CN104294594A - Preparation method for water-repellent oil-repellent superhydrophobic fabric surface - Google Patents
Preparation method for water-repellent oil-repellent superhydrophobic fabric surface Download PDFInfo
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- CN104294594A CN104294594A CN201410482285.7A CN201410482285A CN104294594A CN 104294594 A CN104294594 A CN 104294594A CN 201410482285 A CN201410482285 A CN 201410482285A CN 104294594 A CN104294594 A CN 104294594A
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- repellent
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- 239000005871 repellent Substances 0.000 title claims abstract description 153
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- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920000742 Cotton Polymers 0.000 claims abstract description 126
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 25
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 24
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- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 8
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- 238000000034 method Methods 0.000 claims description 35
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- 239000002904 solvent Substances 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 19
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 19
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 18
- SGNZYJXNUURYCH-UHFFFAOYSA-N 5,6-dihydroxyindole Chemical compound C1=C(O)C(O)=CC2=C1NC=C2 SGNZYJXNUURYCH-UHFFFAOYSA-N 0.000 claims description 17
- YOCIJWAHRAJQFT-UHFFFAOYSA-N 2-bromo-2-methylpropanoyl bromide Chemical group CC(C)(Br)C(Br)=O YOCIJWAHRAJQFT-UHFFFAOYSA-N 0.000 claims description 14
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- -1 siloxane compound Chemical class 0.000 claims description 9
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- 239000003446 ligand Substances 0.000 claims description 7
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- 238000002156 mixing Methods 0.000 claims description 3
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 claims description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical class FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract 3
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- 239000000203 mixture Substances 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 10
- 229910052731 fluorine Inorganic materials 0.000 description 10
- 239000011737 fluorine Substances 0.000 description 10
- 238000004506 ultrasonic cleaning Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
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- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 6
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- 229910052799 carbon Inorganic materials 0.000 description 2
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- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 2
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- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 241000220317 Rosa Species 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical group [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
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- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 229940125368 controlled substance Drugs 0.000 description 1
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- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical group FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- YFSUTJLHUFNCNZ-UHFFFAOYSA-N perfluorooctane-1-sulfonic acid Chemical class OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YFSUTJLHUFNCNZ-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The invention discloses a preparation method for a water-repellent oil-repellent superhydrophobic fabric surface. The preparation method comprises the following steps: (1) weighing a cotton fabric, and preparing a cotton-cellulose macromolecular initiating agent under the action of the initiating agent and a catalyst; (2) grafting monomeric GMA on the prepared cotton-cellulose macromolecular initiating agent, vacuumizing a reaction system and introducing nitrogen, so as to obtain cotton cellulose grafted by the GMA, soaking the cotton cellulose grafted by the GMA in an acid solution, and hydrolyzing epoxy groups to form a cellulose surface rich in hydroxyl groups; and (3) performing acylation reaction between the cotton cellulose grafted by the GMA on the cellulose surface rich in hydroxyl groups and a monomer with low surface energy to obtain the water-repellent oil-repellent superhydrophobic surface. The preparation method is mild in reaction condition, simple, and easy to operate, can be realized at room temperature, and can guarantee the good superhydrophobicity and oil resistance without influencing of the comfort and the mechanical property of the cotton fabric.
Description
Technical Field
The invention relates to a preparation method for constructing a water-repellent, oil-repellent and super-hydrophobic surface on a fiber base, in particular to a preparation method for a water-repellent, oil-repellent and super-hydrophobic fabric surface.
Background
With the intensive research of people on lotus leaves and rose petals in the nature, the super-hydrophobic surface attracts the wide attention of people, the formation of the super-hydrophobic surface is mainly controlled by two factors, one is surface roughness, and the fact of constructing the surface roughness is that a secondary micro-nano structure is constructed; the second is low surface energy modification, and the most important is the adoption of fluorine-containing and long silicon-carbon chain compounds at present. In general, the longer the fluorocarbon chain, the lower the surface energy, and the more favorable it is to construct a fabric having excellent water-and oil-repellent characteristics. The fluorine-containing monomers commonly used at present have longer perfluoroalkyl chains (C is more than or equal to 8), and are easy to be oxidized and decomposed in natural environment to generate organic pollutants which are difficult to degrade, such as perfluorocarboxylic acid or sulfonyl compounds and the like, such as perfluorooctyl sulfonate compounds (PFOS), Perfluorooctanoic acid (PFOA), and the like, and have serious harm to the environment and the human health. In view of the high long-lasting stability of PFOS and the accumulation thereof in the environment, human and animal tissues, PFOS was classified as a newly added Persistent Organic Pollutant (POPs) controlled substance in stockholm convention 2009. In addition, since the side chain fluoroalkyl polymer having 8 or more carbon atoms has high-temperature crystallinity, flexibility of the fiber product is reduced. In addition, the conventional fluorine-containing silane chain liquid-phase self-assembly processing treatment needs to be cured at higher temperature in a later period, and the aging and discoloration of the fiber can be caused by the procedure.
