CN113308754A - Method for preparing high-orientation aramid fiber based on wet spinning - Google Patents
Method for preparing high-orientation aramid fiber based on wet spinning Download PDFInfo
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- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/78—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolycondensation products
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Abstract
The invention discloses a method for preparing high-orientation aramid fiber based on wet spinning, which takes waste aramid yarn, aramid waste gloves and aramid waste fabrics as raw materials, prepares aramid nano-fiber solutions with different concentrations and with a nanoscale structure, high strength, large length-diameter ratio and high temperature resistance as a matrix, and prepares regenerated aramid long fiber with high orientation, high temperature resistance, flame retardance and high strength by regulating and controlling needle specification, coagulation bath components and a drying mode in the wet spinning process. The method solves the problems of poor strength, poor heat resistance, unstable chemical properties and the like of the existing one-dimensional fiber, has simple and easy preparation process, and has wide application prospect in the fields of preparing high-strength high-temperature-resistant functional fabric, functional one-dimensional fiber and the like.
Description
Technical Field
The invention belongs to polymer nano materials, and particularly relates to a method for preparing high-orientation aramid fibers based on wet spinning.
Background
With the development of science and technology, the highly oriented aramid fiber obtained by microfibrillating natural fiber, plant fiber and animal protein fiber by using a spinning technology and replying high orientation stretching provides various uses for human life, and also becomes an important fiber raw material for daily aspects. Meanwhile, the one-dimensional high-orientation fiber shows great application potential in the fields of reinforcement, filtration, functional materials and the like due to the isotropy of the fiber. At present, the preparation of composite functional fiber with a sheath-core layer structure by wet spinning has both excellent processability and wide application prospect, and is subject to blue of researchers, wherein the research thinking focuses on the realization of functional preparation by wrapping functional core layer base material with sheath layer fiber with excellent mechanical strength as a protective layer, and simultaneously, the reprocessing performance (multifunctional woven fabric and device) and the durability of the material are enhanced. However, accompanying the problems, various different and severe application environments put higher requirements on the functionalization of fibers, especially the high performance of the cortical fibers, and it becomes a research hotspot to find a high-strength fiber with excellent physical properties and remarkable chemical stability for constructing an ideal fiber cortical structure, thereby realizing high adaptability, high strength, temperature resistance and long service life of the one-dimensional fiber base material to different environments. Aramid Nano Fibers (ANFs) have unique nanoscale structures, large length-diameter ratio and specific surface area, and simultaneously retain excellent mechanical properties and temperature resistance of the Aramid fibers, so that the Aramid nano fibers become a novel 'construction unit' with great potential for constructing macroscopic composite materials, are applied to various fields including insulation, adsorption filtration, battery diaphragms, flexible electrodes, electromagnetic shielding, intelligent wearing and the like, and play important roles in interface enhancement and material toughening. Due to the highly directional arrangement of self groups and a large number of hydrogen bonds on a nanometer scale, the aramid nano-fiber is endowed with extremely high self-assembly property, and the aramid nano-fiber has a plurality of performance advantages, so that the aramid nano-fiber becomes one of materials with extremely high potential for constructing an ideal skin layer structure of one-dimensional fiber. In addition, the recycling problem of the aramid fiber broke only relates to the conversion of the aramid fiber broke into aramid fiber pulp by using a co-grinding technology, but the dispersion stability of the product is extremely poor due to the difficulty in dispersing the product in aqueous dispersion, the problems of high energy consumption, unobvious economic benefit and the like in the co-grinding process seriously hinder the high-valued recycling of the aramid fiber, the uniform and stable aramid fiber nano-fiber solution prepared by using the waste aramid fiber is used for constructing the one-dimensional high-orientation aramid fiber to realize greater income for construction recycling economy, and the patent publications or reports on the application aspect of the aramid fiber nano-fiber for constructing the high-strength one-dimensional fiber are rare at present.
