CN1240703C - 有机金属骨架材料及其制备方法 - Google Patents
有机金属骨架材料及其制备方法 Download PDFInfo
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- CN1240703C CN1240703C CNB02806061XA CN02806061A CN1240703C CN 1240703 C CN1240703 C CN 1240703C CN B02806061X A CNB02806061X A CN B02806061XA CN 02806061 A CN02806061 A CN 02806061A CN 1240703 C CN1240703 C CN 1240703C
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- 125000002524 organometallic group Chemical group 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 239000004566 building material Substances 0.000 title abstract 2
- 239000000203 mixture 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 16
- -1 cyclic ester Chemical class 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 150000003950 cyclic amides Chemical group 0.000 claims abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 239000012530 fluid Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 62
- 238000000034 method Methods 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- 150000001455 metallic ions Chemical class 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 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 compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002594 sorbent Substances 0.000 claims description 5
- 239000011232 storage material Substances 0.000 claims description 5
- 239000013543 active substance Substances 0.000 claims description 4
- 238000007259 addition reaction Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 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
- 238000006317 isomerization reaction Methods 0.000 claims description 4
- 125000003367 polycyclic group Chemical group 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 compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 238000005576 amination reaction 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
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 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
- 238000007142 ring opening reaction Methods 0.000 claims description 3
- 239000002912 waste gas Substances 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 150000002596 lactones Chemical class 0.000 abstract description 4
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- 150000003839 salts Chemical class 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 125000002534 ethynyl group Chemical group [H]C#C* 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 5
- 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
- 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
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- 239000002994 raw material Substances 0.000 description 4
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- 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
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 239000002253 acid Substances 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- IYABWNGZIDDRAK-UHFFFAOYSA-N allene Chemical compound C=C=C IYABWNGZIDDRAK-UHFFFAOYSA-N 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 238000005810 carbonylation reaction Methods 0.000 description 2
- 239000003054 catalyst Substances 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
