JP2015013830A - Diamine compound and method of producing the same - Google Patents
Diamine compound and method of producing the same Download PDFInfo
- Publication number
- JP2015013830A JP2015013830A JP2013141395A JP2013141395A JP2015013830A JP 2015013830 A JP2015013830 A JP 2015013830A JP 2013141395 A JP2013141395 A JP 2013141395A JP 2013141395 A JP2013141395 A JP 2013141395A JP 2015013830 A JP2015013830 A JP 2015013830A
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- JP
- Japan
- Prior art keywords
- compound
- acid
- bis
- biphenyl
- examples
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- -1 Diamine compound Chemical class 0.000 title abstract description 56
- 238000000034 method Methods 0.000 title abstract description 6
- OBHYCAWKQWTOTE-UHFFFAOYSA-N C1(=CC=CC=C1)C1=CC=CC=C1.NC1=CC=C(C=C1)S(=O)(=O)O Chemical group C1(=CC=CC=C1)C1=CC=CC=C1.NC1=CC=C(C=C1)S(=O)(=O)O OBHYCAWKQWTOTE-UHFFFAOYSA-N 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 10
- GRDXCFKBQWDAJH-UHFFFAOYSA-N 4-acetamidobenzenesulfonyl chloride Chemical compound CC(=O)NC1=CC=C(S(Cl)(=O)=O)C=C1 GRDXCFKBQWDAJH-UHFFFAOYSA-N 0.000 claims description 9
- IRWOUCWCDHCUGN-UHFFFAOYSA-N C1(=CC=CC=C1)C1=CC=CC=C1.C(C)(=O)NC1=CC=C(C=C1)S(=O)(=O)O Chemical group C1(=CC=CC=C1)C1=CC=CC=C1.C(C)(=O)NC1=CC=C(C=C1)S(=O)(=O)O IRWOUCWCDHCUGN-UHFFFAOYSA-N 0.000 claims description 8
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 claims description 8
- 230000000850 deacetylating effect Effects 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- 125000002130 sulfonic acid ester group Chemical group 0.000 abstract description 11
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004305 biphenyl Substances 0.000 abstract description 2
- 235000010290 biphenyl Nutrition 0.000 abstract description 2
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 abstract 1
- 229950000244 sulfanilic acid Drugs 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 238000003381 deacetylation reaction Methods 0.000 description 13
- 238000005886 esterification reaction Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 239000002585 base Substances 0.000 description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 239000004642 Polyimide Substances 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 229920001721 polyimide Polymers 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000004128 high performance liquid chromatography Methods 0.000 description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 6
- 230000006196 deacetylation Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 125000004185 ester group Chemical group 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000032050 esterification Effects 0.000 description 3
- 230000005606 hygroscopic expansion Effects 0.000 description 3
- 229940035429 isobutyl alcohol Drugs 0.000 description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- ISAKRJDGNUQOIC-UHFFFAOYSA-N Uracil Chemical compound O=C1C=CNC(=O)N1 ISAKRJDGNUQOIC-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 description 2
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 2
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 2
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- XNLICIUVMPYHGG-UHFFFAOYSA-N pentan-2-one Chemical compound CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- PGMYKACGEOXYJE-UHFFFAOYSA-N pentyl acetate Chemical compound CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 0 *c(cc1)ccc1S(Cl)(=O)=O Chemical compound *c(cc1)ccc1S(Cl)(=O)=O 0.000 description 1
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 description 1
- GJFNRSDCSTVPCJ-UHFFFAOYSA-N 1,8-bis(dimethylamino)naphthalene Chemical compound C1=CC(N(C)C)=C2C(N(C)C)=CC=CC2=C1 GJFNRSDCSTVPCJ-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- HFZLSTDPRQSZCQ-UHFFFAOYSA-N 1-pyrrolidin-3-ylpyrrolidine Chemical compound C1CCCN1C1CNCC1 HFZLSTDPRQSZCQ-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- HQLKZWRSOHTERR-UHFFFAOYSA-N 2-Ethylbutyl acetate Chemical compound CCC(CC)COC(C)=O HQLKZWRSOHTERR-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- WOYWLLHHWAMFCB-UHFFFAOYSA-N 2-ethylhexyl acetate Chemical compound CCCCC(CC)COC(C)=O WOYWLLHHWAMFCB-UHFFFAOYSA-N 0.000 description 1
- PPDFQRAASCRJAH-UHFFFAOYSA-N 2-methylthiolane 1,1-dioxide Chemical compound CC1CCCS1(=O)=O PPDFQRAASCRJAH-UHFFFAOYSA-N 0.000 description 1
- QMYGFTJCQFEDST-UHFFFAOYSA-N 3-methoxybutyl acetate Chemical compound COC(C)CCOC(C)=O QMYGFTJCQFEDST-UHFFFAOYSA-N 0.000 description 1
- CSDQQAQKBAQLLE-UHFFFAOYSA-N 4-(4-chlorophenyl)-4,5,6,7-tetrahydrothieno[3,2-c]pyridine Chemical compound C1=CC(Cl)=CC=C1C1C(C=CS2)=C2CCN1 CSDQQAQKBAQLLE-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- VGVHNLRUAMRIEW-UHFFFAOYSA-N 4-methylcyclohexan-1-one Chemical compound CC1CCC(=O)CC1 VGVHNLRUAMRIEW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- NVJJUWDZODHGHL-UHFFFAOYSA-N Nc(cc1)ccc1S(Oc(cc1)ccc1-c(cc1)ccc1OS(c(cc1)ccc1N)(=O)=O)(=O)=O Chemical compound Nc(cc1)ccc1S(Oc(cc1)ccc1-c(cc1)ccc1OS(c(cc1)ccc1N)(=O)=O)(=O)=O NVJJUWDZODHGHL-UHFFFAOYSA-N 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ZBUQRSWEONVBES-UHFFFAOYSA-L beryllium carbonate Chemical compound [Be+2].[O-]C([O-])=O ZBUQRSWEONVBES-UHFFFAOYSA-L 0.000 description 1
