CN102154834B - Simple and easy preparation method for super-hydrophobic fiber and textile and application thereof - Google Patents
Simple and easy preparation method for super-hydrophobic fiber and textile and application thereof Download PDFInfo
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- CN102154834B CN102154834B CN 201010593300 CN201010593300A CN102154834B CN 102154834 B CN102154834 B CN 102154834B CN 201010593300 CN201010593300 CN 201010593300 CN 201010593300 A CN201010593300 A CN 201010593300A CN 102154834 B CN102154834 B CN 102154834B
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Abstract
The invention relates to a simple and easy preparation method for super-hydrophobic fiber and textile with high contact angle and low rolling angle and application thereof. Surface chemical modification is directly carried out on intrinsic coarse structures on the surface of the fiber and textile so as to prepare a fiber product with super-hydrophobic performance; the method comprises the following steps of: firstly, cleanly washing materials, then carrying out isocyanate modification on the material, and finally modifying low surface energy material. The raw material is cheap and is easily available; reaction conditions are relatively mild; the operation is simple; and the requirement on the device is low. The obtain product has good super-hydrophobic performance; the contact angle of 10 microliter of water is 156 degrees; and the product has wide application in fields of self-cleaning fibers and textiles.
Description
Technical field
The invention belongs to the manufacture field of functional material, relate to a kind of the have superhydrophobic fibers of high contact angle and low roll angle and the simple method for preparing of fabric specifically, the invention still further relates to the purposes of this superhydrophobic fibers and fabric.
Background technology
Super hydrophobic surface refers to that water contact angle is greater than 150 °, the roll angle surface less than 10 °.Copy the super-hydrophobic phenomenon of nature (as lotus leaf surface, insect wing, petal etc.) constructing super-drainage Research on surface, have important application value in the automatically cleaning field.The factor that influences surface of solids wettability mainly contains two: the one, and surface free energy, the 2nd, surface microstructure.At present, the method for preparing super hydrophobic surface mainly contains sol-gel process, plasma processing method, heterogeneous nucleation method, etching method, vapour deposition process, electrochemical process, self-assembly method etc.All there are shortcomings such as preparation technology's long flow path, consersion unit complexity, raw material be high in these methods and are difficult to realize industrialization.
Summary of the invention
Technical problem: the purpose of this invention is to provide a kind of superhydrophobic fibers, process for making such fabric, overcome the desired experiment condition harshness of conventional method, cost height, be difficult to use in many shortcomings such as large-scale production in the industry, solved above technical problem with simple preparation method.
Technical scheme:
Biomimetic super hydrophobic surface can be realized by two kinds of methods: the one, at the material of rough surface modification low-surface-energy; Another kind method is to utilize hydrophobic material to make up surface roughness.Fiber, fabric itself have very big roughness and multi-level coarse structure, in order to obtain super-hydrophobic fiber, fabric, need not at its surface-assembled or bonding nano particle only needs to modify an effective low-surface-energy material and gets final product with further increase surface roughness.Can obtain superhydrophobic fibers, fabric by this method, greater than 150 degree, roll angle is less than 5 degree at its surperficial contact angle for water droplet.
Fiber, fabric with ultra-hydrophobicity, this ultra-hydrophobicity be by hydroxylated fiber, fabric through isocyanate-modified, carry out finishing with the low-surface-energy material that contains active hydrogen again and obtain.
Described isocyanates is toluene di-isocyanate(TDI) (TDI), diphenyl-methane-4,4 '-vulcabond (MDI), poly methylene poly phenyl poly isocyanate (PAPI), hexamethylene diisocyanate (HDI), XDI (XDI), isofoer diisocyanate (IPDI), dicyclohexyl methyl hydride-4, one or more in 4 '-vulcabond (HMDI), trimethyl hexamethylene diisocyanate (TMDI), the hydrogenated tolylene diisocyanate (HTDI).
Described low-surface-energy material is hydroxy silicon oil, hydroxyl terminated poly-butadiene, carbon number at the pure and mild long-chain amine of the long-chain more than ten (sulphur) and contains in the fluorine-containing low-surface-energy material of active hydrogen one or more; The fluorine-containing low-surface-energy material that contains active hydrogen is for to long-chain (sulphur) alcohol of trifluoro-methoxyaniline and derivative thereof, 4-(4-Trifluoromethoxyphen-l azo) phenol derivmives blend biology, fluoro or in the amine one or more.
Described fiber, fabric are that hydroxyl or amino fiber, fabric are rich in natural, artificial or synthetic surface.
Fiber, process for making such fabric with ultra-hydrophobicity comprise following steps:
(1) material preliminary treatment: fiber, fabric water or ethanol, acetone are cleaned up dried for standby;
(2) isocyanate-modified: with clean dry fiber, the isocyanate solution that fabric places 1wt%, N
2Protection down, dipping reaction 1h in 60～80 ℃ of water-baths or the oil bath takes out, and uses solvent wash;
(3) low-surface-energy modification: with the fiber of isocyanate-modified, the low-surface-energy substance solution that fabric places 1wt%, at N
2Protection is down reacted 1h in 60～80 ℃ of water-baths or the oil bath, takes out, and uses solvent wash, drying.
Used solvent is the nontoxic lower toxicity organic solvent of boiling point about 80 ℃ among the preparation method, a kind of as in ethyl acetate, benzinum, hexane, heptane, petroleum benzin, industrial naptha, toluene, the acetone; Low-surface-energy is handled available solvent such as the alcohols that contains active hydrogen in back and is washed.
Drying condition among the preparation method can be: (1) normal temperature and pressure drying 12～48h; (2) in the vacuum drying chamber, 25～100 ℃ of down dry 0.5～10h.
Beneficial effect: the present invention is an innovation to the technology of preparing of superhydrophobic fibers, fabric, and the ultra-hydrophobicity of resulting product is very good.The present invention has following advantage:
(1) isocyanates selected for use of the present invention is the industrial chemicals commonly used of producing polyurethane, and cheap and easy to get, range of choice is quite extensive.
(2) the low-surface-energy material selected for use of the present invention is long-chain hydrophobic substance or the fluorine-containing low-surface-energy material that contains active hydrogen, and range of choice is quite extensive.
(3) the present invention utilizes the active chemical property of isocyanates, directly modifies the low-surface-energy material at fiber, the fabric face of isocyanate-modified, is preparation superhydrophobic fibers, the very effective method of fabric.Need not introduce nano particle at fiber, fabric face, there be not coming off of nano particle, thereby improve its surface stability, make preparation superhydrophobic fibers, fabric become simple unusually, overcome the loaded down with trivial details difficulty of experiment condition harshness, preparation process in the conventional method.
(4) surfacing of gained of the present invention has good ultra-hydrophobicity, and the contact angle of 10mg water reaches 156 degree, and the roll angle of 10mg water is less than 5 degree.
(5) to use difficulty little in the present invention, so long as fiber and the goods thereof of active hydrogen are rich in the surface, just can be achieved by the material of modifying low-surface-energy after the isocyanate-modified again.
This super hydrophobic material can both well be used in waterproof or hydrophobic stationery and concrete material surface such as goods, cotton and goods thereof, various cellulose membrane material, cotton/chemical fibre blended product, hydrophobic fiber cellulosic material and composite and functional material etc. thereof, also can extensive use in the technical fields such as functionalization of function carbon fiber, Graphene, silica fibre.
Description of drawings
The digital photograph of water droplet on the super-hydrophobic cotton thread of Fig. 1
The digital photograph of water droplet on the super-hydrophobic fabric of Fig. 2
The water contact angle of Fig. 3 superhydrophobic fibers, fabric
The specific embodiment
Embodiment 1:
The material preliminary treatment: after fiber, fabric water or ethanol, acetone cleaned up, dried for standby;
Isocyanate-modified: with clean dry fiber, the isocyanate solution (as Toluene-2,4-diisocyanate, the ethyl acetate solution of 4-vulcabond) that fabric places 1wt%, N
2Protection is down reacted 1h in 60～80 ℃ of water-baths or the oil bath, takes out, with solvent (as ethyl acetate) washing;
Low-surface-energy modification: with the fiber of isocyanate-modified, the low-surface-energy substance solution (as the ethyl acetate solution of hydroxy silicon oil) that fabric places 1wt%, at N
2Protection is down reacted 1h in 60～80 ℃ of water-baths or the oil bath, takes out, with solvent (as ethyl acetate, ethanol) washing, 50 ° of vacuumize 2h.
Embodiment 2:
The material preliminary treatment: after fiber, fabric water or ethanol, acetone cleaned up, dried for standby;
The preparation of isocyanate-terminated low-surface-energy material: as the preparation of isocyanate-terminated silicone oil, with hydroxy silicon oil and Toluene-2,4-diisocyanate, the 4-vulcabond adds in the ethyl acetate solution, and the control isocyanic acid is 2: 1 with the mol ratio with hydroxyl, N
2Protection is down reacted 1h in 60～80 ℃ of water-baths or the oil bath, and is stand-by;
The surface treatment of material: fiber, fabric are put into the ethyl acetate solution of isocyanate-terminated silicone oil, N
2Protection is down reacted 1h in 60～80 ℃ of water-baths or the oil bath, takes out, with solvent (as ethyl acetate, ethanol) washing, 50 ° of vacuumize 2h.
Claims (2)
1. the simple method for preparing of superhydrophobic fibers or fabric is characterized in that:
(1) material preliminary treatment: after fiber or fabric water or ethanol, acetone cleaned up, dried for standby;
(2) preparation of isocyanate-terminated low-surface-energy material: with hydroxy silicon oil and Toluene-2,4-diisocyanate, the 4-vulcabond adds in the ethyl acetate solution, and the mol ratio of control isocyano and hydroxyl is 2: 1, N
2Protection is down reacted 1h in 60～80 ℃ of water-baths or the oil bath, and is stand-by;
(3) surface treatment of material: the fiber that will handle or fabric are put into the ethyl acetate solution of isocyanate-terminated silicone oil, N
2Protection is down reacted 1h in 60～80 ℃ of water-baths or the oil bath, takes out, with ethyl acetate or ethanol washing, 50 ℃ of vacuumize 2h.
2. the superhydrophobic fibers of method according to claim 1 preparation or the application of fabric, it is characterized in that for:
(1) waterproof or hydrophobic stationery and goods thereof;
(2) cotton and goods thereof;
(3) various cellulose membrane materials;
(4) cotton/chemical fibre blended product;
(5) other various composites that prepared by the hydrophobic fiber cellulosic material;
(6) other various materials that prepared by hydroxyl or amino modified artificial fibre.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010593300 CN102154834B (en) | 2010-12-17 | 2010-12-17 | Simple and easy preparation method for super-hydrophobic fiber and textile and application thereof |
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| CN 201010593300 CN102154834B (en) | 2010-12-17 | 2010-12-17 | Simple and easy preparation method for super-hydrophobic fiber and textile and application thereof |
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| CN102154834B true CN102154834B (en) | 2013-07-17 |
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| CN103435738B (en) * | 2013-04-15 | 2016-06-15 | 多喜爱家纺股份有限公司 | A kind of preparation technology of Medical face fabric activity three anti-auxiliary agents |
| CN103590236B (en) * | 2013-10-24 | 2015-05-06 | 浙江理工大学 | Preparation method of super-hydrophobic surface of fabric |
| CN104646258B (en) * | 2013-11-20 | 2017-05-03 | 中国科学院海洋研究所 | Method for quickly preparing super hydrophobic membrane |
| CN104790202B (en) * | 2015-04-22 | 2017-03-15 | 广州大学 | A kind of floride-free durable super-hydrophobic property finishing agent for cotton fabric and its method for finishing of cotton textiles |
| CN105970661B (en) * | 2016-07-20 | 2017-12-22 | 陕西科技大学 | A kind of production method of super-hydrophobic superfine fiber chemical leather |
| CN106480741A (en) * | 2016-09-22 | 2017-03-08 | 广州大学 | A kind of method for sorting of multifunctional textile product |
| KR102528830B1 (en) * | 2017-02-09 | 2023-05-09 | 에보니크 오퍼레이션즈 게엠베하 | Polymers for hydrophobic and oleophobic textile finishing |
| CN106883588B (en) * | 2017-02-28 | 2019-11-15 | 华南理工大学 | One kind is for super-hydrophobic luffa of water-oil separating and preparation method thereof |
| CN109908774B (en) * | 2019-01-23 | 2021-09-03 | 浙江理工大学 | Using SiO2Method for preparing super-hydrophobic microporous membrane on surface of particle modified polyurethane |
| CN110227283B (en) * | 2019-06-24 | 2021-06-08 | 齐鲁工业大学 | Preparation method of super-hydrophobic lignin sponge with oil-water separation function |
| CN110924173A (en) * | 2019-11-18 | 2020-03-27 | 五邑大学 | Preparation method of super-hydrophobic oleophylic polyester fabric |
| CN111455656A (en) * | 2020-04-20 | 2020-07-28 | 陕西科技大学 | Super-hydrophobic cotton fiber textile and preparation method thereof |
| CN111692459A (en) * | 2020-05-28 | 2020-09-22 | 上海海事大学 | Fluorinated silica nanoparticle composite cucurbituril sponge vacuum insulation board core material and preparation method thereof |
| CN112281493A (en) * | 2020-11-16 | 2021-01-29 | 五邑大学 | Fluoride-free waterproof finishing agent and preparation method thereof |
| CN115538150B (en) * | 2022-09-22 | 2024-03-29 | 韶关学院 | Super-hydrophobic and super-oleophylic fabric and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101228312A (en) * | 2005-06-03 | 2008-07-23 | 美利肯公司 | Textile substrates having layered finishing structure |
| CN101831801A (en) * | 2010-05-07 | 2010-09-15 | 黄山华芮科技有限公司 | Durable cellulose fiber and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101228312A (en) * | 2005-06-03 | 2008-07-23 | 美利肯公司 | Textile substrates having layered finishing structure |
| CN101831801A (en) * | 2010-05-07 | 2010-09-15 | 黄山华芮科技有限公司 | Durable cellulose fiber and application thereof |
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Inventor after: Xu Weijian Inventor after: Guo Rui Inventor after: Xiong Yuanqin Inventor after: Pan Shuaijun Inventor after: Peng Jinyang Inventor before: Xu Weijian Inventor before: Pan Shuaijun Inventor before: Xiong Yuanqin Inventor before: Guo Rui Inventor before: Peng Jinyang |
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