Therefore, the application field of fiber base materials and fiber derivatives can be greatly enriched by simply preparing the surface of the water-repellent oil-repellent super-hydrophobic cotton fabric by utilizing the environmentally-friendly perfluoroalkyl short chain (C is less than or equal to 6), and the method has important influence on lossless liquid transportation, micropipettes, self-cleaning textiles, high-grade water-proof and oil-proof clothes, biomedical materials and the like. The cellulose has the advantages of high yield, low price, biodegradability, air permeability, comfort, good mechanical property and the like, the application fields of the cellulose and the derivatives thereof can be expanded by constructing the super-hydrophobic cellulose surface, and the cellulose is expected to be applied in the fields of waterproof and oil-repellent materials, self-cleaning textiles and the like. At present, the preparation of superhydrophobic surfaces is mainly through two routes: (1) constructing a rough structure on the super-hydrophobic surface (2) and modifying a low-surface-energy substance on the rough surface. The main method for increasing the surface roughness comprises the following steps: sol-gel method, induced phase separation method, electrospinning method, etc., however, the practical application of the superhydrophobic surface has not been industrialized yet, and many problems need to be solved. How to prepare the super-hydrophobic surface simply, conveniently and environmentally friendly needs to be explored, and the technical parameters for quantitatively guiding the microstructure of the super-hydrophobic surface need to be further improved.
Disclosure of Invention
The invention aims to: the preparation method of the water-repellent oil-repellent super-hydrophobic fabric surface is characterized in that an ATRP method is adopted to prepare the water-repellent oil-repellent super-hydrophobic surface on a fiber base, and the problems of complex operation, environmental pollution and the like in the preparation of the water-repellent oil-repellent super-hydrophobic surface are solved.
The technical scheme of the invention is as follows:
a preparation method of a water-repellent oil-repellent super-hydrophobic fabric surface comprises the following steps:
(1) weighing cotton fabrics, and preparing a cotton cellulose macroinitiator under the action of an initiator and a catalyst;
(2) grafting monomer GMA on the prepared cotton cellulose macroinitiator, vacuumizing a reaction system, introducing nitrogen to obtain the cotton cellulose grafted with the GMA, soaking the obtained cotton cellulose grafted with the GMA in an acid solution, and hydrolyzing an epoxy group on the acid solution to form a cellulose surface rich in hydroxyl; and
(3) and carrying out acylation reaction on the prepared cotton cellulose grafted with GMA on the surface of the cellulose rich in hydroxyl and a low-surface-energy monomer to obtain a water-repellent oil-repellent super-hydrophobic surface.
Further, the step (1) of weighing cotton fabrics and preparing the cotton cellulose macroinitiator under the action of the initiator and the catalyst comprises the following steps: weighing cotton fabrics, adding a catalyst and a solvent into a container under the stirring action of a magnetic rotor, cooling the container to 10 ℃, then dropwise adding the initiator, finally adding the cotton fabrics, reacting for 1 hour at the temperature of 10 ℃, then heating to 30 ℃, and reacting for 24 hours to obtain the cotton cellulose macroinitiator.
Further, in the step (1), the initiator is 2-bromoisobutyryl bromide, the catalyst is DMAP and triethylamine, the solvent is THF, and the cotton fabric is prepared by the following steps: 2-bromoisobutyryl bromide: DMAP: the mass ratio of triethylamine is 1: 2-8: 0.5: 0.9, 50ml of THF are required per 1g of the cotton fabric.
Further, the step (2) of grafting monomer GMA on the prepared cotton cellulose macroinitiator, vacuumizing a reaction system and introducing nitrogen to obtain the cotton cellulose grafted with GMA, soaking the obtained cotton cellulose grafted with GMA in an acid solution, and hydrolyzing epoxy groups on the cotton cellulose to form a cellulose surface rich in hydroxyl groups comprises the following steps: toluene as solvent, PMDETA as ligand, CuBr and CuCl2Is a catalyst in the major part of the cotton celluloseGrafting monomer GMA on a sub-initiator, vacuumizing a reaction system, introducing nitrogen for three times, reacting at the temperature of 30-60 ℃ for 12-24 hours to obtain GMA-grafted cotton cellulose, soaking the obtained GMA-grafted cotton cellulose in an acid solution for 1 hour, and hydrolyzing epoxy groups on the acid solution to form a cellulose surface rich in hydroxyl groups.
Further, the GMA: PMDETA: CuCl2Molar ratio of 1: 0.01: 0.001, the PMDETA: mass ratio of CuBr 1: 1-1: 1.5.
further, the acidic solution in the step (2) is formed by mixing THF, deionized water and concentrated HCl, and the pH value of the acidic solution is 0-1.
Further, the step (3) of subjecting the cotton cellulose grafted with GMA on the surface of the prepared cellulose rich in hydroxyl groups to acylation reaction with a low-surface-energy monomer to obtain a water-repellent, oil-repellent and super-hydrophobic surface comprises the following steps: and (3) adding dichloromethane serving as a solvent and DMAP (dimethyl propyl ammonium) and triethylamine serving as a catalytic system into another container, adding the cotton cellulose grafted with GMA on the surface of the cellulose rich in hydroxyl obtained in the step (2) into the container, adding a low-surface-energy monomer, and carrying out an acylation reaction under a mild condition to obtain the water-repellent oil-repellent super-hydrophobic surface.
