CN102407079B - Usage of fluorine-containing polyarylether in preparation of asymmetrical film - Google Patents
Usage of fluorine-containing polyarylether in preparation of asymmetrical film Download PDFInfo
- Publication number
- CN102407079B CN102407079B CN 201110209350 CN201110209350A CN102407079B CN 102407079 B CN102407079 B CN 102407079B CN 201110209350 CN201110209350 CN 201110209350 CN 201110209350 A CN201110209350 A CN 201110209350A CN 102407079 B CN102407079 B CN 102407079B
- Authority
- CN
- China
- Prior art keywords
- trifluoromethyl
- preparation
- film
- polyarylether
- anisotropic membrane
- 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
Landscapes
- Polyethers (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to usage of fluorine-containing polyarylether in the preparation of an asymmetrical film and belongs to the fields of high polymer materials and processing technologies thereof. The fluorine-containing polyarylether is polyether-ether-ketone (PEEK) containing trifluoro-methyl-phenyl side groups or polyether nitrile containing trifluoro-methyl-phenyl side groups. A preparation method of the asymmetrical film mainly comprises the following steps of: on the basis of taking m-trifluoro-methyl-phenyl side group hydroquinone and 4,4'-difluoro-diphenyl ketone or 2,6-difluoro-benzonitrile as raw materials, carrying out nucleophilic substitution reaction, and preparing two special materials for manufacturing a trifluoro-methyl polyarylether film; then, preparing the special materials for manufacturing the trifluoro-methyl polyarylether film into a solution; and finally, obtaining the asymmetrical film by a phase inversion method. The special materials for manufacturing the trifluoro-methyl polyarylether film have the advantages of high molecular weight, good thermal performance, good dissolvability and suitability for membrane separation materials; and the preparationtechnology of the asymmetrical film is applicable to a continuous production process.
Description
Technical field
The invention belongs to macromolecular material and machining technology thereof, be specifically related to two kinds of polyarylether films that contain trifluoromethyl and use the synthetic anisotropic membrane that reaches based on two kinds of fluorine resins of resin raw material to prepare.
Background technology
Polyarylether class material is a broad-spectrum class membrane material, is the focus of membrane material research.To be a class contain the macromolecular compound of ehter bond and aromatic ring at main chain to the polyarylether resinoid, mainly contains PAEK, poly (arylene ether nitrile), polyether sulphone etc., generally has good non-oxidizability, heat endurance and chemical stability, corrosion resistance.This base polymer generally can pass through high-temperature fusion, and the method for molding is processed.On the other hand, by destroying the regularity of polyarylether chain, namely in side chain, introduce side group or in main chain, introduce distorted-structure, can improve the dissolubility of this base polymer, be convenient to the method machine-shaping by solution-cast.
Polyarylether polymer generally has higher glass transition temperature and better heat endurance than aliphatic polymer.There are some researches prove that the polyether-ether-ketone and the polyethers nitrile that contain the trifluoromethyl side group all have very good heat endurance, 5% heat decomposition temperature is about 500 ℃; Poly (arylene ether nitrile) is higher than the glass transition temperature of PAEK, and this is because the existence of strong polar group cyano group has strengthened the active force between macromolecular chain.The weightless temperature that contains the trifluoromethyl polymer is higher than methylic polymer, and its reason is the energy that the energy of C-F key is higher than c h bond, and its fracture needs higher temperature than c h bond.
Be that the polyarylether class material of representative is proved to be and can be applicable to separation membrane material with polysulfones (Polysulfone), and successful commercialization, critical role in separation membrane material, occupied.The polyarylether that contains the trifluoromethyl side group because trifluoromethyl group destroys the accumulation between macromolecular chain, further reduces bulk density, increases the free volume of polymer, improves the diffusion barrier permeability.When keeping the polymer chain rigidity, increase the separation degree between the polymer chain, can improve the permeability of gas simultaneously with selective.On this theoretical foundation, trifluoromethyl group is incorporated in the polyarylether polymer, can improve the permeability of gas with selective.In the report of existing document, the polyether-ether-ketone and the polyethers nitrile dense film that contain the trifluoromethyl benzene lateral group are carried out gas-premeable and selectivity test (showing), because the introducing of trifluoromethyl, for great majority gas commonly used, can improve the permeability of gas, not reduce selective simultaneously.For example, m-trifluoromethyl benzene lateral group polyether-ether-ketone is compared with a methylbenzene side group polyether-ether-ketone, and the oxygen permeability is brought up to 0.38Barrer by 0.2Barrer, and the separation of oxygen/nitrogen brings up to 7.4 by 6.7.
