CN103816820A - Hypocrystalline PEEK (polyether-ether-ketone) porous membrane and preparation method thereof - Google Patents
Hypocrystalline PEEK (polyether-ether-ketone) porous membrane and preparation method thereof Download PDFInfo
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- CN103816820A CN103816820A CN201410093924.0A CN201410093924A CN103816820A CN 103816820 A CN103816820 A CN 103816820A CN 201410093924 A CN201410093924 A CN 201410093924A CN 103816820 A CN103816820 A CN 103816820A
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Abstract
The invention provides a hypocrystalline PEEK (polyether-ether-ketone) porous membrane and a preparation method thereof, and belongs to the technical field of polymer materials. The preparation method comprises the following steps: (1) mixing PEEK with polyetherimide; squeezing for granulation through a double-screw extruder to obtain PEEK/polyetherimide granules; (2) adding a slit type outlet membrane at the outlet of the double-screw extruder; squeezing PEEK/polyetherimide granules out through the slit type outlet membrane for membrane forming; feeding formed PEEK/polyetherimide granules into a three-roll machine calender for cooling and forming to obtain a PEEK/polyetherimide membrane; (3) membrane extracting the PEEK/polyetherimide membrane and then washing with isopropyl alcohol and boiling water; drying to obtain a hypocrystalline PEEK porous membrane. The hypocrystalline PEEK porous membrane has excellent properties; the membrane production technology provided by the invention is simple; hypocrystalline PEEK porous membranes with different thicknesses and widths can be prepared.
Description
Technical field
The present invention relates to the technical field of macromolecular material and preparation thereof, be specifically related to a kind of half hitch crystal formation polyether-ether-ketone porous film and preparation method thereof.
Background technology
Membrane separation technique efficiency is high, and cost is low, consumes energy little, simple to operate, and non-secondary pollution, more and more attracts much attention.Different polymeric membranes, to the transmitance of variety classes gas molecule and selective different, therefore, can separate certain gas from admixture of gas.With the competition of traditional isolation technics (distillation, absorption, absorb) in demonstrate unique advantage, its research and development is very rapid.This area research mainly concentrates on exploitation high osmosis, the high desirable novel film materials such as permeability, chemical stability and heat endurance of selecting.Much research shows, on polyether-ether-ketone main chain, contains aromatic ring structure, thus there is good heat resistance and mechanical strength, and chemical stability is fine, and solvent resistance is very excellent, possesses the potential quality of the self-cradling type asymmetric membrane that is prepared with high infiltration coefficient.Along with the raising that development and the various application of polymer science require film properties, polyether-ether-ketone receives much concern as the material of excellent performance.
Summary of the invention
The technical problem to be solved in the present invention is that traditional gas separation membrane cannot normally use under severe rugged environment, the shortcoming that solvent resistance and resistance to elevated temperatures are not given prominence to.The technical solution used in the present invention is by polyether-ether-ketone and PEI blend, to obtain a kind of half hitch crystal formation polyether-ether-ketone porous film, and the preparation method of described half hitch crystal formation polyether-ether-ketone porous film is provided.
Concrete technical scheme provided by the invention is:
A kind of half hitch crystal formation polyether-ether-ketone porous film, described half hitch crystal formation polyether-ether-ketone porous film is plate porous membrane, pore diameter range is 10～50nm.
A preparation method for half hitch crystal formation polyether-ether-ketone porous film, process is as follows:
(1) by after polyether-ether-ketone and PEI blend in 120 ℃ dry 5 hours, extrude granulating with double screw extruder, obtain polyether-ether-ketone/PEI particle;
(2) add slit membrana oralis in the exit of described double screw extruder, described polyether-ether-ketone/PEI particle is imported to three-roller calendar after by slit membrana oralis film extrusion and carry out cooling and shaping, make polyether-ether-ketone/PEI mixture film;
(3) described polyether-ether-ketone/PEI mixture film is used extract respectively wash 3～5 times with isopropyl alcohol and boiling water respectively after 4～6 hours in 120 ℃ of extractions, after being dried, made half hitch crystal formation polyether-ether-ketone porous film.
