CN101980767A - Aromatic halsulfonyl isocyanate compositions and polymers therefrom - Google Patents
Aromatic halsulfonyl isocyanate compositions and polymers therefrom Download PDFInfo
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- CN101980767A CN101980767A CN2009801125266A CN200980112526A CN101980767A CN 101980767 A CN101980767 A CN 101980767A CN 2009801125266 A CN2009801125266 A CN 2009801125266A CN 200980112526 A CN200980112526 A CN 200980112526A CN 101980767 A CN101980767 A CN 101980767A
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- 239000000203 mixture Substances 0.000 title claims abstract description 89
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 31
- 229920000642 polymer Polymers 0.000 title claims description 64
- 239000012948 isocyanate Substances 0.000 title abstract description 21
- 150000002513 isocyanates Chemical class 0.000 title abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 31
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 29
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- -1 halogenated aromatic sulfonylisocyanates Chemical class 0.000 claims description 106
- 238000010276 construction Methods 0.000 claims description 24
- 150000002367 halogens Chemical class 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229920000768 polyamine Polymers 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 239000012528 membrane Substances 0.000 abstract description 45
- 239000000463 material Substances 0.000 abstract description 16
- 238000002360 preparation method Methods 0.000 abstract description 15
- 125000005843 halogen group Chemical group 0.000 abstract description 13
- 239000010408 film Substances 0.000 description 109
- 239000002585 base Substances 0.000 description 80
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 23
- 239000001301 oxygen Substances 0.000 description 21
- 229910052760 oxygen Inorganic materials 0.000 description 21
- 239000000126 substance Substances 0.000 description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 17
- 239000007788 liquid Substances 0.000 description 13
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 13
- 125000002723 alicyclic group Chemical group 0.000 description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000002131 composite material Substances 0.000 description 10
- 238000001728 nano-filtration Methods 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 9
- 125000000524 functional group Chemical group 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 239000012876 carrier material Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 230000035699 permeability Effects 0.000 description 7
- 229920006393 polyether sulfone Polymers 0.000 description 7
- 238000000108 ultra-filtration Methods 0.000 description 7
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 238000010612 desalination reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000002688 persistence Effects 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 239000004695 Polyether sulfone Substances 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- WRJWRGBVPUUDLA-UHFFFAOYSA-N chlorosulfonyl isocyanate Chemical class ClS(=O)(=O)N=C=O WRJWRGBVPUUDLA-UHFFFAOYSA-N 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000001764 infiltration Methods 0.000 description 5
- 238000001471 micro-filtration Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 229920002396 Polyurea Polymers 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 125000001188 haloalkyl group Chemical group 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- 229920006254 polymer film Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 125000003368 amide group Chemical group 0.000 description 3
- 150000001408 amides Chemical class 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 125000002843 carboxylic acid group Chemical group 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 3
- 125000004093 cyano group Chemical group *C#N 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 230000002328 demineralizing effect Effects 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 125000000468 ketone group Chemical group 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 125000002769 thiazolinyl group Chemical group 0.000 description 3
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- 238000009736 wetting Methods 0.000 description 3
- MTZUIIAIAKMWLI-UHFFFAOYSA-N 1,2-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC=C1N=C=O MTZUIIAIAKMWLI-UHFFFAOYSA-N 0.000 description 2
- ZXHZWRZAWJVPIC-UHFFFAOYSA-N 1,2-diisocyanatonaphthalene Chemical compound C1=CC=CC2=C(N=C=O)C(N=C=O)=CC=C21 ZXHZWRZAWJVPIC-UHFFFAOYSA-N 0.000 description 2
- VTILWYBQQRECER-UHFFFAOYSA-N 5-sulfonylcyclohexa-1,3-diene Chemical compound O=S(=O)=C1CC=CC=C1 VTILWYBQQRECER-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- 238000012695 Interfacial polymerization Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- CUFNKYGDVFVPHO-UHFFFAOYSA-N azulene Chemical compound C1=CC=CC2=CC=CC2=C1 CUFNKYGDVFVPHO-UHFFFAOYSA-N 0.000 description 2
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- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 238000005115 demineralization Methods 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
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- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical class ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 2
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 2
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- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
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- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 2
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- ALOCUZOKRULSAA-UHFFFAOYSA-N 1-methylpiperidin-4-amine Chemical group CN1CCC(N)CC1 ALOCUZOKRULSAA-UHFFFAOYSA-N 0.000 description 1
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- 230000000875 corresponding effect Effects 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000005847 immunogenicity Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- VAOCPAMSLUNLGC-UHFFFAOYSA-N metronidazole Chemical compound CC1=NC=C([N+]([O-])=O)N1CCO VAOCPAMSLUNLGC-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- NOUUUQMKVOUUNR-UHFFFAOYSA-N n,n'-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1NCCNC1=CC=CC=C1 NOUUUQMKVOUUNR-UHFFFAOYSA-N 0.000 description 1
- WVFVAVUHWLDTCE-UHFFFAOYSA-N n,n-diaminobenzamide Chemical compound NN(N)C(=O)C1=CC=CC=C1 WVFVAVUHWLDTCE-UHFFFAOYSA-N 0.000 description 1
- OKDQKPLMQBXTNH-UHFFFAOYSA-N n,n-dimethyl-2h-pyridin-1-amine Chemical compound CN(C)N1CC=CC=C1 OKDQKPLMQBXTNH-UHFFFAOYSA-N 0.000 description 1
- DASJFYAPNPUBGG-UHFFFAOYSA-N naphthalene-1-sulfonyl chloride Chemical compound C1=CC=C2C(S(=O)(=O)Cl)=CC=CC2=C1 DASJFYAPNPUBGG-UHFFFAOYSA-N 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 239000004763 nomex Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920006260 polyaryletherketone Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical group C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/78—Halides of sulfonic acids
- C07C309/86—Halides of sulfonic acids having halosulfonyl groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/88—Halides of sulfonic acids having halosulfonyl groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
-
- 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
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
- B01D69/06—Flat membranes
-
- 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
- B01D69/08—Hollow fibre membranes
-
- 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
- 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
- B01D71/69—Polysulfonamides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/30—Polysulfonamides; Polysulfonimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/10—Polysulfonamides; Polysulfonimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/46—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/22—Ortho- or ortho- and peri-condensed systems containing three rings containing only six-membered rings
- C07C2603/24—Anthracenes; Hydrogenated anthracenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/02—Polyureas
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The present invention provides a monomer composition comprising an aromatic halosulfonyl isocyanate having structure I (Formule I) wherein ''m'' is an integer from 2 to 5; ''n'' is an integer from 1 to 5; Ar is a C3-C40 aromatic radical which is free of aliphatic carbon-hydrogen bonds; and X is halogen. The monomer compositions comprising aromatic halosulfonyl isocyanate I are useful in the preparation of polymeric materials useful as membranes which are also provided by the present invention.
Description
Background
The present invention relates to halogenated aromatic sulfonylisocyanates compound and the monomer composition that comprises halogenated aromatic sulfonylisocyanates compound.The disclosure also relates to the polymer composition that is obtained by halogenated aromatic sulfonylisocyanates compound.In addition, the disclosure relates to the method for using polymer composition and the correlated product that comprises polymer composition, and comprises the embodiment that relates to film.
Film has long-term use historical in the separation solution component, and at this, they are as keeping the filter type that some material sees through other materials simultaneously.The character of film and characteristic depend in part on the character in order to the material of making film at least.For feasible economically, film must provide enough circulatioies (per unit membrane area see through logistics speed) and separate (film keeps some composition simultaneously through the ability of other compositions).Film with high throughput and selectivity and useful hydrophily, wettability and chemical-resistant level is used for multiple application, comprises ultrafiltration, micro-filtration, high filter, blood filter.Chemical substance, biologic artifact, bacterium and cell are to the circulation and the selectivity of the pollution negative effect perforated membrane of film.In perforated membrane and application that body fluid contacts, immunogenicity and thrombosis are problems.