Asymmetric membrane is a kind of film of being made up of thicker porous support layer and the thin epidermal area (compacted zone) of one deck, and the shape in porous support layer hole can be divided into finger-shaped hole and spongy hole.Anisotropic membrane with spongy hole supporting layer can be in conjunction with porous layer permeability and good mechanical property, the selective good advantage of compacted zone.By changing filming technology, can obtain the anisotropic membrane of different micro-structurals, be applied to gas or fluid separation applications industrial circle.
Summary of the invention
The technical problem to be solved in the present invention is, prepares the polyarylether film special material that contains trifluoromethyl, and fluorine resin is prepared into anisotropic membrane.
The present invention at first adopts the method for nucleophilic displacement of fluorine polycondensation, with m-trifluoromethylphenyl side group hydroquinones and 4,4 '-difluoro benzophenone or 2, the 6-difluorobenzonilyile carries out polymerization, prepare two kinds of polyarylether film special materials processed that contain trifluoromethyl, the polyarylether film special material that will contain trifluoromethyl again is mixed with solution, adopts phase inversion to make anisotropic membrane.The polyarylether polymer that contains trifluoromethyl is the material that a class has high thermal stability, good filming and sees through and select performance preferably.In addition, the trifluoromethyl in the polyarylether polymer has excellent hydrophobic property, can make the membrane material that makes have good dimensional stability in wet environment.
Fluorinated poly arylene ether among the present invention is the polyether-ether-ketone (also abbreviating the polyether-ether-ketone that contains trifluoromethyl among the present invention as) that contains the trifluoromethyl side group or the polyethers nitrile (also abbreviating the polyethers nitrile that contains trifluoromethyl among the present invention as) that contains the trifluoromethyl side group.
The said polyarylether film special material that contains trifluoromethyl of the present invention is the polyethers nitrile polymer that contains the polyetheretherketonepolymer polymer of trifluoromethyl side group or contain the trifluoromethyl side group, and its structural formula is respectively:
N=50～500 wherein.
Concrete technical scheme of the present invention is as follows.
The purposes of a kind of fluorinated poly arylene ether in the anisotropic membrane preparation has the preparation of the polyarylether film special material that contains trifluoromethyl and two steps of preparation of anisotropic membrane:
The described preparation that contains the polyarylether film special material of trifluoromethyl, be to be 1: 1 m-trifluoromethylphenyl side group hydroquinones and 4 with mol ratio, 4 '-difluoro benzophenone or 2, the 6-difluorobenzonilyile is reactant, be salt forming agent with the Anhydrous potassium carbonate, being solvent with sulfolane or N-methyl pyrrolidone, is azeotropy dehydrant with toluene; Anhydrous potassium carbonate with 1.2 times of suitable m-trifluoromethylphenyl side group hydroquinones amount of substances, the solvent of 3～4 times of reactant quality, the azeotropy dehydrant of solvent volume 20%～60% is put into the reaction vessel that mechanical agitation and water-taker are housed, being warming up to azeotropy dehydrant under the nitrogen protection refluxes, reacted 2～3 hours, get rid of azeotropy dehydrant, be warming up to 170～180 ℃ and continue reaction 3～6 hours; The polymer that obtains is separated out in deionized water, pulverize, washing, drying obtains the polyethers nitrile that contains the polyether-ether-ketone of trifluoromethyl or contain trifluoromethyl;
The preparation of described anisotropic membrane, be that polyarylether film special material, butanols, the good solvent that will contain trifluoromethyl mixes by mass ratio 1: 0～0.5: 4～9, stir after 12～24 hours solution casting on nonwoven, after scraper striking film forming, put into deionized water, after polymer is separated out film forming, film was placed in water 5～12 hours, remove remaining good solvent and butanols; It is dry to put into vacuum drying oven, obtains anisotropic membrane.The diffusion barrier thickness that makes is at 80～200 μ m.
Described good solvent is the N that easily dissolving contains the polyarylether polymer of side group, and the N-dimethylacetylamide is or/and oxolane.At N, when N-dimethylacetylamide and oxolane were made good solvent, the two can adopt any ratio to mix.
In the preparation of anisotropic membrane, the polyarylether film special material, butanols, good solvent that will contain trifluoromethyl mix stir after, can ultrasonic degas 25～35 minutes, be cast on the nonwoven again.Ultrasonic degas will be conducive to improve the quality of anisotropic membrane.
The present invention is incorporated into trifluoromethyl group in the side group of polymer by design, obtains two kinds of soluble poly aromatic ether resins.These two kinds of materials have high thermal stability (higher heat resistance), the polyether-ether-ketone glass transition temperature that contains the trifluoromethyl side group is 134 ℃, temperature of initial decomposition reaches 525 ℃, and the polyethers nitrile glass transition temperature that contains the trifluoromethyl side group is 151 ℃, and temperature of initial decomposition reaches 482 ℃.
The present invention is for containing the polyether-ether-ketone solution of trifluoromethyl, and with N, the N-dimethylacetylamide is the supporting layer that solvent forms the finger-shaped structure easily; With N, the mixed solvent of N-dimethylacetylamide and oxolane is the supporting layer that solvent forms spongelike structure easily.Become mixed solvent owing to add oxolane in the solvent, than single N, N-dimethylacetamide solvent gel postpones, the supporting layer structure that makes is spongy hole or the hole with gradient-structure, this class film can take into account transmission rates and separation is low, and withstand voltage properties is strong, can be used for gas and separate, and also is applicable to micro porous filtration.For containing the polyethers nitrile solution of trifluoromethyl, with N, the mixed solvent of N-dimethylacetylamide and oxolane is the supporting layer that solvent forms finger-shaped easily, and this class film separation is low, but the transmission rates height is applicable to the application of milipore filter aspect.The film-forming process of anisotropic membrane of the present invention is applicable to continuous production procedure.
Description of drawings
Fig. 1 is the infrared spectrum that contains the polyether-ether-ketone of trifluoromethyl side group of the present invention.
Fig. 2 is the infrared spectrum that contains the polyethers nitrile of trifluoromethyl side group of the present invention.
Fig. 3 is the cross section electromicroscopic photograph of the anisotropic membrane that made by the polyether-ether-ketone that contains trifluoromethyl among the embodiment 3.
Fig. 4 is the cross section electromicroscopic photograph of the anisotropic membrane that made by the polyethers nitrile that contains trifluoromethyl among the embodiment 5.
Fig. 5 is the cross section electromicroscopic photograph of the anisotropic membrane that made by the polyether-ether-ketone that contains trifluoromethyl among the embodiment 6.
Fig. 6 is the electromicroscopic photograph that the anisotropic membrane compacted zone of Fig. 5 amplifies.
Fig. 7 is the cross section electromicroscopic photograph of the anisotropic membrane that made by the polyether-ether-ketone that contains trifluoromethyl among the embodiment 8.
Fig. 8 is the cross section electromicroscopic photograph of the anisotropic membrane that made by the polyether-ether-ketone that contains trifluoromethyl among the embodiment 9.
The specific embodiment
With m-trifluoromethylphenyl side group hydroquinones 12.71g (0.05mol); 4; the Anhydrous potassium carbonate of 4 '-difluoro benzophenone 10.91g (0.05mol) and 8.28g; the 54ml sulfolane; 40ml toluene is put into the there-necked flask that mechanical agitation and water-taker are housed, and is warming up to azeotropy dehydrant under the nitrogen protection and refluxes, and reacts after 2.5 hours; get rid of toluene, be warming up to 170～180 ℃ and continue reaction 4 hours.The polymer that obtains is separated out in deionized water, pulverize, washing, drying obtains containing the powder of the polyether-ether-ketone of trifluoromethyl side group.Number-average molecular weight: 40000.It is 134 ℃ that DSC records glass transition temperature.
