Ultra-high molecular weight polyethylene fiber containing multi-branched filler and fibrous filler, and manufacturing method and application of ultra-high molecular weight polyethylene fiber

Abstract

The present invention relates to an ultra-high molecular weight polyethylene fiber comprising a multi-branched filler and a fibrous filler, a method for manufacturing the same, and an application thereof. According to the ultra-high molecular weight polyethylene fiber, the comfort of a fabric can be greatly improved, and meanwhile, the fabric can reach the cutting-resistant EN388-2016 standard level 5. The ultra-high molecular weight polyethylene fiber according to the present invention comprises ultra-high molecular weight polyethylene as a matrix, a multi-branched filler dispersed in the matrix, and a fibrous filler dispersed in the matrix, in which the multi-branched filler has a plurality of dendritic protrusions in the structure thereof, and the matrix is substantially free of agglomerated structures between the fibrous filler and the multi-branched filler.

Description

Technical Field

[0001] The present invention relates to the technical field of fiber manufacturing, and more specifically to an ultra-high molecular weight polyethylene fiber containing multi-branch fillers and fibrous fillers, a manufacturing method thereof and an application thereof. Background Art

[0002] Ultra-high molecular weight polyethylene fiber (UHMWPE) is the fiber with the highest specific strength and specific modulus in the world. It is a fiber spun from polyethylene with a molecular weight of 1 million to 5 million. Ultra-high molecular weight polyethylene fiber is the fiber with the highest specific strength among the currently industrialized fiber materials. It has excellent properties such as high strength, high modulus, wear resistance, and chemical corrosion resistance. It is widely used in safety protection, military, aerospace, ocean, sports and other fields. With the continuous deepening of military-civilian integration, the application of ultra-high molecular weight polyethylene fiber in the civilian market has gradually increased, among which the civilian market dominated by anti-cut gloves has gradually occupied a dominant position. At present, the highest cutting grade of protective gloves made of commonly used ultra-high molecular weight polyethylene fibers is EN388-2016 standard level 3, which does not meet the needs of protection against cut hazards in actual working environments.

[0003] In order to improve the cut resistance level of gloves, a common method is to blend steel wire materials with ultra-high molecular weight polyethylene fibers to achieve ultra-high cut resistance. Although this method can improve the cut resistance of gloves, it cannot achieve compatibility between protective performance and comfort performance because the steel wire is relatively hard, difficult to wear and has poor comfort. At present, inorganic fillers are often added to fill and modify UHMWPE.

[0004] Patent CN104233497A provides a fiber with cut-resistant properties prepared by nanocrystalline silicon carbide and ultra-high molecular weight polyethylene. The method is to put nanocrystalline silicon carbide particles into a solvent, grind them repeatedly with a sand mill, and then put them into the solvent together with ultra-high molecular weight polyethylene, and mix them evenly with high-speed shearing and stirring in an emulsifier to obtain a fiber spinning mixture.

[0005] Patent CN101528998A discloses a composite yarn containing silk threads or fixed-length fibers, wherein the fixed-length fibers used are short-cut hard fibers with a certain aspect ratio, including glass fibers, mineral fibers or metal fibers, which are used to improve the cutting resistance of the yarn.

[0006] Patent CN109610040A discloses pouring glass fiber into a first white oil and mixing to obtain a glass fiber premix, then mixing the glass fiber premix, an antioxidant and UHMWPE powder in a second white oil to obtain a spinning mixture, which is swollen and extruded to form a molten state, cooled to form a gel filament and obtain a composite fiber. Summary of the invention

[0007] The inventors of the present invention have found that although the cut resistance coefficient of gloves can be improved by adding fibrous fillers to fill and modify UHMWPE, the gloves feel hard to wear, and because the fibrous fillers are easily removed from the fiber matrix during the manufacturing process or use, the production environment is polluted, or secondary damage such as itching and allergies are caused to the user, and the protection performance and wearing comfort (especially wearing safety) cannot be unified. To this end, the inventors of the present invention have found through hard research that by adding fibrous fillers (such as hard short fibers) and multi-branched fillers (such as whiskers) as two components into the ultra-high molecular weight polyethylene matrix, the hard short fibers can make up for the deficiency of whiskers being easily brittle, and the whiskers can make up for the defect of hard short fibers being easily removed. At the same time, the combination of the two helps to disperse evenly, and obtains UHMWPE fibers with low shedding, high comfort, high strength and toughness, anti-cutting and high uniformity (low linear density deviation). The present invention is completed based on this discovery.

[0008] Specifically, the present invention relates to the following aspects.

[0009] 1. An ultra-high molecular weight polyethylene fiber, comprising ultra-high molecular weight polyethylene as a matrix, a multi-branched filler (such as whiskers) dispersed in the matrix, and a fibrous filler (hereinafter sometimes referred to as a multi-branched filler and a fibrous filler together, collectively referred to as a filler) dispersed in the matrix, wherein the multi-branched filler has a plurality of (preferably at least 2, more preferably 2-10 or 3-8) branch-like protrusions in its structure, and there is substantially no agglomeration structure between the fibrous filler and the multi-branched filler in the matrix.

[0010] 2. The fiber described in any of the preceding or following aspects, wherein the content of the multi-branched filler is at most 15 parts by weight (preferably 3-10 parts by weight) relative to 100 parts by weight of the ultra-high molecular weight polyethylene, and the content of the fibrous filler is at most 15 parts by weight (preferably 3-10 parts by weight).

[0011] 3. The fiber according to any one of the preceding or following aspects, wherein the Mohs hardness of the filler is greater than the Mohs hardness of the ultra-high molecular weight polyethylene.

[0012] 4. The fiber described in any of the above or below aspects, wherein the viscosity-average molecular weight of the ultra-high molecular weight polyethylene is 1 million to 9 million (preferably 3 million to 5 million).

