CN105056775A - Carbon nanotube toughened and strengthened polysulfone (PSF) hollow fibrous membrane and preparation method thereof - Google Patents
Carbon nanotube toughened and strengthened polysulfone (PSF) hollow fibrous membrane and preparation method thereof Download PDFInfo
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Abstract
The invention provides a carbon nanotube toughened and strengthened polysulfone (PSF) hollow fibrous membrane and a preparation method thereof. The hollow fibrous membrane comprises, by weight parts, 5-20 parts of multiwalled carbon nanotubes, 10-30 parts of PSF, 60-85 parts of solvent and 5-25 parts of additive. The PSF is polysulfone. The carbon nanotubes serve as a small-molecule additive, not only can restrain formation of macropores, but also greatly toughen and strengthen a polysulfone membrane, and have a little effect on the permeability of the membrane. A hollow fiber is good in strength, elasticity and fatigue resistance, and the permeability of the membrane is good.
Description
Technical field
The invention belongs to doughnut technical field of membrane, especially relate to a kind of CNT activeness and quietness PSF hollow-fibre membrane and preparation method thereof.
Background technology
Polysulfones material is the class membrane material applying a lot, due to its good chemical stability, resistance to water, heat resistance, dimensional stability, and preferably film forming and mechanical strength, be widely used in micro-filtration, counter-infiltration, ultrafiltration, electrodialysis, gas separaion, bioengineering, medical treatment etc.Polysulfones resin is the macromolecular compound that a class contains sulfuryl and aromatic ring on main chain, mainly contains bisphenol-a polysulfone, polyarylsulfone (PAS), polyether sulfone, PPSS etc.As can be seen from structure, the both sides of sulfuryl have phenyl ring to form conjugated system, and because sulphur atom is in highest oxidation state, sulfuryl both sides height conjugation in addition, so this resinoid has excellent non-oxidizability, heat endurance and high-temperature fusion stability.
At present, the preparation method that PS membrane is conventional is immersion precipitation phase inversion process (NIPS).This method be first by the homogeneous phase casting solution curtain coating formed at a certain temperature by polysulfones, solvent, non-solvent additive to backing material or extruded by spinning head and form nascent state film, then it is immersed rapidly in non-solvent coagulating bath, by the mutual exchange of the solvent in nascent state film and the non-solvent in coagulating bath, the ratio of continuous reduction film internal solvent thus system is separated, final gel solidification film forming.
Relate generally to thermodynamics and kinetics in polysulfones casting solution generation phase separation, these two factors finally determine morphosis and the performance of PS membrane.The mutual exchange process of the solvent in nascent state film and the non-solvent in coagulating bath is dynamic process, its speed have impact on membrane pore structure to a great extent: under the prerequisite not having other additives, both exchange faster, more easily form large, penetrating finger-like pore, otherwise, little and thin finger-like pore even sponge hole may be formed.From macro property, the form in hole, size, can affect hot strength and the elongation at break of film, i.e. film strength and toughness.Hole more loose penetrating, aperture is larger, hot strength and the elongation at break of film are less; On the contrary, if fenestra is tiny, closely knit, even form sponge structure, hot strength and the elongation at break of film are higher, and intensity and toughness are also better.
Kim, Chakrabarty, Ma etc. have studied additives polyethylene glycol (PEG) to the performance impact of PS membrane.Along with the increase of PEG molal weight and content, the viscosity of system increases, and the diffusion coefficient between non-solvent and solvent reduces, the rate of settling of polymer is reduced, finger-like pore in membrane structure is suppressed and reduces gradually, and fenestra number and porosity increase, and aquifer yield decreases.Tsai etc. with the addition of Small molecular sorbester p17 in polysulfones casting solution, and research finds that sorbester p17 can suppress the generation of finger-like pore, and when its addition is increased to 15% gradually, film section structure gradually becomes spongy hole from a large amount of finger-like pore, and permeability of the membrane can reduce.Equally, non-ionic surfactant Tween 80, owing to can increase the viscosity of casting solution, makes the time lengthening that is separated, and the aperture of film reduces, and permeance property reduces.As can be seen here, no matter be adding of large molecular additives Small molecular surfactant, although macropore can be suppressed to be formed, but also reduce permeability of the membrane energy.
