CN101402625A - Preparation method of aromatic diether dianhydride monomer - Google Patents
Preparation method of aromatic diether dianhydride monomer Download PDFInfo
- Publication number
- CN101402625A CN101402625A CNA2008101551275A CN200810155127A CN101402625A CN 101402625 A CN101402625 A CN 101402625A CN A2008101551275 A CNA2008101551275 A CN A2008101551275A CN 200810155127 A CN200810155127 A CN 200810155127A CN 101402625 A CN101402625 A CN 101402625A
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- CN
- China
- Prior art keywords
- reaction
- add
- polar solvent
- aryl
- acid
- 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 27
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 70
- -1 ether anhydrides Chemical class 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 28
- 125000005543 phthalimide group Chemical class 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical class C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 81
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 76
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 34
- 239000007787 solid Substances 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 27
- 238000010992 reflux Methods 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 25
- VACCAVUAMIDAGB-UHFFFAOYSA-N sulfamethizole Chemical compound S1C(C)=NN=C1NS(=O)(=O)C1=CC=C(N)C=C1 VACCAVUAMIDAGB-UHFFFAOYSA-N 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- 239000002798 polar solvent Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 23
- 238000001291 vacuum drying Methods 0.000 claims description 23
- 238000001914 filtration Methods 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 16
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 15
- 150000008282 halocarbons Chemical class 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- 239000007859 condensation product Substances 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000003949 imides Chemical class 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 229910052794 bromium Inorganic materials 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 10
- 238000001953 recrystallisation Methods 0.000 claims description 10
- 229910004013 NO 2 Inorganic materials 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 9
- 150000008065 acid anhydrides Chemical class 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 9
- 239000012362 glacial acetic acid Substances 0.000 claims description 9
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical group [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 239000012454 non-polar solvent Substances 0.000 claims description 8
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 238000006297 dehydration reaction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 claims description 4
- ZNPSUQQXTRRSBM-UHFFFAOYSA-N 4-n-Pentylphenol Chemical class CCCCCC1=CC=C(O)C=C1 ZNPSUQQXTRRSBM-UHFFFAOYSA-N 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- LRCPOJGBEQAERD-UHFFFAOYSA-M [P].[Br-].C(CCC)[P+](CCCC)(CCCC)CCCC Chemical compound [P].[Br-].C(CCC)[P+](CCCC)(CCCC)CCCC LRCPOJGBEQAERD-UHFFFAOYSA-M 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 3
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 claims description 2
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 claims description 2
- DYDWRTQXOFGWOY-UHFFFAOYSA-N 4-(4-hydroxy-3-methylphenyl)-2,6,6-trimethylcyclohexa-1,3-dien-1-ol Chemical group CC1=C(O)C(C)(C)CC(C=2C=C(C)C(O)=CC=2)=C1 DYDWRTQXOFGWOY-UHFFFAOYSA-N 0.000 claims description 2
- NZGQHKSLKRFZFL-UHFFFAOYSA-N 4-(4-hydroxyphenoxy)phenol Chemical compound C1=CC(O)=CC=C1OC1=CC=C(O)C=C1 NZGQHKSLKRFZFL-UHFFFAOYSA-N 0.000 claims description 2
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 claims description 2
- ZNNSPZOSKINXHF-UHFFFAOYSA-N 5-sulfinylcyclohexa-1,3-diene Chemical compound O=S=C1CC=CC=C1 ZNNSPZOSKINXHF-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims description 2
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 150000004692 metal hydroxides Chemical class 0.000 claims description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims 1
- 238000001308 synthesis method Methods 0.000 abstract 2
- 150000008064 anhydrides Chemical class 0.000 abstract 1
- 150000005826 halohydrocarbons Chemical class 0.000 abstract 1
- 239000003586 protic polar solvent Substances 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 38
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 22
- 229960000935 dehydrated alcohol Drugs 0.000 description 16
- 238000005303 weighing Methods 0.000 description 16
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 14
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 14
- 239000004305 biphenyl Substances 0.000 description 14
- 239000001103 potassium chloride Substances 0.000 description 14
- 235000011164 potassium chloride Nutrition 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 13
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 12
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 12
- 235000010290 biphenyl Nutrition 0.000 description 11
- 229930185605 Bisphenol Natural products 0.000 description 9
- 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 9
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 229960004756 ethanol Drugs 0.000 description 8
- 239000012452 mother liquor Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 230000006837 decompression Effects 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 5
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 150000003141 primary amines Chemical class 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- GEJBNUCMDKIJRA-UHFFFAOYSA-N 2-benzyl-5-nitroisoindole-1,3-dione Chemical compound O=C1C2=CC([N+](=O)[O-])=CC=C2C(=O)N1CC1=CC=CC=C1 GEJBNUCMDKIJRA-UHFFFAOYSA-N 0.000 description 3
- CCTOEAMRIIXGDJ-UHFFFAOYSA-N 4-hydroxy-2-benzofuran-1,3-dione Chemical compound OC1=CC=CC2=C1C(=O)OC2=O CCTOEAMRIIXGDJ-UHFFFAOYSA-N 0.000 description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 3
- 229940073608 benzyl chloride Drugs 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- JCOUALARZIOEOQ-UHFFFAOYSA-N 1,2,3,4-tetramethyl-5-(2,3,4,5-tetramethylphenoxy)benzene Chemical compound CC1=C(C)C(C)=CC(OC=2C(=C(C)C(C)=C(C)C=2)C)=C1C JCOUALARZIOEOQ-UHFFFAOYSA-N 0.000 description 2
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- IYJLTOTUYACXLP-UHFFFAOYSA-N 2-benzyl-4-nitroisoindole-1,3-dione Chemical compound O=C1C=2C([N+](=O)[O-])=CC=CC=2C(=O)N1CC1=CC=CC=C1 IYJLTOTUYACXLP-UHFFFAOYSA-N 0.000 description 2
- UVIDPQKULVZZNK-UHFFFAOYSA-N 2-butyl-5-fluoroisoindole-1,3-dione Chemical compound C1=C(F)C=C2C(=O)N(CCCC)C(=O)C2=C1 UVIDPQKULVZZNK-UHFFFAOYSA-N 0.000 description 2
- FFBUYJAHSNPQDH-UHFFFAOYSA-N 2-ethyl-5-nitroisoindole-1,3-dione Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(CC)C(=O)C2=C1 FFBUYJAHSNPQDH-UHFFFAOYSA-N 0.000 description 2
- RPOHMBLKZOOYJP-UHFFFAOYSA-N 2-methyl-1-phenylhexane-1,1-diol Chemical compound CC(C(O)(O)C1=CC=CC=C1)CCCC RPOHMBLKZOOYJP-UHFFFAOYSA-N 0.000 description 2
- FWIZOFDVGZCRTB-UHFFFAOYSA-N 2-methyl-4-nitroisoindole-1,3-dione Chemical compound C1=CC([N+]([O-])=O)=C2C(=O)N(C)C(=O)C2=C1 FWIZOFDVGZCRTB-UHFFFAOYSA-N 0.000 description 2
