CN113389080B - Aramid fiber modification method - Google Patents
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- CN113389080B CN113389080B CN202110723408.1A CN202110723408A CN113389080B CN 113389080 B CN113389080 B CN 113389080B CN 202110723408 A CN202110723408 A CN 202110723408A CN 113389080 B CN113389080 B CN 113389080B
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/10—Organic non-cellulose fibres
- D21H13/20—Organic non-cellulose fibres from macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H13/26—Polyamides; Polyimides
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Abstract
The invention discloses an aramid fiber modification method, which comprises the steps of modifying aramid chopped fibers by using an aramid nano fiber dispersion liquid, constructing a multi-level micro/nano coarse structure on the surface of the smooth aramid fiber, obtaining aramid composite fibers coated by the aramid nano fibers, and overcoming the problems of high specific surface area, mechanical strength, excellent temperature resistance, smooth and hydrophobic surface, strong inertia, few active groups and the like of the traditional chopped fibers, so that the aramid composite fibers become an optimal construction unit for preparing high-performance composite materials; the high-performance aramid paper is prepared by taking the obtained aramid nanofiber modified aramid chopped fiber as a single raw material, aramid pulp fiber or aramid fibrid is not required to be prepared, the problems of loose paper structure, poor interface bonding force, low mechanical strength and compressive strength and the like caused by large component dimension difference of the aramid paper are solved, and the prepared aramid paper has a compact paper structure, high strength, high modulus and excellent compressive strength and is expected to be applied to the fields of advanced electrical insulation, structural weight-reduction honeycomb materials and the like.
Description
Technical Field
The invention belongs to the fields of polymer fibers and papermaking, and particularly relates to an aramid fiber modification method.
Background
Aramid Fiber (AF) is one of three high-performance fibers, has high strength, high modulus, excellent temperature resistance and chemical stability, and is one of special fibers which are rapidly developed and widely applied in the field of fiber polymer materials in recent years. The composite material can be used as a structural material for bearing load, can also be used as a functional material for playing a role, and is widely applied to the fields of individual protection, electronic communication, petrochemical industry, aerospace and the like. However, due to the characteristics of the aramid fiber, such as smooth and hydrophobic surface, strong inertia, few active groups, poor hydrophilicity and the like, the aramid fiber has weak interfacial bonding force with a matrix when being applied to the fields of resin matrix composite materials and the like, and the comprehensive performance of the material is greatly influenced. The aramid paper prepared by taking the aramid fiber as the raw material can be applied to the fields of advanced electrical insulation, structural weight reduction materials, national defense military industry and the like due to light weight, insulation and high temperature resistance. Because the aramid chopped fibers have smooth surfaces and few active groups, the aramid chopped fibers cannot be independently made into paper, and differential aramid fibers such as aramid pulp and aramid precipitation must be blended as bonding materials, so that the overall performance of the aramid paper is improved. However, the components have large dimensionality difference and are lack of effective combination on all levels of scales, and the strength of the paper mainly comes from random physical lapping and a very small amount of hydrogen bonding among aramid fibers, so that the aramid paper has a plurality of structural and performance defects, such as loose structure, poor interface bonding force, low mechanical strength and compressive strength, poor uniformity, unstable performance and the like. Therefore, optimizing the interface bonding characteristic of aramid paper and improving the comprehensive performance of aramid paper become one of the keys for promoting the industrial application and development of domestic aramid paper.
