KR20200044036A - New polymer and diamine compounds - Google Patents
New polymer and diamine compounds Download PDFInfo
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- KR20200044036A KR20200044036A KR1020207007850A KR20207007850A KR20200044036A KR 20200044036 A KR20200044036 A KR 20200044036A KR 1020207007850 A KR1020207007850 A KR 1020207007850A KR 20207007850 A KR20207007850 A KR 20207007850A KR 20200044036 A KR20200044036 A KR 20200044036A
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- -1 diamine compounds Chemical class 0.000 title claims abstract description 126
- 229920000642 polymer Polymers 0.000 title claims abstract description 57
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 23
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims abstract description 14
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000001424 substituent group Chemical group 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 claims description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 4
- 125000004193 piperazinyl group Chemical group 0.000 claims description 4
- 125000003386 piperidinyl group Chemical group 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 125000003172 aldehyde group Chemical group 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 3
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 3
- 125000004185 ester group Chemical group 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000004985 diamines Chemical class 0.000 abstract description 59
- 239000002994 raw material Substances 0.000 abstract description 12
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 165
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 108
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 106
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 75
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 68
- 239000000243 solution Substances 0.000 description 66
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 63
- 239000002904 solvent Substances 0.000 description 58
- 229920001721 polyimide Polymers 0.000 description 54
- 239000004642 Polyimide Substances 0.000 description 52
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 51
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 42
- 239000002244 precipitate Substances 0.000 description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 39
- 238000001914 filtration Methods 0.000 description 38
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 38
- 238000005406 washing Methods 0.000 description 38
- 239000012043 crude product Substances 0.000 description 37
- 229920005575 poly(amic acid) Polymers 0.000 description 33
- 238000006116 polymerization reaction Methods 0.000 description 33
- 150000001875 compounds Chemical class 0.000 description 30
- 230000015572 biosynthetic process Effects 0.000 description 29
- 238000003786 synthesis reaction Methods 0.000 description 29
- 239000007787 solid Substances 0.000 description 28
- 239000003960 organic solvent Substances 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 25
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 19
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 125000005442 diisocyanate group Chemical group 0.000 description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 17
- 239000000706 filtrate Substances 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 16
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 16
- 239000002585 base Substances 0.000 description 16
- 239000004973 liquid crystal related substance Substances 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 238000005160 1H NMR spectroscopy Methods 0.000 description 14
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- WVOLTBSCXRRQFR-SJORKVTESA-N Cannabidiolic acid Natural products OC1=C(C(O)=O)C(CCCCC)=CC(O)=C1[C@@H]1[C@@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-SJORKVTESA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 12
- WVOLTBSCXRRQFR-DLBZAZTESA-M cannabidiolate Chemical compound OC1=C(C([O-])=O)C(CCCCC)=CC(O)=C1[C@H]1[C@H](C(C)=C)CCC(C)=C1 WVOLTBSCXRRQFR-DLBZAZTESA-M 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 12
- 150000002148 esters Chemical class 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000012044 organic layer Substances 0.000 description 12
- 229910052763 palladium Inorganic materials 0.000 description 12
- 150000000000 tetracarboxylic acids Chemical class 0.000 description 12
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000012528 membrane Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 description 10
- 235000011181 potassium carbonates Nutrition 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 238000006467 substitution reaction Methods 0.000 description 10
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 150000008065 acid anhydrides Chemical class 0.000 description 9
- 238000006358 imidation reaction Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- 238000001556 precipitation Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 5
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 5
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 150000007529 inorganic bases Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 5
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 description 4
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- 239000012024 dehydrating agents Substances 0.000 description 4
- 239000002274 desiccant Substances 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 229940117389 dichlorobenzene Drugs 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 150000007517 lewis acids Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229940017219 methyl propionate Drugs 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- 239000003495 polar organic solvent Substances 0.000 description 4
- 229920003192 poly(bis maleimide) Polymers 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 239000011736 potassium bicarbonate Substances 0.000 description 4
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 4
- 235000015497 potassium bicarbonate Nutrition 0.000 description 4
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 4
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 4
- 229910000160 potassium phosphate Inorganic materials 0.000 description 4
- 235000011009 potassium phosphates Nutrition 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical class CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 4
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 4
- NTURQZFFJDCTMZ-UHFFFAOYSA-N 1-(2-bromoethyl)-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(CCBr)C=C1 NTURQZFFJDCTMZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 229920002396 Polyurea Polymers 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 235000011054 acetic acid Nutrition 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- UTBIMNXEDGNJFE-UHFFFAOYSA-N collidine Natural products CC1=CC=C(C)C(C)=N1 UTBIMNXEDGNJFE-UHFFFAOYSA-N 0.000 description 3
- 238000010511 deprotection reaction Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
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- 235000006408 oxalic acid Nutrition 0.000 description 1
- CDXVUROVRIFQMV-UHFFFAOYSA-N oxo(diphenoxy)phosphanium Chemical compound C=1C=CC=CC=1O[P+](=O)OC1=CC=CC=C1 CDXVUROVRIFQMV-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- 125000000612 phthaloyl group Chemical group C(C=1C(C(=O)*)=CC=CC1)(=O)* 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- CAEWJEXPFKNBQL-UHFFFAOYSA-N prop-2-enyl carbonochloridate Chemical compound ClC(=O)OCC=C CAEWJEXPFKNBQL-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- CYIRLFJPTCUCJB-UHFFFAOYSA-N propyl 2-methoxypropanoate Chemical compound CCCOC(=O)C(C)OC CYIRLFJPTCUCJB-UHFFFAOYSA-N 0.000 description 1
- QQKDTTWZXHEGAQ-UHFFFAOYSA-N propyl carbonochloridate Chemical compound CCCOC(Cl)=O QQKDTTWZXHEGAQ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 229940032159 propylene carbonate Drugs 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- RXFHRKPNLPBDGE-UHFFFAOYSA-N tert-butyl 4-(4-aminophenyl)piperazine-1-carboxylate Chemical compound C1CN(C(=O)OC(C)(C)C)CCN1C1=CC=C(N)C=C1 RXFHRKPNLPBDGE-UHFFFAOYSA-N 0.000 description 1
- YRLQFRXDWBFGMK-UHFFFAOYSA-N tert-butyl 4-(4-aminophenyl)piperidine-1-carboxylate Chemical compound C1CN(C(=O)OC(C)(C)C)CCC1C1=CC=C(N)C=C1 YRLQFRXDWBFGMK-UHFFFAOYSA-N 0.000 description 1
- LZRDHSFPLUWYAX-UHFFFAOYSA-N tert-butyl 4-aminopiperidine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCC(N)CC1 LZRDHSFPLUWYAX-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LVAACBVNZRPHFE-UHFFFAOYSA-N tert-butyl n-[4-(2-hydroxyethyl)phenyl]carbamate Chemical compound CC(C)(C)OC(=O)NC1=CC=C(CCO)C=C1 LVAACBVNZRPHFE-UHFFFAOYSA-N 0.000 description 1
- VGZVDNZGYZZMCK-UHFFFAOYSA-N tert-butyl n-[4-(3-hydroxypropyl)phenyl]carbamate Chemical compound CC(C)(C)OC(=O)NC1=CC=C(CCCO)C=C1 VGZVDNZGYZZMCK-UHFFFAOYSA-N 0.000 description 1
- RWXVMOBDVOAUHW-UHFFFAOYSA-N tert-butyl-chloro-diethylsilane Chemical compound CC[Si](Cl)(CC)C(C)(C)C RWXVMOBDVOAUHW-UHFFFAOYSA-N 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 125000005147 toluenesulfonyl group Chemical group C=1(C(=CC=CC1)S(=O)(=O)*)C 0.000 description 1
- PNQBEPDZQUOCNY-UHFFFAOYSA-N trifluoroacetyl chloride Chemical compound FC(F)(F)C(Cl)=O PNQBEPDZQUOCNY-UHFFFAOYSA-N 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- KYWIYKKSMDLRDC-UHFFFAOYSA-N undecan-2-one Chemical compound CCCCCCCCCC(C)=O KYWIYKKSMDLRDC-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
- C07D487/04—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Polyamides (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
본 발명은, 하기 일반식 (1) 로 나타내는 디아민 화합물에 관한 것이다.
여기서 식 (1) 중, R1, R2, R3 및 R4 는 각각 독립적으로 H, CH3 또는 CF3 을 나타내고, 단, R1, R2, R3 및 R4 중, 반드시 하나는 CH3 또는 CF3 을 나타내고, W1 은, 단결합 또는 페닐렌을 나타내고, W2 는 페닐렌을 나타내고, L 은, 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 알킬렌기를 나타내고, 알킬렌의 CH2 는 산소 원자 등으로 치환되어 있어도 된다. 본 발명은, 입수성이 높은 원료를 사용함으로써, 각종 특성을 용이하게 부여하는 것이 가능한 디아민을 제공할 수 있고, 또한, 그것으로 부터 얻어지는 신규 중합체를 제공할 수 있다.The present invention relates to a diamine compound represented by the following general formula (1).
Here, in formula (1), R 1 , R 2 , R 3 and R 4 each independently represent H, CH 3 or CF 3 , provided that one of R 1 , R 2 , R 3 and R 4 is necessarily one CH 3 or CF 3 , W 1 represents a single bond or phenylene, W 2 represents phenylene, L represents a straight or branched chain alkylene group having 1 to 10 carbon atoms, and CH 2 may be substituted with an oxygen atom or the like. The present invention can provide a diamine capable of easily imparting various properties by using a highly available raw material, and can also provide a novel polymer obtained therefrom.
Description
본 발명은, 액정 배향막에 사용하는 중합체의 원료로서 유용한 신규 디아민 화합물 (본 발명에서는, 간단히 「디아민」 이라고도 한다), 및 그 디아민을 사용하여 얻어지는 중합체에 관한 것이다. 더욱 상세히 서술하면, 본 발명은, 예를 들어, 전자 재료용으로서 적합한 폴리이미드 및 그 원료 모노머인 디아민 화합물에 관한 것이다.The present invention relates to a novel diamine compound (also referred to simply as "diamine" in the present invention) useful as a raw material for a polymer used in a liquid crystal alignment film, and a polymer obtained using the diamine. More specifically, the present invention relates to, for example, a polyimide suitable for use as an electronic material and a diamine compound which is a raw material monomer thereof.
일반적으로, 폴리이미드 수지는, 그 특장인 높은 기계적 강도, 내열성, 절연성, 및 내용제성을 위해서, 액정 표시 소자나 반도체에 있어서의 보호 재료, 절연 재료, 및 컬러 필터 등의 전자 재료로서 널리 사용되고 있다. 또, 최근에는 광 도파로용 재료 등의 광 통신용 재료로서의 용도도 기대되고 있다.In general, polyimide resins are widely used as electronic materials such as protective materials, insulating materials, and color filters in liquid crystal display devices and semiconductors for their high mechanical strength, heat resistance, insulation properties, and solvent resistance. . In addition, recently, use as an optical communication material such as an optical waveguide material is also expected.
최근, 이 분야의 발전은 눈부시고, 그에 대응하여, 사용되는 재료에 대해서도 더욱 더 고도의 특성이 요구되도록 되어 있다. 즉, 단순히 내열성, 내용제성이 우수할 뿐만 아니라, 용도에 따른 성능을 다수 아울러 갖는 것이 기대되고 있다.In recent years, developments in this field have been dazzling, and correspondingly, more and more advanced characteristics are required for the materials used. That is, it is expected that not only is it excellent in heat resistance and solvent resistance, but also has many performances according to the use.
그러나, 폴리이미드, 특히 전체 방향족 폴리이미드 수지의 대표예로서 다용되고 있는 피로멜리트산 무수물 (PMDA) 과 4,4'-디옥시아닐린 (ODA) 으로부터 제조되는 폴리이미드 (카프톤 : 상품명) 에 있어서는, 용해성이 부족하여, 용액으로서 사용할 수는 없기 때문에, 폴리아믹산이라 불리는 전구체를 거쳐, 가열하여 탈수 반응시킴으로써 얻고 있다.However, polyimide, in particular, polyimide produced from pyromellitic anhydride (PMDA) and 4,4'-dioxyaniline (ODA), which are widely used as representative examples of all aromatic polyimide resins (kapton: trade name) Since it lacks solubility and cannot be used as a solution, it is obtained by heating and dehydrating through a precursor called polyamic acid.
또 용매 용해성을 갖는 폴리이미드 (이하 가용성 폴리이미드) 에 있어서는, 종래 다용되어 온 용해도가 높은 N-메틸-2-피롤리돈 (NMP) 이나 γ-부티로락톤 등의 아미드계나 락톤계 유기 용매는 고비점이기 때문에, 용매를 제거하기 위해서는 고온 소성을 피할 수 없었다.Moreover, in the polyimide (hereinafter soluble polyimide) having solvent solubility, amide-based or lactone-based organic solvents such as N-methyl-2-pyrrolidone (NMP) or γ-butyrolactone, which have been conventionally used in high solubility, are used. Because of its high boiling point, high temperature firing could not be avoided in order to remove the solvent.
액정 표시 소자 분야에서는, 최근 플라스틱 기판을 사용한 플렉시블 액정 표시 소자의 연구 개발이 실시되고 있어, 고온 소성이 되면 소자 구성 성분의 변질이 문제가 되기 때문에, 최근 저온 소성이 요망되게 되었다.In the field of liquid crystal display elements, research and development of flexible liquid crystal display elements using plastic substrates have recently been conducted, and deterioration of element components becomes a problem when firing at a high temperature, so low temperature firing has recently been desired.
한편, 높은 용매 용해성을 나타내는 폴리아믹산으로는 충분한 액정 표시 특성이 얻어지지 않아 이미드화에서 기인한 체적 변화도 일어나기 쉽다는 문제점도 있어, 비점이 낮은 유기 용매류에 대하여 가용인 폴리이미드가 요망되게 되었다.On the other hand, polyamic acid exhibiting high solvent solubility has a problem in that sufficient liquid crystal display properties are not obtained and volume change due to imidation is likely to occur, and polyimide soluble in organic solvents having a low boiling point is desired. .
그 해결책으로서, 유기 용매 용해성에 유리한 지환식 디카르복실산 무수물을 이용한 테트라카르복실산 2무수물의 합성법을 생각할 수 있다. 그 일례로서, 무수 트리멜리트산클로라이드나, 무수 핵 수소 첨가 트리멜리트산클로라이드를 원료로서 사용함으로써, 다양한 산 2무수물을 제조하는 것이 알려져 있다 (예를 들어, 특허문헌 1).As the solution, a method for synthesizing tetracarboxylic dianhydride using an alicyclic dicarboxylic anhydride which is advantageous for organic solvent solubility can be considered. As an example thereof, it is known to produce various acid dihydrides by using trimellitic anhydride or trimellitic anhydride as a raw material (for example, Patent Document 1).
한편, 디아민에 대해서는, 상기의 산 2무수물의 예와 마찬가지로, 저렴한 원료를 사용하여 각종 특성을 부여하는 방법은 지금까지 알려져 있지 않았다.On the other hand, as for the diamine, as in the above-mentioned acid anhydride example, a method of imparting various characteristics using inexpensive raw materials has not been known so far.
이미드 고리를 갖는 디아민은 지금까지 몇가지 보고되어 왔지만, 모두 용해성이 낮기 때문에, 디아민이 용해하지 않거나, 또는, 분자량이 늘어나지 않는다는 점이 지적되고 있었다.Several diamines having an imide ring have been reported so far, but it has been pointed out that the diamine does not dissolve or the molecular weight does not increase because all have low solubility.
본 발명은, 저렴하고 입수성이 높은 시판되는 원료를 사용함으로써, 디아민과 산 2무수물로부터 얻어지는 폴리아믹산의 폴리머를 이미드화하지 않으면 얻어지지 않는 각종 특성을 용이하게 부여하는 것이 가능한 고용해성의 디아민의 제조 방법 및 얻어지는 디아민, 그리고, 그것으로부터 얻어지는 신규 중합체를 제공하는 것을 목적으로 한다.The present invention provides a high-solution-soluble diamine capable of easily imparting various properties not obtained by imidizing a polymer of a polyamic acid obtained from a diamine and an acid anhydride by using a commercially available raw material that is inexpensive and highly available. It aims at providing the manufacturing method and the diamine obtained, and the novel polymer obtained from it.
본 발명자들은, 상기 과제를 해결하기 위해서 예의 검토를 실시한 결과, 직사슬 또는 분기 사슬의 알킬렌기를 갖는 기존의 디아민 화합물과, 저렴하고 입수성이 높은 시판되는 화합물을 원료로 하여, 디아민과 산 2무수물로부터 얻어지는 폴리아믹산의 폴리머를 이미드화하지 않으면 얻어지지 않는 각종 특성을 용이하게 부여할 수 있는 중합체의 제조 방법을 알아내어, 발명을 완성하였다.The present inventors conducted diligent investigations to solve the above problems, and as a result, diamines and acids 2 were used as raw materials using conventional diamine compounds having a straight chain or branched chain alkylene group and commercially available compounds with high availability. The method of producing a polymer capable of easily imparting various properties that cannot be obtained without imidizing the polymer of the polyamic acid obtained from the anhydride was completed, and the invention was completed.
본 발명은, 이러한 지견에 기초하는 것이며, 하기를 요지로 하는 것이다.This invention is based on this knowledge, and makes the following a summary.
<1> 하기 일반식 (1) 로 나타내는 디아민 화합물.<1> The diamine compound represented by the following general formula (1).
[화학식 1][Formula 1]
식 (1) 중, In equation (1),
R1, R2, R3 및 R4 는 각각 독립적으로, H, CH3 또는 CF3 을 나타내고, 단, R1, R2, R3 및 R4 중, 반드시 하나는 CH3 또는 CF3 을 나타내고,R 1 , R 2 , R 3 and R 4 each independently represent H, CH 3 or CF 3 with the proviso that one of R 1 , R 2 , R 3 and R 4 must always be CH 3 or CF 3 Represents,
W1 은, 단결합 또는 페닐렌을 나타내고, 페닐렌은, 할로겐기, 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 알킬기, 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 알콕시기, 하이드록실기, 시아노기, 디알킬아미노기 (알킬기는, 각각 독립적으로, 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 알킬기이다), 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 에스테르기, 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 아실기, 카르복실기, 알데히드기, 니트로기, Boc 보호한 아미노기로 이루어지는 제 1 군에서 선택되는 치환기로 치환되어도 되고, 2 개의 W1 은 서로 동일해도 되고 상이해도 되고,W 1 represents a single bond or phenylene, and phenylene is a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a straight or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, Cyano group, dialkylamino group (each alkyl group is a C1-C10 linear or branched chain alkyl group each independently), C1-C10 straight chain or branched chain ester group, C1-C10 straight chain Or it may be substituted with a substituent selected from the first group consisting of a branched acyl group, a carboxyl group, an aldehyde group, a nitro group, and a Boc-protected amino group, and the two W 1 may be the same or different from each other,
W2 는 페닐렌을 나타내고, 페닐렌은, 상기 제 1 군에서 선택되는 치환기로 치환되어도 되고, 2 개의 W2 는 서로 동일해도 되고 상이해도 되고,W 2 represents phenylene, and phenylene may be substituted with a substituent selected from the first group, and two W 2 may be the same or different from each other,
L 은, 상기 제 1 군에서 선택되는 치환기로 치환되어 있어도 되는 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 알킬렌기를 나타내고, L 중의 -CH2- 는, -CH=CH-, -C≡C-, -CF2-, -C(CF3)2-, -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -N(CH3)-, -NHCONH-, -N(Boc)CONH-, -NHCON(Boc)-, -N(Boc)CON(Boc)-, -NHCOO-, -OCONH-, -CO-, -S-, -SO2-, -N(Boc)-, -Si(CH3)2OSi(CH3)2-, -Si(CH3)2OSi(CH3)2OSi(CH3)2-, 피페리딘 고리 및 피페라진 고리로 이루어지는 제 2 군에서 선택되는 기로 치환되어 있어도 되고, 단, 제 2 군에서 선택되는 기끼리는, 탄소 원자를 제외한 동일한 원자끼리가 결합하지 않는 조건으로 서로 이웃해도 된다.L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted with a substituent selected from the first group, and -CH 2 -in L represents -CH = CH-, -C≡C -, -CF 2- , -C (CF 3 ) 2- , -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -N (CH 3 )-, -NHCONH -, -N (Boc) CONH-, -NHCON (Boc)-, -N (Boc) CON (Boc)-, -NHCOO-, -OCONH-, -CO-, -S-, -SO 2 -,- N (Boc)-, -Si (CH 3 ) 2 OSi (CH 3 ) 2- , -Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2- , piperidine ring and piperazine ring It may be substituted with a group selected from the second group consisting of, provided that the groups selected from the second group may be adjacent to each other on the condition that the same atoms other than the carbon atoms are not bonded to each other.
<2> 상기 식 (1) 로 나타내는 디아민 화합물로부터 얻어지는, 중합체.<2> A polymer obtained from the diamine compound represented by the formula (1).
본 발명의 중합체를 함유하는 액정 배향제를 사용함으로써, 전압 유지율 및 러빙 내성이 높고, 축적한 전하를 빠르게 완화시키는 것이 가능한 액정 배향막, 및 표시 특성이 우수한 액정 표시 소자가 제공된다.By using the liquid crystal aligning agent containing the polymer of the present invention, a liquid crystal aligning film having high voltage retention and rubbing resistance and capable of quickly alleviating accumulated charges, and a liquid crystal display device having excellent display characteristics are provided.
본 발명은 상기한 바와 같이, 식 (1) 로 나타내는 디아민 화합물 (이하, 특정 디아민이라고 하는 경우가 있다), 및 그 디아민 화합물로부터 얻어지는 중합체에 관한 것이다.As described above, the present invention relates to a diamine compound represented by formula (1) (hereinafter, sometimes referred to as a specific diamine), and a polymer obtained from the diamine compound.
또, 본 발명의 액정 배향제는, 상기 식 (1) 로 나타내는 구조를 갖는 디아민으로부터 얻어지는 중합체 (이하, 특정 중합체라고도 한다) 를 함유하는 액정 배향제이다.Moreover, the liquid crystal aligning agent of this invention is a liquid crystal aligning agent containing the polymer obtained from the diamine which has the structure represented by said Formula (1) (it is also hereafter referred to as a specific polymer).
이하, 각 조건에 대해서 상세히 서술한다.Hereinafter, each condition is explained in full detail.
<특정 디아민><Specific diamine>
상기한 바와 같이, 본 발명에 의한 디아민 화합물은, 식 (1) 로 나타낸다. 여기서 식 (1) 의 각 치환기는 하기하는 바와 같이 정의된다.As described above, the diamine compound according to the present invention is represented by formula (1). Here, each substituent of formula (1) is defined as follows.
R1, R2, R3 및 R4 는 각각 독립적으로 H, CH3 또는 CF3 을 나타내고, 단, R1, R2, R3 및 R4 중, 반드시 하나는 CH3 또는 CF3 을 나타내고,R 1 , R 2 , R 3 and R 4 each independently represent H, CH 3 or CF 3 , provided that one of R 1 , R 2 , R 3 and R 4 necessarily represents CH 3 or CF 3 ,
W1 은, 단결합 또는 페닐렌을 나타내고, 페닐렌은, 할로겐기, 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 알킬기, 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 알콕시기, 하이드록실기, 시아노기, 디알킬아미노기 (알킬기는, 각각 독립적으로, 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 알킬기이다), 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 에스테르기, 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 아실기, 카르복실기, 알데히드기, 니트로기, Boc 보호한 아미노기로 이루어지는 제 1 군에서 선택되는 치환기로 치환되어도 되고, 2 개의 W1 은 서로 동일해도 되고 상이해도 되고,W 1 represents a single bond or phenylene, and phenylene is a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a straight or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, Cyano group, dialkylamino group (each alkyl group is a C1-C10 linear or branched chain alkyl group each independently), C1-C10 straight chain or branched chain ester group, C1-C10 straight chain Or it may be substituted with a substituent selected from the first group consisting of a branched acyl group, a carboxyl group, an aldehyde group, a nitro group, and a Boc-protected amino group, and the two W 1 may be the same or different from each other,
W2 는 페닐렌을 나타내고, 페닐렌은, 상기 제 1 군에서 선택되는 치환기로 치환되어도 되고, 2 개의 W2 는 서로 동일해도 되고 상이해도 되고,W 2 represents phenylene, and phenylene may be substituted with a substituent selected from the first group, and two W 2 may be the same or different from each other,
L 은, 상기 제 1 군에서 선택되는 치환기로 치환되어 있어도 되는 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 알킬렌기를 나타내고, L 중의 -CH2- 는, -CH=CH-, -C≡C-, -CF2-, -C(CF3)2-, -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -N(CH3)-, -NHCONH-, -N(Boc)CONH-, -NHCON(Boc)-, -N(Boc)CON(Boc)-, -NHCOO-, -OCONH-, -CO-, -S-, -SO2-, -N(Boc)-, -Si(CH3)2OSi(CH3)2-, -Si(CH3)2OSi(CH3)2OSi(CH3)2-, 피페리딘 고리 및 피페라진 고리로 이루어지는 제 2 군에서 선택되는 기로 치환되어 있어도 되고, 단, 제 2 군에서 선택되는 기끼리는, 탄소 원자를 제외한 동일한 원자끼리가 결합하지 않는 조건으로 서로 이웃해도 된다.L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted with a substituent selected from the first group, and -CH 2 -in L represents -CH = CH-, -C≡C -, -CF 2- , -C (CF 3 ) 2- , -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -N (CH 3 )-, -NHCONH -, -N (Boc) CONH-, -NHCON (Boc)-, -N (Boc) CON (Boc)-, -NHCOO-, -OCONH-, -CO-, -S-, -SO 2 -,- N (Boc)-, -Si (CH 3 ) 2 OSi (CH 3 ) 2- , -Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2- , piperidine ring and piperazine ring It may be substituted with a group selected from the second group consisting of, provided that the groups selected from the second group may be adjacent to each other on the condition that the same atoms other than the carbon atoms are not bonded to each other.
R1, R2, R3 및 R4 는 각각 독립적으로 H, CH3 또는 CF3 을 나타내고, 단, R1, R2, R3 및 R4 중, 반드시 하나는 CH3 또는 CF3 을 나타낸다.R 1 , R 2 , R 3 and R 4 each independently represent H, CH 3 or CF 3 , provided that one of R 1 , R 2 , R 3 and R 4 necessarily represents CH 3 or CF 3 .