The infrared spectrum of product is seen Fig. 1, contain the characteristic absorption peak of trifluoromethyl group and carbonyl as can be seen from Figure 1, proves that we have obtained the polyether-ether-ketone that subject polymer contains the trifluoromethyl side group.
Embodiment 2
With m-trifluoromethylphenyl side group hydroquinones 12.71g (0.05mol); 2; the Anhydrous potassium carbonate of 6-difluorobenzonilyile 6.955g (0.05mol) and 8.28g; the 80mlN-methyl pyrrolidone; 40ml toluene is put into the there-necked flask that mechanical agitation and water-taker are housed, and is warming up to azeotropy dehydrant under the nitrogen protection and refluxes, and reacts after 2.5 hours; get rid of toluene, be warming up to 170 ℃ and continue reaction 4 hours.The polymer that obtains is being separated out in a large amount of frozen water, filtering, washing, drying obtains containing the polyethers nitrile pale powder of trifluoromethyl side group.Number-average molecular weight: 42000.Glass transition temperature is asked 151 ℃.
The infrared spectrum of product is seen Fig. 2, contain the characteristic absorption peak of trifluoromethyl group and cyano group as can be seen from Figure 2, proves that we have obtained the polyethers nitrile that subject polymer contains the trifluoromethyl side group.
To be dissolved in 6.25gN by the polyether-ether-ketone 2.5g that contains trifluoromethyl that makes among the embodiment 1, in the mixed solvent of N-dimethylacetylamide and 1.5g oxolane, add 0.25g n-butanol non-solvent again, stir and mixed in 24 hours, ultrasonic degas 30 minutes is cast on the nonwoven, puts into the deionized water coagulating bath after scraper manually strikes off, film body solidifies fully after 2 hours, obtains the anisotropic membrane by the polyether-ether-ketone preparation that contains trifluoromethyl.
Fig. 3 is the cross section electromicroscopic photograph of the polyether-ether-ketone anisotropic membrane that makes of present embodiment.As can be seen from Figure 3, the porous support layer of the asymmetric membrane that is made by polyether-ether-ketone is spongelike structure.
Embodiment 4
To be dissolved in 5.75gN by the polyether-ether-ketone 3g that contains trifluoromethyl that makes among the embodiment 1, in the mixed solvent of N-dimethylacetylamide and 1.5g oxolane, add 0.25g n-butanol non-solvent again, stir and mixed in 24 hours, ultrasonic degas 30 minutes is cast on the nonwoven, puts into the deionized water coagulating bath after scraper manually strikes off, film body solidifies fully after 2 hours, obtains the anisotropic membrane by the polyether-ether-ketone preparation that contains trifluoromethyl.
Embodiment 5
To be dissolved in 6.75gN by the polyethers nitrile 1.5g that contains trifluoromethyl that makes among the embodiment 2, in the mixed solvent of N-dimethylacetylamide and 1.5g oxolane, add 0.25g n-butanol non-solvent again, stir and mixed in 24 hours, ultrasonic degas 30 minutes is cast on the nonwoven, puts into the deionized water coagulating bath after scraper manually strikes off, film body solidifies fully after 3 hours, obtains the anisotropic membrane by the polyethers nitrile preparation that contains trifluoromethyl.
Fig. 4 is the cross section electromicroscopic photograph of the polyethers nitrile anisotropic membrane that contains trifluoromethyl that makes of present embodiment.As can be seen from Figure 4, the anisotropic membrane that is made by the polyethers nitrile have as thin as a wafer compacted zone and the porous support layer of finger-shaped.
Embodiment 6
To be dissolved in 110gN by the polyether-ether-ketone 60g that contains trifluoromethyl that makes among the embodiment 1, in the mixed solvent of N-dimethylacetylamide and 20g oxolane, add 10g n-butanol non-solvent again, stir and mixed in 24 hours, ultrasonic degas 30 minutes is then with gained casting solution continuous film processed on automatic knifing machine, by the matrix of nonwoven as anisotropic membrane, coagulating bath is deionized water, and the scraper height is 150 μ m.Obtain the anisotropic membrane by the polyether-ether-ketone preparation that contains trifluoromethyl, gained anisotropic membrane width is 0.4 meter, about 2.2 meters of length.
