CN108505321A - A kind of method that sol-gel method prepares floride-free super-hydrophobic cotton fabric - Google Patents
A kind of method that sol-gel method prepares floride-free super-hydrophobic cotton fabric Download PDFInfo
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- CN108505321A CN108505321A CN201810255928.2A CN201810255928A CN108505321A CN 108505321 A CN108505321 A CN 108505321A CN 201810255928 A CN201810255928 A CN 201810255928A CN 108505321 A CN108505321 A CN 108505321A
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- Prior art keywords
- cotton fabric
- preparation
- zirconium chloride
- basic zirconium
- ethanol solution
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- 229920000742 Cotton Polymers 0.000 title claims abstract description 91
- 239000004744 fabric Substances 0.000 title claims abstract description 90
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000003980 solgel method Methods 0.000 title claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 192
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 54
- 235000019441 ethanol Nutrition 0.000 claims abstract description 53
- 238000002360 preparation method Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001868 water Inorganic materials 0.000 claims abstract description 23
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 18
- SCPWMSBAGXEGPW-UHFFFAOYSA-N dodecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCC[Si](OC)(OC)OC SCPWMSBAGXEGPW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- HXCHRJMJMALFHP-UHFFFAOYSA-N azanium;ethanol;hydroxide Chemical compound N.O.CCO HXCHRJMJMALFHP-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- 239000002245 particle Substances 0.000 abstract description 12
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 abstract description 9
- 239000004753 textile Substances 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000000835 fiber Substances 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract description 3
- 238000004140 cleaning Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 52
- 230000003068 static effect Effects 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000003760 magnetic stirring Methods 0.000 description 10
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 125000003438 dodecyl group Chemical group [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])* 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229940094933 n-dodecane Drugs 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- -1 alkane siloxanes Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 244000020998 Acacia farnesiana Species 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000016795 Cola Nutrition 0.000 description 1
- 235000011824 Cola pachycarpa Nutrition 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 1
- 229910007746 Zr—O Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 235000016213 coffee Nutrition 0.000 description 1
- 235000013353 coffee beverage Nutrition 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000015205 orange juice Nutrition 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
- D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
- D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
- D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/10—Repellency against liquids
- D06M2200/12—Hydrophobic properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2400/00—Specific information on the treatment or the process itself not provided in D06M23/00-D06M23/18
- D06M2400/02—Treating compositions in the form of solgel or aerogel
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
The invention discloses a kind of methods that sol-gal process prepares floride-free super-hydrophobic cotton fabric.The preparation method selects basic zirconium chloride and ammonium hydroxide as reactive material, absolute ethyl alcohol is as solvent, dodecyltrimethoxysilane is as dressing agent, by infiltrating cotton fabric in the ethanol solution of basic zirconium chloride, then with ammonium hydroxide solgel reaction occurs for the basic zirconium chloride in the ethanol solution of basic zirconium chloride, zirconium hydroxide particle is generated on cotton-textile fibres, and micro-/ nano binary coarse structure is collectively formed with the fiber of cotton fabric；Finally the zirconium hydroxide on cotton-textile fibres is modified using dodecyltrimethoxysilane, floride-free super-hydrophobic cotton fabric is prepared.Preparation method mild condition of the present invention, simple for process, manufacturing cost is cheap, convenient and practical, the water contact angle of the floride-free super-hydrophobic cotton fabric of preparation is 152 ° ~ 156 °, has wide application prospect in fields such as material surface automatically cleaning, water-oil separating and function textiles.
Description
Technical field
The present invention relates to the preparing technical fields of floride-free super-hydrophobic material, and in particular to sol-gel method prepares floride-free super
The method of hydrophobic cotton fabric.
Background technology
Super hydrophobic material refers to that the static contact angle of water droplet and material surface is more than 150 °, while dynamic contact angle is less than
10°.Super hydrophobic material causes the extensive interest of people because of the special wetability in its surface.This special wetability is not only given
The excellent water repellent characteristic of the surface of solids has been given, and has been subtracted in automatically cleaning, anti-corrosion of metal, ice-covering-proof, water-oil separating and pipeline transportation
The fields such as resistance have huge application value.With the experience accumulation of research and practical application to super hydrophobic material, Cassie
With the foundation of Wenzel models, people is allowed to have clear understanding to the condition for preparing super hydrophobic material：Build one it is super-hydrophobic
Surface, it is necessary to have micro-/to receive roughness and low-surface-energy.
