CN114507910B - Nanometer aramid fiber reinforced regenerated cellulose fiber material, preparation method and application - Google Patents
Nanometer aramid fiber reinforced regenerated cellulose fiber material, preparation method and application Download PDFInfo
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- CN114507910B CN114507910B CN202210163675.2A CN202210163675A CN114507910B CN 114507910 B CN114507910 B CN 114507910B CN 202210163675 A CN202210163675 A CN 202210163675A CN 114507910 B CN114507910 B CN 114507910B
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- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 87
- 229920003043 Cellulose fiber Polymers 0.000 title claims abstract description 42
- 239000004627 regenerated cellulose Substances 0.000 title claims abstract description 36
- 239000002657 fibrous material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 229920002678 cellulose Polymers 0.000 claims abstract description 93
- 239000001913 cellulose Substances 0.000 claims abstract description 93
- 239000002131 composite material Substances 0.000 claims abstract description 54
- 239000000835 fiber Substances 0.000 claims abstract description 52
- 238000009987 spinning Methods 0.000 claims abstract description 40
- 239000006185 dispersion Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000004753 textile Substances 0.000 claims abstract description 8
- 229920000742 Cotton Polymers 0.000 claims abstract description 6
- 229920002994 synthetic fiber Polymers 0.000 claims abstract description 6
- 239000012209 synthetic fiber Substances 0.000 claims abstract description 6
- 210000002268 wool Anatomy 0.000 claims abstract description 6
- 229920003235 aromatic polyamide Polymers 0.000 claims description 49
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 48
- 239000004760 aramid Substances 0.000 claims description 41
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000005345 coagulation Methods 0.000 claims description 12
- 230000015271 coagulation Effects 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 238000009775 high-speed stirring Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000002166 wet spinning Methods 0.000 abstract description 5
- 239000004744 fabric Substances 0.000 abstract description 4
- 230000006872 improvement Effects 0.000 abstract description 3
- 230000001360 synchronised effect Effects 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 59
- 239000003513 alkali Substances 0.000 description 9
- 229920000297 Rayon Polymers 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000005507 spraying Methods 0.000 description 5
- 238000003828 vacuum filtration Methods 0.000 description 5
- LFTLOKWAGJYHHR-UHFFFAOYSA-N N-methylmorpholine N-oxide Chemical compound CN1(=O)CCOCC1 LFTLOKWAGJYHHR-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000002608 ionic liquid Substances 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229920002749 Bacterial cellulose Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229920003180 amino resin Polymers 0.000 description 1
- 239000005016 bacterial cellulose Substances 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000007380 fibre production Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
- D01F2/02—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from solutions of cellulose in acids, bases or salts
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/06—Wet spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
- Y02P70/62—Manufacturing or production processes characterised by the final manufactured product related technologies for production or treatment of textile or flexible materials or products thereof, including footwear
Abstract
The invention discloses a nano aramid fiber reinforced regenerated cellulose fiber material, a preparation method and application thereof. Compounding the nanometer aramid fiber aqueous dispersion with cellulose spinning solution, and forming regenerated cellulose composite fiber through wet spinning. The invention not only realizes the synchronous improvement of the dry and wet strength of the regenerated cellulose composite fiber, but also well maintains the fracture toughness of the prepared fiber and improves the maximum dry strength, wet strength and elongation. The regenerated cellulose composite fiber prepared by the method has the characteristics of high strength, low shrinkage, good elasticity and the like, can be singly used or blended with cotton, wool and other synthetic fibers, and is used in the fields of high-grade clothing fabrics, industrial textiles and the like.
Description
Technical Field
The invention belongs to the technical field of textile, and particularly relates to a nano aramid fiber reinforced regenerated cellulose fiber material, a preparation method and application thereof.
