CN115434072B - Preparation method of metal ion crosslinked and toughened cellulose nanofiber material - Google Patents

Preparation method of metal ion crosslinked and toughened cellulose nanofiber material Download PDF

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CN115434072B
CN115434072B CN202211002785.7A CN202211002785A CN115434072B CN 115434072 B CN115434072 B CN 115434072B CN 202211002785 A CN202211002785 A CN 202211002785A CN 115434072 B CN115434072 B CN 115434072B
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cellulose nanofiber
cnf
metal ion
nanofiber cnf
wet
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CN115434072A (en
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韦小丁
刘璇
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Nanchang Innovation Research Institute Of Peking University
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Nanchang Innovation Research Institute Of Peking University
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Abstract

The invention discloses a preparation method of a metal ion crosslinking strengthening and toughening cellulose nanofiber CNF material, which adopts a wet-drawing orientation method to regulate and control the arrangement direction of cellulose nanofiber CNF in situ, so as to prepare the cellulose nanofiber CNF material with fiber orientation arrangement; the interaction between fibers in the cellulose nanofiber CNF material is enhanced by adopting a metal ion crosslinking strategy. By utilizing the invention, the problem of poor mechanical property of the cellulose nanofiber CNF material is solved by in-situ regulating and controlling the arrangement direction of the cellulose nanofiber CNF and the interaction between the cellulose nanofiber CNF and the cellulose nanofiber CNF, and the metal ion crosslinked and toughened cellulose nanofiber CNF-M with oriented fiber and compact structure can be prepared n+ A material. Compared with common CNF material, the CNF-M n+ The material has high strength and high toughness, avoids the cost of sacrificing the toughness while improving the strength of the material, and meets the requirements of the material on high strength and high toughness in the practical application process.

Description

Preparation method of metal ion crosslinked and toughened cellulose nanofiber material
Technical Field
The invention relates to the technical field of green environment-friendly biological material preparation, in particular to a preparation method of a metal ion crosslinked and toughened cellulose nanofiber material.
Background
The cellulose nano-fiber (Cellulose nanofibrils, CNF) is extracted from plant fibers or produced by bacteria, has small density, is degradable, has excellent mechanical properties, is one of the strongest materials found in nature by people so far, and has tensile strength and tensile modulus of 6-7 GPa and 120-140 GPa respectively, which are higher than those of the common chemical fibers.
In addition, ether bond, hydroxyl, carbon-carbon bond and hydrocarbon bond in CNF molecular chain can not absorb visible light, so that the CNF molecular chain has the characteristic of transparency. CNF can self-assemble to form transparent material with disordered network structure through hydrogen bond, and the material is widely applied to the fields of solar cells, supercapacitors, display, wearable equipment and the like. Along with the increasing serious problems of environmental pollution and energy shortage, CNF material is taken as a renewable and degradable biological resource, and the development and application of the CNF material have important significance for saving energy consumption and recycling substances in nature, and assist China to respectively realize the targets of carbon reaching peak and carbon neutralization before 2030 and 2060.
However, the mechanical properties of CNF materials are highly dependent on their own microstructure. On one hand, CNF is generally randomly distributed in the material, and cannot uniformly bear load, so that the effective exertion of the ultra-high strength of CNF is limited; on the other hand, it is difficult to form a dense structure by only hydrogen bonding between CNFs, resulting in the formation of pores inside the material. Furthermore, the actual strength and the theoretical value of the CNF material are far different, and the problem that the mechanical property of the CNF material is poor is not solved effectively.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a metal ion crosslinked and toughened cellulose nanofiber material, so as to solve the problem of poor mechanical properties of CNF materials, prepare the CNF material with oriented fibers and compact structure, and meet the requirements of high strength and high toughness of the material in the practical application process.
In order to achieve the above object, the present invention provides a method for preparing a metal ion crosslinked and toughened cellulose nanofiber material, comprising:
adopting a wet-drawing orientation method to regulate and control the arrangement direction of cellulose nanofiber CNF in situ, and preparing a cellulose nanofiber CNF material with fiber oriented arrangement; and
the interaction between fibers in the cellulose nanofiber CNF material is enhanced by adopting a metal ion crosslinking strategy.
