A through-hole type 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 through-hole type ultra-high molecular weight polyethylene fiber, its manufacturing method and its application.The manufacturing method of the through-hole type ultra-high molecular weight polyethylene fiber of the present application includes the following steps: 1) mix ultra-high molecular weight polyethylene, acid-soluble inorganic particles and solvent to prepare spinning solution, 2) extrude the spinning solution to form spinning stream, 3) remove at least a portion of the solvent from the spinning stream to obtain dry protofilament, 4) stretch the dry protofilament in two or more stages, and at the same time as the one or more stages of these stages are carried out, spray acid solution to the dry protofilament to dissolve the acid-soluble inorganic particles, obtain the through-hole type ultra-high molecular weight polyethylene fiber.The through-hole type ultra-high molecular weight polyethylene fiber of the present application can float on seawater and quickly absorb oil, solving the problem of fast diffusion and difficult collection of oil spill.

Description

TECHNICAL FIELD

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

[0002] Marine oil spill has great harm to marine ecology, how to quickly remove oil and prevent diffusion has always been a difficult problem. Ultra-high molecular weight polyethylene fiber has a density less than water, and can float on the water surface, which is a good choice for oil removal from this perspective. However, the compact and regular molecular chain structure of ultra-high molecular weight polyethylene leads to low oil absorption rate, which makes it difficult to be applied in the field of marine oil removal. The present application solves this problem by using the method of engraving to prepare ultra-high molecular weight polyethylene fiber with oil guiding through holes, and making oil absorption felt. SUMMARY

[0003] The present application aims to provide a fiber with oil guiding through holes and a felt made of the fiber, which can float on the sea water and quickly absorb oil, solving the problems of fast oil spill and difficult collection.

[0004] Specifically, the present application relates to the following aspects.

[0005] 1. A manufacturing method of a through-hole type ultra-high molecular weight polyethylene fiber, comprising the following steps:

[0006] 1) mixing ultra-high molecular weight polyethylene, acid-soluble inorganic particles and a solvent to prepare a spinning solution,

[0007] 2) extruding the spinning solution to form a spinning stream,

[0008] 3) removing at least a part (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 primary filament,

[0009] 4) stretching the dry primary filament in two or more stages (such as 2-10 or 2-6 stages), and at the same time of one or more of these stages, spraying an acid solution to the dry primary filament to dissolve the acid-soluble inorganic particles, to obtain the through-hole type ultra-high molecular weight polyethylene fiber.

[0010] 2. The manufacturing method of any of the preceding or subsequent aspects, wherein in step 1), the amount of the acid-soluble inorganic particles is 0.5-50 parts by weight (preferably 1-10 parts by weight) and the amount of the solvent is 500-1000 parts by weight (preferably 8-20 parts by weight) relative to 100 parts by weight of the ultra-high molecular weight polyethylene.

[0011] 3. The production method according to any one of the preceding or following aspects, wherein in step 1), the solvent is selected from at least one of naphthalene, decalin, tetralin, kerosene, xylene, toluene, petroleum fractions, halogenated hydrocarbons, cycloalkanes, and cycloolefins, preferably decalin.

[0012] 4. The manufacturing method according to any of the preceding or following aspects, wherein in step 1), the average particle size of the acid-soluble inorganic particles is 0.02-20 μm (preferably 0.5-5 μm), the acid-soluble inorganic particles are selected from at least one of calcium carbonate, sodium carbonate, sodium bicarbonate, and magnesium carbonate (preferably calcium carbonate, especially light calcium carbonate), and 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 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 ultra-high molecular weight polyethylene.

[0014] 6. The manufacturing method described in any of the above or below 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 0.20 g / cm3 or more (preferably 0.25-0.60 g / cm3).

[0015] 7. The manufacturing method according to any of the preceding or following aspects, wherein in step 2), stretching is present or absent, the extrusion temperature is 150-250°C (preferably 170-190°C), the spinneret micropore diameter is 0.1-5 mm (preferably 0.5-1.5 mm); when stretching is present, the stretching ratio is 0-50 (preferably 2-20).

[0016] 8. The manufacturing method according to any one of the preceding or following aspects, wherein in step 3), the spinning stream is cooled to obtain gel filaments, and then at least a portion of the solvent is removed by evaporation and / or extraction.

