KR100406362B1 - 복합막 제조용 비대칭 지지막 제조방법 및 이로부터 제조된 투과성 및 기계적 강도가 개선된 비대칭 지지막 - Google Patents
복합막 제조용 비대칭 지지막 제조방법 및 이로부터 제조된 투과성 및 기계적 강도가 개선된 비대칭 지지막 Download PDFInfo
- Publication number
- KR100406362B1 KR100406362B1 KR10-1998-0046469A KR19980046469A KR100406362B1 KR 100406362 B1 KR100406362 B1 KR 100406362B1 KR 19980046469 A KR19980046469 A KR 19980046469A KR 100406362 B1 KR100406362 B1 KR 100406362B1
- Authority
- KR
- South Korea
- Prior art keywords
- solvent
- membrane
- water
- polymer solution
- support membrane
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 75
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000002131 composite material Substances 0.000 title claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 67
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 239000004642 Polyimide Substances 0.000 claims abstract description 23
- 229920001721 polyimide Polymers 0.000 claims abstract description 23
- 239000012046 mixed solvent Substances 0.000 claims abstract description 21
- 230000035699 permeability Effects 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000005191 phase separation Methods 0.000 claims abstract description 12
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 26
- 239000006184 cosolvent Substances 0.000 claims description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 16
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical group O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000011148 porous material Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- -1 1,4-phenylene diamine Imide Chemical class 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/026—Sponge structure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
시료 | γ-BL/NMP 조성 | ΔHmix(혼합용매:물) | P(O2), GPU* | P(N2), GPU | 선택도P(O2)/P(N2) |
1 | 100/0 | 803 | 10.69 | 9.63 | 1.11 |
2 | 90/10 | 487 | 905 | 900 | 1.00 |
3 | 80/20 | 171 | 270 | 262 | 1.03 |
4 | 60/40 | -462 | 17.2 | 17 | 1.01 |
5 | 20/80 | -1727 | 8.69 | 8.0 | 1.09 |
6 | 0/100 | -2356 | 322 | 318 | 1.01 |
시료 | γ-BL/NMP 조성 | ΔHmix(혼합용매:물) | P(O2), GPU |
7 | 100/0 | 803 | 7.69 |
8 | 90/10 | 487 | 872 |
9 | 80/20 | 171 | 262 |
10 | 60/40 | -462 | 17 |
11 | 20/80 | -1727 | 8 |
12 | 0/100 | -2356 | 200 |
시료 | 후처리 | P(O2), GPU* | P(N2), GPU | 선택도P(O2)/P(N2) |
13 | 헥산 처리 | 952 | 102 | 0.932 |
Claims (4)
- 고분자 및 용매로 이루어진 고분자 용액을 비용매 침전 용액에서 상분리법에 의해 비대칭 지지막을 제조하는 방법에 있어서,1)고분자 용액의 총중량을 기준으로 폴리이미드 15~25중량%,를비용매(non-solvent)인 물과의 혼합열이 흡열인 주용매와 비용매와의 혼합열이 발열인 공용매로 이루어진 혼합용매에 용해시켜 고분자 용액을 제조하며, 이 때 상기 주용매와 공용매의 혼합비는 상기 혼합 용매와 비용매인 물과의 혼합열이 흡열이 되도록 하기 수학식(1)로부터 선택되는 고분자 용액 제조 단계; 및[수학식 1]ΔHmix(혼합용매:물)= ω주용매×ΔHmix(주용매:물)+ ω공용매×ΔHmix(공용매:물)(단, 상기 식에서 ΔHmix(주용매:물)및 ΔHmix(공용매:물)은 서로 동량으로 혼합될 때의 혼합열이며, ω는 무게 분율이다)2) 상기 1)단계에서 제조된 고분자 용액을 상분리시켜 제조된 막을 비용매인 물에 침지시켜 비대칭 지지막을 제조하는 단계; 를 포함하여 이루어지는 복합막 제조용 비대칭 지지막 제조 방법
- 제 1항에 있어서, 상기 주용매는 γ-부티로락톤임을 특징으로 하는 방법
- 제 1항에 있어서, 상기 공용매는 N-메틸-2-피롤리돈(NMP), N,N,-디메틸아세트아미드, N,N-디메틸포름아미드 및 그 혼합물로 이루어진 그룹으로 부터 선택된 1종이상의 화합물임을 특징으로 하는 방법
- 청구범위 제1항의 방법에 의해 제조된 투과성 및 기계적 강도가 개선된 비대칭 지지막
Priority Applications (1)
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KR10-1998-0046469A KR100406362B1 (ko) | 1998-10-30 | 1998-10-30 | 복합막 제조용 비대칭 지지막 제조방법 및 이로부터 제조된 투과성 및 기계적 강도가 개선된 비대칭 지지막 |
Applications Claiming Priority (1)
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KR10-1998-0046469A KR100406362B1 (ko) | 1998-10-30 | 1998-10-30 | 복합막 제조용 비대칭 지지막 제조방법 및 이로부터 제조된 투과성 및 기계적 강도가 개선된 비대칭 지지막 |
Publications (2)
Publication Number | Publication Date |
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KR20000028293A KR20000028293A (ko) | 2000-05-25 |
KR100406362B1 true KR100406362B1 (ko) | 2004-02-14 |
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KR10-1998-0046469A KR100406362B1 (ko) | 1998-10-30 | 1998-10-30 | 복합막 제조용 비대칭 지지막 제조방법 및 이로부터 제조된 투과성 및 기계적 강도가 개선된 비대칭 지지막 |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101003947B1 (ko) * | 2008-08-19 | 2010-12-27 | 한국과학기술연구원 | 상전이를 이용한 다공성 고분자막의 제조방법 및 이 다공성고분자막의 템플레이트로의 응용 |
Families Citing this family (1)
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KR100381463B1 (ko) * | 2000-08-23 | 2003-04-26 | 하성용 | 이중 상분리유도법을 이용한 기체분리막 제조방법 |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4307135A (en) * | 1980-04-08 | 1981-12-22 | The United States Of America As Represented By The Secretary Of The Interior | Process for preparing an asymmetric permselective membrane |
JPS5959213A (ja) * | 1982-09-28 | 1984-04-05 | Teijin Ltd | 多孔質支持膜及びそれを用いた複合膜 |
US4532041A (en) * | 1983-05-13 | 1985-07-30 | Exxon Research And Engineering Co. | Asymmetric polyimide reverse osmosis membrane, method for preparation of same and use thereof for organic liquid separations |
KR0153036B1 (ko) * | 1994-09-06 | 1998-11-16 | 강박광 | 복합막 및 그 제조방법 |
KR0153099B1 (ko) * | 1995-01-11 | 1998-11-16 | 강박광 | 물/알코올 용매 분리용 비대칭 중공사막의 제조방법 |
KR0166147B1 (ko) * | 1995-11-23 | 1998-12-15 | 강박광 | 내화학성이 우수한 복합막 및 그 제조방법 |
-
1998
- 1998-10-30 KR KR10-1998-0046469A patent/KR100406362B1/ko not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4307135A (en) * | 1980-04-08 | 1981-12-22 | The United States Of America As Represented By The Secretary Of The Interior | Process for preparing an asymmetric permselective membrane |
JPS5959213A (ja) * | 1982-09-28 | 1984-04-05 | Teijin Ltd | 多孔質支持膜及びそれを用いた複合膜 |
US4532041A (en) * | 1983-05-13 | 1985-07-30 | Exxon Research And Engineering Co. | Asymmetric polyimide reverse osmosis membrane, method for preparation of same and use thereof for organic liquid separations |
KR0153036B1 (ko) * | 1994-09-06 | 1998-11-16 | 강박광 | 복합막 및 그 제조방법 |
KR0153099B1 (ko) * | 1995-01-11 | 1998-11-16 | 강박광 | 물/알코올 용매 분리용 비대칭 중공사막의 제조방법 |
KR0166147B1 (ko) * | 1995-11-23 | 1998-12-15 | 강박광 | 내화학성이 우수한 복합막 및 그 제조방법 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101003947B1 (ko) * | 2008-08-19 | 2010-12-27 | 한국과학기술연구원 | 상전이를 이용한 다공성 고분자막의 제조방법 및 이 다공성고분자막의 템플레이트로의 응용 |
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KR20000028293A (ko) | 2000-05-25 |
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