In the above scheme, in the step of preparing the cellulose nanofiber CNF material with fiber oriented arrangement by adopting the wet-drawing orientation method to regulate and control the arrangement direction of the cellulose nanofiber CNF in situ, the cellulose nanofiber CNF oxidized by tetramethyl piperidine TEMPO is selected to ensure that C on a CNF molecular chain 6 Is substituted by carboxyl.
In the scheme, the diameter of the cellulose nanofiber CNF is between 30 and 70nm.
In the above scheme, in the step of preparing the cellulose nanofiber CNF material with fiber oriented arrangement by adopting the wet-drawing orientation method to regulate and control the arrangement direction of the cellulose nanofiber CNF in situ, the wet-drawing orientation method is adopted to regulate and control the arrangement direction of the cellulose nanofiber CNF in situ, so that the cellulose nanofiber CNF is oriented and arranged along the stretching direction of the material.
In the scheme, the stretching speed of the wet-drawing orientation method is 1-24 mm/min, the stretching strain rate of the cellulose nanofiber CNF material is 20%, and the holding time is 0.5-1 h.
In the above scheme, in the step of enhancing the interaction between fibers in the cellulose nanofiber CNF material by adopting the metal ion crosslinking strategy, metal ions M are introduced into the cellulose nanofiber CNF material n+ Metal ion M n+ Molecular chain C of CNF material with cellulose nanofiber 6 The carboxyl groups are connected through coordination bonds, and interaction between fibers in adjacent cellulose nanofiber CNF is enhanced in a bridging mode.
In the above scheme, the metal ion M n+ Comprises Na + 、Ca 2+ 、Cu 2+ 、Al 3+ Or Fe (Fe) 3+ 。
In the above scheme, the metal ion M n+ The concentration of the solution is 50-60 mM, the treatment time is 72-96 h, and the treatment temperature is 20-30 ℃.
In the above scheme, the method further comprises the following steps after the interaction among fibers in the cellulose nanofiber CNF material is enhanced by adopting a metal ion crosslinking strategy: and cleaning and drying the cellulose nanofiber CNF material subjected to metal ion crosslinking treatment, and performing mould pressing treatment after drying.
In the scheme, the cellulose nanofiber CNF material is cleaned by alternately cleaning with distilled water and ethanol solution; the cellulose nanofiber CNF material is dried by using CNF-M n+ The material is placed in an oven with the temperature of 60-70 ℃ for drying; the cellulose nanofiber CNF material is subjected to die pressing treatment, the pressure is 20-30 MPa, the die pressing time is 6-8 h, and the die pressing temperature is 20-30 ℃.
From the above technical scheme, the invention has the following beneficial effects:
1. according to the preparation method of the metal ion crosslinked and toughened cellulose nanofiber material, provided by the invention, the arrangement direction of cellulose nanofiber CNF and interaction among the cellulose nanofiber CNF can be regulated and controlled in situ by adopting a wet pulling orientation method and a metal ion crosslinking strategy, so that the problem of poor mechanical properties of the cellulose nanofiber CNF material is solved, and the metal ion crosslinked and toughened cellulose nanofiber CNF-M with oriented fibers and compact structure can be prepared n+ A material.
2. The preparation method of the metal ion crosslinked and toughened cellulose nanofiber material provided by the invention prepares the metal ion crosslinked and toughened cellulose nanofiber CNF-M with oriented fibers and compact structures n+ Compared with the common cellulose nanofiber CNF material, the material has high strength and high toughness, wherein CNF-Fe 3+ The tensile strength and toughness of the material respectively reach 451.51MPa and 8.19 MJ.m -3 Compared with the CNF material which is not crosslinked, the tensile strength and the toughness of the CNF material are respectively improved by 60 percent and 80 percent, and the cost of sacrificing the toughness of the CNF material while the material strength is improved is avoided, thereby meeting the requirements of high strength and high toughness of the CNF material in the practical application process.
