CN115433149B - 一种3,3′,4,4′-联苯四羧酸二酐的制备方法 - Google Patents
一种3,3′,4,4′-联苯四羧酸二酐的制备方法 Download PDFInfo
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- CN115433149B CN115433149B CN202211201036.7A CN202211201036A CN115433149B CN 115433149 B CN115433149 B CN 115433149B CN 202211201036 A CN202211201036 A CN 202211201036A CN 115433149 B CN115433149 B CN 115433149B
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- Prior art keywords
- molar ratio
- catalyst
- nickel
- anhydride
- tetracarboxylic dianhydride
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- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000000967 suction filtration Methods 0.000 claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 10
- 239000003446 ligand Substances 0.000 claims abstract description 10
- BTTRMCQEPDPCPA-UHFFFAOYSA-N 4-chlorophthalic anhydride Chemical compound ClC1=CC=C2C(=O)OC(=O)C2=C1 BTTRMCQEPDPCPA-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 230000018044 dehydration Effects 0.000 claims abstract description 8
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 8
- 238000004537 pulping Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000012265 solid product Substances 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims abstract 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 6
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 6
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical group I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 claims description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 6
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- MWUSAETYTBNPDG-UHFFFAOYSA-N (4-chlorobenzoyl) 4-chlorobenzoate Chemical compound C1=CC(Cl)=CC=C1C(=O)OC(=O)C1=CC=C(Cl)C=C1 MWUSAETYTBNPDG-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 4
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical group Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000009518 sodium iodide Nutrition 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- DDFYFBUWEBINLX-UHFFFAOYSA-M tetramethylammonium bromide Chemical compound [Br-].C[N+](C)(C)C DDFYFBUWEBINLX-UHFFFAOYSA-M 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 description 13
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- VHSVJTYBTJCDFL-UHFFFAOYSA-L 1,2-dimethoxyethane;nickel(2+);dibromide Chemical compound Br[Ni]Br.COCCOC VHSVJTYBTJCDFL-UHFFFAOYSA-L 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- OCMNCWNTDDVHFK-UHFFFAOYSA-L dichloronickel;1,2-dimethoxyethane Chemical compound Cl[Ni]Cl.COCCOC OCMNCWNTDDVHFK-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910001509 metal bromide Inorganic materials 0.000 description 1
- 229910001511 metal iodide Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006578 reductive coupling reaction Methods 0.000 description 1
- -1 saturated alkyl nitriles Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- SNOOUWRIMMFWNE-UHFFFAOYSA-M sodium;6-[(3,4,5-trimethoxybenzoyl)amino]hexanoate Chemical compound [Na+].COC1=CC(C(=O)NCCCCCC([O-])=O)=CC(OC)=C1OC SNOOUWRIMMFWNE-UHFFFAOYSA-M 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
- C07D307/89—Benzo [c] furans; Hydrogenated benzo [c] furans with two oxygen atoms directly attached in positions 1 and 3
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
- B01J31/182—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine comprising aliphatic or saturated rings
-
- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
-
- 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
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4205—C-C cross-coupling, e.g. metal catalyzed or Friedel-Crafts type
-
- 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
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/16—Copper
-
- 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
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
本发明提供了一种3,3',4,4'‑联苯四羧酸二酐的制备方法,包括以下步骤:在反应器中依次加入金属铜类催化剂、金属镍类催化剂、配体、碱、添加剂、1,2,4‑苯三酸酐与4‑氯苯酐,在惰性气体保护下,加入有机溶剂,搅拌,升温到指定温度,反应完全后,蒸馏回收溶剂,将混合物中加入氢氧化钠溶液加热水解,冷却至室温后抽滤去除不溶物,随后酸化析出固体,过滤得到的固体产物,水洗打浆后抽滤得四酸中间体,四酸中间体熔融脱水后获得目标产物3,3',4,4'‑联苯四羧酸二酐。本发明在金属铜镍协同催化下,一锅法反应制备3,3',4,4'‑联苯四羧酸二酐,该反应方法不但可以高效的合成目标化合物,产物单一,而且此方法采用单一配体且催化剂便宜易得,原料廉价易得,操作简便,收率良好。
Description
技术领域
本发明属于有机合成领域,具体涉及一种3,3′,4,4′-联苯四羧酸二酐的制备方法。
背景技术
聚酰亚胺作为性能良好的高分子材料,具有良好的力学性能、介电性能、耐辐射性能和耐溶剂性能等,已经得到世界各国的充分认识,其优良的性能使之在航空、5G、微电子、液晶、分离膜等众多领域显示出良好的应用。
3,3′,4,4′-联苯四羧酸二酐是一种重要的聚酰亚胺单体材料,在耐高温的聚酰亚胺材料合成方面具有广泛应用。此外作为重要的精细化学品,也可应用于医药中间体。
目前,合成3,3′,4,4′-联苯四羧酸二酐的方法主要有:
1.使用4-卤代邻苯二甲酸或其衍生物进行自身的还原偶联反应,反应需要加入大量的金属还原剂(锌粉、锰粉)和较为昂贵的金属溴化物或碘化物作为添加剂;
2.在醋酸钯条件下邻苯二甲酸酯的氧化偶联,反应中使用了昂贵的钯催化剂,且产物为异构体混合物,不易分离纯化。
发明内容
有鉴于此,本发明创造旨在提出一种3,3′,4,4′-联苯四羧酸二酐的制备方法,该方法操作简便,重要的是催化剂便宜、原料廉价易得,产物单一,收率良好。
为达到上述目的,本发明创造的技术方案是这样实现的:
一种3,3′,4,4′-联苯四羧酸二酐的制备方法,包括以下步骤:在干燥的反应容器Schlenk管中依次加入金属铜类催化剂、金属镍类催化剂、配体、碱、添加剂、1,2,4-苯三酸酐与4-氯苯酐,将反应容器抽真空并充入惰性气体(氩气或氮气)重复3次,然后惰性气体保护下,加入有机溶剂,在室温下搅拌10分钟,然后升温到指定温度下搅拌至反应完全。反应完全后,蒸馏回收溶剂,将混合物中加入20%氢氧化钠溶液加热水解,冷却至室温后抽滤去除不溶物,随后酸化析出固体,过滤得到的固体产物,水洗打浆后抽滤得四酸中间体,四酸中间体熔融脱水后获得目标产物3,3′,4,4′-联苯四羧酸二酐;
所述方法合成路线如下:
进一步,所述金属铜类催化剂:金属镍类催化剂:配体:碱:添加剂:1,2,4-苯三酸酐:4-氯苯酐:有机溶剂的用量比为摩尔:摩尔:摩尔:摩尔:摩尔:摩尔:摩尔:体积mL=(0.025~0.1):(0.025~0.1):(0.05~0.2):(1~3):(0.5~2):1:(1~1.5):(3~10)。
进一步,所述金属铜类催化剂:金属镍类催化剂:配体:碱:添加剂:1,2,4-苯三酸酐:4-氯苯酐:有机溶剂的用量比为摩尔:摩尔:摩尔:摩尔:摩尔:摩尔:摩尔:体积mL=0.05:0.05:0.1:2:1:1:1:5。
进一步,所述金属铜类催化剂为氯化亚铜、溴化亚铜、碘化亚铜、醋酸铜、氯化铜、溴化铜中的任一种。
进一步,所述金属镍类催化剂为碘化镍、溴化镍、氯化镍、碳酸镍、六水合硝酸镍、氯化镍乙二醇二甲醚络合物、溴化镍乙二醇二甲醚络合物、二(乙酰丙酮)镍中的任一种。
进一步,所述配体为选自下式化合物中的一种或几种,其中R1~R7为氢、卤素、碳数小于20的烷基、芳基或取代的芳基,
进一步,所述碱,其阳离子为Li+、Na+、K+和Cs+中的任一种,阴离子为F–、CO3 2–、HCO3 –、PO4 3–、HPO4 2–、H2PO4 –、OH–、[CH3COO]–、[CF3COO]–、[OMe]–和[OtBu]–中的任一种。
进一步,所述添加剂,其阳离子为Li+、Na+、K+、Cs+、Mg2+、Ca2+、Cu+、Cu2+、Zn2+,Ag+、[(CnH2n+1)4N]+中的任一种,阴离子为F–、Cl–、Br–、I–、BF4 –、NO2 –、NO3 –、SO3 2–、SO4 2–中的任一种;其中,所述n为1到8之间的任意整数。
进一步,所述有机溶剂为甲醇、乙醇、异丙醇、四氢呋喃、2-甲基四氢呋喃、1,4-二氧六环、甲基叔丁基醚、二乙二醇二甲醚、乙二醇二甲醚、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜、1,2-二氯乙烷、氯仿、四氯化碳、苯、甲苯、二甲苯、三甲苯、氯苯、1,2-二氯苯、丙酮、乙腈、C3-C12的饱和烷基腈中的一种或几种。
进一步,所述指定温度为60~140℃,优选的为120~130℃。
与现有技术相比,本发明具有以下有益效果:
本发明公开的3,3′,4,4′-联苯四羧酸二酐的制备方法,使用1,2,4-苯三酸酐与4-氯苯酐,在金属铜镍协同催化催化下,一锅法反应制备3,3′,4,4′-联苯四羧酸二酐,该反应方法不但可以高效的合成目标化合物,产物单一,而且此方法采用单一配体且催化剂便宜易得,原料廉价易得,操作简便,收率良好,反应溶剂可以回收套用,为进一步放大奠定了基础,为合成3,3′,4,4′-联苯四羧酸二酐提供了新方法。
具体实施方式
除有定义外,以下实施例中所用的技术术语具有与本发明创造所属领域技术人员普遍理解的相同含义。以下实施例中所用的试验试剂,如无特殊说明,均为常规生化试剂;所述实验方法,如无特殊说明,均为常规方法。
下面结合实施例来详细说明本发明创造。
实施例1
将碘化亚铜(9.5mg,0.05mmol)和碘化镍(15.6mg,0.05mmol)、2,2′-联吡啶(15.6mg,0.1mmol)、碳酸钾(276.4mg,2mmol)、四甲基溴化铵(154.1mg,1mmol)、1,2,4-苯三酸酐(192.1mg,1mmol)与4-氯苯酐(182.6mg,1mmol)依次加入到干燥的Schlenk管中,将反应容器抽真空并充入氮气重复3次,然后惰性气体保护下,加入干燥的二乙二醇二甲醚(5mL),在室温下搅拌10分钟,然后升温到130℃下搅拌至反应完全。反应完成后,蒸馏回收溶剂,将混合物加入20%氢氧化钠溶液加热水解,冷却至室温后抽滤去除不溶物,随后使用硫酸酸化析出固体,过滤得到的固体产物,水洗打浆后抽滤得四酸中间体,四酸中间体熔融脱水后获得目标产物3,3′,4,4′-联苯四羧酸二酐,收率90%。
实施例2
将碘化亚铜(14.3mg,0.075mmol)和碘化镍(23.4mg,0.075mmol)、1,10-菲啰啉(27mg,0.15mmol)、碳酸钾(414.6mg,3mmol)、四丁基溴化铵(322.4mg,1mmol)、1,2,4-苯三酸酐(192.1mg,1mmol)与4-氯苯酐(219.1mg,1.2mmol)依次加入到干燥的Schlenk管中,将反应容器抽真空并充入氮气重复3次,然后惰性气体保护下,加入干燥的N,N-二甲基甲酰胺(8mL),在室温下搅拌10分钟,然后升温到130℃下搅拌至反应完全。反应完成后,蒸馏回收溶剂,将混合物加入20%氢氧化钠溶液加热水解,冷却至室温后抽滤去除不溶物,随后使用硫酸酸化析出固体,过滤得到的固体产物,水洗打浆后抽滤得四酸中间体,四酸中间体熔融脱水后获得目标产物3,3′,4,4′-联苯四羧酸二酐,收率88%。
实施例3
将溴化亚铜(5.8mg,0.04mmol)和氯化镍(5.2mg,0.04mmol)、1,10-菲啰啉(14.4mg,0.08mmol)、碳酸钾(276.4mg,2mmol)、碘化钠(299.8mg,2mmol)、1,2,4-苯三酸酐(192.1mg,1mmol)与4-氯苯酐(182.6mg,1mmol)依次加入到干燥的Schlenk管中,将反应容器抽真空并充入氮气重复3次,然后惰性气体保护下,加入干燥的N,N-二甲基甲酰胺(5mL),在室温下搅拌10分钟,然后升温到130℃下搅拌至反应完全。反应完成后,蒸馏回收溶剂,将混合物加入20%氢氧化钠溶液加热水解,冷却至室温后抽滤去除不溶物,随后使用硫酸酸化析出固体,过滤得到的固体产物,水洗打浆后抽滤得四酸中间体,四酸中间体熔融脱水后获得目标产物3,3′,4,4′-联苯四羧酸二酐,收率85%。
实施例4
将碘化亚铜(4.8mg,0.025mmol)和碘化镍(7.8mg,0.025mmol)、1,10-菲啰啉(9mg,0.05mmol)、碳酸钾(138.2mg,1mmol)、氯化锂(21.2mg,0.5mmol)、1,2,4-苯三酸酐(192.1mg,1mmol)与4-氯苯酐(273.9mg,1.5mmol)依次加入到干燥的Schlenk管中,将反应容器抽真空并充入氩气重复3次,然后惰性气体保护下,加入干燥的甲苯(4mL),在室温下搅拌10分钟,然后升温到110℃下搅拌至反应完全。反应完成后,蒸馏回收溶剂,将混合物加入20%氢氧化钠溶液加热水解,冷却至室温后抽滤去除不溶物,随后使用硫酸酸化析出固体,过滤得到的固体产物,水洗打浆后抽滤得四酸中间体,四酸中间体熔融脱水后获得目标产物3,3′,4,4′-联苯四羧酸二酐,收率64%。
实施例5
将碘化亚铜(9.5mg,0.05mmol)和碘化镍(15.6mg,0.05mmol)、1,10-菲啰啉(18mg,0.1mmol)、甲醇锂(56.9mg,1.5mmol)、溴化钠(154.4mg,1.5mmol)、1,2,4-苯三酸酐(192.1mg,1mmol)与4-氯苯酐(182.6mg,1mmol)依次加入到干燥的Schlenk管中,将反应容器抽真空并充入氩气重复3次,然后惰性气体保护下,加入干燥的N-甲基吡咯烷酮(10mL),在室温下搅拌10分钟,然后升温到120℃下搅拌至反应完全。反应完成后,蒸馏回收溶剂,将混合物加入20%氢氧化钠溶液加热水解,冷却至室温后抽滤去除不溶物,随后使用硫酸酸化析出固体,过滤得到的固体产物,水洗打浆后抽滤得四酸中间体,四酸中间体熔融脱水后获得目标产物3,3′,4,4′-联苯四羧酸二酐,收率76%。
以上所述仅为本发明创造的较佳实施例而已,并不用以限制本发明创造,凡在本发明创造的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明创造的保护范围之内。
Claims (4)
1.一种3,3',4,4'-联苯四羧酸二酐的制备方法,其特征在于:包括以下步骤:在反应器中依次加入金属铜类催化剂、金属镍类催化剂、配体、碱、添加剂、1,2,4-苯三酸酐与4-氯苯酐,在惰性气体保护下,加入有机溶剂,搅拌,升温到指定温度,反应完全后,蒸馏回收溶剂,将混合物中加入氢氧化钠溶液加热水解,冷却至室温后抽滤去除不溶物,随后酸化析出固体,过滤得到的固体产物,水洗打浆后抽滤得四酸中间体,四酸中间体熔融脱水后获得目标产物3,3',4,4'-联苯四羧酸二酐;
所述方法合成路线如下:
金属铜类催化剂为溴化亚铜或碘化亚铜,金属镍类催化剂为碘化镍或氯化镍,配体为2,2'-联吡啶或1,10-菲啰啉,碱为碳酸钾或甲醇锂,添加剂为四甲基溴化铵、四丁基溴化铵、碘化钠、氯化锂、溴化钠的任一种,有机溶剂为二乙二醇二甲醚、N,N-二甲基甲酰胺、甲苯、N-甲基吡咯烷酮的任一种。
2.根据权利要求1所述的3,3',4,4'-联苯四羧酸二酐的制备方法,其特征在于:所述金属铜类催化剂:金属镍类催化剂:配体:碱:添加剂:1,2,4-苯三酸酐:4-氯苯酐:有机溶剂的用量比为摩尔:摩尔:摩尔:摩尔:摩尔:摩尔:摩尔:体积mL=(0.025~0.1):(0.025~0.1):(0.05~0.2):(1~3):(0.5~2):1:(1~1.5):(3~10)。
3.根据权利要求2所述的3,3',4,4'-联苯四羧酸二酐的制备方法,其特征在于:所述金属铜类催化剂:金属镍类催化剂:配体:碱:添加剂:1,2,4-苯三酸酐:4-氯苯酐:有机溶剂的用量比为摩尔:摩尔:摩尔:摩尔:摩尔:摩尔:摩尔:体积mL=0.05:0.05:0.1:2:1:1:1:5。
4.根据权利要求1所述的3,3',4,4'-联苯四羧酸二酐的制备方法,其特征在于:所述指定温度为110~130℃。
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