CN105755890A - Preparation method of super-hydrophobic oleophobic transparent nanocellulose paper - Google Patents
Preparation method of super-hydrophobic oleophobic transparent nanocellulose paper Download PDFInfo
- Publication number
- CN105755890A CN105755890A CN201610114924.3A CN201610114924A CN105755890A CN 105755890 A CN105755890 A CN 105755890A CN 201610114924 A CN201610114924 A CN 201610114924A CN 105755890 A CN105755890 A CN 105755890A
- Authority
- CN
- China
- Prior art keywords
- super
- preparation
- hydrophobic
- cellulose
- hydrophobic oleophobic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/02—Synthetic cellulose fibres
- D21H13/04—Cellulose ethers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/13—Silicon-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Paper (AREA)
Abstract
The invention relates to a preparation method of super-hydrophobic oleophobic transparent nanocellulose paper, which relates to a preparation method of super-hydrophobic oleophobic and transparent nanocellulose paper, and solves the technical problems that the hydrophobic nano paper prepared by the traditional method is not transparent and poor in hydrophobility and oleophobility. The preparation method comprises the steps: I, preparing a nanocellulose solution; II, preparing a hydrophobic substance; III, suction filtering the nanocellulose solution, and forming a film; and IV, preparing the super-hydrophobic oleophobic transparent nanocellulose paper. A hydrophobic contact angle of the hydrophobic oleophobic transparent nanocellulose paper can reach 150 degrees or more, a rolling angle is smaller than 10 degrees, and an oleophobic contact angle can reach 120 degrees or more; the visible light transmittance reaches 80 percent; and the tensile stress can reach 100MPa or more, and a maximum pyrolysis temperature can reach 350 DEG C or higher. The preparation method belongs to the field of the preparation of the nanocellulose paper.
Description
Technical field
The preparation method that the present invention relates to the transparent nanofiber element paper of a kind of super-hydrophobic oleophobic.
Background technology
Nano-cellulose has that raw material sources is wide, intensity is high, specific surface area is big, good biocompatibility, the advantage such as recycle biodegradable, renewable；Simultaneously because diameter in a few to tens of nano-scale range, length at a few to tens of micro-meter scales, diameter is little, draw ratio is big so that it is demonstrate higher mechanical property, Young's modulus and hot strength respectively 13GPa and 223MPa；Additionally, also have relatively low thermal coefficient of expansion (CTE < 8.5ppmK-1).These significant characteristics make it potential make transparent nanofiber element film paper, be used for packing, high-temperature flexible electronic devices and components substrate, the high-end field such as micro-fluid chip.
But, a large amount of functional group hydroxyl is contained on nano-cellulose surface, very easily absorbs water, and causes transparent nano paper water absorption high, and the directly application in fields such as packaging, electronic device, micro-fluid chips is restricted.
Although the preparation method that the patent of invention that application number is 201310359486.3 reports super-hydrophobic nano paper, but this method is to utilize nano-TiO2The mode directly mixed with nano-cellulose is to build nanometer paper, and the easily reunion of nano inorganic granule, difficult scattering problem cause nanometer paper opaque, it is impossible to be applied to transparent electron field of display；And silane coupler cannot on nanometer paper film forming, and the electric double layer effect of nano-cellulose causes silane coupler to be difficult to load to nano-cellulose surface, and then only nano-TiO2Particle surface is by hydrophobic treatment, and nano-cellulose surface still has great amount of hydroxy group exposed, causes nanometer paper cannot keep hydrophobic property for a long time, it is more difficult to effectively to keep superhydrophobic characteristic.Application number is utilize nano-calcium carbonate and paper-making cellulose fibres In-situ reaction to prepare method super-hydrophobic, self-cleaning papermaking coating for a kind of described in the patent of invention of 201310009106.3, but owing to cellulose fibre is that micron order causes hydrophobic paper opaque and the plain paper of non-nanofiber, poor performance.Although, application number be described in the patent of invention of 201510056699.8 for utilizing sol-gel process to prepare SiO2Modification sol, and cellulosic fabric is carried out sucking filtration quickly process and obtain superhydrophobic fabric, but because fabric is micron order cellulosic material, therefore this hydrophobic fabric is nontransparent material and is not nanometer paper；SiO simultaneously2It is carry out in the basic conditions time sol-gel modified, causes colloidal sol to preserve for a long time, the shelf-life only has a few to tens of hours.Application number be described in the patent of invention of 201510413485.1 for transparent hydrophobic spray and its preparation method and application, it is mainly by Nano-meter SiO_22The surface modification of granule, is then dispersed in methanol, ethanol equal solvent making spray, but Nano-meter SiO_22Directly disperseing of granule is very difficult uniform, and causing reunites causes coating to be difficult to the light transmittance that maintenance is good on transparent carrier；And only by Nano-meter SiO_22Cannot film forming, hydrophobic effect and persistency are all not good enough.
In a word, said method or the object of process are micron order cellulose fibre but not nano-cellulose paper, or the dewatering nano paper of preparation is opaque；In hydrophobic liquid, nano inorganic granule difficulty is dispersed, or hydrophobic liquid difficulty film forming；And nanofiber procatarxis specific surface area is huge, hydroxyl exposed in a large number presents the electric double layer effect much bigger compared with common micro level cellulose fibre, cause and only carry out coupling hydrophobic treatment by silane coupler and be difficult to prove effective, it is necessary to overcome electric double layer effect by film forming matter or surfactant.In addition, whether above-mentioned patent has oleophobic function while all not reporting material superhydrophobic characteristic, namely there is super-hydrophobic oleophobic function and transparent nano-cellulose paper new material is not yet completely prepared, therefore the preparation method that the present invention proposes a kind of super-hydrophobic oleophobic transparent nanofiber element paper new material, to overcome above-mentioned problems, new material is made to be expected to be widely applied to the high-end fields such as packaging, high-temperature flexible electronic devices and components substrate, micro-fluid chip.
