WO2021007943A1 - 一种超高防切割性超高分子量聚乙烯纤维及其制备方法 - Google Patents

一种超高防切割性超高分子量聚乙烯纤维及其制备方法 Download PDF

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Publication number
WO2021007943A1
WO2021007943A1 PCT/CN2019/105436 CN2019105436W WO2021007943A1 WO 2021007943 A1 WO2021007943 A1 WO 2021007943A1 CN 2019105436 W CN2019105436 W CN 2019105436W WO 2021007943 A1 WO2021007943 A1 WO 2021007943A1
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WIPO (PCT)
Prior art keywords
ultra
molecular weight
carbon fiber
weight polyethylene
high molecular
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PCT/CN2019/105436
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English (en)
French (fr)
Inventor
周星余
周海涛
周红波
赵勇
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Xingyu Safety Protection Technology Co Ltd
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Xingyu Safety Protection Technology Co Ltd
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Priority to PL19850783T priority Critical patent/PL3792379T3/pl
Priority to KR1020207022776A priority patent/KR102416634B1/ko
Priority to BR112020019278-3A priority patent/BR112020019278B1/pt
Priority to US16/639,752 priority patent/US12116702B2/en
Priority to AU2019400153A priority patent/AU2019400153B2/en
Priority to EP19850783.2A priority patent/EP3792379B1/en
Priority to CA3088807A priority patent/CA3088807C/en
Priority to MX2020008624A priority patent/MX2020008624A/es
Priority to JP2020535098A priority patent/JP7072657B2/ja
Priority to DK19850783.2T priority patent/DK3792379T3/da
Priority to MYPI2020003082A priority patent/MY199350A/en
Priority to RS20220331A priority patent/RS63105B1/sr
Priority to ES19850783T priority patent/ES2909310T3/es
Priority to ZA2020/04029A priority patent/ZA202004029B/en
Priority to CONC2020/0010963A priority patent/CO2020010963A2/es
Publication of WO2021007943A1 publication Critical patent/WO2021007943A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F8/00—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof
    • D01F8/04—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers
    • D01F8/06—Conjugated, i.e. bi- or multicomponent, artificial filaments or the like; Manufacture thereof from synthetic polymers with at least one polyolefin as constituent
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D1/00—Treatment of filament-forming or like material
    • D01D1/02—Preparation of spinning solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/06—Wet spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D7/00—Collecting the newly-spun products
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/44—Monocomponent 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
    • D01F6/46—Monocomponent 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
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/44—Yarns or threads characterised by the purpose for which they are designed
    • D02G3/442—Cut or abrasion resistant yarns or threads
    • A—HUMAN NECESSITIES
    • A41—WEARING APPAREL
    • A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
    • A41D19/00—Gloves
    • A41D19/015—Protective gloves
    • A41D19/01505—Protective gloves resistant to mechanical aggressions, e.g. cutting. piercing
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/10—Inorganic fibres based on non-oxides other than metals
    • D10B2101/12—Carbon; Pitch
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/02—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins
    • D10B2321/021—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene
    • D10B2321/0211—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polyolefins polyethylene high-strength or high-molecular-weight polyethylene, e.g. ultra-high molecular weight polyethylene [UHMWPE]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/06—Load-responsive characteristics
    • D10B2401/063—Load-responsive characteristics high strength
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2501/00—Wearing apparel
    • D10B2501/04—Outerwear; Protective garments
    • D10B2501/041—Gloves

Definitions

  • the invention relates to the technical field of polyethylene fibers, in particular to an ultra-high anti-cutting ultra-high molecular weight polyethylene fiber and a preparation method thereof.
  • Ultra-high molecular weight polyethylene fiber is currently the fiber with the highest specific strength among industrialized fiber materials. It has excellent high strength, high modulus, wear resistance, chemical corrosion resistance and other properties. It is widely used in national defense and military, offshore cables, personal protection, etc. field. With the continuous deepening of military-civilian integration, the application of ultra-high molecular weight polyethylene fibers in the civilian market has gradually increased, and the civilian market, which is dominated by anti-cut gloves, has gradually occupied a dominant position. At present, the commonly used protective gloves made of 400D ultra-high molecular weight polyethylene fiber have the highest cutting grade of EN388-2003 standard level 3, and they are very unstable, and they are less and more unsuitable for the protection of cut hazards in the actual working environment. .
  • the commonly used method is to blend and weave glass fiber, steel wire and other materials with ultra-high molecular weight polyethylene fiber to achieve the purpose of increasing the ultra-high cut-resistant grade.
  • this method can improve the anti-cutting performance of the gloves, the steel wire is relatively hard (the hardness is not easy to wear and the comfort is poor), and the glass fiber is more brittle and easy to break exposed, the glove feels poor, the wearing comfort is low, and the glass fiber burr is easy Secondary injuries such as itching, stabbing, and scratching to the hand can not achieve the compatibility of protective performance and comfort performance.
  • the ultra-high anti-cutting ultra-high molecular weight polyethylene fiber can be woven into anti-cutting gloves or anti-cutting protective clothing, etc., to achieve high-strength protection performance and better wearing comfort, avoid wear and damage to production equipment, and save production Cost, extend the performance timeliness of cut-resistant gloves or cut-resistant protective clothing.
  • the main technical solutions adopted by the present invention include:
  • One aspect of the present application provides an ultra-high anti-cutting ultra-high molecular weight polyethylene fiber, which comprises an ultra-high molecular weight polyethylene matrix and carbon fiber powder particles dispersed therein, and the content of the carbon fiber powder particles is 0.25-10 wt% .
  • the content of the carbon fiber powder in the ultra-high molecular weight polyethylene-containing matrix is 0.25wt%, 0.5wt%, 1wt%, 1.2wt%, 1.5wt%, 2.0wt%, 2.5wt% , 3.0wt%, 3.5wt%, 4.0wt%, 4.5wt%, 5.0wt%, 5.5wt%, 6.0wt%, 6.5wt%, 7.0wt%, 7.5wt%, 8.0wt%, 8.5wt%, 9.0 wt%, 9.5 wt%, or 10.0 wt%.
  • the present invention also relates to a preparation method of ultra-high anti-cutting ultra-high molecular weight polyethylene fiber, which comprises:
  • the molecular weight of UHMWPE is 200,000, 400,000, 600,000, 800,000, 1 million, 1.2 million, 1.4 million, 1.6 million, 1.8 million, 2 million, 2.2 million, 2.4 million, 2.6 million, 2.8 million, 3 million, 3.2 million, 3.4 million, 3.6 million, 3.8 million, 4 million, 4.2 million, 4.4 million, 4.6 million, 4.8 million, 5 million, 5.2 million, 5.4 million, 5.6 million, 5.8 million Or 6 million.