- AMUJXUBLHTYUAN-UHFFFAOYSA-N 4-nitro-2-propylisoindole-1,3-dione Chemical compound C1=CC([N+]([O-])=O)=C2C(=O)N(CCC)C(=O)C2=C1 AMUJXUBLHTYUAN-UHFFFAOYSA-N 0.000 description 2
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 2
- DCFSQEWFDPNDPQ-UHFFFAOYSA-N 5-chloro-2-methylisoindole-1,3-dione Chemical compound C1=C(Cl)C=C2C(=O)N(C)C(=O)C2=C1 DCFSQEWFDPNDPQ-UHFFFAOYSA-N 0.000 description 2
- GDWIOMYZCZOOHW-UHFFFAOYSA-N CCCN1C(=O)c2cccc(Br)c2C1=O Chemical compound CCCN1C(=O)c2cccc(Br)c2C1=O GDWIOMYZCZOOHW-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- XXFXTBNFFMQVKJ-UHFFFAOYSA-N [diphenyl(trityloxy)methyl]benzene Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(C=1C=CC=CC=1)OC(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XXFXTBNFFMQVKJ-UHFFFAOYSA-N 0.000 description 2
- 150000003973 alkyl amines Chemical class 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 2
- CWHFDTWZHFRTAB-UHFFFAOYSA-N phenyl cyanate Chemical compound N#COC1=CC=CC=C1 CWHFDTWZHFRTAB-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000007867 post-reaction treatment Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 2
- LSVBBJVITBGNFC-UHFFFAOYSA-N 2-butyl-5-nitroisoindole-1,3-dione Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(CCCC)C(=O)C2=C1 LSVBBJVITBGNFC-UHFFFAOYSA-N 0.000 description 1
- ZXLYYQUMYFHCLQ-UHFFFAOYSA-N 2-methylisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(C)C(=O)C2=C1 ZXLYYQUMYFHCLQ-UHFFFAOYSA-N 0.000 description 1
- 206010020843 Hyperthermia Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 125000006159 dianhydride group Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000036031 hyperthermia Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940072395 n-butylphthalimide Drugs 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Indole Compounds (AREA)
Abstract
The invention relates to a synthesis method of dianhydride monomers, in particular to a synthesis method of aromatic diether dianhydride monomers. The use of 3(4) substituted phthalimides to prepare the bis ether anhydrides gives a new intermediate step in the preparation of the bis ether anhydrides. The 3(4) substituted phthalimide is prepared by the drape Rayler reaction principle of the 3(4) substituted-N-alkyl (aryl) phthalimide, and can also be prepared by adding a salt forming agent into a nonpolar protic solvent to react with halohydrocarbon. And the prepared 3(4) substituted-N-alkyl (aryl) phthalimide is adopted to prepare the bisimide and the bisether anhydride, the method has the advantages of easily obtained raw materials, simple preparation method and easy operation, and the purity and the yield of the prepared 3(4) substituted-N-alkyl (aryl) phthalimide are obviously higher than those of the traditional method.
Description
Technical field
The present invention relates to the monomeric synthetic method of a kind of dianhydride class, related in particular to a kind of synthetic method of aromatic diaether dianhydride monomer.
Background technology
Diaether dianhydride is one of important monomer of synthetic ether acid anhydride polyimide type resin, is the intermediate that is used to prepare the polyetherimide of special products such as high temperature resistant terminal, high-strength mechanical component, junctor and corrosion-resistant, fire-retardant, radiation hardness.Also be the good properties-correcting agent of resin.By in dianhydride monomer, introducing ehter bond (O-), make original insoluble PI be dissolved in tetrahydrofuran (THF) (THF), N-Methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), N, N '-dimethyl formamide (DMF) and N, N '-N,N-DIMETHYLACETAMIDE organic solvents commonly used such as (DMAc), and making it have lower second-order transition temperature, processing characteristics improves.
The synthetic method of diaether dianhydride is many, and common have the hydrolysis of four cyano phenyl ether, tetramethyl-phenyl ether oxidation style, halobenzoyl anhydride and hydroxyl phthalic anhydride method, halobenzoyl anhydride method, a phthalic anhydride method etc.These synthetic methods all exist from economy, the improved needs of environment and overall efficiency aspect and expectation.
The very easily oxidation of phenol of using in the four cyano phenyl ether hydrolysis method, reinforced reaching in the reaction process requires absolute anhydrous and oxygen-free, and high to the sealing requirements of device, nitrogen will pass through processed earlier, is difficult for realizing in suitability for industrialized production.
US5101006, EP0460687 use tetramethyl-phenyl ether oxidation style preparation 3,3 ', 4,4 '-phenyl ether tetracarboxylic dianhydride (ODPA), this method raw material sources difficulty, and yield is too low, and by product is many, extremely difficult separation and purification, especially oxidation only is 25.5%, thereby does not have actual application value.
US4837404, EP0119576, US4948904 use halobenzoyl anhydride and hydroxyl phthalic anhydride legal system to be equipped with ODPA, though this route is simple and clear, by product is many, yield is very low, and the hydroxyl phthalic anhydride is by phthalic anhydride sulfonation, hydrolysis, also cause yield low, so this route use value is little.
US5153335, US4870194, US5021168, US5021168, EP0330220, CN1764654A, CN1324794A use the halobenzoyl anhydride legal system to be equipped with diaether dianhydride, from halobenzoyl anhydride, with alkali metal compound in the presence of reaction medium and catalyzer, nucleophilic substitution takes place.Though the product purity height of this method preparation, solvent recuperation is easy, and being has one of synthetic route of competitive capacity most and since the moisture that contains in the raw material difficulty remove fully, and water is bigger to the influence of this reaction, so operate difficulty.
US4933469, US5177002, in intelligent (chemistry with bonding, 1999, NO.5) and Wang Kuntang (chemical engineer, 2000, NO.5) use the phthalic anhydride legal system to be equipped with the bis ether acid anhydride, this method is more sophisticated to be applied on the industrial production, from phthalic anhydride, through methylamine, the nitrated again nitro-N-methyl phthalimide of making, under catalyzer, make ether acid afterwards, be dehydrated into the ether acid anhydride at last through bimolecular condensation etherificate, hydrolysis, acidifying.This method is used methylamine when preparation N-methyl phthalimide, the shortcoming that methylamine showed is dual.Methylamine is not only poisonous, and its boiling temperature is relatively low, so it is to be gasiform under temperature of reaction, needs special poison gas device; The reaction of phthalic anhydride and methylamine is thermopositive reaction in addition, and the phthalic anhydride facile hydrolysis, these two reactions are parallel competing reactions, the heat that produces in the reaction can impel the hydrolysis of phthalic anhydride; Moreover the total efficiency of nitrated preparation nitro-N-methyl phthalimide is relatively low, and needs to use a large amount of concentrated nitric acid and the vitriol oil; It is long that also there is route in this method in addition, causes total efficiency not high, and the three wastes are many, weak points such as cost height.