[0013] 5. The fiber described in any of the preceding or following aspects, wherein the multiple dendrites are the same or different from each other, and the length (from the root) is independently 5-2000 μm (preferably 10-300 μm), and the diameter (root) is independently at most 10 μm (preferably 0.05-3 μm).

[0014] 6. The fiber described in any of the preceding or following aspects, wherein the multi-branched filler is substantially uniformly dispersed in the matrix, or, there is substantially no agglomerated structure of the multi-branched filler in the matrix, or, the minimum distance between any two adjacent multi-branched fillers in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm).

[0015] 7. The fiber according to any one of the preceding or following aspects, wherein the fibrous filler is substantially uniformly dispersed in the matrix, or substantially no agglomerated structure of the fibrous filler exists in the matrix.

[0016] 8. The fiber according to any one of the preceding or following aspects, wherein the minimum distance between any two adjacent fibrous fillers in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm).

[0017] 9. The fiber according to any one of the preceding or following aspects, wherein the minimum distance between the multi-branched filler and any adjacent fibrous filler in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm).

[0018] 10. The fiber described in any one of the preceding or following aspects, wherein the multi-branched filler is selected from at least one of inorganic compound whiskers and organic compound whiskers, preferably at least one of inorganic compound whiskers.

[0019] 11. The fiber described in any of the preceding or following aspects, wherein the inorganic compound is at least one selected from inorganic oxygen-containing compounds, preferably at least one selected from metal oxides, metal hydroxides and metal oxyacid salts, in particular at least one selected from metal oxyacid salts, specifically such as at least one selected from silicon carbide, silicon nitride, aluminum oxide, zinc oxide, magnesium oxide, calcium carbonate, basic magnesium sulfate, aluminum borate, magnesium borate, potassium titanate and calcium sulfate; or, the organic compound is at least one selected from organic polymers, preferably at least one selected from cellulose, polyester, polyamide, poly 4-hydroxybenzoate (PHB).

[0020] 12. The fiber described in any of the preceding or following aspects, wherein the fibrous filler is a one-dimensional linear structure with a length of 1-2000 μm (preferably 50-200 μm), a diameter of up to 40 μm (preferably 1-20 μm), and an aspect ratio of at least 1 (preferably 3-100).

[0021] 13. The fiber described in any of the preceding or following aspects, wherein the fibrous filler is selected from at least one of inorganic hard short fibers and organic hard short fibers, preferably selected from at least one of inorganic hard short fibers.

[0022] 14. The fiber described in any of the preceding or following aspects, wherein the inorganic hard short fibers are selected from at least one of metal fibers, glass fibers, ceramic fibers, mineral fibers, and basalt fibers, or the organic hard short fibers are selected from at least one of carbon fibers, aramid fibers, aromatic polyamide copolymer fibers, heterocyclic polyamide fibers, graphite fibers, silicon carbide fibers, wood fibers, bamboo fibers, sisal fibers, and yew fibers.

[0023] 15. The fiber described in any one of the preceding or following aspects, wherein the multi-branched filler and / or the fibrous filler has been subjected to surface chemical modification, such as surface chemical modification with a silane coupling agent.

[0024] 16. The fiber described in any of the preceding or following aspects, wherein the silane coupling agent is selected from at least one of aminopropyltriethoxysilane, γ-(glycidyloxy)propyltrimethoxysilane, and γ-(methacryloyloxy)propyltrimethoxysilane.

[0025] 17. The fiber described in any of the preceding or following aspects, wherein the multi-branched filler and / or the fibrous filler has been subjected to surface physical modification treatment, such as surface roughening treatment and / or surface polymer coating treatment.

[0026] 18. The fiber described in any of the preceding or following aspects, wherein the polymer is selected from at least one of thermoplastic polymers, thermosetting polymers and rubbers, and preferably selected from at least one of cellulose esters, olefin polymers (polyvinyl acetate, polyvinyl alcohol, perchlorethylene, polyisobutylene, etc.), polyesters, polyethers, polyamides, polyacrylates, α-cyanoacrylates, polyvinyl acetals, ethylene-vinyl acetate copolymers and isocyanates.

[0027] 19. The fiber described in any of the preceding or following aspects, wherein the angle between any two adjacent dendrites is greater than 5° (preferably 30°-90°).

[0028] 20. The polyethylene fiber according to any one of the preceding or following aspects, wherein the linear density deviation rate of a single fiber in the longitudinal direction is at most 50% (preferably at most 15%).

[0029] 21. A method for producing ultra-high molecular weight polyethylene fiber, comprising the following steps:

[0030] 1) optionally subjecting a multi-branched filler (such as whiskers) to a surface chemical modification and / or a surface physical modification to obtain a modified multi-branched filler, wherein the multi-branched filler has a plurality of (preferably at least 2, more preferably 2-10 or 3-8) dendrites in its structure,

[0031] 2) optionally subjecting the fibrous filler to a surface chemical modification and / or a surface physical modification to obtain a modified fibrous filler,

[0032] 3) mixing the multi-branched filler or the modified multi-branched filler, the fibrous filler or the modified fibrous filler, ultra-high molecular weight polyethylene and a solvent to obtain a spinning solution,

[0033] 4) Spinning the spinning solution into the polyethylene fiber.

[0034] 22. The manufacturing method described in any of the preceding or following aspects, wherein before performing the step 1) or the step 2), it also includes a step of drying the multi-branched filler or the fibrous filler, and the drying includes: reducing pressure, a drying temperature of 80-200°C (preferably 90-120°C), and a drying time of 0.5-10h (preferably 1-4h).

[0035] 23. The manufacturing method described in any of the preceding or following aspects, wherein the surface chemical modification treatment includes: using a silane coupling agent, the amount of the silane coupling agent is 0.8-5wt% (preferably 1-3wt%) of the weight of the multi-branched filler or the fibrous filler, the treatment temperature is 40-100°C (preferably 70-90°C), and the treatment time is 1-120min (preferably 5-30min).

