CN108069848A - Preparation method of carboxylic acid compound, carboxylic acid compound and anhydride compound thereof, and polyimide - Google Patents
Preparation method of carboxylic acid compound, carboxylic acid compound and anhydride compound thereof, and polyimide Download PDFInfo
- Publication number
- CN108069848A CN108069848A CN201711132132.XA CN201711132132A CN108069848A CN 108069848 A CN108069848 A CN 108069848A CN 201711132132 A CN201711132132 A CN 201711132132A CN 108069848 A CN108069848 A CN 108069848A
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- CN
- China
- Prior art keywords
- compound
- carboxylic acid
- preparation
- anhydride
- oxidant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- -1 carboxylic acid compound Chemical class 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000004642 Polyimide Substances 0.000 title claims abstract description 14
- 229920001721 polyimide Polymers 0.000 title claims abstract description 14
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 46
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000007800 oxidant agent Substances 0.000 claims abstract description 25
- 230000001590 oxidative effect Effects 0.000 claims abstract description 25
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052721 tungsten Inorganic materials 0.000 claims abstract 2
- 239000010937 tungsten Substances 0.000 claims abstract 2
- YVHAIVPPUIZFBA-UHFFFAOYSA-N Cyclopentylacetic acid Chemical compound OC(=O)CC1CCCC1 YVHAIVPPUIZFBA-UHFFFAOYSA-N 0.000 claims description 66
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 238000007363 ring formation reaction Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 150000004985 diamines Chemical class 0.000 claims description 6
- 150000002825 nitriles Chemical class 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical class COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 claims 1
- 150000003222 pyridines Chemical class 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 3
- 239000011733 molybdenum Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000003586 protic polar solvent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 100
- 238000006243 chemical reaction Methods 0.000 description 98
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 45
- 239000000047 product Substances 0.000 description 37
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 23
- 150000008064 anhydrides Chemical class 0.000 description 23
- 238000012360 testing method Methods 0.000 description 18
- 229960000583 acetic acid Drugs 0.000 description 16
- 229920002472 Starch Polymers 0.000 description 15
- 239000008107 starch Substances 0.000 description 15
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 13
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- WURFKUQACINBSI-UHFFFAOYSA-M ozonide Chemical compound [O]O[O-] WURFKUQACINBSI-UHFFFAOYSA-M 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 8
- 238000005562 fading Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000009965 odorless effect Effects 0.000 description 7
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 210000003097 mucus Anatomy 0.000 description 5
- 229920005575 poly(amic acid) Polymers 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 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 4
- 238000012423 maintenance Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- FHNINJWBTRXEBC-UHFFFAOYSA-N Sudan III Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 FHNINJWBTRXEBC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 3
- 238000005273 aeration Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000009931 harmful effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000003863 metallic catalyst Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- VFNUTEMVQGLDAG-NKVSQWTQSA-N 2-methoxy-4-[(Z)-(5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-ylhydrazinylidene)methyl]phenol Chemical compound COC1=CC(\C=N/NC2=NC=NC3=C2C2=C(CCCC2)S3)=CC=C1O VFNUTEMVQGLDAG-NKVSQWTQSA-N 0.000 description 2
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910017464 nitrogen compound Inorganic materials 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229940099373 sudan iii Drugs 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- XUSNPFGLKGCWGN-UHFFFAOYSA-N 3-[4-(3-aminopropyl)piperazin-1-yl]propan-1-amine Chemical compound NCCCN1CCN(CCCN)CC1 XUSNPFGLKGCWGN-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- NVKGJHAQGWCWDI-UHFFFAOYSA-N 4-[4-amino-2-(trifluoromethyl)phenyl]-3-(trifluoromethyl)aniline Chemical compound FC(F)(F)C1=CC(N)=CC=C1C1=CC=C(N)C=C1C(F)(F)F NVKGJHAQGWCWDI-UHFFFAOYSA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical class [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 1
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 1
- 229910003893 H2WO4 Inorganic materials 0.000 description 1
- 229910007786 Li2WO4 Inorganic materials 0.000 description 1
- HGKYUNQUBLLAJU-UHFFFAOYSA-N NC1=CC=C(OC2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1.C1=CC=CC=C1 Chemical compound NC1=CC=C(OC2=CC=C(C=C2)OC2=CC=C(C=C2)N)C=C1.C1=CC=CC=C1 HGKYUNQUBLLAJU-UHFFFAOYSA-N 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 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 description 1
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000001940 cyclopentanes Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 230000000510 mucolytic effect Effects 0.000 description 1
- PEECTLLHENGOKU-UHFFFAOYSA-N n,n-dimethylpyridin-4-amine Chemical compound CN(C)C1=CC=NC=C1.CN(C)C1=CC=NC=C1 PEECTLLHENGOKU-UHFFFAOYSA-N 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- UYDPQDSKEDUNKV-UHFFFAOYSA-N phosphanylidynetungsten Chemical compound [W]#P UYDPQDSKEDUNKV-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B53/00—Asymmetric syntheses
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C61/00—Compounds having carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C61/06—Saturated compounds having a carboxyl group bound to a five-membered ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1057—Polyimides containing other atoms than carbon, hydrogen, nitrogen or oxygen in the main chain
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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Abstract
The present disclosure provides a method for preparing a carboxylic acid compound, the carboxylic acid compound and an anhydride compound thereof, and polyimide, wherein the method for preparing the carboxylic acid compound comprises mixing an olefin compound and a first oxidant to form a solution, and performing a first oxidation reaction, wherein the first oxidant comprises ozone and a protic solvent; and adding a second oxidant to the solution to perform a second oxidation reaction, so that the olefin compound forms a carboxylic acid compound, wherein the second oxidant comprises hydrogen peroxide, and at least one of the first oxidant and the second oxidant further comprises a tungsten-containing compound, a molybdenum-containing compound or a combination thereof. The disclosure also provides a carboxylic acid compound obtained by the preparation method and an anhydride compound formed by using the carboxylic acid compound.
