CN1247670C - Super-hydrophobic porous polyvinyl chloride film and its preparing process - Google Patents
Super-hydrophobic porous polyvinyl chloride film and its preparing process Download PDFInfo
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- CN1247670C CN1247670C CN 200310115722 CN200310115722A CN1247670C CN 1247670 C CN1247670 C CN 1247670C CN 200310115722 CN200310115722 CN 200310115722 CN 200310115722 A CN200310115722 A CN 200310115722A CN 1247670 C CN1247670 C CN 1247670C
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Abstract
The present invention belongs to the field of multi-hole polyvinyl chloride membrane materials, which particularly relates to a super-hydrophobic multi-hole polyvinyl chloride membrane and a preparation method thereof. The phase inversion method of a solvent and a precipitating agent is used to prepare the multi-hole loose polyvinyl chloride membrane with a surface micro structure piled by micron level particles and nanometer level particles. The contact angle between the membrane and water is bigger than 150 DEG, the rolling angle of the water dropping on the material surface is smaller than 15 DEG, and the multi-hole polyvinyl chloride membrane has good super-hydrophobic performance. The preparation method provides a new method which causes general-purpose plastics to realize the super-hydrophobic performance of a polymer membrane without the modification of any low surface energy substances containing fluorine materials. The preparation method provides a new preparation way for expanding the application field of the general-purpose plastics, and has the advantages of simple operation, simple equipment, mass production and good industrial application prospect.
Description
Technical field
The invention belongs to cellular PVC mould material field, particularly super-hydrophobic cellular PVC film and preparation method thereof.
Background technology
Wetting property is a key character of solid surface, and super-hydrophobic be one of them manifestation mode, the contact angle that is meant solid surface and water is greater than 150 degree, and less roll angle is arranged.At present, the method that makes up super-hydrophobic solid surface mainly contains two kinds: (1) increases the solid surface coarse structure; (2) modify solid surface with low surface energy material such as fluorochemicals.In recent years, people have done number of research projects in the super-hydrophobic solid surface of structure field.A kind of super-hydrophobic, self-cleaning nano structural table facial tissue is disclosed as Chinese patent publication number 1415800.They use silica gel on the plain paper surface, ethyl acetate and lacquer thinner, the nano structure superficial layer that preparation one deck is super-hydrophobic, clean certainly.Chinese patent publication number 1379128 adopts chemical Vapor deposition processs, obtains having the film of array structure, uses the vitriol oil of heat then successively, and a large amount of ultrapure waters and the alcoholic solution that contains hydrophobic agents are handled, and thermal treatment can obtain super double-hydropholic film again.From these two patents as can be seen, the silica gel nanoparticle that the former adopts is easy to reunite, and tends to make result of experiment to fall short of success for lack of final effort.The latter then needs to adopt fluorine-containing hydrophobic agents to handle, and can cause environmental pollution.Chinese patent publication number 1397668 is prepared the polymer nanofiber with super hydrophobic surface by the template extrusion process under the free-floride effect.But this preparation method template used frangible, cost an arm and a leg, the industrial applications prospect is limited.
At present, people are in the research work that makes up super-hydrophobic solid surface, and selection mainly still concentrates on some and has group and some comparatively expensive polymkeric substance such as specific function base such as fluorine, silicon.As tetrafluoroethylene (W.Chen, A.Y.Fadeev, M.C.Heieh, D. ner, J.Youngblod, T.J.McCarthy, Langmuir1999,15,3395), the poly-trimethylammonium methoxy silane (Y.Wu of chemical Vapor deposition process preparation, H.Sugimura, Y.Inoue, 0.Takai, Chem.Vap.Deposition 2002,8,47), class honeycomb shape carbon nanotube (S.Li, H.Li, X.Wang, Y.Song, Y.Liu, L.Jiang, D.Zhu, J.Phys.Chem.B.2002,106,9247).How with common common used material under free-floride participation condition, prepare and have super hydrophobic surface, will be a problem that challenge is more arranged.Science in 2003 has reported the common plastics polyisobutylene has been changed into 160 ° of super hydrophobic surfaces by 104 ° of hydrophobic surfaces.Polyisobutylene at high temperature is dissolved in the mixed solvent of 60% pair-dimethylbenzene/40% methyl ethyl ketone, and cooling makes the solvent evaporates film forming then, polyisobutylene crystallization and form porous-film.Coarse porous surface makes polyisobutylene film surface change into super hydrophobic surface.(H.Y.Erbil，A.L.Demirel，Y.Avc，O.Mert，Science，2003，297，1377)。
As everyone knows, polyvinyl chloride is to be only second to poly second general-purpose plastics, in daily life, is that tubing, bar, the sheet material of polyvinyl chloride all is seen everywhere, and it also is simultaneously a kind of mould material relatively more commonly used.Its smooth film surface is 102 ± 1.2 ° with the contact angle of water, is general hydrophobic material, and it also is the low-down common plastics of a kind of degree of crystallinity.We adopt the phase inversion process of solvent-precipitation agent, preparing surface microstructure is the cellular PVC film that micron and nano-scale particle are piled up, the contact angle of this kind film and water is greater than 150 ° under modifying without any the low surface energy material, water droplet less than 15 °, has good ultra-hydrophobicity in the roll angle of material surface.Polyvinyl chloride is prepared into a kind of super hydrophobic surface that has,, in pipeline transportation, can reduces the inner-walls of duct energy consumption this material is had from clean anti-greasy dirt function.And not using any low surface energy fluorine-containing material in the preparation process, this type material will not have any toxic action to human body, and will be environmentally friendly, pollution-free.This preparation method is simple to operate, and the film ultra-hydrophobicity of preparing is stable, and favorable reproducibility need not any expensive device, and the energy large-scale production has extraordinary industrial applications prospect.
Summary of the invention
One of purpose of the present invention is to provide a kind of new cellular PVC mould material, and this material has super-hydrophobic characteristic.
The preparation method of the cellular PVC film that another object of the present invention is to provide super-hydrophobic.
Super-hydrophobic cellular PVC mould material of the present invention, be the porous-film of surperficial particulate short texture spherical in shape, spherical particle diameters 100nm～1 μ m, hole are 10nm～1 μ m, the contact angle of film and water is at 150 °～172 °, water droplet in the roll angle of material surface less than 1～15 °.
Of the present invention have a super-hydrophobic cellular PVC mould material, is to adopt the inversion of phases method of solvent-precipitation agent to be prepared from the substrate material surface of smooth imporosity structure.
Of the present invention have a super-hydrophobic cellular PVC mould material, and its superhydrophobic property can not disappear through the placement that reaches month, and superhydrophobic property is stable.
Of the present invention have a super-hydrophobic cellular PVC mould material, is the vesicular structure that loosens that the surface is micron and nano particle, and surface tissue is very coarse.
Of the present invention have a super-hydrophobic cellular PVC mould material, is the film that the self-supporting of certain intensity is arranged.
Of the present invention have super-hydrophobic cellular PVC preparation method of film material step and comprise:
(1). polyvinyl chloride (PVC) RESINS is dissolved in the solvent, is made into the preparation liquid that concentration is 1～35wt%.
(2). the substrate material of smooth surface is clean to be handled
(3). precipitation agent on the blade coating of substrate material surface, the polyvinyl chloride coating solution that step (1) is prepared on the rapid again blade coating, wherein the volume ratio of precipitation agent and coating solution is 1: 0.1～1: 8, precipitation agent and solvent are slowly volatilized, and the polyvinyl chloride coating solution slowly forms the super-hydrophobic cellular PVC film of white at substrate surface.
(4). vacuum-drying.
Of the present invention have the super-hydrophobic employed solvent of cellular PVC mould material can be tetrahydrofuran (THF), pimelinketone, tetrahydrofuran (THF) and pimelinketone mixture, tetrahydrofuran (THF) and/or pimelinketone respectively with any mixed solvent of methyl ethyl diketone, ethyl acetate etc.
It is of the present invention that to have the super-hydrophobic employed precipitation agent of cellular PVC mould material can be mixed solvent of water, ethanol, acetone, propyl carbinol, methyl alcohol, n-propyl alcohol, Virahol, ethyl acetate or their any proportionings etc.
It is of the present invention that to have the super-hydrophobic employed substrate material of cellular PVC mould material can be glass, ceramic plate, silicon chip, nylon 6, polyvinylidene difluoride (PVDF), tetrafluoroethylene or synthon etc.
Of the present invention have a super-hydrophobic employed preparation method of cellular PVC mould material, is under modifying without any low surface energy material (as fluorine material), the superhydrophobic characteristic of the ordinary resin film of realization.
Of the present invention have a super-hydrophobic employed preparation method of cellular PVC mould material, easy and simple to handle, equipment is simple, can scale operation, have good industrial applications prospect.
Of the present invention have a super-hydrophobic employed preparation method of cellular PVC mould material, for the Application Areas of expanding general-purpose plastics provides a kind of new preparation approach.