Background
As a textile fiber widely used, the regenerated cellulose fiber has the characteristics of good hygroscopicity, comfortable wearing, excellent spinnability and the like, and is often blended with cotton, wool or various synthetic fibers to be used for various clothing and decorative textiles. The conventional wet spinning viscose fiber preparation process has the problem of great environmental pollution, and is being replaced by a novel environment-friendly cellulose dissolution system, such as Ionic Liquids (ILs), sodium hydroxide (NaOH)/urea/thiourea systems or N-methylmorpholine-N-oxide (NMMO) solvents, and the like. In the process of industrial application of ionic liquid and NMMO solvent systems, the main problem to be solved at present is efficient recovery of the solvent due to the high price of the solvent. And the low-cost NaOH/urea or thiourea aqueous solution cooling solvent can rapidly realize cellulose dissolution, and the novel cellulose composite fiber is obtained through wet spinning. However, the strength problems exhibited by the fibers produced therefrom (especially wet strength, which is usually only about one-half of dry strength), result in fabrics produced from such cellulose fibers that exhibit poor dimensional stability and abrasion resistance. Therefore, the technology research and the process development of the green environment-friendly high-strength regenerated cellulose fiber are realized, the great social and economic benefits are achieved, and the sustainable development and the product upgrading of chemical fiber industry in China are promoted.
As the production process and spinning process of cellulose fibers continue to improve, a number of new classes of reinforced cellulose fibers, such as high wet modulus fibers, high crimped fibers, strong fibers, and the like, emerge. Although the wet strength and wet modulus of the high wet modulus cellulose fiber are improved, the dry strength is still lower, the brittleness is higher, and the product application is limited to a certain extent. The patent CN 107313123A adds different reinforcing agents in the multistage solidification process of viscose fiber production, so that crosslinking occurs among cellulose molecular chains, and the wet strength and the dry strength of the viscose fiber are improved. However, the occurrence of the crosslinking process also leads to an increased brittleness of the fibers. The preparation of composite material by adding organic nano particles into spinning solution is a common scheme for polymer reinforcement, the patent CN104233510A adopts amino resin to reinforce cellulose fiber, the patent CN101775671A adopts a ball milling method to crush bacterial cellulose powder and viscose fiber spinning solution to prepare spinning solution, and the spinning solution is prepared into high-strength viscose fiber. Patent CN104451930a discloses a method for whisker reinforced cellulose fiber, the prepared nano cellulose whisker dispersion system is blended with viscose spinning solution, and a cross-linking agent is added for reaction and then wet spinning is carried out to form high-strength cellulose fiber. In the above-mentioned scheme for reinforcing cellulose fibers by using organic polymers, organic matters are difficult to form a homogeneous system with cellulose due to the extremely strong hydrogen bonding action among cellulose molecular chains, so that a crosslinking system is simultaneously introduced in a large number of processes to avoid phase separation among components. For cellulose fibers, the addition of inorganic nanoparticles can increase the stiffness of the fiber, but can severely reduce the elongation of the fiber material. Therefore, on the premise of ensuring the toughness of the cellulose fiber, the dry and wet strength of the cellulose fiber is effectively improved, and the method is a common technical problem in the scientific research field and the production practice.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a nano aramid fiber reinforced and toughened regenerated cellulose fiber material and a preparation method thereof, so as to solve the problem of insufficient strength and toughness of cellulose fibers prepared by a novel solvent system. The invention adopts a new process and a new method to develop the environment-friendly cellulose composite fiber material with excellent spinnability, high dry and wet strength and good toughness of the obtained fiber, and has wide application prospect.
The invention is realized by the following technical scheme.
In one aspect of the invention, a preparation method of a nano aramid fiber reinforced regenerated cellulose fiber material is provided, comprising the following steps:
s1, preparing a nanometer aramid fiber aqueous dispersion liquid:
the mass ratio is (2-10): (3-15): (200-300) mixing para-aramid chopped fibers, potassium hydroxide and dimethyl sulfoxide, and continuously reacting under the condition of stirring at room temperature to obtain a nano aramid solution;
the mass ratio is (50-300): (1000-2000) pouring the nano aramid fiber solution into deionized water to flocculate nano aramid fiber gel, wherein the mass ratio is (1-15): (100-400) carrying out hydrothermal oxidation reaction on the nano aramid gel and acid, centrifugally separating a product, and then dispersing the product in water again to form nano aramid aqueous dispersion;
s2, preparing a nano aramid fiber/cellulose composite spinning solution:
100, adding the nano aramid fiber aqueous dispersion into a cellulose solution under the condition of high-speed stirring to form nano aramid fiber/cellulose composite spinning solution;
s3, preparing a nanometer aramid fiber/cellulose composite fiber:
and (3) spinning the nano aramid fiber/cellulose composite spinning solution through a spinning device, then feeding the spinning solution into a dilute acid coagulation bath to prepare nano aramid fiber/cellulose composite fiber, drawing, oiling and drying the nano aramid fiber/cellulose composite fiber to obtain the nano aramid fiber reinforced regenerated cellulose fiber material.