Therefore, researchers mainly carry out a great deal of work on the surface modification and enhancement of aramid fibers, and the design and structural enhancement of paper components. (1) The surface modification and enhancement of the aramid fiber mainly comprises chemical modification (chemical etching, surface grafting, coupling agent modification and the like) and physical modification (fibrillation treatment, plasma modification and the like), and aims to improve the bonding area and the bonding strength between the aramid fiber and a matrix by increasing the surface active group content of the aramid fiber or increasing the surface roughness of the fiber, so that the interface bonding condition and the strength performance of the aramid paper are improved. (2) The paper component design and structure enhancement mainly comprise the steps of adding non-aramid fiber external fibers (polyester, polyphenylene sulfide fibers and the like), mixing, dipping resin, hot-pressing enhancement and the like, and aims to improve the strength performance of aramid paper by optimizing the three-dimensional structure of the paper. Previous research work shows that the performance of aramid paper can be improved to a certain extent by the reinforcement methods, but the reinforcement methods are limited by the characteristics of the aramid fiber, research methods, means and other factors, the interface bonding strength of the obtained aramid paper is still difficult to compare favorably with that of common plant fiber paper, the excellent performance of the aramid fiber is not reflected, a series of problems such as high energy consumption, high cost, complex process, harsh conditions and the like can be caused, and most importantly, the strength and the temperature resistance of the fiber are reduced, so that the defects such as unsatisfactory reinforcement effect of the aramid paper, brittle paper, damaged flexibility and the like are caused.
Disclosure of Invention
The invention aims to provide an aramid fiber modification method, which aims to overcome the problems of smooth and hydrophobic surface, strong inertia, few active groups and the like of chopped aramid fibers and enable the chopped aramid fibers to become an excellent building unit for preparing high-performance composite materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
the aramid fiber modification method is characterized in that aramid nanofiber/dimethyl sulfoxide dispersion liquid and aramid chopped fiber/water dispersion liquid are blended to realize in-situ protonation reduction and compounding of the aramid nanofiber, and the aramid nanofiber modified aramid fiber is prepared, wherein the mass ratio of the aramid nanofiber to the aramid chopped fiber is (10-50): (50-90).
Furthermore, the aramid chopped fibers are meta-aramid chopped fibers or para-aramid chopped fibers.
Further, the preparation process of the chopped aramid fiber/water dispersion comprises the following steps: dispersing the aramid chopped fiber in water, and obtaining the aramid chopped fiber/water dispersion liquid with the mass concentration of 0.5-1.5% by discongesting, stirring and dispersing for 15000 r.
Further, the preparation process of the aramid nanofiber/dimethyl sulfoxide dispersion liquid is as follows: taking the recovered para-aramid waste as a raw material, and carrying out deprotonation reaction in a potassium hydroxide/dimethyl sulfoxide/water system to obtain an aramid nano-fiber/dimethyl sulfoxide dispersion liquid with the mass concentration of 0.2-1.0%.
Furthermore, the recovered para-aramid waste material adopts one or more of aramid cloth, aramid waste silk, aramid yarn and aramid gloves.
Further, the specific processes of the in-situ protonation reduction and compounding of the aramid nano-fiber comprise the following steps: injecting the aramid nano fiber/dimethyl sulfoxide dispersion liquid into the aramid chopped fiber/water dispersion liquid through an injector to carry out in-situ protonation reduction and compounding.
Further, in the process of injecting the aramid nano fiber/dimethyl sulfoxide dispersion liquid into the aramid chopped fiber/water dispersion liquid, mechanical stirring is carried out, after injection is completed, mechanical stirring is continued to obtain a modified aramid composite fiber mixed dispersion liquid, and the modified aramid composite fiber mixed dispersion liquid is subjected to suction filtration through a filter membrane to obtain the modified aramid fiber.
Further, the rotation speed of the mechanical stirring is 1500-5000 rpm, and after the injection is finished, the mechanical stirring is continued for 30-60 min.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the invention utilizes the aramid nano-fiber with unique nanoscale structure, high strength and modulus, high specific surface area, high length-diameter ratio and good temperature resistance as the coating modifier of the aramid chopped fiber to construct a multi-level micro/nano coarse structure on the surface of the smooth aramid fiber so as to overcome the problems of smooth surface, strong inertia, few active groups and the like of the chopped fiber, and the aramid fiber becomes an excellent construction unit for preparing the high-performance composite material.