Summary of the invention
In view of this, the present invention is intended to propose a kind of CNT activeness and quietness PSF hollow-fibre membrane and preparation method, and its hollow-fibre membrane has that intensity is high, toughness is good, and the advantage such as permeance property is good.
For achieving the above object, technical scheme of the present invention is achieved in that
A kind of CNT activeness and quietness PSF hollow-fibre membrane, comprises each component of following parts by weight, multi-walled carbon nano-tubes 5 ~ 20 parts, PSF10 ~ 30 part, solvent 60 ~ 85 parts, additive 5 ~ 25 parts; Described PSF is polysulfones.
Using CNT as micromolecule additive, macropore not only can be suppressed to be formed, can also because of the character of self, great activeness and quietness PS membrane, and very micro-on permeability of the membrane impact.
CNT, has another name called Baji-tube, is a kind of One-dimensional Quantum material with special construction, is found in January, 1991 by Japanese physicist Sumio Iijima.The coaxial pipe of several layers to tens of layers that CNT forms primarily of the carbon atom in hexagonal array is formed.Keep fixing distance between layers, about 0.34nm, diameter is generally 2 ~ 20nm.
CNT has good mechanical property, and tensile strength reaches 50 ~ 200GPa, and be 100 times of steel, density but only has 1/6 of steel, at least high than an ordinary graphite fiber order of magnitude; Its elastic modelling quantity can reach 1TPa, suitable with adamantine elastic modelling quantity, is about 5 times of steel.For the CNT of solid wall with ideal structure, its tensile strength is about 800GPa.Although the structure of CNT is similar to the structure of macromolecular material, its structure is much more stable than macromolecular material.CNT is the material with most high specific strength can prepared at present.If PSF and CNT are made composite, composite material exhibits can be made to go out good intensity, elasticity, fatigue resistance and isotropism, bring great improvement to the performance of composite.
Preferably, described solvent is one or more in dimethylacetylamide, 1-METHYLPYRROLIDONE, dimethyl formamide, oxolane.
Preferably, described additive be PEG-4000, PEG-8 00, polyvinylpyrrolidone PVP, ethanol, lithium chloride, acetone one or more.
Preferably, described polysulfones is bisphenol-a polysulfone.
Present invention also offers a kind of method preparing CNT activeness and quietness PSF hollow-fibre membrane as above, first multi-walled carbon nano-tubes and additive are dissolved in solvent, 1 ~ 3h is stirred at 45 ~ 60 DEG C, add PSF again, stir 12 ~ 24h, feed liquid after stirring is placed in the storage tank of hollow-fibre membrane spinning-drawing machine, vacuum defoamation 2 ~ 5h; Be delivered to spinning head by storage tank under the constant voltage effect that feed liquid after deaeration provides at liquid nitrogen, core liquid also enters the cavity of doughnut as support and interior coagulating bath under constant pressure source from the hole, center of spinning head simultaneously; Dynamic analysis of spinning leaves spinning head, through dry-spinning path, enters coagulating basin, through solidifying in coagulating basin, entering wrapping wire groove, being wrapped on wire wrapping wheel, solidifies completely and namely forms hollow-fibre membrane; Described dry-spinning path is the air gap between spinning head and coagulating basin; Preferably, described core liquid is distilled water; Described constant pressure source is liquid nitrogen.
Preferably, the height of described dry-spinning path is 1 ~ 15cm.
Preferably, the feed liquid after described deaeration is delivered to spinning head by storage tank under 0.05MPa ~ 0.3MPa constant voltage, and the temperature of feed liquid is 50 DEG C ~ 60 DEG C.
Preferably, described core liquid enters the cavity of doughnut under the constant voltage of 0.05MPa ~ 0.2MPa from the hole, center of spinning head, and the temperature of core liquid is 30 DEG C ~ 50 DEG C.
Preferably, the rotating speed of described wire wrapping wheel is 17-37m/min.
