CN102407079A - Usage of fluorine-containing polyarylether in preparation of asymmetrical film - Google Patents
Usage of fluorine-containing polyarylether in preparation of asymmetrical film Download PDFInfo
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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 preparation technology 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 synthetic anisotropic membrane preparations that reach based on two kinds of fluorine resins that contain the polyarylether film of trifluoromethyl with resin raw material.
Background technology
Polyarylether class material is broad-spectrum one type of membrane material, is the focus of membrane material research.The polyarylether resinoid is one type of macromolecular compound that on main chain, contains ehter bond and aromatic ring, 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 moulding is processed.On the other hand,, promptly in side chain, introduce side group or in main chain, introduce distorted-structure, can improve the dissolubility of this base polymer, be convenient to method machine-shaping through solution-cast through destroying the regularity of polyarylether chain.
Polyarylether polymer generally has higher glass transition temperature and better heat endurance than aliphatic polymer.Existing research proof, the polyether-ether-ketone and the polyethers nitrile that contain the trifluoromethyl side group all have very good heat endurance, and 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 cyanic acid 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.
With polysulfones (Polysulfone) is that the polyarylether class material of representative is proved to be and can be applicable to separation membrane material, and successful commercialization, in separation membrane material, occupies critical role.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 and the selectivity of gas simultaneously.On this theoretical foundation, trifluoromethyl group is incorporated in the polyarylether polymer, can improve the permeability and the selectivity of gas.In the report of existing document; Polyether-ether-ketone and polyethers nitrile dense film to containing 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 selectivity 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 combine porous layer permeability and good mechanical property, the advantage that the compacted zone selectivity is good.Through 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 that the present invention will solve 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, prepares two kinds of polyarylether system film special materials 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 one type of material that has high thermal stability, good filming property and see through and select performance preferably.In addition, the trifluoromethyl in the polyarylether polymer has excellent hydrophobic property, can make the membrane material that makes in wet environment, have good dimensional stability.
Fluorinated poly arylene ether among the present invention is 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 following.
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 a reactant, is salt forming agent with the Anhydrous potassium carbonate; With sulfolane or N-methyl pyrrolidone is solvent, 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, and is warming up to azeotropy dehydrant under the nitrogen protection and refluxes, and reacts 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 the polyarylether film special material that will contain trifluoromethyl, butanols, good solvent mix 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 to be prone to the N that 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 mixed.
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 help improving the quality of anisotropic membrane.
The present invention is incorporated into trifluoromethyl group in the side group of polymer through 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 as far as 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, and the supporting layer structure that makes is spongy hole or the hole with gradient-structure; This type 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.As far as 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 type film separation is low, but transmission rates is high, 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, as can beappreciated from fig. 1 contain the characteristic absorption peak of trifluoromethyl group and carbonyl, 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, as can beappreciated from fig. 2 contain the characteristic absorption peak of trifluoromethyl group and cyanic acid, 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, after scraper is manually wipeed off, puts into the deionized water coagulating bath; 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.The porous support layer of the asymmetric membrane that as can beappreciated from fig. 3, is made by polyether-ether-ketone is a 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, after scraper is manually wipeed off, puts into the deionized water coagulating bath; 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, after scraper is manually wipeed off, puts into the deionized water coagulating bath; 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 beappreciated from fig. 4, the anisotropic membrane that is made by the polyethers nitrile has compacted zone and the porous support layer of finger-shaped as thin as a wafer.
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 made film with the gained casting solution, then continuously by the matrix of nonwoven as anisotropic membrane on automatic knifing machine; Coagulating bath is a 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 beappreciated from fig. 5; The anisotropic membrane that is made by polyether-ether-ketone has as thin as a wafer compacted zone and gradient porous supporting layer; Figure left side is fine and close epidermal area, can find out that the supporting layer near fine and close epidermal area is the finger-shaped structure, is spongelike structure near the supporting layer of bottom.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 made film with the gained casting solution, then continuously by the matrix of nonwoven as anisotropic membrane on automatic knifing machine; Coagulating bath is a 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 the gained casting solution is being made film on the knifing machine automatically continuously; By the matrix of nonwoven as anisotropic membrane, coagulating bath is a 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 beappreciated from fig. 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, and N-dimethylacetylamide/oxolane mixed solvent will 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 made film with the gained casting solution, then continuously by the matrix of nonwoven as anisotropic membrane on automatic knifing machine; Coagulating bath is a 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.Can find out that from Fig. 7,8 comparison 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 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 (3)
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 a reactant, is salt forming agent with the Anhydrous potassium carbonate; With sulfolane or N-methyl pyrrolidone is solvent, 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, and is warming up to azeotropy dehydrant under the nitrogen protection and refluxes, and reacts 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 the polyarylether film special material that will contain trifluoromethyl, butanols, good solvent mix 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.
2. the purposes of fluorinated poly arylene ether according to claim 1 in the anisotropic membrane preparation is characterized in that described good solvent is N, and the N-dimethylacetylamide is or/and oxolane.
3. the purposes of fluorinated poly arylene ether according to claim 1 and 2 in the 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.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106914153A (en) * | 2017-04-12 | 2017-07-04 | 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 |
| CN117698242A (en) * | 2023-12-18 | 2024-03-15 | 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 |
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| CN106914153A (en) * | 2017-04-12 | 2017-07-04 | 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 |
| CN117698242A (en) * | 2023-12-18 | 2024-03-15 | 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 |
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