Description of drawings
Fig. 1. the embodiment of the invention 3 has the Electronic Speculum structure iron of super-hydrophobic cellular PVC mould material;
Fig. 2. the embodiment of the invention 4 has the Electronic Speculum structure iron of super-hydrophobic cellular PVC mould material;
Fig. 3. the embodiment of the invention 3 has the super-hydrophobic cellular PVC mould material and the contact angle test pattern of water;
Fig. 4. the embodiment of the invention 4 has the super-hydrophobic cellular PVC mould material and the contact angle test pattern of water.
Concrete ten thousand formulas of implementing
Embodiment 1
1 part polyvinyl chloride (PVC) RESINS is dissolved in 18 parts the tetrahydrofuran (THF).Under the room temperature, splash into about 1 volume of ethanol on the glass baseplate that precleaning is good in the culture dish, splash into the polyvinyl chloride solution of about 1.5 times of volumes behind the blade coating rapidly, blade coating is once more gently, solvent-precipitation agent is slowly volatilized, slowly form the porous-film of the short texture of white at substrate surface.After the vacuum-drying 2 hours, on optics contact angle instrument (JY-82 type), carry out the test of material surface wettability.Gained polychloroethylene film surface is 163.6 ± 2.3 ° with the contact angle of water, and roll angle is 3.9 °.JEOL JSM-6700F, AMRAY 191OFE scanning electron microscope shows the vesicular structure that the particle surperficial spherical in shape of polychloroethylene film is piled up, and wherein particle diameter is 100nm～1 μ m, and hole is about 10nm～1 μ m.
Embodiment 2
Press working method and the step of embodiment 1, it is the mixed solvent (volume ratio is 5: 1) of 0.5 volume of ethanol and water that precipitation agent is used instead.Gained polychloroethylene film surface is 161.0 ± 2.0 ° with the contact angle of water, and roll angle is 5 °, and the rounded particle of membrane superficial tissue is piled up, and wherein the particle diameter size is 100nm～1 μ m, and hole is about 10nm～1 μ m.
Embodiment 3
Press working method and the step of embodiment 1, it is the mixed solvent (volume ratio is 2: 1) of 0.3 volume of ethanol and water that precipitation agent is used instead.Gained polychloroethylene film surface is 155.3 ± 2.8 ° with the contact angle of water, and roll angle is 6.7 °, and membrane superficial tissue is ellipse or circular granular is piled up, and wherein the particle diameter size is 100nm～1 μ m, and hole is about 10nm～1 μ m.
Embodiment 4
Press working method and the step of embodiment 1, use precipitation agent instead the acetone of 1 volume and the mixed solvent of water (volume ratio is 5: 1).Gained polychloroethylene film surface is 163.5 ± 2.3 ° with the contact angle of water, and roll angle is 4.7 °, and membrane superficial tissue is ellipse or circular granular is piled up, and wherein the particulate diameter is 100nm～1.5 μ m, and hole is about 10nm～1 μ m.
Embodiment 5
Press working method and the step of embodiment 1, precipitation agent is used instead the ethyl acetate and the ethanol mixed solvent (volume ratio is 5: 1) of 3 volumes.The surface of gained polychloroethylene film and the contact angle of water are 152.1 ± 1.6 °, and roll angle is 8.5 °, and membrane superficial tissue is ellipse or circular granular is piled up, and wherein the particulate diameter is 100nm～1.5 μ m, and hole is about 10nm～1 μ m.
Embodiment 6
Press working method and the step of embodiment 1, with 1 times of use of tetrahydrofuran solution dilution of polyvinyl chloride (PVC) RESINS.The surface of gained polychloroethylene film and the contact angle of water are 169.7 ± 1.5 °, and roll angle is 4.5 °, and membrane superficial tissue is ellipse or circular granular is piled up, and wherein the particulate diameter is 100nm～1 μ m, and hole is about 10nm～1 μ m.
Embodiment 7
Press working method and the step of embodiment 1, with the concentrated 1 times of use of the tetrahydrofuran solution of polyvinyl chloride (PVC) RESINS.With the contact angle of water be 156.4 ± 3.1 °, roll angle is 4.5 °, membrane superficial tissue ovalize particle is piled up, wherein the particulate diameter is 100nm～2 μ m, hole is about 10nm～1 μ m.
Embodiment 8
Press working method and the step of embodiment 1, precipitation agent is used instead the propyl carbinol of 1 volume.The surface of gained polychloroethylene film and the contact angle of water are 150.7 ± 3.2 °, and roll angle is 9.5 °, and membrane superficial tissue is ellipse or circular granular is piled up, and wherein the particulate diameter is 100nm～1 μ m, and hole is about 10nm～1 μ m.
Embodiment 9
Press working method and the step of embodiment 1, polyvinyl chloride (PVC) RESINS is used instead 36 parts pimelinketone dissolving.Gained polychloroethylene film surface is 160.3 ± 2.4 ° with the contact angle of water, and roll angle is 5 °, the vesicular structure that surperficial rounded particle is piled up, and wherein particle diameter is 100nm～1 μ m, hole is about 10nm～1 μ m.
Embodiment 10
Press working method and the step of embodiment 1, polyvinyl chloride (PVC) RESINS is used instead the mixing solutions dissolving of 20 parts tetrahydrofuran (THF) and methyl ethyl diketone.Gained polychloroethylene film surface is 157.3 ± 3.1 ° with the contact angle of water, and roll angle is 9 °, the vesicular structure that surperficial rounded particle is piled up, and wherein particle diameter is 100nm～1.5 μ m, hole is about 10nm～1 μ m.
Embodiment 11
Press working method and the step of embodiment 1,, use precipitation agent instead the acetone of 0.5 volume and the mixed solvent of water (volume ratio is 5: 1) the mixing solutions dissolving that polyvinyl chloride (PVC) RESINS is used 25 parts pimelinketone and methyl ethyl diketone instead.Gained polychloroethylene film surface is 150.3 ± 2.9 ° with the contact angle of water, and roll angle is 12.5 °, the vesicular structure that the rounded particle in film surface is piled up, and wherein particle diameter is 100nm～1.5 μ m, hole is about 10nm～1 μ m.
Embodiment 12
Press working method and the step of embodiment 1, use polyvinyl chloride (PVC) RESINS instead 25 parts pimelinketone and the mixing solutions dissolving of ethyl acetate, precipitation agent is used instead the methyl alcohol of 0.5 volume.Gained polychloroethylene film surface is 151.5 ± 2.8 ° with the contact angle of water, and roll angle is 14.5 °, the vesicular structure that the rounded and oval particle in film surface is piled up, and wherein particle diameter is 100nm～2 μ m, hole is about 10nm～1 μ m.
Claims (5)
1. super-hydrophobic cellular PVC film, it is characterized in that: described film is the porous-film of surperficial particulate short texture spherical in shape, spherical particle diameters 100nm～1 μ m, hole is 10nm～1 μ m, the contact angle of film and water is at 150 °～172 °, water droplet in the roll angle on mould material surface less than 1～15 °.
2. the preparation method of a super-hydrophobic cellular PVC film as claimed in claim 1 is characterized in that: adopt the step of the phase inversion process of solvent-precipitation agent to comprise:
(1). polyvinyl chloride (PVC) RESINS is dissolved in the solvent, is made into the preparation liquid that concentration is 1～35wt%;
(2). precipitation agent on the blade coating of clean substrate material surface, the polyvinyl chloride coating solution that step (1) is prepared on the rapid again blade coating, wherein the volume ratio of precipitation agent and coating solution is 1: 0.1～1: 8, make precipitation agent and solvent evaporates, the polyvinyl chloride coating solution forms super-hydrophobic cellular PVC film at substrate surface;
Described precipitation agent is the mixed solvent of water, ethanol, acetone, propyl carbinol, methyl alcohol, n-propyl alcohol, Virahol, ethyl acetate or their any proportionings.
3. method as claimed in claim 2 is characterized in that: described super-hydrophobic cellular PVC film is further dry under vacuum condition.
4. method as claimed in claim 2 is characterized in that: described solvent be tetrahydrofuran (THF), pimelinketone, tetrahydrofuran (THF) and pimelinketone mixture, tetrahydrofuran (THF) and/or pimelinketone respectively with any mixed solvent of methyl ethyl diketone, ethyl acetate.
5. method as claimed in claim 2 is characterized in that: described substrate material is glass, ceramic plate, silicon chip, nylon 6, polyvinylidene difluoride (PVDF), tetrafluoroethylene or synthon.
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Cited By (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107801367A (en) * | 2017-09-26 | 2018-03-13 | 中国科学院宁波材料技术与工程研究所 | A kind of hydrophobic porous polymer conductive material, preparation method and application |
| CN107801367B (en) * | 2017-09-26 | 2019-04-16 | 中国科学院宁波材料技术与工程研究所 | A kind of hydrophobic porous polymer conductive material, preparation method and application |
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