2. The invention takes aramid nano-fiber/dimethyl sulfoxide (ANF/DMSO) dispersion liquid as a coating modifier of aramid chopped fibers, and the aramid nano-fiber/dimethyl sulfoxide (ANF/DMSO) dispersion liquid is injected into chopped fiber slurry dispersion liquid in a high-pressure injection mode. Under the action of high shearing force, the injected ANF/DMSO contacts water in chopped fiber slurry to quickly complete protonation reduction on the surfaces of the chopped fibers, fine aramid nano fibers or aramid nano fiber networks are separated out by uniform ANF/DMSO phases and are deposited on the surfaces of macroscopic chopped fibers in situ to obtain aramid composite fibers (ANF @ AF) coated with the aramid nano fibers or the aramid nano fiber network structures, the protonation reduction of the aramid nano fibers is realized, the compounding of the aramid nano fibers and the chopped fibers is completed at the same time, the interface bonding strength of the aramid nano fibers and the chopped fibers can be effectively improved, and the efficient and high-strength compounding is realized.
3. The method takes the recovered para-aramid waste materials (aramid cloth, aramid waste silk, aramid yarn and aramid gloves) to replace expensive original aramid fibers as raw materials to prepare the aramid nanofibers, can greatly reduce the preparation cost of the aramid nanofibers, ensures that the molecular weight of the aramid nanofibers is still as high as 43.0kg/mol, not only can endow the aramid nanofibers with excellent strength performance, but also solves the problems of single expensive source, high preparation cost and the like of the aramid nanofibers, and lays a foundation for realizing large-scale production and application of the aramid nanofibers.
4. When the obtained aramid nanofiber modified aramid chopped fibers are used as a single raw material to prepare high-performance aramid paper, aramid pulp fibers or aramid fibrids do not need to be prepared, and the problems of loose paper structure, poor interface bonding force, low mechanical strength and compressive strength and the like caused by large component dimension difference of the aramid paper are solved; meanwhile, the problems of low retention rate, difficult water filtration and the like caused by directly adding the nano-scale aramid nano-fiber into the pulp are also avoided.
5. The novel cellulose composite fiber is prepared by blending the aramid nano-fiber/dimethyl sulfoxide dispersion liquid and the chopped fiber slurry dispersion liquid in an in-situ composite mode, the preparation process is simple, the flow is short, and large-scale and industrial production can be realized; the obtained novel modified aramid fiber has excellent comprehensive performance, can solve the scientific and technical problems in the high-valued application process of the conventional aramid fiber-based material, and obviously improves the interface bonding strength of the aramid fiber-based material; meanwhile, the strength and the toughness of the aramid fiber paper are obviously improved, a new thought and a theoretical guidance can be provided for the preparation of the high-performance aramid fiber paper, and the preparation technology and the theory of the existing nanofiber reinforced composite material can be enriched.
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 an SEM image of a modified aramid fiber obtained in example 4 of the present invention.
Detailed Description
The invention is described in further detail below:
an aramid fiber modification method is characterized in that aramid nanofiber/dimethyl sulfoxide dispersion liquid and aramid chopped fiber/water dispersion liquid are blended to realize in-situ protonation reduction and compounding of aramid nanofiber, and aramid composite fiber coated with an aramid nanofiber network is prepared; wherein the mass ratio of the aramid nano-fiber to the aramid chopped fiber is (10-50): (50-90).
An aramid fiber modification method comprises the following steps:
the method comprises the following steps: preparing aramid chopped fiber/water dispersion: dispersing one of meta-aramid chopped fiber and para-aramid chopped fiber with a certain mass in water, and stirring and dispersing the mixture for 15000r by using a standard defiberizer to obtain chopped fiber slurry with the mass concentration of 0.5-1.5%;
step two: preparing an aramid nano fiber/dimethyl sulfoxide dispersion liquid: taking recovered para-aramid waste (one or more of aramid cloth, aramid waste silk, aramid yarn and aramid gloves) as a raw material, and adding potassium hydroxide/dimethyl sulfoxide/water (KOH/DMSO/H)2O) deprotonation reaction is carried out in the system to prepare aramid nano-fiber/dimethyl sulfoxide dispersion liquid with mass concentration of 0.2-1.0%;
step three: in-situ protonation reduction and recombination: injecting the ANF/DMSO dispersion liquid obtained in the step two into the chopped fiber slurry through an injector to carry out in-situ protonation reduction and compounding; the mass ratio of the ANF/DMSO dispersion liquid to the aramid nano-fiber to the aramid chopped fiber in the slurry is (10-50): (50-90); further, mechanical stirring is needed in the process of injecting the ANF/DMSO into the aramid fiber slurry, and the stirring speed is controlled to be 1500-5000 rpm; further, after the injection is finished, continuously mechanically stirring for 30-60 min at the rotating speed of 1500-5000 rpm to obtain a modified aramid composite fiber mixed dispersion liquid; and further, carrying out suction filtration on the obtained modified aramid composite fiber mixed dispersion liquid through a filter membrane, and intercepting on the filter membrane to obtain the modified aramid fiber.