Disclosure of Invention
The invention aims to provide a method for preparing high-orientation aramid fiber based on wet spinning, which overcomes the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing high-orientation aramid fibers based on wet spinning comprises the following steps:
1) preparing an aramid nanofiber dispersion liquid: sequentially mixing waste aramid fibers, potassium hydroxide, dimethyl sulfoxide and deionized water, and stirring at room temperature for continuous reaction to obtain an aramid nanofiber dispersion liquid;
2) preparing wet-state high-orientation aramid fiber: injecting the aramid nano-fiber solution obtained in the step 1) into different coagulating baths through high-pressure injection, simultaneously drawing long fibers at a fixed drawing speed to sequentially pass through a water bath to remove DMSO and redundant alkali liquor, and collecting the long fibers in a curling manner to obtain wet high-orientation aramid fibers;
3) preparing high-orientation aramid fibers: heating and drying or freeze-drying the wet-state high-orientation aramid fiber obtained in the step 2) to obtain the high-orientation aramid fiber.
Further, the proportion of the waste aramid fiber, potassium hydroxide, dimethyl sulfoxide and deionized water in the step 1) is (3-9) g: (4.5-13.5) g: 300 mL: 12 mL.
Further, the waste aramid fibers in the step 1) are a mixture of waste aramid yarns, waste aramid gloves and waste aramid fabrics.
Further, a high-pressure injection pump is adopted for injection in the step 2), and the specification of a needle head of the high-pressure injection pump is 17-22G.
Further, the pumping speed in the step 2) is 0.5-1mL/min, and the pulling speed is 0.5-1 mL/min.
Further, the coagulation bath in the step 2) is a mixed solution formed by dropwise adding acetic acid into a DMSO (dimethyl sulfoxide) aqueous solution or a mixed solution formed by dropwise adding acetic acid into an acetone aqueous solution, wherein the mass concentration of the acetic acid is 0.15 wt%.
Further, DMSO in the DMSO aqueous solution: h2The volume ratio of O is (5-40) to (95-60); the volume ratio of acetone to water in the acetone aqueous solution is 1:1.
Further, in the step 3), the wet high-orientation aramid fiber is placed on a substrate, and then the substrate is placed in a drying oven for drying, or the substrate is placed in a refrigerator for freezing and then dried in a freeze dryer, wherein the substrate is a glass substrate or a stainless steel substrate.
Further, the heating and drying conditions in the step 3) are as follows: drying at 105 deg.C for 5min, and lyophilizing in step 3) for 2 h.
Further, the diameter of the high-orientation aramid fiber obtained in the step 3) is 68-110 μm.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the invention, waste aramid yarn, waste aramid gloves and waste aramid fabric are used as raw materials, aramid nano-fiber solutions with different concentrations and with a nanoscale structure, high strength, a large length-diameter ratio and high temperature resistance are prepared and obtained as a matrix, and a regenerated aramid long fiber with high orientation is prepared by regulating and controlling the specification of a needle head, coagulation bath components and a drying mode in a wet spinning process, and is expected to be applied to preparation of coaxial functional fibers of a one-dimensional sheath-core layer structure. The preparation method solves the problems of poor strength, poor heat resistance, unstable chemical properties and the like of the existing one-dimensional fiber, has simple and easy preparation process, and has wide application prospect in the fields of preparing high-strength high-temperature-resistant functional fabrics, functional one-dimensional fibers and the like.
The invention solves the problem that the waste aramid fiber is difficult to recover, and realizes high-valued multifunctional application of the fiber. In the wet spinning process, the aramid nano fiber spinning solution endows fibers with certain directionality under the action of a high-pressure injection pump, the fibers are directionally arranged and extruded into a coagulating bath, a water solution provides a large amount of proton donors to ensure that the aramid nano fibers are subjected to proton reduction and simultaneously ensure that the regenerated aramid nano fibers are rapidly solidified and formed, the aramid nano fibers endow high-orientation aramid fibers with high strength and toughness by relying on high homology of the structures of the aramid nano fibers and combining with the action of internal hydrogen bonds, meanwhile, the long fibers are endowed with axial high-orientation structures by virtue of external stable tensile traction force, the fibers can naturally self-contract in the evaporation process of a large amount of water contained in the long fibers in the drying process, the contraction effect is further verified by combining with a cross section profile diagram of the fibers, the negative influence on the structures of the fibers is not generated, and the compact and compact structures in the fibers are further promoted, in the wet spinning process, the fiber is well formed and collected by combining the directional extrusion effect of a high-pressure injection pump on the spinning solution and the axial curling traction effect of the tail end, the regenerated aramid nano long fiber can be rapidly subjected to proton reduction by combining the solidification effect of a coagulation bath, so that the fiber is solidified and formed, the components of the coagulation bath do not have negative influence on the high-orientation structure of the high-orientation aramid fiber, and the high purity and the excellent comprehensive performance of the high-orientation aramid fiber are ensured by removing redundant alkali liquor on the crude fiber through a water bath.
