CN104159657A - 复合膜 - Google Patents
复合膜 Download PDFInfo
- Publication number
- CN104159657A CN104159657A CN201380010309.2A CN201380010309A CN104159657A CN 104159657 A CN104159657 A CN 104159657A CN 201380010309 A CN201380010309 A CN 201380010309A CN 104159657 A CN104159657 A CN 104159657A
- Authority
- CN
- China
- Prior art keywords
- block copolymer
- segment
- crosslinking agent
- coating solution
- carrier
- 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
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- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 239000012528 membrane Substances 0.000 title claims abstract description 11
- 229920001400 block copolymer Polymers 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 23
- 239000000178 monomer Substances 0.000 claims description 18
- 150000001412 amines Chemical class 0.000 claims description 16
- -1 carboxylic acid halides Chemical class 0.000 claims description 15
- 230000009257 reactivity Effects 0.000 claims description 13
- 239000012948 isocyanate Substances 0.000 claims description 7
- 229920002647 polyamide Polymers 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 9
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229940018564 m-phenylenediamine Drugs 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 229920001577 copolymer Polymers 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 239000007822 coupling agent Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000007783 nanoporous material Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 description 2
- 239000012989 trithiocarbonate Substances 0.000 description 2
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 description 1
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- BAHPQISAXRFLCL-UHFFFAOYSA-N 2,4-Diaminoanisole Chemical compound COC1=CC=C(N)C=C1N BAHPQISAXRFLCL-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- LBSXSAXOLABXMF-UHFFFAOYSA-N 4-Vinylaniline Chemical compound NC1=CC=C(C=C)C=C1 LBSXSAXOLABXMF-UHFFFAOYSA-N 0.000 description 1
- DOWVFPAIJRADGF-UHFFFAOYSA-N 4-ethenyl-2-benzofuran-1,3-dione Chemical compound C=CC1=CC=CC2=C1C(=O)OC2=O DOWVFPAIJRADGF-UHFFFAOYSA-N 0.000 description 1
- JJTUDXZGHPGLLC-IMJSIDKUSA-N 4511-42-6 Chemical compound C[C@@H]1OC(=O)[C@H](C)OC1=O JJTUDXZGHPGLLC-IMJSIDKUSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229920002307 Dextran Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 101000738322 Homo sapiens Prothymosin alpha Proteins 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 102100037925 Prothymosin alpha Human genes 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- PGEAEAYLSCKCCO-UHFFFAOYSA-N benzene;n-methylmethanamine Chemical compound CNC.C1=CC=CC=C1 PGEAEAYLSCKCCO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- DXHPZXWIPWDXHJ-UHFFFAOYSA-N carbon monosulfide Chemical compound [S+]#[C-] DXHPZXWIPWDXHJ-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000070 poly-3-hydroxybutyrate Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 238000000235 small-angle X-ray scattering Methods 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- JOLJIIDDOBNFHW-UHFFFAOYSA-N xanomeline Chemical compound CCCCCCOC1=NSN=C1C1=CCCN(C)C1 JOLJIIDDOBNFHW-UHFFFAOYSA-N 0.000 description 1
- 229950006755 xanomeline Drugs 0.000 description 1
Classifications
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- 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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/003—Organic membrane manufacture by inducing porosity into non porous precursor membranes by selective elimination of components, e.g. by leaching
-
- 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
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0032—Organic membrane manufacture by inducing porosity into non porous precursor membranes by elimination of segments of the precursor, e.g. nucleation-track membranes, lithography or laser methods
- B01D67/0034—Organic membrane manufacture by inducing porosity into non porous precursor membranes by elimination of segments of the precursor, e.g. nucleation-track membranes, lithography or laser methods by micromachining techniques, e.g. using masking and etching steps, photolithography
-
- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/32—Use of chain transfer agents or inhibitors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/40—Details relating to membrane preparation in-situ membrane formation
-
- 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
- B01D71/28—Polymers of vinyl aromatic compounds
-
- 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
- B01D71/48—Polyesters
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Laminated Bodies (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
制备复合膜的方法，其包含下列步骤：通过在多孔载体上依次施加不混溶的涂布溶液以在所述载体表面上形成识别层，其中一种涂布溶液包括交联剂和另一种涂布溶液包括嵌段共聚物，所述嵌段共聚物包括牺牲链段和含有反应性侧基的耐久链段，所述反应性侧基与所述交联剂反应形成包括所述牺牲链段微区的交联基质；和除去所述牺牲链段的至少一部分以产生孔隙。
Description
技术领域：
本发明涉及包括多孔载体和识别层的复合膜。
背景技术：
复合膜包括位于下面的多孔载体上的选择性阻挡层或“识别层”。虽然载体对膜提供机械完整性，但它提供了小的流动阻力。在大多数应用中，分离的主要方法是通过识别层提供。代表性种类包括由Cadotte发明的FT-30TM薄膜复合(TFC)膜，参见US 4277344。对于这样的膜，薄膜交联聚酰胺层通过多官能胺(例如，间苯二胺(mPD))和多官能酰卤单体(例如，均苯三甲酰氯(TMC))之间的界面聚合在多孔载体上形成。从不混溶溶液中将单体依次涂布到载体上，并在涂布溶液之间的界面处形成薄的交联聚酰胺。还参见US 6878278；US7815987和US 7905361。
自组装嵌段共聚物已被用来形成用于各种应用的薄膜。该嵌段共聚物包括形成连续相的耐久链段和形成相分离的微区的牺牲链段。该牺牲链段随后蚀刻掉以形成相对均匀的、单分散的、微米级的孔隙。这种膜的实例描述在：US4096099，US 7347953，US 7572669，US 7964107，US 2008/0230514，US2009/0200646和JP11-080414。自组装嵌段共聚物也被考虑用于膜相关的应用。实例描述在US 7438193，US 2009/0208842，US 2009/0239381，US 2010/0292077和US 2010/0036009中。也参见Myungeun Seo，Mark A.Amendt，和Marc A.Hillmyer的“由反应性和多官能嵌段聚合物得到的交联纳米多孔材料”(Cross-linked Nanoporous Materials from Reactive and MultifunctionalBlock Polymers)，Macromolecules，2011，44(23)，第9310-9318页。
为了可用于许多复合膜应用，所述识别层必须与下面的载体形成强固的结合。这个要求限制了自组装嵌段共聚物作为识别层的用途-特别是在膜暴露于高压、反洗或重复移动的应用中。
概述：
本发明包括复合膜以及制造所述复合膜的方法，包括在多孔载体表面上形成识别层。该方法包括以下步骤：在所述载体上依次施加不混溶的涂布溶液，其中一种涂布溶液包括交联剂和另一种涂布溶液包括嵌段共聚物，并且其中所述嵌段共聚物包括牺牲链段和含有反应性侧基的耐久链段，该反应性侧基与交联剂反应并形成包括所述牺牲链段微区的交联基质。从所述交联基质中除去所述牺牲链段以产生孔隙。
交联改善了所述基质的机械稳定性、热稳定性和化学稳定性的一种或多种。通过在所述载体上形成交联基质，反应物能部分地穿过载体表面，生成与所述载体强固结合的识别层。
发明详述：
本发明包括制造复合膜的方法，所述方法包括在多孔载体的表面上形成识别层的步骤。对多孔载体的选择没有特别限制，并且各种结构(例如，平板，盘，中空纤维，管，多孔纤维等)和组成均可使用。代表性的聚合材料包括均聚物、共聚物和聚合物共混物，包括但不限于：聚酰胺类；氟化聚合物，例如聚偏氟乙烯；聚烯烃类，包括聚乙烯和聚丙烯；和聚(芳醚)类，包括聚(芳醚)砜，酮类，氧化膦和腈类，聚酰胺类等)。用于在载体内产生孔隙度的技术没有特别的限制，并且包括相转化(例如，热诱导，扩散诱导等)和径迹蚀刻。虽然期望的孔径将随应用而变化，但在许多优选的实施方案中，载体表面具有等于或大于0.01μm的平均表面孔径，(例如，从0.01到10μm，更优选从0.1到5μm)。虽然可以采用各种方法来确定孔径，但一种优选的技术是使用扫描电子显微镜在1μm×1μm的表面区域内对至少10个、但优选100个随机选择的孔隙进行尺寸平均。该载体可以是各向同性或各向异性(例如Loeb-Sourirajan型或多层复合型)。如果该载体包括多层，则这些层可以包括不同的组成和/或孔隙度。可应用的载体的例子包括常用于微滤和超滤的多孔聚合物膜。可商购的载体可以从多个商业膜生产商获得，所述生产商包括：Asahi，Koch，Memcor，Millipore，Norit和Pall。
识别层优选通过在载体上依次施加不混溶的涂布溶液形成，其中一种所述涂布溶液包括：a)嵌段共聚物，其包括：i)具有反应性侧基的耐久链段和ii)牺牲链段；和b)另一种溶液含有交联剂。一经涂布，所述交联剂和所述嵌段共聚物的所述反应性侧基之间发生反应。该反应发生在所述两种涂布溶液之间的界面处，并生成包括所述牺牲链段微区的交联基质。通过在所述载体上形成所述交联基质，反应混合物能够穿过所述载体的表面。随后的反应产生与所述载体强固结合的识别层。
虽然所述涂布步骤不需要按照特定的顺序，但通常优选在载体上首先涂布交联剂，随后涂布嵌段共聚物。该涂布溶液优选直接施加到载体上而不使用牺牲衬底或偶联剂(例如：不使用玻璃，二氧化硅，含有二氧化硅的偶联剂等)。涂布可以通过喷涂、膜涂、辊涂、或通过使用浸渍槽等等其他应用技术来实现。过量的溶液可以由气刀、干燥器、烘箱等从载体中去除。
交联剂的选择没有特别限定，代表性的种类包括具有多个反应性基团的单体，所述反应基团包括一个或多个与存在于所述嵌段共聚物的耐久链段上的反应性侧基反应的官能团。优选的物质包括多官能异氰酸酯、醇、酸和胺。在一个实施方案中，所述交联剂是水溶性的，以便可以将其均匀地从水基溶液涂布到载体上。
嵌段共聚物的选择没有特别的限定，共聚的方法也没有特别的限定。耐久链段可以衍生自一种或多种单体或低聚物，并且可以包括单烯键式不饱和单体，包括丙烯酸酯(如丙烯酸甲酯，丙烯酸乙酯，丙烯酸叔丁酯，丙烯酸异冰片酯，以及相应的酯)、苯乙烯、乙烯基甲苯、乙烯基萘、和含有单亚乙烯基环的氮杂环化合物，如乙烯基吡啶、和乙烯基吡咯烷酮。另外的合适的单烯键式不饱和单体的例子在US 4224415中描述。耐久链段包括与交联剂反应的反应性侧基。虽然反应性侧基可通过后聚合技术的方式提供，但该基团优选在共聚反应期间引入所述耐久链段，例如通过使用包括多个反应性基团的单体，例如包括一个或多个另外的反应性基团的单亚乙烯基单体。代表性的实例包括4-乙烯基苯基异氰酸酯，4-乙烯基苯基缩水甘油醚，4-乙烯基苯胺，乙烯基邻苯二甲酸酐，甲基丙烯酸缩水甘油酯，甲基丙烯酸羟乙酯，和甲基丙烯酸氨乙酯。
牺牲链段应该能够形成相分离的、微米级和甚至纳米级的区域，并应当能够通过蚀刻至少部分地被除去。在被添加到反应混合物之前，该牺牲链段可以由单体原位聚合、预聚或部分聚合。在优选的实施方案中，所述聚合物或低聚物包括链转移剂(CTA)以促进与上述单体共聚最终形成所述嵌段共聚物的耐久链段。在这样的实施方案中，所述嵌段共聚物通过可逆加成-断裂链转移(RAFT)共聚合的方式形成。虽然本发明并不限于通过RAFT机理形成嵌段共聚物，但与通过自由基聚合形成的共聚物相比，从RAFT机理形成的共聚物生成更交联的基质。在可替代的实施方案中，链转移剂可以合并到用于形成嵌段共聚物的反应混合物内。总体而言，合适的CTA的代表性种类包括那些具有与弱碳-硫键结合的硫代羰基硫部分的化合物。该种类的非限制性的代表性的例子是：二硫代苯甲酸酯，二硫代氨基甲酸酯，和三硫代碳酸酯。
一类可应用为牺牲链段的材料包括脂族聚酯。通过具体实例，聚乳酸(PLA)通过碱水解，例如用温和的碱清洗而容易地除去。其他通过化学方法可去除的牺牲链段的例子包括但不限于，聚(己内酯)，聚(己二酸四亚甲酯)(PTMA)，聚(己二酸1，4-丁二醇酯)，聚(己二酸三亚甲酯)(PTA)，聚(己二酸五亚甲酯)(PPA)，聚(3-羟基丁酸酯)(PHB)，聚(环氧乙烷)，聚(环氧丙烷)，和聚(环氧乙烷-co-环氧丙烷)。可加热去除的牺牲链段的例子包括聚(α-甲基苯乙烯)和聚(α-乙基苯乙烯)。利用辐射可去除的牺牲链段的实例包括聚(甲基丙烯酸甲酯)，聚(甲基丙烯酸乙酯)，聚(甲基丙烯酸丙酯)等。
在一个优选的实施方案中，所述嵌段共聚物包含聚苯乙烯(PS)链段和PLA链段。
所述微区的具体尺寸和形状可以通过改变耐久链段与牺牲链段的总分子量和重量比进行调节。对于大多数应用，耐久链段和牺牲链段的重量比是从约1∶6至2∶1，并且更通常为约1∶3至1∶1。
所述交联基质一经形成，至少部分牺牲链段被除去(例如通过蚀刻)以产生孔隙。用于去除所述牺牲链段的技术没有特别限制，并且非限制性实例包括化学(如酸，碱，臭氧)、热和辐射。在优选的实施方案中，所产生的孔隙是互连的，并具有等于或小于0.5μm，0.1μm，0.05μm或在一些实施方案中等于或小于0.01μm的平均流量尺寸(mean flow size)，如根据ASTM F316-03(2011)方法B用毛细流动孔隙度仪(例如可从Porous Materials，Inc.，20Dutch MillRd.，Ithaca，NY 14850USA获得的那些)所测定的。平均流量孔径(mean flowpore size)的优选范围包括从0.1到0.001μm，0.05至0.001μm和0.01至0.001μm。孔径分布可以通过各种技术确定，包括：小角X-射线散射、电子显微镜和ASTME1343-90(2001)。孔径分布还可以由例如最大孔径除以平均流量孔径(例如，ASTMF316-03(2011)的方法A和B)表征。最大孔径(起泡点孔径)除以平均流量孔径的比率优选小于20，更优选小于10，甚至更优选小于3。或者，孔径分布可以由半高宽(FWHM)除以孔径分布曲线的平均值(例如，如Barrett-Joyner-Halenda(BJH)的孔径和体积分析法(Pore Size and Volume Analysis)通过气体的吸附和冷凝测定的)表征。FWHM除以平均值优选小于1，更优选小于0.5，甚至更优选小于0.2。或者，类似的FWHM的分析测定可以在微分曲线上进行，该微分曲线源自使用舍选法如ASTM E1343-90(2001)的获得的舍选-孔径曲线，孔径从与右旋糖酐分子量相关联的回转半径获得。或者，所述表面FWHM孔径分布可以通过统计分析采用扫描电子显微镜成像的孔隙获得。
与载体相比，识别层优选是相对薄的，例如小于20μm(例如从约0.1至20μm，更优选为从约0.5至5μm)。本发明界面反应技术的使用提供了一种获得通过传统方式无法获得的所需厚度的方法。
以下提供代表性反应流程，其中嵌段共聚物的牺牲链段源自聚乳酸(PLA)。例如，端羟基PLA由铝催化的D，L-交酯的开环聚合制备。然后，S-1-十二烷基-S′-(R，R′-二甲基-R”-乙酸)三硫代碳酸酯(CTA)，用于可逆加成-断裂链转移(RAFT)聚合的含有羧酸的链转移剂，通过酰氯中间体与端羟基偶联。PLA-CTA，苯乙烯单体(S)和3-异氰酸基-2-甲基-1-丙烯(IMP)然后共聚合以形成嵌段共聚物(PLA-b-P(S-co-IMP)，苯乙烯和IMP嵌段形成共聚物的耐久链段，异氰酸酯部分作为反应性侧基。
代表性的反应流程：
反应性嵌段共聚物
所述反应性嵌段共聚物可以从任何合适的溶剂，即与用来涂布所述交联剂的溶液不混溶的溶剂涂布。在上面所示的反应流程中，可使用二氯甲烷。在涂布后，该嵌段共聚物的耐久链段和牺牲链段之间发生微相分离，同时，所述交联剂(例如多官能胺)和所述嵌段共聚物的反应性侧基(如异氰酸酯部分)之间的反应产生耐久链段的交联基质。考虑到其低分子量(例如小于100道尔顿)，至少一些反应性物质(例如多官能胺)在形成交联基质之前穿过所述载体的表面。结果，生成的交联基质与所述载体形成强固的结合。
虽然可以使用各种交联剂，但优选的一类包括多官能胺单体。代表性的多官能胺单体包括至少两个伯胺或仲胺基团和可以是芳族的(例如，间苯二胺，对苯二胺，1，3，5-三氨基苯，1，3，4-三氨基苯，3，5-二氨基苯甲酸，2，4-二氨基甲苯，2，4-二氨基苯甲醚，和苯二甲胺)或脂族的(如，乙二胺，丙二胺，和三(2-二氨基乙基)胺)。优选的多官能胺单体的例子包括具有两个或三个氨基的伯胺，例如间苯二胺，和具有两个氨基的脂族仲胺，如哌嗪。一种优选的多官能胺是间苯二胺(mPD)。多官能胺单体可作为极性溶液(例如水基溶液)施加到多孔载体上。该极性溶液可含有从约0.1至约20重量％，更优选从约0.5至约6重量％的多官能胺单体。一经涂布在多孔载体上，过量的溶液可以任选地去除。
在上述的反应流程中，所述嵌段共聚物的反应性侧基是异氰酸酯部分。更通常地，可以使用宽范围的所谓的胺反应性基团。如本文所用，术语“胺反应性基团”是指在识别层形成期间存在的条件下和时间期间内与多官能胺单体的胺部分反应的侧链官能团。这通常需要在标准大气压和室温下，在几秒钟内接触的实质性反应。胺反应性官能团的代表性例子包括：酰卤(例如酰氯)、酸酐、异氰酸酯和环氧基。优选将嵌段共聚物从与用于涂布所述多官能胺单体的溶液不混溶的溶液，例如非极性溶液，涂布到载体上。如本文所用，术语“不混溶”是指当混合时，该溶液形成多个不同的相。该嵌段共聚物可以以从约0.01至10重量％，优选0.05至3重量％的范围溶解在非极性溶剂中，并且可以作为连续涂布操作的一部分递送。合适的溶剂是能溶解所述嵌段共聚物并且与和所述交联剂结合使用的涂布溶液不混溶的那些。例如，当选择水来涂布所述交联剂时，所述嵌段共聚物可以使用，例如己烷、环己烷、庚烷、和卤代烃如氟里昂(FREON)系列涂布。优选的溶剂包括对臭氧层造成极小威胁，并在燃点和可燃性方面上足够安全以经历常规加工而不采取特别的预防措施的那些。代表性的溶剂包括可从Exxon Chemical Company得到的ISOPARTM。
识别层优选的种类包括由多官能胺和包括反应性酰卤侧基的嵌段共聚物反应而形成的交联聚酰胺。如本文所用，术语“聚酰胺”是指酰胺键(-C(O)NH-)沿着分子链存在的聚合物。
为了本说明书的目的，术语“嵌段共聚物”所指聚合物包含两个或更多个不同的、通过共价键连接的聚合物(例如均聚物、共聚物)链段。不同链段的结合可以任选地包括一个中间的非重复亚单元，通常被称为连接段。本发明中使用的嵌段共聚物可以包含以任意方式排列的任意数量的聚合物嵌段链段(例如，二嵌段、三嵌段、多嵌段、支链嵌段、接枝、线性星形聚合物，梳状、嵌段共聚物、梯度聚合物等)。所述嵌段共聚物可具有线性或支链结构。可应用的嵌段共聚物的非限制性实例由下式说明：
本发明的许多实施方案被描述为“优选的”，以及在一些情况下，某些实施方案、选择、范围、成分、或其他特征被描述为“优选的”。“优选的”特征的描述决不应解释成认为这些特征是本发明必需的、基本的或是关键的。所述范围包括端点。
每个前述的专利文献的全部主题以引用的方式并入本文。
Claims (9)
1.制造复合膜的方法，其包含通过在多孔载体上依次施加不混溶的涂布溶液以在所述载体表面上形成识别层的步骤，其中：
i)一种涂布溶液包括交联剂，
ii)一种涂布溶液包括嵌段共聚物，其中所述嵌段共聚物包括牺牲链段和含有反应性侧基的耐久链段，
iii)所述反应性侧基与所述交联剂反应形成包括所述牺牲链段微区的交联基质，和
其中所述方法包括除去所述牺牲链段的至少一部分以产生孔隙。
2.根据权利要求1所述的方法，其中所述识别层的厚度小于20μm。
3.根据权利要求1所述的方法，其中所述孔隙具有小于0.1μm的平均流量孔径。
4.根据权利要求1所述的方法，其中所述交联剂包括多官能胺单体。
5.根据权利要求1所述的方法，其中所述嵌段共聚物的所述牺牲链段包括聚乳酸。
6.根据权利要求1所述的方法，其中所述嵌段共聚物的所述耐久链段包括聚苯乙烯。
7.根据权利要求1所述的方法，其中所述嵌段共聚物的所述反应性侧基包括下列中的至少一种：酰卤、酸酐、环氧基和异氰酸酯。
8.根据权利要求1所述的方法，其中所述识别层包括交联聚酰胺。
9.根据权利要求1所述的方法，其中所述交联剂包括选自以下的部分：异氰酸酯、酰卤、环氧基和酸酐。
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| PCT/US2013/025655 WO2013126238A1 (en) | 2012-02-21 | 2013-02-12 | Composite membrane |
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| US11567072B2 (en) | 2017-02-22 | 2023-01-31 | Terapore Technologies, Inc. | Ligand bound MBP membranes, uses and method of manufacturing |
| US11571667B2 (en) | 2018-03-12 | 2023-02-07 | Terapore Technologies, Inc. | Isoporous mesoporous asymmetric block copolymer materials with macrovoids and method of making the same |
| US11572424B2 (en) | 2017-05-12 | 2023-02-07 | Terapore Technologies, Inc. | Chemically resistant fluorinated multiblock polymer structures, methods of manufacturing and use |
| US11628409B2 (en) | 2016-04-28 | 2023-04-18 | Terapore Technologies, Inc. | Charged isoporous materials for electrostatic separations |
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| CA3041792A1 (en) * | 2016-11-02 | 2018-05-11 | Trustees Of Tufts College | Fabrication of filtration membranes |
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| WO2013126238A1 (en) | 2013-08-29 |
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| US9440196B2 (en) | 2016-09-13 |
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