CN114920969A - Preparation method of microfibrillated cellulose-based super-hydrophobic protective composite material - Google Patents
Preparation method of microfibrillated cellulose-based super-hydrophobic protective composite material Download PDFInfo
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- 239000001913 cellulose Substances 0.000 title claims abstract description 78
- 229920002678 cellulose Polymers 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 230000001681 protective effect Effects 0.000 title claims abstract description 19
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 26
- 235000013871 bee wax Nutrition 0.000 claims abstract description 19
- 239000012166 beeswax Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000839 emulsion Substances 0.000 claims abstract description 15
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002023 wood Substances 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 7
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 6
- RVWUHFFPEOKYLB-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-oxidopiperidin-1-ium Chemical compound CC1(C)CCCC(C)(C)[NH+]1[O-] RVWUHFFPEOKYLB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 22
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 229920001661 Chitosan Polymers 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000001804 emulsifying effect Effects 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000004528 spin coating Methods 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000002655 kraft paper Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical group CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000000265 homogenisation Methods 0.000 abstract description 3
- 230000001404 mediated effect Effects 0.000 abstract description 3
- 238000002444 silanisation Methods 0.000 abstract description 2
- 238000004806 packaging method and process Methods 0.000 abstract 1
- 238000004381 surface treatment Methods 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 239000011521 glass Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- 238000007605 air drying Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011121 hardwood Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 3
- RPVFYIHRKXUWDA-UHFFFAOYSA-N 2,2,6,6-tetramethyl-1-(2,2,6,6-tetramethylpiperidin-1-yl)oxypiperidine Chemical compound CC1(C)CCCC(C)(C)N1ON1C(C)(C)CCCC1(C)C RPVFYIHRKXUWDA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000002572 peristaltic effect Effects 0.000 description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/042—Coating with two or more layers, where at least one layer of a composition contains a polymer binder
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/60—Deposition of organic layers from vapour phase
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
- C09D191/06—Waxes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C08J2301/02—Cellulose; Modified cellulose
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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
- C08J2401/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2401/08—Cellulose derivatives
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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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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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
- C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
- C08J2491/06—Waxes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention provides a preparation method of a microfibrillated cellulose-based super-hydrophobic protective composite material, which comprises the following steps: firstly, pretreating broadleaf wood bleached sulfate pulp by using a 2, 2, 6, 6-tetramethylpiperidine oxide (TEMPO) mediated oxidation method, preparing microfibrillated cellulose (MFC) through high-pressure homogenization, and pouring the microfibrillated cellulose into a film; then, performing silanization modification on the MFC to prepare modified microfibrillated cellulose (M-MFC), mixing the modified microfibrillated cellulose with beeswax emulsion and nano silicon dioxide dispersion liquid to prepare a composite coating, and coating an MFC film to prepare a coated MFC film; and finally, carrying out surface treatment on the MFC film by adopting a chemical vapor deposition method to prepare the super-hydrophobic protective composite material. The preparation method of the composite material based on the microfibrillated cellulose has excellent super-hydrophobic and protective characteristics, is novel, simple and feasible, and can be applied to surface protection of food packaging and functional labels.
Description
Technical Field
The invention belongs to the field of packaging materials, relates to a preparation method of a green environment-friendly composite material with a super-hydrophobic protection characteristic, and particularly relates to a preparation method of a novel super-hydrophobic protection type composite material based on microfibrillated cellulose.
Background
In recent years, inspired by the superhydrophobicity of the lotus leaf surface in nature, research on the properties, preparation methods and construction of the superhydrophobic surface becomes a focus of attention. In view of sustainable development requirements, much research is now being focused on developing environmentally friendly materials that can be used for superhydrophobic surface structuring to replace traditional fluorine-containing superhydrophobic materials. Cellulose as a natural polymer material has the advantages of greenness, reproducibility, wide material source, biodegradability, excellent biocompatibility and the like.