Summary of the invention
The invention aims to solve the technical problem that nanometer paper is opaque, hydrophobicity is poor prepared by existing method, it is provided that the preparation method of a kind of super-hydrophobic oleophobic transparent nanofiber element paper.
The preparation of purifying cellulose:
The timber of 60 order-120 orders of 3g, agricultural crop straw or waste and old paper powder carry out Chemical Pretreatment extracting remove extracting composition, remove lignin, remove hemicellulose, obtain purifying cellulose.
Extracting processes removes extracting compositions, method:
Wrap the timber of 60 order-120 orders of 3g, agricultural crop straw or waste and old paper powder with filter paper and be placed in the Soxhlet extractor of 250ml, add 240ml toluene-ethano mixed solution, in toluene-ethano mixed solution, toluene and ethanol volume ratio are 2: 1, with 90 DEG C of extracting 10h in water-bath, remove extracting composition.
Remove lignin process as follows:
One, putting in 500mL wide mouthed Erlenmeyer bottle by removing the timber of extracting composition, agricultural crop straw or waste and old paper powder, the mixed solution adding glacial acetic acid, sodium chlorite and deionized water amounts to 300ml, and seals with preservative film；Wherein, glacial acetic acid is 0.2mL, and sodium chlorite is 1g, and remaining liquid is water.Then, will be equipped with the wide mouthed Erlenmeyer bottle of above-mentioned mixed solution and be placed in magnetic force heated and stirred 1h in 75 DEG C of waters bath with thermostatic control；
Two, according to the glacial acetic acid and the 1g sodium chlorite that are initially charged 0.2ml in the mixed solution of step one gained, the order repetitive operation of magnetic force heated and stirred 1h 5 times in 75 DEG C of waters bath with thermostatic control；
Three, the vacuum filtration under 0.08MPa with glass filter or buchner funnel, and constantly wash until filtrate is in neutrality with distilled water, finally leaching to anhydrous liquid, complete to remove the process of lignin, obtain holocellulose.
Remove hemicellulose process as follows:
The wide mouthed Erlenmeyer bottle of the potassium hydroxide solution rinse 500ml adopting mass concentration to be 5%, then holocellulose is added in wide mouthed Erlenmeyer bottle, pour the potassium hydroxide solution that 300ml mass concentration is 5% into, seal, left at room temperature 12h, then heated and stirred 2h in 90 DEG C of thermostat water baths, under 0.08MPa, vacuum filtration is carried out with buchner funnel or glass filter, and with distilled water cyclic washing to filtrate in neutrality, finally leaching to anhydrous liquid, complete to remove the process of hemicellulose, obtain purifying cellulose.
The preparation method of super-hydrophobic oleophobic transparent nanofiber element paper carries out according to following steps:
One, the preparation of nano-cellulose water liquid:
Timber by 60 order-120 orders of 3g, agricultural crop straw or waste and old paper powder carry out Chemical Pretreatment and remove extracting composition, remove lignin, remove hemicellulose, obtain purifying cellulose, again purifying cellulose is added in the beaker of 250ml, adding deionized water to mass concentration is 0.1%-0.3%, add 2g cellulase, pretreatment 2h under 50 DEG C of conditions, then after processing 2h at 90 DEG C, after vacuum filtration washing, again the water liquid that mass concentration is 0.1%-0.3% it is made into, high pressure homogenize machinery then through 600bar processes 30min, obtain nano-cellulose water liquid；
nullOr the timber by 60 order-120 orders of 3g、Agricultural crop straw or waste and old paper powder carry out Chemical Pretreatment and remove extracting composition、Remove lignin、Remove hemicellulose，Obtain purifying cellulose，Again purifying cellulose is loaded in the beaker of 250ml，Adding deionized water to mass concentration is 0.1%-0.3%，It is sequentially added into 0.1g sodium bromide、0.016gTEMPO reagent，Under magnetic agitation，Adding 5ml mass concentration is the liquor natrii hypochloritis of 12%，Add the sodium hydroxide that concentration is 0.5mol/L，Adjustment pH value is 10-10.5，Significant change is no longer there is in sustained response to pH value，Terminate reaction，Add the dehydrated alcohol of 15ml，Through sucking filtration、After washing，Again the oxidized cellulose obtained is placed in 250ml conical flask，Add deionized water 70ml and 0.6g sodium chlorite，With glacial acetic acid adjustment pH value to 4-5，Then at 70 DEG C of magnetic agitation 1h，Sucking filtration、Washing，Obtain carboxylated cellulose element，Then the cellulose water liquid of 0.1%-0.3% again it is made into，Homogenizer mechanical dispersion 4min then through 15000rpm，The high pressure homogenize machinery of 600bar processes 5 times，Powerful ultrasonic 30min under 320W power，Prepare nano-cellulose water liquid；
Two, the preparation of hydrophobic substance:
nullBy mass percentage by the organoalkoxysilane of 2%-10%、The deionized water of 10%-40% and the dehydrated alcohol mixing of 50%-88%，Room temperature magnetic agitation 5 minutes，Add glacial acetic acid or ammonia correspondence adjustment pH value is 3-5 or 8-10，At 25 DEG C of-60 DEG C of temperature after magnetic agitation 1min-60min，Corresponding again add ammonia or glacial acetic acid regulates pH value to 5-6，It is subsequently adding and accounts for organoalkoxysilane、The fluorine containing silane coupling agent of deionized water and dehydrated alcohol gross mass 0.1%-0.2%，At 25 DEG C of-60 DEG C of temperature after magnetic agitation 0.1h-10h，Add and account for organoalkoxysilane、The water-based fluorocarbon resin of deionized water and dehydrated alcohol gross mass 0.5%-1% and the firming agent accounting for fluorocarbon resin quality 0.5%-1%，Stir，Obtain hydrophobic substance；
Wherein water-based fluorocarbon resin is aqueous CTFE-vinylic-ether polymer, buys from Fu Erman new material Science and Technology Ltd. at sunshine, and trade name is FEVE.
