CN114507383B - Preparation method of esterified cellulose loaded MXene high-toughness film - Google Patents
Preparation method of esterified cellulose loaded MXene high-toughness film Download PDFInfo
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- 229920002678 cellulose Polymers 0.000 title claims abstract description 89
- 239000001913 cellulose Substances 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000003756 stirring Methods 0.000 claims abstract description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 241000219000 Populus Species 0.000 claims abstract description 28
- 239000000843 powder Substances 0.000 claims abstract description 28
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 239000011347 resin Substances 0.000 claims abstract description 17
- 229920005989 resin Polymers 0.000 claims abstract description 17
- 239000011159 matrix material Substances 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims abstract description 8
- 235000019743 Choline chloride Nutrition 0.000 claims abstract description 8
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims abstract description 8
- 229960003178 choline chloride Drugs 0.000 claims abstract description 8
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 8
- 238000002791 soaking Methods 0.000 claims abstract description 7
- UKLNMMHNWFDKNT-UHFFFAOYSA-M sodium chlorite Chemical compound [Na+].[O-]Cl=O UKLNMMHNWFDKNT-UHFFFAOYSA-M 0.000 claims abstract description 7
- 229960002218 sodium chlorite Drugs 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 18
- 239000012153 distilled water Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 239000010408 film Substances 0.000 description 51
- 239000002131 composite material Substances 0.000 description 4
- 229920002488 Hemicellulose Polymers 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 239000003094 microcapsule Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000003658 microfiber Substances 0.000 description 2
- 239000002121 nanofiber Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000003864 humus Substances 0.000 description 1
- -1 hydrogen ions Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/08—Cellulose derivatives
- C08J2301/10—Esters of organic acids
- C08J2301/12—Cellulose acetate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Chemical & Material Sciences (AREA)
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- Manufacture Of Macromolecular Shaped Articles (AREA)
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Abstract
The invention discloses a preparation method of an esterified cellulose loaded MXene high-toughness film, which comprises the following steps: 1. proportionally mixing LiF, HCl and Ti 3 AlC 2 Mixing, stirring in water bath, separating and washing to obtain MXene suspension; 2. soaking poplar powder in NaOH, heating and stirring, separating to obtain treated poplar powder, mixing choline chloride and oxalic acid according to a molar ratio to obtain a mixture, mixing the treated poplar powder with the mixture according to a mass ratio, heating and stirring until a viscous liquid is formed, and adding water to obtain a mixed solution; 3. adding sodium chlorite and acetic acid into the mixed solution according to a certain proportion, heating and stirring until the mixture is milky white, filtering and washing to obtain esterified cellulose, and preparing the esterified cellulose into slurry; 4. the MXene suspension is filtered and dried to prepare suspension F, the suspension F is added into slurry to obtain suspension G, the suspension G is dispersed to obtain the esterified cellulose loaded MXene resin matrix, and the esterified cellulose loaded MXene resin matrix is prepared into a film, so that the preparation process is simple, and the film has good wear resistance and water stability.
Description
Technical Field
The invention relates to preparation of a cellulose film, in particular to a preparation method of an esterified cellulose loaded MXene high-toughness film.
Background
The technology for extracting cellulose from natural biomass raw materials has been widely studied and applied, and the exploration and development of the application potential of cellulose films is still a worthy task for improving the service performance of the cellulose films. The processed waste poplar powder is one of effective renewable resources, has great development potential and can be used for manufacturing sustainable polymers. The DES cosolvent composed of choline chloride and oxalic acid can dissolve lignin and hemicellulose, so that cellulose coated by the lignin and the hemicellulose is exposed, and due to the protonation effect of hydrogen ions in the DES cosolvent, the hydroxyl groups of part of cellulose chain segments can be esterified, and the hydrogen bond binding sites among cellulose molecules are promoted. The esterified cellulose after uniform dispersion treatment is intertwined and crosslinked, has more negative charges and has good stability.
