JP4784028B2 - New azoamidine compounds - Google Patents
New azoamidine compounds Download PDFInfo
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- JP4784028B2 JP4784028B2 JP2001288188A JP2001288188A JP4784028B2 JP 4784028 B2 JP4784028 B2 JP 4784028B2 JP 2001288188 A JP2001288188 A JP 2001288188A JP 2001288188 A JP2001288188 A JP 2001288188A JP 4784028 B2 JP4784028 B2 JP 4784028B2
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- 150000001875 compounds Chemical class 0.000 title claims description 46
- 238000006116 polymerization reaction Methods 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 239000003505 polymerization initiator Substances 0.000 claims description 19
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical group C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 claims description 17
- 125000000623 heterocyclic group Chemical group 0.000 claims description 17
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 8
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000004181 carboxyalkyl group Chemical group 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000003172 aldehyde group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000005118 N-alkylcarbamoyl group Chemical group 0.000 claims description 3
- 125000004423 acyloxy group Chemical group 0.000 claims description 3
- 125000004103 aminoalkyl group Chemical group 0.000 claims description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 3
- 125000004966 cyanoalkyl group Chemical group 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims description 3
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- 125000002373 5 membered heterocyclic group Chemical group 0.000 claims 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims 1
- -1 azo compound Chemical class 0.000 description 80
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000003999 initiator Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000012736 aqueous medium Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical group C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical group C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical group C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 125000004429 atom Chemical group 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
- 238000001914 filtration Methods 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- FUGYGGDSWSUORM-UHFFFAOYSA-N 4-hydroxystyrene Chemical compound OC1=CC=C(C=C)C=C1 FUGYGGDSWSUORM-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- LXEKPEMOWBOYRF-UHFFFAOYSA-N [2-[(1-azaniumyl-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidoyl]azanium;dichloride Chemical compound Cl.Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N LXEKPEMOWBOYRF-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- SJNALLRHIVGIBI-UHFFFAOYSA-N allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000460 chlorine Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000002632 imidazolidinyl group Chemical group 0.000 description 2
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical group C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011630 iodine Chemical group 0.000 description 2