Three, nano-cellulose water liquid sucking filtration film forming: pour in glass filter by nano-cellulose water liquid, under 0.08MPa negative pressure, vacuum filtration leaches to the anhydrous liquid of filter membrane, stops vacuum filtration, obtains filter membrane；
Four, super-hydrophobic oleophobic transparent nanofiber element paper is prepared: hydrophobic substance step 2 obtained is poured in glass filter, then under 0.09MPa negative pressure, vacuum filtration leaches to the anhydrous liquid of filter membrane, stop vacuum filtration, take out filter membrane, and at filter membrane surface covered with plastic film, be subsequently placed in the middle of two blocks of plate glass, upper strata glass surface presses a weight again, after heating 24h-48h at 50 DEG C-80 DEG C, obtain super-hydrophobic oleophobic transparent nanofiber element paper.
The hydrophobic contact angle of super-hydrophobic oleophobic transparent nanofiber element paper prepared by the present invention can up to more than 150 °, roll angle less than 10 °, oleophobic contact angle can up to more than 120 °；Visible light transmissivity is up to 80%；The tensile stress of super-hydrophobic oleophobic transparent nanofiber element paper is up to more than 100MPa, maximum pyrolysis temperature, up to more than 350 DEG C (purer nanometer paper improves 18 DEG C), has huge applications potentiality in high-end fields such as packaging, high-temperature flexible electronic devices and components substrate, micro-fluid chips.
The microstructure of the present invention super-hydrophobic oleophobic transparent nanofiber element paper presents sub-micro nano projection structure, and substrate is that hydrophobic membrane polymer covers, similar to Folium Nelumbinis microstructure, thus having super-hydrophobic oleophobic function；Owing to nanometer paper surface is mainly nanoscale projection, the propagation effect of visible ray is less, therefore present higher visible light transmissivity (about 80%), in high-end fields such as packaging, high-temperature flexible electronic devices and components substrate, micro-fluid chips, there is potential using value.
Accompanying drawing explanation
Fig. 1 is the microcosmic scanning electron microscopic picture of gained super-hydrophobic oleophobic transparent nanofiber element paper in experiment one；
Fig. 2 is the optics picture of gained super-hydrophobic oleophobic transparent nanofiber element paper in experiment one；
Fig. 3 is the hydrophobic angle picture of gained super-hydrophobic oleophobic transparent nanofiber element paper in experiment one；
Fig. 4 is the hexadecane oleophobic angle picture of gained super-hydrophobic oleophobic transparent nanofiber element paper in experiment one；
Fig. 5 is the microcosmic scanning electron microscopic picture of gained super-hydrophobic oleophobic transparent nanofiber element paper in experiment two；
Fig. 6 is the optics picture of gained super-hydrophobic oleophobic transparent nanofiber element paper in experiment two；
Fig. 7 is the hydrophobic angle picture of gained super-hydrophobic oleophobic transparent nanofiber element paper in experiment two；
Fig. 8 is the hexadecane oleophobic angle picture of gained super-hydrophobic oleophobic transparent nanofiber element paper in experiment two.
Detailed description of the invention
Technical solution of the present invention is not limited to act detailed description of the invention set forth below, also includes the combination in any between each detailed description of the invention.
Detailed description of the invention one: the preparation method of present embodiment super-hydrophobic oleophobic transparent nanofiber element paper carries out according to following steps:
One, the preparation of nano-cellulose water liquid:
Purifying cellulose is added in the beaker of 250ml, adding deionized water to mass concentration is 0.1%-0.3%, add 2g cellulase, pretreatment 2h under 50 DEG C of conditions, then process after 2h at 90 DEG C, vacuum filtration after washing, be again made into the water liquid that mass concentration is 0.1%-0.3%, high pressure homogenize machinery then through 600bar processes 30min, obtains nano-cellulose water liquid；
nullOr purifying cellulose is loaded in the beaker of 250ml，Adding deionized water to mass concentration is 0.1%-0.3%，It is sequentially added into 0.1g sodium bromide、0.016gTEMPO reagent，Under magnetic agitation，Adding 5ml mass concentration is the liquor natrii hypochloritis of 12%，Add the sodium hydroxide that concentration is 0.5mol/L，Adjustment pH value is 10-10.5，Significant change is no longer there is in sustained response to pH value，Terminate reaction，Add the dehydrated alcohol of 15ml，Through sucking filtration、After washing，Again the oxidized cellulose obtained is placed in 250ml conical flask，Add deionized water 70ml and 0.6g sodium chlorite，With glacial acetic acid adjustment pH value to 4-5，Then at 70 DEG C of magnetic agitation 1h，Sucking filtration、Washing，Obtain carboxylated cellulose element，Then the cellulose water liquid of 0.1%-0.3% again it is made into，Homogenizer mechanical dispersion 4min then through 15000rpm，The high pressure homogenize machinery of 600bar processes 5 times，Powerful ultrasonic 30min under 320W power，Prepare nano-cellulose water liquid；
Two, the preparation of hydrophobic substance:
nullBy mass percentage by the organoalkoxysilane of 2%-10%、The deionized water of 10%-40% and the dehydrated alcohol mixing of 50%-88%，Room temperature magnetic agitation 5 minutes，Add glacial acetic acid or ammonia correspondence adjustment pH value is 3-5 or 8-10，At 25 DEG C of-60 DEG C of temperature after magnetic agitation 1min-60min，Corresponding again add ammonia or glacial acetic acid regulates pH value to 5-6，It is subsequently adding and accounts for organoalkoxysilane、The fluorine containing silane coupling agent of deionized water and dehydrated alcohol gross mass 0.1%-0.2%，At 25 DEG C of-60 DEG C of temperature after magnetic agitation 0.1h-10h，Add and account for organoalkoxysilane、The water-based fluorocarbon resin of deionized water and dehydrated alcohol gross mass 0.5%-1% and the firming agent of water-based fluorocarbon resin quality 0.5%-1%，Stir，Obtain hydrophobic substance；
Three, nano-cellulose water liquid sucking filtration film forming: pour in glass filter by nano-cellulose water liquid, under 0.08MPa negative pressure, vacuum filtration leaches to the anhydrous liquid of filter membrane, stops vacuum filtration, obtains filter membrane；
Four, super-hydrophobic oleophobic transparent nanofiber element paper is prepared: hydrophobic substance step 2 obtained is poured in glass filter, then under 0.09MPa negative pressure, vacuum filtration leaches to the anhydrous liquid of filter membrane, stop vacuum filtration, take out filter membrane, and at filter membrane surface covered with plastic film, be subsequently placed in the middle of two blocks of plate glass, upper strata glass surface presses a weight again, after heating 24h-48h at 50 DEG C-80 DEG C, obtain super-hydrophobic oleophobic transparent nanofiber element paper.