The invention patent of application number 202011106596.5 discloses a preparation method of a micro cellulose/MXene composite film, and mainly aims to solve the problems that the existing MXene composite film is poor in mechanical property and capacitance, and the conductivity of the MXene cellulose composite film shows a linear reduction trend along with the increase of nano cellulose. By preparing MFC@Ti 3 C 2 After Tx microgel, MFC@Ti is then added 3 C 2 The Tx microgel was vacuum filtered through a 0.22 μm pore size mixed cellulose membrane and dried at room temperature to give an independently supported micronized cellulose/MXene composite membrane. The invention patent with the application number of CN201910896661.X discloses a preparation method of oxidized esterified cellulose applied to microcapsules, which comprises the steps of firstly, uniformly mixing cellulose with an oxidant and an esterifying agent, and placing the mixture into a microwave reactor for pre-reaction for 5min to activate the cellulose and the oxidized esterifying agent. Taking out and placing in a flask, and reacting for a certain time at a certain temperature to obtain oxidized esterified cellulose; preparing microcapsules by using the obtained oxidized esterified cellulose as an object and utilizing a solvent evaporation method; and then filtering and washing the product with distilled water, and finally obtaining the cellulose ester microcapsule through vacuum drying.
However, the film prepared by the above method does not have high abrasion resistance, flexibility and foldability, and excellent electrical conductivity, thermal conductivity and biodegradability, and the preparation process is relatively complex, and does not have good economic benefit.
Disclosure of Invention
The invention aims to provide a preparation method of an esterified cellulose loaded MXene high-toughness film, which not only simplifies the preparation process, but also has good wear resistance, water stability and biodegradability.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the preparation method of the esterified cellulose loaded MXene high-toughness film comprises the following steps:
step 1, mixing LiF and 36% by mass of aqueous HCl solution at a ratio of (1.0-2.0 g) to 40mL (1.0-2.0 g), and slowly adding Ti 3 AlC 2 Obtaining a solution A, placing the solution A under a water bath condition, continuously stirring, and finally performing centrifugal separation and washing with deionized water to obtain an MXene suspension B;
step 2, soaking poplar powder in NaOH solution, heating and stirring, centrifugally separating to obtain treated poplar powder, mixing choline chloride and oxalic acid according to a mass ratio of 7: (6-13) to obtain a mixture C, mixing the treated poplar powder with the mixture C according to a mass ratio of 1: (15-20), heating and stirring until a viscous liquid D is formed, and finally, according to a volume ratio of 1: (10-15) adding deionized water into the viscous liquid D to obtain a mixed solution E;
step 3, adding sodium chlorite and acetic acid into the mixed solution E according to the ratio (2-3 g) to 1mL to 100mL, heating and stirring until the solution becomes milky, filtering and washing to obtain esterified cellulose, and adding the esterified cellulose into distilled water to prepare esterified cellulose slurry with the concentration of 20-25 mg/mL;
and 4, firstly, vacuum filtering and drying the MXene suspension B, then adding distilled water with a corresponding volume to prepare a suspension F with the concentration of 5-6mg/mL, then adding the suspension F into esterified cellulose slurry according to the volume ratio of 1:3-4 to obtain a suspension G, then carrying out ultrasonic dispersion treatment on the suspension G to obtain an esterified cellulose loaded MXene resin matrix, and finally preparing the ENCF@MXene film from the esterified cellulose loaded MXene resin matrix.
Further, the water bath temperature in the step 1 is 45 ℃, and the stirring time is 24 hours.
Further, the pH value of the MXene suspension B obtained in the step 1 is 6-7.
Further, the centrifugal separation is carried out in the step 1 by adopting a centrifugal machine with the rotating speed of 3500-4000 r/min.
Further, the concentration of the NaOH solution in the step 2 is 80-100mg/mL.
Further, in the step 2, the heating temperature of immersing poplar powder in NaOH solution is 100 ℃, and the stirring time is 6-8 hours.
Further, in the step 2, the heating temperature after the treated poplar powder is mixed with the mixture C is 100-120 ℃, and the stirring time is 3-5 hours.
