CN101649065B - Method for preparing pollution preventing self-cleaning polyvinylidene fluoride (PVDF) film and product thereof - Google Patents
Method for preparing pollution preventing self-cleaning polyvinylidene fluoride (PVDF) film and product thereof Download PDFInfo
- Publication number
- CN101649065B CN101649065B CN2009100704121A CN200910070412A CN101649065B CN 101649065 B CN101649065 B CN 101649065B CN 2009100704121 A CN2009100704121 A CN 2009100704121A CN 200910070412 A CN200910070412 A CN 200910070412A CN 101649065 B CN101649065 B CN 101649065B
- Authority
- CN
- China
- Prior art keywords
- pvdf
- solution
- pvdf membrane
- alkali
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to a method for preparing a pollution preventing self-cleaning polyvinylidene fluoride (PVDF) film and a product thereof. The method comprises the following processes: (1) PVDF film preparation; and (2) PVDF film processing with alkali liquor, including an alkali-water solution processing process and an alkali-alcohol solution processing process, wherein the alkali-water solution processing process comprises the following steps: soaking the PVDF film in alkali-water solution with the mass concentration of 20-40 percent; processing at 60-80 DEG C for 2-3 hours and then taking out to wash with water; drying and obtaining the PVDF film; the alkali-alcohol solution processing process comprises the following steps: soaking the PVDF film in alkali-alcohol solution with themass concentration of 2-10 percent; processing at 25-40 DEG C for 3-5 minutes and then taking the film out; washing with water and drying; soaking the PVDF film in proper solution to react at 25-60 DEG C for 3-10 minutes; then taking out and fully washing with water; drying and then obtaining the PVDF film; (3) decorating the surface of the PVDF film by organosilane and preparing the pollution preventing self-cleaning polyvinylidene fluoride film. The pollution preventing self-cleaning PVDF film product is prepared by the method.
Description
Technical field
The present invention relates to a kind of organic membrane technology of preparing, be specially the preparation method and the goods thereof of a kind of pollution preventing self-cleaning polyvinylidene fluoride (PVDF) (PVDF) film.
Background technology
Pvdf (PVDF) is a kind of high-molecular weight hypocrystalline organo-fluorine polymer, under specific situation, can form microballoon.Only have reciprocal C-F key and c h bond in the PVDF molecular structure; Therefore pvdf membrane has higher unreactiveness and good weathering resistance; As can resist the damage of chemical substance in UV-induced degraded and the atmosphere, also can resist the erosion of seaweeds bacterium and fungi.The fluorinated material is because the polarizability of C-F key is little, bond length short, so the cohesive force of PVDF molecule is little, and surface free energy is low, and various liquid all are difficult in its surface attachment.Because PVDF has the performance of excellence like this, the top layer of making base materials such as building membrane structure material, glass and textiles commonly used is to increase the weathering resistance of base material.
Lotus leaf has mud and the laudatory title of not dying.Water can be gathered into the free rolling globule automatically at lotus leaf surface, and the rolling of the globule can be taken away surface dirt, and lotus leaf surface is remained totally, and Germany scientist Barthlott professor is with this anti-fouling and self-cleaning phenomenon called after " lotus leaf effect " of lotus leaf.If can lotus leaf effect be applied on the base material that contains the PVDF coating; Then base material in use only relies on rain drop erosion just can keep self-cleaning; Not only can make base material attractive in appearance, keep the good light transmittance can; And saved cleaning and the maintenance of people greatly to substrate surface, this will bring huge economic benefit and social benefit aspect environment protection and the energy conservation.The research that at present both at home and abroad lotus leaf effect is applied on the pvdf membrane is less, and the method for adding nanoparticles that adopts prepares the anti-fouling and self-cleaning surface more.But this method exists nanoparticle to reunite easily, problems such as pvdf membrane light transmission reduction.
