CN110684216A - Highly filled regenerated cellulose-based functional composite material and preparation method thereof - Google Patents
Highly filled regenerated cellulose-based functional composite material and preparation method thereof Download PDFInfo
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- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F2/00—Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
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- C08J2301/02—Cellulose; Modified cellulose
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K2003/382—Boron-containing compounds and nitrogen
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- C08K9/04—Ingredients treated with organic substances
Abstract
The invention discloses a high-filling regenerated cellulose-based functional composite material and a preparation method thereof. The method comprises the steps of mixing a solution consisting of functional filler, strong base, urea and water, then carrying out ball milling to obtain a slurry of the functional filler, and then mechanically stirring and mixing the slurry with a regenerated cellulose solution to obtain a regenerated cellulose-based precursor slurry with high processability. The regenerated cellulose-based precursor slurry can be used for preparing one-dimensional, two-dimensional and three-dimensional regenerated cellulose-based functional composite materials respectively by wet spinning, film casting, mixing with epoxy chloropropane, pouring into a mold after pouring. The precursor slurry prepared by the invention is used as a basic raw material, and even under the condition of high filling content, the filler can still be stably and uniformly dispersed in the system, so that the preparation of the high-performance regenerated cellulose-based composite material is facilitated, and the application field of the regenerated cellulose-based functional composite material is widened.
Description
Technical Field
The invention belongs to the technical field of preparation of functionalized regenerated cellulose-based nano composite materials, and relates to a highly-filled regenerated cellulose-based functional composite material and a preparation method thereof.
Background
The Regenerated Cellulose (RC) is used as a green and environment-friendly biomass material, has abundant storage capacity in the nature, is green and environment-friendly in processing mode, and has very attractive prospect in the field of replacing traditional petroleum-based high polymer materials (such as PP, PE and the like). The material prepared from the regenerated cellulose has excellent mechanical properties, and can be widely applied to the traditional polymer application fields such as fabrics, plastic bags, food packaging and the like. However, with the development of emerging technologies, such as wearable technology, a new demand is provided for polymer materials: it is required to have electrical conductivity, thermal conductivity, electromagnetic shielding and the like while maintaining its mechanical properties. The intrinsic characteristics of the regenerated cellulose material cannot meet the requirements of the development of the new material in the current era, so the development of the regenerated cellulose functionality has important significance for the application of the regenerated cellulose material in the field of new materials.
Introducing a filler with functionality into a polymer is a main method for developing the functionality of a polymer-based composite material, for example, the polymer can be endowed with electromagnetic shielding performance by adding the filler with high conductivity such as graphene, carbon nanotubes or silver nanowires into the polymer; the polymer is added with fillers such as alumina, boron nitride and the like with high thermal conductivity coefficient, so that the polymer can be endowed with better heat transfer performance. The filling content of the filler and its state of dispersion in the matrix are key factors affecting the properties of the composite. On the one hand, the functionality of the composite material can generally be significantly increased only if the filler content is sufficiently high. The traditional processing method for achieving high loading content is to achieve compounding of functional fillers and polymers by melt blending by applying strong shear forces to the filler and polymer melt during processing. However, because a large number of hydroxyl groups exist in the macromolecular chain of the cellulose, strong hydrogen bonds are formed among all the hydroxyl groups in the crystalline region of the cellulose, and therefore the cellulose cannot be blended with the functional filler by a melt processing method. The existing way of blending cellulose and filler is to directly mix the filler and regenerated cellulose solution by means of simple mechanical mixing. However, at high loading levels, it is difficult to achieve uniform dispersion of the filler in the matrix. This is because most functional fillers (such as boron nitride, graphene, carbon nanotubes, etc.) have few surface functional groups, and when the content of the fillers is too high, the fillers are easily agglomerated due to intermolecular forces, so that the mechanical properties, processability, etc. of the composite material are greatly reduced, and the composite material cannot be put into practical production and use, which is not favorable for the development of functional applications of cellulose-based composite materials. Therefore, how to simultaneously realize high filler content filling and uniform dispersion is a key problem which needs to be solved urgently in the field of cellulose-based functional composite materials.
Disclosure of Invention
One of the objects of the present invention is to provide a regenerated cellulose-based precursor slurry having high processability, comprising a regenerated cellulose solution and a functional filler, prepared by the steps of:
and 2, mixing the regenerated cellulose solution with the slurry of the functional filler by a mechanical stirring method to obtain regenerated cellulose-based precursor slurry.
Preferably, in the step 1, the mass ratio of the urea to the water is 15:77, and the ratio of the mass of the strong base to the total mass of the urea and the water is 4-7: 46.
Preferably, in the step 1, the rotation speed of the ball milling is 200-900 rpm, and the ball milling time is 0.25-12 h.
Preferably, in step 1, the strong base is potassium hydroxide, sodium hydroxide or lithium hydroxide.
Preferably, in step 1, the regenerated cellulose solution is prepared by the following method: dissolving a regenerated cellulose raw material in an aqueous solution consisting of strong base and urea at the temperature of between 15 ℃ below zero and 0 ℃, and performing circulating freeze thawing to obtain a colorless and transparent regenerated cellulose solution, wherein the strong base is potassium hydroxide, sodium hydroxide or lithium hydroxide.
Preferably, in the step 2, the mass concentration of the regenerated cellulose in the regenerated cellulose solution is 4-6%.
Preferably, in the step 2, the stirring speed of the mechanical stirring is 500-1000 rpm.
Preferably, in the step 2, the functional filler accounts for 0-80% of the total mass of the regenerated cellulose and the filler in the regenerated cellulose-based precursor slurry.
The second purpose of the invention is to provide a nano composite material with a one-dimensional fiber structure, which is prepared by the precursor slurry and comprises the following steps: the precursor slurry is used as spinning solution, and the regenerated cellulose-based composite material with a one-dimensional structure is prepared in a wet spinning mode.
Preferably, in the wet spinning process, the extrusion speed is 0.6 mm-18 mm/min, and the draw ratio is 1-4.
The invention also aims to provide a nano composite material with a two-dimensional film structure, which is prepared from the precursor slurry and is prepared by the following steps: and dripping the precursor slurry on a casting plate, and preparing the regenerated cellulose-based composite material with the two-dimensional film structure by a film scraping method.
Preferably, the thickness of the scraping film is 100-1500 μm, and the scraping speed is 5-80 m/min.
The fourth purpose of the invention is to provide a nanocomposite material with a three-dimensional aerogel structure, which is prepared from the precursor slurry, and the nanocomposite material is prepared by the following steps: and mixing the precursor slurry with epoxy chloropropane, pouring the mixture into a mold, and freeze-drying to obtain the regenerated cellulose-based composite material with the three-dimensional aerogel structure in a specific shape.
Preferably, the mass of the epichlorohydrin is 50-140% of the mass of the regenerated cellulose.
According to the invention, the surface energy of the filler is reduced by utilizing the p-pi conjugation effect or the hydrogen bond interaction between urea and the filler, and then the filler can be stably dispersed in a regenerated cellulose dissolving system through the hydrophobic-hydrophobic interaction or the hydrophilic-hydrophilic interaction between the regenerated cellulose and the nano filler, so that the precursor slurry with high processability is prepared. The slurry prepared by the method can be further processed to obtain the regenerated cellulose-based composite material with various structures and diversified functions from one dimension to three dimensions.
Compared with the prior art, the invention has the following advantages:
(1) compared with the traditional direct solution blending method, the invention provides the preparation method of the precursor slurry with better dispersibility. The precursor slurry prepared by the invention is used as a basic raw material, and even under the condition of high filling content, the filler can still be stably and uniformly dispersed in the system, thereby being beneficial to preparing the high-performance regenerated cellulose-based composite material.
(2) The precursor slurry prepared by the invention has good processing performance, and the regenerated cellulose-based composite materials with different structures can be obtained by spinning, blade coating or casting and other methods, thereby widening the application field of the regenerated cellulose-based functional composite materials.
Drawings
FIG. 1(a-b) is an SEM photograph showing the dispersion of BNNs in RC in example 1; FIG. 1(c-d) is an SEM photograph showing the dispersion of BNNs in RC in example 2.
FIG. 2(a) is a graph showing the results of apparent viscosities of precursor slurries prepared in examples 1 to 3; FIG. 2(b) is a graph showing the change in absorbance with time of the precursor slurries prepared in examples 1 to 3; FIG. 2(c) is a pictorial representation of a precursor slurry from the preparation of sheets of red for examples 1-3; FIG. 1(d) shows the results of infrared absorption spectrum in example 1; FIGS. 2(e-f) are graphs showing the results of Raman spectra of example 2 and example 3, respectively.
FIG. 3(a) is a physical representation of the RC/BNNs fibers obtained by wet spinning in example 1; FIG. 3(b) is a scanning electron microscope image of knotted individual fibers; FIG. 3(c) is a stress-strain curve of RC/BNNs fibers; FIG. 3(d) is a graph showing the results of thermal conductivity of the RC/BNNs fibers obtained in example 1.
FIG. 4(a) is a schematic representation of an RC/MWCNT thin film obtained by the coating method in example 2; FIG. 4(b) is a display view of a folded and bent film; FIG. 4(c) is a stress-strain curve of an RC/MWCNT thin film; FIG. 4(d) is a graph of thermal conductivity results for the RC/MWCNT thin film.
FIG. 5(a) is a physical diagram of the RC/GNP aerogel obtained by the freeze-drying method in example 3; FIG. 5(b) is a graph showing the results of electromagnetic shielding of the RC/GNP.
Detailed Description
The invention will be further described in detail below by way of examples and figures. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the teachings of the present invention are still within the scope of the present invention.
Example 1: preparation and application of regenerated cellulose/boron nitride nanosheet (RC/BNNs) precursor slurry:
step 1: low temperature dissolution of cellulose
Uniformly mixing 40.2g of deionized water, 7.5g of urea and 3.2g of lithium hydroxide, keeping the temperature at-12 ℃, then adding 3g of cellulose raw material cotton linter pulp of regenerated fibers into the low-temperature dissolving system, and stirring at 500-1000rpm, and performing multiple circulating freeze thawing to obtain a colorless and transparent regenerated cellulose solution.
Step 2: preparation of BNNs slurry:
adding 5.8g of lithium hydroxide, 10.8g of urea and 55ml of water into 1.5g of boron nitride, uniformly mixing, placing in a planetary ball mill at room temperature, carrying out ball milling for 2 hours, specifically, carrying out ball milling for 2 hours at an interval of 5 minutes every 30min, and obtaining BNNs slurry.
And step 3: preparation of one-dimensional regenerated/boron nitride fiber:
and (2) according to the proportion of the filler content of 63mg/g, the cellulose solution obtained in the step (1) and the boron nitride slurry obtained in the step (2) are strongly mechanically stirred (500 rpm-1000 rpm) to obtain RC/BNNs precursor slurry with stable dispersion, the RC/BNNs precursor slurry is used as spinning solution, and then the RC/BNNs heat-conducting fiber with high heat conductivity and the stretching ratio of 2 is prepared by a wet spinning method at a high extrusion speed (12 m/min).
Example 2: preparation and application of regenerated cellulose/multi-wall carbon nanotube (RC/MWCNT) precursor slurry:
step 1: low temperature dissolution of cellulose
40.2g of deionized water, 7.5g of urea and 3.2g of lithium hydroxide are uniformly mixed and then kept at-12 ℃, then 3g of cellulose raw material cotton linter pulp of regenerated fibers are added into the low-temperature dissolving system, and colorless and transparent regenerated cellulose solution is obtained through multiple circulating freeze thawing under the stirring of 500-1000 rpm.
Step 2: preparation of MWCNT paste:
adding 4.3g of lithium hydroxide, 8g of urea and 41ml of water into 2g of MWCNT, uniformly mixing, placing in a planetary ball mill at room temperature, carrying out ball milling for 2 hours, specifically, carrying out ball milling for 2 hours at an interval of 5 minutes every 30 minutes, and obtaining MWCNT slurry.
And step 3: preparing a regenerated fiber/multi-wall carbon nanotube film:
and (2) uniformly mixing the cellulose solution obtained in the step (1) and the MWCNT obtained in the step (2) by strong mechanical stirring (500 rpm-1000 rpm) according to the filler content of 29mg/g to obtain RC/MWCNT precursor slurry with stable dispersion, and then preparing the high-thermal-conductivity RC/MWCNT film with the thickness of 30 mu m at the film scraping speed of 50m/min by a solution blade coating method.
Example 3: preparation and application of regenerated cellulose/graphite nanosheet (RC/GNP) precursor slurry:
step 1: low temperature dissolution of cellulose
40.2g of deionized water, 7.5g of urea and 3.2g of lithium hydroxide are uniformly mixed and then kept at-12 ℃, then 3g of cellulose raw material cotton linter pulp of regenerated fibers are added into the low-temperature dissolving system, and colorless and transparent regenerated cellulose solution is obtained through multiple circulating freeze thawing under the stirring of 500-1000 rpm.
Step 2: preparation of GNP slurry:
adding 3.2g of lithium hydroxide, 6g of urea and 33ml of water into 1g of GNP, uniformly mixing, placing in a planetary ball mill at room temperature, carrying out ball milling for 2 hours, specifically, carrying out ball milling for 2 hours at an interval of 5 minutes every 30 minutes, and obtaining GNP slurry.
And step 3: preparing regenerated cellulose/graphite nanosheet aerogel:
and (3) uniformly mixing the cellulose solution obtained in the step (1) and the boron nitride nanosheet obtained in the step (2) through intensive mechanical stirring (500 rpm-1000 rpm) according to the filler content of 29mg/g to obtain the RC/GNP precursor slurry with stable dispersion. And (3) uniformly mixing the obtained slurry with 0.2g of epoxy chloropropane, filling the mixture into a mold with the thickness of 1.5cm and the diameter of 2.54cm, and freezing and icing the mixture in a refrigerator. And then obtaining the RC/GNP aerogel with excellent electromagnetic shielding performance after vacuum drying.
Comparative example 1
This comparative example 1 is essentially the same as example 1, except that the functional filler is added directly to the regenerated cellulose solution. As a result, it was found that the functional filler could not be uniformly dispersed, and the regenerated cellulose rapidly gelled and could not be reprocessed.
The dispersion of BNNs and MWCNTs in the RC matrix in example 1 and example 2, respectively, is shown in FIG. 1, and it can be seen that the filler is dispersed very uniformly in the matrix even at the filler contents of 63mg/g and 29 mg/g.
In addition, the apparent viscosity, absorbance, infrared spectrum and raman spectrum of three different regenerated cellulose-based precursor slurries prepared in examples 1 to 3 were characterized, and the results are shown in fig. 2. As can be seen from FIG. 2(a), the filler and the regenerated cellulose in the precursor slurry prepared by the invention have good interaction, the viscosity of the precursor slurry is not obviously improved under 63mg/g and 29mg/g respectively, and the precursor slurry has good fluidity; as can be seen from fig. 2(b), the absorbance of the aqueous dispersions of BNNs, MWCNTs and GNPs decreased rapidly with time, indicating that the filler could not be stably dispersed in the aqueous medium. After the regenerated cellulose is added, the absorbance of the slurry is hardly reduced obviously even if the standing time exceeds 70 hours, which shows that the prepared precursor slurry has good stability. Fig. 2(d-f) illustrates the interaction between the filler and the RC, and when the RC is compounded with the above filler, the peaks of the raman spectral response of the filler are significantly shifted, which indicates that the filler and the matrix have good interaction.
In addition, the morphology, mechanical properties and thermal conductivity of the RC/BNNs fibers obtained in example 1 were characterized, as shown in fig. 3. FIG. 3(a) is a diagram of RC/BNNs fibers obtained by wet spinning with RC/BNNs precursor slurry as spinning solution, which shows that the RC/BNNs prepared by the method have good spinnability; FIGS. 3(b) and (c) represent the mechanical properties of RC/BNNs, and as a result, the obtained fiber has good mechanical properties, the strength of the fiber is greater than 80MPa when the filling content is up to 63mg/g, and in addition, the elongation at break of the fiber is 11.7%, so that the fiber has good flexibility. Fig. 3(d) shows the axial thermal conductivity of the RC/BNNs fiber, and compared with pure RC, the axial thermal conductivity is improved by more than 400%, and the thermal management performance of the fiber is significantly improved.
The mechanical properties and thermal conductivity of the RC/MWCNT thin film obtained in example 2 are shown in fig. 4. As can be seen from fig. 4(a) and (b), the obtained RC/MWCNT thin film was not significantly damaged even after repeated folding, indicating that the thin film obtained by the method of example 2 had excellent flexibility. On the other hand, it can be obtained from the stress-strain curve shown in fig. 4(c) that the RC/MWCNT thin film has very good strength, which reaches 48 MPa. Fig. 4(d) represents the thermal conductivity of the RC/MWCNT film, and it can be found that the thermal conductivity of the original film regenerated fiber film is much lower than 10W/mK, and the thermal conductivity of the RC is obviously improved by introducing the MWCNT with high thermal conductivity and realizing uniform dispersion.
The RC/GNP aerogel obtained in example 3 is shown in FIG. 5 (a). Electromagnetic shielding performance at 8.5GHz as shown in fig. 5(b), it can be seen that the electromagnetic shielding performance of the RC aerogel is significantly improved by introducing GNPs having high conductivity.
Claims (10)
1. The preparation method of the regenerated cellulose-based precursor slurry with high processability is characterized by comprising the following specific steps of:
step 1, mixing a solution consisting of functional filler, strong base, urea and water, and then carrying out ball milling to obtain slurry of the functional filler;
and 2, mixing the regenerated cellulose solution with the slurry of the functional filler by a mechanical stirring method to obtain regenerated cellulose-based precursor slurry.
2. The preparation method of the urea-water composite material according to claim 1, wherein in the step 1, the mass ratio of the urea to the water is 15:77, and the ratio of the mass of the strong base to the total mass of the urea and the water is 4-7: 46; the rotation speed of the ball milling is 200-900 rpm, and the ball milling time is 0.25-12 h; the strong base is potassium hydroxide, sodium hydroxide or lithium hydroxide.
3. The method according to claim 1, wherein the regenerated cellulose solution is prepared by the following method in step 1: dissolving a regenerated cellulose raw material in an aqueous solution consisting of strong base and urea at the temperature of between 15 ℃ below zero and 0 ℃, and performing circulating freeze thawing to obtain a colorless and transparent regenerated cellulose solution, wherein the strong base is potassium hydroxide, sodium hydroxide or lithium hydroxide.
4. The preparation method according to claim 1, wherein in the step 2, the mass concentration of the regenerated cellulose in the regenerated cellulose solution is 4-6%; the stirring speed of the mechanical stirring is 500-1000 rpm; in the regenerated cellulose-based precursor slurry, the functional filler accounts for 0-80% of the total mass of the regenerated cellulose and the filler.
5. The regenerated cellulose-based precursor slurry prepared according to the preparation method of any one of claims 1 to 4.
6. Nanocomposite material with a one-dimensional fibrous structure, prepared from a regenerated cellulose-based precursor slurry according to claim 5, characterized by being prepared by: preparing a regenerated cellulose-based composite material with a one-dimensional structure by taking precursor slurry as a spinning solution in a wet spinning way; preferably, in the wet spinning process, the extrusion speed is 0.6 mm-18 mm/min, and the draw ratio is 1-4.
7. Nanocomposite with a two-dimensional thin-film structure, prepared from a reconstituted cellulose-based precursor slurry according to claim 5, characterized by being prepared by: and dripping the precursor slurry on a casting plate, and preparing the regenerated cellulose-based composite material with the two-dimensional film structure by a film scraping method.
8. The nanocomposite as claimed in claim 7, wherein the thickness of the scratch film is 100 to 1500 μm, and the scratch speed is 5 to 80 m/min.
9. Nanocomposite with a three-dimensional aerogel structure, prepared from a reconstituted cellulose-based precursor slurry according to claim 5, characterized by being prepared by the following steps: and mixing the precursor slurry with epoxy chloropropane, pouring the mixture into a mold, and freeze-drying to obtain the regenerated cellulose-based composite material with the three-dimensional aerogel structure in a specific shape.
10. The nanocomposite as claimed in claim 9, wherein the mass of the epichlorohydrin is 50-140% of the mass of the regenerated cellulose.
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