Detailed description of the invention two: present embodiment and detailed description of the invention one are tetraethyl orthosilicate the difference is that organoalkoxysilane described in step 2.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and one of detailed description of the invention one or two the difference is that in step 2 by mass percentage by the organoalkoxysilane of 6%, the deionized water of 20% and 74% dehydrated alcohol mix.Other is identical with one of detailed description of the invention one or two.
Detailed description of the invention four: present embodiment and one of detailed description of the invention one to three are the difference is that adding glacial acetic acid in step 2 or ammonia corresponding adjustment pH value is 3.5 or 8.5.Other is identical with one of detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four are the 17 silica-based trimethoxy silanes of fluorine or the silica-based triethoxysilane of 17 fluorine the difference is that fluorine containing silane coupling agent described in step 2.Other is identical with one of detailed description of the invention one to four.
Detailed description of the invention six: present embodiment and one of detailed description of the invention one to five are the difference is that the fluorine containing silane coupling agent adding organoalkoxysilane, deionized water and dehydrated alcohol gross mass 0.15% in step 2.Other is identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six are the difference is that the water-based fluorocarbon resin added in step 2 and firming agent respectively aqueous CTFE-vinylic-ether polymer and adipic acid adipic dihydrazide.Other is identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven the difference is that in step 2 at 30 DEG C of-55 DEG C of temperature after magnetic agitation 0.8h-9h, add the water-based fluorocarbon resin accounting for organoalkoxysilane, deionized water and dehydrated alcohol gross mass 0.6% and the firming agent accounting for water-based fluorocarbon resin quality 0.5%, stir, obtain hydrophobic substance.Other is identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: present embodiment and one of detailed description of the invention one to eight regulate pH value to 5-6 the difference is that addition ammonia corresponding in step 2 or glacial acetic acid.Other is identical with one of detailed description of the invention one to eight.
Detailed description of the invention ten: present embodiment and one of detailed description of the invention one to nine are the difference is that heating 28h-40h in step 4 at 60 DEG C-70 DEG C.Other is identical with one of detailed description of the invention one to nine.
Adopt following experimental verification effect of the present invention:
Experiment one:
(1) prepared by nano-cellulose:
1. taking the 120 order wood powders of 3g, after wrapping with filter paper, be placed in the Soxhlet extractor of 250ml, be charged with 240ml toluene-ethano mixed solution (toluene and ethanol volume ratio are 2: 1), extracting 10h at 90 DEG C in water-bath, to remove extracting composition；
2. the wood powder removing extracting composition is put in 500mL wide mouthed Erlenmeyer bottle, add the mixed solution of glacial acetic acid, sodium chlorite and deionized water, amount to 300ml, and seal with preservative film；Wherein, glacial acetic acid is 0.2mL, and sodium chlorite is 1g, and remaining liquid is water.Then, will be equipped with the conical flask of above-mentioned mixed solution and be placed at magnetic force heated and stirred 1h in 75 DEG C of waters bath with thermostatic control, obtain mixed solution；According to the glacial acetic acid and the 1g sodium chlorite that are initially charged 0.2ml in the mixed solution of gained, the order repetitive operation of magnetic force heated and stirred 1h 5 times in 75 DEG C of waters bath with thermostatic control；The vacuum filtration under 0.08MPa with glass filter or buchner funnel, and constantly wash with distilled water until filtrate is in neutrality, finally leaching to anhydrous liquid, complete delignification process, obtain holocellulose；
3. by above-mentioned gained holocellulose load 500ml with in the wide mouthed Erlenmeyer bottle after the potassium hydroxide solution rinse that mass concentration is 5%, pour the potassium hydroxide solution that 300ml mass concentration is 5% into, rim of a cup is sealed with preservative film, left at room temperature 12h, so that the abundant swollen fiber of alkali liquor；It is then placed in heated and stirred 2h in 90 DEG C of thermostat water baths.After reaction terminates, under 0.08MPa, carry out vacuum filtration with buchner funnel or glass filter, and with distilled water cyclic washing to filtrate in neutrality, finally leaching to anhydrous liquid, complete hemicellulose process, obtain purifying cellulose；
4. being loaded by the purifying cellulose after above-mentioned sucking filtration in the beaker of 250ml, adding deionized water to mass concentration is 0.1%；Then being charged with 2g cellulase, pretreatment 2h under 50 DEG C of conditions, then after 90 DEG C of high-temperature process 2h, after vacuum filtration washing, again being made into the water liquid of 0.1%, the high pressure homogenize machinery then through 600bar processes 30min, thus preparing nano-cellulose water liquid.