Preferably, the temperature of described coagulating basin and wrapping wire groove is 25 DEG C ~ 45 DEG C.
Relative to prior art, CNT activeness and quietness PSF hollow-fibre membrane of the present invention and preparation method thereof, has following advantage: doughnut of the present invention has good intensity, elasticity, fatigue resistance, and permeability of the membrane can be better.
Detailed description of the invention
The DMAC mentioned in the embodiment of the invention, refers to dimethylacetylamide; NMP is 1-METHYLPYRROLIDONE; DMF is dimethyl formamide; THF is oxolane; PEG-400 is PEG-4000; PEG-800 is PEG-8 00; PVP is polyvinylpyrrolidone.
The present invention will be described in detail below by embodiment.
Embodiment one
A kind of CNT activeness and quietness PSF hollow-fibre membrane, comprises each component of following parts by weight, multi-walled carbon nano-tubes 8 parts, PSF17 part, NMP68 part, PVP5 part, ethanol 2 parts.Described polysulfones PSF is bisphenol-a polysulfone.
By the following method, prepare hollow-fibre membrane: first multi-walled carbon nano-tubes, PVP, ethanol are mixed with NMP, be heated to 45 DEG C, stir 1h, then add PSF, stir 24h, feed liquid after stirring is placed in the storage tank of hollow-fibre membrane spinning-drawing machine, vacuum defoamation 2h; Spinning head is delivered to by storage tank under the 0.15MPa constant voltage effect that feed liquid after deaeration provides at liquid nitrogen, and the temperature of feed liquid is 50 DEG C, enter the cavity of doughnut as support and interior coagulating bath from the hole, center of spinning head under the 0.1MPa that simultaneously core liquid also provides at constant pressure source, and the temperature of core liquid is 40 DEG C; Dynamic analysis of spinning leaves spinning head, through dry-spinning path, enters coagulating basin, through solidifying in coagulating basin, entering wrapping wire groove, being wrapped on wire wrapping wheel, solidifies completely and namely forms hollow-fibre membrane; Described dry-spinning path is the air gap between spinning head and coagulating basin; Described core liquid is distilled water; Described constant pressure source is liquid nitrogen.Described dry-spinning path height is 10cm; The linear velocity of wire wrapping wheel is 17m/min; The temperature of coagulating basin and wrapping wire groove is 40 DEG C.
The intensity of the present embodiment institute wire vent is 0.45kg power, and elongation at break is 165%, and monofilament flux is 268L/m
2h; Wherein intensity and elongation at break are with reference to " plastic tensile method for testing performance GB/T1040-92 ", and monofilament flux is with reference to " hollow fiber ultrafiltration membrane method of testing HYT050-1999 ".
Embodiment two
A kind of CNT activeness and quietness PSF hollow-fibre membrane, comprises each component of following parts by weight, multi-walled carbon nano-tubes 12 parts, PSF18 part, NMP65 part, PEG-4000 5 parts.Described polysulfones is bisphenol-a polysulfone.
By the following method, prepare hollow-fibre membrane: first multi-walled carbon nano-tubes, NMP are mixed with PEG-4000, be heated to 45 DEG C, stir 1h, then add PSF, stir 24h, feed liquid after stirring is placed in the storage tank of hollow-fibre membrane spinning-drawing machine, vacuum defoamation 2h; Spinning head is delivered to by storage tank under the 0.05MPa constant voltage effect that feed liquid after deaeration provides at liquid nitrogen, and the temperature of feed liquid is 60 DEG C, enter the cavity of doughnut as support and interior coagulating bath from the hole, center of spinning head under the 0.1MPa that simultaneously core liquid also provides at constant pressure source, and the temperature of core liquid is 50 DEG C; Dynamic analysis of spinning leaves spinning head, through dry-spinning path, enters coagulating basin, through solidifying in coagulating basin, entering wrapping wire groove, being wrapped on wire wrapping wheel, solidifies completely and namely forms hollow-fibre membrane; Described dry-spinning path is the air gap between spinning head and coagulating basin.Described core liquid is distilled water; Described constant pressure source is liquid nitrogen; Described dry-spinning path height is 5cm; The linear velocity of wire wrapping wheel is 26m/min; The temperature of coagulating basin and wrapping wire groove is 50 DEG C.
