CN105670565A - Self-clean material having self-repair function and preparation method thereof - Google Patents
Self-clean material having self-repair function and preparation method thereof Download PDFInfo
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- CN105670565A CN105670565A CN201410656576.3A CN201410656576A CN105670565A CN 105670565 A CN105670565 A CN 105670565A CN 201410656576 A CN201410656576 A CN 201410656576A CN 105670565 A CN105670565 A CN 105670565A
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Abstract
The present invention discloses a self-clean material having a self-repair function. The material consists of 40-70 wt% of polydopamine capsule wall and 30-60 wt% of core material low in surface energy. An ultrasonic emulsion of the core material low in surface energy is added into a dopamine solution, and the mixture is allowed to stand to obtain the self-clean material having the self-repair function. The material can be deposited on the surface of various substrates and has excellent antifouling and self-cleaning effects. After surface is damaged, thousands of self-cleaning functional repairs can be conducted.
Description
Technical field
The present invention relates to a kind of self-cleaning material and its preparation method with self-repair function.
Background technology
Nature exists the example much with automatically cleaning characteristic, is exactly the most typically lotus leaf. The contaminant particles such as the dust of lotus leaf surface, when lotus leaf surface freely rolls, can be taken away by the globule, thus makes lotus leaf surface keep clean, and this kind of automatically cleaning characteristic of lotus leaf surface is called " lotus leaf effect " by people. Research finds, the micron-nanometer two-stage structure of lotus leaf surface and the comprehensive action of hydrophobicity low-surface energy substance thereof are the basic reasons that its automatically cleaning characteristic realizes. Self-cleaning surface is subject to extensive concern because having the advantage such as antifouling, cleaning, sticky in industry and daily life. By the inspiration of lotus leaf, based on the coarse structure that people are formed by surface fiber of the fabric, build nanoscale rough structure at its micro-scale surface, obtain micron-nanometer two-stage structure, and modified by low-surface energy substance thus obtain the fabric with automatically cleaning characteristic. This kind fabric extensively for waterproof, clothes and the finishing material such as grease proofing, antifouling, can have wide exploitation and application prospect. But, when this kind fabric is subject to machinery scraping, weares and teares or is subject to chemical action destruction, the forfeiture being easy to lose its hydrophobic function and cause its automatically cleaning characteristic, this makes the use of such self-cleaning fabrics be greatly limited. But can select to introduce the material with high-adhesiveness and surface bonding firmly with head it off; PhillipB.Messersmith in 2007 reports that on Science periodical poly-Dopamine HCL can deposit to various substrate surface (Science, 2007,318,426-430). Poly-Dopamine HCL can be selected as tack coat to improve the bonding force of material and substrate, and the oxypolymerization of Dopamine HCL being combined with template of simple and effective can prepare poly-Dopamine HCL capsule, study it and slow release behavior (Chem.Commun.2009,6789-6791); And the forfeiture problem of self-cleaning surface function, this effective method of selfreparing can be adopted, the surperficial self-healing of destruction can be made, it is to increase long-term stability and work-ing life.
Summary of the invention
It is an object of the invention to provide a kind of can the self-cleaning material with self-repair function of repeatedly selfreparing.
A kind of self-cleaning material with self-repair function, it is characterised in that: this material is made up of the poly-Dopamine HCL capsule wall of 40-70wt% and 30-60wt% low surface energy core.
Described low surface energy core is long chain alkane and derivative thereof, is specifically selected from cetylamine, n-Hexadecane, lauryl mercaptan, stearylamine, amino dodecane, dodecane, hexyl mercaptans, silicone oil or fluorochemicals.
There is the preparation method of the self-cleaning material of self-repair function: be added in dopamine solution by the ultrasonic emulsification liquid of low surface energy core, leave standstill the self-cleaning material that can obtain having self-repair function.
The capsule size of the described self-cleaning material with self-repair function is 50nm-5 μm.
The described self-cleaning material with self-repair function can in-situ polymerization deposition to substrate surface, described substrate is glass, timber, fabric, plastics, rubber or wire netting.
The hydrophobicity on its surface is destroyed on the self-cleaning material surface with self-repair function by modes such as Cement Composite Treated by Plasma, atomic oxygen irradiation, sand papering, UV-irradiation, room temperature the hydrophobicity recovered or heat certain temperature voluntarily and recover surperficial can be placed after self-cleaning material surface breakdown, time of recovery is 10-50 minute, and this self-cleaning material surface breakdown-recovery cycle index reaches as high as thousands of times, the long-term stability on surface can be improved.
Compared with prior art, the present invention has the following advantages: (1) self-cleaning material can be deposited on various substrate surface: smooth surface, the surface with microtexture; Water-wetted surface, hydrophobic surface; (2) preparation technology involved by is simple, adopts the method for oxypolymerization to prepare the encapsulated low surfacing of original position; (3) surface has excellent antifouling automatically cleaning effect, and water stain, milk, fruit juice, coffee etc. are not glued in surface, and the dust on surface can rinse through water, and surface is not spontaneously wet out by water; (4) surface can carry out the reparation of the self-cleaning function of thousands of times after destroying: surface is after polishing, plasma body, irradiation destroy, and the self-cleaning function on surface all can be repaired; (5) fabric face that self-cleaning material is modified is combined with substrate firmly: surface is after washing machine washs 50 times, and any change does not occur self-cleaning surface function substantially.