- 229910052740 iodine Chemical group 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- MTMVOHPDHXODNL-UHFFFAOYSA-N methyl 2-[(1-imino-1-methoxy-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidate;hydrochloride Chemical compound Cl.COC(=N)C(C)(C)N=NC(C)(C)C(=N)OC MTMVOHPDHXODNL-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- USPWKWBDZOARPV-UHFFFAOYSA-N pyrazolidine Chemical group C1CNNC1 USPWKWBDZOARPV-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- GPTFSTCGJACCKD-UHFFFAOYSA-N 1-(2-imino-3-methylbutoxy)-3-methylbutan-2-imine Chemical compound CC(C)C(=N)COCC(=N)C(C)C GPTFSTCGJACCKD-UHFFFAOYSA-N 0.000 description 1
- MPRGYQMHQXHYDR-UHFFFAOYSA-N 1-(2-imino-3-methylpentoxy)-3-methylpentan-2-imine Chemical compound CCC(C)C(=N)COCC(=N)C(C)CC MPRGYQMHQXHYDR-UHFFFAOYSA-N 0.000 description 1
- WHFHDVDXYKOSKI-UHFFFAOYSA-N 1-ethenyl-4-ethylbenzene Chemical compound CCC1=CC=C(C=C)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 1
- LEWNYOKWUAYXPI-UHFFFAOYSA-N 1-ethenylpiperidine Chemical compound C=CN1CCCCC1 LEWNYOKWUAYXPI-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- DEFOLOQBRQGSHQ-UHFFFAOYSA-N 2-(3-imino-4-methylhexan-2-yl)oxy-4-methylhexan-3-imine Chemical compound N=C(C(C)CC)C(C)OC(C)C(C(C)CC)=N DEFOLOQBRQGSHQ-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QMYCJCOPYOPWTI-UHFFFAOYSA-N 2-[(1-amino-1-imino-2-methylpropan-2-yl)diazenyl]-2-methylpropanimidamide;hydron;chloride Chemical compound Cl.NC(=N)C(C)(C)N=NC(C)(C)C(N)=N QMYCJCOPYOPWTI-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 description 1
- XUDBVJCTLZTSDC-UHFFFAOYSA-N 2-ethenylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C=C XUDBVJCTLZTSDC-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- GQEXQBZLZJJJMU-UHFFFAOYSA-N 2-methyl-2-[(2-methyl-1-pyrrolidin-1-yliminopropan-2-yl)diazenyl]-n-pyrrolidin-1-ylpropan-1-imine Chemical compound C1CCCN1N=CC(C)(C)N=NC(C)(C)C=NN1CCCC1 GQEXQBZLZJJJMU-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
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Landscapes
- Polymerization Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、水溶性の重合開始剤等として有用なアゾアミジン化合物に関する。
【０００２】
【従来の技術】
近年、高分子化合物の製造は、合理化の追求から高濃度で短時間に重合反応を終了させる検討が盛んに行われている。特に、水溶液中の重合では、重合温度が年々高く設定される傾向にあり、また重合時間も短縮される傾向にある。そのため、例えばレドックス開始剤、過硫酸塩化合物、パーオキシド開始剤やアゾ開始剤といった従来の重合開始剤では、重合温度に対する活性が高すぎて、重合が最後まで十分に進行せず残存するモノマー量が増加する等の問題が発生する傾向にある。
【０００３】
この問題を解決するために、開始剤の添加量を増加する方法や反応の途中で開始剤を添加する方法または活性の異なる開始剤を併用する方法等が検討されている。しかし、開始剤量を増加する方法は、重合途中に開始剤のほとんどが分解してしまうため効果が小さく、反応の途中で開始剤を添加する方法では、重合液の粘性が増加するために添加した開始剤が十分に混合できない等の問題点を有している。
【０００４】
そこで、更にこの問題を解決する方法として、重合中の昇温幅に対応した１０時間半減期温度を有する複数の重合開始剤を併用する方法や重合温度に対応した分解活性を有する開始剤を使用する方法等が考えられている。しかし、複数の重合開始剤を併用する方法、例えば１０時間半減期温度が４５〜６０℃（低温活性）のアゾアミジン塩系の重合開始剤と、１０時間半減期温度が８０〜９０℃（高温活性）の水酸基を有するアゾアミド系の重合開始剤とを併用して重合を行う方法においては、重合反応をうまく制御することができないのが現状である。このような問題点を解決するための手段として、通常の昇温幅（４０℃→９０℃）に対応した分解活性を有する１０時間半減期温度が６０〜７０℃である開始剤を用いることが考えられるが、このような開始剤は現在見つかっていない。従って、１０時間半減期温度が６０〜７０℃である水溶性のアゾ重合開始剤の開発が望まれているのが現状である。
【０００５】
【発明が解決しようとする課題】
本発明は、上記した如き状況に鑑みてなされたものであり、その目的は、水中での１０時間半減期温度が６０〜７０℃であり、水系媒体中の重合において各種モノマーを効率よく重合させることができる水溶性の重合開始剤等として有用な新規なアゾ化合物を提供することにある。
【０００６】
【課題を解決するための手段】
本発明は、一般式［１］
【化２】
で示される化合物又はその塩（以下、本発明のアゾアミジン化合物という。）、の発明である。
【０００７】
また、本発明は、本発明のアゾアミジン化合物から成る重合開始剤、の発明である。
更に、本発明は、本発明のアゾアミジン化合物を重合開始剤として用いることを特徴とするα，β−エチレン性不飽和モノマーの重合方法、の発明である。
【０００８】
即ち、本発明者等は、上記目的を達成すべく鋭意研究を重ねた結果、例えばピロリジン環等の複素環を分子中に有するアゾアミジン化合物が、水中での１０時間半減期温度が６０〜７０℃であり、これを用いることにより水系媒体中の重合を従来の方法よりも効果的に行うことができることを見出し、本発明を完成するに至った。
【０００９】
一般式［１］に於いて、Ｒ1及びＲ2で表される低級アルキル基としては、直鎖状でも分枝状でも或いは環状でもよく、例えば炭素数１〜５、好ましくは炭素数１〜３のものが挙げられ、具体的には、例えばメチル基、エチル基、ｎ-プロピル基、イソプロピル基、ｎ-ブチル基、イソブチル基、tert-ブチル基、sec-ブチル基、ｎ-ペンチル基、イソペンチル基、ネオペンチル基、tert-ペンチル基、sec-ペンチル基、2-メチルブチル基、1-エチルプロピル基、2-エチルプロピル基、シクロプロピル、シクロブチル基、シクロペンチル基等が挙げられるが、これらの中で、メチル基が最も好ましい。
