CN109468874A - A kind of super-hydrophobic transparent conductive paper and preparation method thereof - Google Patents
A kind of super-hydrophobic transparent conductive paper and preparation method thereof Download PDFInfo
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- CN109468874A CN109468874A CN201811282393.4A CN201811282393A CN109468874A CN 109468874 A CN109468874 A CN 109468874A CN 201811282393 A CN201811282393 A CN 201811282393A CN 109468874 A CN109468874 A CN 109468874A
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- 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
- D21H27/00—Special paper not otherwise provided for, e.g. made by multi-step processes
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- 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
- D21H19/00—Coated paper; Coating material
- D21H19/10—Coatings without pigments
- D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
-
- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
-
- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/50—Spraying or projecting
Abstract
The present invention relates to a kind of super-hydrophobic transparent conductive papers and preparation method thereof, comprising the following steps: (1) preparation of nano-silicon dioxide particle；(2) preparation of hydroxyl carbon nano tube；(3) nano-silicon dioxide particle is uniformly mixed with hydroxyl carbon nano tube, and modifying super hydrophobicity is carried out to it；(4) preparation of cellophane paper；(5) mixture obtained in step (3) is coated on cellophane paper, is dried at normal temperature, obtains super-hydrophobic transparent conductive paper.The present invention has the advantages that super-hydrophobic transparent conductive paper, as a kind of advanced composite material (ACM), paper must have good hydrophobic performance, to keep performance more stable；The intensity that cellophane paper is made is high, has preferable electric conductivity, the important role in real life and production；This method process flow is simple to operation, inexpensive, high production efficiency, industrialized production easy to accomplish.
Description
Technical field
The present invention relates to a kind of preparation method of ultra-hydrophobic paper, more specifically to a kind of super-hydrophobic transparent conductive paper and
Preparation method.
Background technique
Nano silica is translucent shape, is a kind of white, nontoxic, amorphous fine powder.It is with following spy
Property: porosity, large specific surface area, polymolecularity, light, chemical stability is good, high temperature resistant, do not burn, thixotropy, extinction,
The performances such as hydrophily, insulating properties.In paper industry, it can effectively improve the whiteness, intensity, wearability of paper；In pesticide
In industry, anticaking agent, dispersing agent can be used as, high-grade nano silica is alternatively arranged as the rubbing agent and drug of toothpaste
Figuration dispersing agent；As delustering agent, nano silica can also substitute high in Art sections such as paint, ink, cosmetics, coating
Expensive titanium dioxide etc..As inside nano silica poly- silicon oxygen and outer surface existing for activated silica alcohol radical and its absorption water,
Make it in hydrophily, is difficult to wet and disperses in organic phase.Further, since its surface, there are hydroxyl, surface can be larger, aggregation
Body always tends to agglomerate, thus the application performance of product is affected, therefore needs to surpass nano-silicon dioxide particle surface
Hydrophobically modified.
In the natural environment, there is a large amount of super-hydrophobic phenomenon, for example, the leaf of certain some plant, butterfly wing and
Insect to foot etc., people life in most typical super-hydrophobic phenomenon be lotus leaf effect, it is excellent that this effect imparts lotus leaf
Self-cleaning ability, because of this excellent performance, so that super-hydrophobic phenomenon gets more and more people's extensive concerning.Super-hydrophobic phenomenon is general
Refer to when water droplet drop is when sample surfaces, contact angle up to 150 ° or more and roll angle lower than 10 ° or less of phenomenon.One
Super hydrophobic surface truly should have biggish static contact angle, while also have lesser roll angle.Due to lotus leaf
The surface texture featur of effect, people obtain two conditions required for preparing super-hydrophobic table: (1) on the surface of the material on construct
Micron and the dual coarse structure of nanometer；(2) low-surface energy substance modification is carried out on the surface of the dual coarse structure of micro-nano.Such as
Sol-gel method, laser or chemical etching method, solvent evaporation method, template, sublimed method and polymer solidified forming method etc..
Superhydrophobic surface structure is furtherd investigate for understanding the super-hydrophobic phenomenon in nature and designing the super hydrophobic material of novel practical
It is of great significance.Meanwhile super hydrophobic material also has broad application prospects in industrial production and daily life.