[0036] 24. The manufacturing method described in any of the preceding or subsequent aspects, wherein the surface physical modification treatment comprises: using a polymer for surface coating, the amount of the polymer used (dry basis) is at least 1%wt% (preferably 5-10wt%) of the weight of the multi-branched filler or the fibrous filler, the treatment temperature is at least 30°C (preferably 40-60°C), and the treatment time is at least 1 min (preferably 5-10 min).

[0037] 25. The manufacturing method described in any of the preceding or subsequent aspects, wherein relative to 100 parts by weight of the ultra-high molecular weight polyethylene, the amount of the multi-branched filler or the modified multi-branched filler (calculated as the multi-branched filler) is at most 50 parts by weight (preferably 5-15 parts by weight), the amount of the fibrous filler or the modified fibrous filler (calculated as the fibrous filler) is at most 50 parts by weight (preferably 3-10 parts by weight), and the amount of the solvent is at least 500 parts by weight (preferably 1000-2000 parts by weight).

[0038] 26. The manufacturing method according to any one of the preceding or following aspects, wherein the step 3) comprises:

[0039] 3-1) mixing the multi-branched filler or the modified multi-branched filler with a portion (e.g., 10-90 wt% or 40-60 wt% of the total amount) of the ultra-high molecular weight polyethylene to obtain a mixture A,

[0040] 3-2) mixing the fibrous filler or the modified fibrous filler with the remaining portion (e.g., 10-90 wt% or 40-60 wt% of the total amount) of the ultra-high molecular weight polyethylene to obtain a mixture B,

[0041] 3-3) mixing the mixture A and the mixture B,

[0042] The solvent is added to one or more of these steps at once or in batches. Preferably, a portion of the solvent (such as 10-90wt% or 40-60wt% of the total amount) is added in step 3-1), and the rest of the solvent is added in step 3-2).

[0043] 27. The manufacturing method described in any of the above or the following aspects, wherein in step 4), the spinning comprises: a gel spinning method, a primary stretching ratio of the spinneret is 3-10, a super stretching temperature is 80-150°C, and a super stretching ratio is 6-20.

[0044] 28. The manufacturing method described in any of the above or the following aspects, wherein before performing step 4), it also includes a step of combing and orienting the spinning solution.

[0045] 29. A fabric comprising the ultra-high molecular weight polyethylene fiber described in any one of the preceding or following aspects or the ultra-high molecular weight polyethylene fiber produced by the production method described in any one of the preceding or following aspects.

[0046] 30. The fabric described in any one of the preceding or following aspects further comprises at least one other fiber selected from natural plant fibers, natural animal fibers, artificial regenerated fibers, synthetic fibers and inorganic fibers.

[0047] Technical Effects

[0048] The multi-branched filler of the present invention can produce an anchoring effect in the fiber matrix, and can be more stably present in the fiber matrix without being easily dislodged, thereby effectively reducing secondary damage to the human body. In particular, during the fiber manufacturing process or the cutting process, the branch-like protrusion structure of the multi-branched filler can remain stable without being dislodged or rolling. In addition, the branch-like protrusion structure of the multi-branched filler can simultaneously bridge both sides of the crack to organize the crack expansion, thereby achieving high strength and high toughness and having anti-cutting performance effects.

[0049] The present invention adds fibrous fillers (such as hard short fibers) and multi-branched fillers (such as whiskers) as two components into an ultra-high molecular weight polyethylene matrix. The hard short fibers can make up for the brittle fracture of whiskers, and the whiskers can make up for the defect that the hard short fibers are easy to fall out. At the same time, the combination of the two helps to disperse evenly, thereby obtaining UHMWPE fibers with low shedding, high comfort, high strength and toughness, anti-cutting and high uniformity (low linear density deviation rate).

[0050] The ultra-high molecular weight polyethylene fiber of the invention can greatly improve the wearing comfort of the fabric, especially the wearing safety, and the fabric can reach level 5 of the cut resistance EN388-2003 standard. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 Schematic diagram of the dispersion of multi-branched fillers and fibrous fillers in a polyethylene matrix according to the present invention. Figure 1 In the figure, H1 represents the length of the dendrites (measured from the root), H2 represents the length of the fibrous filler, and L represents the minimum distance between the multi-branched filler and the adjacent fibrous filler. DETAILED DESCRIPTION

[0052] The specific embodiments of the present invention are described in detail below, but it should be pointed out that the protection scope of the present invention is not limited by these specific embodiments, but is determined by the claims in the appendix.

[0053] All publications, patent applications, patents and other references mentioned in this specification are incorporated herein by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the meanings conventionally understood by those skilled in the art. In the event of a conflict, the definitions in this specification shall prevail.

[0054] When this specification uses the prefix "well-known to those skilled in the art", "prior art" or similar terms to introduce materials, substances, methods, steps, devices or components, etc., the objects introduced by the prefix cover those commonly used in the art when this application is filed, but also include those that are not commonly used at present but will become recognized in the art as being suitable for similar purposes.

[0055] In the context of this specification, by substantially it is meant a deviation of no more than 20%, preferably no more than 10%, 5% or 1%.

[0056] In the context of this specification, the removal of filler from the fiber matrix is ​​characterized by the degree of material shedding from the fiber during the fiber manufacturing process.

[0057] In the context of this specification, the agglomeration is measured as follows: a 10 cm long section is randomly cut from the fiber, the number of agglomerated structures is investigated under a laser microscope, and then scored according to the following criteria. The measurement is repeated 10 times and the average value is taken.

[0058] No reunion: 0,

[0059] Small amount of reunion: less than 2,

[0060] Medium reunion: 3-4,

[0061] Large gatherings: 5 or more.

[0062] In the context of this specification, the linear density deviation rate is measured according to GB / T 14343.

[0063] In the context of this specification, the distance between two fillers or similar expressions means the distance between any point on one filler and any point on the other filler.

