A porous ultra-high molecular weight polyethylene fiber, a method for manufacturing the same, and an application thereof

Abstract

The present application relates to a kind of porous ultra-high molecular weight polyethylene fiber, its manufacturing method and its application.The manufacturing method of the porous ultra-high molecular weight polyethylene fiber of the present application includes the following steps: 1) ultra-high molecular weight polyethylene, acid-soluble inorganic particles and solvent are mixed to prepare spinning solution, 2) the spinning solution is extruded to form spinning stream, 3) at least a portion of the solvent is removed from the spinning stream to obtain dry protofilament, 4) the dry protofilament is stretched in one or more stages to obtain pre-drawing yarn, 5) the pre-drawing yarn is immersed through acidic bath under the condition of ultrasonic or not to dissolve the acid-soluble inorganic particles, to obtain the porous ultra-high molecular weight polyethylene fiber.The surface and internal distribution of the porous ultra-high molecular weight polyethylene fiber of the present application are micro-nano level holes, while ensuring the integrity of the fiber as far as possible, make the fiber more wet, keep the cool feeling of the fiber while comfortable and breathable.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of high-performance fibers, in particular, to a porous ultra-high molecular weight polyethylene fiber, a manufacturing method thereof and an application thereof. BACKGROUND

[0002] Ultra-high molecular weight polyethylene fiber, as the most industrialized high-performance fiber, has been widely used in the fields of military bulletproof, aerospace, marine industry, etc. In order to meet the needs of more and more fields, people have gradually changed from developing and producing fibers to modifying fibers. In order to overcome the problems of single molecular structure, strong chemical inertness, smooth surface and difficulty in compounding of ultra-high molecular weight polyethylene fiber, people have begun to develop porous ultra-high molecular weight polyethylene fiber.

[0003] Patent CN101205633A discloses a preparation method of porous hollow high-strength high-modulus ultra-high molecular weight polyethylene fiber, which is made by using a slit spinneret and a wet spinning process. Patent CN108004605A discloses a medium-strength porous ultra-high molecular weight polyethylene fiber and a preparation method thereof, which is made by using a wet spinning process and forming pores by an extraction solvent, and is used for seawater uranium extraction, etc. Patent CN104746165A discloses an ultra-high molecular weight polyethylene porous fiber and a preparation method thereof, which is made by using a wet spinning process to form a fiber with a porosity of 23.60%-58.99%, and is used for seawater uranium extraction and water absorption material. Patent CN112323158A discloses a preparation method of porous active ultra-high molecular weight polyethylene fiber, polyethylene fiber and application thereof, which is made by forming pores by dissolving inorganic salts such as sodium chloride in water during hot drawing, and is used for cement composite fiber. SUMMARY

[0004] In the prior art, the surface of the ultra-high molecular weight polyethylene fiber is smooth, the molecular structure is inert, and it is difficult to be compounded with organic glue. The prepared composite material has low peeling strength, especially in high-pressure scenarios such as high-pressure airbags, etc., which causes peeling failure. On the other hand, in the prior art, the ultra-high molecular weight polyethylene fiber has a dense structure, the molecular structure is inert, it does not absorb water, and the modulus is high. Therefore, in the application of clothing and home textiles, it is not soft, not moisture-permeable, the touch feeling is not good, not easy to color, and the color fastness is low. The present application provides a porous ultra-high molecular weight polyethylene fiber, which can solve the problems of smooth surface of ultra-high molecular weight polyethylene fiber, difficulty in adsorption and compounding. On the other hand, it can provide good softness and moisture permeability for clothing and home textile fabrics.

[0005] Specifically, the present application relates to the following aspects.

[0006] 1. A manufacturing method of a porous ultra-high molecular weight polyethylene fiber, comprising the following steps:

[0007] 1) mixing ultra-high molecular weight polyethylene, acid-soluble inorganic particles and solvent to prepare a dope,

[0008] 2) extruding the dope to form a spinning stream,

[0009] 3) removing at least a portion (such as at least 50 wt%, preferably at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt% or at least 97 wt%) of the solvent from the spinning stream to obtain a dry as-spun filament,

[0010] 4) drawing the dry as-spun filament in one or more stages (such as 2-10 or 2-6 stages) to obtain a pre-drawn filament,

[0011] 5) immersing the pre-drawn filament through an acid bath under ultrasonic or non-ultrasonic conditions to dissolve the acid-soluble inorganic particles to obtain the porous ultra-high molecular weight polyethylene fiber.

[0012] 2. The manufacturing method according to any of the preceding or subsequent aspects, wherein in step 1), the acid-soluble inorganic particles are used in an amount of 0.5-50 parts by weight (preferably 1-10 parts by weight) and the solvent is used in an amount of 100-3000 parts by weight (preferably 200-400 parts by weight) per 100 parts by weight of the ultra-high molecular weight polyethylene.

[0013] 3. The manufacturing method according to any of the preceding or subsequent aspects, wherein in step 1), the solvent is selected from at least one of white oil, mineral oil, naphthalene, decalin, tetralin, kerosene, xylene, toluene, petroleum distillate, halogenated hydrocarbon, cycloalkane, cycloalkene, preferably decalin.

[0014] 4. The manufacturing method according to any of the preceding or subsequent aspects, wherein in step 1), the acid-soluble inorganic particles have an average particle size of 0.02-50 μm (preferably 0.5-5 μm).

[0015] 5. The manufacturing method according to any of the preceding or subsequent aspects, wherein in step 1), the acid-soluble inorganic particles are selected from at least one of calcium carbonate, sodium carbonate, sodium bicarbonate, magnesium carbonate (preferably calcium carbonate particles, particularly light calcium carbonate particles).

[0016] 6. The manufacturing method according to any of the preceding or subsequent aspects, wherein in step 1), the difference between the relative density of the ultra-high molecular weight polyethylene and the bulk density of the acid-soluble inorganic particles is 0.10 g / cm 3 (preferably 0.25-0.60 g / cm 3 ).

[0017] 7. The production method according to any one of the preceding or following aspects, wherein in step 1), the ultrahigh molecular weight polyethylene has a viscosity average molecular weight of 1 million to 9 million (preferably 3 million to 5 million).

[0018] 8. The production method according to any one of the preceding or following aspects, wherein in step 1), the acid-soluble inorganic particles are mixed with the solvent, and then mixed with the ultrahigh molecular weight polyethylene.

[0019] 9. The production method according to any one of the preceding or following aspects, wherein in step 2), the extrusion temperature is 150 to 250°C (preferably 170 to 190°C) in the presence or absence of stretching; and the draw ratio is 0 to 50 (preferably 2 to 20) in the presence of stretching.

[0020] 10. The production method according to any one of the preceding or following aspects, wherein in step 3), at least a portion of the solvent is removed from the spinning stream by evaporation.

[0021] 11. The production method according to any one of the preceding or following aspects, wherein in step 3), the operating conditions of the evaporation include: the evaporation temperature is higher than the solvent flash temperature by 0.5 to 10°C (preferably 1 to 5°C) in the presence or absence of stretching; and the draw ratio is 1 to 10 (preferably 2 to 5) in the presence of stretching.

[0022] 12. The production method according to any one of the preceding or following aspects, wherein in step 3), the spinning stream is cooled to obtain a gel filament, and then at least a portion of the solvent is removed by evaporation and / or extraction.

[0023] 13. The production method according to any one of the preceding or following aspects, wherein the operating conditions of the cooling include: the cooling temperature is -50 to 100°C (preferably 20 to 50°C) in the presence or absence of stretching; and the draw ratio is 1 to 10 (preferably 2 to 5) in the presence of stretching.

[0024] 14. The production method according to any one of the preceding or following aspects, wherein the operating conditions of the evaporation include: the evaporation temperature is higher than the solvent flash temperature by 0.5 to 10°C (preferably 1 to 5°C) in the presence or absence of stretching; and the draw ratio is 1 to 10 (preferably 2 to 5) in the presence of stretching, or the operating conditions of the extraction include: the extraction temperature is 10 to 150°C (preferably 40 to 90°C) in the presence or absence of stretching; and the draw ratio is 1 to 10 (preferably 2 to 5) in the presence of stretching, and the extraction agent is a volatile hydrocarbon solvent (preferably at least one selected from the group consisting of xylene and heptane).

[0025] 15. The manufacturing method of any of the preceding or following aspects, wherein in step 4), the operating conditions of the stretching include: 1-10 (preferably 2-5) stretching stages, a stretching temperature of 90-170°C (preferably 130-150°C), and a stretching ratio of 2-500 (preferably 4-250).

[0026] 16. The manufacturing method of any of the preceding or following aspects, wherein in step 4), the dry-state precursor filament is first pre-stretched, and then further stretched (referred to as post-stretching) in one or more (such as 1-9 or 1-5) stages, and the pre-stretching ratio is 1-10 (preferably 2-5), and the post-stretching ratio (total) is 2-50 (preferably 5-20).

[0027] 17. The manufacturing method of any of the preceding or following aspects, wherein there is no stretching during the performance of step 5), or there is no stretching operation after the end of step 5).

[0028] 18. The manufacturing method of any of the preceding or following aspects, wherein in step 5), the acid bath comprises at least one acid selected from inorganic acid and organic acid, and a solvent.

[0029] 19. The manufacturing method of any of the preceding or following aspects, wherein the inorganic acid is at least one selected from sulfuric acid, hydrochloric acid, hydrofluoric acid, boric acid, phosphoric acid (preferably at least one selected from sulfuric acid and hydrochloric acid), the organic acid is at least one selected from acetic acid, tartaric acid, oxalic acid, malic acid, citric acid, ascorbic acid, sulfonic acid, sulfinic acid, thiocarboxylic acid (preferably at least one selected from acetic acid and citric acid), and the solvent is at least one selected from glacial acetic acid, ethanol, and water, preferably water.

[0030] 20. The manufacturing method of any of the preceding or following aspects, wherein the pH value of the acid bath is ≤ 6.5 (preferably 2-3).

[0031] 21. The manufacturing method of any of the preceding or following aspects, wherein in step 5), the operating conditions of the dissolving include: a dissolving temperature of 0-80°C (preferably 20-40°C), a dissolving time of 0.5-60 min (preferably 10-20 min), and a frequency of 10-70 Hz (preferably 30-40 Hz) when there is ultrasonic oscillation.

[0032] 22. The manufacturing method of any of the preceding or following aspects, wherein in step 4), an oiling agent is applied to the dry-state precursor filament before the stretching is performed and / or between any two stages.

[0033] 23. The manufacturing method of any of the preceding or following aspects, wherein in step 4) an oiling agent is applied to the dry state filament before the post-drawing is performed and / or between any two stages (if any) of the post-drawing.

[0034] 24. The manufacturing method of any of the preceding or following aspects, wherein the oiling agent is selected from at least one of glycerol ester, mineral oil, laureth, antistatic agent, preferably glycerol ester.

[0035] 25. The manufacturing method of any of the preceding or following aspects, wherein the oiling agent is used in an amount of 0-10% (preferably 0.1-3%).

[0036] 26. A porous ultra-high molecular weight polyethylene fiber obtained by the manufacturing method of any of the preceding or following aspects.

[0037] 27. The polyethylene fiber of any of the preceding or following aspects, having a porosity of 5-40% (preferably 10-20%) and a fiber strength of 10-40 cN / dtex (preferably 15-25 cN / dtex).

[0038] 28. A fabric comprising the porous ultra-high molecular weight polyethylene fiber of any of the preceding or following aspects or manufactured by the manufacturing method of any of the preceding or following aspects.

[0039] 29. The fabric of any of the preceding or following aspects, further comprising at least one other fiber selected from natural plant fibers, natural animal fibers, man-made regenerated fibers, synthetic fibers and inorganic fibers.

[0040] Technical effects

[0041] The porous ultra-high molecular weight polyethylene fiber of the present application has micro-nano scale pores distributed on the surface and inside, which makes the fiber more moisture-conductive while ensuring the integrity of the fiber as much as possible, and keeps the fiber cool and comfortable and breathable. The pore structure is easy to color and color-retain, and is suitable for knitting fields such as clothing and home textiles. The pore structure is easy to absorb, and is suitable for making composite materials and adsorption materials. DETAILED DESCRIPTION

[0042] The specific embodiments of the present application are described in detail below, but it should be noted that the scope of protection of the present application is not limited by these specific embodiments, but is determined by the claims of the appendix.

[0043] All publications, patent applications, patents and other references mentioned in this specification are hereby incorporated by reference. Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art. In case of conflict, the present specification, including definitions, will control.

[0044] When the specification derives a material, substance, method, step, device or component etc. with the word head "known to those skilled in the art", "prior art" or similar, the object derived by the word head covers those which are conventionally used in the art at the time of the present application, but also those which are not yet conventionally used, but will become recognized as suitable for similar purposes in the art.

[0045] In the context of the present application, all numerical values of parameters (e.g. amounts or conditions) are to be understood as being modified in all instances by the term "about", unless they are expressly indicated not to be so modified.

[0046] In the context of the present application, the method for measuring porosity is mercury intrusion method.

[0047] In the context of the present application, the method for measuring fiber strength is GB / T 19975-2005.

[0048] In the context of the present application, the method for measuring average particle size is laser scattering method.

[0049] In the context of the present application, the peeling strength is tested according to FZ / T 60011-2016, the rubbing fastness is tested according to GB / T 3920-2008, and the soaping fastness is tested according to GB / T 3921-2008.

[0050] In the absence of explicit indication, all percentages, parts, ratios, etc. mentioned in the present specification are based on weight, and the pressure is gauge pressure.

[0051] In the context of the present application, any two or more embodiments or aspects of the present application can be combined arbitrarily, and the technical solutions thus formed are part of the original disclosure of the present specification and also fall within the protection scope of the present application.

[0052] According to one embodiment of the present application, there is provided a method for manufacturing a porous ultra-high molecular weight polyethylene fiber, comprising the steps of:

[0053] 1) mixing an ultra-high molecular weight polyethylene, acid-soluble inorganic particles and a solvent to form a spinning solution,

[0054] 2) extruding the spinning solution to form a spinning stream,

[0055] 3) removing at least a portion (such as at least 50 wt%, preferably at least 70 wt%, at least 80 wt%, at least 90 wt%, at least 95 wt% or at least 97 wt%) of the solvent from the spinning stream to obtain a dry as-spun fiber,

[0056] 4) stretching the dry protofilament in one or more stages (such as 2-10 or 2-6 stages) to obtain a pre-drawn filament,

[0057] 5) immersing the pre-drawn filament in an acid bath under ultrasonic or non-ultrasonic conditions to dissolve the acid-soluble inorganic particles to obtain the porous ultrahigh molecular weight polyethylene fiber.

[0058] According to one embodiment of the present application, the ultrahigh molecular weight polyethylene, the antioxidant (optional), the acid-soluble inorganic particles and the solvent are put into a swelling kettle to be swelled, homogenized and prepared into a spinning suspension. Then, the spinning suspension is extruded into a spinning stream through screw shearing dissolution. Subsequently, the spinning stream can be formed into a dry protofilament in two ways: 1) the spinning stream is directly dried to remove the solvent to form a dry protofilament; and 2) the spinning stream is cooled and solidified into a gel pre-drawn filament in a coagulation bath, and then the solvent is removed by extraction or drying to form a dry protofilament.

[0059] According to one embodiment of the present application, in step 1), the acid-soluble inorganic particles are used in an amount of 0.5-50 parts by weight (preferably 1-10 parts by weight) per 100 parts by weight of the ultrahigh molecular weight polyethylene.

[0060] According to one embodiment of the present application, in step 1), the solvent is used in an amount of 100-3000 parts by weight (preferably 200-400 parts by weight) per 100 parts by weight of the ultrahigh molecular weight polyethylene.

[0061] According to one embodiment of the present application, in step 1), the solvent is at least one selected from white oil, mineral oil, naphthalene, decalin, tetrahydronaphthalene, kerosene, xylene, toluene, petroleum distillate, halogenated hydrocarbon, cycloalkane and cycloalkene, preferably decalin.

[0062] According to one embodiment of the present application, in step 1), the acid-soluble inorganic particles have an average particle size of 0.02-50 μm (preferably 0.5-5 μm).

[0063] According to one embodiment of the present application, in step 1), the acid-soluble inorganic particles are not particularly limited and can be any inorganic particles capable of being chemically reacted with an acid (particularly hydrochloric acid or aqueous hydrochloric acid) to be converted into a (water) soluble compound, and at least one selected from calcium carbonate, sodium carbonate, sodium bicarbonate and magnesium carbonate, preferably calcium carbonate, particularly light calcium carbonate particles (which generally have a bulk density of 0.50-0.70 g / cm 3 ) can be mentioned.

[0064] According to one embodiment of the present application, in order to make the technical effects of the present application more excellent, in step 1), the difference (absolute value) between the relative density of the ultra-high molecular weight polyethylene and the bulk density of the acid-soluble inorganic particles is 0.10 g / cm 3 or more, and 0.60 g / cm 3 or less. It is preferable that the relative density of the ultra-high molecular weight polyethylene be greater than the bulk density of the acid-soluble inorganic particles. It is known that the relative density of the ultra-high molecular weight polyethylene is usually 0.90 g / cm 3 .

[0065] According to one embodiment of the present application, in step 1), the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 1 million to 9 million (preferably 3 million to 5 million).

[0066] According to one embodiment of the present application, in order to make the technical effects of the present application more excellent, in step 1), the acid-soluble inorganic particles are mixed with the solvent, and then mixed with the ultra-high molecular weight polyethylene.

[0067] According to one embodiment of the present application, in step 2), the extrusion temperature is 150 to 250°C (preferably 170 to 190°C) in the presence or absence of stretching; and the draw ratio is 0 to 50 (preferably 2 to 20) in the presence of stretching.

[0068] According to one embodiment of the present application, in step 3), at least a part of the solvent is removed from the spinning stream by the method of evaporation (direct evaporation solvent removal method). According to the present application, in addition to the following explicitly described operating conditions, there are no other limitations for the direct evaporation solvent removal method, which can be performed in a manner conventionally known in the art. Here, the operating conditions of the evaporation include the presence or absence of stretching, and the evaporation temperature is higher than the solvent flash temperature by 0.5 to 10°C (preferably 1 to 5°C). The draw ratio is 1 to 10 (preferably 2 to 5) in the presence of stretching.

[0069] According to one embodiment of the present application, in step 3), the spinning stream is cooled to obtain a gel filament (gel spinning method), and then at least a part of the solvent is removed by the method of evaporation and / or extraction. According to the present application, in addition to the following explicitly described operating conditions, there are no other limitations for the gel spinning method, which can be performed in a manner conventionally known in the art.

[0070] According to one embodiment of the present application, the operating conditions of the cooling include the presence or absence of stretching, and the cooling temperature is -50 to 100°C (preferably 20 to 50°C); and the draw ratio is 1 to 10 (preferably 2 to 5) in the presence of stretching.

[0071] According to one embodiment of the present application, the operating conditions of the evaporation include: presence or absence of stretching, the evaporation temperature is higher than the solvent flash evaporation temperature by 0.5-10°C (preferably 1-5°C); in the presence of stretching, the stretching ratio is 1-10 (preferably 2-5).

[0072] According to one embodiment of the present application, the operating conditions of the extraction include: presence or absence of stretching, the extractant is a volatile hydrocarbon solvent, the extraction temperature is 10-150°C (preferably 40-90°C); in the presence of stretching, the stretching ratio is 1-10 (preferably 2-5). Here, as the volatile hydrocarbon solvent, for example, at least one of xylene, heptane can be cited.

[0073] According to one embodiment of the present application, in step 4), the operating conditions of the stretching include: the number of stretching stages is 1-10 (preferably 2-5), the stretching temperature is 90-170°C (preferably 130-150°C), and the stretching ratio is 2-500 (preferably 4-250).

[0074] According to one embodiment of the present application, in step 4), the dry state of the yarn is first pre-stretched, and then further stretched (called post-stretching) in one or more stages (such as 1-9 or 1-5 stages), and the pre-stretching ratio is 1-10 (preferably 2-5), and the post-stretching ratio (total) is 2-50 (preferably 5-20).

[0075] According to one embodiment of the present application, there is no stretching during the performance of step 5), or there is no stretching operation after the end of step 5).

[0076] According to one embodiment of the present application, in step 5), the acid bath contains at least one acid selected from inorganic acid and organic acid, and a solvent.

[0077] According to one embodiment of the present application, the inorganic acid is selected from at least one of sulfuric acid, hydrochloric acid, hydrofluoric acid, boric acid, phosphoric acid, preferably at least one of sulfuric acid, hydrochloric acid, and in particular hydrochloric acid.

[0078] According to one embodiment of the present application, the organic acid is selected from at least one of acetic acid, tartaric acid, oxalic acid, malic acid, citric acid, ascorbic acid, sulfonic acid, sulfinic acid, thiocarboxylic acid, preferably at least one of acetic acid and citric acid.

[0079] According to one embodiment of the present application, the solvent is selected from at least one of glacial acetic acid, ethanol, and water, preferably water.

[0080] According to one embodiment of the present application, the pH value of the acid bath is ≤6.5 (preferably 2-3).

[0081] According to one embodiment of the present application, in step 5), the operation condition of the dissolving includes: the temperature of the dissolving is 0-80°C (preferably 20-40°C), the time of the dissolving is 0.5-60 min (preferably 10-20 min). When there is ultrasonic oscillation, the frequency is 10-70 Hz (preferably 30-40 Hz).

[0082] According to one embodiment of the present application, in step 4), an oil agent is applied to the dry state of the filament before the stretching is performed and / or between any two stages. Alternatively, an oil agent is applied to the dry state of the filament before the post-stretching is performed and / or between any two stages of the post-stretching (if any). According to the present application, due to the roughness of the fiber surface added with the superacid-soluble inorganic particles, the fiber surface is easily damaged during the subsequent drawing process, thus generally requiring oil film protection.

[0083] According to one embodiment of the present application, the oil agent is selected from at least one of glycerol ester, mineral oil, lauryl alcohol polyoxyethylene ether, and antistatic agent, preferably glycerol ester.

[0084] According to one embodiment of the present application, the amount of the oil agent is 0-10% (preferably 0.1-3%).

[0085] According to one embodiment of the present application, the present application further relates to a porous ultrahigh molecular weight polyethylene fiber, which is obtained by the manufacturing method described above.

[0086] According to one embodiment of the present application, the porosity of the polyethylene fiber is 5-40% (preferably 10-20%).

[0087] According to one embodiment of the present application, the fiber strength of the polyethylene fiber is 10-40 cN / dtex (preferably 15-25 cN / dtex).

[0088] According to one embodiment of the present application, the present application further relates to a fabric, which comprises the porous ultrahigh molecular weight polyethylene fiber described above or the porous ultrahigh molecular weight polyethylene fiber manufactured by the manufacturing method described above. According to the present application, as the fabric, a composite fabric is made, the peeling strength of which is ≥20 N / m, and the rubbing fastness and the soaping fastness reach level 5.

[0089] According to one embodiment of the present application, 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.

[0090] Examples

[0091] The present invention will be further described in detail below with reference to examples and comparative examples, but the present invention is not limited to these examples.

[0092] Example 1

[0093] The porous ultra-high molecular weight polyethylene fiber in this embodiment is obtained through the following process:

[0094] The acid-soluble inorganic particles are light calcium carbonate, and the difference between their bulk density and the relative density of ultra-high molecular weight polyethylene is 0.4 g / cm³. 3 The average particle size is 1 μm. After being uniformly dispersed in decahydronaphthalene solvent, it is then mixed with ultra-high molecular weight polyethylene (UHMWPE) to form a swollen suspension. The mass ratio of UHMWPE:calcium carbonate:decahydronaphthalene is 100:2:1300. The suspension is dissolved by screw shearing and extruded at 180℃ under 8 times stretching conditions to form spun fine streams. Direct evaporation is used to remove the solvent, with the evaporation temperature 3℃ higher than the flash evaporation temperature of decahydronaphthalene and a stretching ratio of 3. This step removes at least 95% of the solvent residue. Then, it passes through 3 stretching stages at a stretching temperature of 140-147℃ and a stretching ratio of 20. Afterward, it passes through a dilute hydrochloric acid bath (pH=3, prepared with hydrochloric acid and water) with a stretching ratio of 1.45 and is dissolved by ultrasonic vibration at 30℃ and 30Hz for 15 minutes. Finally, it is oiled by an oiler with an oiling rate of 0.5%, ultimately forming 400D porous UHMWPE fibers. Mercury intrusion porosimetry showed a porosity of 17.8% and a fiber strength of 24.43 cN / dtex. The fibers were woven into a plain weave fabric and then laminated with polyurethane material; the peel strength was tested to be 60.51 N / m. After impregnation and dyeing, the fibers, when knitted into fabric, achieved a color fastness to rubbing and washing of grade 5.

[0095] Example 2

[0096] Same as Example 1, except that the acid-soluble inorganic particles are heavy calcium carbonate, and the difference between their bulk density and the relative density of ultra-high molecular weight polyethylene is 0.27 g / cm³. 3 This embodiment ultimately produces 400D porous ultra-high molecular weight polyethylene fiber. Mercury intrusion porosimetry testing revealed a porosity of 13.5% and a fiber strength of 23.12 cN / dtex. The fiber was woven into a plain weave fabric and then laminated with polyurethane material, achieving a peel strength of 45.02 N / m. After impregnation and dyeing, the fiber, when knitted into fabric, achieved a color fastness to rubbing and washing of grade 5.

[0097] Example 3

[0098] Same as Example 1, except that the acid-soluble inorganic particles are sodium carbonate, and the difference between its bulk density and the relative density of ultra-high molecular weight polyethylene is 0.30 g / cm³. 3The final product of this example is a 400D porous UHMWPE fiber. The porosity is 14.21% and the fiber strength is 25.08 cN / dtex as tested by mercury intrusion method. The fiber is woven into a plain cloth and is compounded with polyurethane material. The peel strength is 46.32 N / m. The fiber is colored by dipping in glue and is knitted into cloth. The rubbing fastness and the soaping fastness are both 5.

[0099] Example 4

[0100] The same as example 1 except that the calcium carbonate is not premixed with the solvent but is mixed directly with the UHMWPE and the solvent. The final product of this example is a 400D porous UHMWPE fiber. The porosity is 8.3% and the fiber strength is 16.71 cN / dtex as tested by mercury intrusion method. The fiber is woven into a plain cloth and is compounded with polyurethane material. The peel strength is 30.05 N / m. The fiber is colored by dipping in glue and is knitted into cloth. The rubbing fastness is 4 and the soaping fastness is 4.

[0101] Example 5

[0102] The same as example 1 except that there is only one drawing section instead of three. The drawing temperature is 155°C and the draw ratio is 13. The final product of this example is a 400D porous UHMWPE fiber. The porosity is 5.6% and the fiber strength is 13.47 cN / dtex as tested by mercury intrusion method. The fiber is woven into a plain cloth and is compounded with polyurethane material. The peel strength is 27.34 N / m. The fiber is colored by dipping in glue and is knitted into cloth. The rubbing fastness is 4 and the soaping fastness is 4.

[0103] Example 6

[0104] The same as example 1 except that there is no drawing in the bath. The final product of this example is a 400D porous UHMWPE fiber. The porosity is 11.2% and the fiber strength is 18.73 cN / dtex as tested by mercury intrusion method. The fiber is woven into a plain cloth and is compounded with polyurethane material. The peel strength is 40.12 N / m. The fiber is colored by dipping in glue and is knitted into cloth. The rubbing fastness is 4 and the soaping fastness is 4.

[0105] Example 7

[0106] The same as example 1, except that citric acid is used, pH = 6.0. The 400D porous UHMWPE fiber is formed in this example. The porosity is 10.2% and the fiber strength is 22.15 cN / dtex by mercury intrusion method. The fiber is woven into a plain cloth and is compounded with polyurethane material. The peel strength is 37.82 N / m. The color fastness to rubbing is 4 and the color fastness to soaping is 4 after the fiber is colored by dipping and knitted into a cloth.

[0107] Example 8

[0108] The same as example 1, except that the direct evaporation of the solvent is not used. Instead, the gel method is used. The cooling temperature is 30°C and the draw ratio during cooling is 2.7. Then the solvent is evaporated. The process is the same as example 1. The 400D porous UHMWPE fiber is formed in this example. The porosity is 15.0% and the fiber strength is 24.15 cN / dtex by mercury intrusion method. The fiber is woven into a plain cloth and is compounded with polyurethane material. The peel strength is 59.23 N / m. The color fastness to rubbing is 5 and the color fastness to soaping is 5 after the fiber is colored by dipping and knitted into a cloth.

[0109] Example 9

[0110] The same as example 1, except that white oil is used as the solvent. The mass ratio of UHMWPE: calcium carbonate: white oil is 100:2:1400. The cooling temperature is 25°C and the draw ratio during cooling is 3.0. Xylene is used for extraction. The extraction temperature is 50°C and the draw ratio during extraction is 2.1. The 400D porous UHMWPE fiber is formed in this example. The porosity is 12.8% and the fiber strength is 20.06 cN / dtex by mercury intrusion method. The fiber is woven into a plain cloth and is compounded with polyurethane material. The peel strength is 35.28 N / m. The color fastness to rubbing is 4 and the color fastness to soaping is 4 after the fiber is colored by dipping and knitted into a cloth.

[0111] Example 10

[0112] The same as example 1, except that the mass ratio of UHMWPE: calcium carbonate: decalin is 100:20:1300. The 400D porous UHMWPE fiber is formed in this example. The porosity is 25.0% and the fiber strength is 8.81 cN / dtex by mercury intrusion method. The fiber is woven into a plain cloth and is compounded with polyurethane material. The peel strength is 23.15 N / m. The color fastness to rubbing is 3 and the color fastness to soaping is 4 after the fiber is colored by dipping and knitted into a cloth.

[0113] Example 11

[0114] The same as example 1, except that the acid-soluble inorganic particles are a mixture of heavy calcium carbonate and light calcium carbonate, and the difference between the bulk density of the acid-soluble inorganic particles and the relative density of the ultra-high molecular weight polyethylene is 0.20 g / cm 3 The final product of this example is a 400D porous ultra-high molecular weight polyethylene fiber. The porosity is 9.5% by mercury porosimetry, and the fiber strength is 10.23 cN / dtex. The fiber is woven into a plain cloth and is compounded with a polyurethane material, and the peel strength is 32.17 N / m. The fiber is colored by dipping in glue, and after being knitted into cloth, the rubbing fastness is 4, and the soaping fastness reaches 4.

[0115] Example 12

[0116] The same as example 1, except that the acid-soluble inorganic particles are magnesium carbonate, and the difference between the bulk density of the acid-soluble inorganic particles and the relative density of the ultra-high molecular weight polyethylene is 0.65 g / cm 3 The final product of this example is a 400D porous ultra-high molecular weight polyethylene fiber. The porosity is 10.6% by mercury porosimetry, and the fiber strength is 7.81 cN / dtex. The fiber is woven into a plain cloth and is compounded with a polyurethane material, and the peel strength is 36.25 N / m. The fiber is colored by dipping in glue, and after being knitted into cloth, the rubbing fastness is 4, and the soaping fastness reaches 4.

[0117] Example 13

[0118] The same as example 1, except that the evaporation temperature is 5°C higher than the decahydronaphthalene flash temperature, and the draw ratio is 5, and at least 98% of the solvent residue is removed. The final product of this example is a 400D porous ultra-high molecular weight polyethylene fiber. The porosity is 15.32% by mercury porosimetry, and the fiber strength is 24.71 cN / dtex. The fiber is woven into a plain cloth and is compounded with a polyurethane material, and the peel strength is 42.31 N / m. The fiber is colored by dipping in glue, and after being knitted into cloth, the rubbing fastness is 5, and the soaping fastness reaches 5.

[0119] Example 14

[0120] The same as example 1, except that dilute sulfuric acid is used, and the pH is 2.0. The final product of this example is a 400D porous ultra-high molecular weight polyethylene fiber. The porosity is 18.9% by mercury porosimetry, and the fiber strength is 23.28 cN / dtex. The fiber is woven into a plain cloth and is compounded with a polyurethane material, and the peel strength is 53.31 N / m. The fiber is colored by dipping in glue, and after being knitted into cloth, the rubbing fastness is 5, and the soaping fastness reaches 5.

[0121] Example 15

[0122] The same as example 1, except that instead of 3 stretching sections, 5 stretching sections were used, with a stretching temperature of 145°C and a stretching ratio of 20. The final product was a 400D porous UHMWPE fiber. The porosity was 16.8% by mercury intrusion method, and the fiber strength was 22.38 cN / dtex. The fiber was woven into a plain cloth and was combined with a polyurethane material, and the peel strength was 41.23 N / m. The fiber was colored by dipping in glue, and after being knitted into cloth, the rubbing fastness was 5 levels, and the soaping fastness reached 5 levels.

[0123] Comparative Example 1

[0124] The fiber was a commercially available LY25 400D UHMWPE fiber.

[0125] Comparative Example 2

[0126] The same as example 1, except that the fiber was first immersed in a bath of dilute hydrochloric acid (hydrochloric acid and water) with a pH of 3, and the stretching ratio in the bath was 1.45, and the fiber was dissolved by ultrasonic oscillation at 30°C and 30 Hz for 15 min, and then 3 stretching sections were used, with a stretching temperature of 140-147°C and a stretching ratio of 20. The final product was a 400D porous UHMWPE fiber. The porosity was 4.3% by mercury intrusion method, and the fiber strength was 18.23 cN / dtex. The fiber was woven into a plain cloth and was combined with a polyurethane material, and the peel strength was 20.12 N / m. The fiber was colored by dipping in glue, and after being knitted into cloth, the rubbing fastness was 2 levels, and the soaping fastness reached 3 levels.

[0127] Comparative Example 3

[0128] The same as example 1, except that the light calcium carbonate was replaced by sodium chloride. The final product was a 400D porous UHMWPE fiber. The porosity was 3.7% by mercury intrusion method, and the fiber strength was 14.58 cN / dtex. The fiber was woven into a plain cloth and was combined with a polyurethane material, and the peel strength was 19.23 N / m. The fiber was colored by dipping in glue, and after being knitted into cloth, the rubbing fastness was 2 levels, and the soaping fastness reached 3 levels.

[0129] Comparative Example 4

[0130] The same as example 1, except that the fiber was first immersed in an acid bath and then solvent removal was performed. This example resulted in too many broken fibers, making it impossible to form effective finished fibers.

[0131]

Claims

1. A method for producing a porous ultra-high molecular weight polyethylene fiber, comprising the steps of: 1) mixing an acid-soluble inorganic particle with a solvent, and then mixing the mixture with an ultra-high molecular weight polyethylene to prepare a dope, wherein the acid-soluble inorganic particle is used in an amount of 0.5 to 50 parts by weight, and the solvent is used in an amount of 100 to 3000 parts by weight, with respect to 100 parts by weight of the ultra-high molecular weight polyethylene, and the acid-soluble inorganic particle is at least one particle selected from the group consisting of calcium carbonate, sodium carbonate, sodium bicarbonate, and magnesium carbonate, 2) extruding the dope to form a spinning stream, 3) removing at least 95 wt% of the solvent from the spinning stream to obtain a dry as-spun fiber, 4) pre-stretching the dry as-spun fiber, and then further stretching the dry as-spun fiber in 1 to 9 stages, referred to as post-stretching, wherein the stretching ratio of the pre-stretching is 1 to 10, and the total stretching ratio of the post-stretching is 2 to 50, and the stretching temperature is 90 to 170°C, to obtain a pre-drawn fiber, 5) immersing the pre-drawn fiber in an acid bath under the condition of stretching with or without ultrasonic wave to dissolve the acid-soluble inorganic particle, to obtain the porous ultra-high molecular weight polyethylene fiber.

2. The method for producing according to claim 1, wherein in the step 1), the acid-soluble inorganic particle is used in an amount of 1 to 10 parts by weight, and the solvent is used in an amount of 200 to 400 parts by weight, with respect to 100 parts by weight of the ultra-high molecular weight polyethylene.

3. The method for producing according to claim 1, wherein in the step 2), the extrusion temperature is 150 to 250°C, with or without stretching, and the stretching ratio is 2 to 50 when stretching is present.

4. The method for producing according to claim 1, wherein in the step 2), the extrusion temperature is 170 to 190°C, with or without stretching, and the stretching ratio is 2 to 20 when stretching is present.

5. The method for producing according to claim 1, wherein in the step 3), at least a part of the solvent is removed from the spinning stream by evaporation, or the spinning stream is cooled to obtain a gel fiber, and then at least a part of the solvent is removed by evaporation and / or extraction.

6. The method for producing according to claim 1, wherein in the step 4), the stretching ratio of the pre-stretching is 2 to 5, and / or the total stretching ratio of the post-stretching is 5 to 20. wherein, in step 1), the difference between the relative density of the ultra-high molecular weight polyethylene and the bulk density of the acid-soluble inorganic particles is 0.25 to 0.60 g / cm 3 .

7. The method for producing according to claim 1, wherein in the step 5), the acid bath comprises at least one acid selected from the group consisting of inorganic acid and organic acid, and a solvent.

8. The method for producing according to claim 7, wherein the inorganic acid is at least one selected from the group consisting of sulfuric acid, hydrochloric acid, boric acid, and phosphoric acid, the organic acid is at least one selected from the group consisting of acetic acid, tartaric acid, oxalic acid, malic acid, citric acid, and ascorbic acid, and the solvent is at least one selected from the group consisting of glacial acetic acid, ethanol, and water. The pH value of the acid bath is ≤ 6.5, the dissolution temperature is 20 to 80°C, the dissolution time is 0.5 to 60 minutes, and the frequency is 10 to 70 Hz when ultrasonic wave is present. ​ ​ ​ ​ ​ 9. The production method of claim 1, wherein in step 5), the operation conditions of the dissolving include: ​ 10. The manufacturing method of claim 1, wherein in step 5), the operating conditions of the dissolving include: The pH value of the acid bath is 2-3, the dissolving temperature is 20-40℃, the dissolving time is 10-20 min, and the frequency is 30-40 Hz when ultrasonic oscillation is used.

11. A porous ultra-high molecular weight polyethylene fiber obtained by the production method according to any one of claims 1 to 10.

12. The polyethylene fiber according to claim 11, having a porosity of 5-40% and a fiber strength of 10-40 cN / dtex.

13. The polyethylene fiber according to claim 11, having a porosity of 10-20% and a fiber strength of 15-25 cN / dtex.

14. A fabric comprising the porous ultra-high molecular weight polyethylene fiber according to claim 11.

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