Description
Technical field
This exposure is related to a kind of preparation method of carboxylic acid compound.
Background technology
The diacid of 2,3,5- tricarboxylic cyclopentyls acetic acid (2,3,5-Tricarboxycyclopentaneacetic acid)
Acid anhydride is the critical materials for making polyimides (Polyimide), can carry out carbon-carbon double bond oxidation by dicyclopentadiene and generate, and
Industrially mainly there are nitrate method, Ozone and membrane by accelerant process for the oxidation technology of alkene.Nitrate method technique can be with relatively mild anti-
Condition control reaction is answered, but exothermic reaction can not be avoided and effectively reduce the generation of ammonia nitrogen compound.Ozone oxidation rate is slow,
It is not easy reaction completely and yield is bad.In addition, olefin oxidation can be alcohols, aldehydes or ketone by membrane by accelerant process, only cannot still meet
Olefin(e) compound is aoxidized to obtain the demand of carboxylic acid compound.
Therefore, it is current urgent problem to be solved to develop a kind of olefin(e) compound and be oxidized into the method for carboxylic acid compound.
The content of the invention
The preparation method for the carboxylic acid compound that one embodiment of this exposure provides includes mixing one olefin(e) compound and one first
Oxidant carries out one first oxidation reaction, wherein first oxidant includes ozone and a proton solvent to form a solution；With
And one second oxidant is added in the solution, one second oxidation reaction of progress makes the olefin(e) compound form monocarboxylic acid compound,
Wherein second oxidant includes hydrogen peroxide；Wherein at least one of first oxidant and second oxidant also include one
Tungstenic compound, a molybdate compound or combinations of the above.
The carboxylic acid compound that one embodiment of this exposure provides, as the carboxylic acid chemical combination as obtained by the above-mentioned preparation method
Object, the wherein carboxylic acid compound be 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid.
The anhydride compound that one embodiment of this exposure provides, by 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid carry out a cyclisation
Reaction is formed, and wherein the fusing point of the anhydride compound is 226 DEG C to 249 DEG C.
The anhydride compound that one embodiment of this exposure provides, as the carboxylic acid compound as obtained by the above-mentioned preparation method
It is formed with cyclizing agent reaction.
The polyimides that one embodiment of this exposure provides, is formed by anhydride compound described above and a diamine reactant.
Above-mentioned purpose, feature and advantage to allow this exposure can be clearer and more comprehensible, a preferred embodiment cited below particularly, and be matched somebody with somebody
Appended schema is closed, is described in detail below.
Description of the drawings
Fig. 1 is the anhydride product of embodiment B11H NMR spectras.
Fig. 2 is the anhydride product of comparative example B1 '1H NMR spectras.
Fig. 3 is the 2,3,5- tricarboxylic cyclopentyl acetic acid of comparative example B2 '1H NMR spectras.
Fig. 4 is the 2,3,5- tricarboxylic cyclopentyl acetic acid of embodiment B31H NMR spectras.
Fig. 5 is the folded figure of Fig. 3 and Fig. 4.
Specific embodiment
This exposure provides a kind of preparation method of carboxylic acid compound, makes olefin(e) compound initial oxidation into ozone using ozone
Compound (ozonide) recycles hydrogen peroxide and metallic catalyst that it is made further to be reoxidised into carboxylic acid compound, such system
Preparation Method can effectively aoxidize the carbon-carbon double bond of olefin(e) compound, and not generate outside the pernicious gases such as ammonia nitrogen compound, tail gas
With the potentiality reacted again of activation can be recycled.In addition, this preparation method can improve the efficiency of ozone decomposition compound decomposition, it can
The security and productivity of process for stabilizing.
This exposure provides a kind of preparation method of carboxylic acid compound, and it includes step S100：Mixed olefins compound and the
One oxidant carries out the first oxidation reaction, which includes ozone and proton solvent to form solution；And step
S200：The second oxidant is added in the solution, the second oxidation reaction is carried out, the olefin(e) compound is made to form carboxylic acid compound, be somebody's turn to do
Second oxidant includes hydrogen peroxide, and wherein at least one of first oxidant and second oxidant also includes tungstenic chemical combination
Object, molybdate compound or combinations of the above.
In one embodiment, the Tungstenic compound or molybdate compound can select first to add in first oxidation reaction
The solution or add the solution in second oxidation reaction, main system for lifting factorization ozonide efficiency.
In one embodiment, which includes phosphotungstic acid, sodium tungstate, tungstate lithium, wolframic acid or combinations of the above, this contains molybdenum chemical combination
Object includes molybdic acid, and the wherein concentration of the Tungstenic compound or the molybdate compound is 1mol% to 10mol%.When the tungstenic chemical combination
When the concentration of object or the molybdate compound is too low, the ozonide resolving time may be caused too long or reaction yield reduces；When
During the excessive concentration of the Tungstenic compound or the molybdate compound, excessive metal residual may be caused to influence its application in product
Property.
