CN115521280A - Method for preparing 3,3', 4' -biphenyl tetracarboxylic acid and dianhydride thereof and obtained product - Google Patents
Method for preparing 3,3', 4' -biphenyl tetracarboxylic acid and dianhydride thereof and obtained product Download PDFInfo
- Publication number
- CN115521280A CN115521280A CN202110709574.6A CN202110709574A CN115521280A CN 115521280 A CN115521280 A CN 115521280A CN 202110709574 A CN202110709574 A CN 202110709574A CN 115521280 A CN115521280 A CN 115521280A
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- Prior art keywords
- reaction
- gas
- chloroprene
- solvent
- weight ratio
- Prior art date
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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 39
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 144
- 239000002904 solvent Substances 0.000 claims abstract description 44
- 150000001336 alkenes Chemical class 0.000 claims abstract description 32
- 239000013067 intermediate product Substances 0.000 claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 28
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 23
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims abstract description 23
- 239000011976 maleic acid Substances 0.000 claims abstract description 23
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 230000001590 oxidative effect Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 claims description 58
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 42
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 36
- 239000007789 gas Substances 0.000 claims description 34
- 238000010438 heat treatment Methods 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000001816 cooling Methods 0.000 claims description 30
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 30
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 24
- 239000011777 magnesium Substances 0.000 claims description 23
- 229910052749 magnesium Inorganic materials 0.000 claims description 23
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 22
- -1 2-chloroprene Grignard reagent Chemical class 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- 239000011592 zinc chloride Substances 0.000 claims description 15
- 235000005074 zinc chloride Nutrition 0.000 claims description 15
- 239000007818 Grignard reagent Substances 0.000 claims description 14
- 238000009835 boiling Methods 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- APQIUTYORBAGEZ-UHFFFAOYSA-N 1,1-dibromoethane Chemical compound CC(Br)Br APQIUTYORBAGEZ-UHFFFAOYSA-N 0.000 claims description 10
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000010791 quenching Methods 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 238000005859 coupling reaction Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 239000003999 initiator Substances 0.000 claims description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 239000012024 dehydrating agents Substances 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- DYHSDKLCOJIUFX-UHFFFAOYSA-N tert-butoxycarbonyl anhydride Chemical compound CC(C)(C)OC(=O)OC(=O)OC(C)(C)C DYHSDKLCOJIUFX-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 3
- 150000004795 grignard reagents Chemical class 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- ZADGQTHIZZOKGE-UHFFFAOYSA-N 1,1,1-trichloro-2,2-diphenylethane Chemical compound C=1C=CC=CC=1C(C(Cl)(Cl)Cl)C1=CC=CC=C1 ZADGQTHIZZOKGE-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 229940099962 diphenyltrichloroethane Drugs 0.000 claims description 2
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 claims description 2
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- 239000005456 alcohol based solvent Substances 0.000 claims 3
- MCIHQMIVQIICBN-UHFFFAOYSA-N (1-chloro-1-phenylpropyl)benzene Chemical compound C1(=CC=CC=C1)C(CC)(Cl)C1=CC=CC=C1 MCIHQMIVQIICBN-UHFFFAOYSA-N 0.000 claims 1
- 239000004973 liquid crystal related substance Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 10
- 238000005899 aromatization reaction Methods 0.000 abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 238000010992 reflux Methods 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 11
- 239000012153 distilled water Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 11
- 239000012295 chemical reaction liquid Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- 238000010168 coupling process Methods 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 230000001476 alcoholic effect Effects 0.000 description 4
- 238000005695 dehalogenation reaction Methods 0.000 description 4
- CQMIJLIXKMKFQW-UHFFFAOYSA-N 4-phenylbenzene-1,2,3,5-tetracarboxylic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(=O)O)=CC(C(O)=O)=C1C1=CC=CC=C1 CQMIJLIXKMKFQW-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 238000006352 cycloaddition reaction Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- UQPSGBZICXWIAG-UHFFFAOYSA-L nickel(2+);dibromide;trihydrate Chemical compound O.O.O.Br[Ni]Br UQPSGBZICXWIAG-UHFFFAOYSA-L 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- ARCGXLSVLAOJQL-UHFFFAOYSA-N anhydrous trimellitic acid Natural products OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- JZALIDSFNICAQX-UHFFFAOYSA-N dichloro-methyl-trimethylsilylsilane Chemical compound C[Si](C)(C)[Si](C)(Cl)Cl JZALIDSFNICAQX-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 229940046149 ferrous bromide Drugs 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- CPSYWNLKRDURMG-UHFFFAOYSA-L hydron;manganese(2+);phosphate Chemical compound [Mn+2].OP([O-])([O-])=O CPSYWNLKRDURMG-UHFFFAOYSA-L 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- ZUVVLBGWTRIOFH-UHFFFAOYSA-N methyl 4-methyl-2-[(4-methylphenyl)sulfonylamino]pentanoate Chemical compound COC(=O)C(CC(C)C)NS(=O)(=O)C1=CC=C(C)C=C1 ZUVVLBGWTRIOFH-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 229910000159 nickel phosphate Inorganic materials 0.000 description 1
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Ni+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 description 1
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen 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-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000004366 reverse phase liquid chromatography Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
- C07C1/326—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom the hetero-atom being a magnesium atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- C07C51/36—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by hydrogenation of carbon-to-carbon unsaturated bonds
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
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- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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Abstract
The invention discloses a method for preparing 3,3', 4' -biphenyl tetracarboxylic acid and dianhydride thereof and an obtained product, wherein the method for preparing the 3,3', 4' -biphenyl tetracarboxylic acid comprises the following steps: mixing dendron [4] ene, maleic acid and a solvent for reaction, and removing the solvent in a system after the reaction is finished to obtain an intermediate product I; reacting the intermediate product I in the presence of an alkaline substance and an oxidant to obtain an intermediate product II; and carrying out post-treatment on the intermediate product II to obtain the 3,3', 4' -biphenyltetracarboxylic acid. 3,3', 4' -biphenyltetracarboxylic dianhydride can be obtained by dehydrating 3,3', 4' -biphenyltetracarboxylic acid. The invention adopts dendritic [4] alkene and maleic acid as raw materials to carry out cycloaddition-oxidation aromatization reaction, the synthesis strategy is novel, noble metal catalysts are not used, and the total yield is higher.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to preparation of 3,3', 4' -biphenyl tetracarboxylic dianhydride, in particular to preparation of 3,3', 4' -biphenyl tetracarboxylic dianhydride through cycloaddition reaction.