그 중에서도, R1 및 R4 가 CH3 또는 CF3 을 나타내고, R2 및 R3 이 수소 원자를 나타내는 것이 바람직하고, 보다 바람직하게는, R1 및 R4 가 메틸기를 나타내고, R2 및 R3 이 수소 원자를 나타내는 것은 용해성이 높다는 점에서 바람직하다.Among them, R 1 and R 4 represent CH 3 or CF 3 , preferably R 2 and R 3 represent a hydrogen atom, more preferably R 1 and R 4 represent a methyl group, and R 2 and R 3 It is preferable from the viewpoint of high solubility to represent a hydrogen atom.
W1 로는, 단결합 또는 1,4-페닐렌기가 바람직하다.As W 1 , a single bond or a 1,4-phenylene group is preferable.
W2 로는, 1,4-페닐렌기가 바람직하다.As W 2 , a 1,4-phenylene group is preferable.
L 의 탄소 원자수 1 내지 10 의 알킬렌으로는, 직사슬이어도 되고 분기여도 되며, -(CH2)n- (단, n 은 1 내지 10) 로 나타내는 직사슬의 알킬렌이나, 1-메틸메탄-1,1-디일, 1-에틸메탄-1,1-디일, 1-프로필메탄-1,1-디일, 1-메틸에탄-1,2-디일, 1-에틸에탄-1,2-디일, 1-프로필에탄-1,2-디일, 1-메틸프로판-1,3-디일, 1-에틸프로판-1,3-디일, 1-프로필프로판-1,3-디일, 2-메틸프로판-1,3-디일, 2-에틸프로판-1,3-디일, 2-프로필프로판-1,3-디일, 1-메틸부탄-1,4-디일, 1-에틸부탄-1,4-디일, 1-프로필부탄-1,4-디일, 2-메틸부탄-1,4-디일, 2-에틸부탄-1,4-디일, 2-프로필부탄-1,4-디일, 1-메틸펜탄-1,5-디일, 1-에틸펜탄-1,5-디일, 1-프로필펜탄-1,5-디일, 2-메틸펜탄-1,5-디일, 2-에틸펜탄-1,5-디일, 2-프로필펜탄-1,5-디일, 3-메틸펜탄-1,5-디일, 3-에틸펜탄-1,5-디일, 3-프로필펜탄-1,5-디일, 1-메틸헥산-1,6-디일, 1-에틸헥산-1,6-디일, 2-메틸헥산-1,6-디일, 2-에틸헥산-1,6-디일, 3-메틸헥산-1,6-디일, 3-에틸헥산-1,6-디일, 1-메틸헵탄-1,7-디일, 2-메틸헵탄-1,7-디일, 3-메틸헵탄-1,7-디일, 4-메틸헵탄-1,7-디일, 1-페닐메탄-1,1-디일, 1-페닐에탄-1,2-디일, 1-페닐프로판-1,3-디일 등의 분기 알킬렌을 들 수 있다.As the alkylene having 1 to 10 carbon atoms, L may be straight or branched, and straight-chain alkylene represented by-(CH 2 ) n- (where n is 1 to 10) or 1-methyl Methane-1,1-diyl, 1-ethylmethane-1,1-diyl, 1-propylmethane-1,1-diyl, 1-methylethane-1,2-diyl, 1-ethylethane-1,2- Diyl, 1-propylethane-1,2-diyl, 1-methylpropane-1,3-diyl, 1-ethylpropane-1,3-diyl, 1-propylpropane-1,3-diyl, 2-methylpropane -1,3-diyl, 2-ethylpropane-1,3-diyl, 2-propylpropane-1,3-diyl, 1-methylbutane-1,4-diyl, 1-ethylbutane-1,4-diyl , 1-propylbutane-1,4-diyl, 2-methylbutane-1,4-diyl, 2-ethylbutane-1,4-diyl, 2-propylbutane-1,4-diyl, 1-methylpentane- 1,5-diyl, 1-ethylpentane-1,5-diyl, 1-propylpentane-1,5-diyl, 2-methylpentane-1,5-diyl, 2-ethylpentane-1,5-diyl, 2-propylpentane-1,5-diyl, 3-methylpentane-1,5-diyl, 3-ethylpentane-1,5-diyl, 3-propylpentane-1,5-diyl, 1-methylhexane-1 , 6-diyl, 1-ethyl Hexane-1,6-diyl, 2-methylhexane-1,6-diyl, 2-ethylhexane-1,6-diyl, 3-methylhexane-1,6-diyl, 3-ethylhexane-1,6- Diyl, 1-methylheptane-1,7-diyl, 2-methylheptane-1,7-diyl, 3-methylheptane-1,7-diyl, 4-methylheptane-1,7-diyl, 1-phenylmethane And branched alkylenes such as -1,1-diyl, 1-phenylethane-1,2-diyl, and 1-phenylpropane-1,3-diyl.
이들 직사슬 또는 분기의 알킬렌 (-CH2-) 은, -CH=CH-, -C≡C-, -CF2-, -C(CF3)2-, -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -N(CH3)-, -NHCONH-, -N(Boc)CONH-, -NHCON(Boc)-, -N(Boc)CON(Boc)-, -NHCOO-, -OCONH-, -CO-, -S-, -SO2-, -N(Boc)-, -Si(CH3)2OSi(CH3)2-, -Si(CH3)2OSi(CH3)2OSi(CH3)2-, 피페리딘 고리, 및 피페라진 고리인 제 2 군에서 선택되는 기로 치환되어 있어도 된다.These straight chain or branched alkylene (-CH 2- ) is -CH = CH-, -C≡C-, -CF 2- , -C (CF 3 ) 2- , -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -N (CH 3 )-, -NHCONH-, -N (Boc) CONH-, -NHCON (Boc)-, -N (Boc) CON ( Boc)-, -NHCOO-, -OCONH-, -CO-, -S-, -SO 2- , -N (Boc)-, -Si (CH 3 ) 2 OSi (CH 3 ) 2- , -Si ( CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2- , may be substituted with a group selected from the second group which is a piperidine ring and a piperazine ring.
단, 이 때, 제 2 군에서 선택되는 기끼리는, 탄소 원자를 제외한 동일한 원자가 결합하지 않는 조건으로 서로 이웃해도 된다. 바꾸어 말하면, 알킬렌을 치환할 수 있는 제 2 군에서 선택되는 기가 복수 있는 경우에, 제 2 군에서 선택되는 기끼리의 사이의 결합부가, 탄소 원자를 제외한 동일한 원자로 결합하게 되는 경우에는, 제 2 군에서 선택되는 기끼리는 서로 이웃할 수는 없다. 제 2 군에서 선택되는 기끼리의 사이의 결합부가, 탄소 원자끼리이거나, 또는, 서로 상이한 원자로 결합하는 것이라면, 제 2 군에서 선택되는 기끼리가 결합할 수 있다. 바람직하게는, 제 2 군에서 선택되는 기끼리의 사이의 결합부가, 탄소 원자끼리이면, 제 2 군에서 선택되는 기끼리가 결합할 수 있다.However, at this time, groups selected from the second group may be adjacent to each other on the condition that the same atoms other than the carbon atom are not bonded. In other words, when there are a plurality of groups selected from the second group capable of substituting the alkylene, when the bonding portion between the groups selected from the second group is bonded to the same atom except the carbon atom, the second group The military selected from the military cannot be adjacent to each other. If the bonding portion between groups selected from the second group is carbon atoms or is bonded to each other with different atoms, groups selected from the second group can be bonded. Preferably, if the bonding portion between groups selected from the second group is between carbon atoms, groups selected from the second group can be bonded.
본 발명의 다른 양태에 의하면, 제 2 군에서 선택되는 기끼리가 서로 이웃하는 경우는 없다.According to another aspect of the present invention, groups selected from the second group are not adjacent to each other.
W1-L-W2 의 바람직한 구조로는, 하기의 구조를 들 수 있지만, 이들에 한정되지 않는다.In a preferred structure of the W 1 -LW 2 is, there can be the following structure, and is not limited to these.
[화학식 2][Formula 2]
[화학식 3][Formula 3]
[화학식 4][Formula 4]
[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
[화학식 8][Formula 8]
<특정 디아민의 제조 방법><Method for producing a specific diamine>
이하에, 전술한 디아민을 얻는 방법에 대해서 설명한다.Below, the method of obtaining the above-mentioned diamine is demonstrated.
본 발명의 특정 디아민을 합성하는 방법은 특별히 한정되지 않지만, 예를 들어, 하기 식 (A) 로 나타내는 비스말레이미드 화합물과, 하기 식 (B) 로 나타내는 화합물을 반응시켜 하기 식 (C) 로 나타내는 화합물을 얻은 후에, 이것을 이미드화하여 하기 식 (D) 로 나타내는 화합물을 얻은 후, 이것을 식 (1) 로 나타내는 화합물로 변환하는 방법을 들 수 있다.Although the method for synthesizing the specific diamine of the present invention is not particularly limited, for example, a bismaleimide compound represented by the following formula (A) and a compound represented by the following formula (B) are reacted to represent the following formula (C). After the compound is obtained, a method of imidizing this to obtain a compound represented by the following formula (D) and converting it into a compound represented by the formula (1) can be given.
[화학식 9][Formula 9]
식 중, R1, R2, R3, R4, W1, W2, 및 L 은 상기의 의미를 나타내고, Q 는 NO2 또는 보호된 아미노기 (NHPro) 를 나타낸다.In the formula, R 1 , R 2 , R 3 , R 4 , W 1 , W 2 , and L represent the above meaning, and Q represents NO 2 or a protected amino group (NHPro).
아미노기의 보호기 (Pro) 로는, 아세틸기, 트리플루오로아세틸기, 피발로일기, tert-부톡시카르보닐기, 에톡시카르보닐기, 이소프로폭시카르보닐기, 2,2,2-트리클로로에톡시카르보닐기, 벤질옥시카르보닐기, 트리메틸실릴기, 트리에틸실릴기, 디메틸페닐실릴기, tert-부틸디메틸실릴기, tert-부틸디에틸실릴기, 9-플루오레닐 메틸옥시카르보닐기, 프탈로일기, 알릴옥시카르보닐기, p-톨루엔술포닐기, o-니트로벤젠술포닐기 등을 사용할 수 있지만, 이들에 한정은 되지 않는다.As the protecting group (Pro) of the amino group, acetyl group, trifluoroacetyl group, pivaloyl group, tert-butoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group, benzyloxy Carbonyl group, trimethylsilyl group, triethylsilyl group, dimethylphenylsilyl group, tert-butyldimethylsilyl group, tert-butyldiethylsilyl group, 9-fluorenyl methyloxycarbonyl group, phthaloyl group, allyloxycarbonyl group, p- A toluene sulfonyl group, o-nitrobenzenesulfonyl group, and the like can be used, but are not limited to these.
식 (B) 로 나타내는 화합물의 사용량은, 식 (A) 로 나타내는 화합물의 1 몰에 대하여, 2 몰 내지 4 몰인 것이 바람직하고, 2 몰 내지 2.5 몰인 것이 더욱 바람직하다. 식 (B) 로 나타내는 화합물을 과잉량으로 함으로써, 반응을 원활하게 진행시키고, 또한 게다가 부생물을 억제할 수 있다.The amount of the compound represented by the formula (B) is preferably 2 mol to 4 mol, more preferably 2 mol to 2.5 mol, per 1 mol of the compound represented by the formula (A). By making the compound represented by Formula (B) an excess amount, the reaction can proceed smoothly and further, by-products can be suppressed.
본 반응은, 바람직하게는 용매 중에서 실시된다.This reaction is preferably carried out in a solvent.
용매는, 각 원료와 반응하지 않는 용매이면, 제한없이 사용할 수 있다. 예를 들어, DMF, DMSO, DMAc, NMP 등의 비프로톤성 극성 유기 용매 ; Et2O, i-Pr2O, THF (테트라하이드로푸란), TBME (tert-부틸메틸에테르), CPME (시클로펜틸메틸에테르), 디옥산 등의 에테르류 ; 펜탄, 헥산, 헵탄, 석유 에테르 등의 지방족 탄화수소류 ; 벤젠, 톨루엔, 자일렌, 메시틸렌, 클로로벤젠, 디클로로벤젠, 니트로벤젠, 테트랄린 등의 방향족 탄화수소류 ; 클로로포름, 디클로로메탄, 사염화탄소, 디클로로에탄 등의 할로겐계 탄화수소류 ; 아세트산메틸, 아세트산에틸, 아세트산부틸, 프로피온산메틸 등의 저급 지방산 에스테르류 ; 아세토니트릴, 프로피오니트릴, 부티로니트릴 등의 니트릴류 ; 등을 사용할 수 있다.The solvent can be used without limitation as long as it is a solvent that does not react with each raw material. For example, aprotic polar organic solvents such as DMF, DMSO, DMAc, and NMP; Ethers such as Et 2 O, i-Pr 2 O, THF (tetrahydrofuran), TBME (tert-butyl methyl ether), CPME (cyclopentyl methyl ether), and dioxane; Aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, and tetralin; Halogen-based hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and dichloroethane; Lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; Nitriles such as acetonitrile, propionitrile, and butyronitrile; Etc. can be used.
이들 용매는, 반응이 일어나기 용이함 등을 고려하여 적절히 선택할 수 있으며, 1 종 단독으로 또는 2 종 이상 혼합하여 사용할 수 있다. 필요에 따라, 적당한 탈수제나 건조제를 사용하여 용매를 건조시키고, 비수용매로서 사용할 수도 있다.These solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used alone or in combination of two or more. If necessary, the solvent may be dried using a suitable dehydrating agent or desiccant and used as a non-aqueous solvent.
용매의 사용량 (반응 농도) 은 특별히 한정되지 않지만, 비스말레이미드 화합물에 대하여, 0.1 ∼ 100 질량배이다. 바람직하게는 0.5 ∼ 30 질량배이며, 더욱 바람직하게는 1 ∼ 10 질량배이다.Although the usage-amount (reaction concentration) of a solvent is not specifically limited, It is 0.1-100 mass times with respect to the bismaleimide compound. It is preferably 0.5 to 30 mass times, more preferably 1 to 10 mass times.
반응 온도는 특별히 한정되지 않지만, ―100 ℃ 부터 사용하는 용매의 비점까지의 범위, 바람직하게는 ―50 ∼ 150 ℃ 이다. 반응 시간은, 통상적으로0.05 ∼ 350 시간, 바람직하게는 0.5 ∼ 100 시간이다.The reaction temperature is not particularly limited, but is in the range from -100 ° C to the boiling point of the solvent used, preferably -50 to 150 ° C. The reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.
본 반응은 필요에 따라, 무기 염기나 유기 염기의 존재하에 있어서, 반응할 수 있다.This reaction can be reacted, if necessary, in the presence of an inorganic base or an organic base.
반응에 사용하는 염기로는, 수산화나트륨, 수산화칼륨, 수산화리튬, 탄산수소나트륨, 탄산수소칼륨, 인산칼륨, 탄산나트륨, 탄산칼륨, 탄산리튬, 탄산세슘 등의 무기 염기 ; tert-부톡시나트륨, tert-부톡시칼륨, 수소화나트륨, 수소화칼륨 등의 염기 ; 트리메틸아민, 트리에틸아민, 트리프로필아민, 트리이소프로필아민, 트리부틸아민, 디이소프로필에틸아민, 피리딘, 퀴놀린, 콜리딘 등의 아민을 사용할 수 있다. 그 중에서도, 트리에틸아민, 피리딘, tert-부톡시나트륨, tert-부톡시칼륨, 수소화나트륨, 수소화칼륨 등이 바람직하다.Examples of the base used for the reaction include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, and cesium carbonate; bases such as tert-butoxy sodium, tert-butoxy potassium, sodium hydride and potassium hydride; An amine such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline or collidine can be used. Especially, triethylamine, pyridine, tert-butoxy sodium, tert-butoxy potassium, sodium hydride, potassium hydride, etc. are preferable.
염기의 사용량으로는 특별히 한정되지 않지만, 비스말레이미드 화합물에 대하여, 0.1 ∼ 100 질량배이다. 바람직하게는 0 ∼ 30 질량배이며, 더욱 바람직하게는 0 ∼ 10 질량배이다.Although it does not specifically limit as a usage-amount of a base, It is 0.1-100 mass times with respect to the bismaleimide compound. It is preferably 0 to 30 mass times, more preferably 0 to 10 mass times.
식 (D) 로 나타내는 화합물은, 식 (C) 로 나타내는 화합물을 이미드화함으로써 얻을 수 있다.The compound represented by formula (D) can be obtained by imidizing the compound represented by formula (C).
이미드화하는 경우, 아민 성분과 비스말레이미드 화합물의 반응으로 얻어진 식 (C) 로 나타내는 화합물의 용액에 촉매를 첨가하는 화학적 이미드화가 간편하다. 화학적 이미드화는, 비교적 저온에서 이미드화 반응이 진행되어, 이미드화의 과정에서 Pro 기의 분해가 잘 일어나지 않기 때문에 바람직하다.In the case of imidization, chemical imidization is simple, in which a catalyst is added to a solution of the compound represented by formula (C) obtained by reaction of an amine component with a bismaleimide compound. Chemical imidation is preferable because the imidation reaction proceeds at a relatively low temperature, and the decomposition of the Pro group does not easily occur in the process of imidization.
화학적 이미드화는, 이미드화시키고자 하는 화합물을, 유기 용매 중에 있어서 염기성 촉매와 산 무수물의 존재하에서 교반함으로써 실시할 수 있다. 본 반응에 사용하는 유기 용매는, 용해성으로부터 N,N-디메틸포름아미드, N-메틸-2-피롤리돈, γ-부티로락톤 등이 바람직하고, 이들은 1 종 또는 2 종 이상을 혼합하여 사용해도 된다.Chemical imidation can be performed by stirring the compound to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride. As for the organic solvent used in this reaction, N, N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, etc. are preferable from solubility, and these are used alone or in combination of two or more. May be
화합물의 농도는, 화합물의 석출이 잘 일어나지 않는다는 관점에서, 1 ∼ 30 질량% 가 바람직하고, 5 ∼ 20 질량% 가 보다 바람직하다.The concentration of the compound is preferably from 1 to 30% by mass, and more preferably from 5 to 20% by mass, from the viewpoint that precipitation of the compound does not easily occur.
염기성 촉매로는 피리딘, 트리에틸아민, 트리메틸아민, 트리부틸아민, 트리옥틸아민 등을 들 수 있다. 그 중에서도 피리딘은 반응을 진행시키는 데에 적당한 염기성을 가지므로 바람직하다. 또, 산 무수물로는 무수 아세트산, 무수 트리멜리트산, 무수 피로멜리트산 등을 들 수 있으며, 그 중에서도 무수 아세트산을 사용하면 반응 종료 후의 정제가 용이해지므로 바람직하다.Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has basicity suitable for advancing the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, and among these, acetic anhydride is preferred because it facilitates purification after completion of the reaction.
이미드화 반응을 실시할 때의 온도는, ―20 ∼ 140 ℃, 바람직하게는 0 ∼ 100 ℃ 이며, 반응 시간은 1 ∼ 100 시간에 실시할 수 있다. 염기성 촉매의 양은 아믹산기의 0.5 ∼ 30 배몰, 바람직하게는 2 ∼ 20 배몰이며, 산 무수물의 양은 아믹산기의 1 ∼ 50 배몰, 바람직하게는 3 ∼ 30 배몰이다.The temperature at the time of performing the imidization reaction is -20 to 140 deg. C, preferably 0 to 100 deg. C, and the reaction time can be carried out in 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 times mole of the amic acid group, preferably 2 to 20 times mole, and the amount of the acid anhydride is 1 to 50 times mole, preferably 3 to 30 times mole of the amic acid group.
Q 가 NO2 인 경우에 식 (D) 로 나타내는 화합물을 환원하여 식 (1) 로 나타내는 특정 디아민을 제조할 때의 조건을 이하에 서술한다.When Q is NO 2 , conditions for producing a specific diamine represented by Formula (1) by reducing the compound represented by Formula (D) are described below.
환원 반응에 사용되는 촉매는, 시판품으로서 입수할 수 있는 활성탄 담지 금속이 바람직하고, 예를 들어, 팔라듐-활성탄, 백금-활성탄, 로듐-활성탄 등을 들 수 있다. 또, 수산화팔라듐, 산화백금, 라니 니켈 등 반드시 활성탄 담지형의 금속 촉매가 아니어도 된다. 일반적으로 널리 사용되고 있는 팔라듐-활성탄이, 양호한 결과가 얻어지므로 바람직하다.The catalyst used for the reduction reaction is preferably an activated carbon-supported metal available as a commercial product, and examples thereof include palladium-activated carbon, platinum-activated carbon, rhodium-activated carbon, and the like. Moreover, it is not necessary to necessarily be a metal catalyst of activated carbon supported type such as palladium hydroxide, platinum oxide, or Raney nickel. Palladium-activated carbon, which is generally widely used, is preferable because good results can be obtained.
이들 반응은, 수소 분위기하, 상압, 또는 가압 조건하에서 실시된다. 또, 철, 주석, 아연 등의 금속, 혹은 이들의 금속염을 프로톤원과 함께 사용하여 니트로기의 환원을 실시해도 된다. 금속과 금속염은 단체로, 혹은 2 종류 이상을 혼합하여 사용해도 된다.These reactions are carried out under a hydrogen atmosphere, normal pressure, or pressurized conditions. Moreover, you may perform reduction of a nitro group using metals, such as iron, tin, zinc, or these metal salts with a proton source. The metal and the metal salt may be used alone or in a mixture of two or more.
프로톤원으로는, 염산 등의 산, 염화암모늄 등의 암모늄염, 메탄올, 에탄올 등의 프로톤성 용매를 사용할 수 있다.As the proton source, acids such as hydrochloric acid, ammonium salts such as ammonium chloride, and protonic solvents such as methanol and ethanol can be used.
환원 반응을 보다 효과적으로 진행시키기 위해서, 활성탄의 공존하에서 반응을 실시하는 경우도 있다. 이 때, 사용하는 활성탄의 양은 특별히 한정되지 않지만, 디니트로 화합물 (D) 에 대하여 1 ∼ 30 질량% 의 범위가 바람직하고, 10 ∼ 20 질량% 가 보다 바람직하다. 또, 환원 반응을 보다 효과적으로 진행시키기 위해서, 가압하에서 반응을 실시하는 경우도 있다. 이 경우, 벤젠 핵의 환원을 피하기 위해서, 20 기압까지의 가압 범위에서 실시한다. 바람직하게는 10 기압까지의 범위에서 반응을 실시한다.In order to advance the reduction reaction more effectively, the reaction may be carried out in the presence of activated carbon. At this time, the amount of activated carbon to be used is not particularly limited, but is preferably in the range of 1 to 30 mass%, more preferably 10 to 20 mass% with respect to the dinitro compound (D). Moreover, in order to advance a reduction reaction more effectively, a reaction may be performed under pressure. In this case, in order to avoid reduction of the benzene nucleus, it is carried out in a pressure range up to 20 atmospheres. Preferably, the reaction is carried out in a range up to 10 atmospheres.
용매는, 각 원료와 반응하지 않는 용매이면, 제한없이 사용할 수 있다. 예를 들어, DMF, DMSO, DMAc, NMP 등의 비프로톤성 극성 유기 용매 ; Et2O, i-Pr2O, TBME, CPME, THF, 디옥산 등의 에테르류 ; 펜탄, 헥산, 헵탄, 석유 에테르 등의 지방족 탄화수소류 ; 벤젠, 톨루엔, 자일렌, 메시틸렌, 클로로벤젠, 디클로로벤젠, 니트로벤젠, 테트랄린 등의 방향족 탄화수소류 ; 클로로포름, 디클로로메탄, 사염화탄소, 디클로로에탄 등의 할로겐계 탄화수소류 ; 아세트산메틸, 아세트산에틸, 아세트산부틸, 프로피온산메틸 등의 저급 지방산 에스테르류 ; 아세토니트릴, 프로피오니트릴, 부티로니트릴 등의 니트릴류 ; 메탄올, 에탄올 등의 알코올류 ; 등을 사용할 수 있다. 이들 용매는, 반응이 일어나기 용이함 등을 고려하여 적절히 선택할 수 있고, 1 종 단독으로 또는 2 종 이상 혼합하여 사용할 수 있다. 필요에 따라, 적당한 탈수제나 건조제를 사용하여 용매를 건조시키고, 비수용매로서 사용할 수도 있다.The solvent can be used without limitation as long as it is a solvent that does not react with each raw material. For example, aprotic polar organic solvents such as DMF, DMSO, DMAc, and NMP; Ethers such as Et 2 O, i-Pr 2 O, TBME, CPME, THF, and dioxane; Aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, and tetralin; Halogen-based hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and dichloroethane; Lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; Nitriles such as acetonitrile, propionitrile, and butyronitrile; Alcohols such as methanol and ethanol; Etc. can be used. These solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used alone or in combination of two or more. If necessary, the solvent may be dried using a suitable dehydrating agent or desiccant and used as a non-aqueous solvent.
용매의 사용량 (반응 농도) 은 특별히 한정되지 않지만, 디니트로 화합물에 대하여, 0.1 ∼ 100 질량배이다. 바람직하게는 0.5 ∼ 30 질량배이며, 더욱 바람직하게는 1 ∼ 10 질량배이다.Although the usage-amount (reaction concentration) of a solvent is not specifically limited, It is 0.1-100 mass times with respect to the dinitro compound. It is preferably 0.5 to 30 mass times, more preferably 1 to 10 mass times.
반응 온도는 특별히 한정되지 않지만, ―100 ℃ 부터 사용하는 용매의 비점까지의 범위, 바람직하게는 ―50 ∼ 150 ℃ 이다. 반응 시간은, 통상적으로0.05 ∼ 350 시간, 바람직하게는 0.5 ∼ 100 시간이다.The reaction temperature is not particularly limited, but is in the range from -100 ° C to the boiling point of the solvent used, preferably -50 to 150 ° C. The reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.
Q 가 보호된 아민 (NHPro) 인 경우에 식 (D) 로 나타내는 화합물을 탈보호하여 식 (1) 로 나타내는 특정 디아민을 제조할 때의 조건을 이하에 서술한다.When Q is a protected amine (NHPro), conditions under which the compound represented by formula (D) is deprotected to produce a specific diamine represented by formula (1) are described below.