Fig. 5 is the cross section electromicroscopic photograph of the polyether-ether-ketone anisotropic membrane that makes of present embodiment.As can be seen from Figure 5, the anisotropic membrane that is made by polyether-ether-ketone has compacted zone and gradient porous supporting layer as thin as a wafer, the figure left side is fine and close epidermal area, and the supporting layer near fine and close epidermal area is the finger-shaped structure as can be seen, and the supporting layer of close bottom is spongelike structure.Fig. 6 is the electromicroscopic photograph that the anisotropic membrane compacted zone of Fig. 5 amplifies.
Embodiment 7
To be dissolved in 131gN by the polyethers nitrile 34g that contains trifluoromethyl that makes among the embodiment 2, in the mixed solvent of N-dimethylacetylamide and 30g oxolane, add 5g n-butanol non-solvent again, stir and mixed in 24 hours, ultrasonic degas 30 minutes is then with gained casting solution continuous film processed on automatic knifing machine, by the matrix of nonwoven as anisotropic membrane, coagulating bath is deionized water, and the scraper height is 150 μ m.Obtain the anisotropic membrane by the polyethers nitrile preparation that contains trifluoromethyl, gained anisotropic membrane width is 0.4 meter, and length is about 2.1 meters.
Embodiment 8
To be dissolved in 150gN by the polyether-ether-ketone 50g that contains trifluoromethyl that makes among the embodiment 1, in the N-dimethylacetylamide, stir and mixed in 24 hours, used the vavuum pump vacuumize degassing then 20 minutes, then with gained casting solution continuous film processed on automatic knifing machine, by the matrix of nonwoven as anisotropic membrane, coagulating bath is deionized water, and the scraper height is 180 μ m.Obtain the anisotropic membrane by the polyether-ether-ketone preparation that contains trifluoromethyl, gained anisotropic membrane width is 0.4 meter, and length is about 2.0 meters.The supporting layer structure is the finger-shaped hole.
Fig. 7 is the cross section electromicroscopic photograph of the polyether-ether-ketone anisotropic membrane that makes of present embodiment.As can be seen from Figure 7, the supporting layer of the polyether-ether-ketone anisotropic membrane that makes of present embodiment is the finger-shaped pore structure.
Embodiment 9
The dose volume ratio is 3: 2 N, N-dimethylacetylamide/oxolane mixed solvent, to be dissolved in this mixed solvent of 150g by the polyether-ether-ketone 50g that contains the trifluoromethyl side group that makes among the embodiment 1, stir and mixed in 24 hours, ultrasonic degas 30 minutes is then with gained casting solution continuous film processed on automatic knifing machine, by the matrix of nonwoven as anisotropic membrane, coagulating bath is deionized water, and the scraper height is 180 μ m.Obtain the anisotropic membrane by the polyether-ether-ketone preparation that contains the trifluoromethyl side group, gained anisotropic membrane width is 0.4 meter, and length is about 2.1 meters.
Fig. 8 is the cross section electromicroscopic photograph of the polyether-ether-ketone anisotropic membrane that makes of present embodiment.From Fig. 7,8 more as can be seen, the supporting layer of the polyether-ether-ketone anisotropic membrane among Fig. 7 is the finger-shaped pore structure.And in the present embodiment, owing to contain oxolane in the solvent, phase separation is relatively slow, thus form the supporting layer with spongy hole, and also supporting layer has gradient-structure, and bigger near a lateral aperture of cortex, and less near a lateral aperture of bottom.
