WO2002076991A1 - Materiaux hybrides organiques-inorganiques, mesoporeux, pour separer les gaz - Google Patents
Materiaux hybrides organiques-inorganiques, mesoporeux, pour separer les gaz Download PDFInfo
- Publication number
- WO2002076991A1 WO2002076991A1 PCT/FR2002/000986 FR0200986W WO02076991A1 WO 2002076991 A1 WO2002076991 A1 WO 2002076991A1 FR 0200986 W FR0200986 W FR 0200986W WO 02076991 A1 WO02076991 A1 WO 02076991A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- diamine
- equal
- tetraazacyclotetradecane
- formula
- porphyrin
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 30
- 239000007789 gas Substances 0.000 title claims abstract description 18
- -1 phosphino group Chemical group 0.000 claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 25
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 claims abstract description 4
- 125000000732 arylene group Chemical group 0.000 claims abstract description 4
- 239000000460 chlorine Substances 0.000 claims abstract description 4
- 230000007062 hydrolysis Effects 0.000 claims abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 4
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 4
- 125000002524 organometallic group Chemical group 0.000 claims abstract description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 3
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 3
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 3
- 125000004429 atom Chemical group 0.000 claims abstract 2
- 150000001768 cations Chemical class 0.000 claims description 18
- MDAXKAUIABOHTD-UHFFFAOYSA-N 1,4,8,11-tetraazacyclotetradecane Chemical compound C1CNCCNCCCNCCNC1 MDAXKAUIABOHTD-UHFFFAOYSA-N 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 150000003254 radicals Chemical class 0.000 claims description 15
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 7
- 238000004873 anchoring Methods 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052770 Uranium Inorganic materials 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 238000010668 complexation reaction Methods 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 229920000768 polyamine Polymers 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 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 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 150000004033 porphyrin derivatives Chemical class 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- UODZHRGDSPLRMD-UHFFFAOYSA-N sym-homospermidine Chemical compound NCCCCNCCCCN UODZHRGDSPLRMD-UHFFFAOYSA-N 0.000 claims description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052753 mercury Inorganic materials 0.000 claims description 4
- UNTMDEHZQNHMOF-UHFFFAOYSA-N n'-[2-(4-aminobutylamino)ethyl]butane-1,4-diamine Chemical compound NCCCCNCCNCCCCN UNTMDEHZQNHMOF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- RRBYUSWBLVXTQN-UHFFFAOYSA-N tricyclene Chemical compound C12CC3CC2C1(C)C3(C)C RRBYUSWBLVXTQN-UHFFFAOYSA-N 0.000 claims description 4
- RRBYUSWBLVXTQN-VZCHMASFSA-N tricyclene Natural products C([C@@H]12)C3C[C@H]1C2(C)C3(C)C RRBYUSWBLVXTQN-VZCHMASFSA-N 0.000 claims description 4
- BDNAQHKHTBURFY-UHFFFAOYSA-N 1,3,7,11,15-pentazacyclooctadecane Chemical compound C1CNCCCNCCCNCNCCCNC1 BDNAQHKHTBURFY-UHFFFAOYSA-N 0.000 claims description 3
- RVJABZUDCPZPPM-UHFFFAOYSA-N 1,4,7,10,13,16-hexazacyclooctadecane Chemical compound C1CNCCNCCNCCNCCNCCN1 RVJABZUDCPZPPM-UHFFFAOYSA-N 0.000 claims description 3
- YUIHIYHUJNXSBM-UHFFFAOYSA-N 1,4,7,10,13-pentaethyl-1,4,7,10,13,16-hexazacyclooctadecane Chemical compound CCN1CCNCCN(CC)CCN(CC)CCN(CC)CCN(CC)CC1 YUIHIYHUJNXSBM-UHFFFAOYSA-N 0.000 claims description 3
- KDCBVVQAMMXRFB-UHFFFAOYSA-N 1,4,7,10,13-pentazacyclopentadecane Chemical compound C1CNCCNCCNCCNCCN1 KDCBVVQAMMXRFB-UHFFFAOYSA-N 0.000 claims description 3
- QBPPRVHXOZRESW-UHFFFAOYSA-N 1,4,7,10-tetraazacyclododecane Chemical compound C1CNCCNCCNCCN1 QBPPRVHXOZRESW-UHFFFAOYSA-N 0.000 claims description 3
- YBXHQNUYHKEXPH-UHFFFAOYSA-N 1,4,7,10-tetraethyl-1,4,7,10,13-pentazacyclopentadecane Chemical compound CCN1CCNCCN(CC)CCN(CC)CCN(CC)CC1 YBXHQNUYHKEXPH-UHFFFAOYSA-N 0.000 claims description 3
- LADZJJOUGVGJHM-UHFFFAOYSA-N 1,4,7,10-tetrazacyclotridecane Chemical compound C1CNCCNCCNCCNC1 LADZJJOUGVGJHM-UHFFFAOYSA-N 0.000 claims description 3
- YDVODBIDDSGKAD-UHFFFAOYSA-N 1,4,7,11-tetrazacyclotetradecane Chemical compound C1CNCCCNCCNCCNC1 YDVODBIDDSGKAD-UHFFFAOYSA-N 0.000 claims description 3
- ITIURFCAPKNNCK-UHFFFAOYSA-N 1,4,7-triazecane Chemical compound C1CNCCNCCNC1 ITIURFCAPKNNCK-UHFFFAOYSA-N 0.000 claims description 3
- ITWBWJFEJCHKSN-UHFFFAOYSA-N 1,4,7-triazonane Chemical compound C1CNCCNCCN1 ITWBWJFEJCHKSN-UHFFFAOYSA-N 0.000 claims description 3
- KUFDRRWNPNXBRF-UHFFFAOYSA-N 1,4,8,12-tetrazacyclopentadecane Chemical compound C1CNCCCNCCNCCCNC1 KUFDRRWNPNXBRF-UHFFFAOYSA-N 0.000 claims description 3
- NWTDWQBLYRISDC-UHFFFAOYSA-N 1,4,8-trimethyl-1,4,8,11-tetrazacyclotetradecane Chemical compound CN1CCCN(C)CCN(C)CCCNCC1 NWTDWQBLYRISDC-UHFFFAOYSA-N 0.000 claims description 3
- DDTINNWIBGBCDP-UHFFFAOYSA-N 1,4-dibenzyl-1,4,8,11-tetrazacyclotetradecane Chemical compound C=1C=CC=CC=1CN(CC1)CCCNCCNCCCN1CC1=CC=CC=C1 DDTINNWIBGBCDP-UHFFFAOYSA-N 0.000 claims description 3
- SFKKKOMLVZVAJW-UHFFFAOYSA-N 1,5,10,14-tetrazacyclooctadecane Chemical compound C1CCNCCCNCCCCNCCCNC1 SFKKKOMLVZVAJW-UHFFFAOYSA-N 0.000 claims description 3
- YXPRJLINFVQPDT-UHFFFAOYSA-N 1,5,9,13-tetrazacyclohexadecane Chemical compound C1CNCCCNCCCNCCCNC1 YXPRJLINFVQPDT-UHFFFAOYSA-N 0.000 claims description 3
- VQFZKDXSJZVGDA-UHFFFAOYSA-N 1,5,9-triazacyclododecane Chemical compound C1CNCCCNCCCNC1 VQFZKDXSJZVGDA-UHFFFAOYSA-N 0.000 claims description 3
- WPWQCVJWAHKQIU-UHFFFAOYSA-N 1-(pyridin-3-ylmethyl)-1,4,8,11-tetrazacyclotetradecane Chemical compound C=1C=CN=CC=1CN1CCCNCCNCCCNCC1 WPWQCVJWAHKQIU-UHFFFAOYSA-N 0.000 claims description 3
- GWXSMIOWBINEFF-UHFFFAOYSA-N 1-methyl-1,4,8,11-tetrazacyclotetradecane Chemical compound CN1CCCNCCNCCCNCC1 GWXSMIOWBINEFF-UHFFFAOYSA-N 0.000 claims description 3
- RGJZJGSQNZWYOF-UHFFFAOYSA-N 10-(2-aminohydrazinyl)decan-1-amine Chemical compound NCCCCCCCCCCNNN RGJZJGSQNZWYOF-UHFFFAOYSA-N 0.000 claims description 3
- KRTGJZMJJVEKRX-UHFFFAOYSA-N 2-phenylethan-1-yl Chemical compound [CH2]CC1=CC=CC=C1 KRTGJZMJJVEKRX-UHFFFAOYSA-N 0.000 claims description 3
- SLRMQYXOBQWXCR-UHFFFAOYSA-N 2154-56-5 Chemical compound [CH2]C1=CC=CC=C1 SLRMQYXOBQWXCR-UHFFFAOYSA-N 0.000 claims description 3
- RXFCIXRFAJRBSG-UHFFFAOYSA-N 3,2,3-tetramine Chemical compound NCCCNCCNCCCN RXFCIXRFAJRBSG-UHFFFAOYSA-N 0.000 claims description 3
- ZAXCZCOUDLENMH-UHFFFAOYSA-N 3,3,3-tetramine Chemical compound NCCCNCCCNCCCN ZAXCZCOUDLENMH-UHFFFAOYSA-N 0.000 claims description 3
- YWYMFYKPCMSZAL-UHFFFAOYSA-N 3-dodecyl-1,5,10,14-tetrazacyclooctadecane Chemical compound CCCCCCCCCCCCC1CNCCCCNCCCNCCCCNC1 YWYMFYKPCMSZAL-UHFFFAOYSA-N 0.000 claims description 3
- IXQUOLGRMATVHL-UHFFFAOYSA-N 3-dodecyl-1,5,9,13-tetrazacyclohexadecane Chemical compound CCCCCCCCCCCCC1CNCCCNCCCNCCCNC1 IXQUOLGRMATVHL-UHFFFAOYSA-N 0.000 claims description 3
- NSCOPASYOISSAC-UHFFFAOYSA-N 4-(10,15,20-triphenyl-21,23-dihydroporphyrin-5-yl)aniline Chemical compound Nc1ccc(cc1)-c1c2ccc(n2)c(-c2ccccc2)c2ccc([nH]2)c(-c2ccccc2)c2ccc(n2)c(-c2ccccc2)c2ccc1[nH]2 NSCOPASYOISSAC-UHFFFAOYSA-N 0.000 claims description 3
- GSPFLHMZYMCPSF-UHFFFAOYSA-N 6-dodecyl-1,4,8,11-tetrazacyclotetradecane Chemical compound CCCCCCCCCCCCC1CNCCNCCCNCCNC1 GSPFLHMZYMCPSF-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- RZOHQCYUTFAJLA-UHFFFAOYSA-N Canavalmine Chemical compound NCCCCNCCCNCCCCN RZOHQCYUTFAJLA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- OTBHHUPVCYLGQO-UHFFFAOYSA-N bis(3-aminopropyl)amine Chemical compound NCCCNCCCN OTBHHUPVCYLGQO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012634 fragment Substances 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 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 3
- FPTWYQKWFMIJPT-UHFFFAOYSA-N n'-[3-[3-(3-aminopropylamino)propylamino]propyl]butane-1,4-diamine Chemical compound NCCCCNCCCNCCCNCCCN FPTWYQKWFMIJPT-UHFFFAOYSA-N 0.000 claims description 3
- VJJWUYZASSXYHG-UHFFFAOYSA-N n'-[3-[3-[3-(3-aminopropylamino)propylamino]propylamino]propyl]butane-1,4-diamine Chemical compound NCCCCNCCCNCCCNCCCNCCCN VJJWUYZASSXYHG-UHFFFAOYSA-N 0.000 claims description 3
- RPSHOHKFHRFBAZ-UHFFFAOYSA-N n'-[4-(4-aminobutylamino)butyl]butane-1,4-diamine Chemical compound NCCCCNCCCCNCCCCN RPSHOHKFHRFBAZ-UHFFFAOYSA-N 0.000 claims description 3
- YGEGSEHHRONOJC-UHFFFAOYSA-N n,n'-dipentylpropane-1,3-diamine Chemical compound CCCCCNCCCNCCCCC YGEGSEHHRONOJC-UHFFFAOYSA-N 0.000 claims description 3
- SBDJKTUGQZJFPC-UHFFFAOYSA-N n-butyl-n'-[2-(butylamino)ethyl]ethane-1,2-diamine Chemical compound CCCCNCCNCCNCCCC SBDJKTUGQZJFPC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000006068 polycondensation reaction Methods 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- ATHGHQPFGPMSJY-UHFFFAOYSA-N spermidine Chemical compound NCCCCNCCCN ATHGHQPFGPMSJY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004434 sulfur atom Chemical group 0.000 claims description 3
- DODDBCGMRAFLEB-UHFFFAOYSA-N thermospermine Chemical compound NCCCCNCCCNCCCN DODDBCGMRAFLEB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- JSILIBDEHPTABZ-UHFFFAOYSA-N 1,4,8,12,16,20-hexazacyclotetracosane Chemical compound C1CCNCCNCCCNCCCNCCCNCCCNC1 JSILIBDEHPTABZ-UHFFFAOYSA-N 0.000 claims description 2
- XHCNINMOALIGKM-UHFFFAOYSA-N 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetrazacyclotetradecane Chemical compound CC1CC(C)(C)NCCNC(C)CC(C)(C)NCCN1 XHCNINMOALIGKM-UHFFFAOYSA-N 0.000 claims description 2
- 238000001994 activation Methods 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 238000007210 heterogeneous catalysis Methods 0.000 claims description 2
- 150000004032 porphyrins Chemical class 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000003860 storage Methods 0.000 claims description 2
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 claims 5
- WGQKYBSKWIADBV-UHFFFAOYSA-N aminomethyl benzene Natural products NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims 4
- ZMOJWEUSGOWQBM-UHFFFAOYSA-N 1-(pyridin-2-ylmethyl)-1,4,8,11-tetrazacyclotetradecane Chemical compound C=1C=CC=NC=1CN1CCCNCCNCCCNCC1 ZMOJWEUSGOWQBM-UHFFFAOYSA-N 0.000 claims 2
- WNEKVKFZHNGHEH-UHFFFAOYSA-N 1-benzyl-1,4,8,11-tetrazacyclotetradecane Chemical compound C=1C=CC=CC=1CN1CCCNCCNCCCNCC1 WNEKVKFZHNGHEH-UHFFFAOYSA-N 0.000 claims 2
- ZHXHPGYNAFIOAJ-UHFFFAOYSA-N n'-[2-[2-[2-(3-aminopropylamino)ethylamino]ethylamino]ethyl]propane-1,3-diamine Chemical compound NCCCNCCNCCNCCNCCCN ZHXHPGYNAFIOAJ-UHFFFAOYSA-N 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910052681 coesite Inorganic materials 0.000 abstract 2
- 229910052906 cristobalite Inorganic materials 0.000 abstract 2
- 235000012239 silicon dioxide Nutrition 0.000 abstract 2
- 229910052682 stishovite Inorganic materials 0.000 abstract 2
- 229910052905 tridymite Inorganic materials 0.000 abstract 2
- 230000005494 condensation Effects 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- 229910021404 metallic carbon Inorganic materials 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000004094 surface-active agent Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000000536 complexating effect Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- OXYZDRAJMHGSMW-UHFFFAOYSA-N 3-chloropropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCCl OXYZDRAJMHGSMW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052747 lanthanoid Inorganic materials 0.000 description 2
- 239000013335 mesoporous material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- FVEFRICMTUKAML-UHFFFAOYSA-M sodium tetradecyl sulfate Chemical compound [Na+].CCCCC(CC)CCC(CC(C)C)OS([O-])(=O)=O FVEFRICMTUKAML-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 150000001260 acyclic compounds Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical class [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000013385 inorganic framework Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000001457 metallic cations Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- MATSOSQWCCPHRT-UHFFFAOYSA-N n'-[2-(2-hydrazinylethylamino)ethyl]hexane-1,6-diamine Chemical compound NCCCCCCNCCNCCNN MATSOSQWCCPHRT-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic Table without C-Metal linkages
Definitions
- the subject of the invention is the development of organic - inorganic, mesoporous hybrid materials which can be used in the field of gas purification.
- Current techniques for separating industrial gases (cryogenic distillation or adsorption on zeolites) as well as those for their purification (cryogenic distillation or catalysis) are not always optimized in economic terms (cryogenics for small quantities) as well as concerns the purity of the gases (the oxygen obtained by adsorption contains 5% of argon, for example).
- gases such as oxygen, hydrogen or carbon monoxide, react selectively and reversibly with transition metal complexes.
- the cobalt (II) complexes of cyclam or cyclene are known to strongly coordinate the oxygen in solution (R. Machida, E. Kimura, M. Kodama; Inorg. Chem. 1983, 22, 2055).
- micellar medium of mesostructured silicas of large specific surfaces (800-1400 m 2 .g "1 ) with a very narrow and adjustable pore distribution between 2 and 10 nm was discovered in 1992 (JS Beck, JC Vartuli , WJ Roth, ME Leonowicz, CT, Kresge, KD Schmitt, CT Chu, DH Oison, EW Sheppard, SB Higgins, JL Schlenker; J. Am. Chem. Soc. 1992, 114, 10834).
- This new family of mesoporous materials results from the cooperative assembly of an inorganic phase around an organic phase made up of surfactants in micellar concentration (JYYing, CP Mehnert, MS Wong; Angew Chem. Int. Ed., 1999, 38, 56-77). Once the material is formed, the elimination of the surfactant releases the porosity of the inorganic framework and thus leads to a porous and organized inorganic phase.
- the subject of the invention is a process for the preparation of organic - inorganic hybrid materials, with porosity and controlled functionality, comprising:
- Z represents either a halogen atom chosen from chlorine, bromine or iodine atoms, or an amino or phosphino group;
- R, R 'and R " identical or different, each independently of one another represent an alkyl radical containing from one to four carbon atoms,
- step (a) being followed a step (b) of anchoring, on the mesoporous silica of formula (III), an equivalent of an organic compound, represented by ( ⁇ ) NH, comprising at least one group -NH- capable of reacting with the function Z of said mesoporous silica, to form the functionalized mesoporous silica represented by the formula (IV):
- step (b) is followed by a step (c) of complexing a metal cation, by reaction of the functionalized mesoporous silica represented by the formula (IV) , with a salt of said cation, to form an organometallic complex (V).
- Ri more particularly represents the divalent radical of formula (R 1a ):
- Ar represents an arylene radical and in particular a phenylene radical, it being understood that: when q is equal to 1, o is different from 0, when q is equal to 1 and that u is equal to 0, the sum r + s + t + v is different from 0, when u is equal to 1, v is different from 0, when u is equal to 1 and q is equal to 0, the sum o + r + s + t is different from 0, when s is equal to 0, and that q and u are each equal to 1, the sum r + 1 is different from 0, and the sum o + r + 1 + v + is less than or equal to 24.
- Ri represents very particularly one of the divalent radicals, - (CH 2 ) X - in which x is between 3 and 20 and is preferably between 3 and 6 inclusive or one of the radicals:
- metallic cation mainly means the cations of the transition metals, the cations of the noble metals, the cations of the lanthanides and the cations of the actinides.
- the metal cation is more particularly chosen from cations of iron, cobalt, europium, uranium, nickel, manganese, copper, chromium, zinc, silver, cadmium, lead, mercury, gold, platinum, palladium, uranium, cerium or gadolinium.
- the metal cation salt is more particularly chosen from chloride, bromide, iodide, fluoride, tetrafluoroborate, sulfate or nitrate of said cation.
- ⁇ (NH) compounds which can be used in the process and its variant as defined above, there are, for example, cyclic compounds, such as polyazacycloalkanes, porphyrin derivatives or polyamines aliphatic.
- polyazacycloalkanes there are more particularly triazacycloalkanes, such as, for example, 1, 4, 7 - triazacyclononane, 1, 4, 8 - triazacyclodecane or 1, 5, 9 - triazacyclododecane, tetraazacycloalcanes, such as, for example, 1, 4, 7, 10 - tetraazacyclododecane (cyclene), 1, 4, 7, 10 - tetraza-cyclotridecane, 1, 4, 7, 11 - tetraazacyclotetradecane, 1, 4, 8, 11 - tetraazacyclotetradecane (or cyclam), 1, 4, 8 - trimethyl 1, 4, 8, 11 - tetraazacyclotetradecane, 1, 4, 8, 12 - tetraazacyclopentadecane, 1, 5, 9, 13 - tetraazacyclohexadecane, 1, 5, 10, 14 - tetraazacycloocta
- porphyrin derivatives there are for example: [4- (2,8,13,17- tetraethyl-3,7, 12,18-tetramethyl-porphyrin-5-yl) -phenylamine], [4- (2,8,13,17- tetraethyl-3,7,12,18-tetramethyl-porphyrin-5-yl) -benzylamine], [4- (15-phenyl-porphyrin-5-yl) -phenylamine], [4- (15-phenyl-porphyrin-5-yl) -benzylamine], [4- (10,15,20-triphenyl-porphyrin-5-yl) -phenylamine], or [4- (10, 15,20-triphenyl-porphyrin-5-yl) -benzylamine].
- aliphatic polyamines and more particularly triazaalkanes such as, for example, 4 - aza-heptan - 1, 7 - diamine, 4 - azaoctan - 1, 8 - diamine or 5 - azanonan - 1, 9 - diamine, tetraazaalcanes, such as, for example, 4, 7 - diazadecan - 1, 10 - diamine, 4, 8 - diazaundecan - 1, 11 - diamine, 5, 9 - diazadodecan -1, 12 - diamine, 5, 8 - diazadodecan - 1, 12 - diamine, 4, 8, diazadodecan -1, 12 - diamine, 5, 9 - diazatridecan - 1, 13 - diamine, 5, 10 - diazatetradecan - 1, 14 - diamine , 6, 10 - diazapentadecan - 1, 15 - diamine, pentaazaalcanes, such as, for example,
- the subject of the present invention is the functionalized mesoporous silica represented by formula (IV), as defined above, as well as the metal complex (V) capable of being obtained by reaction of said compound. formula (IV), with a metal cation salt as defined above.
- a last aspect of the present invention relates to the use of these metallized materials as defined above, to separate a determined gas from a mixture of gases, It comprises bringing said mixture of gases into contact with one of the metallized hybrid gels as defined above, under conditions allowing the absorption of said gas to be separated, followed by the desorption of said gas fixed on the solid and then the recovery of said desorbed gas. This use is preferably applied to the separation of oxygen from the air, either to produce pure oxygen or to remove oxygen from the air.
- the complexing method is general to all the salts of the metals mentioned above and the materials thus prepared are advantageously used in heterogeneous catalysis, for the depollution of effluents, for the purification, activation and storage of gases, for obtaining photoluminescent materials and materials with magnetic or electrical properties.
- the following examples illustrate the invention without, however, limiting it.
- the process which is the subject of the present invention comprises the hydrolysis and polycondensation of a mixture of (3 - chloropropyl) trimethoxysilane and sodium silicate in proportion 1/9, in the presence of nonionic surfactants such as for example TERGITOL TM 15S12 [CH 3 (CH 2 ) 14 - (OCH 2 CH 2 ) i 2 -OH] or the co-polymer block EO 20 PO 70 EO 20 (PLURONIC TM P. 123).
- nonionic surfactants such as for example TERGITOL TM 15S12 [CH 3 (CH 2 ) 14 - (OCH 2 CH 2 ) i 2 -OH] or the co-polymer block EO 20 PO 70 EO 20 (PLURONIC TM P. 123).
- M A indicates that the material has been prepared with TERGITOL TM 15S12
- M B indicates that the material has been prepared with the co-polymer block EO 2 0 PO 70 E0 2 o-
- This indicative letter is followed by the name of the functional group in parentheses.
- a surfactant solution is prepared by mixing 2.0 g (0.34 mmol) of EO20 PO 70 EO20 co-polymer blocks, 70 cm 3 of water and 1 cm 3 of a sulfuric acid solution (4N). The solution is stirred until the surfactant is completely dissolved (approximately one hour). To this transparent solution, 0.9 g (4.5 mmol) of (3-chloropropyl) trimethoxysilane is added. The resulting mixture is stirred for a while. for 5 minutes at room temperature. We then observe the formation of a transparent solution.
- the method can be generalized to all chelating ligands carrying at least one nitrogen atom capable of reacting with the chloro function. It can advantageously be applied to the ligands mentioned above in the description, whether they are polyazacycloalkanes, porphyrins or aliphatic polyamines.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Oxygen, Ozone, And Oxides In General (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002576249A JP4643124B2 (ja) | 2001-03-21 | 2002-03-21 | 気体分離用のメソポーラス有機−無機ハイブリッド材料 |
CA2440990A CA2440990C (fr) | 2001-03-21 | 2002-03-21 | Materiaux hybrides organiques-inorganiques, mesoporeux, pour separer les gaz |
DE60214525T DE60214525T2 (de) | 2001-03-21 | 2002-03-21 | Hybride organisch-anorganische mesoporösen materialien, trennung von gasen |
US10/472,301 US7452845B2 (en) | 2001-03-21 | 2002-03-21 | Mesoporous organic-inorganic hybrid materials for separating gases |
EP02753730A EP1370563B1 (fr) | 2001-03-21 | 2002-03-21 | Materiaux hybrides organiques-inorganiques, mesoporeux, pour separer les gaz |
US12/043,486 US7517512B2 (en) | 2001-03-21 | 2008-03-06 | Mesoporous organic-inorganic hybrid materials for separating gases |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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FR0103802A FR2822470B1 (fr) | 2001-03-21 | 2001-03-21 | Procede de preparation de materiaux hybrides organiques- inorganiques, mesoporeux. nouveau materiaux et leur utilisation pour separer les gaz |
FR0103802 | 2001-03-21 |
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US10472301 A-371-Of-International | 2002-03-21 | ||
US12/043,486 Continuation US7517512B2 (en) | 2001-03-21 | 2008-03-06 | Mesoporous organic-inorganic hybrid materials for separating gases |
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WO2002076991A1 true WO2002076991A1 (fr) | 2002-10-03 |
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PCT/FR2002/000986 WO2002076991A1 (fr) | 2001-03-21 | 2002-03-21 | Materiaux hybrides organiques-inorganiques, mesoporeux, pour separer les gaz |
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US (2) | US7452845B2 (fr) |
EP (1) | EP1370563B1 (fr) |
JP (1) | JP4643124B2 (fr) |
AT (1) | ATE338760T1 (fr) |
CA (1) | CA2440990C (fr) |
DE (1) | DE60214525T2 (fr) |
ES (1) | ES2269741T3 (fr) |
FR (1) | FR2822470B1 (fr) |
WO (1) | WO2002076991A1 (fr) |
Cited By (2)
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EP1745055B1 (fr) * | 2004-04-19 | 2008-06-11 | Commissariat A L'energie Atomique | Materiaux poreux hybrides organique-inorganiques pour la detection de halogenes |
EP2082804A1 (fr) | 2008-01-25 | 2009-07-29 | CPE Lyon Formation Continue et Recherche | Matériaux hybrides organiques/inorganiques contenant du carbène stabilisé |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2005087369A1 (fr) * | 2004-03-16 | 2005-09-22 | The Governing Council Of The University Of Toronto | Materiaux hybrides d'oxyde organometallique poreux |
JP6193874B2 (ja) * | 2011-11-23 | 2017-09-06 | ダウ グローバル テクノロジーズ エルエルシー | 高気孔率メソ細孔性シリカ質の構造 |
US9333484B2 (en) | 2012-12-26 | 2016-05-10 | Exxonmobil Research And Engineering Company | Reversible CO2 fixation via self-assembled siloxanes |
KR102092940B1 (ko) | 2013-04-15 | 2020-03-24 | 삼성전자주식회사 | 이산화탄소 흡착제와 그 제조방법, 이를 포함한 이산화탄소 포집 모듈, 및 이를 이용한 이산화탄소 분리 방법 |
CN109738398B (zh) * | 2018-12-12 | 2021-03-30 | 中南民族大学 | 一种快速可视化纸传感检测重金属银离子的方法 |
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JP3500994B2 (ja) * | 1998-12-17 | 2004-02-23 | 株式会社豊田中央研究所 | メソ多孔体からなる炭化水素ガス吸着剤 |
JP2000281331A (ja) * | 1999-03-26 | 2000-10-10 | Toyota Central Res & Dev Lab Inc | メソ多孔体及びその製造方法 |
FR2796645B1 (fr) * | 1999-07-23 | 2001-09-14 | Air Liquide | Nouveau gel de silice incorporant des motifs polyazacycloalcanes comportant plus de six atomes d'azote, procede de preparation et utilisation |
-
2001
- 2001-03-21 FR FR0103802A patent/FR2822470B1/fr not_active Expired - Lifetime
-
2002
- 2002-03-21 US US10/472,301 patent/US7452845B2/en active Active
- 2002-03-21 AT AT02753730T patent/ATE338760T1/de not_active IP Right Cessation
- 2002-03-21 DE DE60214525T patent/DE60214525T2/de not_active Expired - Lifetime
- 2002-03-21 ES ES02753730T patent/ES2269741T3/es not_active Expired - Lifetime
- 2002-03-21 WO PCT/FR2002/000986 patent/WO2002076991A1/fr active IP Right Grant
- 2002-03-21 EP EP02753730A patent/EP1370563B1/fr not_active Expired - Lifetime
- 2002-03-21 CA CA2440990A patent/CA2440990C/fr not_active Expired - Lifetime
- 2002-03-21 JP JP2002576249A patent/JP4643124B2/ja not_active Expired - Fee Related
-
2008
- 2008-03-06 US US12/043,486 patent/US7517512B2/en not_active Expired - Lifetime
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C.R. ACAD. SCI., SER. IIC: CHIM., vol. 2, no. 1, 1999 * |
CHEMICAL ABSTRACTS, vol. 131, no. 6, 9 August 1999, Columbus, Ohio, US; abstract no. 77055, CORRIU, R.J.P ET AL.: "synthesis by neutral surfactant assembly of ordered mesoporous organic-inorganic hybrid materials incorporating phosphorus centers" XP002186598 * |
CHEMICAL ABSTRACTS, vol. 132, no. 17, 24 April 2000, Columbus, Ohio, US; abstract no. 226577, GRAHAM, U.M. ET AL.: "chemically active aerogels for hot gas clean-up in a IGCC process" XP002186597 * |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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EP1745055B1 (fr) * | 2004-04-19 | 2008-06-11 | Commissariat A L'energie Atomique | Materiaux poreux hybrides organique-inorganiques pour la detection de halogenes |
EP2082804A1 (fr) | 2008-01-25 | 2009-07-29 | CPE Lyon Formation Continue et Recherche | Matériaux hybrides organiques/inorganiques contenant du carbène stabilisé |
US8871877B2 (en) | 2008-01-25 | 2014-10-28 | Universite Claude Bernard Lyon 1 (Ucbl) | Hybrid organic-inorganic materials that contain stabilized carbene |
Also Published As
Publication number | Publication date |
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US7517512B2 (en) | 2009-04-14 |
US20040122250A1 (en) | 2004-06-24 |
DE60214525T2 (de) | 2007-05-16 |
US20080152561A1 (en) | 2008-06-26 |
FR2822470A1 (fr) | 2002-09-27 |
US7452845B2 (en) | 2008-11-18 |
ES2269741T3 (es) | 2007-04-01 |
ATE338760T1 (de) | 2006-09-15 |
FR2822470B1 (fr) | 2003-08-15 |
CA2440990A1 (fr) | 2002-10-03 |
DE60214525D1 (de) | 2006-10-19 |
JP2004536043A (ja) | 2004-12-02 |
EP1370563B1 (fr) | 2006-09-06 |
JP4643124B2 (ja) | 2011-03-02 |
EP1370563A1 (fr) | 2003-12-17 |
CA2440990C (fr) | 2012-05-22 |
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