[0064] Unless otherwise specified, all percentages, parts, ratios, etc. mentioned in this specification are based on weight and pressure is gauge pressure.

[0065] In the context of this specification, there are no specific operating conditions, additives, etc., and those known in the art are directly applicable without particular limitation.

[0066] In the context of this specification, any two or more embodiments of the present invention may be arbitrarily combined, and the technical solutions thus formed belong to part of the original disclosure of this specification and also fall within the protection scope of the present invention.

[0067] According to one embodiment of the present invention, it relates to an ultra-high molecular weight polyethylene fiber. The ultra-high molecular weight polyethylene fiber is generally a monofilament or a filament.

[0068] According to one embodiment of the present invention, the ultra-high molecular weight polyethylene fiber comprises ultra-high molecular weight polyethylene as a matrix, multi-branched fillers (such as whiskers) dispersed in the matrix, and fibrous fillers dispersed in the matrix. If only the branched fillers are added, the branched fillers are irregular, and are easy to cross and bridge during the dispersion process, resulting in uneven dispersion, causing the local weight of the fiber to increase, the linear density deviation rate to be too large, the fiber to be uneven, and the cutting resistance to be insufficient. After adding the fibrous fillers, it is beneficial to disperse the fillers in the axial direction of the fiber, making the fiber more uniform.

[0069] According to the present invention, the multi-branched filler (especially whiskers) and the fibrous filler can be directly purchased from the market or manufactured according to conventional methods known in the relevant technical field, and there is no particular limitation except for the relevant content below.

[0070] According to the present invention, the multi-branched filler and the fibrous filler are sometimes collectively referred to as filler. In addition, the Mohs hardness of the multi-branched filler is greater than the Mohs hardness of the ultra-high molecular weight polyethylene, and the Mohs hardness of the fibrous filler is greater than the Mohs hardness of the ultra-high molecular weight polyethylene, so both are hard fillers.

[0071] According to one embodiment of the present invention, the multi-branched filler has a plurality of (preferably at least 2, more preferably 2-10 or 3-8) branch-like protrusions in its structure. When the number of branch-like protrusions is too large, the multi-branched filler generates a local mass concentration point in the fiber matrix, and the uniformity of the linear density of the ultra-high molecular weight polyethylene fiber along the length direction is too poor (the linear density deviation rate is too large), which may have an adverse effect on the processing performance, and the cutting resistance may be insufficient. In addition, when the number of branch-like protrusions is too small, the risk of the multi-branched filler escaping from the fiber matrix increases, and the cutting resistance may be insufficient.

[0072] According to one embodiment of the present invention, the content of the multi-branched filler is at most 15 parts by weight (preferably 3-10 parts by weight) relative to 100 parts by weight of the ultra-high molecular weight polyethylene. When the content of the multi-branched filler is too low, the cut resistance of the fiber may be insufficient. In addition, when the content of the multi-branched filler is too high, the multi-branched filler is prone to form an agglomeration structure in the fiber matrix, which may cause an unnecessary and significant increase in the fiber modulus, affecting the wearing comfort.

[0073] According to one embodiment of the present invention, the content of the fibrous filler is at most 15 parts by weight (preferably 3-10 parts by weight) relative to 100 parts by weight of the ultra-high molecular weight polyethylene. When the content of the fibrous filler is too low, the cut resistance of the fiber may be insufficient. In addition, when the content of the fibrous filler is too high, the fibrous filler agglomerates in the fiber matrix, which may cause the uniformity of the fiber line density to deteriorate, affecting the wearing comfort.

[0074] According to one embodiment of the present invention, the viscosity-average molecular weight of the ultra-high molecular weight polyethylene is 1 million to 9 million (preferably 3 million to 5 million).

[0075] According to one embodiment of the present invention, the plurality of branch-like protrusions are identical or different from each other, and the length (calculated from the root) is independently 5-2000 μm (preferably 10-300 μm). When the length of the branch-like protrusion is too small, the cut resistance of the fiber may be insufficient, and the risk of the multi-branched filler escaping from the fiber matrix increases. In addition, when the length of the branch-like protrusion is too large, the multi-branched filler produces a local mass concentration point in the fiber matrix, and the uniformity of the linear density of the ultra-high molecular weight polyethylene fiber along the length direction is too poor, which may have an adverse effect on the processing performance, and the cut resistance may be insufficient. Moreover, when the length of the branch-like protrusion is too large, the multi-branched filler is easy to form an agglomerated structure in the fiber matrix, which may cause the uniformity of the fiber linear density to deteriorate, affecting the wearing comfort.

[0076] According to one embodiment of the present invention, the plurality of dendrites are identical to or different from each other, and each independently has a diameter (root) of at most 10 μm (preferably 0.05-3 μm).

[0077] According to one embodiment of the present invention, there is substantially no agglomeration structure between the fibrous filler and the multi-branched filler in the matrix. In the context of this specification, the so-called agglomeration structure refers to a composite structure formed by entanglement or interweaving of multiple fillers (such as between the multi-branched fillers, between the fibrous fillers, or between the multi-branched fillers and the fibrous fillers). According to the present invention, when fillers form an agglomeration structure in a fiber matrix, it may cause the uniformity of fiber line density to deteriorate, affecting wearing comfort.

[0078] According to one embodiment of the present invention, the multi-branched filler is substantially uniformly dispersed in the matrix. In other words, there is substantially no agglomeration structure of the multi-branched filler in the matrix. As a quantitative indicator, the minimum distance between any two adjacent multi-branched fillers in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm).

[0079] According to one embodiment of the present invention, the fibrous filler is substantially uniformly dispersed in the matrix. In other words, there is substantially no agglomeration structure of the fibrous filler in the matrix. As a quantitative indicator, the minimum distance between any two adjacent fibrous fillers in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm).

