CN102397759A - Polyether sulfone hollow fiber filter membrane and its preparation method - Google Patents
Polyether sulfone hollow fiber filter membrane and its preparation method Download PDFInfo
- Publication number
- CN102397759A CN102397759A CN2010102785925A CN201010278592A CN102397759A CN 102397759 A CN102397759 A CN 102397759A CN 2010102785925 A CN2010102785925 A CN 2010102785925A CN 201010278592 A CN201010278592 A CN 201010278592A CN 102397759 A CN102397759 A CN 102397759A
- Authority
- CN
- China
- Prior art keywords
- polyether sulfone
- hollow fiber
- preparation
- diluent
- filter membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention relates to a polyether sulfone hollow fiber membrane and its TIPS (thermally induced phase separation) preparation method. With a pore size of 0.01-0.5 micrometer, the polyether sulfone hollow fiber membrane of the invention has large water flux. Under pressure of 0.1MP and a temperature of 25DEG C, the pure water flux is 450-2600L/M<2>.H. The fiber membrane of the invention has high tensile strength and compression strength, with fracture pressure over 1.0MPa and tensile strength of 20-50MPa, and good chemical resistance, uniform pore size and distribution, good hydrophilicity, as well as other advantages. Besides, the prepared polyether sulfone hollow fiber membrane in the invention can be stored in a dry state after drying without affecting the water flux of the membrane.
Description
Technical field
The present invention relates to a kind of polyether sulfone hollow fiber filter membrane and thermally induced phase separation preparation technology thereof.
Background technology
Membrane separation technique develops over year rapidly at nearly twenty or thirty, is widely used in the wastewater treatment of industry such as chemical industry, food, medicine, electronics, municipal water treatment, and commercialization and domestic drinking water are handled.The description of materials that is used to make film is numerous, from initial cellulose acetate, develops into polypropylene, polyvinyl chloride, polyacrylonitrile, polysulfones, Kynoar, polyether sulfone etc.The film manufacturing process causes phase separation method (NIPS), melt spinning-stretching hole forming method, develops into thermally induced phase separation (TIPS) from initial non-solvent.
Polyether sulfone (PES) is a kind of to be the amorphous thermoplastic resin; Has excellent physical and mechanical properties; Intensity is high, hot strength reaches 84～125PMa; Good rigidly, bending strength 130～172MPa, creep resistant is good, at high temperature uses continuously and in temperature environment jumpy, still can keep stable performance.The polyether sulfone chemical proofing is good; Stable to general acid, alkali, aliphatic hydrocarbon, grease, alcohols etc.; At high temperature can be not by acid and alkali corrosion, can anti-gasoline, cleaning agents such as machine oil, lubricated wet goods oils and fluorine Lyons, it has anti-solvent cracking behavior best in the noncrystalline resin.The polyether sulfone combination property is good, is a kind of membrane material of excellent performance, and polyether sulfone doughnut film strength is high, and the film silk is easy fracture not; Good rigidly, compressive resistance is high; Chemical-resistance is good; Polyether sulfone is widely used in the manufacturing and the application of various diffusion barriers.