Since paper has renewable, environmentally friendly, slim and graceful, the mechanical performances such as flexible and discardable, but simultaneously its there are one
A little insufficient: paper has good electrical insulating property, and mechanical strength is general, since paper contains hydrophilic functional group, has non-
Normal good hygroscopicity, causes the profit of itself to rise, and paper surface be also easy to be stained with by external environment it is dirty without easy to clean；When
With other compound compound tenses, the mechanical property of material can be reduced, or even influences the service life of material.So to make paper
In more fields, can especially be widely used in the energy such as microelectronic product, battery or even field of solar energy.(1) paper
Good hydrophobic performance must be had by opening.The presence of paper super hydrophobic surface makes the moisture of paper material not because of the change of external environment
Change and changes easily, to keep performance more stable, and super hydrophobic surface its unique self-cleaning function, but also plant is fine
Dimension table face have the characteristics that it is antifouling, bear dirty.(2) paper fibre is made to be applied in energy fields such as microelectronics, conductions, paper
Zhang Bixu has relatively high electric conductivity.So such as metal, carbon nanotube, graphene, must partly be led with some conductive materials
Body and organic conductive macromolecule etc. are combined in centainly stable form, thus the higher electric conductivity of paper material.
Production and performance important role of the transparent conductive electrode (TCEs) for filrn photovoltaic devices.Ideal TCE
The sunlight that must have the high grade of transparency maximumlly to absorb so as to solar battery conversion layer, be provided simultaneously with high conductivity to
Reduce the energy loss due to caused by resistance.The leading products of filrn photovoltaic devices in the market be conductive metal oxide such as
Tin indium oxide (ITO) is widely used as leading for transparent conductive electrode because of its high conductivity (10 Ω/sq) and the high grade of transparency (85%)
Electric material.Although ito thin film excellent performance, the high price of indium, the ITO that the deposition technique of the brittleness of itself and valuableness makes
Inexpensive production material can not be become and for constructing flexible solar battery mould group.In recent years, some new materials substitute
Tin indium oxide, such as carbon nanotube (CNT) are built into TCE by solwution method and substrate, so as to using the volume of high performance-price ratio
Flexible electronic product is manufactured to volume production technology.So using high transparency conduction paper as the side such as substrate of printed electronic device
Face using particularly important.
Publication number CN101544838 for Chinese invention patent application to provide a kind of super-hydrophobic nano silica/height poly-
Object composite membrane and preparation method thereof.Poly glycol monomethyl ether (MPEG) and poly- diethoxy siloxanes (PEDS) are subjected to transesterification
Reaction synthesis MPEG-g-PEDS graft polymers, then carries out sol gel reaction, gel powder is distributed to as filler
In high polymeric solution, by the solution coating on substrate, drying and forming-film.Composite membrane is repaired after water/ethanol solution dipping with surface
It adorns agent and carries out surface molecular self assembly, it is dry after being washed away raffinate with n-hexane, it can be obtained with super-hydrophobic nano titanium dioxide
Silicon/high polymer complex film.Although this method is related to a kind of super-hydrophobic nano silica/high polymer complex film, but produced
Journey is complicated, is not suitable for large-scale production and application.
The Chinese invention patent application of Publication No. CN1O614946OA provides a kind of high antibiotic property water proof type of high intensity and leads
After mixing with nano-cellulose suspension by silver nitrate sodium borohydride solution, reaction system is added in electric paper and preparation method thereof
Nano-cellulose/silver/polyaniline is made after adding aniline and persulfuric acid hinge in the immobilized nano-ag composite of standby nanofibers element
Compound is eventually adding beeswax, at high temperature after mixing evenly, nano-cellulose silver polyaniline beeswax compound is obtained, by institute
It obtains compound and is coated on paper surface, up to high-intensitive high antibiotic property water proof type conductive paper.But not reaching for such method is super thin
Water effect, the contact angle to water is only 125 °, and process is comparatively laborious；Due to polyaniline solubility property and mechanical property compared with
Difference also will affect the electric conductivity of paper.
The Chinese invention patent application of Publication No. CN107034722 provides a kind of preparation side of carbon nano tube conductive paper
Method after carbon nanotube passes through graphitization processing, removes impurity inside carbon nanotube, improves the microstructure of carbon nanotube, mention
High crystallinity, makes the regular densification of atomic arrangement, and more readily dispersible between paper fiber, significantly improves carbon nanotube and lead
The comprehensive performance of electric paper.Electric conductivity and thermal conductivity through being graphitized modified conductive paper are substantially improved.But such method is only limitted to
The electric conductivity for improving paper, ultra-hydrophobicity and the transparency without improving paper；It is led with carbon nanotube graphitization to enhance
Electrical property is not used widely at home due to cost and technical reason.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of super-hydrophobic transparent conductive paper and preparation method thereof, the party
Method operating process is simple, function admirable, has very big application prospect.
In order to realize object above, The technical solution adopted by the invention is as follows:
A kind of super-hydrophobic transparent conductive paper and preparation method thereof, comprising the following steps:
(1) preparation of nano-silicon dioxide particle；
(2) preparation of hydroxyl carbon nano tube；
(3) nano-silicon dioxide particle is uniformly mixed with hydroxyl carbon nano tube, and modifying super hydrophobicity is carried out to it；
(4) preparation of cellophane paper；
(5) mixture obtained in step (3) is coated on cellophane paper, is dried, obtains super-hydrophobic at normal temperature
Bright conductive paper.