US3879428, US4017511, US3957862, US4202993, US4247464, US6008374, CN1634904A utilization structure are
(R
1-C
1～8Alkyl or C
6～13Aryl; X-halogen atom or nitro) material and phenates reaction can generate various aryl oxides.Need in the reaction process phenates is separated earlier, but in fact the separation of phenates is an extremely difficult process, because its very easily oxidation so need special equipment when dry and preservation phenates, is unfavorable for the realization of industrialization; In addition, when temperature of reaction is higher than 75 ℃, need 5% quantity of solvent just can make the solid dissolving, thereby reaction system is carried out in mutually at solution, and temperature of reaction is when being higher than 100 ℃, because reaction system is alkalescence, raw material
Self condensation reaction very easily takes place.When the reaction times less than 12h, material content is high in the product, is difficult to separate.Because solvent load is bigger in this reaction process,, cause great solvent waste if reaction solution is directly poured into when in acid or other solution product being separated out.
CN1121514A has proposed a kind of alkylamines having low melting double imide of deriving and has prepared the method for bis ether acid anhydride, this method adopts liquid alkylamine and phthalic acid (phthalic anhydride) the preparation alkyl phthalic imide that contains 3 carbon atoms at least, make the 4-nitro alkyl phthalic imidine after nitrated, form double imide with the reaction of exsiccant bis-phenol an alkali metal salt then, at last double imide is changed into the bis ether acid anhydride.Though this method has avoided using the deficiency of methylamine, but use phthalic anhydride as starting raw material, because the temperature of this reaction is at 150 ℃～175 ℃, the hydrolysis of phthalic anhydride is quickened under this temperature, has reduced the transformation efficiency of phthalic anhydride; In addition, nitrated preparation 4-nitro alkyl phthalic imidine has used a large amount of concentrated nitric acids and the vitriol oil.
Summary of the invention
The objective of the invention is in order to improve existing operational path long, the difficult separation of product, the high deficiency of production cost and a kind of method for preparing aromatic diaether dianhydride monomer is provided.
Technical scheme of the present invention is: the structural formula of the prepared diaether dianhydride monomer of the present invention is as follows:
Wherein R is: C
6～30Aryl, preferred structure (a):
Or structure (b):
R wherein
2Contain following group :-C
yH
2y-,
-O-,-S-
M is 0 or 1, y=1～5;
One of raw material of the present invention contains following structural formula:
Wherein X is: F, Cl, Br or NO
2
Two of raw material of the present invention has following structural formula:
OH-R-OH
Wherein R is: C
6～30Aryl, preferred structure (a):
Or structure (b):
R wherein
2Contain following group :-C
yH
2y-,
-O-,-S-
M is 0 or 1, y=1～5;
This material generates with alkali or strong base weak acid reactant salt in aprotic polar solvent or some polar solvent
MO-R-OM
Wherein M is: K
+, Na
+R is: C
6～30Aryl, preferred structure (a) or structure (b);
A kind of preparation method of aromatic diaether dianhydride monomer, concrete synthesis step is as follows:
The preparation (substitution reaction) of A, 3 (4) replacement-N-alkyl (aryl) phthalic imidines
A, in reaction unit (as mechanical glass stirring rake, thermometer, prolong, there-necked flask), add alkali metal hydroxide, lower aliphatic alcohols, being stirred to alkali metal hydroxide dissolves fully, add 3 (4) substituted phthalimides, 20 ℃～50 ℃ are stirred 4h～6h down, make an alkali metal salt;
B, an alkali metal salt that in aprotic polar solvent, makes above the adding, halocarbon, 100 ℃～150 ℃ are stirred 3h～6h down; Cooling treats that product separates out after-filtration, collects filtrate and filter cake respectively;
C, aftertreatment: with gained filter cake washing in the above-mentioned b step, purify, oven dry obtains white cotton shape 3 (4) replacement-N-alkyl (aryl) phthalic imidines;
Reaction scheme is as follows:
R wherein
1For: C
1～8Alkyl or C
6～13Aryl; X is: F, Cl, Br or NO
2
In this reaction, raw material is 3 (4) substituted phthalimides, and structural formula is:
Or:
A), in reaction unit (as mechanical glass stirring rake, thermometer, prolong, there-necked flask), add 3 (4) substituted phthalimides, salt forming agent, halocarbon and aprotic polar solvent, stir, 100 ℃～140 ℃ are stirred 3h～6h down, cooling, treat that product separates out after-filtration, collect filtrate and filter cake respectively;
B), aftertreatment: with gained filter cake pickling in the above-mentioned a) step, purify, oven dry obtains white cotton shape 3 (4) replacement-N-alkyl (aryl) phthalic imidine crystal;
Reaction scheme is as follows:
R wherein
1For: C
1～8Alkyl or C
6～13Aryl; X is: F, Cl, Br or NO
2
In this reaction, raw material is 3 (4) replacement substituted phthalimides, and the salt forming agent that uses is Anhydrous potassium carbonate, saleratus, yellow soda ash or sodium bicarbonate, and the mol ratio of salt forming agent and raw material is 1～3: 1; The halocarbon that reaction is used is R
1X, wherein R
1Be C
1～8Alkyl or C
6～13Aryl, X are F, Cl, Br or NO
2, the mol ratio of halocarbon and raw material is 1～2: 1; The aprotic polar solvent that reaction is used is DMF, DMAc, NMP, THF or DMSO, and the mass ratio of aprotic polar solvent and halocarbon is 3～5: 1; Use dilute hydrochloric acid to carry out pickling in the post-reaction treatment; Purify with ethanol, toluene, ethylene glycol monomethyl ether etc.;
The preparation (condensation reaction) of B, bis ether two phthalimides (double imide)
A, in reaction unit, add the raw material diphenol, feed nitrogen, add aprotic polar solvent, add alkali or strong base weak acid salts solution then, add non-polar solvent again, backflow 4h～the 6h that anhydrates steams non-polar solvent cooling after dividing water to finish, 3 (4) replacement-N-alkyl (aryl) phthalic imidine and the catalyzer that add the steps A gained then, add aprotic polar solvent again, be warming up to 75 ℃～100 ℃, reaction 10h～48h;
B, aftertreatment: gained solution steaming in the above-mentioned a step is desolventized, and the solid that obtains dilute hydrochloric acid pickling is filtered, recrystallization, and oven dry gets bis ether two phthalimides;
Reaction scheme is as follows:
OH-R-OH→MO-R-OM
Wherein M is: K
+, Na
+R
1For: C
1～8Alkyl or C
6～13Aryl;
R is: C
6～30Aryl, preferred structure (a):
Or structure (b):
R wherein
2Contain following group :-C
yH
2y-,
-O-,-S-
M is 0 or 1, y=1～5;
X is: F, Cl, Br or NO
2
The structural formula of above-mentioned diphenol is OH-R-OH, and wherein R is: C
6～30Aryl is preferably and is structure (a) and structure (b); Preferred diphenol is 2, two (2-hydroxyphenyl) propane of 2-, 2,4 '-dihydroxy-benzene methylmethane, two (2-hydroxyphenyl) methane, 2, two (4-hydroxyphenyl) propane of 2-, 1, two (4-hydroxyphenyl) ethane of 1-, 1, two (4-hydroxyphenyl) propane of 1-, 2, two (4-hydroxyphenyl) pentanes of 2-, 3, two (4-hydroxyphenyl) pentanes of 3-, 4,4 '-dihydroxybiphenyl, 2,4 '-dihydroxybiphenyl benzophenone, 4,4 '-dihydroxyl-3,3,5,5 '-tetramethyl biphenyl, Resorcinol, 4,4 '-dihydroxy diphenylsulphone, 4,4 '-dihydroxyl thionyl benzene, 4,4 '-dihydroxyl diphenyl sulfide, quinhydrones, 4,4 '-dihydroxy diphenyl ether, 3,4 '-dihydroxyl ditan or 4,4 '-dihydroxy benzophenone.
