CN107503228A - A kind of preparation method of the high intensity ultra-hydrophobic paper based on LBL self-assembly and thermal induction processing - Google Patents
A kind of preparation method of the high intensity ultra-hydrophobic paper based on LBL self-assembly and thermal induction processing Download PDFInfo
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- CN107503228A CN107503228A CN201710613410.7A CN201710613410A CN107503228A CN 107503228 A CN107503228 A CN 107503228A CN 201710613410 A CN201710613410 A CN 201710613410A CN 107503228 A CN107503228 A CN 107503228A
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- trimethoxy silane
- hexadecyl trimethoxy
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000012545 processing Methods 0.000 title claims abstract description 15
- 230000006698 induction Effects 0.000 title claims abstract description 12
- 238000001338 self-assembly Methods 0.000 title claims abstract description 12
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 230000004048 modification Effects 0.000 claims abstract description 24
- 238000012986 modification Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 229920001661 Chitosan Polymers 0.000 claims abstract description 13
- GMMZXKSNKIUKOW-UHFFFAOYSA-N [O-2].[O-2].[Ti+4].C(C)O Chemical compound [O-2].[O-2].[Ti+4].C(C)O GMMZXKSNKIUKOW-UHFFFAOYSA-N 0.000 claims abstract description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- WLPSNBGDESCKIL-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO WLPSNBGDESCKIL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000003672 processing method Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- 238000002715 modification method Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 230000003075 superhydrophobic effect Effects 0.000 abstract description 5
- 238000007654 immersion Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract description 2
- 239000000123 paper Substances 0.000 description 62
- 239000002352 surface water Substances 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011111 cardboard Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000011087 paperboard Substances 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 3
- 241000790917 Dioxys <bee> Species 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 235000013312 flour Nutrition 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 208000001491 myopia Diseases 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/71—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes
- D21H17/74—Mixtures of material ; Pulp or paper comprising several different materials not incorporated by special processes of organic and inorganic material
-
- 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
- D21H17/06—Alcohols; Phenols; Ethers; Aldehydes; Ketones; Acetals; Ketals
-
- 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
- D21H17/21—Macromolecular organic compounds of natural origin; Derivatives thereof
- D21H17/24—Polysaccharides
-
- 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
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
- D21H17/69—Water-insoluble compounds, e.g. fillers, pigments modified, e.g. by association with other compositions prior to incorporation in the pulp or 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
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
-
- 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
- D21H27/10—Packing paper
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a kind of preparation method of the high intensity ultra-hydrophobic paper based on LBL self-assembly and thermal induction processing, belong to paper post-processing technical field.Plain paper is placed in concentration to soak 10 ~ 20min in 2 ~ 3g/L chitosan solutions first, number is cleaned 3 ~ 5 times with deionized water after taking-up, in 60 ~ 80 DEG C of dry 10 ~ 20min；Then paper after processing is placed in 10 ~ 20min of immersion in the nano titanium oxide ethanol solution of hexadecyl trimethoxy silane graft modification, taking-up cleans number 3 ~ 5 times with deionized water, in 60 ~ 80 DEG C of dry 10 ~ 20min, the wherein nano titanium oxide ethanol solution concentration of hexadecyl trimethoxy silane graft modification is 2 ~ 4g/L；Be repeated in step 20 ~ 30 time, finally by it is above-mentioned it is treated be placed in 140 ~ 160 DEG C under the conditions of handle 20 ~ 30min, obtain high intensity ultra-hydrophobic paper.The inventive method operates and equipment is simple and easy to get, and it is cumbersome to overcome traditional super-hydrophobic paper preparation technology, the defects of required equipment complex and expensive, is adapted to industrialized production.
Description
Technical field
The present invention relates to a kind of preparation method of the high intensity ultra-hydrophobic paper based on LBL self-assembly and thermal induction processing, category
In paper post-processing technical field.
Background technology
Packaging industry is mainly using petroleum-based plastics such as polyethylene (PE), polypropylene (PP) as packaging material at present, these
The production of petroleum-based plastics not only consumes substantial amounts of petroleum resources, and its a large amount of use can cause serious " white dirt
Dye ", endangers environment.String is rich reserves, wide material sources, cheap renewable biomass resources, is had good
Biocompatibility and biodegradability, avirulent feature.Using it is the paper wrapper of matrix in " green package "
Occupy highly important status in industry.Paper wrapper is used to replace plastic package material to contain liquid or solid matter
Deng, in addition to it should have conventional packaging function, should also play it is waterproof and dampproof, fresh-keeping etc. effect.Such as flour packaging paper bag
Not only there is higher intensity to bear the gravity of its content and slight impact, but also there is higher hydrophobicity
To extend flour storage period.