  • the carbon fiber powder particles have a diameter of 0.1-10 ⁇ m and a length of 0.1-100 ⁇ m.
  • the shape of the particles of the carbon fiber powder is a long rod-shaped particle with a length greater than a diameter; more preferably, the length is 20-60 ⁇ m.
  • the particle length of the carbon fiber powder is 20-30 ⁇ m, 30-40 ⁇ m, 40-50 ⁇ m, or 50-60 ⁇ m.
  • the main component of the carbon fiber powder is microcrystalline graphite, which can be obtained by pulverizing waste carbon fibers or cutting carbon fiber filaments.
  • the carbon fiber powder is surface-treated in advance to activate the surface of the particles of the carbon fiber powder.
  • the interfacial fusion and/or wettability of the carbon fiber powder, the solvent and the ultra-high molecular weight polyethylene powder can be improved, so as to obtain the ultra-high cut-resistant polyethylene fiber with uniform material distribution, better performance and more stable performance.
  • the surface treatment method is any one or a combination of the following: gas phase oxidation, liquid phase oxidation, catalytic oxidation, coupling agent coating, polymer coating, plasma (Plasma) treatment.
  • gas phase oxidation liquid phase oxidation
  • catalytic oxidation coupling agent coating
  • polymer coating plasma (Plasma) treatment.
  • the surface of the carbon fiber particles is weakly polarized, prevents the carbon fiber from agglomerating in the solvent, and improves its dispersion in the solvent, so that it can be more uniformly dispersed in the UHMWPE matrix It can be tightly combined with the ultra-high molecular weight polyethylene matrix to prevent the carbon fiber from peeling off, and improve the performance uniformity and timeliness of the ultra-high molecular weight polyoxyethylene fiber with ultra-high cut resistance.
  • the mass ratio of the ultra-high molecular weight polyethylene, carbon fiber powder, and solvent is 10-40:0.1-1:100; the mass of the solvent refers to the first solvent and The sum of the mass of the second solvent.
  • the obtained mixture is paste-like, and carbon fiber powder that is sufficient to prevent cutting is dispersed in the mixture.
  • the first solvent and the second solvent are only different in the steps of using the solvent, which does not mean that the first solvent and the second solvent are different.
  • the first solvent and the second solvent may be the same solvent or different solvents.
  • the first solvent and the second solvent are both one or more selected from white oil, mineral oil, vegetable oil, paraffin oil and decalin.
  • the molecular weight of the ultra-high molecular weight polyethylene is 2 to 5 million.
  • the extruder is a twin-screw extruder, and the temperature of each zone of the twin-screw is controlled between 100-300°C.
  • the surfactant is alkyl alcohol amide (6502), which is a mild non-ionic surfactant formed by the condensation reaction of coconut oil or palm kernel oil and diethanolamine, or
  • the surfactant is alkyl alcohol amide phosphate.
  • These surfactants have the effects of solubilization and emulsification, antistatic conditioning effects, and no skin irritation. They are often used as detergents and clothing care agents.
  • the surfactant is not limited to the above list, but any surfactant that can emulsify and increase the dispersion of carbon fiber powder in the solvent can be used, such as stearic acid, sodium dodecylbenzene sulfonate, alkyl glucoside (APG), triethanolamine, fatty acid glycerides, fatty acid sorbitan (Span), polysorbate (Tween), sodium dioctyl succinate (aloxol-OT), dodecyl benzene sulfonic acid Sodium, sodium glycocholate and so on.
  • APG alkyl glucoside
  • Triethanolamine fatty acid glycerides
  • Span fatty acid sorbitan
  • Teween polysorbate
  • sodium dioctyl succinate aloxol-OT
  • dodecyl benzene sulfonic acid Sodium sodium glycocholate and so on.
  • the present invention relates to an ultra-high anti-cutting ultra-high molecular weight polyethylene fiber, which is prepared by the preparation method contained in any of the above embodiments.
  • the present invention also relates to an ultra-high anti-cutting glove or anti-cutting suit, comprising a braid woven by the ultra-high anti-cutting ultra-high molecular weight polyethylene fiber prepared by any of the above embodiments or preparation methods.
  • Carbon fiber (CF for short, is a kind of microcrystalline graphite material), is a new type of fiber material with high strength and high modulus fiber with a carbon content of more than 95%. Carbon fiber has "external flexibility and internal rigidity", its mass is lighter than metal aluminum, but its strength is higher than steel, and it has the characteristics of corrosion resistance and high modulus. Carbon fiber has the intrinsic characteristics of carbon materials and the softness and processability of textile fibers. Sex, is a new generation of reinforcing fibers. Its main features are: (1) Both the soft and processability of textile fibers; (2) The tensile strength is above 3500 MPa; (3) The tensile modulus of elasticity is 230 to 430 G Pa.
  • Plasma surface treatment The plasma surface processor is used for treatment.
  • electrons In the low-temperature plasma in a non-thermodynamic equilibrium state, electrons have higher energy, which can break the chemical bonds of the surface molecules of the material and improve the chemical reaction activity of the particles (larger than thermal plasma ), and the temperature of the neutral particles is close to room temperature.
  • carbon fiber powder is used as an additive and dispersed in an ultra-high molecular weight polyethylene fiber matrix material to obtain an ultra-high molecular weight polyethylene fiber with ultra-high anti-cutting performance.
  • the gloves or glove blanks woven from the ultra-high molecular weight polyethylene fiber with ultra-high cut resistance performance of the present invention have Better wearing comfort, such as softer, better touch, no burrs, itching, scratches and other problems, easy to wear, etc.
  • the carbon fiber powder and ultra-high molecular weight polyethylene powder used in the present invention are blended and extruded to produce ultra-high molecular weight polyethylene nascent fibers
  • the carbon fiber has low hardness and high toughness, it will not weaken the anti-cutting performance of the UHMWPE nascent fiber, but also has less wear on the equipment, reducing equipment and production costs, and will not have a negative impact on production efficiency.
  • the carbon fiber powder has strong flexibility and is not easy to pierce the surface of the ultra-high molecular weight polyethylene fiber matrix to escape and cause fiber damage. Therefore, the carbon fiber powder can be retained in the polyethylene fiber matrix for a longer period of time, making it highly resistant to cutting Polyethylene fiber has more durable anti-cutting performance.
  • the carbon fiber powder is first subjected to surface activation treatment to improve the dispersion of the carbon fiber powder and prevent agglomeration in the solvent dispersion.
