Super-tough cellulose aerogel fiber as well as preparation method and use thereof
View Patent ↗A super-tough cellulose aerogel fiber, as well as its preparation method and applications are provided. Specifically, the method includes employing a wet spinning technique; preparing a molecular-level cellulose solution using a cellulose polymer as the raw material; using the molecular-level cellulose solution as the spinning solution, wherein during the spinning process, the cellulose polymer undergoes in-situ self-assembly and hydrogen bonding crosslinking to form a multi-level nanofiber structure, wherein the nanofiber structure is a continuous three-dimensional multi-level pore network structure. The super-tough cellulose aerogel fiber not only has excellent physical properties such as high strength and high toughness, but also possesses good adsorption and heat preservation performance due to a multi-level porous structure, so that the super-tough cellulose aerogel fiber can be applied to weaving and other technical fields, and is widely applied.
1 . A super-tough cellulose aerogel fiber, wherein the super-tough cellulose aerogel fiber comprises a multi-level nanofiber structure obtained by in-situ self-assembling and hydrogen bond cross-linking reaction, and the multi-level nanofiber structure is a continuous three-dimensional multi-level pore network structure, wherein the three-dimensional multi-level pore network structure comprises pores with a pore size of less than 2 nm, mesopores with a pore size of 2-50 nm, and macropores with a pore size of 50-100 nm; wherein
a toughness of the super-tough cellulose aerogel fiber is not less than 5 MJ/m 3 ; and wherein the super-tough cellulose aerogel fiber is prepared by a wet spinning technique, comprising:
(a) dissolving a cellulose polymer into a solvent to obtain a cellulose molecule solution, wherein the solvent comprises an ionic liquid selected from the group consisting of an imidazole type ionic liquid, a pyridine type ionic liquid, and a quaternary ammonium salt type ionic liquid;
(b) allowing the cellulose polymer in the cellulose molecule solution to undergo the in-situ self-assembling and the hydrogen bond cross-linking reaction by the wet spinning technique and simultaneously combining an orientation treatment to obtain a cellulose gel fiber; and
(c) performing a solvent replacement and a drying treatment on the cellulose gel fiber to obtain the super-tough cellulose aerogel fiber; and wherein
when being stretched by an external force, a pore structure in the three-dimensional multi-level pore network structure becomes smaller, a degree of an orientation of the three-dimensional multi-level pore network structure in a length direction gradually increases with a proceeding of stretching.
2 . The super-tough cellulose aerogel fiber according to claim 1 , wherein a source of the cellulose polymer comprises any one, or a combination of two or more of polypolymerized cellulose, lignin fiber, cellulose ether, methylcellulose, hydroxypropylmethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, or a natural plant material;
and/or, the natural plant material comprises any one, or a combination of two or more of cotton, flax, a wood material, straw, husk, and bamboo;
and/or, the cellulose polymer has a degree of polymerization between 6000 and 11000.
3 . The super-tough cellulose aerogel fiber according to claim 2 , wherein
the solvent comprises a mixture of one or more of dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP), dimethylacetamide (DMAC), and deionized water with the ionic liquid;
and/or, the ionic liquid is recycled.
4 . The super-tough cellulose aerogel fiber according to claim 1 , wherein
the toughness of the super-tough cellulose aerogel fiber is not less than 5 MJ/m 3 , with a diameter of 0.1 μm-1 mm, a specific area of 290-372 m 2 /g, a porosity of 80-90%, and a density of 0.18-0.25 g/cm 3 .
5 . The super-tough cellulose aerogel fiber according to claim 1 , wherein the super-tough cellulose aerogel fiber has a maximum tensile strength of 17-30 MPa, an elongation at break of 82-110%, and the toughness of 5-25 MJ/m 3 .
6 . A preparation method of the super-tough cellulose aerogel fiber according to claim 1 , specifically comprising:
(1) dissolving the cellulose polymer into a solvent to obtain a cellulose molecule solution;
(2) allowing the cellulose polymer in the cellulose molecule solution to undergo the in-situ self-assembling and the hydrogen bond cross-linking reaction by the wet spinning technique and simultaneously combining an orientation treatment to obtain a cellulose gel fiber; and
(3) performing a solvent replacement and a drying treatment on the cellulose gel fiber to obtain the super-tough cellulose aerogel fiber.
7 . The preparation method of the super-tough cellulose aerogel fiber according to claim 6 , wherein the wet spinning technique comprises: providing the cellulose molecule solution having a selected concentration as the spinning solution and absolute ethyl alcohol as a coagulating bath, extruding the spinning solution through an injection pump so that the spinning solution flows into the coagulating bath, and the cellulose polymer in the cellulose molecule solution is subjected to the in-situ self-assembling and the hydrogen bond cross-linking reaction, and then performing the orientation treatment to obtain the cellulose gel fiber.
8 . The preparation method of the super-tough cellulose aerogel fiber according to claim 7 , wherein a concentration of the cellulose polymer in the cellulose molecule solution is 0.1-20 wt %.
9 . The preparation method of the super-tough cellulose aerogel fiber according to claim 7 , wherein a dissolution temperature of the cellulose polymer in the solvent is 50-100° C.; a dissolution time is 0.3-96 h.
10 . The preparation method of the super-tough cellulose aerogel fiber according to claim 7 , wherein process conditions adopted in the wet spinning technique comprise: a diameter of a extrusion needle head of the injection pump is 0.1 μm-1 cm, and an extrusion speed of the extrusion needle head of the injection pump is 0.1-1000 mL/min.
11 . The preparation method of the super-tough cellulose aerogel fiber according to claim 7 , wherein an orientation treatment method comprises any one, or a combination of two or more of a flow orientation, a stretching orientation, and a directional freezing orientation.
12 . The preparation method of the super-tough cellulose aerogel fiber according to claim 6 , wherein the replacement solvent comprises any one, or a combination of two or more of water, methanol, ethanol, tert-butanol, acetone, cyclohexane, and n-hexane.
13 . The preparation method of the super-tough cellulose aerogel fiber according to claim 6 , further comprising a drying treatment that comprises any one, or a combination of two or more of a supercritical fluid drying method, a vacuum freeze-drying method, and a vacuum drying method.
14 . A textile prepared from the super-tough cellulose aerogel fiber according to claim 1 .
15 . The super-tough cellulose aerogel fiber according to claim 2 , wherein
the toughness of the super-tough cellulose aerogel fiber is not less than 5 MJ/m 3 , with a diameter of 0.1 μm-1 mm, a specific area of 290-372 m 2 /g, a porosity of 80-90%, and a density of 0.18-0.25 g/cm 3 .
16 . The super-tough cellulose aerogel fiber according to claim 3 , wherein
the toughness of the super-tough cellulose aerogel fiber is not less than 5 MJ/m 3 , with a diameter of 0.1 μm-1 mm, a specific area of 290-372 m 2 /g, a porosity of 80-90%, and a density of 0.18-0.25 g/cm 3 .
17 . The super-tough cellulose aerogel fiber according to claim 2 , wherein the super-tough cellulose aerogel fiber has a maximum tensile strength of 17-30 MPa, an elongation at break of 82-110%, and the toughness of 5-25 MJ/m 3 .
18 . The super-tough cellulose aerogel fiber according to claim 3 , wherein the super-tough cellulose aerogel fiber has a maximum tensile strength of 17-30 MPa, an elongation at break of 82-110%, and the toughness of 5-25 MJ/m 3 .
19 . The preparation method of the super-tough cellulose aerogel fiber according to claim 6 , wherein in the super-tough cellulose aerogel fiber, a source of the cellulose polymer comprises any one, or a combination of two or more of polypolymerized cellulose, lignin fiber, cellulose ether, methylcellulose, hydroxypropylmethyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, or a natural plant material;
and/or, the natural plant material comprises any one, or a combination of two or more of cotton, flax, a wood material, straw, husk, and bamboo;
and/or, the cellulose polymer has a degree of polymerization between 6000 and 11000.