보호기의 탈보호의 방법으로는, 특별히 한정은 되지 않지만, 산 또는 염기 존재하, 가수 분해 후에 중화함으로써 목적물을 얻는 것이 가능하다. 사용하는 산의 예로는, 염산, 황산, 질산, 브롬화수소산 등의 무기산이나 포름산, 아세트산, 옥살산, 트리플루오로아세트산 등의 유기산을 들 수 있으며, 사용하는 염기의 예로는, 수산화나트륨, 탄산수소나트륨, 탄산수소칼륨, 인산칼륨, 탄산나트륨, 탄산칼륨, 탄산리튬, 탄산세슘 등의 무기 염기, 트리메틸아민, 트리에틸아민, 트리프로필아민, 트리이소프로필아민, 트리부틸아민, 디이소프로필에틸아민, 피리딘, 퀴놀린, 콜리딘 등의 유기 아민류 등을 사용해도 된다. 또, 염화알루미늄이나, 트리플루오로보란-디에틸에테르 착물 등의 루이스산 화합물을 사용하여 탈보호를 실시해도 된다. 또, 수소 분위기하의 탈벤질화 반응을 실시해도 된다. 또, 불화수소산, 불화세슘, 불화칼륨, 테트라부틸암모늄플루오리드 등과 같은 불소를 포함하는 산, 무기 염기, 또는 암모늄염 등을 사용해도 된다.Although it does not specifically limit as a method of deprotection of a protecting group, In the presence of an acid or a base, it is possible to obtain a target object by neutralizing after hydrolysis. Examples of the acid used include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, and hydrobromic acid, and organic acids such as formic acid, acetic acid, oxalic acid, and trifluoroacetic acid. Examples of the base used include sodium hydroxide and sodium hydrogen carbonate , Inorganic bases such as potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine , Organic amines such as quinoline and collidine. Moreover, you may perform deprotection using a Lewis acid compound, such as aluminum chloride and a trifluoroborane-diethyl ether complex. Moreover, you may perform a debenzylation reaction in a hydrogen atmosphere. Further, an acid, an inorganic base, or an ammonium salt containing fluorine such as hydrofluoric acid, cesium fluoride, potassium fluoride, tetrabutylammonium fluoride, or the like may be used.
용매에 관해서는, 가수 분해를 방해하지 않는 용매이면 사용할 수 있고, DMF, DMSO, DMAc, NMP 등의 비프로톤성 극성 유기 용매, Et2O, i-Pr2O, TBME, CPME, THF, 디옥산 등의 에테르류, 펜탄, 헥산, 헵탄, 석유 에테르 등의 지방족 탄화수소류, 벤젠, 톨루엔, 자일렌, 메시틸렌, 클로로벤젠, 디클로로벤젠, 니트로벤젠, 테트랄린 등 방향족 탄화수소류, 클로로포름, 디클로로메탄, 사염화탄소, 디클로로에탄 등의 할로겐계 탄화수소류, 아세트산메틸, 아세트산에틸, 아세트산부틸, 프로피온산메틸 등), 니트릴류 (아세토니트릴, 프로피오니트릴, 부티로니트릴 등의 저급 지방산 에스테르류, 메탄올, 에탄올, 1-프로판올, 2-프로판올, 1-부탄올 등의 알코올류, 또는, 물을 사용할 수 있다. 이들 용매는, 반응이 일어나기 용이함 등을 고려하여 적절히 선택할 수 있으며, 이 경우, 상기 용매는 1 종 단독으로 또는 2 종 이상 혼합하여 사용할 수 있다. 또, 루이스산의 사용 등을 고려하여, 적당한 탈수제나 건조제를 사용하여 비수용매로서 사용할 수도 있다.As for the solvent, any solvent that does not interfere with hydrolysis can be used, and aprotic polar organic solvents such as DMF, DMSO, DMAc, NMP, Et 2 O, i-Pr 2 O, TBME, CPME, THF, D Ethers such as oxane, aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, chloroform, dichloro Halogen-based hydrocarbons such as methane, carbon tetrachloride, and dichloroethane, methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc., nitriles (lower fatty acid esters such as acetonitrile, propionitrile, butyronitrile, methanol, ethanol) , 1-propanol, 2-propanol, 1-butanol, alcohols, or water may be used, and these solvents may be appropriately selected in consideration of easy reaction, etc. , The above solvents may be used alone or in combination of two or more, and may be used as a non-aqueous solvent by using a suitable dehydrating agent or drying agent in consideration of the use of Lewis acid or the like.
반응 온도는 ―100 ℃ 부터 사용하는 용매의 비점까지의 범위에서 임의의 온도를 선택할 수 있지만, 바람직하게는 ―50 ∼ 150 ℃ 의 범위이다. 반응 시간은 0.1 ∼ 1000 시간의 범위에서 임의로 선택할 수 있다.The reaction temperature can be any temperature selected from -100 ° C to the boiling point of the solvent used, but is preferably in the range of -50 to 150 ° C. The reaction time can be arbitrarily selected in the range of 0.1 to 1000 hours.
[식 (B) 의 제법][Preparation of formula (B)]
식 (B) 로 나타내는 화합물 중, Q 가 NHPro 인 화합물 (B1) 은, 하기 식 (B1-1) 로 나타내는 디아민과, 아민의 보호기 (Pro) 의 산 클로라이드 혹은, 산 무수물 등을 반응시킴으로써 얻어진다. 이 때, 디아민 (B1-1) 로는, 반응의 복잡화를 억제하는 관점에서, 대칭인 디아민인 것이 바람직하다. 식 중, W1, W2, L, Pro 는 상기의 의미를 나타낸다.Of the compounds represented by the formula (B), the compound (B1) wherein Q is NHPro is obtained by reacting the diamine represented by the following formula (B1-1) with an acid chloride of an amine protecting group (Pro) or an acid anhydride. . At this time, the diamine (B1-1) is preferably a symmetric diamine from the viewpoint of suppressing the complexity of the reaction. In the formula, W 1 , W 2 , L, and Pro represent the above meaning.
[화학식 10][Formula 10]
(Pro)-Cl 로는, 클로로포름산메틸, 클로로포름산에틸, 클로로포름산n-프로필, 클로로포름산i-프로필, 클로로포름산n-부틸, 클로로포름산i-부틸, 클로로포름산t-부틸, 클로로포름산벤질, 클로로포름산-9-플루오레닐, 아세틸클로라이드, 트리플루오로아세틸클로라이드, 피발로일클로라이드, tert-부톡시카르보닐클로라이드, 에톡시카르보닐클로라이드, 이소프로폭시카르보닐클로라이드, 2,2,2-트리클로로에톡시카르보닐클로라이드, 벤질옥시카르보닐클로라이드, 트리메틸실릴클로라이드, 트리에틸실릴클로라이드, 디메틸페닐실릴클로라이드, tert-부틸디메틸실릴클로라이드, tert-부틸디에틸실릴클로라이드, 9-플루오레닐메틸옥시카르보닐클로라이드, 프탈로일클로라이드, 알릴옥시카르보닐클로라이드, p-톨루엔술포닐클로라이드, o-니트로벤젠술포닐클로라이드 등을 들 수 있지만, 이들에 한정은 되지 않는다.As (Pro) -Cl, methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, i-propyl chloroformate, n-butyl chloroformate, i-butyl chloroformate, t-butyl chloroformate, benzyl chloroformate, benzyl chloroform Acid-9-fluorenyl, acetyl chloride, trifluoroacetyl chloride, pivaloyl chloride, tert-butoxycarbonyl chloride, ethoxycarbonyl chloride, isopropoxycarbonyl chloride, 2,2,2-triclo Loethoxycarbonylchloride, benzyloxycarbonylchloride, trimethylsilylchloride, triethylsilylchloride, dimethylphenylsilylchloride, tert-butyldimethylsilylchloride, tert-butyldiethylsilylchloride, 9-fluorenylmethyloxycar Carbonyl chloride, phthaloyl chloride, allyloxycarbonyl chloride, p-toluenesulfonyl chloride, o-nitrobenzenesulfonylchlora Id and the like, but are not limited to these.
(Pro)2O 로는, 2탄산디메틸, 2탄산디에틸, 2탄산디t-부틸, 2탄산디벤질 등을 들 수 있지만, 이들에 한정되지 않는다.Examples of (Pro) 2 O include, but are not limited to, dimethyl dicarbonate, diethyl dicarbonate, dit-butyl dicarbonate, dibenzyl dicarbonate, and the like.
상기의 식 (B1) 로 나타내는 화합물을 얻는 반응은, 바람직하게는 염기의 존재하에 실시된다. 염기로는, 수산화나트륨, 수산화칼륨, 수산화리튬, 탄산수소나트륨, 탄산수소칼륨, 인산칼륨, 탄산나트륨, 탄산칼륨, 탄산리튬, 탄산세슘 등의 무기 염기 ; 트리메틸아민, 트리에틸아민, 트리프로필아민, 트리이소프로필아민, 트리부틸아민, 디이소프로필에틸아민, 피리딘, 퀴놀린, 콜리딘 등의 아민류 ; 수소화나트륨, 수소화칼륨, tert-부톡시나트륨, tert-부톡시칼륨 등을 사용할 수 있다. 염기를 사용하는 경우에는, 반응의 후처리의 조작성을 고려하여, 아민류의 사용이 바람직하다.The reaction for obtaining the compound represented by the formula (B1) is preferably carried out in the presence of a base. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate and cesium carbonate; Amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline and collidine; Sodium hydride, potassium hydride, tert-butoxy sodium, tert-butoxy potassium, and the like can be used. When using a base, it is preferable to use amines in consideration of the operability of the post-treatment of the reaction.
반응 용매로는, 반응 조건하에 있어서 안정적이고, 불활성이고, 목적으로 하는 반응을 방해하지 않는 용매이면 모두 사용할 수 있다. 예를 들어, 디메틸포름아미드, 디메틸술폭시드, 디메틸아세테이트, N-메틸피롤리돈 등의 비프로톤성 극성 유기 용매 ; 디에틸에테르, 이소프로필에테르, THF, TBME, CPME, 디옥산 등의 에테르 ; 펜탄, 헥산, 헵탄, 석유 에테르 등의 지방족 탄화수소 ; 벤젠, 톨루엔, 자일렌, 메시틸렌, 클로로벤젠, 디클로로벤젠, 니트로벤젠, 테트랄린 등의 방향족 탄화수소 ; 클로로포름, 디클로로메탄, 사염화탄소, 디클로로에탄 등의 할로겐계 탄화수소 ; 아세트산메틸, 아세트산에틸, 아세트산부틸, 프로피온산메틸 등의 저급 지방산 에스테르 ; 아세토니트릴, 프로피오니트릴, 부티로니트릴 등의 니트릴 등을 사용할 수 있다.As the reaction solvent, any solvent that is stable under the reaction conditions, is inert, and does not interfere with the desired reaction can be used. For example, aprotic polar organic solvents such as dimethylformamide, dimethyl sulfoxide, dimethyl acetate, and N-methylpyrrolidone; Ethers such as diethyl ether, isopropyl ether, THF, TBME, CPME, and dioxane; Aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, and tetralin; Halogen-based hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, and dichloroethane; Lower fatty acid esters such as methyl acetate, ethyl acetate, butyl acetate and methyl propionate; Nitrile, such as acetonitrile, propionitrile, and butyronitrile, etc. can be used.
이들 용매는, 반응이 일어나기 용이함 등을 고려하여 적절히 선택할 수 있으며, 1 종 단독으로 또는 2 종 이상 혼합하여 사용할 수 있다. 상기 용매는, 적당한 탈수제나 건조제를 사용하여 물을 함유하지 않는 용매로서 사용할 수도 있다.These solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used alone or in combination of two or more. The said solvent can also be used as a solvent which does not contain water using a suitable dehydrating agent or drying agent.
반응 온도는, 바람직하게는, ―100 ℃ 이상부터 사용하는 반응 용매의 비점 온도까지의 온도 범위를 선택할 수 있지만, 보다 바람직하게는 ―50 ∼ 150 ℃, 특히 바람직하게는 0 ∼ 60 ℃ 이다. 반응 시간은, 0.1 ∼ 1000 시간, 보다 바람직하게는 0.5 ∼ 50 시간이다.The reaction temperature is preferably from -100 ° C or higher to a temperature range from the boiling point temperature of the reaction solvent to be used, more preferably -50 to 150 ° C, particularly preferably 0 to 60 ° C. The reaction time is 0.1 to 1000 hours, more preferably 0.5 to 50 hours.
상기 반응식 (1) 에 의해 얻어진 식 2 로 나타내는 화합물은, 증류, 재결정, 또는 실리카 겔 등의 칼럼 크로마토그래피 등으로 정제해도 되지만, 정제하지 않고 그대로 다음 공정에 사용해도 된다.The compound represented by the formula (2) obtained by the reaction formula (1) may be purified by column chromatography such as distillation, recrystallization, or silica gel, but may be used in the next step without purification.
식 (B) 로 나타내는 화합물 중, Q 가 NO2 인 화합물 (B2) 는, 하기 식 (B2-1) 로 나타내는 화합물을 탈보호함으로써 얻어진다. 탈보호의 조건으로는, 상기 방법을 사용할 수 있다. 식 중, W1, W2, L, Pro 는 상기의 의미를 나타낸다.Of the compounds represented by the formula (B), the compound (B2) wherein Q is NO 2 is obtained by deprotecting the compound represented by the following formula (B2-1). As a condition for deprotection, the above method can be used. In the formula, W 1 , W 2 , L, and Pro represent the above meaning.
[화학식 11][Formula 11]
또, 식 (B2-1) 로 나타내는 화합물은, 하기 식 (B2-3) 으로 나타내는 할로겐화 및 술포닐화 {메탄술포닐 (OMs), 에탄술포닐 (OEs), p-톨루엔술포닐 (OTs), 트리플루오로메탄술포닐 (OTf) 등} 된 화합물과, 하기 식 (B2-4) 로 나타내는 니트로화 된 페놀을 반응시킴으로써 얻어진다. 식 중, W1, W2 는 상기의 의미를 나타내고, L1 은 상기 L 로부터 CH2 (엄밀하게 말하면 산소 원자로 치환된 CH2) 를 하나 제거한 알킬렌을 나타낸다.Moreover, the compound represented by Formula (B2-1) is halogenated and sulfonylated with the following Formula (B2-3) {methanesulfonyl (OMs), ethanesulfonyl (OEs), p-toluenesulfonyl (OTs), Trifluoromethanesulfonyl (OTf), etc.} and a nitrated phenol represented by the following formula (B2-4). In the formula, W 1 and W 2 represent the above meaning, and L 1 represents alkylene in which one CH 2 (strictly substituted CH 2 ) is removed from L.
[화학식 12][Formula 12]
본 공정의 반응에 있어서 출발 원료로서 사용하는 식 (B2-3) 으로 나타내는 화합물과, 식 (B2-4) 로 나타내는 니트로화 된 페놀은 시판품으로서 입수하거나, 공지된 방법에 의해 제조할 수 있다.The compound represented by formula (B2-3) used as a starting material in the reaction of this step, and the nitrated phenol represented by formula (B2-4) can be obtained as a commercial product or can be produced by a known method.
반응 형식은, 회전식 (배치식), 유통식 중 어느 것이어도 된다.The reaction type may be either a rotary type (batch type) or a flow type.
반응은, 염기 존재하에서 실시하는 것이 바람직하다. 염기로는, 예를 들어 수산화나트륨, 수산화칼륨 등의 알칼리 금속 수산화물, 탄산나트륨, 탄산칼륨 등의 알칼리 금속 탄산염, 탄산수소나트륨, 탄산수소칼륨 등의 알칼리 금속 중탄산염, 인산칼륨, 1,8-디아자비시클로[5,4,0]-7-운데센 등의 유기 염기 등을 식 (B2-3) 으로 나타내는 화합물에 대하여 1 ∼ 4 당량 사용할 수 있다.It is preferable to perform reaction in presence of a base. As the base, for example, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, potassium phosphate, and 1,8-diazabi 1-4 equivalents can be used with respect to the compound represented by Formula (B2-3), such as an organic base, such as cyclo [5,4,0] -7-undecene.
그 중에서도, 탄산나트륨, 탄산칼륨 등의 알칼리 금속 탄산염이 바람직하다. 특히, 미분말 탄산칼륨을 사용하면, 반응성이 향상되므로 바람직하다. 시판되고 있는 미분말 탄산칼륨으로는, FG-F20 (아사히 가라스 주식회사 제조) (등록상표) 등이 있다.Especially, alkali metal carbonates, such as sodium carbonate and potassium carbonate, are preferable. Particularly, the use of fine powdered potassium carbonate is preferred because it improves reactivity. Commercially available fine powder potassium carbonate includes FG-F20 (manufactured by Asahi Glass Co., Ltd.) (registered trademark) and the like.
반응 용매로는, 디메틸포름아미드 (DMF), 디메틸아세트아미드 (DMAc), 1,3-디메틸-2-이미다졸리디논 (DMI), 디메틸술폭시드 (DMSO), N-메틸피롤리돈이 바람직하고, N-메틸피롤리돈이 특히 바람직하다.As the reaction solvent, dimethylformamide (DMF), dimethylacetamide (DMAc), 1,3-dimethyl-2-imidazolidinone (DMI), dimethyl sulfoxide (DMSO), and N-methylpyrrolidone are preferred. And N-methylpyrrolidone is particularly preferred.
반응 온도는, 예를 들어 ―10 ∼ 100 ℃, 바람직하게는 0 ∼ 80 ℃ 이다.The reaction temperature is, for example, -10 to 100 ° C, preferably 0 to 80 ° C.
반응 시간은, 배치 처리의 경우에는 0.5 ∼ 20 시간, 바람직하게는 1 ∼ 15 시간이다.The reaction time is 0.5 to 20 hours in the case of a batch treatment, preferably 1 to 15 hours.
본 반응은, 바람직하게는 용매 중에서 실시된다. 바람직한 용매나 반응 조건은, 상기 화합물 (1) 의 제조 조건과 동일하다.This reaction is preferably carried out in a solvent. Preferred solvents and reaction conditions are the same as those of the compound (1).
상기 각 반응에 의해 얻어진 각 단계에 있어서의 목적물은, 증류, 재결정, 또는 실리카 겔 등의 칼럼 크로마토그래피 등으로 정제해도 되고, 정제하지 않고, 반응액인 채로 다음의 단계에 제공할 수도 있다.The target product in each step obtained by each of the above reactions may be purified by column chromatography such as distillation, recrystallization, or silica gel, or may be provided in the next step without being purified and remaining as a reaction solution.
<중합체><Polymer>
본 발명의 중합체는, 상기 디아민을 사용하여 얻어지는 중합체이다. 구체예로는, 폴리아믹산, 폴리아믹산에스테르, 폴리이미드, 폴리우레아, 폴리아미드 등을 들 수 있다.The polymer of the present invention is a polymer obtained using the diamine. As a specific example, polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide, etc. are mentioned.
<디이소시아네이트 성분><Diisocyanate component>
상기 일반식 (1) 로 나타내는 디아민과의 반응에 의해 폴리아미드를 부여하는 디이소시아네이트 성분으로서, 예를 들어, 방향족 디이소시아네이트, 지방족 디이소시아네이트 등을 들 수 있다. 바람직한 디이소시아네이트 성분은, 방향족 디이소시아네이트, 지방족 디이소시아네이트이다.As a diisocyanate component which gives a polyamide by reaction with the diamine represented by the said general formula (1), aromatic diisocyanate, aliphatic diisocyanate, etc. are mentioned, for example. Preferred diisocyanate components are aromatic diisocyanate and aliphatic diisocyanate.
여기서, 방향족 디이소시아네이트란, 디이소시아네이트 구조 (O=C=N-Y-N=C=O) 의 기 Y 가, 방향족 고리를 포함하는 구조를 포함하는 것을 말한다. 또 지방족 디이소시아네이트란, 상기 이소시아네이트 구조의 기 Y 가, 고리형 또는 비고리형의 지방족 구조로 이루어지는 것을 말한다.Here, the aromatic diisocyanate means that the group Y of the diisocyanate structure (O = C = N-Y-N = C = O) contains a structure containing an aromatic ring. Moreover, an aliphatic diisocyanate means that the group Y of the said isocyanate structure consists of a cyclic or acyclic aliphatic structure.
방향족 디이소시아네이트의 구체예로는, o-페닐렌디이소시아네이트, m-페닐렌디이소시아네이트, p-페닐렌디이소시아네이트, 톨루엔디이소시아네이트류 (예를 들어, 2,4-디이소시안산톨릴렌), 1,4-디이소시안산-2-메톡시벤젠, 2,5-디이소시안산자일렌류, 2,2'-비스(4-디이소시안산페닐)프로판, 4,4'-디이소시안산디페닐메탄, 4,4'-디이소시안산디페닐에테르, 4,4'-디이소시안산디페닐술폰, 3,3'-디이소시안산디페닐술폰, 2,2'-디이소시안산벤조페논 등을 들 수 있다. 방향족 디이소시아네이트로는, 바람직하게는, m-페닐렌디이소시아네이트, p-페닐렌디이소시아네이트, 2,4-디이소시안산톨릴렌을 들 수 있다.Specific examples of the aromatic diisocyanate include o-phenylenediisocyanate, m-phenylenediisocyanate, p-phenylenediisocyanate, toluene diisocyanates (e.g., tolylene 2,4-diisocyanate), 1,4 -Diisocyanate-2-methoxybenzene, 2,5-diisocyanate xylenes, 2,2'-bis (4-diisocyanate phenyl) propane, 4,4'-diisocyanate diphenylmethane, 4 And 4,4'-diisocyanate diphenyl ether, 4,4'-diisocyanate diphenyl sulfone, 3,3'-diisocyanate diphenyl sulfone, and 2,2'-diisocyanate benzophenone. . As aromatic diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, tolylene 2,4-diisocyanate is preferably mentioned.
지방족 디이소시아네이트의 구체예로는, 이소포론디이소시아네이트, 헥사메틸렌디이소시아네이트, 테트라메틸에틸렌디이소시아네이트 등을 들 수 있다. 지방족 디이소시아네이트로는, 바람직하게는 이소포론디이소시아네이트를 들 수 있다. 그 중에서도, 이소포론디이소시아네이트와 2,4-디이소시안산톨릴렌이 중합 반응성의 관점에서 바람직하고, 또한, 이소포론디이소시아네이트가, 입수성, 중합 반응성의 관점에서 보다 바람직하다.As a specific example of aliphatic diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, tetramethylethylene diisocyanate, etc. are mentioned. As an aliphatic diisocyanate, isophorone diisocyanate is mentioned preferably. Among them, isophorone diisocyanate and tolylene 2,4-diisocyanate are preferred from the viewpoint of polymerization reactivity, and isophorone diisocyanate is more preferred from the viewpoint of availability and polymerization reactivity.
<테트라카르복실산 2무수물><Tetracarboxylic dianhydride>
상기 일반식 (1) 로 나타내는 디아민과의 반응에 의해 폴리이미드 (전구체) 를 부여하는 성분인 테트라카르복실산 2무수물은, 하기 식 (X) 로 나타낸다.The tetracarboxylic dianhydride which is a component that provides a polyimide (precursor) by reaction with the diamine represented by the general formula (1) is represented by the following formula (X).
[화학식 13][Formula 13]
X1 은 테트라카르복실산 유도체에서 유래하는 4 가의 유기기이고, 그 구조는 특별히 한정되는 것은 아니다. 또, 폴리이미드 전구체 중의 X1 은, 중합체의 용매에 대한 용해성이나 액정 배향제로서 사용하는 경우의 도포성, 액정 배향막으로 했을 경우에 있어서의 액정의 배향성, 전압 유지율, 축적 전하 등, 필요하게 되는 특성의 정도에 따라 적절히 선택되며, 동일 중합체 중에 1 종류여도 되고, 2 종류 이상이 혼재하고 있어도 된다.X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited. In addition, X 1 in the polyimide precursor is required such as solubility in a solvent of a polymer and coating properties when used as a liquid crystal aligning agent, alignment property of a liquid crystal when used as a liquid crystal aligning film, voltage retention, and accumulated charge. It is appropriately selected according to the degree of properties, and may be one kind of the same polymer, or two or more kinds may be mixed.
X1 의 구체예를 굳이 나타낸다면, 국제 공개 공보 2015/119168 의 13 항 ∼ 14 항에 게재되는, 식 (X-1) ∼ (X-46) 의 구조 등을 들 수 있다.If deliberately shows a specific example of X 1, it can be given a structure such as the formula (X-1) ~ (X -46) is placed in 13 ~ 14 of International Publication No. 2015/119168.
이하에, 바람직한 X1 의 구조를 나타내지만, 본 발명은 이들에 한정되는 것은 아니다.In the following, represents the structure of a preferred X 1, the present invention is not limited to these.