However, paper wrapper（Paper or cardboard）Main component be cellulose and hemicellulose, there is extremely strong parent
It is water-based, moisture is easily absorbed from surrounding environment, especially under high humidity conditions either and high-moisture materials（Such as fresh agriculture
Product）During contact.The Hydrogenbond that the intensity of Paper or cardboard is depended primarily between cellulosic molecule, and hydrogen bond is to water electrode that its is quick
Sense, after absorbing moisture, hydrogen bond will be reduced rapidly so that the mechanical strength of Paper or cardboard reduces, so as to cause to store and circulating
During paper wrapper compared with cracky, influence product quality.Therefore, the hydrophobic performance of paper wrapper is improved to improving
Packaging quality is significant.
At present, the preparation method on super-hydrophobic paper has largely been reported, including grafting modification, and magnetron sputtering applies
Cloth, supercritical CO2Rapid expansion, plasma etching method etc..But most of preparation method often complex operation, or required
Instrument and equipment complex and expensive.Paper（Huang LH, et al. J. Mater.Sci. 2011,46:2600-2605）Deliver
A kind of straightforward procedure for preparing ultra-hydrophobic paper：Realized by being filled with the nano titanium oxide of silylating reagent into paper pulp super
The preparation of hydrophobic paper.But this method causes substantial amounts of modified nano-titanium dioxide to be covered in fiber surface, cause into fine during paper
Hydrogenbond is greatly decreased between dimension and fiber, so as to cause paper strength inevitably to damage.When silylating reagent nanometer
When the titanium dioxide amount of being filled with is 13%, the water contact angle of handmade paper is up to 157.7 °, but its tensile strength have lost compared with control sample
About 38%.It can be seen that the ultra-hydrophobic paper intensity difference prepared by this method, limits its application as packaging material in practice.
The content of the invention
For the above-mentioned problems of the prior art and deficiency, the present invention provides one kind and is based on LBL self-assembly and thermal induction
The preparation method of the high intensity ultra-hydrophobic paper of processing.The inventive method operates and equipment is simple and easy to get, overcomes traditional super thin
Water paper making process is cumbersome, the defects of required equipment complex and expensive, is adapted to industrialized production.The present invention passes through following technical side
Case is realized.
A kind of preparation method of the high intensity ultra-hydrophobic paper based on LBL self-assembly and thermal induction processing, its specific steps is such as
Under：
（1）Plain paper is placed in concentration to soak 10 ~ 20min in 2 ~ 3g/L chitosan solutions first, deionization is used after taking-up
Water cleaning number 3 ~ 5 times, in 60 ~ 80 DEG C of dry 10 ~ 20min；
（2）Then will be through step（1）Paper after processing is placed in the nano-silica of hexadecyl trimethoxy silane graft modification
To change and 10 ~ 20min is soaked in titanium-ethanol solution, taking-up cleans number 3 ~ 5 times with deionized water, in 60 ~ 80 DEG C of dry 10 ~ 20min,
Wherein nano titanium oxide-ethanol solution concentration of hexadecyl trimethoxy silane graft modification is 2 ~ 4g/L；
（3）It is repeated in step（1）With（2）20 ~ 30 times, finally above-mentioned treated being placed under the conditions of 140 ~ 160 DEG C is handled
20 ~ 30min, obtain high intensity ultra-hydrophobic paper.
The step（1）In chitosan solution pH value be 5 ~ 5.7.
The step（2）The preparation method of the nano titanium oxide of middle hexadecyl trimethoxy silane graft modification：It is first
It is first 95 according to volume ratio by absolute ethyl alcohol and deionized water：5 it is well mixed obtain organic solvent, then according to organic solvent with
Hexadecyl trimethoxy silane liquid-solid ratio is 100：0.5 ~ 0.8mL/g adds hexadecyl trimethoxy silane, in room temperature bar
30 ~ 40min is stirred under part, is then 0.5 ~ 0.8 according still further to hexadecyl trimethoxy silane and nano titanium oxide mass ratio：
4 ~ 5 add nano titanium oxides, under the conditions of 60 ~ 70 DEG C 60 ~ 120min of stirring reaction, after reaction terminates, centrifuge, isolate
Precipitation is washed with absolute ethyl alcohol, and the nano titanium oxide of hexadecyl trimethoxy silane graft modification is obtained after vacuum drying.
