CN112323158A - Preparation method of porous active ultrahigh molecular weight polyethylene fiber, polyethylene fiber and application thereof - Google Patents

Abstract

The invention provides a preparation method of porous active ultra-high molecular weight polyethylene fibers, polyethylene fibers and uses thereof, belonging to the technical field of textile material preparation. The method includes: dispersing fiber-grade ultra-high molecular weight polyethylene resin with a viscosity average molecular weight of not less than 1 million in an organic solvent, and the mass percentage of the ultra-high molecular weight polyethylene resin is 7%-15%; Add inorganic salt, and the addition amount of inorganic salt is 0.3%-10% of the mass of the ultra-high molecular weight polyethylene resin to obtain a spinning solution added with inorganic salt; it is extruded to obtain a spinning stream; after post-treatment, A dry jelly tow is obtained; it obtains porous active ultra-high molecular weight polyethylene fibers after removing at least part of the inorganic salt during the thermal drawing process. The polyethylene fiber prepared by this method has high surface activity, and has the characteristics of easy dyeing, easy dipping, easy crosslinking, easy grafting and the like.

Description

Preparation method of porous active ultrahigh molecular weight polyethylene fiber, polyethylene fiber and application thereof

Technical Field

The invention relates to the technical field of textile material preparation, in particular to a preparation method of porous active ultrahigh molecular weight polyethylene fibers, polyethylene fibers and application thereof.

Background

The ultra-high molecular weight polyethylene fiber contains flexible macromolecular chains, has high-strength and high-modulus mechanical properties, and is the fiber with the highest specific strength and specific modulus at present. Besides excellent mechanical properties, the ultra-high molecular weight polyethylene fiber also has the characteristics of strong wear resistance, impact resistance, low temperature resistance and the like; in terms of chemical properties, the ultrahigh molecular weight polyethylene fiber has the properties of high crystallinity, no functional group, low surface energy and the like, so that the ultrahigh molecular weight polyethylene fiber is stable in chemical properties, and the fiber properties are not changed under the conditions of common acid, alkali, salt and the like. Because the surface of the ultra-high molecular weight polyethylene fiber is smooth and flat, and the interface bonding degree with other materials is low, the phenomena of fading, paint falling and the like are easy to occur when the surface of the ultra-high molecular weight polyethylene fiber is dyed or painted.

Disclosure of Invention

In view of the above, the invention provides a preparation method of porous active ultrahigh molecular weight polyethylene fiber, polyethylene fiber and application thereof, the method has the characteristics of short flow, simple process, low cost, safety, environmental protection and the like, and the polyethylene fiber has high surface activity and has the characteristics of easy dyeing, easy gum dipping, easy crosslinking, easy grafting and the like, thereby being more practical.

In order to achieve the first object, the technical scheme of the preparation method of the porous active ultrahigh molecular weight polyethylene fiber provided by the invention is as follows:

the preparation method of the porous active ultra-high molecular weight polyethylene fiber provided by the invention comprises the following steps:

dispersing fiber-grade ultrahigh molecular weight polyethylene resin with the viscosity-average molecular weight of not less than 100 ten thousand into an organic solvent to prepare a spinning solution with the mass percentage content of the ultrahigh molecular weight polyethylene resin being in the range of 7-15%;

adding inorganic salt into the spinning solution, wherein the addition amount of the inorganic salt is equivalent to the mass percentage content of the ultrahigh molecular weight polyethylene resin and is 0.3-10%, and obtaining the spinning solution added with the inorganic salt;

extruding the spinning solution added with the inorganic salt to obtain spinning trickle;

carrying out post-treatment on the spinning fine flow to obtain a dry jelly glue tow;

and removing at least part of the inorganic salt from the dry gel filament bundle in the hot drafting process to obtain the porous active ultrahigh molecular weight polyethylene fiber.

The preparation method of the porous active ultra-high molecular weight polyethylene fiber provided by the invention can be further realized by adopting the following technical measures.

Preferably, during the step of extruding the spinning solution added with the inorganic salt to obtain the spinning stream, the extruding method is extruding through a spinneret orifice, wherein the diameter of the spinneret orifice ranges from 0.2mm to 2 mm.

Preferably, the organic solvent is one selected from the group consisting of decalin, xylene, paraffin oil, paraffin wax, and white oil.