  • the carbon fiber powder is first made into an additive emulsified material, and then dispersed in a solvent together with the ultra-high molecular weight polyethylene powder to make a mixed material, which is blended and extruded by a screw extruder to obtain the nascent fiber, so that the carbon fiber powder can be uniform and very stable Ground fusion into the ultra-high molecular weight polyethylene fiber matrix, combined with the ultra-high molecular weight polyethylene fiber to form a stable solid, so that the ultra-high molecular weight polyethylene fiber acts as a solid dispersant for the carbon fiber powder, resulting in better cutting resistance and more uniformity , Better quality UHMWPE fiber.
  • the ultra-high anti-cutting ultra-high molecular weight polyethylene fiber of the present invention greatly improves the anti-cutting performance of the polyethylene fiber, and the anti-cutting grade of the knitted gloves and other fabrics can reach EN388-2003 standard 5 stably. More importantly, the ultra-high anti-cutting ultra-high molecular weight polyethylene fiber produced according to the present invention does not need to be blended with steel wire, glass fiber and other materials for reinforcement, and the prepared protective gloves are soft, light and sensitive, and wear for a long time. It is not easy to be fatigued, and realizes the balance of ultra-high anti-cutting and wearing comfort.
  • the overall concept of the present invention is to use a certain amount of carbon fiber powder as one of the raw materials for preparing ultra-high molecular weight polyethylene nascent fibers, so that the carbon fiber powder particles are uniformly and stably fused into the ultra-high molecular weight polyethylene fiber matrix, and The polyethylene fibers are combined into a stable solid to obtain ultra-high anti-cutting ultra-high molecular weight polyethylene fibers.
  • carbon fiber has incomparable "outer softness and inner rigidity" characteristics. It can not only replace other high-hardness inorganic reinforcement materials to make UHMWPE fibers have high anti-cutting performance, but also reduce equipment damage. It has significant advantages in terms of abrasion, preventing piercing of the ultra-high molecular weight polyethylene fiber matrix and weakening of the anti-cutting performance during repeated use.
  • the specific preparation method of the present invention can be carried out according to the following steps:
  • the particles of the carbon fiber powder are preferably rod-shaped, with a diameter of 0.1-10 ⁇ m and a length of 0.1-100 ⁇ m; and the more preferable length is 20-60 ⁇ m.
  • the main component of carbon fiber powder is microcrystalline graphite, which can be obtained by crushing and sieving waste carbon fibers; it can also be obtained by cutting carbon fiber filaments.
  • the main function of surface treatment is to activate the surface of carbon fiber powder particles.
  • the available methods include: gas phase oxidation, liquid phase oxidation, catalytic oxidation, coupling agent coating, polymer coating, and plasma treatment.
  • the surface of the carbon fiber is weakly polarized, which can improve the dispersion of the carbon fiber particles in the solvent and prevent the carbon fiber powder from agglomerating, thereby further improving the uniformity of the dispersion of the carbon fiber particles in the UHMWPE matrix. Interface fusion and/or wettability, so as to obtain better performance of ultra-high cut resistance polyethylene fiber.
  • the solvent is one or more selected from white oil, mineral oil, vegetable oil, paraffin oil and decalin.
  • the ratio of ultra-high molecular weight polyethylene: carbon fiber emulsified material: total mass of solvent is (10-40): (0.1-1): 100.
  • the solvent is one or more selected from white oil, mineral oil, vegetable oil, paraffin oil and decalin.
  • the mixture is blended and extruded through a twin-screw extruder, and then cooled and molded in a coagulation bath to obtain nascent fibers.
  • the temperature of each zone of the twin-screw is controlled between 100-300°C; the nascent fibers are extracted, dried, and subjected to multi-stage heat drawing. After stretching, it is made into ultra-high anti-cutting ultra-high molecular weight polyethylene fiber.
  • This embodiment provides a method for preparing ultra-high anti-cutting ultra-high molecular weight polyethylene fiber, which includes the following steps:
  • the mixed material is blended and extruded through a twin-screw extruder, and the nascent fiber is formed by cooling in a coagulation bath.
  • the resulting nascent fiber is extracted, dried, and subjected to multi-stage hot drafting to make super high Molecular weight polyethylene ultra-high anti-cutting fiber, in which carbon fiber has a 5% dispersion concentration in ultra-high molecular weight polyethylene.
  • the cut-resistant gloves made from the above-mentioned fibers have a soft hand feel, no puncture, and comfortable to wear. They have been tested by EN388-2003 and have a cut-resistant grade of level 5.
  • This embodiment provides a method for preparing ultra-high anti-cutting ultra-high molecular weight polyethylene fiber, which includes the following steps:
  • the mixed material is blended and extruded through a twin-screw extruder, and the nascent fiber is formed by cooling in a coagulation bath.
  • the resulting nascent fiber is extracted, dried, and subjected to multi-stage hot drafting to make super high Ultra-high molecular weight polyethylene anti-cutting fiber, in which the dispersion concentration of carbon fiber in the ultra-high molecular weight polyethylene is 4%.
  • the cut-resistant gloves made from the above-mentioned fibers have a soft hand feel, no puncture, and comfortable to wear. They have been tested by EN388-2003 and have a cut-resistant grade of level 5.
  • This embodiment provides a method for preparing ultra-high anti-cutting ultra-high molecular weight polyethylene fiber, which includes the following steps:
  • the mixed material is blended and extruded through a twin-screw extruder, and the nascent fiber is formed by cooling in a coagulation bath.
  • the resulting nascent fiber is extracted, dried, and subjected to multi-stage hot drafting to make super high Ultra-high molecular weight polyethylene anti-cutting fiber, in which the dispersion concentration of carbon fiber in the ultra-high molecular weight polyethylene is 10%.
  • the cut-resistant gloves made from the above-mentioned fibers have a soft hand feel, no puncture, and comfortable to wear. They have been tested by EN388-2003 and have a cut-resistant grade of level 5.
  • This embodiment provides a method for preparing ultra-high anti-cutting ultra-high molecular weight polyethylene fiber, which includes the following steps:
  • the mixed material is blended and extruded through a twin-screw extruder, and the nascent fiber is formed by cooling in a coagulation bath.
  • the resulting nascent fiber is extracted, dried, and subjected to multi-stage hot drafting to make super high Molecular weight polyethylene ultra-high anti-cutting fiber, in which the dispersion concentration of carbon fiber in ultra-high molecular weight polyethylene is 3.75%.
  • the cut-resistant gloves made from the above-mentioned fibers have a soft hand feel, no puncture, and comfortable to wear. They have been tested by EN388-2003 and have a cut-resistant grade of level 5.
