JP2011136940A - Aromatic polyamine/aromatic dicarboxylic acid salt and method for producing the same - Google Patents
Aromatic polyamine/aromatic dicarboxylic acid salt and method for producing the same Download PDFInfo
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- JP2011136940A JP2011136940A JP2009297719A JP2009297719A JP2011136940A JP 2011136940 A JP2011136940 A JP 2011136940A JP 2009297719 A JP2009297719 A JP 2009297719A JP 2009297719 A JP2009297719 A JP 2009297719A JP 2011136940 A JP2011136940 A JP 2011136940A
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- Prior art keywords
- aromatic
- polyamine
- aromatic polyamine
- group
- aromatic dicarboxylic
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 165
- 229920000768 polyamine Polymers 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 42
- -1 aromatic dicarboxylic acid salt Chemical class 0.000 title claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 32
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims description 37
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000003963 antioxidant agent Substances 0.000 claims description 10
- 230000003078 antioxidant effect Effects 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 150000003606 tin compounds Chemical class 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 4
- 150000003840 hydrochlorides Chemical class 0.000 abstract description 2
- 239000000178 monomer Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 229920000137 polyphosphoric acid Polymers 0.000 description 7
- DPYROBMRMXHROQ-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol Chemical compound NC1=CC(N)=C(O)C=C1O DPYROBMRMXHROQ-UHFFFAOYSA-N 0.000 description 6
- KUMOYHHELWKOCB-UHFFFAOYSA-N 4,6-diaminobenzene-1,3-diol;dihydrochloride Chemical compound Cl.Cl.NC1=CC(N)=C(O)C=C1O KUMOYHHELWKOCB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- LVPMIMZXDYBCDF-UHFFFAOYSA-N isocinchomeronic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)N=C1 LVPMIMZXDYBCDF-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 229920002577 polybenzoxazole Polymers 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- GZNAASVAJNXPPW-UHFFFAOYSA-M tin(4+) chloride dihydrate Chemical compound O.O.[Cl-].[Sn+4] GZNAASVAJNXPPW-UHFFFAOYSA-M 0.000 description 3
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Substances O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- CHTHALBTIRVDBM-UHFFFAOYSA-N furan-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)O1 CHTHALBTIRVDBM-UHFFFAOYSA-N 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FBGKGORFGWHADY-UHFFFAOYSA-N tin(2+);dihydrate Chemical compound O.O.[Sn+2] FBGKGORFGWHADY-UHFFFAOYSA-N 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 239000006200 vaporizer Substances 0.000 description 2
- 0 *C1=C*C(O)=C*1 Chemical compound *C1=C*C(O)=C*1 0.000 description 1
- PXGZQGDTEZPERC-UHFFFAOYSA-N 1,4-cyclohexanedicarboxylic acid Chemical compound OC(=O)C1CCC(C(O)=O)CC1 PXGZQGDTEZPERC-UHFFFAOYSA-N 0.000 description 1
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- HSSYVKMJJLDTKZ-UHFFFAOYSA-N 3-phenylphthalic acid Chemical compound OC(=O)C1=CC=CC(C=2C=CC=CC=2)=C1C(O)=O HSSYVKMJJLDTKZ-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- AHUNLCWALDZRQE-UHFFFAOYSA-N 5-amino-2-azaniumyl-4-sulfanylbenzenethiolate Chemical compound NC1=CC(S)=C(N)C=C1S AHUNLCWALDZRQE-UHFFFAOYSA-N 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- YDYIXCSZWVMZLD-UHFFFAOYSA-N NC1=CC(N)=C(O)C=C1O.NC1=CC(N)=C(O)C=C1O Chemical compound NC1=CC(N)=C(O)C=C1O.NC1=CC(N)=C(O)C=C1O YDYIXCSZWVMZLD-UHFFFAOYSA-N 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001463 antimony compounds Chemical class 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005443 coulometric titration Methods 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- KUMNEOGIHFCNQW-UHFFFAOYSA-N diphenyl phosphite Chemical compound C=1C=CC=CC=1OP([O-])OC1=CC=CC=C1 KUMNEOGIHFCNQW-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- QAGQFDYITIKYIW-UHFFFAOYSA-L disodium;2,5-dicarboxybenzene-1,4-diolate Chemical compound [Na+].[Na+].OC1=CC(C([O-])=O)=C(O)C=C1C([O-])=O QAGQFDYITIKYIW-UHFFFAOYSA-L 0.000 description 1
- HMKRUDCIOKVFQE-UHFFFAOYSA-L disodium;pyridine-2,5-dicarboxylate Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=C(C([O-])=O)N=C1 HMKRUDCIOKVFQE-UHFFFAOYSA-L 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000012210 heat-resistant fiber Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- GMIOYJQLNFNGPR-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid Chemical compound OC(=O)C1=CN=C(C(O)=O)C=N1 GMIOYJQLNFNGPR-UHFFFAOYSA-N 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- CMWCOKOTCLFJOP-UHFFFAOYSA-N titanium(3+) Chemical compound [Ti+3] CMWCOKOTCLFJOP-UHFFFAOYSA-N 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Abstract
Description
本発明は、ポリベンゾアゾールの原料である芳香族ポリアミン／芳香族ジカルボン塩およびその製造方法に関する。 The present invention relates to an aromatic polyamine / aromatic dicarboxylic salt which is a raw material of polybenzoazole and a method for producing the same.
ポリベンゾビスオキサゾールに代表されるポリベンゾアゾールは優れた物性を有する重縮合系ポリマーであり、ポリベンゾビスオキサゾール系化合物については広範な紹介例がある（例えば、特許文献１を参照）。 Polybenzoazole represented by polybenzobisoxazole is a polycondensation polymer having excellent physical properties, and there are extensive examples of introduction of polybenzobisoxazole compounds (see, for example, Patent Document 1).
ポリベンゾアゾールの製造方法としては、４，６−ジアミノレゾルシノール（４，６−ジアミノ−１，３−ベンゼンジオール）、２，５−ジアミノ−１，４−ベンゼンジチオール、などの芳香族ポリアミンと、テレフタル酸、ナフタレンジカルボン酸、ビフェニルジカルボン酸などの芳香族ジカルボン酸又はその塩とを、ポリリン酸などの脱水作用を有する溶剤中で重縮合反応させる方法が最も一般的である。 As a manufacturing method of polybenzoazole, aromatic polyamines such as 4,6-diaminoresorcinol (4,6-diamino-1,3-benzenediol), 2,5-diamino-1,4-benzenedithiol, The most common method is a polycondensation reaction of an aromatic dicarboxylic acid such as terephthalic acid, naphthalenedicarboxylic acid or biphenyldicarboxylic acid or a salt thereof in a solvent having a dehydrating action such as polyphosphoric acid.