The high-orientation aramid fiber prepared by the method has the characteristics of low density, high mechanical strength, good temperature resistance, high sensitivity, high chemical stability, long service life and the like, is expected to be applied to the fields of reinforcement, flame retardance, high-temperature-resistant protective clothing and the like, realizes the efficient recycling of the waste aramid fiber, realizes the functional application of the high-performance high-orientation aramid fiber by a wet spinning technology, and provides greater possibility for the development of circular economy and the integrated utilization of resources.
Drawings
The accompanying drawings are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a morphology chart of a highly oriented aramid fiber obtained in example 3 of the present invention;
FIG. 2 is a SEM image of the surface of a highly oriented aramid fiber obtained in example 3 of the present invention;
FIG. 3 is a Z-direction cross-sectional SEM image of the surface of a highly oriented aramid fiber obtained in example 3 of the present invention;
FIG. 4 is a thermogravimetric curve of the highly oriented aramid fiber obtained in example 3 of the present invention under a nitrogen atmosphere, wherein the initial decomposition temperature is 517 ℃;
FIG. 5 is a tensile strength curve of highly oriented aramid fiber obtained in example 3 of the present invention;
fig. 6 is a graph showing the mechanical strength of the highly oriented aramid fiber obtained in example 3 of the present invention.
Detailed Description
The invention is described in further detail below:
a highly oriented aramid fiber is prepared by wet spinning aramid nano-fiber, and a coagulating bath is a DMSO (DMSO: H) aqueous solution of 0.15 wt% acetic acid2The volume ratio of O is (5-40): 95-60), or the coagulation bath is 0.15 wt% acetic acid in acetone aqueous solution (acetone: h2The volume ratio of O is 1:1), the mass concentration of the aramid nano-fiber solution is 1% -3%, and the diameter of the high-orientation aramid fiber is 68-110 mu m.
A high-orientation aramid fiber prepared based on wet spinning and a preparation method thereof comprise the following steps:
the method comprises the following steps: preparing aramid nano-fiber dispersion liquid, namely respectively sequentially placing 3g, 6g and 9g of aramid waste yarns, aramid waste gloves and aramid waste fabrics, potassium hydroxide (waste aramid fibers: potassium hydroxide in a mass ratio of 1:1.5), 300ml of dimethyl sulfoxide and 12ml of deionized water in a three-neck flask, continuously reacting for several hours at room temperature by high-shear mechanical stirring, and stirring at a rotation speed of 1500-3500r/min for 4-6 hours to obtain the aramid nano-fiber dispersion liquid with the concentration of 1%, 2% and 3%, wherein the diameter of the aramid nano-fiber is 15-20 nm, and the length of the aramid nano-fiber is 15-30 mu m;
step two: preparing wet-state high-orientation aramid fibers, respectively injecting aramid nano fiber solutions with different concentrations into a solidification bath of a DMSO (dimethyl sulfoxide) aqueous solution or an acetone aqueous solution at an injection speed of 0.5-1.0mL/min by using a high-pressure injection pump (the specification of a needle is 17G or 20G), solidifying and forming, then carrying out directional drawing at a traction speed of 0.5-1.0mL/min, carrying out water bath through a water tank with the length of several meters, fully soaking, carrying out proton reduction, removing redundant alkali liquor, and continuously curling and collecting to obtain wet-state high-orientation aramid fibers with randomly adjustable lengths;
step three: preparing high-orientation aramid fibers: and (2) placing the wet high-orientation aramid fiber in a stainless steel or glass substrate, drying in an oven at 105 ℃ for 5min to obtain the high-orientation aramid fiber, or placing the same batch of samples in a refrigerator for pre-freezing, and performing freeze drying for 2h to obtain the high-orientation aramid fiber with the diameter of 68-110 mu m.