[0080] According to one embodiment of the present invention, as a quantitative index of the agglomerated structure, the minimum distance between the multi-branched filler and any adjacent fibrous filler in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm).

[0081] According to one embodiment of the present invention, the multi-branched filler is selected from at least one of inorganic compound whiskers and organic compound whiskers, preferably selected from at least one of inorganic compound whiskers.

[0082] According to one embodiment of the present invention, the inorganic compound is at least one selected from inorganic oxygen-containing compounds, preferably at least one selected from metal oxides, metal hydroxides and metal oxyacid salts, in particular at least one selected from metal oxyacid salts, specifically at least one selected from silicon carbide, silicon nitride, aluminum oxide, zinc oxide, magnesium oxide, calcium carbonate, basic magnesium sulfate, aluminum borate, magnesium borate, potassium titanate and calcium sulfate.

[0083] According to one embodiment of the present invention, the organic compound is at least one selected from organic polymers, preferably at least one selected from cellulose, polyester, polyamide, and poly 4-hydroxybenzoate (PHB).

[0084] According to one embodiment of the present invention, the fibrous filler is a one-dimensional linear structure with a length of 1-2000 μm (preferably 50-200 μm). If the length of the fibrous filler is too small, the cutting resistance of the fiber may be insufficient. In addition, if the length of the fibrous filler is too large, the fibrous filler is likely to form an agglomerated structure in the fiber matrix, which will cause the uniformity of the fiber to deteriorate and affect the wearing comfort.

[0085] According to one embodiment of the present invention, the diameter of the fibrous filler is at most 40 μm (preferably 1-20 μm) and the aspect ratio is at least 1 (preferably 3-100).

[0086] According to one embodiment of the present invention, the fibrous filler is selected from at least one of inorganic hard short fibers and organic hard short fibers, preferably selected from at least one of inorganic hard short fibers.

[0087] According to one embodiment of the present invention, the inorganic hard short fibers are selected from at least one of metal fibers, glass fibers, ceramic fibers, mineral fibers, and basalt fibers.

[0088] According to one embodiment of the present invention, the organic hard short fiber is selected from at least one of carbon fiber, aramid fiber, aromatic polyamide copolymer fiber, heterocyclic polyamide fiber, graphite fiber, silicon carbide fiber, wood fiber, bamboo fiber, sisal fiber and yarrow fiber.

[0089] According to one embodiment of the present invention, the multi-branched filler is subjected to surface chemical modification, such as surface chemical modification with a silane coupling agent. Without surface chemical modification, the anchoring effect of the multi-branched filler on the fiber matrix may be deteriorated, the risk of the multi-branched filler escaping from the fiber matrix increases, and the cutting resistance may be insufficient.

[0090] According to one embodiment of the present invention, the fibrous filler is subjected to surface chemical modification, such as surface chemical modification with a silane coupling agent. Without surface chemical modification, the anchoring effect of the multi-fiber filler on the fiber matrix may be deteriorated, the risk of the fibrous filler escaping from the fiber matrix increases, and the cutting resistance may be insufficient.

[0091] According to one embodiment of the present invention, the silane coupling agent is selected from at least one of aminopropyltriethoxysilane, γ-(glycidyloxy)propyltrimethoxysilane and γ-(methacryloyloxy)propyltrimethoxysilane.

[0092] According to one embodiment of the present invention, the multi-branched filler is subjected to a surface physical modification treatment, such as a surface roughening treatment and / or a surface polymer coating treatment.

[0093] According to one embodiment of the present invention, the fibrous filler is subjected to a surface physical modification treatment, such as a surface roughening treatment and / or a surface polymer coating treatment.

[0094] According to one embodiment of the present invention, the polymer is selected from at least one of thermoplastic polymers, thermosetting polymers and rubbers, preferably selected from at least one of cellulose esters, olefin polymers (polyvinyl acetate, polyvinyl alcohol, perchlorethylene, polyisobutylene, etc.), polyesters, polyethers, polyamides, polyacrylates, a-cyanoacrylates, polyvinyl acetals, ethylene-vinyl acetate copolymers and isocyanates.

[0095] According to one embodiment of the present invention, the angle between any two adjacent branch-like protrusions is greater than 5° (preferably 30°-90°). When the angle is too small, the fiber matrix may not be sufficiently impregnated with the multi-branched filler, resulting in an increased risk of the multi-branched filler escaping from the fiber matrix, and the cutting resistance may be insufficient. In addition, when the angle is too large, the anchoring effect of the multi-branched filler on the fiber matrix may deteriorate, the risk of the multi-branched filler escaping from the fiber matrix increases, and the cutting resistance may be insufficient.

[0096] According to one embodiment of the present invention, the linear density deviation rate of a single fiber of the polyethylene fiber in the length direction is at most 50% (preferably at most 15%). If the linear density deviation is too large, the fiber uniformity is poor and the cutting resistance may be insufficient.

[0097] According to one embodiment of the present invention, the fiber has a single filament fineness of at least 0.5 dtex (preferably 0.9-5 dtex, most preferably 1-3 dtex).

[0098] According to one embodiment of the present invention, it also relates to a method for manufacturing an ultra-high molecular weight polyethylene fiber. According to the present invention, the manufacturing method can be used to manufacture the ultra-high molecular weight polyethylene fiber of the present invention as described above. For this reason, the contents not described or expanded in detail in this document for the manufacturing method can be directly applied to the contents given in the previous text of this specification for the ultra-high molecular weight polyethylene fiber, and will not be repeated here.

[0099] According to one embodiment of the present invention, the method for producing the ultra-high molecular weight polyethylene fiber comprises the following steps:

[0100] 1) optionally subjecting a multi-branched filler (such as whiskers) to a surface chemical modification and / or a surface physical modification to obtain a modified multi-branched filler,

[0101] 2) optionally subjecting the fibrous filler to a surface chemical modification and / or a surface physical modification to obtain a modified fibrous filler,

[0102] 3) mixing the multi-branched filler or the modified multi-branched filler, the fibrous filler or the modified fibrous filler, ultra-high molecular weight polyethylene and a solvent to obtain a spinning solution,

[0103] 4) Spinning the spinning solution into the polyethylene fiber.