(2) preparation of hydrophobic substance:
1. weigh respectively by mass percentage 4% tetraethyl orthosilicate, 40% deionized water, 56% dehydrated alcohol, room temperature magnetic agitation 5 minutes；
2. it is subsequently adding glacial acetic acid (HAc) and regulates pH value to 3.5, at 60 DEG C after magnetic agitation 0.5h；
3. add ammonia, again regulate pH value to 5；
4. the 17 silica-based trimethoxy silanes of fluorine accounting for organoalkoxysilane, deionized water and dehydrated alcohol gross mass 0.1%, magnetic agitation 0.5h at 60 DEG C of temperature it are subsequently adding；
5. add the aqueous CTFE-vinylic-ether polymer accounting for organoalkoxysilane, deionized water and dehydrated alcohol gross mass 0.5% and the adipic acid adipic dihydrazide accounting for aqueous CTFE-vinylic-ether polymer quality 0.5%, after stirring, namely obtain hydrophobic substance.
(3) nano-cellulose water liquid sucking filtration film forming: pour in glass filter by nano-cellulose water liquid, under 0.08MPa negative pressure, vacuum filtration leaches to the anhydrous liquid of filter membrane, stops vacuum filtration, obtains filter membrane.
(4) continue to pour hydrophobic substance in the glass filter of step (3), then under 0.09MPa negative pressure, vacuum filtration leaches to the anhydrous liquid of filter membrane, stop vacuum filtration, filter membrane step (4) obtained again takes out, and at filter membrane surface covered with plastic film, be placed in the middle of two blocks of plate glass, upper strata glass surface presses a weight again, after heating 24h at 80 DEG C, obtain super-hydrophobic oleophobic transparent nanofiber element paper.
The microstructure of the super-hydrophobic oleophobic transparent nanofiber element paper of this experiment preparation presents sub-micro nano projection structure, and substrate is that hydrophobic membrane polymer covers, similar to the Folium Nelumbinis microstructure with super-hydrophobic oleophobic function (Fig. 1)；Owing to nanometer paper surface is mainly nanoscale projection, the propagation effect of visible ray is less, therefore present higher visible light transmissivity (about 80%) (Fig. 2)；Static hydrophobic angle reaches 152.7 ° (Fig. 3), and roll angle is 9.2 °, and the oleophobic angle of hexadecane reaches 124.3 ° (Fig. 4), presents super-hydrophobic fuel shedding quality；The tensile stress of nanometer paper reaches 120MPa, and maximum pyrolysis temperature reaches 360 DEG C (purer nanometer paper improves 28 DEG C), has potential using value in high-end fields such as packaging, high-temperature flexible electronic devices and components substrate, micro-fluid chips.
Experiment two:
(1) prepared by nano-cellulose:
1. the 120 order wood powders of 3g are taken, after wrapping with filter paper, it is placed in the Soxhlet extractor of 250ml, is charged with the toluene-ethano mixed solution (toluene and ethanol volume ratio are 2: 1) of 240ml, extracting 10h at 90 DEG C in water-bath, to remove extracting composition；
2. putting in 500mL wide mouthed Erlenmeyer bottle by the wood powder removing extracting composition, the mixed solution adding glacial acetic acid, sodium chlorite and deionized water amounts to 300ml, and seals with preservative film；Wherein, glacial acetic acid is 0.2mL, and sodium chlorite is 1g, and remaining liquid is water.Then, will be equipped with the conical flask of above-mentioned mixed solution and be placed in magnetic force heated and stirred 1h in 75 DEG C of waters bath with thermostatic control, obtain mixed solution；According to the glacial acetic acid and the 1g sodium chlorite that are initially charged 0.2ml in the mixed solution of gained, and the order repetitive operation of magnetic force heated and stirred 1h 5 times in 75 DEG C of waters bath with thermostatic control；The vacuum filtration under 0.08MPa with glass filter or buchner funnel, and constantly wash with distilled water until filtrate is in neutrality, finally leaching to anhydrous liquid, complete delignification process, obtain holocellulose；
3. holocellulose is loaded 500ml with in the wide mouthed Erlenmeyer bottle after the potassium hydroxide solution rinse that concentration is 5%, pour the potassium hydroxide solution that 300ml mass concentration is 5% into, rim of a cup is sealed with preservative film, left at room temperature 12h, so that the abundant swollen fiber of alkali liquor；It is then placed in heated and stirred 2h in 90 DEG C of thermostat water baths.After reaction terminates, under 0.08MPa, carry out vacuum filtration with buchner funnel or glass filter, and with distilled water cyclic washing to filtrate in neutrality, finally leaching to anhydrous liquid, complete hemicellulose process, obtain purifying cellulose；
4. being loaded by the purifying cellulose after above-mentioned sucking filtration in the beaker of 250ml, adding deionized water to mass concentration is 0.1%；It is sequentially added into 0.1g sodium bromide, 0.016gTEMPO (2,2,6,6-tetramethyl piperidine oxide) reagent；Again under magnetic stirring, it is slowly added to 5ml, mass concentration is the aqueous sodium hypochlorite solution of 12%, it is slow added into the sodium hydroxide that concentration is 0.5mol/L, adjustment pH value is 10-10.5, significant change is no longer there is in sustained response to pH value, terminate reaction, the dehydrated alcohol of 15ml is added again in conical flask, through sucking filtration, after washing, again the oxidized cellulose obtained is placed in 250ml conical flask, add deionized water 70ml and 0.6g sodium chlorite, and regulate pH value to 4-5 with glacial acetic acid, then magnetic agitation 70 DEG C heating 1h, then through sucking filtration, carboxylated cellulose element is obtained after washing；Finally, being again made into the cellulose water liquid of 0.1%, the high pressure homogenize machinery then through homogenizer mechanical dispersion 4min, the 600bar of 15000rpm processes 5 times, powerful ultrasonic 30min under 320W power, thus preparing nano-cellulose water liquid.