In the step s 100, which can once add in into first oxidant and mix, can also be in batches
Addition is mixed into first oxidant.In one embodiment, when carrying out first oxidation reaction, which passes through aeration tube
It is continuously added into the solution and is reacted, and the solution is stirred using mixer, the olefin(e) compound is made to form ozonide,
In first oxidation reaction controlled at 0 DEG C to 30 DEG C, such as 0 DEG C to 5 DEG C or 20 DEG C to 25 DEG C.When the reaction temperature mistake
When low, reactant solubility in solvent system may be caused to reduce, reactant is caused to be precipitated, and then reduces conversion ratio；When this
When reaction temperature is excessively high, ozonide may be caused to decompose, thermal runaway caused by decomposition will make reaction yield and selection rate
It reduces, and thermal runaway may cause quick-fried work etc. unexpected.In one embodiment, which can also include indicator, to
Judge whether first oxidation reaction is finished, the Sudan three (SUDAN III) can be exemplified as, observe the color of the solution
Whether (red) generates variation or colour fading.When first oxidation reaction is completed, stop adding in ozone, be prepared to enter into second oxygen
The step of changing reaction.
In one embodiment, which can also include nitrile solvents, can be exemplified as C2 to C6 nitriles, such as second
Nitrile, propionitrile or butyronitrile, which, which adds in the nitrile solvents, can reduce the usage amount of the proton solvent (such as acetic acid), while this
Body belongs to inertia solution, is not easy to be influenced by ozone or ozonide oxidation.In addition, the boiling point of the nitrile solvents is more molten than the proton
Agent is low, when second oxidation reaction completion is dried, is conducive to the concentration of the carboxylic acid compound.
In one embodiment, after ozone is passed through a period of time, the viscosity of the solution can improve, and then may influence whether
Aeration tube is passed through the efficiency of ozone, therefore, diluent, such as ether, Isosorbide-5-Nitrae-dioxy can be added in first oxidation reaction
Six rings (1,4-dioxane), 1,1- dimethoxy-ethanes (1,1-dimethoxyethane), ethyl acetate, acetone, dichloromethane
Alkane, hydrogen peroxide, water or combinations of the above, to dilute the solution, to promote efficiency.
In one embodiment, which refers to hydroxyl or with hydrionic solvent wherein should in molecule
Proton solvent includes C1 to C8 alcohols, C1 to C8 carboxylic acids, water or combinations of the above, can be exemplified as ethyl alcohol, isopropanol, formic acid, vinegar
Acid, octanoic acid, water or combinations of the above.In one embodiment, which includes polycyclic diene hydrocarbon compound, such as two rings
Pentadiene (dicyclopentadiene).
In step s 200, the solution is by hydrogen peroxide and metallic catalyst (Tungstenic compound or chemical combination containing molybdenum
Object) addition, proceed by second oxidation reaction so that the ozonide is further oxidized to carboxylic acid compound, wherein
The temperature of second oxidation reaction is 60 DEG C to 120 DEG C, such as 70 DEG C to 100 DEG C, time of second oxidation reaction for 6 it is small when
To 50 it is small when, such as 6 hours to 20 it is small when or 6 hours to 12 it is small when.When the reaction temperature is too low, ozonide may be caused
It can not fast decoupled so that the reaction time is elongated, ozonide is caused to be not enough to decompose and residue in product completely, for production
The productivity and application of object may have harmful effect；When the reaction temperature is excessively high, it may cause product that side reaction occurs,
So that yield declines.When the reaction time is too short, ozonide may be caused to be not enough to reaction solution completely and residue in product
In, productivity and application for product may have harmful effect；When the reaction time is long, product may be caused to send out
Raw side reaction so that yield declines.
In one embodiment, the concentration of the hydrogen peroxide is 10wt% to 50wt%, such as 20wt% to 40wt%, when this
When the concentration of hydrogen peroxide is too low, the reaction time may be caused elongated and be unfavorable for producing；When the excessive concentration of the hydrogen peroxide
When, excessive exothermic may be caused to react, there may be harmful effect for yield and productivity.
In one embodiment, in second oxidation reaction, using potassium iodide starch test paper (KI-starch test
Paper) observe whether the solution is presented negative (odorless oxide), determine whether second oxidation reaction has carried out
Finish.
This exposure provides a kind of carboxylic acid compound, is as the carboxylic acid compound obtained by above-mentioned preparation method, wherein should
Carboxylic acid compound is 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid (2 β, 3 α, 5 β-tricarboxycyclopentane-1-
Acetic acid, TCA).In one embodiment, the olefin(e) compound of initial action is bicyclopentadiene, passes through above-mentioned two rank
The oxidation reaction of section, effectively can be oxidized to 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid, yield may be up to by bicyclopentadiene
To more than 70%.
This exposure provides a kind of anhydride compound, is as the carboxylic acid compound obtained by method is prepared as above and cyclisation
Agent reaction is formed.In one embodiment, which is polycarboxylic compounds, such as quaternary carboxylic acid compound should
Polycarboxylic compounds carry out cyclization by the cyclizing agent, and to form the anhydride compound, wherein the cyclizing agent includes second
Acyl chlorides, 4-dimethylaminopyridine, acetic anhydride or combinations of the above.In one embodiment, the temperature of the cyclization for room temperature extremely
60 DEG C, time of cyclization for 2 hours to 8 it is small when.When the temperature of the cyclization is too low, the ring of polycarboxylic compounds
Rate is low, therefore anhydride compound yield reduces；When the cyclization when the temperature is excessively high, side reaction easily occurs so that acid
The yield of acid anhydride product reduces.When too short between when reacted, the low yield of cyclization；When the reaction time is too long, easily occur
Side reaction so that the yield of anhydride product reduces.
This exposure provides a kind of anhydride compound, be by above-mentioned 2 obtained β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid into
Row cyclization is formed, and wherein the fusing point of the anhydride compound is 226 DEG C to 249 DEG C.In one embodiment, 2 β, 3 α, 5 β-
Tricarboxylic cyclopentane acetic acid carries out the cyclization by cyclizing agent, to form 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid diacid
Acid anhydride (2 β, 3 α, 5 β-tricarboxycyclopentyl acetic acid dianhydride), the wherein cyclizing agent include second
Acyl chlorides (acetyl chloride), 4-dimethylaminopyridine (4-dimethylaminopyridine), acetic anhydride (acetic
) or combinations of the above anhydride.2 prepared β of this exposure, 3 α, 5 β-tricarboxylic cyclopentane acetic acid dicarboxylic anhydride, which have, to be higher than
220 DEG C or more of fusing point applied to polyimide material, can assign polyimides high transparency and high-fire resistance.