The present invention provides in a kind of super-hydrophobic transparent conductive paper and preparation method thereof, by the system of nano-silicon dioxide particle
Preparation Method are as follows: 5mL ammonium hydroxide is uniformly mixed with 65mL dehydrated alcohol first, adds 5mL tetraethyl orthosilicate and the anhydrous second of 25mL
The uniform mixed liquor of alcohol, and with magnetic stirrer reaction solution 12 hours, then by system in 6600r/min~10000r/
High speed centrifugation under the conditions of min, centrifugation time are 3 hours, remove supernatant, filter, then washed with dehydrated alcohol, by clean production
Object is dried in vacuo at 60~80 DEG C, and drying time is 3 hours, and nano-silicon dioxide particle is made.
The present invention provides in a kind of super-hydrophobic transparent conductive paper and preparation method thereof, the preparation side of hydroxyl carbon nano tube
Method are as follows: measuring 30mL concentration first is 65% nitric acid solution in the three-necked flask of 100mL, then measures 30mL distilled water in three
In mouth flask, 15 minutes are stirred to get the nitric acid solution for arriving even concentration, weighs 1g carbon nanotube in three equipped with nitric acid solution
It in mouth flask, stirs 10 minutes, is homogeneously dispersed in carbon nanotube in nitric acid solution, reflux condensate device is installed, at 80 DEG C
Lower stirring 4 hours, is cooled to room temperature, then pours into reaction solution in the distilled water of 1000mL, it is clear to pour out upper layer for stratification
Liquid is repeated several times aforesaid operations, makes the pH=7 of liquid, with sand core funnel filtration product, filter cake is cleaned multiple times with aquae destillata, so
Afterwards place the product in drying 24 hours in 65 DEG C of vacuum oven, grinding body mill-drying product is then used, hydroxylating carbon is made
Nanotube.
The present invention provides in a kind of super-hydrophobic transparent conductive paper and preparation method thereof, by nano-silicon dioxide particle and hydroxyl
Base carbon nano tube is distributed in dehydrated alcohol, then that system progress ultrasonic mixing is uniform, and ultrasonic time is 30 minutes, then
Nano-silicon dioxide particle and hydroxyl carbon nano tube are subjected to modifying super hydrophobicity, method of modifying is: by 5g nanoscale dioxy
SiClx particle is distributed in 50mL toluene, and ultrasonic disperse 30min adds one of silane coupling agent or fluorine-containing oxosilane,
Super-hydrophobic nano-silicon dioxide particle hydroxyl carbon nano tube is made.
The present invention provides in a kind of super-hydrophobic transparent conductive paper and preparation method thereof, the silane coupling agent can be
Vinyltrimethoxysilane (A-171), vinyltriethoxysilane (A-151), gamma-aminopropyl-triethoxy-silane (DB-
550), γ-glycidyl ether oxypropyltrimethoxysilane (DB-560), γ-methacryloxypropyl trimethoxy
One of silane (DB-570) or gamma-mercaptopropyltriethoxysilane (DB-580), the fluorine-containing oxosilane can be ten
One of trifluoro octyl trimethoxy oxosilane, perfluoro hexyl trichlorosilane or perfluoro capryl trichlorosilane.
The present invention provides in a kind of super-hydrophobic transparent conductive paper and preparation method thereof, super-hydrophobic nano silicon dioxide granule
Mass percentage be 4~8%, the mass percentage of hydroxylated carbon nanotube is 0.2~1%, the body of dehydrated alcohol
Product percentage composition is 91~95.8%.
The present invention provides in a kind of super-hydrophobic transparent conductive paper and preparation method thereof, by 2,2,6,6- tetramethyl piperidine oxygen
Compound oxycellulose is made nano-cellulose, then is filtered by vacuum, and cellophane paper is made.
The present invention provides in a kind of super-hydrophobic transparent conductive paper and preparation method thereof, 2,2,6,6- tetramethyl piperidines are aoxidized
The method that object oxycellulose prepares nano-cellulose is: first that 2,2,6,6- tetramethyl piperidine oxides and sodium bromide are completely molten
Solution adds sodium hypochlorite, pours into paper pulp after mixing in beaker, is stirred 4 hours in electric mixer, pH control
It between 10~10.5, is eventually adding dehydrated alcohol and terminates reaction, reaction solution is carried out to high-pressure homogeneous, obtained nano-cellulose.