In this reaction, raw material is a diphenol, and the alkali of producing phenates in the reaction is preferably KOH or NaOH, and strong base weak acid salt is preferably K
2CO
3Or Na
2CO
3, the mol ratio of alkali or strong base weak acid salt and raw material is 2～5: 1; Aprotic polar solvent is DMF, DMAc, NMP, THF or DMSO in this reaction, and the mass ratio of aprotic polar solvent and raw material diphenol is 3～5: 1; Non-polar solvent is benzene, toluene or dimethylbenzene, and the mass ratio of non-polar solvent and aprotic polar solvent is 1: 2～6; Catalyzer in this reaction is preferably Tetrabutyl amonium bromide, Red copper oxide or tetrabutyl phosphonium bromide phosphorus, and the mol ratio of itself and raw material is 0.03～0.05: 1; The mol ratio of 3 (4) replacement-N-alkyl (aryl) phthalic imidines and raw material is 2～3: 1 in this reaction; Condensation product can be used ether, ethylene glycol, ethanol, propyl alcohol, acetonitrile or toluene recrystallization in this reaction;
The preparation of C, bis ether tetracid (acidication reaction)
With adding strong alkali aqueous solution in step B gained condensation product bis ether two phthalimides, be heated to backflow under the nitrogen protection, backflow 8h～48h is cooled to the room temperature after-filtration, and adding acid in the solution is regulated the pH value between 0～1, filters, and oven dry gets the bis ether tetracid.
Reaction scheme is as follows:
R wherein
1For: C
1～8Alkyl or C
6～13Aryl; R is: C
6～30Aryl is preferably structure (a) or structure (b);
Highly basic used in this reaction is preferably sodium hydroxide, and used acid is preferably phosphoric acid, hydrochloric acid or sulfuric acid;
The preparation of D, diaether dianhydride (dehydration reaction)
Step C gained bis ether tetracid is joined acetate and diacetyl oxide mixing solutions, perhaps join heating reflux reaction in the toluene; Filter, dry in the vacuum drying oven, get diaether dianhydride.
Reaction scheme is as follows:
Wherein R is: C
6～30Aryl is preferably structure (a) and structure (b);
In this reaction process, if bis ether four acid anhydrides are joined in acetate and the diacetyl oxide mixing solutions, its consumption is that the mol ratio of bis ether four acid anhydrides and acetate is 1: 1～3, wherein acetate and diacetyl oxide mass ratio are 1～3: 1 in acetate and the diacetyl oxide mixing solutions, if bis ether four acid anhydrides are joined in the toluene, its consumption is that the mol ratio of bis ether four acid anhydrides and toluene is 1: 2～5, heating reflux reaction 4h～6h, filter, solid washs with glacial acetic acid, temperature is controlled at 100 ℃～250 ℃ in vacuum drying oven then, and hyperthermia drying time 2h～5h promptly gets diaether dianhydride.
Beneficial effect
In the substitution reaction process, the present invention proposes a kind of method of new preparation 3 (4) replacement-N-alkyl (aryl) phthalic imidines, promptly use 3 (4) substituted phthalimides and alkali metal hydroxide in lower aliphatic alcohols, to form an alkali metal salt, then with halocarbon (R
1X) effect generates 3 (4) replacement-N-alkyl (aryl) phthalic imidines, or add salt forming agent in aprotic polar solvent, makes 3 (4) substituted phthalimides and halocarbon directly act on generation nitro-N-alkyl (aryl) phthalic imidine.This method raw material is easy to get, and the phthalic anhydride of having avoided using deleterious methylamine and facile hydrolysis is as the reaction starting raw material, and the preparation method is simple, easy to operate, the product purity height that obtains, yield height; This product can also prepare primary amine except preparing the diaether dianhydride; The present invention has added catalyzer in condensation reaction, make reaction carry out more fully, improves product yield, and the reclaim under reduced pressure of solvent reduces three-waste pollution simultaneously; The present invention adopts present toluene or acetate to dewater with in the solution of acetic anhydride, use the method for vacuum drying oven high temperature dehydration then, eliminated the existence that also has relatively large bis ether tetracid in the diaether dianhydride after the processed, the melting range of gained target product is narrower, and purity is higher.
1, purity height: using 3 (4) replacement-N-alkyl (aryl) phthalic imidine fusing point melting ranges of the path of preparing of the present invention's proposition is 1 ℃～2 ℃; During dehydration, after in mixture solution, dewatering, about 3 ℃～4 ℃ of diaether dianhydride melting range scope, but continue to use the vacuum drying oven high temperature dehydration, making bis ether tetracid content minimizing in the product, product purity improves, and melting range is less than 1 ℃.
2, the three wastes are few, and are easily separated: temperature of reaction the solvent usage quantity is reduced, and reaction is comparatively complete at 75 ℃～150 ℃, and some by product (as primary amine) in the reaction can extract from mother liquor, thereby has reduced quantity of three wastes; Foreign matter content reduces in the condensation product, and the reclaim under reduced pressure of solvent, and three-waste pollution is reduced.
3, cost is low: when the hydrolysis of bis ether imide prepares the bis ether tetracid, have the by product primary amine to generate, this primary amine can be recycled, and makes utilization ratio of raw materials improve, thereby has reduced cost; In addition, the adding of catalyzer is shortened the time of reaction greatly in the condensation reaction, and raw material reaction is complete; The recovery of solvent has reduced a large amount of costs.
4, processing condition gentleness: the requirement to device is lower, need not high pressure-temperature, and operating process is easy, has certain application value.
Embodiment
To help to understand the present invention by following example, but not limit content of the present invention.
Embodiment 1
Add 11.2 gKOH in the 500ml there-necked flask, the 160g dehydrated alcohol is stirred to dissolving; Add 38.4g4-nitro phthalic imidine then, 25 ℃ are stirred 4h down; Reaction finishes after-filtration, collects mother liquor, and dehydrated alcohol is reclaimed in underpressure distillation; 80 ℃ of following vacuum dryings of filter cake (sylvite).