[화학식 14][Formula 14]
<디카르복실산><Dicarboxylic acid>
상기 일반식 (1) 로 나타내는 디아민과의 반응에 의해 폴리아미드를 부여하는 디카르복실산 성분을 구축하기 위한 모노머 화합물의 구체예로는, 테레프탈산, 이소프탈산, 2-메틸-이소프탈산, 4-메틸-이소프탈산, 5-메틸-이소프탈산, 5-알릴옥시이소프탈산, 5-알릴옥시카르보닐이소프탈산, 5-프로파길옥시이소프탈산, 5-아세틸옥시이소프탈산, 5-벤조일아미드이소프탈산, 테트라플루오로이소프탈산, 메틸테레프탈산, 테트라플루오로테레프탈산, 2,6-나프탈렌디카르복실산, 1,6-나프탈렌디카르복실산, 2,6-안트라센디카르복실산, 1,6-안트라센디카르복실산, 4,4'-디카르복시비페닐, 3,4'-디카르복시비페닐, 2,3'-디카르복시비페닐, 2,4'-디카르복시비페닐, 4,4'-디카르복시디페닐에테르, 3,4'-디카르복시디페닐에테르, 2,3'-디카르복시디페닐에테르, 2,4'-디카르복시디페닐에테르, 3,3'-디카르복시디페닐에테르, 3,3'-디메틸-4,4'-디카르복시비페닐, 4,4'-디메틸-3,3'-디카르복시비페닐, 2,2'-디메틸-4,4'-디카르복시비페닐, 3,3'-디메톡시-4,4'-디카르복시비페닐, 4,4'-디메톡시-3,3'-디카르복시비페닐, 2,2'-디메톡시-4,4'-디카르복시비페닐, 4,4'-디카르복시벤조페논, 3,4'-디카르복시벤조페논, 3,3'-디카르복시벤조페논, 4,4'-디카르복시디페닐메탄, 3,4'-디카르복시디페닐메탄, 3,3'-디카르복시디페닐메탄, 4,4'-디카르복시디페닐아미드, 3,4-디카르복시디페닐아미드, 4,4'-디카르복시디페닐술폰, 3,4'-디카르복시디페닐술폰, 3,3'-디카르복시디페닐술폰, 2,2'-디카르복시디페닐프로판, 1,4-비스(4-카르복시페녹시)벤젠, 1,3-비스(4-카르복시페녹시)벤젠, N-[3{(4-카르복시페닐)카르보닐아미노}페닐](4-카르복시페닐)포름아미드, N-[4{(4-카르복시페닐)카르보닐아미노}페닐](4-카르복시페닐)포름아미드, 4,4'-(4-카르복시페녹시페닐)메탄, 4,4'-비스(4-카르복시페녹시)디페닐술폰, 2,2'-비스[4-(4-카르복시페녹시)페닐]프로판, 2,2-비스(4-카르복시페닐)헥사플루오로프로판, 2,2'-비스[4-(4-카르복시페녹시)페닐]헥사플루오로프로판, 1,5-비스(4-카르복시페닐)펜탄, 1,4-비스(4-카르복시페닐)부탄, 1,3-비스(4-카르복시페닐)프로판, 4,4'-디(카르복시페닐)펜탄-1,5-디오에이트, 4,4'-디(카르복시페닐)헥산-1,6-디오에이트, 4,4'-디(카르복시페닐)헵탄-1,7-디오에이트 등의 방향족 혹은 방향족 함유 디카르복실산 및 이들의 산 할로겐화물 그리고 알킬에스테르화물을 들 수 있다.Specific examples of the monomer compound for constructing a dicarboxylic acid component that provides a polyamide by reaction with the diamine represented by the general formula (1) are terephthalic acid, isophthalic acid, 2-methyl-isophthalic acid, 4- Methyl-isophthalic acid, 5-methyl-isophthalic acid, 5-allyloxyisophthalic acid, 5-allyloxycarbonylisophthalic acid, 5-propagyloxyisophthalic acid, 5-acetyloxyisophthalic acid, 5-benzoylamide isophthalic acid, Tetrafluoroisophthalic acid, methyl terephthalic acid, tetrafluoro terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 1,6-anthracenedicica Leic acid, 4,4'-dicarboxybiphenyl, 3,4'-dicarboxybiphenyl, 2,3'-dicarboxybiphenyl, 2,4'-dicarboxybiphenyl, 4,4'-di Carboxydiphenyl ether, 3,4'-dicarboxydiphenyl ether, 2,3'-dicarboxydiphenyl ether, 2,4'-dicarboxydipe Ether, 3,3'-dicarboxydiphenyl ether, 3,3'-dimethyl-4,4'-dicarboxybiphenyl, 4,4'-dimethyl-3,3'-dicarboxybiphenyl, 2,2 '-Dimethyl-4,4'-dicarboxybiphenyl, 3,3'-dimethoxy-4,4'-dicarboxybiphenyl, 4,4'-dimethoxy-3,3'-dicarboxybiphenyl, 2,2'-dimethoxy-4,4'-dicarboxybiphenyl, 4,4'-dicarboxybenzophenone, 3,4'-dicarboxybenzophenone, 3,3'-dicarboxybenzophenone, 4, 4'-dicarboxydiphenylmethane, 3,4'-dicarboxydiphenylmethane, 3,3'-dicarboxydiphenylmethane, 4,4'-dicarboxydiphenylamide, 3,4-dicarboxydiphenyl Amide, 4,4'-dicarboxydiphenylsulfone, 3,4'-dicarboxydiphenylsulfone, 3,3'-dicarboxydiphenylsulfone, 2,2'-dicarboxydiphenylpropane, 1,4- Bis (4-carboxyphenoxy) benzene, 1,3-bis (4-carboxyphenoxy) benzene, N- [3 {(4-carboxyphenyl) carbonylamino} phenyl] (4-carboxyphenyl) formamide, N- [4 {(4-carboxyphenyl) carbo Amino} phenyl] (4-carboxyphenyl) formamide, 4,4 '-(4-carboxyphenoxyphenyl) methane, 4,4'-bis (4-carboxyphenoxy) diphenylsulfone, 2,2'- Bis [4- (4-carboxyphenoxy) phenyl] propane, 2,2-bis (4-carboxyphenyl) hexafluoropropane, 2,2'-bis [4- (4-carboxyphenoxy) phenyl] hexa Fluoropropane, 1,5-bis (4-carboxyphenyl) pentane, 1,4-bis (4-carboxyphenyl) butane, 1,3-bis (4-carboxyphenyl) propane, 4,4'-di ( Carboxyphenyl) pentane-1,5-dioate, 4,4'-di (carboxyphenyl) hexane-1,6-dioate, 4,4'-di (carboxyphenyl) heptane-1,7-dioate, etc. And aromatic or aromatic-containing dicarboxylic acids, and acid halides and alkyl esters thereof.
나아가서는 1,3-디카르복시시클로헥산, 1,4-디카르복시시클로헥산, 1,2-디카르복시시클로부탄, 1,3-디카르복시시클로부탄, 비스(4-카르복시시클로헥실)메탄, 비스(4-카르복시-3-메틸시클로헥실)메탄, 비스(4-카르복시시클로헥실)에테르, 비스(4-카르복시-3-메틸시클로헥실)에테르 등의 지환식 디카르복실산 및 이들의 산 할로겐화물 그리고 알킬에스테르화물을 들 수 있으며, 또 이들의 2 종류 이상의 혼합물을 사용할 수도 있다.Furthermore, 1,3-dicarboxycyclohexane, 1,4-dicarboxycyclohexane, 1,2-dicarboxycyclobutane, 1,3-dicarboxycyclobutane, bis (4-carboxycyclohexyl) methane, bis ( Alicyclic dicarboxylic acids such as 4-carboxy-3-methylcyclohexyl) methane, bis (4-carboxycyclohexyl) ether, bis (4-carboxy-3-methylcyclohexyl) ether and acid halides thereof, and Alkyl esterification is mentioned, and mixtures of two or more of these can also be used.
상기 식 (1) 로 나타내는 디아민 화합물을 포함하는 디아민 성분과의 중합 반응에 의해, 본원 발명의 중합체를 얻는 데 있어서는, 공지된 합성 수법을 이용할 수 있다. 일반적으로는 디이소시아네이트 성분, 디카르복실산 성분 및 테트라카르복실산 성분에서 선택되는 적어도 1 종과 디아민 성분을 유기 용매 중에서 반응시키는 방법이다. 디이소시아네이트 성분, 디카르복실산 성분 및 테트라카르복실산 성분에서 선택되는 적어도 1 종과 디아민 성분의 반응은, 유기 용매 중에서 비교적 용이하게 진행되고, 또한 부생성물이 발생하지 않는 점에서 유리하다.In obtaining the polymer of the present invention by polymerization reaction with a diamine component containing the diamine compound represented by the formula (1), a known synthetic technique can be used. In general, it is a method of reacting at least one member selected from a diisocyanate component, a dicarboxylic acid component, and a tetracarboxylic acid component and a diamine component in an organic solvent. The reaction of at least one selected from a diisocyanate component, a dicarboxylic acid component and a tetracarboxylic acid component and a diamine component proceeds relatively easily in an organic solvent, and is advantageous in that by-products do not occur.
디이소시아네이트 성분, 디카르복실산 성분 및 테트라카르복실산 성분에서 선택되는 적어도 1 종과 디아민 성분의 반응에 사용하는 유기 용매로는, 생성한 중합체가 용해하는 것이면 특별히 한정되지 않는다. 그 구체예를 이하에 든다.The organic solvent used for the reaction of at least one selected from the diisocyanate component, the dicarboxylic acid component and the tetracarboxylic acid component and the diamine component is not particularly limited as long as the resulting polymer is dissolved. The specific example is given below.
여기서 사용 가능한 유기 용매로는, N,N-디메틸포름아미드, N,N-디메틸아세트아미드, N-메틸-2-피롤리돈, N-에틸-2-피롤리돈, N-메틸카프로락탐, 디메틸술폭시드, 테트라메틸우레아, 피리딘, 디메틸술폰, γ-부티로락톤, 이소프로필알코올, 메톡시메틸펜탄올, 디펜텐, 에틸아밀케톤, 메틸노닐케톤, 메틸에틸케톤, 메틸이소 아밀케톤, 메틸이소프로필케톤, 메틸셀로솔브, 에틸셀로솔브, 메틸셀로솔브아세테이트, 에틸셀로솔브아세테이트, 부틸카르비톨, 에틸카르비톨, 에틸렌글리콜, 에틸렌글리콜모노아세테이트, 에틸렌글리콜모노이소프로필에테르, 에틸렌글리콜모노부틸에테르, 프로필렌글리콜, 프로필렌글리콜모노아세테이트, 프로필렌글리콜모노메틸에테르, 프로필렌글리콜-tert-부틸에테르, 디프로필렌글리콜모노메틸에테르, 디에틸렌글리콜, 디에틸렌글리콜모노아세테이트, 디에틸렌글리콜디메틸에테르, 디프로필렌글리콜모노아세테이트모노메틸에테르, 디프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노에틸에테르, 디프로필렌글리콜모노아세테이트모노에틸에테르, 디프로필렌글리콜모노프로필에테르, 디프로필렌글리콜모노아세테이트모노프로필에테르, 3-메틸-3-메톡시부틸아세테이트, 트리프로필렌글리콜메틸에테르, 3-메틸-3-메톡시부탄올, 디이소프로필에테르, 에틸이소부틸에테르, 디이소부틸렌, 아밀아세테이트, 부틸부티레이트, 부틸에테르, 디이소부틸케톤, 메틸시클로헥센, 프로필에테르, 디헥실에테르, 디옥산, n-헥산, n-펜탄, n-옥탄, 디에틸에테르, 시클로헥사논, 에틸렌카보네이트, 프로필렌카보네이트, 락트산메틸, 락트산에틸, 아세트산메틸, 아세트산에틸, 아세트산n-부틸, 아세트산프로필렌글리콜모노에틸에테르, 피루브산메틸, 피루브산에틸, 3-메톡시프로피온산메틸, 3-에톡시프로피온산메틸에틸, 3-메톡시프로피온산에틸, 3-에톡시프로피온산, 3-메톡시프로피온산, 3-메톡시프로피온산프로필, 3-메톡시프로피온산부틸, 디글라임, 4-하이드록시-4-메틸-2-펜타논, 3-메톡시-N,N-디메틸프로판아미드, 3-에톡시-N,N-디메틸프로판아미드, 3-부톡시-N,N-디메틸프로판아미드 등을 들 수 있다. 이들은 단독으로 사용해도 되고, 혼합하여 사용해도 된다.Examples of the organic solvent usable here include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, Dimethyl sulfoxide, tetramethylurea, pyridine, dimethylsulfone, γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethylamylketone, methylnonylketone, methylethylketone, methylisoamylketone, methyl Isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethyl Glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, di Propylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, Amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate , Propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate , Propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxypropionate methyl, 3-ethoxypropionate methylethyl, 3-methoxypropionic acid ethyl, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3- Propyl methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N -Dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, and the like. These may be used alone or in combination.
또, 유기 용매 중의 수분은 중합 반응을 저해하는 원인이 되므로, 유기 용매는 가능한 한 탈수 건조시킨 것을 사용하는 것이 바람직하다.Moreover, since moisture in the organic solvent causes the polymerization reaction to be inhibited, it is preferable to use a dehydrated and dried organic solvent as much as possible.
디이소시아네이트 성분, 디카르복실산 성분 및 테트라카르복실산 성분에서 선택되는 적어도 1 종과 디아민 성분을 유기 용매 중에서 반응시킬 때에는, 디아민 성분을 유기 용매에 분산 혹은 용해시킨 용액을 교반시키고, 디이소시아네이트 성분, 디카르복실산 성분 및 테트라카르복실산 성분에서 선택되는 적어도 1 종을 그대로, 또는 유기 용매에 분산 혹은 용해시켜 첨가하는 방법, 반대로 디이소시아네이트 성분, 디카르복실산 성분 및 테트라카르복실산 성분에서 선택되는 적어도 1 종을 유기 용매에 분산 혹은 용해시킨 용액에 디아민 성분을 첨가하는 방법, 디이소시아네이트 성분, 디카르복실산 성분 및 테트라카르복실산 성분체에서 선택되는 적어도 1 종과 디아민 성분을 번갈아 첨가하는 방법 등을 들 수 있으며, 이들 중 어느 방법을 사용해도 된다. 또, 디이소시아네이트 성분, 디카르복실산 성분 및 테트라카르복실산 성분에서 선택되는 적어도 1 종 또는 디아민 성분이 복수 종의 화합물로 이루어지는 경우에는, 미리 혼합한 상태에서 반응시켜도 되고, 개별적으로 순차 반응시켜도 되고, 또한 개별적으로 반응시킨 저분자량체를 혼합 반응시켜 고분자량체로 해도 된다.When reacting at least one type selected from a diisocyanate component, a dicarboxylic acid component, and a tetracarboxylic acid component with a diamine component in an organic solvent, a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the diisocyanate component , A method of adding at least one selected from the dicarboxylic acid component and the tetracarboxylic acid component as it is or by dispersing or dissolving it in an organic solvent, conversely, in the diisocyanate component, the dicarboxylic acid component and the tetracarboxylic acid component A method of adding a diamine component to a solution in which at least one selected substance is dispersed or dissolved in an organic solvent, alternately adding at least one selected from diisocyanate component, dicarboxylic acid component and tetracarboxylic acid component and diamine component How to do it, etc., any of these methods The. Moreover, when at least 1 type selected from a diisocyanate component, a dicarboxylic acid component, and a tetracarboxylic-acid component or a diamine component consists of multiple types of compounds, you may react in a pre-mixed state, or may react individually individually. Alternatively, the low-molecular-weight substances reacted individually may be mixed to make a high-molecular-weight substance.
그 때의 중합 온도는 ―20 ℃ 내지 150 ℃ 의 임의의 온도를 선택할 수 있지만, 바람직하게는 ―5 ℃ 내지 100 ℃ 의 범위이다. 또, 반응은 임의의 농도로 실시할 수 있지만, 농도가 지나치게 낮으면 고분자량의 중합체를 얻는 것이 어려워지고, 농도가 지나치게 높으면 반응액의 점성이 지나치게 높아져서 균일한 교반이 곤란해지므로, 디이소시아네이트 성분, 디카르복실산 성분 및 테트라카르복실산 성분에서 선택되는 적어도 1 종과 디아민 성분의 반응 용액 중에서의 합계 농도가, 바람직하게는 1 ∼ 50 질량%, 보다 바람직하게는 5 ∼ 30 질량% 이다. 반응 초기는 고농도로 실시하고, 그 후, 유기 용매를 추가할 수 있다.The polymerization temperature at that time can be any temperature of -20 ° C to 150 ° C, but is preferably in the range of -5 ° C to 100 ° C. Further, the reaction can be carried out at an arbitrary concentration, but if the concentration is too low, it is difficult to obtain a polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring becomes difficult, and thus the diisocyanate component , The total concentration in the reaction solution of at least one selected from the dicarboxylic acid component and the tetracarboxylic acid component and the diamine component is preferably 1 to 50 mass%, more preferably 5 to 30 mass%. The initial reaction is carried out at a high concentration, and thereafter, an organic solvent can be added.
본원 발명의 중합체의 중합 반응에 있어서는, 디이소시아네이트 성분, 디카르복실산 성분 및 테트라카르복실산 성분에서 선택되는 적어도 1 종의 합계 몰수와, 디아민 성분의 합계 몰수의 비는 0.8 ∼ 1.2 인 것이 바람직하다. 통상적인 중축합 반응과 마찬가지로, 이 몰비가 1.0 에 가까울수록 생성하는 중합체의 분자량은 커진다.In the polymerization reaction of the polymer of the present invention, the ratio of the total number of moles of at least one selected from the diisocyanate component, the dicarboxylic acid component and the tetracarboxylic acid component to the total mole number of the diamine component is preferably 0.8 to 1.2. Do. As with the conventional polycondensation reaction, the closer this mole ratio is to 1.0, the greater the molecular weight of the resulting polymer.
본원 발명의 중합체의 반응 용액으로부터, 생성한 중합체를 회수하는 경우에는, 반응 용액을 빈용매에 투입하여 침전시키면 된다. 침전에 사용하는 빈용매로는 메탄올, 아세톤, 헥산, 부틸셀로솔브, 헵탄, 메틸에틸케톤, 메틸이소부틸케톤, 에탄올, 톨루엔, 벤젠, 물 등을 들 수 있다. 빈용매에 투입하여 침전시킨 중합체는 여과하여 회수한 후, 상압 혹은 감압하에서, 상온 혹은 가열하여 건조시킬 수 있다. 또, 침전 회수한 중합체를, 유기 용매에 재용해시켜, 재침전 회수하는 조작을 2 ∼ 10 회 반복하면, 중합체 중의 불순물을 줄일 수 있다. 이 때의 빈용매로서, 예를 들어, 알코올류, 케톤류, 탄화수소 등을 들 수 있고, 이들 중에서 선택되는 3 종류 이상의 빈용매를 사용하면, 보다 한층 정제의 효율이 오르므로 바람직하다.When the produced polymer is recovered from the reaction solution of the polymer of the present invention, the reaction solution may be introduced into a poor solvent and precipitated. Poor solvents used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated by being introduced into the poor solvent is collected by filtration and then dried under normal pressure or reduced pressure at room temperature or by heating. Moreover, if the operation of reprecipitating and recovering the polymer precipitated and reprecipitating and recovering it is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and the use of three or more poor solvents selected from these is preferable since the efficiency of purification is further improved.
이와 같은 본원 발명의 중합체 중, 폴리우레아는, 예를 들어, 하기 식 [1] 로 나타내는 반복 단위를 갖는 중합체이다.Among these polymers of the present invention, polyurea is, for example, a polymer having a repeating unit represented by the following formula [1].
[화학식 15][Formula 15]
(식 [1] 중, A1 은 2 가의 유기기이고, A2 는 하기 식 (A2) 로 나타내는 2 가의 기이고,(In formula [1], A 1 is a divalent organic group, A 2 is a divalent group represented by the following formula (A2),
[화학식 16][Formula 16]
식 (A2) 중, R1, R2, R3, R4, W1, W2, 및 L 은 상기의 의미를 나타내고, C1 및 C2 는 수소 원자 또는 탄소수 1 ∼ 3 의 알킬기이고, 각각 동일해도 되고 상이해도 된다.) In the formula (A2), R 1 , R 2 , R 3 , R 4 , W 1 , W 2 , and L represent the above meaning, C 1 and C 2 are a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, Each may be the same or different.)
상기 식 [1] 에 있어서, A1 및 A2 가 각각 1 종류이고 동일한 반복 단위를 갖는 중합체여도 되고, 또, A1 이나 A2 가 복수 종이고 상이한 구조의 반복 단위를 갖는 중합체여도 된다.In the formula [1], A 1 and A 2 may each be one type and a polymer having the same repeating unit, or may be a polymer in which A 1 or A 2 are plural and have repeating units having different structures.
상기 식 [1] 에 있어서, A1 은 원료인 디이소시아네이트 성분에서 유래하는 기이다. 또, A2 는 원료인 디아민 성분에서 유래하는 기이다.In the formula [1], A 1 is a group derived from a diisocyanate component as a raw material. Moreover, A 2 is a group derived from the diamine component which is a raw material.
본 발명의 바람직한 양태에 의하면, A1 로는 상기에서 예시한 바람직한 디이소시아네이트 성분에서 유래하는 기가 바람직하다.According to a preferred embodiment of the present invention, A 1 is preferably a group derived from the preferred diisocyanate component exemplified above.
폴리이미드 전구체는, 예를 들어, 하기 식 [2] 로 나타내는 반복 단위를 갖는 중합체이다.The polyimide precursor is a polymer having a repeating unit represented by the following formula [2], for example.
[화학식 17][Formula 17]
식 [2] 에 있어서, A3 은, 각각 독립적으로 4 가의 유기기이고, A2 는 상기 식 (A2) 로 나타내는 2 가의 기이다. R11 은, 수소 원자, 또는 탄소수 1 ∼ 5 의 알킬기이고, C1 ∼ C2 는 각각 독립적으로 수소 원자, 또는 치환기를 가져도 되는 탄소수 1 ∼ 10 의 알킬기, 탄소수 2 ∼ 10 의 알케닐기, 또는 탄소수 2 ∼ 10 의 알키닐기이다.In Formula [2], A 3 is a tetravalent organic group each independently, and A 2 is a divalent group represented by the formula (A2). R 11 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and C 1 to C 2 are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or It is an alkynyl group having 2 to 10 carbon atoms.
R11 에 있어서의 상기 알킬기의 구체예로는, 메틸기, 에틸기, 프로필기, i-프로필기, n-부틸기, i-부틸기, s-부틸기, t-부틸기, n-펜틸기 등을 들 수 있다. 가열에 의한 이미드화하기 쉽다는 관점에서, R11 은, 수소 원자, 또는 메틸기가 바람직하다.Specific examples of the alkyl group for R 11 include methyl group, ethyl group, propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, and n-pentyl group. Can be mentioned. From the viewpoint of easy imidization by heating, R 11 is preferably a hydrogen atom or a methyl group.
폴리아미드는, 예를 들어, 하기 식 [3] 으로 나타내는 반복 단위를 갖는 중합체이다.Polyamide is a polymer having a repeating unit represented by the following formula [3], for example.
[화학식 18][Formula 18]
식 [3] 에 있어서, A4 는, 각각 독립적으로 디카르복실산에서 유래하는 2 가의 유기기이고, A2, C1 및 C2 는 상기한 바와 같다.In Formula [3], A 4 is a bivalent organic group each independently derived from dicarboxylic acid, and A 2 , C 1 and C 2 are as described above.
또한, 본 발명의 중합체를 제조할 때에, 디이소시아네이트 성분, 디카르복실산 성분 및 테트라카르복실산 성분 중 2 종 또는 3 종을 동시에, 또는 순차 반응시켜도 되고, 예를 들어, 디이소시아네이트 성분과 테트라카르복실산 성분을 반응시킨 경우에는, 상기 식 [1] 로 나타내는 반복 단위와 상기 식 [2] 로 나타내는 반복 단위를 갖는 중합체인 폴리우레아폴리아믹산이 얻어진다.Moreover, when manufacturing the polymer of this invention, 2 or 3 types of diisocyanate component, dicarboxylic acid component, and tetracarboxylic acid component may be reacted simultaneously or sequentially, for example, diisocyanate component and tetra When the carboxylic acid component is reacted, a polyurea polyamic acid that is a polymer having a repeating unit represented by the formula [1] and a repeating unit represented by the formula [2] is obtained.
<폴리아믹산의 제조 방법><Method for producing polyamic acid>
본 발명에 사용되는 폴리이미드 전구체인 폴리아믹산은, 이하에 나타내는 방법에 의해 합성할 수 있다.The polyamic acid which is a polyimide precursor used in the present invention can be synthesized by the method shown below.
구체적으로는, 테트라카르복실산 2무수물과 디아민을 유기 용매의 존재하에서 ―20 ∼ 150 ℃, 바람직하게는 0 ∼ 70 ℃ 에 있어서, 30 분 ∼ 24 시간, 바람직하게는 1 ∼ 12 시간 반응시킴으로써 합성할 수 있다.Specifically, it is synthesized by reacting tetracarboxylic dianhydride and diamine at -20 to 150 ° C, preferably 0 to 70 ° C, in the presence of an organic solvent for 30 minutes to 24 hours, preferably 1 to 12 hours. can do.
상기의 반응에 사용하는 유기 용매는, 모노머 및 중합체의 용해성으로부터 N,N-디메틸포름아미드, N-메틸-2-피롤리돈, γ-부티로락톤 등이 바람직하고, 이들은 1 종 또는 2 종 이상을 혼합하여 사용해도 된다.The organic solvent used for the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, γ-butyrolactone, etc. from the solubility of monomers and polymers. You may mix and use the above.
중합체의 농도는, 중합체의 석출이 잘 일어나지 않고, 또한 고분자량체가 얻기 쉽다는 관점에서, 1 ∼ 30 질량% 가 바람직하고, 5 ∼ 20 질량% 가 보다 바람직하다.The concentration of the polymer is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint that the precipitation of the polymer does not occur easily and the high molecular weight body is easily obtained.
상기와 같이 하여 얻어진 폴리아믹산은, 반응 용액을 잘 교반시키면서 빈용매에 주입함으로써, 중합체를 석출시켜 회수할 수 있다. 또, 석출을 수 회 실시하고, 빈용매로 세정 후, 상온 혹은 가열 건조시킴으로써 정제된 폴리아믹산의 분말을 얻을 수 있다. 빈용매는, 특별히 한정되지 않지만, 물, 메탄올, 에탄올, 2-프로판올, 헥산, 부틸셀로솔브, 아세톤, 톨루엔 등을 들 수 있고, 물, 메탄올, 에탄올, 2-프로판올 등이 바람직하다.The polyamic acid obtained as described above can be recovered by depositing a polymer by injecting the reaction solution into a poor solvent while stirring well. Moreover, the powder of the purified polyamic acid can be obtained by performing precipitation several times, washing with a poor solvent, and drying at room temperature or by heating. The poor solvent is not particularly limited, and examples include water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, and toluene. Water, methanol, ethanol, 2-propanol, and the like are preferred.
<폴리이미드의 제조 방법><Method for producing polyimide>
본 발명에 사용되는 폴리이미드는, 상기 폴리아믹산을 이미드화함으로써 제조할 수 있다.The polyimide used in the present invention can be produced by imidizing the polyamic acid.
폴리아믹산으로부터 폴리이미드를 제조하는 경우, 디아민 성분과 테트라카르복실산 2무수물의 반응으로 얻어진 상기 폴리아믹산의 용액에 촉매를 첨가하는 화학적 이미드화가 간편하다. 화학적 이미드화는, 비교적 저온에서 이미드화 반응이 진행되고, 이미드화의 과정에서 중합체의 분자량 저하가 잘 일어나지 않기 때문에 바람직하다.When polyimide is prepared from polyamic acid, chemical imidation is simple by adding a catalyst to the solution of the polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride. Chemical imidation is preferable because the imidation reaction proceeds at a relatively low temperature, and the molecular weight of the polymer does not easily decrease in the course of imidization.
화학적 이미드화는, 이미드화시키고자 하는 중합체를, 유기 용매 중에 있어서 염기성 촉매와 산 무수물의 존재하에서 교반함으로써 실시할 수 있다. 유기 용매로는 전술한 중합 반응 시에 사용하는 용매를 사용할 수 있다. 염기성 촉매로는 피리딘, 트리에틸아민, 트리메틸아민, 트리부틸아민, 트리옥틸아민 등을 들 수 있다. 그 중에서도 피리딘은 반응을 진행시키는 데에 적당한 염기성을 가지므로 바람직하다. 또, 산 무수물로는 무수 아세트산, 무수 트리멜리트산, 무수 피로멜리트산 등을 들 수 있으며, 그 중에서도 무수 아세트산을 사용하면 반응 종료 후의 정제가 용이해지므로 바람직하다.Chemical imidation can be performed by stirring the polymer to be imidized in the presence of a basic catalyst and an acid anhydride in an organic solvent. As the organic solvent, a solvent used in the polymerization reaction described above can be used. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferred because it has basicity suitable for advancing the reaction. Further, examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among these, acetic anhydride is preferred because it facilitates purification after completion of the reaction.
이미드화 반응을 실시할 때의 온도는, ―20 ∼ 140 ℃, 바람직하게는 0 ∼ 100 ℃ 이며, 반응 시간은 1 ∼ 100 시간에 실시할 수 있다. 염기성 촉매의 양은 폴리아믹산기의 0.5 ∼ 30 배몰, 바람직하게는 2 ∼ 20 배몰이며, 산 무수물의 양은 폴리아믹산기의 1 ∼ 50 배몰, 바람직하게는 3 ∼ 30 배몰이다. 얻어지는 중합체의 이미드화율은, 촉매량, 온도, 반응 시간을 조절함으로써 제어할 수 있다.The temperature at the time of performing the imidization reaction is -20 to 140 deg. C, preferably 0 to 100 deg. C, and the reaction time can be carried out in 1 to 100 hours. The amount of the basic catalyst is 0.5 to 30 times mole of the polyamic acid group, preferably 2 to 20 times mole, and the amount of the acid anhydride is 1 to 50 times mole, preferably 3 to 30 times mole of the polyamic acid group. The imidation rate of the obtained polymer can be controlled by adjusting the catalyst amount, temperature, and reaction time.
폴리아믹산의 이미드화 반응 후의 용액에는, 첨가한 촉매 등이 잔존하고 있으므로, 이하에 서술하는 수단에 의해, 얻어진 이미드화 중합체를 회수하고, 유기 용매로 재용해하여, 본 발명의 액정 배향제로 하는 것이 바람직하다.Since the added catalyst or the like remains in the solution after the imidization reaction of the polyamic acid, the obtained imidized polymer is recovered by the means described below, and redissolved with an organic solvent to obtain a liquid crystal aligning agent of the present invention. desirable.
상기와 같이 하여 얻어지는 폴리이미드의 용액은, 잘 교반시키면서 빈용매에 주입함으로써, 중합체를 석출시킬 수 있다. 석출을 수 회 실시하고, 빈용매로 세정 후, 상온 혹은 가열 건조시켜 정제된 중합체의 분말을 얻을 수 있다.The solution of the polyimide obtained as described above can be precipitated by injecting it into a poor solvent while stirring well. Precipitation is carried out several times, washed with a poor solvent, and then dried at room temperature or by heating to obtain a purified polymer powder.
상기 빈용매는, 특별히 한정되지 않지만, 메탄올, 2-프로판올, 아세톤, 헥산, 부틸셀로솔브, 헵탄, 메틸에틸케톤, 메틸이소부틸케톤, 에탄올, 톨루엔, 벤젠 등을 들 수 있고, 메탄올, 에탄올, 2-프로판올, 아세톤 등이 바람직하다.The poor solvent is not particularly limited, and examples include methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and the like, and methanol and ethanol. , 2-propanol, acetone and the like are preferred.
<폴리이미드 전구체-폴리아믹산에스테르의 제조><Preparation of polyimide precursor-polyamic acid ester>
본 발명에 사용되는 폴리이미드 전구체인 폴리아믹산에스테르는, 이하에 나타내는 (i), (ii) 또는 (iii) 의 제법으로 제조할 수 있다.The polyamic acid ester which is a polyimide precursor used in the present invention can be produced by the production method of (i), (ii) or (iii) shown below.
(i) 폴리아믹산으로부터 제조하는 경우(i) When prepared from polyamic acid
폴리아믹산에스테르는, 상기와 같이 제조된 폴리아믹산을 에스테르화함으로써 제조할 수 있다. 구체적으로는, 폴리아믹산과 에스테르화제를 유기 용제의 존재하에서 ―20 ℃ ∼ 150 ℃, 바람직하게는 0 ℃ ∼ 50 ℃ 에 있어서, 30 분 ∼ 24 시간, 바람직하게는 1 ∼ 4 시간 반응시킴으로써 제조할 수 있다.The polyamic acid ester can be produced by esterifying the polyamic acid prepared as described above. Specifically, the polyamic acid and the esterifying agent are prepared by reacting at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C in the presence of an organic solvent for 30 minutes to 24 hours, preferably 1 to 4 hours. You can.
에스테르화제로는, 정제에 의해 용이하게 제거할 수 있는 것이 바람직하며, N,N-디메틸포름아미드디메틸아세탈, N,N-디메틸포름아미드디에틸아세탈, N,N-디메틸포름아미드디프로필아세탈, N,N-디메틸포름아미드디네오펜틸부틸아세탈, N,N-디메틸포름아미드디-t-부틸아세탈, 1-메틸-3-p-톨릴트리아젠, 1-에틸-3-p-톨릴트리아젠, 1-프로필-3-p-톨릴트리아젠, 4-(4,6-디메톡시-1,3,5-트리아진-2-일)-4-메틸모르폴리늄클로라이드 등을 들 수 있다. 에스테르화제의 첨가량은, 폴리아믹산의 반복 단위 1 몰에 대하여, 2 ∼ 6 몰 당량이 바람직하다.As the esterifying agent, it is preferable that it can be easily removed by purification, N, N-dimethylformamide dimethylacetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamidedineopentylbutylacetal, N, N-dimethylformamidedi-t-butylacetal, 1-methyl-3-p-tolyltriagene, 1-ethyl-3-p-tolyltriagene , 1-propyl-3-p-tolyltrigen, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride, and the like. The amount of the esterifying agent added is preferably 2 to 6 molar equivalents to 1 mole of the repeating unit of the polyamic acid.
유기 용제로는, 예를 들어, N-메틸-2-피롤리돈, N-에틸-2-피롤리돈 또는 γ-부티로락톤, N,N-디메틸포름아미드, N,N-디메틸아세트아미드, 디메틸술폭시드 또는 1,3-디메틸-이미다졸리디논을 들 수 있다. 또, 폴리이미드 전구체의 용매 용해성이 높은 경우에는, 메틸에틸케톤, 시클로헥사논, 시클로펜타논, 4-하이드록시-4-메틸-2-펜타논, 또는 하기 식 [D-1] ∼ 식 [D-3] 으로 나타내는 용매를 사용할 수 있다.Examples of the organic solvent include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide , Dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone. Moreover, when the solvent solubility of a polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formula [D-1] to formula [ D-3] can be used.
[화학식 19][Formula 19]
식 [D-1] 중, D1 은 탄소수 1 ∼ 3 의 알킬기를 나타내고, 식 [D-2] 중, D2 는 탄소수 1 ∼ 3 의 알킬기를 나타내고, 식 [D-3] 중, D3 은 탄소수 1 ∼ 4 의 알킬기를 나타낸다.In formula [D-1], D 1 represents an alkyl group having 1 to 3 carbon atoms, in formula [D-2], D 2 represents an alkyl group having 1 to 3 carbon atoms, and in formula [D-3], D 3 Represents a C1-C4 alkyl group.
이들 용매는 단독으로 사용해도 되고, 혼합하여 사용해도 된다. 또한, 폴리이미드 전구체를 용해시키지 않는 용매이더라도, 생성한 폴리이미드 전구체가 석출하지 않는 범위에서, 상기 용매에 혼합하여 사용해도 된다. 또, 용매 중의 수분은 중합 반응을 저해하고, 나아가서는 생성한 폴리이미드 전구체를 가수 분해시키는 원인이 되므로, 용매는 탈수 건조시킨 것을 사용하는 것이 바람직하다.These solvents may be used alone or in combination. Moreover, even if it is a solvent which does not melt | dissolve a polyimide precursor, you may use it in the range in which the produced | generated polyimide precursor does not precipitate, mixing with the said solvent. Moreover, since moisture in the solvent inhibits the polymerization reaction and further causes hydrolysis of the resulting polyimide precursor, it is preferable to use a solvent that is dehydrated and dried.
상기의 반응에 사용하는 용매는, 폴리머의 용해성으로부터 N,N-디메틸포름아미드, N-메틸-2-피롤리돈, 또는 γ-부티로락톤이 바람직하고, 이들은 1 종 또는 2 종 이상을 혼합하여 사용해도 된다. 제조 시의 농도는, 폴리머의 석출이 잘 일어나지 않고, 또한 고분자량체가 얻기 쉽다는 점에서, 1 ∼ 30 질량% 가 바람직하고, 5 ∼ 20 질량% 가 보다 바람직하다.The solvent used for the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or γ-butyrolactone from the solubility of the polymer, and these are mixed one or two or more. You may use it. 1-30 mass% is preferable and 5-20 mass% is more preferable at the concentration at the time of manufacture in that precipitation of a polymer does not occur easily and a high molecular weight body is easy to obtain.
(ii) 테트라카르복실산디에스테르디클로라이드와 디아민의 반응에 의해 제조하는 경우(ii) When prepared by reaction of tetracarboxylic acid diester dichloride and diamine
폴리아믹산에스테르는, 테트라카르복실산디에스테르디클로라이드와 디아민으로부터 제조할 수 있다.The polyamic acid ester can be produced from tetracarboxylic acid diester dichloride and diamine.
구체적으로는, 테트라카르복실산디에스테르디클로라이드와 디아민을 염기와 유기 용제의 존재하에서 ―20 ℃ ∼ 150 ℃, 바람직하게는 0 ℃ ∼ 50 ℃ 에 있어서, 30 분 ∼ 24 시간, 바람직하게는 1 ∼ 4 시간 반응시킴으로써 제조할 수 있다.Specifically, tetracarboxylic acid diester dichloride and diamine are present at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C in the presence of a base and an organic solvent, for 30 minutes to 24 hours, preferably 1 to It can be prepared by reacting for 4 hours.
상기 염기에는, 피리딘, 트리에틸아민, 4-디메틸아미노피리딘 등을 사용할 수 있지만, 반응이 온화하게 진행되기 위해서 피리딘이 바람직하다. 염기의 첨가량은, 제거가 용이한 양이고, 또한 고분자량체가 얻기 쉽다는 점에서, 테트라카르복실산디에스테르디클로라이드에 대하여, 2 ∼ 4 배몰인 것이 바람직하다.Pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used as the base, but pyridine is preferred for the reaction to proceed gently. It is preferable that it is 2-4 times mole with respect to the tetracarboxylic-acid diester dichloride because the addition amount of a base is an amount which is easy to remove and a high molecular weight body is easy to obtain.
상기의 반응에 사용하는 용매는, 모노머 및 폴리머의 용해성으로부터 N-메틸-2-피롤리돈, 또는 γ-부티로락톤이 바람직하고, 이들은 1 종 또는 2 종 이상을 혼합하여 사용해도 된다. 제조 시의 폴리머 농도는, 폴리머의 석출이 잘 일어나지 않고, 또한 고분자량체가 얻기 쉽다는 점에서, 1 ∼ 30 질량% 가 바람직하고, 5 ∼ 20 질량% 가 보다 바람직하다. 또, 테트라카르복실산디에스테르디클로라이드의 가수 분해를 방지하기 위해서, 폴리아믹산에스테르의 제조에 사용하는 용매는 가능한 한 탈수되어 있는 것이 바람직하고, 질소 분위기 중에서, 외기의 혼입을 방지하는 것이 바람직하다.The solvent used for the above reaction is preferably N-methyl-2-pyrrolidone or γ-butyrolactone from the solubility of monomers and polymers, and these may be used alone or in combination of two or more. 1-30 mass% is preferable, and 5-20 mass% is more preferable at the point of a polymer concentration at the time of manufacture that precipitation of a polymer does not occur easily and a high molecular weight body is easy to obtain. Moreover, in order to prevent the hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the production of the polyamic acid ester is desirably dehydrated as much as possible, and it is preferable to prevent the incorporation of outside air in a nitrogen atmosphere.
(iii) 테트라카르복실산디에스테르와 디아민으로부터 제조하는 경우(iii) When prepared from tetracarboxylic acid diesters and diamines
폴리아믹산에스테르는, 테트라카르복실산디에스테르와 디아민을 중축합함으로써 제조할 수 있다.The polyamic acid ester can be produced by polycondensing a tetracarboxylic acid diester and diamine.
구체적으로는, 테트라카르복실산디에스테르와 디아민을 축합제, 염기, 및 유기 용제의 존재하에서 0 ℃ ∼ 150 ℃, 바람직하게는 0 ℃ ∼ 100 ℃ 에 있어서, 30 분 ∼ 24 시간, 바람직하게는 3 ∼ 15 시간 반응시킴으로써 제조할 수 있다.Specifically, the tetracarboxylic acid diester and diamine are present in the presence of a condensing agent, a base, and an organic solvent at 0 ° C to 150 ° C, preferably 0 ° C to 100 ° C, for 30 minutes to 24 hours, preferably 3 It can be produced by reacting for 15 hours.
상기 축합제에는, 트리페닐포스파이트, 디시클로헥실카르보디이미드, 1-에틸-3-(3-디메틸아미노프로필)카르보디이미드 염산염, N,N'-카르보닐디이미다졸, 디메톡시-1,3,5-트리아지닐메틸모르폴리늄, O-(벤조트리아졸-1-일)-N,N,N',N'-테트라메틸우로늄테트라플루오로보레이트, O-(벤조트리아졸-1-일)-N,N,N',N'-테트라메틸우로늄헥사플루오로포스페이트, (2,3-디하이드로-2-티옥소-3-벤조옥사졸릴)포스폰산디페닐 등을 사용할 수 있다. 축합제의 첨가량은, 테트라카르복실산디에스테르에 대하여 2 ∼ 3 배몰이 바람직하다.Examples of the condensing agent include triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N'-carbonyldiimidazole, and dimethoxy-1 , 3,5-triazinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluroniumtetrafluoroborate, O- (benzotriazole- 1-yl) -N, N, N ', N'-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzooxazolyl) diphenyl phosphonate, etc. can be used You can. The amount of the condensing agent added is preferably 2 to 3 times the mole relative to the tetracarboxylic acid diester.
상기 염기에는, 피리딘, 트리에틸아민 등의 3 급 아민을 사용할 수 있다. 염기의 첨가량은, 제거가 용이한 양이고, 또한 고분자량체가 얻기 쉽다는 점에서, 디아민 성분에 대하여 2 ∼ 4 배몰이 바람직하다.As the base, tertiary amines such as pyridine and triethylamine can be used. 2-4 times mole is preferable with respect to the diamine component from the point that an addition amount of a base is an amount which is easy to remove and a high molecular weight body is easy to obtain.
또, 상기 반응에 있어서, 루이스산을 첨가제로서 첨가함으로써 반응이 효율적으로 진행된다. 루이스산으로는, 염화리튬, 브롬화리튬 등의 할로겐화리튬이 바람직하다. 루이스산의 첨가량은 디아민 성분에 대하여 0 ∼ 1.0 배몰이 바람직하다.In addition, in the above reaction, the reaction proceeds efficiently by adding a Lewis acid as an additive. As the Lewis acid, lithium halide such as lithium chloride and lithium bromide is preferred. The amount of Lewis acid added is preferably 0 to 1.0 times mole relative to the diamine component.
상기 세 가지 폴리아믹산에스테르의 제조 방법 중에서도, 고분자량의 폴리아믹산에스테르가 얻어지기 때문에, 상기 (i) 또는 상기 (ii) 의 제법이 특히 바람직하다.Among the above three methods for producing polyamic acid esters, the production method of (i) or (ii) is particularly preferred because a high molecular weight polyamic acid ester is obtained.
상기와 같이 하여 얻어지는 폴리아믹산에스테르의 용액은, 잘 교반시키면서 빈용매에 주입함으로써, 폴리머를 석출시킬 수 있다. 석출을 수 회 실시하고, 빈용매로 세정 후, 상온 혹은 가열 건조시켜 정제된 폴리아믹산에스테르의 분말을 얻을 수 있다. 빈용매는, 특별히 한정되지 않지만, 물, 메탄올, 에탄올, 헥산, 부틸셀로솔브, 아세톤, 톨루엔 등을 들 수 있다.The solution of the polyamic acid ester obtained as described above can be precipitated by injecting it into a poor solvent while stirring well. The powder of the purified polyamic acid ester can be obtained by performing precipitation several times, washing with a poor solvent, and drying at room temperature or by heating. The poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, hexane, butyl cellosolve, acetone, and toluene.
본 발명의 중합체를 제조하려면, 상기의 제조 방법에 있어서, 디아민으로서 식 (1) 로 나타내는 디아민을 사용하면 된다. 또, 그 때는 디아민으로서 식 (1) 로 나타내는 것 이외의 것도 사용할 수 있다. 그 구체예를 굳이 나타낸다면, 국제 공개 공보 2015/119168 의 4 항에 게재되는 식 (2) 의 구조에 2 개의 아미노기가 결합한 디아민, 및, 8 항 ∼ 12 항에 게재되는, 식 (Y-1) ∼ (Y-97), 식 (Y-101) ∼ (Y-118) 의 구조에 2 개의 아미노기가 결합한 디아민 ; 국제 공개 공보 2013/008906 의 6 항에 게재되는 식 (2) 의 디아민 ; 국제 공개 공보 2015/122413 의 8 항에 게재되는 식 (1) 의 디아민 ; 국제 공개 공보 2015/060360 의 8 항에 게재되는 식 (3) 의 구조에 2 개의 아미노기가 결합한 디아민 ; 일본 공개 특허 공보 2012-173514 의 8 항에 기재되는 식 (1) 의 디아민 ; 국제 공개 공보 2010-050523 의 9 항에 게재되는 식 (A) ∼ (F) 의 디아민, 등을 들 수 있다.In order to manufacture the polymer of the present invention, in the above production method, a diamine represented by formula (1) may be used as the diamine. Moreover, in that case, what is other than what is represented by Formula (1) can be used as diamine. If the specific example is shown, diamine in which two amino groups are bonded to the structure of formula (2) shown in paragraph 4 of international publication 2015/119168, and formula (Y-1) shown in paragraphs 8 to 12 ) To (Y-97), diamines in which two amino groups are bonded to the structures of formulas (Y-101) to (Y-118); Diamine of formula (2) published in paragraph 6 of international publication 2013/008906; Diamine of formula (1) published in paragraph 8 of international publication 2015/122413; A diamine in which two amino groups are bonded to the structure of formula (3) shown in paragraph 8 of International Publication No. 2015/060360; Diamine of formula (1) described in 8 of Unexamined-Japanese-Patent No. 2012-173514; And diamines of formulas (A) to (F), which are published in paragraph 9 of International Publication No. 2010-050523.
이와 같이 하여 얻어지는 본 발명의 중합체는, 도료로서 사용할 수 있는 것 외에, 절연막, 필름 기판, 액정 배향막, 보호막 등의 용도에 사용할 수 있다.The polymer of the present invention thus obtained can be used as a coating material, and can also be used in applications such as an insulating film, a film substrate, a liquid crystal alignment film, and a protective film.
실시예Example
이하에 실시예를 들어 본 발명을 더욱 상세하게 설명하는데, 본 발명은 이들에 한정되는 것은 아니다.The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these.
실시예에 있어서 사용한 디아민 화합물의 구조를 이하에 나타낸다.The structure of the diamine compound used in Examples is shown below.
<디아민 화합물><Diamine compound>
[화학식 20][Formula 20]
[화학식 21][Formula 21]
[화학식 22][Formula 22]
DA-1 ∼ DA-8, DA-10 ∼ DA-15 는, 문헌 등 미공개의 신규 화합물이며, 이하의 합성예 1 ∼ 14 에서 그 합성법을 상세히 서술한다.DA-1 to DA-8 and DA-10 to DA-15 are novel, unpublished compounds such as literatures, and their synthesis methods are described in detail in Synthesis Examples 1 to 14 below.
DA-9 는 특허문헌 (WO2017-057854) 에 기재된 합성법으로 합성하였다.DA-9 was synthesized by the synthetic method described in Patent Document (WO2017-057854).
실시예 등에서 사용한 유기 용매의 약호는 이하와 같다.The abbreviation of the organic solvent used in Examples etc. is as follows.
NMP : N-메틸-2-피롤리돈.NMP: N-methyl-2-pyrrolidone.
BCS : 부틸셀로솔브.BCS: Butyl cellosolve.
THF : 테트라하이드로푸란.THF: Tetrahydrofuran.
DMF : N,N-디메틸포름아미드.DMF: N, N-dimethylformamide.
CH2Cl2 : 디클로로메탄.CH 2 Cl 2 : dichloromethane.
CHCl3 : 클로로포름.CHCl 3 : chloroform.
MeOH : 메탄올.MeOH: methanol.
EtOH : 에탄올.EtOH: ethanol.
IPA : 이소프로필알코올.IPA: isopropyl alcohol.
1,3-DMCBDA : 1,3-디메틸-1,2,3,4-시클로부탄테트라카르복실산 2무수물1,3-DMCBDA: 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride
<1HNMR 의 측정><Measurement of 1 HNMR>
장치 : 푸리에 변환형 초전도 핵자기 공명 장치 (FT-NMR) 「INOVA-400」 (Varian 제조) 400 ㎒.Apparatus: Fourier transform superconducting nuclear magnetic resonance apparatus (FT-NMR) "INOVA-400" (manufactured by Varian) 400 MHz.
용매 : 중수소화클로로포름 (CDCl3) 또는 중수소화N,N-디메틸술폭시드 ([D6]-DMSO).Solvent: Deuterated chloroform (CDCl 3 ) or deuterated N, N-dimethylsulfoxide ([D 6 ] -DMSO).
표준 물질 : 테트라메틸실란 (TMS).Standard material: Tetramethylsilane (TMS).
(합성예 1) (Synthesis Example 1)
[DA-1] 의 합성 : Synthesis of [DA-1]:
[화학식 23][Formula 23]
3 ℓ 4 구 플라스크에 4-[(4-아미노페녹시)메톡시]아닐린 (230.0 g, 999 m㏖), THF (1600 g) 를 투입하고, 수욕 (水浴) 중에서, 2탄산디-tert-부틸 (218.0 g, 999 m㏖) 을 적하 후, 실온에서 교반하였다. 반응 종료 후, 반응액을 농축하고, 얻어진 잔류물을 실리카 겔 칼럼 크로마토그래피 (아세트산에틸 : 헥산 = 1 : 1 체적비) 로 단리함으로써, [DA-1-1] 을 158.0 g 얻었다.4-[(4-aminophenoxy) methoxy] aniline (230.0 g, 999 mmol) and THF (1600 g) were added to a 3 liter 4-neck flask, and di-tert-dicarbonate was added in a water bath. Butyl (218.0 g, 999 mmol) was added dropwise, followed by stirring at room temperature. After completion of the reaction, the reaction solution was concentrated, and the obtained residue was isolated by silica gel column chromatography (ethyl acetate: hexane = 1: 1 volume ratio) to obtain 158.0 g of [DA-1-1].
3 ℓ 4 구 플라스크에 [DA-1-1] (132.2 g, 400 m㏖), NMP (1300 g) 를 투입하고, 수욕 중에서, 1,3-DMCBDA (40.4 g, 180 m㏖) 를 첨가 후, 실온에서 6 h 교반하였다. 계속해서, 반응액에 피리딘 (85.5 g, 1081 m㏖), 무수 아세트산 (55.2 g, 540 m㏖) 을 투입하고, 60 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (5 ℓ) 에 붓고, 석출물을 여과 분리하였다. 얻어진 미정제물에 MeOH (2 ℓ) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-1-2] 를 180.1 g 얻었다.[DA-1-1] (132.2 g, 400 mmol) and NMP (1300 g) were added to a 3 L 4-neck flask, and 1,3-DMCBDA (40.4 g, 180 mmol) was added in a water bath. , And stirred at room temperature for 6 h. Subsequently, pyridine (85.5 g, 1081 mmol) and acetic anhydride (55.2 g, 540 mmol) were added to the reaction solution and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (5 L), and the precipitate was separated by filtration. 180.1 g of [DA-1-2] was obtained by adding MeOH (2 L) to the obtained crude product and repulsing washing at room temperature.
3 ℓ 4 구 플라스크에 [DA-1-2] (169.8 g, 200 m㏖), CH2Cl2 (2500 g) 를 투입하고, 수욕 중에서, 트리플루오로아세트산 (204.1 g, 1000 m㏖) 을 적하 후, 실온에서 교반하였다. 반응 종료 후, 반응액을 농축하고, 얻어진 미정제물에 순수 (3 ℓ) 를 첨가하고, 트리에틸아민으로 중화하였다. 침전물을 여과하고, 얻어진 미정제물에 THF (500 g), MeOH (700 g) 를 첨가하여, 실온에서 리펄핑 세정함으로써, [DA-1] (백색 고체) 을 106.0 g 얻었다. 목적물의 1H-NMR 의 결과를 이하에 나타낸다. 이 결과로부터, 얻어진 고체가, 목적으로 하는 [DA-1] 인 것을 확인하였다.[DA-1-2] (169.8 g, 200 mmol) and CH 2 Cl 2 (2500 g) were added to a 3 L 4-neck flask, and trifluoroacetic acid (204.1 g, 1000 mmol) was added in a water bath. After dropping, the mixture was stirred at room temperature. After completion of the reaction, the reaction solution was concentrated, pure water (3 L) was added to the obtained crude product, and neutralized with triethylamine. The precipitate was filtered, and THF (500 g) and MeOH (700 g) were added to the obtained crude product, and repulping and washing at room temperature gave 106.0 g of [DA-1] (white solid). The results of 1 H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-1].
