CN109137476A - One kind being based on TiO2The preparation method of the bionic super-hydrophobic cotton fabric of nanotube - Google Patents

One kind being based on TiO2The preparation method of the bionic super-hydrophobic cotton fabric of nanotube Download PDF

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Publication number
CN109137476A
CN109137476A CN201811056837.2A CN201811056837A CN109137476A CN 109137476 A CN109137476 A CN 109137476A CN 201811056837 A CN201811056837 A CN 201811056837A CN 109137476 A CN109137476 A CN 109137476A
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tio
cotton fabric
nanotube
preparation
hydrophobic cotton
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CN201811056837.2A
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徐思峻
董莉
姚理荣
孙启龙
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Nantong University
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Nantong University
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00Treating 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
    • D06M11/32Treating 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
    • D06M11/36Treating 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
    • D06M11/46Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02Natural fibres, other than mineral fibres
    • D06M2101/04Vegetal fibres
    • D06M2101/06Vegetal fibres cellulosic
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10Repellency against liquids
    • D06M2200/12Hydrophobic properties
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/25Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06MTREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/35Abrasion, pilling or fibrillation resistance

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention proposes one kind to be based on TiO2The preparation method of the bionic super-hydrophobic cotton fabric of nanotube comprising the steps of: (1) take TiO2Nano particle is dissolved in NaOH solution, ultrasound, is protected from light after mechanical stirring for above-mentioned solution to be placed in hydrothermal reaction kettle and be reacted;It is later 1 with pickling to supernatant pH that reaction product, which is 7 with distilled water flushing to pH, then is neutral, dry, obtained TiO with distilled water flushing to pH2Nanotube is kept in dark place;(2) TiO is taken2Nanotube is added in the ethanol solution of silane, ultrasonic vibration;Distilled water is added, hydrophobization TiO can be obtained through hydrolysis2Nanotube finishing fluid;(3) cotton fabric is impregnated in hydrophobization TiO under room temperature2It is taken out in nanotube finishing fluid, after dipping and 60 DEG C dries, obtain super-hydrophobic cotton fabric.Cotton fabric prepared by the present invention has good ultra-hydrophobicity, ventilative, automatically cleaning, uvioresistant and wearability good, has extremely significant application prospect.

Description

One kind being based on TiO2The preparation method of the bionic super-hydrophobic cotton fabric of nanotube
Technical field
The present invention relates to functional fabric technical fields, and in particular to one kind is based on TiO2The bionic super-hydrophobic cotton of nanotube is knitted The preparation method of object.
Background technique
Super-hydrophobicity refers to that the contact angle of water droplet and the surface of solids is more than a kind of wetting of 150o and roll angle less than 10o Property.Typical Representative in nature has: lotus leaf, Rice Leaf etc..Super hydrophobic surface due to resist wet, it is anti-stick, automatically cleaning, The good characteristics such as anticorrosion, ice-covering-proof, antifouling and antibiosis, fluid drag-reduction have wide answer in fields such as weaving, aviation, buildings Use potentiality.In order to which in the micro-nano rough interfaces of textile fabric surface construction low-surface-energy, main method is by micro-nano at present Grain arranges to fiber surface the concaveconvex structure for forming similar lotus leaf " mastoid process ".And in fact, other than dot matrix concaveconvex structure, line The micro-nano array such as rice of property, the micro-nano coarse structure of sheet such as butterfly, network-like coarse structure such as nano fiber non-woven fabric, together Sample can be the super-drainage structure for realizing the excellent even unidirectional water guide function of ultra-hydrophobicity.However, textile fabric is mainly by having Machine fiber composition, to strong acid, highly basic poor resistance, soft fabric and surface are rough porous structure, to mechanical property and clothes Comfort requires height, can not utilize etching, the processing of the methods of plated film.Therefore, the nano superhydrophobic textile fabric of non-dairy lug structure It is free on always and studies except this visual field.
