin-screw from the feeding section to the discharge section was 145°C to 190°C, the speed was 110 rpm, and the aperture of the extrusion die was 1 mm.
  • the extruded raw yarn was stretched multiple times at 100°C and then wound up.
  • the stretching ratio was 180 times the extrusion rate.
  • the cooling temperature and medium after stretching were 40°C hot air.
  • the wound fiber was stretched multiple times again at high temperature.
  • the stretching ratio was 5 times and the hot tunnel temperature was 120°C.
  • the fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A5.
  • Basalt fiber (length 1500 ⁇ m, diameter 25 ⁇ m), aluminate coupling agent 411-C, liquid paraffin, and polyethylene wax were placed in a high-speed mixer at a ratio of 6:2:1:1 and mixed at high speed. The temperature was controlled between 70°C and 90°C. The mixing was performed for 1 minute each time, and then stopped for 30 seconds. The total mixing time was about 10 minutes to obtain the treated basalt fiber.
  • Polyethylene with a weight average molecular weight of 1 million, Mw/Mn of 2.7, a thousand carbon methyl number of less than 0.1, and a density of 0.943 g/ cm3 obtained by metallocene catalyst polymerization was blended with treated wollastonite fiber, stearic acid, calcium stearate, and antioxidant 1010 in a ratio of 94:5, 0.3, 0.4, and 0.3 for 3 minutes to obtain a raw material.
  • the raw materials were fed into a screw extruder for melt extrusion.
  • the temperature of the twin-screw from the feeding section to the discharge section was 145°C to 190°C, the speed was 200 rpm, and the aperture of the extrusion die was 5 mm.
  • the extruded raw yarn was stretched multiple times at 120°C and then wound up, with a stretching ratio of 200 times the extrusion rate.
  • the wound fiber was then stretched again at high temperature multiple times, with a stretching ratio of 9 times and a hot tunnel temperature of 125°C.
  • the fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A5.
  • Carbon fibers 1000 ⁇ m in length and 20 ⁇ m in diameter
  • fluorine gas 0.7-0.8 MPa
  • the temperature was 150°C.
  • the reaction lasted for two hours to obtain surface-fluorinated carbon fibers.
  • Glass fiber, fluorinated carbon fiber, silane coupling agent KH560, liquid paraffin, and polyethylene wax are placed in a high-speed mixer in a ratio of 2:4:2:1:1 and mixed at high speed.
  • the temperature is controlled between 70°C and 90°C.
  • the mixture is blended for 1 minute each time, stopped for 30 seconds, and the mixing time is about 10 minutes in total to obtain the treated mixed fiber.
  • the polyethylene obtained by polymerization with a late transition metal catalyst having a weight average molecular weight of 400,000, Mw/Mn of 2.4, a thousand carbon methyl number of less than 0.1, and a density of 0.941 g/ cm3 was blended with the treated mixed fiber, stearic acid, calcium stearate, and antioxidant 1010 in a ratio of 94:5, 0.3, 0.4, and 0.3, and the blending time was 3 minutes to obtain the raw material.
  • the melt was fed into a screw extruder for melt extrusion.
  • the temperature of the twin screw from the feeding section to the discharge section was 145°C to 200°C, the speed was 220 rpm, and the aperture of the extrusion die was 10 mm.
  • the extruded raw fiber was stretched multiple times at 150°C and then wound up, with a stretching ratio of 600 times the extrusion rate.
  • the wound fiber was then stretched again at a high temperature multiple times, with a stretching ratio of 15 times and a hot tunnel temperature of 130°C.
  • the fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A6.
  • the raw materials are fed into a screw extruder for melt extrusion.
  • the temperature of the twin-screw from the feeding section to the discharge section is 145°C to 180°C, the speed is 90 rpm, and the aperture of the extrusion die is 0.5 mm.
  • the extruded raw fiber was stretched multiple times at 80°C and then wound up.
  • the stretching ratio was 400 times the extrusion rate.
  • the cooling temperature and medium after stretching were 20°C air.
  • the wound fiber was stretched multiple times again at high temperature.
  • the stretching ratio was 7 times and the hot tunnel temperature was 100°C.
  • the fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A1.
  • Glass fiber, silane coupling agent KH560, liquid paraffin, and polyethylene wax were placed in a high-speed mixer at a ratio of 6:2:1:1 and mixed at high speed. The temperature was controlled between 70°C and 90°C. The mixture was blended for 1 minute each time, then stopped for 30 seconds. The total mixing time was about 10 minutes to obtain treated glass fiber.
  • the raw materials are fed into a screw extruder for melt extrusion.
  • the temperature of the twin-screw from the feeding section to the discharge section is 145°C to 180°C, the speed is 90 rpm, and the aperture of the extrusion die is 0.5 mm.
  • the extruded raw yarn was stretched multiple times at 80°C and then wound up.
  • the stretching ratio was 40 times the extrusion rate.
  • the cooling temperature and medium after stretching were 20°C air.
  • the wound fiber was stretched multiple times again at high temperature.
  • the stretching ratio was 7 times and the hot tunnel temperature was 100°C.
  • the fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A3.
  • the raw materials are fed into a screw extruder for melt extrusion.
  • the temperature of the twin-screw from the feeding section to the discharge section is 145°C to 180°C, the speed is 90 rpm, and the aperture of the extrusion die is 0.5 mm.
  • the extruded raw yarn was stretched multiple times at 80°C and then wound up.
  • the stretching ratio was 180 times the extrusion rate, and the yarn broke.
  • Glass fiber, silane coupling agent KH560, liquid paraffin, and polyethylene wax were placed in a high-speed mixer at a ratio of 6:2:1:1 and mixed at high speed. The temperature was controlled between 70°C and 90°C. The mixture was blended for 1 minute each time, then stopped for 30 seconds. The total mixing time was about 10 minutes to obtain treated glass fiber.
  • the raw materials are fed into a screw extruder for melt extrusion.
  • the temperature of the twin-screw from the feeding section to the discharge section is 145°C to 180°C, the speed is 90 rpm, and the aperture of the extrusion die is 0.5 mm.
  • the extruded raw yarn was stretched multiple times at 80°C and then wound up.
  • the stretching ratio was 180 times the extrusion rate, and the yarn broke.
  • Glass fiber, silane coupling agent KH560, liquid paraffin, and polyethylene wax were placed in a high-speed mixer at a ratio of 6:2:1:1 and mixed at high speed. The temperature was controlled between 70°C and 90°C. The mixture was blended for 1 minute each time, then stopped for 30 seconds. The total mixing time was about 10 minutes to obtain treated glass fiber.
  • the raw materials are fed into a screw extruder for melt extrusion.
  • the temperature of the twin-screw from the feeding section to the discharge section is 145°C to 180°C, the speed is 90 rpm, and the aperture of the extrusion die is 0.5 mm.
  • the extruded raw yarn was stretched multiple times at 80°C and then wound up.
  • the stretching ratio was 30 times the extrusion rate.
  • the cooling temperature and medium after stretching were 20°C air.
  • the wound fiber was stretched multiple times again at high temperature.
  • the stretching ratio was 4 times and the hot tunnel temperature was 100°C.
  • the fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A3.
  • a method for preparing wear-resistant and cut-resistant ultra-high molecular weight polyethylene fiber comprises the following steps: adding 0.5 parts of silane KH550 coupling agent, 5 parts of nano-silica, 6 parts of basalt staple fibers, 0.2 parts of sodium stearate, 0.2 parts of pentaerythritol tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 0.8 parts of nano-dispersant VK-01 to 1000 parts of white oil; and treating the mixture in a high-speed rotary emulsifier at 8000 r/min for 4 hours at a temperature controlled at 60°C to form a mother liquor.
  • 80 parts of a resin with a weight-average molecular weight of 4,000,000 and a molecular weight distribution of 5.6, an average particle size of 180 ⁇ m, a particle size distribution width (d90-d10)/d50 of 1.2, and a bulk density of 0.34 g/cm3, were added to a ball mill at 50°C.
  • the mother liquor was then slowly added to the mill at a rate of 2 parts per minute and stirred to mix thoroughly.
  • the mixture was then evacuated in a sealed container for 4 hours.
  • the mixture was then wet-spun through a twin-screw extruder, metering pump, and spinning manifold.
  • the fiber was then extracted, dried, drawn, and heat-stretched before being wound up. Testing revealed that the fiber had an A3 cut-resistant grade.
  • blending polyethylene with treated inorganic fibers yields polyethylene fiber products with superior cut resistance compared to pure polyethylene, reaching A3 levels.
  • Polyethylene with a weight-average molecular weight of 150,000 to 1,000,000 and a molecular weight distribution below 3.0 when blended with treated inorganic fibers, exhibits even better stretchability in the spinneret melt, reaching stretch ratios exceeding 180x. When the stretch ratio exceeds 180x in the melt, the fiber product's cut resistance is further enhanced, reaching A5-A6 levels.
  • the cut-resistant fiber prepared by this method is far superior to the method of preparing high-performance fibers by solution dissolution and current melt extrusion in terms of cost, process complexity and environmental protection, and its cutting performance is also better than that of ultra-high molecular weight polyethylene cut-resistant fiber products prepared by the solution method.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