【００１０】
【００１１】
これらの複素環基は、更に置換基を有していてもよい。その置換基は、環を構成する−ＮＨ−の水素原子、或いは同じく−ＣＨ2−又は＝ＣＨ−の水素原子に置換されるものであり、その具体例としては、例えばメチル基、エチル基、ｎ−プロピル基等の低級アルキル基、例えばメトキシ基、エトキシ基、ｎ−プロポキシ基等の低級アルコキシ基、フッ素、塩素、臭素、ヨウ素等のハロゲン原子等が挙げられる。
【００１２】
上記一般式［１］で示される本発明のアゾアミジン化合物の具体例としては、例えば
【化３】
【化４】
【化５】
【化６】
【化７】
【化８】
【００１８】
これらの中でも
【化９】
更に、これらの化合物は塩を構成していてもよい。尚、ここでいう塩としては、例えば硫酸、硝酸、塩酸等の無機酸、酢酸、乳酸、クエン酸等の低級カルボン酸等との塩等が含まれる。
【００１９】
本発明のアゾアミジン化合物は、例えば下記一般式［２］
【化１０】
【００２０】
【化１１】
（式中、
【００２２】
一般式［２］に於いて、Ｒ3で示される低級アルキル基としては、直鎖状でも分枝状でもよく、例えば炭素数１〜６、好ましくは炭素数１〜４のものが挙げられ、具体的には、例えばメチル基、エチル基、ｎ-プロピル基、イソプロピル基、ｎ-ブチル基、イソブチル基、tert-ブチル基、sec-ブチル基、ｎ-ペンチル基、イソペンチル基、tert-ペンチル基、sec-ペンチル基、ネオペンチル基、ｎ-ヘキシル基等が挙げられる。
【００２３】
一般式［２］で示されるアゾジイミノエーテル化合物の具体例としては、例えば2,2'-アゾビス(1-イミノ-2-メチルプロピルメチルエーテル)、2,2'-アゾビス(1-イミノ-2-メチルプロピルエチルエーテル)、2,2'-アゾビス(1-イミノ-2-メチルプロピル-ｎ-プロピルエーテル)、2,2'-アゾビス(1-イミノ-2-メチルプロピルイソプロピルエーテル)、2,2'-アゾビス(1-イミノ-2-メチルプロピル-ｎ-ブチルエーテル)、2,2'-アゾビス(1-イミノ-2-エチルプロピルメチルエーテル)、2,2'-アゾビス(1-イミノ-2-エチルプロピルエチルエーテル)等が挙げられる。
【００２４】
これらアゾジイミノエーテル化合物は市販品を用いてもよいし、例えばアゾビスイソブチロニトリルに塩化水素を反応させる等の常法により得られたものを用いてもよい。
【００２５】
一般式［３］で示されるアミン化合物としては、
【００２６】
反応溶媒としては、例えばトルエン，キシレン，ベンゼン，シクロヘキサン，ｎ-ヘキサン，ｎ-オクタン等の炭化水素類、例えばメタノール，エタノール，ｎ-プロパノール，イソプロパノール，ｎ-ブタノール，イソブタノール，tert-ブ タノール等のアルコール類、例えば四塩化炭素，クロロホルム，塩化メチレン，ジクロロエタン，トリクロロエタン等のハロゲン化炭化水素、例えば酢酸エチル，酢酸ブチル，プロピオン酸メチル等のエステル類、ジメチルホルムアミド、ジメチルスルホキシド、水等が挙げられる。これらは夫々単独で用いても、二種以上適宜組み合わせて用いてもよい。
【００２７】
一般式［３］で示されるアミン化合物の使用量は、使用するアミン化合物及びアゾジイミノエ−テル化合物の種類によって異なるが、アゾジイミノエ−テル化合物に対して通常1.5〜10倍モル、好ましくは２〜５倍モルである。
【００２８】
反応温度は、特に限定されないが、高すぎるとアゾ基が分解し、低すぎると反応速度が遅くなり製造に時間を要するため、通常-10〜40℃好ましくは0〜30℃である。
【００２９】
反応時間は、アゾジイミノエ−テル化合物やアミン化合物の種類により異なるが、通常１〜24時間である。
【００３０】
上記以外の反応の操作及び後処理等は自体公知の同種反応のそれに準じて行えばよい。
【００３１】
尚、本発明の一般式［１］で示されるアゾアミジン化合物を製造する際に使用する上記一般式［２］で示されるアゾジイミノエ−テル化合物及びその塩、並びに上記一般式［３］で示されるアミン化合物は、市販品を用いても或いは常法により適宜製造したものを用いてもよい。
【００３２】
このようにして得られた本発明のアゾアミジン化合物は、加熱又は光照射によって容易にアゾ基が分解し窒素ガスの発生と共にラジカル種を生じるので、その際に各種の重合性モノマーが存在すれば速やかに重合を起こす。そして、既知のアゾアミジン化合物に比して、水、メタノール等に対する溶解性に優れ、その１０時間半減期温度が６０〜７０℃であり、水系媒体中での重合が効率よく行われる。
【００３３】
本発明のアゾアミジン化合物を重合開始剤として用いて、重合性モノマーを重合或いは共重合させるには、本発明のアゾアミジン化合物と、重合性モノマーとを適当な溶媒中或いは無溶媒で、要すれば不活性ガス雰囲気下で常法に従い重合反応を行えばよい。
【００３４】
上記重合性モノマーとしては、例えば下記一般式［４］
【化１２】
（式中、Ｒ6は水素原子、低級アルキル基、カルボキシル基、カルボキシアルキ ル基、アルキルオキシカルボニル基、ヒドロキシアルキルオキシカルボニル基、シアノ基又はアルデヒド基を表し、Ｒ7は水素原子、低級アルキル基、カルボキ シル基、アルキルオキシカルボニル基、ヒドロキシアルキルオキシカルボニル基、シアノ基又はハロゲン原子を表し、Ｒ8は水素原子、低級アルキル基、ハロアルキル基、ヒドロキシル基、置換基を有していてもよいアリール基、脂肪族ヘテロ環基、芳香族ヘテロ環基、ハロゲン原子、アルキルオキシカルボニル基、ヒドロキシアルキルオキシカルボニル基、スルホン酸基、シアノ基、含シアノアルキル基、アシルオキシ基、カルボキシル基、カルボキシアルキル基、アルデヒド基、アミノ基、アミノアルキル基、カルバモイル基、Ｎ−アルキルカルバモイル基、ヒドロキシアルキル基を表す。また、Ｒ6とＲ7とが結合し、隣接する-C=C-と一緒になって脂肪族環を形成していてもよい。）で示されるα，β−エチレン性不飽和モノマー等が挙げられる。
【００３６】
一般式［４］に於いて、Ｒ6〜Ｒ8で示される低級アルキル基としては、直鎖状でも分枝状でも或いは環状でもよく、例えば炭素数１〜６のアルキル基が挙げられ、具体的にはメチル基，エチル基，ｎ-プロピル基，イソプロピル基，ｎ-ブチル基，イソブチル基，tert-ブチル基，sec-ブチル基，ｎ-ペンチル基，イソペンチル基，tert-ペンチル基，１-メチルペンチル基，ｎ-ヘキシル基，イソヘキシル基、シクロプロピル基、シクロペンチル基、シクロヘキシル基等が挙げられる。
【００３７】
Ｒ6及びＲ8で示されるカルボキシアルキル基としては、例えば上記した如き低級アルキル基の水素原子の一部がカルボキシル基に置換されたもの等が挙げられ、具体的には例えばカルボキシメチル基，カルボキシエチル基，カルボキシプロピル基，カルボキシブチル基，カルボキシペンチル基，カルボキシヘキシル基等が挙げられる。
【００３８】
Ｒ6〜Ｒ8で示されるアルキルオキシカルボニル基としては、例えば炭素数２〜11のものが好ましく、具体的には、例えばメトキシカルボニル基，エトキシカルボニル基，プロポキシカルボニル基，ブトキシカルボニル基，ペンチルオキシカルボニル基，ヘキシルオシカルボニル基，ヘプチルオキシカルボニル基，2-エチルヘキシルオキシカルボニル基，オクチルオキシカルボニル基，ノニルオキシカルボニル基，デシルオキシカルボニル基等が挙げられる。
【００３９】