Film by the cellulose acetate preparation is also referred to as semipermeable membrane, the bad performance that this film demonstration is relevant with hydrolysis, bacterium and chemical erosion.Though can manage to improve its permeability, sacrifice other performances, as resistance to pressure and durability, thereby limit its application.
Except classifying according to its aperture, film also can be by its textural classification, for example symmetrical, asymmetric and composite membrane.The feature of symmetric membrane is to have even pore structure at whole membrane material.The feature of asymmetric membrane is to have the on-uniform porosity structure at whole membrane material.Composite membrane is defined as at least one layer film (matrix) with stratification on the porous film carrier.The porous film carrier can be polymer ultrafiltration or micro-filtration membrane.Film is generally the polymer less than about 1 micron thickness.Composite membrane comprises and improves the ultrathin membrane that film properties and dry state store easy degree, and this film surpasses need be at the feature performance benefit of the cellulose membrane of wet condition storage.Yet these composite membranes do not show some premium properties usually, as to the high precipitation matter rate (solute rejection) of water-soluble organic substance and inorganic substances, high current passband, durability (as hear resistance, resistance to pressure and chemical-resistant).
Present film research concentrates on preparation counter-infiltration (" RO "), high filter (" HF "), nanofiltration (" NF "), ultrafiltration (" UF "), pervaporation (" PV "), diffusion dialysis (" DD "), gas separation (" GS ") and the used film of other film separation processes, and utilizes the number of chemical material in pursuing the best film performance.
For example the film of RO and NF film extensively preferentially permeates some ionic species as permoselective membrane, is used for for example demineralization and the softening application of water.Used film type influence is the operating condition of concrete application choice.For example, the spiral that in seawater desalination, uses twine the RO film generally need at least 0.6 cubic metre of every day of about 40-100 atmospheric pressure gradient every square metre of film the film circulation and preferably salt rejection rate be about 99%.Under the situation of the brackish water that generally has about 1/10th brine concentration, need be about 95% in the film circulation and the salt rejection rate of at least 0.8 meter/day of the highest about 20 atmospheric pressure gradient.Yet, under the situation of NF film, break away from son in the circulation of minimum pressure gradient and at least 0.8 meter/day and can be used for seawater or brackish water or drink water demineralizing.
In addition, in order to be used for a lot of application, film need show some performances, such as high-durability, anti-bioadhesive, anti-microorganism adhering, to can be present in the patience of oxidant of processing fluid.In addition, film should provide the patience to pH fluctuation and chemical contamination.
Utilize polyamide TFC, RO and NF film, ined all sorts of ways and made film compound (" TFC ") permoselective membrane.Generally the interfacial polymerization with diamines and diacid chloride prepares polyamide TFC film.For example, by making piperazine or 1,3-phenylenediamine and 1,3, the aqueous solution of 5-benzene three acyl chlorides reacts in nonpolar, volatile water immiscible solvent, can prepare interfacial polymerization TFC film.
Although major progress is arranged, but still observe the film properties reduction relevant with the increase permeate flow by film in membrane technology.Also observing this type performance when handling the highly acid charging with commercially available polyamide nanofiltration (NF) and counter-infiltration (RO) film reduces.Though the performance of this type of film may be enough to the separation that reaches required at first, performance is degenerated fast, and film loses the ability of the metal (as cation and/or organic compound) that keeps dissolving at short notice.Polymer film to sour exhibit stabilization is known.Yet in some cases, when polymer film had porous than low density structures, polymer film may see through the acid of a great deal of dissolving, and the effectively metal cation and the organic compound of separate dissolved.
The improvement film that therefore, need except effective and economy, also have the combination of high selectivity, circulation and chemical-resistant.Also need new polymer composition, described polymer composition can make film have good hydrophily and high crosslink density, and has precipitation matter rate, water flux density and the mechanical endurance to inorganic substances and organic substance of improvement.
Summary of the invention
On the one hand, the invention provides a kind of monomer composition, described monomer composition comprises the halogenated aromatic sulfonylisocyanates with structure I
Wherein " m " is 2 to 5 integer, and " n " is 1 to 5 integer, and Ar is not for containing the C of aliphatic carbon-hydrogen link
3-C
40Aromatic group, X are halogen.
On the other hand, the invention provides a kind of monomer composition, described monomer composition comprises the trivalent halogenated aromatic sulfonylisocyanates with structure I V
With degree of functionality be 2 halosulfonyl groups isocyanates with structure VI
R wherein
1Independent in each appearance place is hydrogen atom, halogen atom, nitro, cyano group, C
1-C
20Aliphatic group, C
3-C
20Alicyclic group or C
3-C
20Aromatic group, " a " are 1 to 4 integer, and X is a halogen.
In another embodiment, the invention provides a kind of monomer composition, described monomer composition comprises the trivalent halogenated aromatic sulfonylisocyanates with structure V
With degree of functionality be 2 halosulfonyl groups isocyanates with structure VI
R wherein
1Independent in each appearance place is hydrogen atom, halogen atom, nitro, cyano group, C
1-C
20Aliphatic group, C
3-C
20Alicyclic group or C
3-C
20Aromatic group, " a " are 1 to 4 integer, and X is a halogen.
On the other hand, the invention provides a kind of polymer composition, described polymer composition comprises the construction unit derived from the halogenated aromatic sulfonylisocyanates with structure I
Wherein " m " is 2 to 5 integer, and " n " is 1 to 5 integer, and Ar is not for containing the C of aliphatic carbon-hydrogen link
3-C
40Aromatic group, X are halogen.
On the other hand, the invention provides a kind of film that comprises polymer composition, wherein polymer composition comprises the construction unit derived from the halogenated aromatic sulfonylisocyanates with structure I
Wherein " m " is 2 to 5 integer, and " n " is 1 to 5 integer, and Ar is not for containing the C of aliphatic carbon-hydrogen link
3-C
40Aromatic group, X are halogen.
On the other hand; the invention provides a kind of separator that comprises the multilayer hollow fiber film; wherein one deck at least of multilayer film comprises the film that is formed by polymer composition, and described polymer composition comprises the construction unit derived from the halogenated aromatic sulfonylisocyanates with structure I
Wherein " m " is 2 to 5 integer, and " n " is 1 to 5 integer, and Ar is not for containing the C of aliphatic carbon-hydrogen link
3-C
40Aromatic group, X are halogen.
By the following detailed description of reference, these and other features of the present invention, aspect and advantage can become and be more readily understood.
Detailed Description Of The Invention
Quoted some terms in following specification and claims, these terms should limit has following implication.
Unless this paper clearly indicates in addition, singulative " " and " described " comprise plural number discussion object.
Incident or situation that " optional " or " randomly " meaning is described subsequently can take place or can not take place, and this description comprises situation that incident takes place and situation about not taking place.
Term used herein " solvent " can refer to the mixture of single solvent or solvent.
As used in whole specification and claim, any quantitative expression modified in available approximate language, and these express the tolerable change, and do not cause the change of related basic function.Therefore, by term for example " pact " numerical value of modifying be not limited to specified exact value.In some cases, approximate language can be corresponding to the accuracy of instrument for measuring numerical value.