The nano titanium oxide of the above-mentioned hexadecyl trimethoxy silane graft modification being prepared be particle diameter 50 ~
100nm's is powdered.
The beneficial effects of the invention are as follows：
（1）Ultra-hydrophobic paper prepared by the inventive method, nanoscale silylating reagent dioxy is realized using layer-by-layer
Change titanium and chitosan multilayer film in the load of paper surface, larger asperity structure has been constructed in paper surface, has been paper table
The realization of face ultra-hydrophobicity constructs good suitable architecture basics；Then pass through follow-up heat treatment so that modified dioxy
Change the outside that the hydrophobic Long carbon chain on titanium tends to multilayer film, the surface energy of paper is reduced, it is achieved thereby that paper surface is superior
Ultra-hydrophobicity.The inventive method operates and equipment is simple and easy to get, and it is cumbersome to overcome traditional super-hydrophobic paper preparation technology,
The defects of required equipment complex and expensive, it is adapted to industrialized production.
（2）Paper prepared by the present invention, not only with super-hydrophobic characteristic, and its strength character has also obtained greatly
Improvement.After tested, paper surface first adsorbs 25 double-deck chitosans/silanization nano titanium oxide multilayer film, then through 150 DEG C
After handling 25min, the water contact angle of paper surface may be up to 153.1 °, and the more unmodified paper blank of tensile strength improves
22.7%.The high intensity ultra-hydrophobic paper of preparation has good in paper wrapper particularly paper food packaging materials field
Application prospect.
Brief description of the drawings
Fig. 1 is the nanometer titanium dioxide for the hexadecyl trimethoxy silane graft modification that the embodiment of the present invention 1 is prepared
Titanium SEM schemes；
Fig. 2 is that super-hydrophobic paper surface water drop static contact angle test photo is prepared in the embodiment of the present invention 2.
Embodiment
With reference to the accompanying drawings and detailed description, the invention will be further described.
Embodiment 1
The preparation method of the high intensity ultra-hydrophobic paper based on LBL self-assembly and thermal induction processing, it is comprised the following steps that：
（1）It is 2g/L chitosan solutions that plain paper is placed in into concentration first（In chitosan solution plus acid for adjusting pH value be 5 ~
5.7）Middle immersion 10min, number is cleaned 3 times with deionized water after taking-up, in 60 DEG C of dry 10min；
（2）Then will be through step（1）Paper after processing is placed in the nano-silica of hexadecyl trimethoxy silane graft modification
Change in titanium-ethanol solution and soak 10min, taking-up cleans number 3 times with deionized water, in 60 DEG C of dry 10min, wherein cetyl
Nano titanium oxide-ethanol solution concentration of trimethoxy silane graft modification is 2g/L；Hexadecyl trimethoxy silane connects
The preparation method of the modified nano titanium oxide of branch：According to volume ratio it is 95 first by absolute ethyl alcohol and deionized water：5 mixing are equal
It is even to obtain organic solvent, it is then 100 according to organic solvent and hexadecyl trimethoxy silane liquid-solid ratio：0.5mL/g is added
Hexadecyl trimethoxy silane, 30min is stirred at ambient temperature, then according still further to hexadecyl trimethoxy silane with receiving
Rice titanium dioxide mass ratio is 0.5：4 add nano titanium oxide, the stirring reaction 60min under the conditions of 60 DEG C, react after terminating,
The precipitation centrifuge, isolated is washed with absolute ethyl alcohol, and hexadecyl trimethoxy silane graft modification is obtained after vacuum drying
Nano titanium oxide, the nano titanium oxide of the hexadecyl trimethoxy silane graft modification being prepared for particle diameter 50 ~
100nm's is powdered, and SEM figures are as shown in Figure 1；
（3）It is repeated in step（1）With（2）20 times, above-mentioned treated being placed under the conditions of 140 DEG C is finally handled into 20min, obtained
To high intensity ultra-hydrophobic paper.