The sylvite that makes above adding in the 500ml there-necked flask adds 25.3g Benzyl Chloride and 100gDMF again, is warming up to 130 ℃, isothermal reaction 4h; Reaction is cooled to 50 ℃ after finishing, and has solid to separate out, and filters, and washing is purified with ethanol, and 120 ℃ of vacuum-drying 2h promptly get 4-nitro-N-benzylphthalimide.
Perhaps, in the 500ml there-necked flask, add 51.8gK
2CO
3, 57.9g4-nitro phthalic imidine, 75.9g Benzyl Chloride and 200gDMF stir and are warming up to 140 ℃ of isothermal reaction 6h; Be cooled to 50 ℃ after reaction finishes, have solid to separate out, filter, earlier with 2% dilute hydrochloric acid pickling, spent glycol methyl ether purification again, 120 ℃ of vacuum-drying 2h promptly get 4-nitro-N-benzylphthalimide.
Add the 18.6g '-biphenyl diphenol in the 500ml there-necked flask, feed nitrogen, add the 120ml dimethyl sulfoxide (DMSO), the NaOH aqueous solution of 18g50% adds 70ml toluene again, and the 5h that anhydrates that refluxes after branch water finishes steams toluene.Be cooled to 60 ℃ and add above-mentioned prepared product 4-nitro-N-benzylphthalimide 28.2g, the 1.3g Tetrabutyl amonium bromide, the 200ml dimethyl sulfoxide (DMSO) is reacted 12h down at 100 ℃.After reaction finishes again decompression state steam down and desolventize, add 300ml hydrochloric acid, filter, the solid ethyl alcohol recrystallization gets the Benzyldiphenyl double imide.
Take by weighing above-mentioned gained condensation product Benzyldiphenyl double imide 52.3g, add the NaOH aqueous solution of 410g15%, reflux 24h under the logical nitrogen state is cooled to 30 ℃ of after-filtration, adds hydrochloric acid in the solution and regulates pH to 0.5, filters and promptly gets biphenyl type diether tetracid.
Take by weighing above-mentioned gained biphenyl type diether tetracid 52.2g, add 23.0g diacetyl oxide and 57.0g acetate, reflux 6h filters, and solid washs with the 120ml glacial acetic acid, and dry 5h in 250 ℃ of baking ovens promptly gets highly purified biphenyl two ether dianhydrides.Fusing point is 285.1 ℃～286.0 ℃, and yield is 98.3%.
Embodiment 2
Add 10.5gKOH in the 500ml there-necked flask, the 130g dehydrated alcohol is stirred to dissolving; Add 36.0g3-nitro phthalic imidine then, 35 ℃ are stirred 4h down; Reaction finishes after-filtration, collects mother liquor, and dehydrated alcohol is reclaimed in underpressure distillation; 85 ℃ of following vacuum dryings of filter cake (sylvite).
The sylvite that makes above adding in the 500ml there-necked flask adds 23.7g Benzyl Chloride and 90gDMF again, is warming up to 140 ℃, isothermal reaction 6h; Reaction is cooled to 45 ℃ after finishing, and has solid to separate out, and filters, and washing is purified with ethanol, and 120 ℃ of vacuum-drying 2h promptly get 3-nitro-N-benzylphthalimide.
Add the 19.1g '-biphenyl diphenol in the 500ml there-necked flask, feed nitrogen, add the 125ml dimethyl sulfoxide (DMSO), the NaOH aqueous solution of 18.7g50% adds 75ml toluene again, and the 5h that anhydrates that refluxes after branch water finishes steams toluene.Be cooled to 55 ℃ and add above-mentioned prepared product 3-nitro-N-benzylphthalimide 29.3g, the 1.5g Tetrabutyl amonium bromide, the 220ml dimethyl sulfoxide (DMSO) is reacted 12h down at 100 ℃.After reaction finishes again decompression state steam down and desolventize, add 250ml hydrochloric acid, filter, the solid ethyl alcohol recrystallization gets the Benzyldiphenyl double imide.
Take by weighing above-mentioned gained condensation product Benzyldiphenyl double imide 44.3g, add the NaOH aqueous solution of 300g13%, reflux 24h under the logical nitrogen state cools off 35 ℃ of after-filtration, adds hydrochloric acid in the solution and regulates pH to 0.7, filters and promptly gets biphenyl type diether tetracid.
Take by weighing above-mentioned gained biphenyl type diether tetracid 48.5g, add 24.0g diacetyl oxide and 58.0g acetate, reflux 6h filters, and solid washs with the 125ml glacial acetic acid, and dry 5h in 250 ℃ of baking ovens promptly gets highly purified biphenyl two ether dianhydrides.Fusing point is 285.6 ℃～286.3 ℃, and yield is 98.5%.
Embodiment 3
Add 13.5gKOH in the 500ml there-necked flask, the 140g dehydrated alcohol is stirred to dissolving; Add 46.3g4-nitro phthalic imidine then, 30 ℃ are stirred 5h down; Reaction finishes after-filtration, collects mother liquor, and dehydrated alcohol is reclaimed in underpressure distillation; 90 ℃ of following vacuum dryings of filter cake (sylvite).
The sylvite that makes above adding in the 500ml there-necked flask adds 32.8g one n-butyl bromide and 90gDMF again, is warming up to 140 ℃, isothermal reaction 6h; Reaction is cooled to 40 ℃ after finishing, and has solid to separate out, filter, and washing, the spent glycol methyl ether is purified, and 100 ℃ of vacuum-drying 2h promptly get 4-nitro-N-butyl phthalimide.
Add the 22.8g dihydroxyphenyl propane in the 500ml there-necked flask, feed nitrogen, add the 100ml dimethyl sulfoxide (DMSO), the NaOH aqueous solution of 16g50% adds 50ml toluene again, and the 6h that anhydrates that refluxes after branch water finishes steams toluene.Be cooled to 70 ℃ of product 4-nitro prepared above the adding-N-butyl phthalimide 45.3g, 1.5g Red copper oxide, the 300ml dimethyl sulfoxide (DMSO) is reacted 10h down at 110 ℃.After reaction finishes again decompression state steam down and desolventize, add 400ml hydrochloric acid, filter, solid spent glycol recrystallization, butyl dihydroxyphenyl propane double imide.
Take by weighing above-mentioned gained condensation product butyl dihydroxyphenyl propane double imide 47.6g, add the NaOH aqueous solution of 350g11%, reflux 23h under the logical nitrogen state cools off 40 ℃ of after-filtration, adds hydrochloric acid in the solution and regulates pH to 0.1, filters and promptly gets bisphenol A-type diether tetracid.
Take by weighing above-mentioned gained bisphenol A-type diether tetracid 54.3g, add 25.2g diacetyl oxide and 60.2g acetate, reflux 6h filters, and solid washs with the 120ml glacial acetic acid, and dry 4h in 150 ℃ of baking ovens promptly gets highly purified bisphenol A-type diaether dianhydride.Fusing point is 186.3 ℃～187.1 ℃, and yield is 96.2%.