Further, in the step (3), the low surface energy monomer is one or more of low-carbon fluorides of heptafluorobutyryl chloride and a long-chain siloxane compound.
Furthermore, every 0.1g of cotton cellulose grafted with GMA on the surface of cellulose rich in hydroxyl groups requires 5-15 ml of dichloromethane, 0.05-0.1 g of DMAP, 0.05-0.15 g of triethylamine and 120-360 mu l of heptafluorobutyrylchloride or long-chain siloxane compound.
Further, the mild condition is that the temperature is kept at 30-45 ℃, and the reaction is carried out in an oscillation water tank for 12-24 hours.
The invention has the advantages that:
1) the water-repellent and oil-repellent super-hydrophobic surface is prepared on a fiber base by adopting an ATRP method, the ATRP method is a controllable free radical polymerization technology, has the advantage of being suitable for controllable polymerization of various vinyl monomers, has tolerance to functional groups in monomer molecules, grafts polymers on the surface of a fiber-based initiator by a grafting method, has the characteristics of simplicity, easiness in operation, mild reaction conditions, easiness in control, various polymerization modes and the like, can be used for synthesizing polymers with controllable molecular weight, narrow molecular weight distribution, clear structure and various structure types by utilizing the ATRP method under the simpler and more convenient condition, and is low in raw material cost and excellent in performance.
2) The method has the advantages of mild reaction conditions, realization at room temperature, simple and convenient process and easy operation. The fabric has good application prospect, ensures good super-hydrophobicity and oil resistance, does not influence the comfort and mechanical properties of cotton fabric, and is expected to provide directions for lossless liquid transportation, micropipettes, self-cleaning textiles, high-grade waterproof and oilproof clothes, functional covering materials and the like.
3) The contact angle between the water-repellent and oil-repellent super-hydrophobic surface prepared by the method and water can reach 160 degrees, and the contact angle between the water-repellent and oil-repellent super-hydrophobic surface and oil after 15 days can reach 100 degrees.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein,
FIG. 1 is an EDS diagram and an element composition table for preparing a cotton macroinitiator according to the preparation method for the surface of the water-repellent oil-repellent super-hydrophobic fabric;
FIG. 2 is an infrared spectrogram of blank cotton and grafted cotton after grafting monomer GMA of the preparation method of the water-repellent oil-repellent super-hydrophobic fabric surface of the invention;
FIG. 3 is a SEM image of the surface of cellulose after grafting monomer heptafluorobutyryl chloride in the preparation method of the surface of the water-repellent, oil-repellent and super-hydrophobic fabric;
FIG. 4 is a water-repellent oil-repellent super-hydrophobic surface XPS spectrum prepared by the water-repellent oil-repellent super-hydrophobic fabric surface preparation method of the present invention;
FIG. 5 is a water static contact angle of a water-repellent, oil-repellent and super-hydrophobic surface prepared in the second embodiment of the method for preparing a water-repellent, oil-repellent and super-hydrophobic fabric surface according to the present invention;
FIG. 6 is a water static contact angle of the water-repellent oil-repellent super-hydrophobic surface prepared in the third embodiment of the method for preparing a water-repellent oil-repellent super-hydrophobic fabric surface according to the present invention;
FIG. 7 is a water static contact angle of the water-repellent oil-repellent super-hydrophobic surface prepared in the fourth example of the method for preparing a water-repellent oil-repellent super-hydrophobic fabric surface according to the present invention; and,
fig. 8 is a static contact angle of oil (n-hexadecane) on the water-repellent oil-repellent super-hydrophobic surface prepared by the method for preparing the water-repellent oil-repellent super-hydrophobic fabric surface of the invention.
Detailed Description
The invention provides a preparation method of a water-repellent oil-repellent super-hydrophobic fabric surface, which comprises the following steps:
(1) weighing cotton fabrics, and preparing a cotton cellulose macroinitiator under the action of an initiator and a catalyst;
(2) grafting monomer GMA on the prepared cotton cellulose macroinitiator, vacuumizing a reaction system, introducing nitrogen to obtain the cotton cellulose grafted with the GMA, soaking the obtained cotton cellulose grafted with the GMA in an acid solution, and hydrolyzing an epoxy group on the acid solution to form a cellulose surface rich in hydroxyl; and
(3) and carrying out acylation reaction on the prepared cotton cellulose grafted with GMA on the surface of the cellulose rich in hydroxyl and a low-surface-energy monomer to obtain a water-repellent oil-repellent super-hydrophobic surface.
The present invention will be described in further detail with reference to specific embodiments in order to make the above objects, features and advantages more apparent and understandable.