Ｒ6〜Ｒ8で示されるヒドロキシアルキルオキシカルボニル基としては、上記した如き炭素数２〜11のアルキルオキシカルボニル基の水素原子の一部がヒドロキシル基に置換されたものが挙げられ、具体的には、例えばヒドロキシメチルオキシカルボニル基、ヒドロキシエチルオキシカルボニル基、ヒドロキシプロピルオキシカルボニル基、ヒドロキシブチルオキシカルボニル基、ヒドロキシペンチルオキシカルボニル基、ヒドロキシヘキシルオキシカルボニル基、ヒドロキシヘプチルオキシカルボニル基、ヒドロキシオクチルオキシカルボニル基、ヒドロキシノニルオキシカルボニル基、ヒドロキシデシルオキシカルボニル基等が挙げられる。
【００４０】
Ｒ7及びＲ8で示されるハロゲン原子としては、フッ素，塩素，臭素，ヨウ素等が挙げられる。
【００４１】
Ｒ8で示されるハロアルキル基としては、例えば上記低級アルキル基がハロゲ ン化（例えばフッ素化，塩素化，臭素化，ヨウ素化等）された炭素数１〜６のものが挙げられ、具体的には、例えばクロロメチル基，ブロモメチル基，トリフルオロメチル基，2-クロロエチル基，3-クロロプロピル基，3-ブロモプロピル基，3,3,3-トリフルオロプロピル基，4-クロロブチル基，5-クロロペンチル基，6-クロロヘキシル基等が挙げられる。
【００４２】
置換基を有していてもよいアリール基のアリール基としては、例えばフェニル基，トリル基，キシリル基，ナフチル基等が挙げられ、また、該置換基としては、例えばアミノ基，ヒドロキシル基，低級アルコキシ基，カルボキシル基等が挙げられる。置換アリール基の具体例としては、例えばアミノフェニル基，トルイジノ基，ヒドロキシフェニル基，メトキシフェニル基，tert-ブトキシフェニル基，カルボキシフェニル基等が挙げられる。
【００４３】
脂肪族ヘテロ環基としては、例えば５員環又は６員環であり、異性原子として１〜３個の例えば窒素原子，酸素原子，硫黄原子等のヘテロ原子を含んでいるもの等が好ましく挙げられ、具体例としては、例えばピロリジル-2-オン基，ピペリジル基，ピペリジノ基，ピペラジニル基，モルホリノ基等が挙げられる。
【００４４】
芳香族ヘテロ環基としては、例えば５員環又は６員環であり、異性原子として１〜３個の例えば窒素原子，酸素原子，硫黄原子等のヘテロ原子を含んでいるもの等が好ましく挙げられ、具体例としては、例えばピリジル基，イミダゾリル基，チアゾリル基，フラニル基，ピラニル基等が挙げられる。
【００４５】
含シアノアルキル基としては、例えば上記した如き低級アルキル基の水素原子の一部がシアノ基に置換されたものが挙げられ、具体的には、例えばシアノメチル基，2-シアノエチル基，2-シアノプロピル基，3-シアノプロピル基，2-シアノブチル基，4-シアノブチル基，5-シアノペンチル基，6-シアノヘキシル基等が挙げられる。
【００４６】
アシルオキシ基としては、例えば炭素数２〜20のカルボン酸由来のものが挙げられ、具体的には、例えばアセチルオキシ基，プロピオニルオキシ基，ブチリルオキシ基，ペンタノイルオキシ基，ヘキサノイルオキシ基，ヘプタノイルオキシ基，オクタノイルオキシ基，ノナノイルオキシ基，デカノイルオキシ基，ベンゾイルオキシ基等が挙げられる。
【００４７】
アミノアルキル基としては、上記した如き低級アルキル基の水素原子の一部がアミノ基に置換されたものが挙げられ、具体的には、例えばアミノメチル基，アミノエチル基，アミノプロピル基，アミノブチル基，アミノペンチル基，アミノヘキシル基等が挙げられる。
【００４８】
Ｎ-アルキルカルバモイル基としては、カルバモイル基の水素原子の一部がアルキル基で置換されたものが挙げられ、具体的には、例えばＮ-メチルカルバモイル基，Ｎ-エチルカルバモイル基，Ｎ-ｎ-プロピルカルバモイル基，Ｎ-イソプロピルカルバモイル基，Ｎ-ｎ-ブチルカルバモイル基，Ｎ-ｔ-ブチルカルバモイル基等が挙げられる。
【００４９】
ヒドロキシアルキル基としては、上記した如き低級アルキル基の水素原子の一部がヒドロキシル基に置換されたものが挙げられ、具体的には、例えばヒドロキシメチル基，ヒドロキシエチル基，ヒドロキシプロピル基，ヒドロキシブチル基，ヒドロキシペンチル基，ヒドロキシヘキシル基等が挙げられる。
【００５０】
また、Ｒ6とＲ7とが結合し、隣接する-C=C-と一緒になって脂肪族環を形成している場合としては、炭素数５〜10の不飽和脂肪族環を形成している場合が挙げられ、環は単環でも多環でもよい。これら環の具体的なものとしては、例えばノルボルネン環、シクロペンテン環、シクロヘキセン環、シクロオクテン環、シクロデセン環等が挙げられる。
【００５１】
一般式［４］で示されるα，β−エチレン性不飽和モノマーの具体例としては、例えばエチレン，プロピレン，ブチレン，イソブチレン等の炭素数２〜20のエチレン性不飽和脂肪族炭化水素類、例えばスチレン，4-メチルスチレン，4-エチルスチレン，ジビニルベンゼン等の炭素数８〜20のエチレン性不飽和芳香族炭化水素類、例えばギ酸ビニル，酢酸ビニル，プロピオン酸ビニル，酢酸イソプロペニル等の炭素数３〜20のアルケニルエステル類、例えば塩化ビニル，塩化ビニリデン，フッ化ビニリデン等の炭素数２〜20の含ハロゲンエチレン性不飽和化合物類、例えばアクリル酸，メタクリル酸，イタコン酸，マレイン酸，フマル酸，クロトン酸，ビニル酢酸，アリル酢酸，ビニル安息香酸等の炭素数３〜20のエチレン性不飽和カルボン酸類（これら酸類は、例えばナトリウム，カリウム等のアルカリ金属塩やアンモニウム塩等の塩であってもよい）、例えばメタクリル酸メチル，メタクリル酸エチル，メタクリル酸プロピル，メタクリル酸ブチル，メタクリル酸2-エチルヘキシル，メタクリル酸ステアリル，アクリル酸メチル，アクリル酸エチル，アクリル酸ブチル，アクリル酸2-エチルヘキシル，メタクリル酸ラウリル，アクリル酸ステアリル，イタコン酸メチル，イタコン酸エチル，マレイン酸メチル，マレイン酸エチル，フマル酸メチル，フマル酸エチル，クロトン酸メチル，クロトン酸エチル，3-ブテン酸メチル等の炭素数４〜20のエチレン性不飽和カルボン酸エステル類、例えばアクリロニトリル，メタクリロニトリル，シアン化アリル等の炭素数３〜20の含シアノエチレン性不飽和化合物類、例えばアクリルアミド，メタクリルアミド等の炭素数３〜20のエチレン性不飽和アミド化合物類、例えばアクロレイン，クロトンアルデヒド等の炭素数３〜20のエチレン性不飽和アルデヒド類、例えばビニルスルホン酸，4-ビニルベンゼンスルホン酸等の炭素数２〜20のエチレン性不飽和スルホン酸類（これら酸類は、ナトリウム、カリウム等のアルカリ金属塩等、塩の形になっているものでもよい）、例えばビニルアミン，アリルアミン等の炭素数２〜20のエチレン性不飽和脂肪族アミン類、例えばビニルアニリン等の炭素数８〜20のエチレン性不飽和芳香族アミン類、例えばＮ-ビニルピロリドン，ビニルピペリジン等の炭素数５〜20のエチレン性不飽和脂肪族ヘテロ環状アミン類、例えばビニルピリジン，1-ビニルイミダゾール等の炭素数５〜20のエチレン性不飽和芳香族ヘテロ環状アミン類、例えばアリルアルコール，クロチルアルコール等の炭素数３〜20のエチレン性不飽和アルコール類、例えば4-ビニルフェノール等の炭素数８〜20のエチレン性不飽和フェノール類等が挙げられる。
【００５２】
重合開始剤として、本発明のアゾアミジン化合物に加えてその他のものを併用してもよい。併用するアゾアミジン化合物以外の重合開始剤としては、例えば2,2'-アゾビスイソブチロニトリル，2,2'-アゾビス(2,4-ジメチルバレロニトリル)，2,2'-アゾビス(2-アミジノプロパン)二塩酸塩，2,2'-アゾビス(2-メチルプロピオンアミジン)二塩酸塩，2,2'-アゾビス〔2-(2-イミダゾリン)-2-イル〕プロパン，2,2'-アゾビスイソブチルアミド ２水和物，ジメチル2,2'-アゾビス(2-メチルプロピオネート)，4,4'-アゾビス(4-シアノ吉草酸)等のアゾ化合物類の他、例えば過酸化ベンゾイル，過酸化ジtert-ブチル等の過酸化物類に代表されるレドックス系重合開始剤や、例えばベンゾインエチルエーテル，ベンゾインイソプロピルエーテル，ベンジルジメチルケタール等の光重合開始剤類等が挙げられる。