The mass ratio of described polyether-ether-ketone and PEI is 20～50:80～50.
The twin-screw place gradient temperature of described double screw extruder is respectively: 280 ℃, and 340 ℃, 350 ℃, 360 ℃, 350 ℃ and 345 ℃.
The temperature of described slit membrana oralis is 350 ℃～360 ℃, and the temperature of described three-roller calendar is 160 ℃～200 ℃, and roller speed is 2～6m/min, and polyether-ether-ketone/PEI mixture film thickness and the width of preparation are adjustable continuously within the specific limits.
Described extract is made up of 1-METHYLPYRROLIDONE, monoethanolamine and distilled water; Wherein the volume fraction of 1-METHYLPYRROLIDONE is 80%～95%, and the volume fraction of monoethanolamine is 2.5%～10%, and the volume fraction of distilled water is 2.5%～10%.
Extrude, extract and collect integral process process as shown in Figure 7.
Compared with traditional polyether-ether-ketone film, half hitch crystal formation polyether-ether-ketone porous film resistance to elevated temperatures provided by the invention, solvent resistance excellence can normally be used under severe rugged environment.Compared with traditional preparation method, filming technology provided by the invention is simple, can prepare thickness and the continuously adjustable polyether-ether-ketone/PEI of width mixture film within the specific limits by the roller speed that regulates three-roller calendar, can prepare thus the half hitch crystal formation polyether-ether-ketone porous film of different-thickness and width.In extract, monoethanolamine can react with PEI, PEI long-chain is interrupted, thereby greatly improved extraction efficiency.
Accompanying drawing explanation
PEI film in Fig. 1 embodiment 1 and 2, polyether-ether-ketone/PEI mixture film, the infrared spectrum of half hitch crystal formation polyether-ether-ketone porous film.
The surperficial SEM figure of PEEK30 in Fig. 2 embodiment 1.
The section SEM of PEEK30 figure in Fig. 3 embodiment 1.
The DSC curve of PEEK30 in Fig. 4 embodiment 1.
The surperficial SEM figure of PEEK40 in Fig. 5 embodiment 2.
The section SEM of PEEK40 figure in Fig. 6 embodiment 2.
Fig. 7 is of the present invention extrudes, extracts and collect integral process process schematic diagram.
The specific embodiment
Below by the specific embodiment, the present invention is described, but is not limited to this.
(1) 120g polyether-ether-ketone is mixed with 280g PEI and be placed in baking oven 120 ℃ and dry 5 hours, extrude granulating with double screw extruder bar, obtain polyether-ether-ketone/PEI particle; Described twin-screw place gradient temperature is respectively: 280 ℃, 340 ℃, 350 ℃, 360 ℃, 350 ℃, 345 ℃;
(2) add slit membrana oralis in the exit of described double screw extruder, described ether ether ketone/PEI particle is imported to three-roller calendar after by described slit membrana oralis film extrusion and carry out cooling and shaping, make polyether-ether-ketone/polyetherimde films; Described twin-screw place gradient temperature is respectively: 280 ℃, 340 ℃, 350 ℃, 360 ℃, 350 ℃, 345 ℃; Slit membrana oralis temperature is 355 ℃; The roller temperature of three-roller calendar is 190 ℃; In the time of the process central roll speed 2m/min extruding, can prepare thickness 2mm, width 150mm polyether-ether-ketone/PEI blend films; When roller speed 6m/min, can prepare thickness 0.1mm, width 50mm polyether-ether-ketone/PEI blend films, be labeled as PEEK30/PEI70;
(3) described polyether-ether-ketone/polyetherimde films is used extract respectively wash 3～5 times with isopropyl alcohol and boiling water respectively after 5 hours in 120 ℃ of extractions, after being dried, made half hitch crystal formation polyether-ether-ketone porous flat plate film, be labeled as PEEK30; In described extract, the volume fraction of 1-METHYLPYRROLIDONE, monoethanolamine, distilled water is respectively 90%, 5%, and 5%.