Research on cellulose-based superhydrophobic materials and their applications is currently in the quest stage. The main problems faced include the following two aspects: firstly, the super-hydrophobic material is difficult to disperse in water and needs an organic solvent to disperse, so that VOC is generated in the preparation process of the super-hydrophobic material, and the influence on the environment is large; secondly, the micro-nano structure on the super-hydrophobic surface is fragile and poor in protection performance, and is easy to damage so as to lose the super-hydrophobic performance. Therefore, the preparation of strong and durable superhydrophobic materials by an easy-to-handle, environmentally friendly method is an urgent need for environmental and social development.
In conclusion, the invention adopts 2, 2, 6, 6-tetramethylpiperidine oxide (TEMPO) to pretreat natural lignocellulose, and combines high-pressure homogenization or other mechanical treatment to prepare microfibrillated cellulose (MFC), which is a novel material with micro-nano size, high length-diameter ratio, high strength, high specific surface area and adjustable surface chemical property, and the hydrophobicity of the microfibrillated cellulose (MFC) can be improved by silanization modification.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of a microfibrillated cellulose-based super-hydrophobic protective composite material, which has the advantages of environmental friendliness, simplicity in preparation, good protective property and the like.
The technical scheme adopted by the invention for solving the technical problem is as follows:
the invention relates to a preparation method of a microfibrillated cellulose-based super-hydrophobic protective composite material, which comprises the steps of firstly taking broadleaf wood bleached sulfate pulp as a raw material, pretreating by adopting 2, 2, 6, 6-tetramethylpiperidine oxide (TEMPO), then preparing microfibrillated cellulose through high-pressure homogenization, and modifying the microfibrillated cellulose through a silane coupling agent to improve the hydrophobic property of the microfibrillated cellulose; then preparing a composite coating by adding the beeswax emulsion and the nano silicon dioxide particles, and coating the microfibrillated cellulose film; and finally, treating the coated microfibrillated cellulose film through chemical vapor deposition to prepare the protective microfibrillated cellulose-based composite material with the super-hydrophobic property.
The preparation method comprises the following steps:
firstly, broad-leaved wood bleached sulfate pulp is used as a raw material, 2, 2, 6, 6-tetramethylpiperidine oxide (TEMPO) is used as a catalyst, a TEMPO/NaBr/NaClO oxidation system is used for pretreating the needle-leaved wood bleached sulfate pulp, the pH value of a mixed solution is adjusted to 10-11 by adding 0.2-0.5 mol/L NaOH solution, and 20-50 mL of anhydrous ethanol is added to stop reaction when the pH value of the mixed system is not changed any more; after suction filtration, washing with deionized water to neutrality to prepare slurry with the mass percent of 1 wt% -4 wt%, homogenizing for 3-10 times under the pressure of 300-1000 Bar after ultrasonic treatment to prepare microfibrillated cellulose (MFC), and preparing the microfibrillated cellulose film through a pouring method.
Step two, the microfibrillated cellulose (MFC) prepared in the step one is used as a raw material, and a silane coupling agent is adoptedpH value of 4-5, temperature of 60-80 ℃, stirring speed of 300-600 r/min, and N 2 And reacting for 2-4 h under the protection of atmosphere to prepare the modified microfibrillated cellulose (M-MFC).
And step three, mixing the modified microfibrillated cellulose (M-MFC) prepared in the step two with the beeswax emulsion and the nano silicon dioxide dispersion liquid according to a proportion, and uniformly stirring to prepare the composite coating.
And step four, coating the composite coating prepared in the step three on the microfibrillated cellulose film to form the coated microfibrillated cellulose film with the micro-rough surface.
And step five, obtaining the super-hydrophobic and anti-dropping coating structure from the coated microfibrillated cellulose film prepared in the step four by a chemical vapor deposition method, thereby preparing the protective microfibrillated cellulose-based composite material with super-hydrophobic property.
Preferably, the mass percentage of the hardwood bleached kraft pulp before pretreatment in step one is 2 wt%.
Preferably, the silane coupling agent used in step two is vinyltrimethoxysilane (A171) in a mass ratio of 2: 1 to microfibrillated cellulose.
