TWI519339B - 過濾膜 - Google Patents
過濾膜 Download PDFInfo
- Publication number
- TWI519339B TWI519339B TW101150900A TW101150900A TWI519339B TW I519339 B TWI519339 B TW I519339B TW 101150900 A TW101150900 A TW 101150900A TW 101150900 A TW101150900 A TW 101150900A TW I519339 B TWI519339 B TW I519339B
- Authority
- TW
- Taiwan
- Prior art keywords
- monomer
- copolymer
- filter membrane
- electrical
- group
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims description 47
- 238000001914 filtration Methods 0.000 title claims description 13
- 239000000178 monomer Substances 0.000 claims description 106
- 239000002245 particle Substances 0.000 claims description 50
- 229920001577 copolymer Polymers 0.000 claims description 48
- 239000012071 phase Substances 0.000 claims description 23
- 239000008346 aqueous phase Substances 0.000 claims description 19
- 229920000642 polymer Polymers 0.000 claims description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 16
- 239000010419 fine particle Substances 0.000 claims description 16
- -1 poly(allylamine) Polymers 0.000 claims description 15
- 239000002671 adjuvant Substances 0.000 claims description 14
- 125000003342 alkenyl group Chemical group 0.000 claims description 12
- 125000003277 amino group Chemical group 0.000 claims description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 10
- 229920000083 poly(allylamine) Polymers 0.000 claims description 10
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 9
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 7
- MNCGMVDMOKPCSQ-UHFFFAOYSA-M sodium;2-phenylethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 MNCGMVDMOKPCSQ-UHFFFAOYSA-M 0.000 claims description 7
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000007334 copolymerization reaction Methods 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 4
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 4
- 239000011859 microparticle Substances 0.000 claims description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 4
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 3
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 2
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 2
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 2
- VKIRRGRTJUUZHS-UHFFFAOYSA-N cyclohexane-1,4-diamine Chemical compound NC1CCC(N)CC1 VKIRRGRTJUUZHS-UHFFFAOYSA-N 0.000 claims description 2
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 claims description 2
- IWBOPFCKHIJFMS-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl) ether Chemical compound NCCOCCOCCN IWBOPFCKHIJFMS-UHFFFAOYSA-N 0.000 claims description 2
- 239000001530 fumaric acid Substances 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 2
- OKPYIWASQZGASP-UHFFFAOYSA-N n-(2-hydroxypropyl)-2-methylprop-2-enamide Chemical compound CC(O)CNC(=O)C(C)=C OKPYIWASQZGASP-UHFFFAOYSA-N 0.000 claims description 2
- QIFCIFLDTQJGHQ-UHFFFAOYSA-M potassium;2-phenylethenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C=CC1=CC=CC=C1 QIFCIFLDTQJGHQ-UHFFFAOYSA-M 0.000 claims description 2
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims 2
- QRIMLDXJAPZHJE-UHFFFAOYSA-N 2,3-dihydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(O)CO QRIMLDXJAPZHJE-UHFFFAOYSA-N 0.000 claims 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 claims 1
- VHOVZANYEUERPV-UHFFFAOYSA-N 2-hydroxypropyl 2-methylprop-2-enoate;3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(O)COC(=O)C(C)=C.CC(=C)C(=O)OCCCO VHOVZANYEUERPV-UHFFFAOYSA-N 0.000 claims 1
- IDWGHKTZFFOKIE-UHFFFAOYSA-N 5-methyldecane-1,9-diamine Chemical compound NCCCCC(CCCC(C)N)C IDWGHKTZFFOKIE-UHFFFAOYSA-N 0.000 claims 1
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical compound CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- VFIJBTVGUHVPPW-UHFFFAOYSA-N [Br].C=C Chemical group [Br].C=C VFIJBTVGUHVPPW-UHFFFAOYSA-N 0.000 claims 1
- 150000004985 diamines Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 17
- 239000007864 aqueous solution Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 15
- 239000000654 additive Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000009835 boiling Methods 0.000 description 10
- 230000004907 flux Effects 0.000 description 10
- 230000000996 additive effect Effects 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 5
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000502 dialysis Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 230000005660 hydrophilic surface Effects 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- LNOLJFCCYQZFBQ-BUHFOSPRSA-N (ne)-n-[(4-nitrophenyl)-phenylmethylidene]hydroxylamine Chemical compound C=1C=C([N+]([O-])=O)C=CC=1C(=N/O)/C1=CC=CC=C1 LNOLJFCCYQZFBQ-BUHFOSPRSA-N 0.000 description 1
- DZSVIVLGBJKQAP-UHFFFAOYSA-N 1-(2-methyl-5-propan-2-ylcyclohex-2-en-1-yl)propan-1-one Chemical compound CCC(=O)C1CC(C(C)C)CC=C1C DZSVIVLGBJKQAP-UHFFFAOYSA-N 0.000 description 1
- AMBFNDRKYCJLNH-UHFFFAOYSA-N 1-(3-piperidin-1-ylpropyl)piperidine Chemical compound C1CCCCN1CCCN1CCCCC1 AMBFNDRKYCJLNH-UHFFFAOYSA-N 0.000 description 1
- XSHISXQEKIKSGC-UHFFFAOYSA-N 2-aminoethyl 2-methylprop-2-enoate;hydron;chloride Chemical compound Cl.CC(=C)C(=O)OCCN XSHISXQEKIKSGC-UHFFFAOYSA-N 0.000 description 1
- WVPCDRJCPIGBBR-UHFFFAOYSA-N 2-chloro-1,3,5-triethylbenzene Chemical compound CCC1=CC(CC)=C(Cl)C(CC)=C1 WVPCDRJCPIGBBR-UHFFFAOYSA-N 0.000 description 1
- IHGZNTAZIJXDST-UHFFFAOYSA-N 2-methylnonane-1,9-diamine Chemical compound NCC(C)CCCCCCCN IHGZNTAZIJXDST-UHFFFAOYSA-N 0.000 description 1
- VFXXTYGQYWRHJP-UHFFFAOYSA-N 4,4'-azobis(4-cyanopentanoic acid) Chemical compound OC(=O)CCC(C)(C#N)N=NC(C)(CCC(O)=O)C#N VFXXTYGQYWRHJP-UHFFFAOYSA-N 0.000 description 1
- XWXRGQOVCSIGOL-UHFFFAOYSA-N C(C)C(CC(C(=O)O)=C)CCCC.C(CCCCC(C)C)OC(C=C)=O Chemical compound C(C)C(CC(C(=O)O)=C)CCCC.C(CCCCC(C)C)OC(C=C)=O XWXRGQOVCSIGOL-UHFFFAOYSA-N 0.000 description 1
- CQSICIWQQMIALH-UHFFFAOYSA-N N(=NC(C)(C)C=1NCCN1)C(C)(C)C=1NCCN1.N1(C=NCC1)CCC Chemical compound N(=NC(C)(C)C=1NCCN1)C(C)(C)C=1NCCN1.N1(C=NCC1)CCC CQSICIWQQMIALH-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- INLLPKCGLOXCIV-UHFFFAOYSA-N bromoethene Chemical compound BrC=C INLLPKCGLOXCIV-UHFFFAOYSA-N 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- PADPKJACPLYMPK-UHFFFAOYSA-N n',n'-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1N(CCN)C1=CC=CC=C1 PADPKJACPLYMPK-UHFFFAOYSA-N 0.000 description 1
- RUSMHXACRXXLKQ-UHFFFAOYSA-N n-(2-aminoethyl)-2-methylprop-2-enamide;hydrochloride Chemical compound Cl.CC(=C)C(=O)NCCN RUSMHXACRXXLKQ-UHFFFAOYSA-N 0.000 description 1
- XHIRWEVPYCTARV-UHFFFAOYSA-N n-(3-aminopropyl)-2-methylprop-2-enamide;hydrochloride Chemical compound Cl.CC(=C)C(=O)NCCCN XHIRWEVPYCTARV-UHFFFAOYSA-N 0.000 description 1
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 1
- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- WVNOXCLUDOCQBH-UHFFFAOYSA-M sodium;2-hydroxyethyl 2-methylprop-2-enoate;2-phenylethenesulfonate Chemical compound [Na+].CC(=C)C(=O)OCCO.[O-]S(=O)(=O)C=CC1=CC=CC=C1 WVNOXCLUDOCQBH-UHFFFAOYSA-M 0.000 description 1
- JJMIAJGBZGZNHA-UHFFFAOYSA-N sodium;styrene Chemical compound [Na].C=CC1=CC=CC=C1 JJMIAJGBZGZNHA-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
- C08F212/30—Sulfur
-
- 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
- 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
- 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
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- 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
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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Description
本發明係有關於濾膜,且特別是有關於一種含電性微粒之濾膜。
目前,以過濾膜除去水中雜質之技術已廣泛應用於日常生活中。過濾膜通常是多孔的高分子膜,其具有細小的膜孔,因而當液體擴散通過過濾膜時,這些膜孔可截留住固體雜質,僅有經純化的液體可通過過濾膜。例如,經逆滲透膜或奈米濾膜純化的水,可直接做為飲用水或為工業上所需的純水。
一般而言,無論是逆滲透膜或奈米濾膜,皆由多層複合結構形成,而其表面為利用界面聚合方法形成之緻密選擇層。而無論過濾膜是作何種應用,在實際應用時,較高的截留率及較高的通量通常可滿足使用者之需求。傳統改善過濾膜通量之方式,係為對過濾膜的表面做改質或加入親水的無機添加劑,例如奈米顆粒或奈米管。然而,表面改質的製程繁複且不易控制,而無機添加劑亦因其仍為無機材料,不易均勻分散於有機高分子所形成之過濾膜中。
因此,業界所需的是一種添加劑,其能有效提高過濾膜之通量及截留率。
本發明之一實施例係提供一種電性微粒,包括:一第
一共聚物或一第二共聚物,此第一共聚物由一第一單體及一第二單體共聚形成,此第二共聚物由此第一單體、此第二單體及一第三單體共聚形成,其中此第一單體包含烯基,且不含羧酸基、磺酸基、羥基及氨基,此第二單體包含烯基,且包含磺酸基或羧酸基,此第三單體包含烯基,且包含羥基或氨基,其中在此第一共聚物及此第二共聚物中,此第一單體之重複單元及此第二單體之重複單元之莫耳比例為200:1~20:1。
本發明之一實施例係更提供一種添加劑,包含如前述之電性微粒;以及一高分子輔助劑,其中該高分子輔助劑為聚(烯丙基胺)、聚烯醇類或前述之組合,且重量平均分子量為約100~100000。
本發明之一實施例係又提供一種過濾膜,包含:一由一含多個醯鹵基之油相單體、一含氨基之水相單體及前述之高分子輔助劑所共聚形成之共聚物膜,其中在該共聚物膜中,該水相單體之重複單元及該油相單體之重複單元以醯胺鍵相互鍵結,該高分子輔助劑與該油相單體之重複單元以醯胺鍵或酯鍵相互鍵結;以及前述之電性微粒,分散於該共聚物膜中。
為讓本發明之上述和其他目的、特徵、和優點能更明顯易懂,下文特舉出較佳實施例,並配合所附圖式,作詳細說明如下:
本發明實施例係提供親水性電性微粒、包含其之添加
劑及包含使用前述添加劑所形成之過濾膜。藉由使用此親水性電性微粒及添加劑,所形成之過濾膜係具有良好的截留率及通量。
第1圖顯示為依照本發明一實施例之親水性之電性微粒形成方法100之流程圖。方法100起始於步驟102,首先提供一第一單體及一第二單體,並將其加入至水中,以形成一水溶液,其中第一單體包含烯基,且不含羧酸基、磺酸基、羥基及氨基,第二單體包含烯基,且包含磺酸基或羧酸基。在一實施例中,此第一單體及第二單體之莫耳比可為約200:1~20:1。此第一單體例如包含苯乙烯及其衍生物、其他含乙烯基、丙烯基之化合物或羧化物,例如甲基苯乙烯、乙基苯乙烯、二乙烯基苯、1,3-丁二烯、異戊二烯、1,4-己二烯、乙酸乙烯酯、乙烯硬酯酸酯(vinyl stearate)、甲基丙烯酸酯、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸異辛酯(2-ethylhexyl acrylate)、甲基丙烯酸縮水甘油酯(glycidyl methacrylate)、丙烯酸十二酯(lauryl acrylate)、N,N-二甲基氨基乙基丙烯酸酯(N,N-dimethylaminoethyl acrylate)、氯乙烯、偏二氯乙烯、溴乙烯或前述之組合。此第二單體可例如包含苯乙烯磺酸鈉、苯乙烯磺酸鉀、衣康酸(itaconic acid)、馬來酸(maleic acid)、富馬酸(fumaric acid)、丙烯酸(acrylic acid)、甲基丙烯酸(methacrylic acid)、異戊二烯磺酸(isoprenesulfonic acid)、2-丙醯胺-2-甲基丙烷磺酸(2-acrylamide-2-methylpropanesulfonic acid)、前述之衍生物或前述之組合。
接著,進行步驟104,加熱步驟102之水溶液至沸騰狀
態。接著,進行步驟106,加入適量的起始劑至步驟104之沸騰水溶液中,並均勻攪拌約數小時,以使第一單體及第二單體進行聚合。在一實施例中,起始劑可例如為過硫酸鉀。最後,得到具有電性微粒之水溶液。在一實施例中,此電性微粒之粒徑可為約1~100nm,且可為圓球、橢圓球或接近圓球之不規則形。此電性微粒可為第一單體及第二單體共聚形成之共聚物(以下稱做第一共聚物)。此第一共聚物之重量平均分子量可為約3000~50000。在此第一共聚物中,由第一單體所形成之重複單元及由第二單體所形成之重複單元之莫耳比例可為約200:1至20:1。此電性微粒之表面可至少帶有磺酸基或羧酸基,因而使此電性微粒具有表面電位-1~-100mV,並呈親水性分散於水中。例如,在以苯乙烯及苯乙烯磺酸鈉各自作為第一單體及第二單體之實施例中,第一共聚物可具有如下之化學式:
其中a為30~200,b為1~10。
第2圖顯示為依照本發明另一實施例之親水性之電性微粒形成方法200之流程圖。在此實施例中,親水性之電性微粒係由第二共聚物形成,其係由第一單體、第二單體及第三單體共聚形成,其中本實施例中之第一單體及第二
單體可使用與第1圖實施例相同的材料。在一實施例中,第三單體可包含烯基,且包含羥基或氨基。
方法100起始於步驟102,首先提供一第一單體及一第二單體,並將其加入至水中,以形成一水溶液。在一實施例中,此含第一單體及第二單體之莫耳比可為約20:1~200:1。
接著,進行步驟204,加熱步驟202之水溶液至沸騰狀態。接著,進行步驟206,加入適量的起始劑(例如過硫酸鉀)至步驟104之沸騰水溶液中,並均勻攪拌約5分鐘至5小時,以使含第一單體及第二單體進行聚合。在一實施例中,起始劑可例如為過硫酸鉀、4,4'-偶氮雙(4-氰基戊酸)(4,4'-Azobis(4-cyanovaleric acid))、偶氮二咪唑啉基丙烷(2,2'-Azobis[2-(2-imidazolin-2-yl)propane])、2,2'-偶氮二異丁基脒二鹽酸鹽(2,2'-Azobis(2-methylpropionamidine)dihydrochloride)、偶氮二羥乙基咪唑啉基丙烷二鹽酸鹽(2,2'-Azobis{2-[1-(2-hydroxyethyl)-2-imidazolin-2-yl]propane}dihydrochloride)、過硫酸銨(ammonium persulfate)或前述之組合。接著,進行步驟208,緩慢加入第三單體至步驟206之沸騰水溶液中,並均勻攪拌約5分鐘至5小時。在一實施例中,此第三單體可例如包含甲基丙醯酸羥乙酯(HEMA)、2-甲基-2-丙烯酸-2,3-二羥基丙酯(Glycerol monomethacrylate)、丙烯酸羥乙酯(2-Hydroxyethyl acrylate,HEA)、N-(2-羥丙基)甲基丙烯醯胺(N-(2-Hydroxypropyl)methacrylamide)、甲基丙烯酸-2-羥基
丙酯(Hydroxypropyl methacrylate)、丙烯胺(allylamine)、二烯丙烯胺(diallylamine)、甲基丙烯酸-2-氨基乙基酯鹽酸鹽(2-Aminoethyl methacrylate hydrochloride)、N-(2-氨乙基)甲基丙烯醯胺鹽酸鹽(N-(2-aminoethyl)methacrylamidehydrochloride)、N-(3-氨丙基)甲基丙烯醯胺鹽酸鹽(N-(3-Aminopropyl)methacrylamide hydrochloride)、2-甲基-2-丙烯酸-2-[(1,1-二甲基乙基)氨]乙酯(2-(tert-Butylamino)ethyl methacrylate)、其他具有烯基且可與醯氯基反應之化合物或前述之組合。此含烯基與羥基之單體相對於含烯基與磺酸基之單體之莫耳比例可為約1:10~10:1。
最後,可得到具有電性微粒之水溶液。此電性微粒可為由第一單體、第二單體及第三單體共聚形成之共聚物(以下稱做第二共聚物)。此第二共聚物之重量平均分子量可為約3000~50000。此第二共聚物可為一嵌段共聚物,且在此第二共聚物中,由第一單體所形成之重複單元與由第二單體所形成之重複單元之莫耳比例可為約200:1~20:1,由第二單體所形成之重複單元與由第三單體所形成之重複單元之莫耳比例可為約1:10~10:1。此電性微粒之表面可至少帶有磺酸基及羥基,因而使此電性微粒具有表面電位-1~-100mV或-30~-70mV,並呈親水性分散於水中。在一實施例中,此電性微粒之平均粒徑可為約1~100nm,且可為圓球、橢圓球或接近圓球之不規則形。
例如,在以苯乙烯、苯乙烯磺酸鈉及甲基丙醯酸羥乙酯各自作為第一單體、第二單體及第三單體之實施例中,
第二共聚物可具有如下之化學式:
其中c為30~200,d為1~10,e為1~10。
第3圖顯示為依照本發明一實施例之過濾膜之形成方法300之流程圖。首光,進行步驟302,提供一水相單體溶液。在本實施例中,水相單體溶液可含一添加劑及一水相單體溶於水中。在一實施例中,此添加劑可包含如前述實施例所述之電性微粒(例如為第一共聚物及/或第二共聚物)及一高分子輔助劑。高分子輔助劑可為含多個氨基或羥基之高分子,例如為聚(烯丙基胺)(poly(allylamine))、聚乙二醇、聚丙二醇、其他聚烯醇類或前述之組合。由於電性微粒及高分子輔助劑皆為有機高分子及具有親水性官能基,此添加劑可溶於水相。在一實施例中,添加劑中之電性微粒與高分子輔助劑之重量比例可為約0.1:1~1:0.1。
方法300還包含步驟304,提供一油相單體溶液。在本實施例中,油相單體溶液可包含一油相單體溶於一有機溶劑中。在一實施例中,油相單體可例如為包含多個醯鹵基之單體,例如1,3,5-三乙醯氯苯(1,3,5-trimesoyl chloride)、對苯二甲醯氯(1,4-benzenedicarbonyl chloride)、間苯二甲醯氯(Isophthaloyl dichloride)或前述之組合。水相單體可例
如為芳香族二胺或脂肪族二胺,例如對苯二胺、間苯二胺、1,4環己二胺(1,4-cyclohexanediamine)、N,N-二苯乙烯二胺(N,N-diphenylethylene diamine)、哌嗪(piperazine)、三甲二哌啶(trimethylene dipiperidine)、間苯二甲胺(m-xylene diamine)、碳醯二胺(carbonyl diamine)、5-甲基壬烷-1,9-二胺(5-methylnonane-1,9-diamine)、2,2'-(乙烯二氧)雙(乙胺)(2,2'-(Ethylenedioxy)bis(ethylamine))或前述之組合。有機溶劑可為任意合適之有機溶劑。需注意的是,步驟302、304之先後順序可不受限制。在一實施例中,油相單體對水相單體之重量比可為約1:7~1:135在某些實施例中,添加劑對水相單體之重量比可為約1:20~1:40。
接著,進行步驟306,提供一基板,並將其靜置於步驟302之水相單體水溶液中,以使添加劑及水相單體吸附於基板表面。接著,進行步驟308,將基板自水相單體溶液中移出,並滴加油相單體至基板表面上,靜置約0.1~100min,以進行界面聚合反應。最後,進行步驟308,加熱基板至30~100℃約0.1~2小時。在一實施例中,亦可在加熱該基板之前,以水及甲醇清洗基板,並置於室溫下乾燥。
由於高分子輔助劑可具有類似於界面活性劑之功能,可幫助油相單體及水相單體在油相-水相界面處進行聚合反應。此外,既然油相單體具有多個醯鹵基,其可與高分子輔助劑之氨基或羥基形成醯胺鍵或酯鍵,並可與水相單體形成之氨基形成醯胺鍵。因此,高分子輔助劑、油相單體之所形成之重複單元及水相單體所形成之重複單元係以醯胺鍵及/或酯鍵相互鍵結而形成共聚物(以下稱為第三共
聚物)。在一實施例中,此第三共聚物之重量平均分子量可約2000~100000。在某些實施例中,過濾膜之厚度可為約100~500nm。
此外,在電性微粒由第一共聚物形成之實施例中,第一共聚物係不會與第三共聚物形成共價鍵結。因此,電性微粒係單獨地均勻分散在所形成之過濾膜中。此外,在電性微粒第二共聚物之實施例中,第二共聚物之羥基或氨基亦可與油相單體之醯鹵基形成酯鍵或醯胺鍵,形成第三共聚物之一部分。
例如,在一特定實施例中,第三共聚物可具有如下之示意化學式:
其中p為50~400,q為1~10,r為1~200,R為電性微粒。
第4圖顯示依照方法300形成之過濾膜之結構示意圖。在此過濾膜400中。由於加入了具有親水性表面402及帶有電性之電性微粒404,係於過濾膜400中增加了大量的微通道406因而可提昇通量,且可提高對高價數離子的截流率及提高通量。
【實施例1】
電性微粒之製備
將10g的苯乙烯、0.4g的苯乙烯磺酸鈉及85g的水加入至250ml之反應瓶中,均勻攪拌並加熱至沸騰約3mins。接著,將0.0876g的過硫酸鉀溶於5g水中,加入至上述沸騰溶液中,持續攪拌2小時。將溶液靜置冷卻,得到一乳狀水溶液。
接著,將30ml乳液倒入透析膜中(截留分子量(MWCO):6-8000、平折寬度(flat width):50mm、長度:50mm),並以透析夾密封,確認乳液無洩漏後置入裝有一公升去離子水之燒杯內,每隔十二個小時更換去離子水,持續一個禮拜,得到一含苯乙烯-苯乙烯磺酸鈉共聚物(poly(styrene-co-sodium styrene sulfonate))之清澈水溶液。苯乙烯-苯乙烯磺酸鈉共聚物(即電性微粒)之表面電位為-64.7mV,平均粒徑為23nm。
【實施例2】
將10g的苯乙烯、0.4g的苯乙烯礦酸鈉及85g的水加入至250ml之反應瓶中,均勻攪拌並加熱至沸騰約3mins。接著,將0.0876g的過硫酸鉀溶於5g水中,加入至上述沸騰溶液中,攪拌約2小時。接著,將0.15g的甲基丙醯酸羥乙酯加入至上述沸騰溶液中,持續攪拌2小時。將溶液靜置冷卻,得到一乳狀水溶液。
接著,將30ml乳液倒入透析膜中(截留分子量(MWCO):6-8000、平折寬度(flat width):50mm、長度:50mm),並以透析夾密封,確認乳液無洩漏後置入裝有一公升去離子水之燒杯內,每隔十二個小時更換去離子水,持續一個禮拜,得到一含苯乙烯-苯乙烯磺酸鈉-甲基丙醯酸羥乙酯三元共聚物之清澈水溶液。乙烯-苯乙烯磺酸鈉-甲基丙醯酸羥乙酯三元共聚物(即電性微粒)之表面電位為-46mV,平均粒徑為24nm。
【實施例3】
過濾膜之製備
將0.2g之實施例1之電性微粒、8g的對苯二胺及0.4g的聚(烯丙基胺)加入391.2g的水中,形成水相單體溶液。將1.2g的1,3,5-三乙醯氯苯加入至598.8g的正己烷中,形成油相單體溶液。接著,將聚醚碸樹脂(PES)基板靜置於水相單體溶液中10min,之後將基板自水相單體溶液中取出,並刮除其上之殘餘水份。接著,將45.8克之油相單體溶液滴加至基板表面,靜置1min。之後,移除正己烷,並以水及甲醇清洗基板表面。將清洗後的基板置於室溫下乾
燥約3min,並接著在約60℃下烘烤約30min,得到厚度為約300~400nm之過濾膜。
【實施例4】
如實施例3之相同方式進行,但實施例1之電性微粒為0.4g。
【實施例5】
如實施例3之相同方式進行,但以0.2g之實施例2之電性微粒取代實施例1之電性微粒。
【實施例6】
如實施例3之相同方式進行,但以0.4g之實施例2之電性微粒取代實施例1之電性微粒。
【實施例7】
如實施例3之相同方式進行,但以0.4g之的聚乙二醇取代聚(烯丙基胺),且以0.2g之實施例2之電性微粒取代實施例1之電性微粒。
【實施例8】
如實施例7之相同方式進行,但實施例2之電性微粒為0.4g。
【比較例1】
如實施例3之相同方式進行,但未加入實施例1之電緎微粒及聚(烯丙基胺)。
【比較例2】
如實施例3之相同方式進行,但未加入實施例1之電
性微粒。
【比較例3】
如實施例3之相同方式進行,但未加入實施例1之電性微粒,且聚(烯丙基胺)為2g。
【比較例4】
如實施例5之相同方式進行,但未加入聚(烯丙基胺)。
【比較例5】
如實施例6之相同方式進行,但未加入聚(烯丙基胺)。
第5圖係顯示實施例1、2之電性微粒經乾燥後之傅立葉紅外線(FTIR)光譜圖。顯示了實施例1和2的電性微粒在1350~1400cm-1的位置均有來自SO3-官能團的S=O吸收峰,且在700~790cm-1、1450~1500cm-1和1600~2000cm-1均有來自苯環的吸收峰。因此,可證明苯乙烯確實已與苯乙烯磺酸鈉形成共聚物。此外,實施例2較實施例1在1670~1740cm-1的位置更多了-CO官能基的吸收峰,且在3000~3500cm-1的位置多了-OH官能基的吸收峰,因而可證明甲基丙醯酸羥乙酯確實已與苯乙烯及/或苯乙烯磺酸鈉形成共聚物。
第6圖係顯示實施例2之TEM圖,由第6圖中可明顯看出電性微粒可為平均直徑約10~100nm之圓球。
此外,實驗數據亦顯示實施例6的濾膜的表面電位係大於商用濾膜NF-90和NF-270(FilmTec Corp.,Minneapolis,MN)的表面電位(在0.001M氯化鉀水溶液中測得)。
實施例3~8、比較例1~5和商用濾膜NF-90、NF-270(FilmTec Corp.,Minneapolis,MN)對於CaCl2之過濾脫鹽性能係整理於表1。表1之測試條件為於壓力5kg/m2下通入400ppm CaCl2之水溶液至實施例3~8及比較例1~5之濾膜。於表1中,所述之PIP為對苯二胺、PAA為聚(烯丙基胺)、PEG為聚乙二醇、HEMA為甲基丙醯酸羥乙酯、TMC為1,3,5-三乙醯氯苯。PIP、高分子輔助劑、電性微粒之重量百分率係指對於水相單體溶液總重之重量百分率,TMC重量百分率係指對於油相單體溶液總重之重量百分率。
由表1可得知的是,實施例3~8之過濾膜,由於加入了適量的添加劑(包含高分子輔助劑及電性微粒),係具有極佳的截留率和通量,例如截留率皆高於90%,顯較比較例1~5大幅提升,且通量更是遠高於比較例1~3和商用濾膜NF-90、NF-270。此外,若僅單獨加入高分子輔助劑,如比較例2、3,雖可提高截留率至70%以上,但無法提高通量。此外,若僅單獨加入電性微粒,雖可提高通量,如比較例4、5,截留率反而更為降低。而當電性微粒具有HEMA時,由於更加強了電性微粒之親水性,不但可提昇截留率,且可大幅提昇通量。此外,當高分子輔助劑是使用聚乙二醇時,無論是截留率及通量皆具有良好的效果。
雖然本發明已以數個較佳實施例揭露如上,然其並非用以限定本發明,任何所屬技術領域中具有通常知識者,在不脫離本發明之精神和範圍內,當可作任意之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
400‧‧‧過濾膜
402‧‧‧親水性表面
404‧‧‧電性微粒
406‧‧‧微通道
第1圖顯示為依照本發明一實施例之親水性之電性微粒形成方法之流程圖。
第2圖顯示為依照本發明另一實施例之親水性之電性微粒形成方法之流程圖。
第3圖顯示為依照本發明一實施例之過濾膜之形成方法之流程圖。
第4圖顯示為依照第3圖之方法形成之過濾膜之結構示意圖。
第5圖係顯示為依照本發明一實施例之電性微粒之傅立葉紅外線(FTIR)光譜圖。
第6圖係顯示為依照本發明一實施例之電性微粒之TEM圖。
400‧‧‧過濾膜
402‧‧‧親水性表面
404‧‧‧電性微粒
406‧‧‧微通道
Claims (14)
- 一種過濾膜,包含:一由一含多個醯鹵基之油相單體、一含氨基之水相單體及一高分子輔助劑所共聚形成之共聚物膜,其中該油相單體在該共聚物膜中,該水相單體之重複單元及該油相單體之重複單元以醯胺鍵相互鍵結,該高分子輔助劑與該油相單體之重複單元以醯胺鍵或酯鍵相互鍵結;以及電性微粒,分散於該共聚物膜中,其中該高分子輔助劑為聚(烯丙基胺)、聚烯醇類或前述之組合,且重量平均分子量為100~100000,其中該電性微粒包括一第一共聚物或一第二共聚物,該第一共聚物由一第一單體及一第二單體共聚形成,該第二共聚物由該第一單體、該第二單體及一第三單體共聚形成,其中該第一單體包含烯基,且不含羧酸基、磺酸基、羥基及氨基,該第二單體包含烯基,且包含磺酸基或羧酸基,該第三單體包含烯基,且包含羥基或氨基,其中在該第一共聚物及該第二共聚物中,該第一單體之重複單元及該第二單體之重複單元之莫耳比例為200:1~20:1。
- 如申請專利範圍第1項所述之過濾膜,分散於該共聚物膜中,其中該電性微粒佔該過濾膜之總重之0.1%~20%。
- 如申請專利範圍第1項所述之過濾膜,其中該電性微粒為該第一共聚物時,該電性微粒係獨立地分散於該過濾膜中。
- 如申請專利範圍第1項所述之過濾膜,其中該電性 微粒為該第二共聚物時,該電性微粒以酯鍵與該共聚物膜共價連接。
- 如申請專利範圍第1項所述之過濾膜,其中該油相單體包含1,3,5-三乙醯氯苯、對苯二甲醯氯(1,4-benzenedicarbonyl chloride)、間苯二甲醯氯(isophthaloyl dichloride)或前述之組合。
- 如申請專利範圍第1項所述之過濾膜,其中該水相單體包含對苯二胺、間苯二胺、1,4環己二胺、N,N-二苯乙烯二胺、哌嗪、三甲二哌啶、間苯二甲胺、碳醯二胺、5-甲基壬烷-1,9-二胺、2,2'-(乙烯二氧)雙(乙胺)或前述之組合。
- 如申請專利範圍第1項所述之過濾膜,其中該電性微粒之粒徑為1~100nm,且表面電位為-1~-100mV。
- 如申請專利範圍第1項所述之過濾膜,其中該過濾膜厚度為100~500nm。
- 如申請專利範圍第1項所述之過濾膜,其中該第二單體包含苯乙烯磺酸鈉、苯乙烯磺酸鉀、丙烯酸、甲基丙烯酸、衣康酸、馬來酸、富馬酸、異戊二烯磺酸、2-丙醯胺-2-甲基丙烷磺酸或前述之組合。
- 如申請專利範圍第1項所述之過濾膜,其中該第一單體包含苯乙烯、甲基苯乙烯、乙基苯乙烯、二乙烯基苯、1,3-丁二烯、異戊二烯、1,4-己二烯、乙酸乙烯酯、乙烯硬酯酸、甲基丙烯酸酯、甲基丙烯酸甲酯、丙烯酸丁酯、丙烯酸異辛酯、甲基丙烯酸縮水甘油酯、丙烯酸十二酯、N,N-二甲基氨基乙基丙烯酸酯、氯乙烯、偏二氯乙烯、溴 乙烯或前述之組合。
- 如申請專利範圍第1項所述之過濾膜,其中該第三單體包含甲基丙醯酸羥乙酯(HEMA)、2-甲基-2-丙烯酸-2,3-二羥基丙酯(Glycerol monomethacrylate)、丙烯酸羥乙酯(2-Hydroxyethyl acrylate,HEA)、N-(2-羥丙基)甲基丙烯醯胺(N-(2-Hydroxypropyl)methacrylamide)、甲基丙烯酸-2-羥基丙酯(Hydroxypropyl methacrylate)或前述之組合。
- 如申請專利範圍第1項所述之過濾膜,其中該第一共聚物為:
- 如申請專利範圍第1項所述之過濾膜,其中該第二共聚物為:
- 如申請專利範圍第1項所述之過濾膜,其中該電性微粒與該高分子輔助劑之重量比例為0.1:1~1:0.1。
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CN101940883A (zh) | 2010-08-03 | 2011-01-12 | 浙江大学 | 一种含纳米沸石分子筛反渗透复合膜的制备方法 |
CN102114392B (zh) | 2010-11-04 | 2013-04-24 | 浙江大学 | 一种含改性纳米沸石分子筛的反渗透复合膜的制备方法 |
CN102585082B (zh) | 2012-01-17 | 2014-02-26 | 上海师范大学 | 甲基丙烯酸-苯乙烯-丙烯酸羟乙酯共聚物分散剂、制备工艺和应用 |
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2012
- 2012-12-28 TW TW101150900A patent/TWI519339B/zh active
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US9212238B2 (en) | 2015-12-15 |
US20140186601A1 (en) | 2014-07-03 |
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