CN102649315A - Polyvinylidene fluoride microporous film prepared through gelatin extrusion tape casting method - Google Patents
Polyvinylidene fluoride microporous film prepared through gelatin extrusion tape casting method Download PDFInfo
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- CN102649315A CN102649315A CN201110043356XA CN201110043356A CN102649315A CN 102649315 A CN102649315 A CN 102649315A CN 201110043356X A CN201110043356X A CN 201110043356XA CN 201110043356 A CN201110043356 A CN 201110043356A CN 102649315 A CN102649315 A CN 102649315A
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Abstract
The invention relates to a process for preparing a polyvinylidene fluoride microporous film through a gelatin extrusion tape casting method. The process is as follows: polyvinylidene fluoride resin and a certain amount of solvent are mixed into gelatin and then are added into an extruder for smelting and extrusion through a feeding machine, and pass through the neck ring mold of a mold and form the film on a continuous heating and uniformly rotating roller or a steel strip, then the film is wound by a winding machine after drying, and eventually, the finished product of the microporous film is obtained. The steel strip is heated by a blaster, and air enters into an air inlet for heating and then passes through a casting machine, and then is discharged through an air outlet. The invention is characterized in that the solid content of gelinite added into the extruder is high, the volatilization quantity of the solvent is less, pollutions to air are less, besides, forming, drying and shaping can be performed at the same time during a thin film preparation process, the film forming rate is high, and the efficiency is high; the film preparing process is simple and flexible; and the film flatness is excellent, the thickness is uniform and adjustable, and the mechanical property is high.
Description
One, technical field
The present invention relates to a kind of gel and extrude the technology that the curtain coating legal system is equipped with polyvinylidene fluoride microporous film, belong to polymer processing field.
Two, background technology
Kynoar (PVDF) is a kind of thermoplastic fluorocarbon resin of function admirable, has outstanding anti-solvent, acid and alkali-resistance, resistance to oxidation, weatherability and chemical stability.The PVDF film in outdoor placement one, not becoming fragile in 20 years does not produce be full of cracks yet, using wavelength is the ultra violet lamp 1 year of 20～400nm, its performance is constant basically.PVDF can only be dissolved in or be partially soluble in oleum, highly basic and the dimethyl formamide minority solvents such as (DMF), the corrosion of acid and alkali, alkali and strong oxidizer and halogen at room temperature.The fusing point of PVDF (about 170 ℃) differs more than 100 ℃ with decomposition temperature (316 ℃), and heat endurance is high, thereby has good processing and forming condition.Because Kynoar has above-mentioned advantage, and the film of ability curtain coating formation better performances, U.S. Millipore company has realized commercialization as filtration and detection with film with polyvinylidene fluoride film in late 1970s.So far, polyvinylidene fluoride film is widely used in fields such as chemical industry, metallurgy, medicine, weaving and food.
At present the main method of preparation polymer microporous film has phase inversion (immersion precipitation, thermally induced phase separation, assisted evaporative thermic are separated etc.), pulling method and sintering process etc., and wherein phase inversion is one of the most frequently used method.Phase inversion is to transform film forming through the liquid-liquid phase separation of controlling polymer solution.
1 immersion precipitation
Immersion precipitation is a preparation PVDF microporous barrier modal method, and its basic principle is in polymer solution, to add non-solvent, and generation is separated, polymer gelization and coming out with the solid form precipitating.In general, immersion precipitation prepares polymer film will satisfy three conditions: the one, and polymer has optimum solvent, so that obtain the polymer solution of high concentration; The 2nd, optimum solvent can be miscible with some non-solvent of polymer; The 3rd, chemical reaction does not take place between polymer, solvent and the non-solvent.Adopt immersion precipitation to prepare microporous barrier, the polymer solution concentration scope is between 10～40%.The too low then film-strength of solution concentration is poor, and the too high then polymer dissolution of concentration is not in good state.