3. The preparation method of the metal ion crosslinked and toughened cellulose nanofiber material provided by the invention is simple and easy to operate, the raw materials are green and degradable, the reaction condition is mild, the preparation process is environment-friendly and pollution-free, no organic solvent or special chemical reagent is needed, the development and application of the material have important significance for saving the energy consumption and recycling the substances in the nature, and the material is expected to help China to realize the targets of carbon peak and carbon neutralization before 2030 and 2060.
Drawings
The invention will be further described with reference to the drawings and examples.
FIG. 1 is a schematic diagram of a preparation process of a metal ion crosslinked and toughened cellulose nanofiber CNF material provided by the invention;
FIG. 2 is a flow chart of a preparation method of the metal ion crosslinked and toughened cellulose nanofiber CNF material provided by the invention;
fig. 3 is a photograph of the surface micro-topography of comparative examples 1 and 2 provided by the present invention, wherein the left graph is the surface micro-topography of comparative example 1 and the right graph is the surface micro-topography of comparative example 2.
Fig. 4 is an infrared spectrum of examples 1 to 5 and comparative example 2 provided by the present invention.
FIG. 5 is a schematic view of the mechanical properties of examples 1-5, comparative example 1 and comparative example 2 provided herein, wherein (a) tensile stress-strain curves; (b) tensile strength; (c) Young's modulus; (d) toughness.
Detailed Description
The present invention will be further described in detail below with reference to specific embodiments and with reference to the accompanying drawings, in order to make the objects, technical solutions and advantages of the present invention more apparent.
Aiming at the problems that the actual strength and the theoretical value of the prior CNF material are far different and the mechanical property of the CNF material is poor, researches show that the arrangement direction of CNF in the material can be regulated and controlled by a wet-drawing orientation method, and the CNF material with fiber orientation arrangement is prepared. In addition, by depositing metal ions on the surface of CNF, the interaction between CNF can be promoted by using a metal ion crosslinking strategy, and small-size pores between CNF and CNF-M can be eliminated, so that CNF-M with compact structure can be prepared n+ A material. However, how to combine wet-drawing orientation method and metal ion crosslinking strategy, in-situ regulate the alignment direction of CNF and the mutual interaction between CNF and CNF-M with compact fiber orientation and structure n+ Materials, while effectively improving the materials thereofStrength and toughness to meet the requirements in practical application are key technical problems to be solved in the green environment-friendly novel material.
In view of the above, the invention provides a preparation method of a metal ion crosslinked and toughened cellulose nanofiber material, which is characterized in that the arrangement direction of CNF is regulated and controlled in situ by a wet drawing orientation method, so that the unordered CNF is arranged in a fiber orientation along the stretching direction of the material, and the anisotropic regular structure of the CNF material is endowed; and a metal ion crosslinking strategy is adopted, metal ions are introduced into the CNF material, and the metal ions and carboxyl groups on the surfaces of adjacent CNFs respectively form strong-binding coordination bonds, so that the bridging effect is fully exerted, and the interaction between fibers in the CNF material is effectively enhanced. The alignment direction of the CNF material and the interaction between the CNF material and the CNF material are regulated in situ by combining a wet-drawing orientation method and a metal ion crosslinking strategy, so that the fiber-oriented and compact-structure high-strength and toughness CNF-M is prepared n+ A material.
As shown in fig. 1 and fig. 2, fig. 1 is a schematic diagram of a preparation process of a metal ion crosslinked and toughened cellulose nanofiber CNF material provided by the present invention, and fig. 2 is a flowchart of a preparation method of a metal ion crosslinked and toughened cellulose nanofiber CNF material provided by the present invention, the method comprises the following steps:
step S1: adopting a wet-drawing orientation method to regulate and control the arrangement direction of cellulose nanofiber CNF in situ, and preparing a cellulose nanofiber CNF material with fiber oriented arrangement;
step S2: the interaction between fibers in the cellulose nanofiber CNF material is enhanced by adopting a metal ion crosslinking strategy.