[0104] According to one embodiment of the present invention, before performing step 1) or step 2), the method further comprises a step of drying the multi-branched filler or the fibrous filler.

[0105] According to one embodiment of the present invention, the drying comprises: reducing pressure, a drying temperature of 80-200° C. (preferably 90-120° C.), and a drying time of 0.5-10 h (preferably 1-4 h).

[0106] According to one embodiment of the present invention, the surface chemical modification treatment includes: using a silane coupling agent, the amount of the silane coupling agent is 0.8-5wt% (preferably 1-3wt%) of the weight of the multi-branched filler or the fibrous filler, the treatment temperature is 40-100°C (preferably 70-90°C), and the treatment time is 1-120min (preferably 5-30min).

[0107] According to one embodiment of the present invention, the surface physical modification treatment includes: using a polymer for surface coating, the amount of the polymer (dry basis) is at least 1%wt% (preferably 5-10wt%) of the weight of the multi-branched filler or the fibrous filler, the treatment temperature is at least 30°C (preferably 40-60°C), and the treatment time is at least 1min (preferably 5-10min).

[0108] According to one embodiment of the present invention, relative to 100 parts by weight of the ultra-high molecular weight polyethylene, the amount of the multi-branched filler or the modified multi-branched filler (calculated as the multi-branched filler) is at most 50 parts by weight (preferably 5-15 parts by weight), the amount of the fibrous filler or the modified fibrous filler (calculated as the fibrous filler) is at most 50 parts by weight (preferably 3-10 parts by weight), and the amount of the solvent is at least 500 parts by weight (preferably 1000-2000 parts by weight).

[0109] According to one embodiment of the present invention, the step 3) comprises:

[0110] 3-1) mixing the multi-branched filler or the modified multi-branched filler with a portion (e.g., 10-90 wt% or 40-60 wt% of the total amount) of the ultra-high molecular weight polyethylene to obtain a mixture A,

[0111] 3-2) mixing the fibrous filler or the modified fibrous filler with the remaining portion (e.g., 10-90 wt% or 40-60 wt% of the total amount) of the ultra-high molecular weight polyethylene to obtain a mixture B,

[0112] 3-3) Mixing the mixture A and the mixture B.

[0113] According to this embodiment of the present invention, by premixing in batches, the filler and the ultra-high molecular weight polyethylene powder can be adsorbed and assembled in appropriate amounts, and the branched or fibrous filler will be embedded in the depressions on the surface of the ultra-high molecular weight polyethylene, and there will be a certain binding force, forming a morphological feature similar to that of a sugar ball. If premixing is not performed, the branched fillers are easy to cross each other, bridge, and form agglomerations, and the fibrous fillers are also easy to intersperse therein to form a spherical thorn structure. In particular, the density of the two is greater than that of the ultra-high molecular weight polyethylene, and it is easy to stratify in the system, resulting in blockage and poor fiber cutting resistance.

[0114] According to one embodiment of the present invention, the solvent is added to one or more of these steps at once or in batches. As a preferred embodiment, it is preferred to add a portion of the solvent (for example, 10-90wt% or 40-60wt% of the total amount) in step 3-1), and add the rest of the solvent in step 3-2). The purpose of adding the solvent is to wet the surface of the additive, increase fluidity and intermolecular forces, make the combination stronger and the mixing more uniform. If no solvent is added, the molecular repulsion between the materials will cause floating dust to be generated during the mixing process, the amount added will be reduced, and the cutting resistance effect will not be achieved. At the same time, unsafe factors such as dust explosion will be introduced.

[0115] According to one embodiment of the present invention, in step 4), the spinning adopts a gel spinning method, including swelling at 60-120°C for 1-3h, dissolving by screw shearing, the dissolving temperature is 180-250°C, extruding the spinning gel, and then spinning through a spinneret. Preferably, under the condition of keeping warm at 100-200°C, flowing through a whisker comber, the whiskers are oriented and arranged in the direction of the spinning solution flow. In addition, the primary stretching ratio of the spinneret is 3-10, the super stretching temperature is 80-150°C, and the super stretching ratio is 6-20 (preferably 8-15).

[0116] The ultra-high molecular weight polyethylene fiber of the present invention can be made into cut-resistant fabrics, including but not limited to at least one of woven fabrics, knitted fabrics, non-woven fabrics, and non-woven fabrics, and its cut resistance reaches level 5 of EN388-2016 standard.

[0117] According to one embodiment of the present invention, the fabric further comprises at least one other fiber selected from natural plant fibers, natural animal fibers, artificial regenerated fibers, synthetic fibers and inorganic fibers.

[0118] Example

[0119] The present invention is further described in detail below using examples, but the present invention is not limited to these examples.

[0120] Example 1

[0121] The ultra-high molecular weight polyethylene fiber of this embodiment comprises ultra-high molecular weight polyethylene as a matrix, multi-branched fillers dispersed in the matrix, and fibrous fillers dispersed in the matrix.

[0122] In this embodiment, the multi-branched filler is a whisker, which is a 1:1 mixture of zinc oxide and calcium sulfate by mass. Its surface is treated with Y-(glycidyloxy)propyltrimethoxysilane and has 4-7 dendrites. The length of each dendrite (from the root) is between 100-250 μm, the diameter (root) is between 0.8-1.5 μm, and the angle between any two adjacent dendrites is between 45-55 degrees.

[0123] In this embodiment, the fibrous filler is glass fiber, the surface of which is treated with Y-(glycidyloxy)propyltrimethoxysilane, has a length of 150 μm and an aspect ratio of 10.