(합성예 2) (Synthesis Example 2)
[DA-2] 의 합성 : Synthesis of [DA-2]:
[화학식 24][Formula 24]
3 ℓ 4 구 플라스크에 4-[3-(4-아미노페녹시)프로폭시]아닐린 (70.0 g, 271 m㏖), THF (500 g) 를 투입하고, 수욕 중에서, 2탄산디-tert-부틸 (59.1 g, 271 m㏖) 을 적하 후, 실온에서 교반하였다. 반응 종료 후, 반응액을 농축하고, 얻어진 잔류물을 실리카 겔 칼럼 크로마토그래피 (아세트산에틸 : 헥산 = 1 : 1 체적비) 로 단리함으로써, [DA-2-1] 을 46.4 g 얻었다.4- [3- (4-aminophenoxy) propoxy] aniline (70.0 g, 271 mmol) and THF (500 g) were added to a 3-L 4-neck flask, and di-tert-butyl dicarbonate in a water bath. (59.1 g, 271 mmol) was added dropwise, followed by stirring at room temperature. After completion of the reaction, the reaction solution was concentrated, and the obtained residue was isolated by silica gel column chromatography (ethyl acetate: hexane = 1: 1 volume ratio) to obtain 46.4 g of [DA-2-1].
3 ℓ 4 구 플라스크에 [DA-2-1] (46.4 g, 129 m㏖), NMP (460 g) 를 투입하고, 수욕 중에서, 1,3-DMCBDA (14.5 g, 65 m㏖) 를 첨가 후, 실온에서 6 h 교반하였다. 계속해서, 반응액에 피리딘 (30.7 g, 388 m㏖), 무수 아세트산 (19.8 g, 194 m㏖) 을 투입하고, 60 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (3 ℓ) 에 붓고, 석출물을 여과 분리하였다. 얻어진 미정제물에 MeOH (400 ㎖) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-2-2] 를 41.1 g 얻었다.[DA-2-1] (46.4 g, 129 mmol) and NMP (460 g) were added to a 3 L 4-neck flask, and 1,3-DMCBDA (14.5 g, 65 mmol) was added in a water bath. , And stirred at room temperature for 6 h. Then, pyridine (30.7 g, 388 mmol) and acetic anhydride (19.8 g, 194 mmol) were added to the reaction solution, and the mixture was stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was separated by filtration. 41.1 g of [DA-2-2] was obtained by adding MeOH (400 mL) to the obtained crude product, and washing by repulping at room temperature.
3 ℓ 4 구 플라스크에 [DA-2-2] (41.1 g, 45 m㏖), CH2Cl2 (600 g) 를 투입하고, 수욕 중에서, 트리플루오로아세트산 (46.4 g, 454 m㏖) 을 적하 후, 실온에서 교반하였다. 반응 종료 후, 반응액을 농축하고, 얻어진 미정제물에 순수 (2 ℓ) 를 첨가하고, 트리에틸아민으로 중화하였다. 침전물을 여과하고, 얻어진 미정제물에 EtOH (100 g) 를 첨가하여, 실온에서 리펄핑 세정함으로써, [DA-2] (백색 고체) 를 25.3 g 얻었다. 목적물의 1H-NMR 의 결과를 이하에 나타낸다. 이 결과로부터, 얻어진 고체가, 목적으로 하는 [DA-2] 인 것을 확인하였다.[DA-2-2] (41.1 g, 45 mmol) and CH 2 Cl 2 (600 g) were added to a 3 L 4-neck flask, and trifluoroacetic acid (46.4 g, 454 mmol) was added in a water bath. After dropping, the mixture was stirred at room temperature. After completion of the reaction, the reaction solution was concentrated, pure water (2 L) was added to the obtained crude product, and neutralized with triethylamine. The precipitate was filtered, and EtOH (100 g) was added to the obtained crude product, followed by repulsing and washing at room temperature to obtain 25.3 g of [DA-2] (white solid). The results of 1 H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-2].
(합성예 3) (Synthesis Example 3)
[DA-3] 의 합성 : Synthesis of [DA-3]:
[화학식 25][Formula 25]
3 ℓ 4 구 플라스크에 4-[6-(4-아미노페녹시)헥실옥시]아닐린 (90.0 g, 300 m㏖), THF (600 g) 를 투입하고, 수욕 중에서, 2탄산디-tert-부틸 (65.4 g, 300 m㏖) 을 적하 후, 실온에서 교반하였다. 반응 종료 후, 반응액을 농축하고, 얻어진 잔류물을 실리카 겔 칼럼 크로마토그래피 (아세트산에틸 : 헥산 = 1 : 1 체적비) 로 단리함으로써, [DA-3-1] 을 48.0 g 얻었다.4- [6- (4-aminophenoxy) hexyloxy] aniline (90.0 g, 300 mmol) and THF (600 g) were added to a 3-L 4-neck flask, and di-tert-dicarbonate was added in a water bath. Butyl (65.4 g, 300 mmol) was added dropwise, followed by stirring at room temperature. After completion of the reaction, the reaction solution was concentrated, and the obtained residue was isolated by silica gel column chromatography (ethyl acetate: hexane = 1: 1 volume ratio) to obtain 48.0 g of [DA-3-1].
3 ℓ 4 구 플라스크에 [DA-3-1] (48.0 g, 120 m㏖), NMP (480 g) 를 투입하고, 수욕 중에서, 1,3-DMCBDA (13.4 g, 60 m㏖) 를 첨가 후, 실온에서 6 h 교반하였다. 계속해서, 반응액에 피리딘 (28.4 g, 360 m㏖), 무수 아세트산 (18.4 g, 180 m㏖) 을 투입하고, 60 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (3 ℓ) 에 붓고, 석출물을 여과 분리하였다. 얻어진 미정제물에 MeOH (400 ㎖) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-3-2] 를 42.5 g 얻었다.[DA-3-1] (48.0 g, 120 mmol) and NMP (480 g) were added to a 3 L 4-neck flask, and 1,3-DMCBDA (13.4 g, 60 mmol) was added in a water bath. , And stirred at room temperature for 6 h. Subsequently, pyridine (28.4 g, 360 mmol) and acetic anhydride (18.4 g, 180 mmol) were added to the reaction solution and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was separated by filtration. 42.5 g of [DA-3-2] was obtained by adding MeOH (400 mL) to the obtained crude product, and repulsing washing at room temperature.
3 ℓ 4 구 플라스크에 [DA-3-2] (42.5 g, 43 m㏖), CH2Cl2 (640 g) 를 투입하고, 수욕 중에서, 트리플루오로아세트산 (43.9 g, 430 m㏖) 을 적하 후, 실온에서 교반하였다. 반응 종료 후, 반응액을 농축하고, 얻어진 미정제물에 순수 (2 ℓ) 를 첨가하고, 트리에틸아민으로 중화하였다. 침전물을 여과하고, 얻어진 미정제물에 MeOH (100 g) 를 첨가하여, 실온에서 리펄핑 세정함으로써, [DA-3] (보라색 고체) 을 26.3 g 얻었다. 목적물의 1H-NMR 의 결과를 이하에 나타낸다. 이 결과로부터, 얻어진 고체가, 목적으로 하는 [DA-3] 인 것을 확인하였다.[DA-3-2] (42.5 g, 43 mmol) and CH 2 Cl 2 (640 g) were added to a 3 L 4-neck flask, and trifluoroacetic acid (43.9 g, 430 mmol) was added in a water bath. After dropping, the mixture was stirred at room temperature. After completion of the reaction, the reaction solution was concentrated, pure water (2 L) was added to the obtained crude product, and neutralized with triethylamine. The precipitate was filtered, MeOH (100 g) was added to the obtained crude product, and re-pulping and washing at room temperature yielded 26.3 g of [DA-3] (purple solid). The results of 1 H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-3].
(합성예 4) (Synthesis Example 4)
[DA-4] 의 합성 : Synthesis of [DA-4]:
[화학식 26][Formula 26]
2 ℓ 4 구 플라스크에 N-Boc-2-(4-아미노페닐)에탄올 (158.7 g, 669 m㏖), 트리에틸아민 (135.4 g, 1338 m㏖), THF (1100 g) 를 투입하고, 수욕 중에서, 에탄술포닐클로라이드 (128.9 g, 1003 m㏖) 를 적하 후, 실온에서 교반하였다. 반응 종료 후, 반응계를 아세트산에틸 (3 ℓ) 에 붓고, 순수 (1 ℓ)를 사용하여 추출을 실시하였다. 추출한 유기층에 무수 황산마그네슘을 첨가하여 탈수 건조시키고, 무수 황산마그네슘을 여과하였다. 얻어진 여과액을 로터리 이배퍼레이터로 용매 증류 제거함으로써, [DA-4-1] 을 224.2 g 얻었다.N-Boc-2- (4-aminophenyl) ethanol (158.7 g, 669 mmol), triethylamine (135.4 g, 1338 mmol) and THF (1100 g) were added to a 2 L 4-neck flask, and water bath Among them, ethanesulfonyl chloride (128.9 g, 1003 mmol) was added dropwise, followed by stirring at room temperature. After completion of the reaction, the reaction system was poured into ethyl acetate (3 L), and extraction was performed using pure water (1 L). Anhydrous magnesium sulfate was added to the extracted organic layer, followed by dehydration drying, and the anhydrous magnesium sulfate was filtered. 224.2 g of [DA-4-1] was obtained by distilling off the obtained filtrate using a rotary evaporator.
3 ℓ 4 구 플라스크에 [DA-4-1] (217.3 g, 660 m㏖), 4-니트로페놀 (101.0 g, 726 m㏖), 탄산칼륨 (136.8 g, 990 m㏖), NMP (1200 g) 를 투입하고, 80 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 아세트산에틸 (2 ℓ) 에 붓고, 1N-염산 수용액으로 중화하였다. 수층을 제거하고, 유기층을 순수 (2 ℓ) 로 세정하였다. 세정한 유기층에 무수 황산마그네슘을 첨가하여 탈수 건조시키고, 무수 황산마그네슘을 여과하였다. 얻어진 여과액을 로터리 이배퍼레이터로 용매 증류 제거하고, IPA (400 g) 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-4-2] 를 164.8 g 얻었다.In a 3 ℓ 4-neck flask [DA-4-1] (217.3 g, 660 mmol), 4-nitrophenol (101.0 g, 726 mmol), potassium carbonate (136.8 g, 990 mmol), NMP (1200 g ) And stirred at 80 ° C. After completion of the reaction, the reaction system was poured into ethyl acetate (2 L), and neutralized with an aqueous 1N-hydrochloric acid solution. The aqueous layer was removed, and the organic layer was washed with pure water (2 L). Anhydrous magnesium sulfate was added to the washed organic layer, followed by dehydration drying, and the anhydrous magnesium sulfate was filtered. The obtained filtrate was distilled off with a rotary evaporator, IPA (400 g) was added, and repulsing and washing at room temperature gave 164.8 g of [DA-4-2].
2 ℓ 4 구 플라스크에 [DA-4-2] (84.3 g, 226 m㏖), 6N-염산 수용액 (200 g), 아세트산에틸 (600 g) 을 투입하고, 60 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (1.2 ℓ) 에 붓고, 1N-수산화나트륨 수용액으로 중화하였다. 수층을 제거하고, 유기층을 순수 (2 ℓ) 로 세정하였다. 세정한 유기층에 무수 황산마그네슘을 첨가하여 탈수 건조시키고, 무수 황산마그네슘을 여과하였다. 얻어진 여과액을 로터리 이배퍼레이터로 용매 증류 제거함으로써, [DA-4-3] 을 60.8 g 얻었다.[DA-4-2] (84.3 g, 226 mmol), 6N-hydrochloric acid aqueous solution (200 g) and ethyl acetate (600 g) were added to a 2 L 4-neck flask and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (1.2 L), and neutralized with an aqueous 1N-sodium hydroxide solution. The aqueous layer was removed, and the organic layer was washed with pure water (2 L). Anhydrous magnesium sulfate was added to the washed organic layer, followed by dehydration drying, and the anhydrous magnesium sulfate was filtered. 60.8 g of [DA-4-3] was obtained by distilling off the obtained filtrate using a rotary evaporator.
2 ℓ 4 구 플라스크에 [DA-4-3] (60.8 g, 235 m㏖), NMP (600 g) 를 투입하고, 수욕 중에서, 1,3-DMCBDA (24.8 g, 111 m㏖) 를 첨가 후, 실온에서 6 h 교반하였다. 계속해서, 반응액에 피리딘 (55.8 g, 705 m㏖), 무수 아세트산 (35.9 g, 352 m㏖) 을 투입하고, 60 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (3 ℓ) 에 붓고, 석출물을 여과 분리하였다. 얻어진 미정제물에 EtOH (1000 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-4-4] 를 79.1 g 얻었다.[DA-4-3] (60.8 g, 235 mmol) and NMP (600 g) were added to a 2 L 4-neck flask, and 1,3-DMCBDA (24.8 g, 111 mmol) was added in a water bath. , And stirred at room temperature for 6 h. Subsequently, pyridine (55.8 g, 705 mmol) and acetic anhydride (35.9 g, 352 mmol) were added to the reaction solution and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was separated by filtration. 79.1 g of [DA-4-4] was obtained by adding EtOH (1000 g) to the obtained crude product and repulsing washing at room temperature.
3 ℓ 4 구 플라스크에 [DA-4-4] (79.0 g, 112 m㏖), DMF (800 g) 를 투입하고, 질소 치환 후, 5 wt% Pd/C (7.9 g) 를 첨가하고, 수소 치환하여 실온에서 교반하였다. 반응 종료 후, 반응액을 0.45 ㎛ 멤브레인 필터로 여과함으로써, Pd/C 를 제거하였다. 얻어진 여과액을 로터리 이배퍼레이터로 용매 증류 제거하고, 아세트산에틸 (1500 g) 을 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-4] (백색 고체) 를 69.9 g 얻었다. 목적물의 1H-NMR 의 결과를 이하에 나타낸다. 이 결과로부터, 얻어진 고체가, 목적으로 하는 [DA-4] 인 것을 확인하였다.[DA-4-4] (79.0 g, 112 mmol) and DMF (800 g) were added to a 3 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (7.9 g) was added, followed by hydrogen. Substituted and stirred at room temperature. After completion of the reaction, the reaction solution was filtered through a 0.45 μm membrane filter to remove Pd / C. The obtained filtrate was distilled off with a rotary evaporator, ethyl acetate (1500 g) was added, and repulping and washing at room temperature gave 69.9 g of [DA-4] (white solid). The results of 1 H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-4].
(합성예 5) (Synthesis Example 5)
[DA-5] 의 합성 : Synthesis of [DA-5]:
[화학식 27][Formula 27]
1 ℓ 4 구 플라스크에 [DA-4-2] (80.6 g, 216 m㏖), THF (300 g), EtOH (100 g) 를 투입하고, 질소 치환 후, 5 wt% Pd/C (8.0 g) 를 첨가하고, 수소 치환하여 실온에서 교반하였다. 반응 종료 후, 반응액을 0.45 ㎛ 멤브레인 필터로 여과함으로써, Pd/C 를 제거하였다. 얻어진 여과액을 로터리 이배퍼레이터로 용매 증류 제거함으로써, [DA-5-1] 을 73.9 g 얻었다.[DA-4-2] (80.6 g, 216 mmol), THF (300 g), and EtOH (100 g) were added to a 1 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (8.0 g) ) Was added, and the mixture was hydrogen-substituted and stirred at room temperature. After completion of the reaction, the reaction solution was filtered through a 0.45 μm membrane filter to remove Pd / C. 73.9 g of [DA-5-1] was obtained by distilling off the obtained filtrate with a solvent by a rotary evaporator.
2 ℓ 4 구 플라스크에 [DA-5-1] (73.9 g, 225 m㏖), NMP (700 g) 를 투입하고, 수욕 중에서, 1,3-DMCBDA (23.7 g, 106 m㏖) 를 첨가 후, 실온에서 6 h 교반하였다. 계속해서, 반응액에 피리딘 (53.4 g, 675 m㏖), 무수 아세트산 (34.5 g, 338 ㏖) 을 투입하고, 60 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (3 ℓ) 에 붓고, 석출물을 여과 분리하였다. 얻어진 미정제물에 EtOH (1000 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-5-2] 를 85.4 g 얻었다.[DA-5-1] (73.9 g, 225 mmol) and NMP (700 g) were added to a 2 L 4-neck flask, and 1,3-DMCBDA (23.7 g, 106 mmol) was added in a water bath. , And stirred at room temperature for 6 h. Subsequently, pyridine (53.4 g, 675 mmol) and acetic anhydride (34.5 g, 338 mol) were added to the reaction solution and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was separated by filtration. EtOH (1000 g) was added to the obtained crude product, and 85.4 g of [DA-5-2] was obtained by repulsing and washing at room temperature.
2 ℓ 4 구 플라스크에 [DA-5-2] (85.4 g, 101 m㏖), 6N-염산 수용액 (200 g), 아세트산에틸 (800 g) 을 투입하고, 50 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (1.2 ℓ) 에 붓고, 트리에틸아민으로 중화하였다. 석출물을 여과 분리하고, 아세트산에틸 (1500 g) 을 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-5] 를 61.1 g 얻었다. 목적물의 1H-NMR 의 결과를 이하에 나타낸다. 이 결과로부터, 얻어진 고체가, 목적으로 하는 [DA-5] 인 것을 확인하였다.[DA-5-2] (85.4 g, 101 mmol), 6N-hydrochloric acid aqueous solution (200 g) and ethyl acetate (800 g) were added to a 2 L 4-neck flask, and the mixture was stirred at 50 ° C. After completion of the reaction, the reaction system was poured into pure water (1.2 L) and neutralized with triethylamine. The precipitate was separated by filtration, ethyl acetate (1500 g) was added, and repulping and washing at room temperature gave 61.1 g of [DA-5]. The results of 1 H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-5].
(합성예 6) (Synthesis Example 6)
[DA-6] 의 합성 : Synthesis of [DA-6]:
[화학식 28][Formula 28]
2 ℓ 4 구 플라스크에 3-(4-tert-부톡시카르보닐아미노페닐)프로판올 (237.3 g, 944 m㏖), 트리에틸아민 (190.0 g, 1888 m㏖), THF (1000 g) 를 투입하고, 수욕 중에서, 에탄술포닐클로라이드 (182.0 g, 1416 m㏖) 를 적하 후, 실온에서 교반하였다. 반응 종료 후, 반응계를 아세트산에틸 (2 ℓ) 에 붓고, 순수 (1 ℓ)를 사용하여 추출을 실시하였다. 추출한 유기층에 무수 황산마그네슘을 첨가하여 탈수 건조시키고, 무수 황산마그네슘을 여과하였다. 얻어진 여과액을 로터리 이배퍼레이터로 용매 증류 제거함으로써, [DA-6-1] 을 324.2 g 얻었다.3- (4-tert-butoxycarbonylaminophenyl) propanol (237.3 g, 944 mmol), triethylamine (190.0 g, 1888 mmol), THF (1000 g) was added to a 2 L 4-neck flask. , Ethanesulfonyl chloride (182.0 g, 1416 mmol) was added dropwise in a water bath, followed by stirring at room temperature. After completion of the reaction, the reaction system was poured into ethyl acetate (2 L), and extraction was performed using pure water (1 L). Anhydrous magnesium sulfate was added to the extracted organic layer, followed by dehydration drying, and the anhydrous magnesium sulfate was filtered. 324.2 g of [DA-6-1] was obtained by distilling off the obtained filtrate using a rotary evaporator.
3 ℓ 4 구 플라스크에 [DA-6-1] (324.2 g, 944 m㏖), 4-니트로페놀 (150.0 g, 1078 m㏖), 탄산칼륨 (203.0 g, 1470 m㏖), NMP (1700 g) 를 투입하고, 80 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 아세트산에틸 (4 ℓ) 에 붓고, 1N-염산 수용액으로 중화하였다. 수층을 제거하고, 유기층을 순수 (2 ℓ) 로 세정하였다. 세정한 유기층에 무수 황산마그네슘을 첨가하여 탈수 건조시키고, 무수 황산마그네슘을 여과하였다. 얻어진 여과액을 로터리 이배퍼레이터로 용매 증류 제거하고, IPA (2000 g) 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-6-2] 를 173.4 g 얻었다.In a 3 ℓ 4-neck flask [DA-6-1] (324.2 g, 944 mmol), 4-nitrophenol (150.0 g, 1078 mmol), potassium carbonate (203.0 g, 1470 mmol), NMP (1700 g ) And stirred at 80 ° C. After completion of the reaction, the reaction system was poured into ethyl acetate (4 L) and neutralized with a 1N-hydrochloric acid aqueous solution. The aqueous layer was removed, and the organic layer was washed with pure water (2 L). Anhydrous magnesium sulfate was added to the washed organic layer, followed by dehydration drying, and the anhydrous magnesium sulfate was filtered. The obtained filtrate was distilled off with a rotary evaporator, IPA (2000 g) was added, and repulsing and washing at room temperature yielded 173.4 g of [DA-6-2].
2 ℓ 4 구 플라스크에 [DA-6-2] (86.7 g, 233 m㏖), 6N-염산 수용액 (180 g), 아세트산에틸 (700 g) 을 투입하고, 60 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (1 ℓ) 에 붓고, 1N-수산화나트륨 수용액으로 중화하였다. 수층을 제거하고, 유기층을 순수 (2 ℓ) 로 세정하였다. 세정한 유기층에 무수 황산마그네슘을 첨가하여 탈수 건조시키고, 무수 황산마그네슘을 여과하였다. 얻어진 여과액을 로터리 이배퍼레이터로 용매 증류 제거함으로써, [DA-6-3] 을 62.6 g 얻었다.[DA-6-2] (86.7 g, 233 mmol), 6N-hydrochloric acid aqueous solution (180 g) and ethyl acetate (700 g) were added to a 2 L 4-neck flask, and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (1 L), and neutralized with an aqueous 1N-sodium hydroxide solution. The aqueous layer was removed, and the organic layer was washed with pure water (2 L). Anhydrous magnesium sulfate was added to the washed organic layer, followed by dehydration drying, and the anhydrous magnesium sulfate was filtered. 62.6 g of [DA-6-3] was obtained by distilling off the obtained filtrate using a rotary evaporator.
2 ℓ 4 구 플라스크에 [DA-6-3] (62.6 g, 230 m㏖), NMP (900 g) 를 투입하고, 수욕 중에서, 1,3-DMCBDA (25.5 g, 114 m㏖) 를 첨가 후, 실온에서 6 h 교반하였다. 계속해서, 반응액에 피리딘 (54.5 g, 690 m㏖), 무수 아세트산 (35.2 g, 345 m㏖) 을 투입하고, 60 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (4 ℓ) 에 붓고, 석출물을 여과 분리하였다. 얻어진 미정제물에 MeOH (500 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-6-4] 를 82.0 g 얻었다.[DA-6-3] (62.6 g, 230 mmol) and NMP (900 g) were added to a 2 L 4-neck flask, and 1,3-DMCBDA (25.5 g, 114 mmol) was added in a water bath. , And stirred at room temperature for 6 h. Subsequently, pyridine (54.5 g, 690 mmol) and acetic anhydride (35.2 g, 345 mmol) were added to the reaction solution and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (4 L), and the precipitate was separated by filtration. 82.0 g of [DA-6-4] was obtained by adding MeOH (500 g) to the obtained crude product, and repulsing washing at room temperature.
5 ℓ 4 구 플라스크에 [DA-6-4] (80.0 g, 109 m㏖), DMF (3200 g) 를 투입하고, 질소 치환 후, 5 wt% Pd/C (8.0 g) 를 첨가하고, 수소 치환하여 60 ℃ 에서 교반하였다. 반응 종료 후, 반응액을 0.45 ㎛ 멤브레인 필터로 여과함으로써, Pd/C 를 제거하였다. 얻어진 여과액을 로터리 이배퍼레이터로 용매 증류 제거하고, 아세트산에틸 (1000 g) 을 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-6] (적자색 고체) 을 59.1 g 얻었다. 목적물의 1H-NMR 의 결과를 이하에 나타낸다. 이 결과로부터, 얻어진 고체가, 목적으로 하는 [DA-6] 인 것을 확인하였다.[DA-6-4] (80.0 g, 109 mmol) and DMF (3200 g) were added to a 5 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (8.0 g) was added, followed by hydrogen. Substituted and stirred at 60 ° C. After completion of the reaction, the reaction solution was filtered through a 0.45 μm membrane filter to remove Pd / C. The obtained filtrate was distilled off with a rotary evaporator, ethyl acetate (1000 g) was added, and repulsed and washed at room temperature to obtain 59.1 g of [DA-6] (reddish-purple solid). The results of 1 H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-6].
(합성예 7) (Synthesis Example 7)
[DA-7] 의 합성 : Synthesis of [DA-7]:
[화학식 29][Formula 29]
1 ℓ 4 구 플라스크에 [DA-6-2] (86.7 g, 233 m㏖), THF (350 g), EtOH (90 g) 를 투입하고, 질소 치환 후, 5 wt% Pd/C (8.7 g) 를 첨가하고, 수소 치환하여 실온에서 교반하였다. 반응 종료 후, 반응액을 0.45 ㎛ 멤브레인 필터로 여과함으로써, Pd/C 를 제거하였다. 얻어진 여과액을 로터리 이배퍼레이터로 용매 증류 제거함으로써, [DA-7-1] 을 65.8 g 얻었다.[DA-6-2] (86.7 g, 233 mmol), THF (350 g), and EtOH (90 g) were added to a 1 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (8.7 g) ) Was added, and the mixture was hydrogen-substituted and stirred at room temperature. After completion of the reaction, the reaction solution was filtered through a 0.45 μm membrane filter to remove Pd / C. 65.8 g of [DA-7-1] was obtained by distilling off the obtained filtrate using a rotary evaporator.
2 ℓ 4 구 플라스크에 [DA-7-1] (65.8 g, 192 m㏖), NMP (700 g) 를 투입하고, 수욕 중에서, 1,3-DMCBDA (21.4 g, 96 m㏖) 를 첨가 후, 실온에서 6 h 교반하였다. 계속해서, 반응액에 피리딘 (45.6 g, 576 m㏖), 무수 아세트산 (29.8 g, 292 ㏖) 을 투입하고, 60 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (3 ℓ) 에 붓고, 석출물을 여과 분리하였다. 얻어진 미정제물에 MeOH (1000 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-7-2] 를 83.0 g 얻었다.[DA-7-1] (65.8 g, 192 mmol) and NMP (700 g) were added to a 2 L 4-neck flask, and 1,3-DMCBDA (21.4 g, 96 mmol) was added in a water bath. , And stirred at room temperature for 6 h. Subsequently, pyridine (45.6 g, 576 mmol) and acetic anhydride (29.8 g, 292 mol) were added to the reaction solution, and the mixture was stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (3 L), and the precipitate was separated by filtration. 83.0 g of [DA-7-2] was obtained by adding MeOH (1000 g) to the obtained crude product, and repulsing washing at room temperature.