Currently, sol-gel method prepare super-hydrophobic cotton fabric generally by surface of cotton fabric carry out solgel reaction,
Then cotton fabric is dried, reuses long chain alkane siloxanes or fluorine-containing alkane siloxanes is modified.Bae GY etc. are with just
Silester is presoma, is reacted with ammonium hydroxide under alkaline environment, and dehydrating condensation is carried out, and generates particle；Particle is collected, grain is made
Cotton fabric, is then immersed in particle dispersion by sub- dispersion liquid, stirring a period of time, then dries；Finally, it is put by perfluor alkane
In solution made of base acrylate solid, carry out silicic acid anhydride, obtain super-hydrophobic cotton fabric (Bae GY, Jeong YG,
Min BG. Superhydrophobic PET Fabrics Achieved by Silica Nanoparticles and
Water-repellent Agent.FIBERS&POLYMERS.2010,11,976-981.).This method prepares super-hydrophobic cotton and knits
The process of object is more complex, it is necessary first to nano-particle be made, then cotton fabric impregnates in particle dispersion, at last hydrophobization
Three steps are managed, preparation process is cumbersome, and the sample used is expensive, is unfavorable for the industrialized production of the super-hydrophobic cotton fabric prepared；
Meanwhile fluorine-containing material has been used in the super-hydrophobic cotton fabric of preparation, environment can be damaged.
In the prior art, the method for preparing super-hydrophobic coat mainly has phase separation method, sol-gal process, template, electrification
Learn sedimentation, self-assembly method and vapour deposition process etc..Although the preparation method of many super-hydrophobic coats has tended to be ripe, big portion
Divide the low-surface energy substance that the product preparation process of superhydrophobic characteristic is relatively complicated, process conditions are harsh, some needs are expensive, or
It is to have the chemical substance of pollution to environment containing fluorine etc., while it is prepared super hydrophobic surface durability, chemical-resistant stability, resistance to
Mill property, heat-resisting quantity are insufficient, limit its extensive use in real life production.The widespread demand of super-hydrophobic cotton fabric,
It determines and needs to simplify preparation flow.It studies and is directly manufactured particle and cotton fabric silicic acid anhydride by sol-gel method as a result,
Step is combined into one, and simplifies preparation flow, and use not fluorine-containing low-surface energy substance, economic and environment-friendly, is of great significance.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to which it is floride-free super thin to provide a kind of sol-gel method preparation
The method of water cotton fabric.The preparation method selects basic zirconium chloride (ZrOCl2·8H2) and ammonium hydroxide (NH O3·H2O) it is used as reactant
Matter, absolute ethyl alcohol are used as dressing agent as solvent, dodecyltrimethoxysilane (DTMS), by infiltrating cotton fabric in chlorine
In the ethanol solution of zirconium oxide, then with ammonium hydroxide solgel reaction occurs for the basic zirconium chloride in the ethanol solution of basic zirconium chloride,
Zirconium hydroxide particle is generated on cotton-textile fibres, and micro-/ nano binary coarse structure is collectively formed with the fiber of cotton fabric；Most
The zirconium hydroxide on cotton-textile fibres is modified using dodecyltrimethoxysilane afterwards, the super thin of free-floride is prepared
Water cotton fabric.
The purpose of the present invention is achieved through the following technical solutions.
A kind of method that sol-gel method prepares floride-free super-hydrophobic cotton fabric, includes the following steps：
(1) basic zirconium chloride is added in absolute ethyl alcohol, stirs to being completely dissolved, obtains the ethanol solution of basic zirconium chloride；
(2) cotton fabric is placed in the ethanol solution for the basic zirconium chloride that step (1) obtains, stirring to cotton fabric is moistened completely
It is wet；Ammonium hydroxide is added dropwise, continues stirring 20~40 minutes；Dodecyltrimethoxysilane solution is added dropwise again, it is small to continue stirring 4~6
When；
(3) cotton fabric is taken out, is washed with absolute ethyl alcohol, dries, obtains floride-free super-hydrophobic cotton fabric.