The aramid paper is prepared by taking aramid nanofiber modified aramid chopped fibers as raw materials through the steps of dispersing, dehydrating, forming, squeezing, drying, hot pressing and the like.
The invention provides a modification method of aramid fiber by using Aramid Nanofiber (ANF) with a unique nanoscale structure, high strength and modulus, high specific surface area, high length-diameter ratio, good temperature resistance and wet strength as a coating modifier of the aramid chopped fiber, wherein the aramid nanofiber/dimethyl sulfoxide (ANF/DMSO) dispersion liquid and the aramid chopped fiber are mixed to realize fiber in-situ protonation reduction and compounding to obtain aramid composite fiber (ANF @ AF) coated with the aramid nanofiber or aramid nanofiber network structure, and a multi-level micro/nano coarse structure is constructed on the surface of the smooth aramid fiber to form an excellent construction unit for preparing the high-performance composite material. Meanwhile, the obtained modified aramid chopped fiber is used as a single raw material to prepare the high-performance aramid paper, and aramid pulp fiber or aramid fibrid does not need to be prepared, so that the problems of loose paper structure, poor interface bonding force, low mechanical strength and compressive strength and the like caused by large component dimension difference of the aramid paper are solved.
The present invention will be described in detail with reference to examples. It should be noted that, in the present application, the embodiments and features of the embodiments 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
An aramid fiber modification method is characterized in that aramid nanofiber/dimethyl sulfoxide dispersion liquid and aramid chopped fiber/water dispersion liquid are blended to realize in-situ protonation reduction and compounding of aramid nanofiber, and aramid composite fiber coated with an aramid nanofiber network is prepared; wherein the mass ratio of the aramid nano fiber to the aramid fiber is 10:90.
an aramid fiber modification method comprises the following steps:
the method comprises the following steps: preparing aramid chopped fiber/water dispersion: dispersing one of meta-aramid chopped fiber and para-aramid chopped fiber with a certain mass in water, and stirring and dispersing the mixture by a standard defiberizer for 15000r to obtain chopped fiber slurry with the mass concentration of 1.5%;
step two: preparing an aramid nano fiber/dimethyl sulfoxide dispersion liquid: the recovered para-aramid fabric is used as a raw material to be oxidized in hydrogenPotassium/dimethyl sulfoxide/water (KOH/DMSO/H)2O) deprotonation reaction is carried out in a system to prepare an aramid nano-fiber/dimethyl sulfoxide dispersion liquid with the mass concentration of 0.2%;
step three: in-situ protonation reduction and recombination: injecting the ANF/DMSO dispersion liquid obtained in the step two into the chopped fiber slurry through an injector to carry out in-situ protonation reduction and compounding; the mass ratio of the ANF/DMSO dispersion liquid to the aramid nano-fibers to the aramid chopped fibers in the slurry is 10:90, respectively; further, mechanical stirring is needed in the process of injecting the ANF/DMSO into the cellulose pulp, and the stirring speed is controlled at 1500rpm; further, after the injection is finished, continuously mechanically stirring for 30min at the rotating speed of 1500rpm to obtain a composite fiber mixed dispersion liquid; and further, carrying out suction filtration on the obtained modified aramid composite fiber mixed dispersion liquid through a filter membrane, and intercepting on the filter membrane to obtain the modified aramid fiber.