This exposure provides a kind of polyimides, is to be formed by such as above-mentioned anhydride compound and a diamine reactant.
The preparation of carboxylic acid compound
Embodiment A1
Weigh bicyclopentadiene (25g, purity：95%, label：Sigma-Aldrich), acetic acid (420g, Chun Du≤
99.7%, label：J.T.Baker), No. three solution (1mL, concentration of the Sudan：100mg/10mL ethyl acetate solutions, SUDAN
III, 1- [4- (Phenylazo) phenylazo] -2-naphthol, Technical grade, label：Sigma-Aldrich)
And pure water (45g) is into 1 liter of reaction bulb, and the temperature of above-mentioned solution is adjusted in a manner of water-bath after 0 DEG C, to utilize ozone machine
(EMEC-TW, model：UV-200-2, gas source are oxygen bottle, purity 99%) it is passed through ozone (flow：5L/min) and with
Mixer stirs (rotating speed：300rpm), reaction solution is red at this time.The red for being continually fed into ozone to reaction solution is faded.
Then, by tungstate lithium (2.47g, 5mol%, lithium tungstate, Li2WO4, purity 99%, label：
Sigma-Aldrich), hydrogen peroxide (215mL, concentration：30wt%, label：Sigma-Aldrich.) above-mentioned reaction solution is added in,
And be heated to 90 DEG C, when solution is heated to 60 DEG C, solution starts heat release, control solution be maintained at 90 DEG C 8 it is small when after, with iodine
It is negative (odorless oxide) to change maculanin test paper (KI-starch test paper) test reaction liquid, by reaction solution in 70 DEG C
After being concentrated into syrupy shape under water-bath, ether (20mL, purity 99%, label are added in：Sigma-Aldrich) wash products, Yu Zhen
Carboxylic acid product (40.3g, 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid) is can obtain after the lower drying of sky, as a result such as table 1.
Embodiment A2
Except metallic catalyst is changed to sodium tungstate dihydrate (3.1g, 5mol%, sodium tungstate
Dihydrate, Na2WO4·2H2O, purity 99%, label：Sigma-Aldrich), remaining step is all identical with embodiment A1,
Carboxylic acid product (42.3g, 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid) is can obtain, as a result such as table 1.
Embodiment A3
Sodium tungstate dihydrate (3.1g, 5mol%), acetic acid (420g) and pure water (45g) are weighed into 1 liter of reaction bulb,
After the temperature that above-mentioned solution is adjusted in a manner of water-bath is 25 DEG C, ozone (flow is passed through using ozone machine：5L/min) and with stirring
Machine stirs (rotating speed：300rpm), while by bicyclopentadiene (25g, purity：95%, label：Sigma-Aldrich) progressively drip
It adds in above-mentioned reaction solution, after bicyclopentadiene is added dropwise, by the Sudan No. three solution (1mL, concentration：100mg/10mL acetic acid
Ethyl ester solution) it adds in above-mentioned reaction solution, reaction solution is red at this time.The red for being continually fed into ozone to reaction solution is faded.
Then, above-mentioned reaction solution is heated to 90 DEG C, at this time by hydrogen peroxide (215g, concentration in a manner of being added dropwise：
It 30wt%) is added dropwise in above-mentioned reaction solution, with the dropwise addition of hydrogen peroxide, solution starts heat release, treats that whole hydrogen peroxide are added dropwise
After, continuous heating using maintain reaction solution as reflux state, by reaction solution reflux 8 it is small when after, with potassium iodide and starch solution
(KI-starch) test reaction liquid is negative (odorless oxide), after reaction solution is concentrated into syrupy shape under 70 DEG C of water-baths, is added
Enter ether (20mL) wash products, carboxylic acid product (40.0g, 2 β, 3 α, 5 β-tricarboxylic cyclopentane is can obtain after dry under vacuum
Acetic acid), as a result such as table 1.
Embodiment A4
Bicyclopentadiene (25g) and acetic acid (225g) is taken to be placed in 1 liter of reaction bulb and mix, and it is molten to add in the Sudan three
Liquid (1mL, concentration：100mg/10mL ethyl acetate solutions) indicator when ending as ozone reaction, then, is stirred with paddle
It mixes reaction solution and is passed through ozone (flow using ozone machine：5L/min), the temperature of reaction solution is kept in a manner of water-bath as room temperature,
After ozone is passed through a period of time, solution viscosity improve thus influence aeration tube be passed through the efficiency of ozone gas, at this point, adding in
Hydrogen oxide (100g, 30wt%) dilute reaction solution is simultaneously continually fed into ozone to the color fading of indicator.
Then, by molybdenum trioxide (1.36g, 5mol%, MoO3, Molybdenum oxide, label：Sigma-
Aldrich) add in above-mentioned reaction, and reaction is heated to about 80 DEG C, at this point, reaction starts heat release and continues emergent gas,
After heat release about 30 minutes, gas escaped quantity gradually tails off.Then, hydrogen peroxide (214g, 30%) is progressively added dropwise to, and is persistently added
After heat makes it be back to when small (about 15) overnight, reaction solution, will be anti-with not residue ozone compound after KI-starch solution testings
After liquid is answered to remove solvent with 90 DEG C of water-bath with evaporation mode, carboxylic acid product (39.4g, 2 β, 3 α, 5 β-tricarboxylic cyclopentane second is obtained
Acid), as a result such as table 1.
