CN103143273A - Preparation method of aromatic polymer porous membrane - Google Patents
Preparation method of aromatic polymer porous membrane Download PDFInfo
- Publication number
- CN103143273A CN103143273A CN2013100686539A CN201310068653A CN103143273A CN 103143273 A CN103143273 A CN 103143273A CN 2013100686539 A CN2013100686539 A CN 2013100686539A CN 201310068653 A CN201310068653 A CN 201310068653A CN 103143273 A CN103143273 A CN 103143273A
- Authority
- CN
- China
- Prior art keywords
- membrane
- preparation
- aromatic polymer
- casting solution
- film
- 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.)
- Granted
Links
Images
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 the membrane material technology, be specially a kind of preparation method of aromatic polymer perforated membrane.This aromatic polymer refers to PPTA [Poly (para-Phenylene Terephthalamide), PPTA], and described perforated membrane comprises flat sheet membrane and hollow-fibre membrane.
Background technology
Meta-aromatic polyamide is that the macromolecular flexibility of poly (PMIA) is stronger, has physical-mechanical property preferably, dissolve in some organic solvent and form isotropic aqueous solution, processing characteristics is preferably arranged, adopt the solution phase conversion method to can be made into the PMIA porous film material.Also have relevant report about the PMIA film with loose structure both at home and abroad at present.Such as: Chinese patent CN1681875A[assistant assistant wood is firm etc., Teijin Ltd] introduced a kind of manufacture method of the PMIA of containing perforated membrane, it will contain the polymer solution curtain coating of PMIA and amide solvent to supporting mass, then be impregnated in the acid amides coagulating bath that contains with the immiscible material of PMIA and solidify, make perforated membrane; Chinese patent CN1625436A[space field is thorough, NOK Corp.] introduced the manufacture method of the hollow fiber porous film of a kind of PMIA, it makes the film making solution that contains PMIA, PVP and inorganic salts from 70 ℃ or above dual annular nozzle ejection, then the moisturizing processing makes the PMIA hollow fiber porous film after the dry-wet spinning moulding; One kind of United States Patent (USP) U.S.Patent6103862[is used for the nematic liquid crystal thin-film material of liquid crystal cell and preparation method thereof (Alignment film material for a liquid crystal cell and a method for preparing the same)] introduced a kind of thin-film material that is used for liquid crystal cell of novelty, it is mainly by PMIA and carbanion reaction, halogenated functional group is substituted onto on PMIA, make the good battery diaphragm of humidity resistance.
The contraposition aromatic polyamide is that PPTA is the most representative aromatic polyamide, and large molecule is rigidity, and lyotropic liquid crystalline is arranged, and has good heat resistance, chemical reagent resistance, is the important source material of preparation high-performance aromatic polyamide fibre.Compare 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 its dissolving, therefore masking is difficult, though so so far relevant for the patent literature of PPTA fiber, not yet see the patent literature of relevant 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 that a kind of preparation method of aromatic polymer perforated membrane is provided.This preparation method is take aromatic polymer PPTA as filmogen, adopts solution phase conversion method (wet method or do-wet method) filming technology, has that preparation process is simple, flow process is short, easy to control, efficient is high, is suitable for the characteristics such as industrializing implementation; The porosity of gained PPTA perforated membrane is high, pore-size distribution is even, permeability is better, have the fibrillation structure, filter the characteristics such as interception capacity is strong, anti-compactibility is strong, can be used for the film separation system under the severe rugged environment 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 sheet membrane and hollow-fibre membrane, this preparation method adopts following perforated membrane casting solution and solution phase conversion method 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, is selected from mean molecule quantity and is 600～20000 PEG, mean molecule quantity and be at least a in 10000～100000 PVP; Described solvent is the concentrated sulfuric acid of mass concentration 98～100wt%;
The filming technology of described perforated membrane is:
1) configuration casting solution
Described PPTA resin and solvent concentrated sulfuric acid solution are mixed in described ratio, stir swelling under 30～40 ℃, form transparent mixture of viscous form, then add described ratio pore-foaming agent, be warming up to 80～85 ℃, after fully mixing, vacuum defoamation forms uniform casting solution;
2) preparation plate porous membrane or hollow fiber porous film