The method takes waste aramid yarn, waste aramid gloves and waste aramid fabric as raw materials, prepares aramid nano-fiber solutions with nano-scale structures, high strength, large length-diameter ratio and high temperature resistance and different concentrations as a matrix, and prepares the regenerated aramid long fiber with high orientation, high temperature resistance, flame retardance and high strength by regulating and controlling the specification of a needle head, coagulation bath components and a drying mode in the wet spinning process. Solves the problems of poor strength, poor heat resistance, unstable chemical properties and the like of the existing one-dimensional fiber, and has simple and easy preparation process. The method comprises the steps of preparing an aramid nano-fiber dispersion liquid, preparing wet aramid nano-fiber long fibers, preparing the aramid nano-fiber long fibers and the like to obtain the regenerated high-orientation aramid fibers with adjustable diameters and lengths. The preparation process is simple and easy to implement, and the obtained high-orientation aramid fiber has wide application prospects in the fields of preparation of high-strength high-temperature-resistant functional fabrics, functional one-dimensional fibers and the like.
The present invention will be described in detail with reference to examples. It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
The following detailed description is illustrative of the embodiments and is intended to provide further details of the invention. Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention.
Example 1
A highly oriented aramid fiber prepared by wet spinning from aramid nanofibers in a coagulation bath of 0.15 wt% acetic acid in DMSO aqueous solution, wherein the weight ratio of DMSO: h2The volume ratio of O is 5:95, the concentration of the aramid nano fiber solution is 1%, and the diameter of the obtained regenerated aramid long fiber with high orientation is 110 mu m;
a method for preparing high-orientation aramid fibers based on wet spinning comprises the following steps:
the method comprises the following steps: preparing an aramid nano-fiber dispersion liquid, sequentially placing 3g of a mixture of aramid waste yarns, aramid waste gloves and aramid waste fabrics, 4.5g of potassium hydroxide, 300ml of dimethyl sulfoxide and 12ml of deionized water in a three-neck flask, continuously reacting for several hours at room temperature by high-shear mechanical stirring, and stirring at a set rotating speed of 1500r/min for 4 hours to obtain an aramid nano-fiber dispersion liquid with the concentration of 1%, wherein the diameter of the obtained aramid nano-fiber is 15-20 nm, and the length of the obtained aramid nano-fiber is 15-30 mu m;
step two: preparing wet high-orientation aramid fiber by using a high-pressure injection pump and assemblingThe 17G injection needle injects the aramid nano-fiber solution with the concentration of 1% into a coagulating bath at the injection speed of 0.5mL/min so as to quickly solidify and form the long fiber, and the composition proportion of the coagulating bath is a DMSO (dimethyl sulfoxide) aqueous solution of 0.15 wt% acetic acid, wherein the DMSO: h2The volume ratio of O is 5:95, then the fiber is directionally stretched at the traction speed of 0.5mL/min, water bath is carried out through a water tank with the length of several meters, the fiber is fully soaked, proton reduction is carried out, redundant alkali liquor is removed, and continuous curling and collection are carried out to obtain wet-state high-orientation aramid fiber with the length being adjustable at will;
step three: preparing high-orientation aramid fibers, and placing the wet high-orientation aramid fibers in a glass substrate and drying the glass substrate in an oven for 5min to obtain the high-orientation aramid fibers with the diameter of 110 microns.
Example 2
A highly oriented aramid fiber prepared by wet spinning from aramid nanofibers in a coagulation bath of 0.15 wt% acetic acid in DMSO aqueous solution, wherein the weight ratio of DMSO: h2The volume ratio of O is 10:90, the concentration of the aramid nano fiber solution is 1%, and the diameter of the obtained regenerated aramid long fiber with high orientation is 92 mu m;
a method for preparing high-orientation aramid fibers based on wet spinning comprises the following steps:
the method comprises the following steps: preparing an aramid nano-fiber dispersion liquid, sequentially placing 3g of a mixture of aramid waste yarns, aramid waste gloves, aramid waste fabrics and the like, 4.5g of potassium hydroxide, 300ml of dimethyl sulfoxide and 12ml of deionized water in a three-neck flask, continuously reacting for several hours at room temperature by high-shear mechanical stirring, and stirring at a set rotating speed of 2000r/min for 4 hours to obtain an aramid nano-fiber dispersion liquid with the concentration of 1%, wherein the diameter of the obtained aramid nano-fiber is 15-20 nm, and the length of the obtained aramid nano-fiber is 15-30 mu m;
step two: preparing wet high-orientation aramid fiber, injecting 1% aramid nano-fiber solution into a coagulating bath at an injection speed of 0.8mL/min by using a high-pressure injection pump and an injection needle with the specification of 22G to enable the long fiber to be rapidly solidified and formed, wherein the coagulating bath is a DMSO (dimethyl sulfoxide) aqueous solution of 0.15 wt% acetic acid in composition ratioMedium DMSO (dimethylsulfoxide): h2The volume ratio of O is 10:90, then the fiber is directionally stretched at the traction speed of 1mL/min, water bath is carried out through a water tank with the length of several meters, the fiber is fully soaked, proton is reduced, redundant alkali liquor is removed, and continuous curling and collection are carried out to obtain wet-state high-orientation aramid fiber with the length being adjustable at will;
step three: preparing high-orientation aramid fibers, and placing the wet high-orientation aramid fibers in a glass substrate and drying the glass substrate in an oven for 5min to obtain the high-orientation aramid fibers with the diameter of 92 microns.