Background
3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) is a precursor for preparing 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA), and 3,3', 4' -biphenyltetracarboxylic dianhydride (BPDA) is an important anhydride precursor of high-performance polyimide, and a polyimide material obtained by using the precursor as a monomer shows very good heat resistance, water resistance and mechanical properties, and is a super heat-resistant resin with the highest heat resistance temperature so far. The dielectric constant of the polyimide material prepared from BPDA is only about 2.5, and the dielectric strength is 100-300 KV. Mm -1 These properties can be maintained at a high level over a wide temperature and frequency range, and thus are more suitable for high frequency electronic communication. The main preparation methods of 3,3', 4' -biphenyl tetracarboxylic dianhydride currently comprise:
1) A dehalogenation coupling method of 4-chloro (bromo) -phthalate is carried out by Nihon Shuangshi Kabushiki Kaisha in 80 s, dehalogenation coupling of halogenated phthalate under existence of Pd type metal catalyst, alkali and reducer, acidifying to obtain 3,3', 4' -biphenyl tetracarboxylic acid, and dewatering to obtain BPDA. The method is not perfect in recent years and is the most important industrialized method at present. See CN 11056678A, CN111620769A, etc., however, the use of noble metal catalyst increases the preparation cost;
2) The dehalogenation coupling method of 4-chloro (bromo) -phthalic acid ester is proposed by Changchun chemical company Bowenxian et al, said method adopts 4-chloro/bromo-phthalic acid dimethyl ester as raw material, and makes dehalogenation coupling reaction in the presence of bis (triphenylphosphine) nickel dichloride catalyst and zinc powder as reducing agent, said reaction requires no water and needs no N 2 Protecting, hydrolyzing and acidifying the generated ester to obtain 3,3', 4' -biphenyltetracarboxylic acid, and dehydrating to obtain BPDA (bisphenol A), see US5081281A; CN1021439C and the like; however, the method has poor process stability and generates more metal salt waste residues;
) Dimethyl phthalate is oxidatively coupled by oxygen in the presence of palladium acetate and ligand to obtain 3,3', 4' -biphenyltetracarboxylic acid, and then BPDA is obtained by dehydration, wherein the raw materials used in the method are most economical, but the conversion rate of the reaction is low (usually less than 10%), and various isomers exist, and the final product can be obtained by matching with a complex separation process. See US,4292435,1981; US,4581469, 1986, etc.;
4) Anhydrous trimellitic acid monoacyl chloride coupling method, which is to perform decarboxylation coupling to obtain BPDA by using dichlorotetramethyldisilane as a reducing agent under the condition of palladium catalyst. Although this process has a high conversion, the raw materials are expensive and not readily available. See EP 339 455,1989.
In summary, the current main methods for preparing 3,3', 4' -biphenyltetracarboxylic acid and BPDA adopt palladium catalysts, and the use of noble metal palladium catalysts is one of the main reasons for the high cost of the current 3,3', 4' -biphenyltetracarboxylic acid and BPDA. Therefore, the development of a non-noble metal-catalyzed, simple and efficient synthetic route has important significance for reducing the production cost of 3,3', 4' -biphenyltetracarboxylic acid and BPDA.
Disclosure of Invention
The present invention is directed to solving the problems of the general use of noble metal catalysts for the preparation of 3,3', 4' -biphenyltetracarboxylic acid and 3,3', 4' -biphenyltetracarboxylic dianhydride, and provides a method for preparing 3,3', 4' -biphenyltetracarboxylic acid and dianhydride thereof, wherein the method comprises: the 3,3', 4' -biphenyl tetracarboxylic dianhydride is prepared by cycloaddition-oxidative aromatization reaction of dendritic [4] alkene and maleic acid, the method mixes the dendritic [4] alkene and the maleic acid, realizes the series cycloaddition-oxidative aromatization reaction by a one-pot method to obtain the 3,3', 4' -biphenyl tetracarboxylic dianhydride, and further obtains the 3,3', 4' -biphenyl tetracarboxylic dianhydride by dehydration of acetic anhydride, thereby realizing a novel method for preparing the 3,3', 4' -biphenyl tetracarboxylic dianhydride and the 3,3', 4' -biphenyl tetracarboxylic dianhydride.
An object of the present invention is to provide a method for preparing 3,3', 4' -biphenyltetracarboxylic acid, comprising:
(1) Mixing dendron [4] ene, maleic acid and a solvent for reaction, and removing the solvent in a system after the reaction is finished to obtain an intermediate product I;
(2) Reacting the intermediate product I in the presence of an alkaline substance and an oxidant to obtain an intermediate product II;
(3) And carrying out post-treatment on the intermediate product II to obtain the 3,3', 4' -biphenyltetracarboxylic acid.
Wherein the structure of the dendron [4] alkene in the step (1) is shown as a formula (i). In the step (1), D-A cycloaddition reaction of dendritic [4] alkene and maleic acid is carried out, and the obtained intermediate product is bi-1, 2,5, 6-tetrahydrophthalic acid, and the structure of the intermediate product is shown as the formula (ii):
wherein, in the step (2), the intermediate product I is subjected to oxidative aromatization to form an intermediate product II.
In a preferred embodiment, in step (1), the solvent is at least one selected from the group consisting of alcoholic solvents, tetrahydrofuran, ethyl acetate, and 1, 4-dioxane.
In a further preferred embodiment, in step (1), the alcoholic solvent is selected from alcoholic solvents with a boiling point lower than 150 ℃, preferably at least one selected from methanol, ethanol, n-propanol, isopropanol, n-butanol.
In a further preferred embodiment, the solvent in the system is removed by distillation in step (1).
In a preferred embodiment, in step (1), the weight ratio of dendron [4] ene to solvent is 1 (5 to 200); and/or the weight ratio of the dendron [4] alkene to the maleic acid is 1 (1-4).
Wherein, the excessive maleic acid in the system can be removed by water washing.
In a further preferred embodiment, in step (1), the weight ratio of dendron [4] ene to solvent is 1 (10 to 100); and/or the weight ratio of the dendron [4] alkene to the maleic acid is 1 (2-2.5).
For example, in step (1), the weight ratio of dendron [4] ene to alcoholic solvent is 1; and/or the weight ratio of dendron [4] ene to maleic acid is 1, 1.
In a preferred embodiment, in step (1), the reaction temperature is 45 to 105 ℃ and the reaction time is 4 to 12 hours.
In a further preferred embodiment, in step (1), the reaction is carried out below the boiling point of the solvent.
For example, in the step (1), the reaction temperature is 45 ℃, 55 ℃, 65 ℃, 75 ℃, 85 ℃, 95 ℃, 105 ℃ or 115 ℃, and the reaction time is 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours or 12 hours.
In a preferred embodiment, the alkaline substance is an inorganic alkaline substance, preferably at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.
In a preferred embodiment, the oxidizing agent is at least one selected from hydrogen peroxide, potassium persulfate and ammonium persulfate.
In a further preferred embodiment, the oxidizing agent is hydrogen peroxide, for example, 30% hydrogen peroxide by mass.
In a preferred embodiment, the weight ratio of basic substance to dendron [4] ene is (0.6-2): 1; and/or the weight ratio of the oxidant to the dendritic [4] ene is (2-6): 1.
In a further preferred embodiment, the weight ratio of basic substance to dendron [4] ene is (0.9-1.5): 1; and/or the weight ratio of the oxidant to the dendritic [4] ene is (4-5): 1.