Further, the heating temperature in the step 3 is 100 ℃, and the stirring time is 3-4 hours.
Further, the step 4 adopts a suction filtration method, a casting method, a mould pressing method or a hot pressing method to prepare the ENCF@MXene film from the esterified cellulose loaded MXene resin matrix.
The invention has the following beneficial effects:
(1) According to the invention, the wooden structure of poplar powder is firstly deconstructed by sodium hydroxide in advance under the condition of heating and stirring, lignin attached to cellulose and hemicellulose is partially dissolved and coated, then simple heating, dissolving, filtering and cleaning treatment are utilized, unnecessary impurity removal steps are not needed, the preparation and processing technology is greatly simplified, the preparation and processing technology is simplified, the MXene suspension is added into esterified cellulose slurry, and then the esterified cellulose slurry is subjected to ultrasonic dispersion treatment, so that an ENCF@MXene resin matrix is obtained, and finally the ENCF@MXene film is prepared by adopting the existing film forming technology, so that the preparation and processing technology has high economic benefit.
(2) The crosslinking and interlocking between cellulose micro/nano fibers are realized through the action of hydrogen bonds and Van der Waals force (interaction between hydroxyl groups and carbonyl groups of esterified cellulose), and the enhancement effect formed by uniformly dispersing the lamellar MXene between the lamellar structures of the film is realized, so that the ENCF@MXene film has good mechanical property. The self-reinforced compact lamellar structure based on the ENCF@MXene film ensures that the ENCF@MXene film has high surface strength and wear resistance due to the sliding action of MXene in the friction process. Moreover, the surface of the ENCF@MXene film has a compact cross-linked structure, the cross-linked structure of the micro/nano fiber intertwining is difficult to be destroyed by water molecules, and the ENCF@MXene film can not be deconstructed even if being soaked in water for more than 3 months, so that the ENCF@MXene film has good water stability.
(3) The raw material adopted by the invention is wood processing waste poplar powder, which is one of the most typical biomass green natural materials, and has the characteristics of wide sources, large reserves and environmental protection; the used solvent is green and environment-friendly, so that the ENCF@MXene film can be degraded by microorganisms in the natural environment and converted into humus, and can also be recovered, crushed and reused, thereby effectively realizing the high-value utilization of waste wood, being environment-friendly and sustainable.
Drawings
Fig. 1: a structural simulation of the encf@mxene film prepared in example 1;
fig. 2: SEM image of layered MXene prepared in example 1;
fig. 3: infrared spectra of ENCF and encf@mxene films prepared in example 1;
fig. 4: coefficient of friction curve graph of the ENCF@MXene film prepared in example 2 under different conditions;
fig. 5: dry friction abrasion mark morphology graph of the ENCF@MXene film prepared in example 2 under a light mirror;
fig. 6: the encf@mxene thin film prepared in example 3 has a heat dissipation and temperature reduction curve graph;
fig. 7: the pliability and foldability of the encf@mxene film prepared in example 3 are demonstrated;
fig. 8: stress-strain curve of the encf@mxene film prepared in example 3.
Detailed Description
The following examples are given to illustrate the present invention in further detail, but are not to be construed as limiting the invention thereto.
Example 1
The preparation method of the esterified cellulose loaded MXene high-toughness film comprises the following steps:
step 1, 1g LiF and 40mL of 36% HCl aqueous solution by mass fraction are mixed uniformly, and then 1.5g Ti is slowly added 3 AlC 2 Obtaining a solution A, placing the solution A under the water bath condition of 45 ℃ and continuously stirring for 24 hours, and finally adopting a centrifuge with the rotating speed of 3500r/min to carry out centrifugal separation and washing with deionized water to obtain MXene suspension B with the pH value of 6;
step 2, soaking poplar powder in 80mg/mL NaOH solution, stirring for 8 hours at 100 ℃, separating to obtain treated poplar powder, mixing 14g of choline chloride, 12g of oxalic acid and 2g of treated poplar powder, stirring for 3 hours at 110 ℃ until a viscous liquid D is formed, and finally adding deionized water into the viscous liquid D according to the volume ratio of 1:10 to obtain a mixed solution E;
step 3, adding 2g of sodium chlorite and 1mL acetic acid into 100mL of mixed solution E, stirring at a high temperature of 100 ℃ for 3 hours until the solution turns into milky white, filtering and washing to obtain esterified cellulose ENCF, and adding the esterified cellulose into distilled water to prepare esterified cellulose slurry with the concentration of 20 mg/mL;
and 4, firstly, vacuum filtering and drying the MXene suspension B, then adding distilled water to prepare suspension F with the concentration of 5mg/mL, then adding the suspension F into esterified cellulose slurry according to the volume ratio of 1:3 to obtain suspension G, then carrying out ultrasonic dispersion treatment on the suspension G for 30min to obtain an esterified cellulose loaded MXene resin matrix, and finally carrying out suction filtration on the esterified cellulose loaded MXene resin matrix ENCF@MXene to prepare the film.
Example 2
The preparation method of the esterified cellulose loaded MXene high-toughness film comprises the following steps:
step 1, uniformly mixing 1g of LiF and 40mL of 36% HCl aqueous solution by mass fraction, and then slowly adding 1g of Ti 3 AlC 2 Obtaining a solution A, then placing the solution A under the water bath condition of 45 ℃ and continuously stirring for 24 hoursFinally, centrifugal separation is carried out by adopting a centrifugal machine with the rotating speed of 4000r/min, and MXene suspension B with the pH value of 7 is obtained after washing by deionized water;
step 2, soaking poplar powder in 100mg/mL NaOH solution and stirring at 100 ℃ for 6 hours, separating to obtain treated poplar powder, mixing 14g of choline chloride, 26g of oxalic acid and 4g of treated poplar powder, stirring at 100 ℃ for 4 hours until a viscous liquid D is formed, and finally adding deionized water into the viscous liquid D according to the volume ratio of 1:12 to obtain a mixed solution E;
step 3, adding 2g of sodium chlorite and 1mL of acetic acid into 100mL of mixed solution E, stirring at a high temperature of 100 ℃ for 4 hours until the solution turns into milky white, filtering and washing to obtain esterified cellulose ENCF, and adding the esterified cellulose into distilled water to prepare esterified cellulose slurry with the concentration of 20 mg/mL;
and 4, firstly, vacuum filtering and drying the MXene suspension B, then adding distilled water to prepare a suspension F with the concentration of 6mg/mL, then adding the suspension F into esterified cellulose slurry according to the volume ratio of 1:3.5 to obtain a suspension G, then carrying out ultrasonic dispersion treatment on the suspension G for 40min to obtain an esterified cellulose loaded MXene resin matrix, and finally carrying out suction filtration on the esterified cellulose loaded MXene resin matrix ENCF@MXene to prepare the film.
Example 3
The preparation method of the esterified cellulose loaded MXene high-toughness film comprises the following steps:
step 1, uniformly mixing 2g LiF and 40mL of 36% HCl aqueous solution by mass fraction, and then slowly adding 2g Ti 3 AlC 2 Obtaining a solution A, placing the solution A under the water bath condition of 45 ℃ and continuously stirring for 24 hours, and finally adopting a centrifugal machine with the rotating speed of 4000r/min to carry out centrifugal separation and washing with deionized water to obtain an MXene suspension B with the pH value of 6;
step 2, soaking poplar powder in a 90mg/mL NaOH solution and stirring for 7 hours at 100 ℃, separating to obtain treated poplar powder, mixing 14g of choline chloride, 20g of oxalic acid and 2.8g of treated poplar powder, stirring for 5 hours at 120 ℃ until a viscous liquid D is formed, and finally, according to a volume ratio of 1:13 adding deionized water into the viscous liquid D to obtain a mixed solution E;
step 3, adding 3g of sodium chlorite and 1mL of acetic acid into 100mL of mixed solution E, stirring at a high temperature of 100 ℃ for 3 hours until the solution turns into milky white, filtering and washing to obtain esterified cellulose ENCF, and adding the esterified cellulose into distilled water to prepare esterified cellulose slurry with the concentration of 22 mg/mL;
and 4, firstly, vacuum filtering and drying the MXene suspension B, then adding distilled water to prepare a suspension F with the concentration of 6mg/mL, then adding the suspension F into esterified cellulose slurry according to the volume ratio of 1:4 to obtain a suspension G, then carrying out ultrasonic dispersion treatment on the suspension G for 50min to obtain an esterified cellulose loaded MXene resin matrix, and finally carrying out suction filtration on the esterified cellulose loaded MXene resin matrix ENCF@MXene to prepare the film.