The manufacturing approach of hollow-fibre membrane mainly contains non-solvent and causes phase separation method (NIPS), melt spinning-stretching hole forming method and thermally induced phase separation (TIPS).It is the technology that is applied to the diffusion barrier preparation the earliest that non-solvent causes phase separation method (NIPS); Development has had quite long history so far; Technology is very ripe; Present most of hollow-fibre membrane manufacturer is all adopting this technology, removes the TPO non-polar material and can not adopt non-solvent to cause phase separation method (NIPS) to prepare the hollow-fibre membrane because there not being suitable solvent, and other most polymeric material can cause phase separation method (NIPS) with non-solvent and prepare hollow-fibre membrane.Polyether sulfone (PES) though hydrophily better than Kynoar materials such as (PVDF); But hydrophily is still not enough; So when making hollow-fibre membrane with polyether sulfone (PES); Need carry out chemical modification increasing its hydrophily to polyether sulfone, or with the polyblend of good hydrophilic property, also need add hydrophilic additive.Described a kind of preparation method of polyether sulfone hollow-fibre membrane like Chinese patent publication number CN1579603A, in preparation liquid, added big molecule of hydrophily and pore former, adopted non-solvent to cause the dry-wet spinning technology of phase separation method (NIPS), pure water flux is 200L/m
2H (0.1MPa, 25 ℃), however need hygrometric state to preserve with the polyether sulfone hollow-fibre membrane that non-solvent causes the phase separation method manufacturing, and because of the film silk of dry state can make the pure water flux of film silk descend, hygrometric state is preserved and is unfavorable for storing and transportation.Introduced like Chinese patent publication number CN101507904A and a kind ofly to have caused phase separation method with non-solvent and prepare polyether sulfone and cellulose powder composite hyperfiltration membrane; Because cellulose molecular chain has a plurality of hydroxyls; Improve the hydrophily of film, remedied the more weak shortcoming of the hydrophilic not enough contamination resistance of polyether sulfone materials.The hydrophilicity of this composite hyperfiltration membrane improves, and has stronger contamination resistance and the characteristic of damming preferably, water flux 120.8～136.6L/m
2H, tensile strength is about 7.5MPa.Yet it is still lower to cause film that phase separation method (NIPS) the makes intensity that to also have big shortcoming be exactly film silk in some is used with non-solvent.Chinese patent publication number CN 1631501A has introduced a kind of blend polyethersulfone doughnut cellulous dialyzing and ultra filtrating membrane; With polyether sulfone is main material of preparing; Polymer or copolymer, cellulose and ester blend thereof with the polyethylene base class; And add pore-foaming agent, solvent is processed spinning solution; Cause phase separation method (NIPS) dry-wet spinning technology with non-solvent and make nascent hollow fiber ultrafiltration membrane, the axial and radially biaxial tension and the processing of guarantor hole of process again makes blend polyethersulfone doughnut cellulous dialyzing and ultra filtrating membrane after the drying.Though after the moulding of film silk through axially with biaxial tension radially after intensity though raising is arranged slightly, the final intensity of film silk can be very not high yet.
Melt spinning-stretching hole forming method is to stretching through the hollow fibre filament after the melt spinning moulding; Receive tension; The filament wall produces the slit; Form the micropore of many perforation hollow fiber walls, prepare hollow-fibre membrane with the method, what be equipped with hollow-fibre membrane with melt spinning-stretching pore-forming legal system mainly is nonpolar TPO membrane material.Chinese patent ZL200510049263.2 has introduced the preparation method of a kind of polyethylene hollow fiber hydrophilic microporous membrane modification; Utilize higher hydroaropic substance and the polyethylene melt blending of some surface abilities, prepare the polyethylene hollow fiber microporous barrier through melt spinning-stretching technique.The porosity of prepared polyethylene hollow fiber microporous barrier is 40～80%, average pore size 0.1～5.0 μ m.Melt spinning-stretching hole forming method has characteristics such as technology is simple, cost is low, pollution-free, but since the hole on the wall tear by pulling force and form, the out-of-shape in hole, the size in hole and skewness, the size in hole is difficult to control.
Thermally induced phase separation (TIPS) is the manufacturing approach of a kind of hollow-fibre membrane of getting up of developed recently; Its principle is earlier with polymer and diluent mixture formation homogeneous phase solution when the high temperature, makes it to become hollow fiber through extruding spinning, in cooling procedure; Phase process can take place in system; This process is divided two types, and one type is that solid-liquid is separated, and one type is liquid-liquid phase separation.After phase-splitting, it is continuous phase that system forms with the polymer, and diluent is the two phase structure of decentralized photo, at this moment selects suitable extractant to extract diluent again.The hot strength of the general tunica fibrosa for preparing with thermally induced phase separation (TIPS) is higher; Use same membrane material; The hot strength of the hollow-fibre membrane of thermally induced phase separation preparation is more than 5 times of hollow-fibre membrane hot strength that cause the phase separation method preparation with non-solvent; And pore size is controlled easily; Can must remain in the hygrometric state as the hollow-fibre membrane silk that non-solvent causes phase separation method (NIPS) preparation with the hollow-fibre membrane of thermally induced phase separation (TIPS) preparation; In case, promptly use the water flux of alcohol activation caudacoria silk to reduce greatly or lose water flux fully because after non-solvent caused the prepared film silk dehydration drying of phase separation method, how many fenestras can shrink.With thermally induced phase separation (TIPS) preparation hollow-fibre membrane is the trend of Future Development, and lot of domestic and international company is all carrying out the research and development that thermally induced phase separation is made hollow-fibre membrane, but mostly is in the research and development stage.