Preferably, in step S1, the reaction is continued for 3 to 10 days under stirring at room temperature.
The hydrothermal reaction temperature is 120-160 ℃, and the hydrothermal time is 2-6 hours.
Preferably, the acid of the hydrothermal oxidation reaction is one or more of nitric acid, sulfuric acid, hypochlorous acid or perchloric acid.
Preferably, the mass concentration of the nano-aramid aqueous dispersion is 0.5-5wt%.
Preferably, the cellulose content of the cellulose solution is 2-20wt%.
Preferably, the solvent in the cellulose solution is 3-10wt% of alkaline compound, 3-20wt% of urea or thiourea, and the balance is water;
the alkaline compound includes one or any combination of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, ammonium hydroxide, or tetrabutylammonium hydroxide.
Preferably, in step S3, the mass fraction of acid in the dilute acid coagulation bath is 3-5wt%.
Preferably, the acid in the dilute acid coagulation bath comprises one or a combination of several of sulfuric acid, phosphoric acid, oxalic acid, perchloric acid or permanganic acid.
In another aspect of the invention, the invention provides the nano aramid fiber reinforced regenerated cellulose fiber material prepared by the method.
In still another aspect of the invention, the prepared nano-aramid reinforced regenerated cellulose fiber material is applied to textiles as a single use or blended with cotton, wool and other synthetic fibers.
Due to the adoption of the technical scheme, the invention has the following beneficial effects:
according to the invention, firstly, the para-aramid fiber is stripped by utilizing the potassium hydroxide/dimethyl sulfoxide composite solvent to form the nano-aramid fiber solution, and the nano-aramid fiber oxidized by acid can be well dispersed in the aqueous solution, so that the good dispersion of the nano-aramid fiber in the composite material is ensured. Simultaneously, amide groups on the molecular chain of the nanometer aramid fiber and carboxyl groups introduced through oxidization can easily form hydrogen bond action with a large number of hydroxyl groups on the molecular chain of the cellulose, so that the composite fiber realizes better reinforcing effect. The destruction and remolding process of the hydrogen bond action can absorb a large amount of energy, so that the toughness of the composite fiber material is synchronously improved. Compounding the nanometer aramid fiber aqueous dispersion with cellulose spinning solution, and forming regenerated cellulose composite fiber through wet spinning. Not only realizes the synchronous improvement of the dry and wet strength of the regenerated cellulose composite fiber, but also well maintains the fracture toughness of the prepared fiber, the maximum dry strength can reach 3.8cN/dtex, the wet strength can reach 3.09cN/dtex, and the elongation is not less than 15 percent. At the same time, the nano aramid fiber has smaller size and excellent dispersion, and the intrinsic color of the cellulose fiber is not changed after the nano aramid fiber is added. The regenerated cellulose composite fiber prepared by the method has the characteristics of high strength, low shrinkage, good elasticity and the like, can be singly used or blended with cotton, wool and other synthetic fibers, and is used in the fields of high-grade clothing fabrics, industrial textiles and the like.
The dry strength of the composite regenerated cellulose fiber prepared by the method can be improved by more than 30% compared with that of the conventional viscose cellulose fiber, and the wet strength can be improved by more than 40%.
