CN103143273B - Preparation method of aromatic polymer porous membrane - Google Patents
Preparation method of aromatic polymer porous membrane Download PDFInfo
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- CN103143273B CN103143273B CN201310068653.9A CN201310068653A CN103143273B CN 103143273 B CN103143273 B CN 103143273B CN 201310068653 A CN201310068653 A CN 201310068653A CN 103143273 B CN103143273 B CN 103143273B
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Abstract
The invention discloses a preparation method of an aromatic polymer porous membrane. The porous membrane comprises a flat membrane and a hollow fibrous membrane. The preparation method adopts the following porous membrane casting solution and solution-phase conversion membrane preparation technique. The membrane casting solution comprises the following components in percentage by mass: 1.5-15 wt% of PPTA (poly(p-phenylene terephthalamide)), 4.5-10 wt% of pore-forming agent and 86.5-94 wt% of solvent. The pore-forming agent is a soluble high polymer selected from at least one of PEGs (polyethylene glycols) with the average molecular weight of 600-20000 and PVPs (polyvinyl pyrrolidones) with the average molecular weight of 10000-100000; and the solvent is 98-100 wt% concentrated sulfuric acid. The porous membrane preparation technique comprises the following steps: 1) preparing the membrane casting solution; and 2) preparing the flat porous membrane by a wet process, or preparing the hollow fiber porous membrane by dry-wet spinning formation.
Description
Technical field
The present invention relates to membrane material technology, be specially a kind of preparation method of aromatic polymer perforated membrane.This aromatic polymer refers to PPTA [Poly (para-PhenyleneTerephthalamide), PPTA], and described perforated membrane comprises Flat Membrane and hollow-fibre membrane.
Background technology
Meta-aromatic polyamide and poly (PMIA) macromolecular flexibility stronger, there is good physical-mechanical property, dissolve in some organic solvent and form isotropic aqueous solution, there is good processing characteristics, adopt solution phase inversion to can be made into PMIA porous film material.The domestic and international PMIA film also existing relevant report about having loose structure at present.Such as: [assistant assistant wood is firm for Chinese patent CN1681875A, Teijin Ltd] describe a kind of manufacture method containing PMIA perforated membrane, it by the polymer solution curtain coating containing PMIA and amide solvent on supporting mass, then be impregnated in the acid amides coagulating bath containing the material immiscible with PMIA and solidify, make perforated membrane; [space field is thorough for Chinese patent CN1625436A, NOK Corp.] describe the manufacture method of the hollow fiber porous film of a kind of PMIA, it makes film making solution containing PMIA, PVP and inorganic salts from the double loop nozzle ejection of 70 DEG C or more, then moisturizing process obtains PMIA hollow fiber porous film after dry-wet spinning is shaping; United States Patent (USP) U.S.Patent6103862 [a kind of nematic liquid crystal thin-film material for liquid crystal cell and preparation method thereof (Alignment film material fora liquid crystal cell and a method for preparing the same)] describes a kind of thin-film material for liquid crystal cell of novelty, it is mainly reacted by PMIA and carbanion, halogenated functional group is substituted onto on PMIA, the battery diaphragm that obtained humidity resistance is good.
Contraposition aromatic polyamide and PPTA are the representational aromatic polyamides of most, and large molecule is rigidity, has lyotropic liquid crystalline, have excellent heat resistance, chemical reagent resistance, are the important source material of preparation high-performance aromatic polyamide fibre.Compared with PMIA, PPTA has more excellent physical-mechanical property, but because the decomposition temperature of PPTA is low, and only the concentrated sulfuric acid can make it dissolve, therefore masking difficulty, though so there is the patent literature about PPTA fiber so far, there is not yet the patent literature about aromatic polymer PPTA porous film material.
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is, provides a kind of preparation method of aromatic polymer perforated membrane.This preparation method for filmogen, adopts solution phase inversion (wet method or dry-wet method) filming technology with aromatic polymer PPTA, has that preparation process is simple, flow process is short, easy to control, efficiency is high, is suitable for the features such as industrializing implementation; The porosity of gained PPTA perforated membrane is high, pore-size distribution is comparatively even, permeability is better, have filtration structures, filter the features such as strong, the resistance to compactibility of interception capacity is strong, can be used for the UF membrane system under the harsh environmental conditions such as acid-alkali medium, organic solvent, water-oil separating.