Embodiment A5
Take bicyclopentadiene (2.5g), acetonitrile (89g, acetonitrile, CH3CN, purity 99%, label：Sigma-
Aldrich) and acetic acid (8.9g) is placed in 1 liter of reaction bulb and mixes, and it is whole as ozone reaction to add in the Sudan three (10mg)
When indicator, then, liquid is stirred to react with stirrer and is passed through ozone (flow using ozone machine：1L/min), with ice
Water-bath mode keeps the temperature of reaction solution to be passed through ozone to the color fading of indicator for 0 DEG C.
Then, by above-mentioned reaction solution concentrate after, formed syrupy shape mucus, then, by sodium tungstate dihydrate (62mg,
1mol%), hydrogen peroxide (13mL, concentration：Above-mentioned reaction solution 30wt%) is added in, is stirred to said mixture after being completely dissolved,
Reaction solution is heated to 90 DEG C, when maintenance 8 is small, with potassium iodide starch test paper (KI-starch test paper) test reaction liquid
After negative (odorless oxide), reaction solution is concentrated into syrupy shape under 70 DEG C of water-baths, carboxylic is can obtain after dry under vacuum
Acid product (4.2g, 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid), as a result such as table 1.
Embodiment A6
Take bicyclopentadiene (10g), acetonitrile (173g) and formic acid (17g, formic acid, Chun Du≤99%, label：
Sigma-Aldrich) it is placed in 1 liter of reaction bulb and mixes, and adds in when the Sudan No. three (10mg) ends as ozone reaction
Indicator then, is stirred to react liquid with stirrer and is passed through ozone (flow using ozone machine：1L/min), with ice-water bath side
Formula keeps the temperature of reaction solution to be passed through ozone to the color fading of indicator for 0 DEG C.
Then, by sodium tungstate dihydrate (250mg, 1mol%), hydrogen peroxide (33g, concentration：It 30wt%) adds in above-mentioned
Reaction solution, and being heated to 85 DEG C makes reaction solution flow back, and when reflux maintenance 16 is small, is surveyed with potassium iodide and starch (KI-starch) test paper
After reaction solution is tried as negative (odorless oxide), reaction solution is concentrated into syrupy shape under 70 DEG C of water-baths, after dry under vacuum
Carboxylic acid product (15.9g, 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid) is can obtain, as a result such as table 1.
Embodiment A7
Except acetic acid is changed to sad (octaonoic acid, purity>98%, label：Sigma-Aldrich) and heat
Outside when time maintenance 16 is small, remaining step is all identical with embodiment A5, can obtain carboxylic acid product (3.5g, 2 β, 3 α, 5 β-tricarboxylic
Cyclopentane acetic acid), as a result such as table 1.
Embodiment A8
Except acetic acid is changed to pure water and heating time maintain 48 it is small when in addition to, remaining step is all identical with embodiment A5,
Carboxylic acid product (3.8g, 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid) is can obtain, as a result such as table 1.
Embodiment A9
Take bicyclopentadiene (400g), acetonitrile (3.2kg, acetonitrile, CH3CN, purity 99%, label：Sigma-
Aldrich) and acetic acid (700g) is placed in 10 liters of reactors and mixes, and it is whole as ozone reaction to add in the Sudan three (50mg)
When indicator, then, liquid is stirred to react with blender and is passed through ozone (flow using ozone machine：10L/min), with ice
Water-bath mode keeps the temperature of reaction solution to be passed through ozone to the color fading of indicator for 0 DEG C.
Then, after above-mentioned reaction solution being taken out (510g) and concentration, syrupy shape mucus (256g) is formed, then, by phosphorus tungsten
Sour (phosphotungstic acid, 256mg), hydrogen peroxide (761mL, concentration：Above-mentioned concentration of reaction solution 30wt%) is added in,
After stirring is completely dissolved to said mixture, reaction solution is heated to 90 DEG C, when maintenance 8 is small, reaction solution is evaporated, makes its concentration
To syrupy shape, carboxylic acid product (96g, 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid) is can obtain after dry under vacuum, as a result such as table
1。
Embodiment A10
Except by wolframic acid (H2WO4, 192mg) it will enter outside concentration of reaction solution, remaining mode is identical with embodiment A9, and
To 101.9g carboxylic acid products (2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid), as a result such as table 1.
Comparative examples A 1 '
In addition to not adding tungstate lithium, remaining step is all identical with embodiment A1, but the reaction solution of this Comparative examples A 1 '
The negative reaction (KI-starch test paper is non-discolouring) for just making reaction solution that odorless oxide be presented on the 2nd need to be passed through, can obtain carboxylic acid production
Object (32.5g, 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid), as a result such as table 1.
Comparative examples A 2 '
Take sodium tungstate dihydrate (0.623g, 5mol%) and Aliquat(0.765g, N-Methyl-N, N,
N-trioctylammonium chloride, purity 88.2~90.6%, label：Sigma-Aldrich) in 100mL reaction bulbs
In, add in hydrogen peroxide (42.8g, concentration：30wt%) stirring after ten minutes, takes bicyclopentadiene (5g) to add in reaction bulb, and
Reaction solution is progressively heated to 90 DEG C, when reaction solution reaction 16 is small, using KI-starch solution testings to be negative, by reaction solution with
60 DEG C of water-bath heating concentration obtains black mucus after removing solvents, by this black mucus with dichloromethane (10mL,
Dichloromethane, CH2Cl2, 99%, label：Duksan Pure Chemicals Co., LTD) after cleaning 3 times, it will be glutinous
Liquid is dry under vacuum environment, can obtain 4.1g products, but the product with1H NMR analyze the signal for having no carboxylic acid, as a result such as table 1.