The method has simple process, does not need special equipment, and is easy to realize industrial production. The components of the co-alkali solution selected by the invention are all cheap industrial raw materials, and the dissolution of cellulose and the preparation scheme of the aramid nanofiber aqueous dispersion have the feasibility of large-scale production.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The present invention will be described in detail with reference to specific examples, wherein the exemplary embodiments and descriptions of the present invention are provided for the purpose of illustration and are not intended to be limiting.
The invention provides a preparation method of a nano aramid fiber reinforced regenerated cellulose fiber material, which comprises the following steps:
step 1, preparing a nano aramid fiber aqueous dispersion liquid:
the mass ratio is (2-10): (3-15): (200-300) continuously reacting para-aramid fiber, potassium hydroxide and dimethyl sulfoxide for 3-10 days under the condition of stirring at room temperature to obtain a nano aramid solution; the mass ratio is (50-300): (1000-2000) pouring the nano aramid solution into deionized water to flocculate nano aramid gel, and removing components such as potassium hydroxide, dimethyl sulfoxide and the like through vacuum filtration to obtain the nano aramid gel; the mass ratio is (1-15): (100-400) dispersing the gel in an acidic aqueous solution, carrying out hydrothermal oxidation reaction for 2-6 hours at the temperature of 120-160 ℃, and dispersing the product in water again after centrifugal separation to form the nano-aramid aqueous dispersion with the mass concentration of 0.5-5wt%.
Wherein the acidic environment for the oxidation of the nanoaramid gel is provided by an oxidizing strong acid, preferably an oxidizing strong acid comprising one or a combination of several of nitric acid, sulfuric acid, hypochlorous acid or perchloric acid.
Step 2, preparing a nano aramid/cellulose composite spinning solution:
according to the mass fraction of cellulose in the solution being 2-20wt%, placing the cellulose in a pre-cooled solvent, and rapidly dissolving the cellulose by high-speed stirring to obtain a transparent cellulose solution with high solubility; and (2) adding the nano aramid fiber aqueous dispersion liquid obtained in the step (1) into the cellulose solution under the condition of high-speed stirring according to the mass ratio of cellulose to nano aramid fiber of 100:0.5-100:5 to form the nano aramid fiber/cellulose composite spinning solution.
The solvent composition of the cellulose solution in the step 2 is 3-10wt% of alkaline compound, 3-20wt% of urea or thiourea, and the balance of water, wherein the total weight of the solvent composition is 100%; wherein the alkaline compound comprises one or any combination of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, ammonium hydroxide or tetrabutylammonium hydroxide.
Step 3, preparing the nanometer aramid fiber/cellulose composite fiber:
and (3) spraying the nano aramid fiber/cellulose composite spinning solution obtained in the step (2) through a spinning device, then entering a dilute acid coagulation bath with the mass fraction of 3-5wt% to prepare the nano aramid fiber/cellulose composite fiber, further drafting, oiling and drying the nano aramid fiber/cellulose composite fiber to obtain the nano aramid fiber reinforced regenerated cellulose fiber material.
The acid in the dilute acid coagulation bath comprises one or a combination of a plurality of sulfuric acid, phosphoric acid, oxalic acid, perchloric acid or permanganic acid.
The invention will be described in further detail by means of specific examples.
Example 1
1) Preparing nano aramid fiber aqueous dispersion liquid:
2g para-aramid fiber and 4g potassium hydroxide are put into 200ml dimethyl sulfoxide solvent, and continuously stirred for 3 days at room temperature to obtain brownish red nanometer aramid fiber solution; pouring 200ml of the nano aramid solution into 1500ml of water to flocculate nano aramid gel, and removing components such as potassium hydroxide, dimethyl sulfoxide and the like through vacuum filtration to obtain the nano aramid gel; 1g of the gel was subjected to a hydrothermal oxidation reaction in 200ml of a nitric acid/sulfuric acid mixture solution in which the mass concentration of nitric acid was 8.75wt% and the mass concentration of sulfuric acid was 37.5wt%, the hydrothermal reaction temperature was 120℃and the hydrothermal time was 6 hours; after the hydrothermal process is finished, the product is centrifugally separated and then is dispersed in water again to form the nano aramid fiber aqueous dispersion with the mass concentration of 0.5 percent.