また、ポリベンゾアゾールの原料として、芳香族ポリアミンと芳香族ジカルボン酸との塩を用いる製造方法や、芳香族ポリアミンと芳香族ジカルボン酸塩からポリベンゾアゾールを製造する方法が紹介されている（例えば、特許文献２および３）。
また、特定官能基を有する２種の芳香族ジカルボン酸基を含むポリベンゾアゾールも報告されている（例えば、特許文献４）。
Also, as a raw material of polybenzoazole, a production method using a salt of an aromatic polyamine and an aromatic dicarboxylic acid and a method of producing polybenzoazole from an aromatic polyamine and an aromatic dicarboxylate are introduced (for example, Patent Documents 2 and 3).
Moreover, polybenzoazole containing two kinds of aromatic dicarboxylic acid groups having a specific functional group has also been reported (for example, Patent Document 4).
ポリベンゾアゾールに用いられる芳香族ポリアミン／芳香族ジカルボン酸塩は、芳香族ポリアミンと芳香族ジカルボン酸の化学組成比が１：１であり、末端停止剤添加などによる重合度制御を行わない場合は、極めて高い重合度のポリベンゾアゾールが得られるはずである。しかし、芳香族ポリアミン／芳香族ジカルボン酸塩は、芳香族ポリアミンの一部が酸化により、分解を受けていると考えられ、結果として芳香族ポリアミンと芳香族ジカルボン酸の化学組成比がずれ、ポリベンゾアゾールの重合度が上がらないという問題があった。 Aromatic polyamine / aromatic dicarboxylate used in polybenzoazole has a chemical composition ratio of aromatic polyamine and aromatic dicarboxylic acid of 1: 1, and the degree of polymerization is not controlled by adding a terminal terminator. A polybenzoazole with a very high degree of polymerization should be obtained. However, in the aromatic polyamine / aromatic dicarboxylate, it is considered that a part of the aromatic polyamine is decomposed due to oxidation. As a result, the chemical composition ratio of the aromatic polyamine and the aromatic dicarboxylic acid is shifted, There was a problem that the degree of polymerization of benzoazole did not increase.
本発明は、特定官能基を有する芳香族ジカルボン酸と芳香族ポリアミンからなるモノマー塩に関するものであり、ポリベンゾアゾールの製造に適した品質の芳香族ポリアミン／芳香族ジカルボン酸塩を提供することを目的とする。 The present invention relates to a monomer salt composed of an aromatic dicarboxylic acid having a specific functional group and an aromatic polyamine, and provides an aromatic polyamine / aromatic dicarboxylate of a quality suitable for the production of polybenzoazole. Objective.
上記課題を解決するため、本発明者らは鋭意検討を行い、芳香族ポリアミン／芳香族ジカルボン酸塩の製造方法についての本発明を完成した。本発明の構成を以下に示す。 In order to solve the above-mentioned problems, the present inventors have intensively studied and completed the present invention regarding a method for producing an aromatic polyamine / aromatic dicarboxylate. The configuration of the present invention is shown below.
１． 下記一般式（Ａ）および（Ｂ）
で表わされる芳香族ポリアミンおよびそれらの塩酸塩からなる群より選ばれる１種の水溶液に、
下記一般式（Ｃ）および（Ｄ）
で表される芳香族ジカルボン酸及びそのアルカリ金属塩からなる群より選ばれる１種の水溶液を、温度７０度以下、かつ、該芳香族ポリアミン及び該芳香族ポリアミン塩酸塩からなる群の合計と、該芳香族ジカルボン酸、及び該芳香族ジカルボン酸アルカリ金属塩からなる群の合計、とのモル比が１．０〜１．２となる条件にて添加して反応させることを特徴とする、下記一般式（Ｅ）〜（Ｈ）
からなる群より選ばれる少なくとも１種の芳香族ポリアミン／芳香族ジカルボン塩の製造方法。
1. The following general formulas (A) and (B)
In one aqueous solution selected from the group consisting of aromatic polyamines represented by
The following general formulas (C) and (D)
A total of a group consisting of the aromatic polyamine and the aromatic polyamine hydrochloride, and one aqueous solution selected from the group consisting of an aromatic dicarboxylic acid represented by the following formula: The aromatic dicarboxylic acid and the total of the group consisting of the aromatic dicarboxylic acid alkali metal salts are added and reacted under the condition that the molar ratio is 1.0 to 1.2. General formula (E)-(H)
A process for producing at least one aromatic polyamine / aromatic dicarboxylic salt selected from the group consisting of:
２． 反応時間が５〜１０分間であり、かつ反応温度が４０〜７０℃であることを特徴とする上記１項記載の芳香族ポリアミン／芳香族ジカルボン塩の製造方法。
３． 酸化防止剤を、芳香族ポリアミン１モルあたり０．１〜５．０ｍｏｌ添加することを特徴とする上記１項又は２項に記載の芳香族ポリアミン／芳香族ジカルボン塩の製造方法。
４． 酸化防止剤が二価のスズ化合物である上記３項に記載の芳香族ポリアミン／芳香族ジカルボン塩の製造方法。
５． 上記１項〜４項のいずれかに記載の製造方法によって製造された、メジアン径が５〜５０μｍである芳香族ポリアミン／芳香族ジカルボン酸塩。
６． 上記１項〜４項のいずれかに記載の製造方法によって製造された、水分含有率が１０００ｐｐｍ以下である芳香族ポリアミン／芳香族ジカルボン酸塩。
2. 2. The method for producing an aromatic polyamine / aromatic dicarboxylic salt according to the above item 1, wherein the reaction time is 5 to 10 minutes and the reaction temperature is 40 to 70 ° C.
3. 3. The method for producing an aromatic polyamine / aromatic dicarboxylic salt as described in 1 or 2 above, wherein an antioxidant is added in an amount of 0.1 to 5.0 mol per mol of the aromatic polyamine.
4). 4. The method for producing an aromatic polyamine / aromatic dicarboxylic salt as described in 3 above, wherein the antioxidant is a divalent tin compound.
5. An aromatic polyamine / aromatic dicarboxylate salt having a median diameter of 5 to 50 μm produced by the production method according to any one of 1 to 4 above.
6). An aromatic polyamine / aromatic dicarboxylate salt produced by the production method according to any one of items 1 to 4 and having a water content of 1000 ppm or less.
本発明の製造方法によって得られる芳香族ポリアミン／芳香族ジカルボン酸塩を原料として用いることにより、重合度が高いポリベンゾアゾールを得ることができる。 By using the aromatic polyamine / aromatic dicarboxylate obtained by the production method of the present invention as a raw material, a polybenzoazole having a high degree of polymerization can be obtained.