Preferably, in step (1), the mol/ of a concentration of 0.007mol/L~0.035 of the ethanol solution of the basic zirconium chloride
L。
Preferably, in step (2), the solid-liquid ratio of the ethanol solution of the cotton fabric and basic zirconium chloride is 0.005~
0.0125：1g/mL.
Preferably, in step (2), the mass concentration of the ammonium hydroxide is 25wt%~28wt%.
Preferably, in step (2), the volume ratio of absolute ethyl alcohol is in the dripping quantity of ammonium hydroxide and the ethanol solution of basic zirconium chloride
0.15:1~0.3:1.
After ammonium hydroxide is added dropwise, the basic zirconium chloride in the ethanol solution of ammonium hydroxide and basic zirconium chloride occurs sol gel reaction and generates
Zirconium hydroxide particle insoluble in ethyl alcohol forms micro-/ nano binary coarse structure on surface of cotton fabric；By adjust ammonium hydroxide with
The relative usage of the ethanol solution of basic zirconium chloride generates the zirconium hydroxide of different content, adjusts the micro- of the fiber surface of cotton fabric
Structure is seen, to which the floride-free super-hydrophobic cotton fabric of different water contact angles be prepared.
Preferably, in step (2), the solvent of the dodecyltrimethoxysilane solution is absolute ethyl alcohol, solution
A concentration of 0.015mol/L~0.03mol/L.
Preferably, in step (2), the dripping quantity of dodecyltrimethoxysilane solution and the ethanol solution of basic zirconium chloride
The volume ratio of middle absolute ethyl alcohol is 0.05:1~0.1:1.
Preferably, step (1)~(2) process carries out under the conditions of 25~30 DEG C.
Preferably, in step (3), the number of the absolute ethyl alcohol washing is 3~6 times.
Preferably, in step (3), the temperature of the drying is 60~100 DEG C.
Preferably, the water contact angle for the floride-free super-hydrophobic cotton fabric being prepared is 152 °~156 °.
Compared with prior art, the invention has the advantages that and advantageous effect：
(1) present invention prepares floride-free super-hydrophobic cotton fabric using sol-gel method, and, operation simple with preparation process is easily
The good feature of control, stability, and without using fluorine material, compared with current most of super-hydrophobic fluorine materials used, tool
There is environment-friendly advantage；
(2) water contact angle of floride-free super-hydrophobic cotton fabric prepared by the method for the present invention is 152 °~156 °, in material surface
The fields such as automatically cleaning, water-oil separating and function textile have wide application prospect；
(3) preparation method of the present invention need not carry out any pretreatment to cotton fabric, under the conditions of room temperature (25~30 DEG C)
It carries out, mild condition is simple for process, and manufacturing cost is cheap, convenient and practical, is conducive to the industrialized production of super-hydrophobic cotton fabric.
Description of the drawings
Fig. 1 is that floride-free super-hydrophobic cotton prepared by the ethanol solution in embodiment 1 using different molar concentration basic zirconium chlorides is knitted
The Static water contact angles schematic diagram of object；
Fig. 2 is that the floride-free super-hydrophobic cotton fabric prepared in embodiment 2 carries out the separative efficiency figure of water-oil separating experiment；
Fig. 3 is that the Static water contact angles after the floride-free super-hydrophobic cotton fabric progress solvent resistance test prepared in embodiment 3 show
It is intended to；
Fig. 4 is that the liquid static contact angle that the floride-free super-hydrophobic cotton fabric prepared in embodiment 4 carries out in anti-pollution experiment shows
It is intended to；
Fig. 5 is the FT-IR test results of the zirconium hydroxide particle in the floride-free super-hydrophobic cotton fabric prepared in embodiment 5
Figure.
Specific implementation mode
Technical scheme of the present invention is described in further detail below in conjunction with specific embodiment and attached drawing, but the present invention
Protection domain and embodiment it is without being limited thereto.