Summary of the invention
To the deficiency that prior art exists, the technical problem that quasi-solution of the present invention is determined is that a kind of preparation method and goods thereof of pollution preventing self-cleaning polyvinylidene fluoride (PVDF) film are provided.This preparing method's technology is simple, and easy handling is convenient to industrializing implementation, and prepared polyvinylidene fluoride film has good self-cleaning function, does not influence the light transmission of pvdf membrane simultaneously.
The technical scheme that the present invention solves said preparing method's technical problem is: design a kind of preparation method of pollution preventing self-cleaning polyvinylidene fluoride (PVDF) film, this preparation method comprises following technology:
1.PVDF the preparation of film: the PVDF powder is dissolved in acetone, N or the dimethylacetamide solvent; Being mixed with massfraction is the PVDF solution of 5-10%; 50-70 ℃ of following constant temperature stirs 1-2h, and standing and defoaming 30min films; Under 90-180 ℃ of condition, dry, promptly obtain pvdf membrane;
2. alkali lye is handled pvdf membrane: comprise that alkali-aqueous solution is handled and alkali-alcoholic solution is handled two kinds of technologies:
Alkali-aqueous solution treatment process is: pvdf membrane is immersed in alkali-aqueous solution of mass concentration 20-40%, after handling 2-3h under 60-80 ℃, takes out washing, promptly get after the oven dry; Said alkali-aqueous solution is the NaOH-aqueous solution, the LiOH-aqueous solution or the KOH-aqueous solution;
Alkali-alcoholic solution treatment process is: earlier pvdf membrane is immersed in alkali-alcoholic solution of mass concentration 2-10%, after handling 3-5min under 25-40 ℃, takes out film, washing, oven dry; Pvdf membrane is immersed in again and reacts 3-10min in the suitable solution under 25-60 ℃, take out then, fully washing promptly gets after the oven dry; Said alkali-alcoholic solution is NaOH-alcoholic solution, LiOH-alcoholic solution or KOH-alcoholic solution; Said suitable solution is meant mass concentration (4-8%) KMnO
4The H of/(20-30%) the KOH-aqueous solution, or mass concentration 98%
2SO
4Solution;
3.PVDF film finishing: earlier organosilane is dissolved in the organic solvent, processing volumetric concentration is the organosilane solution of 1/10-1/3, is placed in the encloses container that relative humidity is 60-80% for use; Said organosilane is at least a in METHYL TRICHLORO SILANE, dimethyldichlorosilane(DMCS), trimethylchlorosilane and the fluoroalkyl silanes; Said organic solvent is benzene, toluene, ether, vinylaether or oxyethane; Go on foot in the pvdf membrane that alkali lye was handled is immersed in the organosilane solution in the said encloses container surface treatment 20-30min with the 2nd again; The organic solvent washing that pvdf membrane after the processing is used said dissolving organosilane is at normal temperatures earlier once used 1: 1 ethanol-water solution thorough washing of ethanol and volume ratio respectively again, 100-120 ℃ of oven dry down, promptly makes described anti-fouling and self-cleaning pvdf membrane then.
The technical scheme that the present invention solves said goods technical problem is: design a kind of anti-fouling and self-cleaning pvdf membrane goods, these anti-fouling and self-cleaning pvdf membrane goods adopt anti-fouling and self-cleaning pvdf membrane preparation method of the present invention to process.
Compared with prior art, preparing method's novelty of the present invention ground adopts strong base solution that pre-treatment is carried out on pvdf (PVDF) film surface, has improved the grafting performance of pvdf membrane; Adopt organosilane solution that pvdf membrane is carried out finishing again, process method is simple, easy handling; Easy industrial implementation, prepared pvdf membrane surface can form the micron-nanometer dual structure that is similar to lotus leaf surface, and dirt is few in this pvdf membrane surface contact area; Adhesive power is very low; Be easy under rain drop erosion, tumble, have good super-hydrophobic and anti-fouling and self-cleaning performance, do not influence the light transmission of pvdf membrane simultaneously with water droplet.