2 ℓ 4 구 플라스크에 [DA-7-2] (83.0 g, 96 m㏖), 6N-염산 수용액 (170 g), 아세트산에틸 (700 g) 을 투입하고, 60 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (1 ℓ) 에 붓고, 트리에틸아민으로 중화하였다. 석출물을 여과 분리하고, 아세트산에틸 (500 g) 을 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-7] 을 25.2 g 얻었다. 목적물의 1H-NMR 의 결과를 이하에 나타낸다. 이 결과로부터, 얻어진 고체가, 목적으로 하는 [DA-7] 인 것을 확인하였다.[DA-7-2] (83.0 g, 96 mmol), 6N-hydrochloric acid aqueous solution (170 g) and ethyl acetate (700 g) were added to a 2 L 4-neck flask, and stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (1 L) and neutralized with triethylamine. The precipitate was separated by filtration, ethyl acetate (500 g) was added, and 25.2 g of [DA-7] was obtained by washing with repulping at room temperature. The results of 1 H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-7].
(합성예 8) (Synthesis Example 8)
[DA-8] 의 합성 : Synthesis of [DA-8]:
[화학식 30][Formula 30]
1 ℓ 4 구 플라스크에 2-(4-니트로페닐)에틸아민염산염 (50.0 g, 247 m㏖), 트리에틸아민 (27.5 g, 271 m㏖), THF (500 g) 를 투입하고, 수욕 중에서, 1,3-DMCBDA (27.1 g, 121 m㏖) 를 첨가 후, 실온에서 6 h 교반하였다. 반응 종료 후, 반응계를 순수 (1.5 ℓ) 에 붓고, 석출물을 여과 분리함으로써, [DA-8-1] 을 67.2 g 얻었다.2- (4-nitrophenyl) ethylamine hydrochloride (50.0 g, 247 mmol), triethylamine (27.5 g, 271 mmol) and THF (500 g) were added to a 1 L 4-neck flask, and in a water bath, After adding 1,3-DMCBDA (27.1 g, 121 mmol), the mixture was stirred at room temperature for 6 h. After completion of the reaction, 67.2 g of [DA-8-1] was obtained by pouring the reaction system into pure water (1.5 L) and filtering the precipitate.
1 ℓ 4 구 플라스크에 [DA-8-1] (67.2 g, 121 m㏖), 아세트산 (400 g) 을 투입하고, 100 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (1.5 ℓ) 에 붓고, 석출물을 여과 분리하였다. 얻어진 미정제물에 MeOH (60 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-8-2] 를 30.4 g 얻었다.[DA-8-1] (67.2 g, 121 mmol) and acetic acid (400 g) were added to a 1 L 4-neck flask and stirred at 100 ° C. After the reaction was completed, the reaction system was poured into pure water (1.5 L), and the precipitate was separated by filtration. 30.4 g of [DA-8-2] was obtained by adding MeOH (60 g) to the obtained crude product, and repulsing washing at room temperature.
1 ℓ 4 구 플라스크에 [DA-8-2] (30.4 g, 58 m㏖), DMF (450 g) 를 투입하고, 질소 치환 후, 5 wt% Pd/C (3.0 g) 를 첨가하고, 수소 치환하여 실온에서 교반하였다. 반응 종료 후, 반응액을 0.45 ㎛ 멤브레인 필터로 여과함으로써, Pd/C 를 제거하였다. 얻어진 여과액을 순수 (3 ℓ) 에 붓고, 석출물을 여과 분리하였다. 얻어진 미정제물에 MeOH (80 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-8] (백색 고체) 을 25.9 g 얻었다. 목적물의 1H-NMR 의 결과를 이하에 나타낸다. 이 결과로부터, 얻어진 고체가, 목적으로 하는 [DA-8] 인 것을 확인하였다.[DA-8-2] (30.4 g, 58 mmol) and DMF (450 g) were added to a 1 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (3.0 g) was added and hydrogen was added. Substituted and stirred at room temperature. After completion of the reaction, the reaction solution was filtered through a 0.45 μm membrane filter to remove Pd / C. The obtained filtrate was poured into pure water (3 L), and the precipitate was separated by filtration. 25.9 g of [DA-8] (white solid) was obtained by adding MeOH (80 g) to the obtained crude product, and washing by repulping at room temperature. The results of 1 H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-8].
(합성예 9) (Synthesis Example 9)
[DA-10] 의 합성 : Synthesis of [DA-10]:
[화학식 31][Formula 31]
1 ℓ 4 구 플라스크에 2-(4-니트로페닐)에틸아민염산염 (25.0 g, 123 m㏖), 트리에틸아민 (14.2 g, 140 m㏖), THF (250 g) 를 투입하고, 수욕 중에서, 1,2,3,4-시클로부탄테트라카르복실산 2무수물 (11.7 g, 60 m㏖) 을 첨가 후, 실온에서 6 h 교반하였다. 반응 종료 후, 반응계를 순수 (2 ℓ) 에 붓고, 석출물을 여과 분리하였다. 얻어진 미정제물에 IPA (500 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-10-1] 을 21.8 g 얻었다.2- (4-nitrophenyl) ethylamine hydrochloride (25.0 g, 123 mmol), triethylamine (14.2 g, 140 mmol) and THF (250 g) were added to a 1 L 4-neck flask, and in a water bath, After adding 1,2,3,4-cyclobutanetetracarboxylic dianhydride (11.7 g, 60 mmol), the mixture was stirred at room temperature for 6 h. After completion of the reaction, the reaction system was poured into pure water (2 L), and the precipitate was separated by filtration. IPDA (500 g) was added to the obtained crude product, and 21.8 g of [DA-10-1] was obtained by repulsing and washing at room temperature.
1 ℓ 4 구 플라스크에 [DA-10-1] (21.8 g, 41 m㏖), 피리딘 (28.5 g, 360 m㏖), 무수 아세트산 (20.1 g, 197 ㏖), NMP (225 g) 를 투입하고, 60 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (2 ℓ) 에 붓고, 석출물을 여과 분리하였다. 얻어진 미정제물에 MeOH (400 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-10-2] 를 19.3 g 얻었다.[DA-10-1] (21.8 g, 41 mmol), pyridine (28.5 g, 360 mmol), acetic anhydride (20.1 g, 197 mol), and NMP (225 g) were added to a 1 L 4-neck flask. , And stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (2 L), and the precipitate was separated by filtration. 19.3 g of [DA-10-2] was obtained by adding MeOH (400 g) to the obtained crude product, and repulsing washing at room temperature.
1 ℓ 4 구 플라스크에 [DA-10-2] (19.3 g, 39 m㏖), DMF (400 g) 를 투입하고, 질소 치환 후, 5 wt% Pd/C (2.0 g) 를 첨가하고, 수소 치환하여 실온에서 교반하였다. 반응 종료 후, 반응액을 0.45 ㎛ 멤브레인 필터로 여과함으로써, Pd/C 를 제거하였다. 얻어진 여과액을 순수 (3 ℓ) 에 붓고, 석출물을 여과 분리하였다. 얻어진 미정제물에 MeOH (300 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-10] (백색 고체) 을 15.2 g 얻었다. 목적물의 1H-NMR 의 결과를 이하에 나타낸다. 이 결과로부터, 얻어진 고체가, 목적으로 하는 [DA-10] 인 것을 확인하였다.[DA-10-2] (19.3 g, 39 mmol) and DMF (400 g) were added to a 1 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (2.0 g) was added and hydrogen was added. Substituted and stirred at room temperature. After completion of the reaction, the reaction solution was filtered through a 0.45 μm membrane filter to remove Pd / C. The obtained filtrate was poured into pure water (3 L), and the precipitate was separated by filtration. 15.2 g of [DA-10] (white solid) was obtained by adding MeOH (300 g) to the obtained crude product and washing by repulping at room temperature. The results of 1 H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-10].
(합성예 10) (Synthesis Example 10)
[DA-11] 의 합성 : Synthesis of [DA-11]:
[화학식 32][Formula 32]
1 ℓ 4 구 플라스크에 N,N'-비스[2-(4-아미노페닐)에틸]우레아 (134.4 g, 450 m㏖), DMF (650 g) 를 투입하고, 수욕 중에서 2탄산디-tert-부틸 (32.8 g, 150 m㏖) 을 적하 후, 실온에서 교반하였다. 반응 종료 후, 반응액을 농축하고, 순수 (1.5 ℓ) 를 첨가하고, 석출물을 여과 분리하였다. 얻어진 미정제물에 CHCl3 (1.5 ℓ) 을 첨가하고, 10 wt% 아세트산 수용액 (1.5 ℓ) 을 사용하여, 유기층을 세정하였다. 또한, 유기층을 트리에틸아민으로 중화하고, 순수 (2 ℓ) 로 세정 후, 농축함으로써, [DA-11-1] 을 50.8 g 얻었다.N, N'-bis [2- (4-aminophenyl) ethyl] urea (134.4 g, 450 mmol) and DMF (650 g) were added to a 1 liter 4-neck flask, and di-tert-dicarbonate was added in a water bath. Butyl (32.8 g, 150 mmol) was added dropwise, followed by stirring at room temperature. After completion of the reaction, the reaction solution was concentrated, pure water (1.5 L) was added, and the precipitate was separated by filtration. CHCl 3 (1.5 L) was added to the obtained crude material, and the organic layer was washed with 10 wt% acetic acid aqueous solution (1.5 L). Further, 50.8 g of [DA-11-1] was obtained by neutralizing the organic layer with triethylamine, washing with pure water (2 L), and concentration.
2 ℓ 4 구 플라스크에 [DA-11-1] (49.0 g, 123 m㏖), NMP (500 g) 를 투입하고, 수욕 중에서 1,3-DMCBDA (13.5 g, 60 m㏖) 를 첨가 후, 실온에서 6 h 교반하였다. 계속해서, 반응액에 피리딘 (29.4 g, 369 m㏖), 무수 아세트산 (18.8 g, 185 ㏖) 을 투입하고, 50 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (2.5 ℓ) 에 붓고, 석출물을 여과 분리하였다. 계속해서, 얻어진 미정제물에 THF (800 g) 를 첨가하고, 완전 용해한 후, 40 ℃ 에서 고체가 석출할 때까지 농축하고, MeOH (200 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-11-2] 를 47.7 g 얻었다.[DA-11-1] (49.0 g, 123 mmol) and NMP (500 g) were added to a 2 L 4-neck flask, and 1,3-DMCBDA (13.5 g, 60 mmol) was added in a water bath, Stir at room temperature for 6 h. Subsequently, pyridine (29.4 g, 369 mmol) and acetic anhydride (18.8 g, 185 mol) were added to the reaction solution and stirred at 50 ° C. After completion of the reaction, the reaction system was poured into pure water (2.5 L), and the precipitate was separated by filtration. Subsequently, THF (800 g) was added to the obtained crude product, and after complete dissolution, it was concentrated until a solid precipitated at 40 ° C, MeOH (200 g) was added, and repulsed and washed at room temperature, [DA -11-2] to obtain 47.7 g.
1 ℓ 4 구 플라스크에 [DA-11-2] (47.7 g, 48 m㏖), CHCl3 (480 g) 을 투입하고, 수욕 중에서, 트리플루오로아세트산 (55.7 g, 484 m㏖) 을 적하 후, 50 ℃ 에서 교반하였다. 반응 종료 후, 반응액을 헥산 (500 g) 에 붓고, 석출물을 여과 분리하였다. 다음으로, 얻어진 미정제물에 MeOH (500 g) 를 첨가하고, 트리에틸아민으로 중화하고, 석출물을 여과 분리하였다. 계속해서, 얻어진 미정제물에 DMF (300 g) 를 첨가하고, 60 ℃ 로 가열하여 완전 용해시킨 후, 40 ℃ 에서 고체가 석출할 때까지 농축하고, THF (600 g) 를 첨가하여, 실온에서 리펄핑 세정함으로써, [DA-11] (백색 고체) 을 25.2 g 얻었다. 목적물의 1H-NMR 의 결과를 이하에 나타낸다. 이 결과로부터, 얻어진 고체가, 목적으로 하는 [DA-11] 인 것을 확인하였다.[DA-11-2] (47.7 g, 48 mmol) and CHCl 3 (480 g) were added to a 1 L 4-neck flask, and trifluoroacetic acid (55.7 g, 484 mmol) was added dropwise in a water bath. , And stirred at 50 ° C. After the reaction was completed, the reaction solution was poured into hexane (500 g), and the precipitate was separated by filtration. Next, MeOH (500 g) was added to the obtained crude product, neutralized with triethylamine, and the precipitate was separated by filtration. Subsequently, DMF (300 g) was added to the obtained crude product, and it was completely dissolved by heating to 60 ° C., and then concentrated until a solid precipitated at 40 ° C., THF (600 g) was added, and the mixture was removed at room temperature. 25.2 g of [DA-11] (white solid) was obtained by pulping and washing. The results of 1 H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-11].
(합성예 11) (Synthesis Example 11)
[DA-12] 의 합성 : Synthesis of [DA-12]:
[화학식 33][Formula 33]
500 mℓ 4 구 플라스크에 1-(4-니트로페닐)-4-피페리딘아민 (39.0 g, 116 m㏖), NMP (400 g) 를 투입하고, 수욕 중에서 1,3-DMCBDA (12.8 g, 47 m㏖) 를 첨가 후, 50 ℃ 에서 6 h 교반하였다. 계속해서, 반응액에 피리딘 (27.6 g, 349 m㏖), 무수 아세트산 (17.8 g, 175 ㏖) 을 투입하고, 50 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (2 ℓ) 에 붓고, 석출물을 여과 분리하였다. 계속해서, 얻어진 미정제물에 MeOH (250 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-12-1] 을 32.1 g 얻었다.1- (4-nitrophenyl) -4-piperidineamine (39.0 g, 116 mmol) and NMP (400 g) were added to a 500 mℓ 4-neck flask, and 1,3-DMCBDA (12.8 g, After adding 47 mmol), the mixture was stirred at 50 ° C for 6 h. Subsequently, pyridine (27.6 g, 349 mmol) and acetic anhydride (17.8 g, 175 mol) were added to the reaction solution and stirred at 50 ° C. After completion of the reaction, the reaction system was poured into pure water (2 L), and the precipitate was separated by filtration. Subsequently, 32.1 g of [DA-12-1] was obtained by adding MeOH (250 g) to the obtained crude product, and repulsing washing at room temperature.
2 ℓ 4 구 플라스크에 [DA-12-1] (32.1 g, 51 m㏖), DMF (960 g) 를 투입하고, 질소 치환 후, 5 wt% Pd/C (3.2 g) 를 첨가하고, 수소 치환하여 50 ℃ 에서 교반하였다. 반응 종료 후, 반응액을 여과 분리하고, 얻어진 여과물에 2N-염산 수용액 (1 ℓ) 을 첨가하고, 0.45 ㎛ 멤브레인 필터로 여과함으로써, Pd/C 를 제거하였다. 얻어진 여과액에 염기성이 될 때까지 트리에틸아민을 첨가하고, 석출물을 여과 분리하였다. 또한, 얻어진 미정제물에 MeOH (100 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-12] (연지색 고체) 를 22.1 g 얻었다. 목적물의 1H-NMR 의 결과를 이하에 나타낸다. 이 결과로부터, 얻어진 고체가, 목적으로 하는 [DA-12] 인 것을 확인하였다.[DA-12-1] (32.1 g, 51 mmol) and DMF (960 g) were added to a 2 L 4-neck flask, followed by nitrogen substitution, followed by addition of 5 wt% Pd / C (3.2 g), hydrogen Substituted and stirred at 50 ° C. After completion of the reaction, the reaction solution was separated by filtration, Pd / C was removed by adding a 2N-hydrochloric acid aqueous solution (1 L) to the obtained filtrate, and filtering with a 0.45 µm membrane filter. Triethylamine was added to the obtained filtrate until it became basic, and the precipitate was separated by filtration. In addition, 22.1 g of [DA-12] (light green solid) was obtained by adding MeOH (100 g) to the obtained crude product and repulsing and washing at room temperature. The results of 1 H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-12].
(합성예 12) (Synthesis Example 12)
[DA-13] 의 합성 : Synthesis of [DA-13]:
[화학식 34][Formula 34]
2 ℓ 4 구 플라스크에 4-아미노-1-tert-부톡시카르보닐피페리딘 (70.0 g, 350 m㏖), NMP (700 g) 를 투입하고, 수욕 중에서 1,3-DMCBDA (38.4 g, 171 m㏖) 를 첨가 후, 실온에서 6 h 교반하였다. 계속해서, 반응액에 피리딘 (82.9 g, 1049 m㏖), 무수 아세트산 (53.5 g, 524 ㏖) 을 투입하고, 50 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (3.5 ℓ) 에 붓고, 석출물을 여과 분리하였다. 계속해서, 얻어진 미정제물에 MeOH (300 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-13-1] 을 92.0 g 얻었다.4-amino-1-tert-butoxycarbonylpiperidine (70.0 g, 350 mmol) and NMP (700 g) were added to a 2 L 4-neck flask, and 1,3-DMCBDA (38.4 g, in a water bath). 171 mmol) and stirred at room temperature for 6 h. Subsequently, pyridine (82.9 g, 1049 mmol) and acetic anhydride (53.5 g, 524 mol) were added to the reaction solution and stirred at 50 ° C. After completion of the reaction, the reaction system was poured into pure water (3.5 L), and the precipitate was separated by filtration. Subsequently, 92.0 g of [DA-13-1] was obtained by adding MeOH (300 g) to the obtained crude product, and repulsing washing at room temperature.
2 ℓ 4 구 플라스크에 [DA-13-1] (92.0 g, 170 m㏖), CHCl3 (920 g) 을 투입하고, 수욕 중에서 트리플루오로아세트산 (193.3 g, 1700 ㏖) 을 적하 후, 50 ℃ 에서 교반하였다. 반응 종료 후, 석출물을 여과 분리하고, 얻어진 미정제물에 아세트산에틸 (300 g) 을 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-13-2] 를 97.8 g 얻었다.[DA-13-1] (92.0 g, 170 mmol) and CHCl 3 (920 g) were added to a 2 L 4-neck flask, and trifluoroacetic acid (193.3 g, 1700 mol) was added dropwise in a water bath, followed by 50 It was stirred at ℃. After completion of the reaction, the precipitate was filtered off, ethyl acetate (300 g) was added to the obtained crude product, and repulping and washing at room temperature gave 97.8 g of [DA-13-2].
1 ℓ 4 구 플라스크에 [DA-13-2] (40.0 g, 65 m㏖), 2-(4-니트로페닐)에틸브로마이드 (32.8 g, 143 m㏖), 탄산칼륨 (35.9 g, 260 m㏖), NMP (400 g) 를 투입하고, 60 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (2 ℓ) 에 붓고, 석출물을 여과 분리하였다. 얻어진 미정제물에 MeOH (200 g) 를 첨가하고, 60 ℃ 에서 리펄핑 세정함으로써, [DA-13-3] 을 27.5 g 얻었다.In a 1 ℓ 4-neck flask [DA-13-2] (40.0 g, 65 mmol), 2- (4-nitrophenyl) ethyl bromide (32.8 g, 143 mmol), potassium carbonate (35.9 g, 260 mmol) ), NMP (400 g) was added, and the mixture was stirred at 60 ° C. After completion of the reaction, the reaction system was poured into pure water (2 L), and the precipitate was separated by filtration. 27.5 g of [DA-13-3] was obtained by adding MeOH (200 g) to the obtained crude product and washing by repulping at 60 ° C.
3 ℓ 4 구 플라스크에 [DA-13-3] (29.3 g, 43 m㏖), DMF (900 g) 를 투입하고, 질소 치환 후, 5 wt% Pd/C (2.9 g) 를 첨가하고, 수소 치환하여 60 ℃ 에서 교반하였다. 반응 종료 후, 반응액을 농축하고, 얻어진 미정제물에 2N-염산 수용액 (1 ℓ) 을 첨가하고, 0.45 ㎛ 멤브레인 필터로 여과함으로써, Pd/C 를 제거하였다. 얻어진 여과액에 염기성이 될 때까지 트리에틸아민을 첨가하고, 석출물을 여과 분리하였다. 또한, 얻어진 미정제물에 MeOH (100 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-13] (피부색 고체) 을 8.7 g 얻었다. 목적물의 1H-NMR 의 결과를 이하에 나타낸다. 이 결과로부터, 얻어진 고체가, 목적으로 하는 [DA-13] 인 것을 확인하였다.[DA-13-3] (29.3 g, 43 mmol) and DMF (900 g) were added to a 3 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (2.9 g) was added, followed by hydrogen. Substituted and stirred at 60 ° C. After completion of the reaction, the reaction solution was concentrated, Pd / C was removed by adding a 2N-hydrochloric acid aqueous solution (1 L) to the obtained crude product and filtering through a 0.45 µm membrane filter. Triethylamine was added to the obtained filtrate until it became basic, and the precipitate was separated by filtration. Furthermore, 8.7 g of [DA-13] (skin solid) was obtained by adding MeOH (100 g) to the obtained crude product and repulsing and washing at room temperature. The results of 1 H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-13].
(합성예 13) (Synthesis Example 13)
[DA-14] 의 합성 : Synthesis of [DA-14]:
[화학식 35][Formula 35]
500 mℓ 4 구 플라스크에 tert-부틸4-(4-아미노페닐)피페리딘-1-카르복실레이트 (22.8 g, 82 m㏖), NMP (230 g) 를 투입하고, 수욕 중에서 1,3-DMCBDA (8.9 g, 40 m㏖) 를 첨가 후, 실온에서 6 h 교반하였다. 계속해서, 반응액에 피리딘 (39.1 g, 494 m㏖), 무수 아세트산 (25.2 g, 247 ㏖) 을 투입하고, 50 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (1.5 ℓ) 에 붓고, 석출물을 여과 분리하였다. 계속해서, 얻어진 미정제물에 MeOH (100 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-14-1] 을 28.5 g 얻었다.Tert-butyl4- (4-aminophenyl) piperidine-1-carboxylate (22.8 g, 82 mmol) and NMP (230 g) were added to a 500 mℓ 4-neck flask and 1,3- in a water bath. After adding DMCBDA (8.9 g, 40 mmol), the mixture was stirred at room temperature for 6 h. Subsequently, pyridine (39.1 g, 494 mmol) and acetic anhydride (25.2 g, 247 mol) were added to the reaction solution and stirred at 50 ° C. After the reaction was completed, the reaction system was poured into pure water (1.5 L), and the precipitate was separated by filtration. Subsequently, 28.5 g of [DA-14-1] was obtained by adding MeOH (100 g) to the obtained crude product, and repulsing washing at room temperature.
500 mℓ 4 구 플라스크에 [DA-14-1] (28.5 g, 39 m㏖), CHCl3 (290 g) 을 투입하고, 수욕 중에서 트리플루오로아세트산 (43.9 g, 385 ㏖) 을 적하 후, 50 ℃ 에서 교반하였다. 반응 종료 후, 석출물을 여과 분리하고, 얻어진 미정제물에 MeOH (150 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-14-2] 를 29.2 g 얻었다.[DA-14-1] (28.5 g, 39 mmol) and CHCl 3 (290 g) were added to a 500 mℓ 4-neck flask, and trifluoroacetic acid (43.9 g, 385 mol) was added dropwise in a water bath, followed by 50 It was stirred at ℃. After the completion of the reaction, the precipitate was separated by filtration, MeOH (150 g) was added to the obtained crude product, and repulping and washing at room temperature yielded [DA-14-2] of 29.2 g.
1 ℓ 4 구 플라스크에 [DA-14-2] (28.5 g, 37 m㏖), 2-(4-니트로페닐)에틸브로마이드 (29.5 g, 111 m㏖), 트리에틸아민 (30.0 g, 296 m㏖), NMP (290 g) 를 투입하고, 80 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (2.5 ℓ) 에 붓고, 석출물을 여과 분리하였다. 얻어진 미정제물에 MeOH (250 g) 를 첨가하고, 60 ℃ 에서 리펄핑 세정함으로써, [DA-14-3] 을 26.1 g 얻었다.In a 1 ℓ 4-neck flask [DA-14-2] (28.5 g, 37 mmol), 2- (4-nitrophenyl) ethyl bromide (29.5 g, 111 mmol), triethylamine (30.0 g, 296 m Mol) and NMP (290 g) were added and stirred at 80 ° C. After completion of the reaction, the reaction system was poured into pure water (2.5 L), and the precipitate was separated by filtration. 26.1 g of [DA-14-3] was obtained by adding MeOH (250 g) to the obtained crude product and washing by repulping at 60 ° C.
3 ℓ 4 구 플라스크에 [DA-14-3] (26.1 g, 31 m㏖), DMF (800 g) 를 투입하고, 질소 치환 후, 5 wt% Pd/C (2.6 g) 를 첨가하고, 수소 치환하여 80 ℃ 에서 교반하였다. 반응 종료 후, 반응액을 농축하고, 얻어진 미정제물에 2N-염산 수용액 (1 ℓ) 을 첨가하고, 0.45 ㎛ 멤브레인 필터로 여과함으로써, Pd/C 를 제거하였다. 얻어진 여과액에 염기성이 될 때까지 트리에틸아민을 첨가하고, 석출물을 여과 분리하였다. 또한, 얻어진 미정제물에 MeOH (100 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-14] (피부색 고체) 를 12.3 g 얻었다. 목적물의 1H-NMR 의 결과를 이하에 나타낸다. 이 결과로부터, 얻어진 고체가, 목적으로 하는 [DA-14] 인 것을 확인하였다.[DA-14-3] (26.1 g, 31 mmol) and DMF (800 g) were added to a 3 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (2.6 g) was added and hydrogen was added. Substituted and stirred at 80 ° C. After completion of the reaction, the reaction solution was concentrated, Pd / C was removed by adding a 2N-hydrochloric acid aqueous solution (1 L) to the obtained crude product and filtering through a 0.45 µm membrane filter. Triethylamine was added to the obtained filtrate until it became basic, and the precipitate was separated by filtration. Moreover, 12.3 g of [DA-14] (skin solid) was obtained by adding MeOH (100 g) to the obtained crude product and repulsing and washing at room temperature. The results of 1 H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-14].