The high intensity ultra-hydrophobic paper paper surface water contact angle that the present embodiment is prepared is up to 151.2 °, and tensile strength is more not
Modified paper blank improves 11.9%.
Embodiment 2
The preparation method of the high intensity ultra-hydrophobic paper based on LBL self-assembly and thermal induction processing, it is comprised the following steps that：
（1）It is 2.5g/L chitosan solutions that plain paper is placed in into concentration first（In chitosan solution plus acid for adjusting pH value be 5 ~
5.7）Middle immersion 15min, number is cleaned 4 times with deionized water after taking-up, in 70 DEG C of dry 15min；
（2）Then will be through step（1）Paper after processing is placed in the nano-silica of hexadecyl trimethoxy silane graft modification
Change in titanium-ethanol solution and soak 15min, taking-up cleans number 4 times with deionized water, in 70 DEG C of dry 15min, wherein cetyl
Nano titanium oxide-ethanol solution concentration of trimethoxy silane graft modification is 3g/L；Hexadecyl trimethoxy silane connects
The preparation method of the modified nano titanium oxide of branch：According to volume ratio it is 95 first by absolute ethyl alcohol and deionized water：5 mixing are equal
It is even to obtain organic solvent, it is then 100 according to organic solvent and hexadecyl trimethoxy silane liquid-solid ratio：0.6mL/g is added
Hexadecyl trimethoxy silane, 35min is stirred at ambient temperature, then according still further to hexadecyl trimethoxy silane with receiving
Rice titanium dioxide mass ratio is 0.6：4.5 add nano titanium oxides, under the conditions of 65 DEG C stirring reaction 100min, reaction terminate
Afterwards, the precipitation centrifuge, isolated is washed with absolute ethyl alcohol, and hexadecyl trimethoxy silane graft modification is obtained after vacuum drying
Nano titanium oxide, the nano titanium oxide of the hexadecyl trimethoxy silane graft modification being prepared for particle diameter 50 ~
100nm's is powdered；
（3）It is repeated in step（1）With（2）25 times, above-mentioned treated being placed under the conditions of 150 DEG C is finally handled into 25min, obtained
To high intensity ultra-hydrophobic paper.
High intensity ultra-hydrophobic paper paper surface water drop static contact angle test photo such as Fig. 2 institutes that the present embodiment is prepared
Show, as can be seen from Figure 2 water droplet it is not unfolded in paper surface and in near-sighted spherical, high intensity ultra-hydrophobic paper paper surface water
For contact angle up to 153.1 °, the more unmodified paper blank of tensile strength improves 22.7%.
Embodiment 3
The preparation method of the high intensity ultra-hydrophobic paper based on LBL self-assembly and thermal induction processing, it is comprised the following steps that：
（1）It is 3g/L chitosan solutions that plain paper is placed in into concentration first（In chitosan solution plus acid for adjusting pH value be 5 ~
5.7）Middle immersion 20min, number is cleaned 5 times with deionized water after taking-up, in 80 DEG C of dry 20min；
（2）Then will be through step（1）Paper after processing is placed in the nano-silica of hexadecyl trimethoxy silane graft modification
Change in titanium-ethanol solution and soak 20min, taking-up cleans number 5 times with deionized water, in 80 DEG C of dry 20min, wherein cetyl
Nano titanium oxide-ethanol solution concentration of trimethoxy silane graft modification is 4g/L；Hexadecyl trimethoxy silane connects
The preparation method of the modified nano titanium oxide of branch：According to volume ratio it is 95 first by absolute ethyl alcohol and deionized water：5 mixing are equal
It is even to obtain organic solvent, it is then 100 according to organic solvent and hexadecyl trimethoxy silane liquid-solid ratio：0.8mL/g is added
Hexadecyl trimethoxy silane, 40min is stirred at ambient temperature, then according still further to hexadecyl trimethoxy silane with receiving
Rice titanium dioxide mass ratio is 0.8：5 add nano titanium oxides, under the conditions of 70 DEG C stirring reaction 120min, reaction terminate
Afterwards, the precipitation centrifuge, isolated is washed with absolute ethyl alcohol, and hexadecyl trimethoxy silane graft modification is obtained after vacuum drying
Nano titanium oxide, the nano titanium oxide of the hexadecyl trimethoxy silane graft modification being prepared for particle diameter 50 ~
100nm's is powdered；
（3）It is repeated in step（1）With（2）30 times, above-mentioned treated being placed under the conditions of 160 DEG C is finally handled into 30min, obtained
To high intensity ultra-hydrophobic paper.
