CN101220165B - Underwater ultra-oleophobic polyalcohol membrane of bionic structure and method for producing the same - Google Patents
Underwater ultra-oleophobic polyalcohol membrane of bionic structure and method for producing the same Download PDFInfo
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- CN101220165B CN101220165B CN2007103037794A CN200710303779A CN101220165B CN 101220165 B CN101220165 B CN 101220165B CN 2007103037794 A CN2007103037794 A CN 2007103037794A CN 200710303779 A CN200710303779 A CN 200710303779A CN 101220165 B CN101220165 B CN 101220165B
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Abstract
The invention pertains to the field of super oleophobic polymer membrane, which more particularly relates to an underwater super oleophobic polymer membrane that has bionic structure and a preparationmethod thereof. The non-fluoric underwater super oleophobic polymer membrane with the bionic structure uses scale of fishes as a natural template and carries out primary forming with polydimethylsilo xane so as to obtain a template that has scale negative structure, then secondary forming is carried out by using in-situ polymerization of monomer solution of polymer and the underwater super oleophobic polymer membrane that has the bionic structure is obtained. The polymer membrane duplicates the micronano composite structure of the scale and shows super oleophobic property under water, namely acontact angle to oil is greater than 150 degrees. The super oleophobic polymer membrane of the invention has no harm to human body and no pollution to the environment.
Description
Technical field
The invention belongs to the ultra-oleophobic polyalcohol membrane field, particularly underwater ultra-oleophobic polyalcohol membrane of biomimetic features and preparation method thereof.
Background technology
Wetting property is a key property of solid surface.The solid that possesses super oleophobic properties plays an important role in daily life and scientific research.The surface that how to prepare super oleophobic is the focus that people study always.The material of modifying low surface energy in the substrate with micron and nanometer composite structure is that people prepare one of important means of super oleophobic material.This type of bibliographical information has " super oleophobic surface " (Tsujii, K., Yamamoto, T., Onda, the T.﹠amp that delivers on " applied chemistry " magazine 1997,36,1011～1012; Shibuichi, S.Super oil-repellent surfaces.Angew.Chem.Int.Ed.); " super two carbon nano-tube films of dredging " (Li, H.J.et a1.Super-" amphiphobic " the aligned carbon nanotube films.Angew.Chem.Int.Ed.) that delivers on " applied chemistry " magazine 2001,40,1743～1746; " advanced material " magazine 2004,16, " constructing the method for super-double-hydrophobic surface " of delivering on 302～305 (Xie, Q.D.et al.Facile creation of a super-amphiphobiccoating surface with bionic microstructure.Adv.Mater.) with biomimetic features; " the super-hydrophobic super oleophobic polythiophene film of synthesizing stable " (Nicolas, M., Guittard, the F.﹠amp that delivers on " applied chemistry " magazine 2006,45,2251～2254; G é ribaldi, S.Synthesis of stable super water-andoil-repellent polythiophene films.Angew.Chem.Int.Ed.).From this type of document as can be seen, the long chain alkane that the material of these low surface energies is normally fluorine-containing has toxicity and environment is had the character of pollution, and this has hindered the development of super oleophobic surface greatly.
The a lot of biologies of occurring in nature all have self-cleaning effect.For example lotus leaf surface has super-hydrophobic character, can take away the dust of leaf surfaces in the above when water droplet rolls.Equally, the fish in the water also has self-cleaning effect, also can keep the cleaning on own surface when fish freely moves about in water.The scale on its surface not only can reduce the friction to current, can play the effect that stops bacterium to contact with pollutent equally.Find that in the wetting property on fish surface fish scale has the character of super oleophobic under water by research oiliness drop.Therefore, the surface of bionical preparation with fish scale structure and character provides a new thinking for preparing novel super oleophobic material.
Summary of the invention
The objective of the invention is to overcome the super oleophobic material of preparation and can only use the defective of fluorochemicals, a kind of underwater ultra-oleophobic polyalcohol membrane of not fluorine-containing biomimetic features is provided.