(합성예 14) (Synthesis Example 14)
[DA-15] 의 합성 : Synthesis of [DA-15]:
[화학식 36][Formula 36]
1 ℓ 4 구 플라스크에 tert-부틸4-(4-아미노페닐)피페라진-1-카르복실레이트 (33.2 g, 120 m㏖), NMP (330 g) 를 투입하고, 수욕 중에서 1,3-DMCBDA (13.1 g, 59 m㏖) 를 첨가 후, 실온에서 6 h 교반하였다. 계속해서, 반응액에 피리딘 (28.4 g, 359 m㏖), 무수 아세트산 (18.3 g, 180 ㏖) 을 투입하고, 50 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (2 ℓ) 에 붓고, 석출물을 여과 분리하였다. 계속해서, 얻어진 미정제물에 MeOH (150 g) 를 첨가하고, 실온에서 리펄핑 세정함으로써, [DA-15-1] 을 40.7 g 얻었다.Tert-butyl4- (4-aminophenyl) piperazine-1-carboxylate (33.2 g, 120 mmol) and NMP (330 g) were added to a 1 liter 4-neck flask, and 1,3-DMCBDA in a water bath. (13.1 g, 59 mmol) was added, followed by stirring at room temperature for 6 h. Subsequently, pyridine (28.4 g, 359 mmol) and acetic anhydride (18.3 g, 180 mol) were added to the reaction solution and stirred at 50 ° C. After completion of the reaction, the reaction system was poured into pure water (2 L), and the precipitate was separated by filtration. Subsequently, 40.7 g of [DA-15-1] was obtained by adding MeOH (150 g) to the obtained crude product, and repulsing washing at room temperature.
2 ℓ 4 구 플라스크에 [DA-15-1] (40.7 g, 55 m㏖), CHCl3 (400 g) 을 투입하고, 수욕 중에서 트리플루오로아세트산 (62.6 g, 548 ㏖) 을 적하 후, 50 ℃ 에서 교반하였다. 반응 종료 후, 석출물을 여과 분리하고, 얻어진 미정제물에 THF (200 g) 를 첨가하고, 50 ℃ 에서 리펄핑 세정함으로써, [DA-15-2] 를 21.8 g 얻었다.[DA-15-1] (40.7 g, 55 mmol) and CHCl 3 (400 g) were added to a 2 L 4-neck flask, and trifluoroacetic acid (62.6 g, 548 mol) was added dropwise in a water bath, followed by 50 It was stirred at ℃. After completion of the reaction, the precipitate was separated by filtration, THF (200 g) was added to the obtained crude product, and 21.8 g of [DA-15-2] was obtained by repulsing and washing at 50 ° C.
500 mℓ 4 구 플라스크에 [DA-15-2] (21.8 g, 28 m㏖), 2-(4-니트로페닐)에틸브로마이드 (14.3 g, 62 m㏖), 트리에틸아민 (11.4 g, 113 m㏖), NMP (220 g) 를 투입하고, 80 ℃ 에서 교반하였다. 반응 종료 후, 반응계를 순수 (1 ℓ) 에 붓고, 석출물을 여과 분리하였다. 얻어진 미정제물에 MeOH (200 g) 를 첨가하고, 60 ℃ 에서 리펄핑 세정함으로써, [DA-15-3] 을 17.9 g 얻었다.[DA-15-2] (21.8 g, 28 mmol), 2- (4-nitrophenyl) ethyl bromide (14.3 g, 62 mmol), triethylamine (11.4 g, 113 m) in a 500 mℓ 4-neck flask Mol) and NMP (220 g) were added and stirred at 80 ° C. After completion of the reaction, the reaction system was poured into pure water (1 L), and the precipitate was separated by filtration. 17.9 g of [DA-15-3] was obtained by adding MeOH (200 g) to the obtained crude material and washing by repulping at 60 ° C.
3 ℓ 4 구 플라스크에 [DA-14-3] (17.9 g, 21 m㏖), DMF (540 g) 를 투입하고, 질소 치환 후, 5 wt% Pd/C (1.8 g) 를 첨가하고, 수소 치환하여 80 ℃ 에서 교반하였다. 반응 종료 후, 반응액을 농축하고, 얻어진 미정제물에 2N-염산 수용액 (500 ㎖) 을 첨가하고, 0.45 ㎛ 멤브레인 필터로 여과함으로써, Pd/C 를 제거하였다. 얻어진 여과액에 염기성이 될 때까지 트리에틸아민을 첨가하고, 석출물을 여과 분리하였다. 또한, 얻어진 미정제물에 MeOH (50 g) 를 첨가하고, 60 ℃ 에서 리펄핑 세정함으로써, [DA-15] (피부색 고체) 를 5.7 g 얻었다. 목적물의 1H-NMR 의 결과를 이하에 나타낸다. 이 결과로부터, 얻어진 고체가, 목적으로 하는 [DA-15] 인 것을 확인하였다.[DA-14-3] (17.9 g, 21 mmol) and DMF (540 g) were added to a 3 L 4-neck flask, and after nitrogen substitution, 5 wt% Pd / C (1.8 g) was added, followed by hydrogen. Substituted and stirred at 80 ° C. After completion of the reaction, the reaction solution was concentrated, Pd / C was removed by adding a 2N-hydrochloric acid aqueous solution (500 mL) to the obtained crude product and filtration through a 0.45 μm membrane filter. Triethylamine was added to the obtained filtrate until it became basic, and the precipitate was separated by filtration. Further, 5.7 g of [DA-15] (skin color solid) was obtained by adding MeOH (50 g) to the obtained crude product, and repulsing and washing at 60 ° C. The results of 1 H-NMR of the target product are shown below. From this result, it was confirmed that the obtained solid was the target [DA-15].
<디아민 화합물의 실온 시에 있어서의 NMP 에 대한 포화 용해도의 측정><Measurement of saturated solubility of diamine compound in NMP at room temperature>
(실시예 1) (Example 1)
디아민 화합물 [DA-1] 을 60 ℃ 로 가열한 NMP (2 g) 에 용해되지 않는게 생길 때까지 첨가하고, 60 ℃ 에서 1 시간 교반하였다. 가열 후, 실온에서 6 시간 방랭하고, 침전물을 제거하여, 실온 시에 있어서의 [DA-1] 의 NMP 포화 용액을 제조하였다. 계속해서, 표품으로서, 1 wt% 의 [DA-1] 의 NMP 용액을 제조하고, HPLC 를 사용하여, 피크 면적을 측정하였다. 마지막으로, 제조한 포화 용액 (1 g) 에 NMP (39 g) 를 첨가하여 피크 면적을 측정하고, [DA-1] 의 실온 시에 있어서의 NMP 에 대한 포화 용해도를 산출하였다.The diamine compound [DA-1] was added to NMP (2 g) heated to 60 ° C. until insoluble, and stirred at 60 ° C. for 1 hour. After heating, it was allowed to cool at room temperature for 6 hours, and the precipitate was removed to prepare a saturated NMP solution of [DA-1] at room temperature. Subsequently, a 1 wt% [DA-1] NMP solution was prepared as a sample, and the peak area was measured using HPLC. Finally, NMP (39 g) was added to the prepared saturated solution (1 g) to measure the peak area, and the saturated solubility of [DA-1] in NMP at room temperature was calculated.
(실시예 2 ∼ 9, 비교예 1 ∼ 2) (Examples 2 to 9 and Comparative Examples 1 to 2)
표 1 에 나타내는 바와 같이, 실시예 1 과 동일한 방법을 사용하여 실시예 2 ∼ 9 도 산출하였다. 또, 비교예 1 ∼ 2 도 동일한 방법으로 산출하였다.As shown in Table 1, Examples 2-9 were also calculated using the same method as in Example 1. Moreover, Comparative Examples 1-2 were computed by the same method.
표 1 에 나타내는 바와 같이, 실시예 1 ∼ 9 의 본 발명의 디아민 화합물 (DA-1 ∼ DA-8, DA-11) 의 실온 시에 있어서의 NMP 에 대한 포화 용해도는, 비교예 1 의 디아민 화합물 (DA-9) 와 비교해서, 양호한 용해성을 나타내는 것이 확인되었다. 또, 실시예 8 의 디아민 화합물 (DA-8) 의 실온 시에 있어서의 NMP 에 대한 포화 용해도는, 비교예 2 의 디아민 화합물 (DA-10) 과 비교해서, 양호한 용해성을 나타내는 것도 확인되었다. 이상으로부터, 디아민 화합물을 본 발명의 구조로 함으로써, NMP 에 대한 용해성의 향상이 가능한 것이 시사되었다.As shown in Table 1, the saturation solubility of the diamine compounds (DA-1 to DA-8, DA-11) of the present invention in Examples 1 to 9 at room temperature is the diamine compounds of Comparative Example 1 It was confirmed that it showed good solubility compared with (DA-9). Moreover, it was also confirmed that the saturated solubility of the diamine compound (DA-8) of Example 8 in NMP at room temperature showed good solubility compared to the diamine compound (DA-10) of Comparative Example 2. From the above, it was suggested that the solubility in NMP can be improved by using the diamine compound as the structure of the present invention.
<중합체의 분자량의 측정><Measurement of molecular weight of polymer>
실시예에 있어서의 폴리이미드, 폴리아믹산, 폴리아믹산에스테르의 분자량은, (주) Shodex 사 제조 상온 겔 침투 크로마토그래피 (GPC) 장치 (GPC-101), Shodex 사 제조 칼럼 (KD-803, KD-805) 을 사용하여 이하와 같이 하여 측정하였다.The molecular weights of the polyimide, polyamic acid, and polyamic acid ester in Examples are normal temperature gel permeation chromatography (GPC) equipment (GPC-101) manufactured by Shodex Co., Ltd., and columns manufactured by Shodex (KD-803, KD-) 805) was measured as follows.
칼럼 온도 : 50 ℃ Column temperature: 50 ℃
용리액 : DMF (첨가제로서, 브롬화리튬-수화물 (LiBr·H2O) 이 30 m㏖/ℓ, 인산·무수 결정 (o-인산) 이 30 m㏖/ℓ, THF 가 10 ㎖/ℓ) Eluent: DMF (as an additive, lithium bromide-hydrate (LiBrH 2 O) is 30 mmol / L, phosphoric anhydride (o-phosphoric acid) is 30 mmol / L, THF is 10 mL / L)
유속 : 1.0 ㎖/분Flow rate: 1.0 ml / min
검량선 작성용 표준 샘플 : 토소사 제조 TSK 표준 폴리에틸렌옥사이드 (분자량 약 900,000, 150,000, 100,000, 30,000), 및, 폴리머 래버러토리사 제조 폴리에틸렌글리콜 (분자량 약 12,000, 4,000, 1,000).Standard sample for calibration curve preparation: TSK standard polyethylene oxide (molecular weights about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol (molecular weights about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.
(중합예 1) (Polymerization Example 1)
CBDA 를 0.18 g (0.93 ㏖) 과 DA-1 을 0.64 g (1.0 m㏖) 을 NMP (7.48 g) 중, 실온에서 16 시간 반응시켜, 폴리아믹산-폴리이미드 중합 용액 (PI-1) 을 조제하였다. 이 폴리아믹산-폴리이미드는, 수 평균 분자량이 약 29500 이었다.CBDA was reacted with 0.18 g (0.93 mol) and DA-1 with 0.64 g (1.0 mmol) in NMP (7.48 g) at room temperature for 16 hours to prepare a polyamic acid-polyimide polymerization solution (PI-1). . This polyamic acid-polyimide had a number average molecular weight of about 29500.
(중합예 2) (Polymerization Example 2)
CBDA 를 0.18 g (0.93 ㏖) 과 DA-2 를 0.70 g (1.0 m㏖) 을 NMP (7.98 g) 중, 실온에서 16 시간 반응시켜, 폴리아믹산-폴리이미드 중합 용액 (PI-2) 를 조제하였다. 이 폴리아믹산-폴리이미드는, 수 평균 분자량이 약 30000 이었다.CBDA was reacted with 0.18 g (0.93 mol) and DA-2 with 0.70 g (1.0 mmol) in NMP (7.98 g) at room temperature for 16 hours to prepare a polyamic acid-polyimide polymerization solution (PI-2). . This polyamic acid-polyimide had a number average molecular weight of about 30000.
(중합예 3) (Polymerization Example 3)
CBDA 를 0.18 g (0.93 ㏖) 과 DA-3 을 0.78 g (1.0 m㏖) 을 NMP (8.74 g) 중, 실온에서 16 시간 반응시켜, 폴리아믹산-폴리이미드 중합 용액 (PI-3) 을 조제하였다. 이 폴리아믹산-폴리이미드는, 수 평균 분자량이 약 32000 이었다.A polyamic acid-polyimide polymerization solution (PI-3) was prepared by reacting 0.18 g (0.93 mol) of CBDA and 0.78 g (1.0 mmol) of DA-3 in NMP (8.74 g) at room temperature for 16 hours. . This polyamic acid-polyimide had a number average molecular weight of about 32000.
(중합예 4) (Polymerization Example 4)
CBDA 를 0.18 g (0.93 ㏖) 과 DA-4 를 0.64 g (1.0 m㏖) 을 NMP (7.44 g) 중, 실온에서 16 시간 반응시켜, 폴리아믹산-폴리이미드 중합 용액 (PI-4) 를 조제하였다. 이 폴리아믹산-폴리이미드는, 수 평균 분자량이 약 14800 이었다.A polyamic acid-polyimide polymerization solution (PI-4) was prepared by reacting 0.18 g (0.93 mol) of CBDA and 0.64 g (1.0 mmol) of DA-4 in NMP (7.44 g) at room temperature for 16 hours. . This polyamic acid-polyimide had a number average molecular weight of about 14800.
(중합예 5) (Polymerization Example 5)
CBDA 를 0.18 g (0.93 ㏖) 과 DA-5 를 0.64 g (1.0 m㏖) 을 NMP (7.44 g) 중, 실온에서 16 시간 반응시켜, 폴리아믹산-폴리이미드 중합 용액 (PI-5) 를 조제하였다. 이 폴리아믹산-폴리이미드는, 수 평균 분자량이 약 9900 이었다.A polyamic acid-polyimide polymerization solution (PI-5) was prepared by reacting 0.18 g (0.93 mol) of CBDA and 0.64 g (1.0 mmol) of DA-5 in NMP (7.44 g) at room temperature for 16 hours. . This polyamic acid-polyimide had a number average molecular weight of about 9900.
(중합예 6) (Polymerization Example 6)
CBDA 를 0.18 g (0.93 ㏖) 과 DA-6 을 0.67 g (1.0 m㏖) 을 NMP (7.69 g) 중, 실온에서 16 시간 반응시켜, 폴리아믹산-폴리이미드 중합 용액 (PI-6) 을 조제하였다. 이 폴리아믹산-폴리이미드는, 수 평균 분자량이 약 8700 이었다.A polyamic acid-polyimide polymerization solution (PI-6) was prepared by reacting 0.18 g (0.93 mol) of CBDA with 0.67 g (1.0 mmol) of DA-6 in NMP (7.69 g) at room temperature for 16 hours. . This polyamic acid-polyimide had a number average molecular weight of about 8700.
(중합예 7) (Polymerization Example 7)
CBDA 를 0.18 g (0.93 ㏖) 과 DA-7 을 0.67 g (1.0 m㏖) 을 NMP (7.69 g) 중, 실온에서 16 시간 반응시켜, 폴리아믹산-폴리이미드 중합 용액 (PI-7) 을 조제하였다. 이 폴리아믹산-폴리이미드는, 수 평균 분자량이 약 16900 이었다.A polyamic acid-polyimide polymerization solution (PI-7) was prepared by reacting 0.18 g (0.93 mol) of CBDA with 0.67 g (1.0 mmol) of DA-7 in NMP (7.69 g) at room temperature for 16 hours. . This polyamic acid-polyimide had a number average molecular weight of about 16900.
(중합예 8) (Polymerization Example 8)
CBDA 를 0.18 g (0.93 ㏖) 과 DA-8 을 0.46 g (1.0 m㏖) 을 NMP (5.78 g) 중, 실온에서 16 시간 반응시켜, 폴리아믹산-폴리이미드 중합 용액 (PI-8) 을 조제하였다. 이 폴리아믹산-폴리이미드는, 수 평균 분자량이 약 8900 이었다.A polyamic acid-polyimide polymerization solution (PI-8) was prepared by reacting 0.18 g (0.93 mol) of CBDA and 0.46 g (1.0 mmol) of DA-8 in NMP (5.78 g) at room temperature for 16 hours. . This polyamic acid-polyimide had a number average molecular weight of about 8900.
(중합예 9) (Polymerization Example 9)
CBDA 를 0.18 g (0.93 ㏖) 과 DA-9 를 0.40 g (1.0 m㏖) 을 NMP (5.28 g) 중, 실온에서 16 시간 반응시켜, 폴리아믹산-폴리이미드 중합 용액 (PI-9) 를 조제하였다. 이 폴리아믹산-폴리이미드는, 수 평균 분자량이 약 13600 이었다.0.18 g (0.93 mol) of CBDA and 0.40 g (1.0 mmol) of DA-9 were reacted in NMP (5.28 g) at room temperature for 16 hours to prepare a polyamic acid-polyimide polymerization solution (PI-9). . This polyamic acid-polyimide had a number average molecular weight of about 13600.
(중합예 10) (Polymerization Example 10)
CBDA 를 0.18 g (0.93 ㏖) 과 DA-10 을 0.43 g (1.0 m㏖) 을 NMP (5.53 g) 중, 실온에서 16 시간 반응시켜, 폴리아믹산-폴리이미드 중합 용액 (PI-10) 을 조제하였다. 이 폴리아믹산-폴리이미드는, 수 평균 분자량이 약 8500 이었다.0.18 g (0.93 mol) of CBDA and 0.43 g (1.0 mmol) of DA-10 were reacted in NMP (5.53 g) at room temperature for 16 hours to prepare a polyamic acid-polyimide polymerization solution (PI-10). . This polyamic acid-polyimide had a number average molecular weight of about 8500.
(중합예 11) (Polymerization Example 11)
CBDA 를 0.18 g (0.93 ㏖) 과 DA-11 을 0.78 g (1.0 m㏖) 을 NMP (8.71 g) 중, 실온에서 16 시간 반응시켜, 폴리아믹산-폴리이미드 중합 용액 (PI-11) 을 조제하였다. 이 폴리아믹산-폴리이미드는, 수 평균 분자량이 약 9600 이었다.0.18 g (0.93 mol) of CBDA and 0.78 g (1.0 mmol) of DA-11 were reacted in NMP (8.71 g) at room temperature for 16 hours to prepare a polyamic acid-polyimide polymerization solution (PI-11). . This polyamic acid-polyimide had a number average molecular weight of about 9600.
(중합예 12) (Polymerization Example 12)
CBDA 를 0.18 g (0.93 ㏖) 과 DA-12 를 0.57 g (1.0 m㏖) 을 NMP (6.78 g) 중, 실온에서 16 시간 반응시켜, 폴리아믹산-폴리이미드 중합 용액 (PI-12) 를 조제하였다. 이 폴리아믹산-폴리이미드는, 수 평균 분자량이 약 11200 이었다.A polyamic acid-polyimide polymerization solution (PI-12) was prepared by reacting 0.18 g (0.93 mol) of CBDA and 0.57 g (1.0 mmol) of DA-12 in NMP (6.78 g) at room temperature for 16 hours. . This polyamic acid-polyimide had a number average molecular weight of about 11200.
<폴리아믹산-폴리이미드의 용해성의 측정><Measurement of solubility of polyamic acid-polyimide>
(실시예 10) (Example 10)
폴리아믹산-폴리이미드 중합 용액 (PI-1) 3 g 에 BCS 를 첨가하여 교반하고, 폴리아믹산-폴리이미드가 6 질량%, NMP 가 54 질량%, BCS 가 40 질량% 가 되도록 용액 (A-1) 을 조제하고, 실온, 냉동 (―20 ℃) 시에서의 폴리아믹산-폴리이미드의 용해성을 확인하였다.BCS was added to 3 g of the polyamic acid-polyimide polymerization solution (PI-1) and stirred, and the solution (A-1) so that the polyamic acid-polyimide was 6 mass%, NMP was 54 mass%, and BCS was 40 mass%. ) Was prepared, and the solubility of the polyamic acid-polyimide at room temperature and freezing (--20 ° C) was confirmed.
(실시예 11 ∼ 19, 비교예 3 ∼ 4) (Examples 11 to 19, Comparative Examples 3 to 4)
표 2 에 나타내는 바와 같이, 실시예 10 과 동일한 방법을 사용하여, 실시예 11 ∼ 19 의 용해성을 확인하였다. 또, 비교예 3 ∼ 4 도 동일한 방법으로 용해성을 확인하였다. 또한, 용해성을 하기의 기준으로 나타낸다.As shown in Table 2, the solubility of Examples 11 to 19 was confirmed using the same method as in Example 10. Moreover, solubility was confirmed also in Comparative Examples 3-4 by the same method. In addition, solubility is shown by the following criteria.
○ : 탁함, 석출물, 겔화 없음 ○: No cloudiness, precipitates, or gelation
△ : 소량의 탁함 있음 △: There is a small amount of turbidity
× : 탁함, 석출물, 겔화 있음 ×: turbidity, precipitate, gelation
표 2 에 나타내는 바와 같이, 실시예 10 ∼ 19 의 본 발명의 디아민 화합물 (DA-1 ∼ DA-8, DA-11 ∼ DA-12) 을 중합하고, 빈용매인 BCS 로 희석한 폴리아믹산-폴리이미드 용액은, 실온, 및 냉동 (―20 ℃) 시에서도, 바니시에 탁함, 석출물, 겔화 등은 없고, 양호한 용해성을 나타내는 것이 확인되었다. 한편, 비교예 3, 4 의 폴리아믹산-폴리이미드 용액은, 실온, 및 냉동 (―20 ℃) 시에, 바니시에 탁함, 석출물, 겔화 등이 확인되었다. 이상으로부터, 폴리아믹산-폴리이미드를 중합할 때의 디아민 화합물을 본 발명의 구조로 함으로써, 폴리머의 용해성의 향상이 가능한 것이 시사되었다.As shown in Table 2, the polyamic acid-polyyi obtained by polymerizing the diamine compounds (DA-1 to DA-8, DA-11 to DA-12) of the present inventions of Examples 10 to 19 and diluting them with poor solvent BCS. It was confirmed that the mid-solution exhibited good solubility without roominess, precipitate, gelling, etc., even at room temperature and freezing (--20 ° C). On the other hand, in the polyamic acid-polyimide solutions of Comparative Examples 3 and 4, at room temperature and freezing (--20 ° C), turbidity, precipitates, and gelation of the varnish were confirmed. From the above, it was suggested that the solubility of the polymer can be improved by making the diamine compound for polymerizing the polyamic acid-polyimide the structure of the present invention.
산업상 이용가능성Industrial availability
본 발명의 디아민 및 그것으로부터 얻어지는 중합체는, 저렴한 원료를 사용하여, 각종 특성을 용이하게 부여할 수 있기 때문에 도료, 전자 재료 등의 분야, 예를 들어 액정 배향막 등으로서의 유용성이 기대된다.Since the diamine of the present invention and the polymer obtained therefrom can easily impart various properties using inexpensive raw materials, usefulness is expected in fields such as paints and electronic materials, for example, liquid crystal alignment films.
Claims (2)
R1, R2, R3 및 R4 는 각각 독립적으로 H, CH3 또는 CF3 을 나타내고, 단, R1, R2, R3 및 R4 중, 반드시 하나는 CH3 또는 CF3 을 나타내고,
W1 은, 단결합 또는 페닐렌을 나타내고, 페닐렌은, 할로겐기, 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 알킬기, 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 알콕시기, 하이드록실기, 시아노기, 디알킬아미노기 (알킬기는, 각각 독립적으로, 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 알킬기이다), 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 에스테르기, 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 아실기, 카르복실기, 알데히드기, 니트로기, Boc 보호한 아미노기로 이루어지는 제 1 군에서 선택되는 치환기로 치환되어도 되고, 2 개의 W1 은 서로 동일해도 되고 상이해도 되고,
W2 는 페닐렌을 나타내고, 페닐렌은, 상기 제 1 군에서 선택되는 치환기로 치환되어도 되고, 2 개의 W2 는 서로 동일해도 되고 상이해도 되고,
L 은, 상기 제 1 군에서 선택되는 치환기로 치환되어 있어도 되는 탄소수 1 ∼ 10 의 직사슬 또는 분기 사슬의 알킬렌기를 나타내고, L 중의 -CH2- 는, -CH=CH-, -C≡C-, -CF2-, -C(CF3)2-, -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -N(CH3)-, -NHCONH-, -N(Boc)CONH-, -NHCON(Boc)-, -N(Boc)CON(Boc)-, -NHCOO-, -OCONH-, -CO-, -S-, -SO2-, -N(Boc)-, -Si(CH3)2OSi(CH3)2-, -Si(CH3)2OSi(CH3)2OSi(CH3)2-, 피페리딘 고리 및 피페라진 고리로 이루어지는 제 2 군에서 선택되는 기로 치환되어 있어도 되고, 단, 제 2 군에서 선택되는 기끼리는, 탄소 원자를 제외한 동일한 원자가 결합하지 않는 조건으로 서로 이웃해도 된다.The diamine compound represented by the following general formula (1).
R 1 , R 2 , R 3 and R 4 each independently represent H, CH 3 or CF 3 , provided that one of R 1 , R 2 , R 3 and R 4 necessarily represents CH 3 or CF 3 ,
W 1 represents a single bond or phenylene, and phenylene is a halogen group, a linear or branched alkyl group having 1 to 10 carbon atoms, a straight or branched alkoxy group having 1 to 10 carbon atoms, a hydroxyl group, Cyano group, dialkylamino group (each alkyl group is a C1-C10 linear or branched chain alkyl group each independently), C1-C10 straight chain or branched chain ester group, C1-C10 straight chain Or it may be substituted with a substituent selected from the group consisting of a branched acyl group, a carboxyl group, an aldehyde group, a nitro group, a Boc-protected amino group, and two W 1 may be the same or different from each other,
W 2 represents phenylene, and phenylene may be substituted with a substituent selected from the first group, and two W 2 may be the same or different from each other,
L represents a linear or branched alkylene group having 1 to 10 carbon atoms which may be substituted with a substituent selected from the first group, and -CH 2 -in L represents -CH = CH-, -C≡C -, -CF 2- , -C (CF 3 ) 2- , -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -N (CH 3 )-, -NHCONH -, -N (Boc) CONH-, -NHCON (Boc)-, -N (Boc) CON (Boc)-, -NHCOO-, -OCONH-, -CO-, -S-, -SO 2 -,- N (Boc)-, -Si (CH 3 ) 2 OSi (CH 3 ) 2- , -Si (CH 3 ) 2 OSi (CH 3 ) 2 OSi (CH 3 ) 2- , piperidine ring and piperazine ring It may be substituted with a group selected from the second group consisting of, provided that the groups selected from the second group may be adjacent to each other on the condition that the same atoms other than the carbon atom are not bonded.
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