A preparation method of a water-repellent and oil-repellent super-hydrophobic fabric surface comprises the following steps:
the method comprises the following steps: weighing cotton fabrics, and preparing a cotton cellulose macroinitiator under the action of an initiator and a catalyst;
in one embodiment, this step may be specifically performed as follows: firstly, pre-treating the cotton fabric, including soaping, ethanol ultrasonic cleaning for 20min, THF ultrasonic cleaning for 10min, and then drying and cooling at low temperature for later use. Weighing cotton fabrics, adding a catalyst and a solvent into a container under the stirring action of a magnetic rotor, cooling the container to 10 ℃, then dropwise adding the initiator, finally adding the cotton fabrics, reacting for 1 hour under the condition of 10 ℃, then heating to 30 ℃, and reacting for 24 hours to obtain the cotton cellulose macroinitiator, wherein the initiator is 2-bromoisobutyryl bromide, the catalyst is DMAP, triethylamine and THF, the solvent is THF, and the cotton fabrics are prepared by the following steps: 2-bromoisobutyryl bromide: DMAP: the mass ratio of triethylamine is 1: 2-8: 0.5: 0.9, 50ml of THF are required per 1g of the cotton fabric. And after the reaction is finished, cleaning the cotton cellulose macroinitiator by using ethanol and THF.
Referring to fig. 1, fig. 1 is an EDS diagram and an element composition table of a method for preparing a cotton macroinitiator according to the present invention. As shown in FIG. 1, EDS spectra were taken on the prepared cotton macroinitiator, and Br element signals were detected, indicating that the initiator was successfully immobilized on cotton cellulose.
Step two: grafting monomer GMA on the prepared cotton cellulose macroinitiator, vacuumizing a reaction system, introducing nitrogen to obtain the cotton cellulose grafted with the GMA, soaking the obtained cotton cellulose grafted with the GMA in an acid solution, and hydrolyzing an epoxy group on the acid solution to form a cellulose surface rich in hydroxyl; and
in one embodiment, this step may be specifically performed as follows: toluene as solvent, PMDETA as ligand, CuBr and CuCl2Is a catalyst, wherein the GMA: PMDETA: CuCl2Molar ratio of 1: 0.01: 0.001, the PMDETA: mass ratio of CuBr 1: 1-1: 1.5. then, grafting monomer GMA on the cotton cellulose macroinitiator, vacuumizing a reaction system, introducing nitrogen for three times, reacting at the temperature of 30-60 ℃ for 12-24 hours to obtain GMA-grafted cotton cellulose, and soaking the obtained GMA-grafted cotton cellulose in an acid solution, wherein the acid solution is formed by mixing THF (tetrahydrofuran), deionized water and concentrated HCl, and the pH value of the acid solution is 0-1. After the soaking time is 1 hour, the epoxy groups on the surface of the cellulose are hydrolyzed to form a cellulose surface rich in hydroxyl groups.
Referring to fig. 2, fig. 2 is an infrared spectrogram of blank cotton and grafted cotton after grafting monomer GMA of the method for preparing the surface of the water-repellent, oil-repellent and super-hydrophobic fabric of the present invention. As shown in FIG. 2, the cotton cellulose macroinitiator successfully grafted with GMA monomer is at 1730cm-1C ═ O elongation vibration was exhibited.
Step three: carrying out acylation reaction on the prepared cotton cellulose grafted with GMA on the surface of the cellulose rich in hydroxyl and a low-surface-energy monomer to obtain a water-repellent oil-repellent super-hydrophobic surface;
in one embodiment, this step may be specifically performed as follows: adding dichloromethane serving as a solvent and DMAP (dimethyl propyl methacrylate) and triethylamine serving as a catalytic system into another container, adding the cotton cellulose grafted with GMA on the surface of the cellulose rich in hydroxyl obtained in the step (2) into the container, and then adding a low-surface-energy monomer, wherein the low-surface-energy monomer is one or more of low-carbon fluorides of heptafluorobutyryl chloride and long-chain siloxane compounds, and 5-15 ml of dichloromethane, 0.05-0.1 g of DMAP, 0.05-0.15 g of triethylamine and 120-360 mu l of heptafluorobutyryl chloride or long-chain siloxane compounds are required for every 0.1g of the cotton cellulose grafted with GMA on the surface of the cellulose rich in hydroxyl. Acylation then takes place under mild conditions, such as: and keeping the temperature at 30-45 ℃, and reacting in an oscillation water tank for 12-24 hours to obtain the water-repellent oil-repellent super-hydrophobic surface. After the reaction is finished, the mixture is washed clean by THF, dichloromethane and ethanol and dried at 80 ℃.
Referring to fig. 3, fig. 3 is a SEM image of a surface of cellulose grafted with monomer heptafluorobutyryl chloride according to the method for preparing a water-and oil-repellent fabric surface of the present invention, and as shown in fig. 3, the microstructure of the prepared water-and oil-repellent super-hydrophobic surface fiber is shown.
Referring to fig. 8, fig. 8 is a static contact angle of oil (n-hexadecane) on the water-repellent oil-repellent super-hydrophobic surface prepared by the method for preparing the water-repellent oil-repellent super-hydrophobic fabric surface of the present invention. As shown in fig. 8, the contact angle between the water-repellent and oil-repellent super-hydrophobic surface prepared by the method and oil (n-hexadecane) reaches 100 degrees after 15 days, and oil drops do not infiltrate into the sample, which shows that the material prepared by the three steps has good oleophobic property.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are further described below. The invention is not limited to the embodiments listed but also comprises any other known variations within the scope of the invention as claimed.
First, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The present invention is described in detail by using the schematic structural diagrams, etc., and for convenience of illustration, the schematic diagrams are not enlarged partially according to the general scale when describing the embodiments of the present invention, and the schematic diagrams are only examples, which should not limit the scope of the present invention. In addition, the actual fabrication process should include three-dimensional space of length, width and depth.
In addition, the acronyms referred to in the invention are all fixed acronyms in the field, wherein part of the letters are explained as follows: ATRP: atom transfer radical; DMAP: 4-dimethylaminopyridine; GMA: glycidyl methacrylate; PMDETA: pentamethyldiethylenetriamine; THF: tetrahydrofuran; PDMS: polydimethylsiloxane; EDS diagram: an energy spectrum; SEM image: electronic scanning and image display; XPS spectrum: and (3) analyzing a spectrogram by X-ray photoelectron spectroscopy.
Example one
The embodiment prepares the water-repellent and oil-repellent super-hydrophobic surface according to the following steps:
first step, preparation of cotton cellulose macroinitiator
In the experiment, the pretreatment of the cotton fabric comprises soaping, ethanol ultrasonic cleaning for 20min, THF ultrasonic cleaning for 10min, low-temperature drying and cooling for later use. About 1g of cotton fabric was weighed, and the mass ratio m (cotton: 2-bromoisobutyryl bromide: DMAP: triethylamine) was 1: 2: 0.5: 0.9 calculating the dosage of each reagent, adding 50ml of THF into a round-bottom flask, then adding DMAP and triethylamine, cooling the round-bottom flask to 10 ℃ in an ice bath, dropwise adding an initiator 2-bromoisobutyryl bromide, then adding the cotton fabric, reacting for 1h, heating to 30 ℃, continuing to react for 24h, and carrying out the whole reaction under the stirring of a magnetic rotor. After the reaction, the reaction mixture was washed with ethanol and THF.
Second step, graft GMA monomer and epoxy group hydrolysis
Adding 0.5g of the cotton cellulose macroinitiator prepared above into toluene as a solvent, PMDETA as a ligand, CuBr and CuCl2As catalyst, the monomer is GMAIn the system, the reagent composition is 1mol/LGMA, 0.01mol/LPMDETA and 0.001mol/LCuCl2N (PMDETA: CuBr) ═ 1: 1, in the presence of CuBr and CuCl2After the solution is added into a round-bottom flask, vacuum pumping is carried out immediately, nitrogen is introduced for three times, and the reaction is carried out for 12 hours at the temperature of 30 ℃ to obtain the cotton cellulose grafted with GMA. After the reaction, the reaction mixture was washed with THF, dichloromethane and methanol repeatedly 2 times. And (3) putting the obtained GMA grafted cotton cellulose into an acid solution, and reacting for 1 hour at normal temperature to hydrolyze an epoxy group, wherein the pH value of the acid solution is 0.1.
Thirdly, preparing the water-repellent and oil-repellent ultraphobic surface
In another round-bottom flask, solvent dichloromethane, catalyst DMAP and triethylamine are added, finally, low surface energy monomer heptafluorobutyryl chloride is slowly dropped into the flask, and the preparation conditions take 0.1g of sample as an example, 0.1g of cotton cellulose grafted with GMA monomer needs 5ml of dichloromethane, 0.05g of DMAP, 0.05g of triethylamine and 120 mu l of heptafluorobutyryl chloride, and the mixture is reacted for 12 hours in a shaking water tank at 30 ℃. After the reaction is finished, the mixture is washed clean by THF, dichloromethane and ethanol and dried at 80 ℃.
Example two
The embodiment prepares the water-repellent and oil-repellent super-hydrophobic surface according to the following steps:
first step, preparation of cotton cellulose macroinitiator
In the experiment, the pretreatment of the cotton fabric comprises soaping, ethanol ultrasonic cleaning for 20min, THF ultrasonic cleaning for 10min, low-temperature drying and cooling for later use. About 1g of cotton fabric was weighed, and the mass ratio m (cotton: 2-bromoisobutyryl bromide: DMAP: triethylamine) was 1: 2: 0.5: 0.9 calculating the dosage of each reagent, adding 50ml of THF into a round-bottom flask, then adding DMAP and triethylamine, cooling the round-bottom flask to 10 ℃ in an ice bath, dropwise adding an initiator 2-bromoisobutyryl bromide, then adding the cotton fabric, reacting for 1h, heating to 30 ℃, continuing to react for 24h, and carrying out the whole reaction under the stirring of a magnetic rotor. After the reaction, the reaction mixture was washed with ethanol and THF.