2) Preparing a nano aramid/cellulose composite spinning solution:
the cellulose is placed in 100ml of a common alkali system cellulose solvent which is precooled to the temperature of minus 5 ℃ according to 6g of cellulose, wherein the common alkali system solvent contains 6g of sodium hydroxide, 12g of urea and the balance of water. The cellulose dissolving system is stirred at a high speed to quickly dissolve cellulose, so that a transparent cellulose solution with high solubility is obtained; adding the nano aramid fiber aqueous dispersion obtained in the step 1 into the cellulose solution under the condition of high-speed stirring according to the mass ratio of cellulose to nano aramid fiber of 100:0.5 to form nano aramid fiber/cellulose composite spinning solution;
3) Preparing a nano aramid/cellulose composite fiber:
and (3) spraying the nano aramid fiber/cellulose composite spinning solution obtained in the step (2) through a spinning device, then entering into 3% oxalic acid coagulation bath to prepare nano aramid fiber/cellulose composite fiber, and further carrying out drafting, oiling and drying to obtain the nano aramid fiber reinforced regenerated cellulose fiber material of the embodiment (1).
Example 2
1) Preparing nano aramid fiber aqueous dispersion liquid:
putting 4g of para-aramid fiber and 8g of potassium hydroxide into 300ml of dimethyl sulfoxide solvent, and continuously stirring for 6 days at room temperature to obtain a brownish red nanometer aramid solution; pouring 50ml of the nano aramid solution into 1000ml of water to flocculate nano aramid gel, and removing components such as potassium hydroxide, dimethyl sulfoxide and the like through vacuum filtration to obtain the nano aramid gel; 3g of the gel was subjected to a hydrothermal oxidation reaction in 150ml of a hypochlorous acid/perchloric acid mixture solution in which the mass concentration of hypochlorous acid was 10wt% and the mass concentration of perchloric acid was 8wt%, the hydrothermal reaction temperature was 130℃and the hydrothermal time was 5 hours; and after the hydrothermal process is finished, centrifugally separating the product, and dispersing the product into water again to form the nano-aramid fiber aqueous dispersion with the mass concentration of 1%.
2) Preparing a nano aramid/cellulose composite spinning solution:
the cellulose is placed in 100ml of a common alkali system cellulose solvent which is precooled to the temperature of minus 5 ℃ according to 2g, wherein the common alkali system solvent contains 8g of lithium hydroxide, 20g of thiourea and the balance of water. The cellulose dissolving system is stirred at a high speed to quickly dissolve cellulose, so that a transparent cellulose solution with high solubility is obtained; adding the nano aramid fiber aqueous dispersion obtained in the step 1 into the cellulose solution under the condition of high-speed stirring according to the mass ratio of cellulose to nano aramid fiber of 100:1 to form nano aramid fiber/cellulose composite spinning solution;
3) Preparing a nano aramid/cellulose composite fiber:
and (3) spraying the nano aramid fiber/cellulose composite spinning solution obtained in the step (2) through a spinning device, then entering into a dilute sulfuric acid coagulation bath with the weight percent of 5% to prepare the nano aramid fiber/cellulose composite fiber, and further carrying out drafting, oiling and drying to obtain the nano aramid fiber reinforced regenerated cellulose fiber material of the embodiment (2).
Example 3
1) Preparing nano aramid fiber aqueous dispersion liquid:
10g of para-aramid fiber and 15g of potassium hydroxide are put into 260ml of dimethyl sulfoxide solvent, and continuously stirred for 8 days at room temperature to obtain brownish red nanometer aramid solution; pouring 200ml of the nano aramid solution into 2000ml of water to flocculate nano aramid gel, and removing components such as potassium hydroxide, dimethyl sulfoxide and the like through vacuum filtration to obtain the nano aramid gel; 15g of the gel were subjected to a hydrothermal oxidation reaction in 400ml of a nitric acid/sulfuric acid mixture solution in which the mass concentration of nitric acid was 10wt% and the mass concentration of sulfuric acid was 35wt%, the hydrothermal reaction temperature was 160℃and the hydrothermal time was 2 hours; and after the hydrothermal process is finished, centrifugally separating the product, and dispersing the product into water again to form the nano-aramid fiber aqueous dispersion with the mass concentration of 5%.