A cut-resistant fiber and a preparation method therefor. The preparation method comprises the following steps: carrying out surface treatment on an inorganic fiber material, to improve the affinity of the inorganic fiber material to a polyethylene base material; mixing narrow-molecular-weight-distribution polyethylene obtained by polymerization using a single-site catalyst, the treated inorganic fiber material, and a processing aid to form a blend; feeding the obtained blend into a double-screw extruder for melt blending, and obtaining an undrawn fiber melt by means of a spinneret; carrying out high-temperature high-ratio drawing on the undrawn fiber melt at a drawing ratio of greater than 180 times until an inorganic fiber reaches a unidirectionally oriented state, and then cooling the inorganic fiber; and carrying out high-temperature multi-ratio drawing again on the cooled inorganic fiber to obtain a cut-resistant polyethylene composite fiber. Compared with the prior art, the preparation method solves the problems such as environmental pollution, high cost and tedious steps generated in conventional ultrahigh-molecular-weight polyethylene fiber preparation and modification carried out on this basis.

Description

一种耐切割纤维及其制备方法Cut-resistant fiber and preparation method thereof 技术领域Technical Field

本发明涉及高分子材料技术领域,尤其是涉及耐切割纤维及其制备方法。The present invention relates to the technical field of polymer materials, in particular to a cut-resistant fiber and a preparation method thereof.

背景技术Background Art

随着科学技术突飞猛进的发展,工程技术界对特种纤维的需求在不断增长,高性能聚乙烯纤维具有轻质高强、使用周期长、耐磨、高强、耐湿、耐腐蚀等特性,而普遍用于拖曳绳、负力绳索、救捞绳、防切割手套等。近几年,高性能纤维的使用在防切割领域逐渐增多,如民用、警用防切割手套、军用服装等。对于高性能纤维的防切割性能需且也逐渐加大。高性能聚乙烯纤维由于其原料低成本,高强高模等特性,在该领域的应用也逐渐得到了发展。With the rapid advancement of science and technology, the demand for specialty fibers in the engineering and technical community is growing. High-performance polyethylene fibers, characterized by their lightweight, high strength, long service life, wear resistance, high strength, moisture resistance, and corrosion resistance, are widely used in towing ropes, load-bearing ropes, rescue ropes, and cut-resistant gloves. In recent years, the use of high-performance fibers has gradually increased in the cut-resistant field, such as civilian and police cut-resistant gloves and military clothing. The demand for high-performance fibers with excellent cut-resistant properties is also increasing. Due to its low raw material cost and high strength and modulus, high-performance polyethylene fibers have gradually gained application in this field.

目前对于应用于防切割领域的聚乙烯纺丝的方法可以主要分为三大类:At present, the methods for polyethylene spinning used in the field of cut resistance can be mainly divided into three categories:

第一类包括是中国专利CN200980146604、中国专利CN201410264678、国际申请公开号第W02005/066401A1、美国专利US430577等公开的以溶剂首先对高分子量聚乙烯进行溶胀溶解后,挤出成聚乙烯原丝。对原丝进行溶剂萃取干燥等步骤除去溶剂,最后进行多级拉伸,得到高强高模聚乙烯纤维。这类方法可以得到高强高模的超高分子量聚乙烯纤维制品,该类产品具有优异的力学性能及较优的防切割性能,一般防切割等级可达到EN388-2级,是目前防切割制品的主流纤维原料。但是由于超高分子量聚乙烯纤维加工难度大,生产工艺复杂,成本较高,生产过程中溶剂的挥发回收等问题较难解决,对环境影响较大,且防切割性能并不能满足在防切割领域要求较高的产品。The first category includes methods disclosed in Chinese Patents CN200980146604, CN201410264678, International Application Publication No. WO2005/066401A1, and U.S. Patent No. 430577, in which high-molecular-weight polyethylene is first swelled and dissolved with a solvent and then extruded into polyethylene filaments. The filaments are then subjected to solvent extraction and drying to remove the solvent, and finally to multi-stage stretching to obtain high-strength and high-modulus polyethylene fibers. This type of method can produce high-strength and high-modulus ultra-high molecular weight polyethylene fiber products, which have excellent mechanical properties and relatively good cut resistance. The general cut resistance grade can reach EN388-2, making them the mainstream fiber raw material for cut-resistant products. However, ultra-high molecular weight polyethylene fibers are difficult to process, have complex production processes, and are expensive. Problems such as solvent volatilization and recovery during the production process are difficult to resolve, resulting in a significant impact on the environment. In addition, the cut resistance performance does not meet the requirements of products with high cut resistance requirements.

第二类主要包括中国专利CN106149085A、中国专利CN107326462A、中国专利CN108315833A等公开的,在超高分子量聚乙烯纺丝的基础上进行进一步增强。主要方法是将石墨烯、纳米二氧化硅、碳纤维、玻璃纤维等纳米材料及无机材料混入超高分子量聚乙烯原料中,通过纺丝工艺加工获得高防切割性能的纤维制品。该方法制备得到的纤维制品虽然可获得较超高分子量聚乙烯纤维更优异的防切割效果,但加工成本极高,且难度很高。主要在于将纳米级无机材料均匀分散在溶剂中的同时还能均匀分散在纤维制品中不发生团聚十分困难,需要对无机物及纳米材料进行如乳化、接枝等条件苛刻的改性操作;其次混入纳米及无机材料的溶剂要回收再利用也非常困难,废溶剂处理成本极高。The second category, primarily encompassing those disclosed in Chinese patents CN106149085A, CN107326462A, and CN108315833A, further enhances the properties of ultra-high molecular weight polyethylene (UHMWPE) spinning. The main approach involves mixing nanomaterials and inorganic materials, such as graphene, nanosilica, carbon fiber, and glass fiber, into the UHMWPE raw material. This process then produces fiber products with high cut-resistant properties through a spinning process. While the fiber products produced by this method offer superior cut-resistant properties compared to UHMWPE fibers, the processing costs and complexity are extremely high. The main challenge is the difficulty of uniformly dispersing the nanoscale inorganic materials in the solvent while also preventing agglomeration within the fiber product. This requires demanding modification procedures such as emulsification and grafting of the inorganic and nanomaterials. Furthermore, the solvents mixed with the nanomaterials and inorganic materials are difficult to recycle, resulting in extremely high costs for waste solvent disposal.