According to the embodiment of the invention, in step S1, the arrangement direction of the cellulose nanofiber CNF is regulated and controlled in situ by adopting a wet-drawing orientation method, and the cellulose nanofiber CNF material with fiber oriented arrangement is prepared by selecting cellulose nanofiber CNF oxidized by tetramethyl piperidine TEMPO, so that C on a CNF molecular chain is ensured 6 Is substituted by carboxyl. Wherein the cellulose nanofiber CNF has a diameter between 30 and 70nm, alternatively the cellulose nanofiber CNF may have a diameter of 30nm, 40nm, 50nm, 60nm or 70nm. Cellulose nanofiber CNThe oxidation method of F includes but is not limited to tetramethyl piperidine TEMPO oxidation method, the raw material of cellulose nanofiber CNF includes but is not limited to sheet film, when the raw material is CNF dispersion liquid, the film can be prepared by vacuum filtration method.
In step S1, the alignment direction of the cellulose nanofibers CNF is adjusted in situ by a wet-drawing orientation method, so that the cellulose nanofibers CNF are aligned along the stretching direction of the material. The stretching speed of the wet stretching orientation method is 1-24 mm/min, the stretching strain rate of the cellulose nanofiber CNF material is 20%, and the retention time is 0.5-1 h. Alternatively, the wet-draw orientation process may have a draw speed of 1mm/min, 12mm/min, 24mm/min and a hold time of 0.5h, 0.75h, 1h.
According to the embodiment of the invention, in the step S2, the metal ion crosslinking strategy is adopted to enhance the interaction between fibers in the cellulose nanofiber CNF material, namely, the metal ion crosslinking strategy is adopted to introduce metal ions M into the cellulose nanofiber CNF material n+ The interaction among fibers in the cellulose nanofiber CNF material is enhanced, and the metal ion crosslinking strengthening and toughening cellulose nanofiber CNF-M with oriented fibers and compact structure is prepared n+ A material. Specifically, preparing 50-60 mM metal ion solution, placing the fiber orientation CNF material obtained in the step S1 into the metal ion solution, soaking for 72-96 hours at 20-30 ℃, and then washing with distilled water to obtain CNF-M n+ A material. Alternatively, the metal ion solution is 50mM, 55mM, 60mM, the treatment temperature may be 20 ℃,25 ℃, 30 ℃, and the treatment time may be 96 hours, 84 hours, 72 hours.
In step S2, the metal ions used include Na + 、Ca 2+ 、Cu 2+ 、Al 3+ Or Fe (Fe) 3+ . Molecular chain C of metal ion and cellulose nanofiber CNF material 6 The carboxyl groups are connected through coordination bonds, and the interaction between adjacent cellulose nanofiber CNFs is enhanced in a bridging manner. The concentration of the metal ion solution is 50-60 mM, the treatment time is 72-96 h, and the treatment temperature is 20-30 ℃. Alternatively, the metal ion solution is 50mM, 55mM, 60mM, and the treatment temperature may be 20℃at 25℃at,The treatment time can be 96 hours, 84 hours and 72 hours at 30 ℃.
According to the embodiment of the invention, in the method, in the step S2, a metal ion crosslinking strategy is adopted to introduce metal ions M into the cellulose nanofiber CNF material n+ Thereafter, the method further comprises: and cleaning and drying the cellulose nanofiber CNF material subjected to metal ion crosslinking treatment, and performing mould pressing treatment after drying.
Wherein, the cellulose nanofiber CNF material is cleaned by alternately cleaning with distilled water and ethanol solution. The cellulose nanofiber CNF material is dried by using CNF-M n+ The material is placed in an oven with the temperature of 60-70 ℃ for drying. The cellulose nanofiber CNF material is subjected to die pressing treatment, the pressure is 20-30 MPa, the die pressing time is 6-8 h, and the die pressing temperature is 20-30 ℃. Optionally, the drying temperature is 60 ℃, 65 ℃, 70 ℃, the pressure is 20MPa, 25MPa, 30MPa, the molding time is 8h, 7h, 6h, and the molding temperature is 20 ℃,25 ℃, 30 ℃.
According to an embodiment of the present invention, CNF-M after molding treatment n+ The material has high strength and high toughness, wherein CNF-Fe 3+ The tensile strength and toughness of the material respectively reach 451.51MPa and 8.19 MJ.m -3 The tensile strength and toughness of the CNF material are improved by 60% and 80%, respectively, compared with that of the CNF material which is not crosslinked.