- 229910000023 beryllium carbonate Inorganic materials 0.000 description 1
- WPJWIROQQFWMMK-UHFFFAOYSA-L beryllium dihydroxide Chemical compound [Be+2].[OH-].[OH-] WPJWIROQQFWMMK-UHFFFAOYSA-L 0.000 description 1
- 229910001865 beryllium hydroxide Inorganic materials 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 229940043232 butyl acetate Drugs 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- AYBCUKQQDUJLQN-UHFFFAOYSA-N hydridoberyllium Chemical compound [H][Be] AYBCUKQQDUJLQN-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 description 1
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 229910000032 lithium hydrogen carbonate Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- RSHAOIXHUHAZPM-UHFFFAOYSA-N magnesium hydride Chemical compound [MgH2] RSHAOIXHUHAZPM-UHFFFAOYSA-N 0.000 description 1
- 229910012375 magnesium hydride Inorganic materials 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- XDKQUSKHRIUJEO-UHFFFAOYSA-N magnesium;ethanolate Chemical compound [Mg+2].CC[O-].CC[O-] XDKQUSKHRIUJEO-UHFFFAOYSA-N 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- GFYHSKONPJXCDE-UHFFFAOYSA-N sym-collidine Natural products CC1=CN=C(C)C(C)=C1 GFYHSKONPJXCDE-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- 229940035893 uracil Drugs 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Images
Abstract
Description
本発明は、工業的に有用なスルホン酸エステル基を含むジアミン化合物及びその製造方法に関するものである。 The present invention relates to an industrially useful diamine compound containing a sulfonic acid ester group and a method for producing the same.
ジアミン化合物は、有機化学分野及び高分子化学分野で広く用いられている化合物であり、ファインケミカル、医農薬原料および樹脂原料、さらには電子情報材料や光学材料など、工業用途として多岐にわたる分野で有用な化合物である。近年、エステル基を有するジアミン化合物を原料とした材料の研究が盛んで、例えば、溶媒への溶解度が向上するポリイミド共重合体が得られる(特許文献1)、耐熱性等の諸特性に優れ、機械的強度が高く、かつ低い線膨張係数を有して熱的寸法安定性に優れたポリイミド共重合体が得られる(特許文献2)、低熱膨張、低吸湿膨張性の耐熱絶縁材料が得られる(非特許文献1)等の報告がなされている。そのため、これらジアミン化合物に要求される性能も益々多様化、高度化してきており、透明性に優れた材料、例えば、白色で、且つ、着色しにくいスルホン酸エステル基を含有したジアミンが望まれている。 Diamine compounds are widely used in the fields of organic chemistry and polymer chemistry, and are useful in a wide range of industrial applications such as fine chemicals, medical and agricultural chemical raw materials and resin raw materials, and electronic information materials and optical materials. A compound. In recent years, research on materials using a diamine compound having an ester group as a raw material has been actively conducted, for example, a polyimide copolymer having improved solubility in a solvent can be obtained (Patent Document 1), and excellent in various properties such as heat resistance, A polyimide copolymer having high mechanical strength and a low coefficient of linear expansion and excellent thermal dimensional stability can be obtained (Patent Document 2), and a heat-resistant insulating material having low thermal expansion and low hygroscopic expansion can be obtained. (Nonpatent literature 1) etc. are reported. Therefore, the performance required for these diamine compounds has been diversified and advanced, and materials having excellent transparency, for example, diamines containing sulfonic acid ester groups that are white and difficult to color are desired. Yes.
従来のジアミン化合物は、一般的に着色していることが多く、また、空気酸化により着色し易く、製造時に着色したり、保管中にも着色が進行する等の欠点があり、透明性が求められる材料への制限が出てくるなどの欠点があった。 Conventional diamine compounds are often colored in general, are easily colored by air oxidation, and have disadvantages such as coloring during production and progressing during storage, and transparency is required. There were drawbacks such as restrictions on the materials used.
本発明は、白色で、且つ、着色しにくいスルホン酸エステル基を含有したジアミン化合物およびその製造方法を提供することを目的とする。 An object of the present invention is to provide a diamine compound containing a sulfonic acid ester group which is white and hardly colored, and a method for producing the diamine compound.
本発明者らは、上記従来技術の現状に鑑み、鋭意検討の結果、スルホン酸エステル基を含有することで白色、且つ着色しにくい新規ジアミン化合物と、その製造方法を見出した。 As a result of intensive studies, the present inventors have found a novel diamine compound that is white and difficult to color by containing a sulfonic acid ester group, and a method for producing the same.
すなわち、本発明のジアミン化合物は、下記式(1) That is, the diamine compound of the present invention has the following formula (1)
で示される4,4’−ビス(4−アミノベンゼンスルホン酸)ビフェニルである。 It is 4,4'-bis (4-aminobenzenesulfonic acid) biphenyl shown by these.
本発明のジアミン化合物の製造方法は、下記式(2)で示される4−アセトアミドベンゼンスルホン酸クロライドと、 The method for producing a diamine compound of the present invention includes 4-acetamidobenzenesulfonic acid chloride represented by the following formula (2),
下記式(3)で示される4,4’−ビフェノールとを、塩基下でエステル化させて得られた、 Obtained by esterifying 4,4'-biphenol represented by the following formula (3) with a base,
下記式(4)で示される4,4’−ビス(4−アセトアミドベンゼンスルホン酸)ビフェニルを、脱アセチル化することにより得られる、 Obtained by deacetylating 4,4'-bis (4-acetamidobenzenesulfonic acid) biphenyl represented by the following formula (4):
下記式(1)で示される4,4’−ビス(4−アミノベンゼンスルホン酸)ビフェニルの製造方法である。 This is a method for producing 4,4'-bis (4-aminobenzenesulfonic acid) biphenyl represented by the following formula (1).