Another object of the present invention is to provide a kind of preparation method of underwater ultra-oleophobic polyalcohol membrane of not fluorine-containing biomimetic features.
The underwater ultra-oleophobic polyalcohol membrane of not fluorine-containing biomimetic features of the present invention is that fish scale with fish is as natural template, carry out figuration one time by polydimethylsiloxane (PDMS), obtain having the template of the negative structure of fish scale, monomer solution in-situ polymerization with polymkeric substance carries out the secondary figuration again, obtains having the ultra-oleophobic polyalcohol membrane of fish scale structure.This polymeric film has duplicated the micron and nanometer composite structure of fish scale, shows the characteristic of excess of export oleophobic under water, promptly to the contact angle of oil greater than 150 °.
The underwater ultra-oleophobic polyalcohol membrane of not fluorine-containing biomimetic features of the present invention is the micron and nanometer composite structure that has the fish scale surface on the surface of polymeric film, swelling after absorbing water under water, this polymeric film takes place, form the composite membrane of one deck water and polymkeric substance coexistence at polymer film surface, this composite membrane shows the excess of export oleophobic property in water, promptly composite membrane to the contact angle of oil greater than 150 °.
Described polymkeric substance is a kind of in polyacrylamide, polyacrylic acid, sodium polyacrylate, polyacrylic acid potassium, poly-N,N-DMAA, poly-N-ethyl acrylamide, poly N-isopropyl acrylamide, poly N-vinyl pyrrolidone, the poly N-vinyl hexanolactam or greater than a kind of mixture.
The underwater ultra-oleophobic polyalcohol membrane of not fluorine-containing biomimetic features of the present invention is to adopt the method for turning over mould to be prepared, and this method may further comprise the steps:
1) fish-skin that will have a fish scale peels, and puts into gradient alcohol and dewaters, and puts into baking oven then and dries, and obtains the fish-skin that exsiccant has fish scale;
2) be that 8: 1～15: 1 mixed obtains mixture with polydimethylsiloxane and solidifying agent according to mass ratio, then mixture is poured on the fish-skin that has the fish scale one side that step 1) obtains, transferred to temperature after in vacuum vessel, vacuumizing and be in 70～80 ℃ the baking oven and solidify;
3) with step 2) polydimethylsiloxane after solidifying and the mixture of solidifying agent and the fish-skin that has a fish scale peel off, and obtains the mixture template that the surface has the solidified polydimethylsiloxane and the solidifying agent of fish scale antistructure;
4) with polymer monomer, initiator, linking agent, the water-soluble mixing solutions that obtains of catalyzer, then mixing solutions is poured in the mixture template of polydimethylsiloxane that step 3) obtains and solidifying agent, wherein polymer monomer quality percentage composition is 10%～80% in the mixing solutions, initiator quality percentage composition is 0.1%～1%, linking agent quality percentage composition is 0.1%～1%, the catalyst quality percentage composition is 0%～0.1%, and surplus is a water;
5) with wavelength being the ultraviolet irradiation step 4 of 365nm) mixing solutions on the template makes polymer monomer generation polymerization, the polydimethylsiloxane after polymkeric substance and the curing and the mixture template of solidifying agent are peeled off, obtained having the underwater ultra-oleophobic polyalcohol membrane of fish scale structure;
Or the template that step 4) has a mixing solutions is placed temperature is that 4～80 ℃ environment polymerization is after 1～24 hour, the polydimethylsiloxane after polymkeric substance and the curing and the mixture template of solidifying agent are peeled off, obtained having the underwater ultra-oleophobic polyalcohol membrane of fish scale structure.
The mass concentration of described gradient alcohol is preferably 50%, 70%, 85%, 95%, 100%.
Described polymer monomer material is a kind of in acrylamide, vinylformic acid, sodium acrylate, potassium acrylate, N,N-DMAA, N-ethyl acrylamide, N-N-isopropylacrylamide, N-vinyl pyrrolidone, the N-caprolactam or greater than a kind of mixture.