Description of drawings
Fig. 1 (a) is the pvdf membrane surface of not surface modification and the contact angle photo figure of water;
Fig. 1 (b) is the anti-fouling and self-cleaning effect photo figure of the pvdf membrane (Fig. 1 (a) film) of not surface modification;
Fig. 2 (a) for the pvdf membrane surface of a kind of embodiment of preparation method of the present invention (embodiment 1) gained after the pre-treatment of the NaOH aqueous solution, after modifying through organosilane again, with the contact angle photo figure of water;
Fig. 2 (b) is the anti-fouling and self-cleaning effect photo figure on the pvdf membrane of a kind of embodiment gained of preparation method of the present invention (Fig. 2 (a) film) surface;
Fig. 3 (a) for the pvdf membrane surface of a kind of embodiment of preparation method of the present invention (embodiment 2) gained after the pre-treatment of KOH-ethanolic soln, after modifying through organosilane again, with the contact angle photo figure of water;
Fig. 3 (b) is the anti-fouling and self-cleaning effect photo figure on the pvdf membrane of a kind of embodiment gained of preparation method of the present invention (Fig. 3 (a) film) surface;
Fig. 4 (a) is that the pvdf membrane of a kind of embodiment of preparation method of the present invention (the 1st step of embodiment 1) gained has the pvdf membrane surface atom force microscope figure of micrometer structure;
Fig. 4 (b) is the AFM figure of pvdf membrane pvdf membrane coated with nanometre structure behind surface chemical modification of a kind of embodiment of preparation method of the present invention (embodiment 1) gained.
Embodiment
Further narrate the present invention below in conjunction with embodiment and accompanying drawing thereof.
To the dissatisfactory problem of present pvdf membrane anti-fouling and self-cleaning performance; Mentality of designing of the present invention is that " lotus leaf effect " principle is applied among the preparation method of anti-fouling and self-cleaning pvdf membrane; Adopt alkaline solution that the pvdf membrane surface is handled; In the hope of introducing hydroxyl on the pvdf membrane surface, overcome pvdf membrane and have higher unreactiveness, itself does not contain the defective of reactive group; Be convenient to the organosilane hydrolysis produces in the chemical bath deposition reaction silanol base and the lip-deep hydroxyl of pvdf membrane firm chemically bonded takes place, make a kind of novel anti-fouling and self-cleaning pvdf membrane.
Anti-fouling and self-cleaning (or super-hydrophobic) the pvdf membrane preparation method (abbreviation preparation method) of the present invention's design comprises following technology:
1.PVDF membrane prepare: the PVDF powder is dissolved in the solvent, and being mixed with massfraction is the PVDF solution of 5-10%, and 50-70 ℃ of following constant temperature stirs 1-2h, and standing and defoaming 30min films, and under 90-180 ℃ of condition, dries, and promptly obtains pvdf membrane; Described solvent is acetone, N or N,N-DIMETHYLACETAMIDE;
2. alkali lye is handled pvdf membrane: alkali lye is handled pvdf membrane and is comprised that alkali-aqueous solution is handled and alkali-alcoholic solution is handled two kinds of technologies:
Alkali-aqueous solution treatment process is: pvdf membrane is immersed in alkali-aqueous solution of mass concentration 20-40%, handles 2-3h down at 60-80 ℃, take out washing then, oven dry is promptly directly introduced hydroxyl on the pvdf membrane surface; Said alkali-aqueous solution is the NaOH-aqueous solution, the LiOH-aqueous solution or the KOH-aqueous solution;
Alkali-alcoholic solution treatment process is: earlier pvdf membrane is immersed in alkali-alcoholic solution of mass concentration 2-10%, handles 3-5min down at 25-40 ℃, take out pvdf membrane; Washing; After the oven dry, pvdf membrane is immersed in reacts 3-10min in the suitable solution under 25-60 ℃ again, take out film then; Fully washing, oven dry promptly gets; Said alkali-alcoholic solution is NaOH-alcoholic solution, LiOH-alcoholic solution or KOH-alcoholic solution, and described suitable solution is meant mass concentration (4-8%) KMnO
4The dense H of/(20-30%) the KOH-aqueous solution, or mass concentration 98%
2SO
4Solution.This technological design principle is the two keys of elimination reaction generation C=C that HF takes place in alkali-alcoholic solution earlier pvdf membrane, utilizes said KMnO again
4/ KOH solution or dense H
2SO
4Open the two keys of C=C, introduce hydroxyl on the pvdf membrane surface.Alkali-alcoholic solution treatment process seems complicated than alkali-aqueous solution technology, but it has reduced the consumption and the reaction times of alkali significantly, and advantage is obvious.
3.PVDF film finishing: earlier organosilane is dissolved in the organic solvent, processing volumetric concentration is the organosilane solution of 1/10-1/3, is placed in the encloses container that relative humidity is 60-80% for use; Said organosilane is at least a in METHYL TRICHLORO SILANE, dimethyldichlorosilane(DMCS), trimethylchlorosilane and the fluoroalkyl silanes; Said organic solvent is benzene, toluene, ether, vinylaether or oxyethane; The pvdf membrane of again the 2nd step alkali lye being handled is immersed in the organosilane solution in the said encloses container surface treatment 20-30min; The organic solvent washing that pvdf membrane after the processing is used said dissolving organosilane is at normal temperatures earlier once used 1: 1 ethanol-water solution thorough washing of ethanol and volume ratio respectively again, 100-120 ℃ of oven dry down, promptly makes described anti-fouling and self-cleaning pvdf membrane then.
Anti-fouling and self-cleaning pvdf membrane goods of the present invention adopt anti-fouling and self-cleaning pvdf membrane preparation method of the present invention to process.Utilize the collection ash experiment test method of exploitations such as Young contact angle and the A.Born of Univ Bonn Germany to detect the surperficial hydrophobic self-cleaning property of pvdf membrane; Test result shows; The contact angle of the present invention prepared pvdf membrane surface and water has good ultra-hydrophobicity up to (referring to embodiment and accompanying drawing 1-3) more than 155 °.Drop is spherical on the film surface, and roll angle is little, when drop tumbles, can easily the dirt on film surface be taken away, and has shown good anti-fouling and self-cleaning performance.
The present invention is based on " lotus leaf effect " principle, adopt PVDF solution coating constructing micrometre structure; Handle pvdf membrane with suitable alkali lye again; Produce hydrophilic radical; And then utilize organosilane generation hydrolytic-polymeric reaction to generate the ZGK 5 of nanostructure, and be deposited on the pvdf membrane surface, successfully go out to be similar to the micron-nanometer structure dual structure (referring to Fig. 4) of lotus leaf surface at the film surface construction; Dirt is not easy to adhere to, and has improved the hydrophobicity and the self-cleaning function of pvdf membrane.Preparing method of the present invention does not use nanoparticle, does not exist nanoparticle to reunite easily, reduces the problem of pvdf membrane light transmission.
The present invention does not address part and is applicable to prior art.
Provide preparing method's of the present invention specific embodiment below.Specific embodiment does not limit claim of the present invention.
Embodiment 1
1.PVDF membrane prepare: the PVDF powder is dissolved in the dimethyl formamide solution, and the preparation massfraction is 5% PVDF solution, and 60 ℃ of constant temperature stir 2h, and standing and defoaming 30min films, and 90 ℃ of oven dry make the pvdf membrane with micrometer structure.
2. alkali lye is handled pvdf membrane: pvdf membrane is immersed in the NaOH-aqueous solution of mass concentration 35%, handles 3h down at 60 ℃, take out pvdf membrane then, washing, oven dry.
3.PVDF film finishing: preparation contains the toluene solution of volume(tric)fraction 8% METHYL TRICHLORO SILANE and 12% dimethyldichlorosilane(DMCS); Place it in relative humidity and be in 80% the encloses container for use; Go on foot in the pvdf membrane that the NaOH solution-treated is crossed is immersed in the toluene solution in the said encloses container the 2nd again; Carry out surface treatment 30min, the pvdf membrane after handling is taken out, use toluene, ethanol and 1: 1 ethanol-water solution of volume ratio thorough washing at normal temperatures successively; Behind oven dry 10min under 120 ℃, promptly obtain pvdf membrane with anti-fouling and self-cleaning function.
The contrast experiment not pvdf membrane of surface modification and the contact angle of water has only 88 ° (referring to Fig. 1 (a)), and the dirt on film surface is difficult to tumble (referring to Fig. 1 (b)) with water droplet.The pvdf membrane behind the present embodiment surface modification and the contact angle of water be (referring to Fig. 2 (a)) up to 157 °, and the water droplet on gained pvdf membrane surface is very round, with pvdf membrane surface contact area seldom; When pvdf membrane tilts (roll angle) 1 °; Water droplet tumbles from this surface rapidly; The water droplet that rolls across behind the certain distance still is spherical shape; And the water droplet surface aggregation a large amount of dusts, the pvdf membrane surface after water droplet rolls across very clean (referring to Fig. 2 (b)) explains that pvdf membrane of the present invention surface has good anti-fouling and self-cleaning effect.
Embodiment 2
1.PVDF membrane prepare: the PVDF powder is dissolved in the dimethylacetamide solution, and the preparation massfraction is 5% PVDF solution, and 70 ℃ of constant temperature stir 1.5h, and standing and defoaming 30min films, and 120 ℃ of oven dry make the pvdf membrane with micrometer structure.
2. alkali lye is handled pvdf membrane: pvdf membrane is immersed in the KOH-ethanolic soln of mass concentration 5%, behind 40 ℃ of processing 3min, takes out pvdf membrane, washing, oven dry; Again pvdf membrane is immersed mass concentration 4%KMnO
4In/30%KOH-the aqueous solution, react 10min under the room temperature, take out washing, oven dry.
3.PVDF film finishing: preparation contains the toluene solution of volume(tric)fraction 7.4% METHYL TRICHLORO SILANE and 12.6% dimethyldichlorosilane(DMCS); Place it in relative humidity and be in 80% the encloses container for use; Go on foot in the pvdf membrane that alkali lye was handled is immersed in the toluene solution in the said encloses container the 2nd again; Carry out surface treatment 20min, the pvdf membrane after handling is taken out, use toluene, ethanol and 1: 1 alcohol-water of volume ratio thorough washing at normal temperatures successively; Dry 12min down at 100 ℃, promptly obtain pvdf membrane with anti-fouling and self-cleaning function.
Through detecting, the contact angle of present embodiment gained pvdf membrane and water is 155 ° (referring to Fig. 3 (a)), and when pvdf membrane tilts 4 ° the time, water droplet is easy to the dirt that film is surperficial and takes away (referring to Fig. 3 (b)), demonstrates the good hydrophobic self-cleaning property.
Embodiment 3
1.PVDF the preparation of film: with embodiment 1 step 1.
2. alkali lye is handled pvdf membrane: pvdf membrane is immersed in the LiOH-aqueous solution of mass concentration 25%, handles 2.5h at 80 ℃, take out pvdf membrane then, washing, oven dry.
3.PVDF film finishing: preparation contains the FAS [(CF of volume(tric)fraction 8%
3(CF
2)
8(CH
2)
2-Si (OCH
3)
3] benzole soln, place it in relative humidity and be in 60% the encloses container, for use; Go on foot in the pvdf membrane that the LiOH-aqueous solution was handled is immersed in the benzole soln in the said encloses container the 2nd again; Carry out surface treatment 30min, the pvdf membrane after handling is taken out, use benzene, ethanol and 1: 1 ethanol-water solution of volume ratio thorough washing at normal temperatures successively; Dry 10min down at 120 ℃, promptly obtain pvdf membrane with anti-fouling and self-cleaning function.
Through detecting, the contact angle of present embodiment gained pvdf membrane and water is 155 °; When pvdf membrane tilts 3 ° the time, water droplet is easy to the dirt on film surface is taken away, and demonstrates the good hydrophobic self-cleaning property.
Embodiment 4
1.PVDF the preparation of film: with embodiment 1 step 1.
2. alkali lye is handled pvdf membrane: pvdf membrane is immersed in the KOH-methanol solution of mass concentration 2%, 25 ℃ handle 5min after, take out pvdf membrane, washing, dry by the fire in; Pvdf membrane is immersed in 98% dense H more then
2SO
4In the solution, 60 ℃ of reaction 3min take out fully washing, oven dry.
3.PVDF film finishing: preparation contains the diethyl ether solution of volume(tric)fraction 8% METHYL TRICHLORO SILANE and 20% trimethylchlorosilane; Place it in relative humidity and be in 70% the encloses container; For use, go on foot in the pvdf membrane that the KOH solution-treated is crossed is immersed in the diethyl ether solution in the said encloses container the 2nd again, carry out surface treatment 30min; Pvdf membrane after handling is taken out; Use ether, ethanol and 1: 1 ethanol-water solution of volume ratio thorough washing at normal temperatures successively, behind oven dry 10min under 110 ℃, promptly obtain pvdf membrane with anti-fouling and self-cleaning function.
Through detecting, the contact angle of present embodiment gained pvdf membrane and water is 155 °; When tilting pvdf membrane 4 ° the time, water droplet is easy to the dirt on film surface is taken away, and demonstrates the good hydrophobic self-cleaning property.
Embodiment 5
1.PVDF the preparation of film: with embodiment 1 step 1.
2. alkali lye is handled pvdf membrane: pvdf membrane is immersed in the NaOH-methanol solution of mass concentration 10%, behind 30 ℃ of processing 4min, takes out pvdf membrane, washing, oven dry; Again pvdf membrane is immersed mass concentration 8%KMnO
4In/20%KOH-the aqueous solution, react 3min under the room temperature, take out washing, oven dry.
3.PVDF film finishing: preparation contains the vinylaether solution of volume(tric)fraction 5% METHYL TRICHLORO SILANE and 6% trimethylchlorosilane; Place it in relative humidity and be in 60% the encloses container for use; To be immersed in the vinylaether solution in the said encloses container through the pvdf membrane that the 2nd step handled again; Carry out surface treatment 25min, the pvdf membrane after handling is taken out, use vinylaether, ethanol and 1: 1 alcohol-water of volume ratio thorough washing at normal temperatures successively; Behind oven dry 10min under 120 ℃, promptly obtain pvdf membrane with anti-fouling and self-cleaning function.
Through detecting, the contact angle of present embodiment gained pvdf membrane and water is 156 °; When tilting pvdf membrane 3 ° the time, water droplet is easy to the dirt on film surface is taken away, and demonstrates the good hydrophobic self-cleaning property.
Claims (1)
1. the preparation method of a pollution preventing self-cleaning polyvinylidene fluoride (PVDF) film, this preparation method comprises following technology:
(1) preparation of .PVDF film: the PVDF powder is dissolved in acetone, N or the dimethylacetamide solvent; Being mixed with massfraction is the PVDF solution of 5-10%; 50-70 ℃ of following constant temperature stirs 1-2h, and standing and defoaming 30min films; Under 90-180 ℃ of condition, dry, promptly obtain pvdf membrane;
(2). alkali lye is handled pvdf membrane: comprise that alkali-aqueous solution is handled and alkali-alcoholic solution is handled two kinds of technologies:
Alkali-aqueous solution treatment process is: pvdf membrane is immersed in alkali-aqueous solution of mass concentration 20-40%, after handling 2-3h under 60-80 ℃, takes out washing, promptly get after the oven dry; Said alkali-aqueous solution is the NaOH-aqueous solution, the LiOH-aqueous solution or the KOH-aqueous solution;
Alkali-alcoholic solution treatment process is: earlier pvdf membrane is immersed in alkali-alcoholic solution of mass concentration 2-10%, after handling 3-5min under 25-40 ℃, takes out film, washing, oven dry; Pvdf membrane is immersed in again and reacts 3-10min in the suitable solution under 25-60 ℃, take out then, fully washing promptly gets after the oven dry; Said alkali-alcoholic solution is NaOH-alcoholic solution, LiOH-alcoholic solution or KOH-alcoholic solution; Said suitable solution is meant mass concentration (4-8%) KMnO
4The H of/(20-30%) the KOH-aqueous solution, or mass concentration 98%
2SO
4Solution;
(3) .PVDF film finishing: earlier organosilane is dissolved in the organic solvent, processing volumetric concentration is the organosilane solution of 1/10-1/3, is placed in the encloses container that relative humidity is 60-80% for use; Said organosilane is at least a in METHYL TRICHLORO SILANE, dimethyldichlorosilane(DMCS), trimethylchlorosilane and the fluoroalkyl silanes; Said organic solvent is benzene, toluene, ether, vinylaether or oxyethane; Go on foot in the pvdf membrane that alkali lye was handled is immersed in the organosilane solution in the said encloses container surface treatment 20-30min with (2) again; The organic solvent washing that pvdf membrane after the processing is used said dissolving organosilane is at normal temperatures earlier once used 1: 1 ethanol-water solution thorough washing of ethanol and volume ratio respectively again, 100-120 ℃ of oven dry down, promptly makes described anti-fouling and self-cleaning pvdf membrane then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100704121A CN101649065B (en) | 2009-09-11 | 2009-09-11 | Method for preparing pollution preventing self-cleaning polyvinylidene fluoride (PVDF) film and product thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100704121A CN101649065B (en) | 2009-09-11 | 2009-09-11 | Method for preparing pollution preventing self-cleaning polyvinylidene fluoride (PVDF) film and product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101649065A CN101649065A (en) | 2010-02-17 |
| CN101649065B true CN101649065B (en) | 2012-02-08 |
Family
ID=41671405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009100704121A Expired - Fee Related CN101649065B (en) | 2009-09-11 | 2009-09-11 | Method for preparing pollution preventing self-cleaning polyvinylidene fluoride (PVDF) film and product thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101649065B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352547B (en) * | 2011-07-15 | 2014-01-08 | 沈健芬 | Conductive super-hydrophobic carbon nanometer tube/polymer composite film and preparation method thereof |
| CN103570251B (en) * | 2012-08-01 | 2016-01-27 | 青岛大学 | A kind of preparation method of the super-hydrophobic coat that insulate |
| CN102911390B (en) * | 2012-10-22 | 2015-02-18 | 程向东 | Modified film material for bioartificial liver |
| CN105396474B (en) * | 2014-09-05 | 2017-12-19 | 中国石油化工股份有限公司 | A kind of method for moistening organic-silicon-modified Polyolefin Hollow Fiber with special parent |
| CN105381723B (en) * | 2014-09-05 | 2017-11-07 | 中国石油化工股份有限公司 | A kind of preparation method of super-hydrophobic Flat Membrane |