Example 4
The preparation method of the esterified cellulose loaded MXene high-toughness film comprises the following steps:
step 1, evenly mixing 4g LiF and 80mL of 36% HCl aqueous solution by mass fraction, and then slowly adding 4g Ti 3 AlC 2 Obtaining a solution A, placing the solution A under the water bath condition of 45 ℃ and continuously stirring for 24 hours, and finally adopting a centrifuge with the rotating speed of 3500r/min to centrifuge and separate, and washing with deionized water to obtain an MXene suspension B with the pH value of 7;
step 2, soaking poplar powder in 100mg/mL NaOH solution and stirring for 7 hours at 100 ℃, separating to obtain treated poplar powder, mixing 14g of choline chloride, 16g of oxalic acid and 2g of treated poplar powder, stirring for 5 hours at 100 ℃ until a viscous liquid D is formed, and finally, according to the volume ratio of 1:15 adding deionized water into the viscous liquid D to obtain a mixed solution E;
step 3, adding 3g of sodium chlorite and 1.5. 1.5 mL acetic acid into 100mL of mixed solution E, stirring at a high temperature of 100 ℃ for 4 hours until the solution turns into milky white, filtering and washing to obtain esterified cellulose ENCF, and adding the esterified cellulose into distilled water to prepare esterified cellulose slurry with the concentration of 25 mg/mL;
and 4, firstly, vacuum filtering and drying the MXene suspension B, then adding distilled water to prepare suspension F with the concentration of 5mg/mL, then adding the suspension F into esterified cellulose slurry according to the volume ratio of 1:3 to obtain suspension G, then carrying out ultrasonic dispersion treatment on the suspension G for 60min to obtain an esterified cellulose loaded MXene resin matrix, and finally carrying out suction filtration on the esterified cellulose loaded MXene resin matrix ENCF@MXene to prepare the film.
FIG. 1 is a schematic diagram of the structure of an ENCF@MXene film prepared in example 1, wherein esterified cellulose subjected to uniform dispersion treatment is entangled and crosslinked, MXene is uniformly dispersed in a crosslinked network structure of cellulose, and the adhesion strength of a sheet MXene on an esterified cellulose skeleton can be increased by suction filtration film formation.
Fig. 2 is an SEM image of MXene prepared in example 1, and it is apparent that MXene etched by this method has an accordion-like layered structure, and carriers can rapidly move in the layered structure under the acceleration of energy, contributing to the transfer of thermal energy, and imparting thermal conductivity to the insulating cellulose film.
FIG. 3 is an infrared spectrum of the ENCF and ENCF@MXene films prepared in example 1, showing a diffraction peak similar to that of the esterified cellulose ENCF film, showing that MXene is dispersed and loaded into the cellulose skeleton due to a decrease in diffraction intensity, thereby limiting the detection depth of infrared light.
FIG. 4 is a graph of the coefficient of friction of the ENCF@MXene film prepared in example 2 under various loads, where the coefficient of friction under dry friction conditions is very close to that under PAO lubricant dripping, demonstrating that MXene plays a key enhancing role in the improvement of mechanical and surface properties.
FIG. 5 is a plot of the wear scar morphology under a mirror of the ENCF@MXene film prepared from example 2, which has a relatively flat surface, strong mechanical strength, and a low wear rate.