The technical scheme that the present invention solve the technical problem is, design a kind of preparation method of aromatic polymer perforated membrane, described perforated membrane comprises Flat Membrane and hollow-fibre membrane, this preparation method adopts following perforated membrane casting solution and solution phase inversion filming technology, and the mass fraction of described casting solution consists of:
PPTA 1.5～15wt%，
Pore-foaming agent 4.5 ~ 10wt%,
Solvent 86.5 ~ 94wt%, each component sum is 100%,
Described pore-foaming agent is soluble high-molecular, be selected from mean molecule quantity be 600 ~ 20000 PEG, mean molecule quantity be at least one in the PVP of 10000 ~ 100000; Described solvent is the concentrated sulfuric acid of mass concentration 98 ~ 100wt%;
The filming technology of described perforated membrane is:
1) casting solution is configured
Described PPTA resin and solvent concentrated sulfuric acid solution are mixed in described ratio, stirs swelling at 30 ~ 40 DEG C, form clear viscous shape mixture, then add described ratio pore-foaming agent, be warming up to 80 ~ 85 DEG C, fully after mixing, vacuum defoamation, forms uniform casting solution;
2) plate porous membrane or hollow fiber porous film is prepared
(1) plate porous membrane is prepared
At room temperature gained casting solution blade coating is made plate porous membrane on cleaned glass plate, and immerses immediately in the bath of 15 ~ 18 DEG C of ultrafiltration water condensation, keep 24h curing molding, after put into 50 ~ 60 DEG C of hot water and soak 3 ~ 4h; Or put into and add a small amount of sulphur aqueous acid, at 50 ~ 60 DEG C, soak 3 ~ 4h, then put into absolute ethyl alcohol immersion 1 ~ 2h, and then by washed with de-ionized water, remove acid residual in film and absolute ethyl alcohol, obtain described aromatic polymer plate porous membrane;
(2) hollow fiber porous film is prepared
Described casting solution is measured through measuring pump, is extruded by hollow spinning nozzle, behind suitable the air gap, be immersed in 15 ~ 18 DEG C of coagulating baths, obtain porous to come into being hollow fiber porous film, then wash through extraction, after rolling step, namely obtain described aromatic polymer hollow fiber porous film.
Compared with prior art, aromatic polymer method for preparing porous film of the present invention adopts solution phase inversion (wet method or dry-wet method), has that filming technology is simple, flow process is short, efficiency is high, can effectively regulate the features such as fenestra aperture size.Adopt the aromatic polymer PPTA perforated membrane of preparation method's gained of the present invention, owing to adding a large amount of water-soluble low molecular weight polymer pore-foaming agent, gained film can be made to have larger pure water flux, different molecular weight pore-foaming agent also can make the separation accuracy of film increase simultaneously, adding the less pore-foaming agent of mean molecule quantity can make the rejection of gained film improve, and there is corrosion resistance due to aromatic polymer PPTA perforated membrane, inoranic membrane can be substituted use under certain harsh environmental conditions, greatly save production cost, be easy to industrializing implementation and promote.
Accompanying drawing explanation
Fig. 1 is the surface network shape pore structure photo figure of preparation method's gained aromatic polymer perforated membrane of the present invention;
Fig. 2 is the section configuration structure photo figure of preparation method's gained aromatic polymer perforated membrane of the present invention.The finger-like pore structure of obvious visible longitudinal section in white box in fig. 2.
Specific implementation method
The present invention is described further below in conjunction with embodiment and accompanying drawing thereof.
The aromatic polymer PPTA method for preparing porous film (abbreviation preparation method) of the present invention's design, described perforated membrane comprises Flat Membrane and hollow-fibre membrane, described preparation method adopts following perforated membrane casting solution and solution phase inversion (wet method or dry-wet method) filming technology
The mass fraction of described casting solution consists of:
PPTA 1.5～15wt%，
Pore-foaming agent 4.5 ~ 10wt%,
Solvent 86.5 ~ 94wt%, each component sum is 100%,
Described pore-foaming agent is soluble high-molecular, be selected from mean molecule quantity be 600 ~ 20000 PEG, mean molecule quantity be at least one in the PVP of 10000 ~ 100000; When pore-foaming agent is selected two or more, its mixed proportion is any; Described solvent is the concentrated sulfuric acid of mass concentration 98 ~ 100wt%.