2) Preparing a nano aramid/cellulose composite spinning solution:
the cellulose is placed in 100ml of a common alkali system cellulose solvent which is precooled to the temperature of minus 5 ℃ according to 20g, wherein the common alkali system solvent comprises 10g of sodium bicarbonate and lithium bicarbonate, 18g of urea and the balance of water. The cellulose dissolving system is stirred at a high speed to quickly dissolve cellulose, so that a transparent cellulose solution with high solubility is obtained; adding the nano aramid fiber aqueous dispersion obtained in the step 1 into the cellulose solution under the condition of high-speed stirring according to the mass ratio of cellulose to nano aramid fiber of 100:2 to form nano aramid fiber/cellulose composite spinning solution;
3) Preparing a nano aramid/cellulose composite fiber:
and (3) spraying the nano aramid fiber/cellulose composite spinning solution obtained in the step (2) through a spinning device, then entering into 4wt% perchloric acid and permanganic acid coagulation bath to prepare the nano aramid fiber/cellulose composite fiber, further drafting, oiling and drying to obtain the nano aramid fiber reinforced regenerated cellulose fiber material of the embodiment (3).
Example 4
1) Preparing nano aramid fiber aqueous dispersion liquid:
6g of para-aramid fiber and 12g of potassium hydroxide are put into 300ml of dimethyl sulfoxide solvent, and continuously stirred for 7 days at room temperature to obtain brownish red nanometer aramid solution; pouring 300ml of the nano aramid solution into 1800ml of water to flocculate nano aramid gel, and removing components such as potassium hydroxide, dimethyl sulfoxide and the like through vacuum filtration to obtain the nano aramid gel; 10g of the gel was subjected to a hydrothermal oxidation reaction in 100ml of a nitric acid/sulfuric acid mixture solution in which the mass concentration of nitric acid was 12wt% and the mass concentration of sulfuric acid was 37wt%, the hydrothermal reaction temperature was 120℃and the hydrothermal time was 4 hours; and after the hydrothermal process is finished, centrifugally separating the product, and dispersing the product into water again to form the nano-aramid water dispersion with the mass concentration of 3%.
2) Preparing a nano aramid/cellulose composite spinning solution:
the cellulose according to 8g is placed in 100ml of co-alkali system cellulose solvent precooled to-5 ℃, wherein the co-alkali system solvent comprises 8g of ammonium hydroxide and tetrabutylammonium hydroxide, 12g of urea and the balance of water. The cellulose dissolving system is stirred at a high speed to quickly dissolve cellulose, so that a transparent cellulose solution with high solubility is obtained; adding the nano aramid fiber aqueous dispersion obtained in the step 1 into the cellulose solution under the condition of high-speed stirring according to the mass ratio of cellulose to nano aramid fiber of 100:5 to form nano aramid fiber/cellulose composite spinning solution;
3) Preparing a nano aramid/cellulose composite fiber:
and (3) spraying the nano aramid fiber/cellulose composite spinning solution obtained in the step (2) through a spinning device, then entering into a 4wt% phosphoric acid coagulation bath to prepare the nano aramid fiber/cellulose composite fiber, and further carrying out drafting, oiling and drying to obtain the nano aramid fiber reinforced regenerated cellulose fiber material of the embodiment (4).
The fibrous materials prepared in examples 1-4 were tested for material properties as follows by table 1.