Second step, graft GMA monomer and epoxy group hydrolysis
Adding 0.5g of the cotton cellulose macroinitiator prepared above into toluene as a solvent, PMDETA as a ligand, CuBr and CuCl2As a catalyst, in the system of GMA monomer, the reagent composition is 1mol/LGMA, 0.01mol/LPMDETA and 0.001mol/LCuCl2N (PMDETA: CuBr) ═ 1: 1.5 in the presence of CuBr and CuCl2After the solution is added into a round-bottom flask, vacuumizing and introducing nitrogen for three times immediately, and reacting for 24 hours at 45 ℃ to obtain the GMA grafted cotton cellulose. After the reaction, the reaction mixture was washed with THF, dichloromethane and methanol repeatedly 2 times. And (3) putting the obtained GMA grafted cotton cellulose into an acid solution, and reacting for 1h at normal temperature to hydrolyze an epoxy group, wherein the pH value of the acid solution is 0.64.
Thirdly, preparing the water-repellent and oil-repellent ultraphobic surface
In another round-bottom flask, solvent dichloromethane, catalyst DMAP and triethylamine are added, finally, low surface energy monomer heptafluorobutyryl chloride is slowly dropped into the flask, and the preparation conditions take 0.1g of sample as an example, 0.1g of cotton cellulose grafted with GMA monomer needs 10ml of dichloromethane, 0.05g of DMAP, 0.09g of triethylamine and 120 mu l of heptafluorobutyryl chloride to react for 24 hours in a shaking water tank at 30 ℃. After the reaction is finished, the mixture is washed clean by THF, dichloromethane and ethanol and dried at 80 ℃.
Referring to fig. 5, fig. 5 shows the water-repellent, oil-repellent and super-hydrophobic surface prepared in this embodiment, where fig. 5 shows the water static contact angle of the water-repellent, oil-repellent and super-hydrophobic surface prepared in the second embodiment of the method for preparing the surface of the water-repellent, oil-repellent and super-hydrophobic fabric of the present invention. As shown in fig. 5, the contact angle of the water-repellent, oil-repellent and ultrahydrophobic surface prepared by the present embodiment with water is greater than 150 °, which indicates that the surface of the prepared material has been made to be ultrahydrophobic.
EXAMPLE III
The embodiment prepares the water-repellent and oil-repellent super-hydrophobic surface according to the following steps:
first step, preparation of cotton cellulose macroinitiator
In the experiment, the pretreatment of the cotton fabric comprises soaping, ethanol ultrasonic cleaning for 20min, THF ultrasonic cleaning for 10min, low-temperature drying and cooling for later use. About 1g of cotton fabric was weighed, and the mass ratio m (cotton: 2-bromoisobutyryl bromide: DMAP: triethylamine) was 1: 4: 0.5: 0.9 calculating the dosage of each reagent, adding 50ml of THF into a round-bottom flask, then adding DMAP and triethylamine, cooling the round-bottom flask to 10 ℃ in an ice bath, dropwise adding an initiator 2-bromoisobutyryl bromide, then adding the cotton fabric, reacting for 1h, heating to 30 ℃, continuing to react for 24h, and carrying out the whole reaction under the stirring of a magnetic rotor. After the reaction, the reaction mixture was washed with ethanol and THF.
Second step, graft GMA monomer and epoxy group hydrolysis
Adding 0.5g of the cotton cellulose macroinitiator prepared above into toluene as a solvent, PMDETA as a ligand, CuBr and CuCl2As a catalyst, in the system of GMA monomer, the reagent composition is 1mol/LGMA, 0.01mol/LPMDETA and 0.001mol/LCuCl2N (PMDETA: CuBr) ═ 1: 1, in the presence of CuBr and CuCl2After the solution is added into a round-bottom flask, vacuumizing and introducing nitrogen for three times immediately, and reacting for 24 hours at 45 ℃ to obtain the GMA grafted cotton cellulose. After the reaction, the reaction mixture was washed with THF, dichloromethane and methanol repeatedly 2 times. And (3) putting the obtained GMA grafted cotton cellulose into an acid solution, and reacting for 1h at normal temperature to hydrolyze an epoxy group, wherein the pH value of the acid solution is 0.64.
Thirdly, preparing the water-repellent and oil-repellent ultraphobic surface
In another round-bottom flask, solvent dichloromethane, catalyst DMAP and triethylamine are added, finally, low surface energy monomer heptafluorobutyryl chloride is slowly dropped into the flask, and the preparation conditions take 0.1g of sample as an example, 0.1g of cotton cellulose grafted with GMA monomer needs 10ml of dichloromethane, 0.05g of DMAP, 0.09g of triethylamine and 120 mu l of heptafluorobutyryl chloride to react for 24 hours in a shaking water tank at 30 ℃. After the reaction is finished, the mixture is washed clean by THF, dichloromethane and ethanol and dried at 80 ℃.
Referring to fig. 6, fig. 6 shows the water-repellent, oil-repellent and super-hydrophobic surface prepared in this example, where fig. 6 shows the water static contact angle of the water-repellent, oil-repellent and super-hydrophobic surface prepared in the third example of the method for preparing the surface of the water-repellent, oil-repellent and super-hydrophobic fabric of the present invention. As shown in fig. 6, the contact angle of the water-repellent, oil-repellent and ultrahydrophobic surface prepared in this embodiment with water is 155 °, which indicates that the surface of the prepared material has been made to be ultrahydrophobic.