Described filming technology is specific as follows:
1) casting solution is configured
Described PPTA resin and concentrated sulfuric acid solution are mixed in described ratio, stir swelling at 30 ~ 40 DEG C, form clear viscous shape mixture, then add pore-foaming agent, be warming up to 80 ~ 85 DEG C, fully after mixing, vacuum defoamation, forms uniform casting solution;
2) plate porous membrane or hollow fiber porous film is prepared
(1) plate porous membrane is prepared
Solution phase inversion (wet method) is adopted to prepare PPTA plate porous membrane: at room temperature gained casting solution blade coating to be made Flat Membrane on cleaned glass plate, and immerse in 15 ~ 18 DEG C of ultrafiltration water condensation baths immediately, keep 24h curing molding, after put into 50 ~ 60 DEG C of hot water and soak 3 ~ 4h, or put into and add a small amount of sulphur aqueous acid, 3 ~ 4h is soaked at 50 ~ 60 DEG C, put into absolute ethyl alcohol again and soak 1 ~ 2h, and then by washed with de-ionized water, remove acid residual in film and absolute ethyl alcohol, namely aromatic polymer PPTA plate porous membrane of the present invention is obtained.
(2) hollow fiber porous film is prepared
Solution phase inversion (dry-wet spinning shaping) is adopted to make PPTA hollow fiber porous film: to be measured through measuring pump by described casting solution, extruded by hollow spinning nozzle, be immersed in 15 ~ 18 DEG C of coagulating baths behind suitable the air gap, obtain porous to come into being hollow-fibre membrane, wash through extraction again, after the operation such as winding, namely obtain described aromatic polymer PPTA hollow fiber porous film.Described suitable the air gap is known technology.
Adopt aromatic polymer method for preparing porous film of the present invention both can prepare PPTA hollow fiber porous film, also can prepare PPTA plate porous membrane.Described aromatic polymer doughnut membrane preparation method is an important innovations point of the present invention.Due in dry-wet spinning process, extruded velocity is fast, in spinning head, the flow orientation effect of casting solution is remarkable, in addition the macromolecular rigidity of PPTA is strong, the disorientation effect that dynamic analysis of spinning leaves spinning head moment is weak, and under winding tensions effect, nascent hollow-fibre membrane keeps higher macromolecular orientation state structure, demonstrate good mechanical property, therefore without the need to carrying out after-drawing process again.
One or more that soluble pore former described in the present invention is the PEG of mean molecule quantity 600 ~ 20000, mean molecule quantity is the PVP of 10000 ~ 100000 etc. are with the mixture of arbitrary proportion.For the present invention, after phragmoplast is tied to form film, pore-foaming agent is washed out by dissolving after extraction is washed, and forms many stripping micropores (see Fig. 1,2) mutually run through in film.Meanwhile, after adding a large amount of pore-foaming agent in system, obviously can reduce the viscosity of system, be conducive to the abundant mixing of system, ensure the homogeneity of gained membrane material.
The present invention does not address part and is applicable to prior art.
Describe the present invention further below in conjunction with specific embodiment, but specific embodiment is only as the concrete case of technical scheme of the present invention, does not limit the protection domain of the present patent application claim.
Embodiment 1
Be in the concentrated sulfuric acid of 98wt% in 86.5wt% concentration by the PPTA resin dissolves of mass fraction (lower with) 3.5wt%, after add pore-foaming agent PEG6000, being warming up to 80 DEG C dissolves completely, deaeration in vacuum drying oven, namely obtains required casting solution.Casting solution normal temperature blade coating is made Flat Membrane, and immerses immediately in 16 DEG C of ultrafiltration water, curing molding 24h.Carry out extraction at the film obtained being put into respectively frozen water 5 DEG C, normal temperature 25 DEG C and hot water 50 DEG C and wash 24h.Then carry out performance test: with Liquid Residue on washed with de-ionized water film, after under 0.1Mpa, filter pure water, measure its water flux.The water flux of gained film is respectively 132.70(L/m
2h), 149.28(L/m
2and 165.87(L/m h)
2h).
Embodiment 2
Described in embodiment 1, when other conditions are constant, pore-foaming agent is changed into the PEG that molecular weight is respectively 2000,10000 or 20000, put into frozen water 5 DEG C extraction and wash 24h.Then carry out performance test: with Liquid Residue on washed with de-ionized water film, after under 0.1Mpa, filter pure water, measure its water flux; The water flux of gained film is respectively 79.62(L/m
2h), 82.94(L/m
2and 99.52(L/m h)
2h).
Embodiment 3
By the PPTA resin dissolves of 2.0wt% in mass fraction 88wt% concentration be in the concentrated sulfuric acid of 98wt%, after add the composite pore-forming of PVP60000, PEG2000 of 10wt%, be warming up to 80 DEG C and dissolve completely, deaeration in vacuum drying oven, namely obtain required casting solution.Casting solution normal temperature blade coating is made Flat Membrane, and obtained film carries out extraction at putting into normal temperature 25 DEG C, hot water 50 DEG C respectively and washes 24h.Then carry out performance test: with Liquid Residue on washed with de-ionized water film, after under 0.1Mpa, filter pure water, measure its water flux.The water flux of gained film is respectively 265.39(L/m
2and 281.98(L/m h)
2h).