[0124] In this embodiment, the amount of whiskers is 7 parts by weight and the amount of glass fibers is 7 parts by weight relative to 100 parts by weight of ultra-high molecular weight polyethylene. The viscosity average molecular weight of the ultra-high molecular weight polyethylene is 4.5 million.

[0125] In this embodiment, 10 cm of ultra-high molecular weight polyethylene fiber was observed with a laser microscope and it was found that the whiskers and glass fibers were basically evenly dispersed in the matrix, no whiskers or glass fibers or agglomeration structures between the two were observed in the matrix, and the minimum distance between any two adjacent whiskers in the matrix was greater than 100 μm, and the minimum distance between the whiskers and adjacent glass fibers in the matrix was greater than 20 μm.

[0126] In this embodiment, after measurement, the single fiber fineness of the ultra-high molecular weight polyethylene fiber of this embodiment is 2.9 dtex.

[0127] The fiber manufacturing method of this embodiment includes the following steps:

[0128] 1) treating the whiskers with a silane coupling agent to obtain modified whiskers;

[0129] 2) Modifying the glass fiber with a silane coupling agent to obtain modified glass fiber,

[0130] 3) mixing the modified whiskers, the modified glass fibers, the ultra-high molecular weight polyethylene and the solvent decalin to obtain a spinning solution,

[0131] 4) Spinning the spinning solution into the polyethylene fiber.

[0132] Before the silane coupling agent treatment, the whiskers and glass fibers were dried separately at a drying temperature of 100° C. and a drying time of 3 h.

[0133] When the silane coupling agent is used for treatment, the amount of the silane coupling agent used is 2 wt % of the weight of the whisker and the glass fiber, respectively. The treatment temperature is 80° C. and the treatment time is 20 min.

[0134] During the mixing process, 100 parts by weight of ultra-high molecular weight polyethylene, 9 parts by weight of modified whiskers (calculated as whiskers), 9 parts by weight of modified glass fibers (calculated as glass fibers), and 1500 parts by weight of solvent are used. First, the modified whiskers are mixed with 50%wt% of ultra-high molecular weight polyethylene and 50% of solvent to obtain mixture A, and then the modified glass fibers are mixed with 50%wt% of ultra-high molecular weight polyethylene and 50% of solvent to obtain mixture B, and finally the mixture A and the mixture B are mixed. The gel spinning method is adopted, the primary stretching ratio of the spinneret is 8, the super-stretching temperature is 145°C, and the super-stretching ratio is 10. The spinning solution passes through a combing orientation zone before spinning.

[0135] The ultra-high molecular weight polyethylene fibers were coated with spandex and then knitted into gloves on a 13-needle glove loom for the EN388-2016 cut resistance test.

[0136] Example 2

[0137] Compared with Example 1, the whiskers and glass fibers are not treated with a silane coupling agent. The single-filament fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.9 dtex.

[0138] Example 3

[0139] Compared with Example 1, the whiskers have 25-30 dendrites, each with a length (from the root) of 35-100 μm and a diameter (from the root) of 0.5-1.5 μm. The single-filament fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.5 dtex.

[0140] Example 4

[0141] Compared with Example 1, the whiskers have 2-3 dendrites, each with a length (from the root) of 150-250 μm and a diameter (from the root) of 0.8-1.2 μm. The single-filament fineness of the ultra-high molecular weight polyethylene fiber of this example is 1.9 dtex.

[0142] Example 5

[0143] Compared with Example 1, the amount of modified whiskers (calculated as whiskers) used is 20 parts by weight for 100 parts by weight of ultra-high molecular weight polyethylene. The single-filament fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.3 dtex.

[0144] Example 6

[0145] Compared with Example 1, the length of each dendrite (calculated from the root) is between 1200-1800 μm. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.9 dtex.

[0146] Example 7

[0147] Compared with Example 1, the diameter (root) of each dendrite is between 18 and 25 μm. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.2 dtex.

[0148] Example 8

[0149] Compared with Example 1, the length of the glass fiber is 1000 μm and the aspect ratio is 50. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.5 dtex.

[0150] Example 9

[0151] Compared with Example 1, the angle between any two adjacent dendrites is between 130 and 150 degrees. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.5 dtex.

[0152] Example 10

[0153] Compared with Example 1, the angle between any two adjacent dendrites is between 5 and 20 degrees. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.3 dtex.

[0154] Embodiment 11

[0155] Compared with Example 1, only the surface treatment form of the whiskers and glass fibers is changed, and polyacrylate is used for coating. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.5 dtex.

[0156] Example 12

[0157] Compared with Example 1, the super-drawing ratio is 4. The single-filament fineness of the ultra-high molecular weight polyethylene fiber of this example is 3.5 dtex.

[0158] Example 13

[0159] Compared with Example 1, there is no premixing step, and the modified whiskers and modified glass fibers are directly mixed with the entire amount of polyethylene powder and then added to the solvent. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this example is 2.9 dtex.

[0160] Comparative Example 1

[0161] Compared with Example 1, only whiskers are added without glass fibers. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this comparative example is 2.5 dtex.

[0162] Comparative Example 2

[0163] Compared with Example 1, whiskers are not added, and only glass fibers are added. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this comparative example is 1.9 dtex.

[0164] Comparative Example 3

[0165] Compared with Example 1, the glass fiber is replaced by glass microbeads with a diameter of 1 μm. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this comparative example is 1.9 dtex.

[0166] Comparative Example 4

[0167] The fiber is commercially available LY25 ultra-high molecular weight polyethylene fiber, which does not contain whiskers and glass fibers. The single fiber fineness of the ultra-high molecular weight polyethylene fiber of this comparative example is 1.2 dtex.

[0168]

[0169]

Claims

1. An ultra-high molecular weight polyethylene fiber, comprising ultra-high molecular weight polyethylene as a matrix, a multi-branched filler (such as whiskers) dispersed in the matrix, and a fibrous filler (hereinafter sometimes referred to as a multi-branched filler and a fibrous filler together, collectively referred to as a filler) dispersed in the matrix, wherein the multi-branched filler has a plurality of (preferably at least 2, more preferably 2-10 or 3-8) branch-like protrusions in its structure, and there is substantially no agglomeration structure between the fibrous filler and the multi-branched filler in the matrix.

2. The fiber of claim 1, wherein the content of the multi-branched filler is at most 15 parts by weight (preferably 3-10 parts by weight) and the content of the fibrous filler is at most 15 parts by weight (preferably 3-10 parts by weight) relative to 100 parts by weight of the ultra-high molecular weight polyethylene.

3. The fiber of claim 1, wherein the viscosity-average molecular weight of the ultra-high molecular weight polyethylene is 1 million to 9 million (preferably 3 million to 5 million).

4. The fiber of claim 1, wherein the plurality of dendrites are identical or different from each other, and each independently has a length (from the root) of 5-2000 μm (preferably 10-300 μm), and a diameter (root) of at most 10 μm (preferably 0.05-3 μm).

5. The fiber of claim 1, wherein the multi-branched filler is substantially uniformly dispersed in the matrix, or, there is substantially no agglomerated structure of the multi-branched filler in the matrix, or, the minimum distance between any two adjacent multi-branched fillers in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm).

6. The fiber of claim 1, wherein the fibrous filler is substantially uniformly dispersed in the matrix, or, there is substantially no agglomerated structure of the fibrous filler in the matrix, or, the minimum distance between any two adjacent fibrous fillers in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm).

7. The fiber of claim 1, wherein the minimum distance between the multi-branched filler and any adjacent fibrous filler in the matrix is ​​greater than 0.1 μm (preferably greater than 5 μm).

8. The fiber of claim 1, wherein the multi-branched filler is selected from at least one of inorganic compound whiskers and organic compound whiskers, preferably at least one of inorganic compound whiskers.

9. The fiber of claim 8, wherein the inorganic compound is at least one selected from inorganic oxygen-containing compounds, preferably at least one selected from metal oxides, metal hydroxides and metal oxyacid salts, in particular at least one selected from metal oxyacid salts, specifically at least one selected from silicon carbide, silicon nitride, aluminum oxide, zinc oxide, magnesium oxide, calcium carbonate, basic magnesium sulfate, aluminum borate, magnesium borate, potassium titanate and calcium sulfate; or, the organic compound is at least one selected from organic polymers, preferably at least one selected from cellulose, polyester, polyamide, poly 4-hydroxybenzoate (PHB).

10. The fiber of claim 1, wherein the fibrous filler is a one-dimensional linear structure having a length of 1-2000 μm (preferably 50-200 μm), a diameter of up to 40 μm (preferably 1-20 μm), and an aspect ratio of at least 1 (preferably 3-100).

11. The fiber of claim 1, wherein the fibrous filler is selected from at least one of inorganic hard short fibers and organic hard short fibers, preferably selected from at least one of inorganic hard short fibers.

12. The fiber of claim 11, wherein the inorganic hard short fibers are selected from at least one of metal fibers, glass fibers, ceramic fibers, mineral fibers, and basalt fibers, or the organic hard short fibers are selected from at least one of carbon fibers, aramid fibers, aromatic polyamide copolymer fibers, heterocyclic polyamide fibers, graphite fibers, silicon carbide fibers, wood fibers, bamboo fibers, sisal fibers, and yew fibers.

13. The fiber of claim 1, wherein the angle between any two adjacent dendrites is greater than 5° (preferably 30°-90°).

14. The polyethylene fiber according to claim 1, wherein the linear density deviation rate of a single fiber in the longitudinal direction is at most 50% (preferably at most 15%).

15. A method for producing ultra-high molecular weight polyethylene fiber, comprising the following steps: 1) optionally subjecting a multi-branched filler (such as whiskers) to a surface chemical modification and / or a surface physical modification to obtain a modified multi-branched filler, wherein the multi-branched filler has a plurality of (preferably at least 2, more preferably 2-10 or 3-8) dendrites in its structure, 2) optionally subjecting the fibrous filler to a surface chemical modification and / or a surface physical modification to obtain a modified fibrous filler, 3) mixing the multi-branched filler or the modified multi-branched filler, the fibrous filler or the modified fibrous filler, ultra-high molecular weight polyethylene and a solvent to obtain a spinning solution, 4) Spinning the spinning solution into the polyethylene fiber.

16. The manufacturing method according to claim 15, wherein before performing step 1) or step 2), it further comprises a step of drying the multi-branched filler or the fibrous filler, wherein the drying comprises: Reduce pressure, the drying temperature is 80-200°C (preferably 90-120°C), and the drying time is 0.5-10h (preferably 1-4h).

17. The manufacturing method according to claim 15, wherein the step 3) comprises: 3-1) mixing the multi-branched filler or the modified multi-branched filler with a portion (e.g., 10-90 wt% or 40-60 wt% of the total amount) of the ultra-high molecular weight polyethylene to obtain a mixture A, 3-2) mixing the fibrous filler or the modified fibrous filler with the remaining portion (e.g., 10-90 wt% or 40-60 wt% of the total amount) of the ultra-high molecular weight polyethylene to obtain a mixture B, 3-3) mixing the mixture A and the mixture B, The solvent is added to one or more of these steps at once or in batches. Preferably, a portion of the solvent (such as 10-90wt% or 40-60wt% of the total amount) is added in step 3-1), and the rest of the solvent is added in step 3-2).

18. The manufacturing method of claim 15, wherein in step 4), the spinning comprises: In the gel spinning method, the primary stretching ratio of the spinneret is 3-10, the super stretching temperature is 80-150°C, and the super stretching ratio is 6-20.

19. A fabric comprising the ultra-high molecular weight polyethylene fiber of claim 1 or the ultra-high molecular weight polyethylene fiber manufactured by the manufacturing method of claim 15.

Images