【００５３】
重合反応の方法としては、例えば溶液重合、バルク重合、懸濁重合、乳化重合等が挙げられる。
【００５４】
溶液重合で用いられる溶媒としては、例えばテトラヒドロフラン，ジエチルエーテル，ジオキサン等のエーテル類、メタノール，エタノール，イソプロパノール等のアルコール類、Ｎ,Ｎ-ジメチルホルムアミド、ジメチルスルホキシド、水等が挙げられる。これらの溶媒は夫々単独で用いても、二種以上適宜組み合わせて用いてもよい。
また、乳化重合を行う場合には、通常この分野で使用される界面活性剤を用いてもよい。
【００５５】
重合反応は不活性ガス雰囲気下で行うことが望ましい。不活性ガスとしては、例えば窒素ガス，アルゴンガス等が挙げられる。
【００５６】
重合開始剤としての本発明のアゾアミジン化合物の使用量は、重合しようとする重合性モノマーの種類によっても変動するが、本発明のアゾアミジン化合物を単独で使用する場合には、重合性モノマーに対して通常0.01〜100重量％、好ましく は0.05〜50重量％である。尚、本発明のアゾアミジン化合物とそれ以外の重合開始剤とを併用する場合には、併用する重合開始剤の種類と、使用する重合性モノマーの種類及び目的とするポリマーの意図する物性等を考慮して適宜その割合を選択すればよい。
【００５７】
重合性モノマーの重合反応時に於ける溶媒中の濃度は、重合性モノマーの種類によっても異なるが通常５〜100重量％（無溶媒）、好ましくは10〜60重量％である。
【００５８】
重合温度は特に限定されないが、低すぎるとアゾ基の分解が少ないため重合の進行が遅くなり、高すぎるとアゾ基の分解が多くなりすぎ重合の制御が困難となるため通常20〜150℃、好ましくは30〜100℃である。また、水系媒体中で重合反応を行う場合、重合温度は30〜100℃が好ましい。尚、その際に用いられる水系媒体としては、例えば水、水−メタノール混合溶液、水−エタノール混合溶液、メタノール、エタノール等が挙げられ、中でも水が好ましい。
【００５９】
重合反応時間は、反応温度や反応させる重合性モノマー及び使用する本発明のアゾアミジン化合物の種類、或いは濃度等の反応条件により異なるが、通常２〜24時間である。
【００６０】
本発明のアゾアミジン化合物は、既知のアゾアミジン化合物と比べ、水及びメタノール等に対する溶解性に優れ、また、１０時間半減期温度が従来はなかった６０〜７０℃であるので、これを重合開始剤として用いることにより水系媒体中で効率よく重合反応を行うことができ、更に他の重合開始剤と併用した場合も、温度制御等を容易に行うことができる。
【００６１】
以下に実施例及び実験例を挙げて本発明を更に詳細に説明するが、本発明はこれらにより何ら限定されるものではない。
【００６２】
【実施例】
実施例１
アゾビスイソブチロニトリル 60g、メタノール 28g、トルエン 270mlの懸濁液に塩化水素 32gを導入し反応させて合成した２，２’−アゾビス（１−イミノ−１−メトキシ−２−メチルプロパン）塩酸塩のトルエン懸濁液にピロリジン 62gを加え室温で７時間反応を行った。一夜放置後、結晶を濾取、乾燥して２，２’−アゾビス（２−メチル−１−（１−ピロリジニル）イミノプロパン塩酸塩の淡黄色結晶 50gを得た。
実施例２
アゾビスイソブチロニトリル 60gのメタノール 28g、トルエン 270ml懸濁液に塩化水素 32gを導入し反応させて合成した２，２’−アゾビス（１−イミノ−１−メトキシ−２−メチルプロパン）塩酸塩のトルエン懸濁液をアンモニアで中和後、濾過して得た２，２’−アゾビス（１−イミノ−１−メトキシ−２−メチルプロパン）のトルエン溶液にピロリジン 62gを加え７時間反応を行った。一夜放置後、反応液に酢酸エチルを注入した後、結晶を濾取、乾燥して２，２’−アゾビス（２−メチル−１−（１−ピロリジニル）イミノプロパンの淡黄色結晶10gを得た。
１H-NMRδppm（CD3OD)：1.52 (12H, s, -CH3),1.95 (8H, m,β位ピロリジン環), 3.50 (8H, m,α位ピロリジン環),4.7ppm(2H,br,=N-H)
【００６４】
実施例３
アクリルアミド20gを蒸留水378gに溶解し、窒素雰囲気下、70℃に加温した後、実施例１で得られたアゾアミジン化合物の塩酸塩0.019mol/Lを溶解した水溶液2mlを注入して、70℃で重合を行った。所定時間毎に反応液の一部をサンプリングし、メタノールを加えて沈殿させポリマーを分離し、乾燥して時間毎の重合率を夫々測定した。結果を表１に示す。
【００６５】
比較例１
実施例１で得られたアゾアミジン化合物の塩酸塩の代わりに、既存の代表的なアゾアミジン化合物である２，２'-アゾビス（２-メチルプロピオンアミジン）塩酸塩（以下、比較化合物１と略記する。）を実施例３と同様にして重合率を測定した。結果を表１に併せて示す。
【００６６】
比較例２
実施例１で得られたアゾアミジン化合物の塩酸塩の代わりに、既存の代表的なアゾアミジン化合物である２，２'-アゾビス［Ｎ−(２-ヒドロキエチル)−２−メチルプロピオンアミド］（以下、比較化合物2と略記する。）を実施例３と同様にして重合率を測定した。結果を表１に併せて示す。
【００６７】
【表１】
表１から明らかな如く、重合温度を７０℃にした場合の本願発明のアゾアミジン化合物の重合率と既存の比較化合物１及び２のそれとを比較すると、重合時間が４時間を越えると重合率が１０％以上良くなることが判る。
【００６９】
【発明の効果】
以上述べた如く、本発明は、水、メタノール等の溶媒に対する溶解性に優れた新規なアゾアミジン化合物を提供するものであり、該アゾアミジン化合物は水中での１０時間半減期温度が６０〜７０℃であり、水溶媒系の重合においてこれを用いることにより、各種モノマーを効率よく重合させることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an azoamidine compound useful as a water-soluble polymerization initiator or the like.
[0002]
[Prior art]
In recent years, the production of polymer compounds has been actively studied to complete the polymerization reaction in a short time at a high concentration in pursuit of rationalization. In particular, in the polymerization in an aqueous solution, the polymerization temperature tends to be set higher year by year, and the polymerization time tends to be shortened. Therefore, for example, conventional polymerization initiators such as redox initiators, persulfate compounds, peroxide initiators and azo initiators are too active for the polymerization temperature, and the amount of monomer remaining without the polymerization proceeding sufficiently to the end. There is a tendency for problems such as increase.
[0003]
In order to solve this problem, methods for increasing the amount of initiator added, methods for adding an initiator in the middle of the reaction, methods for using initiators having different activities, and the like have been studied. However, the method of increasing the amount of initiator is less effective because most of the initiator decomposes during the polymerization, and the method of adding the initiator during the reaction adds it because the viscosity of the polymerization solution increases. However, there are problems such as inadequate mixing of the initiator.
[0004]
Therefore, as a method for further solving this problem, a method using a plurality of polymerization initiators having a 10-hour half-life temperature corresponding to the temperature increase range during polymerization or an initiator having a decomposition activity corresponding to the polymerization temperature is used. The method of doing is considered. However, a method using a plurality of polymerization initiators together, for example, an azoamidine salt polymerization initiator having a 10-hour half-life temperature of 45 to 60 ° C. (low-temperature activity) and a 10-hour half-life temperature of 80 to 90 ° C. (high-temperature activity) In the method in which the polymerization is carried out in combination with an azoamide-based polymerization initiator having a hydroxyl group), the polymerization reaction cannot be controlled well. As a means for solving such a problem, an initiator having a decomposition activity corresponding to a normal temperature increase range (40 ° C. → 90 ° C.) having a 10-hour half-life temperature of 60 to 70 ° C. is used. Although considered, no such initiator is currently found. Accordingly, it is currently desired to develop a water-soluble azo polymerization initiator having a 10-hour half-life temperature of 60 to 70 ° C.
[0005]
[Problems to be solved by the invention]
The present invention has been made in view of the situation as described above, and its purpose is that the 10-hour half-life temperature in water is 60 to 70 ° C., and various monomers are efficiently polymerized in polymerization in an aqueous medium. It is an object to provide a novel azo compound useful as a water-soluble polymerization initiator and the like.
[0006]
[Means for Solving the Problems]
The present invention relates to a general formula [1]
[Chemical 2]
Or a salt thereof (hereinafter referred to as the azoamidine compound of the present invention).
[0007]
The present invention is also an invention of a polymerization initiator comprising the azoamidine compound of the present invention.
Furthermore, the present invention is an invention of a polymerization method of an α, β-ethylenically unsaturated monomer, characterized by using the azoamidine compound of the present invention as a polymerization initiator.
[0008]
That is, as a result of intensive studies to achieve the above object, the present inventors have found that an azoamidine compound having a heterocyclic ring such as a pyrrolidine ring in the molecule has a 10-hour half-life temperature in water of 60 to 70 ° C. Thus, it has been found that the polymerization in the aqueous medium can be performed more effectively than the conventional method by using this, and the present invention has been completed.
[0009]
In the general formula [1], R 1 And R 2 The lower alkyl group represented by the formula may be linear, branched or cyclic, and examples thereof include those having 1 to 5 carbon atoms, preferably 1 to 3 carbon atoms. Group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, sec-pentyl group Group, 2-methylbutyl group, 1-ethylpropyl group, 2-ethylpropyl group, cyclopropyl, cyclobutyl group, cyclopentyl group and the like. Among these, methyl group is most preferable.
[0010]
[0011]
These heterocyclic groups may further have a substituent. The substituent is a hydrogen atom of —NH— constituting the ring, or —CH— 2 -Or = CH--substituted by a hydrogen atom, and specific examples thereof include lower alkyl groups such as a methyl group, an ethyl group and an n-propyl group, such as a methoxy group, an ethoxy group and an n-propoxy group. And the like, lower halogen groups such as fluorine, chlorine, bromine and iodine.
[0012]
Specific examples of the azoamidine compound of the present invention represented by the general formula [1] include, for example,
[Chemical 3]
[Formula 4]
[Chemical formula 5]
[Chemical 6]
[Chemical 7]
[Chemical 8]
[0018]
Among these
[Chemical 9]
Further, these compounds may constitute a salt. Examples of the salt herein include salts with inorganic acids such as sulfuric acid, nitric acid and hydrochloric acid, and lower carboxylic acids such as acetic acid, lactic acid and citric acid.
[0019]
The azoamidine compound of the present invention includes, for example, the following general formula [2]
[Chemical Formula 10]
[0020]
Embedded image
(Where
[0022]
In the general formula [2], R Three The lower alkyl group represented by may be linear or branched, and examples thereof include those having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include methyl groups and ethyl groups. , N-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, sec-butyl, n-pentyl, isopentyl, tert-pentyl, sec-pentyl, neopentyl, n- A hexyl group etc. are mentioned.
[0023]
Specific examples of the azodiiminoether compound represented by the general formula [2] include 2,2′-azobis (1-imino-2-methylpropylmethyl ether), 2,2′-azobis (1-imino- 2-methylpropyl ethyl ether), 2,2'-azobis (1-imino-2-methylpropyl-n-propyl ether), 2,2'-azobis (1-imino-2-methylpropyl isopropyl ether), 2 , 2'-azobis (1-imino-2-methylpropyl-n-butyl ether), 2,2'-azobis (1-imino-2-ethylpropylmethyl ether), 2,2'-azobis (1-imino- 2-ethylpropylethyl ether) and the like.
[0024]
As these azodiimino ether compounds, commercially available products may be used, or those obtained by a conventional method such as reacting azobisisobutyronitrile with hydrogen chloride may be used.
[0025]
As the amine compound represented by the general formula [3],
[0026]
Examples of the reaction solvent include hydrocarbons such as toluene, xylene, benzene, cyclohexane, n-hexane and n-octane, such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol and the like. Alcohols such as halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, dichloroethane, and trichloroethane; esters such as ethyl acetate, butyl acetate, and methyl propionate; dimethylformamide, dimethyl sulfoxide, and water. . These may be used alone or in appropriate combination of two or more.
[0027]
The amount of the amine compound represented by the general formula [3] varies depending on the type of amine compound and azodiiminoether compound to be used, but is usually 1.5 to 10 times mol, preferably 2 to 5 times that of the azodiiminoether compound. Is a mole.
[0028]
The reaction temperature is not particularly limited, but if it is too high, the azo group decomposes, and if it is too low, the reaction rate is slow and time is required for production. Therefore, it is usually −10 to 40 ° C., preferably 0 to 30 ° C.
[0029]
The reaction time varies depending on the kind of azodiiminoether compound or amine compound, but is usually 1 to 24 hours.
[0030]
The operation and post-treatment of reactions other than those described above may be carried out in accordance with those of the same type of reaction known per se.
[0031]
The azodiimine ether compound represented by the above general formula [2] and a salt thereof used in the production of the azoamidine compound represented by the general formula [1] of the present invention, and the amine represented by the above general formula [3] As the compound, a commercially available product may be used, or a compound appropriately produced by a conventional method may be used.
[0032]
The azoamidine compound of the present invention thus obtained easily decomposes by heating or light irradiation to generate radical species with generation of nitrogen gas. Causes polymerization. And compared with a known azoamidine compound, it is excellent in solubility in water, methanol and the like, its 10-hour half-life temperature is 60 to 70 ° C., and polymerization in an aqueous medium is efficiently performed.
[0033]
In order to polymerize or copolymerize a polymerizable monomer using the azoamidine compound of the present invention as a polymerization initiator, the azoamidine compound of the present invention and the polymerizable monomer may be used in a suitable solvent or without a solvent, if necessary. What is necessary is just to perform a polymerization reaction according to a conventional method in an active gas atmosphere.
[0034]
Examples of the polymerizable monomer include the following general formula [4].
Embedded image
(Wherein R 6 Represents a hydrogen atom, a lower alkyl group, a carboxyl group, a carboxyalkyl group, an alkyloxycarbonyl group, a hydroxyalkyloxycarbonyl group, a cyano group or an aldehyde group, and R 7 Represents a hydrogen atom, a lower alkyl group, a carboxy group, an alkyloxycarbonyl group, a hydroxyalkyloxycarbonyl group, a cyano group or a halogen atom; 8 Is a hydrogen atom, lower alkyl group, haloalkyl group, hydroxyl group, aryl group which may have a substituent, aliphatic heterocyclic group, aromatic heterocyclic group, halogen atom, alkyloxycarbonyl group, hydroxyalkyloxycarbonyl Group, sulfonic acid group, cyano group, cyanoalkyl group, acyloxy group, carboxyl group, carboxyalkyl group, aldehyde group, amino group, aminoalkyl group, carbamoyl group, N-alkylcarbamoyl group, and hydroxyalkyl group. R 6 And R 7 And may be combined with the adjacent —C═C— to form an aliphatic ring. ), Β-ethylenically unsaturated monomers and the like.
[0036]
In the general formula [4], R 6 ~ R 8 The lower alkyl group represented by may be linear, branched or cyclic, and examples thereof include an alkyl group having 1 to 6 carbon atoms, specifically a methyl group, an ethyl group, an n-propyl group, Isopropyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, 1-methylpentyl group, n-hexyl group, isohexyl group, cyclopropyl Group, cyclopentyl group, cyclohexyl group and the like.
[0037]
R 6 And R 8 Examples of the carboxyalkyl group represented by the formula include those in which a part of hydrogen atoms of the lower alkyl group as described above is substituted with a carboxyl group, and specifically include, for example, a carboxymethyl group, a carboxyethyl group, a carboxypropyl group, and the like. Group, carboxybutyl group, carboxypentyl group, carboxyhexyl group and the like.
[0038]
R 6 ~ R 8 As the alkyloxycarbonyl group represented by formula (2), for example, those having 2 to 11 carbon atoms are preferable. Specifically, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxy group. Examples include carbonyl group, heptyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group and the like.
[0039]
R 6 ~ R 8 Examples of the hydroxyalkyloxycarbonyl group represented by formula (1) include those in which a part of hydrogen atoms of the alkyloxycarbonyl group having 2 to 11 carbon atoms is substituted with a hydroxyl group. Oxycarbonyl group, hydroxyethyloxycarbonyl group, hydroxypropyloxycarbonyl group, hydroxybutyloxycarbonyl group, hydroxypentyloxycarbonyl group, hydroxyhexyloxycarbonyl group, hydroxyheptyloxycarbonyl group, hydroxyoctyloxycarbonyl group, hydroxynonyloxycarbonyl Group, hydroxydecyloxycarbonyl group and the like.
[0040]
R 7 And R 8 Examples of the halogen atom represented by are fluorine, chlorine, bromine, iodine and the like.
[0041]
R 8 Examples of the haloalkyl group represented by formula (1) include those having 1 to 6 carbon atoms in which the lower alkyl group is halogenated (for example, fluorinated, chlorinated, brominated, iodinated, etc.). For example, chloromethyl group, bromomethyl group, trifluoromethyl group, 2-chloroethyl group, 3-chloropropyl group, 3-bromopropyl group, 3,3,3-trifluoropropyl group, 4-chlorobutyl group, 5-chloropentyl Group, 6-chlorohexyl group and the like.
[0042]
Examples of the aryl group that may have a substituent include a phenyl group, a tolyl group, a xylyl group, and a naphthyl group. Examples of the substituent include an amino group, a hydroxyl group, and a lower group. An alkoxy group, a carboxyl group, etc. are mentioned. Specific examples of the substituted aryl group include aminophenyl group, toluidino group, hydroxyphenyl group, methoxyphenyl group, tert-butoxyphenyl group, carboxyphenyl group and the like.
[0043]
As the aliphatic heterocyclic group, for example, a 5-membered ring or a 6-membered ring, and those having 1 to 3 hetero atoms such as nitrogen atom, oxygen atom, sulfur atom and the like as isomer atoms are preferably exemplified. Specific examples include pyrrolidyl-2-one group, piperidyl group, piperidino group, piperazinyl group, morpholino group and the like.
[0044]
Preferred examples of the aromatic heterocyclic group include 5-membered rings or 6-membered rings, and those containing 1 to 3 hetero atoms such as nitrogen, oxygen and sulfur atoms as isomer atoms. Specific examples include a pyridyl group, an imidazolyl group, a thiazolyl group, a furanyl group, and a pyranyl group.
[0045]
Examples of the cyanoalkyl group include those in which a part of the hydrogen atoms of the lower alkyl group as described above are substituted with a cyano group. Specific examples include a cyanomethyl group, a 2-cyanoethyl group, and a 2-cyanopropyl group. Group, 3-cyanopropyl group, 2-cyanobutyl group, 4-cyanobutyl group, 5-cyanopentyl group, 6-cyanohexyl group and the like.
[0046]
Examples of the acyloxy group include those derived from a carboxylic acid having 2 to 20 carbon atoms. Specific examples include acetyloxy group, propionyloxy group, butyryloxy group, pentanoyloxy group, hexanoyloxy group, heptanoyl. Examples thereof include an oxy group, an octanoyloxy group, a nonanoyloxy group, a decanoyloxy group, and a benzoyloxy group.
[0047]
Examples of the aminoalkyl group include those in which a part of the hydrogen atoms of the lower alkyl group as described above is substituted with an amino group. Specific examples include an aminomethyl group, an aminoethyl group, an aminopropyl group, and aminobutyl. Group, aminopentyl group, aminohexyl group and the like.