(2) preparation of hydrophobic substance:
Weigh respectively by mass percentage 5% tetraethyl orthosilicate, 20% deionized water, 75% dehydrated alcohol, room temperature magnetic agitation 5 minutes；It is subsequently adding ammonia and regulates pH value to 8.5, under 25 DEG C of room temperatures after magnetic agitation 10min；Add glacial acetic acid, again regulate pH value to 6；
It is subsequently adding the 17 silica-based triethoxysilanes of fluorine accounting for organoalkoxysilane, deionized water and dehydrated alcohol gross mass 0.2%, at 25 DEG C of temperature after magnetic agitation 10h；Add the aqueous CTFE-vinylic-ether polymer accounting for organoalkoxysilane, deionized water and dehydrated alcohol gross mass 0.5% and the adipic acid adipic dihydrazide firming agent accounting for aqueous CTFE-vinylic-ether polymer quality 0.5%, after stirring, namely obtain hydrophobic substance.
(3) nano-cellulose water liquid sucking filtration film forming: pour in glass filter by nano-cellulose water liquid, under 0.08MPa negative pressure, vacuum filtration leaches to the anhydrous liquid of filter membrane, stops vacuum filtration, obtains filter membrane.
(4) continue to pour hydrophobic substance in the glass filter of step (3), then under 0.09MPa negative pressure, vacuum filtration leaches to the anhydrous liquid of filter membrane, stop vacuum filtration, filter membrane step (4) obtained again takes out, and at filter membrane surface covered with plastic film, be placed in the middle of two blocks of plate glass, upper strata glass surface presses a weight again, after heating 48h at 50 DEG C, obtain super-hydrophobic oleophobic transparent nanofiber element paper.
Its microstructure presents sub-micro nano projection structure, and substrate is that hydrophobic membrane polymer covers, similar to the Folium Nelumbinis microstructure with super-hydrophobic oleophobic function (Fig. 5)；Owing to nanometer paper surface is mainly nanoscale projection, the propagation effect of visible ray is less, therefore present higher visible light transmissivity (about 80%) (Fig. 6)；Static hydrophobic angle reaches 153.3 ° (Fig. 7), and roll angle is 9.0 °, and the oleophobic angle of hexadecane reaches 125.7 ° (Fig. 8), presents super-hydrophobic fuel shedding quality；The tensile stress of nanometer paper reaches 100MPa, and maximum pyrolysis temperature reaches 350 DEG C (purer nanometer paper improves 18 DEG C), has potential using value in high-end fields such as packaging, high-temperature flexible electronic devices and components substrate, micro-fluid chips.
Claims (10)
1. the preparation method of super-hydrophobic oleophobic transparent nanofiber element paper, it is characterised in that the preparation method of super-hydrophobic oleophobic transparent nanofiber element paper carries out according to following steps:
One, the preparation of nano-cellulose water liquid:
Purifying cellulose is added in the beaker of 250ml, adding deionized water to mass concentration is 0.1%-0.3%, add 2g cellulase, pretreatment 2h under 50 DEG C of conditions, then process after 2h at 90 DEG C, vacuum filtration after washing, be again made into the water liquid that mass concentration is 0.1%-0.3%, high pressure homogenize machinery then through 600bar processes 30min, obtains nano-cellulose water liquid；
nullOr purifying cellulose is loaded in the beaker of 250ml，Adding deionized water to mass concentration is 0.1%-0.3%，It is sequentially added into 0.1g sodium bromide、0.016gTEMPO reagent，Under magnetic agitation，Adding 5ml mass concentration is the liquor natrii hypochloritis of 12%，Add the sodium hydroxide that concentration is 0.5mol/L，Adjustment pH value is 10-10.5，Significant change is no longer there is in sustained response to pH value，Terminate reaction，Add the dehydrated alcohol of 15ml，Through sucking filtration、After washing，Again the oxidized cellulose obtained is placed in 250ml conical flask，Add deionized water 70ml and 0.6g sodium chlorite，With glacial acetic acid adjustment pH value to 4-5，Then at 70 DEG C of magnetic agitation 1h，Sucking filtration、Washing，Obtain carboxylated cellulose element，Then the cellulose water liquid of 0.1%-0.3% again it is made into，Homogenizer mechanical dispersion 4min then through 15000rpm、The high pressure homogenize machinery of 600bar processes 5 times，Powerful ultrasonic 30min under 320W power，Prepare nano-cellulose water liquid；
Two, the preparation of hydrophobic substance:
nullBy mass percentage by the organoalkoxysilane of 2%-10%、The deionized water of 10%-40% and the dehydrated alcohol mixing of 50%-88%，Room temperature magnetic agitation 5 minutes，Add glacial acetic acid or ammonia correspondence adjustment pH value is 3-5 or 8-10，At 25 DEG C of-60 DEG C of temperature after magnetic agitation 1min-60min，Corresponding again add ammonia or glacial acetic acid regulates pH value to 5-6，It is subsequently adding and accounts for organoalkoxysilane、The fluorine containing silane coupling agent of deionized water and dehydrated alcohol gross mass 0.1%-0.2%，At 25 DEG C of-60 DEG C of temperature after magnetic agitation 0.1h-10h，Add and account for organoalkoxysilane、The water-based fluorocarbon resin of deionized water and dehydrated alcohol gross mass 0.5%-1% and the firming agent of water-based fluorocarbon resin quality 0.5%-1%，Stir，Obtain hydrophobic substance；
Three, nano-cellulose water liquid sucking filtration film forming: pour in glass filter by nano-cellulose water liquid, under 0.08MPa negative pressure, vacuum filtration leaches to the anhydrous liquid of filter membrane, stops vacuum filtration, obtains filter membrane；
Four, super-hydrophobic oleophobic transparent nanofiber element paper is prepared: hydrophobic substance step 2 obtained is poured in glass filter, then under 0.09MPa negative pressure, vacuum filtration leaches to the anhydrous liquid of filter membrane, stop vacuum filtration, take out filter membrane, and at filter membrane surface covered with plastic film, be subsequently placed in the middle of two blocks of plate glass, upper strata glass surface presses a weight again, after heating 24h-48h at 50 DEG C-80 DEG C, obtain super-hydrophobic oleophobic transparent nanofiber element paper.
