WO2005123750A1 - Metallosiloxane-metallic oxide compound5 oxygen enriching membrane comprising metallosiloxane, and method for preparing the same - Google Patents
Metallosiloxane-metallic oxide compound5 oxygen enriching membrane comprising metallosiloxane, and method for preparing the same Download PDFInfo
- Publication number
- WO2005123750A1 WO2005123750A1 PCT/KR2005/001856 KR2005001856W WO2005123750A1 WO 2005123750 A1 WO2005123750 A1 WO 2005123750A1 KR 2005001856 W KR2005001856 W KR 2005001856W WO 2005123750 A1 WO2005123750 A1 WO 2005123750A1
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- WO
- WIPO (PCT)
- Prior art keywords
- unsubstituted
- halogen
- substituted
- metallosiloxane
- substrituted
- Prior art date
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 79
- 239000001301 oxygen Substances 0.000 title claims abstract description 79
- 239000012528 membrane Substances 0.000 title claims abstract description 77
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 21
- 229940125898 compound 5 Drugs 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 41
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 22
- 229910052736 halogen Inorganic materials 0.000 claims description 21
- 150000002367 halogens Chemical group 0.000 claims description 21
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 18
- 229920000642 polymer Polymers 0.000 claims description 16
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052796 boron Inorganic materials 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000004745 nonwoven fabric Substances 0.000 claims description 14
- 239000002759 woven fabric Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 12
- 229910052732 germanium Inorganic materials 0.000 claims description 12
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 12
- 239000011133 lead Substances 0.000 claims description 12
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 229910052718 tin Inorganic materials 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- 239000004088 foaming agent Substances 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 238000003475 lamination Methods 0.000 claims description 8
- 239000002952 polymeric resin Substances 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 229920003002 synthetic resin Polymers 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000011135 tin Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- -1 ethylene, propylene, methyl Chemical group 0.000 claims description 6
- 238000005187 foaming Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052776 Thorium Inorganic materials 0.000 claims description 5
- 229910052770 Uranium Inorganic materials 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 5
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052785 arsenic Inorganic materials 0.000 claims description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052790 beryllium Inorganic materials 0.000 claims description 5
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 229910052793 cadmium Inorganic materials 0.000 claims description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000011575 calcium Substances 0.000 claims description 5
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052738 indium Inorganic materials 0.000 claims description 5
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 238000010030 laminating Methods 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052753 mercury Inorganic materials 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052758 niobium Inorganic materials 0.000 claims description 5
- 239000010955 niobium Substances 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052762 osmium Inorganic materials 0.000 claims description 5
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- 239000010948 rhodium Substances 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052701 rubidium Inorganic materials 0.000 claims description 5
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052712 strontium Inorganic materials 0.000 claims description 5
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052715 tantalum Inorganic materials 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052714 tellurium Inorganic materials 0.000 claims description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052716 thallium Inorganic materials 0.000 claims description 5
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229940106691 bisphenol a Drugs 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- ICGLPKIVTVWCFT-UHFFFAOYSA-N 4-methylbenzenesulfonohydrazide Chemical compound CC1=CC=C(S(=O)(=O)NN)C=C1 ICGLPKIVTVWCFT-UHFFFAOYSA-N 0.000 claims description 2
- MWRWFPQBGSZWNV-UHFFFAOYSA-N Dinitrosopentamethylenetetramine Chemical compound C1N2CN(N=O)CN1CN(N=O)C2 MWRWFPQBGSZWNV-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000012644 addition polymerization Methods 0.000 claims description 2
- VJRITMATACIYAF-UHFFFAOYSA-N benzenesulfonohydrazide Chemical compound NNS(=O)(=O)C1=CC=CC=C1 VJRITMATACIYAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 claims description 2
- 238000012643 polycondensation polymerization Methods 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- 239000011247 coating layer Substances 0.000 claims 1
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- 230000035699 permeability Effects 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 13
- 239000000839 emulsion Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 239000001913 cellulose Substances 0.000 description 4
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- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XZIIFPSPUDAGJM-UHFFFAOYSA-N 6-chloro-2-n,2-n-diethylpyrimidine-2,4-diamine Chemical compound CCN(CC)C1=NC(N)=CC(Cl)=N1 XZIIFPSPUDAGJM-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
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- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 229940035044 sorbitan monolaurate Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F19/00—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
Definitions
- the present invention relates to an oxygen enriching membrane which selectively increases oxygen content in the air, and a method for preparing the same, and more particularly to an oxygen enriching membrane having superior oxygen permeability and selectivity while maintaining superior mechanical strength, and a method for preparing the same.
- the air we breathe consists of about 20.9% of oxygen and about 78.1 % of nitrogen.
- a membrane that is selectively more permeable to oxygen than nitrogen in the air is called the oxygen enriching membrane.
- Air passing through the oxygen enriching membrane has a relatively higher oxygen content.
- the oxygen enriching membrane can improve fuel efficiency of internal combustion engines of vehicles, contributing to energy saving. Also, it can be widely used in the fields of medicine, oxidation processing, and environmental engineering which do not require high-level oxygen content.
- the oxygen enriching membrane can i be utilized in the fields requiring nitrogen-rich environment, e.g., fermentation processes. Using the oxygen enriching membrane, it is possible to separate gas with a simple apparatus.
- the first commercially successful oxygen enriching membrane was one having improved membrane strength through copolymerization of siloxane and carbonate (see W. J. Ward III, J. Membrane Sci., 1 , 99, 1976).
- research was performed using a graft copolymer of styrene and dimethylsiloxane, introducing an amide into the main chain using tetramethyldisiloxane and aliphatic dicarboxylate, substituting a variety of siloxanes at the para position of polystyrene, and so forth (see Y. Kawakami, J. Polym.
- the present invention provides a metallosiloxane-metallic oxide compound represented by Formula 1 below.
- the invention also provides an oxygen enriching membrane comprising the metallosiloxane-metallic oxide compound, and a metallosiloxane compound represented by Formula 2 below or a mixture thereof.
- the invention further provides a method for preparing a metallosiloxane-metallic oxide compound comprising the steps of treating the metallosiloxane compound represented by Formula 2 with heat and acid or base to dissociate it into the metallosiloxane ion represented by Formula 3 below and adsorbing the metallosiloxane ion on the surface of the metal oxide represented by Formula 1.
- the invention further provides a method for preparing an oxygen enriching membrane comprising the steps of coating the metallosiloxane-metallic oxide compound powder represented by Formula 1 on woven or non-woven fabric and laminating another woven or non-woven fabric on the metallosiloxane-metallic oxide compound layer.
- the invention further provides a method for preparing an oxygen enriching membrane comprising the steps of uniformly distributing the metallosiloxane represented by Formula 2 in a polymerization monomer, polymerizing the polymerization monomer, and coating the resultant polymer on woven or non-woven fabric.
- the invention further provides a method for preparing a membrane comprising the steps of uniformly distributing the metallosiloxane represented by Formula 2 and an air-permeable foaming agent in polymer resin, foaming the air-permeable foaming agent, and processing the polymer resin into a membrane,
- M 1 is a metal selected from the group consisting of aluminum, boron, manganese, chromium, lead, titanium, tin, and germanium
- M 2 0 is an oxide of a metal selected from the group consisting of aluminum, arsenic, gold, boron, barium, beryllium, bismuth, calcium, niobium, cadmium, cerium, cobalt, chromium, cesium, copper, iron, gallium, germanium, mercury, indium, potassium, lanthanum, lithium, magnesium, manganese, molybdenum, iridium, sodium, nickel, osmium, lead, palladium, platinum, rubidium, rhodium, ruthenium, antimony, silicon, tin, strontium, tantalum, tellurium, thorium, titanium, thallium, uranium, vanadium, tungsten, zinc, and zirconium
- each of R 1 , R 2 , R 3 , and R 4 is hydrogen, halogen, unsubstituted or substrituted CrC 6 alkyl, unsubstituted or substrituted C 2 -C 6 alkenyl, or unsubstituted or substrituted phenyl, wherein the substituted C- ⁇ -C-6 alkyl, C 2 -C6 alkenyl, and phenyl are substituted by at least one substituent selected from the group consisting of R 6 Si R 6 halogen and R 7 where each of R 5 , R 6 , and R 7 is hydrogen, halogen, unsubstituted or halogen-substituted C ⁇ -C 6 alkyl, unsubstituted or halogen-substituted C 2 -C 6 alkenyl, or unsubstituted or halogen-substituted phenyl.
- the polymerization monomer used in preparing the oxygen enriching membrane of the invention is at least one addition polymerization monomer selected from the group consisting of ethylene, propylene, methyl methacrylate, and styrene, or at least one condensation polymerization monomer selected from the group consisting of terephthalate/ethylene glycol, bisphenol-A/diphenyl carbonate, phenol/aldehyde, and urea/aldehyde.
- the air-permeable foaming agent used in preparing the oxygen enriching membrane of the invention is at least one selected from the group consisting of azobicarbonamide, p-toluenesulfonylhydrazide, benzenesulfonylhydrazide, and dinitrosopentamethylenetetramine.
- FIG. 1 is a schematic view of metallosiloxane compounds adhered on the surface of metal oxide particles.
- FIG. 2 is a schematic view of the pendant model showing motion of the metallosiloxane unit caused by relative pressure difference across the membrane.
- FIG. 3 is a schematic view of an apparatus for testing oxygen enriching performance of the oxygen enriching membrane according to an embodiment of the present invention. ⁇ Symbols used in the drawings> 1 : oxygen enriching membrane 2: pressure gauge 3: flow meter
- the metallosiloxane represented by Formula 2 can be prepared from any compound having a siloxyl group. Because the distance from the central metal to oxygen atoms is longer than usual covalent bonds, the binding force between them is relatively weak. Accordingly, the bond between the metal and oxygen is relatively easily dissociated by heat, and an acid or base, to give the metallosiloxane ion repressed by Formula 3 according to Scheme 1 below. [Scheme 1]
- the metallic oxide (M 2 0) is present in the form of particles.
- the process of Scheme 2 occurs at the surface of a metallic oxide (M 2 0) particle and the resultant metallosiloxane-metallic oxide compound has a structure shown in FIG. 1. Since the metallosiloxane-metallic oxide compound of the invention is present in the form of particles and is used in a powder form, a means to fix the particles or powders is required. In the present invention, woven or non-woven fabric may be used to fix the metallosiloxane-metallic oxide compound.
- the metallosiloxane-metallic oxide compound powder is coated on woven or non-woven fabric to a predetermined thickness and another woven or non-woven fabric is laminated thereon.
- a lamination membrane in which metallosiloxane-metallic oxide compound powder layer(s) is formed between the woven or non-woven fabric is obtained.
- the lamination membrane itself can be used as an oxygen enriching membrane. Also, it can be laminated along with other lamination membranes to be described later as oxygen enriching membranes.