The present invention provides in a kind of super-hydrophobic transparent conductive paper and preparation method thereof, by ultra-hydrophobic conductive nanometer titanium dioxide
Silicon particle and 0~1% hydroxylating carbon nanotube mixture are evenly distributed on cellophane paper, and method is spin coating, spraying or are applied
One of cloth, then be dried at normal temperature, super-hydrophobic transparent conductive paper is made.
The technical effects of the invention are that:
1, so that nano-silicon dioxide particle is in good dispersity using ultrasonic wave, make nanometer titanium dioxide silicon grain
It is poly- that it is not susceptible to wadding between son, while reactant can be accelerated in the mixing and reaction of microcosmic particle.
2, for super-hydrophobic transparent conductive paper as a kind of advanced composite material (ACM), paper must have good hydrophobic performance, contact
Up to 155 °, the presence of paper super hydrophobic surface changes the moisture of paper material easily because of the variation of external environment at angle
Become, to keep performance more stable.
3, the intensity of cellophane paper is high, has preferable electric conductivity, high-cost tin indium oxide (ITO) can be replaced to be used as one
The production and performance important role of kind transparent conductive electrode (TCEs) for filrn photovoltaic devices.
4, this method process flow is simple, easily operated, cost is relatively low, high production efficiency, industrialized production easy to accomplish.
The present invention will be further explained below with reference to the attached drawings.
Detailed description of the invention
Fig. 1 nano silica scanning electron microscope (SEM) photograph
Fig. 2 nano-silicon dioxide particle and hydroxylating carbon nanotube mixture scanning electron microscope (SEM) photograph
The hydroxyl carbon nano tube of Fig. 3 different content and the relation curve of paper transparency
The water surface contact angle of Fig. 4 super-hydrophobic transparent conductive paper
The hydroxyl carbon nano tube and cellophane paper electric conductivity detection curve of Fig. 5 different content
Specific embodiment
Illustrate the present invention below by way of specific embodiment, but the present invention is not only limited to this embodiment, should not be understood as
Limitation to protection scope of the present invention, person skilled in art can do some non-intrinsically safes according to the content of aforementioned present invention
Modifications and adaptations.
Embodiment 1
(1) preparation of nano-silicon dioxide particle；
Nano-silicon dioxide particle the preparation method comprises the following steps: 5mL ammonium hydroxide is uniformly mixed with 65mL dehydrated alcohol first, then plus
Enter the uniform mixed liquor of 5mL tetraethyl orthosilicate and 25mL dehydrated alcohol, and with magnetic stirrer reaction solution 12 hours, then
By system, high speed centrifugation, centrifugation time are 3 hours under the conditions of 6600r/min, remove supernatant, filter, then use dehydrated alcohol
Washing, clean product vacuum is dry, and drying time is 3 hours, and nanosized silica particles are made.By nanometer titanium dioxide
Silicon particle carries out modifying super hydrophobicity, and method of modifying is: 5g nanosized silica particles being distributed in 50mL toluene, ultrasound
Disperse 30min, nano-silicon dioxide particle is made, nano silica scanning electron microscope (SEM) photograph is shown in as shown in Fig. 1.
(2) preparation of hydroxyl carbon nano tube；
Hydroxyl carbon nano tube the preparation method comprises the following steps: first measure 30mL concentration be 65% nitric acid solution in 100mL's
In three-necked flask, then measure 30mL distilled water in three-necked flask, stir 15 minutes to get arrive even concentration nitric acid solution,
1g carbon nanotube is weighed in the three-necked flask equipped with nitric acid solution, stirs 10 minutes, carbon nanotube is made to be homogeneously dispersed in nitre
In acid solution, reflux condensate device is installed, is stirred 4 hours at 80 DEG C, is cooled to room temperature, reaction solution is then poured into 1000mL
Distilled water in, stratification pours out supernatant liquor, and aforesaid operations are repeated several times, make the pH=7 of liquid, with sand core funnel mistake
Product is filtered, filter cake is cleaned multiple times with aquae destillata, then place the product in drying 24 hours in 65 DEG C of vacuum oven, is then used
Hydroxyl carbon nano tube is made in grinding body mill-drying product.
(3) nano-silicon dioxide particle is uniformly mixed with hydroxyl carbon nano tube, and modifying super hydrophobicity is carried out to it；
The mass percentage of super-hydrophobic nano silicon dioxide granule is 5%, the quality percentage of hydroxylated carbon nanotube
Content is 1%, and the volumn concentration of dehydrated alcohol is 94%, and weighed super-hydrophobic silica particle and hydroxylating carbon are received
Mitron is added to absolute ethanol, and adds vinyltrimethoxysilane (A-171), is uniformly mixed and is carried out modifying super hydrophobicity, receives
Rice silicon dioxide granule and hydroxylating carbon nanotube mixture scanning electron microscope (SEM) photograph are as shown in Fig. 2.
