CN114703665B - Super-hydrophilic-super-oleophobic self-healing fabric and preparation method thereof - Google Patents

Super-hydrophilic-super-oleophobic self-healing fabric and preparation method thereof Download PDF

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Publication number
CN114703665B
CN114703665B CN202210511107.7A CN202210511107A CN114703665B CN 114703665 B CN114703665 B CN 114703665B CN 202210511107 A CN202210511107 A CN 202210511107A CN 114703665 B CN114703665 B CN 114703665B
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super
hydrophilic
oleophobic
fabric
chitosan
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CN114703665A (en
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符思达
徐之光
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Jiaxing University
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Jiaxing University
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    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • 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
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/12—Processes in which the treating agent is incorporated in microcapsules
    • 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
    • D06M2200/11—Oleophobic properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/20—Controlling water pollution; Waste water treatment
    • Y02A20/204—Keeping clear the surface of open water from oil spills

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

The invention discloses a preparation method of a super-hydrophilic-super-oleophobic self-healing fabric, which is characterized by comprising the following steps of: (1) preparing chitosan acetic acid solution: dissolving chitosan in acetic acid solution; (2) preparing a super-hydrophilic-super-oleophobic solution: adding Capstone FS-60 into the chitosan acetic acid solution prepared in the step (1), then adding sodium tripolyphosphate, and uniformly stirring at normal temperature; (3) Adding dopamine into the super-hydrophilic-super-oleophobic solution prepared in the step (2), and uniformly stirring for 8-24 hours at normal temperature in an ultraviolet box; (4) Immersing the fabric into the solution prepared in the step (3), and heating for 15-30 minutes at 80-120 ℃. The invention also discloses the super-hydrophilic-super-oleophobic self-healing fabric prepared by the preparation method. Compared with the prior art, the super-hydrophilic-super-oleophobic self-healing fabric can prolong the service life.