Comparative examples A 3 '
By pure water (222g), trifluoracetic acid (0.22g, trifluoroacetic acid, purity 99%, label：Sigma-
Aldrich)、After 336 (3.82g) and bicyclopentadiene (25g) add in 1 liter of reactor, with the rotating speed of 500rpm
Above-mentioned solution is stirred, solution is made to form lotion, ozone (flow is passed through using ozone machine：After 1L/min) fading to lotion, it is passed through
Solution is simultaneously heated to 90 DEG C of reactions by oxygen, and the ozonide reacted into solution (is surveyed after decomposing completely with KI-starch solution
Examination), aqueous solution is concentrated and dried, can obtain carboxylic acid product (11.9g, 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid), as a result such as table
1。
Comparative examples A 4 '
Weigh bicyclopentadiene (2.5g), acetic acid (42mL), the Sudan No. three solution (1mL, concentration：100mg/10mL acetic acid
Ethyl ester) and pure water (5mL) into 100mL reaction bulbs, at room temperature stir and be passed through ozone (flow using ozone machine：5L/
Min), heat release is to 50 DEG C after ozone is passed through for reaction solution, after being continually fed into ozone to the red colour fading of reaction solution.Add in peroxidating
Hydrogen (22g, concentration：30wt%), stir 2 at room temperature, still have ozonide with KI-starch starch paper test reaction liquid
It reacts (test paper becomes purple from white).Reaction solution is concentrated under 70 DEG C, when reaction solution is concentrated into syrupy shape, reaction solution
Fast decoupled simultaneously releases a large amount of gases, obtains not soluble in water and organic solvent pitch shape product, as a result such as table 1.
Comparative examples A 5 '
Take acetic acid (420g), pure water (45g) that bicyclopentadiene (25g) is added dropwise acetic acid water in 1 liter of reactor
Solution after dripping bicyclopentadiene, adds in the Sudan No. three indicator solution 1mL (1mL, concentration：100mg/10mL acetic acid second
Ester), ozone is continually fed into using ozone machine, and the temperature of reaction solution is controlled in 25 DEG C with water-bath, ozone is passed through to reaction solution
It fades.Then, by ferric nitrate hydrate (76mg, 1mol%, ferric nitrate 9-hydrate, Fe (NO3)3·9H2O,
Purity>98%, label：J.T.Baker), hydrogen peroxide (215g, concentration：It 30wt%) adds in reaction solution and heats, make reaction solution
Reflux, reaction solution reflux 16 it is small when after, reaction solution using KI solution testings for feminine gender (odorless oxide in ie in solution).By reaction solution
It with 70 DEG C of concentrations of water-bath, and is cleaned with ether (20mL), after dry under vacuum environment, obtains black mucus (30.5g), as a result
Such as table 1.By black mucolytic in deuterated dimethyl sulfoxide-D6 (d6- DMSO), with1H NMR spectras are analyzed, in 9.58,5.45ppm
There is the signal of impurity at place.
Table 1
The preparation example of anhydride compound
Embodiment B1
Weigh carboxylic acid product (6.2g, 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid), the 4-dimethylaminopyridine of embodiment A5
(58mg, 4-dimethylaminopyridine, DMAP, purity：99%, label：Alfa Aesar) to will after 50mL reaction bulbs
Acetic anhydride (23g, acetic anhydride, purity 99%, label：Sigma-Aldrich) add in and stir, and with oil bath side
Formula makes reacting liquid temperature reach 50 DEG C, and solid is begun with after about 30 minutes and is generated in reaction solution, persistently stir 4 it is small when after, will be mixed
Liquid filtering is closed, the solid filtered out is sequentially cleaned with toluene, acetonitrile, ether (each 10mL), by the solid after cleaning in vacuum ring
Under border after drying, anhydride product (2.5g, 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid dicarboxylic anhydride) is obtained.
This solid is with the automatic melting point detector (models of BUCHI：M-565 the scope for) measuring fusing point is 226 DEG C to 249 DEG C
(initial temperature is 160 DEG C, heating rate：10 DEG C/min), wherein 226 DEG C are the temperature for starting melting.Detailed results such as table 2.
With d6- DMSO dissolves anhydride product, with shown in FIG. 11H NMR spectras are analyzed, and obtain following signal：3.73ppm
(t,1H)；3.67~3.63ppm (m, 1H)；3.45~3.43ppm (m, 1H)；3.12~3.00ppm (m, 3H)；2.55~
2.53ppm(m,1H)；2.45~2.42ppm (m, 1H).By anhydride product after water is hydrolyzed, free mass spectrograph is spilt with electricity
(THERMO Q Exactive Plus) analyzes its aqueous solution, can obtain M+Signal value be 261.06, M-Signal value be
259.05。
Embodiment B2
The carboxylic acid product (4.2g, 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid) of Example A5 add in chloroacetic chloride (30g,
Acetyl chloride, purity 98%, label：Alfa Aesar), and with 60 DEG C of oil bath heating reaction solutions it is made to generate reflux
Phenomenon, when making above-mentioned reaction solution reaction 4 small after, reaction solution generates solid, more solids is precipitated this reaction solution ice bath, connects
It, by this reacting liquid filtering to collect solid, after sequentially cleaning solid with acetonitrile, ether (each 10mL), by above-mentioned solid in true
The lower drying of sky can obtain anhydride product (1.16g, yield 32%, 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid dicarboxylic anhydride).
With d6- DMSO dissolves anhydride product, with1H NMR spectras are analyzed, and obtain following signal：3.73ppm(t,1H)；
3.67~3.63ppm (m, 1H)；3.45~3.43ppm (m, 1H)；3.12~3.00ppm (m, 3H)；2.55~2.53ppm (m,
1H)；2.45~2.42ppm (m, 1H).
Comparative example B1 '
Exo-2,3,5- tricarboxylic cyclopentanes are bought by Shi Feng scientific ＆ technical corporation (SHIFENG TECHNOLOGY CO., LTD.)
Acetic acid dicarboxylic anhydride (exo-TCAAH, model：DH-103), with the automatic melting point detector (models of BUCHI：M-565 fusing point) is measured
Scope is 205 DEG C to 210 DEG C, and (initial temperature is 160 DEG C, heating rate：10℃/min).Detailed results such as table 2.Separately with d6-
DMSO dissolves such commercially available exo-TCAAH, obtains shown in Fig. 21H NMR spectras.
Compared to commercial product, 2 prepared β of this exposure, 3 α, 5 β-tricarboxylic cyclopentane acetic acid dicarboxylic anhydride, which have, to be higher than
220 DEG C or more of fusing point.And from1H NMR spectras understand that the two should have identical molecular formula but be different configurational formulas, also
Both i.e. isomer each other.
Table 2
Comparative example B2 '
Take the exo-2 of comparative example B1 ' (commercially available), 3,5- tricarboxylic cyclopentane acetic acid dicarboxylic anhydride (TCAAH, models：DH-
103) plus water after, be hydrolyzed at 60 DEG C reaction 1 it is small when after, 2,3,5- tricarboxylic cyclopentyl acetic acid can be formed,1H NMR
(d6- DMSO) spectrum atlas is as shown in figure 3, spectral characteristic is:12.35ppm(s,4H),3.15ppm(t,1H),3.04ppm(q,
1H),2.70ppm(m,1H),2.59ppm(q,1H),2.33ppm(m,2H),2.20ppm(m,1H),1.89ppm(m,1H)。
Embodiment B3
The anhydride product (2.5g, 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid dicarboxylic anhydride) of Example B1, utilizes comparative example
After the hydrolysis of B2 ' same methods, 2,3,5- tricarboxylic cyclopentyl acetic acid are also formed,1H NMR(d6- DMSO) spectrum atlas such as Fig. 4
It is shown, and its spectral characteristic be 12.03ppm (s, 4H), 3.05ppm (t, 1H), 2.94ppm (m, 2H), 2.81ppm (m, 1H),
2.53ppm(m,2H),2.35ppm(m,1H),2.10ppm(m,1H)。
Folded figure as shown in Figure 5 is can obtain after Fig. 3 and Fig. 4 are folded figure.And from1Knowable to H NMR spectras, both Fig. 3 and Fig. 4
Should have identical molecular formula but for different configurational formulas, that is, the two isomer each other.
The preparation example of polyamic acid
Embodiment C1-C5
Polyamic acid synthesis step：
The anhydride product for testing reaction bulb and embodiment B1 in baking oven is removed into aqueous vapor, takes diamines (0.012mol) in three necks
Bottle, reaction bulb will set up temperature in logical nitrogen and measurement, and vacuum pumping nitrogen filling makes reaction bulb for 3 times full of nitrogen, in room temperature and nitrogen
Gas is continually fed into lower addition dry N-methylpyrrolidone (NMP, N-Methyl-2-pyrrolidone) and dissolves diamines, and diamines is molten
It is slow added into anhydride product (0.012mol) after solution and anhydrous NMP (N-Methyl-2-pyrrolidone) makes the solid ingredient be
Less than 20%, obtain polyamic acid solution when design temperature (see the following table 3) reaction 24 is small.
Polyimides synthesis step：
Above-mentioned polyamic acid solution is added in into pyridine (pyridine, 0.024mol) and acetic anhydride (0.024mol), reaction
Bottle be continually fed into nitrogen, and be heated to 120 DEG C reaction 8 it is small when, after reaction solution instill methanol aqueous solution (1:1) precipitation made is consolidated
Body is crossed filter solid and is cleaned using isopropanol, and by above-mentioned solid, drying can obtain polyimides powder under vacuum.
The manufacture of Kapton：
Above-mentioned polyamic acid solution is coated on glass plate, drying in vacuum drying oven is put into, to be less than the true of 10torr
Be dried under Altitude, and after the temperature conditionss of baking oven is room temperatures to 100 DEG C when small (1), hold temperature 1 it is small when, then by temperature tune
Whole to 200 DEG C when small (1), reach 200 DEG C and then hold temperature 1 it is small when after, directly take out glass plate, glass plate be immersed in the water
Afterwards with ultrasonic vibrate to test piece it is release after, you can Kapton.Then by the T of KaptongAnd TdIt is recorded in
Table 3.
Comparative example C1 '
Exo-2 except using comparative example B1 ' (commercially available), 3,5- tricarboxylic cyclopentane acetic acid dicarboxylic anhydride (TCAAH, models：
DH-103 outside), remaining step is all identical with embodiment C1, obtains Kapton.Then by polyimides (PI) film
TgAnd TdIt is recorded in table 3.
Table 3
Exo-2,3,5- tricarboxylic cyclopentyl acetic acid dicarboxylic anhydrides, is made by nitrate method.
2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid dicarboxylic anhydride, are made (application examples) by Ozone.
ODA:4,4- oxydiphenyls amine (4,4-Oxydianiline).
TFDB:2,2'- bis- (trifluoromethyl) benzidine (2,2'-bis (trifluoromethyl) benzidine).
BAPP:4,4'- (4,4'- isopropylidene diphenyl -1,1'- dioxies) diphenylamines (4,4 '-(4,4 ' -
Isopropylidenediphenyl-1,1’-diyldioxy)dianiline)。
TPE-Q:Double (4- amino-benzene oxygens) benzene (1,4-Bis (4-aminophenoxy) benzene) of 1,4-.