The intensity of the present embodiment institute wire vent is 0.65kg power, and elongation at break is 180%, and monofilament flux is 245L/m
2h; Wherein intensity and elongation at break are with reference to " plastic tensile method for testing performance GB/T1040-92 ", and monofilament flux is with reference to " hollow fiber ultrafiltration membrane method of testing HYT050-1999 ".
Embodiment three
A kind of CNT activeness and quietness PSF hollow-fibre membrane, comprises each component of following parts by weight, multi-walled carbon nano-tubes 10 parts, PSF18 part, NMP65 part, PEG-8 007 part.Described polysulfones is bisphenol-a polysulfone.
By the following method, prepare hollow-fibre membrane: first multi-walled carbon nano-tubes, PEG-8 00 are mixed with NMP, be heated to 45 DEG C, stir 1h, then add PSF, stir 24h, feed liquid after stirring is placed in the storage tank of hollow-fibre membrane spinning-drawing machine, vacuum defoamation 2h; Spinning head is delivered to by storage tank under the 0.1MPa constant voltage effect that feed liquid after deaeration provides at liquid nitrogen, and the temperature of feed liquid is 50 DEG C, enter the cavity of doughnut as support and interior coagulating bath from the hole, center of spinning head under the 0.1MPa that simultaneously core liquid also provides at constant pressure source, and the temperature of core liquid is 40 DEG C; Dynamic analysis of spinning leaves spinning head, through dry-spinning path, enters coagulating basin, through solidifying in coagulating basin, entering wrapping wire groove, being wrapped on wire wrapping wheel, solidifies completely and namely forms hollow-fibre membrane; Described dry-spinning path is the air gap between spinning head and coagulating basin.Described core liquid is distilled water; Described constant pressure source is liquid nitrogen; Described dry-spinning path height is 10cm; Wire wrapping wheel rotating speed is 20m/min; The temperature of coagulating basin and wrapping wire groove is 35 DEG C.
The intensity of the present embodiment institute wire vent is 0.5kg power, and elongation at break is 210%, and monofilament flux is 256L/m
2h.Wherein intensity and elongation at break are with reference to " plastic tensile method for testing performance GB/T1040-92 ", and monofilament flux is with reference to " hollow fiber ultrafiltration membrane method of testing HYT050-1999 ".
Contrast experiment
A kind of PSF hollow-fibre membrane, comprises each component of following parts by weight, PSF18 part, NMP68 part, PVP4 part, PEG-4008 part ethanol 2 parts.Described polysulfones is bisphenol-a polysulfone.
By the following method, prepare hollow-fibre membrane: PVP, PEG-400, ethanol are mixed with NMP, be heated to 45 DEG C, stir 1h, then add PSF, stir 24h, the feed liquid after stirring is placed in the storage tank of hollow-fibre membrane spinning-drawing machine, vacuum defoamation 2h; Spinning head is delivered to by storage tank under the 0.15MPa constant voltage effect that feed liquid after deaeration provides at liquid nitrogen, and the temperature of feed liquid is 50 DEG C, enter the cavity of doughnut as support and interior coagulating bath from the hole, center of spinning head under the 0.1MPa that simultaneously core liquid also provides at constant pressure source, and the temperature of core liquid is 40 DEG C; Dynamic analysis of spinning leaves spinning head, through dry-spinning path, enters coagulating basin, through solidifying in coagulating basin, entering wrapping wire groove, being wrapped on wire wrapping wheel, solidifies completely and namely forms hollow-fibre membrane; Described core liquid is distilled water; Described constant pressure source is liquid nitrogen; Described dry-spinning path is the air gap between spinning head and coagulating basin.Described dry-spinning path height is 10cm; The linear velocity of wire wrapping wheel is 17r/min; The temperature of coagulating basin and wrapping wire groove is 40 DEG C.