(1) preparation plate porous membrane
At room temperature gained casting solution blade coating is made plate porous membrane on clean glass plate, and immerses immediately in the coagulating bath of 15～18 ℃ of ultrafiltration water, keep the 24h curing molding, after put into 50～60 ℃ of hot water and soak 3～4h; Perhaps put into the aqueous solution that adds a small amount of sulfuric acid, soak 3～4h under 50～60 ℃, then put into absolute ethyl alcohol and soak 1～2h, and then use washed with de-ionized water, remove residual acid and absolute ethyl alcohol in film, namely get described aromatic polymer plate porous membrane;
(2) preparation hollow fiber porous film
Described casting solution is measured through measuring pump, extruded by the hollow spinning nozzle, behind suitable the air gap, be immersed in 15～18 ℃ of coagulating baths, obtain the nascent hollow fiber porous film of porous, then through after extracting the operation of washing, reel, 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 conversion method (wet method or do-wet method), has that filming technology is simple, flow process is short, efficient is high, can effectively regulate the characteristics 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 agents, can make the gained film have larger pure water flux, the different molecular weight pore-foaming agent also can make the separation accuracy of film increase simultaneously, add the less pore-foaming agent of mean molecule quantity that the rejection of gained film is improved, and because aromatic polymer PPTA perforated membrane has corrosion resistance, can substitute inoranic membrane uses under certain severe rugged environment condition, greatly save production cost, be easy to industrializing implementation and promote.
Description of drawings
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 obviously visible longitudinal section in white box in Fig. 2.
Specific implementation method
Further narrate the present invention 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 sheet membrane and hollow-fibre membrane, described preparation method adopts following perforated membrane casting solution and solution phase conversion method (wet method or dried-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, is selected from mean molecule quantity and is 600～20000 PEG, mean molecule quantity and be at least a in 10000～100000 PVP; When the pore-foaming agent selection was two or more, its mixed proportion was any; Described solvent is the concentrated sulfuric acid of mass concentration 98～100wt%.
Described filming technology is specific as follows:
1) configuration casting solution
Described PPTA resin and concentrated sulfuric acid solution are mixed in described ratio, stir swelling under 30～40 ℃, form transparent mixture of viscous form, then add pore-foaming agent, be warming up to 80～85 ℃, after fully mixing, vacuum defoamation forms uniform casting solution;
2) preparation plate porous membrane or hollow fiber porous film
(1) preparation plate porous membrane
adopt solution phase conversion method (wet method) preparation PPTA plate porous membrane: at room temperature gained casting solution blade coating is made flat sheet membrane on clean glass plate, and immerse immediately in the coagulating bath of 15～18 ℃ of ultrafiltration water, keep the 24h curing molding, after put into 50～60 ℃ of hot water and soak 3～4h, perhaps put into the aqueous solution that adds a small amount of sulfuric acid, soak 3～4h under 50～60 ℃, put into again absolute ethyl alcohol and soak 1～2h, and then use washed with de-ionized water, remove residual acid and absolute ethyl alcohol in film, namely obtain aromatic polymer PPTA plate porous membrane of the present invention.
(2) preparation hollow fiber porous film
Adopt solution phase conversion method (dry-wet spinning shaping) to make the PPTA hollow fiber porous film: described casting solution is measured through measuring pump, extruded by the hollow spinning nozzle, through suitably being immersed in 15～18 ℃ of coagulating baths behind the air gap, obtain the nascent hollow-fibre membrane of porous, after passing through again the operations such as extraction is washed, coiling, 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 the PPTA hollow fiber porous film, also can prepare the PPTA plate porous membrane.Described aromatic polymer doughnut membrane preparation method is an important innovations point of the present invention.In the dry-wet spinning process, extruded velocity is fast, in spinning head, the flow orientation effect of casting solution is remarkable, the macromolecular rigidity of PPTA is strong in addition, a little less than dynamic analysis of spinning left the spinning head disorientation effect of moment, under the effect of coiling pulling force, nascent hollow-fibre membrane kept higher macromolecular orientation attitude structure, demonstrate mechanical property preferably, therefore need not to carry out again after-drawing and process.