本発明は、上記一般式（Ａ）および（Ｂ）のそれぞれで表わされる芳香族ポリアミンおよびそれらの塩酸塩からなる群より選ばれる１種の水溶液に、上記一般式（Ｃ）および（Ｄ）で表される芳香族ジカルボン酸及びそのアルカリ金属塩からなる群より選ばれる１種の水溶液を、温度７０度以下、かつ、該芳香族ポリアミン、及び該芳香族ポリアミン塩酸塩からなる群（以下、芳香族ポリアミン類と称することがある）の合計と、該芳香族ジカルボン酸、及び該芳香族ジカルボン酸アルカリ金属塩からなる群（以下、芳香族ジカルボン酸類と称することがある）の合計とのモル比が１．０〜１．２となる条件にて添加して反応させることを特徴とする、上記一般式（Ｅ）〜（Ｈ）のいずれか１つである芳香族ポリアミン／芳香族ジカルボン塩の製造方法に関する。 The present invention provides an aqueous solution selected from the group consisting of the aromatic polyamines represented by the above general formulas (A) and (B) and their hydrochlorides in the above general formulas (C) and (D). One aqueous solution selected from the group consisting of the aromatic dicarboxylic acid and alkali metal salt thereof represented by a temperature of 70 degrees or less and the group consisting of the aromatic polyamine and the aromatic polyamine hydrochloride (hereinafter referred to as aromatic The molar ratio of the sum of the aromatic dicarboxylic acid and the group consisting of alkali metal salts of the aromatic dicarboxylic acid (hereinafter sometimes referred to as aromatic dicarboxylic acids) The aromatic polyamine / aromatic dicarboxylic salt of any one of the above general formulas (E) to (H), wherein the reaction is carried out under the conditions of 1.0 to 1.2 It relates to a method for manufacturing.
本発明で用いる芳香族ポリアミンに関して、上記一般式（Ａ）および（Ｂ）におけるＡｒ１は炭素数４〜２０の４価の芳香族基であり、１〜２個の環員窒素原子を含有していてもよい。Ａｒ１として例えば、
本発明の製造方法においては、上記の芳香族ポリアミン又はその塩酸塩を、水溶液にして用いる（当該水溶液を、以下、芳香族ポリアミン水溶液と称することがある）。溶解の際に用いる水は、窒素やヘリウムなどの不活性ガスで脱気した水が好ましい。また、芳香族ポリアミンは酸化されやすく、水への溶解を高温で行うと水溶液が薄い桃色に着色しやすくなるため、酸化を抑制するために、室温、つまり０〜４０℃くらいで行うことが好ましく、１０〜３０℃にて行うとより好ましい。 In the production method of the present invention, the aromatic polyamine or a hydrochloride thereof is used as an aqueous solution (hereinafter, the aqueous solution may be referred to as an aromatic polyamine aqueous solution). The water used for dissolution is preferably water deaerated with an inert gas such as nitrogen or helium. In addition, aromatic polyamines are easily oxidized, and when dissolved in water at a high temperature, the aqueous solution tends to be colored pale pink. Therefore, it is preferable to carry out at room temperature, that is, about 0 to 40 ° C. in order to suppress oxidation. It is more preferable to carry out at 10 to 30 ° C.
本発明で用いられる上記の芳香族ポリアミン水溶液の濃度はなるべく高いほうが好ましいが、０．５〜１．５ｍｏｌ／Ｌであると好ましく、０．６〜１．０ｍｏｌ／Ｌであるとより好ましい。 The concentration of the aromatic polyamine aqueous solution used in the present invention is preferably as high as possible, but is preferably 0.5 to 1.5 mol / L, and more preferably 0.6 to 1.0 mol / L.
本発明の製造方法では、前記一般式（Ｃ）及び（Ｄ）で表される芳香族ジカルボン酸、つまり、２，５−ジヒドロキシテレフタル酸、２，５−ピリジンジカルボン酸、２，５−ピラジンジカルボン酸、及びそれらのアルカリ金属塩からなる群より選ばれる１種以上を水溶液にして用いる（当該水溶液を、以下、芳香族ジカルボン酸水溶液と称することがある）。また、上記の芳香族ジカルボン酸を、水酸化リチウム、水酸化ナトリウム、水酸化カリウム、水酸化セシウム、炭酸水素ナトリウム、炭酸カリウムなどのアルカリ金属化合物を含む水溶液に溶解し、芳香族ジカルボン酸アルカリ金属塩の水溶液としてもよい。 In the production method of the present invention, the aromatic dicarboxylic acid represented by the general formulas (C) and (D), that is, 2,5-dihydroxyterephthalic acid, 2,5-pyridinedicarboxylic acid, 2,5-pyrazinedicarboxylic acid. One or more selected from the group consisting of acids and their alkali metal salts are used in the form of an aqueous solution (this aqueous solution may hereinafter be referred to as an aromatic dicarboxylic acid aqueous solution). In addition, the above aromatic dicarboxylic acid is dissolved in an aqueous solution containing an alkali metal compound such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium bicarbonate, potassium carbonate, and the like. An aqueous salt solution may be used.
芳香族ジカルボン酸又はそのアルカリ金属塩の溶解に用いる水も、窒素やヘリウムなどの不活性ガスで脱気した水が好ましい。芳香族ジカルボン酸又はそのアルカリ金属塩を水に溶解する時の温度は５０℃以上が好ましく、５０〜９０℃がより好ましく、６０〜８０℃であると更に好ましく、最も好ましいのは７０℃である。
芳香族ジカルボン酸水溶液の濃度はなるべく高いほうが好ましいが、０．２〜０．４ｍｏｌ／Ｌが好ましく、０．２５〜０．３５ｍｏｌ／Ｌであるとより好ましい。
The water used for dissolving the aromatic dicarboxylic acid or its alkali metal salt is also preferably water deaerated with an inert gas such as nitrogen or helium. The temperature at which the aromatic dicarboxylic acid or its alkali metal salt is dissolved in water is preferably 50 ° C. or higher, more preferably 50 to 90 ° C., still more preferably 60 to 80 ° C., and most preferably 70 ° C. .
The concentration of the aromatic dicarboxylic acid aqueous solution is preferably as high as possible, but is preferably 0.2 to 0.4 mol / L, and more preferably 0.25 to 0.35 mol / L.
なお、本発明の製造方法においては、得られる塩を用いて製造するポリベンゾアゾールの必要な物性・品質に支障が生じない範囲において、前記一般式（Ｃ）及び（Ｄ）で表される芳香族ジカルボン酸以外のジカルボン酸を共に用いても良い。そのような他のジカルボン酸としては、テレフタル酸、イソフタル酸、２，６−ナフタレンジカルボン酸、４，４’−ビフェニルジカルボン酸、２，５−フランジカルボン酸、１，４−シクロヘキサンジカルボン酸などが挙げられる。これら他のジカルボン酸の使用量は、前記一般式（Ｃ）及び（Ｄ）で表される芳香族ジカルボン酸との合計のモル量基準で３０モル％以下であると好ましく、１０モル％以下であるとより好ましい。 In the production method of the present invention, the fragrances represented by the general formulas (C) and (D) are within the range where the necessary physical properties and quality of the polybenzoazole produced using the obtained salt are not affected. A dicarboxylic acid other than the group dicarboxylic acid may be used together. Examples of such other dicarboxylic acids include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 2,5-furandicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like. Can be mentioned. The amount of these other dicarboxylic acids used is preferably 30 mol% or less based on the total molar amount with the aromatic dicarboxylic acids represented by the general formulas (C) and (D), and is 10 mol% or less. More preferably.