Embodiment 1
Floride-free super-hydrophobic cotton fabric is prepared using sol-gel method, is as follows：
(1) under room temperature, basic zirconium chloride (ZrOCl is weighed respectively2·8H2O it) is added in absolute ethyl alcohol, is placed in magnetic stirring apparatus
Upper stirring 30 minutes, until be completely dissolved, obtain concentration be respectively 0.007mol/L, 0.014mol/L, 0.021mol/L,
The ethanol solution of the basic zirconium chloride of 0.028mol/L and 0.035mol/L；
(2) under room temperature, 0.2g cotton fabrics are placed in the ethanol solution for the basic zirconium chloride that step (1) obtains to (solid-liquid ratio is equal
It is 0.005：1g/mL), it is subsequently placed on magnetic stirring apparatus and stirs 30 minutes, cotton fabric is made to be no longer entirely wetted；Mass concentration is added dropwise
For the ammonia spirit of 25wt%, the volume ratio of the absolute ethyl alcohol in the ethanol solution of ammonium hydroxide and basic zirconium chloride is 0.2:1, continue to stir
It mixes 20 minutes；The ethanol solution (a concentration of 0.015mol/L) of dodecyltrimethoxysilane, dodecyl front three are added dropwise again
The volume ratio of absolute ethyl alcohol is 0.05 in the dripping quantity of the ethanol solution of oxysilane and the ethanol solution of basic zirconium chloride:1, continue
Stirring 4 hours；
(3) cotton fabric is taken out, is washed 3 times with absolute ethyl alcohol, is subsequently placed in 80 DEG C of baking ovens and dries, obtain floride-free super-hydrophobic
Cotton fabric.
Using the Static water contact of floride-free super-hydrophobic cotton fabric prepared by the ethanol solution of different molar concentration basic zirconium chlorides
Angle schematic diagram is as shown in Figure 1, as shown in Figure 1, in a concentration of 0.007 mol/L of the ethanol solution of basic zirconium chloride, Static Water
Contact angle has reached 152.5 °, has super-hydrophobic effect；It is quiet in a concentration of 0.028mol/L of the ethanol solution of basic zirconium chloride
State water contact angle has reached 156 °, while roll angle only has 10 °, has excellent ultra-hydrophobicity；Meanwhile as shown in Figure 1, when
When the ethanol solution concentration of basic zirconium chloride increases, there is small size decline in the static contact angle of cotton fabric, this is because by molten
The zirconium hydroxide particle that glue-gel reaction generates is excessive, causes the degree of roughness of surface of cotton fabric to decline, under Static water contact angles
Drop, but it is both greater than 150 ° always, and there is ultra-hydrophobicity.
Embodiment 2
Floride-free super-hydrophobic cotton fabric is prepared using sol-gel method, is as follows：
(1) under room temperature, basic zirconium chloride (ZrOCl is weighed respectively2·8H2O it) is added in absolute ethyl alcohol, is placed in magnetic stirring apparatus
Upper stirring 30 minutes, until being completely dissolved, obtains the ethanol solution of the basic zirconium chloride of a concentration of 0.007mol/L；
(2) under room temperature, 0.2g cotton fabrics are placed in the ethanol solution for the basic zirconium chloride that step (1) obtains to (solid-liquid ratio is equal
It is 0.005：1g/mL), it is subsequently placed on magnetic stirring apparatus and stirs 30 minutes, cotton fabric is made to be no longer entirely wetted；Mass concentration is added dropwise
For the ammonia spirit of 26wt%, the volume ratio of the absolute ethyl alcohol in the ethanol solution of ammonium hydroxide and basic zirconium chloride is 0.15:1, continue
Stirring 20 minutes；The ethanol solution (a concentration of 0.02mol/L) of dodecyltrimethoxysilane, dodecyl front three are added dropwise again
The volume ratio of absolute ethyl alcohol is 0.08 in the dripping quantity of the ethanol solution of oxysilane and the ethanol solution of basic zirconium chloride:1, continue
Stirring 4 hours；
(3) cotton fabric is taken out, is washed 4 times with absolute ethyl alcohol, is subsequently placed in 60 DEG C of baking ovens and dries, obtain floride-free super-hydrophobic
Cotton fabric.
Water-oil separating experiment is carried out with the super-hydrophobic cotton fabric of preparation, selects n-dodecane and normal heptane as water-oil separating
The oily substance of experiment, mixes with deionized water respectively, carries out water-oil separating experiment.
Separative efficiency such as Fig. 2 institute of the floride-free super-hydrophobic cotton fabric of preparation to two kinds of oily substances of n-dodecane and normal heptane
Show, as shown in Figure 2, for n-dodecane/aqueous mixtures after 5 separation, water-oil separating efficiency is higher than 96%；Normal heptane/water is mixed
Object is closed after 5 separation, water-oil separating efficiency is higher than 95%.