The high intensity ultra-hydrophobic paper paper surface water contact angle that the present embodiment is prepared is up to 167.4 °, and tensile strength is more not
Modified paper blank improves 8.7%.
Above in association with accompanying drawing to the present invention embodiment be explained in detail, but the present invention be not limited to it is above-mentioned
Embodiment, can also be before present inventive concept not be departed from those of ordinary skill in the art's possessed knowledge
Put that various changes can be made.
Claims (3)
1. a kind of preparation method of the high intensity ultra-hydrophobic paper based on LBL self-assembly and thermal induction processing, it is characterised in that specific
Step is as follows：
（1）Plain paper is placed in concentration to soak 10 ~ 20min in 2 ~ 3g/L chitosan solutions first, deionization is used after taking-up
Water cleaning number 3 ~ 5 times, in 60 ~ 80 DEG C of dry 10 ~ 20min；
（2）Then will be through step（1）Paper after processing is placed in the nano-silica of hexadecyl trimethoxy silane graft modification
To change and 10 ~ 20min is soaked in titanium-ethanol solution, taking-up cleans number 3 ~ 5 times with deionized water, in 60 ~ 80 DEG C of dry 10 ~ 20min,
Wherein nano titanium oxide-ethanol solution concentration of hexadecyl trimethoxy silane graft modification is 2 ~ 4g/L；
（3）It is repeated in step（1）With（2）20 ~ 30 times, finally above-mentioned treated being placed under the conditions of 140 ~ 160 DEG C is handled
20 ~ 30min, obtain high intensity ultra-hydrophobic paper.
2. the preparation side of the high intensity ultra-hydrophobic paper according to claim 1 based on LBL self-assembly and thermal induction processing
Method, it is characterised in that：The step（1）In chitosan solution pH value be 5 ~ 5.7.
3. the preparation side of the high intensity ultra-hydrophobic paper according to claim 1 based on LBL self-assembly and thermal induction processing
Method, it is characterised in that：The step（2）The preparation side of the nano titanium oxide of middle hexadecyl trimethoxy silane graft modification
Method：According to volume ratio it is 95 first by absolute ethyl alcohol and deionized water：5 it is well mixed obtain organic solvent, then according to organic
Solvent is 100 with hexadecyl trimethoxy silane liquid-solid ratio：0.5 ~ 0.8mL/g adds hexadecyl trimethoxy silane,
30 ~ 40min is stirred under room temperature condition, is then according still further to hexadecyl trimethoxy silane and nano titanium oxide mass ratio
0.5~0.8：4 ~ 5 add nano titanium oxide, 60 ~ 120min of stirring reaction under the conditions of 60 ~ 70 DEG C, react after terminating, centrifugation,
The precipitation isolated is washed with absolute ethyl alcohol, and the nanometer two of hexadecyl trimethoxy silane graft modification is obtained after vacuum drying
Titanium oxide.
Priority Applications (1)
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| CN112774255A (en) * | 2019-11-08 | 2021-05-11 | 迈迪生物科技有限公司 | Super-hydrophobic oil-water separation membrane with self-cleaning characteristic and preparation and application thereof |
| CN113506508A (en) * | 2021-08-07 | 2021-10-15 | 河北师范大学 | Super-hydrophobic physical unclonable structural color anti-counterfeiting label and preparation method thereof |
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| CN109162149A (en) * | 2018-07-18 | 2019-01-08 | 六安市星星包装股份有限公司 | A kind of production method of the super-hydrophobic compound corrugated case based on nano-titanium dioxide |
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| CN112774255B (en) * | 2019-11-08 | 2022-10-11 | 迈迪生物科技有限公司 | Super-hydrophobic oil-water separation membrane with self-cleaning characteristic and preparation and application thereof |
| CN114232389A (en) * | 2021-05-17 | 2022-03-25 | 齐鲁工业大学 | Super-hydrophobic paper and preparation method thereof |
| CN113506508A (en) * | 2021-08-07 | 2021-10-15 | 河北师范大学 | Super-hydrophobic physical unclonable structural color anti-counterfeiting label and preparation method thereof |
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