本発明の製造方法においては、上記芳香族ポリアミン水溶液に、上記の芳香族ポリカルボン酸水溶液を添加することが肝要である。特開２００７−１６１７５７号公報では、芳香族ポリアミン／芳香族ジカルボン塩の製造に関して、本願発明とは逆の添加法が記載されているが、この方法だと得られる芳香族ポリアミン／芳香族ジカルボン塩が着色しやすくなる。このような着色した芳香族ポリアミン／芳香族ジカルボン塩を原料に用いてポリベンズアゾールを製造した場合、重合反応が十分に進行しなかったり、得られたポリベンズアゾールの物性や品質に異常があったりすることがある。 In the production method of the present invention, it is important to add the aromatic polycarboxylic acid aqueous solution to the aromatic polyamine aqueous solution. In JP-A-2007-161757, an addition method opposite to that of the present invention is described for the production of an aromatic polyamine / aromatic dicarboxylic salt, but the aromatic polyamine / aromatic dicarboxylic salt obtained by this method is described. Becomes easy to color. When polybenzazole is produced using such a colored aromatic polyamine / aromatic dicarboxylic salt as a raw material, the polymerization reaction does not proceed sufficiently, or the physical properties and quality of the obtained polybenzazole are abnormal. Sometimes.
上記芳香族ポリアミン水溶液に、上記の芳香族ポリカルボン酸水溶液を添加する際、生成する塩の着色防止の為にできるだけ短時間で行うことが好ましく、スケールにも依存するが、１０分を超えない時間で添加することが好ましい。同様の理由で塩を形成させる反応時間が長いと塩が着色する傾向があるため、反応時間は短いほうが好ましく、スケールにも依存するが、反応時間は３０分未満が好ましく、５〜１０分であるとより好ましい。 When adding the above-mentioned aromatic polycarboxylic acid aqueous solution to the above-mentioned aromatic polyamine aqueous solution, it is preferably performed in as short a time as possible to prevent coloring of the resulting salt, and it does not exceed 10 minutes depending on the scale. It is preferable to add in time. For the same reason, if the reaction time for forming the salt is long, the salt tends to be colored. Therefore, the reaction time is preferably short, and depending on the scale, the reaction time is preferably less than 30 minutes, preferably from 5 to 10 minutes. More preferably.
本発明の製造方法において、芳香族ポリアミン類と芳香族ジカルボン酸類とを７０℃以上の高温で反応させると、生成する塩が着色しやすいため、反応温度は７０℃以下にすることが肝要であり、４０〜７０℃とするとより好ましく、５０〜６０℃であると更に好ましい。 In the production method of the present invention, when an aromatic polyamine and an aromatic dicarboxylic acid are reacted at a high temperature of 70 ° C. or higher, the resulting salt is likely to be colored. Therefore, it is important that the reaction temperature be 70 ° C. or lower. The temperature is more preferably 40 to 70 ° C, and further preferably 50 to 60 ° C.
芳香族ポリアミン類は芳香族ジカルボン酸類に対して等量またはやや過剰に添加する必要がある。すなわち、前記芳香族ポリアミン、及び前記芳香族ポリアミン塩酸塩からなる群の合計と、該芳香族ジカルボン酸、及び該芳香族ジカルボン酸アルカリ金属塩からなる群の合計とのモル比を１．０〜１．２とすることが肝要であり、１．０〜１．１であると好ましく、１．０〜１．０５であるより好ましい。芳香族ジカルボン酸が過剰だと、高重合度のポリベンズアゾールを与える芳香族ポリアミン／芳香族ジカルボン酸塩を得ることが難しい。 Aromatic polyamines should be added in the same amount or slightly in excess relative to the aromatic dicarboxylic acids. That is, the molar ratio of the total of the group consisting of the aromatic polyamine and the aromatic polyamine hydrochloride and the total of the group consisting of the aromatic dicarboxylic acid and the alkali metal salt of the aromatic dicarboxylic acid is 1.0 to It is important to set it to 1.2, preferably 1.0 to 1.1, and more preferably 1.0 to 1.05. If the aromatic dicarboxylic acid is excessive, it is difficult to obtain an aromatic polyamine / aromatic dicarboxylate salt that gives a polybenzazole having a high degree of polymerization.
上記のように、芳香族ポリアミン類の水溶液に芳香族ジカルボン酸類の水溶液を添加すると、芳香族ポリアミン／芳香族ジカルボン酸塩が沈殿するので、この粗芳香族ポリアミン／芳香族ジカルボン酸塩をろ過して、水洗を行い、塩化ナトリウムや塩化カリウムなどの副生物、または未反応の芳香族ポリアミン類を除去し、高純度の芳香族ポリアミン／芳香族ジカルボン酸塩を得る。ろ過、水洗操作は不活性ガス雰囲気下で行うことが好ましく、また、水洗に使用する水も予め不活性ガスで脱気した水を使用することが好ましい。なお、水洗は、塩の生成反応時に使用した水の量に対して、２〜３倍量の水で行うことが望ましい。 As described above, when an aqueous solution of an aromatic dicarboxylic acid is added to an aqueous solution of an aromatic polyamine, an aromatic polyamine / aromatic dicarboxylate precipitates. Therefore, the crude aromatic polyamine / aromatic dicarboxylate is filtered. Then, washing with water is performed to remove by-products such as sodium chloride and potassium chloride, or unreacted aromatic polyamines to obtain a high-purity aromatic polyamine / aromatic dicarboxylate. The filtration and washing operations are preferably performed in an inert gas atmosphere, and the water used for washing is preferably water that has been degassed with an inert gas in advance. In addition, it is desirable to perform water washing with 2 to 3 times the amount of water with respect to the amount of water used during the salt formation reaction.