Summary of the invention
The present invention provides that a kind of water flux is higher, film-strength is higher, pore size and the polyether sulfone hollow fiber filter membrane that is more evenly distributed.
Polyether sulfone hollow fiber filter membrane of the present invention, its preparation raw material comprises the component of following percetage by weight: polyethersulfone resin 30～60%, diluent 20～50%, inorganic pore former 5～25%; The aperture of said hollow-fibre membrane is 0.01～0.5 μ m, and under 0.1MPa, 25 ℃ of conditions, pure water flux is 450～2600L/m2h, fracture pressure＞1.0MPa, and hot strength is 20～50MPa.
Preferably, said polyethersulfone resin is the extrusion grade resin, and molecular weight (weight average molecular weight) is 3～200,000 dalton.
Preferably, said diluent is selected from one or more in o-phthalic acid dibutyl ester, diisooctyl phthalate, dibutyl phthalate, repefral, phthalic acid two isodecyl fat, dioctyl adipate, chlorinated paraffin wax and the soybean oil;
Preferably, one or more in said inorganic pore former be the hydrophobic nano level calcium carbonate, silica, zinc oxide, kaolin and the talcum powder.
In a preferred embodiment of the invention, the preparation raw material comprises the component of following percetage by weight: polyethersulfone resin 30-40%, diluent 35～45%, inorganic pore former 5～20%.
In another preferred embodiment of the present invention, the preparation raw material comprises the component of following percetage by weight: polyethersulfone resin 40-60%, diluent 20～40%, inorganic pore former 20～25%.
The present invention also provides the thermic of the above-mentioned polyether sulfone hollow fiber filter membrane preparation method (TIPS) that is separated; Comprise the steps: that (1) is according to the composition of raw materials in the claim 1: polyethersulfone resin 30～60%; Diluent 20～50%; Inorganic pore former 5～25% is prepared raw material, and the above-mentioned raw materials high-speed mixing is even;
(2) the mixture fusion one-step method in 310～400 ℃ double screw extruder with step (1) gained is extruded into hollow fiber, gets into 20～60 ℃ tank cooling forming then;
(3) behind the doughnut process diluent extractant and extraction of inorganic pore former extractant and extraction with step (2) collection, obtain the polyether sulfone hollow-fibre membrane.
Further, after the doughnut film preparation of the present invention, can after super-dry, preserve.
Preferably, among the said preparation method, said polyethersulfone resin is the extrusion grade resin, and molecular weight (weight average molecular weight) is 3～200,000 dalton.Preferably, said diluent is selected from one or more in o-phthalic acid dibutyl ester, diisooctyl phthalate, dibutyl phthalate, repefral, phthalic acid two isodecyl fat, dioctyl adipate, chlorinated paraffin wax and the soybean oil.Preferably, one or more in said inorganic pore former be the hydrophobic nano level calcium carbonate, silica, zinc oxide, kaolin and the talcum powder.
Preferably, among the said preparation method, the diluent extractant is selected from one or more in n-hexane, cyclohexane, ethanol, gasoline and the carrene.
Preferably, among the above-mentioned preparation method, described inorganic pore former extractant is selected from sulfuric acid, hydrochloric acid, NaOH and potassium hydroxide.
Preferably, the draw ratio of said double screw extruder is 20～48: 1.
The present invention is even with the pore size of the hollow fiber filter membrane of thermally induced phase separation (TIPS) preparation, pore size distribution is even, porosity is high, and film-strength is high, and hot strength reaches 20～50MPa, fracture pressure＞1.0MPa; Water flux is high, and pure water flux is 450～2,600L/m
2H (0.1MPa, 25 ℃); Pore size controlled (be dispersed in the mixed material uniformly through the control pore former, but the uniformity of control hole, the size size in the hole of controlling diaphragm easily of control pore former), the aperture is 0.01～0.5 μ m; Chemical-resistance is good, cleans easily; Need not add the hydrophilic modifying agent, can dry state preserve, dried film silk can not lose original water flux, directly uses during use to get final product, and need not carry out extra activation step.The polyether sulfone hollow-fibre membrane of the present invention preparation can be used for filtration treatment and the purification of industry and municipal water treatment, domestic drinking water filtration treatment, food and medicine, the aspects such as pre-treatment of counter-infiltration.
The specific embodiment
To combine accompanying drawing to introduce polyether sulfone hollow-fibre membrane of the present invention and preparation method thereof in detail below.
Embodiment 1: by weight taking by weighing 50% polyethersulfone resin (molecular weight: 50; 000), 20% o-phthalic acid dibutyl ester, 10% repefral, 20% nanoscale hydrophobic type calcium carbonate (particle diameter: 30-40nm) material is evenly mixed with homogenizer; The material that stirs is through 380 ℃ double screw extruder fusion plastification, through bushing type spinning head (the outer tube diameter is 3.0mm, and the inner central tube diameter is 1.2mm); The spinning head central tube feeds nitrogen; Be extruded into hollow fiber, the air of process 5cm is apart from getting into 30 ℃ of tank cooling formings then, and the doughnut after the moulding is collected with wire wrapping wheel.Doughnut after the collection extracts diluent o-phthalic acid dibutyl ester, repefral with n-hexane respectively; With 2M hydrochloric acid inorganic pore former calcium carbonate is extracted, external diameter 1.52mm, internal diameter 0.86mm, porosity 72%, the bubble point pressure that makes the polyether sulfone hollow-fibre membrane is that 0.32MPa, pure water flux are 932L/m
2H (0.1MPa, 25 ℃), fracture pressure＞1.0MPa, hot strength 39.6MPa, the water contact angle of film outer surface are 38 °.
Embodiment 2: adopt embodiment 1 preparation method and technology; Difference at prescription 50,000), (particle diameter: 30-40nm) with homogenizer material is uniformly mixed evenly, the material that stirs is through 350 ℃ double screw extruder fusion plastification extrusion molding for 20% o-phthalic acid dibutyl ester, 20% phthalic acid, two isodecyl fat, 20% nanoscale hydrophobic type calcium carbonate by weight taking by weighing 40% polyethersulfone resin (molecular weight:; Spinning technique embodiment 1 is identical; Doughnut after the collection extracts diluent o-phthalic acid dibutyl ester, phthalic acid two isodecyl fat and inorganic pore former calcium carbonate respectively and extracts with cyclohexane and 2M hydrochloric acid respectively, the polyether sulfone that makes (PES) hollow-fibre membrane external diameter 1.63mm, internal diameter 0.90mm; Porosity 75%; Bubble point pressure is 0.27MPa, and pure water flux is 1,285L/m
2H (0.1MPa, 25 ℃), fracture pressure＞1.0MPa, hot strength 32.7MPa, the water contact angle of film outer surface are 37 °.
Embodiment 3: adopt embodiment 1 preparation method and technology; Difference is being filled a prescription by weight taking by weighing 40% polyethersulfone resin (molecular weight: 50; 000), meter level hydrophobic type zinc oxide (particle diameter: 60nm) material is uniformly mixed evenly in 20% o-phthalic acid dibutyl ester, 20% phthalic acid, the two isodecyl fat, 20% with homogenizer; The material that stirs is through 370 ℃ double screw extruder fusion plastification extrusion molding, spinning technique and extraction and to extract treatment process identical with embodiment 1.Doughnut after the collection extracts diluent o-phthalic acid dibutyl ester, repefral and inorganic pore former zinc oxide respectively and extracts with alcohol and 2M sulfuric acid respectively; The polyether sulfone that makes (PES) hollow-fibre membrane external diameter 1.53mm; Internal diameter 0.88mm, porosity 75%, bubble point pressure is 0.24MPa; Pure water flux is 1,525L/m
2H (0.1MPa, 25 ℃), fracture pressure＞1.0MPa, hot strength 36.7MPa, the water contact angle of film outer surface are 37 °.
Embodiment 4: adopt embodiment 1 preparation method and technology; Difference is being filled a prescription by weight taking by weighing 35% polyethersulfone resin (molecular weight: 50; 000), 30% diisooctyl phthalate, 20% dibutyl phthalate, 15% hydrophobic silica (particle diameter: 10nm) material is uniformly mixed evenly with homogenizer; The material that stirs is through 335 ℃ double screw extruder fusion plastification moulding, and spinning technique is identical with embodiment 1.Hollow fibre filament after the collection extracts diluent diisooctyl phthalate, dibutyl phthalate and inorganic pore former silica and extract with n-hexane and 5% sodium hydroxide solution respectively.The hollow-fibre membrane external diameter 1.41mm that makes, internal diameter 0.80mm, porosity 77%, bubble point pressure is 0.27MPa, pure water flux is 1,856L/m
2H (0.1MPa, 25 ℃), fracture pressure＞1.0MPa, hot strength 26.2MPa, the water contact angle of film outer surface are 34 °.
Can find out from above-mentioned each embodiment; Its each parameter of polyether sulfone hollow fiber filter membrane of the foregoing description preparation is all in following scope: the aperture of said hollow-fibre membrane is 0.01～0.5 μ m; Under 0.1MPa, 25 ℃ of conditions; Pure water flux is 450～2600L/m2h, fracture pressure＞1.0MPa, and hot strength is 20～50MPa.Polyether sulfone hollow fiber filter membrane of the present invention is compared with existing filter membrane, and its water flux is higher, and film strength is better.But kept dry after the filter membrane preparation of the present invention is directly used during use to get final product, and does not need other activation step.
The above is merely preferred embodiment of the present invention, and is in order to restriction the present invention, not all within spirit of the present invention and principle, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a polyether sulfone hollow fiber filter membrane is characterized in that, the preparation raw material comprises the component of following percetage by weight: polyethersulfone resin 30～60%, diluent 20～50%, inorganic pore former 5～25%.
2. polyether sulfone hollow fiber filter membrane as claimed in claim 1 is characterized in that, the preparation raw material comprises the component of following percetage by weight: polyethersulfone resin 30-40%, diluent 35～45%, inorganic pore former 5～20%.
3. polyether sulfone hollow fiber filter membrane as claimed in claim 1 is characterized in that, the preparation raw material comprises the component of following percetage by weight: polyethersulfone resin 40-60%, diluent 20～40%, inorganic pore former 20～25%.
4. like each described polyether sulfone hollow fiber filter membrane of claim 1-3, it is characterized in that the aperture of said hollow-fibre membrane is 0.01～0.5 μ m, under 0.1MPa, 25 ℃ of conditions, pure water flux is 450～2600L/m
2H, fracture pressure＞1.0MPa, hot strength is 20～50MPa.
5. polyether sulfone hollow fiber filter membrane as claimed in claim 1 is characterized in that, said polyethersulfone resin is the extrusion grade resin, and weight average molecular weight is 30,000～200,000.
6. like each described polyether sulfone hollow fiber filter membrane of claim 1-3; It is characterized in that said diluent is selected from one or more in o-phthalic acid dibutyl ester, diisooctyl phthalate, dibutyl phthalate, repefral, phthalic acid two isodecyl fat, dioctyl adipate, chlorinated paraffin wax and the soybean oil; Said inorganic pore former is one or more in calcium carbonate, silica, zinc oxide, kaolin and the talcum powder, and said calcium carbonate, silica, zinc oxide, kaolin and talcum powder all are the hydrophobic nano level.
7. the thermic of the described polyether sulfone hollow fiber filter membrane of claim 1 preparation method that is separated is characterized in that, comprises the steps:
(1) according to the composition of raw materials in the claim 1: polyethersulfone resin 30～60%, diluent 20～50%, inorganic pore former 5～25% is prepared raw material, and above-mentioned raw materials is mixed;
(2) mixture with step (1) gained melt extrudes into hollow fiber in 310～400 ℃ double screw extruder, gets into 20～60 ℃ tank cooling forming then;
(3) after the doughnut of step (2) being collected passes through diluent extractant and inorganic pore former agent extraction and extraction respectively, obtain the polyether sulfone hollow-fibre membrane.
8. preparation method as claimed in claim 7 is characterized in that, said polyethersulfone resin is the extrusion grade resin, and weight average molecular weight is 30,000～200,000.
9. preparation method as claimed in claim 7 is characterized in that the diluent extractant is selected from one or more in n-hexane, cyclohexane, ethanol, gasoline and the carrene.
10. preparation method as claimed in claim 7 is characterized in that, described inorganic pore former extractant is selected from one or more in sulfuric acid, hydrochloric acid, NaOH and the potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010278592.5A CN102397759B (en) | 2010-09-08 | 2010-09-08 | Polyether sulfone hollow fiber filter membrane and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010278592.5A CN102397759B (en) | 2010-09-08 | 2010-09-08 | Polyether sulfone hollow fiber filter membrane and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102397759A true CN102397759A (en) | 2012-04-04 |
| CN102397759B CN102397759B (en) | 2014-05-14 |
Family
ID=45880643
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010278592.5A Active CN102397759B (en) | 2010-09-08 | 2010-09-08 | Polyether sulfone hollow fiber filter membrane and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102397759B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525003A (en) * | 2014-11-05 | 2015-04-22 | 华玉叶 | Polyether sulfone hollow fiber membrane preparation method |
| CN110152505A (en) * | 2019-06-10 | 2019-08-23 | 泰州禾益新材料科技有限公司 | A kind of preparation method of bilayer polysulfone hollow fibre ultrafiltration membrane |
| CN111686591A (en) * | 2019-03-15 | 2020-09-22 | 恩特格里斯公司 | Composite hollow fibers and related methods and products |
| CN114028328A (en) * | 2021-12-16 | 2022-02-11 | 安徽联谊药业股份有限公司 | Aminotoluic acid injection and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5022990A (en) * | 1989-01-12 | 1991-06-11 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyvinylidene fluoride porous membrane and a method for producing the same |
| CN1265048A (en) * | 1996-12-10 | 2000-08-30 | 旭化成工业株式会社 | Porous polyvinylidene fluoride resin film and process for producing same |
| CN1883779A (en) * | 2006-05-19 | 2006-12-27 | 广州美能材料科技有限公司 | Process for preparing composite hollow fiber membrane |
| CN1899678A (en) * | 2005-07-19 | 2007-01-24 | 天津工业大学 | Method for producing hollow fiber film |
| CN101362057A (en) * | 2008-01-30 | 2009-02-11 | 清华大学 | Method for preparing polyvinylidene fluoride porous membrane |
| CN101396641A (en) * | 2008-10-31 | 2009-04-01 | 孟广祯 | Composite thermotropic phase separation film-making method |
| JP2009095812A (en) * | 2007-10-19 | 2009-05-07 | Kawasaki Heavy Ind Ltd | Separation membrane consisting of polyethersulfone, method for manufacturing the same, and undiluted solution of deposition |
| CN102107121A (en) * | 2009-12-29 | 2011-06-29 | 林金建 | Method for preparing hollow fiber microporous membrane by thermally-induced phase separation method |
-
2010
- 2010-09-08 CN CN201010278592.5A patent/CN102397759B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5022990A (en) * | 1989-01-12 | 1991-06-11 | Asahi Kasei Kogyo Kabushiki Kaisha | Polyvinylidene fluoride porous membrane and a method for producing the same |
| CN1265048A (en) * | 1996-12-10 | 2000-08-30 | 旭化成工业株式会社 | Porous polyvinylidene fluoride resin film and process for producing same |
| CN1899678A (en) * | 2005-07-19 | 2007-01-24 | 天津工业大学 | Method for producing hollow fiber film |
| CN1883779A (en) * | 2006-05-19 | 2006-12-27 | 广州美能材料科技有限公司 | Process for preparing composite hollow fiber membrane |
| JP2009095812A (en) * | 2007-10-19 | 2009-05-07 | Kawasaki Heavy Ind Ltd | Separation membrane consisting of polyethersulfone, method for manufacturing the same, and undiluted solution of deposition |
| CN101362057A (en) * | 2008-01-30 | 2009-02-11 | 清华大学 | Method for preparing polyvinylidene fluoride porous membrane |
| CN101396641A (en) * | 2008-10-31 | 2009-04-01 | 孟广祯 | Composite thermotropic phase separation film-making method |
| CN102107121A (en) * | 2009-12-29 | 2011-06-29 | 林金建 | Method for preparing hollow fiber microporous membrane by thermally-induced phase separation method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525003A (en) * | 2014-11-05 | 2015-04-22 | 华玉叶 | Polyether sulfone hollow fiber membrane preparation method |
| CN111686591A (en) * | 2019-03-15 | 2020-09-22 | 恩特格里斯公司 | Composite hollow fibers and related methods and products |
| CN110152505A (en) * | 2019-06-10 | 2019-08-23 | 泰州禾益新材料科技有限公司 | A kind of preparation method of bilayer polysulfone hollow fibre ultrafiltration membrane |
| CN114028328A (en) * | 2021-12-16 | 2022-02-11 | 安徽联谊药业股份有限公司 | Aminotoluic acid injection and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102397759B (en) | 2014-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dzinun et al. | Morphological study of co-extruded dual-layer hollow fiber membranes incorporated with different TiO2 loadings | |
| CN102219969B (en) | Polyvinylidene fluoride-polyether sulfone blended hollow fiber membrane and thermally induced phase separation preparation method | |
| CN101590374B (en) | Polyvinylidene fluoride hollow fiber film and preparation method thereof | |
| JP5832907B2 (en) | Method for producing polyolefin microporous membrane | |
| CN100579638C (en) | Modified polyvinyl chloride hollow fiber microporous memebrane and method for preparing the same | |
| WO2011069441A1 (en) | Method for preparing composite multilayer porous hollow fiber membrane and device and product thereof | |
| CN103111189B (en) | High-flux polyvinylidene fluoride hollow fiber membrane | |
| WO1981000969A1 (en) | Polyvinylidene fluoride resin hollow filament microfilter and process for producing same | |
| KR20110120202A (en) | Porous multilayer filter and method for producing same | |
| KR20070113375A (en) | Asymmetric poly(vinylidene fluoride) hollow fiber membranes and methods to make membranes | |
| CN108079795A (en) | A kind of classifying porous polyvinylidene fluoride hollow fiber composite membrane and its manufacturing method | |
| CN101485961B (en) | Method for preparing polyvinylidene fluoride hollow fiber alloy film | |
| CN102397759B (en) | Polyether sulfone hollow fiber filter membrane and its preparation method | |
| CN110548411A (en) | Preparation method of asymmetric polyolefin film | |
| Cui et al. | EVOH in situ fibrillation and its effect of strengthening, toughening and hydrophilic modification on PVDF hollow fiber microfiltration membrane via TIPS process | |
| CN111346520A (en) | Asymmetric polyolefin degassing membrane and preparation method thereof | |
| KR20160081612A (en) | PVDF porous hollow fiber membrane and the preparing method thereof | |
| KR20140073331A (en) | Manufacturing method of PTFE membrane having porosity using blowing agent | |
| JP6596329B2 (en) | Method for producing polyolefin microporous membrane | |
| CN104968422B (en) | The manufacturing method of porous hollow fibres film and porous hollow fibres film | |
| JP2013144264A (en) | Method for producing porous polysulfone-based membrane | |
| KR101426000B1 (en) | PTFE hollow fibertype membrane for membrane distillation and manufacturing method thereof | |
| Wang et al. | Preparation of poly (4‐methyl‐1‐pentene) asymmetric or microporous hollow‐fiber membranes by melt‐spun and cold‐stretch method | |
| KR20190129890A (en) | Separator and Manufacturing Method | |
| CN103537203A (en) | Thermally-induced phase separation polyvinylidene fluoride hollow fiber membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160504 Address after: 510660, Guangzhou, Guangdong Province, Tianhe District Road, Huang Chau Industrial Zone on the first floor of seven Patentee after: Guangzhou Meineng Materials Technology Co., Ltd. Address before: 621000 Mianyang city of Sichuan Province Branch Park No. 249 Middle Road Patentee before: Mianyang Midea Material Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20220124 Address after: 226372 No. 5, Poyanghu Road, Sutong science and Technology Industrial Park, Nantong City, Jiangsu Province Patentee after: JIANGSU MEINENG FILM MATERIAL TECHNOLOGY CO.,LTD. Address before: 510660 first floor, building 7, Huangzhou Industrial Zone, chepo Road, Tianhe District, Guangdong Province Patentee before: MEMSTAR (GUANGZHOU) Co.,Ltd. |
|
| TR01 | Transfer of patent right |