第三类主要包括中国专利CN201780040580.9、中国专利CN201880081866.6、中国专利CN201080007173.6等使用无机纤维与聚乙烯纤维进行混编后形成耐磨纤维制品,这类纤维制品制成手套或织物后,无机纤维易刺出纤维,影响舒适度,且混编成本也相对较高。The third category mainly includes Chinese patents CN201780040580.9, CN201880081866.6, CN201080007173.6, etc., which use inorganic fibers and polyethylene fibers to mix and knit to form wear-resistant fiber products. After these fiber products are made into gloves or fabrics, the inorganic fibers are easy to pierce out, affecting the comfort, and the mixing cost is also relatively high.

发明内容Summary of the Invention

本发明的目的就是为了解决上述问题而提供一种耐切割纤维及其制备方法,解决了传统超高分子量聚乙烯纤维制备及在此基础上进行改性产生的环境污染、成本高、步骤繁琐等问题。The purpose of the present invention is to provide a cut-resistant fiber and a preparation method thereof in order to solve the above problems, thereby solving the problems of environmental pollution, high cost, and complicated steps caused by the preparation of traditional ultra-high molecular weight polyethylene fibers and their modification.

本发明的目的通过以下技术方案实现:The purpose of the present invention is achieved through the following technical solutions:

本发明第一方面提供一种耐切割纤维的制备方法,包括以下步骤:A first aspect of the present invention provides a method for preparing a cut-resistant fiber, comprising the following steps:

S1:将无机纤维材料进行表面处理,提高所述无机纤维材料对聚乙烯基料的亲和性;S1: surface treating the inorganic fiber material to improve the affinity of the inorganic fiber material to the polyethylene base material;

S2:将由单活性中心催化剂聚合得到的窄分子量分布聚乙烯、S1中处理后的无机纤维材料、加工助剂混合,构成共混料;S2: Mixing the narrow molecular weight distribution polyethylene obtained by polymerization with a single active site catalyst, the inorganic fiber material treated in S1, and a processing aid to form a blend;

S3:将S2中获得的共混料喂入双螺杆挤出机进行熔体共混,通过喷丝板获得未拉伸纤维熔体;S3: feeding the blend obtained in S2 into a twin-screw extruder for melt blending, and obtaining an undrawn fiber melt through a spinneret;

S4:将未拉伸纤维熔体在高温下进行高倍拉伸,拉伸倍率大于180倍,直至无机纤维达到单向取向状态后冷却;S4: stretching the unstretched fiber melt at a high ratio at a high temperature, with a stretching ratio greater than 180 times, until the inorganic fiber reaches a unidirectional orientation state, and then cooling;

S5:将S4中冷却后的无机纤维再次进行高温多倍拉伸,获得耐切割聚乙烯复合纤维。S5: The inorganic fiber cooled in S4 is subjected to high-temperature multiple stretching again to obtain a cut-resistant polyethylene composite fiber.

进一步地,所述无机纤维包含碳纤维、玻璃纤维、硅灰石纤维、玄武岩纤维中的一种或多种的混合物。Furthermore, the inorganic fiber comprises a mixture of one or more of carbon fiber, glass fiber, wollastonite fiber, and basalt fiber.

进一步地,S1中,所述无机纤维材料长径比大于50。Furthermore, in S1, the aspect ratio of the inorganic fiber material is greater than 50.

进一步地,S1中,所述无机纤维材料的长度范围为1-1500μm,优选为300-1500μm。Furthermore, in S1, the length of the inorganic fiber material ranges from 1 to 1500 μm, preferably from 300 to 1500 μm.

进一步地,S1中,无机纤维材料的直径为1-40μm ,优选为5-25μm。Furthermore, in S1, the diameter of the inorganic fiber material is 1-40 μm, preferably 5-25 μm.

进一步地,S1中,所述表面处理为偶联剂处理、表面化学改性处理、表面包覆处理、等离子处理中的一种或多种。Furthermore, in S1, the surface treatment is one or more of coupling agent treatment, surface chemical modification treatment, surface coating treatment, and plasma treatment.

进一步地,S1中,所述窄分子量分布聚乙烯的重均分子量介于15万-100万之间,分子量分布低于3.0。Furthermore, in S1, the weight average molecular weight of the narrow molecular weight distribution polyethylene is between 150,000 and 1,000,000, and the molecular weight distribution is lower than 3.0.

进一步地,S3中,双螺杆挤出机挤出温度为160℃-240℃,喷丝板温度为180℃-250℃。Furthermore, in S3, the extrusion temperature of the twin-screw extruder is 160°C-240°C, and the spinneret temperature is 180°C-250°C.

进一步地,S4中,进行高倍拉伸的时的温度为60℃-150℃。Furthermore, in S4, the temperature during high-ratio stretching is 60°C-150°C.

进一步地,S4中,冷却温度为5℃-40℃,冷却介质为空气或水。Furthermore, in S4, the cooling temperature is 5°C-40°C, and the cooling medium is air or water.

进一步地,S5,高温多倍拉伸的倍率为5-20倍,温度为70℃-130℃。Furthermore, in S5, the ratio of high-temperature multiple stretching is 5-20 times, and the temperature is 70°C-130°C.

本发明第二方面提供一种如上述制备方法得到的耐切割纤维。A second aspect of the present invention provides a cut-resistant fiber obtained by the above preparation method.

本发明的构思核心在于:The core concept of the present invention is:

目前对于聚乙烯熔融纺丝无法形成耐切割纤维的主要原因首先在于通过熔融纺丝的纤维分子量相对较低,低分子量的聚乙烯往往具有较低的耐磨性,对耐切割性能不利。本发明使用重均分子量高于10万的聚乙烯首先提升了聚乙烯基料的耐磨性,同时采用窄分子量分布的聚乙烯分子链结构,使聚乙烯分子量分布低于3.0,进一步减少低分子量对于分子链间滑移或解缠的效应,提升聚乙烯基料的耐磨性及耐切割性。The main reason why polyethylene melt spinning cannot currently form cut-resistant fibers is that the molecular weight of the fibers produced by melt spinning is relatively low. Low-molecular-weight polyethylene often has low wear resistance, which is detrimental to cut resistance. The present invention uses polyethylene with a weight-average molecular weight greater than 100,000 to first improve the wear resistance of the polyethylene base material. At the same time, the polyethylene molecular chain structure with a narrow molecular weight distribution is adopted, with the polyethylene molecular weight distribution being less than 3.0, further reducing the effect of low molecular weight on slippage or untangling between molecular chains, thereby improving the wear resistance and cut resistance of the polyethylene base material.