Embodiment 4
Add 11.2gKOH in the 500ml there-necked flask, the 160g dehydrated alcohol is stirred to dissolving; Add the 38.4g4-chlorophthalimide then, 10.1g monochloro methane and 100gDMF stir and are warming up to backflow, steam dehydrated alcohol; Be warming up to 130 ℃ of isothermal reaction 4h; Reaction is cooled to 50 ℃ after finishing, and has solid to separate out, and filters, and washing is purified with toluene, and 110 ℃ of vacuum-drying 2h promptly get 4-chloro-N-methyl phthalimide.
Add the 11.0g Resorcinol in the 500ml there-necked flask, feed nitrogen, add the 50ml dimethyl sulfoxide (DMSO), the NaOH aqueous solution of 16g50% adds 20ml benzene again, and the 5h that anhydrates that refluxes after branch water finishes steams benzene.Be cooled to 80 ℃ and add above-mentioned products therefrom 4-chloro-N-methyl phthalimide 41.2g, 1.8g Red copper oxide, the 300ml dimethyl sulfoxide (DMSO) is reacted 12h down at 80 ℃.After reaction finishes again decompression state steam down and desolventize, add 400ml hydrochloric acid, filter, solid spent glycol recrystallization, triphen bis ether two phthalimides.
Take by weighing above-mentioned gained condensation product triphen bis ether two phthalimide 42.8g, add the NaOH aqueous solution of 267g12%, reflux 24h under the logical nitrogen state cools off 25 ℃ of after-filtration, adds hydrochloric acid in the solution and regulates pH to 0.4, filters and promptly gets the triphenylmethyl ether tetracid.
Take by weighing above-mentioned gained triphenylmethyl ether tetracid 43.8g, add 20.4g diacetyl oxide and 60g acetate, reflux 6h filters, and solid washs with 100ml acetate, and dry 4h in 230 ℃ of baking ovens promptly gets highly purified triphen two ether dianhydrides.Fusing point is 265.4 ℃～266.1 ℃, and yield is 97.8%.
Embodiment 5
Add 11.2gKOH in the 500ml there-necked flask, the 110g dehydrated alcohol is stirred to dissolving; Add 38.4g3-bromine phthalic imidine then, 30 ℃ are stirred 5h down; Reaction finishes after-filtration, collects mother liquor, and dehydrated alcohol is reclaimed in underpressure distillation; 90 ℃ of following vacuum dryings of filter cake (sylvite); The sylvite that makes above adding in the 500ml there-necked flask adds 15.7g one chloropropane and 85gDMF again, is warming up to 140 ℃, isothermal reaction 6h; Reaction is cooled to 50 ℃ after finishing, and has solid to separate out, and filters, and washing is purified with toluene, and 100 ℃ of vacuum-drying 2h promptly get 3-bromo-N-propyl phthalimide.
Add the 25.0g bisphenol S in the 1000ml there-necked flask, feed nitrogen, add the 120ml dimethyl sulfoxide (DMSO), the NaOH aqueous solution of 16g50% adds 40ml toluene again, and the 5h that anhydrates that refluxes after branch water finishes steams toluene.Be cooled to 70 ℃ and add above-mentioned products therefrom 3-bromo-N-propyl phthalimide 41.2g, the 1.2g Tetrabutyl amonium bromide, the 320ml dimethyl sulfoxide (DMSO) is reacted 18h down at 90 ℃.After reaction finishes again decompression state steam down and desolventize, add 400ml hydrochloric acid, filter, solid ether recrystallization gets bisphenol S diether type two phthalimides.
Take by weighing above-mentioned gained condensation product bisphenol S diether type two phthalimide 56.8g, the NaOH aqueous solution that adds 210g15%, reflux 24h under the logical nitrogen state cools off 30 ℃ of after-filtration, add hydrochloric acid in the solution and regulate pH to 0.7, filter and promptly get bisphenol S type diether tetracid.
Take by weighing above-mentioned gained bisphenol S type diether tetracid 57.8g, add 25.0g diacetyl oxide and 70.0g acetate, reflux 6h filters, and solid washs with the 100ml glacial acetic acid, and dry 3h in 200 ℃ of baking ovens promptly gets highly purified bisphenol S dianhydride.Fusing point is 251.0 ℃～252.1 ℃, and yield is 96.2%.
Embodiment 6
Add 11.2gKOH in the 500ml there-necked flask, the 110g dehydrated alcohol is stirred to dissolving; Add 38.4g4-nitro phthalic imidine then, 30 ℃ are stirred 5h down; Reaction finishes after-filtration, collects mother liquor, and dehydrated alcohol is reclaimed in underpressure distillation; 90 ℃ of following vacuum dryings of filter cake (sylvite); The sylvite that makes above adding in the 500ml there-necked flask adds 15.7g monochlorethane and 85gDMF again, is warming up to 140 ℃, isothermal reaction 6h; Reaction is cooled to 50 ℃ after finishing, and has solid to separate out, filter, and washing, the spent glycol methyl ether is purified, and 100 ℃ of vacuum-drying 2h promptly get 4-nitro-N-ethyl phthalimide.
Add the 18.6g '-biphenyl diphenol in the 1000ml there-necked flask, feed nitrogen, add the 90ml dimethyl sulfoxide (DMSO), the NaOH aqueous solution of 16g50% adds 30ml benzene again, and the 5h that anhydrates that refluxes after branch water finishes steams benzene.Be cooled to 70 ℃ and add above-mentioned products therefrom 4-nitro-N-ethyl phthalimide 41.2g, 1.0g tetrabutyl phosphonium bromide phosphorus, the 400ml dimethyl sulfoxide (DMSO) is reacted 24h down at 90 ℃.After reaction finishes again decompression state steam down and desolventize, add 400ml hydrochloric acid, filter, solid acetonitrile recrystallization gets biphenyl type diether two phthalimides.
Take by weighing above-mentioned gained condensation product biphenyl type diether two phthalimide 50.4g, add the NaOH aqueous solution of 420g12%, reflux 24h under the logical nitrogen state cools off 35 ℃ of after-filtration, adds hydrochloric acid in the solution and regulates pH to 0.6, filters and promptly gets biphenyl type diether tetracid.
Take by weighing above-mentioned gained biphenyl type diether tetracid 51.4g, add 25.0g diacetyl oxide and 60.0g acetate, reflux 6h filters, and solid washs with the 100ml glacial acetic acid, and dry 5h in 250 ℃ of baking ovens promptly gets highly purified biphenyl two ether dianhydrides.Fusing point is 285.3 ℃～286.2 ℃, and yield is 98.1%.
Embodiment 7
Add 13.5gKOH in the 500ml there-necked flask, the 140g dehydrated alcohol is stirred to dissolving; Add 46.3g4-fluorine phthalic imidine then, 30 ℃ are stirred 5h down; Reaction finishes after-filtration, collects mother liquor, and dehydrated alcohol is reclaimed in underpressure distillation; 90 ℃ of following vacuum dryings of filter cake (sylvite); The sylvite that makes above adding in the 500ml there-necked flask adds 32.8g one n-butyl bromide and 90gDMF again, is warming up to 140 ℃, isothermal reaction 6h; Reaction is cooled to 40 ℃ after finishing, and has solid to separate out, and filters, and washing is purified with ethanol, and 100 ℃ of vacuum-drying 2h promptly get 4-fluoro-N-butyl phthalimide.