Preferably, when the organic solvent is a volatile organic solvent, the post-treatment method comprises the steps of:

the spinning trickle is subjected to air cooling forming to obtain a formed intermediate product;

and removing the solvent in the formed intermediate product through a shaft, wherein the shaft is internally provided with circulating air, and the atmosphere of the circulating air is selected from one atmosphere or a combination atmosphere of a plurality of atmospheres of nitrogen, carbon dioxide and inert gas.

Preferably, when the organic solvent is a non-volatile organic solvent, the post-treatment method comprises the steps of:

the spinning trickle enters an extraction tank for extraction to obtain wet tows, wherein volatile alkane or halohydrocarbon liquid is arranged in the extraction tank;

and the wet tows pass through a shaft to remove the extractant in the shaft, wherein the shaft is internally provided with circulating air, and the atmosphere of the circulating air is selected from one atmosphere or a combination atmosphere of a plurality of atmospheres of nitrogen, carbon dioxide and inert gas.

Preferably, the value range of the gas temperature of the circulating air in the shaft is 40-90 ℃; the value range of the gas flow velocity of the circulating air in the shaft is 0.2-5 m/s.

Preferably, during the hot drawing of the dry gel filament bundle, the hot drawing parameters respectively include:

first hot drawing: the temperature is between 135 and 138 ℃, and the drafting multiple is between 2.0 and 4.0 times;

second hot drawing: the temperature is in the range of 138-143 ℃, and the drafting multiple is in the range of 1.2-2.0 times;

third hot drawing: the temperature is in the range of 138-140 ℃, and the drafting multiple is in the range of 1.01-1.2 times.

Preferably, the inorganic salt is water-soluble powder inorganic salt, and the value range of the particle size is 10nm-90000 nm.

Preferably, the inorganic salt is selected from one or a mixture of several of sodium chloride, potassium chloride, sodium sulfate and potassium sulfate.

Preferably, during the step of removing at least part of the inorganic salt from the dried jelly glue tow during hot drawing to obtain the porous active ultrahigh molecular weight polyethylene fiber, at least part of the inorganic salt is removed by washing with water.

Preferably, the step of removing at least part of the inorganic salts by washing is performed in a deionized water bath, wherein the range of the water bath stroke of the fibers immersed in the deionized water bath is 1m to 4m, and the range of the number of the deionized water bath is 2 to 4.

Preferably, an ultrasonic device and/or an auxiliary heating device are arranged in the deionized water bath. Preferably, the deionized water in the deionized water bath is deionized water with fluidity.

Preferably, the temperature of the deionized water ranges from 20 ℃ to 80 ℃.

Preferably, the dried gel tow is subjected to a hot-drawing process to remove at least a part of the inorganic salt, and then the dried gel tow further comprises a step of removing water by air-drying and/or hot-air blowing of a desalted product obtained by removing at least a part of the inorganic salt, thereby obtaining the porous active ultrahigh molecular weight polyethylene fiber.

In order to achieve the second object, the technical scheme of the porous active ultrahigh molecular weight polyethylene fiber provided by the invention is as follows:

the porous active ultrahigh molecular weight polyethylene fiber provided by the invention is prepared by the preparation method of the porous active ultrahigh molecular weight polyethylene fiber provided by the invention, wherein the surface of the porous active ultrahigh molecular weight polyethylene fiber has pores with the average diameter of 10nm-90000 nm.

In order to achieve the third purpose, the technical scheme of the application of the porous active ultrahigh molecular weight polyethylene fiber provided by the invention is as follows:

the application of the porous active ultrahigh molecular weight polyethylene fiber provided by the invention comprises the following steps:

the porous active ultrahigh molecular weight polyethylene fiber provided by the invention is prepared into short fiber with the length value range of 5mm-100 mm.

The short fibers are dispersed into cement, so that the cement has the properties of strength increase and cracking resistance.