Embodiment 4
Described in embodiment 3, when other conditions are constant, the PPTA solid content added in casting solution system is reduced to 1.75wt%, and obtained film carries out performance test: with Liquid Residue on washed with de-ionized water film, after under 0.1Mpa, filter pure water, measure its water flux.The water flux of gained film is respectively 318.47(L/m
2and 331.74(L/m h)
2h).
Embodiment 5
Described in embodiment 4, when other conditions are constant, after the extraction condition of washing changes immersion 50 DEG C of hot water into, take out after putting into absolute ethyl alcohol 2h and carry out performance test: with the Liquid Residue on washed with de-ionized water film, after under 0.1Mpa, filter pure water, measuring its water flux is 364.92(L/m
2h).
Embodiment 6
By the PPTA resin dissolves of 1.5wt% in mass fraction 88.5wt% concentration be in the concentrated sulfuric acid of 98wt%, after add 10wt% PVP40000 and PEG2000 be the composite pore-forming of 1: 1, be warming up to 80 DEG C to dissolve completely, deaeration in vacuum drying oven, namely obtain required casting solution.Casting solution normal temperature blade coating is made Flat Membrane, and obtained film is cured shaping at putting into normal temperature 25 DEG C, and take out after a film part for solidified forming is put into absolute ethyl alcohol 1h, another part is immersed in 50 DEG C of hot water and takes out after 1h; Then respectively performance test is carried out to film: with Liquid Residue on washed with de-ionized water film, after under 0.1Mpa, filter pure water, measure its water flux.The water flux of gained film is respectively 527.44(L/m
2and 331.74(L/m h)
2h).
Embodiment 7
Described in embodiment 6, when other conditions are constant, in pore-foaming agent, do not add PVP, the film of solidified forming is immersed in extraction in 50 DEG C of hot water and carries out performance test after washing: with Liquid Residue on washed with de-ionized water film, after under 0.1Mpa, filter pure water, measuring its water flux is 165.87(L/m
2h).
Embodiment 8
Described in embodiment 3, when other conditions are constant, in casting solution, do not add pore-foaming agent, performance test carried out to obtained film: with the Liquid Residue on washed with de-ionized water film, after under 0.1Mpa, filter pure water, measuring its water flux is 119.43(L/m
2h).
Embodiment 9
Described in embodiment 6, when other conditions are constant, preparation 2g/L, 0.03wt%1000ml NaOH ovalbumin solution (pH=11) is carried out retaining test.
Performance test: with Liquid Residue on washed with de-ionized water film, the first precompressed 20 minutes under 0.1Mpa of PPTA film, then the ovalbumin solution configured is filtered, within every 5 minutes, connect a filtered solution respectively, an albumen stoste, under dual-beam UV, visible light divides photometer (UV1901) to irradiate, record absorbance, measuring its filtration flux is 454.69(L/m
2h), rejection reaches 92.47%.
Embodiment 10
Described in embodiment 3, each condition remains unchanged, and casting solution is made PPTA hollow-fibre membrane through dry-wet spinning technique, and the air gap height is 10mm, and spinneret draft is 6.
Performance test: platen press in adopting, filter pure water under 0.1Mpa, measure its water flux, gained water flux is 521.21(L/m
2h).
The calculating of PPTA membrane flux J of the present invention is according to following formula:
J=V/(Sⅹt)
Wherein V is the volume (L) through water, and S is membrane area (m
2), t is the testing time (h).
Comparative example 1
Comparative example's 1 to embodiment 6, can demonstrate the reduction along with PPTA solid content, and significantly increasing appears in the flux of PPTA film, and it is because being the raising due to membrane porosity.
Comparative example 2
Comparative example 1 ~ 7 and embodiment 8, can demonstrate the effect that pore-foaming agent serves stripping pore-forming in system.Meanwhile, the feature of the filtration structures that PPTA has, also impels in film and forms network-like pore structure and finger-like pore structure (see Fig. 1,2).
Comparative example 3
Extract the flux ratio after washing comparatively by PPTA film in embodiment 1 through 3 temperature, can find out the increase along with water temperature, the flux obtained is in rising trend.This is that pore-foaming agent accelerates to separate out, the result that inner void increases because high temperature bath makes film double diffusion speed in process of setting accelerate.