The aramid paper is prepared by taking aramid nanofiber modified aramid chopped fibers as raw materials through the steps of dispersing, dehydrating, forming, squeezing, drying, hot pressing and the like, wherein the mass ratio of the aramid nanofiber to the aramid chopped fibers is 10:90.
example 2
An aramid fiber modification method is characterized in that aramid nanofiber/dimethyl sulfoxide dispersion liquid and aramid chopped fiber/water dispersion liquid are blended to realize in-situ protonation reduction and compounding of aramid nanofiber, and aramid composite fiber coated with an aramid nanofiber network is prepared; wherein the mass ratio of the aramid nano-fiber to the aramid fiber is 20:80.
an aramid fiber modification method comprises the following steps:
the method comprises the following steps: preparing aramid chopped fiber/water dispersion: dispersing one of meta-aramid chopped fiber and para-aramid chopped fiber with a certain mass in water, and stirring and dispersing the mixture by a standard defiberizer for 15000r to obtain chopped fiber slurry with the mass concentration of 1.2%;
step two: preparing an aramid nano fiber/dimethyl sulfoxide dispersion liquid: to the recovered pairThe waste aramid fiber yarn is produced with potassium hydroxide, dimethyl sulfoxide and water (KOH/DMSO/H)2O) deprotonation reaction is carried out in the system to prepare aramid nano-fiber/dimethyl sulfoxide dispersion liquid with the mass concentration of 0.4%;
step three: in-situ protonation reduction and recombination: injecting the ANF/DMSO dispersion liquid obtained in the second step into the chopped fiber slurry through an injector to carry out in-situ protonation reduction and compounding; the mass ratio of the ANF/DMSO dispersion liquid to the aramid nano-fibers to the aramid chopped fibers in the slurry is 20:80; further, mechanical stirring is required in the process of injecting the ANF/DMSO into the cellulose pulp, and the stirring speed is controlled at 2000rpm; further, after the injection is finished, continuously mechanically stirring for 40min at the rotating speed of 2000rpm to obtain a composite fiber mixed dispersion liquid; and further, carrying out suction filtration on the obtained modified aramid composite fiber mixed dispersion liquid through a filter membrane, and intercepting on the filter membrane to obtain the modified aramid fiber.
The aramid paper is prepared by taking aramid nanofiber modified aramid chopped fibers as raw materials through the steps of dispersing, dehydrating, forming, squeezing, drying, hot pressing and the like, wherein the mass ratio of the aramid nanofiber to the aramid chopped fibers is 20:80.
example 3
An aramid fiber modification method is characterized in that aramid nanofiber/dimethyl sulfoxide dispersion liquid and aramid chopped fiber/water dispersion liquid are blended to realize in-situ protonation reduction and compounding of the aramid nanofiber, and aramid composite fiber coated with an aramid nanofiber network is prepared; wherein the mass ratio of the aramid nano-fiber to the aramid fiber is 30:70.
an aramid fiber modification method comprises the following steps:
the method comprises the following steps: preparing aramid chopped fiber/water dispersion: dispersing one of meta-aramid chopped fiber and para-aramid chopped fiber with a certain mass in water, and stirring and dispersing the mixture by a standard defiberizer for 15000r to obtain chopped fiber slurry with the mass concentration of 1.0%;
step two: preparation of aramid nanofiber/dimethylSulfoxide dispersion liquid: the recovered para-aramid yarn waste is used as a raw material to be added into potassium hydroxide/dimethyl sulfoxide/water (KOH/DMSO/H)2O) deprotonation reaction is carried out in the system to prepare aramid nano-fiber/dimethyl sulfoxide dispersion liquid with the mass concentration of 0.5%;
step three: in-situ protonation reduction and recombination: injecting the ANF/DMSO dispersion liquid obtained in the step two into the chopped fiber slurry through an injector to carry out in-situ protonation reduction and compounding; the mass ratio of the ANF/DMSO dispersion liquid to the aramid nano-fibers to the aramid chopped fibers in the slurry is 30:70; further, mechanical stirring is required in the process of injecting the ANF/DMSO into the cellulose pulp, and the stirring speed is controlled at 3000rpm; further, after the injection is finished, continuously mechanically stirring for 40min at the rotating speed of 3000rpm to obtain a composite fiber mixed dispersion liquid; and further, carrying out suction filtration on the obtained modified aramid composite fiber mixed dispersion liquid through a filter membrane, and retaining the dispersion liquid on the filter membrane to obtain the modified aramid fiber.