为了进一步提升纤维的耐切割性能,在提升聚乙烯基料耐磨的基础上,进一步将无机纤维材料与窄分子量分布聚乙烯进行熔体共混。本发明充分利用了窄分子量分布聚乙烯熔体高拉伸倍率的特性,在聚乙烯熔体从喷丝板喷出后,高速拉伸,使聚乙烯纤维拉伸倍率高于180倍,将共混于聚乙烯熔体内的无机纤维材料充分取向,形成其平行于纤维制品方向。取向状态的无机纤维填料大幅提升了纤维制品的耐切割制品。To further enhance the fiber's cut resistance, the present invention not only improves the wear resistance of the polyethylene base material but also melt-blends an inorganic fiber material with a narrow molecular weight distribution polyethylene. This invention leverages the high draw ratio of the narrow molecular weight distribution polyethylene melt. After the polyethylene melt is ejected from the spinneret, it is stretched at high speed, achieving a draw ratio of over 180 times. This fully orients the inorganic fiber material blended in the polyethylene melt, parallel to the fiber product's direction. This oriented inorganic fiber filler significantly enhances the fiber product's cut resistance.

本发明通过使用合理的分子量分布及分子量范围的聚乙烯原料,及具有针对性的加工工艺,使无机纤维材料在聚乙烯纤维内均匀分散,并形成取向结构,得到了具有耐切割特性的聚乙烯纤维制品。与现在的耐切割纤维及制备方法相比,本专利的耐切割纤维制品体现优势如下:This invention utilizes polyethylene raw materials with a reasonable molecular weight distribution and molecular weight range, and a targeted processing technology to uniformly disperse the inorganic fiber material within the polyethylene fiber and form an oriented structure, resulting in a polyethylene fiber product with cut-resistant properties. Compared with existing cut-resistant fibers and preparation methods, the cut-resistant fiber products of this patent have the following advantages:

1)纺丝过程中不需要使用溶剂,无混料及冷却过程,大幅简化高性能聚乙烯纤维纺丝流程。1) No solvent is required during the spinning process, and there is no mixing or cooling process, which greatly simplifies the high-performance polyethylene fiber spinning process.

2)大幅降低由于处理溶剂及回收溶剂导致的生产成本高,且过程更环保。2) Greatly reduce the high production costs caused by solvent treatment and solvent recovery, and the process is more environmentally friendly.

3)生产过程中处于无溶剂状态,大幅提升了生产过程中的安全系数。3) The production process is in a solvent-free state, which greatly improves the safety factor of the production process.

4)无机纤维处理方式简单,减少处理步骤,降低处理成本。4) The inorganic fiber processing method is simple, which reduces the processing steps and reduces the processing cost.

具体实施方式DETAILED DESCRIPTION

下面结合具体实施例对本发明进行详细说明,以下实施例将有助于本领域的技术人员进一步理解本发明,但不以任何形式限制本发明。应当指出的是,对本领域的普通技术人员来说,在不脱离本发明构思的前提下,还可以做出若干变形和改进。这些都属于本发明的保护范围。The present invention will be described in detail below with reference to specific embodiments. The following embodiments will help those skilled in the art further understand the present invention, but are not intended to limit the present invention in any form. It should be noted that those skilled in the art may make various modifications and improvements without departing from the scope of the present invention. These modifications and improvements are all within the scope of protection of the present invention.

本技术方案中如未明确说明的制备手段、材料、结构或组成配比等特征,均视为现有技术中公开的常见技术特征。Any features such as preparation methods, materials, structures or composition ratios that are not clearly described in this technical solution shall be deemed to be common technical features disclosed in the prior art.

实施例中聚乙烯原料的表征数据由以下方法获得:The characterization data of the polyethylene raw materials in the examples were obtained by the following method:

拉伸性能测试采用《ANSI/ISEA 2016》中的方法与设备,对成品丝的抗切割等级进行测试。The tensile properties test uses the methods and equipment in "ANSI/ISEA 2016" to test the cut resistance level of the finished yarn.

实施例1Example 1

将玻璃纤维(长度尺寸为600μm,直径为10μm)、硅烷偶联剂KH560、液体石蜡、聚乙烯蜡以6:2:1:1的比例置于高速混合机中,进行高速混合,温度控制在70℃-90℃之间,每次共混1分钟,停30秒,混合时间共约10分钟,获得处理后的玻璃纤维。Glass fiber (length 600 μm, diameter 10 μm), silane coupling agent KH560, liquid paraffin, and polyethylene wax were placed in a high-speed mixer at a ratio of 6:2:1:1 and mixed at high speed. The temperature was controlled between 70°C and 90°C. The mixing was performed for 1 minute each time, followed by a 30-second pause. The total mixing time was about 10 minutes to obtain the treated glass fiber.

取后过渡金属催化剂聚合得到的重均分子量为15万,Mw/Mn为2.8,千碳甲基数<0.1,密度为0.945g/cm 3的聚乙烯。将聚乙烯与处理后的玻璃纤维、抗氧剂1010、硬脂酸锌以95:4.5:0.2:0.3的比例进行共混,共混时间3分钟,获得原料。 Polyethylene having a weight average molecular weight of 150,000, an Mw/Mn ratio of 2.8, a thousand carbon methyl groups less than 0.1, and a density of 0.945 g/ cm3 , obtained by polymerization using a late transition metal catalyst, was blended with treated glass fiber, antioxidant 1010, and zinc stearate in a ratio of 95:4.5:0.2:0.3 for 3 minutes to obtain a raw material.

将原料喂入螺杆挤出机中进行熔体挤出。双螺杆从喂料段温度到出料温度为145℃~180℃,转速90转/min,挤出口模的孔径为0.5mm。The raw materials are fed into a screw extruder for melt extrusion. The temperature of the twin-screw from the feeding section to the discharge section is 145°C to 180°C, the speed is 90 rpm, and the aperture of the extrusion die is 0.5 mm.

将挤出后的原丝在80℃下进行多倍拉伸后收卷,拉伸倍率为挤出速率为400倍,拉伸后冷却温度及介质为20℃空气。将收卷后的纤维再次进行高温多倍拉伸,拉伸倍率为7倍,热甬道温度为100℃。The extruded raw fiber was stretched multiple times at 80°C and then wound up. The stretching ratio was 400 times the extrusion rate. The cooling temperature and medium after stretching were 20°C air. The wound fiber was stretched multiple times again at high temperature. The stretching ratio was 7 times and the hot tunnel temperature was 100°C.

将高温多倍拉伸后的纤维进行防切割测试,防切割性可达A5。The fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A5.

实施例2Example 2

将碳纤维(长度尺寸为1000μm,直径为7μm)、氟气置于密闭反应釜中,氟气压力0.7-0.8Mpa,温度150℃下,反应持续两小时,获得表面氟化的碳纤维。Carbon fibers (1000 μm in length and 7 μm in diameter) and fluorine gas were placed in a sealed reactor. The fluorine gas pressure was 0.7-0.8 MPa and the temperature was 150°C. The reaction lasted for two hours to obtain surface-fluorinated carbon fibers.