- 238000003379 elimination reaction Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000006187 pill Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UYISKGVFPMWFJV-UHFFFAOYSA-N terephthalic acid;zinc Chemical group [Zn].OC(=O)C1=CC=C(C(O)=O)C=C1 UYISKGVFPMWFJV-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N acetaldehyde dimethyl acetal Natural products COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
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- 230000032050 esterification Effects 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000005826 halohydrocarbons Chemical class 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
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- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
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- 239000008204 material by function Substances 0.000 description 1
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- 150000007530 organic bases Chemical class 0.000 description 1
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- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- 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
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- B01J35/643—
Abstract
本发明涉及一种制备有机金属骨架材料的方法，包括使包含金属盐和至少一种能与金属离子配位的至少二齿有机化合物的流体混合物在至少一种碱和溶剂存在下反应，其中所述溶剂含有至少一种环状酰胺(内酰胺)和/或至少一种环状酯(内酯)。
Description
本发明涉及新的有机金属骨架材料、一种制备它们的方法以及它们作为吸附剂、干燥剂、阻燃剂、活性物质的储藏材料或储存材料或催化剂的用途。
有机金属骨架材料本身已知。关于该主题，我们参见科学出版物-Yaghi等人，J.Solid State Chem.(固态化学杂志)，第152卷(1)，3-20，该文献总结了该技术领域迄今为止的发展。EP-A 0 790 253中描述了一种制备这类材料的方法。该专利要求保护的制备微孔材料的方法包括将包含至少一种其中所定义金属离子的溶液与具有含有多齿官能团的亚结构的配体在其中所定义模板化合物存在下混合。作为这类材料的应用，该出版物提及一种从气体和液体中除去杂质的方法。在该出版物中，既没提及也没建议所述材料的其它用途。所述方法(该方法用非常少的量来进行)得到对于这类材料的工业规模生产而言不令人满意的产率，例如对于对苯二甲酸锌骨架，产率低于70％。该文献和其它现有技术都没有描述例如对于使用有机骨架材料作为催化剂的、提供所需高产率的、工业上相关的制备方法。
本发明的目的是提供一种制备这类骨架材料的方法，该方法首先可以以工业规模和高产率制备这类材料，其次还导致原则上是新的材料。
我们发现该目的通过使用N-甲基吡咯烷酮作为溶剂或溶剂组分来制备有机金属骨架材料而实现。以此方式，骨架材料可以以高产率来生产。
因此，本发明
提供一种制备有机金属骨架材料的方法，该方法包括使包含金属盐和至少一种能与金属离子配位的至少二齿有机化合物的流体混合物，例如溶液或悬浮体在至少一种碱和溶剂存在下反应，其中所述溶剂包含至少一种环状酰胺(内酰胺)和/或至少一种环状酯(内酯)，例如N-甲基吡咯烷酮；
提供一种有机金属微孔骨架材料，该材料包含金属离子和至少一种与其配位连接的至少二齿有机化合物，该材料可通过包括使包含金属盐和至少一种能与金属离子配位的至少二齿有机化合物的流体混合物，例如溶液或悬浮体在至少一种碱和溶剂存在下反应的方法制备，其中所述溶剂包含至少一种环状酰胺(内酰胺)和/或至少一种环状酯(内酯)，例如N-甲基吡咯烷酮；以及
提供所述有机金属骨架材料作为催化剂、吸附剂、干燥剂、阻燃剂、储藏材料、活性物质的储存材料、传感器材料、颜料或电子元件的用途。
本发明所用金属盐中的可能金属成分是元素周期表第Ia、IIa、IIIa、IVa-VIIIa和Ib-VIb族元素，其中特别优选锌、铜、镍、钯、铂、钌、铼和钴。
作为能与金属离子配位的至少二齿有机化合物，原则上可使用适于该目的且满足上述条件的所有化合物。该有机化合物尤其必须具有至少两个可与金属盐的金属离子、尤其是与上述Ia、IIa、IIIa、IVa-VIIIa和Ib-VIb族金属形成键的中心。这些有机化合物可尤其选自如下物质：
取代和未取代的单环和多环芳族二羧酸以及含有至少一个杂原子的取代和未取代的单环和多环芳族二羧酸。
具体实例是：
苯、萘、吡啶或喹啉的二羧酸。
本发明方法中使用的溶剂是包含单独的环状酰胺和/或环状酯或还与适合的共溶剂一起的溶剂。适合的共溶剂原则上是所有能溶解所述至少二齿有机化合物的质子和/或非质子有机溶剂。可提及的实例是：
芳族溶剂，例如苯、氯苯、甲苯或二甲苯，或卤代烃，例如氯仿。
可使用的碱是所有能使上述二齿化合物脱质子的有机碱。具体实例是：
三乙胺，氢氧化四烷基铵，例如氢氧化四丙基铵。
因此，本发明还涉及一种上述其中所述碱选自有机胺类的方法。
本发明有机金属骨架材料的制备例如按如下进行：首先将有机化合物溶解在一种溶剂或溶剂混合物中，之后优选在连续搅拌下加入金属盐。所述金属盐的加入可通过任何所需方法来进行。
当所述溶液一变均匀，就开始添加碱。
通过过滤、离心分离或喷雾干燥，将反应之后得到的包含有机金属骨架材料的沉淀从反应混合物的母液中分离出来。为了除去附着的溶剂和残留碱，可将以此方式分离出来的骨架材料进行干燥步骤。在该干燥步骤中，优选将压力降低，以使有机金属骨架材料的孔至少部分变空。
上述顺序的工艺步骤也可以以本领域熟练技术人员公知的方式进行改变，或者所述步骤也可按其它顺序进行。
因此，本发明还涉及一种包含金属离子和至少一种与其配位连接的至少二齿有机化合物的有机金属微孔骨架材料，该材料可通过包括使包含金属盐和至少一种能与金属离子配位的至少二齿有机化合物的流体混合物，例如溶液或悬浮体在至少一种碱和溶剂存在下反应的方法制备，其中所述溶剂包含至少一种环状酰胺(内酰胺)和/或至少一种环状酯(内酯)。
根据本发明得到的有机金属骨架材料含有微孔，按照Pure AppliedChem(纯应用化学).
45，第71页及以下、尤其是第79页(1976)的定义，这些微孔对本发明而言是直径为2nm或以下的孔。微孔的存在可由根据DIN66131、66134的确定有机金属骨架材料在77K下的氮气保留能力的吸着测量结果看出。此处，具有I型形状的典型等温线表明存在微孔。
根据Langmuir模型(DIN 66131，66134)计算的比表面积优选高于5m2/g，更优选高于50m2/g，尤其高于500m2/g，并且可延伸到高于2000m2/g的范围。
本发明的有机金属骨架材料尤其用作吸附剂、干燥剂、阻燃剂、活性物质的储藏材料或储存材料、传感器材料、颜料、电子元件或催化剂，尤其是用作可广泛应用的催化剂。
催化剂的应用领域尤其是：
氧化，还原，开环反应，C-C偶联反应和环氧化，C-C键的形成如烷基化、酰化；加成反应如羰基化、胺化、水合，醚化、烷氧基化；消去反应如脱羰、脱羧、脱水；脱氢和氢化，异构化，C-C键断裂如裂化和氢化裂化；重整；低聚，聚合；废气和废水的催化提纯，光催化。
因此，本发明还涉及一种使至少一种有机化合物反应的方法，其中使该有机化合物与根据本发明的至少一种催化剂接触。
当本发明的有机金属骨架材料用作催化剂时特别有利，因为它们的催化剂性能可通过改变金属和/或能与金属离子配位的至少二齿有机化合物而改变或调节。因此，例如C-C叁键的反应可通过本发明的含锌有机金属骨架材料来催化。本发明的催化剂适用于制备式I或II的化合物的方法：
其中R1是氢或脂族、脂环族、芳脂族、芳族或杂环基团或酰基，其中各取代基可含有不与炔属物质或丙二烯系物质反应的其它取代基，基团R相互独立地是氢或可相互连接形成环的脂族、脂环族、芳脂族、芳族或杂环基团，以及m是0或1，所述方法通过在气相、液相或超临界相中在升高的温度下将式III化合物
R1OH III
加成到式IV或V的炔属物质或丙二烯系物质上而进行，
其中R1和R定义如上。
适合的反应原料是任何炔烃、丙二烯系物质或其混合物。然而，一般使用工业上容易获得的具有2-8个碳原子或3-8个碳原子的炔属物质和丙二烯系物质。特别优选丙炔和丙二烯，尤其是其中存在这些物质的烃料流。
含有羟基的化合物R1OH可以是水、任何醇、酚或羧酸。一般而言，优选醇，尤其是具有1-16个碳原子的链烷醇，单环酚类和低分子量羧酸，例如具有1-16个碳原子的那些。特别优选低级醇，尤其是甲醇。
含有羟基的化合物的加成反应在多相催化剂存在下，在气相、液相或超临界相中，在固定床上或在流化床中，于25-400℃、优选100-250℃、特别优选120-200℃的温度下，在取决于所用原料一般为0.1-100巴、尤其是0.8-20巴的压力(或者是基于原料的各分压总和的压力)下进行。
因此，例如丙炔或丙二烯与甲醇的反应可取决于反应条件而选择性地生成2-甲氧基丙烯或2，2-二甲氧基丙烷。可由本发明得到的式I烯醇醚和式II二烷氧基化合物是制备活性化合物和香料的有价值的中间体。这些烯醇醚尤其是例如用于制备作为制备异植醇用的中间体的γ，δ-不饱和酮的广受欢迎的原料。
若尤其要得到所述烯醇醚，则通过消去1摩尔R1OH，可将式II化合物以本身公知的方式转变成相应的式I烯醇醚。用于该目的的许多方法见于DE-A-35 35 128、DE-A-37 22 891、DE-A-38 04 162、ChemicalAbstracts(化学文摘)，第94卷(19)；156 241及以后和DE-A-19544450。
有关制备上述化合物的其它细节可见于EP-A 1050 510，本申请此处全面引入其相关内容作为参考。
同样，乙烯基酯可由相应的酸和乙炔来制备，使得一般可通过本领域熟练技术人员公知的方法来活化取代的炔属物质或丙二烯系物质。
其它金属，例如Cu、Pd、Au、Ru、Ni、Rh、Co和Pt可催化氢化反应和脱氢反应，包括例如燃料电池应用中甲醇向氢气的转化。
由于有机金属骨架材料的广泛可变性，若选定的作为骨架成分的金属是其氧化态可容易改变的金属，例如已知的许多过渡金属，则它们一般也可用于氧化、环氧化和还原反应。
除改变骨架金属成分之外，其催化行为也可通过改变有机成分来控制。若例如将羧酸、磺酸、三氟磺酸或其它酸性基团引入有机成分中，则所得有机金属骨架材料可用作异构化、酯化、醚化、烷氧基化、水合、脱水、闭环反应和开环反应或C-C偶联反应中的多相固体酸。
可提及的其它反应是：
C-C键形成反应，例如烷基化、酰化；加成反应，例如羰基化、胺化、水合；消去反应，例如脱羰、脱羧；脱氢和氢化；C-C键断裂，例如裂化和氢化裂化；重整；氧化和环氧化；低聚、聚合；废气和废水的催化提纯、光催化。
若有机成分带有胺基，或者例如将吡啶的二羧酸酯用作有机成分，则这些材料可用于碱催化。
若将烷基取代的芳族二羧酸用作有机成分，则可制备随后适于借助空气在该烷基链上形成氢过氧化物的有机金属骨架材料，以将这些过氧化物用于烯烃的多相催化选择性环氧化。