Example 3
A highly oriented aramid fiber prepared by wet spinning from aramid nanofibers in a coagulation bath of 0.15 wt% acetic acid in DMSO aqueous solution, wherein the weight ratio of DMSO: h2The volume ratio of O is 10:90, the concentration of the aramid nano-fiber solution is 2 percent, and the high-orientation aramid fiber with the diameter of the regenerated high-orientation aramid long fiber of 110 mu m is obtained;
a method for preparing high-orientation aramid fibers based on wet spinning comprises the following steps:
the method comprises the following steps: preparing an aramid nano-fiber dispersion liquid, sequentially placing 6g of a mixture of aramid waste yarns, aramid waste gloves, aramid waste fabrics and the like, 9g of potassium hydroxide, 300ml of dimethyl sulfoxide and 12ml of deionized water in a three-neck flask, continuously reacting for several hours at room temperature by high-shear mechanical stirring, and stirring and reacting for 5 hours at a set rotating speed of 2500r/min to obtain an aramid nano-fiber dispersion liquid with the concentration of 2%, wherein the diameter of the obtained aramid nano-fiber is 15-20 nm, and the length of the obtained aramid nano-fiber is 15-30 mu m;
step two: preparing wet high-orientation aramid fibers, injecting an aramid nano fiber solution with the concentration of 2% into a coagulating bath at the injection speed of 0.8mL/min by using a high-pressure injection pump and an injection needle with the specification of 22G so as to quickly solidify and form long fibers, wherein the composition ratio of the coagulating bath is a DMSO (dimethyl sulfoxide) aqueous solution of 0.15 wt% of acetic acid, wherein the DMSO: h2The O volume ratio is 10:90, then the oriented drawing is carried out at a drawing speed of 1mL/min, water bath is carried out through a water tank with the length of several meters, the full immersion, proton reduction and excess alkali liquor removal are carried out, and the curling is continuously carried outCollecting the wet-state high-orientation aramid fiber with the length being adjustable at will;
step three: preparing high-orientation aramid fibers, and placing the wet high-orientation aramid fibers on a stainless steel substrate and drying the wet high-orientation aramid fibers in an oven for 5min to obtain the high-orientation aramid fibers with the diameter of 110 microns.