上記の、ろ過後の湿潤した芳香族ポリアミン／芳香族ジカルボン酸塩は、遠心、吸引、加圧などの方法で粗く脱水することが好ましく、加熱下減圧または加熱した窒素などの不活性ガスを吹き付けることで乾燥する。この時、残存水分率が高い状態で加熱すると芳香族ポリアミン／芳香族ジカルボン酸塩が変色劣化しやすく、加熱前に芳香族ポリアミン／芳香族ジカルボン酸塩の残存水分率を５０質量％以下程度まで低下させておくことが好ましい。乾燥時の温度は、塩の変色劣化を防ぐために８０℃以下が好ましい。乾燥時の温度は残存水分率が高い初期段階では低温で、時間とともに温度を上げるという方法も有効である。また、均一乾燥、ダマの形成の抑制、加えて乾燥時間の短縮のため、芳香族ポリアミン／芳香族ジカルボン酸塩を攪拌しながら、系内を減圧して乾燥させる方法も有効である。また、乾燥時間の短縮のため、水溶性の有機溶剤、例えばメタノール、エタノール、アセトンなどに置換するという方法も可能であるが、乾燥後、芳香族ポリアミン／芳香族ジカルボン酸塩中に残存する有機溶媒がポリベンゾアゾール重合時に悪影響を与える場合があり、好ましい方法ではない。 The above-mentioned wet aromatic polyamine / aromatic dicarboxylate after filtration is preferably roughly dehydrated by a method such as centrifugation, suction, or pressurization, and sprayed with an inert gas such as nitrogen under reduced pressure or heated. To dry. At this time, the aromatic polyamine / aromatic dicarboxylate tends to be discolored and deteriorated when heated in a state where the residual moisture content is high, and the residual moisture content of the aromatic polyamine / aromatic dicarboxylate is reduced to about 50% by mass or less before heating. It is preferable to lower it. The temperature during drying is preferably 80 ° C. or lower in order to prevent discoloration deterioration of the salt. It is also effective to use a method in which the temperature during drying is low in the initial stage where the residual moisture content is high, and the temperature is increased with time. In addition, a method of drying the system while reducing the pressure while stirring the aromatic polyamine / aromatic dicarboxylate is also effective for uniform drying, suppression of lumps formation, and shortening of the drying time. In order to shorten the drying time, a method of substituting with a water-soluble organic solvent such as methanol, ethanol, acetone or the like is possible. However, after drying, the organic residue remaining in the aromatic polyamine / aromatic dicarboxylate The solvent may adversely affect the polybenzoazole polymerization and is not a preferred method.
本発明の製造方法においては、酸化防止剤を芳香族ポリアミンに対して０．１〜５ｍｏｌ％添加することが好ましい。そのような酸化防止剤としては、スズ（ＩＩ）、鉄（ＩＩ）、銅（Ｉ）、チタン（ＩＩＩ）などの金属塩、あるいはホスホン酸などのリン化合物、亜硫酸などの硫黄化合物などが挙げられるが、スズ（ＩＩ）の金属塩、特に塩化スズ（ＩＩ）の使用が好ましく、塩化スズ（ＩＩ）であれば二水和物でも好ましい。該酸化防止剤の添加は、芳香族ポリアミン類を水に溶解するに先立って、その水や芳香族ポリアミン類自身に前もって添加しておくのが好ましいが、芳香族ポリアミン／芳香族ジカルボン酸塩の生成反応や、芳香族ポリアミン／芳香族ジカルボン酸塩塩を精製する過程において、複数回に分け添加しても良い。特に、前記の粗芳香族ポリアミン／芳香族ジカルボン酸塩を水洗する際の水に芳香族ポリアミンに対して、０．０１〜０．１ｍｏｌ％となる量の上記酸化防止剤を添加しておくのも好適である。 In the manufacturing method of this invention, it is preferable to add 0.1-5 mol% of antioxidant with respect to aromatic polyamine. Examples of such antioxidants include metal salts such as tin (II), iron (II), copper (I), and titanium (III), phosphorus compounds such as phosphonic acid, and sulfur compounds such as sulfurous acid. However, it is preferable to use a metal salt of tin (II), particularly tin (II) chloride, and dihydrate is also preferable if it is tin (II) chloride. The antioxidant is preferably added to the water or the aromatic polyamine itself prior to dissolving the aromatic polyamine in water, but the aromatic polyamine / aromatic dicarboxylate In the production reaction and the process of purifying the aromatic polyamine / aromatic dicarboxylate salt, they may be added in multiple portions. In particular, the antioxidant is added in an amount of 0.01 to 0.1 mol% with respect to the aromatic polyamine in the water when the crude aromatic polyamine / aromatic dicarboxylate is washed with water. Is also suitable.
本発明の製造方法により、メジアン径が５〜５０μｍの前記芳香族ポリアミン／芳香族ジカルボン酸塩を製造することができる。当該メジアン径は５〜３０μｍであるとより好ましく、５〜１５μｍであると更に好ましい。当該メジアン径は、レーザー回折／散乱式粒度分布測定装置により求めたものが好ましい。 By the production method of the present invention, the aromatic polyamine / aromatic dicarboxylate having a median diameter of 5 to 50 μm can be produced. The median diameter is more preferably 5 to 30 μm, and further preferably 5 to 15 μm. The median diameter is preferably determined by a laser diffraction / scattering particle size distribution analyzer.
本発明の製造方法により得られる、前記芳香族ポリアミン／芳香族ジカルボン酸塩は、水分率が１０００ｐｐｍ（質量基準）以下であると好ましく、９５０ｐｐｍ以下であるとより好ましい。 The aromatic polyamine / aromatic dicarboxylate obtained by the production method of the present invention preferably has a moisture content of 1000 ppm (mass basis) or less, and more preferably 950 ppm or less.
本発明の製造方法による芳香族ポリアミン／芳香族ジカルボン酸塩を用いて、国際公開第２００５／１００４４２号パンフレット等に示されている方法で重合反応を行うことにより、際立って良好な品質・物性のポリベンゾアゾールを得ることができる。すなわち、脱水剤と溶媒を兼ねたポリリン酸を重合溶媒に用い、芳香族ポリアミン／芳香族ジカルボン酸塩を８０〜２００℃で加熱混合することで、重縮合させ、ポリベンゾアゾールの重合溶液、すなわちドープを得る。ポリリン酸の脱水作用を高めるために、五酸化二りんを添加することも行われる。また、重合反応時に、本発明の製造方法において添加すると好ましいものとして前記した酸化防止剤を、芳香族ポリアミン／芳香族ジカルボン酸塩１モルあたり、０．１〜３．０モル％、好ましくは０．２〜２．０モル％添加しても良い。 By using the aromatic polyamine / aromatic dicarboxylate produced by the production method of the present invention and carrying out the polymerization reaction by the method shown in International Publication No. 2005/100442 pamphlet or the like, the remarkably good quality and physical properties are obtained. Polybenzoazole can be obtained. That is, polyphosphoric acid serving as a dehydrating agent and a solvent is used as a polymerization solvent, and an aromatic polyamine / aromatic dicarboxylate is heated and mixed at 80 to 200 ° C. to cause polycondensation, and a polybenzoazole polymerization solution, Get dope. In order to enhance the dehydrating action of polyphosphoric acid, diphosphorus pentoxide is also added. Further, during the polymerization reaction, it is preferable to add the above-mentioned antioxidant in the production method of the present invention in an amount of 0.1 to 3.0 mol%, preferably 0, per mol of aromatic polyamine / aromatic dicarboxylate. .2 to 2.0 mol% may be added.