  • This embodiment provides a method for preparing ultra-high anti-cutting ultra-high molecular weight polyethylene fiber, which includes the following steps:
  • the mixed material is blended and extruded through a twin-screw extruder, and the nascent fiber is formed by cooling in a coagulation bath.
  • the resulting nascent fiber is extracted, dried, and subjected to multi-stage hot drafting to make super high Molecular weight polyethylene ultra-high anti-cutting fiber, in which the dispersion concentration of carbon fiber in ultra-high molecular weight polyethylene is 2%.
  • the cut-resistant gloves made from the above-mentioned fibers have a soft hand feel, no puncture, and comfortable to wear. They are tested by EN388-2003 and have a cut-resistant grade of 4.
  • Example 2 This example is on the basis of Example 1, without any surface treatment of the carbon fibers, and the carbon fibers are agglomerated in the emulsified material.
  • Example 1 The ultra-high molecular weight polyethylene ultra-high anti-cutting fiber was prepared, and the dispersion concentration of the carbon fiber in the ultra-high molecular weight polyethylene was 5%.
  • the carbon fiber without surface activation treatment is easy to agglomerate, and the prepared fiber yarn has poor spinnability, and the cut resistance performance of gloves woven from the fiber is also unstable.
  • Example 1 The carbon fiber in Example 1 is replaced with 750g boron nitride with a length of 10-20um.
  • Example 1 The ultra-high molecular weight polyethylene ultra-high anti-cutting fiber was prepared, and the dispersion concentration of boron nitride in the ultra-high molecular weight polyethylene was 5%.
  • the fiber yarn obtained has poor spinnability. With the extension of the time of use, the gloves woven by the fiber have their anti-cutting performance rapidly deteriorated, and the surface of the gloves exhibits burrs and hardness, and the hand feel and wearing comfort are poor.
  • Example 1 The carbon fiber in Example 1 is replaced with 750g tungsten carbide with a length of 10-20um.
  • Example 1 For other conditions and processing procedures, refer to Example 1.
  • the ultra-high molecular weight polyethylene ultra-high anti-cutting fiber was prepared, and the dispersion concentration of tungsten carbide in the ultra-high molecular weight polyethylene was 5%.
  • the fiber yarn obtained has poor spinnability. With the extension of the time of use, the gloves woven by the fiber have their anti-cutting performance rapidly deteriorated, and the surface of the gloves exhibits burrs and hardness, and the hand feel and wearing comfort are poor.
  • the ultra-high anti-cutting ultra-high molecular weight polyethylene fibers prepared in Examples 1-6 and Comparative Examples 1-2 were knitted into 13-needle protective gloves. Workers who had undergone the same operation in the same post were worn and used for 1 day (1d) and 20 After 20 days, test the performance of the gloves. The test results are as follows:
  • the cut-resistant grade of the gloves and other fabrics woven from the ultra-high cut-resistant ultra-high molecular weight polyethylene fiber of the present invention can indeed stably reach the EN388-2003 standard 4-5. More importantly, the ultra-high cut-resistant ultra-high molecular weight polyethylene fiber produced according to the present invention does not need to be blended with steel wire, glass fiber and other materials for reinforcement, and the prepared protective gloves are soft, light, sensitive, and wearable. The comfort is good, and it is not easy to fatigue after long-term wear.
  • Example 6 the test results of Example 6 are not unstable, mainly due to the uneven distribution of carbon fibers in the ultra-high molecular weight polyethylene matrix.
  • the surface damage produces burrs, and the partial release of the inorganic reinforcing material also weakens the cutting resistance.
  • the carbon fiber reinforced polyethylene gloves of the present invention exhibit exceptional durability. After repeated use, the anti-cutting performance is almost equal to that of the newly made product, and the quality is soft and smooth, and the wearer has a good experience.
  • the inorganic high-hardness reinforcing material used in Comparative Example 1 has high hardness but poor flexibility, it is easy to pierce the surface of the ultra-high molecular weight polyethylene fiber matrix, causing damage and part of the high-hardness reinforcing material falls off.
  • the anti-cutting performance drops faster.
  • the present invention uses carbon fiber as an anti-cutting reinforcement material additive, and the prepared anti-cutting gloves have anti-cutting performance that can be compared with the addition of inorganic high-hardness materials such as boron nitride and tungsten carbide.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Artificial Filaments (AREA)
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Abstract

本发明涉及一种超高防切割超高分子量聚乙烯纤维，其包含超高分子量聚乙烯基质和分散于其中的碳纤维粉末颗粒，所述碳纤维粉末颗粒的含量为0.25～10wt％。本发明还涉及超高防切割超高分子量聚乙烯纤维的制备方法和由其编织的防切割手套。经测试证明，由所述超高防切割超高分子量聚乙烯纤维编织的手套，手感柔软、无扎刺感、佩戴舒适，经EN388-2003测试，防切割等级为4-5级。相比较于以往其他无机高度硬度增强材料的应用，本发明的超高防切割超高分子量聚乙烯纤维生产过程对设备损耗较好，且编织的防切割手套耐用度更高，防切割性能保持得更久。

Description

一种超高防切割性超高分子量聚乙烯纤维及其制备方法 技术领域
本发明涉及聚乙烯纤维技术领域，尤其是一种超高防切割性超高分子量聚乙烯纤维及其制备方法。
背景技术
超高分子量聚乙烯纤维是目前已经工业化纤维材料中比强度最高的纤维，具有优异的高强、高模、耐磨、耐化学腐蚀等性能，广泛地应用在国防军事、海工缆绳、个体防护等领域。随着军民融合的不断深入，超高分子量聚乙烯纤维在民用市场的应用逐渐增大，其中以防切割手套为主的民用市场逐渐占据主导地位。目前，常用的400D超高分子量聚乙烯纤维制成的防护手套，其切割等级最高为EN388-2003标准3级，且非常不稳定，越来越不适应实际工作环境中对割伤危害防护的需求。
为提高手套的防切割等级，常用的方法是将玻璃纤维、钢丝等材料与超高分子量聚乙烯纤维混纺编织，达到提超高防切割等级的目的。这种方法虽然可以提高手套的防切割性能，但是由于钢丝比较硬(硬度大不易佩戴且舒适性差)，而玻璃纤维比较脆易断裂外露、手套手感差、佩戴舒适度低，且玻璃纤维毛刺容易对手部造成瘙痒、扎伤、戳划等二次伤害，无法实现防护性能与舒适性能的兼容。
另外，目前业内有人提出通过将无机高硬度材料加入到高分子聚乙烯粉料中混炼制成高分子量聚乙烯初生纤维，以增强聚乙烯纤维的防切割性能。虽然该方法确实可提高聚乙烯纤维的防切割性能，但仍然存在两个比较明显的问题：(1)该些无机高硬度材料硬度较大，不仅对制备设备的磨损较大，需频繁更换设备局部装置，增加了设备投资，同时也影响了生产效率；(2)经实际使用亦发现，这些高硬度材料因柔韧度低、 易在反复使用过程中刺破聚乙烯纤维基质，从聚乙烯纤维中脱出而使聚乙烯纤维表面受到损伤且高强防切割性能失效。
发明内容
(一)要解决的技术问题
有鉴于此，发明人希望提供一种超高防切割性超高分子量聚乙烯纤维及其制备方法，以克服现有技术存在的问题。所述超高防切割性超高分子量聚乙烯纤维能编织成防切割手套或防切割防护服等，实现高强防护性能和较好的佩戴舒适性，并避免对生产设备造成磨损和损伤，节省生产成本，延长防切割手套或防切割防护服的性能时效性。