The porous active ultrahigh molecular weight polyethylene fiber prepared by the preparation method of the porous active ultrahigh molecular weight polyethylene fiber provided by the invention has micropores on the surface, improves the surface activity of the fiber, has the characteristics of easiness in dyeing, impregnation, crosslinking, grafting and the like, and can solve the problems that the surface of the existing ultrahigh molecular weight polyethylene fiber is not easy to treat and is difficult to be compatible with other materials. For example, the fiber containing active porous ultra-high molecular weight polyethylene fiber is immersed into a dye solution, and the dye solution is attached to the surface of the fiber through micropores, so that the purpose of fiber dyeing is achieved, and meanwhile, the fiber is uniform in color and luster and high in color fastness. For another example, the active porous high molecular weight polyethylene fiber is prepared into short fiber with the length of 5-100mm, and the short fiber is dispersed in cement, can realize the functions of strengthening and cracking resistance on the cement, and can be used for the field of non-reinforced buildings or buildings with special requirements.

Drawings

Various other advantages and benefits will become apparent to those of ordinary skill in the art upon reading the following detailed description of the preferred embodiments. The drawings are only for purposes of illustrating the preferred embodiments and are not to be construed as limiting the invention. Also, like reference numerals are used to refer to like parts throughout the drawings. In the drawings:

FIG. 1 is a flow chart of the steps of the method for preparing porous active ultra-high molecular weight polyethylene fibers provided by the invention.

Detailed Description

In view of the above, the invention provides a preparation method of porous active ultrahigh molecular weight polyethylene fiber, polyethylene fiber and application thereof, the method has the characteristics of short flow, simple process, low cost, safety, environmental protection and the like, and the polyethylene fiber has the characteristics of higher surface activity, easiness in dyeing, easiness in gum dipping, easiness in crosslinking, easiness in grafting and the like, so that the polyethylene fiber is more practical.

To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description will be made on the preparation method of porous active ultra-high molecular weight polyethylene fiber, polyethylene fiber and its use, and the specific implementation manner, structure, characteristics and effects thereof according to the present invention with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.

The term "and/or" herein is merely an association describing an associated object, meaning that three relationships may exist, e.g., a and/or B, with the specific understanding that: both a and B may be included, a may be present alone, or B may be present alone, and any of the three cases can be provided.

Preparation method of porous active ultrahigh molecular weight polyethylene fiber

Referring to the attached fig. 1, the preparation method of the porous active ultra-high molecular weight polyethylene fiber provided by the invention comprises the following steps:

step S1: dispersing fiber-grade ultrahigh molecular weight polyethylene resin with the viscosity-average molecular weight of not less than 100 ten thousand into an organic solvent to prepare spinning solution with the mass percentage content of the ultrahigh molecular weight polyethylene resin being 7-15%. In this embodiment, the ultrahigh molecular weight polyethylene resin is used for preparing the fiber by a solution spinning method (i.e., a gel spinning method), and the used resin needs to have a molecular weight of more than 100 ten thousand and meet fiber-grade requirements, so that normal solution spinning can be ensured, and the molecular weight is less than 100 ten thousand or non-fiber-grade resin, which causes that the solution viscosity is low and the spinnability is poor, or the obtained solution gel particles are more and cannot meet the requirement of high-power thermal stretching subsequently, thereby causing that the fiber quality is low and cannot meet the market requirement. Higher molecular weights, i.e., greater than 600 ten thousand, are not conducive to the preparation of high concentration spinning solutions, cause an increase in the production cost, and are not conducive to industrial implementation.

Step S2: adding inorganic salt into the spinning solution, wherein the addition amount of the inorganic salt is equivalent to the mass percentage content of the ultra-high molecular weight polyethylene resin and is 0.3-10%, and obtaining the spinning solution added with the inorganic salt. Wherein, controlling the addition amount of the inorganic powder is one of the key steps for smoothly implementing the technical scheme. Mainly characterized in that the addition amount of the inorganic powder is low, the occupied space is less, and the requirements of fiber holes cannot be met; the inorganic powder is added too much, so that the fiber spinning is hindered, and the problems of broken filaments, weak mechanical property and the like easily occur due to the obvious influence on the mechanical property of the fiber. It has been found through studies that the amount of inorganic powder added is also influenced by multiple factors such as the type and size of the powder, and it is necessary to design the inorganic powder according to conditions such as the size and porosity of the fiber.

Step S3: extruding the spinning solution added with the inorganic salt to obtain spinning trickle;

step S4: and (4) carrying out post-treatment on the spinning fine flow to obtain the dry jelly glue silk bundle.