本発明の新規ジアミン化合物、すなわち、4,4’−ビス(4−アミノベンゼンスルホン酸)ビフェニルは、ジアミン化合物であるにもかかわらず、化合物内に剛直なスルホン酸エステル基を導入したことで白色の化合物となり、且つ、空気による酸化を受けにくくなり、製造時の着色もないことから、透明性が求められるポリイミド、ポリアミド、エポキシ樹脂等の原料として有望である。また、本化合物は、エステル基を含有していることから、溶媒への溶解度の向上、耐熱性の向上、高い機械的強度、低線膨張性、低熱膨張性、低吸湿膨張性等の優れた機能性を有するポリイミドの原料、例えばフレキシブル回路基板用ベースフィルム材料、感光性耐熱性ポリマー、液晶配向膜等の原料として有望である。 Although the novel diamine compound of the present invention, ie, 4,4′-bis (4-aminobenzenesulfonic acid) biphenyl, is a diamine compound, it has a white color due to the introduction of a rigid sulfonic acid ester group in the compound. It is promising as a raw material for polyimides, polyamides, epoxy resins and the like that are required to be transparent. In addition, since this compound contains an ester group, it has excellent solubility in a solvent, improved heat resistance, high mechanical strength, low linear expansion, low thermal expansion, low hygroscopic expansion, and the like. It is promising as a raw material for functional polyimide materials such as base film materials for flexible circuit boards, photosensitive heat-resistant polymers, and liquid crystal alignment films.
以下に、本発明のジアミン化合物およびそのジアミン化合物の製造方法について詳細に記載する。 Below, it describes in detail about the diamine compound of this invention, and the manufacturing method of the diamine compound.
本発明は、下記式(1)で示される、4,4’−ビス(4−アミノベンゼンスルホン酸)ビフェニルである。 The present invention is 4,4'-bis (4-aminobenzenesulfonic acid) biphenyl represented by the following formula (1).
上記式(1)で示される4,4’−ビス(4−アミノベンゼンスルホン酸)ビフェニルは、白色であると共に、着色しにくい化合物である。例えば、空気雰囲気下、40℃で7日間保管しても、色目にほとんど変化は無く着色は認められない。 4,4'-bis (4-aminobenzenesulfonic acid) biphenyl represented by the above formula (1) is a compound that is white and hardly colored. For example, even when stored in an air atmosphere at 40 ° C. for 7 days, there is almost no change in color and no coloring is observed.
上記式(1)で示される化合物を製造するとき、まず下記式(2) When producing the compound represented by the above formula (1), first, the following formula (2)
で示される4−アセトアミドベンゼンスルホン酸クロライドと、下記式(3) 4-acetamidobenzenesulfonic acid chloride represented by the following formula (3)
で示される4,4’−ビフェノールとを塩基下でエステル化させることにより、中間体の下記式(4)で示される4,4’−ビス(4−アセトアミドベンゼンスルホン酸)ビフェニルを製造することが出来る。 To produce 4,4′-bis (4-acetamidobenzenesulfonic acid) biphenyl represented by the following formula (4) as an intermediate by esterification with 4,4′-biphenol represented by the formula: I can do it.
式(2)で示される4−アセトアミドベンゼンスルホン酸クロライドと、式(3)で示される4,4’−ビフェノールとの反応割合は、4−アセトアミドベンゼンスルホン酸クロライド1モルに対して、4,4’−ビフェノールを0.3〜1.0モルが好ましく、より好ましくは、0.4〜0.6モル使用する。4,4’−ビフェノールを0.3モル以上とすることで、反応未達による収率低下を防止できることが期待され、また1.0モル以下とすることで、反応物から4,4’−ビフェノールを除去するエネルギーが少なくなり、廃棄物も少なくなるため経済的であるので好ましい。 The reaction ratio of 4-acetamidobenzenesulfonic acid chloride represented by the formula (2) and 4,4′-biphenol represented by the formula (3) is 4 with respect to 1 mol of 4-acetamidobenzenesulfonic acid chloride. The amount of 4'-biphenol is preferably 0.3 to 1.0 mol, more preferably 0.4 to 0.6 mol. It is expected that the yield reduction due to unreachable reaction can be prevented by setting the 4,4′-biphenol to 0.3 mol or more, and by reducing the amount to 1.0 mol or less, 4,4′-biphenol can be obtained from the reaction product. This is preferable because it requires less energy to remove biphenol and less waste, which is economical.
エステル化反応は、塩基の存在下で、式(2)で示される4−アセトアミドベンゼンスルホン酸クロライドと、式(3)で示される4,4’−ビフェノールとを反応させる。 In the esterification reaction, 4-acetamidobenzenesulfonic acid chloride represented by the formula (2) is reacted with 4,4′-biphenol represented by the formula (3) in the presence of a base.
エステル化反応に好ましく使用される塩基としては、例えば、アルカリ金属水素化物、アルカリ土類金属水素化物、アルカリ金属水酸化物、アルカリ土類金属水酸化物、アルカリ金属炭酸塩、アルカリ土類金属炭酸塩、アルカリ金属炭酸水素塩、アルカリ金属アルコキシド、アルカリ土類金属アルコキシド、アルカリ金属フッ化物、アミン等が挙げられる。 Examples of the base preferably used in the esterification reaction include alkali metal hydride, alkaline earth metal hydride, alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate, alkaline earth metal carbonate. Examples thereof include salts, alkali metal hydrogen carbonates, alkali metal alkoxides, alkaline earth metal alkoxides, alkali metal fluorides, and amines.
アルカリ金属水素化物としては、水素化リチウム、水素化ナトリウム、水素化カリウム等が挙げられる。 Examples of the alkali metal hydride include lithium hydride, sodium hydride, potassium hydride and the like.