2. the preparation method of super-hydrophobic oleophobic transparent nanofiber element paper according to claim 1, it is characterised in that organoalkoxysilane described in step 2 is tetraethyl orthosilicate.
3. the preparation method of super-hydrophobic oleophobic transparent nanofiber element paper according to claim 1, it is characterised in that in step 2 by mass percentage by the organoalkoxysilane of 6%, the deionized water of 20% and 74% dehydrated alcohol mixing.
4. the preparation method of super-hydrophobic oleophobic transparent nanofiber element paper according to claim 1, it is characterised in that step 2 adds glacial acetic acid or ammonia correspondence to regulate pH value be 3.5 or 8.5.
5. the preparation method of super-hydrophobic oleophobic transparent nanofiber element paper according to claim 1, it is characterised in that fluorine containing silane coupling agent described in step 2 is the 17 silica-based trimethoxy silanes of fluorine or the silica-based triethoxysilane of 17 fluorine.
6. the preparation method of super-hydrophobic oleophobic transparent nanofiber element paper according to claim 1, it is characterised in that add the fluorine containing silane coupling agent of organoalkoxysilane, deionized water and dehydrated alcohol gross mass 0.15% in step 2.
7. the preparation method of super-hydrophobic oleophobic transparent nanofiber element paper according to claim 1, it is characterised in that the water-based fluorocarbon resin added in step 2 and firming agent respectively aqueous CTFE-vinylic-ether polymer and adipic acid adipic dihydrazide.
8. the preparation method of super-hydrophobic oleophobic transparent nanofiber element paper according to claim 1, it is characterized in that in step 2 at 30 DEG C of-55 DEG C of temperature after magnetic agitation 0.8h-9h, add the water-based fluorocarbon resin accounting for organoalkoxysilane, deionized water and dehydrated alcohol gross mass 0.6% and the firming agent accounting for water-based fluorocarbon resin quality 0.5%, stir, obtain hydrophobic substance.
9. the preparation method of super-hydrophobic oleophobic transparent nanofiber element paper according to claim 1, it is characterised in that corresponding in step 2 add ammonia or glacial acetic acid regulates pH value to 5-6.
10. the preparation method of super-hydrophobic oleophobic transparent nanofiber element paper according to claim 1, it is characterised in that heat 28h-40h in step 4 at 60 DEG C-70 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610114924.3A CN105755890B (en) | 2016-03-01 | 2016-03-01 | The preparation method of super-hydrophobic oleophobic transparent nanofiber element paper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610114924.3A CN105755890B (en) | 2016-03-01 | 2016-03-01 | The preparation method of super-hydrophobic oleophobic transparent nanofiber element paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105755890A true CN105755890A (en) | 2016-07-13 |
| CN105755890B CN105755890B (en) | 2017-11-10 |
Family
ID=56331611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610114924.3A Active CN105755890B (en) | 2016-03-01 | 2016-03-01 | The preparation method of super-hydrophobic oleophobic transparent nanofiber element paper |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105755890B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107313279A (en) * | 2017-06-28 | 2017-11-03 | 常州市沃兰特电子有限公司 | A kind of preparation method of super-hydrophobicity paper |
| CN108560314A (en) * | 2017-12-15 | 2018-09-21 | 华南理工大学 | A kind of nano-cellulose based super hydrophobic coating and preparation method thereof |
| CN108931565A (en) * | 2018-08-13 | 2018-12-04 | 山东农业大学 | The construction method of nano-cellulose paper base biosensor |
| CN109091699A (en) * | 2018-08-24 | 2018-12-28 | 郑州大学 | A kind of preparation method of styptic sponge and its styptic sponge of preparation |
| CN109235141A (en) * | 2018-08-22 | 2019-01-18 | 广西大学 | A kind of preparation method and applications of wrapping paper barriers function coating lotion |
| CN110204753A (en) * | 2019-06-04 | 2019-09-06 | 齐鲁工业大学 | A kind of cellulose nanometer fibril base hydrophobic composite membrane material and preparation method thereof |
| CN110452307A (en) * | 2019-07-24 | 2019-11-15 | 衢州学院 | A kind of modified nanometer cellulose and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851295A (en) * | 2010-06-30 | 2010-10-06 | 东北林业大学 | Preparation method of homogenized fine nano-cellulose fiber |
| WO2015153536A1 (en) * | 2014-03-31 | 2015-10-08 | Api Intellectual Property Holdings, Llc | Nanocellulose production using lignosulfonic acid |
| CN105206431A (en) * | 2015-10-12 | 2015-12-30 | 中国林业科学研究院木材工业研究所 | Electrode material preparing method and electrode material prepared through same |
| CN105349036A (en) * | 2015-11-30 | 2016-02-24 | 东南大学 | Water-based transparent super-amphiphobic nano-paint and preparation method and application thereof |
-
2016
- 2016-03-01 CN CN201610114924.3A patent/CN105755890B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851295A (en) * | 2010-06-30 | 2010-10-06 | 东北林业大学 | Preparation method of homogenized fine nano-cellulose fiber |