In a preferred embodiment, in step (2), the intermediate product I, the basic substance, and water are mixed (preferably, water and the basic substance are added to the intermediate product I), then heating treatment is performed, then an oxidizing agent is slowly added dropwise to the system, and after the addition, the reaction is continued while maintaining the temperature (preferably, after the reaction is completed, cooling to room temperature) to obtain the intermediate product II.
In a further preferred embodiment, in the step (2), the intermediate product I, the basic substance, and water are mixed (preferably, water and the basic substance are added to the intermediate product I), heated to 30 to 80 ℃, and then an oxidizing agent is slowly added dropwise to the system, and after the addition, the temperature is maintained to continue the reaction for 1 to 3 hours (preferably, after the reaction is completed, the reaction is cooled to room temperature), thereby obtaining the intermediate product II.
For example, the reaction mixture is heated to 30 ℃, 40 ℃, 50 ℃,60 ℃,70 ℃ or 80 ℃ and hydrogen peroxide is slowly added dropwise into the system, and the reaction is continued for 1 hour, 1.5 hours, 2 hours, 2.5 hours or 3 hours while maintaining the temperature after the addition.
In a further preferred embodiment, the weight ratio of water to dendron [4] ene is (5-40): 1, preferably (10-30): 1.
In a preferred embodiment, in step (3), the post-processing includes:
(3.1) adding a reducing substance to the intermediate product II (to neutralize excess oxidizing agent);
(3.2) adjusting the pH value of the system to 1-5, preferably 2-3;
(3.3) filtering and washing to obtain the 3,3', 4' -biphenyltetracarboxylic acid.
In a preferred embodiment, the reducing substance is selected from sodium bisulfite and/or sodium hydrosulfite, preferably sodium bisulfite.
In a further preferred embodiment, the weight ratio of the reducing substance to the oxidizing agent is 1: (50 to 500), for example, 1.
In a preferred embodiment, in step (3.2), concentrated hydrochloric acid is used to adjust the pH, for example, to 36.5% by weight.
In a preferred embodiment, the method of making said dendron [4] ene comprises: 2-chloroprene is used as an initial raw material, and the dendron [4] alkene is obtained through a Grignard reagent coupling reaction.
In a further preferred embodiment, the method of making said dendron [4] ene comprises: firstly, preparing a 2-chloroprene format reagent, wherein the structure is shown as a formula (iii); and reacting the 2-chloroprene format reagent with 2-chloroprene to obtain the dendritic [4] ene.
In a further preferred embodiment, the method of making said dendron [4] ene comprises:
(I) Preparation of 2-chloroprene Grignard reagent: mixing the dried magnesium chips, an initiator and a solvent under a protective atmosphere, stirring, heating to a set temperature, and then adding anhydrous zinc chloride and the solvent; then dropwise adding the solution containing 2-chloroprene and the solvent into a reaction container, and reacting to obtain a 2-chloroprene form reagent solution;
wherein, after the anhydrous zinc chloride is added, the magnesium can reduce the added small amount of anhydrous zinc chloride to form a primary battery effect and increase the reaction activity of the magnesium.
(II) preparation of dendron [4] ene: and (2) dropwise adding 2-chloroprene into the reaction system in the step (I) at the temperature of-10 ℃, sequentially adding a cocatalyst and a transition metal catalyst after dropwise adding is finished, heating for reaction, and performing post-treatment after the reaction is finished to obtain the dendron [4] alkene.
For example, in the step (II), 2-chloroprene is added dropwise to the reaction system of the step (1) at-8 ℃, -5 ℃, -2 ℃, 0 ℃,2 ℃,5 ℃ or 8 ℃.
In a preferred embodiment, in step (I), the initiator is selected from at least one of dibromoethane and/or elemental iodine.
In a preferred embodiment, in step (I), the solvent is selected from at least one of diglyme (DGDE), triglyme, hexamethylphosphoramide.
In the invention, the dendron [4] ene is generated by Grignard coupling based on 2-chloroprene as a starting material. The invention firstly aims at the problem that the boiling points of a reaction solvent (tetrahydrofuran normal-pressure boiling point 66 ℃) and the dendritic [4] alkene (normal-pressure boiling point 72 ℃) are close to each other and are not suitable for separation in the method for synthesizing the dendritic [4] alkene by predecessor, and improves the synthesis and separation efficiency of the dendritic [4] alkene by adopting the high-boiling point solvent and optimizing the reaction conditions.
In a preferred embodiment, in step (I), the weight ratio of magnesium chips to 2-chloroprene is 1 (1 to 4); and/or the weight ratio of the initiator to the 2-chloroprene is (0.01-0.2) to 1; and/or the weight ratio of the anhydrous zinc chloride to the 2-chloroprene is (0.01-0.2) to 1; and/or the molar volume ratio of the 2-chloroprene to the total added solvent is (0.1 mol-5 mol): 1L.
In a further preferred embodiment, in step (I), the weight ratio of magnesium turnings to 2-chloroprene is 1 (2 to 2.5); and/or the weight ratio of the initiator to the 2-chloroprene is (0.05-0.1) to 1; and/or the weight ratio of the anhydrous zinc chloride to the 2-chloroprene is (0.02-0.08) 1; and/or the molar volume ratio of the 2-chloroprene to the total DGDE added is (0.5 mol-2.5 mol): 1L.
In a preferred embodiment, in step (I), heating is carried out to a temperature of from 30 ℃ to 90 ℃; heating is carried out for 5 to 50 minutes.
In a further preferred embodiment, in step (I), heating is to 35 ℃ to 75 ℃; heating is carried out for 10 to 30 minutes.
Wherein the purpose of the heating is to activate the magnesium chips. For example, in step (I), heating to 35 ℃,45 ℃, 55 ℃, 65 ℃ or 75 ℃; heating is carried out for 10 minutes, 15 minutes, 20 minutes, 25 minutes, or 30 minutes.
In a preferred embodiment, in the step (I), the solution containing 2-chloroprene and the solvent is dropped into the reaction vessel for 1 to 8 hours while controlling the reaction temperature not to exceed 70 ℃.
In a further preferred embodiment, in the step (I), the solution containing 2-chloroprene and the solvent is dropped into the reaction vessel for 2 to 6 hours while controlling the reaction temperature not to exceed 60 ℃.
In a preferred embodiment, in step (I), the protective atmosphere is selected from at least one of nitrogen, argon, helium, for example nitrogen.
In a preferred embodiment, in step (I), the reaction is completed and refluxed for 1 to 2 hours to produce a 2-chloroprene Grignard reagent solution.
In a preferred embodiment, in step (II), the cocatalyst is selected from at least one of triphenylphosphine, diphenyltrichloroethane, and diphenyldiphenylphosphinopropane, for example triphenylphosphine.
In a preferred embodiment, in step (II), the transition metal catalyst is selected from at least one of copper salt, nickel salt, iron salt, and manganese salt.
In a further preferred embodiment, the copper salt is selected from one or a mixture of two or more of copper acetate, copper bromide, copper chloride, copper sulfate, copper nitrate and copper phosphate; the nickel salt is selected from one or a mixture of two or more of nickel acetate, nickel chloride, nickel bromide, nickel sulfate, nickel nitrate and nickel phosphate; the ferric salt is selected from one or a mixture of two or more of ferrous bromide, ferric bromide, ferrous chloride, ferric chloride, ferrous sulfate, ferric sulfate, ferrous nitrate, ferric nitrate, ferrous phosphate, ferric phosphate, ferrous ammonium sulfate, potassium ferrocyanide and potassium ferricyanide; the manganese salt is selected from one or a mixture of two or more of manganese acetate, manganese chloride, manganese bromide, manganese sulfate, manganese nitrate, manganese phosphate and manganese oxalate.
In a preferred embodiment, in step (II), the weight ratio of the transition metal salt catalyst to the 2-chloroprene added dropwise in step (I) is 1 (20 to 2500), preferably 1 (50 to 2000).
For example, the weight ratio of the transition metal salt catalyst to the 2-chloroprene added dropwise in step (I) is 1.
In a preferred embodiment, in step (II), the weight ratio of the 2-chloroprene used in step (II) to the 2-chloroprene used in step (I) (0.2 to 2) to 1 and the weight ratio of the cocatalyst to the 2-chloroprene used in step (I) 1 (10 to 1500) are used.
In a further preferred embodiment, in step (II), the weight ratio of the 2-chloroprene used in step (II) to the 2-chloroprene used in step (I) (0.5 to 1.5): 1, and the weight ratio of the cocatalyst to the 2-chloroprene used in step (I) (1) ((20 to 1000)).
In a preferred embodiment, in step (II), the temperature is raised to 10 to 40 ℃, preferably 15 to 35 ℃ (e.g. 20 to 30 ℃, e.g. room temperature).
In a preferred embodiment, in step (II), the post-treatment comprises: adding acid to quench the reaction and adjusting the pH value to 6-9, reducing the reaction system to a negative pressure state, cooling and collecting volatile substances, and further rectifying to obtain the dendritic [4] ene.
In a further preferred embodiment, the acid is selected from concentrated sulfuric acid and/or phosphoric acid; and/or, adjusting the pH value to 7-8; and/or, reducing the vacuum degree of the reaction system to 10-100 mmHg, preferably 20-30 mmHg.
In a preferred embodiment, the solvent in the original reaction system is recycled by vacuum distillation.
The second purpose of the invention is to provide a preparation method of 3,3', 4' -biphenyl tetracarboxylic dianhydride, which comprises the following steps: firstly, 3', 4' -biphenyl tetracarboxylic acid is prepared by the preparation method which is one of the purposes of the invention, and then the 3,3', 4' -biphenyl tetracarboxylic acid is dehydrated to obtain the 3,3', 4' -biphenyl tetracarboxylic dianhydride.
In a preferred embodiment, dehydration is carried out using a dehydrating agent to obtain 3,3', 4' -biphenyltetracarboxylic dianhydride.
In a further preferred embodiment, the dehydrating agent is selected from at least one of acetic anhydride, propionic anhydride, di-tert-butyl dicarbonate.
In the invention, a method for preparing 3,3', 4' -biphenyl tetracarboxylic dianhydride based on 2-chloroprene as a starting material through Grignard coupling to generate dendron [4] alkene, and then performing cycloaddition-oxidative aromatization reaction of the dendron [4] alkene and maleic acid is provided. The method firstly aims at the problem that the boiling points of a reaction solvent (tetrahydrofuran normal-pressure boiling point 66 ℃) and the dendritic [4] alkene (normal-pressure boiling point 72 ℃) are close to and are not suitable for separation in the method for synthesizing the dendritic [4] alkene by predecessor, the high-boiling point solvent is adopted, the reaction conditions are optimized, the synthesis and separation efficiency of the dendritic [4] alkene is improved, then the dendritic [4] alkene is mixed with maleic acid, the series cycloaddition-oxidative aromatization reaction is realized by a one-pot method, a novel method for preparing 3,3', 4' -biphenyl tetracarboxylic acid is realized, and 3,3', 4' -biphenyl tetracarboxylic dianhydride can be obtained by further dehydrating acetic anhydride.
The third purpose of the invention is to provide 3,3', 4' -biphenyltetracarboxylic acid obtained by the preparation method.
The fourth object of the present invention is to provide 3,3', 4' -biphenyltetracarboxylic dianhydride obtained by the second object of the present invention.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein. In the following, the various technical solutions can in principle be combined with each other to obtain new technical solutions, which should also be regarded as specifically disclosed herein.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention provides a method for preparing 3,3', 4' -biphenyl tetracarboxylic acid and 3,3', 4' -biphenyl tetracarboxylic dianhydride by adopting dendritic [4] alkene and maleic acid as raw materials through cycloaddition-oxidative aromatization reaction, the method has novel synthesis strategy, no use of noble metal catalyst and higher total yield;
(2) The atom economy of the cycloaddition-oxidation aromatization reaction is high, the reaction condition is mild, and the potential industrialization prospect is realized;
(3) The dendron [4] alkene is generated by taking 2-chloroprene as a starting material through Grignard coupling, and meanwhile, a high boiling point melting point is adopted, and the boiling point of the dendron [4] alkene is 72 ℃ under normal pressure, so that a corresponding Grignard reagent is prepared in a high boiling point solvent, and a coupling reaction catalyzed by transition metal avoids a complicated separation method of the dendron [4] alkene, and lays a foundation for a subsequent cycloaddition strategy.
Drawings
FIG. 1 shows a chemical reaction process schematic of the process of the present invention for preparing 3,3'4,4' -biphenyltetracarboxylic acid and dianhydride thereof;
FIG. 2 is a NMR spectrum of dendron [4] ene prepared in accordance with the present invention;
FIG. 3 is a NMR spectrum of 3,3'4,4' -biphenyltetracarboxylic acid prepared according to the present invention;
FIG. 4 is a high performance liquid chromatography spectrum of 3,3'4,4' -biphenyltetracarboxylic acid prepared according to the present invention.
Detailed Description
While the present invention will be described in detail and with reference to the specific drawings and examples, it is to be understood that the following examples are included merely for purposes of illustration and are not intended to limit the scope of the invention, as other insubstantial modifications and adaptations of the invention may occur to those skilled in the art in light of the present disclosure.
It is to be further understood that the various features described in the following detailed description may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention can be made, as long as the idea of the present invention is not violated, and the technical solution formed thereby is part of the original disclosure of the present specification, and also falls into the protection scope of the present invention.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
[ example 1 ]
400g of dried magnesium chips, 80g of dibromoethane and 200mL of diglyme (DGDE) were sequentially added to a reaction tank, nitrogen gas was introduced while stirring, the mixture was heated to about 35 ℃ to activate the magnesium chips for 20 minutes, then the heating was stopped, and 20g of anhydrous zinc chloride and 2800mL of DGDE were sequentially added. 2000mL of the DGDE solution containing 900g of 2-chloroprene was then added dropwise to the reaction tank over a period of 2 to 3 hours while controlling the reaction temperature not to exceed 60 ℃ and allowing gases to evolve during the reaction. Then refluxing for 1-2 hours to generate L with the molar concentration of 1mol -1 A DGDE solution of 2-chloroprene Grignard reagent (C).
Cooling the reaction tank to zero, then dropwise adding 450g of 2-chloroprene, after dropwise adding, sequentially adding 45g of triphenylphosphine and 18g of copper chloride, heating to room temperature for reacting for 28 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction liquid so that the pH value of the reaction liquid is between 7.0 and 8.0. Then the vacuum degree of the reaction tank is reduced to 20-30 mmHg, the volatile substances are collected by cooling, 542.50g of intermediate product dendron [4] alkene is obtained by further rectification, the yield is 51 percent, and the solvent in the reaction tank is recovered by reduced pressure distillation to obtain DGDE.
Adding all the dendritic [4] ene obtained in the previous step, 8kg of ethanol and 1200g of maleic acid into a reaction kettle in sequence, reacting at 75 ℃ for 8 hours, and distilling to remove the ethanol; and then sequentially adding 12kg of distilled water and 500g of potassium carbonate, heating to 75 ℃, slowly dropwise adding 2.7kg of 30wt% hydrogen peroxide into the system, maintaining the temperature after dropwise adding, continuously reacting for 2 hours, cooling to room temperature, and adding sufficient sodium bisulfite to neutralize excessive hydrogen peroxide. Then dripping 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is 2-3, finally filtering and washing with deionized water to obtain the 3,3', 4' -biphenyltetracarboxylic acid, wherein the yield is 73%, and the purity is more than 98.5%. Refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain a product, namely 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ example 2 ]
380g of dried magnesium chips, 20g of dibromoethane and 180mL of diglyme (DGDE) are sequentially added into a reaction tank, nitrogen is introduced into the reaction tank for stirring, the reaction tank is heated to about 35 ℃ to activate the magnesium chips for 20 minutes, then the heating is stopped, and 50g of anhydrous zinc chloride and 2700mL of DGDE are sequentially added. 1800mL of a DGDE solution containing 880g of 2-chloroprene was then added dropwise to the reaction vessel over a period of 2-3 hours with evolution of gas during the reaction. Then refluxing for 1-2 hours to obtain L with a molar concentration of 1mol -1 A DGDE solution of 2-chloroprene Grignard reagent (C).
And cooling the reaction tank to zero, then dropwise adding 1000g of 2-chloroprene, sequentially adding 20g of triphenylphosphine and 9g of copper bromide after dropwise adding is finished, heating to room temperature for reaction for 26 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction liquid so that the pH value of the reaction liquid is between 7.0 and 8.0. Then the vacuum degree of the reaction tank is reduced to 20-30 mmHg, the volatile substances are collected by cooling, 628.60g of intermediate product dendron [4] alkene is obtained by further rectification, the yield is 60 percent, and the solvent in the reaction tank is recovered by reduced pressure distillation to obtain DGDE.
Adding dendritic [4] ene, 31.4kg methanol and 1100g maleic acid into a reaction kettle in sequence, reacting at 55 ℃ for 6 hours, and distilling to remove the methanol; then, 15kg of distilled water and 565.7g of sodium hydroxide are sequentially added, 2.6kg of 30wt% hydrogen peroxide is slowly added into the system after the system is heated to 30 ℃, the temperature is maintained after the addition is finished, the reaction is continued for 2 hours, the reaction is cooled to the room temperature, and sufficient sodium bisulfite is added to neutralize the excessive hydrogen peroxide. Then dripping 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is 2-3, finally filtering and washing with deionized water to obtain the 3,3', 4' -biphenyltetracarboxylic acid, wherein the yield is 79%, and the purity is more than 98.5%. Refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain a product, namely 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ example 3 ] A method for producing a polycarbonate
480g of dried magnesium chips, 89g of dibromoethane and 163mL of diglyme (DGDE) are sequentially added into a reaction tank, nitrogen is introduced into the reaction tank for stirring, the reaction tank is heated to about 75 ℃ to activate the magnesium chips for 20 minutes, then the heating is stopped, and 60g of anhydrous zinc chloride and 2260mL of DGDE are sequentially added. 1600mL of DGDE solution containing 890g of 2-chloroprene was then added dropwise to the reaction tank over a period of 2-3 hours, with evolution of gas during the reaction. Then refluxing for 1-2 hours to generate L with the molar concentration of 1mol -1 A DGDE solution of 2-chloroprene Grignard reagent (C).
Cooling the reaction tank to zero, then adding 1335g of 2-chloroprene dropwise, after the dropwise addition is finished, sequentially adding 27g of triphenylphosphine and 12g of copper nitrate, heating to room temperature for reaction for 30 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction so that the pH value of the reaction solution is between 7.0 and 8.0. Then reducing the vacuum degree of the reaction tank to 20-30 mmHg, cooling, collecting volatile substances, further rectifying to obtain 578.65g of intermediate dendritic [4] ene with the yield of 55%, and recovering the solvent in the reaction tank by reduced pressure distillation to obtain the DGDE.
Adding dendritic [4] ene, 12kg ethanol and 1150g maleic acid into a reaction kettle in sequence, reacting at 65 ℃ for 10 hours, and distilling to remove ethanol; and then adding 17.4kg of distilled water and 515g of sodium carbonate in sequence, heating to 50 ℃, slowly dropwise adding 2.5kg of 30wt% hydrogen peroxide into the system, maintaining the temperature after dropwise adding, continuously reacting for 2 hours, cooling to room temperature, and adding sufficient sodium bisulfite to neutralize excessive hydrogen peroxide. Then dripping 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is 2-3, finally filtering and washing with deionized water to obtain the 3,3', 4' -biphenyltetracarboxylic acid, wherein the yield is 80%, and the purity is more than 98.5%. Refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain a product, namely 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ example 4]
390g of dried magnesium chips, 60g of dibromoethane and 600mL of diglyme (DGDE) are added into a reaction tank in sequence, nitrogen is introduced into the reaction tank for stirring, the reaction tank is heated to about 55 ℃ to activate the magnesium chips for 20 minutes, then the heating is stopped, and 80g of anhydrous zinc chloride and 1000mL of DGDE are added in sequence. 2200mL of DGDE solution containing 1100g of 2-chloroprene is dripped into the reaction tank for 4-5 hours, and gas is released in the reaction process. Then refluxing for 1-2 hours to obtain L with a molar concentration of 1mol -1 A DGDE solution of 2-chloroprene Grignard reagent (C).
Cooling the reaction tank to zero, then adding 1190g of 2-chloroprene dropwise, after the dropwise addition is finished, sequentially adding 50g of triphenylphosphine and 20g of copper phosphate, heating to room temperature for reaction for 32 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction liquid so that the pH value of the reaction liquid is between 7.0 and 8.0. And then reducing the vacuum degree of the reaction tank to 20-30 mmHg, cooling, collecting volatile substances, further rectifying to obtain 539.84g of intermediate dendritic [4] alkene with the yield of 45%, and recovering the solvent in the reaction tank by reduced pressure distillation to obtain the DGDE.