Step S5: and removing at least part of inorganic salt from the dry gel tow in the hot drawing process to obtain the porous active ultrahigh molecular weight polyethylene fiber. The obtained dry jelly glue tow does not have good fiber orientation and crystallinity, and the dry jelly glue tow needs to be subjected to a hot stretching process so as to endow the fiber with higher crystallinity and orientation, thereby having good fiber mechanical property. The technical scheme aims to firstly remove inorganic salt on the surface of the fiber, generate holes on the surface of the fiber and endow the fiber with active space, and does not completely remove the inorganic salt in the fiber.

Wherein, in the step process of extruding the spinning solution added with the inorganic salt to obtain the spinning trickle, the extrusion method is spinneret orifice extrusion, wherein the diameter range of the spinneret orifice is 0.2mm-2 mm.

Wherein the organic solvent is one selected from decalin, xylene, paraffin oil, paraffin wax and white oil.

Wherein, when the organic solvent is volatile organic solvent, the post-processing method comprises the following steps:

step SA 1: the spinning trickle is shaped by air cooling to obtain a shaped intermediate product;

step SA 2: and (3) the formed intermediate product passes through a shaft to remove the solvent in the formed intermediate product, wherein the shaft is internally provided with circulating air, and the atmosphere of the circulating air is selected from one atmosphere or a combination atmosphere of a plurality of atmospheres of nitrogen, carbon dioxide and inert gas.

Wherein, when the organic solvent is a non-volatile organic solvent, the post-treatment method comprises the following steps:

step SB 1: and (3) the spinning trickle enters an extraction tank for extraction to obtain wet tows, wherein volatile alkane or halohydrocarbon liquid is arranged in the extraction tank. In the embodiment, the extractant is preferably an environment-friendly, safe and environment-friendly extractant, such as gasoline and dichloromethane.

Step SB 2: and (3) the wet tows pass through a shaft to remove the extractant, wherein circulating air is arranged in the shaft, and the atmosphere of the circulating air is selected from one atmosphere or a combination atmosphere of a plurality of atmospheres of nitrogen, carbon dioxide and inert gas.

Wherein the value range of the gas temperature of the circulating air in the channel is 40-90 ℃; the value range of the gas flow velocity of the circulating air in the channel is 0.2-5 m/s.

Wherein, at the jelly glue silk bundle of dry state in the hot drafting process, the hot drafting parameter includes respectively:

step SC 1: first hot drawing: the temperature is between 135 and 138 ℃, and the drafting multiple is between 2.0 and 4.0 times;

step SC 2: second hot drawing: the temperature is in the range of 138-143 ℃, and the drafting multiple is in the range of 1.2-2.0 times;

step SC 3: third hot drawing: the temperature is in the range of 138-140 ℃, and the drafting multiple is in the range of 1.01-1.2 times.

In this example, after the above-mentioned 3 times of drawing, an ultrahigh molecular weight polyethylene fiber was obtained.

Wherein the inorganic salt is water-soluble powder inorganic salt, and the value range of the particle size is 10nm-90000 nm.

Wherein the inorganic salt is selected from one or a mixture of several of sodium chloride, potassium chloride, sodium sulfate and potassium sulfate.

Wherein, in the step process of removing at least part of inorganic salt from the dry jelly glue tow in the hot drafting process to obtain the porous active ultrahigh molecular weight polyethylene fiber, the method for removing at least part of inorganic salt is to remove at least part of inorganic salt through water washing.

Wherein, the step of removing at least part of inorganic salt through water washing is carried out in a deionized water bath, wherein, the value range of the water bath stroke of the fiber immersed in the deionized water bath is 1m-4m, and the value range of the number of the stages of the deionized water bath is 2-4 stages. Wherein, the ultra-high molecular weight polyethylene sample containing water-soluble inorganic powder enters a deionized water tank, the inorganic powder on the surface of the fiber is firstly dissolved, and inorganic salt enters a water bath.

Wherein, an ultrasonic device and/or an auxiliary heating device are arranged in the deionized water bath. Wherein, in order to increase the dissolving speed of the inorganic salt, an ultrasonic device and an auxiliary heating device are arranged in the deionized water bath. The ultrasonic wave can accelerate inorganic salt to be dissolved into water bath, meanwhile, water molecules are enhanced to permeate into the fibers, and the inorganic salt wrapped inside the fibers is further removed; the water bath is given certain auxiliary heating, and the migration of inorganic ions can be accelerated.