- separation of a gaseous mixture through a porous membrane can be explained by the following four principles. First, Knudsen diffusion occurs when the pore size is smaller than the mean free path of a specific gas molecule. Second, surface diffusion occurs by interaction with the pore surface. Third, capillary diffusion occurs by condensation of a specific liquid.
- FIG. 2 is a schematic diagram for illustrating the pendant model. According to the pendant model, a plurality of metallosiloxane units protruding inside the pore move freely like cilia.
- the metallosiloxane units align almost vertically to the direction of the pore, as seen in FIG. 2 (a). If the pressure is relatively high, the metallosiloxane units align almost parallel to the direction of the pore, as seen in FIG. 2 (b).
- the oxygen enriching membrane of the present invention not only offers superior oxygen selectivity and permeability even with a low pressure difference, but also has good strength and is not easily torn thanks to the lamination membrane structure. Also, since it is prepared by fixing the metallosiloxai e-metallic oxide compound in the powder form on woven or non-woven fabric and laminating them repeatedly, membranes with uniform pore size can be produced in large amounts.
- the metallosiloxane unit moves freely, so that superior permeability and selectivity are obtained even at low pressure. Since the compound having 4 to 1000 siloxane units, the m and n values in Formula 1 , is suspended and fixed to the metallic oxide (M 2 0), it offers good oxygen enriching performance even with a low pressure difference by the pendant model. Besides laminating the metallosiloxane-metallic oxide compound powder, a method of dissolving the metallosiloxane compound in a polymerization monomer and polymerizing the monomer to obtain a membrane is practicable. The metallosiloxane represented by Formula 2 dissolves well in most monomers of matrix polymer resins.
- the metallosiloxane After dissolving the metallosiloxane in a monomer of a matrix polymer resin to an adequate concentration, it is stirred sufficiently and the monomer is polymerized. Then, a polymer is obtained in which the metallosiloxane is uniformly distributed in the matrix. The resultant matrix polymer is coated on woven or non-woven fabric to obtain a lamination membrane. The resultant lamination membrane can act as an oxygen enriching membrane. Also, it is possible to prepare a membrane using an air-permeable foaming agent. That is, the metallosiloxane is added to a polymer which has not yet solidified just after polymerization. The polymer is stirred so ⁇ that the metallosiloxane is dispersed uniformly.
- Sample A Preparation of aluminosiloxane-metallic oxide compound 2.7 kg of silica (Si0 2 ) sieved to 80 mesh was put in a kneader. 300 g of aluminosiloxane (150 g of Sc.101 and Sc.011 each, Silochem LTD.) was mixed with the silica. Kneading was performed for 60 minutes while heating to 200-250 ° C and rotating at 60-120 rpm, to obtain a metallosiloxane-silica compound.
- Sample B-1 Preparation of aluminosiloxane emulsion for fabric coating 100 mL of MMA (methyl methacrylate), 100 mL of EMA (ethyl methacrylate), and 20 g of aluminosiloxane were put in a beaker. The mixture was stirred at room temperature to completely dissolve it (a monomer solution was obtained). A mixture of 1000 mL of distilled water, 10 g of sorbitan monolaurate polyethylene oxide (Tween 20), a surfactant, and 0.1 g of APS (ammonium persulfate), an initiator, was added to the reactor. The mixture was heated to 40 ° C while stirring (a surfactant solution was obtained). The monomer solution was added to the surfactant solution in a dropwise fashion. Reaction was performed at 80 °C for 4 hours to obtain an aluminosiloxane emulsion for fabric coating.
- MMA methyl methacrylate
- EMA ethyl
- Sample B-2 Preparation of aluminosiloxane emulsion for fabric foam coating 0.3 wt% per 100 wt% of the polymer of a foaming agent was added to the aluminosiloxane emulsion (sample B-1 ), and dispersed uniformly.
- Sample B-3 Preparation of polymer foaming master batch comprising aluminosiloxane 200 g of aluminosiloxane and 0.3 wt% per 100 wt% of the polymer of an air-permeable foaming agent were mixed with 800 g of PP to prepare a master batch.
- Preparation Example 1 Aluminosiloxane-metallic oxide compound coated fabric Fabric with a thickness of 1 mm was cut to a size of 30 cm * 30 cm.
- the aluminosiloxane-metallic oxide compound powder (sample A) was put on the fabric and the vibrator was turned on, so that the powder penetrated the fabric.
- a 1 :1 mixture of those having a particle size of 60 mesh and 120 mesh or one having a particle size of 80 mesh was used.
- Preparation Example 2 Aluminosiloxane emulsion coated fabric Fabric with a thickness of 1 mm was cut to a size of 30 cm x 30 cm.
- the fabric was immersed in the emulsion of sample B-1 , dried in the air, and heated in an oven at 180 °C for 30 minutes for crosslinking.
- Preparation Example 3 Aluminosiloxane emulsion foamed fabric Fabric with a thickness of 1 mm was cut to a size of 30 cm * 30 cm.
- the fabric was immersed in the emulsion of sample B-2, dried in the air, and heated to 165 °C for foaming.
- Preparation Example 4 Preparation of polymer foam membrane comprising aluminosiloxane The master batch of sample B-3 was put in a mold and heated to the foaming temperature to obtain a polymer foam membrane comprising aluminosiloxane.
- Preparation Example 5 Napped fabric comprising aluminosiloxane Fabric comprising aluminosiloxane was napped for use as a support of the masks used in the examples.
- An oxygen enriching membrane prepared by laminating a metallosiloxane-metallic oxide compound and dissolving metallosiloxane in a monomer or foaming metallosiloxane in a polymer resin by adding an air-permeable foaming agent has superior oxygen permeability and selectivity, and good strength. In addition, mass production becomes possible and high quality is attained.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to an oxygen enriching membrane comprising a metallosiloxane-metallic oxide compound, a metallosiloxane compound, or a mixture thereof, and a method for preparing the same. The oxygen enriching membrane of the present invention has superior oxygen permeability and selectivity and good strength, and ensures mass production and high quality.
Description
METALLOSILOXANE-METALLIC OXIDE COMPOUND, OXYGEN ENRICHING MEMBRANE COMPRISING METALLOSILOXANE, AND METHOD FOR PREPARING THE SAME
BACKGROUND OF THE INVENTION
(a) Field of the Invention The present invention relates to an oxygen enriching membrane which selectively increases oxygen content in the air, and a method for preparing the same, and more particularly to an oxygen enriching membrane having superior oxygen permeability and selectivity while maintaining superior mechanical strength, and a method for preparing the same.
(b) Description of the Related Art The air we breathe consists of about 20.9% of oxygen and about 78.1 % of nitrogen. A membrane that is selectively more permeable to oxygen than nitrogen in the air is called the oxygen enriching membrane. Air passing through the oxygen enriching membrane has a relatively higher oxygen content. Accordingly, the oxygen enriching membrane can improve fuel efficiency of internal combustion engines of vehicles, contributing to energy saving. Also, it can be widely used in the fields of medicine, oxidation processing, and environmental engineering which do not require high-level oxygen content. Also, since enriched nitrogen is simultaneously obtained accompanied with oxygen enrichment, the oxygen enriching membrane can i
be utilized in the fields requiring nitrogen-rich environment, e.g., fermentation processes. Using the oxygen enriching membrane, it is possible to separate gas with a simple apparatus. Thus, it is not limited in place or mobility. Since the 1980s, gas separation using membranes has undergone a lot of developments. Although membrane separation is inadequate for obtaining massive oxygen at a high concentration, compared with the freezing method it has drawn a lot of attention recently since it consumes less energy during the separation process. Since Kammermeyer first used silicone rubber for separation of gas in 1957 (K. Kammermeyer, Ind. Eng. Chem., 49, 1685, 1957), methyl-based polysiloxanes have been known to be superior to any other polymers in oxygen permeation properties until the advent of polytrimethylsilylpropyne (R. L. Riley et al., USP 4,243,701 ). However, if the membrane was made thin to improve oxygen permeability, it was torn easily. There was a need to solve this problem. The first commercially successful oxygen enriching membrane was one having improved membrane strength through copolymerization of siloxane and carbonate (see W. J. Ward III, J. Membrane Sci., 1 , 99, 1976). In this regard, research was performed using a graft copolymer of styrene and dimethylsiloxane, introducing an amide into the main chain using tetramethyldisiloxane and aliphatic dicarboxylate, substituting a variety of siloxanes at the para position of polystyrene, and so forth (see Y. Kawakami, J. Polym. Sci., Part A, 25, 1591 , 1987).
Fluorine-substituted derivatives were also used as oxygen enriching membranes. This was because the higher the content of fluorine atoms, the higher the solubility of gaseous oxygen. Yoshio et al. synthesized a poly(phenylacetylene) derivative having a trifluoromethyl in the benzene ring to prepare an oxygen enriching membrane having an oxygen selectivity over nitrogen of 2.1 (see Y. Hayakawa, M. Nishida, T. Aoki, and H. Muramatsu, J. Polym. Sci., Part A, 30, 873, 1992). Paul et al. synthesized tetra-halogenated polycarbonates in which four hydrogen atoms of bisphenol A were substituted with halogen atoms, such as chlorine and bromine, to prepare oxygen enriching membranes having an oxygen selectivity over nitrogen of 6.37 and 7.47 (see D. R. Paul, J. Membrane Sci., 34, 185, 1987). However, in spite of these efforts, oxygen permeability tends to decrease as oxygen selectivity over nitrogen increases. Oxygen permeability can be improved by increasing a pressure difference across the membrane, but then a lot of energy is required to separate the oxygen. Korean Patent Publication No. 2001-0018930 disclosed a cellulose-based oxygen enriching membrane which is not torn easily, sacrificing neither oxygen selectivity nor oxygen permeability. However, it is limited in oxygen selectivity and permeability because of the structural limit of cellulose. In addition, it is inadequate for mass production, since an activation process is necessary to loosen the cellulose structure. SUMMARY OF THE INVENTION It is an object of the present invention to provide a
metallosiloxane-metallic oxide compound for improving oxygen permeability and selectivity of an oxygen enriching membrane. It is another object of the invention to provide an oxygen enriching membrane having superior oxygen permeability and selectivity, and that is not torn easily and has good strength. It is still another object of the invention to provide a method for preparing the metallosiloxane-metallic oxide compound. It is further another object of the invention to provide a method for preparing the oxygen enriching membrane. To attain the objects, the present invention provides a metallosiloxane-metallic oxide compound represented by Formula 1 below. The invention also provides an oxygen enriching membrane comprising the metallosiloxane-metallic oxide compound, and a metallosiloxane compound represented by Formula 2 below or a mixture thereof. The invention further provides a method for preparing a metallosiloxane-metallic oxide compound comprising the steps of treating the metallosiloxane compound represented by Formula 2 with heat and acid or base to dissociate it into the metallosiloxane ion represented by Formula 3 below and adsorbing the metallosiloxane ion on the surface of the metal oxide represented by Formula 1. The invention further provides a method for preparing an oxygen enriching membrane comprising the steps of coating the metallosiloxane-metallic oxide compound powder represented by Formula 1
on woven or non-woven fabric and laminating another woven or non-woven fabric on the metallosiloxane-metallic oxide compound layer. The invention further provides a method for preparing an oxygen enriching membrane comprising the steps of uniformly distributing the metallosiloxane represented by Formula 2 in a polymerization monomer, polymerizing the polymerization monomer, and coating the resultant polymer on woven or non-woven fabric. The invention further provides a method for preparing a membrane comprising the steps of uniformly distributing the metallosiloxane represented by Formula 2 and an air-permeable foaming agent in polymer resin, foaming the air-permeable foaming agent, and processing the polymer resin into a membrane,
each of R1, R2, R3, and R4 is hydrogen, halogen,
unsubstituted or substrituted CrC6 alkyl, unsubstituted or substrituted C2-C6 alkenyl, or unsubstituted or substrituted phenyl, wherein the substituted C-ι-C-6 alkyl, C2-C6 alkenyl, and phenyl are substituted by at least one substituent selected from the group consisting of R6 Si R6 halogen and R7 where each of R5, R6, and R7 is hydrogen, halogen, unsubstituted or halogen-substituted Cι-C6 alkyl, unsubstituted or halogen-substituted C2-C6 alkenyl, or unsubstituted or halogen-substituted phenyl.
The definition of the substituents applies to all the formulas and schemes in this description. Preferably, M1 is aluminum or boron, because they form covalent and coordinate bonds better than other metal elements. Preferably, the polymerization monomer used in preparing the oxygen enriching membrane of the invention is at least one addition polymerization monomer selected from the group consisting of ethylene, propylene, methyl methacrylate, and styrene, or at least one condensation polymerization monomer selected from the group consisting of terephthalate/ethylene glycol, bisphenol-A/diphenyl carbonate, phenol/aldehyde, and urea/aldehyde. And, preferably, the air-permeable foaming agent used in preparing the oxygen enriching membrane of the invention is at least one selected from the group consisting of azobicarbonamide, p-toluenesulfonylhydrazide, benzenesulfonylhydrazide, and dinitrosopentamethylenetetramine. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view of metallosiloxane compounds adhered on the surface of metal oxide particles. FIG. 2 is a schematic view of the pendant model showing motion of the metallosiloxane unit caused by relative pressure difference across the membrane. FIG. 3 is a schematic view of an apparatus for testing oxygen enriching performance of the oxygen enriching membrane according to an embodiment of the present invention.
<Symbols used in the drawings> 1 : oxygen enriching membrane 2: pressure gauge 3: flow meter
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereunder is given a more detailed description of the present invention. The metallosiloxane represented by Formula 2 can be prepared from any compound having a siloxyl group. Because the distance from the central metal to oxygen atoms is longer than usual covalent bonds, the binding force between them is relatively weak. Accordingly, the bond between the metal and oxygen is relatively easily dissociated by heat, and an acid or base, to give the metallosiloxane ion repressed by Formula 3 according to Scheme 1 below. [Scheme 1]
The metallosiloxane ion readily reacts with a metal oxide particle to give the metallosiloxane-metallic oxide compound represented by Formula 1 according to Scheme 2 below. [Scheme 2]
The metallic oxide (M20) is present in the form of particles. The process of Scheme 2 occurs at the surface of a metallic oxide (M20) particle and the resultant metallosiloxane-metallic oxide compound has a structure shown in FIG. 1. Since the metallosiloxane-metallic oxide compound of the invention is present in the form of particles and is used in a powder form, a means to fix the particles or powders is required. In the present invention, woven or non-woven fabric may be used to fix the metallosiloxane-metallic oxide compound. The metallosiloxane-metallic oxide compound powder is coated on woven or non-woven fabric to a predetermined thickness and another woven or non-woven fabric is laminated thereon. If this process is repeated at least once, a lamination membrane in which metallosiloxane-metallic oxide compound powder layer(s) is formed between the woven or non-woven fabric is obtained. The lamination membrane itself can be used as an oxygen enriching membrane. Also, it can be laminated along with other lamination membranes to be described later as oxygen enriching membranes. In general, separation of a gaseous mixture through a porous membrane can be explained by the following four principles. First, Knudsen diffusion occurs when the pore size is smaller than
the mean free path of a specific gas molecule. Second, surface diffusion occurs by interaction with the pore surface. Third, capillary diffusion occurs by condensation of a specific liquid. Fourth, in a molecular sieve, the pore acts as a sieve that passes only the molecules smaller than the pore size. In non-porous membranes, it can be explained by dissolution of gas at the membrane surface and penetration by diffusion. Here, solubility of oxygen to the membrane and degree of diffusion are important factors. Adding to these, the pendant model was proposed to explain the peculiar characteristics of the oxygen enriching membrane (Jaejin Hong, Research on gas separation of siloxylcellulose membrane, Dankook University, Thesis for doctorate, 1998). FIG. 2 is a schematic diagram for illustrating the pendant model. According to the pendant model, a plurality of metallosiloxane units protruding inside the pore move freely like cilia. When the pressure applied to the oxygen enriching membrane is relatively low, the metallosiloxane units align almost vertically to the direction of the pore, as seen in FIG. 2 (a). If the pressure is relatively high, the metallosiloxane units align almost parallel to the direction of the pore, as seen in FIG. 2 (b). The oxygen enriching membrane of the present invention not only offers superior oxygen selectivity and permeability even with a low pressure difference, but also has good strength and is not easily torn thanks to the lamination membrane structure. Also, since it is prepared by fixing the metallosiloxai e-metallic oxide compound in the powder form on woven or non-woven fabric and laminating them repeatedly, membranes with uniform
pore size can be produced in large amounts. Also, differently from cellulose, the metallosiloxane unit moves freely, so that superior permeability and selectivity are obtained even at low pressure. Since the compound having 4 to 1000 siloxane units, the m and n values in Formula 1 , is suspended and fixed to the metallic oxide (M20), it offers good oxygen enriching performance even with a low pressure difference by the pendant model. Besides laminating the metallosiloxane-metallic oxide compound powder, a method of dissolving the metallosiloxane compound in a polymerization monomer and polymerizing the monomer to obtain a membrane is practicable. The metallosiloxane represented by Formula 2 dissolves well in most monomers of matrix polymer resins. After dissolving the metallosiloxane in a monomer of a matrix polymer resin to an adequate concentration, it is stirred sufficiently and the monomer is polymerized. Then, a polymer is obtained in which the metallosiloxane is uniformly distributed in the matrix. The resultant matrix polymer is coated on woven or non-woven fabric to obtain a lamination membrane. The resultant lamination membrane can act as an oxygen enriching membrane. Also, it is possible to prepare a membrane using an air-permeable foaming agent. That is, the metallosiloxane is added to a polymer which has not yet solidified just after polymerization. The polymer is stirred so π
that the metallosiloxane is dispersed uniformly. Then, an air-permeable foaming agent is added to obtain a polymer foam having numerous micropores. If the polymer foam is processed into a membrane, it can act as an oxygen enriching membrane. Hereinafter, the present invention is described in further detail through examples. However, the following examples are only for the understanding of the invention and the invention is not limited to or by the following examples.
EXAMPLES
Sample A: Preparation of aluminosiloxane-metallic oxide compound 2.7 kg of silica (Si02) sieved to 80 mesh was put in a kneader. 300 g of aluminosiloxane (150 g of Sc.101 and Sc.011 each, Silochem LTD.) was mixed with the silica. Kneading was performed for 60 minutes while heating to 200-250 °C and rotating at 60-120 rpm, to obtain a metallosiloxane-silica compound.
Sample B-1 : Preparation of aluminosiloxane emulsion for fabric coating 100 mL of MMA (methyl methacrylate), 100 mL of EMA (ethyl methacrylate), and 20 g of aluminosiloxane were put in a beaker. The mixture was stirred at room temperature to completely dissolve it (a monomer solution was obtained). A mixture of 1000 mL of distilled water, 10 g of sorbitan monolaurate polyethylene oxide (Tween 20), a surfactant,
and 0.1 g of APS (ammonium persulfate), an initiator, was added to the reactor. The mixture was heated to 40 °C while stirring (a surfactant solution was obtained). The monomer solution was added to the surfactant solution in a dropwise fashion. Reaction was performed at 80 °C for 4 hours to obtain an aluminosiloxane emulsion for fabric coating.
Sample B-2: Preparation of aluminosiloxane emulsion for fabric foam coating 0.3 wt% per 100 wt% of the polymer of a foaming agent was added to the aluminosiloxane emulsion (sample B-1 ), and dispersed uniformly.
Sample B-3: Preparation of polymer foaming master batch comprising aluminosiloxane 200 g of aluminosiloxane and 0.3 wt% per 100 wt% of the polymer of an air-permeable foaming agent were mixed with 800 g of PP to prepare a master batch.
Preparation Example 1 : Aluminosiloxane-metallic oxide compound coated fabric Fabric with a thickness of 1 mm was cut to a size of 30 cm * 30 cm.
After placing the fabric on a vibrator, the aluminosiloxane-metallic oxide compound powder (sample A) was put on the fabric and the vibrator was turned on, so that the powder penetrated the fabric. For the aluminosiloxane metallic oxide powder, a 1 :1 mixture of those having a
particle size of 60 mesh and 120 mesh or one having a particle size of 80 mesh was used.
Preparation Example 2: Aluminosiloxane emulsion coated fabric Fabric with a thickness of 1 mm was cut to a size of 30 cm x 30 cm.
The fabric was immersed in the emulsion of sample B-1 , dried in the air, and heated in an oven at 180 °C for 30 minutes for crosslinking.
Preparation Example 3: Aluminosiloxane emulsion foamed fabric Fabric with a thickness of 1 mm was cut to a size of 30 cm * 30 cm.
The fabric was immersed in the emulsion of sample B-2, dried in the air, and heated to 165 °C for foaming.
Preparation Example 4: Preparation of polymer foam membrane comprising aluminosiloxane The master batch of sample B-3 was put in a mold and heated to the foaming temperature to obtain a polymer foam membrane comprising aluminosiloxane.
Preparation Example 5: Napped fabric comprising aluminosiloxane Fabric comprising aluminosiloxane was napped for use as a support of the masks used in the examples.
The fabrics and foam membranes of Preparation Example 1 to
Preparation Example 5 were laminated as in Table 1 below to prepare oxygen enriching membranes of Example 1 to Example 9. For each oxygen enriching membrane, oxygen enriching performance was measured as follows. The results as compared with the oxygen concentration in air (Comparative Example 1 ) are given in Table 1. A 1 :4 (in molar ratio) mixture gas of oxygen and nitrogen was used for oxygen enriching performance measurement. The test apparatus is shown in FIG. 3. Oxygen concentration was determined by gas chromatography. The analysis conditions were as follows. Column: 3" * 1/8" Filler: 6D/6D molecular sieve 5 A Oven temperature: 60 °C Detector: TCD Carrier gas: Helium (20 mL/min) [Table 1]
Claims
1. A metallosiloxane-metallic oxide compound represented by Formula 1 below:
each of R1, R2, R3, and R4 is hydrogen, halogen, 
unsubstituted or substrituted C-i-C6 alkyl, unsubstituted or substrituted C2-C6 alkenyl, or unsubstituted or substrituted phenyl, wherein the substituted Cι-C6 alkyl, C2-C6 alkenyl, and phenyl are substituted by at least one substituent selected from the group consisting of
-Si R° halogen and R7 where each of R5, R6, and R7 is hydrogen, halogen, unsubstituted or halogen-substituted C-I-CΘ alkyl, unsubstituted or halogen-substituted C2-C6 alkenyl, or unsubstituted or halogen-substituted phenyl.
2. The metallosiloxane-metallic oxide compound of claim 1 , wherein M1 is aluminum or boron.
3. An oxygen enriching membrane comprising a metallosiloxane-metallic oxide compound represented by Formula 1 below, a metallosiloxane compound represented by Formula 2 below, or a mixture thereof:
each of R1, R2, R3, and R4 is hydrogen, halogen, 
unsubstituted or substrituted C1-C-6 alkyl, unsubstituted or substrituted C2-C6 alkenyl, or unsubstituted or substrituted phenyl, wherein the substituted Cι-C6 alkyl, C2-C6 alkenyl, and phenyl are substituted by at least one substituent selected from the group consisting of R5 SI RB halogen and R7 where each of R5, R6, and R7 is hydrogen, halogen, unsubstituted or halogen-substituted CrC6 alkyl, unsubstituted or halogen-substituted C2-Cβ alkenyl, or unsubstituted or halogen-substituted phenyl.
4. The oxygen enriching membrane of claim 3, wherein M1 is aluminum or boron.
5. The oxygen enriching membrane of claim 3, which is a lamination membrane comprising the metallosiloxane-metallic oxide compound, the metallosiloxane compound, or the mixture thereof.
6. The oxygen enriching membrane of claim 5, which comprises a powder layer comprising the metallosiloxane-metallic oxide compound represented by Formula 1 between at least two sheets of woven or non-woven fabric.
7. The oxygen enriching membrane of claim 5, wherein a matrix polymer in which the metallosiloxane is dispersed is coated on woven or non-woven fabric.
8. The oxygen enriching membrane of claim 5, which is a foamed membrane having micropores wherein the metallosiloxane compound is dispersed in a matrix polymer.
9. A method for preparing a metallosiloxane-metallic oxide compound comprising the steps of: treating the metallosiloxane compound represented by Formula 2 below with heat and an acid or base to dissociate it into the metallosiloxane ions represented by Formula 3 below; and adsorbing the metallosiloxane ions on the surface of the metal oxide particle represented by Formula 1 below:
each of R1, R2, R3, and R4 is hydrogen, halogen, 
unsubstituted or substrituted C1-C-6 alkyl, unsubstituted or substrituted C2-C6 alkenyl, or unsubstituted or substrituted phenyl, wherein the substituted C-i-Cβ alkyl, C2-C6 alkenyl, and phenyl are substituted by at least one substituent selected from the group consisting of
halogen and 
where each of R5, R6, and R7 is hydrogen, halogen, unsubstituted or halogen-substituted C-i-Ce alkyl, unsubstituted or halogen-substituted C2-Cδ alkenyl, or unsubstituted or halogen-substituted phenyl.
10. A method for preparing an oxygen enriching membrane comprising the steps of: coating the metallosiloxane-metallic oxide compound powder represented by Formula 1 below on woven or non-woven fabric; and laminating another woven or non-woven fabric on the metallosiloxane-metallic oxide compound powder coating layer:
halogen and 
where each of R5, R6, and R7 is hydrogen, halogen, unsubstituted or halogen-substituted Cι-C6 alkyl, unsubstituted or halogen-substituted C2-C6 alkenyl, or unsubstituted or halogen-substituted phenyl.
11. A method for preparing an oxygen enriching membrane comprising the steps of uniformly distributing the metallosiloxane represented by Formula 2 below in a polymerization monomer; polymerizing the polymerization monomer; and coating the resultant polymer on woven or non-woven fabric:
each of R1, R2, R3, and R4 is hydrogen, halogen, 
unsubstituted or substrituted Ci-Cβ alkyl, unsubstituted or substrituted C2-C6 alkenyl, or unsubstituted or substrituted phenyl, wherein the substituted Cι-C6 alkyl, C2-C6 alkenyl, and phenyl are substituted by at least one substituent selected from the group consisting of Rs Si R6 halogen and R7 where each of R5, Rδ, and R7 is hydrogen, halogen, unsubstituted or halogen-substituted Ci-Cβ alkyl, unsubstituted or halogen-substituted C2-Cβ alkenyl, or unsubstituted or halogen-substituted phenyl.
12. The method of claim 11 , wherein the polymerization monomer is at least one addition polymerization monomer selected from the group consisting of ethylene, propylene, methyl methacrylate, and styrene, or at least one condensation polymerization monomer selected from the group consisting of terephthalate/ethylene glycol, bisphenol-A/diphenyl carbonate, phenol/aldehyde, and urea/aldehyde.
13. A method for preparing a membrane comprising the steps of: uniformly distributing the metallosiloxane represented by Formula 2 below and an air-permeable foaming agent in polymer resin; foaming the polymer resin; and processing the polymer resin into a membrane,
halogen and 
where each of R5, R6, and R7 is hydrogen, halogen, unsubstituted or halogen-substituted CrC6 alkyl, unsubstituted or halogen-substituted C2-C6 alkenyl, or unsubstituted or halogen-substituted phenyl.
14. The method of claim 13, wherein the air-permeable foaming agent is at least one selected from the group consisting of azobicarbonamide, p-toluenesulfonylhydrazide, benzenesulfonylhydrazide, and dinitrosopentamethylenetetramine.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040044444A KR20050119375A (en) | 2004-06-16 | 2004-06-16 | Oxygen enriching membrane made of metallosiloxane and process preparing the same |
| KR10-2004-0044444 | 2004-06-16 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2005123750A1 true WO2005123750A1 (en) | 2005-12-29 |
Family
ID=35509617
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2005/001856 WO2005123750A1 (en) | 2004-06-16 | 2005-06-16 | Metallosiloxane-metallic oxide compound5 oxygen enriching membrane comprising metallosiloxane, and method for preparing the same |
Country Status (3)
| Country | Link |
|---|---|
| KR (1) | KR20050119375A (en) |
| TW (1) | TW200617016A (en) |
| WO (1) | WO2005123750A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1914267A1 (en) * | 2006-10-17 | 2008-04-23 | J & J Chemical Co. | Modified blowing agent surface-treated with metallic siloxylated compound and polymer resin composition including the same |
| JP2008101210A (en) * | 2006-10-17 | 2008-05-01 | J & J Chemical Co Ltd | Method for modifying foaming agent |
| US8512870B2 (en) | 2009-12-30 | 2013-08-20 | Cheil Industries, Inc. | Transparent resin for encapsulation material and electronic device including the same |
| US8552251B2 (en) | 2010-10-08 | 2013-10-08 | Kimberly-Clark Worldwide, Inc. | Article with health-benefit agent delivery system |
| US9238348B2 (en) | 2010-10-08 | 2016-01-19 | Kimberly-Clark Worldwide, Inc. | Method of manufacture of article for delivering health-benefit agent |
| CN113244964A (en) * | 2021-06-03 | 2021-08-13 | 陕西延长石油（集团）有限责任公司 | Metal complex catalyst and synthesis process of diphenyl carbonate |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113912880A (en) * | 2021-08-23 | 2022-01-11 | 四川新达粘胶科技有限公司 | Oxygen-enriched film and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS61291018A (en) * | 1985-06-17 | 1986-12-20 | Teijin Ltd | Gas permeable laminated body |
| KR20010018930A (en) * | 1999-08-24 | 2001-03-15 | 한정련 | Novel oxygen enriching membrane |
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2004
- 2004-06-16 KR KR1020040044444A patent/KR20050119375A/en not_active Application Discontinuation
-
2005
- 2005-06-16 WO PCT/KR2005/001856 patent/WO2005123750A1/en active Application Filing
- 2005-06-16 TW TW094120070A patent/TW200617016A/en unknown
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS61291018A (en) * | 1985-06-17 | 1986-12-20 | Teijin Ltd | Gas permeable laminated body |
| KR20010018930A (en) * | 1999-08-24 | 2001-03-15 | 한정련 | Novel oxygen enriching membrane |
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| Title |
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| LAI J.Y. ET AL: "TPX/Siloxane Blend Membrane for Oxygen", JOURNAL OF APPLIED POLYMER SCIENCE, vol. 34, no. 2, 1987, pages 559 - 569 * |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1914267A1 (en) * | 2006-10-17 | 2008-04-23 | J & J Chemical Co. | Modified blowing agent surface-treated with metallic siloxylated compound and polymer resin composition including the same |
| JP2008101210A (en) * | 2006-10-17 | 2008-05-01 | J & J Chemical Co Ltd | Method for modifying foaming agent |
| EP1921107A2 (en) * | 2006-10-17 | 2008-05-14 | J & J Chemical Co. | Method of modifying blowing agent |
| EP1921107A3 (en) * | 2006-10-17 | 2008-12-24 | J & J Chemical Co. | Method of modifying blowing agent |
| US7939573B2 (en) | 2006-10-17 | 2011-05-10 | J & J Chemical Co. | Modified blowing agent surface-treated with metallic siloxylated compound and polymer resin composition including the same |
| US8512870B2 (en) | 2009-12-30 | 2013-08-20 | Cheil Industries, Inc. | Transparent resin for encapsulation material and electronic device including the same |
| US8552251B2 (en) | 2010-10-08 | 2013-10-08 | Kimberly-Clark Worldwide, Inc. | Article with health-benefit agent delivery system |
| US9238348B2 (en) | 2010-10-08 | 2016-01-19 | Kimberly-Clark Worldwide, Inc. | Method of manufacture of article for delivering health-benefit agent |
| CN113244964A (en) * | 2021-06-03 | 2021-08-13 | 陕西延长石油（集团）有限责任公司 | Metal complex catalyst and synthesis process of diphenyl carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200617016A (en) | 2006-06-01 |
| KR20050119375A (en) | 2005-12-21 |
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