Described initiator is 2,2-diethoxy acetophenone, Ammonium Persulfate 98.5, Potassium Persulphate or Sodium Persulfate.
Described linking agent is N, N '-methylene-bisacrylamide.
Described catalyzer is N, N, N ', N '-tetramethyl-diethylamine.
After the used fish scale of the present invention passes through figuration of PDMS, the reusable repeatedly figuration that carries out.
The present invention has following characteristics:
(1) prepared underwater ultra-oleophobic polyalcohol membrane has micro-nano compound coarse structure, and this ultra-oleophobic polyalcohol membrane shows the excess of export oleophobic property under water, promptly to the contact angle of oil greater than 150 °.
(2) prepared underwater ultra-oleophobic polyalcohol membrane is to no any infringement of human body and environmentally safe.
(3) prepared underwater ultra-oleophobic polyalcohol membrane pattern is controlled, by using natural fish scale as template, can obtain to have the polymer surfaces of fish scale structure.
(4) prepared underwater ultra-oleophobic polyalcohol membrane has the character of hydrogel, can absorb water under water and expand, and effect with water conservation, ultra-oleophobic polyalcohol membrane surface and water can form the composite membrane of one deck water and polymkeric substance coexistence in the time of under water, have strengthened the character of super oleophobic under water greatly.
(5) underwater ultra-oleophobic polyalcohol membrane with biomimetic features of the present invention is expected to be used to administer marine oil pollution, the oil transportation, and the transportation of microfluid surface etc.
(6) the underwater ultra-oleophobic polyalcohol membrane preparation method with biomimetic features of the present invention is simple, and raw material is easy to get, and is economical and practical; Used fish scale template can repeatedly be used.
Description of drawings
Fig. 1. the electron scanning micrograph of the underwater ultra-oleophobic polyalcohol membrane with biomimetic features of the embodiment of the invention 1.
Fig. 2. oil droplet is at the microscopic appearance photo on the underwater ultra-oleophobic polyalcohol membrane surface of the biomimetic features of the embodiment of the invention 1.
Embodiment
Embodiment 1
1) fish-skin that will have a fish scale peels, and puts into mass concentration successively and is 50%, 70%, 85%, 95%, 100% gradient alcohol and dewater, and the baking oven of putting into temperature then and be 50～70 ℃ is dried, and obtains the fish-skin that exsiccant has fish scale.
2) with PDMS (184 silicone elastomer base; DOW Corning Corporation is U.S.A) with solidifying agent (184 silicone elastomer curing agent; DOW Corning Corporation U.S.A) mixes according to mass ratio 10: 1, and mixture is poured on the fish-skin that the step 1) exsiccant has the fish scale one side, transfers to temperature after vacuumizing and be in 70～80 ℃ the baking oven to solidify 2 hours in vacuum vessel.
3) mixture of PDMS after will solidifying and solidifying agent is peeled off with the fish-skin that has fish scale, obtains showing the solidified PDMS with fish scale antistructure and the mixture template of solidifying agent.
4) with acrylamide, 2,2-diethoxy acetophenone, N, N '-methylene-bisacrylamide is water-soluble, mixing solutions is poured in the mixture of PDMS after the curing that step 3) obtains and solidifying agent.Acrylamide quality percentage composition is 40%, 2 in the mixing solutions, and 2-diethoxy acetophenone quality percentage composition is 0.8%, N, and N '-methylene-bisacrylamide quality percentage composition is 0.8%, and surplus is a water.
5) with wavelength be the ultraviolet irradiation step 4 of 365nm) mixed solution that obtains 30～90 minutes, make acrylamide generation polymerization.
6) PDMS after polyacrylamide polymers that step 5) is obtained and the curing and the mixture template of solidifying agent are peeled off, and obtain having the underwater ultra-oleophobic polyalcohol membrane of fish scale structure.