It is many about the related patents of superhydrophobic fabric at present, if Chinese invention patent is " a kind of super-hydrophobic antibiotic fabric In preparation method " (CN 108385375A), a kind of preparation method of super-hydrophobic antibiotic fabric is disclosed, this method is at room temperature Fabric is handled using the Tris buffer solution of dopamine, then fabric is impregnated in silver nitrate, ammonium citrate and boric acid Mixed solution in, obtain the fabric harsh surface that is constructed by nano silver after taking out drying;Again with floride-free water repellent to nano silver The fabric harsh surface of construction is post-processed, and fabric low-surface-energy is assigned;As Chinese invention patent is " a kind of graphene-based super thin In water fabric and preparation method thereof " (CN 107858825A), a kind of preparation method of graphene-based superhydrophobic fabric is disclosed, This method first carries out surface to graphene oxide with the silane coupling agent of the base containing S-H and is modified, and obtains the modification oxygen of surface base containing S-H Graphite alkene;Then, at room temperature, modified graphene oxide and end-vinyl dimethyl silicone polymer are dispersed in a solvent simultaneously Uniform stirring adds crosslinking agent and photoinitiator, continues stirring and forms uniform solution;Finally, using dip coating by fabric It is immersed in the mixed solution of preparation, by ultraviolet light after taking-up, makes to adhere on modified graphene oxide on the fabric S-H base and end-vinyl dimethyl silicone polymer on C=C double bond occur mercapto alkene reaction, be finally made graphene-based super thin Water fabric.But these methods for preparing superhydrophobic fabric have complex steps, the caducous problem of modified layer at present
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of based on TiO2The bionic super-hydrophobic cotton fabric of nanotube Preparation method, by with silane-modified TiO2Nano material, it is obtained to be based on TiO2The bionic super-hydrophobic cotton fabric of nanotube is not Only have many advantages, such as good ultra-hydrophobicity, also there is good ventilative, automatically cleaning, uvioresistant, and the company for passing through chemical bond Meet the TiO that can effectively promote silicon fluoride modification2Fastness between nanotube and cotton fabric improves wearability.
The present invention provides a kind of based on TiO2The preparation method of the bionic super-hydrophobic cotton fabric of nanotube includes following step It is rapid:
(1) TiO is taken2Nano particle is dissolved in NaOH solution, and ultrasound is at the first time, incites somebody to action after being protected from light the second time of mechanical stirring Above-mentioned solution, which is placed in hydrothermal reaction kettle, to react;Reaction product distilled water flushing is to pH for 7 later with pickling to supernatant PH is 1, then is neutral, dry, obtained TiO with distilled water flushing to pH2Nanotube is kept in dark place;
(2) TiO is taken2Nanotube is added in the ethanol solution of silane, the ultrasonic vibration third time;Distilled water, warp is added Hydrophobization TiO can be obtained in the 4th time of hydrolysis2Nanotube finishing fluid;
(3) cotton fabric is impregnated in hydrophobization TiO under room temperature2In nanotube finishing fluid, taken out simultaneously after impregnating for the 5th time 60 DEG C of drying, obtain super-hydrophobic cotton fabric.
As further improvement of the invention, silane includes perfluoro capryl triethoxysilane, and the ethyl alcohol of the silane is molten Liquid is volume between 2-10mL, and the mass concentration of the perfluoro capryl triethoxysilane is between 1%-5%.
As further improvement of the invention, the TiO2Nano particle and the mass ratio of the NaOH solution are 1:(80- 100), the TiO2The mass ratio of nanotube and the perfluoro capryl triethoxysilane is (3-6): 1, the distilled water and institute It states perfluoro capryl triethoxysilane (25-50): 1, the cotton fabric and hydrophobization TiO2The mass ratio of nanotube finishing fluid is 1:(35-45)。
As further improvement of the invention, the cotton fabric and hydrophobization TiO2The bath raio of nanotube finishing fluid is 1: (35-45), dip time 3-5h.
Improved as of the invention further, in step (1) in the hydrothermal reaction kettle 100-150 DEG C of reaction 24- 48h。
As further improvement of the invention, the ultrasonic power is 500-700W.
As further improvement of the invention, the speed of agitator is 300-500r/min.
As further improvement of the invention, the TiO2The quality of nano particle is between 0.6g~2g.
As further improvement of the invention, the volume of the NaOH solution is between 60mL~180mL, the NaOH The concentration of solution is between 8-12mol/L.
It is clear to upper layer using 0.1-0.5mol/L HCl pickling in the step (1) as further improvement of the invention Night pH is 1.
Improved as of the invention further, the first time between 0.5-1h, second time between 12-15h, The third time, the 4th time, the 5th time was between 3-5h between 1-3h between 1-2h.
The invention has the following beneficial effects: the method for the present invention simple process, prepared cotton fabric not only has well Ultra-hydrophobicity, also have many advantages, such as good ventilative, automatically cleaning, uvioresistant, and can effectively mention by the connection of chemical bond Rise the TiO of silicon fluoride modification2Fastness between nanotube and cotton fabric improves wearability, in various bedding, sanitary material The fields such as material, ornament materials have extremely significant application prospect.
Detailed description of the invention
Fig. 1 is the contact angle figure of dipping front and back cotton fabric.
Specific embodiment
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the invention is clearly and completely described, Obviously, the embodiment described is the embodiment of part of representative of the invention, rather than whole embodiments, this field are general Other all embodiments obtained belong to protection of the invention to logical technical staff without making creative work Range.
A kind of silane-modified TiO2The preparation method of nanotube super hydrophobic material comprising the steps of:
(1) (0.6-2) gTiO is taken2Nano particle is dissolved in the NaOH solution of (60-180) mL (8-12) mol/L, (500- Above-mentioned solution is placed in hydrothermal reaction kettle by 700W) ultrasound 0.5-1h after being protected from light mechanical stirring (300-500r/min) 12-15h, 100-150 DEG C of reaction 24-48h;Reaction product distilled water flushing uses (0.1-0.5) mol/LHCl pickling extremely after being 7 to pH Supernatant pH is 1, then is neutral, dry, obtained TiO with distilled water flushing to pH2Nanotube is kept in dark place;
(2) TiO is taken2It is molten between the ethyl alcohol of 1%-5% that nanotube is added to perfluoro capryl triethoxysilane mass concentration In liquid (2-10) mL, (500-700W) ultrasonic vibration 1-2h;Distilled water is added, hydrophobization can be obtained through hydrolysis 1-3h TiO2Nanotube finishing fluid;
(3) 1g cotton fabric is impregnated in (35-45) mL hydrophobization TiO under room temperature2In nanotube finishing fluid, impregnate (3-5h) It takes out afterwards and 60 DEG C dries, obtain super-hydrophobic cotton fabric.
Embodiment 1 is based on TiO2The preparation of the bionic super-hydrophobic cotton fabric of nanotube
(1) 0.6g TiO is taken2In nano particle and 60mL 12mol/LNaOH solution, 500W ultrasound 1h is protected from light machinery and stirs Above-mentioned solution is placed in hydrothermal reaction kettle after mixing (300r/min) 15h, hydro-thermal reaction is for 24 hours at 100 DEG C;Reaction product distillation It is after 7 with 0.5mol/LHCL pickling to supernatant pH is 1 that water, which is flushed to pH, then with distilled water flushing to pH is neutrality, TiO is made in 150 DEG C of dryings2Nanotube is kept in dark place;
(2) 0.3gTiO is taken2Nanotube is added to 10mL 10g/L perfluoro capryl triethoxysilane and is dissolved in 10mL ethyl alcohol In, 500W ultrasonic vibration 2h;5g distilled water is added, hydrophobization TiO can be obtained through hydrolysis 3h2Nanotube finishing fluid;
(3) 1g cotton fabric is impregnated in 35mL hydrophobization TiO under room temperature2In nanotube finishing fluid, taken out simultaneously after impregnating 3h 60 DEG C of drying, obtain super-hydrophobic cotton fabric.
Embodiment 2 is based on TiO2The preparation of the bionic super-hydrophobic cotton fabric of nanotube
(1) 1g TiO is weighed2Nano particle is dissolved in 80mL 8mol/L NaOH solution, and 700W ultrasound 30min is protected from light machine Above-mentioned solution is placed in hydrothermal reaction kettle after tool stirring (500r/min) 12h, hydro-thermal reaction 48h at 150 DEG C;Reaction product is used Distilled water flushing to pH be 7 after with 0.1mol/LHCL pickling to supernatant PH be 1, then with distilled water flushing to pH be it is neutral, TiO is made in the 150 DEG C of dryings of above-mentioned product2Nanotube is kept in dark place;
(2) 0.6gTiO is taken2Nanotube is added to 10mL 10g/L perfluoro capryl triethoxysilane and is dissolved in 2mL ethyl alcohol, 700W ultrasonic vibration 1h;2.5g distilled water is added, hydrophobization TiO can be obtained through hydrolysis 1h2Nanotube finishing fluid;
(3) 1g cotton fabric is impregnated in 45mL hydrophobization TiO under room temperature2In nanotube finishing fluid, 60 are taken out after impregnating 5h DEG C drying, obtain super-hydrophobic cotton fabric.
Embodiment 3 is based on TiO2The preparation of the bionic super-hydrophobic cotton fabric of nanotube
(1) 2g TiO is taken2In nano particle and 180mL 10mol/L NaOH solution, 600W ultrasound 45min is protected from light machinery Above-mentioned solution is placed in hydrothermal reaction kettle after stirring (400r/min) 13h, 120 DEG C of reaction 36h;Reaction product is rushed with distilled water It with 0.3mol/LHCL pickling to supernatant pH is 1 that wash pH, which be after 7, then with distilled water flushing to pH is neutrality, 150 DEG C It is dry, TiO is made2Nanotube is kept in dark place;
(2) 0.45g TiO is taken2Nanotube is added to 10mL 10g/L perfluoro capryl triethoxysilane and is dissolved in 4mL ethyl alcohol In, 600W ultrasonic vibration 1.5h;4g distilled water is added, hydrophobization TiO can be obtained through hydrolysis 2h2Nanotube finishing fluid;
(3) 1g cotton fabric is impregnated in 40mL hydrophobization TiO under room temperature2In nanotube finishing fluid, taken out simultaneously after impregnating 4h 60 DEG C of drying, obtain super-hydrophobic cotton fabric.
Embodiment 4 is based on TiO2The preparation of the bionic super-hydrophobic cotton fabric of nanotube
(1) 1.5g TiO is taken2In nano particle and 150mL 10mol/L NaOH solution, 600W ultrasound 50min is protected from light machine Above-mentioned solution is placed in hydrothermal reaction kettle after tool stirring (400r/min) 14h, 130 DEG C of reaction 40h;Reaction product distilled water It with 0.4mol/LHCL pickling to supernatant pH is 1 that be flushed to pH, which be after 7, then with distilled water flushing to pH is neutrality, 150 TiO is made in DEG C drying2Nanotube is kept in dark place;
(2) 0.45g TiO is taken2Nanotube is added to 10mL 10g/L perfluoro capryl triethoxysilane and is dissolved in 6mL ethyl alcohol In, 600W ultrasonic vibration 2h;4g distilled water is added, hydrophobization TiO can be obtained through hydrolysis 3h2Nanotube finishing fluid;
(3) 1g cotton fabric is impregnated in 40mL hydrophobization TiO under room temperature2In nanotube finishing fluid, taken out simultaneously after impregnating 4h 60 DEG C of drying, obtain super-hydrophobic cotton fabric.
Those skilled in the art is not under conditions of departing from the spirit and scope of the present invention that claims determine, also Various modifications can be carried out to the above content.Therefore the scope of the present invention is not limited in above explanation, but by The range of claims determines.

Claims (10)

1. a kind of preparation method of the bionic super-hydrophobic cotton fabric based on TiO2 nanotube, which is characterized in that comprise the steps of:
(1) TiO is taken2Nano particle is dissolved in NaOH solution, and ultrasound is at the first time, and being protected from light after the second time of mechanical stirring will be above-mentioned Solution, which is placed in hydrothermal reaction kettle, to react;Reaction product is after 7 with distilled water flushing to pH 1, then be neutral, dry, obtained TiO with distilled water flushing to pH2Nanotube is kept in dark place;
(2) TiO is taken2Nanotube is added in the ethanol solution of silane, the ultrasonic vibration third time;Distilled water is added, it is anti-through hydrolyzing Answered for the 4th time hydrophobization TiO can be obtained2Nanotube finishing fluid;
(3) cotton fabric is impregnated in hydrophobization TiO under room temperature2In nanotube finishing fluid, is taken out after impregnating for the 5th time and 60 DEG C are dried It is dry, obtain super-hydrophobic cotton fabric.
2. a kind of preparation method of bionic super-hydrophobic cotton fabric based on TiO2 nanotube according to claim 1, special Sign is: the silane includes perfluoro capryl triethoxysilane, and the ethanol solution of the silane is volume between 2-10mL, institute The mass concentration of perfluoro capryl triethoxysilane is stated between 1%-5%.
3. a kind of preparation method of bionic super-hydrophobic cotton fabric based on TiO2 nanotube according to claim 2, special Sign is: the TiO2Nano particle and the mass ratio of the NaOH solution are 1:(80-100), the TiO2Nanotube with it is described The mass ratio of perfluoro capryl triethoxysilane is (3-6): 1, the distilled water and the perfluoro capryl triethoxysilane (25-50): 1, the cotton fabric and hydrophobization TiO2The mass ratio of nanotube finishing fluid is 1:(35-45).
4. a kind of preparation method of bionic super-hydrophobic cotton fabric based on TiO2 nanotube according to claim 1, special Sign is: in step (1) in the hydrothermal reaction kettle 100-150 DEG C of reaction 24-48h.
5. a kind of preparation method of bionic super-hydrophobic cotton fabric based on TiO2 nanotube according to claim 1, special Sign is: the ultrasonic power is 500-700W.
6. a kind of preparation method of bionic super-hydrophobic cotton fabric based on TiO2 nanotube according to claim 1, special Sign is: the speed of agitator is 300-500r/min.
7. a kind of preparation method of bionic super-hydrophobic cotton fabric based on TiO2 nanotube according to claim 1, special Sign is: the TiO2The quality of nano particle is between 0.6g~2g.
8. a kind of preparation method of bionic super-hydrophobic cotton fabric based on TiO2 nanotube according to claim 1, special Sign is: the volume of the NaOH solution is between 60mL~180mL, and the concentration of the NaOH solution is between 8-12mol/L.
9. a kind of preparation method of bionic super-hydrophobic cotton fabric based on TiO2 nanotube according to claim 1, special Sign is: using in the step (1) 0.1-0.5mol/LHCl pickling to supernatant pH for 1.
10. a kind of preparation method of bionic super-hydrophobic cotton fabric based on TiO2 nanotube according to claim 1, special Sign is: the first time, second time, the third time was between 1-2h, institute between 12-15h between 0.5-1h Stated for the 4th time between 1-3h, the 5th time is between 3-5h.
CN201811056837.2A 2018-09-11 2018-09-11 One kind being based on TiO2The preparation method of the bionic super-hydrophobic cotton fabric of nanotube Pending CN109137476A (en)

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