上記重合反応は、溶媒中で行う反応、無溶媒の加熱溶融反応のいずれも採用できるが、例えば、後述する反応溶媒中で攪拌下に加熱反応させるのが好ましい。反応温度は、５０℃から５００℃が好ましく、１００℃から３５０℃がさらに好ましい。５０℃より温度が低いと反応が進みにくく、５００℃より温度が高いと分解等の副反応が起こりやすくなるためである。反応時間は温度条件にもよるが、通常は１時間から数十時間である。反応は加圧下から減圧下で行うことができる。 The polymerization reaction may be either a reaction performed in a solvent or a solventless heating and melting reaction. For example, it is preferable to carry out a heating reaction with stirring in a reaction solvent described later. The reaction temperature is preferably 50 ° C to 500 ° C, more preferably 100 ° C to 350 ° C. This is because if the temperature is lower than 50 ° C., the reaction hardly proceeds, and if the temperature is higher than 500 ° C., side reactions such as decomposition tend to occur. Although the reaction time depends on temperature conditions, it is usually 1 hour to several tens of hours. The reaction can be carried out under pressure or under reduced pressure.
上記重合反応は、通常、無触媒でも進行するが、必要に応じて、三酸化アンチモンに代表されるアンチモン化合物、酢酸第一錫、塩化錫、オクチル酸錫、ジブチル錫オキシド、ジブチル錫ジアセテートといった錫化合物、酢酸カルシウムのようなアルカリ土類金属塩、炭酸ナトリウム、炭酸カリウムのようなアルカリ金属塩等、亜リン酸ジフェニル、亜リン酸トリフェニル等の亜リン酸等のような触媒を用いても良い。 The polymerization reaction usually proceeds even without a catalyst, but if necessary, an antimony compound typified by antimony trioxide, stannous acetate, tin chloride, tin octylate, dibutyltin oxide, dibutyltin diacetate, etc. Using catalysts such as tin compounds, alkaline earth metal salts such as calcium acetate, alkali metal salts such as sodium carbonate and potassium carbonate, phosphorous acid such as diphenyl phosphite and triphenyl phosphite Also good.
上記重合反応に際しては、必要に応じてポリリン酸以外の溶媒も用いることが出来る。好ましい溶媒としては１―メチル―２−ピロリドン、１―シクロヘキシル−２―ピロリドン、ジメチルアセトアミド、ジメチルスルホキシド、ジフェニルエーテル、ジフェニルスルホン、ジクロロメタン、クロロロホルム、テトラヒドロフラン、ｏ−クレゾール、ｍ−クレゾール、ｐ−クレゾール、リン酸等を挙げることが出来るがこれに限定されるものではない。
ポリベンゾアゾールの分解及び着色を防ぐため、上記重合反応は乾燥した不活性ガス（窒素、アルゴンなど）雰囲気下で行うことが望ましい。
In the polymerization reaction, a solvent other than polyphosphoric acid can be used as necessary. Preferred solvents include 1-methyl-2-pyrrolidone, 1-cyclohexyl-2-pyrrolidone, dimethylacetamide, dimethyl sulfoxide, diphenyl ether, diphenyl sulfone, dichloromethane, chloroform, tetrahydrofuran, o-cresol, m-cresol, p-cresol, Although phosphoric acid etc. can be mentioned, it is not limited to this.
In order to prevent decomposition and coloring of polybenzoazole, the polymerization reaction is desirably performed in a dry inert gas (nitrogen, argon, etc.) atmosphere.
本発明の製造方法による芳香族ポリアミン／芳香族ジカルボン酸塩を原料として用いて上記のように重合反応を行うことにより、濃度２．５ｍｇ／８ｍＬのメタンスルホン酸溶液試料を用いて２５℃にて測定した特有粘度が１６〜３０ｄＬ／ｇ、より好ましくは１７〜２０ｄＬ／ｇという非常に高重合度で、かつ、その他の品質や物性も良好なポリベンゾアゾールを得ることができる。
このように得られたポリベンゾアゾールドープは１５０〜２００℃の温度で紡糸ノズルあるいはダイから押出し、水洗によりポリリン酸等の溶媒を抽出除去し、乾燥することで、高強度、高弾性率、高耐熱性を有する繊維やフィルムに成型加工される。
By carrying out the polymerization reaction as described above using the aromatic polyamine / aromatic dicarboxylate according to the production method of the present invention as a raw material, a methanesulfonic acid solution sample having a concentration of 2.5 mg / 8 mL is used at 25 ° C. A polybenzoazole having a very high degree of polymerization such as a measured specific viscosity of 16 to 30 dL / g, more preferably 17 to 20 dL / g, and other good quality and physical properties can be obtained.
The polybenzoazole dope thus obtained is extruded from a spinning nozzle or die at a temperature of 150 to 200 ° C., and extracted by removing a solvent such as polyphosphoric acid by washing with water, and dried to obtain high strength, high elastic modulus, high Molded into heat-resistant fiber or film.
以下、実施例及び比較例により本発明をさらに具体的に説明するが、本発明はこれらによっていささかも限定されるものではない。なお、以下の実施例における各測定値は次の方法により求めた値である。 EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited at all by these. In addition, each measured value in the following examples is a value obtained by the following method.
１） 芳香族ポリアミン／芳香族ジカルボン酸塩の水分率
芳香族ポリアミン／芳香族ジカルボン酸塩の水分率は、水分気化カールフィッシャー法にて行った。水分気化装置および水分滴定装置（ともに平沼産業株式会社製）を用い、資料を窒素雰囲気下で専用容器に採取し、密栓後、水分気化装置にセットし、１５０℃で過熱発生した水分を電量滴定した。
1) Moisture content of aromatic polyamine / aromatic dicarboxylate The moisture content of aromatic polyamine / aromatic dicarboxylate was measured by the moisture vaporization Karl Fischer method. Using a moisture vaporizer and a moisture titrator (both manufactured by Hiranuma Sangyo Co., Ltd.), collect the data in a special container under a nitrogen atmosphere, place it in a sealed container, place it in the moisture vaporizer, and perform coulometric titration on the moisture generated at 150 ° C. did.
２） 芳香族ポリアミン／芳香族ジカルボン酸塩のメジアン径の測定
芳香族ポリアミン／芳香族ジカルボン酸塩の粒度分布は以下のように測定した。レーザー回折／散乱式粒度分布測定装置（堀場製作所製 ＬＡ−９２０）中にｎ−プロパノールに分散させた塩の分散液をセットし、湿式バッチセルにて測定し、レーザーが粒子に当たって散乱することを利用して粒度分布を算出した。測定原理はＭｉｅ散乱理論を用いて粒度分布の計算を行った。
2) Measurement of median diameter of aromatic polyamine / aromatic dicarboxylate The particle size distribution of aromatic polyamine / aromatic dicarboxylate was measured as follows. Set up a dispersion of salt dispersed in n-propanol in a laser diffraction / scattering particle size distribution analyzer (LA-920, manufactured by HORIBA, Ltd.), measure in a wet batch cell, and use the fact that the laser hits the particles and scatters. The particle size distribution was calculated. As the measurement principle, the particle size distribution was calculated using Mie scattering theory.
３） ポリマーの特有粘度（ηｉｎｈ）
ポリマーの特有粘度（ηｉｎｈ）は、メタンスルホン酸を用いてポリマー試料濃度２．５ｍｇ／８ｍＬで２５℃において測定した相対粘度（ηｒｅｌ）を基に下記式により求めた値である。
ηｉｎｈ＝（ｌｎηｒｅｌ）／Ｃ
（ηｒｅｌは相対粘度、Ｃは試料濃度を表す）
3) Specific viscosity of polymer (η inh )
The specific viscosity (η inh ) of the polymer is a value obtained from the following formula based on the relative viscosity (η rel ) measured at 25 ° C. at a polymer sample concentration of 2.5 mg / 8 mL using methanesulfonic acid.
η inh = (lnη rel ) / C
(Η rel is relative viscosity, C is sample concentration)
［実施例１］ ４，６−ジアミノレゾルシノール／２，５−ジヒドロキシテレフタル酸塩（以下、ＯＨ−ＰＢＯと略称することがある）の製造
４，６−ジアミノレゾルシノール二塩酸塩１４質量部を、塩化スズ（ＩＩ）二水和物０．０１４８質量を添加し、窒素で脱気した水８０質量部に溶解した。溶解は窒素でバブリングさせながら行った。２，５−ジヒドロキシテレフタル酸１２．３６１質量部を、０．５８ｍｏｌ／Ｌ水酸化ナトリウム水溶液２２０質量部に窒素で脱気しながら７０℃で溶解させた。該４，６−ジアミノレゾルシノール二塩酸塩水溶液に、該２，５−ジヒドロキシテレフタル酸二ナトリウム塩水溶液を添加し、４，６−ジアミノレゾルシノール／２，５−ジヒドロキシテレフタル酸塩の白色〜薄黄色沈殿を形成させた。この際、反応温度は５５℃であり、反応は５分間行った。得られた塩を、ろ過し、塩化スズ（ＩＩ）二水和物０．０２質量部を溶解させ、窒素で脱気した水３００質量部に分散混合し、再度ろ過を行った。この分散混合、ろ過操作を３回繰り返し行った。水洗、ろ過した塩を窒素雰囲気中、フィルター上で吸引し、脱水した。脱水後、７０℃、１Ｐａで減圧乾燥を２４時間行い、４，６−ジアミノレゾルシノール／２，５−ジヒドロキシテレフタル酸塩（ＯＨ−ＰＢＯ）１９．８質量部を得た。得られたＯＨ−ＰＢＯは薄黄色で、水分率は６００ｐｐｍであり、メジアン径は９．９μｍであった。
[Example 1] Production of 4,6-diaminoresorcinol / 2,5-dihydroxyterephthalate (hereinafter sometimes abbreviated as OH-PBO) 14 parts by mass of 4,6-diaminoresorcinol dihydrochloride 0.0148 mass of tin (II) dihydrate was added and dissolved in 80 mass parts of water deaerated with nitrogen. Dissolution was performed while bubbling with nitrogen. 12.361 parts by mass of 2,5-dihydroxyterephthalic acid was dissolved at 70 ° C. while degassing with nitrogen in 220 parts by mass of 0.58 mol / L sodium hydroxide aqueous solution. The 2,5-dihydroxyterephthalic acid disodium salt aqueous solution is added to the 4,6-diaminoresorcinol dihydrochloride aqueous solution, and a white to light yellow precipitate of 4,6-diaminoresorcinol / 2,5-dihydroxyterephthalate is added. Formed. At this time, the reaction temperature was 55 ° C., and the reaction was performed for 5 minutes. The obtained salt was filtered, 0.02 parts by mass of tin (II) chloride dihydrate was dissolved, dispersed and mixed in 300 parts by mass of water deaerated with nitrogen, and filtered again. This dispersion mixing and filtration operation was repeated three times. The salt washed and filtered was sucked on a filter in a nitrogen atmosphere and dehydrated. After dehydration, drying under reduced pressure at 70 ° C. and 1 Pa was performed for 24 hours to obtain 19.8 parts by mass of 4,6-diaminoresorcinol / 2,5-dihydroxyterephthalate (OH—PBO). The obtained OH-PBO was light yellow, the moisture content was 600 ppm, and the median diameter was 9.9 μm.
［実施例２］ ４，６−ジアミノレゾルシノール／２，５−ピリジンジカルボン酸塩（以下、Ｎ−ＰＢＯと略称することがある）の製造
４，６−ジアミノレゾルシノール二塩酸塩１４質量部を、塩化スズ（ＩＩ）二水和物０．０１４８質量を添加し、窒素で脱気した水８０質量部に溶解した。溶解は窒素でバブリングさせながら行った。２，５−ピリジンジカルボン酸１０．６９４質量部を、０．５８ｍｏｌ／Ｌ水酸化ナトリウム水溶液２２０質量部に窒素で脱気しながら７０℃で溶解させた。該４，６−ジアミノレゾルシノール二塩酸塩水溶液に、該２，５−ピリジンジカルボン酸二ナトリウム塩水溶液を添加し、４，６−ジアミノレゾルシノール／２，５−ピリジンジカルボン酸塩の白色〜薄桃色沈殿を形成させた。この際、反応温度は５５℃であり、反応は５分間行った。得られた塩を、ろ過し、塩化スズ（ＩＩ）二水和物０．０２質量部を溶解させ、窒素で脱気した水３００質量部に分散混合し、再度ろ過を行った。この分散混合、ろ過操作を３回繰り返し行った。水洗、ろ過した塩を窒素雰囲気中、フィルター上で吸引し、脱水した。脱水後、７０℃、１Ｐａで減圧乾燥を２４時間行い、４，６−ジアミノレゾルシノール／２，５−ピリジンジカルボン酸塩（Ｎ−ＰＢＯ）１７．８質量部を得た。得られたＮ−ＰＢＯは白色〜薄桃色で、水分率は９００ｐｐｍであり、メジアン径は１３μｍであった。
[Example 2] Production of 4,6-diaminoresorcinol / 2,5-pyridinedicarboxylate (hereinafter sometimes abbreviated as N-PBO) 14 parts by mass of 4,6-diaminoresorcinol dihydrochloride 0.0148 mass of tin (II) dihydrate was added and dissolved in 80 mass parts of water deaerated with nitrogen. Dissolution was performed while bubbling with nitrogen. 10.694 parts by mass of 2,5-pyridinedicarboxylic acid was dissolved at 70 ° C. while degassing with nitrogen in 220 parts by mass of 0.58 mol / L sodium hydroxide aqueous solution. The 2,5-pyridinedicarboxylic acid disodium salt aqueous solution is added to the 4,6-diaminoresorcinol dihydrochloride aqueous solution, and a white to light pink precipitate of 4,6-diaminoresorcinol / 2,5-pyridinedicarboxylate Formed. At this time, the reaction temperature was 55 ° C., and the reaction was performed for 5 minutes. The obtained salt was filtered, 0.02 parts by mass of tin (II) chloride dihydrate was dissolved, dispersed and mixed in 300 parts by mass of water deaerated with nitrogen, and filtered again. This dispersion mixing and filtration operation was repeated three times. The salt washed and filtered was sucked on a filter in a nitrogen atmosphere and dehydrated. After dehydration, drying under reduced pressure at 70 ° C. and 1 Pa was performed for 24 hours to obtain 17.8 parts by mass of 4,6-diaminoresorcinol / 2,5-pyridinedicarboxylate (N-PBO). The obtained N-PBO was white to pale pink, had a moisture content of 900 ppm, and had a median diameter of 13 μm.