Term used herein " aromatic group " is meant to have the atomic arrangement that comprises at least one aromatic group of monovalence at least.Have at least that the atomic arrangement that comprises at least one aromatic group of monovalence can comprise hetero atom, for example nitrogen, sulphur, selenium, silicon and oxygen, but perhaps exclusiveness is made up of carbon and hydrogen.Term used herein " aromatic group " includes but not limited to phenyl, pyridine radicals, furyl, thienyl, naphthyl, phenylene and xenyl.As above mention, aromatic group comprises at least one aromatic group.Aromatic group is always the circulus with 4n+2 " delocalized electron ", wherein " n " is for equaling 1 or bigger integer, for example phenyl (n=1), thienyl (n=1), furyl (n=1), naphthyl (n=2), Azulene base (n=2), anthryl explanations such as (n=3).Aromatic group also can comprise non-aromatics part.For example, benzyl is for comprising the aromatic group of benzyl ring (aromatic group) and methylene (non-aromatics part).Similarly, tetralyl is fused to non-aromatics part-(CH for comprising
2)
4-aromatic group (C
6H
3) aromatic group.For simplicity; term used herein " aromatic group " limits and comprises wide region functional group; as alkyl, thiazolinyl, alkynyl, haloalkyl, halogenated aromatic group, conjugated diene, alcohol radical, ether, aldehyde radical, ketone group, carboxylic acid group, acyl group (for example carboxylic acid derivates, as ester and acid amides), amido, nitro etc.For example, the 4-aminomethyl phenyl is the C that comprises methyl
7Aromatic group, described methyl are alkyl functional group.Similarly, the 2-nitrobenzophenone is the C that comprises nitro
6Aromatic group, nitro are functional group.Aromatic group comprises the halogenated aromatic group, as 4-trifluoromethyl, hexafluoro isopropylidene two (4-benzene-1-base oxygen bases) (that is ,-OPhC (CF
3)
2PhO-), 4-chloromethylbenzene-1-base, 3-trifluoro vinyl-2-thienyl, 3-benzenyl trichloride-1-base (that is 3-CCl,
3Ph-), 4-(3-bromine third-1-yl) benzene-1-base (that is 4-BrCH,
2CH
2CH
2Ph-) etc.The other example of aromatic group comprises 4-pi-allyl oxygen base benzene-1-oxygen base, 4-aminobenzene-1-base (that is 4-H,
2NPh-), 3-amino carbonyl benzene-1-base (that is NH,
2COPh-), 4-Benzoylbenzene-1-base, dicyano di-2-ethylhexylphosphine oxide (4-benzene-1-base oxygen base) (that is ,-OPhC (CN)
2PhO-), 3-methylbenzene-1-base, di-2-ethylhexylphosphine oxide (4-benzene-1-base oxygen base) (that is ,-OPhCH
2PhO-), 2-ethylo benzene-1-base, phenyl vinyl, 3-formoxyl-2-thienyl, 2-hexyl-5-furyl, hexa-methylene-1,6-two (4-benzene-1-base oxygen bases) (that is ,-OPh (CH
2)
6PhO-), 4-hydroxymethyl benzene-1-base (that is 4-HOCH,
2Ph-), 4-mercapto methyl benzene-1-base (that is 4-HSCH,
2Ph-), 4-methyl sulfenyl benzene-1-base (that is 4-CH,
3SPh-), 3-methoxybenzene-1-base, 2-methoxycarbonyl benzene-1-base oxygen base (for example, cresotinic acid acidic group), 2-nitro methylbenzene-1-base (that is 2-NO,
2CH
2Ph), 3-trimethyl silyl benzene-1-base, 4-t-butyldimethylsilyl benzene-1-base, 4-vinyl benzene-1-base, ethenylidene two (phenyl) etc.Term " C
3-C
10Aromatic group " comprise and contain at least 3 but the aromatic group of no more than 10 carbon atoms.Aromatic group 1-imidazole radicals (C
3H
2N
2-) expression C
3Aromatic group.Benzyl (C
7H
7-) expression C
7Aromatic group.
Term used herein " alicyclic group " is meant to have monovalence at least and comprise ring-type but the group of the atomic arrangement of non-aromatics." alicyclic group " of this paper definition do not comprise aromatic group." alicyclic group " can comprise one or more monocycle parts.For example, cyclohexyl methyl (C
6H
11CH
2-) be alicyclic group, this alicyclic group comprises cyclohexyl ring (ring-type but the atomic arrangement of non-aromatics) and methylene (non-loop section).Alicyclic group can comprise hetero atom, for example nitrogen, sulphur, selenium, silicon and oxygen, but perhaps exclusiveness is made up of carbon and hydrogen.For simplicity; term used herein " alicyclic group " limits and comprises wide region functional group; as alkyl, thiazolinyl, alkynyl, haloalkyl, conjugated diene, alcohol radical, ether, aldehyde radical, ketone group, carboxylic acid group, acyl group (for example carboxylic acid derivates, as ester and acid amides), amido, nitro etc.For example, 4-methyl ring penta-1-base is for comprising the C of methyl
6Alicyclic group, described methyl are alkyl functional group.Similarly, 2-nitro ring fourth-1-base is for comprising the C of nitro
4Alicyclic group, nitro are functional group.Alicyclic group can comprise one or more halogen atoms that can be identical or different.Halogen atom comprises for example fluorine, chlorine, bromine and iodine.The alicyclic group that comprises one or more halogen atoms comprises 2-trifluoromethyl hexamethylene-1-base, 4-bromine difluoro methyl ring suffering-1-base, 2-difluoro chloromethyl hexamethylene-1-base, hexafluoro isopropylidene-2, and 2-two (hexamethylene-4-yl) (that is ,-C
6H
10C (CF
3)
2C
6H
10-), 2-chloromethyl hexamethylene-1-base, 3-difluoro methylene hexamethylene-1-base, 4-trichloromethyl hexamethylene-1-base oxygen base, 4-dichloro bromomethyl hexamethylene-1-base sulfenyl, 2-bromoethyl ring penta-1-base, 2-bromopropyl hexamethylene-1-base oxygen base (for example, CH
3CHBrCH
2C
6H
10O-) etc.The other example of alicyclic group comprise 4-pi-allyl oxygen basic ring oneself-the amino hexamethylene of 1-base, 4--1-base (that is H,
2NC
6H
10-), 4-amino carbonyl ring penta-1-base (that is NH,
2COC
5H
8-), 4-acetyl group oxygen basic ring oneself-1-base, 2,2-dicyano isopropylidene two (hexamethylenes-4-base oxygen bases) (that is ,-OC
6H
10C (CN)
2C
6H
10O-), 3-methyl cyclohexane-1-base, di-2-ethylhexylphosphine oxide (hexamethylene-4-base oxygen base) (that is ,-OC
6H
10CH
2C
6H
10O-), 1-ethyl ring fourth-1-base, cyclopropyl vinyl, 3-formoxyl-2-tetrahydrofuran base, 2-hexyl-5-tetrahydrofuran base, hexa-methylene-1,6-two (hexamethylenes-4-base oxygen bases) (that is ,-OC
6H
10(CH
2)
6C
6H
10O-), 4-hydroxymethyl hexamethylene-1-base (that is 4-HOCH,
2C
6H
10-), 4-mercapto methyl hexamethylene-1-base (that is 4-HSCH,
2C
6H
10-), 4-methyl sulfenyl hexamethylene-1-base (that is 4-CH,
3SC
6H
10-), 4-methoxyl group hexamethylene-1-base, 2-methoxycarbonyl hexamethylene-1-base oxygen base (2-CH
3OCOC
6H
10O-), 4-nitro methyl cyclohexane-1-base (that is NO,
2CH
2C
6H
10-), 3-trimethyl silyl hexamethylene-1-base, 2-t-butyldimethylsilyl ring penta-1-base, 4-trimethoxysilylethylgroup group hexamethylene-1-base (for example, (CH
3O)
3SiCH
2CH
2C
6H
10-), 4 vinyl cyclohexene-1-base, ethenylidene two (cyclohexyl) etc.Term " C
3-C
10Alicyclic group " comprise and contain at least 3 but the alicyclic group of no more than 10 carbon atoms.Alicyclic group 2-tetrahydrofuran base (C
4H
7O-) expression C
4Alicyclic group.Cyclohexyl methyl (C
6H
11CH
2-) expression C
7Alicyclic group.
Term used herein " aliphatic group " be meant have monovalence at least by non-annularity organic group linear or that the branching atomic arrangement is formed.Aliphatic group limits and comprises at least one carbon atom.The atomic arrangement that comprises aliphatic group can comprise hetero atom, for example nitrogen, sulphur, silicon, selenium and oxygen, but perhaps exclusiveness is made up of carbon and hydrogen.For simplicity; term used herein " aliphatic group " limits and comprises the part of wide region functional group as " the linear or branching atomic arrangement of non-annularity "; as alkyl, thiazolinyl, alkynyl, haloalkyl, conjugated diene, alcohol radical, ether, aldehyde radical, ketone group, carboxylic acid group, acyl group (for example carboxylic acid derivates, as ester and acid amides), amido, nitro etc.For example, 4-methylpent-1-base is for comprising the C of methyl
6Aliphatic group, described methyl are alkyl functional group.Similarly, 4-nitro fourth-1-base is for comprising the C of nitro
4Aliphatic group, nitro are functional group.Aliphatic group can be for containing the haloalkyl of one or more halogen atoms, and halogen atom can be identical or different.Halogen atom comprises for example fluorine, chlorine, bromine and iodine.The aliphatic group that comprises one or more halogen atoms comprise alkyl halide trifluoromethyl, difluoro bromomethyl, difluoro chloromethyl, hexafluoro isopropylidene, chloromethyl, difluorovinylidene, trichloromethyl, dichloro bromomethyl, bromoethyl, 2-bromine trimethylene (for example ,-CH
2CHBrCH
2-) etc.The other example of aliphatic group comprise pi-allyl, amino carbonyl (that is ,-CONH
2), carbonyl, 2,2-dicyano isopropylidene (that is ,-CH
2C (CN)
2CH
2-), methyl (that is ,-CH
3), methylene (that is ,-CH
2-), ethyl, ethylidene, formoxyl (that is ,-CHO), hexyl, hexa-methylene, hydroxymethyl (that is ,-CH
2OH), mercapto methyl (that is ,-CH
2SH), methyl mercapto (that is ,-SCH
3), methyl sulfenyl methyl (that is ,-CH
2SCH
3), methoxyl group, methoxycarbonyl (that is CH,
3OCO-), the nitro methyl (that is ,-CH
2NO
2), thiocarbonyl, trimethyl silyl (that is (CH,
3)
3Si-), t-butyldimethylsilyl, 3-trimethoxy-silylpropyl (that is (CH,
3O)
3SiCH
2CH
2CH
2-), vinyl, ethenylidene etc.As another example, C
1-C
10Aliphatic group comprises at least 1 but no more than 10 carbon atoms.Methyl (that is CH,
3-) be C
1The example of aliphatic group.Decyl (that is CH,
3(CH
2)
9-) be C
10The example of aliphatic group.
As above mention, in one embodiment, the invention provides a kind of monomer composition, described monomer composition comprises the halogenated aromatic sulfonylisocyanates with structure I
Wherein " m " is 2 to 5 integer, and " n " is 1 to 5 integer, and Ar is not for containing the C of aliphatic carbon-hydrogen link
3-C
40Aromatic group, X are halogen.In one embodiment, " m " is 2.In another embodiment, " m " is 3.In another embodiment, " n " is 1, and in another embodiment, " n " is 2.
The representative halogenated aromatic sulfonylisocyanates that universal architecture I comprises is illustrated in the table 1.One skilled in the art should appreciate that the relation between each structure of project 1a-1h of universal architecture I and table 1.For example, the structure of project 1a is represented the kind that universal architecture I comprises, wherein Ar is C
6Aromatic ring (phenyl ring), variable " n " is 1, and " m " is 3, and X is a chlorine.
Table 1
As another example, the project 1b of table 1 illustrates a kind of halogenated aromatic sulfonylisocyanates, and wherein Ar is a naphthalene, and " n " is 1, and " m " is 2, and X is a chlorine.The project 1c of table 1 illustrates a kind of halogenated aromatic sulfonylisocyanates, and wherein Ar is a phenoxy group benzene, and " n " is 1, and " m " is 2, and X is a chlorine.
In one embodiment, the invention provides a kind of halogenated aromatic sulfonylisocyanates with structure I, wherein group Ar is C
6-C
20Aromatic group.In some embodiments, 5 group Ar are the trivalent aromatic group with structure I I
For example, the structure of project 1e is represented the kind that universal architecture I comprises, wherein Ar has structure I I, promptly trisubstituted phenyl ring, and wherein at least two substituting groups are positioned at mutually the ring position of " position " each other.
In one embodiment, the invention provides a kind of halogenated aromatic sulfonylisocyanates with structure I, wherein group Ar is the trivalent aromatic group with structure III
As an example, the project 1b of table 1 illustrates a kind of halogenated aromatic sulfonylisocyanates, and wherein Ar is trisubstituted naphthalene nucleus.
In another embodiment, halogenated aromatic sulfonylisocyanates provided by the invention has structure I V.
In another embodiment, halogenated aromatic sulfonylisocyanates provided by the invention has structure V.
In one embodiment, halogenated aromatic sulfonylisocyanates composition further comprises degree of functionality and is at least 2 C
3-C
40Aromatic monomer.In another embodiment, further to comprise degree of functionality be 2 C to halogenated aromatic sulfonylisocyanates composition
3-C
40Aromatic monomer.Expression used herein " degree of functionality is 2 " means aromatic monomer and comprises a halosulfonyl groups (SO
2X) and a NCO (NCO).In one embodiment, degree of functionality is that 2 halosulfonyl groups isocyanates has structure VI
R wherein
1Independent in each appearance place is hydrogen atom, halogen atom, nitro, cyano group, C
1-C
20Aliphatic group, C
3-C
20Alicyclic group or C
3-C
20Aromatic group, " a " are 1 to 4 integer, and X is a halogen.
In one embodiment, the invention provides a kind of halosulfonyl groups isocyanates that comprises structure I and degree of functionality and be the halosulfonyl groups isocyanate composition of 2 the halosulfonyl groups isocyanates with structure VI, wherein X is a chlorine.In one embodiment, the R of structure VI
1Be electrophilic group, for example the chloroformyl base.The chloroformyl basis representation C that this paper limits
1Aliphatic group (COCl).Radicals R
1Other unrestricted example comprise carbonyl halide, alpha-halogen ketone group, haloformate, acid anhydrides, phosphoryl halogen, glycidyl ether.
In another embodiment, the invention provides that a kind of to comprise halogenated aromatic sulfonylisocyanates with structure I and degree of functionality be 2 and have a halosulfonyl groups isocyanate composition of the second halogenated aromatic sulfonylisocyanates of structure VII
Wherein X is a halogen.
In another embodiment, the invention provides that a kind of to comprise halogenated aromatic sulfonylisocyanates with structure I and degree of functionality be 2 and have a halosulfonyl groups isocyanate composition of the second halogenated aromatic sulfonylisocyanates of structure VIII
Wherein X is a halogen.
On the other hand, the invention provides a kind of polymer composition, described polymer composition comprises the construction unit derived from the halogenated aromatic sulfonylisocyanates with structure I
Wherein " m " is 2 to 5 integer, and " n " is 1 to 5 integer, and Ar is not for containing the C of aliphatic carbon-hydrogen link
3-C
40Aromatic group, X are halogen.The example that comprises derived from the polymer composition of the construction unit of the halogenated aromatic sulfonylisocyanates with structure I can be the polysulfonamide-polyurea polymer of piperazine and monomer V polymerization preparation; polysulfonamide-the polyurea polymer of piperazine and monomer 1c (table 1) polymerization preparation, the polysulfonamide-polyurea polymer of piperazine and monomer 1d (table 1) polymerization preparation.In one embodiment, comprising polymer composition derived from the construction unit of the halogenated aromatic sulfonylisocyanates with structure I further comprises and is at least 2 C derived from degree of functionality
3-C
40The construction unit of aromatic monomer, for example polymer composition of the halosulfonyl groups isocyanate composition prepared in reaction by comprising halosulfonyl groups isocyanates V and halosulfonyl groups isocyanates VII.In another embodiment; polymer provided by the invention comprises derived from the construction unit of halosulfonyl groups isocyanates I with derived from the construction unit of at least a other electrophilic monomer, electrophilic monomer such as paraphthaloyl chloride, toluene di-isocyanate(TDI), trimellitic anhydride acyl chlorides, 5-isocyanate group m-phthaloyl chloride, 5-chloroformyl oxygen base m-phthaloyl chloride, 5-chlorosulfonyl m-phthaloyl chloride, m-phthaloyl chloride, pyromellitic trimethylsilyl chloride and combination thereof.
In one embodiment; the invention provides a kind of polymer composition; described polymer composition comprises derived from the construction unit of the halosulfonyl groups isocyanates with structure I with derived from the construction unit of at least a other electrophilic monomer; electrophilic monomer is selected from m-phthaloyl chloride; paraphthaloyl chloride; pyromellitic trimethylsilyl chloride; inclined to one side benzene three formyl chlorides; 1; 3-cyclohexane dimethyl chloride; 1; 4-cyclohexane dimethyl chloride; cyclohexane three formyl halides; 2; 3-pyridine dimethyl chloride; 2; 6-pyridine dimethyl chloride; the trimellitic anhydride carboxylic acid halides; equal benzene tetramethyl acyl chlorides; pyromellitic acid dianhydride; pyridine three formyl halides; decanedioyl halogen; nonanedioyl halogen; adipyl halogen; dodecane two carboxylic acid halides; toluene di-isocyanate(TDI); di-2-ethylhexylphosphine oxide (phenyl isocyanate); naphthalene diisocyanate; the ditolyl vulcabond; 1; hexamethylene-diisocyanate; phenylene diisocyanate; isocyanate group phenyl-diformyl halogen; halo formoxyl oxygen base phenyl-diformyl halogen; dihalo sulfonyl benzene; halosulfonyl groups phenyl-diformyl halogen; cyclobutane two formyl halides; piperazine-N; N '-two formyl halide; lupetazin-N; N '-two formyl halide; dihalo formic acid benzene dimethanol ester; dihalo formic acid benzenediol ester; haloformic acids benzenetriol ester; phosgene; surpalite; triphosgene; N; N '-carbonyl dimidazoles; isocyanuric acid N; N '; N " triacetyl halogen; isocyanuric acid N; N ', N " three propionyl halogen; pentamethylene tetramethyl carboxylic acid halides and combination thereof.
In one embodiment, the invention provides a kind of polymer composition, described polymer composition comprises derived from the construction unit of the halosulfonyl groups isocyanates with structure I with derived from the construction unit of the oligomer of carboxylic acid halides end-blocking.The oligomer of carboxylic acid halides end-blocking be exemplified as piperazine and one or more excessive m-phthaloyl chlorides; m-phthaloyl chloride; paraphthaloyl chloride; pyromellitic trimethylsilyl chloride; inclined to one side benzene three formyl chlorides; 2; 3-pyridine dimethyl chloride; 2; 6-pyridine dimethyl chloride; the trimellitic anhydride carboxylic acid halides; equal benzene tetramethyl acyl chlorides; pyromellitic acid dianhydride; pyridine three formyl halides; toluene di-isocyanate(TDI); di-2-ethylhexylphosphine oxide (phenyl isocyanate); naphthalene diisocyanate; the ditolyl vulcabond; phenylene diisocyanate; isocyanate group phenyl-diformyl halogen; halo formoxyl oxygen base phenyl-diformyl halogen; dihalo sulfonyl benzene; halosulfonyl groups phenyl-diformyl halogen; dihalo formic acid benzene dimethanol ester; dihalo formic acid benzenediol ester; haloformic acids benzenetriol ester; phosgene; surpalite; triphosgene and N, the product of the reaction of N '-carbonyl dimidazoles.
Polymer composition provided by the invention comprises at least one the urea groups NH base/construction unit that produces from halogenated aromatic sulfonylisocyanates I.Believe that having urea groups NH base is in order to strengthen polymer composition and liquid, aqueous interaction, and the hydrogen bond between the group (for example, sulfoamido) of deriving by urea groups NH base with from the halogenosulfonic acid ester group provides the structural intergrity of extra level in containing the goods of polymer composition of the present invention.In embodiment, believe to have urea groups NH base particular importance with one or more diamines (for example in piperazine) preparation polymer composition that only contains secondary amine.
In one embodiment, polymer composition provided by the invention comprises derived from the construction unit of the halogenated aromatic sulfonylisocyanates with structure I with derived from the construction unit of the polyamine compound with structure I X
R wherein
2Be C
1-C
20Aliphatic group, C
3-C
20Alicyclic group or C
3-C
20Aromatic group, R
3And R
4Independent in each appearance place is hydrogen atom, C
1-C
20Aliphatic group, C
3-C
20Alicyclic group or C
3-C
20Aromatic group, " c " are 1 to 10 integer.Structure I X comprises wherein R
2Can with R
3And R
4Form the situation of circulus together, for example represent C at structure I X
4During-diamines piperazine, wherein " c " is 1, R
2For-CH
2CH
2-, R
3And R
4Be respectively-CH
2-, and R
3Be connected to R by the carbon-to-carbon singly-bound
4
In one embodiment, but the polyamine compound per molecule with structure I X comprises two amino (that is, " c " is 1).The unrestricted example of the polyamine compound that universal architecture IX comprises comprises polyvinylamine, ethylenediamine, diethylenediamine or piperazine, o-phenylenediamine (phenylene diamine), m-phenylene diamine (MPD), p-phenylenediamine (PPD), cyclohexanediamine, the hexamethylene triamine, benzene dimethylamine, chlorobenzene diethylenetriamine, the benzene triamine, two (aminobenzyl) aniline, tetramino benzene, tetramino biphenyl, four (amino methyl) methane, N, N '-diphenyl ethylene diamine, aminobenzamide, amino benzoyl hydrazine, two (aminobenzyl) aniline, N, N '-dialkyl group-1, the 3-phenylenediamine, N-alkyl-1, the 3-phenylenediamine, melamine.In one embodiment, the polyamine with structure I X is 1,3,5-triaminobenzene, piperazine, 4-amino methyl piperidines, 1,4-phenylenediamine, 1,3-phenylenediamine or two or more aforementioned polyamine combination of compounds.
In one embodiment, the suitable molecular weight of polymer composition of the present invention is greater than about 1,000g/mol.In some embodiments, the molecular weight of composition is less than about 200,000g/mol.In one embodiment, the suitable molecular weight of polymer composition of the present invention is about 1, and 000g/mol is to about 200,000g/mol.In one embodiment, the molecular weight of polymer composition is about 1, and 000g/mol is to about 40,000g/mol, and about 40,000 to about 80,000g/mol, about 80,000 to about 120, and 000g/mol, or about 120,000g/mol be to about 200,000g/mol.In one embodiment, polymer composition is that to comprise derived from the construction unit of the halogenated aromatic sulfonylisocyanates with structure I and degree of functionality be 2 C
3-C
40The copolymer of aromatic monomer.In different embodiments, polymer composition provided by the invention is homopolymers, random copolymer, block copolymer or graft copolymer.
In one embodiment, polymer composition comprises one or more additives.Can select the characteristic and the character of the goods that additive to affect made by composition.Can use the mixture of additive.During composition mixes the formation composition, can mix examples of such additives in the time that is fit to.Exemplary additives comprises extender, lubricant, flow ability modifying agent, filler, fire retardant, pigment, dyestuff, colouring agent, UV light stabilizing agent, antioxidant, impact modifier, heat stabilizer, dripping inhibitor, plasticizer, releasing agent, nucleator, fluorescent whitening agent, fire-proofing chemical, antistatic additive, blowing agent etc.If exist, additive can for based on about 0.1% weight of composition total weight to about 40% weight.
In certain embodiments, form amberplex with polymer composition provided by the invention.In certain other embodiments, by several different methods polymer composition is molded as useful goods, for example, form goods by injection-molded, extrusion molding, rotational molding, foam moulded, calendering molding, blowing, hot forming, compacting, melt-spun etc.In one embodiment, polymer composition can be drawn or is spun into the shape of fiber, sheet or film.In another embodiment, polymer composition can be drawn or is spun into the plurality of fibers that limits film.Fiber can be elasticity, and has relative high-mechanical property.The fiber that is fit to can be doughnut.In one embodiment, arrange that fiber limits pad or film.In addition, film can be carried on second film that self does not form from the composition that comprises embodiment of the present invention.
In one embodiment, polymer composition provided by the invention is used for film or sheet, and film or sheet can be bored a hole or porous.In one embodiment, film or sheet are continuous, and are impermeability.The sheet and the film that are fit to can have surface topology on one or two first type surface.This topological structure can comprise patterning micro-structural and/or ridge, to increase available surface area or available contact area.In certain embodiments, sheet or film can be porous or permeability, so as fluid can by or flow through.This sheet or film are film type.By for example boring a hole, stretch, expand, foam or one or more of extraction, can give membrane permeability.The appropriate methodology of making film comprises foaming, cutting or curtain coating.In one embodiment, available weaving or non woven fibre formation film.In one embodiment, film provided by the invention is formed on the surface of porous substrate (for example, porous polymer film).
Multiple technologies at preparation film known in the art.For example, form film and can use dried phase separation membrane manufacturing process, wherein dissolved polymers forms membrane structure by making sufficient solvent evaporation precipitation; Wetting phase diffusion barrier manufacturing process, wherein dissolved polymers is bathed precipitation formation membrane structure by immersing non-solvent; Do-wetting phase diffusion barrier manufacturing process, the method is for doing mutually and the combination of wetting phase manufacturing process; Or thermal induction phase separation membrane manufacturing process, wherein dissolved polymers precipitates or solidifies the formation membrane structure by the control cooling.In addition, before being used for separating application, film can make film adjust process or preprocessing process through film.Exemplary process can comprise thermal annealing discharging stress, with balance in the solution that is similar to the feed stream that film will contact.
In one embodiment, film is three dimensional matrix or has the lattice structure that comprises many joints that these joints are by many fibril interconnection.The joint and the surface of fibril can limit the many holes in the film, and can limit by film from a major side surface to many interconnecting channels or hole that another opposite major side surface is extended zigzag path.In one embodiment, film can limit the hole of a lot of interconnection, and the hole of these interconnection is communicated with the environment liquid of the opposite major opposing side of adjacent membrane.Membrane material allows liquid substance (for example liquid, aqueous material) to drench and can be expressed as the function of one or more character by the tendency in hole.These character comprise film the surface can, the size in the feeler that connects of surface tension, membrane material and the liquid substance of liquid substance, hole or the effective compatibility of flow area and membrane material and liquid substance.Film can have a plurality of subgrades.Subgrade can be identical or different mutually.In one aspect, one or more subgrades can comprise embodiment of the present invention, and other subgrades can provide character such as for example enhancing, selective filter, pliability, carrying, flow-control.Film according to embodiment of the present invention can be of different sizes, and some are with reference to using-concrete Standard Selection.Each film can be formed by multilayer tablet or film, can be formed by fabric or pad, and can comprise non-layer of the present invention, can comprise that perhaps two or more are aforementioned.
Film according to embodiment of the present invention preparation can have one or more predetermined character.These character can comprise the wettable of one or more dry transportation films, wet/dried circulation ability, the filtration of polar liquid or solution, the flow velocity of liquid, aqueous or solution, the surface electrical negativity, flowing and/or persistence under low pH condition, flowing and/or persistence under high pH condition, flowing and/or persistence of room temperature condition, flowing and/or persistence of hot conditions, flowing and/or persistence of high pressure, permeability to the predetermined wavelength energy, to the permeability of acoustic energy or to the carrying of catalytic specie.Persistence is meant that coating keeps the ability that works in a continuous manner, for example more than 1 day or more than a circulation (wet/as to do, hot/cold, high/low pH etc.).In one embodiment, film is about 100 ℃ to about 125 ℃ to the patience of temperature, for example in the HIGH PRESSURE TREATMENT operation.
Fluid can be depending on one or more factors by the flow velocity of film, for example, can be depending on physics and/or chemical property, fluid properties (for example, viscosity, pH, solute etc.), environmental properties (for example, temperature, pressure etc.) and the similar factor of film.
In one embodiment, use membrane filtration water.The pressure reduction that film is striden in filter membrane response makes the solution of water from the water solution flow of high relatively solute concentration to low relatively solute concentration.Therefore, in one embodiment, film operationally makes liquid or fluid stream pass through at least a portion material with predetermined direction.Motive power can be infiltration or wicking, perhaps can be by drivings such as one or more concentration gradients, barometric gradient, thermogrades.In another embodiment, film has the desalination percentage greater than 75%.In one embodiment, film is the reverse osmosis membrane in the water treatment system.In another embodiment, film stops ion to flow through.Ion comprises metal ion.
Other application that are fit to can comprise liquid filtering, the Chemical Decomposition based on polarity, pervaporation, gas separations, electrochemistry in industry (as chlor-alkali production and electrochemical applications), super acidic catalyst, or are used as the medium of enzyme in fixing.
Micro-filtration membrane can be filtered has about 20 nanometers to the particulate of about 10,000 nanometer linear dimensions or the suspended substance of micelle.Milipore filter can have average aperture less than about 100 nanometers, and can keep the material of about 300 dalton to about 500,000 Dalton molecular weights.The material of removing that is fit to comprises sugar, biomolecule, polymer and micelle.NF membrane receives increasing concern in the low-pressure water desalination.These films are electronegative usually, and by electrical charge rejection (Donnan exclusion) desalination.Also remove in addition and have the organic substance of about 200 dalton to about 500 Dalton molecular weights.High filter can be used relative fine and close film with counter-infiltration (RO).This type of dense film can have enough sizes or chemically active hole or perforation, so that differentially handle little molecule from the water that contacts with the film surface, as salt and low-molecular-weight organic matter.Suitable RO film according to embodiment of the present invention can comprise the high pressure RO film (5MPa is to about 10MPa driving pressure) that is used for seawater desalination; The pressure RO (1MPa is to about 5MPa driving pressure) that is used for the brackish water desalination; With the nanofiltration that is used for the water section demineralization or " pine " RO (0.3MPa removes 0-20%NaCl to about 1MPa driving pressure).Two kinds of films of ultrafiltration and micro-filtration all are used for thin-film composite membrane as the intermediate layer carrier.These films can be used for multiple water and purify, and it should be noted that nanofiltration, counter-infiltration, film and high filter most.
In one embodiment, the invention provides a kind of composite membrane, described composite membrane comprises the polymer composition of the present invention at least one side that is positioned at porous carrier materials.Term " composite membrane " is meant laminated or is coated on the composite of the matrix at least one side of porous carrier materials.Term " carrier material " is meant any base material that can apply matrix in the above.Also comprise pellicle (especially micro-filtration and ultrafiltration kind), fabric, filtering material etc.In one embodiment, porous carrier materials can be made up of any suitable porous material, includes but not limited to paper, modified cellulose, weaving glass fiber, porous or nonwoven polymer fibre plate.Porous carrier materials can comprise polymer, for example polysulfones, polyether sulfone, polyacrylonitrile, cellulose esters, polyolefin, polyester, polyurethane, polyamide, Merlon, polyethers, PAEK, polypropylene, PPSU, polyvinyl chloride, polyvinylidene fluoride and combination thereof; Ceramic membrane; Cellular glass; Porous metals; Or the combination of two or more aforementioned polymer, glass and metal.Composite membrane can be configured as sheet, hollow tube, film or flat or spirality film filter.In another embodiment, carrier material is polysulfones, polyether sulfone, SPSF, sulfonated polyether sulfone, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), polyvinyl chloride, polystyrene, Merlon, polyacrylonitrile, Nomex, nylon, polyamide, polyimides, melamine, thermosetting polymer, polyether-ketone, polyether-ether-ketone, polyphenylene sulfide.In one embodiment, porous carrier materials is selected from polyolefin, polysulfones, polyethers, polysulfonamide, polyamine, polysulfide, melamine polymers and combination thereof.
In one embodiment, the invention provides a kind of desalter that comprises water treatment system, described water treatment system comprises the film that contains derived from halogenated aromatic sulfonylisocyanates compound of the present invention.In another embodiment, the invention provides a kind of milipore filter, described milipore filter is derived from halogenated aromatic sulfonylisocyanates compound of the present invention.In another embodiment, the invention provides a kind of bio-separation device, described bio-separation device comprises can make the film of a kind of biofluid composition from another kind of biofluid component separation.
On the other hand; the invention provides a kind of separator that comprises the multilayer hollow fiber film; wherein one deck at least of multilayer film comprises the film that is formed by polymer composition, and described polymer composition comprises the construction unit derived from the halogenated aromatic sulfonylisocyanates with structure I
Wherein " m " is 2 to 5 integer, and " n " is 1 to 5 integer, and Ar is not for containing the C of aliphatic carbon-hydrogen link
3-C
40Aromatic group, X are halogen.
Halogenated aromatic sulfonylisocyanates compound of the present invention and the polymer composition that is obtained by described halosulfonyl groups isocyanate compound can prepare by several different methods, and the method that provides in the disclosure test portion is provided.
Embodiment
All raw materials are available from Aldrich Chemical Company.On 400MHz BrukerNMR spectrometer, carry out
1H NMR.
Embodiment 1: preparation 2, two (the chlorosulfonyl)-6-isocyanate group naphthalenes 1 of 4-
Add triphosgene (19.57g to the 500mL round-bottomed flask that is equipped with magnetic stirring apparatus, nitrogen bubbler, nitrogen inlet and temperature probe, 65.94mmol), 2-amino naphthalenes-6, (10.0g cools off 32.96mmol) with anhydrous chlorobenzene (100mL), and with cooling bath the 8-disulfonic acid.Slowly added pyridine through 15 minutes: imidazole catalyst (0.625g pyridine: the independent solution in anhydrous chlorobenzene (50rnL) the 0.125g imidazoles).Then other 30 minutes of 5-10 ℃ of stirring reaction.After at this moment, raise the temperature to 55 ℃ of experience 4 hours, further be elevated to other 5 hours of 135 ℃ of experience then.Make mixture be cooled to environment temperature then, under reduced pressure concentrate, obtain two chloro sulfonyl isocyanate compounds 1, be a kind of yellow solid.
1H?NMR(CDCl
3)：8.90(m，1H)；8.88(d，J＝2.0，1H)；8.54(d，J＝1.8，1H)；8.25(d，J＝8.8，1H)；7.66(dd，J＝8.9，2.0，1H).
Embodiment 2: preparation comprises the microporous barrier derived from the construction unit of two chloro sulfonyl isocyanate compounds 1
To test micropore poly (ether-sulfone) ultrafiltration membrane (" carrier ") and be immersed in and comprise 2% weight piperazine and 0.1% weight N in the water, the aqueous solution of N-dimethyl aminopyridine was room temperature experience 1 minute.Take out carrier, clean any remaining water droplet, so that the micropore polyether sulfone carrier with piperazine aqueous solution dipping to be provided.Also available other commercially available micropore milipore filters are as carrier, P series poly (ether-sulfone) ultrafiltration membrane for example, and available from GE Water, Trevose PA.
The solution of two chloro sulfonyl isocyanate compounds 1 in ISOPAR-G is heated to about 100 ℃, is poured on then on the surface of impregnated carrier.The solution of two chloro sulfonyl isocyanate compounds 1 with kept 2 minutes through contacting of impregnated carrier, the temperature of organic solution is reduced to about 40 ℃ during this period.Organic solution is from the carrier decantation; treated carrier solidified 6 minutes at 120 ℃ in baking oven; cool to room temperature then is to provide the microporous barrier that comprises the micropore polyether sulfone carrier that applies with polysulfonamide-polyureas (comprising the construction unit derived from two chloro sulfonyl isocyanates 1 and piperazine).
Embodiment 3: the film of estimating preparation in embodiment 2
The microporous barrier of preparation cutting sample (5 " * 3 ") from embodiment 2, and be fixed in the film test platform of cross-current chamber (cross-flow cell).Sample is used in the salting liquid that contains 2000ppm NaCl in the deionized water and handled 1 hour 800psi and 20 ℃.After at this moment, collect the penetrant of writing time, measure collected volume, measure permeate conductivity (μ S), obtain salt and pass through percentage with Oakton Acorn CON 6 conductivity meters from each repeated test.Membrane permeability (A value) is from data computation, and these data comprise pressure, membrane area, writing time and penetrant volume.When film remains in the experimental rig, film was handled 30 minutes 225psi and 20 ℃ with the aqueous solution of clorox (70ppm) in deionized water.After handling with the liquor natrii hypochloritis, film is with washed with de-ionized water 30 minutes, is used in the salting liquid that contains 2000ppm NaCl in the deionized water then and handles 1 hour 800psi and 20 ℃.Collect penetrant through writing time, through between this moment, measure the penetrant volume,, obtain the salt that the liquor natrii hypochloritis handles caudacoria and pass through percentage as preceding mensuration permeate conductivity.Calculate membrane permeability (A value) once more.
Data show that the microporous barrier of preparation is effectively as reverse osmosis membrane in embodiment 2, and these data are collected in the following table 2.Data show, handle with clorox that in regeneration step film properties is reduced.Data in the comparing embodiment 1 (CE-1) also illustrate, the film of embodiment 3 is at least with embodiment 3 used identical preparations and comprise derived from piperazine and 2,4 the same function well of known microporous barrier of the construction unit of 6-three (chlorosulfonyl) naphthalene.The microporous barrier that those skilled in the art will appreciate that comparing embodiment 1 is without any urea groups NH base, a kind ofly thinks the architectural feature that improves microporous barrier overall performance provided by the invention.
Table 2
Previous embodiment only is an illustrative, only is used to illustrate features more of the present invention.Accessory claim is intended to the same claimed widely the present invention with its consideration, and the embodiment that this paper proposes be the explanation from the embodiment of the possible embodiment selection of various institutes.Therefore, the applicant's is intended that the selectional restriction that accessory claim is not used to illustrate the embodiment of feature of the present invention.As used in claims, word " comprise " and grammatical variants logically also subtend (subtend) and comprising change and the phrase of different range, such as but not limited to " substantially by ... form and by ... composition ".Scope is provided where necessary, and these scopes comprise all subranges therebetween.Wish that those skilled in the art can expect the variation in these scopes, and not when the public provides, these variations should be interpreted as far as possible being contained by accessory claim.Should expect that also progress of science and technology can make now because equivalent and substitute that the language inaccuracy is not expected become possibility, these variations also should be interpreted as being contained by accessory claim as far as possible.
Claims (10)
1. monomer composition, described monomer composition comprises the halogenated aromatic sulfonylisocyanates with structure I
Wherein " m " is 2 to 5 integer, and " n " is 1 to 5 integer, and Ar is not for containing the C of aliphatic carbon-hydrogen link
3-C
40Aromatic group, X are halogen.
2. the monomer composition of claim 1, wherein Ar is the trivalent aromatic group with structure I I
3. the monomer composition of claim 1, wherein Ar is the trivalent aromatic group with structure III
4. the monomer composition of claim 1, described monomer composition comprises the compound with structure I V
5. the monomer composition of claim 1, described monomer composition comprises the compound with structure V
6. polymer composition, described polymer composition comprises the construction unit derived from the halogenated aromatic sulfonylisocyanates with structure I
Wherein " m " is 2 to 5 integer, and " n " is 1 to 5 integer, and Ar is not for containing the C of aliphatic carbon-hydrogen link
3-C
40Aromatic group, X are halogen.
7. the polymer composition of claim 6, wherein Ar is the trivalent aromatic group with structure I I
8. the polymer composition of claim 6, wherein Ar is the trivalent aromatic group with structure III
9. the polymer composition of claim 6, described polymer composition further comprises the construction unit derived from the polyamine compound with structure I X
R wherein
2, R
3And R
4Independent in each appearance place is hydrogen atom, C
1-C
20Aliphatic group, C
3-C
20Alicyclic group or C
3-C
20Aromatic group, " c " are 1 to 10 integer.
10. film that comprises polymer composition, wherein polymer composition comprises the construction unit derived from the halogenated aromatic sulfonylisocyanates with structure I
Wherein " m " is 2 to 5 integer, and " n " is 1 to 5 integer, and Ar is not for containing the C of aliphatic carbon-hydrogen link
3-C
40Aromatic group, X are halogen.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/056415 | 2008-03-27 | ||
| US12/056400 | 2008-03-27 | ||
| US12/056,400 US20090242831A1 (en) | 2008-03-27 | 2008-03-27 | Aromatic halosulfonyl isocyanate compositions |
| US12/056,415 US20090242479A1 (en) | 2008-03-27 | 2008-03-27 | Aromatic halosulfonyl isocyanate compositions |
| PCT/US2009/036718 WO2009120492A1 (en) | 2008-03-27 | 2009-03-11 | Aromatic halsulfonyl isocyanate compositions and polymers therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101980767A true CN101980767A (en) | 2011-02-23 |
Family
ID=40843379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009801125266A Pending CN101980767A (en) | 2008-03-27 | 2009-03-11 | Aromatic halsulfonyl isocyanate compositions and polymers therefrom |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP2259865A1 (en) |
| JP (1) | JP2011522058A (en) |
| CN (1) | CN101980767A (en) |
| WO (1) | WO2009120492A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698620A (en) * | 2012-06-12 | 2012-10-03 | 浙江大学 | Method for preparing reverse osmosis composite membrane by taking hyperbranched polymer as monomer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4259255A (en) * | 1976-08-18 | 1981-03-31 | Bayer Aktiengesellschaft | Process for the production of isocyanates |
| US4265745A (en) * | 1977-05-25 | 1981-05-05 | Teijin Limited | Permselective membrane |
| US5693227A (en) * | 1994-11-17 | 1997-12-02 | Ionics, Incorporated | Catalyst mediated method of interfacial polymerization on a microporous support, and polymers, fibers, films and membranes made by such method |
| CN1525878A (en) * | 2000-05-23 | 2004-09-01 | Ge��˹Ī���˹��˾ | Acid stable membranes for nanofiltration |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE947159C (en) * | 1953-01-31 | 1956-08-09 | Bayer Ag | Process for the preparation of isocyanates bearing sulfochloride groups |
| US3652599A (en) * | 1970-03-02 | 1972-03-28 | Upjohn Co | Novel azidosulfonylcarbanilates |
| DE2855938A1 (en) * | 1978-12-23 | 1980-07-10 | Bayer Ag | ISOCYANATOARYLSULFOCHLORIDE, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN THE PRODUCTION OF POLYISOCYANATE-POLYADDITION PRODUCTS |
| DE2945867A1 (en) * | 1979-11-14 | 1981-06-04 | Bayer Ag, 5090 Leverkusen | SUBSTITUTED POLYISOCYANATES OR POLYISOCYANATE MIXTURES OF THE DIPHENYLMETHANE RANGE CONTAINING CHLORSULFONYL GROUPS, A METHOD FOR THE PRODUCTION THEREOF AND THEIR USE IN THE PRODUCTION OF POLYISOCDYANITION-POLYISADDYANITION-POLYISADYANADINE POLYES |
| DE3004694A1 (en) * | 1980-02-08 | 1981-08-13 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING AROMATICALLY BONDED SULFOCHLORIDE GROUPS WITH AROMATIC ISOCYANATES |
| JP4423726B2 (en) * | 2000-02-21 | 2010-03-03 | 三井化学株式会社 | Novel aromatic diisocyanate compound and process for producing the same |
-
2009
- 2009-03-11 JP JP2011501886A patent/JP2011522058A/en active Pending
- 2009-03-11 EP EP09724821A patent/EP2259865A1/en not_active Withdrawn
- 2009-03-11 CN CN2009801125266A patent/CN101980767A/en active Pending
- 2009-03-11 WO PCT/US2009/036718 patent/WO2009120492A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4259255A (en) * | 1976-08-18 | 1981-03-31 | Bayer Aktiengesellschaft | Process for the production of isocyanates |
| US4265745A (en) * | 1977-05-25 | 1981-05-05 | Teijin Limited | Permselective membrane |
| US5693227A (en) * | 1994-11-17 | 1997-12-02 | Ionics, Incorporated | Catalyst mediated method of interfacial polymerization on a microporous support, and polymers, fibers, films and membranes made by such method |
| CN1525878A (en) * | 2000-05-23 | 2004-09-01 | Ge��˹Ī���˹��˾ | Acid stable membranes for nanofiltration |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102698620A (en) * | 2012-06-12 | 2012-10-03 | 浙江大学 | Method for preparing reverse osmosis composite membrane by taking hyperbranched polymer as monomer |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2009120492A1 (en) | 2009-10-01 |
| EP2259865A1 (en) | 2010-12-15 |
| JP2011522058A (en) | 2011-07-28 |
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