In the 500ml there-necked flask, add the 22.8g dihydroxyphenyl propane, feed nitrogen, the NaOH aqueous solution of 16g50%, 50ml water, heated and stirred 30min adds 400ml toluene again, the backflow 4h that anhydrates, be cooled to 60 ℃ and add above-mentioned products therefrom 4-fluoro-N-butyl phthalimide 41.2g, 1.2g tetrabutyl phosphonium bromide phosphorus, reflux state is reaction 8h down.Filtered while hot, solid propyl alcohol recrystallization gets bisphenol A-type diether two phthalimides.
Take by weighing above-mentioned gained condensation product bisphenol A-type diether two phthalimide 48.2g, the NaOH aqueous solution that adds 400g12%, reflux 24h under the logical nitrogen state cools off 25 ℃ of after-filtration, add hydrochloric acid in the solution and regulate pH to 0.2, filter and promptly get bisphenol A-type diether tetracid.
Take by weighing above-mentioned gained bisphenol A-type diether tetracid 55.6g, add 25.0g diacetyl oxide and 60.0g acetate, reflux 6h filters, and solid washs with the 100ml glacial acetic acid, and dry 4h in 150 ℃ of baking ovens promptly gets highly purified bisphenol A-type diaether dianhydride.Fusing point is 186.1 ℃～187.2 ℃, and yield is 96.5%.
Embodiment 8
Add 11.2gKOH in the 500ml there-necked flask, the 110g dehydrated alcohol is stirred to dissolving; Add 38.4g3-nitro phthalic imidine then, 30 ℃ are stirred 5h down; Reaction finishes after-filtration, collects mother liquor, and dehydrated alcohol is reclaimed in underpressure distillation; 90 ℃ of following vacuum dryings of filter cake (sylvite).
The sylvite that makes above adding in the 500ml there-necked flask adds 15.7g one chloropropane and 85gDMF again, is warming up to 140 ℃, isothermal reaction 6h; Reaction is cooled to 50 ℃ after finishing, and has solid to separate out, and filters, and washing is purified with toluene, and 100 ℃ of vacuum-drying 2h promptly get 3-nitro-N-propyl phthalimide.
In the 500ml there-necked flask, add above-mentioned products therefrom 3-nitro-N-propyl phthalimide 41.2g, 1.2g Tetrabutyl amonium bromide, 220ml dimethyl sulfoxide (DMSO), 100g toluene, be heated to backflow, till the moisture in the system has been divided substantially, and then toluene told; 100 ℃ of reaction 13h down continue to heat up.After reaction finishes again decompression state steam down and desolventize, filter, solid washes with water, phenyl ether two phthalimides.
Take by weighing above-mentioned gained condensation product phenyl ether two phthalimide 56.8g, add the NaOH aqueous solution of 250g15%, be heated to backflow 12h, reaction finishes the H of back Dropwise 5 0%
2SO
4134.5g, regulate pH to 0.3, continue backflow 1h.Cool off 20 ℃ of after-filtration, the product distilled water wash, 100 ℃ of vacuum-drying 2h～3h promptly obtain product phenyl ether tetracid.
Take by weighing above-mentioned gained phenyl ether tetracid 36.4g, add 120g toluene, reflux 6h filters, and solid washs with the 100ml glacial acetic acid, and dry 2h in 100 ℃ of baking ovens is warming up to 250 ℃ then and continues dry 4h, promptly gets highly purified phenyl ether tetracarboxylic dianhydride.Fusing point is 227.5 ℃～228.1 ℃, and yield is 97.0%.
Claims (8)
1, a kind of preparation method of aromatic diaether dianhydride monomer, concrete synthesis step is as follows:
The preparation (substitution reaction) of A, 3 (4) replacement-N-alkyl (aryl) phthalic imidines
A, add alkali metal hydroxide in reaction unit, lower aliphatic alcohols is stirred to alkali metal hydroxide and dissolves fully, adds 3 (4) substituted phthalimides, and 20 ℃～50 ℃ are stirred 4h～6h down, make an alkali metal salt;
B, an alkali metal salt that in aprotic polar solvent, makes above the adding, halocarbon, 100 ℃～150 ℃ are stirred 3h～6h down; Cooling treats that product separates out after-filtration, collects filtrate and filter cake respectively;
C, aftertreatment: with gained filter cake washing in the above-mentioned b step, purify, oven dry obtains white cotton shape 3 (4) replacement-N-alkyl (aryl) phthalic imidines;
Or:
A), in reaction unit, add 3 (4) substituted phthalimides, salt forming agent, halocarbon, aprotic polar solvent stirs, 100 ℃～140 ℃ are stirred 3h～6h down, cooling treats that product separates out after-filtration, collects filtrate and filter cake respectively;
B), aftertreatment: with gained filter cake pickling in the above-mentioned a) step, purify, oven dry obtains white cotton shape 3 (4) replacement-N-alkyl (aryl) phthalic imidine crystal;
The preparation (condensation reaction) of B, bis ether two phthalimides (double imide)
A, in reaction unit, add the raw material diphenol, feed nitrogen, add aprotic polar solvent, add alkali or strong base weak acid salts solution then, add non-polar solvent again, backflow 4h～the 6h that anhydrates steams non-polar solvent cooling after dividing water to finish, 3 (4) replacement-N-alkyl (aryl) phthalic imidine and the catalyzer that add the steps A gained then, add aprotic polar solvent again, be warming up to 75 ℃～100 ℃, reaction 10h～48h;
B, aftertreatment: gained solution steaming in the above-mentioned a step is desolventized, and the solid that obtains dilute hydrochloric acid pickling is filtered, recrystallization, and oven dry gets bis ether two phthalimides;
The preparation of C, bis ether tetracid (acidication reaction)
With adding strong alkali aqueous solution in step B gained condensation product bis ether two phthalimides, be heated to backflow under the nitrogen protection, backflow 8h～48h, cooled and filtered, adding acid in the solution is regulated the pH value between 0～1, filters, and oven dry gets the bis ether tetracid.
The preparation of D, diaether dianhydride (dehydration reaction)
Step C gained bis ether tetracid is joined acetate and diacetyl oxide mixing solutions, perhaps join heating reflux reaction in the toluene; Filter, washing is dried in the vacuum drying oven, gets diaether dianhydride.
2, method according to claim 1 is characterized in that prepared aromatic diaether dianhydride monomer structural formula is as follows:
Wherein R is: C
6～30Aryl, preferred structure (a):
Or structure (b):
R wherein
2Be following group :-C
yH
2y-,
-O-,-S-
M is 0 or 1, y=1～5.