取茂金属催化剂聚合得到的重均分子量为15万,Mw/Mn为2.9,千碳甲基数<0.1,密度为0.948g/cm 3的聚乙烯与氟化碳纤维、氟橡胶、抗氧剂1010、抗氧剂PS802以95:4.5:0.1:0.2:0.2的比例进行共混获得碳纤维/聚乙烯共混物,共混时间3分钟。 Polyethylene with a weight average molecular weight of 150,000, Mw/Mn of 2.9, a thousand carbon methyl number of <0.1, and a density of 0.948 g/ cm3 obtained by metallocene catalyst polymerization was blended with fluorinated carbon fiber, fluororubber, antioxidant 1010, and antioxidant PS802 in a ratio of 95:4.5:0.1:0.2:0.2 to obtain a carbon fiber/polyethylene blend, and the blending time was 3 minutes.

将碳纤维/聚乙烯共混物喂入螺杆挤出机中进行熔体挤出。双螺杆从喂料段温度到出料温度为145℃~190℃,转速90转/min,挤出口模的孔径为0.4mm。The carbon fiber/polyethylene blend was fed into a screw extruder for melt extrusion. The twin-screw extruder had a temperature of 145°C to 190°C from the feed section to the discharge section, a rotation speed of 90 rpm, and an extrusion die aperture of 0.4 mm.

将挤出后的原丝在60℃进行多倍拉伸后收卷,拉伸倍率为挤出速率的300倍,拉伸后冷却温度及介质为20℃水浴。将收卷后的纤维再次进行高温多倍拉伸,拉伸倍率为8倍,热甬道温度为110℃。The extruded raw fiber was stretched multiple times at 60°C and then wound up. The stretching ratio was 300 times the extrusion rate. The cooling temperature and medium after stretching were 20°C water bath. The wound fiber was stretched multiple times again at high temperature. The stretching ratio was 8 times and the hot channel temperature was 110°C.

将高温多倍拉伸后的纤维进行防切割测试,防切割性可达A5。The fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A5.

实施例3Example 3

将硅灰石纤维(长度尺寸为300μm,直径为5μm)、钛酸酯偶联剂JN-9、液体石蜡、聚乙烯蜡以6:2:1:1的比例置于高速混合机中,进行高速混合,温度控制在70℃-90℃之间,每次共混1分钟,停30秒,混合时间共约10分钟,获得处理后的硅灰石纤维。Wollastonite fiber (length 300 μm, diameter 5 μm), titanate coupling agent JN-9, liquid paraffin, and polyethylene wax were placed in a high-speed mixer at a ratio of 6:2:1:1 and mixed at high speed. The temperature was controlled between 70°C and 90°C. The mixture was blended for 1 minute each time, then stopped for 30 seconds. The total mixing time was about 10 minutes to obtain the treated wollastonite fiber.

取茂金属催化剂聚合得到的重均分子量为40万,Mw/Mn为2.9,千碳甲基数<0.1,密度为0.941g/cm 3的聚乙烯与处理后的硅灰石纤维、硬脂酸、硬脂酸钙、抗氧剂1010以94、5、0.3、0.4、0.3的比例进行共混,共混时间3分钟获得原料。 Polyethylene with a weight average molecular weight of 400,000, Mw/Mn of 2.9, a thousand carbon methyl number of <0.1, and a density of 0.941 g/ cm3 obtained by metallocene catalyst polymerization was blended with treated wollastonite fiber, stearic acid, calcium stearate, and antioxidant 1010 in a ratio of 94:5, 0.3, 0.4, and 0.3 for 3 minutes to obtain a raw material.

将原料喂入螺杆挤出机中进行熔体挤出。双螺杆从喂料段温度到出料温度为145℃~190℃,转速110转/min,挤出口模的孔径为1mm。The raw materials were fed into a screw extruder for melt extrusion. The temperature of the twin-screw from the feeding section to the discharge section was 145°C to 190°C, the speed was 110 rpm, and the aperture of the extrusion die was 1 mm.

将挤出后的原丝在100℃进行多倍拉伸后收卷,拉伸倍率为挤出速率的180倍,拉伸后冷却温度及介质为40℃热空气。将收卷后的纤维再次进行高温多倍拉伸,拉伸倍率为5倍,热甬道温度为120℃。The extruded raw yarn was stretched multiple times at 100°C and then wound up. The stretching ratio was 180 times the extrusion rate. The cooling temperature and medium after stretching were 40°C hot air. The wound fiber was stretched multiple times again at high temperature. The stretching ratio was 5 times and the hot tunnel temperature was 120°C.

将高温多倍拉伸后的纤维进行防切割测试,防切割性可达A5。The fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A5.

实施例4Example 4

将玄武岩纤维(长度尺寸为1500μm,直径为25μm)、铝酸酯偶联剂411-C、液体石蜡、聚乙烯蜡以6:2:1:1的比例置于高速混合机中,进行高速混合,温度控制在70℃-90℃之间,每次共混1分钟,停30秒,混合时间共约10分钟,获得处理后的玄武岩纤维。Basalt fiber (length 1500 μm, diameter 25 μm), aluminate coupling agent 411-C, liquid paraffin, and polyethylene wax were placed in a high-speed mixer at a ratio of 6:2:1:1 and mixed at high speed. The temperature was controlled between 70°C and 90°C. The mixing was performed for 1 minute each time, and then stopped for 30 seconds. The total mixing time was about 10 minutes to obtain the treated basalt fiber.

取茂金属催化剂聚合得到的重均分子量为100万,Mw/Mn为2.7,千碳甲基数<0.1,密度为0.943g/cm 3的聚乙烯与处理后的硅灰石纤维、硬脂酸、硬脂酸钙、抗氧剂1010以94、5、0.3、0.4、0.3的比例进行共混,共混时间3分钟获得原料。 Polyethylene with a weight average molecular weight of 1 million, Mw/Mn of 2.7, a thousand carbon methyl number of less than 0.1, and a density of 0.943 g/ cm3 obtained by metallocene catalyst polymerization was blended with treated wollastonite fiber, stearic acid, calcium stearate, and antioxidant 1010 in a ratio of 94:5, 0.3, 0.4, and 0.3 for 3 minutes to obtain a raw material.

将原料喂入螺杆挤出机中进行熔体挤出。双螺杆从喂料段温度到出料温度为145℃~190℃,转速200转/min,挤出口模的孔径为5mm。The raw materials were fed into a screw extruder for melt extrusion. The temperature of the twin-screw from the feeding section to the discharge section was 145°C to 190°C, the speed was 200 rpm, and the aperture of the extrusion die was 5 mm.

将挤出后的原丝在120℃进行多倍拉伸后收卷,拉伸倍率为挤出速率的200倍。将收卷后的纤维再次进行高温多倍拉伸,拉伸倍率为9倍,热甬道温度为125℃。The extruded raw yarn was stretched multiple times at 120°C and then wound up, with a stretching ratio of 200 times the extrusion rate. The wound fiber was then stretched again at high temperature multiple times, with a stretching ratio of 9 times and a hot tunnel temperature of 125°C.

将高温多倍拉伸后的纤维进行防切割测试,防切割性可达A5。The fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A5.

实施例5Example 5

将碳纤维(长度尺寸为1000μm,直径为20μm)、氟气置于密闭反应釜中,氟气压力0.7-0.8Mpa,温度150℃下,反应持续两小时,获得表面氟化的碳纤维。Carbon fibers (1000 μm in length and 20 μm in diameter) and fluorine gas were placed in a closed reactor. The fluorine gas pressure was 0.7-0.8 MPa and the temperature was 150°C. The reaction lasted for two hours to obtain surface-fluorinated carbon fibers.