| CN106256417B (en) * | 2015-06-18 | 2018-11-02 | 中国石油化工股份有限公司 | A kind of preparation method of high-performance organic gas seperation film |
| CN107778515B (en) * | 2017-09-30 | 2019-06-28 | 河南大学 | A kind of short-cut method preparing the super-hydrophobic polycarbonate plate of automatically cleaning yellow |
| CN108031298A (en) * | 2017-12-19 | 2018-05-15 | 广东石油化工学院 | A kind of magnetism ultra-hydrophobic polyvinylidene fluoride electrospinning film and its preparation method and application |
| CN109868652A (en) * | 2019-03-07 | 2019-06-11 | 扬州金泉旅游用品有限公司 | A method of preparing hydrophobic and antifouling fabric and cloth |
| CN112467270B (en) * | 2020-11-03 | 2022-10-28 | 浙江锋锂新能源科技有限公司 | Composite air suction element, preparation method thereof and flatulence-preventing self-repairing soft-package lithium battery |
-
2009
- 2009-09-11 CN CN2009100704121A patent/CN101649065B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101649065A (en) | 2010-02-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101649065B (en) | Method for preparing pollution preventing self-cleaning polyvinylidene fluoride (PVDF) film and product thereof | |
| CN101463140B (en) | Preparation of ultra-hydrophobic polyvinylidene fluoride membrane and product thereof | |
| Latthe et al. | Self–cleaning superhydrophobic coatings: Potential industrial applications | |
| Liu et al. | Transparent, durable and thermally stable PDMS-derived superhydrophobic surfaces | |
| Mozumder et al. | Recent developments in multifunctional coatings for solar panel applications: A review | |
| Dalawai et al. | Recent advances in durability of superhydrophobic self-cleaning technology: a critical review | |
| Cho et al. | Robust multifunctional superhydrophobic coatings with enhanced water/oil separation, self-cleaning, anti-corrosion, and anti-biological adhesion | |
| CN101663249B (en) | Preparation of super water repellent surface | |
| Zhang et al. | A facile method to fabricate superhydrophobic cotton fabrics | |
| Xue et al. | Fabrication of robust and antifouling superhydrophobic surfaces via surface-initiated atom transfer radical polymerization | |
| CN103938432B (en) | There is the preparation method of the superhydrophobic fibers cellulosic material of micro-nano structure | |
| CN104924379B (en) | Super-hydrophobic wood and preparation method thereof | |
| Jiang et al. | Facile fabrication of robust fluorine-free self-cleaning cotton textiles with superhydrophobicity, photocatalytic activity, and UV durability | |
| CN106800885A (en) | A kind of large-scale preparation method of transparent hydrophobic/super-amphiphobic coating | |
| Chen et al. | Two-step approach for fabrication of durable superamphiphobic fabrics for self-cleaning, antifouling, and on-demand oil/water separation | |
| CN104449357A (en) | Transparent super-hydrophobic coating material and method for preparing transparent super-hydrophobic coating by transparent super-hydrophobic coating material | |
| Xue et al. | Mechanically durable superhydrophobic surfaces by binding polystyene nanoparticles on fibers with aluminum phosphate followed by hydrophobization | |
| Wang et al. | Progress in fabrication and applications of micro/nanostructured superhydrophobic surfaces | |
| Pan et al. | Fabrication of superhydrophobic coatings on cotton fabric using ultrasound-assisted in-situ growth method | |
| Zhang et al. | Fabrication of transparent superhydrophobic glass with fibered-silica network | |
| Wang et al. | Durable superhydrophobic coating based on inorganic/organic double-network polysiloxane and functionalized nanoparticles | |
| CN112851960B (en) | Super-hydrophobic metal organic framework material and preparation method and application thereof | |
| Liu et al. | All-water-based superhydrophobic coating with reversible wettability for oil-water separation and wastewater purification | |
| Jiang et al. | The robust superhydrophobic SiO2/Diatomite/PDMS/KH-570/Me-MQ composite coating for self-cleaning application of building surface | |
| Liu et al. | Eco-friendly fabrication of transparent superhydrophobic coating with excellent mechanical robustness, chemical stability, and long-term outdoor durability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120208 Termination date: 20160911 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |