CN109499371B - Polyphenylene sulfone lining film and preparation method thereof - Google Patents
Polyphenylene sulfone lining film and preparation method thereof Download PDFInfo
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- CN109499371B CN109499371B CN201811338154.6A CN201811338154A CN109499371B CN 109499371 B CN109499371 B CN 109499371B CN 201811338154 A CN201811338154 A CN 201811338154A CN 109499371 B CN109499371 B CN 109499371B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- Chemical & Material Sciences (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a polyphenylene sulfone lining film and a preparation method thereof, polyphenylene sulfone (PPSU) is dissolved in a polar solvent, hydrophilic polymer and micromolecule additive are added, casting solution is prepared after mixing, the mixture is stirred for 8 to 24 hours at the temperature of 40 to 100 ℃, and then vacuum defoaming is carried out for 8 to 24 hours; feeding the support tube into steam of 80-180 ℃ for a period of time, and taking out the support tube, wherein the steam is a polar solvent and/or a micromolecular additive; extruding the membrane casting solution through a spinning nozzle, attaching the membrane casting solution to a taken-out support tube, and then immersing the support tube into a gel bath at the temperature of 5-95 ℃ for immersion type phase conversion to prepare a primary gel-formed membrane wire; fully soaking the membrane filaments in hot water for 12-24 h; soaking the soaked membrane filaments in a glycerol aqueous solution for 12 hours; taking out the membrane wires, and airing to obtain the polyphenylene sulfone lining membrane in a dry state. The preparation method of the invention processes the support tube at high temperature to soften the support tube, thereby enlarging the pore and enhancing the combination degree of the feed liquid and the support tube; the prepared PPSU lining film has better peeling strength and chemical resistance.
Description
Technical Field
The invention relates to a polyphenylene sulfone lining film and a preparation method thereof.
Background
In the last 90 th century, MBRs have been widely used in sewage treatment markets in europe and north america, but have been developing very rapidly in china, and by 2017, the total MBR scale has exceeded 1000 million tons/day, and the maximum treatment scale of a single MBR sewage plant has reached 60 million tons/day. MBR is popular because of advantages such as good water quality, little occupation of land, but also has suffered from scaling because of high cost, poor reliability. Over the last 10 years, MBR membrane performance, engineering and design levels, and operating water levels have increased substantially, and MBRs have made significant advances in reducing costs and improving reliability. Compared with the PVDF lining film on the market at present, the PPSU film has better chemical resistance, higher peel strength, lower cost and good application prospect.
Currently, very little research has been conducted on polyphenylene sulfone membranes, and patent publication No. CN104411388A discloses a homogeneous ultrafiltration membrane prepared from sulfonated polyphenylene sulfone, and patent publication No. CN105854649B discloses a solvent-resistant polyphenylene sulfone nanofiltration membrane containing modified microporous spheres, but neither patent is an inner liner membrane.
Disclosure of Invention
The invention aims to provide a polyphenylene sulfone lining film and a preparation method thereof, the process steps are simple, the cost is low, and the prepared polyphenylene sulfone lining film has good peeling strength and chemical resistance and good application prospect.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method of making a polyphenylene sulfone liner membrane comprising the steps of:
(1) dissolving polyphenylene sulfone (PPSU) in a polar solvent, adding a hydrophilic polymer and a micromolecular additive, mixing to prepare a casting solution, stirring at 40-100 ℃ for 8-24h, taking the material, observing the dissolution condition, and performing vacuum defoaming for 8-24h after the dissolution is determined to be complete; wherein the mass fraction of the polyphenylene sulfone (PPSU) in the casting solution is 10-30%, the mass fraction of the hydrophilic polymer is 1-20%, the mass fraction of the small molecular additive is 1-20%, and the mass fraction of the polar solvent is 40-80%;
(2) feeding the support tube into steam, which is the polar solvent and/or the small molecule additive, for a certain period of time, and then taking out the support tube, wherein the temperature of the steam is 80-180 ℃;
(3) extruding the membrane casting solution through a spinning nozzle, attaching the membrane casting solution to the taken support tube, and then immersing the support tube into a gel bath at the temperature of 5-95 ℃ for immersion type phase conversion to prepare a primary gel-formed membrane wire;
(4) fully soaking the membrane filaments in hot water for 12-24h to finish the replacement and cleaning of a solvent and a non-solvent, and reducing the soaking time;
(5) in order to protect the pores and prevent the pores from shrinking or collapsing, soaking the membrane filaments after soaking in a glycerol aqueous solution for 12 hours;
(6) and taking out the membrane wire, and airing to obtain the polyphenylene sulfone lining membrane in a dry state.
Preferably, the hydrophilic polymer is composed of one or more of sulfonated polyether ether ketone (SPEEK), Sulfonated Polysulfone (SPSU), polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, polyacrylate, polyvinyl acetate, polyether, polyoxyethylene, polyoxypropylene, or a modification or copolymer of these polymers.
Preferably, the small molecule additive is composed of one or more of water, ethanol, ethylene glycol, glycerol, diethylene glycol, triethylene glycol, inorganic salts, sulfolane and oxalic acid.
Preferably, the polar solvent is composed of one or more of dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylpyrrolidone, trimethyl phosphate and triethyl phosphate.
Preferably, in the step (2), the stay tube stays in the steam for 5s or more, and sufficient action time is given, so that the peel strength of the lining film is enhanced.
Preferably, in the step (3), the height of the bottom of the spinneret from the liquid surface of the gel bath is 10mm or more, namely the height of the air section is 10mm or more, and the gel bath is a mixture of the polar solvent and deionized water, and the ratio of the polar solvent to the deionized water is 1:10-3: 5.
Preferably, in the step (4), the hot water is deionized water, and the temperature of the hot water is 50-90 ℃.
Preferably, in the step (5), the mass fraction of glycerol in the glycerol aqueous solution is 10-20%, and the temperature of the glycerol aqueous solution is 30-50 ℃.
A polyphenylene sulfone lining film is prepared by the preparation method.
Preferably, the polyphenylene sulfone-lined membrane is a microfiltration membrane, an ultrafiltration membrane or a nanofiltration membrane.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages: according to the polyphenylene sulfone lining film and the preparation method thereof, polyphenylene sulfone (PPSU) is adopted to prepare the lining film, the chemical resistance of the PPSU material is better than that of PVDF, and the cost is lower; meanwhile, the support tube is treated at high temperature by taking a polar solvent and/or a small molecular additive as steam, so that the support tube is softened, the pores are enlarged, and the binding degree of the feed liquid and the support tube is enhanced; the prepared PPSU lining film has better peel strength and chemical resistance, lower cost and good application prospect.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
160g of polyphenylene sulfone (PPSU) was dissolved in 600g of NMP, and 100g of PVP, 50g of PEG and 20g of glycerol were added, and after stirring at 80 ℃ for 24 hours, vacuum defoaming was performed for 8 hours. The gel bath was a mixture of 50% DMAC and 50% deionized water at 60 ℃. The steam zone temperature was 160 deg.C, the support tube residence time in this zone was 8s, and the steam used was 50% DMAC and 50% DI water. Under these conditions, a hollow fiber-lined membrane was obtained.
Tests prove that the prepared hollow fiber lining membrane has the outer diameter of 2.2mm and the peel strength of 0.8MPa, is higher than that of a PVDF lining membrane in the same supporting tube and process, is soaked in a NaOH solution with the pH =12 for 20 days, the appearance and the strength of the PPSU lining membrane are not obviously changed, the color of the PVDF lining membrane is darkened, and defluorination degradation is carried out.
Example 2
150g of polyphenylene sulfone (PPSU) was dissolved in 250g of NMP and 300g of DMAC, and 80g of PVP, 80g of PEG and 10g of triethylene glycol were added, and after stirring at 80 ℃ for 24 hours, vacuum deaeration was carried out for 8 hours. The gel bath used a mixture of 60% DMF and 40% deionized water at 55 ℃. The temperature in the steam zone was 130 deg.C, the residence time of the support tube in this zone was 6s, and the steam used was 50% NMP and 50% deionized water. Under these conditions, a hollow fiber-lined membrane was obtained.
Tests prove that the prepared hollow fiber lining membrane has the outer diameter of 2.2mm and the peel strength of 0.7MPa, is higher than that of a PVDF lining membrane in the same supporting tube and process, is soaked in a NaOH solution with the pH =14 for 30 days, the appearance and the strength of the PPSU lining membrane are not obviously changed, the color of the PVDF lining membrane is blackened, membrane filaments are fragile, and severe defluorination degradation is caused.
The above-mentioned embodiments are merely illustrative of the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered in the scope of the present invention.
Claims (10)
1. A method of preparing a polyphenylene sulfone liner film, comprising: the method comprises the following steps:
(1) dissolving polyphenylene sulfone (PPSU) in a polar solvent, adding a hydrophilic polymer and a micromolecular additive, mixing to prepare a casting solution, stirring at the temperature of 40-100 ℃ for 8-24h, and then defoaming in vacuum for 8-24 h; wherein the mass fraction of the polyphenylene sulfone (PPSU) in the casting solution is 10-30%, the mass fraction of the hydrophilic polymer is 1-20%, the mass fraction of the small molecular additive is 1-20%, and the mass fraction of the polar solvent is 40-80%;
(2) feeding the support tube into steam, which is the polar solvent, for a period of time, and taking out the support tube, wherein the temperature of the steam is 80-180 ℃;
(3) extruding the membrane casting solution through a spinning nozzle, attaching the membrane casting solution to the taken support tube, and then immersing the support tube into a gel bath at the temperature of 5-95 ℃ for immersion type phase conversion to prepare a primary gel-formed membrane wire;
(4) fully soaking the membrane filaments in hot water for 12-24 h;
(5) soaking the soaked membrane filaments in a glycerol aqueous solution for 12 hours;
(6) and taking out the membrane wire, and airing to obtain the polyphenylene sulfone lining membrane in a dry state.
2. The method of claim 1, wherein the polyphenylene sulfone liner film comprises: the hydrophilic polymer is composed of one or more of sulfonated polyether ether ketone (SPEEK), Sulfonated Polysulfone (SPSU), polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylic acid, polyacrylate, polyvinyl acetate, polyether, polyoxyethylene, polyoxypropylene or modified substances or copolymers of these polymers.
3. The method of claim 1, wherein the polyphenylene sulfone liner film comprises: the small molecular additive is composed of one or more of water, ethanol, ethylene glycol, glycerol, diethylene glycol, triethylene glycol, inorganic salt, sulfolane and oxalic acid.
4. The method of claim 1, wherein the polyphenylene sulfone liner film comprises: the polar solvent is composed of one or more of dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methyl pyrrolidone, trimethyl phosphate and triethyl phosphate.
5. The method of claim 1, wherein the polyphenylene sulfone liner film comprises: in the step (2), the stay tube stays in the steam for more than or equal to 5 s.
6. The method of claim 1, wherein the polyphenylene sulfone liner film comprises: in the step (3), the height from the bottom of the spinneret to the liquid level of the gel bath is 10mm or more, the gel bath is a mixture of the polar solvent and deionized water, and the ratio of the polar solvent to the deionized water is 1:10-3: 5.
7. The method of claim 1, wherein the polyphenylene sulfone liner film comprises: in the step (4), the hot water is deionized water, and the temperature of the hot water is 50-90 ℃.
8. The method of claim 1, wherein the polyphenylene sulfone liner film comprises: in the step (5), the mass fraction of glycerol in the glycerol aqueous solution is 10-20%, and the temperature of the glycerol aqueous solution is 30-50 ℃.
9. A polyphenylene sulfone-lined membrane obtained by the production method according to any one of claims 1 to 8.
10. A polyphenylene sulfone-lined film according to claim 9, characterized in that: the polyphenylene sulfone lining membrane is a microfiltration membrane, an ultrafiltration membrane or a nanofiltration membrane.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811338154.6A CN109499371B (en) | 2018-11-12 | 2018-11-12 | Polyphenylene sulfone lining film and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811338154.6A CN109499371B (en) | 2018-11-12 | 2018-11-12 | Polyphenylene sulfone lining film and preparation method thereof |
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| Publication Number | Publication Date |
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| CN109499371A CN109499371A (en) | 2019-03-22 |
| CN109499371B true CN109499371B (en) | 2021-10-15 |
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Citations (5)
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|---|---|---|---|---|
| CN102394282A (en) * | 2011-11-25 | 2012-03-28 | 佛山市金辉高科光电材料有限公司 | Lithium ion secondary battery porous multilayer diaphragm and manufacture method thereof |
| CN104411388A (en) * | 2012-04-20 | 2015-03-11 | 巴斯夫欧洲公司 | Ultrafiltration membranes fabricated from sulfonated polyphenylenesulfones |
| CN104857868A (en) * | 2014-02-25 | 2015-08-26 | 中国科学院生态环境研究中心 | PDMS-KIT-6 composite membrane for separating organic steam and preparation method thereof |
| CN105854649A (en) * | 2016-05-25 | 2016-08-17 | 北京林业大学 | Preparation method of novel polyphenylene sulfone solvent-resistant nanofiltration membrane containing modified micropore spheres |
| CN105964154A (en) * | 2016-06-22 | 2016-09-28 | 广州中国科学院先进技术研究所 | Preparation of PVDF hollow fibrous membrane of hydrophilic high-adhesion-strength liner |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090191398A1 (en) * | 2008-01-25 | 2009-07-30 | General Electric Company | Membranes comprising hydrophilic coatings |
| US7985339B2 (en) * | 2008-08-25 | 2011-07-26 | General Electric Company | Polyarylether compositions bearing zwitterion functionalities |
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2018
- 2018-11-12 CN CN201811338154.6A patent/CN109499371B/en active Active
Patent Citations (5)
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|---|---|---|---|---|
| CN102394282A (en) * | 2011-11-25 | 2012-03-28 | 佛山市金辉高科光电材料有限公司 | Lithium ion secondary battery porous multilayer diaphragm and manufacture method thereof |
| CN104411388A (en) * | 2012-04-20 | 2015-03-11 | 巴斯夫欧洲公司 | Ultrafiltration membranes fabricated from sulfonated polyphenylenesulfones |
| CN104857868A (en) * | 2014-02-25 | 2015-08-26 | 中国科学院生态环境研究中心 | PDMS-KIT-6 composite membrane for separating organic steam and preparation method thereof |
| CN105854649A (en) * | 2016-05-25 | 2016-08-17 | 北京林业大学 | Preparation method of novel polyphenylene sulfone solvent-resistant nanofiltration membrane containing modified micropore spheres |
| CN105964154A (en) * | 2016-06-22 | 2016-09-28 | 广州中国科学院先进技术研究所 | Preparation of PVDF hollow fibrous membrane of hydrophilic high-adhesion-strength liner |
Non-Patent Citations (1)
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| "添加剂对聚亚苯基砜和聚偏氟乙烯微孔膜性能的影响";金艳;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20141215(第12期);正文第4，16，18，22-23，28页及表3-1 * |
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