Comparative example 4
The flux result of comparative example 4,5,6, can find out that the membrane flux of the film after using soaked in absolute ethyl alcohol has obvious growth.This is because absolute ethyl alcohol intermiscibility is fine, the reason that the material of not easily stripping in film effectively can be washed out.
Comparative example 5
Comparative example 6,7 flux result, can find out under identical PPTA solids content, adds a small amount of PVP porosity can be made to have larger lifting in pore-foaming agent.This mainly the large molecule of ketone in body series, serve the effect of phase-splitting, accelerate the double diffusion speed in hygrometric state film between solvent and coagulating agent, simultaneously PVP also can promote the formation of filtration structures.
Comparative example 6
Observed by SEM and the test of rejection of embodiment 9 pairs of films, can find out that PPTA membrane aperture scope of the present invention is approximately 0.01 ~ 0.5 μm, effectively can retain ovalbumin.
Claims (3)
1. a preparation method for aromatic polymer perforated membrane, described perforated membrane comprises Flat Membrane and hollow-fibre membrane, this system
Preparation Method adopts following perforated membrane casting solution and solution phase inversion filming technology, and the mass fraction of described casting solution consists of:
PPTA 1.5~15wt%，
Pore-foaming agent 4.5 ~ 10wt%,
Solvent 86.5 ~ 94wt%, each component sum is 100%,
Described pore-foaming agent is soluble high-molecular, be selected from mean molecule quantity be 600 ~ 20000 PEG, mean molecule quantity be at least one in the PVP of 10000 ~ 100000; Described solvent is the concentrated sulfuric acid of mass concentration 98 ~ 100wt%;
The filming technology of described perforated membrane is:
1) casting solution is configured
Described PPTA resin and the solvent concentrated sulfuric acid are mixed by described mass fraction, stirs swelling at 30 ~ 40 DEG C, form clear viscous shape mixture, then add the pore-foaming agent of described mass fraction, be warming up to 80 ~ 85 DEG C, fully after mixing, vacuum defoamation, forms uniform casting solution;
2) plate porous membrane or hollow fiber porous film is prepared
(1) plate porous membrane is prepared
At room temperature gained casting solution blade coating is made plate porous membrane on cleaned glass plate, and immerses immediately in the bath of 15 ~ 18 DEG C of ultrafiltration water condensation, keep 24h curing molding, after put into 50 ~ 60 DEG C of hot water and soak 3 ~ 4h; Or put into and add a small amount of sulphur aqueous acid, at 50 ~ 60 DEG C, soak 3 ~ 4h, then put into absolute ethyl alcohol immersion 1 ~ 2h, and then by washed with de-ionized water, remove acid residual in film and absolute ethyl alcohol, obtain described aromatic polymer plate porous membrane;
(2) hollow fiber porous film is prepared
Described casting solution is measured through measuring pump, is extruded by hollow spinning nozzle, behind suitable the air gap, be immersed in 15 ~ 18 DEG C of coagulating baths, obtain porous to come into being hollow fiber porous film, then wash through extraction, after rolling step, namely obtain described aromatic polymer hollow fiber porous film.
2. the aromatic polymer hollow fiber porous film prepared according to aromatic polymer method for preparing porous film described in claim 1.
3. the aromatic polymer plate porous membrane prepared according to aromatic polymer method for preparing porous film described in claim 1.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104233499A (en) * | 2013-06-17 | 2014-12-24 | 东华大学 | Preparation method of aromatic polyarmide fiber containing heterlcyclic rings |
| CN103537198B (en) * | 2013-09-27 | 2016-06-29 | 中国科学院广州化学研究所 | A kind of Kevlar nano fiber porous film and preparation method thereof and application |
| CN103521091A (en) * | 2013-10-25 | 2014-01-22 | 滁州品创生物科技有限公司 | Composite hollow fiber membrane |
| CN104353372B (en) * | 2014-11-07 | 2016-05-11 | 天津工业大学 | A kind of preparation method of aromatic polyamide hollow fiber porous film |
| CN104801205B (en) * | 2015-04-20 | 2017-06-06 | 天津工业大学 | A kind of preparation method of the enhanced PPTA hollow-fibre membranes of homogeneity |
| CN109354871A (en) * | 2018-11-14 | 2019-02-19 | 天津工业大学 | A kind of preparation method of heat-insulating flame-retardant poly(p-phenylene terephthalamide) resistant to high temperature (PPTA) porous material |
| CN112575411B (en) * | 2020-11-29 | 2022-04-05 | 中国科学院金属研究所 | Wet spinning preparation method of high-strength and high-conductivity single-walled carbon nanotube fiber |
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