From PEEK30 and PEEK30/PEI70 infrared spectrum (accompanying drawing 1) can find out, polyether-ether-ketone/polyetherimide amine blends Central Asia amido link characteristic absorption peak 1720cm-1 has disappeared after extraction, illustrates that the PEI in mixture has extracted completely.From the surface picture (accompanying drawing 2) of PEEK30 SEM and section photo (accompanying drawing 3), can find out, the polyether-ether-ketone film after extraction has formed through hole structure.From the DSC curve of PEEK30, (accompanying drawing 4) can be found out, half hitch crystal formation polyether-ether-ketone porous film provided by the invention is all very stable before 250 ℃, and fusing point is 333 ℃, has good heat-resisting quantity, and this kind of perforated membrane is only dissolved in the concentrated sulfuric acid, and solvent resistance excellence is described.
Embodiment 2
The quality of polyether-ether-ketone and PEI in embodiment 1 is changed to respectively to 160g and 240g, and the roller temperature of three-roller calendar is changed to 180 ℃.Repeat embodiment 1, obtain half hitch crystal formation polyether-ether-ketone porous film, be labeled as PEEK40.Fig. 5 and Fig. 6 provide the surface of PEEK40 and the SEM of section figure.Characterization result is similar to embodiment 1.
Embodiment 3
The quality of polyether-ether-ketone and PEI in embodiment 1 is changed to respectively to 80g and 320g, slit membrana oralis temperature is changed to 350 ℃, the roller temperature of three-roller calendar is changed to 200 ℃, extraction time is changed to 6 hours, and in extract, the volume fraction of 1-METHYLPYRROLIDONE, monoethanolamine, distilled water is changed to respectively 80%, 10%, 10%.Repeat embodiment 1, obtain half hitch crystal formation polyether-ether-ketone porous film, be labeled as PEEK20.Characterization result is similar to embodiment 1.
Embodiment 4
The quality of polyether-ether-ketone and PEI in embodiment 1 is changed to respectively to 200g and 200g, slit membrana oralis temperature is changed to 360 ℃, the roller temperature of three-roller calendar is changed to 160 ℃, extraction time is changed to 4 hours, and in extract, the volume fraction of 1-METHYLPYRROLIDONE, monoethanolamine, distilled water is changed to respectively 95%, 2.5%, 2.5%.Repeat embodiment 1, obtain half hitch crystal formation polyether-ether-ketone porous film, be labeled as PEEK50.Characterization result is similar to embodiment 1.
Above content is in conjunction with concrete preferred embodiment further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For the person of ordinary skill of the art, can be according to technical scheme of the present invention and inventive concept, make corresponding change and substitute, and performance or purposes identical, all should be considered as protection scope of the present invention.
Claims (6)
1. a half hitch crystal formation polyether-ether-ketone porous film, is characterized in that, described half hitch crystal formation polyether-ether-ketone porous film is plate porous membrane, and pore diameter range is 10～50nm.
2. a preparation method for the half hitch crystal formation polyether-ether-ketone porous film of claim 1, is characterized in that,
(1) by after polyether-ether-ketone and PEI blend in 120 ℃ dry 5 hours, extrude granulating with double screw extruder, obtain polyether-ether-ketone/PEI particle;
(2) add slit membrana oralis in the exit of described double screw extruder, described polyether-ether-ketone/PEI particle is imported to three-roller calendar after by slit membrana oralis film extrusion and carry out cooling and shaping, make polyether-ether-ketone/PEI mixture film;
(3) described polyether-ether-ketone/PEI mixture film is used extract respectively wash 3～5 times with isopropyl alcohol and boiling water respectively after 4～6 hours in 120 ℃ of extractions, after being dried, made half hitch crystal formation polyether-ether-ketone porous film.
3. the preparation method of half hitch crystal formation polyether-ether-ketone porous film according to claim 2, is characterized in that, the mass ratio of described polyether-ether-ketone and PEI is 20～50:80～50.
4. the preparation method of half hitch crystal formation polyether-ether-ketone porous film according to claim 2, is characterized in that, the twin-screw place gradient temperature of described double screw extruder is respectively: 280 ℃, and 340 ℃, 350 ℃, 360 ℃, 350 ℃ and 345 ℃.
5. the preparation method of half hitch crystal formation polyether-ether-ketone porous film according to claim 2, is characterized in that, the temperature of described slit membrana oralis is 350 ℃～360 ℃, and the temperature of described three-roller calendar is 160 ℃～200 ℃, and roller speed is 2～6m/min.
6. the preparation method of half hitch crystal formation polyether-ether-ketone porous film according to claim 2, is characterized in that, described extract is made up of 1-METHYLPYRROLIDONE, monoethanolamine and distilled water; Wherein the volume fraction of 1-METHYLPYRROLIDONE is 80%～95%, and the volume fraction of monoethanolamine is 2.5%～10%, and the volume fraction of distilled water is 2.5%～10%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750258A (en) * | 2017-01-24 | 2017-05-31 | 吉林大学 | Film stage polyetheretherketoneresin resin PP Pipe Compound, preparation method and the application in polyether-ether-ketone/PEI alloy firm is prepared |
| CN108148411A (en) * | 2018-01-15 | 2018-06-12 | 吉林大学 | It is a kind of can hot-working, low Tg cyano-containing polyimides, polyimide film, polyimide powder and its application |
| CN108499369A (en) * | 2018-03-08 | 2018-09-07 | 四川大学 | Polyether-ether-ketone hollow-fibre membrane, its method for controlling aperture and preparation method |
| CN108854606A (en) * | 2018-07-04 | 2018-11-23 | 四川大学 | The preparation method of super hydrophilic polyether-ether-ketone hollow-fibre membrane |
| CN114534513A (en) * | 2022-03-23 | 2022-05-27 | 烟台大学 | Polyether-ether-ketone hollow fiber porous membrane and preparation method thereof |
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| CN1745887A (en) * | 2004-09-08 | 2006-03-15 | 比亚迪股份有限公司 | Production of polyolefin microporous membrane |
| CN101234304A (en) * | 2007-02-02 | 2008-08-06 | 中国科学院化学研究所 | Polyether-ether-ketone porous film and preparation thereof |
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| US5997741A (en) * | 1994-12-05 | 1999-12-07 | Asahi Kasei Kogyo Kabushiki Kaisha | Process for preparing a polyether ether ketone membrane |
| CN1377908A (en) * | 2001-03-14 | 2002-11-06 | 住友化学工业株式会社 | Method for producing resin film material and resin film material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106750258A (en) * | 2017-01-24 | 2017-05-31 | 吉林大学 | Film stage polyetheretherketoneresin resin PP Pipe Compound, preparation method and the application in polyether-ether-ketone/PEI alloy firm is prepared |
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| CN108148411A (en) * | 2018-01-15 | 2018-06-12 | 吉林大学 | It is a kind of can hot-working, low Tg cyano-containing polyimides, polyimide film, polyimide powder and its application |
| CN108499369A (en) * | 2018-03-08 | 2018-09-07 | 四川大学 | Polyether-ether-ketone hollow-fibre membrane, its method for controlling aperture and preparation method |
| CN108854606A (en) * | 2018-07-04 | 2018-11-23 | 四川大学 | The preparation method of super hydrophilic polyether-ether-ketone hollow-fibre membrane |
| CN114534513A (en) * | 2022-03-23 | 2022-05-27 | 烟台大学 | Polyether-ether-ketone hollow fiber porous membrane and preparation method thereof |
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