2 thermally induced phase separations (TIPS)
Thermally induced phase separation (TIPS) is a kind of new technology for preparing microporous barrier that just grows up after the eighties in 20th century, and it has been opened up phase separation method and has prepared the new way of microporous barrier, and it is various to make the structure of film.The TIPS legal system is equipped with microporous barrier and mainly comprises following step.
1) select the diluent of a kind of higher boiling, low relative molecular mass, at high temperature, with mixed with polymers, preparation polymer-diluent homogeneous phase solution.
2) this pyrosol is prefabricated into required form, like film, bulk, doughnut etc.
3) with the certain speed cooling, inductive phase is separated.
4) with the method for solvent extraction or decompression, remove diluent, promptly obtain microporous membrane material after the drying.
The preparation microporous barrier mainly contains following advantage: but control hole footpath and porosity size have various pore structure form, the kind of membrane material increases greatly, and film-forming process is prone to serialization.
3 assisted evaporative thermics be separated (TAEPS)
In the control that is prepared in microcellular structure of traditional P VDF microporous barrier its limitation being arranged, when preparing the PVDF microporous barrier like immersion precipitation, is solvent with DMF; Can form big and short finger-like pore at the upper epidermis of film, the aggregation of spherocrystal is formed on the bottom, and is solvent with DMAc; Forming the finger-like pore that almost traverses whole film, is solvent with NMP, forms wide and long finger-like pore; And TEP forms dendritic crystal on the surface, is the aggregation of spherocrystal at section.Obtain spongy, the asymmetric or anisotropic microcellular structure of rule, must add some inorganic or organic additives.When preparing the PVDF microporous barrier,, form bigger cavity between spherocrystal because the stronger crystallization trend of PVDF forms the microcellular structure that contains spherocrystal easily with TIPS.And prepare the PVDF microporous barrier with TAEPS, can pass through the influence factor in the adjustment preparation process, thereby obtain different microporous membrane structure.TAEPS can be divided into three processes: stir polymer solution on hot platform (1) with constant temperature bath; (2) with solution-cast to certain thickness platform, with the temperature identical heating with the first step; (3) polymer solution is together put into baking oven together with platform, with device platform is sealed, heated polymerizable thing solution makes the evaporation of solvent and non-solvent.TAEPS is a kind of novel evaporation masking technique, can be used for polymer and high-melting-point dicyandiamide solution, can obtain the membrane structure of different shape, has remedied the limitation of TIPS method and immersion precipitation legal system film.
The method of the above-mentioned PVDF of preparation microporous barrier all belongs to solwution method, and using the amount of solvent is 70～90%, and the solvent evaporates amount is big in the film-forming process, and solid content is low.And gel to extrude The tape casting be that polymer is mixed into gel with required little solvent at a certain temperature, extrude through extruder then, and on roller that continues heating and uniform rotation or steel band the method for casting film-forming.
Three, summary of the invention
The objective of the invention is to above-mentioned polyvinylidene fluoride microporous film preparation method's defective and provide a kind of gel to extrude the technology that the curtain coating legal system is equipped with polyvinylidene fluoride microporous film; Be characterized in that the solvent evaporates amount is few, solid content is high; Casting film-forming and dry solidification are accomplished at roller or steel band synchronously, and technology is simple, film forming speed is fast and efficient is high, thickness is evenly adjustable.
The capital equipment that the present invention relates to is extruder and steel band casting machine; On the preparation history of microporous barrier, can be described as and have initiative trial; Through lot of test with to the continuous transformation of casting machine, for the industrialization of polymer microporous film, produce in enormous quantities and established solid foundation.
The objective of the invention is to realize that by following technical measures wherein said material concentration is weight fraction except that specified otherwise.
Gel is extruded the technology that the curtain coating legal system is equipped with polyvinylidene fluoride microporous film and is comprised following processing step:
1,100 parts of polyvinylidene fluoride resins is become levigelinite with 12～25 parts of stirring solvent, this gelinite is joined in the extruder (2) through feeder (1).
2, in the step 1, the solvent that adds in the polyvinylidene fluoride resin can be N, N-dimethylacetylamide (DMAC), N, dinethylformamide (DMF) and N-methyl pyrrolidone (NMP), or mixed solvent wherein.
3, material under 200～215 ℃ in screw extruder (2) plastifying fusion extrude, through mould mouth mould (3) casting film-forming.
4, film casting is to steel band (5), and steel band (5) through casting machine, is discharged through air outlet (4,8) after air entering air inlet (6, the 7) heating through the air blast heating then.
5, by winder (9) rolling film forming, finally obtain the microporous barrier finished product after the steel band drying of passing through to heat continuously.
The present invention compares prior art and has following advantage:
1, the present invention has improved the preparation method of traditional polyvinylidene fluoride microporous film; Adopt the roller or the steel band of easy continuous heating, uniform rotation to carry cast film; Film forming, drying, typing are carried out simultaneously, and rate of film build is high, technical process is simple, energy savings.
2, the gelinite that forms of polymer and solvent can pass through extruder fusion extrusion casting film forming, and solvent evaporates forms micropore in the forming process, and the solvent load of this film-forming method is few, and solid content is high, and the mechanical strength that makes film is high.
3, the present invention adopts roller or steel band casting film-forming, film forming evenly and thickness can arbitrarily adjust, adapt to industrialization, produce continuously.
Four, concrete embodiment
Through embodiment the present invention is specifically described below.It is important to point out that embodiment only is used for the present invention is further specified; Can not be interpreted as the restriction to protection domain of the present invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment one
In 10kg PVDF, add 2kg N, N-dimethylacetylamide (DMAC) at room temperature stirs into even gel.Afterwards gelinite is added in the metering feeding device (1) of extruder, under 200～215 ℃ in screw extruder (2) plastifying fusion extrude, go up casting film-forming through mould mouth mould (3) at the steel band (5) of 80 ℃ uniform rotation, the steel band rotating speed is 3 rev/mins.Through after the steel band drying of continuous heating by winder (9) rolling film forming, finally obtain the microporous barrier finished product.The thickness of film is 20 μ m, and the thickness deviation of vertical, transverse direction is all less than 0.5 μ m, and micropore size is 2～5 μ m, and voidage is 43%, and the water flux under the 0.1MPa pressure is 180L/m2h.
Embodiment two
In 10kg PVDF, add 2kg N, dinethylformamide (DMF) at room temperature stirs into even gel.Afterwards gelinite is added in the metering feeding device (1) of extruder, under 200～215 ℃ in screw extruder (2) plastifying fusion extrude, go up casting film-forming through mould mouth mould (3) at the steel band (5) of 70 ℃ uniform rotation, the steel band rotating speed is 3 rev/mins.Through after the steel band drying of continuous heating by winder (9) rolling film forming, finally obtain the microporous barrier finished product.The thickness of film is 20 μ m, and the thickness deviation of vertical, transverse direction is all less than 0.5 μ m, and micropore size is 2～5 μ m, and voidage is 40%, and the water flux under the 0.1MPa pressure is 175L/m2h.
Embodiment three
In 10kg PVDF, add 2kg N-methyl pyrrolidone (NMP), at room temperature stir into even gel.Afterwards gelinite is added in the metering feeding device (1) of extruder, under 200～215 ℃ in screw extruder (2) plastifying fusion extrude, go up casting film-forming through mould mouth mould (3) at the steel band (5) of 100 ℃ uniform rotation, the steel band rotating speed is 3 rev/mins.Through after the steel band drying of continuous heating by winder (9) rolling film forming, finally obtain the microporous barrier finished product.The thickness of film is 20 μ m, and the thickness deviation of vertical, transverse direction is all less than 0.5 μ m, and micropore size is 2～5 μ m, and voidage is 50%, and the water flux under the 0.1MPa pressure is 195L/m2h.
Five, description of drawings
Figure of description is that gel is extruded the process chart that the curtain coating legal system is equipped with polyvinylidene fluoride microporous film.
Claims (5)
- Gel is extruded the curtain coating legal system and is equipped with polyvinylidene fluoride microporous film and is meant Kynoar (be called for short PVDF) resin and its good solvent are mixed into the even gel body, extrudes the method that the curtain coating processes becomes film through extruder then.1. a gel is extruded the technology that the curtain coating legal system is equipped with polyvinylidene fluoride microporous film, it is characterized in that comprising following processing step: (1) with polyvinylidene fluoride resin at a certain temperature with required solvent gel; (2) melt extrude through extruder; (3) casting film-forming on roller that continues heating and uniform rotation or steel band, roller or steel band inwall evenly heating make dry rapidly, the demoulding fast of its surperficial film; (4) dried film take-up is the polyvinylidene fluoride microporous film finished product.
- 2. gel as claimed in claim 1 is extruded the technology that the curtain coating legal system is equipped with polyvinylidene fluoride microporous film; It is characterized in that described solvent can select N for use; N-dimethylacetylamide (DMAC), N-methyl pyrrolidone (NMP), N; Dinethylformamides (DMF) etc. and the good solvent of polyvinylidene fluoride resin compatibility, its addition is 10～20%.
- 3. gel as claimed in claim 1 is extruded the technology that the curtain coating legal system is equipped with polyvinylidene fluoride microporous film; It is characterized in that polyvinylidene fluoride resin and solvent can at room temperature be mixed into the underflow material or be mixed into even gel at a certain temperature, extrude through screw extruder.
- 4. gel as claimed in claim 1 is extruded the technology that the curtain coating legal system is equipped with polyvinylidene fluoride microporous film, it is characterized in that preparing the polyvinyladine floride microporous barrier and melt extrudes temperature between 200～220 ℃.
- 5. gel as claimed in claim 1 is extruded the technology that the curtain coating legal system is equipped with polyvinylidene fluoride microporous film, it is characterized in that thin film-forming method is simple, flexibly, can select that steel band is extruded curtain coating, roller is extruded film-forming methods such as curtain coating for use.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103213227A (en) * | 2013-05-09 | 2013-07-24 | 宝应县润华静电涂装工程有限公司 | Film forming system for preparing perfluorinated ionic membrane in slobbering method and film forming process of film forming system |
| CN103242660A (en) * | 2013-05-27 | 2013-08-14 | 刘江萍 | Preparation method of high-dielectric film |
| CN103350497A (en) * | 2013-05-14 | 2013-10-16 | 郑泓 | Special precision extrusion system for polyvinylidene fluoride |
| CN103831211A (en) * | 2014-03-21 | 2014-06-04 | 厦门大学 | Device for manufacturing salivating film by using airstream solution |
| CN104015371A (en) * | 2014-06-19 | 2014-09-03 | 陕西科技大学 | Method for preparing polyvinylidene fluoride (PVDF) orientation film and method for enhancing polycaprolactone (PCL) by utilizing PVDF orientation film |
| CN104139517A (en) * | 2014-07-22 | 2014-11-12 | 广州市合诚化学有限公司 | Quick detection device and method for filler content |
| CN105835272A (en) * | 2016-04-20 | 2016-08-10 | 肇庆市宏华电子科技有限公司 | Cast film drying equipment |
| CN107009559A (en) * | 2017-03-17 | 2017-08-04 | 天津工业大学 | A kind of preparation method of three-dimension code diaphragm |
| CN107303734A (en) * | 2016-04-18 | 2017-10-31 | 北京化工大学 | Gel extrusion curtain coating method prepares polyvinylidene fluoride microporous film |
| CN112157849A (en) * | 2020-08-28 | 2021-01-01 | 王园红 | Cooling plastic wrap device capable of controlling air cooling and water cooling combination according to moving speed |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5013339A (en) * | 1989-12-05 | 1991-05-07 | The Dow Chemical Company | Compositions useful for making microporous polyvinylidene fluoride membranes, and process |
| JP2003518537A (en) * | 1999-12-23 | 2003-06-10 | アクセンタス パブリック リミテッド カンパニー | Membrane with microporous structure |
| CN101370572A (en) * | 2006-01-11 | 2009-02-18 | 东洋纺织株式会社 | Polyvinylidene fluoride hollow yarn type microporous film and process for production of the same |
| CN101632903A (en) * | 2009-07-07 | 2010-01-27 | 河北工业大学 | Polyvinylidene fluoride microporous film and preparation method |
| CN101728549A (en) * | 2009-12-10 | 2010-06-09 | 山东东岳神舟新材料有限公司 | High-temperature proton exchange compound film |
-
2011
- 2011-02-23 CN CN201110043356XA patent/CN102649315A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5013339A (en) * | 1989-12-05 | 1991-05-07 | The Dow Chemical Company | Compositions useful for making microporous polyvinylidene fluoride membranes, and process |
| JP2003518537A (en) * | 1999-12-23 | 2003-06-10 | アクセンタス パブリック リミテッド カンパニー | Membrane with microporous structure |
| CN101370572A (en) * | 2006-01-11 | 2009-02-18 | 东洋纺织株式会社 | Polyvinylidene fluoride hollow yarn type microporous film and process for production of the same |
| CN101632903A (en) * | 2009-07-07 | 2010-01-27 | 河北工业大学 | Polyvinylidene fluoride microporous film and preparation method |
| CN101728549A (en) * | 2009-12-10 | 2010-06-09 | 山东东岳神舟新材料有限公司 | High-temperature proton exchange compound film |
Non-Patent Citations (2)
| Title |
|---|
| 李洪飞，苑会林,王婧: ""凝胶挤出流延聚氟乙烯薄膜的研究"", 《塑料工业》 * |
| 顾明浩等: ""聚偏氟乙烯微孔膜制备方法研究进展"", 《工业水处理》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103213227B (en) * | 2013-05-09 | 2015-02-04 | 宝应县润华静电涂装工程有限公司 | Film forming system for preparing perfluorinated ionic membrane in slobbering method and film forming process of film forming system |
| CN103213227A (en) * | 2013-05-09 | 2013-07-24 | 宝应县润华静电涂装工程有限公司 | Film forming system for preparing perfluorinated ionic membrane in slobbering method and film forming process of film forming system |
| CN103350497A (en) * | 2013-05-14 | 2013-10-16 | 郑泓 | Special precision extrusion system for polyvinylidene fluoride |
| CN103350497B (en) * | 2013-05-14 | 2016-01-13 | 郑泓 | A kind of Special precision extrusion system for polyvinylidene fluoride |
| CN103242660A (en) * | 2013-05-27 | 2013-08-14 | 刘江萍 | Preparation method of high-dielectric film |
| CN103242660B (en) * | 2013-05-27 | 2015-12-23 | 刘江萍 | A kind of method preparing high dielectric thin film |
| CN103831211A (en) * | 2014-03-21 | 2014-06-04 | 厦门大学 | Device for manufacturing salivating film by using airstream solution |
| CN104015371A (en) * | 2014-06-19 | 2014-09-03 | 陕西科技大学 | Method for preparing polyvinylidene fluoride (PVDF) orientation film and method for enhancing polycaprolactone (PCL) by utilizing PVDF orientation film |
| CN104139517A (en) * | 2014-07-22 | 2014-11-12 | 广州市合诚化学有限公司 | Quick detection device and method for filler content |
| CN107303734A (en) * | 2016-04-18 | 2017-10-31 | 北京化工大学 | Gel extrusion curtain coating method prepares polyvinylidene fluoride microporous film |
| CN105835272A (en) * | 2016-04-20 | 2016-08-10 | 肇庆市宏华电子科技有限公司 | Cast film drying equipment |
| CN107009559A (en) * | 2017-03-17 | 2017-08-04 | 天津工业大学 | A kind of preparation method of three-dimension code diaphragm |
| CN112157849A (en) * | 2020-08-28 | 2021-01-01 | 王园红 | Cooling plastic wrap device capable of controlling air cooling and water cooling combination according to moving speed |
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Application publication date: 20120829 |