Preferably, in the third step, the dosage of the beeswax emulsion (prepared by emulsifying chitosan, wherein the absolute dry mass ratio of the beeswax to the chitosan is 2: 1, and the solid content of the beeswax emulsion is 10 wt%) in the composite coating is 90 wt%; the dosage of the nano silicon dioxide dispersion liquid (solid content is 20 wt%, particle size is 50nm) is 6 wt%; the amount of modified microfibrillated cellulose (solids content 1 wt%) was 4 wt%.
Preferably, the coating method in the fourth step is spin coating and roll coating.
Preferably, in the fifth step, trimethoxymethylsilane (1mL) and deionized water (10mL) are respectively placed in a beaker and are placed in a vacuum drying dish together with the coated microfibrillated cellulose film to react for 2h at 120 ℃.
The invention has the beneficial effects that:
(1) the microfibrillated cellulose has the advantages of environmental protection and reproducibility, and the preparation method has the advantages of simple process and high efficiency.
(2) The modified microfibrillated cellulose (M-MFC) has micro-nano size and hydrophobic property, is beneficial to construction of a super-hydrophobic micro-nano rough structure, and the prepared composite coating can obtain a coating structure with good super-hydrophobic property by combining the beeswax emulsion and the nano silicon dioxide particles.
(3) The chemical vapor deposition method is adopted to prepare the super-hydrophobic composite material, so that the use of an organic solvent is avoided, and the preparation method has the advantages of simple production process, firm coating, good protection and the like.
Drawings
FIG. 1 is a flow chart of the preparation of a composite material.
FIG. 2 shows performance index data of the composite material of example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of the composite material of example 1 of the present invention.
FIG. 4 shows performance index data of the composite material of example 2 of the present invention.
FIG. 5 is a SEM image of the composite material of example 2.
Detailed Description
The present invention will be further described with reference to the following specific embodiments and the accompanying drawings, and the scope of the present invention is not limited to the following specific embodiments.
Example 1
The super-hydrophobic protective composite material with the mass ratio of the nano silicon dioxide to the modified microfibrillated cellulose of 6: 4 is prepared, and the flow chart is shown in figure 1.
(1) Preparation of microfibrillated cellulose (MFC) from hardwood bleached kraft pulp by 2, 2, 6, 6-Tetramethylpiperidinooxide (TEMPO) mediated oxidation
1) Weighing a certain amount of broadleaf wood bleached sulfate pulp, soaking in water for 24 hours, preparing pulp with the pulp concentration of 1 wt%, putting the pulp into a three-neck flask, stirring for 4 hours, respectively weighing TEMPO (1% by mass of oven-dried pulp) and NaBr (10% by mass of oven-dried pulp), dissolving the TEMPO and NaBr in deionized water, and heating in a water bath at 40 ℃ until the TEMPO and NaBr are completely dissolved.
2) Diluting NaClO with effective chlorine more than or equal to 8% to 10% with deionized water according to the using amount of 10mmol/g (10 mmol pure NaClO per gram of pulp sample), dropwise adding 0.1mol/L HCl solution to adjust the pH value to about 10.5, then pouring the mixed solution of TEMPO and NaBr into a three-neck flask for stirring, and adjusting the pH value of the mixed solution to 10.5 by using 0.5mol/L NaOH solution.
3) Dropwise adding a NaClO solution into the reaction system by using a peristaltic pump for carrying out an oxidation reaction, monitoring the pH value of the reaction system in real time, and dropwise adding a 0.5mol/L NaOH solution to keep the pH value of the reaction system at 10-11 all the time; and when the NaClO solution is added dropwise and the pH value of the reaction system is not changed any more, adding a proper amount of absolute ethyl alcohol to terminate the reaction.
4) Filtering the reaction solution to leave slurry, washing the slurry with deionized water until the slurry is neutral, and preparing the slurry into a fiber suspension with the mass percentage of 1 wt%; and (3) carrying out ultrasonic treatment on the suspension for 60min under the condition of power of 800W, pouring the suspension into a feeding barrel of a high-pressure homogenizer, and homogenizing for 4 times under the pressure condition of 700Bar to obtain the MFC.