作为有机金属骨架材料的高表面积和它们的孔隙率的结果，也可将它们用作吸附剂、干燥剂、阻燃剂、药物缓释用储藏材料和储存材料。
此外，由于这些材料的高孔隙率和表面积，它们也可例如在气体检测或诸如“化学芯片”应用领域中用作传感器或用于传感器。
也可将这些化合物用于或用作电子元件或功能材料。
取决于具体应用，本发明的有机金属骨架材料可以在反应器中以粉末形式使用或成型为挤出物、丸粒、颗粒、环形等或施用于载体上，例如作为由金属或聚合物制成的蒸馏填料或蜂窝体和编织筛上的涂料。这些反应取决于具体应用可在液相、气相或超临界相中进行。
此外，可使用塑料领域中已知的所有成型和加工方法，例如挤出、共挤出和掺入共混聚合物中。
下列实施例将解释本发明。
实施例
实施例1
在反应烧瓶中，将24.9g对苯二甲酸溶解在43.6g 1-甲基-2-吡咯烷酮与8.6g氯苯和24.9g二甲基甲酰胺的混合物中，并将所得混合物在搅拌下升温至70℃。向该溶液中加入52.2g硝酸锌。一小时后，同样在70℃下，向该悬浮体中加入30g三乙胺。将所得溶液在70℃下搅拌另外2小时。将沉淀的白色对苯二甲酸锌骨架材料滤出，并在室温下干燥，随后在200℃下烘焙。由两个干燥步骤产生的重量损失为23wt％。基于锌的用量、产率为87％。
比表面积的测定使用Micromeritics的仪器(ASAP 2000)通过容量分析来进行，根据Langmuir模型的计算值为1063m2/g。
实施例2
将1320g 1-甲基-2-吡咯烷酮置于反应烧瓶中，在30分钟内与64.2g对苯二甲酸混合。在连续搅拌下在1小时内向该溶液中加入87.6g硝酸铜，并使混合物均化。最后，在2小时内加入81g三乙胺，并将该混合物搅拌另外1小时。
将产物滤出，用约2升水洗涤，并在真空干燥箱中于150℃下干燥。
基于铜的用量，产率为88％。
在77K下的氮气等温线的记录(见图)表明微孔材料的典型I型等温线达到p/p°＜0.9。
相对压力，P/Po
由该图计算的Langmuir比表面积为334m2/g。
实施例3(4-叔丁基苯甲酸乙烯酯的制备)
将2.5g实施例1中制备的催化剂与100g 1-甲基-2-吡咯烷酮一起置于高压釜中，并与40g 4-叔丁基苯甲酸混合。在对高压釜施加5巴的氮气后，加热至180℃，随后引入20巴的乙炔，并通过引入额外量的乙炔以将该压力保持24小时。将所得反应混合物通过GC进行分析，表明所用酸的转化率为94％，4-叔丁基苯甲酸乙烯酯的选择性为83％。
实施例4(2-甲氧基丙烯的制备)
将55g按实施例1所述制备的催化剂以丸粒形式安装于差式循环反应器中。借助HPLC泵以1.5g/h供入液体料流(甲醇/环己烷的10∶1混合物)。在250℃下将丙炔以6g/h的气体流速引入。丙炔的转化率为30％，2-甲氧基丙烯的选择性为80％。
当不用催化剂重复该实验时，没有观察到丙炔发生反应。
Claims (9)
1.一种制备有机金属骨架材料的方法，包括使包含金属盐和至少一种能与金属离子配位的至少二齿有机化合物的流体混合物在至少一种碱和溶剂存在下反应，其中所述溶剂包含至少一种环状酰胺和/或至少一种环状酯，并且其中所述骨架材料根据Langmuir法测定的比表面积＞50m2/g。
2.如权利要求1所述的方法，其中所述金属选自锌、铜、钴、镍、钯、铂、钌、铼的金属盐及其两种或更多种的混合物。
3.如权利要求1或2所述的方法，其中所述碱选自有机胺类。
4.如权利要求1或2所述的方法，其中所述有机化合物选自取代和未取代的单环和多环芳族二羧酸以及含有至少一个杂原子的取代和未取代的单环和多环芳族二羧酸。
5.一种有机金属微孔骨架材料，该材料包含金属离子和至少一种与其配位连接的至少二齿有机化合物，该材料可通过根据权利要求1-4中任一项的方法制备。
6.如权利要求5所述的有机金属骨架材料，其由Langmuir法测定的比表面积＞500m2/g。
7.如权利要求5或6所述的有机金属骨架材料作为催化剂、吸附剂、干燥剂、阻燃剂、活性物质的储藏材料或储存材料、传感器材料、颜料或电子元件的用途。
8.一种使至少一种有机化合物反应的方法，其中使该有机化合物与至少一种如权利要求7所述的催化剂接触。
9.如权利要求8所述的方法，其中所述反应选自氧化、还原、开环反应、C-C偶联反应、环氧化、加成反应、胺化、水合、醚化、烷氧基化、脱羰、脱羧、脱水、脱氢、氢化、异构化、C-C键断裂、重整、异构化、低聚、聚合；废气和废水的催化提纯、光催化。
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| US5648508A (en) * | 1995-11-22 | 1997-07-15 | Nalco Chemical Company | Crystalline metal-organic microporous materials |
| DE19544450A1 (de) | 1995-11-29 | 1997-06-05 | Basf Ag | Verfahren zur Herstellung von Enolethern |
| DE19726670A1 (de) | 1997-06-23 | 1998-12-24 | Basf Ag | Verfahren zur Addition von Hydroxylgruppen enthaltenden Verbindungen an Alkine oder Allene |
| WO1999005151A1 (en) | 1997-07-25 | 1999-02-04 | Isis Innovation Limited | Porous solid products of 1,3,5-benzenetricarboxylate and metal ions |
| GB9807294D0 (en) * | 1998-04-03 | 1998-06-03 | Eghb 73 Limited | Method and apparatus for generating ozone |
| DE10111230A1 (de) | 2001-03-08 | 2002-09-19 | Basf Ag | Metallorganische Gerüstmaterialien und Verfahren zu deren Herstellung |
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2001
- 2001-03-08 DE DE10111230A patent/DE10111230A1/de not_active Withdrawn
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- 2002-03-07 JP JP2002569846A patent/JP4216074B2/ja not_active Expired - Fee Related
- 2002-03-07 EP EP02727373A patent/EP1373277B1/de not_active Expired - Lifetime
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- 2002-03-07 DE DE50213078T patent/DE50213078D1/de not_active Expired - Lifetime
- 2002-03-07 CN CNB02806061XA patent/CN1240703C/zh not_active Expired - Fee Related
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- 2002-03-07 US US10/469,826 patent/US7119219B2/en not_active Expired - Fee Related
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| KR100830083B1 (ko) | 2008-05-20 |
| ATE416180T1 (de) | 2008-12-15 |
| US7119219B2 (en) | 2006-10-10 |
| CN1494546A (zh) | 2004-05-05 |
| WO2002070526A1 (de) | 2002-09-12 |
| ZA200306959B (en) | 2004-09-06 |
| MXPA03007873A (es) | 2004-04-02 |
| KR20040007460A (ko) | 2004-01-24 |
| DE50213078D1 (de) | 2009-01-15 |
| EP1373277B1 (de) | 2008-12-03 |
| JP4216074B2 (ja) | 2009-01-28 |
| JP2004534737A (ja) | 2004-11-18 |
| CA2440114A1 (en) | 2002-09-12 |
| EP1373277A1 (de) | 2004-01-02 |
| CA2440114C (en) | 2010-10-26 |
| DE10111230A1 (de) | 2002-09-19 |
| US20040097724A1 (en) | 2004-05-20 |
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