The pore-foaming agent of solubility described in the present invention is that PEG, the mean molecule quantity of mean molecule quantity 600～20000 is one or more mixtures with arbitrary proportion of PVP of 10000～100000 etc.For the present invention, after phragmoplast was tied to form film, pore-foaming agent is dissolved washing out after extraction is washed, and forms many stripping micropores that mutually run through (referring to Fig. 1,2) in film.Simultaneously, after adding a large amount of pore-foaming agents in system, can obviously reduce the viscosity of system, be conducive to the abundant mixing of system, guarantee the homogeneity of gained membrane material.
The present invention does not address part and is applicable to prior art.
Further narrate the present invention below in conjunction with specific embodiment, but specific embodiment does not limit the protection domain of the present patent application claim only as the concrete case of technical scheme of the present invention.
Embodiment 1
Be in the concentrated sulfuric acid of 98wt% with the PPTA resin dissolves of mass fraction (lower with) 3.5wt% in 86.5wt% concentration, after add pore-foaming agent PEG6000, be warming up to 80 ℃ of dissolvings fully, deaeration in vacuum drying oven namely obtains required casting solution.Casting solution normal temperature blade coating is made flat sheet membrane, and immerse immediately in 16 ℃ of ultrafiltration water curing molding 24h.The film that obtains is put into respectively to extract under 50 ℃ of 5 ℃ of frozen water, 25 ℃ of normal temperature and hot water wash 24h.Then carry out performance test: with Liquid Residue on the washed with de-ionized water film, filter pure water afterwards under 0.1Mpa, measure its water flux.The water flux of gained film is respectively 132.70(L/m
2H), 149.28(L/m
2H) and 165.87(L/m
2H).
Embodiment 2
Described according to embodiment 1, in the constant situation of other conditions, change pore-foaming agent into molecular weight and be respectively 2000,10000 or 20000 PEG, put into 5 ℃ of extractions of frozen water and wash 24h.Then carry out performance test: with Liquid Residue on the washed with de-ionized water film, filter pure water afterwards under 0.1Mpa, measure its water flux; The water flux of gained film is respectively 79.62(L/m
2H), 82.94(L/m
2H) and 99.52(L/m
2H).
Embodiment 3
Be in the concentrated sulfuric acid of 98wt% with the PPTA resin dissolves of 2.0wt% in mass fraction 88wt% concentration, after add the PVP60000 of 10wt%, the composite pore-forming of PEG2000, be warming up to 80 ℃ fully the dissolving, deaeration in vacuum drying oven namely obtains required casting solution.Casting solution normal temperature blade coating is made flat sheet membrane, and the film that makes is put into respectively to extract under 50 ℃ of 25 ℃ of normal temperature, hot water and is washed 24h.Then carry out performance test: with Liquid Residue on the washed with de-ionized water film, filter pure water afterwards under 0.1Mpa, measure its water flux.The water flux of gained film is respectively 265.39(L/m
2H) and 281.98(L/m
2H).
Embodiment 4
Described according to embodiment 3, in the constant situation of other conditions, the PPTA solid content that adds in the casting solution system is reduced to 1.75wt%, prepared film carries out performance test: with Liquid Residue on the washed with de-ionized water film, filter pure water afterwards under 0.1Mpa, measure its water flux.The water flux of gained film is respectively 318.47(L/m
2H) and 331.74(L/m
2H).
Embodiment 5
Described according to embodiment 4, in the constant situation of other conditions, after the extraction condition of washing changes into and soaks 50 ℃ of hot water, put into to take out after absolute ethyl alcohol 2h and carry out performance test: with the Liquid Residue on the washed with de-ionized water film, filter pure water afterwards under 0.1Mpa, measuring its water flux is 364.92(L/m
2H).
Embodiment 6
Be in the concentrated sulfuric acid of 98wt% with the PPTA resin dissolves of 1.5wt% in mass fraction 88.5wt% concentration, after add the PVP40000 of 10wt% and the composite pore-forming that PEG2000 is 1: 1, be warming up to 80 ℃ of dissolvings fully, deaeration in vacuum drying oven namely obtains required casting solution.Casting solution normal temperature blade coating is made flat sheet membrane, and the film that makes is put under 25 ℃ of normal temperature and is cured shaping, takes out after the film part of solidified forming is put into absolute ethyl alcohol 1h, and another part is immersed in 50 ℃ of hot water and takes out after 1h; Then film is carried out respectively performance test: with Liquid Residue on the washed with de-ionized water film, filter pure water afterwards under 0.1Mpa, measure its water flux.The water flux of gained film is respectively 527.44(L/m
2H) and 331.74(L/m
2H).
Embodiment 7
Described according to embodiment 6, in the constant situation of other conditions, do not add PVP in pore-foaming agent, the film of solidified forming is immersed in carries out performance test after in 50 ℃ of hot water, extraction is washed: with Liquid Residue on the washed with de-ionized water film, filter pure water afterwards under 0.1Mpa, measuring its water flux is 165.87(L/m
2H).
Embodiment 8
Described according to embodiment 3, in the constant situation of other conditions, do not add pore-foaming agent in casting solution, prepared film is carried out performance test: the Liquid Residue with on the washed with de-ionized water film, filter pure water afterwards under 0.1Mpa, measuring its water flux is 119.43(L/m
2H).
Embodiment 9
Described according to embodiment 6, in the constant situation of other conditions, preparation 2g/L, 0.03wt%1000ml NaOH ovalbumin solution (pH=11) is held back test.
Performance test: with Liquid Residue on the washed with de-ionized water film, the first precompressed 20 minutes under 0.1Mpa of PPTA film, then filter the ovalbumin solution that configures, connect respectively one time filtered solution in every 5 minutes, an albumen stoste, divide under photometer (UV1901) irradiation at the dual-beam UV, visible light and record absorbance, measuring its filtration flux is 454.69(L/m
2H), rejection reaches 92.47%.
Embodiment 10
Described according to embodiment 3, each condition remains unchanged, and casting solution is made the 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, the 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 for seeing through the volume (L) of water, and S is membrane area (m
2), t is testing time (h).
Comparative example 1
The comparative example 1 to embodiment 6, can demonstrate the reduction along with the 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 pore-foaming agent has played the stripping pore-forming in system effect.Meanwhile, the feature of the fibrillation structure that PPTA has is also impelled and is formed network-like pore structure and finger-like pore structure (referring to Fig. 1,2) in film.
Comparative example 3
By the flux ratio of PPTA film in embodiment 1 after 3 temperature extractions are washed, can find out the increase along with water temperature, resulting flux is in rising trend.This is to accelerate because high temperature bath makes film double diffusion speed in process of setting, and pore-foaming agent accelerates to separate out, the result that inner void increases.
Comparative example 4
Comparative example 4,5,6 flux result can be found out and use the membrane flux of the film after soaked in absolute ethyl alcohol that obvious growth is arranged.This is because the absolute ethyl alcohol intermiscibility is fine, the reason that the material that is difficult for stripping in film effectively can be washed out.
Comparative example 5
Comparative example 6,7 flux results can be found out under identical PPTA solids content, add a small amount of PVP can make porosity that larger lifting is arranged in pore-foaming agent.This is mainly the large molecule of ketone has played phase-splitting in body series effect, has accelerated the double diffusion speed between solvent and coagulating agent in the hygrometric state film, and PVP also can promote the formation of fibrillation structure simultaneously.
Comparative example 6
Observe and the test of the rejection of 9 pairs of films of embodiment by SEM, can find out that PPTA membrane aperture scope of the present invention is approximately 0.01～0.5 μ m, can hold back effectively to ovalbumin.
Claims (3)
1. the preparation method of an aromatic polymer perforated membrane, described perforated membrane comprises flat sheet membrane and hollow-fibre membrane, and this preparation method adopts following perforated membrane casting solution and solution phase conversion method 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, is selected from mean molecule quantity and is 600 ~ 20000 PEG, mean molecule quantity and be at least a in 10000 ~ 100000 PVP; Described solvent is the concentrated sulfuric acid of mass concentration 98 ~ 100wt%;
The filming technology of described perforated membrane is:
1) configuration casting solution
Described PPTA resin and the solvent concentrated sulfuric acid are mixed in described ratio, stir swelling under 30 ~ 40 ℃, form transparent mixture of viscous form, then add described ratio pore-foaming agent, be warming up to 80 ~ 85 ℃, after fully mixing, vacuum defoamation forms uniform casting solution;
2) preparation plate porous membrane or hollow fiber porous film
(1) preparation plate porous membrane
At room temperature gained casting solution blade coating is made plate porous membrane on clean glass plate, and immerses immediately in the coagulating bath of 15 ~ 18 ℃ of ultrafiltration water, keep the 24h curing molding, after put into 50 ~ 60 ℃ of hot water and soak 3 ~ 4h; Perhaps put into the aqueous solution that adds a small amount of sulfuric acid, soak 3 ~ 4h under 50 ~ 60 ℃, then put into absolute ethyl alcohol and soak 1 ~ 2h, and then use washed with de-ionized water, remove residual acid and absolute ethyl alcohol in film, namely get described aromatic polymer plate porous membrane;
(2) preparation hollow fiber porous film
Described casting solution is measured through measuring pump, extruded by the hollow spinning nozzle, behind suitable the air gap, be immersed in 15 ~ 18 ℃ of coagulating baths, obtain the nascent hollow fiber porous film of porous, then through after extracting the operation of washing, reel, namely obtain described aromatic polymer hollow fiber porous film.
2. aromatic polymer hollow fiber porous film of aromatic polymer method for preparing porous film preparation according to claim 1.
3. aromatic polymer plate porous membrane of aromatic polymer method for preparing porous film preparation according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310068653.9A CN103143273B (en) | 2013-03-05 | 2013-03-05 | Preparation method of aromatic polymer porous membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310068653.9A CN103143273B (en) | 2013-03-05 | 2013-03-05 | Preparation method of aromatic polymer porous membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103143273A true CN103143273A (en) | 2013-06-12 |
| CN103143273B CN103143273B (en) | 2015-05-27 |
Family
ID=48541749
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310068653.9A Active CN103143273B (en) | 2013-03-05 | 2013-03-05 | Preparation method of aromatic polymer porous membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103143273B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103521091A (en) * | 2013-10-25 | 2014-01-22 | 滁州品创生物科技有限公司 | Composite hollow fiber membrane |
| CN103537198A (en) * | 2013-09-27 | 2014-01-29 | 中国科学院广州化学研究所 | Kevlar nano fiber porous membrane, and preparation method and application thereof |
| CN104233499A (en) * | 2013-06-17 | 2014-12-24 | 东华大学 | Preparation method of aromatic polyarmide fiber containing heterlcyclic rings |
| CN104353372A (en) * | 2014-11-07 | 2015-02-18 | 天津工业大学 | Preparation method of aromatic polyamide hollow fiber porous membrane |
| CN104801205A (en) * | 2015-04-20 | 2015-07-29 | 天津工业大学 | Preparation method for homogeneous enhanced PPTA hollow fiber membrane |
| 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 |
| CN112575411A (en) * | 2020-11-29 | 2021-03-30 | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5523034A (en) * | 1993-04-12 | 1996-06-04 | E. I. Du Pont De Nemours And Company | Solution of PPD-T and PVP and articles made therefrom |
| CN1256474C (en) * | 2003-12-10 | 2006-05-17 | 中国石化仪征化纤股份有限公司 | Manufacturing method of poly p phenylene diamine terephthalamide fiber |
| CN101220530A (en) * | 2007-01-08 | 2008-07-16 | 上海艾麦达化纤科技有限公司 | Production of uniform polyphenylene terephthalamide fibre |
| CN101555631B (en) * | 2008-04-10 | 2011-04-06 | 中国神马集团有限责任公司 | Industrial method for preparing PPTA spinning slurry with solid sulphuric acid |
-
2013
- 2013-03-05 CN CN201310068653.9A patent/CN103143273B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5523034A (en) * | 1993-04-12 | 1996-06-04 | E. I. Du Pont De Nemours And Company | Solution of PPD-T and PVP and articles made therefrom |
| CN1256474C (en) * | 2003-12-10 | 2006-05-17 | 中国石化仪征化纤股份有限公司 | Manufacturing method of poly p phenylene diamine terephthalamide fiber |
| CN101220530A (en) * | 2007-01-08 | 2008-07-16 | 上海艾麦达化纤科技有限公司 | Production of uniform polyphenylene terephthalamide fibre |
| CN101555631B (en) * | 2008-04-10 | 2011-04-06 | 中国神马集团有限责任公司 | Industrial method for preparing PPTA spinning slurry with solid sulphuric acid |
Non-Patent Citations (1)
| Title |
|---|
| 王睦铿: "高性能PPTA薄膜的制备和应用", 《化工新型材料》 * |
Cited By (10)
| 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 |
| CN103537198A (en) * | 2013-09-27 | 2014-01-29 | 中国科学院广州化学研究所 | Kevlar nano fiber porous membrane, and preparation method and application thereof |
| 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 |
| CN104353372A (en) * | 2014-11-07 | 2015-02-18 | 天津工业大学 | Preparation method of aromatic polyamide hollow fiber porous membrane |
| CN104801205A (en) * | 2015-04-20 | 2015-07-29 | 天津工业大学 | Preparation method for homogeneous enhanced PPTA hollow fiber membrane |
| EP3095508A1 (en) * | 2015-04-20 | 2016-11-23 | Tianjin Polytechnic University | Method for preparing homogeneous braid-reinforced ppta hollow fiber membrane |
| 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 |
| CN112575411A (en) * | 2020-11-29 | 2021-03-30 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103143273B (en) | 2015-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103143273B (en) | Preparation method of aromatic polymer porous membrane | |
| CN100484616C (en) | PVC hollow fiber ultrafiltration membrane preparation method | |
| CN1272093C (en) | Method for preparing polyvinylidene fluoride flat plate microporous compound film | |
| CN105327623A (en) | Cellulose acetate nanofiltration membrane and preparing method thereof | |
| CN103386257B (en) | A kind of preparation method of the nanofiber composite hyperfiltration membrane based on electrostatic spinning technique | |
| CN104248918B (en) | A kind of method that semi-intercrossing network method prepares hydrophilic anti-pollution composite hyperfiltration membrane | |
| CN101293185A (en) | Method for producing polyvinylidene fluoride porous membrane | |
| CN105413486A (en) | Cellulose acetate commixed nano-filtration membrane and preparation method thereof | |
| KR102054838B1 (en) | Cellulosic membrane for water treatment with good anti-fouling property and Method thereof | |
| CN101485961B (en) | Method for preparing polyvinylidene fluoride hollow fiber alloy film | |
| CN101721928A (en) | High-strength and hydrophilic polysulfone hollow fiber ultrafiltration membrane | |
| Tsai et al. | Pervaporation of water/alcohol mixtures through chitosan/cellulose acetate composite hollow‐fiber membranes | |
| WO2013151248A1 (en) | Silicone polymer asymmetric composite membrane and production method therefor | |
| CN101224392A (en) | Fabricating method of fiber powder modified polymer microporous film | |
| CN103801202B (en) | Regenerated cellulose milipore filter and preparation method thereof | |
| CN103521091A (en) | Composite hollow fiber membrane | |
| CN105233703A (en) | Preparation method of high flux cellulose microfiltration membrane | |
| CN104353372A (en) | Preparation method of aromatic polyamide hollow fiber porous membrane | |
| CN103463994A (en) | Hollow polysulfone fiber film for water purifying cup and preparation method thereof | |
| CN103816817B (en) | Alkali-resistant cellulose membrane and preparation method thereof | |
| CN105032215B (en) | The preparation method of high-intensity high-throughput aromatic polyamides perforated membrane | |
| CN112808019B (en) | Method for preparing polyaryletherketone tubular membrane by using green solvent thermal-induced phase method | |
| CN105435654B (en) | The preparation method of single skin hollow-fibre membrane | |
| CN109621744A (en) | A kind of preparation method of the hollow-fibre membrane based on double critical solution temperature systems | |
| CN1124175C (en) | Preparation method of dry type polyacrylointrile ultrafiltration membrane |
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 |