Claims (2)
1. the fluorinated poly arylene ether purposes in the anisotropic membrane preparation has the preparation of the polyarylether film special material that contains trifluoromethyl and two steps of preparation of anisotropic membrane:
The described preparation that contains the polyarylether film special material of trifluoromethyl, be to be 1: 1 m-trifluoromethylphenyl side group hydroquinones and 4 with mol ratio, 4'-difluoro benzophenone or 2, the 6-difluorobenzonilyile is reactant, be salt forming agent with the Anhydrous potassium carbonate, being solvent with sulfolane or N-methyl pyrrolidone, is azeotropy dehydrant with toluene; Anhydrous potassium carbonate with 1.2 times of suitable m-trifluoromethylphenyl side group hydroquinones amount of substances, the solvent of 3～4 times of reactant quality, the azeotropy dehydrant of solvent volume 20%～60% is put into the reaction vessel that mechanical agitation and water-taker are housed, being warming up to azeotropy dehydrant under the nitrogen protection refluxes, reacted 2～3 hours, get rid of azeotropy dehydrant, be warming up to 170～180 ℃ and continue reaction 3～6 hours; The polymer that obtains is separated out in deionized water, pulverize, washing, drying obtains the polyethers nitrile that contains the polyether-ether-ketone of trifluoromethyl or contain trifluoromethyl;
The preparation of described anisotropic membrane, be that polyarylether film special material, butanols, the good solvent that will contain trifluoromethyl mixes by mass ratio 1: 0～0.5: 4～9, stir after 12～24 hours solution casting on nonwoven, after scraper striking film forming, put into deionized water, after polymer is separated out film forming, film was placed in water 5～12 hours, remove remaining good solvent and butanols; It is dry to put into vacuum drying oven, obtains anisotropic membrane; Described good solvent is N, and the N-dimethylacetylamide is or/and oxolane.
2. the purposes of fluorinated poly arylene ether according to claim 1 in anisotropic membrane preparation, it is characterized in that, in the preparation of described anisotropic membrane, the polyarylether film special material, butanols, good solvent that will contain trifluoromethyl mix stir after, ultrasonic degas 25～35 minutes is cast on the nonwoven again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110209350 CN102407079B (en) | 2011-07-26 | 2011-07-26 | Usage of fluorine-containing polyarylether in preparation of asymmetrical film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110209350 CN102407079B (en) | 2011-07-26 | 2011-07-26 | Usage of fluorine-containing polyarylether in preparation of asymmetrical film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102407079A CN102407079A (en) | 2012-04-11 |
| CN102407079B true CN102407079B (en) | 2013-09-25 |
Family
ID=45909604
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110209350 Expired - Fee Related CN102407079B (en) | 2011-07-26 | 2011-07-26 | Usage of fluorine-containing polyarylether in preparation of asymmetrical film |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102407079B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106914153B (en) * | 2017-04-12 | 2018-10-02 | 江苏拓邦环保科技有限公司 | A kind of complex reverse osmosis membrane |
| CN114181053A (en) * | 2021-12-29 | 2022-03-15 | 大连理工大学盘锦产业技术研究院 | Preparation method of diphenol monomer with lateral group containing trifluoromethyl and polyarylether polymer thereof |
| CN117698242B (en) * | 2023-12-18 | 2024-09-24 | 江苏君华特种高分子材料股份有限公司 | Reinforced polyaryletherketone composite material with high interface adhesion and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583699A (en) * | 2004-06-13 | 2005-02-23 | 吉林大学 | 3-trifluoromethyl-4-chlorophenyl paradioxybenzene, its synthesis and polyaryl ether ketone therefrom |
| CN1594254A (en) * | 2004-07-09 | 2005-03-16 | 吉林大学 | (4-(4'-trifluoromethyl)phenoxy phenyl)-hydroquinone and its synthesis method and application in polymer material |
| CN1670055A (en) * | 2004-12-31 | 2005-09-21 | 吉林大学 | Preparation of photosensitive fluorine-containing poly(aryl ether) materials and use thereof |
| CN101381455A (en) * | 2008-10-08 | 2009-03-11 | 吉林大学 | Polyarylether material bearing a sulfonic acid group on a pendant group, and preparation method and application thereof |
-
2011
- 2011-07-26 CN CN 201110209350 patent/CN102407079B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583699A (en) * | 2004-06-13 | 2005-02-23 | 吉林大学 | 3-trifluoromethyl-4-chlorophenyl paradioxybenzene, its synthesis and polyaryl ether ketone therefrom |
| CN1594254A (en) * | 2004-07-09 | 2005-03-16 | 吉林大学 | (4-(4'-trifluoromethyl)phenoxy phenyl)-hydroquinone and its synthesis method and application in polymer material |
| CN1670055A (en) * | 2004-12-31 | 2005-09-21 | 吉林大学 | Preparation of photosensitive fluorine-containing poly(aryl ether) materials and use thereof |
| CN101381455A (en) * | 2008-10-08 | 2009-03-11 | 吉林大学 | Polyarylether material bearing a sulfonic acid group on a pendant group, and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 含氟侧基聚芳醚酮的合成与表征;王贵宾等;《高等学校化学学报》;20000831;第21卷(第8期);第1325页第1行至第1326页第6行，附图1-3 * |
| 王贵宾等.含氟侧基聚芳醚酮的合成与表征.《高等学校化学学报》.2000,第21卷(第8期),第1325页第1行至第1326页第6行，附图1-3. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102407079A (en) | 2012-04-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103261279B (en) | Quaternised polybenzimidazole | |
| CN106008978B (en) | A kind of oxatyl-containing lateral group polyarylether analog copolymer, preparation method and its application at the film hydrophilically modified aspect of ultrafiltration | |
| CN108291026A (en) | With intrinsic micro porous TROGER alkali polymer | |
| Xu et al. | Acid induced self-assembly strategy to synthesize ordered mesoporous carbons from biomass | |
| CN109546191B (en) | Mixed matrix type anion membrane and preparation method thereof | |
| CN103113589B (en) | Side-chain sulfonated polyaryletherketone sulphone as well as preparation method and application | |
| CN101434697B (en) | Side chain type sulphonation polyarylether ketone based on naphthalene ring and preparation thereof | |
| CN106366636A (en) | Metal-organic framework nanocrystal loaded polyurethane foam as well as preparation and application thereof | |
| CN102407079B (en) | Usage of fluorine-containing polyarylether in preparation of asymmetrical film | |
| CN101381455B (en) | Side base sulfonic acid type polyarylether material, and preparation method and application thereof | |
| CN102585204A (en) | Side-chain sulfonic acid type polyarylether, preparation method thereof and application of polyarylether in preparation of proton exchange membrane | |
| CN102728247A (en) | Preparation method of composite forward osmosis membrane | |
| Mathieu et al. | Macroporous poly (ionic liquid)/ionic liquid gels via CO 2-based emulsion-templating polymerization | |
| CN106310974B (en) | A kind of flexible self-supporting carbon molecular sieve@graphene composite films and preparation method thereof | |
| CN102492131A (en) | Polyaryl ether nitrile resin, polyaryl ether nitrile film and preparation method thereof | |
| Wang et al. | Recent progress on the poly (arylene ether) s-based electrospun nanofibers for high-performance applications | |
| CN102174199A (en) | Polyether sulfone containing side group as well as preparation method and application thereof in gas separation membrane | |
| Xie et al. | Poly (aryl ether ketone) composite membrane as a high‐performance lithium‐ion batteries separator | |
| CN103406034A (en) | Preparation method of polyether block amide microporous film for film distillation process | |
| CN104971633A (en) | Preparation method of composite forward osmosis membrane made from polyaramid | |
| CN100586541C (en) | Method for preparing polyvinylidene fluoride microporous filtering film | |
| CN106076128B (en) | A method of the hydrophilic ultrafiltration membrane of polyarylether containing carboxyl is prepared by phenolphthalein structure polyarylether hydrolysis/reduction | |
| CN103804680B (en) | Crystal type sulfonated polyether ketone, polyetherketoneetherketoneketone and preparation method thereof | |
| CN113842783B (en) | Acid-resistant high-flux polyarylether composite nanofiltration membrane, and preparation method and application thereof | |
| CN109119662A (en) | Poly- (hetero) aryl indole anion-exchange membrane of a kind of double pectinations of long-chain branch and preparation method thereof |
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: 20130925 Termination date: 20200726 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |