CN103816820B - A kind of semicrystalline polyether-ether-ketone porous film and preparation method thereof - Google Patents
A kind of semicrystalline polyether-ether-ketone porous film and preparation method thereof Download PDFInfo
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- CN103816820B CN103816820B CN201410093924.0A CN201410093924A CN103816820B CN 103816820 B CN103816820 B CN 103816820B CN 201410093924 A CN201410093924 A CN 201410093924A CN 103816820 B CN103816820 B CN 103816820B
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Abstract
Semicrystalline polyether-ether-ketone porous film of the present invention and preparation method thereof belongs to technical field of polymer materials.Its preparation process comprises: (1) by polyether-ether-ketone and PEI blended, 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 ether ether ketone/PEI particle is carried out cooling and shaping by importing three-roller calendar after described slit membrana oralis film extrusion, obtained polyether-ether-ketone/polyetherimde films; (3) wash after described polyether-ether-ketone/PEI membrane extraction with isopropyl alcohol and boiling water, obtained hypocrystalline polyether-ether-ketone porous film after dry.Semicrystalline polyether-ether-ketone porous film of the present invention has excellent performance; Filming technology provided by the invention is simple, can prepare the semicrystalline polyether-ether-ketone porous film of different-thickness and width.
Description
Technical field
The present invention relates to the technical field of macromolecular material and preparation thereof, be specifically related to a kind of semicrystalline 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 membrane, to the transmitance of variety classes gas molecule and selective difference, therefore, can be separated certain gas from admixture of gas.With the competition of conventional separation techniques (distill, absorption, absorb) in demonstrate unique advantage, its research and development is very rapid.This area research mainly concentrates on the desirable novel film materials such as exploitation high osmosis, high selective penetrated property, chemical stability and heat endurance.Much research shows, containing aromatic ring structure on polyether-ether-ketone main chain, so have good heat resistance and mechanical strength, and chemical stability is fine, and solvent resistance is very excellent, possesses the potential quality that preparation has the self-cradling type asymmetric membrane of Thief zone 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, 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 blended, obtain a kind of semicrystalline polyether-ether-ketone porous film, and provide the preparation method of described semicrystalline polyether-ether-ketone porous film.
Concrete technical scheme provided by the invention is:
A kind of semicrystalline polyether-ether-ketone porous film, described semicrystalline polyether-ether-ketone porous film is plate porous membrane, and pore diameter range is 10 ~ 50nm.
A preparation method for semicrystalline polyether-ether-ketone porous film, process is as follows:
(1) by polyether-ether-ketone and PEI blended after in 120 DEG C of dryings 5 hours, extrude granulating with double screw extruder, obtain polyether-ether-ketone/PEI particle;
(2) slit membrana oralis is added in the exit of described double screw extruder, described polyether-ether-ketone/PEI particle is carried out cooling and shaping by importing three-roller calendar after slit membrana oralis film extrusion, obtained polyether-ether-ketone/PEI mixture film;
(3) described polyether-ether-ketone/PEI mixture film extract is respectively washed 3 ~ 5 times with isopropyl alcohol and boiling water in 120 DEG C of extractions after 4 ~ 6 hours respectively, obtained semicrystalline polyether-ether-ketone porous film after dry.
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 DEG C, 340 DEG C, 350 DEG C, 360 DEG C, 350 DEG C and 345 DEG C.
The temperature of described slit membrana oralis is 350 DEG C ~ 360 DEG C, and the temperature of described three-roller calendar is 160 DEG C ~ 200 DEG C, and roller speed is 2 ~ 6m/min, the polyether-ether-ketone/PEI mixture film thickness of preparation and width continuously adjustabe 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, semicrystalline polyether-ether-ketone porous film resistance to elevated temperatures provided by the invention, solvent resistance are excellent, normally can use under severe rugged environment.Compared with traditional preparation method, filming technology provided by the invention is simple, thickness and width continuously adjustable polyether-ether-ketone/PEI mixture film within the specific limits can be prepared by regulating the roller speed of three-roller calendar, the semicrystalline polyether-ether-ketone porous film of different-thickness and width can be prepared thus.In extract, monoethanolamine can react with PEI, is interrupted by PEI long-chain, thus substantially increases extraction efficiency.
Accompanying drawing explanation
PEI film in Fig. 1 embodiment 1 and 2, polyether-ether-ketone/PEI mixture film, the infrared spectrum of semicrystalline polyether-ether-ketone porous film.
The surperficial SEM figure of PEEK30 in Fig. 2 embodiment 1.
In Fig. 3 embodiment 1, the section SEM of PEEK30 schemes.
The DSC curve of PEEK30 in Fig. 4 embodiment 1.
The surperficial SEM figure of PEEK40 in Fig. 5 embodiment 2.
In Fig. 6 embodiment 2, the section SEM of PEEK40 schemes.
Fig. 7 is of the present invention extrudes, extracts and collects integral process process schematic.
Detailed description of the invention
Below by detailed description of the invention, the present invention is described, but is not limited to this.
Embodiment 1
(1) 120g polyether-ether-ketone is mixed with 280g PEI to be placed in baking oven 120 DEG C and to 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 DEG C, 340 DEG C, 350 DEG C, 360 DEG C, 350 DEG C, 345 DEG C;
(2) add slit membrana oralis in the exit of described double screw extruder, described ether ether ketone/PEI particle is carried out cooling and shaping by importing three-roller calendar after described slit membrana oralis film extrusion, obtained polyether-ether-ketone/polyetherimde films; Described twin-screw place gradient temperature is respectively: 280 DEG C, 340 DEG C, 350 DEG C, 360 DEG C, 350 DEG C, 345 DEG C; Slit membrana oralis temperature is 355 DEG C; The roller temperature of three-roller calendar is 190 DEG C; Thickness 2mm, width 150mm polyether-ether-ketone/PEI blend films can be prepared when the process central roll speed 2m/min extruded; Thickness 0.1mm, width 50mm polyether-ether-ketone/PEI blend films can be prepared during roller speed 6m/min, be labeled as PEEK30/PEI70;
(3) described polyether-ether-ketone/polyetherimde films extract is respectively washed 3 ~ 5 times with isopropyl alcohol and boiling water in 120 DEG C of extractions after 5 hours respectively, after dry, obtained semicrystalline polyether-ether-ketone porous flat plate film, is labeled as PEEK30; In described extract, the volume fraction of 1-METHYLPYRROLIDONE, monoethanolamine, distilled water is respectively 90%, and 5%, 5%.
As can be seen from PEEK30 and PEEK30/PEI70 infrared spectrum (accompanying drawing 1), polyether-ether-ketone/polyetherimide amine blends Central Asia amido link characteristic absorption peak 1720cm-1 disappears after the extraction, illustrates that the PEI in mixture has extracted completely.As can be seen from the surface picture (accompanying drawing 2) and cross-section photographs (accompanying drawing 3) of PEEK30 SEM, the polyether-ether-ketone film after extraction defines through hole structure.As can be seen from (accompanying drawing 4) on the DSC curve of PEEK30, semicrystalline polyether-ether-ketone porous film provided by the invention is all very stable before 250 DEG C, and fusing point is 333 DEG C, has good heat-resisting quantity, and this kind of perforated membrane is only dissolved in the concentrated sulfuric acid, illustrate that solvent resistance is excellent.
Embodiment 2
The quality of polyether-ether-ketone and PEI in embodiment 1 is changed to 160g and 240g respectively, and the roller temperature of three-roller calendar is changed to 180 DEG C.Repeat embodiment 1, obtain semicrystalline polyether-ether-ketone porous film, be labeled as PEEK40.Fig. 5 and Fig. 6 provides the surface of PEEK40 and the SEM figure of section.Characterization result is similar to embodiment 1.
Embodiment 3
The quality of polyether-ether-ketone and PEI in embodiment 1 is changed to 80g and 320g respectively, slit membrana oralis temperature is changed to 350 DEG C, the roller temperature of three-roller calendar is changed to 200 DEG C, extraction time is changed to 6 hours, and in extract, the volume fraction of 1-METHYLPYRROLIDONE, monoethanolamine, distilled water is changed to 80%, 10%, 10% respectively.Repeat embodiment 1, obtain semicrystalline 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 200g and 200g respectively, slit membrana oralis temperature is changed to 360 DEG C, the roller temperature of three-roller calendar is changed to 160 DEG C, extraction time is changed to 4 hours, and in extract, the volume fraction of 1-METHYLPYRROLIDONE, monoethanolamine, distilled water is changed to 95%, 2.5%, 2.5% respectively.Repeat embodiment 1, obtain semicrystalline 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 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 preparation method for semicrystalline polyether-ether-ketone porous film, is characterized in that,
(1) by polyether-ether-ketone and PEI blended after in 120 DEG C of dryings 5 hours, extrude granulating with double screw extruder, obtain polyether-ether-ketone/PEI particle;
(2) slit membrana oralis is added in the exit of described double screw extruder, described polyether-ether-ketone/PEI particle is carried out cooling and shaping by importing three-roller calendar after slit membrana oralis film extrusion, obtained polyether-ether-ketone/PEI mixture film;
(3) described polyether-ether-ketone/PEI mixture film extract is respectively washed 3 ~ 5 times with isopropyl alcohol and boiling water in 120 DEG C of extractions after 4 ~ 6 hours respectively, obtained semicrystalline polyether-ether-ketone porous film after dry.
2. the preparation method of semicrystalline polyether-ether-ketone porous film according to claim 1, is characterized in that, the mass ratio of described polyether-ether-ketone and PEI is 20 ~ 50:80 ~ 50.
3. the preparation method of semicrystalline polyether-ether-ketone porous film according to claim 1, is characterized in that, the twin-screw place gradient temperature of described double screw extruder is respectively: 280 DEG C, 340 DEG C, 350 DEG C, 360 DEG C, 350 DEG C and 345 DEG C.
4. the preparation method of semicrystalline polyether-ether-ketone porous film according to claim 1, is characterized in that, the temperature of described slit membrana oralis is 350 DEG C ~ 360 DEG C, and the temperature of described three-roller calendar is 160 DEG C ~ 200 DEG C, and roller speed is 2 ~ 6m/min.
5. the preparation method of semicrystalline polyether-ether-ketone porous film according to claim 1, 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%.
6. the semicrystalline polyether-ether-ketone porous film that the preparation method of the semicrystalline polyether-ether-ketone porous film described in any one of Claims 1 to 5 obtains, it is characterized in that, described semicrystalline polyether-ether-ketone porous film is plate porous membrane, and pore diameter range is 10 ~ 50nm.
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| CN106750258B (en) * | 2017-01-24 | 2019-09-03 | 吉林大学 | Film stage polyetheretherketoneresin resin PP Pipe Compound, preparation method and preparing the application in polyether-ether-ketone/polyetherimide alloy firm |
| CN108148411B (en) * | 2018-01-15 | 2020-06-02 | 吉林大学 | Thermally processable low-Tg cyano-group-containing polyimide, polyimide film, polyimide powder and application thereof |
| 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 |
| CN114534513B (en) * | 2022-03-23 | 2023-03-17 | 烟台大学 | Polyether-ether-ketone hollow fiber porous membrane and preparation method 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 |
| 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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Patent Citations (4)
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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 |
| 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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