Example 4
A highly oriented aramid fiber prepared by wet spinning from aramid nanofibers in a coagulation bath of 0.15 wt% acetic acid in DMSO aqueous solution, wherein the weight ratio of DMSO: h2The volume ratio of O is 30:70, the concentration of the aramid nano-fiber solution is 2 percent, and the high-orientation aramid fiber with the diameter of the regenerated high-orientation aramid long fiber of 85 mu m is obtained;
a method for preparing high-orientation aramid fibers based on wet spinning comprises the following steps:
the method comprises the following steps: preparing an aramid nano-fiber dispersion liquid, sequentially placing 6g of a mixture of aramid waste yarns, aramid waste gloves, aramid waste fabrics and the like, 9g of potassium hydroxide, 300ml of dimethyl sulfoxide and 12ml of deionized water in a three-neck flask, continuously reacting for several hours at room temperature by high-shear mechanical stirring, and stirring and reacting for 5 hours at a set rotating speed of 2500r/min to obtain an aramid nano-fiber dispersion liquid with the concentration of 2%, wherein the diameter of the obtained aramid nano-fiber is 15-20 nm, and the length of the obtained aramid nano-fiber is 15-30 mu m;
step two: preparing wet high-orientation aramid fibers, injecting an aramid nano fiber solution with the concentration of 2% into a coagulating bath at the injection speed of 0.8mL/min by using a high-pressure injection pump and an injection needle with the specification of 17G so as to quickly solidify and form long fibers, wherein the composition ratio of the coagulating bath is a DMSO (dimethyl sulfoxide) aqueous solution of 0.15 wt% of acetic acid, wherein the DMSO: h2The volume ratio of O is 30:70, then the fiber is directionally stretched at the traction speed of 0.5mL/min, water bath is carried out through a water tank with the length of several meters, the fiber is fully soaked, proton reduction is carried out, redundant alkali liquor is removed, and continuous curling and collection are carried out to obtain wet-state high-orientation aramid fiber with the length being adjustable at will;
step three: preparing high-orientation aramid fibers, namely placing the wet high-orientation aramid fibers on a stainless steel substrate, pre-freezing the wet high-orientation aramid fibers in a refrigerator, and carrying out freeze drying for 2 hours to obtain the high-orientation aramid fibers with the diameter of 85 microns.
Example 5
A highly oriented aramid fiber prepared by wet spinning from aramid nanofibers in a coagulation bath of 0.15 wt% acetic acid in DMSO aqueous solution, wherein the weight ratio of DMSO: h2The volume ratio of O is 40:60, the concentration of the aramid nano-fiber solution is 3 percent, and the high-orientation aramid fiber with the diameter of the regenerated high-orientation aramid long fiber of 68 mu m is obtained;
a method for preparing high-orientation aramid fibers based on wet spinning comprises the following steps:
the method comprises the following steps: preparing an aramid nano-fiber dispersion liquid, sequentially placing 9g of a mixture of aramid waste yarns, aramid waste gloves, aramid waste fabrics and the like, 13.5g of potassium hydroxide, 300ml of dimethyl sulfoxide and 12ml of deionized water in a three-neck flask, continuously reacting for several hours at room temperature by high-shear mechanical stirring, and stirring and reacting for 6 hours at a set rotating speed of 3500r/min to obtain an aramid nano-fiber dispersion liquid with the concentration of 3%, wherein the diameter of the obtained aramid nano-fiber is 15-20 nm, and the length of the obtained aramid nano-fiber is 15-30 mu m;
step two: preparing wet high-orientation aramid fibers, injecting 3% aramid nano-fiber solution into a coagulating bath at an injection speed of 0.5mL/min by using a high-pressure injection pump and an injection needle with the specification of 22G so as to quickly solidify and form long fibers, wherein the composition ratio of the coagulating bath is a DMSO (dimethyl sulfoxide) aqueous solution of 0.15 wt% acetic acid, wherein the DMSO: h2The volume ratio of O is 40:60, then the fiber is directionally stretched at the traction speed of 0.6mL/min, water bath is carried out through a water tank with the length of several meters, the fiber is fully soaked, proton reduction is carried out, redundant alkali liquor is removed, and continuous curling and collection are carried out to obtain wet-state high-orientation aramid fiber with the length being adjustable at will;
step three: preparing high-orientation aramid fibers, and placing the wet high-orientation aramid fibers in a glass substrate and drying the glass substrate in an oven for 5min to obtain the high-orientation aramid fibers with the diameter of 68 mu m.