FIG. 6 is a graph of the heat sink profile of an ENCF@MXene film prepared from example 3, which has metal conductivity of transition metal carbide and excellent thermal conductivity due to the loading of MXene in the ENCF@MXene film on the cellulose backbone and the hydroxyl or terminal oxygen on the surface of the MXene material, as compared to an esterified cellulose ENCF film.
FIG. 7 is a view showing the flexibility and foldability of the ENCF@MXene film prepared in example 3, and it was found that the ENCF@MXene film has excellent flexibility and does not break or fail even after being folded in half.
FIG. 8 is a stress strain plot of an ENCF@MXene film prepared in example 3 of the present invention having a higher tensile stress at break than an esterified cellulose ENCF film.
Claims (9)
1. The preparation method of the esterified cellulose loaded MXene high-toughness film is characterized by comprising the following steps of:
step 1, mixing LiF and 36% HCl aqueous solution according to the ratio (1.0-2.0 g) to 40mL (1.0-2.0 g), and slowly adding Ti 3 AlC 2 Obtaining a solution A, placing the solution A under a water bath condition, continuously stirring, and finally performing centrifugal separation and washing with deionized water to obtain an MXene suspension B;
step 2, soaking poplar powder in NaOH solution, heating and stirring, centrifugally separating to obtain treated poplar powder, mixing choline chloride and oxalic acid according to a mass ratio of 7: (6-13) to obtain a mixture C, mixing the treated poplar powder with the mixture C according to a mass ratio of 1: (15-20), heating and stirring until a viscous liquid D is formed, and finally, according to a volume ratio of 1: (10-15) adding deionized water into the viscous liquid D to obtain a mixed solution E;
step 3, adding sodium chlorite and acetic acid into the mixed solution E according to the proportion (2-3 g) to 1mL to 100mL, heating and stirring until the solution becomes milky, filtering and washing to obtain esterified cellulose, and adding the esterified cellulose into distilled water to prepare esterified cellulose slurry with the concentration of 20-25 mg/mL;
and 4, firstly, vacuum filtering and drying the MXene suspension B, then adding distilled water with a corresponding volume to prepare a suspension F with the concentration of 5-6mg/mL, then adding the suspension F into esterified cellulose slurry according to the volume ratio of 1:3-4 to obtain a suspension G, then carrying out ultrasonic dispersion treatment on the suspension G to obtain an esterified cellulose loaded MXene resin matrix, and finally preparing the ENCF@MXene film from the esterified cellulose loaded MXene resin matrix.
2. The method for preparing the esterified cellulose supported MXene high toughness film according to claim 1, wherein the water bath temperature of the step 1 is 45 ℃ and the stirring time is 24 hours.
3. The method for preparing the esterified cellulose-supported MXene high-toughness film according to claim 1, wherein the pH value of the MXene suspension B obtained in the step 1 is 6-7.
4. The method for preparing the esterified cellulose-supported MXene high-toughness film according to claim 1, wherein the step 1 adopts a centrifugal machine with the rotating speed of 3500-4000r/min for centrifugal separation.
5. The method for preparing the esterified cellulose supported MXene high-toughness film according to claim 1, wherein the concentration of the NaOH solution in the step 2 is 80-100mg/mL.
6. The method for preparing the esterified cellulose-supported MXene high-toughness film according to claim 1, wherein the heating temperature of immersing the poplar powder in the NaOH solution in the step 2 is 100 ℃, and the stirring time is 6-8 hours.
7. The method for preparing the esterified cellulose-supported MXene high-toughness film according to claim 1, wherein the heating temperature after the treated poplar powder is mixed with the mixture C in the step 2 is 100-120 ℃, and the stirring time is 3-5 hours.
8. The method for preparing the esterified cellulose supported MXene high toughness film according to claim 1, wherein the heating temperature in the step 3 is 100 ℃, and the stirring time is 3-4 hours.
9. The method for preparing the esterified cellulose supported MXene high-toughness film according to claim 1, wherein the step 4 is to prepare the ENCF@MXene film from the esterified cellulose supported MXene resin substrate by a suction filtration method, a casting method, a mould pressing method or a hot pressing method.
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