Example four
The embodiment prepares the water-repellent and oil-repellent super-hydrophobic surface according to the following steps:
first step, preparation of cotton cellulose macroinitiator
In the experiment, the pretreatment of the cotton fabric comprises soaping, ethanol ultrasonic cleaning for 20min, THF ultrasonic cleaning for 10min, low-temperature drying and cooling for later use. About 1g of cotton fabric was weighed, and the mass ratio m (cotton: 2-bromoisobutyryl bromide: DMAP: triethylamine) was 1: 8: 0.5: 0.9 calculating the dosage of each reagent, adding 50ml of THF into a round-bottom flask, then adding DMAP and triethylamine, cooling the round-bottom flask to 10 ℃ in an ice bath, dropwise adding an initiator 2-bromoisobutyryl bromide, then adding the cotton fabric, reacting for 1h, heating to 30 ℃, continuing to react for 24h, and carrying out the whole reaction under the stirring of a magnetic rotor. After the reaction, the reaction mixture was washed with ethanol and THF.
Second step, graft GMA monomer and epoxy group hydrolysis
Adding 0.5g of the cotton cellulose macroinitiator prepared above into toluene as a solvent, PMDETA as a ligand, CuBr and CuCl2As a catalyst, in the system of GMA monomer, the reagent composition is 1mol/LGMA, 0.01mol/LPMDETA and 0.001mol/LCuCl2N (PMDETA: CuBr) ═ 1: 1, in the presence of CuBr and CuCl2After the solution is added into a round-bottom flask, vacuum pumping is carried out immediately, nitrogen is introduced for three times, and the reaction is carried out for 24 hours at the temperature of 60 ℃ to obtain the cotton cellulose grafted with GMA. After the reaction, the reaction mixture was repeatedly washed with THF, dichloromethane and methanol2 times. And (3) putting the obtained GMA grafted cotton cellulose into an acid solution, and reacting for 1 hour at normal temperature to hydrolyze an epoxy group, wherein the pH value of the acid solution is 1.
Thirdly, preparing the water-repellent and oil-repellent ultraphobic surface
In another round-bottom flask, solvent dichloromethane, catalyst DMAP and triethylamine are added, finally, low surface energy monomer heptafluorobutyryl chloride is slowly dropped into the flask, and the preparation conditions take 0.1g of sample as an example, 0.1g of cotton cellulose grafted with GMA monomer needs 15ml of dichloromethane, 0.1g of DMAP, 0.15g of triethylamine and 360 mu l of heptafluorobutyryl chloride to react for 24 hours at 45 ℃ in a shaking water tank. After the reaction is finished, the mixture is washed clean by THF, dichloromethane and ethanol and dried at 80 ℃.
Referring to fig. 7, fig. 7 shows the water-repellent, oil-repellent and super-hydrophobic surface prepared in this example, where fig. 7 shows the water static contact angle of the water-repellent, oil-repellent and super-hydrophobic surface prepared in the fourth example of the method for preparing the surface of the water-repellent, oil-repellent and super-hydrophobic fabric of the present invention. As shown in fig. 7, the contact angle of the water-repellent, oil-repellent and ultrahydrophobic surface prepared by the present embodiment with water is greater than 150 °, which indicates that the surface of the prepared material has been made to be ultrahydrophobic.
In the four embodiments, the cotton cellulose grafted with GMA on the surface of the cellulose rich in hydroxyl and the monomer heptafluorobutyryl chloride with low surface energy are subjected to acylation reaction, so that the obtained water-repellent and oil-repellent super-hydrophobic surface contains fluorine. Referring to fig. 4, fig. 4 is an XPS spectrum of a water-repellent, oil-repellent and super-hydrophobic surface prepared by the method for preparing a surface of a water-repellent, oil-repellent and super-hydrophobic fabric according to the present invention. As can be seen from a comparison of FIGS. 4(a) and (b), a signal of fluorine was detected on the prepared fluorine-containing cotton fabric, indicating that the fluorine-containing monomer was successfully grafted onto the cotton fabric; FIG. 4(b) shows the relationship between the peak of the fluorine element spectrum and the content of the fluorine monomer, and the larger the amount of the fluorine monomer, the higher the peak value.
In conclusion, the invention discloses a preparation method of a water-repellent, oil-repellent and super-hydrophobic fabric surface, which makes full use of ATRP polymerization controllable grafting technology based on the prior art, has mild reaction conditions, can be realized at room temperature, and has simple and convenient process and easy operation. The fabric has good application prospect, does not influence the comfort and mechanical properties of cotton fabrics while ensuring good super-hydrophobicity and oil resistance, and can be well applied to lossless liquid transportation, micropipettes, self-cleaning textiles, high-grade waterproof and oilproof clothes, biomedical materials and the like.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a water-repellent oil-repellent super-hydrophobic fabric surface is characterized by comprising the following steps:
(1) weighing cotton fabrics, and preparing a cotton cellulose macroinitiator under the action of an initiator and a catalyst;
(2) grafting monomer GMA on the prepared cotton cellulose macroinitiator, vacuumizing a reaction system, introducing nitrogen to obtain the cotton cellulose grafted with the GMA, soaking the obtained cotton cellulose grafted with the GMA in an acid solution, and hydrolyzing an epoxy group on the acid solution to form a cellulose surface rich in hydroxyl; and
(3) and carrying out acylation reaction on the prepared cotton cellulose grafted with GMA on the surface of the cellulose rich in hydroxyl and a low-surface-energy monomer to obtain a water-repellent oil-repellent super-hydrophobic surface.