[0017] 9. The manufacturing method described in any of the above or below aspects, wherein the cooling operating conditions include: with or without stretching, the cooling temperature is -50-100°C (preferably 20-50°C); when stretching is present, the stretching ratio is 1-10 (preferably 2-5).

[0018] 10. The manufacturing method described in any of the above or following aspects, wherein the operating conditions of the evaporation include: with or without stretching, the evaporation temperature is 0.5-10°C (preferably 1-5°C) higher than the solvent flash temperature; when stretching is present, the stretching ratio is 1-10 (preferably 2-5); or, the operating conditions of the extraction include: with or without stretching, the extraction agent is a volatile hydrocarbon solvent (preferably selected from at least one of xylene and heptane), the extraction temperature is 10-150°C (preferably 40-90°C); when stretching is present, the stretching ratio is 1-10 (preferably 2-5).

[0019] 11. The manufacturing method described in any of the above or following aspects, wherein in step 4), the stretching operating conditions include: 1-10 stretching sections (preferably 2-5), a stretching temperature of 90-170°C (preferably 130-150°C), and a stretching ratio of 2-500 (preferably 4-250).

[0020] 12. The manufacturing method described in any of the above or following aspects, wherein in step 4), the dry raw yarn is first pre-stretched, and then the dry raw yarn is further stretched (called post-stretching) in one or more stages (such as 1-9 or 1-5), and the spraying is carried out while the post-stretching is being carried out.

[0021] 13. The manufacturing method according to any one of the preceding or following aspects, wherein the stretching ratio of the pre-stretching is 1-10 (preferably 2-5), and the stretching ratio (total) of the post-stretching is 2-50 (preferably 5-20).

[0022] 14. The production method according to any one of the preceding or following aspects, wherein in step 4), the acidic solution comprises at least one acid selected from inorganic acids and organic acids, and a solvent, and the pH value of the acidic bath is ≤ 6 (preferably 2-3).

[0023] 15. The production method described in any of the preceding or following aspects, wherein the inorganic acid is selected from at least one of sulfuric acid, hydrochloric acid, hydrofluoric acid, boric acid, and phosphoric acid (preferably selected from at least one of sulfuric acid and hydrochloric acid), 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, and thiocarboxylic acid (preferably selected from at least one of acetic acid and citric acid), and the solvent is selected from at least one of glacial acetic acid, ethanol, and water, preferably water.

[0024] 16. The manufacturing method described in any of the preceding or following aspects, wherein in step 4), the spraying operating conditions include: spraying pressure 0.1-10 MPa (preferably 0.5-1 MPa), spraying time 1-120 min (preferably 10-30 min), and spraying temperature 0-100°C (preferably 30-50°C).

[0025] 17. The manufacturing method described in any of the above or the following aspects further includes the steps of washing, extrusion curling and cutting the through-hole ultra-high molecular weight polyethylene fiber.

[0026] 18. The manufacturing method according to any one of the preceding or following aspects, wherein an oil is applied to the dry raw yarn before the post-stretching is performed.

[0027] 19. The method of any one of the preceding or following aspects, wherein at least one of glycerides, mineral oils, lauryl alcohol polyoxyethylene ether, and antistatic agents, preferably glycerides, is used in an amount of 0-10% (preferably 0.1-3%).

[0028] 20. The 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.

[0029] 21. The manufacturing method described in any of the above or following aspects, wherein in step 3), the operating conditions of the evaporation include: with or without stretching, the evaporation temperature is 0.5-10°C (preferably 1-5°C) higher than the solvent flash temperature; when stretching is present, the stretching ratio is 1-10 (preferably 2-5).

[0030] 22. A through-hole ultra-high molecular weight polyethylene fiber obtained by the production method described in any one of the above or below aspects.

[0031] 23. The through-hole ultra-high molecular weight polyethylene fiber described in any of the above or below aspects has a porosity of 1% to 50% (preferably 20% to 30%) and a fiber strength of 1-35 cN / dtex (preferably 5-15 cN / dtex).

[0032] 24. A through-hole ultra-high molecular weight polyethylene staple fiber obtained by the manufacturing method described in any of the above or below aspects, with a curl of at least 1 / 25mm (preferably 3-5 / 25mm) and a length of at least 3mm (preferably 38-78mm).