Wherein the deionized water in the deionized water bath is the deionized water with fluidity. It can realize the inorganic salt content in the deionized water tank to be stable.

Wherein the temperature of the deionized water ranges from 20 ℃ to 80 ℃.

Wherein, after removing at least part of inorganic salt in the hot drafting process of the dry jelly glue tow, the method also comprises the step of airing and/or hot air blowing the desalted product obtained by removing at least part of inorganic salt to remove water in the desalted product, so as to obtain the porous active ultrahigh molecular weight polyethylene fiber.

Porous active ultra-high molecular weight polyethylene fiber

The porous active ultrahigh molecular weight polyethylene fiber provided by the invention is prepared by the preparation method of the porous active ultrahigh molecular weight polyethylene fiber provided by the invention, wherein the surface of the porous active ultrahigh molecular weight polyethylene fiber has pores with the average diameter of 10nm-90000 nm.

Use of porous active ultra-high molecular weight polyethylene fibers

One application of the porous active ultra-high molecular weight polyethylene fiber provided by the invention comprises the following steps:

step SD 1: the porous active ultrahigh molecular weight polyethylene fiber provided by the invention is prepared into short fiber with the length value range of 5mm-100 mm;

step SD 2: the short fibers are dispersed in the cement, so that the cement has the properties of strength increase and cracking resistance.

In addition, the fiber containing active porous ultrahigh molecular weight polyethylene is immersed into the dye solution, and the dye solution is attached to the surface of the fiber through micropores, so that the purpose of fiber dyeing is realized, and meanwhile, the fiber is uniform in color and luster and high in color fastness. For another example, the active porous high molecular weight polyethylene fiber is prepared into short fiber with the diameter of 0.5-100mm, and the short fiber is dispersed in cement, can realize the functions of strengthening and cracking resistance on the cement, and can be used for the field of non-rib buildings or buildings with special requirements.

Examples

Example 1

Dispersing the ultrahigh molecular weight polyethylene resin with the viscosity average molecular weight of 400 ten thousand into decalin (the mass ratio of the ultrahigh molecular weight polyethylene to the decalin is 10:90), adding sodium chloride particles with the average diameter of 100nm (the mass ratio of the sodium chloride to the ultrahigh molecular weight polyethylene resin is 6:94), swelling at 95 ℃ for 4 hours, heating to 170 ℃ to obtain a spinning solution, metering by a metering pump, and extruding through a spinneret orifice with the diameter of 0.8mm to form a spinning trickle. The spinning stream is dried by a channel with the nitrogen temperature of 80 ℃ and the length of 9m to obtain dry raw silk. Sequentially subjecting the dry precursor to primary drafting at 138 ℃ by 3.5 times; secondary drafting at 142 deg.c and 1.2 times; 138 ℃ and 1.01 times of three-stage drafting. After primary drafting and secondary drafting respectively, carrying out ultrasonic water bath treatment with the length of 2m to finally obtain the ultra-high molecular weight polyethylene fiber with the surface having holes with the average diameter of 80 nm.

Example 2

Dispersing the ultra-high molecular weight polyethylene resin with the viscosity average molecular weight of 600 ten thousand into decalin (the mass ratio of the ultra-high molecular weight polyethylene to the decalin is 7:93), adding sodium chloride particles with the average diameter of 10000nm (the mass ratio of the sodium chloride to the ultra-high molecular weight polyethylene resin is 0.3:99.7), swelling at 90 ℃ for 4 hours, heating to 180 ℃ to obtain a spinning solution, metering by a metering pump, and extruding through a spinneret orifice with the diameter of 1mm to form a spinning trickle. The spinning stream is dried by a channel with the nitrogen temperature of 80 ℃ and the length of 9m to obtain dry raw silk. Sequentially subjecting the dry precursor to primary drafting at 138 ℃ by 4 times; secondary drafting at 143 ℃ and 1.3 times; three-stage drawing at 140 deg.C by 1.10 times. And respectively carrying out ultrasonic water bath treatment with the length of 2m before primary drafting, after primary drafting and after secondary drafting, and finally obtaining the ultra-high molecular weight polyethylene fiber with the surface having holes with the average diameter of 5000 nm.

Example 3

Dispersing the ultra-high molecular weight polyethylene resin with the viscosity average molecular weight of 600 ten thousand into decalin (the mass ratio of the ultra-high molecular weight polyethylene to the decalin is 7:93), adding sodium chloride particles with the average diameter of 10nm (the mass ratio of the sodium chloride to the ultra-high molecular weight polyethylene resin is 10:90), swelling for 4 hours at 99 ℃, heating to 180 ℃ to obtain a spinning solution, metering by a metering pump, and extruding through a spinneret orifice with the diameter of 1mm to form a spinning trickle. The spinning stream is dried by a channel with the nitrogen temperature of 80 ℃ and the length of 9m to obtain dry raw silk. Sequentially subjecting the dry precursor to primary drafting at 138 ℃ by 4 times; secondary drafting at 143 ℃ and 2 times; 140 ℃ and 1.01 times of three-stage drafting. After primary drafting, secondary drafting and tertiary drafting, carrying out ultrasonic water bath treatment with the length of 2m, and finally obtaining the ultra-high molecular weight polyethylene fiber with the surface having holes with the average diameter of 5 nm.

Example 4

Dispersing the ultra-high molecular weight polyethylene resin with the viscosity average molecular weight of 600 ten thousand into decalin (the mass ratio of the ultra-high molecular weight polyethylene to the decalin is 7:93), adding potassium chloride particles with the average diameter of 200nm (the mass ratio of the potassium chloride to the ultra-high molecular weight polyethylene resin is 6:94), swelling for 4 hours at 99 ℃, heating to 180 ℃ to obtain a spinning solution, metering by a metering pump, and extruding through a spinneret orifice with the diameter of 1mm to form a spinning trickle. The spinning stream is dried by a channel with the nitrogen temperature of 80 ℃ and the length of 9m to obtain dry raw silk. Sequentially subjecting the dry precursor to primary drafting at 138 ℃ by 4 times; secondary drafting at 143 ℃ and 2 times; 140 ℃ and 1.01 times of three-stage drafting. After primary drafting, secondary drafting and tertiary drafting, carrying out 2m long ultrasonic water bath treatment, and finally obtaining the ultra-high molecular weight polyethylene fiber with the surface having holes with the average diameter of 180 nm.

Example 5

Dispersing the ultra-high molecular weight polyethylene resin with the viscosity average molecular weight of 200 ten thousand into decalin (the mass ratio of the ultra-high molecular weight polyethylene to the decalin is 15:85), adding sodium chloride particles with the average diameter of 50nm (the mass ratio of the sodium chloride to the ultra-high molecular weight polyethylene resin is 4:96), swelling at 90 ℃ for 4 hours, heating to 160 ℃ to obtain a spinning solution, metering by a metering pump, and extruding through a spinneret orifice with the diameter of 0.8mm to form a spinning trickle. The spinning stream is dried by a channel with the nitrogen temperature of 60 ℃ and the length of 9m to obtain dry raw silk. Sequentially subjecting the dry precursor to primary drafting at 138 ℃ by 4 times; secondary drafting at 143 ℃ and 2 times; 140 ℃ and 1.01 times of three-stage drafting. After primary drafting, secondary drafting and tertiary drafting, carrying out ultrasonic water bath treatment with the length of 2m, and finally obtaining the ultra-high molecular weight polyethylene fiber with the surface having holes with the average diameter of 40 nm.

Example 6

Dispersing the ultrahigh molecular weight polyethylene resin with the viscosity average molecular weight of 400 ten thousand into decalin (the mass ratio of the ultrahigh molecular weight polyethylene to the decalin is 10:90), adding sodium chloride particles with the average diameter of 100nm (the mass ratio of the sodium chloride to the ultrahigh molecular weight polyethylene resin is 6:94), swelling at 95 ℃ for 4 hours, heating to 170 ℃ to obtain a spinning solution, metering by a metering pump, and extruding through a spinneret orifice with the diameter of 0.8mm to form a spinning trickle. Extracting the spinning stream by using a gasoline extracting agent to obtain wet tows containing gasoline, and drying the wet tows in a channel with the nitrogen temperature of 50 ℃ and the length of 9m to obtain dry raw yarns. Sequentially subjecting the dry precursor to primary drafting at 138 ℃ by 3.5 times; secondary drafting at 142 deg.c and 1.2 times; 138 ℃ and 1.01 times of three-stage drafting. After primary drafting and secondary drafting respectively, carrying out ultrasonic water bath treatment with the length of 2m, and finally obtaining the ultra-high molecular weight polyethylene fiber with the surface having holes with the average diameter of 80 nm.