The above water-oil separating experiment shows that the super-hydrophobic cotton fabric prepared has good water-oil separating and reusability
Energy.
Embodiment 3
Floride-free super-hydrophobic cotton fabric is prepared using sol-gel method, is as follows：
(1) under room temperature, basic zirconium chloride (ZrOCl is weighed respectively2·8H2O it) is added in absolute ethyl alcohol, is placed in magnetic stirring apparatus
Upper stirring 30 minutes, until being completely dissolved, obtains the ethanol solution of the basic zirconium chloride of concentration 0.028mol/L；
(2) under room temperature, 0.4g cotton fabrics are placed in the ethanol solution for the basic zirconium chloride that step (1) obtains to (solid-liquid ratio is equal
It is 0.01：1g/mL), it is subsequently placed on magnetic stirring apparatus and stirs 30 minutes, cotton fabric is made to be no longer entirely wetted；Mass concentration is added dropwise
For the ammonia spirit of 25wt%, the volume ratio of the absolute ethyl alcohol in the ethanol solution of ammonium hydroxide and basic zirconium chloride is 0.2:1, continue to stir
It mixes 30 minutes；The ethanol solution (a concentration of 0.015mol/L) of dodecyltrimethoxysilane, dodecyl front three are added dropwise again
The volume ratio of absolute ethyl alcohol is 0.05 in the dripping quantity of the ethanol solution of oxysilane and the ethanol solution of basic zirconium chloride:1, continue
Stirring 5 hours；
(3) cotton fabric is taken out, is washed 5 times with absolute ethyl alcohol, is subsequently placed in 80 DEG C of baking ovens and dries, obtain floride-free super-hydrophobic
Cotton fabric.
The super-hydrophobic cotton fabric prepared is impregnated with the liquid of different solubilities 72 hours, then take out drying, measure static
Water contact angle evaluates the chemical stability of the super-hydrophobic cotton fabric of preparation.
The results are shown in Figure 3 for the static water contact angular measurement of the super-hydrophobic cotton fabric of preparation, from the figure 3, it may be seen that is prepared is super
Hydrophobic cotton fabric impregnates 72 in deionized water, boiling water, saturated nacl aqueous solution, ethyl alcohol, toluene, acetone and tetrahydrofuran respectively
After hour and drying, still it is more than 150 ° with the static contact angle of water, there is super-hydrophobic effect, it was demonstrated that the super-hydrophobic cotton of preparation
Fabric has good chemical resistance.
Embodiment 4
Floride-free super-hydrophobic cotton fabric is prepared using sol-gel method, is as follows：
(1) under room temperature, basic zirconium chloride (ZrOCl is weighed respectively2·8H2O it) is added in absolute ethyl alcohol, is placed in magnetic stirring apparatus
Upper stirring 30 minutes, until being completely dissolved, obtains the ethanol solution of the basic zirconium chloride of concentration 0.028mol/L；
(2) under room temperature, 0.4g cotton fabrics are placed in the ethanol solution for the basic zirconium chloride that step (1) obtains to (solid-liquid ratio is equal
It is 0.01：1g/mL), it is subsequently placed on magnetic stirring apparatus and stirs 30 minutes, cotton fabric is made to be no longer entirely wetted；Mass concentration is added dropwise
For the ammonia spirit of 25wt%, the volume ratio of the absolute ethyl alcohol in the ethanol solution of ammonium hydroxide and basic zirconium chloride is 0.2:1, continue to stir
It mixes 30 minutes；The ethanol solution (a concentration of 0.015mol/L) of dodecyltrimethoxysilane, dodecyl front three are added dropwise again
The volume ratio of absolute ethyl alcohol is 0.05 in the dripping quantity of the ethanol solution of oxysilane and the ethanol solution of basic zirconium chloride:1, continue
Stirring 4 hours；
(3) cotton fabric is taken out, is washed 5 times with absolute ethyl alcohol, is subsequently placed in 80 DEG C of baking ovens and dries, obtain floride-free super-hydrophobic
Cotton fabric.
Static contact angle of the different liquids on the super-hydrophobic cotton fabric of preparation is measured, the stain resistance of cotton fabric is evaluated.