| WO2015153536A1 (en) * | 2014-03-31 | 2015-10-08 | Api Intellectual Property Holdings, Llc | Nanocellulose production using lignosulfonic acid |
| CN105206431A (en) * | 2015-10-12 | 2015-12-30 | 中国林业科学研究院木材工业研究所 | Electrode material preparing method and electrode material prepared through same |
| CN105349036A (en) * | 2015-11-30 | 2016-02-24 | 东南大学 | Water-based transparent super-amphiphobic nano-paint and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 李慧媛等: ""纳米二氧化硅/纳米纤维素复合材料制备及性能分析"", 《农业工程学报》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107313279A (en) * | 2017-06-28 | 2017-11-03 | 常州市沃兰特电子有限公司 | A kind of preparation method of super-hydrophobicity paper |
| CN108560314A (en) * | 2017-12-15 | 2018-09-21 | 华南理工大学 | A kind of nano-cellulose based super hydrophobic coating and preparation method thereof |
| CN108560314B (en) * | 2017-12-15 | 2021-06-08 | 华南理工大学 | Nano-cellulose-based super-hydrophobic coating and preparation method thereof |
| CN108931565A (en) * | 2018-08-13 | 2018-12-04 | 山东农业大学 | The construction method of nano-cellulose paper base biosensor |
| CN109235141A (en) * | 2018-08-22 | 2019-01-18 | 广西大学 | A kind of preparation method and applications of wrapping paper barriers function coating lotion |
| CN109091699A (en) * | 2018-08-24 | 2018-12-28 | 郑州大学 | A kind of preparation method of styptic sponge and its styptic sponge of preparation |
| CN109091699B (en) * | 2018-08-24 | 2022-02-18 | 郑州大学 | Preparation method of hemostatic sponge and hemostatic sponge prepared by preparation method |
| CN110204753A (en) * | 2019-06-04 | 2019-09-06 | 齐鲁工业大学 | A kind of cellulose nanometer fibril base hydrophobic composite membrane material and preparation method thereof |
| CN110204753B (en) * | 2019-06-04 | 2022-02-08 | 齐鲁工业大学 | Cellulose nano-fibril based hydrophobic composite membrane material and preparation method thereof |
| CN110452307A (en) * | 2019-07-24 | 2019-11-15 | 衢州学院 | A kind of modified nanometer cellulose and preparation method thereof |
| CN110452307B (en) * | 2019-07-24 | 2021-05-11 | 衢州学院 | Modified nano-cellulose and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105755890B (en) | 2017-11-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105755890A (en) | Preparation method of super-hydrophobic oleophobic transparent nanocellulose paper | |
| CN105672014B (en) | The preparation method of super-hydrophobic magnetic Nano cellulose paper | |
| Kargarzadeh et al. | Advances in cellulose nanomaterials | |
| CN104845301B (en) | A kind of ultraviolet light screener and preparation method thereof and polylactic acid film comprising the ultraviolet light screener and preparation method thereof | |
| CN103102419B (en) | Method for preparing nano microcrystalline cellulose by hydrolyzing phyllostachys edulis fiber with cellulase | |
| CN103866487B (en) | The preparation method of a kind of nano micro crystal cellulose/chitosan/polyvinyl alcohol composite nanometer film | |
| CN107384326B (en) | Preparation method of gelatin chitosan-nano silicon dioxide multi-core phase change energy storage microcapsule | |
| CN104300164B (en) | A kind of preparation method of compound proton exchange membrane | |
| CN105672023A (en) | Cellulose fiber assembly and production method for same, fibrillated cellulose fiber and production method for same, and cellulose fiber complex | |
| CN102942354B (en) | Preparation method of transparent aerogel | |
| CN106633967A (en) | Titanium dioxide/lignin-based composite nanoparticle, and preparation method and application thereof | |
| CN102616794B (en) | Preparation method for high-dispersibility nanometer silicon dioxide | |
| CN109971014A (en) | A kind of nano-cellulose composite material and preparation method and application | |
| CN106867042A (en) | The tape casting prepares nano-cellulose/chitosan/polyvinyl alcohol composite membrane and its application in biological antibiotic film | |
| CN104693464A (en) | Preparation method of lignin-nanocelluose reinforced polylactic acid composite film | |
| CN103882624A (en) | Preparation method for water-resistant nano microcrystalline cellulose/polyvinyl alcohol/polyacrylic acid/silicon dioxide composite nanofiber membrane | |
| CN109776883A (en) | A kind of preparation method of NCC/ modified konjac glucomannan degradable films | |
| CN110591133A (en) | Environment-friendly production process for improving strength of regenerated cellulose membrane | |
| CN109232993A (en) | A kind of preparation method of cellulose/micrometer fibers element long filament porous small ball | |
| CN110067149A (en) | High-intensitive, haze and transparency nanometer paper the method with holocellulose preparation | |
| WO2023017687A1 (en) | Type ii unmodified cellulose microfibers, and method for manufacturing type ii unmodified cellulose microfibers and compact of same | |
| CN108866674B (en) | High-oil-absorption-capacity nano oil-absorption fiber and preparation method thereof | |
| CN110144762A (en) | A kind of preparation method of cellulose extrusion coating paper | |
| US20220340688A1 (en) | Sulfonated fine cellulose fiber and method for producing same | |
| CN104250415A (en) | Uvioresistant polyving alcohol-xylan composite membrane as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |