JPH04198167A - Production of maleimides - Google Patents
Production of maleimidesInfo
- Publication number
- JPH04198167A JPH04198167A JP2325522A JP32552290A JPH04198167A JP H04198167 A JPH04198167 A JP H04198167A JP 2325522 A JP2325522 A JP 2325522A JP 32552290 A JP32552290 A JP 32552290A JP H04198167 A JPH04198167 A JP H04198167A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- tin
- substituted
- reaction
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 150000003923 2,5-pyrrolediones Chemical class 0.000 title description 2
- -1 N- substituted maleinamic acid Chemical class 0.000 claims abstract description 30
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 239000002798 polar solvent Substances 0.000 claims abstract description 9
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 20
- 238000006297 dehydration reaction Methods 0.000 claims description 16
- 230000018044 dehydration Effects 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001412 amines Chemical class 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000008096 xylene Substances 0.000 abstract description 3
- 150000003738 xylenes Chemical class 0.000 abstract description 2
- 238000006358 imidation reaction Methods 0.000 abstract 3
- 230000015572 biosynthetic process Effects 0.000 abstract 2
- 238000010533 azeotropic distillation Methods 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 26
- 239000003377 acid catalyst Substances 0.000 description 13
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- FSQQTNAZHBEJLS-UPHRSURJSA-N maleamic acid Chemical compound NC(=O)\C=C/C(O)=O FSQQTNAZHBEJLS-UPHRSURJSA-N 0.000 description 11
- 150000007513 acids Chemical class 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 8
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000010992 reflux Methods 0.000 description 5
- 239000012024 dehydrating agents Substances 0.000 description 4
- 150000003606 tin compounds Chemical class 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 150000003141 primary amines Chemical class 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- ALHBQZRUBQFZQV-UHFFFAOYSA-N tin;tetrahydrate Chemical compound O.O.O.O.[Sn] ALHBQZRUBQFZQV-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 2
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- LWHKXKZPLXYXRO-UHFFFAOYSA-L dichloro-bis(ethenyl)stannane Chemical compound C=C[Sn](Cl)(Cl)C=C LWHKXKZPLXYXRO-UHFFFAOYSA-L 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical compound OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- RCFKIGITIBNPQE-UHFFFAOYSA-N methyl 2,2-difluoro-3-oxopentanoate Chemical compound CCC(=O)C(F)(F)C(=O)OC RCFKIGITIBNPQE-UHFFFAOYSA-N 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- 235000011007 phosphoric acid Nutrition 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- 239000001119 stannous chloride Substances 0.000 description 2
- ZSUXOVNWDZTCFN-UHFFFAOYSA-L tin(ii) bromide Chemical compound Br[Sn]Br ZSUXOVNWDZTCFN-UHFFFAOYSA-L 0.000 description 2
- JTDNNCYXCFHBGG-UHFFFAOYSA-L tin(ii) iodide Chemical compound I[Sn]I JTDNNCYXCFHBGG-UHFFFAOYSA-L 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- DFQUBYCHLQAFOW-NSCUHMNNSA-N (e)-4-(methylamino)-4-oxobut-2-enoic acid Chemical compound CNC(=O)\C=C\C(O)=O DFQUBYCHLQAFOW-NSCUHMNNSA-N 0.000 description 1
- RGFQVACBIDGKBN-SREVYHEPSA-N (z)-4-(2-methylanilino)-4-oxobut-2-enoic acid Chemical compound CC1=CC=CC=C1NC(=O)\C=C/C(O)=O RGFQVACBIDGKBN-SREVYHEPSA-N 0.000 description 1
- MZRKEXUFISGDKS-PLNGDYQASA-N (z)-4-(3-nitroanilino)-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)NC1=CC=CC([N+]([O-])=O)=C1 MZRKEXUFISGDKS-PLNGDYQASA-N 0.000 description 1
- BEWIWYDBTBVVIA-PLNGDYQASA-N (z)-4-(butylamino)-4-oxobut-2-enoic acid Chemical compound CCCCNC(=O)\C=C/C(O)=O BEWIWYDBTBVVIA-PLNGDYQASA-N 0.000 description 1
- GYTRFGDAJKCLKB-VURMDHGXSA-N (z)-4-(chloroamino)-4-oxo-2-phenylbut-2-enoic acid Chemical compound ClNC(=O)\C=C(C(=O)O)\C1=CC=CC=C1 GYTRFGDAJKCLKB-VURMDHGXSA-N 0.000 description 1
- DEWAGGNAHQGYBD-SREVYHEPSA-N (z)-4-(cyclohexylamino)-4-oxobut-2-enoic acid Chemical compound OC(=O)\C=C/C(=O)NC1CCCCC1 DEWAGGNAHQGYBD-SREVYHEPSA-N 0.000 description 1
- NWODYZCQADERLP-HNENSFHCSA-N (z)-4-(octadecylamino)-4-oxobut-2-enoic acid Chemical compound CCCCCCCCCCCCCCCCCCNC(=O)\C=C/C(O)=O NWODYZCQADERLP-HNENSFHCSA-N 0.000 description 1
- PTDZPBBGCHHKCY-HJWRWDBZSA-N (z)-4-(octylamino)-4-oxobut-2-enoic acid Chemical compound CCCCCCCCNC(=O)\C=C/C(O)=O PTDZPBBGCHHKCY-HJWRWDBZSA-N 0.000 description 1
- OEMHMEWQGZQJSC-PEPZGXQESA-N (z)-4-[3-[[(z)-3-carboxyprop-2-enoyl]amino]-4-methylanilino]-4-oxobut-2-enoic acid Chemical compound CC1=CC=C(NC(=O)\C=C/C(O)=O)C=C1NC(=O)\C=C/C(O)=O OEMHMEWQGZQJSC-PEPZGXQESA-N 0.000 description 1
- BSSNZUFKXJJCBG-UPHRSURJSA-N (z)-but-2-enediamide Chemical compound NC(=O)\C=C/C(N)=O BSSNZUFKXJJCBG-UPHRSURJSA-N 0.000 description 1
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- IKCLCGXPQILATA-UHFFFAOYSA-N 2-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1Cl IKCLCGXPQILATA-UHFFFAOYSA-N 0.000 description 1
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- UXIAYWKXDXAWJB-PLNGDYQASA-N 3-[[(z)-3-carboxyprop-2-enoyl]amino]benzoic acid Chemical compound OC(=O)\C=C/C(=O)NC1=CC=CC(C(O)=O)=C1 UXIAYWKXDXAWJB-PLNGDYQASA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- UAEPNZWRGJTJPN-UHFFFAOYSA-N Methylcyclohexane Natural products CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 1
- 229920001890 Novodur Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- 229910021623 Tin(IV) bromide Inorganic materials 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- BTVURVLQSDTSSS-UHFFFAOYSA-L bis(triethylstannyl) sulfate Chemical class CC[Sn](CC)(CC)OS(=O)(=O)O[Sn](CC)(CC)CC BTVURVLQSDTSSS-UHFFFAOYSA-L 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 1
- 229940106681 chloroacetic acid Drugs 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- PEGCFRJASNUIPX-UHFFFAOYSA-L ditert-butyltin(2+);dichloride Chemical compound CC(C)(C)[Sn](Cl)(Cl)C(C)(C)C PEGCFRJASNUIPX-UHFFFAOYSA-L 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- BFWMWWXRWVJXSE-UHFFFAOYSA-M fentin hydroxide Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(O)C1=CC=CC=C1 BFWMWWXRWVJXSE-UHFFFAOYSA-M 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011403 purification operation Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229940108184 stannous iodide Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- NJASUIDIZMMYED-UHFFFAOYSA-N tetra(propan-2-yl)stannane Chemical compound CC(C)[Sn](C(C)C)(C(C)C)C(C)C NJASUIDIZMMYED-UHFFFAOYSA-N 0.000 description 1
- TWRYZRQZQIBEIE-UHFFFAOYSA-N tetramethoxystannane Chemical compound [Sn+4].[O-]C.[O-]C.[O-]C.[O-]C TWRYZRQZQIBEIE-UHFFFAOYSA-N 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001662 tin mineral Inorganic materials 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical class [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
- CVNKFOIOZXAFBO-UHFFFAOYSA-J tin(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Sn+4] CVNKFOIOZXAFBO-UHFFFAOYSA-J 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- BOEGBYDAWIJZGT-UHFFFAOYSA-N trichloromethyltin Chemical compound ClC(Cl)(Cl)[Sn] BOEGBYDAWIJZGT-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- CDIFRACRLLNHOO-UHFFFAOYSA-N trimethyl(2-trimethylstannylethynyl)stannane Chemical group C[Sn](C)(C)C#C[Sn](C)(C)C CDIFRACRLLNHOO-UHFFFAOYSA-N 0.000 description 1
- NDUYAGLANMHJHF-UHFFFAOYSA-N triphenyl(prop-2-enyl)stannane Chemical compound C=1C=CC=CC=1[Sn](C=1C=CC=CC=1)(CC=C)C1=CC=CC=C1 NDUYAGLANMHJHF-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Pyrrole Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はＮ−置換マレインアミド酸類を金属スズおよび
スズ元素を含有する化合物の中から選ばれた少なくとも
一種の触媒の存在下で、無水マレイン酸を供給しながら
脱水イミド化反応を行うことを特徴とするＮ−置換マレ
イミド類の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention is directed to converting N-substituted maleamide acids into maleic anhydride in the presence of at least one catalyst selected from metal tin and compounds containing the tin element. The present invention relates to a method for producing N-substituted maleimides, characterized by carrying out a dehydration imidization reaction while supplying an acid.
Ｎ−置換マレイミド類は、種々な樹脂、農薬、置薬等の
原料として有用であり、特に近年スチレン系樹脂の耐熱
性改暮のために大量に利用され、またその他の樹脂の改
質用コモノマーやポリマーブレンド用コポリマー等とし
て用いられようとしている。N-substituted maleimides are useful as raw materials for various resins, agricultural chemicals, medicines, etc. In recent years, they have been used in large quantities to improve the heat resistance of styrenic resins, and are also used as comonomers for modifying other resins. It is expected to be used as a copolymer for polymer blends.
〔従来の技術）
Ｎ−置換マレイミド類の製造方法としては古（からいく
つかの方法が知られている。−船釣な製造方法は無水マ
レイン酸と一級アミンとを反応させてＮ−１１１０マレ
インアミド酸とし、これを脱水閉環させてイミド化する
方法である。これには大別すると脱水剤を用いる方法と
触媒による方法がある。[Prior art] Several methods have been known since ancient times for producing N-substituted maleimides. - The traditional production method involves reacting maleic anhydride with a primary amine to produce N-1110 maleimide. This is a method of converting an amic acid into an amic acid and dehydrating and ring-closing it to imidize it.This method can be roughly divided into a method using a dehydrating agent and a method using a catalyst.
脱水剤を用いる方法では、例えば４米国特許第２４４４
５３号やオルガニンク ソンセシス 第４１巻、第９３
頁で公知なように、無水酢酸のような脱水剤を等モル以
上用いて反応を行う。この方法は、反応条件が温和であ
り、また反応収率が比較的高いために優れてはいるが、
高価な脱水剤を大量に使用したり、また反応後に煩雑な
生成物分離処理をしなければならないために製品である
マレイミドのコストが高くなり、経済的な量産方法とは
なり難い。In the method using a dehydrating agent, for example, 4 U.S. Pat. No. 2,444
No. 53 and Organinck Sonthesis Volume 41, No. 93
The reaction is carried out using a dehydrating agent such as acetic anhydride in an amount equal to or more than the same molar amount. Although this method is superior because the reaction conditions are mild and the reaction yield is relatively high,
Since a large amount of expensive dehydrating agent is used and complicated product separation treatment is required after the reaction, the cost of the maleimide product increases, making it difficult to use as an economical mass production method.
これに比べて、触媒による脱水イミド化法は大量の高価
な副原料を消費しないので、基本的には優れた経済的製
造法になり得る方法である。In comparison, the catalytic dehydration imidization method does not consume a large amount of expensive auxiliary raw materials, so it can basically be a superior economical production method.
この方法としで、特公昭５１−４００７８号においてマ
レインアミド−酸類を酸触媒により脱水し、生成水を共
沸除去しながら分子内で閉環させてイミド化する方法が
知られている。酸触媒としては硫酸、燐酸の様な無ＩＩ
酸、また：ま有機のパラトルエンスルホン酸の様なｐＫ
ａ ３以下の強酸が使われている。As this method, a method is known in Japanese Patent Publication No. 51-40078 in which maleamide-acids are dehydrated with an acid catalyst, and the resulting water is azeotropically removed while ring-closing within the molecule to imidize. As an acid catalyst, non-II such as sulfuric acid and phosphoric acid are used.
Acids, also: pK like organic para-toluenesulfonic acid
a A strong acid of 3 or less is used.
この際に、特公昭５５−４６３９４号では、マレインア
ミドｅｌｉ、類の溶解性を高めるために非プロトン性極
性溶剤を共沸溶剤に混合した溶剤系が用いられている。In this case, in Japanese Patent Publication No. 55-46394, a solvent system in which an aprotic polar solvent is mixed with an azeotropic solvent is used in order to increase the solubility of maleamide eli.
特開昭６０−１１４６５号の様に酸触媒として強酸型の
イオン交換体を用いたり、あるいは上述のような強酸触
媒の存在下で無水マレイン酸と一級アミンとを反応させ
ることにより、直接的にマレイミド類を得る方法を知ら
れている。Directly by using a strong acid type ion exchanger as an acid catalyst as in JP-A-60-11465, or by reacting maleic anhydride with a primary amine in the presence of a strong acid catalyst as described above. It is known how to obtain maleimides.
さらに、特公昭５１−４００７８号、特開昭６１−５０
６６号や特開昭６２−６３５６２号では酸触媒の存在下
に安定削として！合禁止剤やアルコール類を添加して反
応させたり、酸触媒の存在下に微量の金属化合物を添加
して反応させている。Furthermore, Japanese Patent Publication No. 51-40078, Japanese Patent Publication No. 61-50
No. 66 and JP-A No. 62-63562 as stable cutting in the presence of an acid catalyst! The reaction is carried out by adding an inhibitor or alcohol, or by adding a trace amount of a metal compound in the presence of an acid catalyst.
また、特開昭６１−６０６４７号では、無水マレイン酸
と一級アミンを有機溶剤中で反応させてマレインアミド
酸のスラリーを得て、触媒の存在下または非存在下に、
該溶剤が還流する第二の反応器中へこのスラリーを間欠
的または連続的に冷力［Ｉ している。この際の触媒と
しては、前記と同様の燐または硫黄のオキシ酸、あるい
はそれらのアルカリ金属塩またはアルカリ土類金属塩が
好適とされている。またさらに、エステル化反応に慣用
される触媒と同一の金属（Ｎｉ、Ｃｏ、 Ｃｕ、 Ｚｎ
、 Ｓｎ、 Ａ１． Ｂ、Ｓｂ、 Ｌｉ、１、Ｃｒ、Ｔ
ｉ、 Ｖ 、 Ｍｎ、 Ｆｅ）の化合物も用いられると
記載されている。Furthermore, in JP-A-61-60647, maleic anhydride and a primary amine are reacted in an organic solvent to obtain a slurry of maleamic acid, and in the presence or absence of a catalyst,
The slurry is intermittently or continuously cooled into a second reactor where the solvent is refluxed. As the catalyst in this case, the same phosphorus or sulfur oxy acids as mentioned above, or their alkali metal salts or alkaline earth metal salts are said to be suitable. Furthermore, the same metals (Ni, Co, Cu, Zn
, Sn, A1. B, Sb, Li, 1, Cr, T
It is also stated that compounds (i, V, Mn, Fe) can also be used.
しかしこれらの金属化合物に関しては、酸触媒と異なっ
て、触媒としての具体的説明が明示されていない。実施
例では酸触媒が使われ、個別の金属化合物の例示も全く
記載されていない。However, unlike acid catalysts, no specific explanation has been given regarding these metal compounds as catalysts. In the examples, an acid catalyst is used, and no examples of individual metal compounds are described.
これら公知の触媒的脱水イミド化方法に共通して不可欠
な要素はブレンステッド酸性の強い酸触媒であり、例え
ば硫酸類、燐酸類、臭化水素酸、フルオロスルホン酸等
の様な無機プロトン酸、あるいはクロロ酢酸、フルオロ
酢酸、トリフルオロメタンスルホン酸やスルホン型イオ
ン交換樹脂等のような有機プロトン酸に代表される酸強
度の強いブレンステッド酸を酸触媒として用いることで
ある。An essential element common to these known catalytic dehydration imidization methods is a strong Bronsted acid catalyst, such as inorganic protonic acids such as sulfuric acids, phosphoric acids, hydrobromic acid, fluorosulfonic acid, etc. Alternatively, a Brønsted acid with strong acid strength, typified by organic protonic acids such as chloroacetic acid, fluoroacetic acid, trifluoromethanesulfonic acid, and sulfone type ion exchange resin, is used as the acid catalyst.
触媒による脱水イミド化法は大量の高価な副原料を消費
しない直接的反応なので、基本的には優れた経済的製造
法になり得る方法である。The catalytic dehydration imidization method is a direct reaction that does not consume large amounts of expensive auxiliary raw materials, so it can basically be an excellent economical production method.
しかしながら、マレイミドの工業的用途から判断して以
下の理由から従来公知の方法は、いずれも未だ技術的ま
たは経済的に満足されるものではない。However, judging from the industrial use of maleimide, none of the conventionally known methods is still technically or economically satisfactory for the following reasons.
（１）前記のような公知の無機または有機の強酸を用い
ても反応の選択率または収率が十分ではない。(1) Even if the known inorganic or organic strong acids described above are used, the reaction selectivity or yield is insufficient.
（２）触媒として多量に用いられる無機酸や高価な有機
酸は、有機相との分液性がよくないために、反応後の分
離回収が容易ではない。(2) Inorganic acids and expensive organic acids that are used in large amounts as catalysts have poor separation properties from the organic phase, so it is not easy to separate and recover them after the reaction.
（３）酸触媒は製品を汚染し易く、また比較的低選択率
のために副生物が多く混入する。製品からこれらを除去
するために水洗分液などの煩雑な精製が不可欠となる。(3) Acid catalysts tend to contaminate products, and because of their relatively low selectivity, many by-products are mixed in. In order to remove these from products, complicated purification such as washing with water and separating them is essential.
（４）前記（３）のため大量の洗浄水の排水処理をしな
ければならない。(4) Because of (3) above, a large amount of washing water must be treated as waste water.
（５）触媒の強酸を高温で多量に使用するため、反応器
および周辺装置力頌（食材料となり、高価となる。(5) Because the strong acid of the catalyst is used in large amounts at high temperatures, the reactor and peripheral equipment are used as food materials and are expensive.
本発明者らは従来の酸触媒の有する上記５項目の問題点
を根本的に解決するため触媒探索を行った。その結果、
前述のような酸触媒を用いなくても、金属スズおよびス
ズ元素を含有する化合物の中から選ばれた少なくとも一
種の触媒を添加するだけで、目的に沿って脱水イミド化
出来ることを蒐いだした（特願平１−１５２４３２およ
び特願平２−１０８７６９）。The present inventors conducted a catalyst search in order to fundamentally solve the above five problems of conventional acid catalysts. the result,
It was discovered that dehydrated imidization can be carried out according to the purpose without using an acid catalyst as mentioned above, simply by adding at least one catalyst selected from metal tin and compounds containing the tin element. (Japanese Patent Applications Hei 1-152432 and Hei 2-108769).
〔発明が解決しようとする課題］
しかしながら、金属スズおよびスズ元素を含有する化合
物の中から選ばれた少なくとも一種を触媒としてＮ−置
換マレイミドを製造する上記方法は、副生物の量および
Ｎ−置換マレイミドの収率とも未だ充分満足できるもの
とは言えない。[Problems to be Solved by the Invention] However, the above method for producing N-substituted maleimide using at least one selected from metal tin and compounds containing the tin element as a catalyst does not reduce the amount of by-products and the N-substitution. The yield of maleimide is still not completely satisfactory.
［課題を解決するための手段〕
本発明者らは上記問題点を解決するため鋭意検討を行っ
た。その結果、金属スズおよびスズ元素を含有する化合
物の中から選ばれた少な（とも−種の触媒の存在下で、
凡−置換マレインアミド酸を脱水イミド化し、Ｎ−置換
マレイミドを製造する際に、無水マレイン酸を供給しな
がら脱水イミド化反応を行えば、Ｎｌ’換マシマレイミ
ド率が大幅に向上できることを兇いだ９木発明を完成す
るに至った。[Means for Solving the Problems] The present inventors conducted extensive studies to solve the above problems. As a result, in the presence of a small number of catalysts selected from among metallic tin and compounds containing elemental tin,
It has been shown that the Nl'-converted mashimaleimide ratio can be greatly improved if the dehydration imidization reaction is carried out while supplying maleic anhydride when producing N-substituted maleimide by dehydration imidization of ordinary-substituted maleamic acid. This led to the completion of the invention.
すなわち、本発明は、Ｎ−置換マレインアミド酸類を、
水と共沸する有機溶剤と有機非プロトン性極性溶剤から
成る混合溶媒中で加熱脱水し、生成する水を共沸除去し
ながら脱水イミド化するに際し、金属スズおよびスズ元
素を含有する化合物の中から選ばれた少なくとも一種の
触媒の存在下で、無水マレイン酸を供給しながら脱水イ
ミド化反応を行うことを特徴とするＮ−置換マレイミド
の製造方法である。That is, the present invention provides N-substituted maleamidic acids,
When heating and dehydrating in a mixed solvent consisting of an organic solvent that is azeotropic with water and an organic aprotic polar solvent, and dehydrating and imidizing while removing the generated water azeotropically, a compound containing tin metal and the tin element is This is a method for producing an N-substituted maleimide, characterized by carrying out a dehydration imidization reaction while supplying maleic anhydride in the presence of at least one catalyst selected from the following.
以下、具体的に本発明の詳細な説明する。Hereinafter, the present invention will be specifically explained in detail.
本発明に原料として用いられるＮ−買換マレインアミド
酸類の例としては以下のものを例示できる。Ｎ−ｉ換モ
ノマレイユ／アミド酸類の代表例としては、Ｎ−メチル
マレインアミド酸、Ｎ−ブチルマレインアミド酸、Ｎ−
オクチルマレインアミド酸、Ｎ−ドブノルマレインアミ
ド酸、Ｎ−ステアリルマレインアミド酸、Ｎ−シクロへ
キシルマレインアミド酸、Ｎ−フェニルマレインアミド
酸、Ｎ−（ｏ−トリル）マレインアミド酸、Ｎ−ドブノ
ルフェニルマレインアミド酸、Ｎ−クロロフェニルマレ
インアミド酸、Ｎ−ジクロロフェニルマレインアミド酸
、Ｎ−（０−またはｐ−ヒドロキシフェニル）マレイン
アミド酸、Ｎ−（ｏ−またはｍ−メトキシフェニル）マ
レインアミド酸、Ｎ−（ｍ−ヒドロキシカルボニルフェ
ニル）マレインアミド酸、Ｎ −（ｍ−ニトロフェニル
）マレインアミド酸などがある。Examples of the N-purchased maleamic acids used as raw materials in the present invention include the following. Representative examples of N-i-converted monomaleyl/amic acids include N-methylmaleamic acid, N-butylmaleamic acid, N-
Octylmaleamic acid, N-dobnormaleamic acid, N-stearylmaleamic acid, N-cyclohexylmaleamic acid, N-phenylmaleamic acid, N-(o-tolyl)maleamic acid, N-dobnormaleamic acid Norphenylmaleamic acid, N-chlorophenylmaleamic acid, N-dichlorophenylmaleamic acid, N-(0- or p-hydroxyphenyl)maleamic acid, N-(o- or m-methoxyphenyl)maleamic acid, Examples include N-(m-hydroxycarbonylphenyl)maleamic acid and N-(m-nitrophenyl)maleamic acid.
Ｎ−置換ビスマレインアミド酸の例としては、Ｎ、Ｎ’
−（ｍ−またはＰ−フェニレン）ビス−マレインアミ
ド酸、Ｎ、Ｎ’ −（２，４−トリレン）ビス−マレイ
ンアミド酸、Ｎ、Ｎ’ −（４゜４゛−ジフェニルメタ
ン）ビス−マレインアミド酸、Ｎ、Ｎ’ （４，４
°−ジフェニルエーテル）ビス−マレインアミド酸、Ｎ
、Ｎ’ −（４，４゜−ジフェニルケトン）ビス−マレ
インアミド酸、Ｎ、Ｎ“−（４，４’−ジフェニルジサ
ルファイド）ビス−マレインアミド酸、Ｎ、Ｎ’ −（
４，４°−ジフェニルスルホン）ビス−マレインアミド
酸などがある。Examples of N-substituted bismaleamic acids include N, N'
-(m- or P-phenylene)bis-maleamidic acid, N,N'-(2,4-tolylene)bis-maleamidic acid, N,N'-(4゜4゛-diphenylmethane)bis-maleamide Acid, N, N' (4,4
°-diphenyl ether)bis-maleamic acid, N
, N'-(4,4°-diphenylketone)bis-maleamidic acid, N,N"-(4,4'-diphenyldisulfide)bis-maleamidic acid, N,N'-(
Examples include 4,4°-diphenylsulfone)bis-maleamic acid.
これらのＮ−置換マレインアミド酸は、公知の方法にし
たがって、それぞれに対応する無水マレイン酸またはそ
の置換体と９級モノーまたはジ−アミン類とを溶剤中で
混合して反応することによりほぼ定量的に得られる。These N-substituted maleamic acids can be almost quantified by mixing and reacting the corresponding maleic anhydride or its substituted product with a 9th class mono- or di-amine in a solvent according to a known method. can be obtained.
本発明おいては、上記の方法で合成したマレインアミド
酸として単離したものを脱水反応の原料としても良いし
、無水マレイン酸またはその置換体と９級アミン類とか
ら溶剤中でマレインアミド酸を合成し、二わをそのまま
脱水反応に用いることも出来る。In the present invention, maleamic acid isolated as synthesized by the above method may be used as a raw material for the dehydration reaction, or maleic anhydride or its substituted product and 9th-class amines are combined to form maleamic acid in a solvent. It is also possible to synthesize Niwa and use it as it is in the dehydration reaction.
本発明の方法で、触媒として用いられる金属スズおよび
スズ元素を含有する化合物としては、以下の物を例示す
ることができる。Examples of the metal tin and the compound containing the tin element used as a catalyst in the method of the present invention include the following.
金属スズは形状に制限はないが、微粉末が好ましい。There are no restrictions on the shape of metal tin, but fine powder is preferred.
スズ元素を含有する化合物としては、二価および四価の
スズの酸化物、水酸化物、カルボン酸塩、アルコキサイ
ド、ハロゲン化物、鉱酸塩および有機スズ化合物などを
例示することができる。Examples of compounds containing the tin element include divalent and tetravalent tin oxides, hydroxides, carboxylates, alkoxides, halides, mineral salts, and organic tin compounds.
スズの酸化物および水酸化物としては、酸化第一スズ、
酸化第二スズおよび水酸什第−スズ、水酸化第二スズが
使用できる。Examples of tin oxides and hydroxides include stannous oxide,
Stannous oxide and stannic hydroxide, stannic hydroxide can be used.
スズの有機カルボン酸塩としては、脂肪族、脂環族また
は芳委族の一価または多価カルボン酸のスズ塩である。The organic carboxylic acid salt of tin is a tin salt of an aliphatic, alicyclic, or aromatic monovalent or polyvalent carboxylic acid.
このようなカルボン酸の代表例としては、例えば酢酸、
プロピオン酸、酪酸、２−エチルヘキサン酸、オクチル
酸、ラウリル酸、ステアリン酸、グリシン、乳酸、こは
く酸、グルタル酸、アジピン酸、アゼライン酸、マレイ
ン酸、フマル酸、クエン酸、シクロへキシルカルボン酸
、ナフテン酸、安息香酸、トリル酸、クロル安息香酸、
フタル酸、テレフタル酸などを例示できる。Representative examples of such carboxylic acids include acetic acid,
Propionic acid, butyric acid, 2-ethylhexanoic acid, octylic acid, lauric acid, stearic acid, glycine, lactic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, maleic acid, fumaric acid, citric acid, cyclohexylcarboxylic acid , naphthenic acid, benzoic acid, tolylic acid, chlorbenzoic acid,
Examples include phthalic acid and terephthalic acid.
また、スズのアルコキサイドの例とじては、スズのメト
キシド、エトキシド、ｎ−プロポキシド、ｉ−プロポキ
シド、叶ブトキンド、５ｅｃ−ブトキシド、ｔｅｒｔ−
ブトキッド、ペンタオキンド、ヘキサオキシド、フェノ
キシト、ヘンジルオキシトなどが例示できる。Further, examples of tin alkoxides include tin methoxide, ethoxide, n-propoxide, i-propoxide, tin butokind, 5ec-butoxide, tert-
Examples include butoquid, pentaoquinde, hexoxide, phenoxyte, henzyl oxide, and the like.
スズハロゲン化物は、塩化第一スズ、塩化第二スズ、臭
化第一スズ、臭化第二スズ、ヨウ化第−スズ、ヨウ化第
二スズ、ジクロロスズビスアセチルアセトネート、ジク
ロルジ−ｎ−ブチルスズ、ジクロルジーｔｅｒｔ−ブチ
ルスズ、ジクロルジビニルスズ、ジクロルジビニルスズ
、トリクロルメチルスズ、トリクロルフェニルスズ、ト
リエチルブロモスズ、トリメチルブロムスズのようなハ
ロゲン含有のスズ化合物である。Tin halides include stannous chloride, stannic chloride, stannous bromide, stannic bromide, stannous iodide, stannic iodide, dichlorotin bisacetylacetonate, dichlorodi-n- These are halogen-containing tin compounds such as butyltin, dichlorodi-tert-butyltin, dichlordivinyltin, dichlordivinyltin, trichloromethyltin, trichlorphenyltin, triethylbromostin, and trimethylbromostin.
さらに、スズの鉱酸塩の例とじては、スズの硫酸塩、硝
酸塩、リン酸塩、ビス（トリエチルスズ）硫酸塩などを
例示できる。Furthermore, examples of tin mineral salts include tin sulfates, nitrates, phosphates, and bis(triethyltin) sulfates.