［製造例１］ ポリベンゾビスオキサゾールの製造
実施例１及び実施例２で得た２種類の塩を用いて、ＯＨ−ＰＢＯ４．０７質量部、Ｎ−ＰＢＯ７．４質量部（ＯＨ−ＰＢＯとＮ−ＰＢＯとのモル比＝２）、ポリリン酸２３．８質量部、五酸化ニリン１４．２質量部を秤量し、１００ｍＬフラスコ反応器に添加した。加えて芳香族アミンの酸化防止剤として塩化スズ（ＩＩ）二水和物を０．０８質量部添加した。ポリリン酸中におけるポリマー濃度は１７．８質量％であった。重合は８０℃で３０分、１５０℃で６時間、１６０℃で５時間、１８０℃で２０時間撹拌を行い、反応を終了させた。最終的に得られたポリマー（ポリベンゾビスオキサゾール）の特有粘度は１７．８ｄＬ／ｇであった。
[Production Example 1] Production of polybenzobisoxazole Using the two types of salts obtained in Example 1 and Example 2, 4.07 parts by mass of OH-PBO, 7.4 parts by mass of N-PBO (OH-PBO and N -Mole ratio with PBO = 2), 23.8 parts by mass of polyphosphoric acid, and 14.2 parts by mass of niline pentoxide were weighed and added to a 100 mL flask reactor. In addition, 0.08 parts by mass of tin (II) chloride dihydrate was added as an antioxidant for the aromatic amine. The polymer concentration in polyphosphoric acid was 17.8% by mass. The polymerization was stirred at 80 ° C. for 30 minutes, 150 ° C. for 6 hours, 160 ° C. for 5 hours, and 180 ° C. for 20 hours to complete the reaction. The specific viscosity of the finally obtained polymer (polybenzobisoxazole) was 17.8 dL / g.
［比較例１］ ＯＨ−ＰＢＯの製造（特開２００７−１６１７５７号公報の添加方法）
２，５−ジヒドロキシテレフタル酸の水酸化ナトリウム水溶液に、４，６−ジアミノレゾルシノール二塩酸塩水溶液を添加し、反応時間が６０分であった以外は、実施例１と同様に操作を行った。得られたＯＨ−ＰＢＯは、黄色で、水分率は９００ｐｐｍ、メジアン径は６４μｍであった。
[Comparative Example 1] Production of OH-PBO (addition method disclosed in JP 2007-161757 A)
The operation was performed in the same manner as in Example 1 except that a 4,6-diaminoresorcinol dihydrochloride aqueous solution was added to a sodium hydroxide aqueous solution of 2,5-dihydroxyterephthalic acid and the reaction time was 60 minutes. The obtained OH-PBO was yellow, had a moisture content of 900 ppm, and a median diameter of 64 μm.
［比較例２］ Ｎ−ＰＢＯの製造（特開２００７−１６１７５７号公報の添加方法）
２，５−ピリジンジカルボン酸の水酸化ナトリウム水溶液に、４，６−ジアミノレゾルシノール二塩酸塩水溶液を添加し、反応時間が６０分であった以外は、実施例２と同様に操作を行った。得られたＮ−ＰＢＯは薄桃色〜桃色で、水分率は７８０ｐｐｍ、メジアン径は６８μｍであった。
[Comparative Example 2] Manufacture of N-PBO (Addition Method of Japanese Patent Application Laid-Open No. 2007-161757)
The same operation as in Example 2 was performed, except that an aqueous 4,6-diaminoresorcinol dihydrochloride solution was added to an aqueous sodium hydroxide solution of 2,5-pyridinedicarboxylic acid, and the reaction time was 60 minutes. The obtained N-PBO was light pink to pink, had a moisture content of 780 ppm and a median diameter of 68 μm.
［比較製造例１］ ポリベンゾビスオキサゾールの製造
比較例１で得られたＯＨ−ＰＢＯと、比較例２で得られたＮ−ＰＢＯを用いた以外は、製造例１と同様に操作を行った。得られたポリマーの特有粘度は１５．４ｄＬ／ｇであった。
[Comparative Production Example 1] Production of polybenzobisoxazole The same operation as in Production Example 1 was performed except that OH-PBO obtained in Comparative Example 1 and N-PBO obtained in Comparative Example 2 were used. . The specific viscosity of the obtained polymer was 15.4 dL / g.
本発明の製造方法による芳香族ポリアミン／芳香族ジカルボン酸塩は、ゴムやプラスチックの補強材、耐熱フェルトといった産業資材、消防服や安全手袋といった防護用途などでの利用に好適なポリベンゾアゾールの原料として非常に好適である。 The aromatic polyamine / aromatic dicarboxylate produced by the production method of the present invention is a raw material of polybenzoazole suitable for use as a reinforcing material for rubber and plastic, industrial materials such as heat-resistant felt, and protective applications such as fire-fighting clothes and safety gloves. Is very suitable.
Claims (6)
で表わされる芳香族ポリアミンおよびそれらの塩酸塩からなる群より選ばれる１種の水溶液に、
下記一般式（Ｃ）および（Ｄ）
で表される芳香族ジカルボン酸及びそのアルカリ金属塩からなる群より選ばれる１種の水溶液を、温度７０度以下、かつ、該芳香族ポリアミン、及び該芳香族ポリアミン塩酸塩からなる群の合計と、該芳香族ジカルボン酸、及び該芳香族ジカルボン酸アルカリ金属塩からなる群の合計、とのモル比が１．０〜１．２となる条件にて添加して反応させることを特徴とする、下記一般式（Ｅ）〜（Ｈ）
のうち少なくとも１種の芳香族ポリアミン／芳香族ジカルボン塩の製造方法。 The following general formulas (A) and (B)
In one aqueous solution selected from the group consisting of aromatic polyamines represented by
The following general formulas (C) and (D)
A total of a group consisting of the aromatic polyamine and the aromatic polyamine hydrochloride, and one aqueous solution selected from the group consisting of an aromatic dicarboxylic acid represented by the formula (1) and an alkali metal salt thereof. The aromatic dicarboxylic acid and the total of the group consisting of the aromatic dicarboxylic acid alkali metal salts are added and reacted under the condition that the molar ratio is 1.0 to 1.2. The following general formulas (E) to (H)
A process for producing at least one aromatic polyamine / aromatic dicarboxylic salt.
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