(4) preparation of cellophane paper；
It is by the method that 2,2,6,6- tetramethyl piperidine oxides oxycellulose prepares nano-cellulose: first weighs needle
Wood pulp 40g, then 2 are weighed, 2,6,6- tetramethyl piperidine oxides 0.64g and sodium bromide 6.4g are dissolved completely in beaker, then plus
Enter 500mL sodium hypochlorite, pour into paper pulp after mixing, stirred 4 hours in electric mixer, pH is controlled 10~10.5
Between, being eventually adding dehydrated alcohol to reaction solution becomes white, terminates reaction, is eventually adding dehydrated alcohol and terminates reaction, will be anti-
It answers liquid to carry out high-pressure homogeneous, nano-cellulose is made, be filtered by vacuum 12 hours, cellophane paper is made.
(5) mixture obtained in step (3) is coated on cellophane paper, is dried, obtains super-hydrophobic at normal temperature
Bright conductive paper.The hydroxylating carbon nanotube mixture of super-hydrophobic 5% nano-silicon dioxide particle and 1% is sprayed on cellophane paper
On, it is dried at normal temperature, is made super-hydrophobic transparent conductive paper, the hydroxyl carbon nano tube of different content and paper transparency
Relation curve is as shown in Fig. 3, and the water surface contact angle of super-hydrophobic transparent conductive paper is as shown in Fig. 4, the hydroxyl of different content
Carbon nano tube and cellophane paper electric conductivity detection curve are as shown in Fig. 5, as known to Fig. 5, as hydroxyl carbon nano tube contains
Amount increases, and the electric conductivity of super-hydrophobic transparent conductive paper increases.
Embodiment 2
(1) preparation of nano-silicon dioxide particle；
Nano-silicon dioxide particle the preparation method comprises the following steps: 5mL ammonium hydroxide is uniformly mixed with 65mL dehydrated alcohol first, then plus
Enter the uniform mixed liquor of 5mL tetraethyl orthosilicate and 25mL dehydrated alcohol, and with magnetic stirrer reaction solution 12 hours, then
By system, high speed centrifugation, centrifugation time are 3 hours under the conditions of 8000r/min, remove supernatant, filter, then use dehydrated alcohol
Washing, clean product vacuum is dry, and drying time is 3 hours, and nanosized silica particles are made.By nanometer titanium dioxide
Silicon particle carries out modifying super hydrophobicity, and method of modifying is: 5g nanosized silica particles being distributed in 50mL toluene, ultrasound
Disperse 30min, nano-silicon dioxide particle is made, nano silica scanning electron microscope (SEM) photograph is shown in as shown in Fig. 1.
(2) preparation of hydroxyl carbon nano tube；
Hydroxyl carbon nano tube the preparation method comprises the following steps: first measure 30mL concentration be 65% nitric acid solution in 100mL's
In three-necked flask, then measure 30mL distilled water in three-necked flask, stir 15 minutes to get arrive even concentration nitric acid solution,
1g carbon nanotube is weighed in the three-necked flask equipped with nitric acid solution, stirs 10 minutes, carbon nanotube is made to be homogeneously dispersed in nitre
In acid solution, reflux condensate device is installed, is stirred 4 hours at 80 DEG C, is cooled to room temperature, reaction solution is then poured into 1000mL
Distilled water in, stratification pours out supernatant liquor, and aforesaid operations are repeated several times, make the pH=7 of liquid, with sand core funnel mistake
Product is filtered, filter cake is cleaned multiple times with aquae destillata, then place the product in drying 24 hours in 65 DEG C of vacuum oven, is then used
Hydroxyl carbon nano tube is made in grinding body mill-drying product.
(3) nano-silicon dioxide particle is uniformly mixed with hydroxyl carbon nano tube, and modifying super hydrophobicity is carried out to it；
The mass percentage of super-hydrophobic nano silicon dioxide granule is 6%, the quality percentage of hydroxylated carbon nanotube
Content is 0.6%, and the volumn concentration of dehydrated alcohol is 93.4%, by weighed super-hydrophobic silica particle and hydroxylating
Carbon nanotube is added to absolute ethanol, and is added γ-methacryloxypropyl trimethoxy silane (DB-570), and mixing is equal
Even carry out modifying super hydrophobicity, nano-silicon dioxide particle and hydroxylating carbon nanotube mixture scanning electron microscope (SEM) photograph are as shown in Fig. 2.