アルカリ土類金属水素化物としては、水素化ベリリウム、水素化マグネシウム、水素化カルシウム等が挙げられる。 Examples of the alkaline earth metal hydride include beryllium hydride, magnesium hydride, calcium hydride and the like.
アルカリ金属水酸化物としては、水酸化リチウム、水酸化ナトリウム、水酸化カリウム等が挙げられる。 Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like.
アルカリ土類金属水酸化物としては、水酸化ベリリウム、水酸化マグネシウム、水酸化カルシウム等が挙げられる。 Examples of the alkaline earth metal hydroxide include beryllium hydroxide, magnesium hydroxide, calcium hydroxide and the like.
アルカリ金属炭酸塩としては、炭酸リチウム、炭酸ナトリウム、炭酸カリウム等が挙げられる。 Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate and the like.
アルカリ土類金属炭酸塩としては、炭酸ベリリウム、炭酸マグネシウム、炭酸カルシウム等が挙げられる。 Examples of the alkaline earth metal carbonate include beryllium carbonate, magnesium carbonate, and calcium carbonate.
アルカリ金属炭酸水素塩としては、炭酸水素ナトリウム、炭酸水素カリウム、炭酸水素リチウム等が挙げられる。 Examples of the alkali metal hydrogen carbonate include sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydrogen carbonate and the like.
アルカリ金属アルコキシドとしては、ナトリウムメトキシド、ナトリウムエトキシド、ナトリウムt − ブトキシド、カリウムメトキシド、カリウムエトキシド、カリウムt − ブトキシド等が挙げられる。 Examples of the alkali metal alkoxide include sodium methoxide, sodium ethoxide, sodium t-butoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide and the like.
アルカリ土類金属アルコキシドとしては、マグネシウムジエトキシド、マグネシウムジメトキシド等が挙げられる。 Examples of the alkaline earth metal alkoxide include magnesium diethoxide and magnesium dimethoxide.
アルカリ金属フッ化物としては、フッ化ナトリウム、フッ化カリウム、フッ化セシウムなどが挙げられる。 Examples of the alkali metal fluoride include sodium fluoride, potassium fluoride, cesium fluoride and the like.
アミンとしては、トリメチルアミン、トリエチルアミン、トリブチルアミン、N、N−ジメチルアニリン、ジメチルベンジルアミン、N,N,N’,N’−テトラメチル−1,8−ナフタレンジアミン等の三級アミン、ピリジン、ピロール、ウラシル、コリジン、ルチジン等の複素芳香族アミン、1,8−ジアザ−ビシクロ[5.4.0]−7−ウンデセン、1,5−ジアザ−ビシクロ[4.3.0]−5−ノネン等の環状アミジン等が挙げられる。 As amines, tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, dimethylbenzylamine, N, N, N ′, N′-tetramethyl-1,8-naphthalenediamine, pyridine, pyrrole , Heteroaromatic amines such as uracil, collidine and lutidine, 1,8-diaza-bicyclo [5.4.0] -7-undecene, 1,5-diaza-bicyclo [4.3.0] -5-nonene And cyclic amidines.
これらの塩基は単独で用いても良いし、2種類以上を混合して用いても良い。これらの塩基のうち、トリエチルアミン、ピリジンが液体で取り扱いが容易であり、沸点が低いため除去が容易であることから特に好ましい。 These bases may be used alone or in combination of two or more. Of these bases, triethylamine and pyridine are particularly preferable because they are liquid and easy to handle, and are easy to remove because of their low boiling point.
塩基の使用量は、4−アセトアミドベンゼンスルホン酸クロライドに対して、1.0〜3.0モル倍量が好ましく、より好ましくは1.0〜1.5モル倍量にすると良い。塩基を1.0モル倍量以上とすることで、反応未達による収率低下を防止でき、3.0モル倍量以下とすることで、塩基除去に必要なエネルギーが少なくなり、廃棄物も少なくなるので好ましい。 The amount of the base used is preferably 1.0 to 3.0 mol times, more preferably 1.0 to 1.5 mol times the amount of 4-acetamidobenzenesulfonic acid chloride. By reducing the amount of the base to 1.0 mol times or more, it is possible to prevent a decrease in yield due to failure to achieve the reaction. Since it decreases, it is preferable.
エステル化反応で好ましく用いる溶媒としては、例えばスルホキシド化合物、スルホラン化合物、アミド化合物、ニトリル化合物、エーテル化合物、炭化水素化合物、ケトン化合物、エステル化合物等を好適に用いることができる。 As a solvent preferably used in the esterification reaction, for example, a sulfoxide compound, a sulfolane compound, an amide compound, a nitrile compound, an ether compound, a hydrocarbon compound, a ketone compound, an ester compound and the like can be preferably used.
スルホキシド化合物としては、ジメチルスルホキシド、ジエチルスルホキシド等が挙げられる。 Examples of the sulfoxide compound include dimethyl sulfoxide and diethyl sulfoxide.
スルホラン化合物としては、スルホラン、メチルスルホラン等が挙げられる。 Examples of the sulfolane compound include sulfolane and methyl sulfolane.
アミド化合物としては、N,N−ジメチルアセトアミド、N,N−ジエチルアセトアミド、N,N −ジメチルホルムアミド、2− ピロリドン、N−メチル−2−ピロリドン、ヘキサメチルホスホリックトリアミド、1,3−ジメチル− 2−イミダゾリノジン等が挙げられる。 Examples of amide compounds include N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, 2-pyrrolidone, N-methyl-2-pyrrolidone, hexamethylphosphoric triamide, 1,3-dimethyl. -2-imidazolinodin etc. are mentioned.
ニトリル化合物としては、アセトニトリル、プロピオニトリル、ブチロニトリル、イソブチロニトリル、ベンゾニトリル等が挙げられる。 Examples of nitrile compounds include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like.