3, method according to claim 1 is characterized in that the structural formula of (4) substituted phthalimides of 3 described in the steps A is:
Described halocarbon is R
1X, wherein R
1Be C
1～8Alkyl or C
6～13Aryl, X are F, Cl, Br or NO
2Alkali metal hydroxide is KOH, NaOH or LiOH; Lower aliphatic alcohols is dehydrated alcohol, methyl alcohol or propyl alcohol; Aprotic polar solvent is N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, tetrahydrofuran (THF) or dimethyl sulfoxide (DMSO); Salt forming agent is Anhydrous potassium carbonate, saleratus, yellow soda ash or sodium bicarbonate.
4, method according to claim 1 is characterized in that the mol ratio of alkali metal hydroxide and 3 (4) substituted phthalimides is 1～3: 1 among steps A, a; The mol ratio of lower aliphatic alcohols and 3 (4) substituted phthalimides is 3～6: 1; The aprotic polar solvent that reaction is used and the mass ratio of lower aliphatic alcohols are 1～3: 1; The halocarbon that reaction is used and the mol ratio of 3 (4) substituted phthalimides are 1～2: 1; Steps A, a) in salt forming agent with 3 (4) replacement substituted phthalimides mol ratios be 1～3: 1; Halocarbon and 3 (4) mol ratios that replace substituted phthalimide are 1～2: 1; The mass ratio of its aprotic polar solvent and halocarbon is 3～5: 1.
5, method according to claim 1, the structural formula that it is characterized in that the diphenol described in the step B is OH-R-OH, wherein R is: C
6～30Aryl, preferred structure (a):
Or structure (b):
R wherein
2Be following group :-C
yH
2y-,
-O-,-S-
M is 0 or 1, y=1～5.
6, method according to claim 1, it is characterized in that the diphenol described in the step B is preferably 2, two (2-hydroxyphenyl) propane of 2-, 2,4 '-dihydroxy-benzene methylmethane, two (2-hydroxyphenyl) methane, 2, two (4-hydroxyphenyl) propane of 2-, 1, two (4-hydroxyphenyl) ethane of 1-, 1, two (4-hydroxyphenyl) propane of 1-, 2, two (4-hydroxyphenyl) pentanes of 2-, 3, two (4-hydroxyphenyl) pentanes of 3-, 4,4 '-dihydroxybiphenyl, 2,4 '-dihydroxybiphenyl benzophenone, 4,4 '-dihydroxyl-3,3,5,5 '-tetramethyl biphenyl, Resorcinol, 4,4 '-dihydroxy diphenylsulphone, 4,4 '-dihydroxyl thionyl benzene, 4,4 '-dihydroxyl diphenyl sulfide, quinhydrones, 4,4 '-dihydroxy diphenyl ether, 3,4 '-dihydroxyl ditan or 4,4 '-dihydroxy benzophenone; Alkali described in the step B is KOH or NaOH, and described strong base weak acid salt is K
2CO
3Or Na
2CO
3Aprotic polar solvent is N, N '-dimethyl formamide, N, N '-N,N-DIMETHYLACETAMIDE, N-Methyl pyrrolidone, tetrahydrofuran (THF) or dimethyl sulfoxide (DMSO); Non-polar solvent is benzene, toluene or dimethylbenzene; Catalyzer is Tetrabutyl amonium bromide, Red copper oxide or tetrabutyl phosphonium bromide phosphorus.
7, method according to claim 1, the mol ratio that it is characterized in that the highly basic described in the step B or strong base weak acid salt and diphenol is 2～5: 1; The mass ratio of aprotic polar solvent and raw material diphenol is 3～5: 1; The mass ratio of non-polar solvent and aprotic polar solvent is 1: 2～6; The mol ratio of catalyzer and diphenol is 0.03～0.05: 1; The mol ratio of 3 (4) replacement-N-alkyl (aryl) phthalic imidines and diphenol is 2～3: 1.
8, method according to claim 1 is characterized in that the highly basic described in the step C is sodium hydroxide; Acid is phosphoric acid, hydrochloric acid or sulfuric acid; Acetate and diacetyl oxide mass ratio are 1～3: 1 in acetate described in the step D and the diacetyl oxide mixing solutions, and bis ether four acid anhydride consumptions are that the mol ratio of bis ether four acid anhydrides and acetate is 1: 1～3; Bis ether four acid anhydrides are joined in the toluene, and the consumption of bis ether four acid anhydrides is that the mol ratio of bis ether four acid anhydrides and toluene is 1: 2～5; Heating reflux reaction 4h～6h filters, and solid washs with glacial acetic acid, and temperature is controlled at 100 ℃～250 ℃ in vacuum drying oven, and drying time is 2h～5h.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102276563A (en) * | 2011-06-15 | 2011-12-14 | 中国科学院长春应用化学研究所 | Bisphenol F tetracarboxylic dianhydride and preparation method thereof |
| CN106279085A (en) * | 2016-08-17 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of preparation method mixing isomery bis ether tetracarboxylic acid dianhydride |
| CN110483454A (en) * | 2019-09-06 | 2019-11-22 | 湖南师范大学 | A kind of preparation method of two ether dianhydride of aromatic series |
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| CN102276563A (en) * | 2011-06-15 | 2011-12-14 | 中国科学院长春应用化学研究所 | Bisphenol F tetracarboxylic dianhydride and preparation method thereof |
| US10829449B2 (en) | 2016-03-29 | 2020-11-10 | Sabic Global Technologies B.V. | Methods of manufacture of bis(ether anhydride)s and polyetherimides |
| CN106279085A (en) * | 2016-08-17 | 2017-01-04 | 万华化学集团股份有限公司 | A kind of preparation method mixing isomery bis ether tetracarboxylic acid dianhydride |
| CN106279085B (en) * | 2016-08-17 | 2018-07-10 | 万华化学集团股份有限公司 | A kind of preparation method for mixing isomery bis ether tetracarboxylic acid dianhydride |
| EP3917918A1 (en) * | 2019-01-31 | 2021-12-08 | SHPP Global Technologies B.V. | Method of making a biphenol dianhydride composition, method for purification of a biphenol dianhydride, and poly(etherimide)s derived from the biphenol dianhydride |
| US11623908B2 (en) | 2019-01-31 | 2023-04-11 | Shpp Global Technologies B.V. | Method for purification of a biphenol tetraacid composition and a biphenol tetraacid composition |
| CN111978277A (en) * | 2019-05-22 | 2020-11-24 | 南京康德祥医药科技有限公司 | Preparation method of bisphenol A type diether dianhydride |
| CN110483454A (en) * | 2019-09-06 | 2019-11-22 | 湖南师范大学 | A kind of preparation method of two ether dianhydride of aromatic series |
| CN110483454B (en) * | 2019-09-06 | 2023-04-25 | 湖南师范大学 | Preparation method of aromatic diether dianhydride |
| CN115232093A (en) * | 2022-08-22 | 2022-10-25 | 陕西泰合利华工业有限公司 | Method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalic acid ester |
| CN115232093B (en) * | 2022-08-22 | 2023-10-27 | 陕西泰合利华工业有限公司 | Method for preparing high-purity (4-phthalic anhydride) formyloxy-4-phthalate |
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