The intensity of this contrast experiment institute wire vent is 0.35kg power, and elongation at break is 35%, and monofilament flux is 260L/m
2h.Wherein intensity and elongation at break are with reference to " plastic tensile method for testing performance GB/T1040-92 ", and monofilament flux is with reference to " hollow fiber ultrafiltration membrane method of testing HYT050-1999 ".
The foregoing is only the preferred embodiment of the invention; not in order to limit the invention; within all spirit in the invention and principle, any amendment done, equivalent replacement, improvement etc., within the protection domain that all should be included in the invention.
Claims (10)
1. a CNT activeness and quietness PSF hollow-fibre membrane, is characterized in that: each component comprising following parts by weight, multi-walled carbon nano-tubes 5 ~ 20 parts, PSF10 ~ 30 part, solvent 60 ~ 85 parts, additive 5 ~ 25 parts; Described PSF is polysulfones.
2. CNT activeness and quietness PSF hollow-fibre membrane according to claim 1, is characterized in that: described solvent is one or more in dimethylacetylamide, 1-METHYLPYRROLIDONE, dimethyl formamide, oxolane.
3. CNT activeness and quietness PSF hollow-fibre membrane according to claim 1, is characterized in that: described additive be PEG-4000, PEG-8 00, polyvinylpyrrolidone PVP, ethanol, lithium chloride, acetone one or more.
4. CNT activeness and quietness PSF hollow-fibre membrane according to claim 1, is characterized in that: described polysulfones is bisphenol-a polysulfone.
5. prepare the method for the CNT activeness and quietness PSF hollow-fibre membrane according to any one of Claims 1 to 4 for one kind, it is characterized in that: first multi-walled carbon nano-tubes and additive are dissolved in solvent, 1 ~ 3h is stirred at 45 ~ 60 DEG C, add PSF again, stir 12 ~ 24h, feed liquid after stirring is placed in the storage tank of hollow-fibre membrane spinning-drawing machine, vacuum defoamation 2 ~ 5h; Be delivered to spinning head by storage tank under the constant voltage effect that feed liquid after deaeration provides at liquid nitrogen, core liquid also enters the cavity of doughnut as support and interior coagulating bath under constant pressure source from the hole, center of spinning head simultaneously; Dynamic analysis of spinning leaves spinning head, through dry-spinning path, enters coagulating basin, through solidifying in coagulating basin, entering wrapping wire groove, being wrapped on wire wrapping wheel, solidifies completely and namely forms hollow-fibre membrane; Described dry-spinning path is the air gap between spinning head and coagulating basin; Preferably, described core liquid is distilled water; Described constant pressure source is liquid nitrogen.
6. preparation method according to claim 5, is characterized in that: the height of described dry-spinning path is 1 ~ 15cm.
7. preparation method according to claim 5, is characterized in that: the feed liquid after described deaeration is delivered to spinning head by storage tank under 0.05MPa ~ 0.3MPa constant voltage, and the temperature of feed liquid is 50 DEG C ~ 60 DEG C.
8. preparation method according to claim 5, is characterized in that: described core liquid enters the cavity of doughnut under the constant voltage of 0.05MPa ~ 0.2MPa from the hole, center of spinning head, and the temperature of core liquid is 30 DEG C ~ 50 DEG C.
9. preparation method according to claim 5, is characterized in that: the linear velocity of described wire wrapping wheel is 17-37m/min.
10. preparation method according to claim 5, is characterized in that: the temperature of described coagulating basin and wrapping wire groove is 25 DEG C ~ 45 DEG C.
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| CN109603582A (en) * | 2019-01-22 | 2019-04-12 | 天津工业大学 | A kind of preparation method and its product of polymer toughening film |
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Effective date of registration: 20191008 Address after: Room F-201, Rongzhi Zhongchuang Space, 398 Jintang Highway, Dongli District, Tianjin Patentee after: Tianjin Hualin Zhida Environmental Protection Technology Co., Ltd. Address before: Double Town Industrial Park 300350 Tianjin District of Jinnan City Patentee before: TIANJIN WATERKING MEMBRANE TECHNOLOGY CO., LTD. |