[0033] 25. A fabric comprising the through-hole ultra-high molecular weight polyethylene fiber described in any one of the preceding or following aspects or the through-hole ultra-high molecular weight polyethylene short fiber described in any one of the preceding or following aspects.

[0034] 26. The fabric according to any one of the preceding or following aspects, further comprising at least one other fiber selected from the group consisting of natural plant fibers, natural animal fibers, artificial regenerated fibers, synthetic fibers, and inorganic fibers.

[0035] 27. Use of the fabric according to any one of the preceding or following aspects as an absorbent material (especially oil-absorbing felt).

[0036] Technical Effects

[0037] The present invention adopts an etching method to prepare ultra-high molecular weight polyethylene fibers with oil-conducting holes. Pre-set calcium carbonate particles are dissolved in the drawing stage to form concave holes. Then, through super-stretching, the concave holes are extended radially to form oil-conducting holes. After the fibers are curled, shaped, and cut short, they are air-laid and pressed into felt. The produced felt can float on the sea, and leaked oil can be quickly absorbed into the interior of the fibers through the capillary effect and is not easy to escape. The ultra-high molecular weight polyethylene felt can float on the water surface, effectively covering the oil leakage area and preventing the oil from spreading. The fiber surface and interior are covered with oil-conducting holes. Through the wicking effect, the leaked oil can be quickly absorbed into the fiber and stored to prevent back leakage, achieving an excellent oil absorption effect. The products made by the air-laid process have more fluffy tissues and larger pores than those made by the traditional combing process, which is convenient for oil absorption and retention. DETAILED DESCRIPTION

[0038] The specific embodiments of the present invention are described in detail below. However, it should be noted that the protection scope of the present invention is not limited by these specific embodiments, but is determined by the claims in the appendix.

[0039] 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 commonly understood by those skilled in the art. In the event of conflict, the definitions in this specification will prevail.

[0040] 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, the objects introduced by the prefix include 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 generally recognized in the art to be suitable for similar purposes.

[0041] In the context of the present invention, all numerical values ​​for parameters (eg, amounts or conditions) are to be understood as being modified in all instances by the term "about," regardless of whether "about" actually appears before the numerical value.

[0042] In the context of the present invention, the method for measuring porosity is mercury intrusion porosimetry.

[0043] In the context of the present invention, the fiber strength is measured according to GB / T 19975.

[0044] In the context of the present invention, the method for measuring the average particle size is laser light scattering.

[0045] In the context of the present invention, the method for measuring oil absorption is the weighing method. Cut an oil absorption felt piece of equal weight W0, immerse it in standard oil for 5 min, take it out, drain and absorb the surface oil with a paper towel, and weigh it W1. (W1-W0) / W0x100=oil absorption rate %.

[0046] All percentages, parts, ratios, etc. mentioned in the present specification are based on weight, unless otherwise indicated. All pressures are gauge pressures, unless otherwise indicated.

[0047] In the context of the present invention, any two or more embodiments or aspects of the present invention 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 invention.

[0048] According to one embodiment of the present invention, a method for manufacturing a through-hole type ultra-high molecular weight polyethylene fiber is provided. According to the present invention, the so-called "through-hole type ultra-high molecular weight polyethylene fiber" refers to an ultra-high molecular weight polyethylene fiber having a through-hole from one end to the other end in the cross section thereof.

[0049] According to one embodiment of the present invention, the method for manufacturing a through-hole type ultra-high molecular weight polyethylene fiber comprises the following steps:

[0050] 1) mixing an ultra-high molecular weight polyethylene, acid-soluble inorganic particles and a solvent to form a spinning solution,

[0051] 2) extruding the spinning solution to form a spinning stream,

[0052] 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,

[0053] 4) stretching the dry as-spun fiber in two or more stages (such as 2-10 or 2-6 stages), and at the same time as one or more of these stages is performed, spraying an acid solution to the dry as-spun fiber to dissolve the acid-soluble inorganic particles to obtain the through-hole type ultra-high molecular weight polyethylene fiber.

[0054] According to one embodiment of the present invention, in step 1), the amount of the acid-soluble inorganic particles is 0.5-50 parts by weight (preferably 1-10 parts by weight) per 100 parts by weight of the ultra-high molecular weight polyethylene.

[0055] According to one embodiment of the present invention, in step 1), the amount of the solvent is 500-1000 parts by weight (preferably 8-20 parts by weight) per 100 parts by weight of the ultra-high molecular weight polyethylene.

[0056] According to one embodiment of the present application, in step 1), the solvent is at least one selected from the group consisting of naphthalene, decalin, tetralin, kerosene, xylene, toluene, petroleum distillate, halogenated hydrocarbon, naphthene, naphthene hydrocarbon, and the like, preferably decalin.

[0057] According to one embodiment of the present application, in step 1), the average particle size of the acid-soluble inorganic particles is 0.02 to 20 μm (preferably 0.5 to 5 μm).

[0058] 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 the group consisting of calcium carbonate, sodium carbonate, sodium bicarbonate, and magnesium carbonate, preferably calcium carbonate, particularly light calcium carbonate particles (having a bulk density of generally 0.50 to 0.70 g / cm 3 ) can be mentioned.

[0059] 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 0.20 g / cm 3 (preferably 0.25 to 0.60 g / cm 3 ). It is preferable that the relative density of the ultra-high molecular weight polyethylene is 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 generally 0.90 to 0.97 g / cm 3 .

[0060] According to one embodiment of the present application, the viscosity average molecular weight of the ultra-high molecular weight polyethylene is 1 to 9 million (preferably 3 to 5 million).

[0061] According to one embodiment of the present application, in step 1), the acid-soluble inorganic particles are mixed with the solvent, and then mixed with the ultra-high molecular weight polyethylene.

[0062] According to one embodiment of the present application, in step 2), the extrusion temperature is 150 to 250°C (preferably 170 to 190°C), and the spinneret orifice diameter is 0.1 to 5 mm (preferably 0.5 to 1.5 mm) in the presence or absence of stretching. In the presence of stretching, the draw ratio is 0 to 50 (preferably 2 to 20).

[0063] According to one embodiment of the present invention, in step 3), at least a portion of the solvent is removed from the spinning stream by evaporation (direct evaporation desolvation method). According to the present invention, there are no other limitations on the direct evaporation desolvation method except for the following specific operating conditions, and it can be carried out in a manner conventionally known in the art. Here, the operating conditions of the evaporation include: with or without stretching, and the evaporation temperature is 0.5-10°C (preferably 1-5°C) higher than the solvent flash temperature. When stretching is present, the stretch ratio is 1-10 (preferably 2-5).

[0064] According to one embodiment of the present invention, in step 3), the spinning stream is cooled to obtain gel filaments (gel spinning method), and then at least a portion of the solvent is removed by evaporation and / or extraction. According to the present invention, except for the following operating conditions, there are no other limitations on the gel spinning method and it can be carried out according to methods conventionally known in the art.

[0065] According to one embodiment of the present invention, the cooling operation conditions include: with or without stretching, the cooling temperature is -50-100°C (preferably 20-50°C). When stretching is present, the stretching ratio is 1-10 (preferably 2-5).

[0066] According to one embodiment of the present invention, the evaporation operating conditions include: with or without stretching, the evaporation temperature is 0.5-10°C (preferably 1-5°C) higher than the solvent flash temperature. When stretching is present, the stretching ratio is 1-10 (preferably 2-5).

[0067] According to one embodiment of the present invention, the extraction operating conditions include: with or without stretching, an extraction temperature of 10-150°C (preferably 40-90°C); when stretching is present, a stretch ratio of 1-10 (preferably 2-5). The extraction solvent is a volatile hydrocarbon solvent, preferably at least one selected from xylene and heptane.

[0068] According to one embodiment of the present invention, in step 4), the stretching operating conditions include: 1-10 stretching sections (preferably 2-5), a stretching temperature of 90-170°C (preferably 130-150°C), and a stretching ratio of 2-500 (preferably 4-250).

[0069] According to one embodiment of the present invention, an oil is applied to the dry raw yarn before the stretching process and / or between any two stages. Alternatively, an oil is applied to the dry raw yarn before the post-stretching process and / or between any two stages (if any) of the post-stretching process. According to the present invention, since the surface of the fiber to which the peracid-soluble inorganic particles are added is rough, it is easily abraded during the subsequent stretching process, resulting in powder loss or fiber surface damage, and therefore an oil film protection is generally required.

[0070] According to one embodiment of the present invention, the oil is selected from at least one of glycerides, mineral oil, lauryl alcohol polyoxyethylene ether, and antistatic agents, preferably glycerides. Here, the amount of the oil is 0-10% (preferably 0.1-3%).

[0071] According to one embodiment of the present invention, in step 4), the dry raw yarn is first pre-stretched, and then further stretched (called post-stretching) in one or more stages (such as 1-9 or 1-5), and the spraying is performed while the post-stretching is performed.

[0072] According to one embodiment of the present invention, the stretching ratio of the pre-stretching is 1-10 (preferably 2-5), and the stretching ratio (total) of the post-stretching is 2-50 (preferably 5-20).

[0073] According to one embodiment of the present invention, in step 4), the acidic liquid comprises at least one acid selected from inorganic acids and organic acids, and a solvent.

[0074] According to one embodiment of the present invention, the pH value of the acidic bath is ≤6 (preferably 2-3).

[0075] According to one embodiment of the present invention, the inorganic acid is selected from at least one of sulfuric acid, hydrochloric acid, hydrofluoric acid, boric acid, and phosphoric acid (preferably selected from at least one of sulfuric acid and hydrochloric acid).

[0076] According to one embodiment of the present invention, 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, and thiocarboxylic acid (preferably selected from at least one of acetic acid and citric acid).

[0077] According to one embodiment of the present invention, the solvent is selected from at least one of glacial acetic acid, ethanol, and water, preferably water.

[0078] According to one embodiment of the present invention, in step 4), the spraying operating conditions include: spraying pressure 0.1-10 MPa (preferably 0.5-1 MPa), spraying time 1-120 min (preferably 10-30 min), and spraying temperature 0-100°C (preferably 30-50°C).

[0079] According to one embodiment of the present invention, the manufacturing method further comprises the steps of washing, extruding, curling and cutting the through-hole ultra-high molecular weight polyethylene fibers.

[0080] According to one embodiment of the present invention, there is also provided a through-hole ultra-high molecular weight polyethylene fiber obtained by the manufacturing method described in any of the preceding or following aspects of this specification. According to the present invention, the through-hole ultra-high molecular weight polyethylene fiber has a porosity of 1% to 50% (preferably 20% to 30%) and a fiber strength of 1-35 cN / dtex (preferably 5-15 cN / dtex).

[0081] According to one embodiment of the present invention, there is also provided a through-hole ultra-high molecular weight polyethylene staple fiber obtained by the manufacturing method described in any of the preceding or following aspects of this specification. According to the present invention, the through-hole ultra-high molecular weight polyethylene staple fiber has a crimp of at least 1 per 25 mm (preferably 3-5 per 25 mm) and a length of at least 3 mm (preferably 38-78 mm).

[0082] According to one embodiment of the present invention, a fabric is provided, comprising the through-hole ultra-high molecular weight polyethylene fiber or the through-hole ultra-high molecular weight polyethylene staple fiber described in any of the preceding or following aspects of this specification. The fabric is particularly suitable for use as an adsorbent material (particularly oil-absorbing felt).

[0083] 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.

[0084] Example

[0085] The present invention is further described in detail below using examples and comparative examples, but the present invention is not limited to these examples.

[0086] Example 1

[0087] The through-hole ultra-high molecular weight polyethylene fiber of this embodiment is obtained by the following process:

[0088] The acid-soluble inorganic particles are light calcium carbonate, the difference between its bulk density and the relative density of ultra-high molecular weight polyethylene is 0.32g / cm 3The average particle size is 2μm. After being evenly dispersed with decalin solvent, it is mixed with ultra-high molecular weight polyethylene to form a swelling suspension. The molecular weight of ultra-high molecular weight polyethylene is 4.5 million. The mass ratio of ultra-high molecular weight polyethylene: calcium carbonate: decalin is 100:5:1300. The suspension is dissolved by screw shearing and extruded at 180°C and 8 times stretching to form a spinning fine stream. The spinneret micropore diameter is 1mm. The solvent is removed by direct evaporation. The evaporation temperature is 3°C higher than the flash temperature of decalin and the stretching ratio is 3. This step removes at least 95% of the solvent residue. The yarn then undergoes three stretching stages at a temperature of 140°C and a stretch ratio of 120, followed by a 3-fold pre-stretch and an 8-fold post-spinning total draft. Simultaneously, it is sprayed with dilute hydrochloric acid (prepared with hydrochloric acid and water) with a pH of 2.5 at a pressure of 0.7 MPa, a spray time of 20 minutes, and a spray temperature of 40°C. The yarn is then oiled with an oil tanker at an oiling rate of 0.5%, ultimately forming the finished filament. The yarn is then cleaned, extruded, crimped, and chopped to obtain staple fibers, which are then pressed into oil-absorbing felt.

[0089] Example 2

[0090] The same as Example 1, except that the amount of calcium carbonate added was 0.6 parts by weight.

[0091] Example 3

[0092] Same as Example 1, except that the average particle size of calcium carbonate is 0.1 μm.

[0093] Example 4

[0094] Same as Example 1, except that the average particle size of calcium carbonate added is 10 μm.

[0095] Example 5

[0096] The same as Example 1, except that the amount of calcium carbonate added was 10 parts by weight.

[0097] Example 6

[0098] As in Example 1, calcium carbonate was not premixed with the solvent, but was directly mixed with the ultra-high molecular weight polyethylene and the solvent.

[0099] Example 7

[0100] Same as Example 1, except that the acid-soluble inorganic particles are magnesium carbonate, and the difference between its bulk density and the relative density of ultra-high molecular weight polyethylene is 0.70 g / cm 3 .

[0101] Example 8

[0102] Same as Example 1, except that the acid-soluble inorganic particles are heavy calcium carbonate, and the difference between its bulk density and the relative density of ultra-high molecular weight polyethylene is 0.15 g / cm3 .

[0103] Example 9

[0104] The same as Example 1, except that the ultra-high molecular weight polyethylene has a molecular weight of 5 million.

[0105] Example 10

[0106] The same as Example 1, except that the ultra-high molecular weight polyethylene has a molecular weight of 2.5 million.

[0107] Example 11

[0108] The same as Example 1, except that the amount of decalin is 2000 parts.

[0109] Example 12

[0110] The same as Example 1, except that the spinneret aperture is 2.0 mm.

[0111] Example 13

[0112] The same as Example 1, except that dilute sulfuric acid, pH = 2, is used.

[0113] Comparative Example 1

[0114] The same as Example 1, except that the light calcium carbonate is replaced by sodium chloride.

[0115] Comparative Example 2

[0116] The same as Example 1, except that the dilute hydrochloric acid is sprayed first, followed by 3-fold pre-drawing and 8-fold total drawing after spinning, compared to Example 1.

[0117] Comparative Example 3

[0118] The fiber is commercially available Forceon LY25 400D ultra-high molecular weight polyethylene fiber.

[0119] Comparative Example 4

[0120] The same as Example 1, except that the amount of calcium carbonate added is 60 parts by weight.

[0121] Comparative Example 5

[0122] The same as Example 1, except that the average particle size of the calcium carbonate is 50 μm.

[0123] Comparative Example 6

[0124] The same as Example 1, except that before the direct evaporation method is used to remove the solvent, three stretching sections are first performed, the stretching temperature is 140°C, the stretching ratio is 120, and then 3 times pre-stretching and 8 times post-spinning total stretching are performed. At the same time, it is sprayed with dilute hydrochloric acid (hydrochloric acid and water) with a pH of 2.5, a spraying pressure of 0.7 MPa, a spraying time of 20 minutes, and a spraying temperature of 40°C. This method cannot form finished silk.

[0125]

Claims

1. A method for producing a through-hole ultra-high molecular weight polyethylene fiber, comprising the following steps: 1) Mix ultra-high molecular weight polyethylene, acid-soluble inorganic particles and solvent to make a spinning solution, The amount of the acid-soluble inorganic particles is 1-50 parts by weight relative to 100 parts by weight of the ultra-high molecular weight polyethylene, the amount of the solvent is 100-1300 parts by weight, the average particle size of the acid-soluble inorganic particles is 0.5-5 μm, and the difference between the relative density of the ultra-high molecular weight polyethylene and the bulk density of the acid-soluble inorganic particles is 0.20 g / cm 3 above, In step 1), the acid-soluble inorganic particles are mixed with the solvent and then mixed with the ultra-high molecular weight polyethylene. wherein the acid-soluble inorganic particles are light calcium carbonate, 2) Extruding the spinning solution to form a spinning stream, wherein the diameter of the spinneret micropores is 0.1-1.5 mm, 3) removing at least 95 wt% of the solvent from the spinning stream to obtain dry raw yarn, 4) pre-stretching the dry precursor, and then further stretching the dry precursor in 1-9 stages, referred to as post-stretching, and while performing the post-stretching, spraying an acidic liquid on the dry precursor to dissolve the acid-soluble inorganic particles to obtain the through-hole ultra-high molecular weight polyethylene fiber, Wherein in step 4), the stretching temperature is 90-170° C., the stretching ratio of the pre-stretching is 1-10, and the total stretching ratio of the post-stretching is 2-50. 2 . The production method according to claim 1 , wherein in step 1), the amount of the acid-soluble inorganic particles is 1-10 parts by weight, and the amount of the solvent is 400-2000 parts by weight, relative to 100 parts by weight of the ultra-high molecular weight polyethylene.

3. The production method according to claim 1, wherein in step 1), the viscosity-average molecular weight of the ultra-high molecular weight polyethylene is 1 million to 9 million.

4. The manufacturing method according to claim 1, 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 0.25-0.60 g / cm 3 .

5. The manufacturing method according to claim 1, wherein in step 2), stretching is present or absent, the extrusion temperature is 150-250°C, the spinneret micropore diameter is 0.5-1.5 mm; when stretching is present, the stretching ratio is 2-50. The manufacturing method according to claim 1 , wherein in step 4), the stretching temperature is 130-150° C. The manufacturing method according to claim 1 , wherein in step 4), the post-stretching comprises 1 to 5 stages.

8. The manufacturing method according to claim 1, wherein the stretching ratio of the pre-stretching is 2-5, and the total stretching ratio of the post-stretching is 5-20. 9 . The production method according to claim 1 , wherein in step 4), the acidic solution comprises at least one acid selected from inorganic acids and organic acids, and a solvent, and the pH value of the acidic solution is 2-3.

10. The production method according to claim 9, wherein the inorganic acid is selected from at least one of sulfuric acid, hydrochloric acid, boric acid, and phosphoric acid; the organic acid is selected from at least one of acetic acid, tartaric acid, oxalic acid, malic acid, citric acid, and ascorbic acid; and the solvent is selected from at least one of glacial acetic acid, ethanol, and water.

11. The manufacturing method according to claim 1, wherein in step 4), the operating conditions of the spraying include: The spraying pressure is 0.1-10MPa, the spraying time is 1-120min, and the spraying temperature is 30-50℃.

12. The manufacturing method according to claim 1, wherein in step 4), the operating conditions of the spraying include: The spraying pressure is 0.5-1MPa and the spraying time is 10-30min.

13. The manufacturing method according to claim 1, further comprising the steps of washing, extruding, curling and cutting the through-hole ultra-high molecular weight polyethylene fiber.

14. A through-hole ultra-high molecular weight polyethylene fiber obtained by the manufacturing method according to any one of claims 1 to 12, having a porosity of 1% to 50% and a fiber strength of 1 to 35 cN / dtex.

15. The through-hole ultra-high molecular weight polyethylene fiber according to claim 14, wherein the porosity is 20%-30% and the fiber strength is 5-15 cN / dtex.

16. A through-hole ultra-high molecular weight polyethylene staple fiber obtained by the manufacturing method according to claim 13, wherein the curvature thereof is 3-5 per 25 mm and the length is 38-78 mm. 17 . A fabric comprising the through-hole ultra-high molecular weight polyethylene fiber according to claim 14 or the through-hole ultra-high molecular weight polyethylene short fiber according to claim 16 .

18. Use of the fabric according to claim 17 as an adsorbent material.

Images