Example 7

Dispersing the ultra-high molecular weight polyethylene resin with the viscosity-average molecular weight of 400 ten thousand into paraffin oil (the mass ratio of the ultra-high molecular weight polyethylene to the paraffin oil is 8:92), adding potassium chloride particles with the average diameter of 100nm (the mass ratio of the potassium chloride to the ultra-high molecular weight polyethylene resin is 6:94), swelling at 95 ℃ for 4 hours, heating to 170 ℃ to obtain spinning solution, metering by a metering pump, and extruding through a spinneret orifice with the diameter of 0.8mm to form spinning trickle. Extracting the spinning stream by using a gasoline extracting agent to obtain wet tows containing gasoline, and drying the wet tows in a channel with the nitrogen temperature of 50 ℃ and the length of 9m to obtain dry raw yarns. Sequentially subjecting the dry precursor to primary drafting at 138 ℃ by 3.5 times; secondary drafting at 142 deg.c and 1.2 times; 138 ℃ and 1.01 times of three-stage drafting. After primary drafting and secondary drafting respectively, carrying out ultrasonic water bath treatment with the length of 2m, and finally obtaining the ultra-high molecular weight polyethylene fiber with the surface having holes with the average diameter of 80 nm.

Example 8

Dispersing the ultra-high molecular weight polyethylene resin with the viscosity-average molecular weight of 400 ten thousand into white oil (the mass ratio of the ultra-high molecular weight polyethylene to the white oil is 8:92), adding potassium chloride particles with the average diameter of 100nm (the mass ratio of the potassium chloride to the ultra-high molecular weight polyethylene resin is 6:94), swelling at 95 ℃ for 4 hours, heating to 170 ℃ to obtain spinning solution, metering by a metering pump, and extruding through a spinneret orifice with the diameter of 0.8mm to form spinning trickle. And extracting the spinning stream by using a dichloromethane extracting agent to obtain wet tows containing dichloromethane, and feeding the wet tows into a channel with the nitrogen temperature of 50 ℃ and the length of 9m for drying to obtain dry raw fibers. Sequentially subjecting the dry precursor to primary drafting at 138 ℃ by 3.5 times; secondary drafting at 142 deg.c and 1.2 times; 138 ℃ and 1.01 times of three-stage drafting. After primary drafting and secondary drafting respectively, carrying out ultrasonic water bath treatment with the length of 2m, and finally obtaining the ultra-high molecular weight polyethylene fiber with the surface having holes with the average diameter of 80 nm.

While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.

It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.

Claims (10)

1. A preparation method of porous active ultra-high molecular weight polyethylene fiber is characterized by comprising the following steps:

a) dispersing fiber-grade ultrahigh molecular weight polyethylene resin with the viscosity-average molecular weight of not less than 100 ten thousand into an organic solvent to prepare a spinning solution with the mass percentage content of the ultrahigh molecular weight polyethylene resin being in the range of 7-15%;

b) adding inorganic salt into the spinning solution, wherein the addition amount of the inorganic salt is equivalent to the mass percentage content of the ultrahigh molecular weight polyethylene resin and is 0.3-10%, and obtaining the spinning solution added with the inorganic salt;

c) extruding the spinning solution added with the inorganic salt to obtain spinning trickle;

d) carrying out post-treatment on the spinning fine flow to obtain a dry jelly glue tow;

e) and removing at least part of the inorganic salt from the dry gel filament bundle in the hot drafting process to obtain the porous active ultrahigh molecular weight polyethylene fiber.

2. The method for preparing porous active ultra-high molecular weight polyethylene fiber according to claim 1, wherein the extrusion method is extrusion through a spinneret orifice during the step of extruding the spinning solution added with inorganic salt to obtain a spinning stream, wherein the diameter of the spinneret orifice ranges from 0.2mm to 2 mm.