Example 6
Based onThe method comprises the following steps of preparing high-orientation aramid fiber by wet spinning, wherein the high-orientation aramid fiber is prepared from aramid nano-fiber by wet spinning, a coagulating bath is 0.15 wt% of acetic acid in acetone water solution, and acetone: h2The volume ratio of O is 1:1, the concentration of the aramid nano fiber solution is 3 percent, and the diameter of the obtained regenerated aramid long fiber with high orientation is 90 mu m;
a method for preparing high-orientation aramid fibers based on wet spinning comprises the following steps:
the method comprises the following steps: preparing an aramid nano-fiber dispersion liquid, sequentially placing 9g of a mixture of aramid waste yarns, aramid waste gloves, aramid waste fabrics and the like, 13.5g of potassium hydroxide, 300ml of dimethyl sulfoxide and 12ml of deionized water in a three-neck flask, continuously reacting for several hours at room temperature by high-shear mechanical stirring, and stirring and reacting for 6 hours at a set rotating speed of 3500r/min to obtain an aramid nano-fiber dispersion liquid with the concentration of 3%, wherein the diameter of the obtained aramid nano-fiber is 15-20 nm, and the length of the obtained aramid nano-fiber is 15-30 mu m;
step two: preparing wet high-orientation aramid fibers, injecting an aramid nano fiber solution with the concentration of 3% into a coagulating bath at the injection speed of 0.5mL/min by using a high-pressure injection pump and a 17G injection needle to enable the long fibers to be rapidly solidified and formed, wherein the coagulating bath is an acetone aqueous solution of 0.15 wt% acetic acid, and the weight ratio of acetone: h2The volume ratio of O is 1:1, then the fiber is directionally stretched at the traction speed of 0.8mL/min, water bath is carried out through a water tank with the length of several meters, the fiber is fully soaked, proton reduction is carried out, redundant alkali liquor is removed, and continuous curling and collection are carried out to obtain wet-state high-orientation aramid fiber with the length being adjustable at will;
step three: preparing high-orientation aramid fibers, and placing the wet high-orientation aramid fibers on a stainless steel substrate and drying the wet high-orientation aramid fibers in an oven for 5min to obtain the high-orientation aramid fibers with the diameter of 90 mu m.
Example 7
A highly oriented aramid fiber prepared by wet spinning from aramid nanofibers in a coagulation bath of 0.15 wt% acetic acid in acetone in water, wherein the weight ratio of acetone: h2The volume ratio of O is 1:1,the concentration of the aramid nano fiber solution is 2 percent, and the high-orientation aramid fiber with the diameter of the regenerated high-orientation aramid long fiber of 88 mu m is obtained;
a method for preparing high-orientation aramid fibers based on wet spinning comprises the following steps:
the method comprises the following steps: preparing an aramid nano-fiber dispersion liquid, sequentially placing 6g of a mixture of aramid waste yarns, aramid waste gloves, aramid waste fabrics and the like, 9g of potassium hydroxide, 300ml of dimethyl sulfoxide and 12ml of deionized water in a three-neck flask, continuously reacting for several hours at room temperature by high-shear mechanical stirring, and stirring and reacting for 5 hours at a set rotating speed of 3500r/min to obtain an aramid nano-fiber dispersion liquid with the concentration of 2%, wherein the diameter of the obtained aramid nano-fiber is 15-20 nm, and the length of the obtained aramid nano-fiber is 15-30 mu m;
step two: preparing wet high-orientation aramid fibers, injecting an aramid nano fiber solution with the concentration of 2% into a coagulating bath at the injection speed of 1.0mL/min by using a high-pressure injection pump and a 17G injection needle to enable the long fibers to be rapidly solidified and formed, wherein the coagulating bath is an acetone aqueous solution of 0.15 wt% acetic acid, and the weight ratio of acetone: h2The volume ratio of O is 1:1, then the fiber is directionally stretched at a traction speed of 1mL/min, water bath is carried out through a water tank with the length of several meters, the fiber is fully soaked, proton is reduced, redundant alkali liquor is removed, and continuous curling and collection are carried out to obtain wet-state high-orientation aramid fiber with the length being adjustable at will;
step three: preparing high-orientation aramid fiber, placing the wet high-orientation aramid fiber on a stainless steel substrate, pre-freezing in a refrigerator, and carrying out freeze drying for 2 hours to obtain the high-orientation aramid fiber with the diameter of 88 mu m.
The high-orientation aramid fiber prepared in the embodiment 3 of the invention is detected and characterized, and part of indexes are as follows: 1. the resulting fiber, as shown in FIG. 1, can be stored in a wound roll and exhibits excellent flexibility. The diameter of the fiber is 110 μm as shown in FIG. 2; 2. the mechanical properties of the fibers were tested and the tensile strength of the fibers as shown in fig. 5: 199.27cN, elongation at break: 11.5 percent; 3. the thermal stability of the fibers was analyzed, and as shown in fig. 4, the initial thermal decomposition temperature of the fibers: 530.5 ℃; 4. the single fiber can be suspended to a weight of 100g without deformation or breakage as shown in fig. 6. The method takes waste aramid yarn, waste aramid gloves and waste aramid fabric as raw materials, prepares aramid nano-fiber solutions with nano-scale structures, high strength, large length-diameter ratio and high temperature resistance and different concentrations as a matrix, and prepares the regenerated aramid long fiber with high orientation, high temperature resistance, flame retardance and high strength by regulating and controlling the specification of a needle head, coagulation bath components and a drying mode in the wet spinning process. The preparation process is simple and easy to implement, and has wide application prospect in the fields of preparing high-strength high-temperature-resistant functional fabrics, functional one-dimensional fibers and the like.