DAS:4,4' diaminodiphenyl sulfone (4,4 '-Diaminodiphenylsulfone).
It can obtain from the ermal physics analysis result of above-mentioned table 3, polyimides of the invention is compared to commercially available isomer
Diacid anhydride product has preferable thermophysical property, since the soft display base material or alignment film material of new generation need preferably
Thermophysical property, that is to say, that the T of those materialsgWith TdNumerical value demand is higher, therefore the present invention has more compared to commercial product
The application value in above application field.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and deformation, but these corresponding changes and deformation can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (18)
1. a kind of preparation method of carboxylic acid compound, which is characterized in that include
An olefin(e) compound and one first oxidant are mixed to form a solution, carries out one first oxidation reaction, first oxidation
Agent includes ozone and a proton solvent；And
One second oxidant is added in the solution, one second oxidation reaction is carried out, the olefin(e) compound is made to form monocarboxylic acid chemical combination
Object, second oxidant include hydrogen peroxide；
Wherein at least one of first oxidant and second oxidant also comprising a Tungstenic compound, a molybdate compound or
Combinations of the above.
2. preparation method according to claim 1, which is characterized in that a diluent is added in first oxidation reaction,
The diluent includes ether, 1,4- dioxane, 1,1- dimethoxy-ethanes, ethyl acetate, acetone, dichloromethane, peroxidating
Hydrogen, water or combinations of the above.
3. preparation method according to claim 1, which is characterized in that the proton solvent includes C1 to C8 alcohols, C1 to C8
Carboxylic acid, water or combinations of the above.
4. preparation method according to claim 1, which is characterized in that first oxidant is also molten to C6 nitriles comprising C2
Agent.
5. preparation method according to claim 1, which is characterized in that the concentration of the hydrogen peroxide for 10wt% extremely
50wt%.
6. preparation method according to claim 1, which is characterized in that the Tungstenic compound includes phosphotungstic acid, sodium tungstate, tungsten
Sour lithium, wolframic acid or combinations of the above, the molybdate compound include molybdic acid.
7. preparation method according to claim 1, which is characterized in that the concentration of the Tungstenic compound or the molybdate compound
For 1mol% to 10mol%.
8. preparation method according to claim 1, which is characterized in that the olefin(e) compound is polycyclic diene hydrocarbon compound.
9. preparation method according to claim 1, which is characterized in that in first oxidation reaction, which is continuously added into
To the solution.
10. preparation method according to claim 1, which is characterized in that the temperature of first oxidation reaction is 0 DEG C to 30
℃。
11. preparation method according to claim 1, which is characterized in that the temperature of second oxidation reaction is 60 DEG C to 120
℃。
12. preparation method according to claim 11, which is characterized in that the time of second oxidation reaction for 6 hours extremely
50 it is small when.
13. a kind of carboxylic acid compound is as the carboxylic acid compound obtained by method described in claim 1, the wherein carboxylic acid
Compound be 2 β, 3 α, 5 β-tricarboxylic cyclopentane acetic acid.
14. a kind of anhydride compound is to carry out a cyclization as the carboxylic acid compound described in claim 13 to be formed, wherein
The fusing point of the anhydride compound is 226 DEG C to 249 DEG C.
15. a kind of anhydride compound is anti-as the carboxylic acid compound obtained by method described in claim 1 and a cyclizing agent
It should be formed.
16. anhydride compound according to claim 15, which is characterized in that the cyclizing agent includes chloroacetic chloride, 4- diformazan ammonia
Yl pyridines, acetic anhydride or combinations of the above.
17. anhydride compound according to claim 15, which is characterized in that the carboxylic acid compound is polybasic carboxylic acid chemical combination
Object.
18. a kind of polyimides is formed as the anhydride compound described in claim 15 and a diamine reactant.
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| CN109503617A (en) * | 2019-01-22 | 2019-03-22 | 青岛科技大学 | A kind of preparation method of 3- carboxymethyl -1,2,4- pentamethylene tricarboxylic acids -1,4:2,3- dianhydride |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB872355A (en) * | 1960-04-26 | 1961-07-05 | Grace W R & Co | Improvements in or relating to the production of a tetrabasic acid and esters thereof |
| CN101382703A (en) * | 2007-09-03 | 2009-03-11 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| CN104583275A (en) * | 2012-08-31 | 2015-04-29 | 吉坤日矿日石能源株式会社 | Polyimide, and alicyclic tetracarboxylic acid dianhydride for use in production of same |
-
2017
- 2017-11-15 TW TW106139418A patent/TW201819348A/en unknown
- 2017-11-15 CN CN201711132132.XA patent/CN108069848A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB872355A (en) * | 1960-04-26 | 1961-07-05 | Grace W R & Co | Improvements in or relating to the production of a tetrabasic acid and esters thereof |
| CN101382703A (en) * | 2007-09-03 | 2009-03-11 | Jsr株式会社 | Liquid crystal aligning agent and liquid crystal display element |
| CN104583275A (en) * | 2012-08-31 | 2015-04-29 | 吉坤日矿日石能源株式会社 | Polyimide, and alicyclic tetracarboxylic acid dianhydride for use in production of same |
Non-Patent Citations (1)
| Title |
|---|
| KANGO FUJITANI等: "Oxidative cleavage with hydrogen peroxide:preparation of polycarboxylic acids from cyclic olefins", 《J.OLEO SCI.》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503617A (en) * | 2019-01-22 | 2019-03-22 | 青岛科技大学 | A kind of preparation method of 3- carboxymethyl -1,2,4- pentamethylene tricarboxylic acids -1,4:2,3- dianhydride |
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