(2) Preparation of microfibrillated cellulose film
Firstly weighing 80g of MFC (for 30min by ultrasonic treatment), adding a certain amount of glycerol and polyethylene glycol 600 solution, then adding 80g of deionized water, uniformly mixing, slowly pouring into a glass plate groove of 11cm multiplied by 11cm, placing in a forced air drying oven at 40 ℃ for drying, and taking down the MFC film for later use after complete drying.
(3) Preparation of modified microfibrillated cellulose
Adding a certain amount of silane coupling agent A171 into a mixed solution of absolute ethyl alcohol/water (volume ratio of 9: 1), adjusting the pH value of the system to about 4 by using an acetic acid solution, and hydrolyzing the silane coupling agent for 20min in advance. Heating the water bath kettle to 80 ℃ in advance, pouring the mixed solution into a three-neck flask, adding microfibrillated cellulose, connecting an inclined port of the three-neck flask with a condensing tube, and adding a solvent into the condensing tube 2 Under the protection of atmosphere, the cellulose is fully dispersed under the high-speed shearing of 600r/min, the reaction is carried out for 2h at the temperature of about 80 ℃, the modified microfibrillated cellulose (M-MFC) suspension is filtered, washed and placed in a refrigerator for storage.
(4) Preparation of composite coatings
1) 3.00g of chitosan powder was slowly added to a 1% acetic acid solution, heated in a water bath at 50 ℃ and stirred until clear and transparent. Heating the chitosan solution to 85 ℃, adding 6.00g of beeswax, continuously stirring for 20min, and homogenizing by a homogenizer for 5min to prepare beeswax emulsion.
2) Weighing 30.00g of beeswax emulsion, mixing nano silicon dioxide and modified microfibrillated cellulose according to the mass ratio of 6: 4, adding 10 wt% of beeswax emulsion, emulsifying by a high-speed shearing emulsifying machine for 3min, and uniformly mixing to obtain the composite coating.
(5) Preparation of coated microfibrillated cellulose film
And (3) putting the cut microfibrillated cellulose film on a platform of a glue homogenizing instrument, setting the rotating speed to be 2000r/min, and setting the spin-coating time to be 60 s. And (3) sucking 4mL of the composite coating by using a syringe, dripping the composite coating on the cellulose film, placing the coated microfibrillated cellulose film in a glass plate after the spin coating is finished, and drying the microfibrillated cellulose film under a natural condition.
(6) Preparation of super-hydrophobic protective composite material
And (2) putting the coated microfibrillated cellulose film into a vacuum drying dish, simultaneously putting two small beakers, putting 10mL of deionized water into one beaker, putting 1mL of trimethoxymethylsilane into the other beaker, and completely pumping out the air in the drying dish to form a vacuum environment. And (3) putting the drying dish into an electric heating air blast drying box, and reacting for 2h at 120 ℃ to prepare the super-hydrophobic protective composite material. The performance index of the composite is shown in FIG. 2; figure 3 shows a scanning electron micrograph of the composite.
Example 2
The super-hydrophobic protective composite material with the mass ratio of the nano silicon dioxide to the modified microfibrillated cellulose of 4: 6 is prepared, and the flow chart is shown in figure 1.
(1) Preparation of microfibrillated cellulose (MFC) from hardwood bleached kraft pulp by 2, 2, 6, 6-Tetramethylpiperidinooxide (TEMPO) mediated oxidation
1) Weighing a certain amount of broadleaf wood bleached sulfate pulp, soaking in water for 24 hours, preparing pulp with the pulp concentration of 1 wt%, putting the pulp into a three-neck flask, stirring for 4 hours, respectively weighing TEMPO (1% by mass of oven-dried pulp) and NaBr (10% by mass of oven-dried pulp), dissolving the TEMPO and NaBr in deionized water, and heating in a water bath at 40 ℃ until the TEMPO and NaBr are completely dissolved.