The results are shown in Figure 4 for the liquid static contact angle determination of the super-hydrophobic cotton fabric of preparation, as shown in Figure 4, deionization
The static contact angle of water, ink, cola, milk, orange juice and coffee on the super-hydrophobic cotton fabric surface of preparation is all higher than 150 °, tool
There is super-hydrophobic effect, it was demonstrated that the super-hydrophobic cotton fabric of preparation has good stain resistance.
Embodiment 5
Floride-free super-hydrophobic cotton fabric is prepared using sol-gel method, is as follows：
(1) under room temperature, basic zirconium chloride (ZrOCl is weighed respectively2·8H2O it) is added in absolute ethyl alcohol, is placed in magnetic stirring apparatus
Upper stirring 30 minutes, until being completely dissolved, obtains the ethanol solution of the basic zirconium chloride of concentration 0.035mol/L；
(2) under room temperature, 0.5g cotton fabrics are placed in the ethanol solution for the basic zirconium chloride that step (1) obtains to (solid-liquid ratio is equal
It is 0.0125：1g/mL), it is subsequently placed on magnetic stirring apparatus and stirs 30 minutes, cotton fabric is made to be no longer entirely wetted；It is dense that quality is added dropwise
Degree is the ammonia spirit of 28wt%, and the volume ratio of the absolute ethyl alcohol in the ethanol solution of ammonium hydroxide and basic zirconium chloride is 0.3:1, continue
Stirring 40 minutes；The ethanol solution (a concentration of 0.03mol/L) of dodecyltrimethoxysilane, dodecyl front three are added dropwise again
The volume ratio of absolute ethyl alcohol is 0.1 in the dripping quantity of the ethanol solution of oxysilane and the ethanol solution of basic zirconium chloride:1, continue
Stirring 6 hours；
(3) cotton fabric is taken out, is washed 6 times with absolute ethyl alcohol, is subsequently placed in 100 DEG C of baking ovens and dries, is obtained floride-free super thin
Water cotton fabric.
After in step (2), will infiltrate cotton fabric solution centrifugation, dried to obtaining precipitation particles, then into
Row FT-IR tests, the results are shown in Figure 5.As seen from Figure 5, in 1118cm-1And 1045cm-1Place's Si-O-Si keys are formed,
472cm-1And 527cm-1Place's Zr-O keys are formed, and show to generate Zr (OH)4；In 1459cm-1Place-(CH2) n and 1395cm-1Place-
CH3Key is formed, then shows dodecyltrimethoxysilane modification on zirconium hydroxide particle.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by the embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. a kind of method that sol-gel method prepares floride-free super-hydrophobic cotton fabric, which is characterized in that include the following steps：
(1) basic zirconium chloride is added in absolute ethyl alcohol, stirs to being completely dissolved, obtains the ethanol solution of basic zirconium chloride；
(2) cotton fabric is placed in the ethanol solution for the basic zirconium chloride that step (1) obtains, stirring to cotton fabric is no longer entirely wetted；
Ammonium hydroxide is added dropwise, continues stirring 20~40 minutes；Dodecyltrimethoxysilane solution is added dropwise again, continues stirring 4~6 hours；
(3) cotton fabric is taken out, is washed with absolute ethyl alcohol, dries, obtains floride-free super-hydrophobic cotton fabric.
2. preparation method according to claim 1, which is characterized in that in step (1), the ethanol solution of the basic zirconium chloride
A concentration of 0.007mol/L~0.035mol/L.
3. preparation method according to claim 1, which is characterized in that in step (2), the cotton fabric and basic zirconium chloride
The solid-liquid ratio of ethanol solution is 0.005~0.0125：1g/mL.
4. preparation method according to claim 1, which is characterized in that in step (2), the mass concentration of the ammonium hydroxide is
25wt%~28wt%.
5. preparation method according to claim 1, which is characterized in that in step (2), the dripping quantity and basic zirconium chloride of ammonium hydroxide
Ethanol solution in absolute ethyl alcohol volume ratio be 0.15:1~0.3:1.
6. preparation method according to claim 1, which is characterized in that in step (2), the dodecyl trimethoxy silicon
The solvent of alkane solution is absolute ethyl alcohol, a concentration of 0.015mol/L~0.03mol/L of solution.
7. preparation method according to claim 1, which is characterized in that in step (2), the dodecyl trimethoxy silicon
The volume ratio of absolute ethyl alcohol is 0.05 in the dripping quantity of alkane solution and the ethanol solution of basic zirconium chloride:1~0.1:1.
8. preparation method according to claim 1, which is characterized in that step (1)~(2) process is in 25~30 DEG C of conditions
Lower progress.
9. preparation method according to claim 1, which is characterized in that in step (3), the number of the absolute ethyl alcohol washing
It is 3~6 times；The temperature of the drying is 60~100 DEG C.
10. preparation method according to claim 1, which is characterized in that the water for the floride-free super-hydrophobic cotton fabric being prepared
Contact angle is 152 °~156 °.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109763316A (en) * | 2019-01-11 | 2019-05-17 | 中北大学 | A kind of preparation method of durable efficiently quick super-hydrophobic water-oil separating cotton fabric |
| CN111035838A (en) * | 2019-12-10 | 2020-04-21 | 昆明医科大学第二附属医院 | Trachea fixing band for patient in burn department |
| CN112921643A (en) * | 2021-01-26 | 2021-06-08 | 西安理工大学 | ZrO (ZrO)2Preparation method of @ PET fiber oil-water separation material |
| CN113913996A (en) * | 2021-11-09 | 2022-01-11 | 罗莱生活科技股份有限公司 | Modal/cotton/viscose blended fabric and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1178778A (en) * | 1967-03-02 | 1970-01-21 | Basf Ag | Finishing Cellulosic Fibrous Material |
| CN1559915A (en) * | 2004-02-16 | 2005-01-05 | 华南理工大学 | Process of preparing zirconium oxide nano powder by supersonic sol-gel process |
| CN101397754A (en) * | 2008-11-03 | 2009-04-01 | 东华大学 | Method for preparing floride-free super-hydrophobic cotton fabric |
| CN101786900A (en) * | 2010-02-05 | 2010-07-28 | 河北理工大学 | Preparation method of quaternary xerogel |
| CN103290674A (en) * | 2012-02-28 | 2013-09-11 | 明仁精细化工（嘉兴）有限公司 | Treatment method and treatment liquid for preparing fluoride-free super-hydrophobic cotton fabric |
-
2018
- 2018-03-27 CN CN201810255928.2A patent/CN108505321B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1178778A (en) * | 1967-03-02 | 1970-01-21 | Basf Ag | Finishing Cellulosic Fibrous Material |
| CN1559915A (en) * | 2004-02-16 | 2005-01-05 | 华南理工大学 | Process of preparing zirconium oxide nano powder by supersonic sol-gel process |
| CN101397754A (en) * | 2008-11-03 | 2009-04-01 | 东华大学 | Method for preparing floride-free super-hydrophobic cotton fabric |
| CN101786900A (en) * | 2010-02-05 | 2010-07-28 | 河北理工大学 | Preparation method of quaternary xerogel |
| CN103290674A (en) * | 2012-02-28 | 2013-09-11 | 明仁精细化工（嘉兴）有限公司 | Treatment method and treatment liquid for preparing fluoride-free super-hydrophobic cotton fabric |
Non-Patent Citations (4)
| Title |
|---|
| A.SENGUPTA ET AL.: "Developing superhydrophobic and oleophobic nanostructure by a facile chemical transformation of zirconium hydroxide surface", 《APPLIED SURFACE SCIENCE》 * |
| 汪多仁: "《绿色纳米化学品》", 31 July 2007, 科学技术文献出版社 * |
| 马世昌，等: "《化学物质辞典》", 30 April 1999, 陕西科学技术出版社 * |
| 黄琪等: "纳米氧化锆的制备工艺研究", 《浙江树人大学学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109763316A (en) * | 2019-01-11 | 2019-05-17 | 中北大学 | A kind of preparation method of durable efficiently quick super-hydrophobic water-oil separating cotton fabric |
| CN111035838A (en) * | 2019-12-10 | 2020-04-21 | 昆明医科大学第二附属医院 | Trachea fixing band for patient in burn department |
| CN112921643A (en) * | 2021-01-26 | 2021-06-08 | 西安理工大学 | ZrO (ZrO)2Preparation method of @ PET fiber oil-water separation material |
| CN113913996A (en) * | 2021-11-09 | 2022-01-11 | 罗莱生活科技股份有限公司 | Modal/cotton/viscose blended fabric and preparation method thereof |
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