有機スズ化合物としては、アリルトリフェニルスズ、ビ
ス（トリメチルスズ）アセチレン、ヘキサメチルジスズ
、テトラメチルスズ、テトラ−Ｉ−プロピルスズ、トリ
ーｎブチルシクロベンタソエニルスズ、水酸化トリフェ
ニルスズなどの有機スズ仕合物も使用できる。Examples of organic tin compounds include allyltriphenyltin, bis(trimethyltin)acetylene, hexamethyldistin, tetramethyltin, tetra-I-propyltin, tri-n-butylcyclobentasoenyltin, and triphenyltin hydroxide. A tin compound can also be used.
これらの金属スズおよびスズ元素を含有する化合物の中
では、酸化第一スズ、水酸什第−スズ、水酸化第二スズ
、塩化第一スズ、塩化第二スズ、および二価のスズの有
機カルボン酸塩、アルコキサイドが好ましい。Among these metallic tin and compounds containing the element tin, stannous oxide, stannous hydroxide, stannic hydroxide, stannous chloride, stannic chloride, and divalent tin organic Carboxylate salts and alkoxides are preferred.
これらの触媒は通常は単独で用いられるが、必要に応じ
て二種類以上を混合使用することもできる。 触媒の使
用量は特に制限はないが、原料マレインアミド酸１モル
に対して通常０．１〜２０モル％（スズとして０．００
１−０．２グラムｊ宗子）、好ましくは、０．５〜１０
モル％（スズとして０．００５〜０゜］ダラム原子）の
範囲である。These catalysts are usually used alone, but two or more types can be used in combination if necessary. There is no particular restriction on the amount of catalyst used, but it is usually 0.1 to 20 mol% (0.00% as tin) per 1 mol of raw maleamic acid.
1-0.2 grams j Munezi), preferably 0.5-10
The range is mol % (0.005 to 0° as tin Durham atoms).
無水マレイン酸の使用量はＮ−置換マレインアミド酸を
合成する際は原料に使用する９級アミンのアミノ基に対
するモル比が１．０−１．１の範囲で、好すしくは１．
０１−１．０５の範囲である。脱水イミド化に際し、供
給する無水マレイン酸の量はＮ−買換マレインアミド酸
を合成する際に使用する９級アミンのアミノ基に対する
モル比が０．０２−１．０の範囲である。The amount of maleic anhydride to be used is such that when synthesizing N-substituted maleamic acid, the molar ratio of the 9th class amine used as a raw material to the amino group is in the range of 1.0-1.1, preferably 1.
It is in the range of 01-1.05. During the dehydration imidization, the amount of maleic anhydride supplied is such that the molar ratio of the 9th class amine to the amino group used when synthesizing the N-purchased maleamic acid ranges from 0.02 to 1.0.
本発明における水と共沸する有ＩＩ溶剤は、反応によっ
て生成する水を反応系外に共沸除去するために用いられ
る。この共沸溶剤は５０〜２００°Ｃの範囲の温度で水
を共沸でき、かつ反応に不活性なものであればよい。例
えば、ベンゼン、トルエン、エチルベンゼン、キシレン
類、キュメン、クロルベンゼン、アニソール、ジクロル
エタン、ジェトキシエタン、シクロヘキサノン、メチル
エチルケトン、メチルイソブチルケトン、トＩＪオキサ
ンなどがあり、好ましくは、溶剤の特性と価格を考慮し
てキシレン類がよく用いられる。The II solvent that is azeotropic with water in the present invention is used to azeotropically remove water produced by the reaction from the reaction system. This azeotropic solvent may be one that can azeotropically distill water at a temperature in the range of 50 to 200°C and is inert to the reaction. Examples include benzene, toluene, ethylbenzene, xylenes, cumene, chlorobenzene, anisole, dichloroethane, jetoxyethane, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexane. types are often used.
才だ、有機非プロトン性極性溶媒はマレインアミド酸と
触媒の熔Ｗ１＊度を高めるため乙こ用いられるが、例え
ば、ジメチルホルムアミド、ジメチルアセトアミド、ジ
メチルスルホキシド、スルホラン、メチルイソブチルケ
トン、Ｔ−ブチロラクトン、ヘキサメチルホスホルアミ
ド、Ｎ−メチルピコリドン、テトラメチル尿素、１．３
−ジメチル−２−イミダプリンノンなどが用いられるが
、好まじくは、ジメチルホルムアミド、ジメチルアセト
アミド、ジメチルスルホキシドなどが用いられる。Organic aprotic polar solvents are often used to increase the degree of melting of maleamic acid and the catalyst, such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, sulfolane, methyl isobutyl ketone, T-butyrolactone, Hexamethylphosphoramide, N-methylpicolidone, tetramethylurea, 1.3
-dimethyl-2-imidapurinone and the like are used, preferably dimethylformamide, dimethylacetamide, dimethylsulfoxide and the like.
本発明の脱水イミド化反応では、水と共沸する有機溶剤
に有機非プロトン性極性溶剤を添加または混合した溶剤
が用いられる。混合溶剤の使用量は、マレインアミド酸
の原料濃度として、通常、０．１〜５モル／ｎ、好まし
くは、０．５〜４モル／Ｐの範囲である。混合溶剤中の
極性溶剤の組成は通常容積で０．１〜５０％、好ましく
は、１〜２０％の範囲の中から選ばれる。In the dehydration imidization reaction of the present invention, a solvent is used in which an organic aprotic polar solvent is added or mixed with an organic solvent that is azeotropic with water. The amount of the mixed solvent used is usually in the range of 0.1 to 5 mol/n, preferably 0.5 to 4 mol/P, as the raw material concentration of maleamic acid. The composition of the polar solvent in the mixed solvent is usually selected from the range of 0.1 to 50% by volume, preferably 1 to 20%.
反応温度は５０〜２００°Ｃ１好ましくは、８０〜１８
０°Ｃの範囲が用いられる。反応圧力は特に制限はなく
、通常は常圧で好まし〈実施される。The reaction temperature is 50-200°C, preferably 80-18°C.
A range of 0°C is used. There is no particular restriction on the reaction pressure, and the reaction is usually preferably carried out at normal pressure.
反応時間は、通常０．５〜１０時間の範囲であり、好ま
しくは、１〜５時間の範囲である。The reaction time is usually in the range of 0.5 to 10 hours, preferably in the range of 1 to 5 hours.
本発明の方法では、反応は回分式、半連続式または連続
式で実施することができる。通常はマレインアミド酸、
水と共沸する有機ン容剤、有機非プロトン性極性溶剤、
触媒等を反応器に供給する。In the process of the invention, the reaction can be carried out batchwise, semi-continuously or continuously. Usually maleamic acid,
Organic solvents that are azeotropic with water, organic aprotic polar solvents,
Supply catalyst etc. to the reactor.
反応器はその後または予め加熱し、この共沸溶剤を所定
時間加熱還流させながら生成する水を反応器内から共沸
分離することにより脱水反応を進行させる際に、無水マ
レイン酸を供給しながらマレインアミド酸をマレイミド
に転化する。The reactor is heated afterwards or in advance, and the azeotropic solvent is heated under reflux for a predetermined period of time, and water produced is azeotropically separated from the reactor to advance the dehydration reaction. Converts amic acid to maleimide.
この際、原料のマレインアミド酸類は別途に合成して使
用しなくても、上記の共沸溶剤またはこれと極性溶剤と
の混合溶剤中で無水マレイン酸に９級アミンを添加する
公知の方法によって合成し、引き続いて直接これに触媒
および無水マレイン酸を供給しながら還流させ、上記と
同様にして共沸脱水反応させることができる。マレイン
アミド酸類はほぼ定量的に合成できるので、通常はこの
方が経済的である。At this time, the raw material maleamic acids do not need to be synthesized and used separately, but can be prepared by the known method of adding a 9th class amine to maleic anhydride in the above-mentioned azeotropic solvent or a mixed solvent of this and a polar solvent. The azeotropic dehydration reaction can be carried out in the same manner as described above by directly supplying a catalyst and maleic anhydride to the mixture and refluxing it. Since maleamic acids can be synthesized almost quantitatively, this method is usually more economical.
得られた反応混合物は、萎発器によって両溶剤を蒸発回
収した後、簡単な抽出、晶析または蒸留などにより、マ
レイミドの粗製品が得られる。After evaporating and recovering both solvents from the resulting reaction mixture using a withering device, a crude product of maleimide is obtained by simple extraction, crystallization, or distillation.
マレイミドの粗製品は適当な抽出、晶析、洗浄、蒸留な
どの慣用の精製操作によって容易に実用に適する高純度
製品とされる。必要に応して適当な溶剤に溶かして実用
に供することもてきる。The crude product of maleimide can be easily converted into a high-purity product suitable for practical use through conventional purification operations such as suitable extraction, crystallization, washing, and distillation. If necessary, it can be dissolved in an appropriate solvent for practical use.
また、本発明のスズ金属系触媒は、従来の強酸触媒と異
なり、腐食性を示さない。従って、通常の安価な装置材
料が使用できるので、製造設備も極めて経済的になる。Furthermore, the tin metal catalyst of the present invention does not exhibit corrosive properties, unlike conventional strong acid catalysts. Therefore, the manufacturing equipment becomes extremely economical, since common inexpensive device materials can be used.
［実施例〕
次に実施例によって本発明を更に具体的に説明するが、
本発明はこれらに限定されるものではない。 実施例の
中で、Ｎ−フェニルマレイミドの収率は、原料として用
いたアニリンを基準として計算した。[Example] Next, the present invention will be explained in more detail with reference to Examples.
The present invention is not limited to these. In the examples, the yield of N-phenylmaleimide was calculated based on aniline used as a raw material.
実施例１
水分離器付還流冷却器、撹拌機、温度計を備えた３００
ｍ１フラスコ中へ無水マレイン酸（以下ＭＡＮと略記）
１９．８ｇ （０，２０２モル、対アニリンモル比
１．０１） 、キシレン（以下χｙと略記） ７０ｍ１
とジメチルホルムアミド（以下ＤＭＦと略記） ｌ０ｍ
１を仕込み、８０°Ｃで撹拌下にアニリン（以下ＡＮと
略記） １８．６ｇ （０，２０モル）とＸｙ２０ｍ
ｌの混合液を１５分間にわたって定量供給し、さらに９
０°しで１５分間熟成反応させてＮ−フェニルマレイン
アミド酸（以下ＰＭＡと略記）を合成した。Example 1 300 equipped with reflux condenser with water separator, stirrer, and thermometer
Maleic anhydride (hereinafter abbreviated as MAN) into the m1 flask
19.8g (0,202 mol, molar ratio to aniline 1.01), xylene (hereinafter abbreviated as χy) 70ml
and dimethylformamide (hereinafter abbreviated as DMF) 10m
1 was prepared, and while stirring at 80°C, 18.6 g (0.20 mol) of aniline (hereinafter abbreviated as AN) and Xy20m were added.
1 of the mixture was metered over 15 minutes, and then 9
The mixture was aged at 0° for 15 minutes to synthesize N-phenylmaleamic acid (hereinafter abbreviated as PMA).
この白色粉末スラリーに、触媒として酸化第−スズ１．
３５ｇ （スズとして］０．０ｍｇ原子、ＡＮに対し
５．０モル％）を添加した後、Ｍ Ａ Ｎ １．５７ｇ
（０，０１６モル、対アニリンモル比０．０８）をＤ
Ｍ Ｆ ３ｃｃに溶解した溶液を０．５ｃｃ供給し、昇
温しで内容物を加熱還流させた。反応により生成する水
を共沸分離しながら約１４０°Ｃで還流を続け、１０分
間隔で上記したＭＡＮのＤＭＦ溶液を０．５ｃｃづつ供
給した。This white powder slurry was added with 1.5% tin oxide as a catalyst.
After adding 35 g (as tin) of 0.0 mg atoms, 5.0 mol % relative to AN), 1.57 g of M A N
(0,016 mol, molar ratio to aniline 0.08) is D
0.5 cc of a solution dissolved in 3 cc of M F was supplied, and the temperature was raised to heat the contents to reflux. Refluxing was continued at about 140° C. while water produced by the reaction was azeotropically separated, and 0.5 cc of the above-mentioned MAN solution in DMF was fed at 10 minute intervals.
脱水反応が終了するのに２時間要した。It took 2 hours for the dehydration reaction to complete.
反応終了後、反応液を濃縮乾量した後Ｘ）’３５ｈｌで
抽出し、Ｎ−フェニルマレイミド（以下ＰＭＩと略記）
を含む抽出液と抽残に分離し、それぞれを液体クロマト
グラフィーで定！した結果、ＰＭ■収率は９４．０χで
、未反応（７）ＰＭＡが４．０ＸＩＯ１収された。After the reaction was completed, the reaction solution was concentrated to dryness and extracted with 35 ml of N-phenylmaleimide (hereinafter abbreviated as PMI).
Separate into extract and raffinate containing , and determine each using liquid chromatography! As a result, the PM2 yield was 94.0χ, and 4.0XIO1 of unreacted (7) PMA was recovered.
比較例１
実施例１において、初めにフラスコ内にＭＡＮ２１．４
ｇ （０，２１８モル）を仕込み、後からＭＡＮのＤ
Ｍ Ｆ 溶液は供給しなかった以外は、実施例１と全
く同様に反応を行った。その結果、反応を完結するのに
要した時間は２時間であった。また、反応成績は、ＰＭ
Ｉ収率９２．Ｏχで未反応のＰＭＡが３．５χ回収され
た。Comparative Example 1 In Example 1, MAN21.4 was initially placed in the flask.
g (0,218 mol) and then MAN's D
The reaction was carried out in exactly the same manner as in Example 1, except that the M F solution was not supplied. As a result, the time required to complete the reaction was 2 hours. In addition, the reaction results are PM
I yield 92. 3.5x of unreacted PMA was recovered.
比較例２
実施例１において、初めにフラスコ内にＭ、ＡＮ１９．
８ｇ （０，２０２モル）を仕込み、後からＶＡＮの
１）Ｍ Ｆｍ液は供給しなかった以外は、実施例１と全
く同様に反応を行った。その結果、反応を完結するのに
要した時間は２時間であった。また、反応成績は、ＰＭ
Ｉ収率８７． ＯＫで未反応のＰＭＡが７．１χ回収さ
れた。Comparative Example 2 In Example 1, M, AN19.
The reaction was carried out in exactly the same manner as in Example 1, except that 8 g (0,202 mol) was charged and VAN's 1)M Fm solution was not supplied afterwards. As a result, the time required to complete the reaction was 2 hours. In addition, the reaction results are PM
I yield 87. 7.1x of OK and unreacted PMA was recovered.
実施例２
実施例１において、後からＶ Ａ Ｎｏ、３９ｇ（０，
００４モル、対アニリンモル比０．０２）をＤ Ｍ Ｆ
３ｃｃに溶解した以外は実施例１と全く同様に反応を
行った。Example 2 In Example 1, V A No., 39g (0,
004 mol, molar ratio to aniline 0.02)
The reaction was carried out in exactly the same manner as in Example 1 except that the solution was dissolved in 3 cc.
その結果、反応時間は２時間で、ＰＭＴ収率９２．１χ
であり、未反応のＰＭＡが４．０χ回収された。As a result, the reaction time was 2 hours, and the PMT yield was 92.1χ
Therefore, 4.0x of unreacted PMA was recovered.
実施例３
実施例１において、後からＭ Ａ Ｎ３．］４４ｇ０．
０３２モル５対アニリンモル比０．１．６）をＤ Ｍ
Ｆ ３ｃｃに溶解した以外は実施例１と全（同様に反応
を行った。Example 3 In Example 1, M A N3. ]44g0.
032 mole 5 to aniline molar ratio 0.1.6)
The reaction was carried out in the same manner as in Example 1 except that it was dissolved in 3 cc of F.
その結果、反応時間は２時間で、ＰＭＩ収率９５．ｌχ
であり、未反応のＰＭＡが３．０χ回収された。As a result, the reaction time was 2 hours, and the PMI yield was 95. lχ
Therefore, 3.0x of unreacted PMA was recovered.
［発明の効果］
本発明は、金属スズおよびスズ元素を含有する化合物の
中から選ばれた少なくとも一種の触媒の存在下、Ｎ−？
ｌＦ換マシマレインアミド酸水イミド化する際に、無水
マレイン酸を供給しながら脱水イミド化反応をすること
により、副生物の生成を抑制し、Ｎ−置換マレイミドの
収率が大きく向上し、その効果は著しく大きなものであ
る。[Effects of the Invention] The present invention provides N-?
By carrying out the dehydration imidization reaction while supplying maleic anhydride during IF-converted masimaleamide acid water imidization, the production of by-products is suppressed, and the yield of N-substituted maleimide is greatly improved. The effect is significantly large.
特許出願人 三井東圧化学株式会社Patent applicant Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
溶剤と有機非プロトン性極性溶剤から成る混合溶剤中で
加熱脱水し、生成する水を共沸除去しながら脱水イミド
化するに際し、金属スズおよびスズ元素を含有する化合
物の中から選ばれた少なくとも一種の触媒の存在下で、
無水マレイン酸を供給しながら脱水イミド化反応を行う
ことを特徴とするＮ−置換マレイミド類の製造方法。 ２）供給する無水マレイン酸の量がＮ−置換マレインア
ミド酸類を合成する際に使用した一級アミンに対しアミ
ノ基のモル比で０．０２−１．０である特許請求の範囲
第１項記載の方法。[Claims] 1) N-substituted maleamidic acids are heated and dehydrated in a mixed solvent consisting of an organic solvent that is azeotropic with water and an organic aprotic polar solvent, and the resulting water is azeotropically removed while being dehydrated. When imidizing, in the presence of at least one catalyst selected from metal tin and compounds containing the tin element,
A method for producing N-substituted maleimides, which comprises carrying out a dehydration imidization reaction while supplying maleic anhydride. 2) The amount of maleic anhydride supplied is 0.02-1.0 in molar ratio of amino groups to the primary amine used in synthesizing the N-substituted maleamidic acids. the method of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2325522A JPH04198167A (en) | 1990-11-29 | 1990-11-29 | Production of maleimides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2325522A JPH04198167A (en) | 1990-11-29 | 1990-11-29 | Production of maleimides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04198167A true JPH04198167A (en) | 1992-07-17 |
Family
ID=18177817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2325522A Pending JPH04198167A (en) | 1990-11-29 | 1990-11-29 | Production of maleimides |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04198167A (en) |
-
1990
- 1990-11-29 JP JP2325522A patent/JPH04198167A/en active Pending
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