Accompanying drawing explanation
Fig. 1 is the wetting behavior after the low surface energy self-cleaning material of various finishing selfreparing. A-fabric, b-sponge, c-printer paper, d-PET, e-glass.
Fig. 2 is the reparation behavior after surface abrasion.
Embodiment
Embodiment 1
After stearylamine aqueous solution ultrasonic emulsification, emulsion is joined in the dopamine solution of 2.0mg/mL, and solution will be put into clean fabric, after placing 3h, obtain the fabric of the encapsulated stearylamine of finishing, finally adopt distilled water repeatedly to rinse, dry after cleaning. Capsule is of a size of 750nm, and the contact angle of water, fruit juice etc. is greater than 150 by dried sample surfaceso, water, fruit juice, milk, coffee etc. are not all glued by surface, can play cleaning action. After dry surface Cement Composite Treated by Plasma, surface is changed into ultra-hydrophilic surface by super-hydrophobic, and the super-hydrophobicity placing 10h or heat treated 30min surface in room temperature is recovered. And the ultra-hydrophobicity through 100 plasma treatment rear surfaces still can recover voluntarily.
Embodiment 2
After n-Hexadecane aqueous solution ultrasonic emulsification, emulsion is joined in the dopamine solution of 0.5mg/mL, and solution will be put into clean fabric, after placing 2h, obtain the fabric of the encapsulated stearylamine of finishing, finally adopt distilled water repeatedly to rinse, dry after cleaning. Capsule is of a size of 100nm, and the contact angle of water, fruit juice etc. is greater than 150 ° by dried sample surfaces, and water, fruit juice, milk, coffee etc. are not all glued by surface, can play cleaning action. Dry surface is after the load of 1N rubs, and surface is changed into ultra-hydrophilic surface by super-hydrophobic, and the super-hydrophobicity placing 6h or heat treated 10min surface in room temperature is recovered.And the ultra-hydrophobicity through 1000 plasma treatment rear surfaces still can recover voluntarily.
Embodiment 3
After hexyl mercaptans aqueous solution ultrasonic emulsification, emulsion is joined in the dopamine solution of 0.2mg/mL, and solution will be put into clean fabric, after placing 2h, obtain the fabric of the encapsulated stearylamine of finishing, finally adopt distilled water repeatedly to rinse, dry after cleaning. Capsule is of a size of 50nm, and the contact angle of water, fruit juice etc. is greater than 150 ° by dried sample surfaces, and water, fruit juice, milk, coffee etc. are not all glued by surface, can play cleaning action. Dry surface is after sand papering, and surface is changed into ultra-hydrophilic surface by super-hydrophobic, and the super-hydrophobicity placing 6h or heat treated 10min surface in room temperature is recovered. And the ultra-hydrophobicity through 1000 plasma treatment rear surfaces still can recover voluntarily.
Embodiment 4
After methyl-silicone oil aqueous solution ultrasonic emulsification, emulsion is joined in the dopamine solution of 3.0mg/mL, and solution will be put into clean fabric, after placing 2h, obtain the fabric of the encapsulated stearylamine of finishing, finally adopt distilled water repeatedly to rinse, dry after cleaning. Capsule is of a size of 2.5 μm, and the contact angle of water, fruit juice etc. is greater than 150 ° by dried sample surfaces, and water, fruit juice, milk, coffee etc. are not all glued by surface, can play cleaning action. After dry surface washs 50 times in washing machine, surface still keeps super water-based.
Embodiment 5
After n-Hexadecane aqueous solution ultrasonic emulsification, emulsion is joined in the dopamine solution of 1.0mg/mL, and solution will be put into clean glass, after placing 2h, obtain the glass of the encapsulated stearylamine of finishing, finally adopt distilled water repeatedly to rinse, dry after cleaning. Capsule is of a size of 460nm, and the contact angle of water is 110 ° by dried sample surfaces, and water, fruit juice, milk, coffee etc. are not all glued by surface, some soil are placed on surface in addition, water droplet is dripped to surface, and the soil on surface can be walked by water punching, and surface has self-cleaning function.
Embodiment 6
After PFO aqueous solution ultrasonic emulsification, emulsion is joined in the dopamine solution of 4.0mg/mL, and solution will be put into clean polyethylene terephthalate (PET), after placing 10h, obtain the PET of the encapsulated stearylamine of finishing, distilled water is finally adopted repeatedly to rinse, dry after cleaning. Capsule is of a size of 4.7 μm, and the contact angle of water is 118 ° by dried sample surfaces, and all various leaves such as water, fruit juice, milk, coffee, edible oil are dripped and do not glue by surface.
Embodiment 7
After whiteruss solution ultrasonic emulsification, emulsion is joined in the dopamine solution of 1.5mg/mL, and solution will be put into clean glass, after placing 20h, obtain the glass of the encapsulated stearylamine of finishing, finally adopt distilled water repeatedly to rinse, dry after cleaning. Capsule is of a size of 630nm, and the contact angle of water is 112 ° by dried sample surfaces, and water, fruit juice, milk, coffee etc. are not all glued by surface, some soil are placed on surface in addition, water droplet is dripped to surface, and the soil on surface can be walked by water punching, and surface has self-cleaning function.
Embodiment 8
After whiteruss solution ultrasonic emulsification, emulsion is joined in the dopamine solution of 1.5mg/mL, and solution will be put into sponge, after placing 20h, obtain the sponge of the encapsulated stearylamine of finishing, finally adopt distilled water repeatedly to rinse, dry after cleaning. Capsule is of a size of 630nm, and the contact angle of water is 152 ° by dried sample surfaces, and the super hydrophobic surface of this kind of porous can carry out oily water separation.
Claims (6)
1. one kind has the self-cleaning material of self-repair function, it is characterised in that: this material is made up of the poly-Dopamine HCL capsule wall of 40-70wt% and 30-60wt% low surface energy core.
2. material as claimed in claim 1, it is characterised in that: described low surface energy core is long chain alkane and derivative thereof.
3. material as claimed in claim 2, it is characterised in that: described long chain alkane and derivative thereof are cetylamine, n-Hexadecane, lauryl mercaptan, stearylamine, amino dodecane, dodecane, hexyl mercaptans, silicone oil or fluorochemicals.
4. material as claimed in claim 1, it is characterised in that: the capsule size of described material is 50nm-5 μm.
5. material as claimed in claim 1, it is characterised in that: described material can in-situ polymerization deposition to substrate surface, described substrate is glass, timber, fabric, plastics, rubber or wire netting.
6. the preparation method of material as claimed in claim 1, it is characterised in that: the ultrasonic emulsification liquid of low surface energy core is added in dopamine solution, leaves standstill the self-cleaning material that can obtain having self-repair function.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110358345A (en) * | 2019-08-21 | 2019-10-22 | 中国科学院兰州化学物理研究所 | A kind of microcapsule-type anti-fouling agent and preparation method thereof, a kind of antifouling paint and preparation method thereof |
| CN111470785A (en) * | 2020-04-07 | 2020-07-31 | 东莞奔迅汽车玻璃有限公司 | Self-cleaning glass |
| CN111549568A (en) * | 2020-05-13 | 2020-08-18 | 兰州交通大学 | Preparation method of super-hydrophobic paper |
| CN112045808A (en) * | 2019-06-06 | 2020-12-08 | 广西大学 | Bionic super-hydrophobic wood and preparation method thereof |
| CN112376273A (en) * | 2020-11-25 | 2021-02-19 | 兰州交通大学 | Preparation method of super-hydrophobic fabric |
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| CN102149450A (en) * | 2008-07-10 | 2011-08-10 | 德克萨斯州立大学董事会 | Water purification membranes with improved fouling resistance |
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| CN103951843A (en) * | 2014-03-11 | 2014-07-30 | 中国科学院长春应用化学研究所 | Preparation method of extrusion resistant, fire preventing and super hydrophobic sponge |
| CN104018141A (en) * | 2014-06-13 | 2014-09-03 | 哈尔滨工业大学 | Preparation method and application of flexible and durable super-hydrophobic coating |
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| CN102149450A (en) * | 2008-07-10 | 2011-08-10 | 德克萨斯州立大学董事会 | Water purification membranes with improved fouling resistance |
| EP2246439A1 (en) * | 2009-04-24 | 2010-11-03 | Lifescan Scotland Limited | Analytical test strips |
| CN102961893A (en) * | 2012-11-07 | 2013-03-13 | 清华大学 | Super-hydrophobic and super-oleophylic oil-water separating mesh membrane and preparation method thereof |
| CN103951843A (en) * | 2014-03-11 | 2014-07-30 | 中国科学院长春应用化学研究所 | Preparation method of extrusion resistant, fire preventing and super hydrophobic sponge |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112045808A (en) * | 2019-06-06 | 2020-12-08 | 广西大学 | Bionic super-hydrophobic wood and preparation method thereof |
| CN110358345A (en) * | 2019-08-21 | 2019-10-22 | 中国科学院兰州化学物理研究所 | A kind of microcapsule-type anti-fouling agent and preparation method thereof, a kind of antifouling paint and preparation method thereof |
| CN111470785A (en) * | 2020-04-07 | 2020-07-31 | 东莞奔迅汽车玻璃有限公司 | Self-cleaning glass |
| CN111470785B (en) * | 2020-04-07 | 2024-04-23 | 东莞奔迅汽车玻璃有限公司 | Self-cleaning glass |
| CN111549568A (en) * | 2020-05-13 | 2020-08-18 | 兰州交通大学 | Preparation method of super-hydrophobic paper |
| CN112376273A (en) * | 2020-11-25 | 2021-02-19 | 兰州交通大学 | Preparation method of super-hydrophobic fabric |
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Application publication date: 20160615 |