2) Diluting NaClO with effective chlorine more than or equal to 8% to 10% with deionized water according to the using amount of 10mmol/g (10 mmol pure NaClO per gram of pulp sample), dropwise adding 0.1mol/L HCl solution to adjust the pH value to about 10.5, then pouring the mixed solution of TEMPO and NaBr into a three-neck flask for stirring, and adjusting the pH value of the mixed solution to 10.5 by using 0.5mol/L NaOH solution.
3) Dropwise adding a NaClO solution into the reaction system by using a peristaltic pump to perform an oxidation reaction, monitoring the pH value of the reaction system in real time, and dropwise adding a 0.5mol/L NaOH solution to keep the pH value of the reaction system at 10-11 all the time; and when the NaClO solution is added dropwise and the pH value of the reaction system is not changed any more, adding a proper amount of absolute ethyl alcohol to terminate the reaction.
4) Filtering the reaction solution to leave slurry, washing the slurry with deionized water until the slurry is neutral, and preparing the slurry into a fiber suspension with the mass percentage of 1 wt%; and (3) carrying out ultrasonic treatment on the suspension for 60min under the condition of power of 800W, pouring the suspension into a feeding barrel of a high-pressure homogenizer, and homogenizing for 4 times under the pressure condition of 700Bar to obtain the MFC.
(2) Preparation of microfibrillated cellulose film
Firstly weighing 80g of MFC (for 30min by ultrasonic treatment), adding a certain amount of glycerol and polyethylene glycol 600 solution, then adding 80g of deionized water, uniformly mixing, slowly pouring into a glass plate groove of 11cm multiplied by 11cm, placing in a forced air drying oven at 40 ℃ for drying, and taking down the MFC film for later use after complete drying.
(3) Preparation of modified microfibrillated cellulose
Adding a certain amount of silane coupling agent A171 into a mixed solution of absolute ethyl alcohol/water (volume ratio of 9: 1), adjusting the pH value of the system to about 4 by using an acetic acid solution, and hydrolyzing the silane coupling agent for 20min in advance. Heating the water bath kettle to 80 ℃ in advance, pouring the mixed solution into a three-neck flask, adding microfibrillated cellulose, connecting an inclined port of the three-neck flask with a condensing tube, and adding a solvent into the condensing tube 2 Under the protection of atmosphere, shearing at high speed of 600r/minFully dispersing cellulose, reacting at 80 deg.C for 2 hr, suction filtering and washing the modified microfibrillated cellulose (M-MFC) suspension, and storing in refrigerator.
(4) Preparation of composite coatings
1) 3.00g of chitosan powder was slowly added to a 1% acetic acid solution, heated in a water bath at 50 ℃ and stirred until clear and transparent. Heating the chitosan solution to 85 deg.C, adding 6.00g beeswax, stirring for 20min, homogenizing with homogenizer for 5min to obtain beeswax emulsion.
2) Weighing 30.00g of beeswax emulsion, mixing nano silicon dioxide and modified microfibrillated cellulose according to the mass ratio of 4: 6, adding 10 wt% of beeswax emulsion, emulsifying by a high-speed shearing emulsifying machine for 3min, and uniformly mixing to obtain the composite coating.
(5) Preparation of coated microfibrillated cellulose film
And (3) putting the cut microfibrillated cellulose film on a platform of a glue homogenizing instrument, setting the rotating speed to be 2000r/min, and setting the spin-coating time to be 60 s. And (3) sucking 4mL of the composite coating by using a syringe, dripping the composite coating on the cellulose film, placing the coated microfibrillated cellulose film in a glass plate after the spin coating is finished, and drying the microfibrillated cellulose film under a natural condition.
(6) Preparation of super-hydrophobic protective composite material
And (2) putting the coated microfibrillated cellulose film into a vacuum drying dish, simultaneously putting two small beakers, putting 10mL of deionized water into one beaker, putting 1mL of trimethoxymethylsilane into the other beaker, and completely pumping out the air in the drying dish to form a vacuum environment. And (3) putting the drying vessel into an electric heating forced air drying box, and reacting for 2 hours at 120 ℃ to prepare the super-hydrophobic protective composite material. FIG. 4 shows performance metrics of a composite material; figure 5 shows a scanning electron micrograph of the composite.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the inventive concept, and these changes and modifications are all within the scope of the present invention.
Claims (6)
1. A preparation method of a microfibrillated cellulose-based super-hydrophobic protection type composite material is characterized by comprising the following steps of: the preparation method comprises the following steps:
firstly, broad-leaved wood bleached sulfate pulp is used as a raw material, 2, 2, 6, 6-tetramethylpiperidine oxide (TEMPO) is used as a catalyst, a TEMPO/NaBr/NaClO oxidation system is used for pretreating the broad-leaved wood bleached sulfate pulp, 0.2-0.5 mol/L NaOH solution is added to adjust the pH value of a mixed solution to 10-11, and 20-50 mL of absolute ethyl alcohol is added to stop reaction when the pH value of the mixed system is not changed any more; after suction filtration, washing with deionized water to neutrality to prepare slurry with the mass percent of 1 wt% -4 wt%, homogenizing for 3-10 times under the pressure of 300-1000 Bar after ultrasonic treatment to prepare microfibrillated cellulose (MFC), and preparing the microfibrillated cellulose film through a pouring method.
Step two, taking the microfibrillated cellulose (MFC) prepared in the step one as a raw material, and adopting a silane coupling agent to stir at the conditions of pH value of 4-5, temperature of 60-80 ℃, stirring speed of 300-600 r/min and N 2 And reacting for 2-4 h under the protection of atmosphere to prepare the modified microfibrillated cellulose (M-MFC).
And step three, mixing the modified microfibrillated cellulose (M-MFC) prepared in the step two with the beeswax emulsion and the nano silicon dioxide dispersion liquid according to a proportion, and uniformly stirring to prepare the composite coating.
And step four, coating the composite coating prepared in the step three on the microfibrillated cellulose film to form the coated microfibrillated cellulose film with the micro-rough surface.
And step five, obtaining the super-hydrophobic and anti-falling coating structure from the coated microfibrillated cellulose film prepared in the step four by a chemical vapor deposition method, thereby preparing the protective microfibrillated cellulose composite material with super-hydrophobic property.
2. The method of claim 1, wherein the method comprises the steps of: in the first step, the mass percentage of the broadleaf wood bleached kraft pulp is 1-4 wt%.
3. The method of claim 1, wherein the method comprises the steps of: in the second step, the adopted silane coupling agent is vinyl trimethoxy silane (A171), and the mass ratio of the vinyl trimethoxy silane to the microfibrillated cellulose is 1: 1-3: 1.
4. The method of claim 1 for preparing a microfibrillated cellulose based superhydrophobic protective composite, wherein: in the third step, the beeswax emulsion in the composite coating is prepared by emulsifying chitosan, the mass ratio of the beeswax to the chitosan is 2: 1-4: 1, and the dosage of the beeswax emulsion (the solid content is 10 wt%) is 60-90 wt%; the particle size range of the nano silicon dioxide dispersion liquid (with the solid content of 20 wt%) is 10-60 nm, and the using amount is 1-20 wt%; the dosage of the modified microfibrillated cellulose (solid content is 1 wt%) is 1 wt% -20 wt%.
5. The method of claim 1 for preparing a microfibrillated cellulose based superhydrophobic protective composite, wherein: the coating method in the fourth step is one of spin coating, roll coating and blade coating.
6. The method of claim 1, wherein the method comprises the steps of: in the fifth step, the chemical vapor deposition method comprises the steps of respectively placing 1-10 mL of trimethoxy methylsilane and 1-10 mL of deionized water in a beaker, placing the beaker together with the coated microfibrillated cellulose film in a vacuum drying dish, and reacting for 1-4 hours at the temperature of 100-130 ℃.
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