将玻璃纤维、氟化碳纤维、硅烷偶联剂KH560、液体石蜡、聚乙烯蜡以2:4:2:1:1的比例置于高速混合机中,进行高速混合,温度控制在70℃-90℃之间,每次共混1分钟,停30秒,混合时间共约10分钟,获得处理后的混合纤维。Glass fiber, fluorinated carbon fiber, silane coupling agent KH560, liquid paraffin, and polyethylene wax are placed in a high-speed mixer in a ratio of 2:4:2:1:1 and mixed at high speed. The temperature is controlled between 70°C and 90°C. The mixture is blended for 1 minute each time, stopped for 30 seconds, and the mixing time is about 10 minutes in total to obtain the treated mixed fiber.

取后过渡金属催化剂聚合得到的重均分子量为40万,Mw/Mn为2.4,千碳甲基数<0.1,密度为0.941g/cm 3的聚乙烯与处理后的混合纤维、硬脂酸、硬脂酸钙、抗氧剂1010以94、5、0.3、0.4、0.3的比例进行共混,共混时间3分钟获得原料。 The polyethylene obtained by polymerization with a late transition metal catalyst having a weight average molecular weight of 400,000, Mw/Mn of 2.4, a thousand carbon methyl number of less than 0.1, and a density of 0.941 g/ cm3 was blended with the treated mixed fiber, stearic acid, calcium stearate, and antioxidant 1010 in a ratio of 94:5, 0.3, 0.4, and 0.3, and the blending time was 3 minutes to obtain the raw material.

喂入螺杆挤出机中进行熔体挤出。双螺杆从喂料段温度到出料温度为145℃~200℃,转速220转/min,挤出口模的孔径为10mm。The melt was fed into a screw extruder for melt extrusion. The temperature of the twin screw from the feeding section to the discharge section was 145°C to 200°C, the speed was 220 rpm, and the aperture of the extrusion die was 10 mm.

将挤出后的原丝150℃进行多倍拉伸后收卷,拉伸倍率为挤出速率的600倍。将收卷后的纤维再次进行高温多倍拉伸,拉伸倍率为15倍,热甬道温度为130℃。The extruded raw fiber was stretched multiple times at 150°C and then wound up, with a stretching ratio of 600 times the extrusion rate. The wound fiber was then stretched again at a high temperature multiple times, with a stretching ratio of 15 times and a hot tunnel temperature of 130°C.

将高温多倍拉伸后的纤维进行防切割测试,防切割性可达A6。The fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A6.

对比例1Comparative Example 1

取后过渡金属催化剂聚合得到的重均分子量为15万,Mw/Mn为2.8,千碳甲基数<0.1,密度为0.945g/cm 3的聚乙烯。将聚乙烯与抗氧剂1010、硬脂酸锌以99.5:0.2:0.3的比例进行共混,共混时间3分钟,获得原料。 Polyethylene having a weight average molecular weight of 150,000, an Mw/Mn ratio of 2.8, a kilo-carbon methyl number of less than 0.1, and a density of 0.945 g/ cm³ , obtained by polymerization using a late transition metal catalyst, was blended with antioxidant 1010 and zinc stearate in a ratio of 99.5:0.2:0.3 for 3 minutes to obtain a raw material.

将原料喂入螺杆挤出机中进行熔体挤出。双螺杆从喂料段温度到出料温度为145℃~180℃,转速90转/min,挤出口模的孔径为0.5mm。The raw materials are fed into a screw extruder for melt extrusion. The temperature of the twin-screw from the feeding section to the discharge section is 145°C to 180°C, the speed is 90 rpm, and the aperture of the extrusion die is 0.5 mm.

将挤出后的原丝在80℃下进行多倍拉伸后收卷,拉伸倍率为挤出速率为400倍,拉伸后冷却温度及介质为20℃空气。将收卷后的纤维再次进行高温多倍拉伸,拉伸倍率为7倍,热甬道温度为100℃。The extruded raw fiber was stretched multiple times at 80°C and then wound up. The stretching ratio was 400 times the extrusion rate. The cooling temperature and medium after stretching were 20°C air. The wound fiber was stretched multiple times again at high temperature. The stretching ratio was 7 times and the hot tunnel temperature was 100°C.

将高温多倍拉伸后的纤维进行防切割测试,防切割性可达A1。The fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A1.

对比例2Comparative Example 2

将玻璃纤维、硅烷偶联剂KH560、液体石蜡、聚乙烯蜡以6:2:1:1的比例置于高速混合机中,进行高速混合,温度控制在70℃-90℃之间,每次共混1分钟,停30秒,混合时间共约10分钟,获得处理后的玻璃纤维。Glass fiber, silane coupling agent KH560, liquid paraffin, and polyethylene wax were placed in a high-speed mixer at a ratio of 6:2:1:1 and mixed at high speed. The temperature was controlled between 70°C and 90°C. The mixture was blended for 1 minute each time, then stopped for 30 seconds. The total mixing time was about 10 minutes to obtain treated glass fiber.

取后过渡金属催化剂聚合得到的重均分子量为15万,Mw/Mn为2.8,千碳甲基数<0.1,密度为0.945g/cm 3的聚乙烯。将聚乙烯与处理后的玻璃纤维、抗氧剂1010、硬脂酸锌以95:4.5:0.2:0.3的比例进行共混,共混时间3分钟,获得原料。 Polyethylene having a weight average molecular weight of 150,000, an Mw/Mn ratio of 2.8, a thousand carbon methyl groups less than 0.1, and a density of 0.945 g/ cm3 , obtained by polymerization using a late transition metal catalyst, was blended with treated glass fiber, antioxidant 1010, and zinc stearate in a ratio of 95:4.5:0.2:0.3 for 3 minutes to obtain a raw material.

将原料喂入螺杆挤出机中进行熔体挤出。双螺杆从喂料段温度到出料温度为145℃~180℃,转速90转/min,挤出口模的孔径为0.5mm。The raw materials are fed into a screw extruder for melt extrusion. The temperature of the twin-screw from the feeding section to the discharge section is 145°C to 180°C, the speed is 90 rpm, and the aperture of the extrusion die is 0.5 mm.

将挤出后的原丝在80℃下进行多倍拉伸后收卷,拉伸倍率为挤出速率为40倍,拉伸后冷却温度及介质为20℃空气。将收卷后的纤维再次进行高温多倍拉伸,拉伸倍率为7倍,热甬道温度为100℃。The extruded raw yarn was stretched multiple times at 80°C and then wound up. The stretching ratio was 40 times the extrusion rate. The cooling temperature and medium after stretching were 20°C air. The wound fiber was stretched multiple times again at high temperature. The stretching ratio was 7 times and the hot tunnel temperature was 100°C.

将高温多倍拉伸后的纤维进行防切割测试,防切割性可达A3。The fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A3.

对比例3Comparative Example 3

取后过渡金属催化剂聚合得到的重均分子量为15万,Mw/Mn为2.8,千碳甲基数<0.1,密度为0.945g/cm 3的聚乙烯。将聚乙烯与未处理的玻璃纤维、抗氧剂1010、硬脂酸锌以95:4.5:0.2:0.3的比例进行共混,共混时间3分钟,获得原料。 Polyethylene having a weight average molecular weight of 150,000, an Mw/Mn ratio of 2.8, a kilo-carbon methyl number of less than 0.1, and a density of 0.945 g/ cm³ , obtained by polymerization using a late transition metal catalyst, was blended with untreated glass fiber, antioxidant 1010, and zinc stearate in a ratio of 95:4.5:0.2:0.3 for 3 minutes to obtain a raw material.

将原料喂入螺杆挤出机中进行熔体挤出。双螺杆从喂料段温度到出料温度为145℃~180℃,转速90转/min,挤出口模的孔径为0.5mm。The raw materials are fed into a screw extruder for melt extrusion. The temperature of the twin-screw from the feeding section to the discharge section is 145°C to 180°C, the speed is 90 rpm, and the aperture of the extrusion die is 0.5 mm.

将挤出后的原丝在80℃下进行多倍拉伸后收卷,拉伸倍率为挤出速率为180倍,出现断丝。The extruded raw yarn was stretched multiple times at 80°C and then wound up. The stretching ratio was 180 times the extrusion rate, and the yarn broke.

对比例4Comparative Example 4

将玻璃纤维、硅烷偶联剂KH560、液体石蜡、聚乙烯蜡以6:2:1:1的比例置于高速混合机中,进行高速混合,温度控制在70℃-90℃之间,每次共混1分钟,停30秒,混合时间共约10分钟,获得处理后的玻璃纤维。Glass fiber, silane coupling agent KH560, liquid paraffin, and polyethylene wax were placed in a high-speed mixer at a ratio of 6:2:1:1 and mixed at high speed. The temperature was controlled between 70°C and 90°C. The mixture was blended for 1 minute each time, then stopped for 30 seconds. The total mixing time was about 10 minutes to obtain treated glass fiber.

取后过渡金属催化剂聚合得到的重均分子量为15万,Mw/Mn为5.4,千碳甲基数<0.1,密度为0.952g/cm 3的聚乙烯。将聚乙烯与处理后的玻璃纤维、抗氧剂1010、硬脂酸锌以95:4.5:0.2:0.3的比例进行共混,共混时间3分钟,获得原料。 Polyethylene having a weight average molecular weight of 150,000, an Mw/Mn ratio of 5.4, a thousand carbon methyl groups less than 0.1, and a density of 0.952 g/cm 3 , obtained by polymerization using a late transition metal catalyst, was blended with treated glass fiber, antioxidant 1010, and zinc stearate in a ratio of 95:4.5:0.2:0.3 for 3 minutes to obtain a raw material.

将原料喂入螺杆挤出机中进行熔体挤出。双螺杆从喂料段温度到出料温度为145℃~180℃,转速90转/min,挤出口模的孔径为0.5mm。The raw materials are fed into a screw extruder for melt extrusion. The temperature of the twin-screw from the feeding section to the discharge section is 145°C to 180°C, the speed is 90 rpm, and the aperture of the extrusion die is 0.5 mm.

将挤出后的原丝在80℃下进行多倍拉伸后收卷,拉伸倍率为挤出速率为180倍,出现断丝。The extruded raw yarn was stretched multiple times at 80°C and then wound up. The stretching ratio was 180 times the extrusion rate, and the yarn broke.

对比例5Comparative Example 5

将玻璃纤维、硅烷偶联剂KH560、液体石蜡、聚乙烯蜡以6:2:1:1的比例置于高速混合机中,进行高速混合,温度控制在70℃-90℃之间,每次共混1分钟,停30秒,混合时间共约10分钟,获得处理后的玻璃纤维。Glass fiber, silane coupling agent KH560, liquid paraffin, and polyethylene wax were placed in a high-speed mixer at a ratio of 6:2:1:1 and mixed at high speed. The temperature was controlled between 70°C and 90°C. The mixture was blended for 1 minute each time, then stopped for 30 seconds. The total mixing time was about 10 minutes to obtain treated glass fiber.

取后过渡金属催化剂聚合得到的重均分子量为15万,Mw/Mn为5.4,千碳甲基数<0.1,密度为0.952g/cm 3的聚乙烯。将聚乙烯与处理后的玻璃纤维、抗氧剂1010、硬脂酸锌以95:4.5:0.2:0.3的比例进行共混,共混时间3分钟,获得原料。 Polyethylene having a weight average molecular weight of 150,000, an Mw/Mn ratio of 5.4, a thousand carbon methyl groups less than 0.1, and a density of 0.952 g/cm 3 , obtained by polymerization using a late transition metal catalyst, was blended with treated glass fiber, antioxidant 1010, and zinc stearate in a ratio of 95:4.5:0.2:0.3 for 3 minutes to obtain a raw material.

将原料喂入螺杆挤出机中进行熔体挤出。双螺杆从喂料段温度到出料温度为145℃~180℃,转速90转/min,挤出口模的孔径为0.5mm。The raw materials are fed into a screw extruder for melt extrusion. The temperature of the twin-screw from the feeding section to the discharge section is 145°C to 180°C, the speed is 90 rpm, and the aperture of the extrusion die is 0.5 mm.

将挤出后的原丝在80℃下进行多倍拉伸后收卷,拉伸倍率为挤出速率为30倍,拉伸后冷却温度及介质为20℃空气。将收卷后的纤维再次进行高温多倍拉伸,拉伸倍率为4倍,热甬道温度为100℃。The extruded raw yarn was stretched multiple times at 80°C and then wound up. The stretching ratio was 30 times the extrusion rate. The cooling temperature and medium after stretching were 20°C air. The wound fiber was stretched multiple times again at high temperature. The stretching ratio was 4 times and the hot tunnel temperature was 100°C.

将高温多倍拉伸后的纤维进行防切割测试,防切割性可达A3。The fiber after high temperature multiple stretching is subjected to cut resistance test, and the cut resistance can reach A3.

对比例6Comparative Example 6

一种耐磨防切割超高分子量聚乙烯纤维的制备方法,向1000份白油中加入0.5份硅烷KH550偶联剂,5份纳米二氧化硅, 6份玄武岩短纤, 0.2份硬脂酸钠,0.2份四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯,0.8份纳米分散剂VK-01,在8000r/min的高速旋转乳化机中处理4小时,温度控制在60℃,形成母液。取80份重均分子量400万,分子量分布5.6的树脂原料,树脂平均粒径为180μm,粒径分布宽度(d90-d10)/d50:1.2,堆积密度0.34g/cm3,加入到球磨机中,控制温度50℃,再以2份/分钟的速度缓慢将母液加入到球磨机中,搅拌混合均匀,然后将混合液在密封容器内抽真空4小时,之后混合溶液经湿法纺丝工艺,经过双螺杆挤出机、计量泵、纺丝箱体挤出,经过萃取、干燥、牵伸及热拉伸卷绕成形。该纤维经测试,该纤维防切割等级为A3。A method for preparing wear-resistant and cut-resistant ultra-high molecular weight polyethylene fiber comprises the following steps: adding 0.5 parts of silane KH550 coupling agent, 5 parts of nano-silica, 6 parts of basalt staple fibers, 0.2 parts of sodium stearate, 0.2 parts of pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], and 0.8 parts of nano-dispersant VK-01 to 1000 parts of white oil; and treating the mixture in a high-speed rotary emulsifier at 8000 r/min for 4 hours at a temperature controlled at 60°C to form a mother liquor. 80 parts of a resin with a weight-average molecular weight of 4,000,000 and a molecular weight distribution of 5.6, an average particle size of 180 μm, a particle size distribution width (d90-d10)/d50 of 1.2, and a bulk density of 0.34 g/cm3, were added to a ball mill at 50°C. The mother liquor was then slowly added to the mill at a rate of 2 parts per minute and stirred to mix thoroughly. The mixture was then evacuated in a sealed container for 4 hours. The mixture was then wet-spun through a twin-screw extruder, metering pump, and spinning manifold. The fiber was then extracted, dried, drawn, and heat-stretched before being wound up. Testing revealed that the fiber had an A3 cut-resistant grade.

表1Table 1

由上表可知,聚乙烯与处理后的无机纤维进行共混后,可获得较纯聚乙烯耐切割性能更优异的聚乙烯纤维制品,耐切割性能可达A3水平。使用重均分子量为15万~100万、分子量分布低于3.0的聚乙烯在与处理后的无机纤维混合后,出喷丝板熔体状态下可获得更优异的可拉伸性能,拉伸倍率可高于180倍。当熔体状态下拉伸倍率高于180倍,纤维制品的耐切割性能可再次提升,达到A5-A6水平。As shown in the table above, blending polyethylene with treated inorganic fibers yields polyethylene fiber products with superior cut resistance compared to pure polyethylene, reaching A3 levels. Polyethylene with a weight-average molecular weight of 150,000 to 1,000,000 and a molecular weight distribution below 3.0, when blended with treated inorganic fibers, exhibits even better stretchability in the spinneret melt, reaching stretch ratios exceeding 180x. When the stretch ratio exceeds 180x in the melt, the fiber product's cut resistance is further enhanced, reaching A5-A6 levels.

使用本方法制备得到的耐切割纤维在成本、工艺复杂程度以及环保方面都远优于使用溶液溶解及目前的熔融挤出的方法制备高性能纤维的方法,切割性也优于使用溶液法制备得到的超高分子量聚乙烯耐切割纤维制品。The cut-resistant fiber prepared by this method is far superior to the method of preparing high-performance fibers by solution dissolution and current melt extrusion in terms of cost, process complexity and environmental protection, and its cutting performance is also better than that of ultra-high molecular weight polyethylene cut-resistant fiber products prepared by the solution method.

上述的对实施例的描述是为便于该技术领域的普通技术人员能理解和使用发明。熟悉本领域技术的人员显然可以容易地对这些实施例做出各种修改,并把在此说明的一般原理应用到其他实施例中而不必经过创造性的劳动。因此,本发明不限于上述实施例,本领域技术人员根据本发明的揭示,不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。The above description of the embodiments is intended to facilitate understanding and use of the invention by those skilled in the art. It will be apparent that those skilled in the art can readily make various modifications to these embodiments and apply the general principles described herein to other embodiments without requiring inventive effort. Therefore, the present invention is not limited to the above-described embodiments. 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 present invention, should be within the scope of protection of the present invention.

Claims (10)

一种耐切割纤维的制备方法,其特征在于,包括以下步骤:A method for preparing a cut-resistant fiber, characterized by comprising the following steps: S1:将无机纤维材料进行表面处理,提高所述无机纤维材料对聚乙烯基料的亲和性;S1: surface treating the inorganic fiber material to improve the affinity of the inorganic fiber material to the polyethylene base material; S2:将由单活性中心催化剂聚合得到的窄分子量分布聚乙烯、S1中处理后的无机纤维材料、加工助剂混合,构成共混料;S2: Mixing the narrow molecular weight distribution polyethylene obtained by polymerization with a single active site catalyst, the inorganic fiber material treated in S1, and a processing aid to form a blend; S3:将S2中获得的共混料喂入双螺杆挤出机进行熔体共混,通过喷丝板获得未拉伸纤维熔体;S3: feeding the blend obtained in S2 into a twin-screw extruder for melt blending, and obtaining an undrawn fiber melt through a spinneret; S4:将未拉伸纤维熔体在高温下进行高倍拉伸,拉伸倍率大于180倍,直至无机纤维达到单向取向状态后冷却;S4: stretching the unstretched fiber melt at a high ratio at a high temperature, with a stretching ratio greater than 180 times, until the inorganic fiber reaches a unidirectional orientation state, and then cooling; S5:将S4中冷却后的无机纤维再次进行高温多倍拉伸,获得耐切割聚乙烯复合纤维。S5: The inorganic fiber cooled in S4 is subjected to high-temperature multiple stretching again to obtain a cut-resistant polyethylene composite fiber. 根据权利要求1所述的一种耐切割纤维的制备方法,其特征在于,S1中,所述无机纤维包含碳纤维、玻璃纤维、硅灰石纤维、玄武岩纤维中的一种或多种的混合物。The method for preparing a cut-resistant fiber according to claim 1, characterized in that in S1, the inorganic fiber comprises a mixture of one or more of carbon fiber, glass fiber, wollastonite fiber, and basalt fiber. 根据权利要求1所述的一种耐切割纤维的制备方法,其特征在于,S1中,所述无机纤维材料长径比大于50。The method for preparing a cut-resistant fiber according to claim 1, characterized in that, in S1, the aspect ratio of the inorganic fiber material is greater than 50. 根据权利要求1所述的一种耐切割纤维的制备方法,其特征在于,S1中,所述表面处理为偶联剂处理、表面化学改性处理、表面包覆处理、等离子处理中的一种或多种。The method for preparing a cut-resistant fiber according to claim 1, characterized in that in S1, the surface treatment is one or more of coupling agent treatment, surface chemical modification treatment, surface coating treatment, and plasma treatment. 根据权利要求1所述的一种耐切割纤维的制备方法,其特征在于,S1中,所述窄分子量分布聚乙烯的重均分子量介于15万-100万之间,分子量分布低于3.0。The method for preparing a cut-resistant fiber according to claim 1, characterized in that, in S1, the weight average molecular weight of the narrow molecular weight distribution polyethylene is between 150,000 and 1,000,000, and the molecular weight distribution is less than 3.0. 根据权利要求1所述的一种耐切割纤维的制备方法,其特征在于,S3中,双螺杆挤出机挤出温度为160℃-240℃,喷丝板温度为180℃-250℃。The method for preparing a cut-resistant fiber according to claim 1, characterized in that, in S3, the extrusion temperature of the twin-screw extruder is 160°C-240°C, and the spinneret temperature is 180°C-250°C. 根据权利要求1所述的一种耐切割纤维的制备方法,其特征在于,S4中,进行高倍拉伸的时的温度为60℃-150℃。The method for preparing a cut-resistant fiber according to claim 1, characterized in that, in S4, the temperature during high-ratio stretching is 60°C-150°C. 根据权利要求1所述的一种耐切割纤维的制备方法,其特征在于,S4中,冷却温度为5℃-40℃,冷却介质为空气或水。The method for preparing a cut-resistant fiber according to claim 1, characterized in that, in S4, the cooling temperature is 5°C-40°C, and the cooling medium is air or water. 根据权利要求1所述的一种耐切割纤维的制备方法,其特征在于,S5,高温多倍拉伸的倍率为5-20倍,温度为70℃-130℃。The method for preparing a cut-resistant fiber according to claim 1, characterized in that, in S5, the high-temperature multiple stretching ratio is 5-20 times, and the temperature is 70°C-130°C. 一种如权利要求1至9中任意一项所述制备方法得到的耐切割纤维。A cut-resistant fiber obtained by the preparation method according to any one of claims 1 to 9.
PCT/CN2024/116564 2024-01-23 2024-09-03 Cut-resistant fiber and preparation method therefor Pending WO2025156639A1 (en)

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