Adding dendritic [4] ene, 8.5kg of n-propanol and 1000g of maleic acid into a reaction kettle in sequence, reacting for 8 hours at 95 ℃, and distilling to remove the n-propanol; then, 11kg of distilled water and 600g of potassium carbonate are sequentially added, 2.3kg of 30wt% hydrogen peroxide is slowly dripped into the system after the distilled water and the potassium carbonate are heated to 44 ℃, the temperature is maintained after the dripping is finished, the reaction is continued for 2 hours, the reaction is cooled to the room temperature, and sufficient sodium bisulfite is added to neutralize the excessive hydrogen peroxide. Then dripping 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is 2-3, finally filtering and washing with deionized water to obtain the 3,3', 4' -biphenyltetracarboxylic acid, wherein the yield is 73%, and the purity is more than 98.5%. Refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain a product, namely 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ example 5 ] A method for producing a polycarbonate
440g of dried magnesium chips, 70g of dibromoethane and 240mL of diglyme (DGDE) were sequentially charged into a reaction tank, nitrogen gas was introduced into the reaction tank to stir the mixture, the mixture was heated to about 66 ℃ to activate the magnesium chips for 20 minutes, heating was stopped, and 30g of anhydrous zinc chloride and 2900mL of DGDE were sequentially charged into the reaction tank. Then 2100mL of DGDE solution containing 940g of 2-chloroprene was added dropwise into the reaction tank over 3 to 4 hours, with gas evolution during the reaction. Then refluxing for 1-2 hours to generate L with the molar concentration of 1mol -1 A DGDE solution of 2-chloroprene Grignard reagent (C).
Cooling the reaction tank to zero, then dripping 660g of 2-chloroprene, after dripping is finished, sequentially adding 16g of triphenylphosphine and 5g of nickel chloride, heating to room temperature for reaction for 27 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction liquid so that the pH value of the reaction liquid is between 7.0 and 8.0. Then the vacuum degree of the reaction tank is reduced to 20-30 mmHg, volatile substances are collected by cooling, 517.55g of intermediate product dendron [4] alkene is obtained by further rectification, the yield is 46%, and the solvent in the reaction tank is recovered by reduced pressure distillation to obtain DGDE.
Adding dendritic [4] ene, 9kg of ethanol and 1200g of maleic acid into a reaction kettle in sequence, reacting for 8 hours at 67 ℃, and distilling to remove the ethanol; then, 12kg of distilled water and 545g of sodium carbonate are sequentially added, 2.2kg of 30wt% hydrogen peroxide is slowly added into the system after the distilled water and the sodium carbonate are heated to 58 ℃, the temperature is maintained after the addition, the reaction is continued for 2 hours, the reaction is cooled to the room temperature, and sufficient sodium bisulfite is added to neutralize the excessive hydrogen peroxide. Then dripping 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is 2-3, finally filtering and washing with deionized water to obtain the 3,3', 4' -biphenyltetracarboxylic acid, wherein the yield is 72%, and the purity is more than 98.5%. Refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain a product, namely 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ example 6 ]
420g of dried magnesium chips, 60g of dibromoethane and 200mL of diglyme (DGDE) were sequentially charged into a reaction tank, stirred with introduction of nitrogen gas, heated to about 55 ℃ to activate the magnesium chips for 20 minutes, and then the heating was stopped, and 40g of anhydrous zinc chloride and 2700mL of DGDE were sequentially charged. 2000mL of DGDE solution containing 910g of 2-chloroprene was then added dropwiseThe dropping time is 2-3 hours in the reaction tank, and gas is released in the reaction process. Then refluxing for 1-2 hours to generate L with the molar concentration of 1mol -1 A DGDE solution of 2-chloroprene Grignard reagent (C).
Cooling the reaction tank to zero, then dropwise adding 950g of 2-chloroprene, after dropwise adding, sequentially adding 5g of triphenylphosphine and 2g of nickel bromide, heating to room temperature for reaction for 30 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction liquid so that the pH value of the reaction liquid is between 7.0 and 8.0. Then, the vacuum degree of the reaction tank is reduced to 20-30 mmHg, volatile substances are collected by cooling, 573.06g of the intermediate dendritic [4] ene is obtained by further rectification, the yield is 53%, and the solvent in the reaction tank is recovered by reduced pressure distillation to obtain the DGDE.
Adding dendron [4] ene, 8kg of methanol and 1280g of maleic acid into a reaction kettle in sequence, reacting at 45 ℃ for 8 hours, and distilling to remove the methanol; then, 12kg of distilled water and 550g of sodium hydroxide are sequentially added, 2.8kg of 30wt% hydrogen peroxide is slowly dripped into the system after the distilled water and the sodium hydroxide are heated to 74 ℃, the temperature is maintained after the dripping is finished, the reaction is continued for 2 hours, and then the reaction is cooled to the room temperature, and sufficient sodium bisulfite is added to neutralize the excessive hydrogen peroxide. Then dripping 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is 2-3, finally filtering and washing with deionized water to obtain the 3,3', 4' -biphenyltetracarboxylic acid, wherein the yield is 81 percent, and the purity is more than 98.5 percent. Refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain a product, namely 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ example 7 ]
430g of dried magnesium chips, 46g of dibromoethane and 220mL of diglyme (DGDE) were sequentially added to a reaction tank, nitrogen was introduced to the reaction tank to stir the mixture, the mixture was heated to about 55 ℃ to activate the magnesium chips for 20 minutes, heating was stopped, and 40g of anhydrous zinc chloride and 2900mL of DGDE were sequentially added. 2000mL of DGDE solution containing 920g of 2-chloroprene is added into the reaction tank dropwise for 3-4 hours, and gas is released in the reaction process. Then refluxing for 1-2 hours to generate L with the molar concentration of 1mol -1 A DGDE solution of 2-chloroprene Grignard reagent (C).
Cooling the reaction tank to zero, then adding 670g of 2-chloroprene dropwise, after the dropwise addition is finished, sequentially adding 3g of triphenylphosphine and 1g of nickel sulfate, heating to room temperature for reaction for 28 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction so as to enable the pH value of the reaction solution to be between 7.0 and 8.0. And then reducing the vacuum degree of the reaction tank to 20-30 mmHg, cooling, collecting volatile substances, further rectifying to obtain 737.10g of intermediate dendritic [4] alkene with the yield of 68%, and recovering the solvent in the reaction tank by reduced pressure distillation to obtain the DGDE.
Adding dendritic [4] ene, 7.5kg of n-butanol and 1501g of maleic acid into a reaction kettle in sequence, reacting at 105 ℃ for 6 hours, and distilling to remove the n-butanol; then 7.5kg of distilled water and 1126g of potassium carbonate are added in sequence, 3.0kg of 30wt% hydrogen peroxide is slowly added into the system after the system is heated to 47 ℃, the temperature is maintained to continue to react for 2 hours after the addition is finished, then the system is cooled to the room temperature, and sufficient sodium bisulfite is added to neutralize the excessive hydrogen peroxide. Then dripping 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is 2-3, finally filtering and washing with deionized water to obtain the 3,3', 4' -biphenyltetracarboxylic acid, wherein the yield is 74%, and the purity is more than 98.5%. Refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain a product, namely 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ example 8 ]
390g of dried magnesium chips, 45g of dibromoethane and 150mL of diglyme (DGDE) were sequentially added to a reaction tank, nitrogen was introduced into the reaction tank to stir the mixture, the mixture was heated to about 55 ℃ to activate the magnesium chips for 20 minutes, heating was stopped, and 17g of anhydrous zinc chloride and 2500mL of DGDE were sequentially added thereto. 2000mL of DGDE solution containing 850g of 2-chloroprene was then added dropwise to the reaction vessel over a period of 2-3 hours, with evolution of gas during the reaction. Then refluxing for 4-6 hours to obtain L with a molar concentration of 1mol -1 A DGDE solution of 2-chloroprene Grignard reagent (C).
Cooling the reaction tank to zero, then dropping 1030g of 2-chloroprene, after dropping, sequentially adding 0.85g of triphenylphosphine and 0.43g of nickel sulfate, heating to room temperature for reaction for 30 hours, and adding a proper amount of concentrated sulfuric acid to quench the reaction so as to enable the pH value of the reaction solution to be between 7.0 and 8.0. And then reducing the vacuum degree of the reaction tank to 20-30 mmHg, cooling, collecting volatile substances, further rectifying to obtain 518.06g of intermediate dendritic [4] alkene with the yield of 51%, and recovering the solvent in the reaction tank by reduced pressure distillation to obtain the DGDE.
Adding dendritic [4] ene, 12kg ethanol and 1080g maleic acid into a reaction kettle in sequence, reacting at 55 ℃ for 6 hours, and distilling to remove the ethanol; and then, sequentially adding 12kg of distilled water and 540g of sodium carbonate, heating to 38 ℃, slowly dropwise adding 2.4kg of 30wt% hydrogen peroxide into the system, maintaining the temperature after dropwise adding, continuously reacting for 2 hours, cooling to room temperature, and adding sufficient sodium bisulfite to neutralize excessive hydrogen peroxide. Then dripping 36.5wt% of concentrated hydrochloric acid into the reaction system until the pH value of the system is 2-3, finally filtering and washing with deionized water to obtain the 3,3', 4' -biphenyltetracarboxylic acid, wherein the yield is 88%, and the purity is more than 98.5%. Refluxing and dehydrating the obtained 3,3', 4' -biphenyl tetracarboxylic acid by acetic anhydride, and cooling and crystallizing to obtain a product, namely 3,3', 4' -biphenyl tetracarboxylic dianhydride.
[ Experimental examples ]
1. Characterization of nuclear magnetic resonance
The chemical structures of dendron [4] ene and 3,3', 4' -biphenyltetracarboxylic acid prepared in examples 1 to 8 were verified by nuclear magnetic resonance. Wherein, the first and the second end of the pipe are connected with each other,
taking the nuclear magnetic resonance hydrogen spectrum of the dendron [4] ene prepared in example 1 as an example, as shown in fig. 2, in the nuclear magnetic resonance hydrogen spectrum, multiplets of which the number is about delta =6.44ppm are assigned to the carbon number 2 and the carbon number 5 in the main chain structure, and the multiplets are shifted to a low field by the anisotropy effect of the adjacent double bond structure and the shielding effect of pi electrons; two broad doublets at δ =5.19ppm and δ =5.11ppm were assigned to terminal carbons on the main chain, and split off under the influence of a single hydrogen on adjacent carbons, respectively; the remaining two multiplets at δ =5.25ppm and δ =5.07ppm are attributed to the carbon on the branch, δ =7.62ppm is the solvent peak of deuterated chloroform; the single peak around δ =1.56ppm is the water peak, indicating that the intermediate dendron [4] ene is produced.
For the final product 3,3', 4' -biphenyltetracarboxylic acid, as shown in fig. 3, in the nmr hydrogen spectrum, a broad peak with δ =12.3ppm to 13.7ppm is attributed to the hydrogen on the carboxylic acid, which is shifted to a low field by the electron withdrawing effect of the carbonyl group; the doublet at δ =8.09ppm is attributed to carbon No. 5 and carbon No. 5' on the benzene ring structure, the doublet at δ =8.54ppm is attributed to carbon No. 2 and carbon No. 2' beside the carbonyl group in the benzene ring structure, the doublet at δ =8.16ppm lower chemical shift is attributed to carbon No. 6 and carbon No. 6' on the aromatic structure, δ =2.50ppm is the solvent peak of deuterated dimethyl sulfoxide, and δ =3.33ppm is the water peak, which indicates that the final product 3,3', 4' -biphenyltetracarboxylic acid is prepared.
The results of nuclear magnetic resonance hydrogen spectra analysis of dendron [4] ene and 3,3', 4' -biphenyltetracarboxylic acid prepared in examples 2 to 8 were the same as those of example 1, i.e., 3', 4' -biphenyltetracarboxylic acid was efficiently synthesized.
2. High performance liquid chromatography characterization
The 3,3', 4' -biphenyltetracarboxylic dianhydride prepared in example 1 was hydrolyzed to produce 3,3', 4' -biphenyltetracarboxylic acid, and the peak of the chromatogram with a retention time of 5.5 minutes was 3,3', 4' -biphenyltetracarboxylic acid by reverse phase chromatography analysis, and the result is shown in fig. 4. As can be seen in FIG. 4, the corresponding integrated area is greater than 98.5%, indicating that the 3,3', 4' -biphenyltetracarboxylic dianhydride prepared by this method has a good purity.
The conventional anhydride purity analysis method is to analyze and confirm the purity by hydrolyzing anhydride into acid, which is a universal method in the industry at present.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (14)
1. A process for preparing 3,3', 4' -biphenyltetracarboxylic acid comprising:
(1) Mixing dendron [4] ene, maleic acid and a solvent for reaction, and removing the solvent in a system after the reaction is finished to obtain an intermediate product I;
(2) Reacting the intermediate product I in the presence of an alkaline substance and an oxidant to obtain an intermediate product II;
(3) And carrying out post-treatment on the intermediate product II to obtain the 3,3', 4' -biphenyltetracarboxylic acid.
2. The method of claim 1,
in the step (1), the solvent is selected from at least one of alcohol solvents, tetrahydrofuran, ethyl acetate and 1, 4-dioxane, preferably, the alcohol solvents are selected from alcohol solvents with the boiling point of less than 150 ℃; and/or the presence of a gas in the gas,
in the step (1), the weight ratio of the dendron [4] alkene to the solvent is 1 (5-200), preferably 1 (10-100); and/or the presence of a gas in the atmosphere,
in the step (1), the weight ratio of the dendron [4] alkene to the maleic acid is 1 (1-4), preferably 1 (2-2.5); and/or the presence of a gas in the gas,
in the step (1), the reaction temperature is 45-105 ℃, and the reaction time is 4-12 hours.
3. The method of claim 1,
the alkaline substance is an inorganic alkaline substance, preferably at least one of sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate; and/or the presence of a gas in the gas,
the weight ratio of the alkaline substance to the dendritic [4] ene is (0.6-2) to 1, preferably (0.9-1.5) to 1; and/or the presence of a gas in the gas,
the oxidant is selected from at least one of hydrogen peroxide, potassium persulfate and ammonium persulfate; and/or the presence of a gas in the gas,
the weight ratio of the oxidant to the dendritic [4] ene is (2-6): 1, preferably (4-5): 1.
4. The method according to claim 1, wherein in the step (2), the intermediate product I, the alkaline substance and water are mixed and then subjected to heating treatment, then the oxidizing agent is slowly added dropwise into the system, and the temperature is maintained after the dropwise addition is finished, so that the reaction is continued to obtain the intermediate product II; preferably, the weight ratio of water to dendron [4] ene is (5-40): 1, preferably (10-30): 1.
5. The method of claim 1, wherein in step (3), the post-processing comprises:
(3.1) adding a reducing substance to the intermediate product II;
(3.2) adjusting the pH value of the system to 1-5, preferably 2-3;
(3.3) filtering and washing to obtain 3,3', 4' -biphenyltetracarboxylic acid;
preferably, the first and second liquid crystal display panels are,
the reducing substance is selected from sodium bisulfite and/or sodium hydrosulfite, preferably sodium bisulfite; and/or the presence of a gas in the atmosphere,
the weight ratio of the reducing substance to the oxidizing agent is 1: (50-500).
6. The method according to any one of claims 1 to 5, wherein said dendron [4] ene is prepared by a process comprising: 2-chloroprene is used as an initial raw material, and the dendron [4] alkene is obtained through a Grignard reagent coupling reaction.
7. The method of claim 6, wherein the method of making dendron [4] ene comprises:
(I) Preparation of 2-chloroprene Grignard reagent: mixing the dried magnesium chips, an initiator and a solvent under a protective atmosphere, stirring, heating to a set temperature, and then adding anhydrous zinc chloride and the solvent; then, dropwise adding a solution containing 2-chloroprene and the solvent into a reaction container, and reacting to obtain a 2-chloroprene format reagent solution;
(II) preparation of dendron [4] ene: and (3) dropwise adding 2-chloroprene into the reaction system in the step (I) at the temperature of-10 ℃, sequentially adding a cocatalyst and a transition metal catalyst after dropwise adding, heating for reaction, and performing post-treatment after the reaction to obtain the dendritic [4] ene.
8. The method of claim 7,
in the step (I), the initiator is selected from at least one of dibromoethane and/or elementary iodine; and/or the presence of a gas in the gas,
in step (I), the solvent is selected from at least one of diglyme, triglyme, hexamethylphosphoramide; and/or the presence of a gas in the gas,
in the step (I), heating to 30-90 ℃; heating for 5-50 minutes; and/or the presence of a gas in the gas,
in the step (I), a solution containing 2-chloroprene and the solvent is dropwise added to a reaction vessel for 1 to 8 hours while controlling the reaction temperature not to exceed 70 ℃.
9. The method of claim 7, wherein in step (I), the weight ratio of magnesium chips to 2-chloroprene is 1 (1 to 4); and/or the weight ratio of the initiator to the 2-chloroprene is (0.01-0.2) to 1; and/or the weight ratio of the anhydrous zinc chloride to the 2-chloroprene is (0.01-0.2) to 1; and/or the molar volume ratio of the 2-chloroprene to the total solvent is (0.1 mol-5 mol): 1L.
10. The method of claim 7,
in step (II), the cocatalyst is selected from at least one of triphenylphosphine, diphenyltrichloroethane and diphenylchloropropane; and/or the presence of a gas in the gas,
in the step (II), the transition metal catalyst is selected from at least one of copper salt, nickel salt, iron salt and manganese salt; and/or the presence of a gas in the atmosphere,
in the step (II), the weight ratio of the transition metal salt catalyst to the 2-chloroprene dropwise added in the step (I) is 1 (20-2500), preferably 1 (50-2000); and/or the presence of a gas in the gas,
in the step (II), the weight ratio of the 2-chloroprene adopted in the step (II) to the 2-chloroprene adopted in the step (I) (0.2-2): 1, and the weight ratio of the cocatalyst to the 2-chloroprene adopted in the step (I) (1) ((10-1500)); and/or the presence of a gas in the gas,
in step (II), the temperature is raised to 10 to 40 ℃, preferably 15 to 35 ℃; and/or the presence of a gas in the atmosphere,
in step (II), the post-treatment comprises: adding acid to quench the reaction and adjusting the pH value to 6-9, reducing the reaction system to a negative pressure state, cooling and collecting volatile substances, and further rectifying to obtain the dendron [4] alkene.
11. 3,3', 4' -biphenyltetracarboxylic acid obtained by the production method according to any one of claims 1 to 10.
12. A method for preparing 3,3', 4' -biphenyl tetracarboxylic dianhydride, comprising: 3,3', 4' -biphenyltetracarboxylic acid is prepared by the preparation method according to any one of claims 1 to 10, and then the 3,3', 4' -biphenyltetracarboxylic acid is dehydrated to obtain 3,3', 4' -biphenyltetracarboxylic dianhydride.
13. The preparation method according to claim 12, characterized in that dehydration is carried out using a dehydrating agent to obtain 3,3', 4' -biphenyltetracarboxylic dianhydride, preferably, the dehydrating agent is at least one selected from acetic anhydride, propionic anhydride, di-tert-butyl dicarbonate.
14. 3,3', 4' -biphenyltetracarboxylic dianhydride obtained by the production method according to claim 12 or 13.
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| CN101016284A (en) * | 2007-02-13 | 2007-08-15 | 北京益利精细化学品有限公司 | Preparing method of 3,4,3',4'-biphenyltetracarbosylic dianhydride |
| CN101659647A (en) * | 2008-08-26 | 2010-03-03 | 比亚迪股份有限公司 | Method for preparing diphenyl tetracarboxylic dianhydride |
| CN102329289A (en) * | 2011-07-19 | 2012-01-25 | 中国科学院长春应用化学研究所 | Method for preparing biphenyltetracarboxylic dianhydride (BPDA) |
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| CN101016284A (en) * | 2007-02-13 | 2007-08-15 | 北京益利精细化学品有限公司 | Preparing method of 3,4,3',4'-biphenyltetracarbosylic dianhydride |
| CN101659647A (en) * | 2008-08-26 | 2010-03-03 | 比亚迪股份有限公司 | Method for preparing diphenyl tetracarboxylic dianhydride |
| CN102329289A (en) * | 2011-07-19 | 2012-01-25 | 中国科学院长春应用化学研究所 | Method for preparing biphenyltetracarboxylic dianhydride (BPDA) |
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