2. The method for producing a water-and oil-repellent ultrahydrophobic fabric surface according to claim 1, characterized in that: weighing cotton fabrics in the step (1), and preparing the cotton cellulose macroinitiator under the action of the initiator and the catalyst, wherein the step comprises the following steps: weighing cotton fabrics, adding a catalyst and a solvent into a container under the stirring action of a magnetic rotor, cooling the container to 10 ℃, then dropwise adding the initiator, finally adding the cotton fabrics, reacting for 1 hour at the temperature of 10 ℃, then heating to 30 ℃, and reacting for 24 hours to obtain the cotton cellulose macroinitiator.
3. The method for producing a water-and oil-repellent ultrahydrophobic fabric surface according to claim 2, characterized in that: in the step (1), the initiator is 2-bromoisobutyryl bromide, the catalyst is DMAP and triethylamine, the solvent is THF, and the cotton fabric is prepared by the following steps: 2-bromoisobutyryl bromide: DMAP: the mass ratio of triethylamine is 1: 2-8: 0.5: 0.9, 50ml of THF are required per 1g of the cotton fabric.
4. The method for preparing the surface of the water-repellent oil-repellent super-hydrophobic fabric according to claim 1, wherein the step (2) of grafting monomer GMA on the prepared cotton cellulose macroinitiator, vacuumizing the reaction system and introducing nitrogen to obtain GMA-grafted cotton cellulose, soaking the obtained GMA-grafted cotton cellulose in an acid solution, and hydrolyzing epoxy groups on the obtained GMA-grafted cotton cellulose to form a cellulose surface rich in hydroxyl groups comprises the following steps: toluene as solvent, PMDETA as ligand, CuBr and CuCl2Grafting a monomer GMA on the cotton cellulose macroinitiator as a catalyst, vacuumizing a reaction system, introducing nitrogen for three times, reacting at the temperature of 30-60 ℃ for 12-24 hours to obtain the cotton cellulose grafted with the GMA, and soaking the obtained cotton cellulose grafted with the GMA in waterWhen the cellulose is soaked in an acid solution for 1 hour, epoxy groups on the cellulose are hydrolyzed to form a cellulose surface rich in hydroxyl groups.
5. The method for producing a water-and oil-repellent ultrahydrophobic fabric surface according to claim 4, characterized in that the GMA: PMDETA: CuCl2Molar ratio of 1: 0.01: 0.001, the PMDETA: mass ratio of CuBr 1: 1-1: 1.5.
6. the method for preparing the surface of the water-repellent oil-repellent super-hydrophobic fabric according to claim 1, wherein the acidic solution in the step (2) is formed by mixing THF, deionized water and concentrated HCl, and the pH value of the acidic solution is 0-1.
7. The method for preparing the surface of the water-repellent oil-repellent super-hydrophobic fabric according to claim 1, wherein the step of subjecting the GMA-grafted cotton cellulose on the prepared hydroxyl-rich cellulose surface to acylation reaction with a low surface energy monomer in step (3) to obtain a water-repellent oil-repellent super-hydrophobic surface comprises: and (3) adding dichloromethane serving as a solvent and DMAP (dimethyl propyl ammonium) and triethylamine serving as a catalytic system into another container, adding the cotton cellulose grafted with GMA on the surface of the cellulose rich in hydroxyl obtained in the step (2) into the container, adding a low-surface-energy monomer, and carrying out an acylation reaction under a mild condition to obtain the water-repellent oil-repellent super-hydrophobic surface.
8. The method for preparing the surface of the water-repellent oil-repellent super-hydrophobic fabric according to claim 7, wherein the low surface energy monomer in the step (3) is one or more of low carbon fluorides of heptafluorobutyryl chloride and long chain siloxane compound.
9. The method for preparing the surface of the water-repellent oil-repellent super-hydrophobic fabric according to claim 8, wherein 5 to 15ml of dichloromethane, 0.05 to 0.1g of DMAP, 0.05 to 0.15g of triethylamine and 120 to 360 μ l of heptafluorobutyrylchloride or long-chain siloxane compound are required per 0.1g of GMA-grafted cotton cellulose on the surface of the cellulose rich in hydroxyl groups.
10. The method for preparing the surface of the water-repellent oil-repellent super-hydrophobic fabric according to claim 7, wherein the mild condition is that the temperature is kept at 30-45 ℃ and the reaction is carried out in a shaking water tank for 12-24 hours.
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