3. The method of claim 1, wherein the organic solvent is one selected from the group consisting of decalin, xylene, paraffin oil, paraffin wax and white oil.

4. The method for preparing porous active ultra-high molecular weight polyethylene fiber according to claim 1, wherein when the organic solvent is a volatile organic solvent, the post-treatment method comprises the following steps:

f) the spinning trickle is subjected to air cooling forming to obtain a formed intermediate product;

g) and removing the solvent in the formed intermediate product through a shaft, wherein the shaft is internally provided with circulating air, and the atmosphere of the circulating air is selected from one atmosphere or a combination atmosphere of a plurality of atmospheres of nitrogen, carbon dioxide and inert gas.

5. The method for preparing porous active ultra-high molecular weight polyethylene fiber according to claim 1, wherein when the organic solvent is a non-volatile organic solvent, the post-treatment method comprises the steps of:

i) the spinning stream enters an extraction tank for extraction to obtain wet tows, wherein volatile alkane or halohydrocarbon liquid is arranged in the extraction tank;

II) the wet tows pass through a shaft to remove the extracting agent, wherein the shaft is internally provided with circulating air, and the atmosphere of the circulating air is selected from one atmosphere or a combination atmosphere of a plurality of atmospheres of nitrogen, carbon dioxide and inert gas.

6. The method for preparing porous active ultrahigh molecular weight polyethylene fiber according to claim 4 or 5, wherein the temperature of the gas forming the circulating air in the shaft ranges from 40 ℃ to 90 ℃; the value range of the gas flow velocity of the circulating air in the shaft is 0.2-5 m/s.

7. The method of claim 1, wherein the thermal drawing parameters of the dry gel tow respectively comprise:

first hot drawing: the temperature is between 135 and 138 ℃, and the drafting multiple is between 2.0 and 4.0 times;

second hot drawing: the temperature is in the range of 138-143 ℃, and the drafting multiple is in the range of 1.2-2.0 times;

third hot drawing: the temperature is in the range of 138-140 ℃, and the drafting multiple is in the range of 1.01-1.2 times.

8. The method for preparing the porous active ultra-high molecular weight polyethylene fiber according to claim 1, wherein the inorganic salt is water-soluble powder inorganic salt, and the particle size ranges from 10nm to 90000 nm;

preferably, the inorganic salt is selected from one or a mixture of several of sodium chloride, potassium chloride, sodium sulfate and potassium sulfate;

preferably, during the step of removing at least part of the inorganic salt from the dry jelly glue tow during hot drawing to obtain the porous active ultrahigh molecular weight polyethylene fiber, at least part of the inorganic salt is removed by washing with water;

preferably, the step of removing at least part of the inorganic salt by washing is carried out in a deionized water bath, wherein the range of the water bath stroke of the fiber immersed in the deionized water bath is 1m-4m, and the range of the number of the deionized water bath is 2-4;

preferably, an ultrasonic device and/or an auxiliary heating device are arranged in the deionized water bath;

preferably, the deionized water in the deionized water bath is the deionized water with fluidity;

preferably, the temperature of the deionized water ranges from 20 ℃ to 80 ℃;

preferably, the dried gel tow is subjected to a hot-drawing process to remove at least a part of the inorganic salt, and then the dried gel tow further comprises a step of removing water by air-drying and/or hot-air blowing of a desalted product obtained after at least a part of the inorganic salt is removed, thereby obtaining the porous active ultrahigh molecular weight polyethylene fiber.

9. A porous active ultrahigh molecular weight polyethylene fiber produced by the method for producing a porous active ultrahigh molecular weight polyethylene fiber according to any one of claims 1 to 8, wherein the surface of the porous active ultrahigh molecular weight polyethylene fiber has pores with an average diameter of 10nm to 90000 nm.

10. Use of the porous activated ultra high molecular weight polyethylene fiber of claim 9, characterized in that it comprises the steps of:

the porous active ultra-high molecular weight polyethylene fiber of claim 9 prepared into staple fiber with length ranging from 5mm to 20 mm;

the short fibers are dispersed into cement, so that the cement has the properties of strength increase and cracking resistance.

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