Description

Super-hydrophilic-super-oleophobic self-healing fabric and preparation method thereof
Technical Field
The invention relates to the technical field of fabric surface modification, in particular to a super-hydrophilic-super-oleophobic self-healing fabric and a preparation method thereof.
Background
The super-hydrophilic and super-oleophobic fabric has a very wide application prospect. In recent years, the phenomenon of oil pollution of water quality has been paid more attention to, and how to separate oil from water has become an urgent problem. Superhydrophobic-superoleophilic fabrics have been widely used for oil-water separation, but such fabrics are easily contaminated, and generally have a lower oil density than water, and the water layer easily blocks oil layer penetration. The super-hydrophilic and super-oleophobic fabric can effectively solve the problem, and under the action of gravity, water permeates through the fabric, and oil is prevented by the fabric, so that the purpose of oil-water separation is achieved. In the self-cleaning field, when the super-hydrophilic and super-oleophobic fabric polluted by oil stains is immersed in water, the oil layer and the interface are not tightly adhered due to the super-oleophobic property, the super-hydrophilicity of the super-hydrophilic and super-oleophobic fabric can enable the water to be immersed in the interface between the fabric and the oil layer, and the immersed water layer can easily strip the oil stains from the surface of the fabric, so that the aim of cleaning is achieved.
The invention patent of the invention with the patent application number of CN201910102432.6 (publication number of CN 109825179A), namely a water-based super-hydrophilic super-oleophobic coating, a preparation method and application thereof, is that a water-based fluorocarbon surfactant, a polyether modified organosilicon leveling agent, a dispersing agent, a thickening agent and deionized water are added into a reaction kettle at room temperature for stirring; then hydrophilic fumed silica nano particles and silica micropowder are added and stirred; finally adding the aqueous resin and stirring. The method can realize super-hydrophilic super-oleophobic in the air, is simple and easy to implement, avoids the use of organic solvents, and only uses water as a solvent. The aqueous super-hydrophilic super-oleophobic coating can be applied to filtration treatment of an oil-water mixture.
Nevertheless, there are still some unresolved problems in this field. The firmness of the super-hydrophilic-super-oleophobic coating is not ideal, and the super-hydrophilic-super-oleophobic coating is easily damaged by outside physics or chemistry to lose the characteristics, thereby influencing the service life of the super-hydrophilic-super-oleophobic coating.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a preparation method of a super-hydrophilic-super-oleophobic self-healing fabric capable of prolonging service life aiming at the current state of the art.
The second technical problem to be solved by the invention is to provide the super-hydrophilic-super-oleophobic self-healing fabric prepared by the preparation method.
The technical scheme adopted by the invention for solving the first technical problem is as follows: the preparation method of the super-hydrophilic-super-oleophobic self-healing fabric is characterized by comprising the following steps of:
(1) Preparing chitosan acetic acid solution: dissolving chitosan in acetic acid solution;
(2) Preparing a super-hydrophilic-super-oleophobic solution: adding Capstone FS-60 into the chitosan acetic acid solution prepared in the step (1), then adding sodium tripolyphosphate, and uniformly stirring at normal temperature;
(3) Adding dopamine into the super-hydrophilic-super-oleophobic solution prepared in the step (2), and uniformly stirring for 8-24 hours at normal temperature in an ultraviolet box;
(4) Immersing the fabric into the solution prepared in the step (3), and heating for 15-30 minutes at 80-120 ℃ to obtain the required super-hydrophilic-super-oleophobic self-healing fabric.
Preferably, in step (1), the concentration of the acetic acid solution is 1 to 3wt%.
Preferably, in the step (1), the chitosan is added in an amount of 1 to 5wt%.
Preferably, in the step (1), the deacetylation degree of the chitosan is 85% -95% and the molecular weight is 20-150 ten thousand.
Preferably, in the step (2), the Capstone FS-60 is added in an amount of 1 to 3wt%.
Preferably, in the step (2), the sodium tripolyphosphate is added in an amount of 1 to 5wt%.
Preferably, in the step (3), the addition amount of the dopamine is 1-5 wt%.
Preferably, in the step (3), the setting parameters of the ultraviolet box are: 254/365nm, 50-100 mW cm -2 。
Preferably, in the step (4), the fabric is heated after being soaked in the solution prepared in the step (3) for 1 to 5 minutes.
The invention solves the second technical problem by adopting the technical proposal that: the super-hydrophilic super-oleophobic self-healing fabric prepared by the preparation method.
Compared with the prior art, the invention has the advantages that:
(1) The preparation method adopts a water-based mode, and is environment-friendly and safe;
(2) The polydopamine microcapsule is formed on the surface of the fabric, so that the self-healing property can be realized in a slow release mode of the hydrophilic-oleophobic compound, and compared with the traditional method, the self-healing cycle number is more, and the effect is better;
(3) Dopamine is adopted as an adhesion medium, has the characteristic of universal adhesion, and is suitable for a wide range of substrates.
Drawings
FIG. 1 shows the contact angle and the contact angle before and after self-healing of the super-hydrophilic-super-oleophobic fabric prepared in example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the embodiments of the drawings.
Example 1:
(1) Preparing chitosan acetic acid solution: 3wt% chitosan (degree of deacetylation 90wt%, molecular weight 50 ten thousand) was dissolved in 2wt% acetic acid solution;
(2) Preparing a super-hydrophilic-super-oleophobic solution: adding 2wt% of capstone FS-60 into the chitosan acetic acid solution prepared in the step (1), then adding 3wt% of sodium tripolyphosphate, and uniformly stirring at normal temperature;
(3) Adding 2wt% of dopamine into the super-hydrophilic-super-oleophobic solution prepared in the step (2), and placing the mixture in an ultraviolet box (365 nm,50mW cm) -2 ) Uniformly stirring at normal temperature for 12 hours;
(4) Immersing the fabric into the solution prepared in the step (3) for 3 minutes, and then heating at 100 ℃ for 20 minutes to obtain the required super-hydrophilic-super-oleophobic self-healing fabric.
Example 2:
(1) Preparing chitosan acetic acid solution: 1wt% chitosan (degree of deacetylation 85wt%, molecular weight 20 ten thousand) was dissolved in acetic acid solution with concentration of 1 wt%;
(2) Preparing a super-hydrophilic-super-oleophobic solution: adding 1wt% of capstone FS-60 into the chitosan acetic acid solution prepared in the step (1), then adding 1wt% of sodium tripolyphosphate, and uniformly stirring at normal temperature;
(3) Adding 1wt% dopamine into the super-hydrophilic-super-oleophobic solution prepared in the step (2), and placing the mixture in an ultraviolet box (254 nm,100mW cm -2 ) Uniformly stirring at normal temperature for 8 hours;
(4) Immersing the fabric into the solution prepared in the step (3) for 1 minute, and then heating at 80 ℃ for 15 minutes to obtain the required super-hydrophilic-super-oleophobic self-healing fabric.
Example 3:
(1) Preparing chitosan acetic acid solution: 5wt% chitosan (degree of deacetylation 95wt%, molecular weight 150 ten thousand) was dissolved in acetic acid solution with a concentration of 3wt%;
(2) Preparing a super-hydrophilic-super-oleophobic solution: adding 3wt% of capstone FS-60 into the chitosan acetic acid solution prepared in the step (1), then adding 5wt% of sodium tripolyphosphate, and uniformly stirring at normal temperature;
(3) Adding 5wt% of dopamine into the super-hydrophilic-super-oleophobic solution prepared in the step (2), and placing the mixture in an ultraviolet box (254 nm,100mW cm -2 ) Uniformly stirring at normal temperature for 24 hours;
(4) Immersing the fabric into the solution prepared in the step (3) for 5 minutes, and then heating at 120 ℃ for 30 minutes to obtain the required super-hydrophilic-super-oleophobic self-healing fabric.
Example 4:
(1) Preparing chitosan acetic acid solution: 1wt% chitosan (degree of deacetylation 85wt%, molecular weight 20 ten thousand) was dissolved in acetic acid solution with concentration of 1 wt%;
(2) Preparing a super-hydrophilic-super-oleophobic solution: adding 1wt% of capstone FS-60 into the chitosan acetic acid solution prepared in the step (1), then adding 1wt% of sodium tripolyphosphate, and uniformly stirring at normal temperature;
(3) Adding 5wt% of dopamine into the super-hydrophilic-super-oleophobic solution prepared in the step (2), and placing the mixture in an ultraviolet box (365 nm, 50-mW cm) -2 ) Uniformly stirring at normal temperature for 24 hours;
(4) Immersing the fabric into the solution prepared in the step (3) for 5 minutes, and then heating at 120 ℃ for 30 minutes to obtain the required super-hydrophilic-super-oleophobic self-healing fabric.
Example 5:
(1) Preparing chitosan acetic acid solution: 5wt% chitosan (degree of deacetylation 95wt%, molecular weight 150 ten thousand) was dissolved in acetic acid solution with a concentration of 3wt%;
(2) Preparing a super-hydrophilic-super-oleophobic solution: adding 3wt% of capstone FS-60 into the chitosan acetic acid solution prepared in the step (1), then adding 5wt% of sodium tripolyphosphate, and uniformly stirring at normal temperature;
(3) Adding 1wt% of dopamine into the super-hydrophilic-super-oleophobic solution prepared in the step (2), and placing the mixture in an ultraviolet box (365 nm,80mW cm) -2 ) Uniformly stirring at normal temperature for 8 hours;
(4) Immersing the fabric into the solution prepared in the step (3) for 1 minute, and then heating at 80 ℃ for 15 minutes to obtain the required super-hydrophilic-super-oleophobic self-healing fabric.
Comparative example 1:
(1) Preparing chitosan acetic acid solution: 3wt% chitosan (degree of deacetylation 90wt%, molecular weight 50 ten thousand) was dissolved in 2wt% acetic acid solution;
(2) Preparing a super-hydrophilic-super-oleophobic solution: adding 2wt% of capstone FS-60 into the chitosan acetic acid solution prepared in the step (1), then adding 3wt% of sodium tripolyphosphate, and uniformly stirring at normal temperature;
(3) An aqueous solution of dopamine at a concentration of 2wt% was prepared and the fabric was immersed in the aqueous solution of dopamine in an ultraviolet oven (365 nm,50mW cm -2 ) Uniformly stirring at normal temperature for 12 hours, and taking out and airing the fabric;
(4) Immersing the fabric treated in the step (3) into the super-hydrophilic-super-oleophobic solution prepared in the step (2) for 3 minutes, and then heating at 100 ℃ for 20 minutes to obtain the treated fabric.
Note that: the above Capstone FS-60 (trade name) is an aqueous anionic surfactant manufactured by DuPont.
The wettability and breathability of the fabrics produced in examples 1-5 are shown in table 1.
Table 1:
the self-healing properties of the fabrics prepared in example 1 and comparative example 1 are shown in table 2.
Table 2:
note that:
(1) The self-healing treatment method comprises the steps of dripping distilled water on the surface of the destroyed fabric until the surface is wet, and then putting the fabric into a baking oven for heating at 100 ℃ for 30 minutes;
(2) Washing test: according to AATCC61-2006 No.2A standard test;
(3) Abrasion resistance test: tested according to ASTM D4966 standard.
The contact angle and the contact angle before and after self-healing of the superhydrophilic-superoleophobic fabric prepared in example 1 are shown in fig. 1.
As can be seen from tables 1 to 2 and fig. 1:
(1) The fabric as it is has super-hydrophilic-super-oleophilic properties, the fabrics prepared in examples 1-5 have super-hydrophilic-super-oleophobic properties, the air permeability of the treated fabric is not affected, the surface wetting property of the treated fabric is destroyed after being destroyed by washing and friction, and the fabric becomes super-hydrophilic-oleophilic, but the fabric is restored to the super-hydrophilic-super-oleophobic state after the self-healing treatment;
the working principle is as follows: the chitosan nanoparticle is formed by the attraction of positive and negative charges of chitosan and sodium tripolyphosphate, and meanwhile, the nanoparticle can wrap a hydrophilic-oleophobic compound (Capstone FS-60) to enter the interior; and adding dopamine, wherein the dopamine is polymerized in an aqueous solution under the action of ultraviolet light to form the polydopamine microcapsule. The microcapsule can encapsulate chitosan nanoparticles, and meanwhile, the surface of the microcapsule can be linked with a free hydrophilic-oleophobic compound (Capstone FS-60), and finally, the PDA microcapsule is adhered to the surface of a fabric by the general adhesion characteristic of the PDA.
When the hydrophilic-oleophobic properties of the fabric surface are physically or chemically destroyed, the hydrophilic-oleophobic properties can be recovered by simply wetting with distilled water and heating, because: the pH value of distilled water is about 7, and after the distilled water permeates into nano particles, the charge density of cations in chitosan molecules can be reduced, so that the cations and anions in the original crosslinked chitosan nano particles are separated, and a loose nano particle structure can release a hydrophilic-oleophobic compound (Capstone FS-60) to a PDA microcapsule; under the action of heat, the Brownian motion of the hydrophilic-oleophobic compound (Capstone FS-60) is accelerated, and the compound can quickly migrate to the surface of the material and bond with active groups in PDA, so that the hydrophilic-oleophobic property of the surface is endowed.
(2) It can be seen from comparative examples 1 and 1 that, although the superhydrophilic-superhydrophobic (high) oleophobic state can be achieved both after the first treatment and after the first self-healing, example 1 maintains the superhydrophilic-superhydrophobic state after the tenth self-healing, whereas comparative example 1 becomes the superhydrophilic-oleophobic state after the second self-healing, to the superhydrophilic-oleophobic state after the tenth self-healing;
this is because example 1 forms a chitosan nanoparticle-loaded polydopamine microcapsule that can slowly release a hydrophilic-oleophobic compound (Capstone FS-60) to the substrate surface, achieving a greater number of self-healing. In comparative example 1, however, the polydopamine coating was modified on the surface of the fabric, and then the chitosan nanoparticle was adhered with the polydopamine coating, and the chitosan nanoparticle would excessively release the hydrophilic-oleophobic compound (Capstone FS-60) to the surface of the substrate during the self-healing process, resulting in a large loss of the hydrophilic-oleophobic compound (Capstone FS-60), so the self-healing effect was poor.

Claims (6)

1. The preparation method of the super-hydrophilic-super-oleophobic self-healing fabric is characterized by comprising the following steps of:
(1) Preparing chitosan acetic acid solution: dissolving chitosan in acetic acid solution;
(2) Preparing a super-hydrophilic-super-oleophobic solution: adding Capstone FS-60 into the chitosan acetic acid solution prepared in the step (1), then adding sodium tripolyphosphate, and uniformly stirring at normal temperature;
(3) Adding dopamine into the super-hydrophilic-super-oleophobic solution prepared in the step (2), and uniformly stirring for 8-24 hours at normal temperature in an ultraviolet box;
(4) Immersing the fabric into the solution prepared in the step (3), and heating for 15-30 minutes at 80-120 ℃ to obtain the required super-hydrophilic-super-oleophobic self-healing fabric;
in the step (1), the addition amount of the chitosan is 1-5wt%;
in the step (2), the addition amount of the Capstone FS-60 is 1-3wt%;
in the step (2), the adding amount of the sodium tripolyphosphate is 1-5wt%;
in the step (3), the addition amount of the dopamine is 1-5 wt%.
2. The method of manufacturing according to claim 1, characterized in that: in the step (1), the concentration of the acetic acid solution is 1-3 wt%.
3. The method of manufacturing according to claim 1, characterized in that: in the step (1), the deacetylation degree of the chitosan is 85% -95%, and the molecular weight is 20-150 ten thousand.
4. The method of manufacturing according to claim 1, characterized in that: in the step (3), the setting parameters of the ultraviolet box are as follows: 254/365nm, 50-100 mW cm -2 。
5. The production method according to any one of claims 1 to 4, characterized in that: in the step (4), the fabric is soaked in the solution prepared in the step (3) for 1-5 minutes and then heated.
6. A superhydrophilic-superoleophobic self-healing fabric produced by the production method according to any one of claims 1 to 5.
CN202210511107.7A 2022-05-11 2022-05-11 Super-hydrophilic-super-oleophobic self-healing fabric and preparation method thereof Active CN114703665B (en)

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CN103316507B (en) * 2013-06-06 2014-12-03 华南理工大学 Super-hydrophilic and underwater-super-oleophobic oil-water separation mesh membrane, and preparation method and application thereof
CN106860422A (en) * 2015-12-10 2017-06-20 中国科学院大连化学物理研究所 Alginic acid alkali-polycation microcapsules and its for bioactivator embedding
CN110004710B (en) * 2019-03-26 2020-04-28 华南理工大学 Super-hydrophilic underwater super-oleophobic and super-oleophilic oil super-hydrophobic fabric and preparation method and application thereof
CN110372886B (en) * 2019-06-28 2021-12-17 浙江工业大学 Chitosan/polysulfonyl betaine double-network self-healing hydrogel and preparation method thereof
CN110983791B (en) * 2019-12-10 2022-03-11 上海驰纺材料科技有限公司 Microcapsule with integrated ultraviolet shielding function and preparation method thereof

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