The aramid paper is prepared by taking aramid nanofiber modified aramid chopped fibers as raw materials through the steps of dispersing, dehydrating, forming, squeezing, drying, hot pressing and the like, wherein the mass ratio of the aramid nanofiber to the aramid chopped fibers is 30:70.
example 4
An aramid fiber modification method is characterized in that aramid nanofiber/dimethyl sulfoxide dispersion liquid and aramid chopped fiber/water dispersion liquid are blended to realize in-situ protonation reduction and compounding of aramid nanofiber, and aramid composite fiber coated with an aramid nanofiber network is prepared; wherein the mass ratio of the aramid nano-fiber to the aramid fiber is 40:60.
a method for modifying aramid fibers comprises the following steps:
the method comprises the following steps: preparing aramid chopped fiber/water dispersion: dispersing one of meta-aramid chopped fiber and para-aramid chopped fiber with a certain mass in water, and stirring and dispersing the mixture by a standard defiberizer for 15000r to obtain chopped fiber slurry with the mass concentration of 0.8%;
step two: preparing an aramid nano fiber/dimethyl sulfoxide dispersion liquid: the recovered para-aramid glove waste is used as a raw material to be processed in the presence of potassium hydroxide/dimethyl sulfoxide/water (KOH/DMSO/H)2O) deprotonation reaction is carried out in the system to prepare aramid nano-fiber/dimethyl sulfoxide dispersion liquid with the mass concentration of 0.7%;
step three: in-situ protonation reduction and recombination: injecting the ANF/DMSO dispersion liquid obtained in the step two into the chopped fiber slurry through an injector to carry out in-situ protonation reduction and compounding; the mass ratio of the ANF/DMSO dispersion liquid to the aramid nano-fibers to the aramid chopped fibers in the slurry is 40:60, adding a solvent to the mixture; further, mechanical stirring is required in the process of injecting the ANF/DMSO into the cellulose pulp, and the stirring speed is controlled at 4000rpm; further, after the injection is finished, continuously mechanically stirring for 50min at the rotating speed of 4000rpm to obtain a composite fiber mixed dispersion liquid; and further, carrying out suction filtration on the obtained modified aramid composite fiber mixed dispersion liquid through a filter membrane, and intercepting on the filter membrane to obtain the modified aramid fiber.
The aramid paper is prepared by taking aramid nanofiber modified aramid chopped fibers as raw materials through the steps of dispersing, dehydrating, forming, squeezing, drying, hot pressing and the like, wherein the mass ratio of the aramid nanofiber to the aramid chopped fibers is 40:60.
example 5
An aramid fiber modification method is characterized in that aramid nanofiber/dimethyl sulfoxide dispersion liquid and aramid chopped fiber/water dispersion liquid are blended to realize in-situ protonation reduction and compounding of aramid nanofiber, and aramid composite fiber coated with an aramid nanofiber network is prepared; wherein the mass ratio of the aramid nano-fiber to the aramid fiber is 50:50.
an aramid fiber modification method comprises the following steps:
the method comprises the following steps: preparing an aramid chopped fiber/water dispersion liquid: dispersing one of meta-aramid chopped fiber and para-aramid chopped fiber with a certain mass in water, and stirring and dispersing the mixture by a standard defiberizer for 15000r to obtain chopped fiber slurry with the mass concentration of 0.5%;
step two: preparing an aramid nano fiber/dimethyl sulfoxide dispersion liquid: the recovered para-aramid waste silk is used as a raw material to be treated in the presence of potassium hydroxide/dimethyl sulfoxide/water (KOH/DMSO/H)2O) deprotonation reaction is carried out in a system to prepare an aramid nano-fiber/dimethyl sulfoxide dispersion liquid with the mass concentration of 1.0%;
step three: in-situ protonation reduction and recombination: injecting the ANF/DMSO dispersion liquid obtained in the second step into the chopped fiber slurry through an injector to carry out in-situ protonation reduction and compounding; the mass ratio of the ANF/DMSO dispersion liquid to the aramid nano-fibers to the aramid chopped fibers in the slurry is 50:50; further, mechanical stirring is needed in the process of injecting the ANF/DMSO into the cellulose pulp, and the stirring speed is controlled at 5000rpm; further, after the injection is finished, continuously mechanically stirring for 60min at the rotating speed of 5000rpm to obtain a composite fiber mixed dispersion liquid; and further, carrying out suction filtration on the obtained modified aramid composite fiber mixed dispersion liquid through a filter membrane, and intercepting on the filter membrane to obtain the modified aramid fiber.
The aramid paper is prepared by taking aramid nanofiber modified aramid chopped fibers as raw materials through the steps of dispersing, dehydrating, forming, squeezing, drying, hot pressing and the like, wherein the mass ratio of the aramid nanofiber to the aramid chopped fibers is 50:50.
the modified aramid chopped fiber prepared in the embodiment 4 of the invention and the aramid paper made by the modified aramid chopped fiber are detected and characterized, and part of indexes are as follows: 1. average length of modified aramid fiber: 4.2mm; 2. specific surface area of composite fiber: 7.2m2(ii)/g; 3. aramid paper: quantification: 60g/m2Thickness: 0.055mm, tensile strength: 82MPa, tear strength: 1465mN, compressive strength: 25.9kV/mm.
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 scope of the present invention is defined by the claims, and is intended to include equivalents of the 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 (5)
1. The aramid fiber modification method is characterized in that aramid nanofiber/dimethyl sulfoxide dispersion liquid and aramid chopped fiber/water dispersion liquid are blended to realize in-situ protonation reduction and compounding of the aramid nanofiber, and the aramid nanofiber modified aramid fiber is prepared, wherein the mass ratio of the aramid nanofiber to the aramid chopped fiber is (10-50): (50-90);
the preparation process of the aramid chopped fiber/water dispersion liquid comprises the following steps: dispersing the aramid chopped fibers in water, and obtaining an aramid chopped fiber/water dispersion liquid with the mass concentration of 0.5-1.5% by discongesting, stirring and dispersing 15000 r;
the preparation process of the aramid nano-fiber/dimethyl sulfoxide dispersion liquid is as follows: taking the recovered para-aramid waste material as a raw material, and carrying out deprotonation reaction in a potassium hydroxide/dimethyl sulfoxide/water system to obtain an aramid nanofiber/dimethyl sulfoxide dispersion liquid with the mass concentration of 0.2-1.0%;
the in-situ protonation reduction and compounding process of the aramid nano fiber comprises the following specific steps: injecting the aramid nano fiber/dimethyl sulfoxide dispersion liquid into the aramid chopped fiber/water dispersion liquid through an injector to carry out in-situ protonation reduction and compounding.
2. The method for modifying aramid fiber according to claim 1, wherein the aramid chopped fibers are meta-aramid chopped fibers or para-aramid chopped fibers.
3. The method for modifying aramid fiber as claimed in claim 1, wherein the recovered para-aramid waste material is one or more of aramid cloth, aramid waste silk, aramid yarn and aramid gloves.
4. The aramid fiber modification method according to claim 1, wherein in the process of injecting the aramid nanofiber/dimethyl sulfoxide dispersion liquid into the aramid chopped fiber/water dispersion liquid, mechanical stirring is performed, after the injection is completed, the mechanical stirring is continued to obtain a modified aramid composite fiber mixed dispersion liquid, and the modified aramid composite fiber mixed dispersion liquid is subjected to suction filtration through a filter membrane to obtain the modified aramid fiber.
5. The aramid fiber modification method of claim 4, wherein the rotation speed of the mechanical stirring is 1500-5000 rpm, and after the injection is completed, the mechanical stirring is continued for 30-60 min.
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