(4) preparation of cellophane paper；
It is by the method that 2,2,6,6- tetramethyl piperidine oxides oxycellulose prepares nano-cellulose: first weighs needle
Wood pulp 40g, then 2 are weighed, 2,6,6- tetramethyl piperidine oxides 0.64g and sodium bromide 6.4g are dissolved completely in beaker, then plus
Enter 500mL sodium hypochlorite, pour into paper pulp after mixing, stirred 4 hours in electric mixer, pH is controlled 10~10.5
Between, being eventually adding dehydrated alcohol to reaction solution becomes white, terminates reaction, is eventually adding dehydrated alcohol and terminates reaction.It will be anti-
It answers liquid to carry out high-pressure homogeneous, nano-cellulose is made, be filtered by vacuum 12 hours, cellophane paper is made.
(5) mixture obtained in step (3) is coated on cellophane paper, is dried, obtains super-hydrophobic at normal temperature
Bright conductive paper.The hydroxylating carbon nanotube mixture of super-hydrophobic 6% nano-silicon dioxide particle and 0.6% is spin-coated on transparent
It on paper, is dried at normal temperature, super-hydrophobic transparent conductive paper, the hydroxyl carbon nano tube and paper transparency of different content is made
Relation curve it is as shown in Fig. 3, the water surface contact angle of super-hydrophobic transparent conductive paper is as shown in Fig. 4, the hydroxyl of different content
Base carbon nano tube and cellophane paper electric conductivity detection curve are as shown in Fig. 5, as known to Fig. 5, with hydroxyl carbon nano tube
Content increases, and the electric conductivity of super-hydrophobic transparent conductive paper increases.
Embodiment 3
(1) preparation of nano-silicon dioxide particle；
Nano-silicon dioxide particle the preparation method comprises the following steps: 5mL ammonium hydroxide is uniformly mixed with 65mL dehydrated alcohol first, then plus
Enter the uniform mixed liquor of 5mL tetraethyl orthosilicate and 25mL dehydrated alcohol, and with magnetic stirrer reaction solution 12 hours, then
By system, high speed centrifugation, centrifugation time are 3 hours under the conditions of 9000r/min, remove supernatant, filter, then use dehydrated alcohol
Washing, clean product vacuum is dry, and drying time is 3 hours, and nanosized silica particles are made.By nanometer titanium dioxide
Silicon particle carries out modifying super hydrophobicity, and method of modifying is: 5g nanosized silica particles being distributed in 50mL toluene, ultrasound
Disperse 30min, nano-silicon dioxide particle is made, nano silica scanning electron microscope (SEM) photograph is shown in as shown in Fig. 1.
(2) preparation of hydroxyl carbon nano tube；
Hydroxyl carbon nano tube the preparation method comprises the following steps: first measure 30mL concentration be 65% nitric acid solution in 100mL's
In three-necked flask, then measure 30mL distilled water in three-necked flask, stir 15 minutes to get arrive even concentration nitric acid solution,
1g carbon nanotube is weighed in the three-necked flask equipped with nitric acid solution, stirs 10 minutes, carbon nanotube is made to be homogeneously dispersed in nitre
In acid solution, reflux condensate device is installed, is stirred 4 hours at 80 DEG C, is cooled to room temperature, reaction solution is then poured into 1000mL
Distilled water in, stratification pours out supernatant liquor, and aforesaid operations are repeated several times, make the pH=7 of liquid, with sand core funnel mistake
Product is filtered, filter cake is cleaned multiple times with aquae destillata, then place the product in drying 24 hours in 65 DEG C of vacuum oven, is then used
Hydroxyl carbon nano tube is made in grinding body mill-drying product.
(3) nano-silicon dioxide particle is uniformly mixed with hydroxyl carbon nano tube, and modifying super hydrophobicity is carried out to it；
The mass percentage of super-hydrophobic nano silicon dioxide granule is 7%, the quality percentage of hydroxylated carbon nanotube
Content is 0.1%, and the volumn concentration of dehydrated alcohol is 92.9%, by weighed super-hydrophobic silica particle and hydroxylating
Carbon nanotube is added to absolute ethanol, and adds ten trifluoro octyl trimethoxy silanes, is uniformly mixed and is carried out modifying super hydrophobicity, receives
Rice silicon dioxide granule and hydroxylating carbon nanotube mixture scanning electron microscope (SEM) photograph are as shown in Fig. 2.
(4) preparation of cellophane paper；
It is by the method that 2,2,6,6- tetramethyl piperidine oxides oxycellulose prepares nano-cellulose: first weighs needle
Wood pulp 40g, then 2 are weighed, 2,6,6- tetramethyl piperidine oxides 0.64g and sodium bromide 6.4g are dissolved completely in beaker, then plus
Enter 500mL sodium hypochlorite, pours into paper pulp after mixing；It is stirred 4 hours in electric mixer, pH is controlled 10~10.5
Between, being eventually adding dehydrated alcohol to reaction solution becomes white, terminates reaction, is eventually adding dehydrated alcohol and terminates reaction.It will be anti-
It answers liquid to carry out high-pressure homogeneous, nano-cellulose is made.Cellophane paper is made in vacuum filtration 12 hours.