Therefore, the preparation method of the metal ion crosslinked and toughened cellulose nanofiber material provided by the invention firstly provides a combination of a wet-drawing orientation method and a metal ion crosslinking strategy, and the arrangement direction of CNF and the interaction between CNF are regulated in situ to prepare the CNF-M with oriented fiber and compact structure n+ The strength and toughness of the material are effectively improved.
The following describes the invention in further detail with reference to examples, which are not intended to limit the invention thereto.
Examples 1 to 5:
(1) A TEMPO-oxidized nano Bacterial Cellulose (BC) film, a sample with a thickness of 3mm sheared to 150 x 30;
(2) And carrying out wet drawing orientation treatment on the BC film by adopting an Instron3369 type universal mechanical testing machine, wherein the drawing speed is 24mm/min, the drawing strain rate of the BC film is 20%, and the holding time is 1h.
(3) NaCl (example 1), caCl 2 (example 2), cuCl 2 ·2H 2 O (example 3), alCl 3 ·6H 2 O (example 4), feCl 3 ·6H 2 O (example 5) was placed in distilled water and subjected to ultrasonic vibration at 25℃for 10min, respectively, to prepare a metal ion solution having a concentration of 50 mM.
(4) Immersing the BC film obtained in the step (1) into the metal ion solution respectively, and immersing for 96 hours at 20 ℃ to obtain BC-M n+ A film.
(5) The BC-M obtained in the step (4) is subjected to n+ The film is sequentially cleaned by distilled water, ethanol and distilled water alternately, and then is dried at 60 ℃.
(6) The BC-M obtained in the step (5) is subjected to n+ The film is subjected to die pressing treatment under the pressure of 20MPa for 8 hours at the die pressing temperature of 20 ℃.
(7) BC-M obtained in step (6) n+ The films, i.e., examples 1, 2, 3, 4, and 5, are referred to as BC-Na, respectively + 、BC-Ca 2+ 、BC-Cu 2+ 、BC-Al 3+ 、BC-Fe 3+ 。
Comparative example 1
(1) Cutting TEMPO oxidized BC films into 150X 30 samples;
(2) And (3) drying the BC film obtained in the step (1) at a drying temperature of 60 ℃.
(3) And (3) carrying out die pressing treatment on the BC film obtained in the step (2), wherein the pressure is 20MPPa, the die pressing time is 8h, and the die pressing temperature is 20 ℃.
(4) The BC film obtained in step (3), comparative example 1, was designated BC-1.
Comparative example 2
(1) Cutting TEMPO oxidized BC films into 150X 30 samples;
(2) And carrying out wet drawing orientation treatment on the BC film by adopting a universal mechanical testing machine, wherein the drawing speed is 24mm/min, the drawing strain rate of BC is 20%, and the holding time is 1h.
(3) And (3) drying the BC film obtained in the step (2) at a drying temperature of 60 ℃.
(4) And (3) performing die pressing treatment on the BC film obtained in the step (3), wherein the pressure is 20MPa, the die pressing time is 8h, and the die pressing temperature is 20 ℃.
(5) The BC film obtained in step (4), comparative example 2, was designated BC-2.
Fig. 1 is a schematic diagram of a preparation process of the metal ion crosslinked and toughened cellulose nanofiber CNF material provided by the invention, and shows the preparation process of the BC thin films with high toughness in examples 1 to 5, so that the preparation process is simple and easy to operate, the reaction condition is mild, the preparation process is environment-friendly and pollution-free, and no organic solvent or special chemical reagent is required.
Microcosmic appearance characterization:
the microscopic morphologies of comparative examples 1 and 2 were characterized by a Fei Quanta 200 Scanning Electron Microscope (SEM). The metal spraying treatment was performed on comparative example 1 and comparative example 2 before observation.
Fig. 3 is a photograph of the surface micro-topography of comparative examples 1 and 2 provided by the present invention, wherein the left graph is the surface micro-topography of comparative example 1 and the right graph is the surface micro-topography of comparative example 2. Comparative example 1 was not subjected to wet drawing orientation treatment, and BC inside the film was in a random distribution state. Comparative example 2 after the wet drawing orientation treatment, BC was aligned neatly and tightly in the drawing direction. From this, it can be demonstrated that the wet-drawing orientation method effectively imparts an oriented structure to the film fibers by controlling the arrangement direction of BC in situ.
Chemical structure characterization:
the chemical structures of examples 1 to 5 and comparative example 2 were analyzed by infrared spectroscopy using a Nicolet Nexus 670 type infrared spectrometer, and the scanning wave number range was 4000 to 400cm -1 。
Fig. 4 is an infrared spectrum of examples 1 to 5 and comparative example 2 provided by the present invention. Comparative example 2 at 1425cm -1 And 1625cm -1 Symmetrical and asymmetrical stretching vibration peaks of the carboxylic acid group appear respectively. Furthermore, at 1722cm -1 A characteristic peak of-c=o bond in the carboxylic acid group appears. For example 1, at 1722cm -1 And 1625cm -1 The characteristic peak of the relevant carboxylic acid group was shifted (1705 cm -1 And 1610cm -1 ) And its strength was significantly reduced, indicating that only part of the carboxylic acid groups were reacted with Na + Interactions occur. Further, for examples 2 to 5, at 1722cm -1 The characteristic peak at 1625cm disappeared -1 The characteristic peak at this point is shifted to 1635cm -1 About this point, it is shown that the metal ions interact with carboxylic acid groups on the surface of the BC thin film, and the bridging effect is fully exerted between adjacent BC.
Mechanical property test:
the tensile strength of the test examples 1 to 5, the tensile strength of the test comparative example 1 and the tensile strength of the test comparative example 2 are tested by using a SEMtester 100 type tensile tester, the interval is 10mm, the tensile speed is 0.5mm/min, and the number of test samples is not less than 5. The thickness of the sample was measured by a screw micrometer, and the thickness was averaged three times. The toughness of the experimental examples 1 to 5 and comparative example 2 was calculated by integrating the area under the stress-strain curve.
FIG. 5 is a schematic view of the mechanical properties of examples 1-5, comparative example 1 and comparative example 2 provided herein, wherein (a) tensile stress-strain curves; (b) tensile strength; (c) Young's modulus; (d) toughness. The tensile strength of comparative example 2 was significantly improved as compared to comparative example 1, thereby demonstrating that the wet-draw orientation method can effectively improve the tensile strength of BC films. As can be seen by comparison, examples 1-5 all have tensile strength, tensile modulus and toughness exceeding comparative example 2, and the metal crosslinking strategy does not reduce the toughness and tensile strain of examples 1-5 while increasing the tensile strength. The tensile strength of examples 1 to 5 is proportional to the valence of the metal ion, and the tensile strength of the metal ion is proportional to the valence of the metal ion obtained in example 1 (BC-Na + ) Tensile strength was increased to example 5 (BC-Fe) at 315.36MPa 3+ ) The tensile strength was 451.51MPa ((b) of FIG. 5). At the same time, the tensile modulus and toughness for examples 1 to 5 also have a similar tendency to increase ((c) in fig. 5 and (d) in fig. 5).
The results and analysis show that the wet-drawing orientation method and the metal ion crosslinking strategy are combined, so that the BC can uniformly and effectively share the load, and coordination bonds with self-healing capability can be introduced between the BC, and the BC material is endowed with excellent strength and toughness.
Therefore, the preparation method of the metal ion crosslinked and toughened cellulose nanofiber material provided by the invention can be used for preparing the high-strength and high-toughness cellulose nanofiber CNF material by combining a wet-drawing orientation method and a metal ion crosslinking strategy. In-situ control of the alignment direction of CNF by wet-drawing orientation method, and combination of metal ion crosslinking strategy, na is introduced into CNF material + 、Ca 2+ 、Cu 2+ 、Al 3+ And Fe (Fe) 3+ (CNF-M n+ ) Promote the interaction between CNF, eliminate the small-size pores in the material, fully exert the inherent ultra-high strength of CNF, and prepare high-strength and toughness CNF-M with oriented fiber and compact structure n+ A material. The metal ions related to the invention exert bridging effect between CNFs through coordination bonds and electrostatic effect, and effectively improve the tensile strength and toughness of BC materials. Wherein Fe is 3+ The bridging effect of the (C) is most obvious, and after the cross-linking modification, CNF-Fe 3+ The tensile strength and toughness of the material can reach 451.51MPa and 8.19 MJ.m respectively -3 The tensile strength and toughness of the CNF material are improved by 60% and 80%, respectively, compared with that of the CNF material which is not crosslinked. The preparation method opens up new possibilities for the wide utilization of natural CNF, and helps to prepare a new generation of high-strength and high-toughness CNF material.
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.

Claims (3)

1. A method for preparing a metal ion crosslinked and toughened cellulose nanofiber material, which is characterized by comprising the following steps:
adopting a wet-drawing orientation method to regulate and control the arrangement direction of cellulose nanofiber CNF in situ, and preparing a cellulose nanofiber CNF material with fiber oriented arrangement; and
adopting a metal ion crosslinking strategy to enhance the interaction between fibers in the cellulose nanofiber CNF material;
the method comprises the steps of preparing a cellulose nanofiber CNF material with fiber directional arrangement by adopting a wet-drawing directional method to regulate the arrangement direction of cellulose nanofiber CNF in situ, wherein the diameter of the cellulose nanofiber CNF is 30-70 nm; the stretching speed of the wet-drawing orientation method is 1-24 mm/min, the stretching strain rate of the cellulose nanofiber CNF material is 20%, and the holding time is 0.5-1 h;
in the step of enhancing the interaction between fibers in the cellulose nanofiber CNF material by adopting a metal ion crosslinking strategy, metal ions M are introduced into the cellulose nanofiber CNF material n+ Metal ion M n+ Molecular chain C of CNF material with cellulose nanofiber 6 The carboxyl groups are connected through coordination bonds, so that the interaction between fibers in adjacent cellulose nanofiber CNF is enhanced in a bridging manner; the metal ion M n+ Comprises Na + 、Ca 2+ 、Cu 2+ 、Al 3+ Or Fe (Fe) 3+ The method comprises the steps of carrying out a first treatment on the surface of the The metal ion M n+ The concentration of the solution is 50-60 mM, the treatment time is 72-96 hours, and the treatment temperature is 20-30 ℃;
the method further comprises the following steps of after the interaction among fibers in the cellulose nanofiber CNF material is enhanced by adopting a metal ion crosslinking strategy: cleaning and drying the cellulose nanofiber CNF material subjected to metal ion crosslinking treatment, and performing mould pressing treatment after drying; wherein, the cellulose nanofiber CNF material is cleaned by alternately cleaning with distilled water and ethanol solution; the cellulose nanofiber CNF material is dried by using CNF-M n+ The material is placed in an oven with the temperature of 60-70 ℃ for drying; and carrying out die pressing treatment on the cellulose nanofiber CNF material, wherein the pressure is 20-30 MPa, the die pressing time is 6-8 h, and the die pressing temperature is 20-30 ℃.
2. The method for preparing a cellulose nanofiber material reinforced and toughened by metal ion crosslinking according to claim 1, wherein the arrangement direction of cellulose nanofiber CNF is regulated and controlled in situ by a wet drawing orientation method, and in the step of preparing the cellulose nanofiber CNF material with fiber orientation arrangement, cellulose nanofiber CNF oxidized by tetramethyl piperidine TEMPO is selected, so that C on a CNF molecular chain is ensured 6 Is substituted by carboxyl.
3. The method for preparing a metal ion crosslinked and toughened cellulose nanofiber material according to claim 2, wherein in the step of preparing a cellulose nanofiber CNF material in which fibers are aligned by adopting a wet-drawing alignment method to control the alignment direction of cellulose nanofiber CNF in situ, the alignment direction of cellulose nanofiber CNF is controlled in situ by adopting the wet-drawing alignment method, so that the cellulose nanofiber CNF is aligned along the stretching direction of the material.
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