エーテル化合物としては、モノグライム、ジグライム、トリグライム、テトラグライム、ジエチルエーテル、ジイソプロピルエーテル、ジ−n−ブチルエーテル、t−ブチルメチルエーテル、シクロペンチルメチルエーテル、テトラヒドロフラン(THF)、テトラヒドロピラン、1,4−ジオキサン、1,3−ジオキソラン、アニソール、モルホリン等が挙げられる。 Examples of ether compounds include monoglyme, diglyme, triglyme, tetraglyme, diethyl ether, diisopropyl ether, di-n-butyl ether, t-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran (THF), tetrahydropyran, 1,4-dioxane, 1,3-dioxolane, anisole, morpholine and the like can be mentioned.
炭化水素化合物としては、トルエン、キシレン、メシチレン、n−ヘキサン、n−ヘプタン、シクロヘキサン、メチルシクロヘキサン等が挙げられる。 Examples of the hydrocarbon compound include toluene, xylene, mesitylene, n-hexane, n-heptane, cyclohexane, methylcyclohexane, and the like.
ケトン化合物としては、アセトン、メチルエチルケトン、メチルイソブチルケトン、2−ペンタノン、3−ペンタノン、2−ヘキサノン、2−ヘプタノン、4−ヘプタノン、ジイソブチルケトン、シクロヘキサノン、メチルシクロヘキサノン、イソホロン等が挙げられる。 Examples of the ketone compound include acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 4-heptanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, and isophorone.
エステル化合物としては、酢酸メチル、酢酸エチル、酢酸プロピル、酢酸イソプロピル、酢酸ブチル、酢酸イソブチル、酢酸ペンチル、酢酸イソペンチル、3−メトキシブチルアセタート、2−エチルブチルアセタート、2−エチルヘキシルアセタート、酢酸シクロヘキシル、プロピオン酸メチル、プロピオン酸エチル、プロピオン酸ブチル、酪酸メチル、酪酸エチル、酪酸ブチル、γ−ブチロラクトン等が挙げられる、
これらの中でもアセトニトリル、テトラヒドロフラン、トルエン、アセトン、酢酸エチルが、沸点が低いため除去が容易であることから好ましい。
Examples of ester compounds include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, pentyl acetate, isopentyl acetate, 3-methoxybutyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, acetic acid. Cyclohexyl, methyl propionate, ethyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, γ-butyrolactone, etc.
Among these, acetonitrile, tetrahydrofuran, toluene, acetone, and ethyl acetate are preferable because of their low boiling point and easy removal.
エステル化溶媒は、単独で用いても良いし、2種類以上を混合して用いても良い。 An esterification solvent may be used independently and may be used in mixture of 2 or more types.
エステル化溶媒の使用量は、通常、4−アセトアミドベンゼンスルホン酸クロライドに対して0.1〜20重量倍の範囲である。 The amount of the esterification solvent used is usually in the range of 0.1 to 20 times the weight of 4-acetamidobenzenesulfonic acid chloride.
エステル化反応は、窒素雰囲気下で実施することが好ましい。窒素雰囲気下で実施することにより、系内に酸素が混入することを防ぐことで、純度低下を抑制することが出来る。 The esterification reaction is preferably carried out in a nitrogen atmosphere. By carrying out in a nitrogen atmosphere, purity deterioration can be suppressed by preventing oxygen from entering the system.
エステル化反応の反応温度は、通常、0〜150℃が好ましく、より好ましくは、0〜70℃である。0℃以上とすることで反応が速やかに進行し、150℃以下にすることで副反応を抑制し、収率低下を防ぐことができる。 The reaction temperature for the esterification reaction is usually preferably 0 to 150 ° C, more preferably 0 to 70 ° C. When the temperature is 0 ° C. or higher, the reaction proceeds rapidly, and when the temperature is 150 ° C. or lower, side reactions can be suppressed and yield reduction can be prevented.
エステル化反応の反応時間は、通常、0.5〜20時間の範囲である。 The reaction time of the esterification reaction is usually in the range of 0.5 to 20 hours.
エステル化反応終了後は、反応混合物に晶析溶媒を添加することで結晶が析出し、これを単離することで中間体化合物が得られる。得られた中間体は、再結晶を行っても良い。 After completion of the esterification reaction, crystals are precipitated by adding a crystallization solvent to the reaction mixture, and an intermediate compound is obtained by isolating the crystals. The obtained intermediate may be recrystallized.
エステル化反応に好ましく使用される晶析溶媒としては、例えば、水、アルコール化合物等を好適に用いることができる。 As a crystallization solvent preferably used in the esterification reaction, for example, water, an alcohol compound, or the like can be suitably used.
アルコール化合物としては、メタノ−ル、エタノール、1−プロパノール、2−プロパノール、1−ブタノール、2−ブタノール、イソブチルアルコール、tert−ブチルアルコール、メトキシエタノール、エトキシエタノール、1−メトキシ−2−プロパノール等が挙げられる。 Examples of alcohol compounds include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, methoxyethanol, ethoxyethanol, and 1-methoxy-2-propanol. Can be mentioned.
これらの晶析溶媒は単独で用いても良いし、2種類以上を混合して用いても良い。これらの晶析溶媒のうち、水、メタノール、エタノール、2−プロパノールが安価に入手できることから特に好ましい。 These crystallization solvents may be used alone or in combination of two or more. Of these crystallization solvents, water, methanol, ethanol, and 2-propanol are particularly preferable because they are available at low cost.
また、エステル化反応終了後に中間体を単離することなく次工程に用いても良い。 Moreover, you may use for the following process, without isolating an intermediate body after completion | finish of esterification reaction.