(5) mixture obtained in step (3) is coated on cellophane paper, is dried, obtains super-hydrophobic at normal temperature
Bright conductive paper.The hydroxylating carbon nanotube mixture of super-hydrophobic 7% nano-silicon dioxide particle and 0.4% is coated on transparent
It on paper, is dried at normal temperature, the hydroxyl carbon nano tube and paper transparency of super-hydrophobic transparent conductive paper different content is made
Relation curve it is as shown in Fig. 3, the water surface contact angle of super-hydrophobic transparent conductive paper is as shown in Fig. 4, the hydroxyl of different content
Base carbon nano tube and cellophane paper electric conductivity detection curve are as shown in Fig. 5, as known to Fig. 5, with hydroxyl carbon nano tube
Content increases, and the electric conductivity of super-hydrophobic transparent conductive paper increases.
In conclusion the paper prepared has well using super-hydrophobic transparent conductive paper and preparation method thereof of the invention
Hydrophobic performance, performance is more stable, and the intensity of cellophane paper is high, has preferable electric conductivity, and the method process is simple, easy to operate
High production efficiency, industrialized production easy to accomplish.
It should be understood that for those of ordinary skills, it can be modified or changed according to the above description,
And all these modifications and variations should all belong to the protection domain of appended claims of the present invention.
Claims (9)
1. a kind of super-hydrophobic transparent conductive paper and preparation method thereof, which comprises the following steps:
(1) 5mL ammonium hydroxide is uniformly mixed by the preparation of nano-silicon dioxide particle with 65mL dehydrated alcohol, and 5mL silicic acid tetrem is added
The uniform mixed liquor of ester and 25mL dehydrated alcohol, and with magnetic stirrer reaction solution 12 hours, then by system high speed from
The heart removes supernatant, filtering, then is washed with dehydrated alcohol, and clean product vacuum is dry, and nanometer titanium dioxide silicon grain is made
Son；
(2) preparation of hydroxyl carbon nano tube measures 30mL concentration and burns for 65% nitric acid solution and 30mL distilled water in three mouthfuls
In bottle, the nitric acid solution of even concentration is stirred to get, 1g carbon nanotube is weighed in the three-necked flask equipped with nitric acid solution, makes carbon
Nanotube is homogeneously dispersed in nitric acid solution, is installed reflux condensate device, is stirred 4 hours, be cooled to room temperature, so at 80 DEG C
Reaction solution is poured into distilled water afterwards, stratification, pours out supernatant liquor, aforesaid operations are repeated several times, make the pH=7 of liquid,
With sand core funnel filtration product, filter cake is cleaned multiple times with aquae destillata, then place the product in drying in vacuum oven, is then used
Hydroxyl carbon nano tube is made in grinding body mill-drying product；
(3) nano-silicon dioxide particle is uniformly mixed with hydroxyl carbon nano tube, and modifying super hydrophobicity is carried out to it, 5g is received
Meter level silicon dioxide granule is distributed in 50mL toluene, adds one of silane coupling agent or fluorine-containing oxosilane, is made super
Hydrophobic nano-silicon dioxide particle hydroxyl carbon nano tube；
(4) nano-cellulose is made in 2,2,6,6- tetramethyl piperidine oxides oxycelluloses by the preparation of cellophane paper, then into
Row vacuum filtration, is made cellophane paper；
(5) mixture obtained in step (3) is coated on cellophane paper, is dried at normal temperature, obtains super-hydrophobic transparent and lead
Electric paper.
2. a kind of super-hydrophobic transparent conductive paper according to claim 1 and preparation method thereof, which is characterized in that the step
Suddenly in (1) nano-silicon dioxide particle the preparation method comprises the following steps: 5mL ammonium hydroxide is uniformly mixed with 65mL dehydrated alcohol first, then plus
Enter the uniform mixed liquor of 5mL tetraethyl orthosilicate and 25mL dehydrated alcohol, and with magnetic stirrer reaction solution 12 hours, then
By system, high speed centrifugation, centrifugation time are 3 hours under the conditions of 6600r/min~10000r/min, remove supernatant, filter,
It is washed again with dehydrated alcohol, clean product is dried in vacuo at 60~80 DEG C, drying time is 3 hours, and nanometer two is made
Silicon oxide particle.