(二)技术方案
为了达到上述目的，本发明采用的主要技术方案包括：
本申请的一个方面，提供一种超高防切割性超高分子量聚乙烯纤维，其包含超高分子量聚乙烯基质和分散于其中的碳纤维粉末颗粒，所述碳纤维粉末颗粒的含量为0.25～10wt％。
典型但非限制的，所述碳纤维粉末在所述含超高分子量聚乙烯基质中的含量为0.25wt％、0.5wt％、1wt％、1.2wt％、1.5wt％、2.0wt％、2.5wt％、3.0wt％、3.5wt％、4.0wt％、4.5wt％、5.0wt％、5.5wt％、6.0wt％、6.5wt％、7.0wt％、7.5wt％、8.0wt％、8.5wt％、9.0wt％、9.5wt％或10.0wt％。
若碳纤维粉末含量过高则导致聚乙烯基质比重过少，会使制得的聚乙烯纤维可纺性变差(在纺织过程中易断)，而碳纤维粉末含量过低则达不到预定的增加防切割性能的目的。
本发明还涉及一种超高防切割性超高分子量聚乙烯纤维的制备方法，其包括：
S1:将碳纤维粉末与第一溶剂、表面活性剂混合乳化，制成碳纤维粉末乳化料；
S2:将所述碳纤维粉末乳化料与分子量为20-600万的超高分子量聚乙 烯粉料一同分散于第二溶剂中制得混合料；
S3:将所述混合料通过挤出机共混挤出，经过凝固浴冷却成型制得初生纤维，将初生纤维萃取、干燥、多级热牵伸，制得超高防切割超高分子量聚乙烯纤维。
典型但非限制地，超高分子量聚乙烯的分子量为20万、40万、60万、80万、100万、120万、140万、160万、180万、200万、220万、240万、260万、280万、300万、320万、340万、360万、380万、400万、420万、440万、460万、480万、500万、520万、540万、560万、580万或600万。
在本发明的一个优选实施例中，所述碳纤维粉末的颗粒的直径为0.1-10μm，长度为0.1-100μm。进一步地，所述碳纤维粉末的颗粒的形状为长度大于直径的长棒状颗粒；更优选长度为20-60μm。典型但非限制的，所述碳纤维粉末的颗粒长度为20-30μm、30-40μm、40-50μm或50-60μm。
在本发明的一个优选实施例中，所述碳纤维粉末的主要成分是微晶石墨，既可由废旧碳纤维粉碎制取也可由碳纤维长丝切割而成。
在本发明的一个优选实施例中，所述碳纤维粉末预先经过表面处理，使碳纤维粉末的颗粒表面活性化。借此，可提高碳纤维粉末与溶剂、超高分子量聚乙烯粉料的界面融合性和/或湿润性，从而获得材料分布均匀、性能更好更稳定的超高防切割聚乙烯纤维。
在本发明的一个优选实施例中，所述表面处理的方法为以下任一种或几种的组合：气相氧化、液相氧化、催化氧化、偶联剂涂层、聚合物涂层、等离子体(电浆)处理。通过前述方式之一种的表面处理，使碳纤维颗粒表面带有弱极性、防止碳纤维在溶剂中的团聚，提高其在溶剂中的分散度，从而可更均匀地分散于超高分子量聚乙烯基质中，并能够与超高分子量聚乙烯基质紧密结合，防止碳纤维剥离，提高超高防切割性超高分子量聚氧乙烯纤维的性能均一性和时效性。
在本发明的一个优选实施例中，所述超高分子量聚乙烯、碳纤维粉 末、溶剂的质量之比为10～40:0.1～1:100；所述溶剂的质量是指所述第一溶剂和第二溶剂质量之和。
按照上述质量配比，使制得的混合料为膏状，且混合料内分散有足以起到较好防切割作用的碳纤维粉末。需要说明的本申请中，第一溶剂和第二溶剂只是溶剂使用的步骤不同，并不代表第一溶剂与第二溶剂不同。换句话说，第一溶剂和第二溶剂可为相同溶剂，也可为不同溶剂。
优选地，所述第一溶剂和第二溶剂均为选自白油、矿物油、植物油、石蜡油及十氢化萘中的一种或几种。
在本发明的一个优选实施例中，所述超高分子量聚乙烯的分子量为200-500万。
超高分子量聚乙烯的分子量越高，防切割性能和机械强度也越高，但若分子量过大则导致粘度太大，挤出制纤维丝时难度也较大，不易成丝，制备过程中对设备要求较高、设备损耗较大。经反复试验，分子量为200-500万时得到的防切割聚乙烯纤维丝各方面性能最优,且对设备损耗低。
在本发明的一个优选实施例中，所述挤出机为双螺杆挤出机，其双螺杆各区温度控制在100-300℃之间。
在本发明的一个优选实施例中，所述表面活性剂为烷基醇酰胺(6502)，其是采用椰子油或棕榈仁油和二乙醇胺缩合反应而成的温和非离子型表面活性剂，或所述表面活性剂为烷基醇酰胺磷酸酯。这些表面活性剂具有增溶、乳化的作用，具有抗静电调理作用，无皮肤刺激性的特点，常用作洗洁精、衣物护理剂等。当然，表面活性剂不限于前述所列，但凡能起到乳化和增加碳纤维粉末在溶剂中分散度的表面活性剂均可，如硬脂酸、十二烷基苯磺酸钠、烷基葡糖苷(APG)、三乙醇胺、脂肪酸甘油酯、脂肪酸山梨坦(司盘)、聚山梨酯(吐温)、二辛基琥珀酸磺酸钠(阿洛索-OT)、十二烷基苯磺酸钠、甘胆酸钠等等。
本发明涉及一种超高防切割性超高分子量聚乙烯纤维，其是采用上 述任一实施例所载的制备方法制备得到。
本发明还涉及一种超高防切割手套或防切割服，包含上述任一实施例或制备方法制备的所述超高防切割超高分子量聚乙烯纤维维编织而成的编织物。
碳纤维(carbon fiber，简称CF，是一种微晶石墨材料)，是一种含碳量在95％以上的高强度、高模量纤维的新型纤维材料。碳纤维“外柔内刚”，质量比金属铝轻，但强度却高于钢铁，并且具有耐腐蚀、高模量的特性，碳纤维具有碳材料的固有本征特性，又兼备纺织纤维的柔软可加工性，是新一代增强纤维。其主要特点有：(1)兼具纺织纤维的柔软可加工性；(2)抗拉强度在3500兆帕以上；(3)抗拉弹性模量230到430G帕。
等离子表面处理：使用等离子表面处理器进行处理，处于非热力学平衡状态下的低温等离子体中，电子具有较高的能量，可以断裂材料表面分子的化学键，提高粒子的化学反应活性(大于热等离子体)，而中性粒子的温度接近室温，这些优点为热敏性高分子聚合物表面改性提供了适宜的条件。通过低温等离子体表面处理，材料面发生多种的物理、化学变化。表面得到了清洁，去除了碳化氢类污物，如油脂，辅助添加剂等，或产生刻蚀而粗糙，或形成致密的交联层，或引入含氧极性基团(羟基、羧基)，这些基因对各类涂敷材料具有促进其粘合的作用，在粘合和油漆应用时得到了优化。
(三)有益效果
本发明的有益效果是：
(1)本发明通过将碳纤维粉末作为添加剂，分散在超高分子量聚乙烯纤维基质材料中，获得一种具有超高防切割性能的超高分子量聚乙烯纤维。相比于现有技术中，将玻璃纤维、钢丝等材料与超高分子量聚乙烯纤维混纺编织的方法，本发明的超高防切割性能的超高分子量聚乙烯纤维编织成的手套或手套胚具有更佳的佩戴舒适性，如更柔软、触摸感更 好、无毛刺瘙痒、戳划等问题，易于佩戴等。
(2)相较于其他的如氮化硼、碳化钨等无机高硬度材料作为增强添加剂，本发明使用的碳纤维粉末与超高分子量聚乙烯粉料共混挤出制造超高分子量聚乙烯初生纤维时，由于碳纤维硬度较低而韧性较大，故不仅不会削弱超高分子量聚乙烯初生纤维抗切割性能，并且对设备磨损较小，减少设备和生产成本，对生产效率也不会产生负面影响。此外，碳纤维粉末具有较强的柔软性，不容易刺破超高分子量聚乙烯纤维基质表面而脱出并造成纤维损伤，故可使碳纤维粉末更持久地保留在聚乙烯纤维基质中，使高防切割聚乙烯纤维具有更持久的防切割性能。
(3)进一步地，本发明在制备超高防切割性能的超高分子量聚乙烯纤维时，将碳纤维粉末先经过表面活化处理，以提高碳纤维粉末的分散度，防止在溶剂分散中团聚，然后将碳纤维粉末先制成添加剂乳化料，然后与超高分子量聚乙烯粉料一同分散于溶剂中制成混合料，采用螺杆挤出机共混挤出制得初生纤维，使碳纤维粉末能够均匀且十分稳定地融合到超高分子量聚乙烯纤维基质中，与超高分子量聚乙烯纤维结合为稳固体、使超高分子量聚乙烯纤维充当了碳纤维粉末的固体分散剂，制得防切割性能更优异、更均一、品质更好的超高分子量聚乙烯纤维。
综上所述，本发明的超高防切割超高分子量聚乙烯纤维大大提高了聚乙烯纤维的防切割性能，所织成的手套等织物的抗切割等级可稳定达到EN388-2003标准5级。更重要的是，根据本发明生产的超高防切割性超高分子量聚乙烯纤维，不需与钢丝、玻璃纤维等材料混纺补强，而制得的防护手套质地柔软、轻巧灵敏，长时间穿着不易疲劳，实现了超高防切割和佩戴舒适度的兼顾。
具体实施方式
为了更好的解释本发明，以便于理解，下面通过具体实施例，对本发明作详细描述。
本发明的整体构思为：将一定量的碳纤维粉末作为超高分子量聚乙烯初生纤维的制备原料之一，使碳纤维粉末颗粒均匀且稳定地融合到超高分子量聚乙烯纤维基质中，与超高分子量聚乙烯纤维结合为稳固体，得到超高防切割超高分子量聚乙烯纤维。相比较于其他高硬度无机增强材料，碳纤维具有不可比拟的“外柔内刚”特性，不仅可取代其他高硬度无机增强材料使超高分子量聚乙烯纤维具备高防切割性能，同时在减少对设备磨损、在反复使用中防止刺破超高分子量聚乙烯纤维基质导致防切割性能变弱等方面，具有显著优势。
优选地，本发明的具体的制备方法可按照如下步骤进行：
(1)准备碳纤维粉末
碳纤维粉末的颗粒优选为棒状，直径为0.1-10μm，长度为0.1-100μm；而更优选的长度为20-60μm。
碳纤维粉末的主要成分是微晶石墨，可由废旧的碳纤维粉碎、过筛制取；也可以碳纤维长丝切割制得。
(2)将碳纤维粉末进行表面处理
表面处理的主要作用是使碳纤维粉末的颗粒表面活化，可采用的方法包括：气相氧化、液相氧化、催化氧化、偶联剂涂层、聚合物涂层、等离子体处理。
碳纤维颗粒经活化处理后，使碳纤维表面带有弱极性，可提高碳纤维颗粒在溶剂中的分散度，防止碳纤维粉末团聚、从而进一步提高碳纤维颗粒在超高分子量聚乙烯基质中的分散均匀度、界面融合性和/或湿润性，从而获得性能更好的超高防切割聚乙烯纤维。
(3)制碳纤维粉末的乳化料
取一部分溶剂，将处理好的碳纤维粉末与表面活性剂一起加入到该部分溶剂中，进行高剪切乳化，制成碳纤维粉末乳化料。溶剂为选自白油、矿物油、植物油、石蜡油及十氢化萘中的一种或几种。
(4)制混合料：将分子量为20-600万(优选40-80万)的超高分子 量聚乙烯粉料和碳纤维粉末乳化料加入到剩余的溶剂中制成混合料。
其中，超高分子量聚乙烯：碳纤维乳化料：溶剂总质量之比为(10～40)：(0.1～1)：100。
其中，溶剂为选自白油、矿物油、植物油、石蜡油及十氢化萘中的一种或几种。
(5)制防切割聚乙烯纤维
将混合料通过双螺杆挤出机共混挤出，经过凝固浴冷却成型制得初生纤维，其双螺杆各区温度控制在100-300℃之间；将初生纤维萃取、干燥、经过多级热牵伸后制成超高防切割超高分子量聚乙烯纤维。
以下结合具体实施例对本发明方案的技术效果进一步说明。
实施例1
本实施例提供一种超高防切割超高分子量聚乙烯纤维的制备方法，其包括如下步骤：
(1)取长度为10-20um的750g碳纤维粉末，用等离子体对碳纤维粉末进行表面处理，处理时间为1h。
(2)称量100kg白油，取出5kg，将处理好的碳纤维粉末及5ml表面活性剂(月桂基磺化琥珀酸单酯二钠)加入到所取5kg白油中进行高剪切乳化，剪切速率为2800r/min，乳化时间30min，得到碳纤维乳化料。
(3)取分子量为200万、平均粒径100um的超高分子量聚乙烯粉料15kg，将所取15kg超高分子量聚乙烯粉料及乳化好的碳纤维乳化料加入到所剩95kg白油中混合均匀，混合时间1h，得到混合料。
(4)将混合好的混合料经双螺杆挤出机共混挤出，经过凝固浴冷却成型制得初生纤维，所得的初生纤维经萃取、干燥、经过多级热牵伸后制成超高分子量聚乙烯超高防切割纤维,其中碳纤维在超高分子量聚乙烯分散浓度为5％。
利用上述纤维制得的防切割手套，手感柔软、无扎刺感、佩戴舒适，经EN388-2003测试，防切割等级为5级。
实施例2
本实施例提供一种超高防切割超高分子量聚乙烯纤维的制备方法，其包括如下步骤：
(1)取长度为20-30um的800g碳纤维粉末，用等离子体对碳纤维粉末进行表面处理，处理时间为1h。
(2)称量100kg白油，取出5kg，将处理好的碳纤维粉末及15ml表面活性剂(椰油酸单乙醇酰胺磺基琥珀酸单酯二钠DMSS)加入到所取5kg白油中进行高剪切乳化，剪切速率为2800r/min，乳化时间30min，得到碳纤维粉末乳化料。
(3)取分子量为300万，平均粒径100um的超高分子量聚乙烯粉料20kg，将所取20kg超高分子量聚乙烯粉料及乳化好的碳纤维粉末乳化料加入到所剩95kg白油中混合均匀，混合时间1h，得到混合料。
(4)将混合好的混合料经双螺杆挤出机共混挤出，经过凝固浴冷却成型制得初生纤维，所得的初生纤维经萃取、干燥、经过多级热牵伸后制成超高分子量聚乙烯超高防切割纤维，其中碳纤维在超高分子量聚乙烯分散浓度为4％。
利用上述纤维制得的防切割手套，手感柔软、无扎刺感、佩戴舒适，经EN388-2003测试，防切割等级为5级。
实施例3
本实施例提供一种超高防切割超高分子量聚乙烯纤维的制备方法，其包括如下步骤：
(1)取长度为30-60um的1000g碳纤维粉末，用等离子体对碳纤维粉末进行表面处理，处理时间为1h。
(2)称量100kg白油，取出5kg，将处理好的碳纤维粉末及10ml表面活性剂(单月桂基磷酸酯MAP)加入到所取5kg白油中进行高剪切乳化，剪切速率为2800r/min，乳化时间30min，得到碳纤维粉末乳化料。
(3)取分子量为260万，平均粒径100um的超高分子量聚乙烯粉料 10kg，将所取10kg超高分子量聚乙烯粉料及乳化好的碳纤维粉末乳化料加入到所剩95kg白油中混合均匀，混合时间1h，得到混合料。
(4)将混合好的混合料经双螺杆挤出机共混挤出，经过凝固浴冷却成型制得初生纤维，所得的初生纤维经萃取、干燥、经过多级热牵伸后制成超高分子量聚乙烯超高防切割纤维，其中碳纤维在超高分子量聚乙烯分散浓度为10％。
利用上述纤维制得的防切割手套，手感柔软、无扎刺感、佩戴舒适，经EN388-2003测试，防切割等级为5级。
实施例4
本实施例提供一种超高防切割超高分子量聚乙烯纤维的制备方法，其包括如下步骤：
(1)取长度为20-30um的750g碳纤维粉末，用等离子体对碳纤维粉末进行表面处理，处理时间为1h。
(2)称量100kg白油，取出5kg，将处理好的碳纤维粉末及10ml表面活性剂(单十二烷基磷酸酯钾MAPK)加入到所取5kg白油中进行高剪切乳化，剪切速率为2800r/min，乳化时间30min，得到碳纤维粉末乳化料。
(3)取分子量为360万，平均粒径100um的超高分子量聚乙烯粉料20kg，将所取20kg超高分子量聚乙烯粉料及乳化好的碳纤维粉末乳化料加入到所剩95kg白油中混合均匀，混合时间1h，得到混合料。
(4)将混合好的混合料经双螺杆挤出机共混挤出，经过凝固浴冷却成型制得初生纤维，所得的初生纤维经萃取、干燥、经过多级热牵伸后制成超高分子量聚乙烯超高防切割纤维，其中碳纤维在超高分子量聚乙烯分散浓度为3.75％。
利用上述纤维制得的防切割手套，手感柔软、无扎刺感、佩戴舒适，经EN388-2003测试，防切割等级为5级。
实施例5
本实施例提供一种超高防切割超高分子量聚乙烯纤维的制备方法，其包括如下步骤：
(1)取长度为40-60um的600g碳纤维粉末，用等离子体对碳纤维粉末进行表面处理，处理时间为1h。
(2)称量100kg植物油，取出5kg，将处理好的碳纤维粉末及10ml表面活性剂(月桂醇醚磷酸酯钾MAEPK)加入到所取5kg植物油中进行高剪切乳化，剪切速率为2800r/min，乳化时间30min，制得碳纤维粉末乳化料。
(3)取分子量为40万，平均粒径100um的超高分子量聚乙烯粉料30kg，将所取30kg超高分子量聚乙烯粉料及乳化好的碳纤维粉末乳化料加入到所剩95kg植物油中混合均匀，混合时间1h，得到混合料。
(4)将混合好的混合料经双螺杆挤出机共混挤出，经过凝固浴冷却成型制得初生纤维，所得的初生纤维经萃取、干燥、经过多级热牵伸后制成超高分子量聚乙烯超高防切割纤维，其中碳纤维在超高分子量聚乙烯分散浓度为2％。
利用上述纤维制得的防切割手套，手感柔软、无扎刺感、佩戴舒适，经EN388-2003测试，防切割等级为4级。
实施例6
本实施例是在实施例1的基础上，不对碳纤维进行任何表面处理，碳纤维在乳化料呈团聚状。其他条件和处理程序参见实施例1，制得超高分子量聚乙烯超高防切割纤维，且碳纤维在超高分子量聚乙烯分散浓度为5％。不经表面活化处理的碳纤维容易聚团，所制得的纤维丝可纺性较差，由该纤维编织的手套其防切割性能也表现得不稳定。
对比例1
将实施例1中碳纤维替换为长度为10-20um的750g的氮化硼。其他条件和处理程序参见实施例1，制得超高分子量聚乙烯超高防切割纤维，且氮化硼在超高分子量聚乙烯分散浓度为5％。所制得的纤维丝其可纺性 较差。由该纤维编织的手套随着使用时间的延长，其防切割性能快速变差，且手套表面表现得毛刺、质硬，手感和佩戴舒适些都较差。
对比例2
将实施例1中碳纤维替换为长度为10-20um的750g的碳化钨。其他条件和处理程序参见实施例1，制得超高分子量聚乙烯超高防切割纤维，且碳化钨在超高分子量聚乙烯分散浓度为5％。所制得的纤维丝其可纺性较差。由该纤维编织的手套随着使用时间的延长，其防切割性能快速变差，且手套表面表现得毛刺、质硬，手感和佩戴舒适些都较差。
将实施例1-6和对比例1-2所制备的超高防切割超高分子量聚乙烯纤维编织成13针防护手套，经同种岗位同种操作的工人穿戴使用1天(1d)和20天(20d)后，分别测试手套的性能，测试结果如下表：
Figure PCTCN2019105436-appb-000001
由以上实施例测试结果可知，本发明的超高防切割超高分子量聚乙烯纤维所织成的手套等织物，防切割等级确实可稳定达到EN388-2003标准4-5级。更重要的是，根据本发明生产的超高防切割性超高分子量聚乙 烯纤维，不需与钢丝、玻璃纤维等材料混纺进行补强，而制得的防护手套质地柔软、轻巧、灵敏、佩戴舒适度好，长时间穿着不易疲劳。
此外，由实施例1-5与实施例6比较可知，实施例6的测试结果不不太稳定，主要是由于碳纤维在超高分子聚乙烯基质中分布不均所致。
实施例1-6与对比例1-2比较，对比例1-2的高防切割手套在使用约1天时，其防切割值和等级与本发明实施例1-6相当，但在使用20天后，对比例1-2的手套防切割性能激剧下降，且表面出现毛糙现象、手套变得较硬，舒适感很差。其中实施例6截取3个不同位置进行取样测试，得到一个范围值。对比例1-2的手套主要是因为在20天的使用过程中，反复弯折扭捏等原因，其中的高硬度无机增强材料因不具有柔韧性、会直接刺破聚乙烯基质，导致聚乙烯基质表面破损产生毛刺，而无机增强材料部分脱出也削弱了防切割性能。反之，本发明采用碳纤维增强的聚乙烯手套，则表现出异常耐用性、反复使用后，防切割性能与刚制得的产品几乎相当，且质软光滑，佩戴者体验很好。
由此说明，由于对比例1使用的无机高硬度增强材料硬度虽高、但柔软性较差，导致其容易刺破超高分子量聚乙烯纤维基质表面，造成损伤同时部分高硬度增强材料脱落，导致防切割性能下降较快。且本发明使用碳纤维作为防切割增强材料添加剂，制备的防切割手套，其防切割性能确实能与添加氮化硼、碳化钨等无机高硬度材料相媲美。
此外，据申请人近半年的实验制备研究，发现以对比例1-2中的无机高硬度添加材料增强高分子量聚乙烯纤维的防切割性能时，该高分子量聚乙烯纤维在制备过程中对挤出机的螺杆等设备磨损十分严重，设备折旧非常快，对设备的磨损表现十分显著；而本发明用碳纤维替代这些无机高硬度增强材料后，则几乎与以往单纯生产超高分子量聚乙烯纤维对设备的磨损状况相当。

Claims (11)

  1. 一种超高防切割超高分子量聚乙烯纤维，其特征在于，其包含超高分子量聚乙烯基质和分散于基质中的碳纤维粉末颗粒，所述碳纤维粉末颗粒的含量为0.25～10wt％。
  2. 一种超高防切割超高分子量聚乙烯纤维的制备方法，其特征在于，包括：
    S1:将碳纤维粉末与第一溶剂、表面活性剂混合乳化，制成碳纤维粉末乳化料；
    S2:将所述碳纤维粉末乳化料与分子量为20-600万的超高分子量聚乙烯粉料一同分散于第二溶剂中制得混合料；
    S3:将所述混合料通过挤出机共混挤出，经过凝固浴冷却成型制得初生纤维，将初生纤维萃取、干燥、多级热牵伸，制得超高防切割超高分子量聚乙烯纤维。
  3. 根据权利要求2所述的制备方法，其特征在于，所述碳纤维粉末的颗粒直径为0.1-10μm，长度为0.1-100μm；优选地，所述碳纤维粉末的颗粒的形状为长度大于直径的长棒状颗粒。
  4. 根据权利要求3所述的制备方法，其特征在于，所述碳纤维粉末的主要成分是微晶石墨，由废旧碳纤维粉碎制取。
  5. 根据权利要求2或3所述的制备方法，其特征在于，所述碳纤维粉末预先经过表面处理，使碳纤维粉末的颗粒表面活性化。
  6. 根据权利要求5所述的制备方法，其特征在于，所述表面处理的方法为以下任一种或几种的组合：气相氧化、液相氧化、催化氧化、偶联剂涂层、聚合物涂层和等离子体处理。
  7. 根据权利要求2或3所述的制备方法，其特征在于，所述超高分子量聚乙烯、碳纤维粉末、溶剂的质量之比为10～40:0.1～1:100；所述溶剂的质量是指所述第一溶剂和第二溶剂质量之和。
  8. 根据权利要求2所述的制备方法，其特征在于，所述超高分子量聚乙烯的分子量优选为200-500万。
  9. 根据权利要求2所述的制备方法，其特征在于，所述挤出机为双螺杆挤出机，其双螺杆各区温度控制在100-300℃。
  10. 一种超高防切割超高分子量聚乙烯纤维，其是采用权利要求2-9任一项所述的制备方法制备得到。
  11. 一种超高防切割手套或防切割服，包含由权利要求10所述的超高防切割超高分子量聚乙烯纤维维编织而成的编织物。
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