次に、上記で得られた4,4’−ビス(4−アセトアミドベンゼンスルホン酸)ビフェニルを、脱アセチル化することにより下記式(1)で示される4,4’−ビス(4−アミノベンゼンスルホン酸)ビフェニルを製造することが出来る。 Next, 4,4′-bis (4-aminobenzene) represented by the following formula (1) is obtained by deacetylating the 4,4′-bis (4-acetamidobenzenesulfonic acid) biphenyl obtained above. Sulfonic acid) biphenyl can be produced.
脱アセチル化方法としては、一般的に酸またはアルカリを用いて加水分解する方法が知られている。しかしながら、酸またはアルカリを用いると、エステル基を含有している化合物の場合は、エステル基の加水分解も進行するという欠点があった。本発明においては、剛直なスルホン酸エステル基を導入したことで、酸に対して安定な化合物となり、目的物のスルホン酸エステル基の加水分解を抑制できる。この結果、本発明においては、酸を用いた脱アセチル化が最も好ましい。酸を用いることにより、スルホン酸エステル基の加水分解が抑制され、収率よく目的物が得られる。 As a deacetylation method, a method of hydrolysis using an acid or alkali is generally known. However, when an acid or alkali is used, in the case of a compound containing an ester group, there is a drawback that hydrolysis of the ester group also proceeds. In the present invention, by introducing a rigid sulfonic acid ester group, it becomes a compound which is stable against acid, and hydrolysis of the target sulfonic acid ester group can be suppressed. As a result, in the present invention, deacetylation using an acid is most preferred. By using an acid, hydrolysis of the sulfonic acid ester group is suppressed, and the target product can be obtained in high yield.
これらの酸は単独で用いても良いし、2種類以上を混合して用いても良い。これらの酸のうち、塩酸、硫酸が後処理の容易な点から特に好ましい。 These acids may be used alone or in combination of two or more. Of these acids, hydrochloric acid and sulfuric acid are particularly preferred from the viewpoint of easy post-treatment.
酸の使用量は、4,4’−ビス(4−アセトアミドベンゼンスルホン酸)ビフェニルに対して、1.0〜20.0モル倍量が好ましく、より好ましくは2.0〜10.0モル倍量にすると良い。塩基を2.0モル倍量以上とすることで、反応未達による収率低下を防止でき、10.0モル倍量以下とすることで、酸除去に必要なエネルギーが少なくなり、廃棄物も少なくなるので好ましい。 The amount of the acid used is preferably 1.0 to 20.0 mol times, more preferably 2.0 to 10.0 mol times based on 4,4′-bis (4-acetamidobenzenesulfonic acid) biphenyl. A good amount. By reducing the amount of the base to 2.0 mol times or more, a decrease in yield due to unreachable reaction can be prevented, and by setting the amount to 10.0 mol times or less, energy required for acid removal is reduced, and waste is also reduced. Since it decreases, it is preferable.
脱アセチル化に好ましく使用される溶媒としては、例えば、アルコール化合物、エーテル化合物、炭化水素化合物、ニトリル化合物等を好適に用いることができる。 As a solvent preferably used for deacetylation, for example, an alcohol compound, an ether compound, a hydrocarbon compound, a nitrile compound, or the like can be suitably used.
アルコール化合物としては、メタノ−ル、エタノール、1−プロパノール、2−プロパノール、1−ブタノール、2−ブタノール、イソブチルアルコール、tert−ブチルアルコール、メトキシエタノール、エトキシエタノール、1−メトキシ−2−プロパノール等が挙げられる。 Examples of alcohol compounds include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, methoxyethanol, ethoxyethanol, and 1-methoxy-2-propanol. Can be mentioned.
エーテル化合物としては、グライム、ジグライム、テトラヒドロフラン、ジオキサン等が挙げられる。 Examples of the ether compound include glyme, diglyme, tetrahydrofuran, dioxane and the like.
炭化水素化合物としては、トルエン、キシレン、メシチレン、ヘキサン、シクロヘキサン、ヘプタン、メチルシクロヘキサン等が挙げられる。 Examples of the hydrocarbon compound include toluene, xylene, mesitylene, hexane, cyclohexane, heptane, methylcyclohexane and the like.
ニトリル化合物としては、アセトニトリル、プロピオニトリル、ブチロニトリル、イソブチロニトリル、ベンゾニトリル等が挙げられる。 Examples of nitrile compounds include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like.
これらの中でもテトラヒドロフラン、2−プロパノール、トルエンが、沸点が低いため除去が容易であることから好ましい。 Among these, tetrahydrofuran, 2-propanol, and toluene are preferable because of their low boiling point and easy removal.
脱アセチル化反応の溶媒は、単独で用いても良いし、2種類以上を混合して用いても良い。 The solvent for the deacetylation reaction may be used alone or in combination of two or more.
溶媒の使用量は、通常、4,4’−ビス(4−アセトアミドベンゼンスルホン酸)ビフェニルに対して0.1〜20重量倍の範囲である。 The amount of the solvent used is usually in the range of 0.1 to 20 times the weight of 4,4'-bis (4-acetamidobenzenesulfonic acid) biphenyl.
脱アセチル化反応は、窒素雰囲気下で実施することが好ましい。窒素雰囲気下で実施することにより、系内に酸素が混入することを防ぐことで、純度低下を抑制することが出来る。 The deacetylation reaction is preferably performed in a nitrogen atmosphere. By carrying out in a nitrogen atmosphere, purity deterioration can be suppressed by preventing oxygen from entering the system.
脱アセチル化の反応温度は、通常、0〜150℃が好ましく、より好ましくは、50〜120℃である。50℃以上とすることで反応が速やかに進行し、120℃以下にすることで副反応を抑制し、収率低下を防ぐことができる。 The reaction temperature for deacetylation is usually preferably 0 to 150 ° C, more preferably 50 to 120 ° C. When the temperature is 50 ° C. or higher, the reaction proceeds rapidly, and when the temperature is 120 ° C. or lower, side reactions can be suppressed and yield reduction can be prevented.