3. a kind of super-hydrophobic transparent conductive paper according to claim 1 and preparation method thereof, which is characterized in that the step
Suddenly in (2), hydroxyl carbon nano tube the preparation method comprises the following steps: first measure 30mL concentration be 65% nitric acid solution in 100mL's
In three-necked flask, then 30mL distilled water is measured in three-necked flask, stir 15 minutes to get the nitric acid solution for arriving even concentration；
1g carbon nanotube is weighed in the three-necked flask equipped with nitric acid solution, stirs 10 minutes, carbon nanotube is made to be homogeneously dispersed in nitre
In acid solution；Reflux condensate device is installed, is stirred 4 hours at 80 DEG C, is cooled to room temperature, reaction solution is then poured into 1000mL
Distilled water in, stratification pours out supernatant liquor, and aforesaid operations are repeated several times, make the pH=7 of liquid, with sand core funnel mistake
Product is filtered, filter cake is cleaned multiple times with aquae destillata, then place the product in drying 24 hours in 65 DEG C of vacuum oven, is then used
Hydroxyl carbon nano tube is made in grinding body mill-drying product.
4. a kind of super-hydrophobic transparent conductive paper according to claim 1 and preparation method thereof, which is characterized in that the step
Suddenly nano-silicon dioxide particle and hydroxyl carbon nano tube are distributed in dehydrated alcohol in (3), system is then subjected to ultrasound
It is uniformly mixed, ultrasonic time is 30 minutes, and nano-silicon dioxide particle and hydroxyl carbon nano tube are then carried out super-hydrophobic change
Property, method of modifying is: 5g nanosized silica particles being distributed in 50mL toluene, ultrasonic disperse 30min, adds silicon
Super-hydrophobic nano-silicon dioxide particle hydroxyl carbon nano tube is made in alkane coupling agent or one of fluorine silicon chlorine and alkane.
5. a kind of super-hydrophobic transparent conductive paper according to claim 4 book and preparation method thereof, which is characterized in that described
Silane coupling agent can be vinyltrimethoxysilane (A-171), vinyltriethoxysilane (A-151), γ-aminopropyl
Triethoxysilane (DB-550), γ-glycidyl ether oxypropyltrimethoxysilane (DB-560), γ-methacryl
One of oxygroup propyl trimethoxy silicane (DB-570) or gamma-mercaptopropyltriethoxysilane (DB-580), described contains
Fluorine oxosilane can be in ten trifluoro octyl trimethoxy oxosilane, perfluoro hexyl trichlorosilane or perfluoro capryl trichlorosilane
It is a kind of.
6. a kind of super-hydrophobic transparent conductive paper according to claim 5 and preparation method thereof, which is characterized in that described
The mass percentage of super-hydrophobic nano silicon dioxide granule is 4~8%, and the mass percentage of hydroxylated carbon nanotube is
0.2~1%, the volumn concentration of dehydrated alcohol is 91~95.8%.
7. a kind of super-hydrophobic transparent conductive paper according to claim 1 and preparation method thereof, which is characterized in that the step
Suddenly in (4), by 2,2,6,6- tetramethyl piperidine oxides oxycelluloses, nano-cellulose is made, then be filtered by vacuum, makes
Obtain cellophane paper.
8. a kind of super-hydrophobic transparent conductive paper according to claim 7 and preparation method thereof, which is characterized in that 2,2,6,
The method that 6- tetramethyl piperidine oxides oxycellulose prepares nano-cellulose is: first aoxidizing 2,2,6,6- tetramethyl piperidine
Object and sodium bromide are dissolved completely in beaker, are added sodium hypochlorite, are poured into paper pulp after mixing, in electric mixer
Stirring 4 hours, pH control between 10~10.5, be eventually adding dehydrated alcohol terminate reaction, reaction solution is carried out it is high-pressure homogeneous,
Nano-cellulose is made.
9. a kind of super-hydrophobic transparent conductive paper according to claim 1 and preparation method thereof, which is characterized in that the step
Suddenly in (5), the hydroxylating carbon nanotube mixture of ultra-hydrophobic conductive nano-silicon dioxide particle and 0~1% is evenly distributed on
On cellophane paper, method is spin coating, one of spraying or coating, then is dried at normal temperature, and obtained super-hydrophobic transparent is led
Electric paper.
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| CN111395054A (en) * | 2020-03-27 | 2020-07-10 | 深圳市旺盈彩盒纸品有限公司 | Flexible transparent conductive hydrophobic paper and preparation method thereof |
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| WO2022073315A1 (en) * | 2020-10-08 | 2022-04-14 | 苏州大学 | Precursor for super-hydrophobic composite coating and preparation method therefor |
| CN114790364A (en) * | 2022-04-01 | 2022-07-26 | 哈尔滨工程大学 | Hydrophobic carbon nanotube-based super-hydrophobic coating with anti-icing function and preparation method thereof |
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