WO2002070526A1 - Metallorganische gerüsmaterialien und verfahren zu deren herstellung - Google Patents
Metallorganische gerüsmaterialien und verfahren zu deren herstellung Download PDFInfo
- Publication number
- WO2002070526A1 WO2002070526A1 PCT/EP2002/002523 EP0202523W WO02070526A1 WO 2002070526 A1 WO2002070526 A1 WO 2002070526A1 EP 0202523 W EP0202523 W EP 0202523W WO 02070526 A1 WO02070526 A1 WO 02070526A1
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- WIPO (PCT)
- Prior art keywords
- organic compound
- solvent
- metal
- organometallic
- framework material
- Prior art date
Links
- 125000002524 organometallic group Chemical group 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- 239000004566 building material Substances 0.000 title abstract 2
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 18
- -1 cyclic ester Chemical class 0.000 claims abstract description 14
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 150000003950 cyclic amides Chemical group 0.000 claims abstract description 7
- 239000012530 fluid Substances 0.000 claims abstract description 6
- 150000003951 lactams Chemical class 0.000 claims abstract description 6
- 150000002596 lactones Chemical class 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 5
- 239000003463 adsorbent Substances 0.000 claims description 5
- 239000002274 desiccant Substances 0.000 claims description 5
- 238000006735 epoxidation reaction Methods 0.000 claims description 5
- 239000003063 flame retardant Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical class [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 239000011232 storage material Substances 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Chemical class 0.000 claims description 4
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 4
- 230000036571 hydration Effects 0.000 claims description 4
- 238000006703 hydration reaction Methods 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 238000006317 isomerization reaction Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 208000005156 Dehydration Diseases 0.000 claims description 3
- 238000007792 addition Methods 0.000 claims description 3
- 238000005576 amination reaction Methods 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 238000010504 bond cleavage reaction Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 230000006324 decarbonylation Effects 0.000 claims description 3
- 238000006606 decarbonylation reaction Methods 0.000 claims description 3
- 238000006114 decarboxylation reaction Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000006266 etherification reaction Methods 0.000 claims description 3
- 239000012621 metal-organic framework Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000006384 oligomerization reaction Methods 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 claims description 3
- 239000000049 pigment Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 238000002407 reforming Methods 0.000 claims description 3
- 238000007142 ring opening reaction Methods 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Chemical class 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical class [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 150000001361 allenes Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 150000000475 acetylene derivatives Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 150000002084 enol ethers Chemical class 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YOWQWFMSQCOSBA-UHFFFAOYSA-N 2-methoxypropene Chemical compound COC(C)=C YOWQWFMSQCOSBA-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 241001104043 Syringa Species 0.000 description 2
- 235000004338 Syringa vulgaris Nutrition 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000006184 cosolvent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- ZLHVSEPPILCZHH-UHFFFAOYSA-N ethenyl 4-tert-butylbenzoate Chemical compound CC(C)(C)C1=CC=C(C(=O)OC=C)C=C1 ZLHVSEPPILCZHH-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012229 microporous material Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UYISKGVFPMWFJV-UHFFFAOYSA-N terephthalic acid;zinc Chemical compound [Zn].OC(=O)C1=CC=C(C(O)=O)C=C1 UYISKGVFPMWFJV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- HEWZVZIVELJPQZ-UHFFFAOYSA-N 2,2-dimethoxypropane Chemical compound COC(C)(C)OC HEWZVZIVELJPQZ-UHFFFAOYSA-N 0.000 description 1
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KEVYVLWNCKMXJX-ZCNNSNEGSA-N Isophytol Natural products CC(C)CCC[C@H](C)CCC[C@@H](C)CCC[C@@](C)(O)C=C KEVYVLWNCKMXJX-ZCNNSNEGSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 238000006664 bond formation reaction Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000008096 xylene 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
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
-
- 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
- C07F19/005—Metal compounds according to more than one of main groups C07F1/00 - C07F17/00 without metal-C linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0237—Amines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- 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 System
- C07F1/08—Copper compounds
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/06—Zinc compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- B01J35/643—
Definitions
- the present invention relates to new organometallic framework materials, a process for their preparation and their use as an adsorbent, drying agent, flame retardant, storage material or depot of active substances or catalysts.
- Organometallic framework materials are known per se. We refer to the scientific publication by Yaghi et. al. in J. Solid State Chem., Vol. 152 (1), 3-20, which summarizes the previous developments in this technical field. A process for producing such materials is described in EP-A 0 790 253.
- the method claimed there for producing a microporous material comprises mixing a solution comprising at least one metal ion as defined therein with a ligand which has substructures with multidentate functional groups in the presence of a template compound as defined therein.
- a method for removing impurities from gases and liquids is mentioned in this document as a use for such materials. Further uses of the materials described there are neither mentioned nor hinted at in this publication.
- organometallic framework substances can be produced in high yield if N-methylpyrrolidone is used as solvent or as solvent component.
- the present invention thus relates to a process for producing an organometallic framework material comprising the reaction of a fluid mixture, such as, for example, a solution or suspension comprising a metal salt with at least one organic compound which is at least bidentate and is suitable for coordination with metal ions in the presence of at least one base and a solvent , wherein the solvent contains at least one cyclic amide (lactam) and / or at least one cyclic ester (lactone), such as N-methylpyrrolidone, an organometallic, microporous framework material containing a metal ion and coordinated with at least one at least bidentate organic compound , can be produced by a process which involves the reaction of a fluid mixture, such as, for example, a solution or suspension of a metal salt with at least one organic compound suitable for coordination with metal ions in the presence of at least one Base and a solvent, the solvent at least one cyclic amide (lactam) and / or at least one cyclic ester (lactone), such as
- the elements of groups Ia, Ha, lilac, IVa-Villa and Ib-VIb of the periodic table are suitable as metal components within the metal salt used according to the invention, zinc, copper, nickel, palladium, platinum, ruthenium, rhenium and cobalt being particularly preferred are called.
- organic compound suitable for this purpose and fulfilling the above conditions are suitable as at least bidentate organic compounds suitable for coordination with metal ions.
- the organic compound must in particular have at least two centers which can form a bond with the metal ions of a metal salt, in particular with the metals of the aforementioned groups Ia, Ha, lilac, IVa-Villa and Ib-VIb.
- These can be selected in particular from: substituted or unsubstituted, mononuclear or polynuclear aromatic dicarboxylic acids and substituted or unsubstituted, mononuclear or multinuclear aromatic dicarboxylic acids having at least one heteroatom.
- Dicarboxylic acids of benzene, naphthalene, pyridine or quinoline Dicarboxylic acids of benzene, naphthalene, pyridine or quinoline.
- the solvent used in the process according to the invention is a solvent which comprises a cyclic amide and / or a cyclic ester either alone or together with a suitable cosolvent.
- a suitable cosolvent for example, all protic and / or aprotic organic solvents are own cosolvents, which are able to dissolve the at least bidentate organic compounds. Examples include:
- Aromatic solvents e.g. Benzene, chlorobenzene, toluene, xylene or halogenated hydrocarbons, e.g. Chloroform.
- the present invention also relates to a process as described above, the base being selected from organic amines.
- the organic compound is dissolved in the solvent or solvent mixture and then, preferably with constant stirring, the metal salt is added.
- the metal salt can be supplied by any method.
- the base is added.
- the precipitate obtained after the reaction which comprises the organometallic framework material, is separated from the mother liquor of the reaction mixture obtained by means of filtration, centrifugation or spray drying.
- the framework material thus separated can be subjected to a drying step in order to remove adhering solvent and residual base.
- the pressure is reduced during the drying step in order to at least partially empty the pores of the organometallic framework material.
- the present invention also relates to an organometallic, microporous scaffold material containing a metal ion and thus coordinatively connected at least one at least bidentate organic compound, which by a process that the reaction of a fluid mixture, such as. B. a solution or suspension of a metal salt with at least one at least bidentate organic compound suitable for coordination with metal ions in the presence of at least one base and a solvent, wherein the solvent at least one cyclic amide (lactam) and / or at least one cyclic ester (Lactone) contains.
- the organometallic framework materials obtained according to the invention contain micropores, in the present case micropores being those with a diameter of 2 nm or less, as defined in Pure Applied Chem. 45, pp. 71 ff, in particular p. 79 (1976).
- micropores being those with a diameter of 2 nm or less, as defined in Pure Applied Chem. 45, pp. 71 ff, in particular p. 79 (1976).
- the presence of micropores can be recognized by means of sorption measurements to determine the absorption capacity of the organometallic framework materials for nitrogen at 77K in accordance with DLN 66131, 66134.
- the typical isothermal profile in type I form indicates the presence of micropores.
- the calculated specific surface areas according to the Langmuir model are preferably above 5 m 2 / g, more preferably above 50 m 2 / g, in particular above 500 m 2 / g and can rise in the range up to above 2000 m 2 / g.
- organometallic framework materials according to the invention are used in particular as an adsorbent, drying agent, flame retardant, storage material or depot of active substances, sensor material, pigment, electronic component or as catalysts, in particular as catalysts, where they can be widely used.
- Areas of application in catalysis include:
- Oxidations, reductions, ring opening reactions, C-C linkages and epoxidations, C-C bond formations such as alkylations, acylations; Additions such as carbonylations, aminations, hydrations, etherifications, alkoxylations; Eliminations such as decarbonylations, decarboxylations, dehydrations; Dehydrogenation and hydrogenation, isomerization, C-C bond cleavage such as cracking and hydrocracking; reforming; Oligomerizations, polymerizations; Cleaning catalysis for exhaust and waste water, photocatalysis.
- the present invention also relates to a process for reacting at least one organic compound, the organic compound being brought into contact with at least one catalyst according to the invention.
- the organometallic framework materials according to the invention are particularly advantageous in that their catalyst performance can be varied or tailored by varying the metal and / or the at least bident organic compound suitable for coordination with metal ions.
- implementations of CC triple bonds are catalyzed with the zinc-containing organometallic framework materials according to the invention.
- the catalyst according to the invention is suitable for use in a process for the preparation of compounds of the formulas I or II OR 1 OR 1
- R 1 is hydrogen or an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radical or an acyl radical, where these radicals can carry further substituents which do not react with acetylenes or allenes, the radicals R independently of one another for hydrogen, or are aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic radicals, which can be connected to form a ring, and m represents 0 or 1, by adding compounds of the formula III
- R 1 and R have the meaning given above, in the gas, liquid or supercritical phase at elevated temperature.
- Any alkynes or allenes or mixtures thereof can be considered as starting materials for the reaction.
- technically easily accessible acetylenes and allenes with 2 to 8 C atoms or 3 to 8 C atoms will be used. turn.
- Propyne and allene and in particular hydrocarbon streams containing them are particularly preferred.
- the compound R ⁇ H containing hydroxyl groups can be water, any alcohol, a phenol or a carboxylic acid.
- alcohols in particular come, especially alkanols with 1 to 16 carbon atoms, mononuclear phenols and low molecular weight carboxylic acids, e.g. with 1 to 16 carbon atoms.
- Lower alcohols and in particular methanol are particularly preferably used.
- the hydroxyl group-containing compounds are added in the presence of the heterogeneous catalyst in the gas, liquid or supercritical phase either over a fixed bed or in a fluidized bed at temperatures from 25 to 400 ° C., preferably 100 to 250 ° C. and particularly preferably 120 to 200 ° C. and pressures depending on the starting material used, typically from 0.1 to 100 bar, in particular 0.8 to 20 bar (all pressures based on the sum of the partial pressures of the starting materials).
- 2-methoxypropene or 2,2-dimethoxypropane can be selectively formed from propyne or allene with methanol, depending on the reaction conditions.
- the enol ethers of the formula I obtainable according to the invention and the dialkoxy compounds of the formula II are valuable intermediates for the preparation of active substances and fragrances.
- the enol ethers in particular are sought-after starting materials e.g. for the production of ⁇ , ⁇ -unsaturated ketones as pre-products for the production of isophytol.
- the compounds of the formula II can be converted into the corresponding enol ethers of the formula I in a manner known per se by splitting off one mole of R r OH.
- R r OH There are numerous from DE-A-35 35 128, DE-A-37 22 891, DE-A-38 04 162, Chemical Abstracts, Vol. 94 (19); Methods known from 156 241 f and DE-A-19544450.
- the organometallic framework materials can also be used in oxidation, epoxidation and reduction reactions if a metal is selected as the framework that is able to change its oxidation state easily, e.g. known from many metals of the sub-group elements.
- catalytic behavior can also be controlled by modifying the organic component. If, for example, carboxylic acid, sulfonic acid, trifluorosulfonic acid or other acidic residues are introduced into the organic building block, the resulting organometallic framework material can be used as heterogeneous solid acid in isomerizations, esterifications, etherifications, alkoxylations, hydrations, dehydrations, ring closure and ring opening reactions or CC- Shortcuts are used.
- CC bond formation such as alkylations, acylations; Additions such as carbonylations, aminations, hydrations, eliminations such as decarbonylations, decarboxylations; Dehydrogenation and hydrogenation, CC bond cleavage such as Cracking and hydrocracking; reforming; Oxidations and epoxidations; Oligomerizations, polymerizations; Cleaning catalysis for exhaust and waste water, photocatalysis.
- organic building block is provided with amm groups or, for example, dicarboxylates of pyridine are used as the building block, the use of these materials for base catalysis opens up.
- alkyl-substituted aromatic dicarboxylic acids are used as organic building blocks, it is possible to produce organometallic framework materials which are later suitable for forming hydroperoxides on the alkyl chains by means of air in order to use them for the heterogeneous catalytic selective epoxidation of olefins.
- the metal-organic framework materials can also be used as adsorbents, drying agents, flame retardants, storage materials and depots for sustained release of pharmaceuticals.
- these materials can be used as sensors or in sensors for e.g. Gas detection or in application areas such as "Chemistry on a chip” due to the high porosity and surface of the materials.
- the compounds are also used in or as electronic components or functional materials.
- the organometallic framework materials according to the invention can be used in powder form or in the form of strands, pellets, granules, rings, etc., in a reactor, or applied to supports, for example as coverings on distillation packs or mesh panels and knitted metal or polymer fabrics.
- the reactions can take place in the liquid, gaseous or supercritical phase.
- the product was filtered off and washed with about 2 liters of water and dried at 150 ° C. in a vacuum drying cabinet.
- Example 2 2.5 g of the catalyst prepared in Example 1 were placed in 100 g of 1-methyl-2-pyrrolidone in an autoclave, and 40 g of 4-tert-butylbenzoic acid were added. After 5 bar of nitrogen had been injected, the mixture was heated to 180 ° C., then 20 bar of acetylene were added and the mixture was metered in over a period of 24 hours. The discharge from the reaction was analyzed by GC and, with a conversion of 94% to the acid used, showed a selectivity of 83% to the 4-tert-butylbenzoic acid vinyl ester.
- a catalyst prepared according to Example 1 in tablet form were installed in a differential circuit reactor.
- 1.5 g / h of a liquid stream (mixture of metlianol / cyclohexane 10: 1) were metered in via an HPLC pump.
- Propyne was fed in at a gas flow of 6 g / h at 250 ° C.
- the conversion was 30% of propyne with a selectivity to 2-methoxypropene of 80%.
Abstract
Description
Claims
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US10/469,826 US7119219B2 (en) | 2001-03-08 | 2002-03-07 | Organometallic building materials and method for producing the same |
JP2002569846A JP4216074B2 (ja) | 2001-03-08 | 2002-03-07 | 有機金属骨格材料およびその製造方法 |
DE50213078T DE50213078D1 (de) | 2001-03-08 | 2002-03-07 | Metallorganische gerüstmaterialien und verfahren zu deren herstellung |
MXPA03007873A MXPA03007873A (es) | 2001-03-08 | 2002-03-07 | Materiales de estructura organometalicos y metodo para producir los mismos. |
CA2440114A CA2440114C (en) | 2001-03-08 | 2002-03-07 | Organometallic framework materials and process for preparing them |
EP02727373A EP1373277B1 (de) | 2001-03-08 | 2002-03-07 | Metallorganische gerüstmaterialien und verfahren zu deren herstellung |
KR1020037011668A KR100830083B1 (ko) | 2001-03-08 | 2002-03-07 | 유기 금속 구조 재료 및 이의 제조 방법 |
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DE10111230A DE10111230A1 (de) | 2001-03-08 | 2001-03-08 | Metallorganische Gerüstmaterialien und Verfahren zu deren Herstellung |
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EP (1) | EP1373277B1 (de) |
JP (1) | JP4216074B2 (de) |
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AT (1) | ATE416180T1 (de) |
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DE (2) | DE10111230A1 (de) |
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JP2007533846A (ja) * | 2003-11-24 | 2007-11-22 | ビーエーエスエフ アクチェンゲゼルシャフト | 結晶性多孔質有機金属骨格物質を製造する方法 |
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Also Published As
Publication number | Publication date |
---|---|
CA2440114C (en) | 2010-10-26 |
EP1373277A1 (de) | 2004-01-02 |
JP4216074B2 (ja) | 2009-01-28 |
ZA200306959B (en) | 2004-09-06 |
JP2004534737A (ja) | 2004-11-18 |
CN1494546A (zh) | 2004-05-05 |
EP1373277B1 (de) | 2008-12-03 |
MY131002A (en) | 2007-07-31 |
US7119219B2 (en) | 2006-10-10 |
KR100830083B1 (ko) | 2008-05-20 |
ATE416180T1 (de) | 2008-12-15 |
MXPA03007873A (es) | 2004-04-02 |
DE10111230A1 (de) | 2002-09-19 |
KR20040007460A (ko) | 2004-01-24 |
CN1240703C (zh) | 2006-02-08 |
US20040097724A1 (en) | 2004-05-20 |
DE50213078D1 (de) | 2009-01-15 |
CA2440114A1 (en) | 2002-09-12 |
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