The embodiments described above are merely preferred embodiments of the present invention, and should not be considered as limitations of the present invention, and features in the embodiments and examples in the present application may be arbitrarily combined with each other without conflict. The protection scope of the present invention is defined by the claims, and includes equivalents of technical features of the claims. I.e., equivalent alterations and modifications within the scope hereof, are also intended to be within the scope of the invention.
Claims (10)
1. A method for preparing high-orientation aramid fibers based on wet spinning is characterized by comprising the following steps:
1) preparing an aramid nanofiber dispersion liquid: sequentially mixing waste aramid fibers, potassium hydroxide, dimethyl sulfoxide and deionized water, and stirring at room temperature for continuous reaction to obtain an aramid nanofiber dispersion liquid;
2) preparing wet-state high-orientation aramid fiber: injecting the aramid nano-fiber solution obtained in the step 1) into different coagulating baths through high-pressure injection, simultaneously drawing long fibers at a fixed drawing speed to sequentially pass through a water bath to remove DMSO and redundant alkali liquor, and collecting the long fibers in a curling manner to obtain wet high-orientation aramid fibers;
3) preparing high-orientation aramid fibers: heating and drying or freeze-drying the wet-state high-orientation aramid fiber obtained in the step 2) to obtain the high-orientation aramid fiber.
2. The method for preparing the highly-oriented aramid fiber based on wet spinning according to claim 1, wherein the proportion of the waste aramid fiber, potassium hydroxide, dimethyl sulfoxide and deionized water in the step 1) is (3-9) g: (4.5-13.5) g: 300 mL: 12 mL.
3. The method for preparing the highly oriented aramid fiber based on wet spinning according to claim 1, wherein the waste aramid fiber in the step 1) is a mixture of waste aramid yarn, waste aramid gloves and waste aramid fabric.
4. The method for preparing the highly oriented aramid fiber based on the wet spinning method as claimed in claim 1, wherein the step 2) is performed by injecting with a high pressure injection pump, and the needle gauge of the high pressure injection pump is 17G-22G.
5. The method for preparing the highly oriented aramid fiber based on the wet spinning as claimed in claim 4, wherein the pumping speed in the step 2) is 0.5-1mL/min, and the drawing speed is 0.5-1 mL/min.
6. The method for preparing highly oriented aramid fiber based on wet spinning according to claim 1, wherein the coagulation bath in step 2) is a mixture of acetic acid added dropwise to a DMSO water solution or a mixture of acetic acid added dropwise to an acetone water solution, wherein the mass concentration of acetic acid is 0.15 wt%.
7. The method for preparing the highly oriented aramid fiber based on the wet spinning method as claimed in claim 6, wherein the ratio of DMSO in the DMSO aqueous solution is as follows: h2The volume ratio of O is (5-40) to (95-60); the volume ratio of acetone to water in the acetone aqueous solution is 1:1.
8. The method for preparing the highly-oriented aramid fiber based on the wet spinning method as claimed in claim 1, wherein the highly-oriented aramid fiber in a wet state in the step 3) is placed on a substrate, and then is placed in an oven for drying, or is placed in a refrigerator for freezing and then is dried in a freeze dryer, and the substrate is a glass substrate or a stainless steel substrate.
9. The method for preparing the highly oriented aramid fiber based on wet spinning according to claim 1, wherein the heating and drying conditions in the step 3) are as follows: drying at 105 deg.C for 5min, and lyophilizing in step 3) for 2 h.
10. The method for preparing the highly-oriented aramid fiber based on the wet spinning as claimed in claim 1, wherein the diameter of the highly-oriented aramid fiber obtained in the step 3) is 68-110 μm.
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