TABLE 1 comparison of the Properties of examples and comparative examples
As can be seen from Table 1, the nano aramid fiber reinforced and toughened regenerated cellulose fiber material prepared by the invention is far superior to the comparative example in mechanical property. The introduction of the nanometer aramid fiber not only realizes the synchronous improvement of the dry and wet strength of the regenerated cellulose composite fiber, but also well maintains the fracture toughness of the prepared fiber, the maximum dry tensile strength of the fiber can reach 3.8cN/dtex, the wet strength can reach 3.09cN/dtex, and the dry elongation is not less than 15 percent. The dry tensile strength is not less than 3.25 (cN/dtex), the wet tensile strength is not less than 2.56 (cN/dtex), the wet elongation (%) is not more than 23%, and the water expansion degree is not more than 70%. Based on the performance advantages, the regenerated cellulose composite fiber prepared by the method can meet the requirement of single use or blending with cotton, wool and other synthetic fibers, and has important application prospects in the fields of high-grade clothing fabrics, industrial textiles and the like.
The invention is not limited to the above embodiments, and based on the technical solution disclosed in the invention, a person skilled in the art may make some substitutions and modifications to some technical features thereof without creative effort according to the technical content disclosed, and all the substitutions and modifications are within the protection scope of the invention.
Claims (8)
1. The preparation method of the nano aramid fiber reinforced regenerated cellulose fiber material is characterized by comprising the following steps of:
s1, preparing a nano aramid fiber aqueous dispersion liquid:
the mass ratio is (2-10): (3-15): (200-300) mixing para-aramid chopped fibers, potassium hydroxide and dimethyl sulfoxide, and continuously reacting under the condition of stirring at room temperature to obtain a nano aramid solution;
the mass ratio is (50-300): (1000-2000) pouring the nano aramid fiber solution into deionized water to flocculate nano aramid fiber gel, wherein the mass ratio is (1-15): (100-400) carrying out hydrothermal oxidation reaction on the nano aramid gel and acid, centrifugally separating a product, and then dispersing the product in water again to form nano aramid aqueous dispersion;
the mass concentration of the nano aramid fiber aqueous dispersion is 0.5-5 wt%;
s2, preparing a nano aramid/cellulose composite spinning solution:
100, adding the nano aramid fiber aqueous dispersion into a cellulose solution under the condition of high-speed stirring to form nano aramid fiber/cellulose composite spinning solution;
the cellulose content in the cellulose solution is 2-20 wt%;
s3, preparing a nano aramid/cellulose composite fiber:
and (3) spinning the nano aramid fiber/cellulose composite spinning solution through a spinning device, then feeding the spinning solution into a dilute acid coagulation bath to prepare nano aramid fiber/cellulose composite fiber, drawing, oiling and drying the nano aramid fiber/cellulose composite fiber to obtain the nano aramid fiber reinforced regenerated cellulose fiber material.
2. The method for preparing a nano aramid fiber reinforced regenerated cellulose fiber material according to claim 1, wherein in step S1, the continuous reaction is performed for 3-10 days under the condition of stirring at room temperature;
the hydrothermal reaction temperature is 120-160 ℃, and the hydrothermal time is 2-6 hours.
3. The method for preparing the nano-aramid fiber reinforced regenerated cellulose fiber material according to claim 1, wherein the acid of the hydrothermal oxidation reaction is one or more of nitric acid, sulfuric acid, hypochlorous acid or perchloric acid.
4. The method for preparing the nano-aramid fiber reinforced regenerated cellulose fiber material according to claim 1, wherein the solvent in the cellulose solution is 3-10wt% of alkaline compound, 3-20wt% of urea or thiourea, and the balance is water;
the alkaline compound includes one or any combination of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, ammonium hydroxide, or tetrabutylammonium hydroxide.
5. The method for producing a nano-aramid fiber reinforced regenerated cellulose fiber material according to claim 1, wherein in step S3, the mass fraction of the acid in the dilute acid coagulation bath is 3-5wt%.
6. The method for preparing a nano-aramid fiber reinforced regenerated cellulose fiber material according to claim 5, wherein the acid in the dilute acid coagulation bath comprises one or a combination of several of sulfuric acid, phosphoric acid, oxalic acid, perchloric acid or permanganic acid.
7. The nano-aramid fiber reinforced regenerated cellulose fiber material prepared by the method of any one of claims 1 to 6.
8. The use of the nanoaramid-reinforced regenerated cellulose fiber material of claim 7 as a sole or blended with cotton, wool and synthetic fibers in textiles.
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