7) the polyacrylamide film of fish scale structure is put into water and wash repeatedly, remove unreacted acrylamide monomer.Have biomimetic features underwater ultra-oleophobic polyalcohol membrane electron scanning micrograph as shown in Figure 1; Oil droplet at the microscopic appearance photo on the underwater ultra-oleophobic polyalcohol membrane surface of biomimetic features as shown in Figure 2.
Embodiment 2
1) obtains exsiccant and have the fish-skin method of fish scale with embodiment 1.
2) with PDMS (184 silicone elastomer base; DOW Corning Corporation is U.S.A) with solidifying agent (184 silicone elastomer curing agent; DOW Corning Corporation U.S.A) mixes according to mass ratio 10: 1, and mixture is poured on the fish-skin that the step 1) exsiccant has the fish scale one side, transfers to temperature after vacuumizing and be in 70～80 ℃ the baking oven to solidify 2 hours in vacuum vessel.
3) mixture of PDMS after will solidifying and solidifying agent is peeled off with the fish-skin that has fish scale, obtains showing the solidified PDMS with fish scale antistructure and the mixture template of solidifying agent.
4) with vinylformic acid, 2,2-diethoxy acetophenone, N, N '-methylene-bisacrylamide is water-soluble, mixing solutions is poured in the mixture of PDMS after the curing that step 3) obtains and solidifying agent.Vinylformic acid quality percentage composition is 40%, 2 in the mixing solutions, and 2-diethoxy acetophenone quality percentage composition is 0.8%, N, and N '-methylene-bisacrylamide quality percentage composition is 0.8%, and surplus is a water.
5) with wavelength be the ultraviolet irradiation step 4 of 365nm) mixed solution that obtains 30～90 minutes, make vinylformic acid generation polymerization.
6) PDMS after acrylic acid polymer that step 5) is obtained and the curing and the mixture template of solidifying agent are peeled off, and obtain having the underwater ultra-oleophobic polyalcohol membrane of fish scale structure.
7) the polypropylene sorrel of fish scale structure is put into water and wash repeatedly, remove unreacted Acrylic Acid Monomer.
Embodiment 3
1) obtains exsiccant and have the fish-skin method of fish scale with embodiment 1.
2) with PDMS (184 silicone elastomer base; DOW Corning Corporation is U.S.A) with solidifying agent (184 silicone elastomer curing agent; DOW Corning Corporation U.S.A) mixes according to mass ratio 10: 1, and mixture is poured on the fish-skin that the step 1) exsiccant has the fish scale one side, transfers to temperature after vacuumizing and be in 70～80 ℃ the baking oven to solidify 4 hours in vacuum vessel.
3) mixture of PDMS after will solidifying and solidifying agent is peeled off with the fish-skin that has fish scale, obtains showing the solidified PDMS with fish scale antistructure and the mixture template of solidifying agent.
4) with acrylamide, vinylformic acid, 2,2-diethoxy acetophenone, N, N '-methylene-bisacrylamide is water-soluble, mixing solutions is poured in the mixture of PDMS after the curing that step 3) obtains and solidifying agent.Acrylamide quality percentage composition is 20% in the mixing solutions, and vinylformic acid quality percentage composition is 20%, 2, and 2-diethoxy acetophenone quality percentage composition is 0.8%, N, and N '-methylene-bisacrylamide quality percentage composition is 0.8%, and surplus is a water.
5) with wavelength be the ultraviolet irradiation step 4 of 365nm) mixed solution that obtains 30～90 minutes, make acrylamide and vinylformic acid generation polymerization.
6) PDMS after the polymkeric substance of polyacrylamide that step 5) is obtained and polyacrylic acid blend and the curing and the mixture template of solidifying agent are peeled off, and obtain having the underwater ultra-oleophobic polyalcohol membrane of fish scale structure.
7) film of the polyacrylamide of fish scale structure and polyacrylic acid blend is put into water and wash repeatedly, remove unreacted acrylamide and Acrylic Acid Monomer.
Embodiment 4
1) obtains exsiccant and have the fish-skin method of fish scale with embodiment 1.
2) with PDMS (184 silicone elastomer base; DOW Corning Corporation is U.S.A) with solidifying agent (184 silicone elastomer curing agent; DOW Corning Corporation U.S.A) mixes according to mass ratio 10: 1, and mixture is poured on the fish-skin that the step 1) exsiccant has the fish scale one side, transfers to temperature after vacuumizing and be in 70～80 ℃ the baking oven to solidify 3 hours in vacuum vessel.
3) mixture of PDMS after will solidifying and solidifying agent is peeled off with the fish-skin that has fish scale, obtains showing the solidified PDMS with fish scale antistructure and the mixture template of solidifying agent.
4) with vinylformic acid, sodium acrylate, Ammonium Persulfate 98.5, N, N '-methylene-bisacrylamide is water-soluble, mixing solutions is poured in the mixture of PDMS after the curing that step 3) obtains and solidifying agent.Vinylformic acid quality percentage composition is 20% in the mixing solutions, and the quality percentage composition of sodium acrylate is 10%, and Ammonium Persulfate 98.5 quality percentage composition is 0.3%, N, and N '-methylene-bisacrylamide quality percentage composition is 0.3%, and surplus is a water.
5) to place temperature be 60 ℃ environment 1～24 hour to the template that step 4) is had a mixing solutions, makes vinylformic acid, sodium acrylate generation polymerization.
6) PDMS after the polymkeric substance of polyacrylic acid that step 5) is obtained and sodium polyacrylate blend and the curing and the mixture template of solidifying agent are peeled off, and obtain having the underwater ultra-oleophobic polyalcohol membrane of fish scale structure.
7) film of the polyacrylic acid of fish scale structure and sodium polyacrylate blend is put into water and wash repeatedly, remove unreacted vinylformic acid, sodium acrylate monomers.
Embodiment 5
1) obtains exsiccant and have the fish-skin method of fish scale with embodiment 1.
2) with PDMS (184 silicone elastomer base; DOW Corning Corporation is U.S.A) with solidifying agent (184 silicone elastomer curing agent; DOW Corning Corporation U.S.A) mixes according to mass ratio 10: 1, and mixture is poured on the fish-skin that the step 1) exsiccant has the fish scale one side, transfers to temperature after vacuumizing and be in 70～80 ℃ the baking oven to solidify 2 hours in vacuum vessel.
3) mixture of PDMS after will solidifying and solidifying agent is peeled off with the fish-skin that has fish scale, obtains showing the solidified PDMS with fish scale antistructure and the mixture template of solidifying agent.
4) with acrylamide, Ammonium Persulfate 98.5, N, N, N ', N '-tetramethyl-diethylamine is water-soluble, mixing solutions is poured in the mixture of PDMS after the curing that step 3) obtains and solidifying agent.Acrylamide quality percentage composition is 20% in the mixing solutions, and Ammonium Persulfate 98.5 quality percentage composition is 0.2%, N, N, and N ', N '-tetramethyl-diethylamine quality percentage composition is 0.07%, surplus is a water.
5) to place temperature be 20 ℃ environment 3 hours to the template liquid that step 4) is had a mixing solutions, makes acrylamide generation polymerization.
6) PDMS after polyacrylamide polymers that step 5) is obtained and the curing and the mixture template of solidifying agent are peeled off, and obtain having the underwater ultra-oleophobic polyalcohol membrane of fish scale structure.
7) the polyacrylamide film of fish scale structure is put into water and wash repeatedly, remove unreacted acrylamide monomer.
Embodiment 6
1) obtains exsiccant and have the fish-skin method of fish scale with embodiment 1.
2) with PDMS (184 silicone elastomer base; DOW Corning Corporation is U.S.A) with solidifying agent (184 silicone elastomer curing agent; DOW Corning Corporation U.S.A) mixes according to mass ratio 10: 1, and mixture is poured on the fish-skin that the step 1) exsiccant has the fish scale one side, transfers to temperature after vacuumizing and be in 70～80 ℃ the baking oven to solidify 3 hours in vacuum vessel.
3) mixture of PDMS after will solidifying and solidifying agent is peeled off with the fish-skin that has fish scale, obtains showing the solidified PDMS with fish scale antistructure and the mixture template of solidifying agent.
4) with N-N-isopropylacrylamide, Ammonium Persulfate 98.5, N, N '-methylene-bisacrylamide is water-soluble, mixing solutions is poured in the mixture of PDMS after the curing that step 3) obtains and solidifying agent.N-N-isopropylacrylamide quality percentage composition is 50% in the mixing solutions, and Ammonium Persulfate 98.5 quality percentage composition is 0.5%, N, and N '-methylene-bisacrylamide quality percentage composition is 0.5%, and surplus is a water.
5) to place temperature be 60 ℃ environment 1～24 hour to the template that step 4) is had a mixing solutions, makes N-N-isopropylacrylamide generation polymerization.
6) PDMS after N-isopropyl acrylamide polyalcohol that step 5) is obtained and the curing and the mixture template of solidifying agent are peeled off, and obtain having the underwater ultra-oleophobic polyalcohol membrane of fish scale structure.
7) the poly N-isopropyl acrylamide film of fish scale structure is put into water and wash repeatedly, remove unreacted N-N-isopropylacrylamide monomer.
Embodiment 7
1) obtains exsiccant and have the fish-skin method of fish scale with embodiment 1.
2) with PDMS (184 silicone elastomer base; DOW Corning Corporation is U.S.A) with solidifying agent (184 silicone elastomer curing agent; DOW Corning Corporation U.S.A) mixes according to mass ratio 10: 1, and mixture is poured on the fish-skin that the step 1) exsiccant has the fish scale one side, transfers to temperature after vacuumizing and be in 70～80 ℃ the baking oven to solidify 3 hours in vacuum vessel.
3) mixture of PDMS after will solidifying and solidifying agent is peeled off with the fish-skin that has fish scale, obtains showing the solidified PDMS with fish scale antistructure and the mixture template of solidifying agent.
4) with N-vinyl pyrrolidone, Potassium Persulphate, N, N '-methylene-bisacrylamide is water-soluble, mixing solutions is poured in the mixture of PDMS after the curing that step 3) obtains and solidifying agent.N-vinyl pyrrolidone quality percentage composition is 35% in the mixing solutions, and Ammonium Persulfate 98.5 quality percentage composition is 0.4%, N, and N '-methylene-bisacrylamide quality percentage composition is 0.4%, and surplus is a water.
5) to place temperature be 60 ℃ environment 1～24 hour to the template that step 4) is had a mixing solutions, makes N-vinyl pyrrolidone generation polymerization.
6) PDMS after N-vinyl pyrrolidone polymer that step 5) is obtained and the curing and the mixture template of solidifying agent are peeled off, and obtain having the underwater ultra-oleophobic polyalcohol membrane of fish scale structure.
7) the poly N-vinyl pyrrolidone film of fish scale structure is put into water and wash repeatedly, remove unreacted N-vinylpyrrolidone monomer.
Embodiment 8
1) obtains exsiccant and have the fish-skin method of fish scale with embodiment 1.
2) with PDMS (184 silicone elastomer base; DOW Corning Corporation is U.S.A) with solidifying agent (184 silicone elastomer curing agent; DOW Corning Corporation U.S.A) mixes according to mass ratio 10: 1, and mixture is poured on the fish-skin that the step 1) exsiccant has the fish scale one side, transfers to temperature after vacuumizing and be in 70～80 ℃ the baking oven to solidify 3 hours in vacuum vessel.
3) mixture of PDMS after will solidifying and solidifying agent is peeled off with the fish-skin that has fish scale, obtains showing the solidified PDMS with fish scale antistructure and the mixture template of solidifying agent.
4) with N,N-DMAA, N-N-isopropylacrylamide, Ammonium Persulfate 98.5, N, N '-methylene-bisacrylamide is water-soluble, mixing solutions is poured in the mixture of PDMS after the curing that step 3) obtains and solidifying agent.Vinylformic acid quality percentage composition is 20% in the mixing solutions, and the quality percentage composition of sodium acrylate is 20%, and Ammonium Persulfate 98.5 quality percentage composition is 0.4%, N, and N '-methylene-bisacrylamide quality percentage composition is 0.4%, and surplus is a water.
5) to place temperature be 60 ℃ environment 1～24 hour to the template that step 4) is had a mixing solutions, makes N,N-DMAA, N-N-isopropylacrylamide generation polymerization.
6) PDMS after the poly-N,N-DMAA that step 5) is obtained and the polymkeric substance of poly N-isopropyl acrylamide blend and the curing and the mixture template of solidifying agent are peeled off, and obtain having the underwater ultra-oleophobic polyalcohol membrane of fish scale structure.
7) film of the poly-N,N-DMAA of fish scale structure and poly N-isopropyl acrylamide blend is put into water and wash repeatedly, remove unreacted N,N-DMAA, N-N-isopropylacrylamide monomer.
Claims (8)
1. the underwater ultra-oleophobic polyalcohol membrane of a biomimetic features, it is characterized in that: described underwater ultra-oleophobic polyalcohol membrane is the micron and nanometer composite structure that has the fish scale surface on the surface of polymeric film, swelling after absorbing water under water, this polymeric film takes place, form the composite membrane of one deck water and polymkeric substance coexistence at polymer film surface, this composite membrane shows the excess of export oleophobic property in water, composite membrane to the contact angle of oil greater than 150 °;
Described polymkeric substance is a kind of in polyacrylamide, polyacrylic acid, sodium polyacrylate, polyacrylic acid potassium, poly-N,N-DMAA, poly-N-ethyl acrylamide, poly N-isopropyl acrylamide, poly N-vinyl pyrrolidone, the poly N-vinyl hexanolactam or greater than a kind of mixture.
2. the preparation method of a underwater ultra-oleophobic polyalcohol membrane according to claim 1, it is to adopt the method for turning over mould to be prepared, and it is characterized in that this method may further comprise the steps:
1) fish-skin that will have a fish scale peels, and puts into gradient alcohol and dewaters, and puts into baking oven then and dries, and obtains the fish-skin that exsiccant has fish scale;
2) be that 8: 1～15: 1 mixed obtains mixture with polydimethylsiloxane and solidifying agent according to mass ratio, then mixture is poured on the fish-skin that has the fish scale one side that step 1) obtains, transferred to temperature after in vacuum vessel, vacuumizing and be in 70～80 ℃ the baking oven and solidify;
3) with step 2) polydimethylsiloxane after solidifying and the mixture of solidifying agent and the fish-skin that has a fish scale peel off, and obtains the mixture template that the surface has the solidified polydimethylsiloxane and the solidifying agent of fish scale antistructure;
4) with polymer monomer, initiator, linking agent, the water-soluble mixing solutions that obtains of catalyzer, then mixing solutions is poured in the mixture template of polydimethylsiloxane that step 3) obtains and solidifying agent, wherein polymer monomer quality percentage composition is 10%～80% in the mixing solutions, initiator quality percentage composition is 0.1%～1%, linking agent quality percentage composition is 0.1%～1%, the catalyst quality percentage composition is 0%～0.1%, and surplus is a water;
5) with wavelength being the ultraviolet irradiation step 4 of 365nm) mixing solutions on the template makes polymer monomer generation polymerization, the polydimethylsiloxane after polymkeric substance and the curing and the mixture template of solidifying agent are peeled off, obtained having the underwater ultra-oleophobic polyalcohol membrane of fish scale structure;
Or the template that step 4) has a mixing solutions is placed temperature is that 4～80 ℃ environment polymerization is after 1～24 hour, the polydimethylsiloxane after polymkeric substance and the curing and the mixture template of solidifying agent are peeled off, obtained having the underwater ultra-oleophobic polyalcohol membrane of fish scale structure;
Described polymer monomer material is a kind of in acrylamide, vinylformic acid, sodium acrylate, potassium acrylate, N,N-DMAA, N-ethyl acrylamide, N-N-isopropylacrylamide, N-vinyl pyrrolidone, the poly N-vinyl hexanolactam or greater than a kind of mixture.
3. method according to claim 2 is characterized in that: the temperature in the described baking oven of step 1) is 50～70 ℃.
4. method according to claim 2 is characterized in that: the step 5) wavelength is the ultraviolet irradiation step 4 of 365nm) time of mixing solutions on the template is 30～90 minutes.
5. method according to claim 2 is characterized in that: the mass concentration of described gradient alcohol is 50%, 70%, 85%, 95%, 100%.
6. method according to claim 2 is characterized in that: described initiator is 2,2-diethoxy acetophenone, Ammonium Persulfate 98.5, Potassium Persulphate or Sodium Persulfate.
7. method according to claim 2 is characterized in that: described linking agent is N, N '-methylene-bisacrylamide.
8. method according to claim 2 is characterized in that: described catalyzer is N, N, N ', N '-tetramethyl-diethylamine.
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| CN102140218B (en) * | 2010-01-28 | 2013-07-24 | 中国科学院化学研究所 | Ultra-oleophobic underwater self-cleaning polymer composite film with biomimic structure and manufacturing method thereof |
| CN102643397B (en) * | 2012-04-26 | 2013-06-12 | 北京航空航天大学 | Preparation method of underwater pH-responsive super-oleophobic reversible adhesion interface switch |
| CN103524766B (en) * | 2012-07-04 | 2016-08-10 | 中国科学院化学研究所 | Surface has the preparation method of the underwater ultra-oleophobic polyalcohol membrane of micro nano structure |
| CN103030105B (en) * | 2012-12-25 | 2015-10-28 | 江苏大学 | A kind of liquid assist formation method preparing super oleophobic surface |
| CN106622312A (en) * | 2017-01-20 | 2017-05-10 | 合肥学院 | Method for preparing silver phosphate nano-particle film by taking fish scales as template |
| CN108129938A (en) * | 2017-12-22 | 2018-06-08 | 浙江银鹿新材料有限公司 | A kind of superoleophobic UV photocurings gloss oil |
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| WO2004055110A1 (en) * | 2002-12-13 | 2004-07-01 | Kaneka Corporation | Thermoplastic polyimide resin film, multilayer body and method for manufacturing printed wiring board composed of same |
| CN1854174A (en) * | 2005-04-20 | 2006-11-01 | 中国科学院化学研究所 | Ultra-hydrophobic polymer thin film and its production |
| CN101200550A (en) * | 2007-11-14 | 2008-06-18 | 汪静 | Method for preparing template imitating micro-nano structure surface |
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2007
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004055110A1 (en) * | 2002-12-13 | 2004-07-01 | Kaneka Corporation | Thermoplastic polyimide resin film, multilayer body and method for manufacturing printed wiring board composed of same |
| CN1854174A (en) * | 2005-04-20 | 2006-11-01 | 中国科学院化学研究所 | Ultra-hydrophobic polymer thin film and its production |
| CN101200550A (en) * | 2007-11-14 | 2008-06-18 | 汪静 | Method for preparing template imitating micro-nano structure surface |
Non-Patent Citations (2)
| Title |
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| 金美花，江雷等.超疏水性聚二甲基硅氧烷膜的制备及其表面吸附性研究.高等学校化学学报第28卷 第5期.2007,第28卷(第5期),第996-998页. |
| 金美花,江雷等.超疏水性聚二甲基硅氧烷膜的制备及其表面吸附性研究.高等学校化学学报第28卷 第5期.2007,第28卷(第5期),第996-998页. * |
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