脱アセチル化反応の反応時間は、通常、0.5〜20時間の範囲である。
脱アセチル化反応後は、反応液を中和した後、中和液に晶析溶媒を添加することで結晶が析出し、これを単離することで、式(1)で示される4,4’−ビス(4−アミノベンゼンスルホン酸)ビフェニルが得られる。得られた化合物は、再結晶を行っても良い。
The reaction time of the deacetylation reaction is usually in the range of 0.5 to 20 hours.
After the deacetylation reaction, the reaction solution is neutralized, and then a crystal is precipitated by adding a crystallization solvent to the neutralization solution. By isolating the crystals, 4,4 represented by the formula (1) is obtained. '-Bis (4-aminobenzenesulfonic acid) biphenyl is obtained. The obtained compound may be recrystallized.
脱アセチル化反応に好ましく使用される晶析溶媒としては、例えば、水、アルコール化合物、炭化水素化合物等を好適に用いることができる。 As a crystallization solvent preferably used for the deacetylation reaction, for example, water, alcohol compounds, hydrocarbon compounds and the like can be suitably used.
アルコール化合物としては、例えばメタノ−ル、エタノール、1−プロパノール、2−プロパノール、1−ブタノール、2−ブタノール、イソブチルアルコール、tert−ブチルアルコール、メトキシエタノール、エトキシエタノール、1−メトキシ−2−プロパノール等が挙げられる。 Examples of alcohol compounds include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, methoxyethanol, ethoxyethanol, 1-methoxy-2-propanol, and the like. Is mentioned.
炭化水素化合物としては、トルエン、キシレン、メシチレン、n−ヘキサン、n−ヘプタン、シクロヘキサン、メチルシクロヘキサン等が挙げられる。 Examples of the hydrocarbon compound include toluene, xylene, mesitylene, n-hexane, n-heptane, cyclohexane, methylcyclohexane, and the like.
これらの晶析溶媒は単独で用いても良いし、2種類以上を混合して用いても良い。これらの晶析溶媒のうち、水、メタノール、エタノール、2−プロパノール、トルエンが本化合物の純度を向上させるのに特に好ましい。 These crystallization solvents may be used alone or in combination of two or more. Of these crystallization solvents, water, methanol, ethanol, 2-propanol, and toluene are particularly preferable for improving the purity of the present compound.
上記により得られた、式(1)で示されるジアミン化合物は、化合物内に剛直なスルホン酸エステル基を導入したことにより、ジアミン化合物であるにもかかわらず白色の化合物であり、且つ、空気による酸化を受けにくく、製造時の着色もない。また、保管時における着色を抑制することが出来る。 The diamine compound represented by the formula (1) obtained as described above is a white compound despite the fact that it is a diamine compound by introducing a rigid sulfonic acid ester group into the compound, and is based on air. Less susceptible to oxidation and no coloration during manufacturing. Moreover, coloring at the time of storage can be suppressed.
このジアミン化合物は、透明性が求められるポリイミド、ポリアミド、エポキシ樹脂等の原料として有望である。また、エステル基を含有していることから、溶媒への溶解度の向上、耐熱性の向上、高い機械的強度、低線膨張性、低熱膨張性、低吸湿膨張性等の優れた機能性を有するポリイミドの原料、例えばフレキシブル回路基板用ベースフィルム材料、感光性耐熱性ポリマー、液晶配向膜等の原料として有望である。 This diamine compound is promising as a raw material for polyimide, polyamide, epoxy resin, and the like that require transparency. In addition, since it contains an ester group, it has excellent functionality such as improved solubility in solvents, improved heat resistance, high mechanical strength, low linear expansion, low thermal expansion, and low hygroscopic expansion. It is promising as a raw material for polyimide raw materials, such as base film materials for flexible circuit boards, photosensitive heat-resistant polymers, and liquid crystal alignment films.
以下、実施例により具体的に説明する。 Hereinafter, specific examples will be described.
実施例1において、ジアミン化合物中の4,4’−ビス(4−アミノベンゼンスルホン酸)ビフェニルの含有量、すなわち4,4’−ビス(4−アミノベンゼンスルホン酸)ビフェニルの化学純度は、高速液体クロマトグラフィー法(以下、「HPLC」と略す。)で、以下の分析条件で分析したもの(HPLC area%)である。
・カラム: YMC―Pack ODS−AM303 4.6φ×250mm
・カラム温度: 40℃
・移動相:
A:0.05%(v/v)リン酸水溶液
B:アセトニトリル
(グラジエント) 0min. A:B=50:50
5min. A:B=50:50
30min. A:B=10:90
・流量:1ml/min
・注入量: 0.5μl
・検出: 紫外(UV)検出 波長254nm
・分析時間: 30分
・分析サンプル調製:サンプル0.05gを秤量し、アセトニトリル25mlに溶解させた。
In Example 1, the content of 4,4′-bis (4-aminobenzenesulfonic acid) biphenyl in the diamine compound, that is, the chemical purity of 4,4′-bis (4-aminobenzenesulfonic acid) biphenyl is high speed. This is a liquid chromatography method (hereinafter abbreviated as “HPLC”) analyzed under the following analysis conditions (HPLC area%).
Column: YMC-Pack ODS-AM303 4.6φ × 250mm
-Column temperature: 40 ° C
・ Mobile phase:
A: 0.05% (v / v) phosphoric acid aqueous solution B: Acetonitrile (gradient) 0 min. A: B = 50: 50
5 min. A: B = 50: 50
30 min. A: B = 10: 90
・ Flow rate: 1 ml / min
・ Injection volume: 0.5 μl
・ Detection: Ultraviolet (UV) detection, wavelength 254nm
Analysis time: 30 minutes Preparation of analysis sample: 0.05 g of sample was weighed and dissolved in 25 ml of acetonitrile.
また、中間体の4,4’−ビス(4−アセトアミドベンゼンスルホン酸)ビフェニルの化学純度についても、上記HPLCの分析条件により分析した。 The chemical purity of the intermediate 4,4'-bis (4-acetamidobenzenesulfonic acid) biphenyl was also analyzed under the above HPLC analysis conditions.
(実施例1)
温度計、冷却管および撹拌機を取り付けた500ml四つ口フラスコに、4,4’−ビフェノール12.1g(0.065mol)、4−アセトアミドベンゼンスルホン酸クロライド31.6g(0.135mol)、テトラヒドロフラン100gを仕込み、系内を窒素置換した。これにトリエチルアミン14.5g(0.143mol)を40℃付近で滴下した。この混合液を50℃で3時間撹拌しエステル化反応を行った。反応が終了した後、水と2−プロパノールを加え、析出した結晶を単離した。得られた中間体は、HPLC純度99.3%であった。
Example 1
In a 500 ml four-necked flask equipped with a thermometer, condenser and stirrer, 12.1 g (0.065 mol) of 4,4′-biphenol, 31.6 g (0.135 mol) of 4-acetamidobenzenesulfonic acid chloride, tetrahydrofuran 100 g was charged and the system was purged with nitrogen. To this, 14.5 g (0.143 mol) of triethylamine was added dropwise at around 40 ° C. This mixture was stirred at 50 ° C. for 3 hours to carry out an esterification reaction. After the reaction was completed, water and 2-propanol were added, and the precipitated crystals were isolated. The resulting intermediate had an HPLC purity of 99.3%.
得られた中間体にテトラヒドロフラン30g、2−プロパノール75gと35%塩酸40.7g(0.390mol)を加え、75℃で5時間撹拌し脱アセチル化反応を行った。反応が終了した後、28%アンモニア水31.6g(0.520mol)で中和することで、ジアミン化合物を含んだスラリーを得た。得られたスラリー中のジアミン化合物は、HPLC純度96.0%であった。また、脱アセチル化時のスルホン酸エステル基の加水分解は0.5%であった。 To the obtained intermediate, 30 g of tetrahydrofuran, 75 g of 2-propanol and 40.7 g (0.390 mol) of 35% hydrochloric acid were added, followed by stirring at 75 ° C. for 5 hours for deacetylation reaction. After the reaction was completed, the slurry was neutralized with 31.6 g (0.520 mol) of 28% aqueous ammonia to obtain a slurry containing a diamine compound. The diamine compound in the obtained slurry had an HPLC purity of 96.0%. The hydrolysis of the sulfonic acid ester group during deacetylation was 0.5%.
得られたスラリーに水と2−プロパノールを加え、5℃まで冷却し、これを濾過、乾燥することで白色結晶のジアミン化合物28.0gを得た。得られたジアミン化合物は、HPLC純度97.9%、収率85.0%であった。 Water and 2-propanol were added to the resulting slurry, cooled to 5 ° C., filtered and dried to obtain 28.0 g of a white crystalline diamine compound. The obtained diamine compound had an HPLC purity of 97.9% and a yield of 85.0%.
図1に、実施例1で得られたジアミン化合物の水素核磁気共鳴(1H−NMR)スペクトルチャート、図2に赤外(IR)吸収スペクトルチャートを示す。なお1H−NMRは、図中に記載の測定条件で行った。 FIG. 1 shows a hydrogen nuclear magnetic resonance ( 1 H-NMR) spectrum chart of the diamine compound obtained in Example 1, and FIG. 2 shows an infrared (IR) absorption spectrum chart. 1 H-NMR was performed under the measurement conditions described in the figure.
以上の結果をもって、得られたジアミン化合物が4,4’−ビス(4−アミノベンゼンスルホン酸)ビフェニルであることを同定した。 Based on the above results, the obtained diamine compound was identified as 4,4'-bis (4-aminobenzenesulfonic acid) biphenyl.
(参考例1)
実施例1において、脱アセチル化反応時に、35%塩酸の代わりに48%水酸化ナトリウム水溶液32.5g(0.390mol)を使用し、75℃、5時間反応させた以外は、実施例1と同様に実施したところ、脱アセチル化時のスルホン酸エステル基の加水分解は99%以上で、目的物のHPLC純度は1%以下となり、目的物はほとんど得られなかった。
(Reference Example 1)
In Example 1, except that 32.5 g (0.390 mol) of 48% sodium hydroxide aqueous solution was used in place of 35% hydrochloric acid during the deacetylation reaction, and the reaction was performed at 75 ° C. for 5 hours, Example 1 When carried out in the same manner, hydrolysis of the sulfonate group at the time of deacetylation was 99% or more, and the HPLC purity of the target product was 1% or less, and the target product was hardly obtained.
(参考例2)
実施例1で得られたジアミン化合物を空気雰囲気下、40℃で7日間保管したところ、色目にほとんど変化は無く着色は認められなかった。また、比較として4,4’−ジアミノジフェニルエーテルを同条件で保管したところ、色目が初期の黄土色から7日間保管後に薄茶色に変化しており着色が認められた。
(Reference Example 2)
When the diamine compound obtained in Example 1 was stored at 40 ° C. for 7 days in an air atmosphere, there was almost no change in color and no coloring was observed. For comparison, when 4,4′-diaminodiphenyl ether was stored under the same conditions, the color changed from an initial ocher color to a light brown color after 7 days of storage, and coloring was observed.
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CN115108918A (en) * | 2021-03-23 | 2022-09-27 | 北京英力精化技术发展有限公司 | Preparation method of 3,3',4,4' -tetraaminobiphenyl |
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CN115108918A (en) * | 2021-03-23 | 2022-09-27 | 北京英力精化技术发展有限公司 | Preparation method of 3,3',4,4' -tetraaminobiphenyl |
CN115108918B (en) * | 2021-03-23 | 2023-06-02 | 湖北汇达科技发展有限公司 | Preparation method of 3,3', 4' -tetraminobiphenyl |
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