[0048]
Examples of the N-alkylcarbamoyl group include those in which a part of the hydrogen atoms of the carbamoyl group are substituted with an alkyl group. Specific examples include an N-methylcarbamoyl group, an N-ethylcarbamoyl group, and an Nn- group. Examples thereof include a propylcarbamoyl group, an N-isopropylcarbamoyl group, an Nn-butylcarbamoyl group, and an Nt-butylcarbamoyl group.
[0049]
Examples of the hydroxyalkyl group include those in which a part of the hydrogen atoms of the lower alkyl group as described above is substituted with a hydroxyl group. Specific examples include a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group. Group, hydroxypentyl group, hydroxyhexyl group and the like.
[0050]
R 6 And R 7 Is bonded with the adjacent -C = C- to form an aliphatic ring, the case where an unsaturated aliphatic ring having 5 to 10 carbon atoms is formed, The ring may be monocyclic or polycyclic. Specific examples of these rings include a norbornene ring, a cyclopentene ring, a cyclohexene ring, a cyclooctene ring, a cyclodecene ring, and the like.
[0051]
Specific examples of the α, β-ethylenically unsaturated monomer represented by the general formula [4] include ethylenically unsaturated aliphatic hydrocarbons having 2 to 20 carbon atoms such as ethylene, propylene, butylene and isobutylene, for example, Carbon number such as styrene, 4-methylstyrene, 4-ethylstyrene, divinylbenzene, etc., ethylenically unsaturated aromatic hydrocarbons having 8-20 carbon atoms, such as vinyl formate, vinyl acetate, vinyl propionate, isopropenyl acetate 3-20 alkenyl esters, for example, halogen-containing ethylenically unsaturated compounds having 2-20 carbon atoms such as vinyl chloride, vinylidene chloride, vinylidene fluoride, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid , Crotonic acid, vinyl acetic acid, allyl acetic acid, vinyl benzoic acid, etc. The acid may be an alkali metal salt such as sodium or potassium, or a salt such as ammonium salt), for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, methacryl Stearyl acid, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, stearyl acrylate, methyl itaconate, ethyl itaconate, methyl maleate, ethyl maleate, methyl fumarate, fumarate Ethylenically unsaturated carboxylic acid esters having 4 to 20 carbon atoms such as ethyl acrylate, methyl crotonate, ethyl crotonate and methyl 3-butenoate, for example, 3 to 20 carbon atoms such as acrylonitrile, methacrylonitrile and allyl cyanide Cyanoethylenic properties of Saturated compounds, for example, ethylenically unsaturated amide compounds having 3 to 20 carbon atoms such as acrylamide and methacrylamide, for example, ethylenically unsaturated aldehydes having 3 to 20 carbon atoms such as acrolein and crotonaldehyde, such as vinyl sulfonic acid, C2-C20 ethylenically unsaturated sulfonic acids such as 4-vinylbenzenesulfonic acid (these acids may be in the form of salts such as alkali metal salts such as sodium and potassium), such as vinylamine, C2-C20 ethylenically unsaturated aliphatic amines such as allylamine, for example, C8-20 ethylenically unsaturated aromatic amines such as vinylaniline, such as N-vinylpyrrolidone, vinylpiperidine, etc. 5-20 ethylenically unsaturated aliphatic heterocyclic amines such as vinyl pyridine, 1-vinyl imidazole C5-C20 ethylenically unsaturated aromatic heterocyclic amines such as ruthenium, for example, C3-C20 ethylenically unsaturated alcohols such as allyl alcohol and crotyl alcohol, for example carbon such as 4-vinylphenol Examples thereof include ethylenically unsaturated phenols having a number of 8 to 20.
[0052]
In addition to the azoamidine compound of the present invention, other polymerization initiators may be used in combination. Examples of the polymerization initiator other than the azoamidine compound used in combination include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2- Amidinopropane) dihydrochloride, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [2- (2-imidazolin) -2-yl] propane, 2,2'- In addition to azo compounds such as azobisisobutyramide dihydrate, dimethyl 2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), for example, benzoyl peroxide And redox polymerization initiators typified by peroxides such as di-tert-butyl peroxide, and photopolymerization initiators such as benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal.
[0053]
Examples of the polymerization reaction method include solution polymerization, bulk polymerization, suspension polymerization, and emulsion polymerization.
[0054]
Examples of the solvent used in the solution polymerization include ethers such as tetrahydrofuran, diethyl ether and dioxane, alcohols such as methanol, ethanol and isopropanol, N, N-dimethylformamide, dimethyl sulfoxide, water and the like. These solvents may be used alone or in combination of two or more.
Moreover, when performing emulsion polymerization, you may use the surfactant normally used in this field | area.
[0055]
The polymerization reaction is desirably performed in an inert gas atmosphere. Examples of the inert gas include nitrogen gas and argon gas.
[0056]
The amount of the azoamidine compound of the present invention used as a polymerization initiator varies depending on the type of polymerizable monomer to be polymerized, but when the azoamidine compound of the present invention is used alone, Usually, it is 0.01 to 100% by weight, preferably 0.05 to 50% by weight. When the azoamidine compound of the present invention is used in combination with other polymerization initiators, the type of polymerization initiator used in combination, the type of polymerizable monomer used, and the intended physical properties of the target polymer are considered. The ratio may be selected as appropriate.
[0057]
The concentration of the polymerizable monomer in the solvent during the polymerization reaction varies depending on the type of the polymerizable monomer, but is usually 5 to 100% by weight (no solvent), preferably 10 to 60% by weight.
[0058]
The polymerization temperature is not particularly limited, but if it is too low, the progress of the polymerization is slow because there is little decomposition of the azo group, and if it is too high, the decomposition of the azo group becomes too much and it is difficult to control the polymerization. Preferably it is 30-100 degreeC. Moreover, when performing a polymerization reaction in an aqueous medium, the polymerization temperature is preferably 30 to 100 ° C. In addition, as an aqueous medium used in that case, water, a water-methanol mixed solution, a water-ethanol mixed solution, methanol, ethanol etc. are mentioned, for example, Water is especially preferable.
[0059]
The polymerization reaction time varies depending on the reaction temperature, the polymerizable monomer to be reacted, and the reaction conditions such as the type or concentration of the azoamidine compound of the present invention to be used, but is usually 2 to 24 hours.
[0060]
The azoamidine compound of the present invention is superior in solubility in water, methanol and the like as compared with known azoamidine compounds, and has a 10-hour half-life temperature of 60 to 70 ° C., which has not been conventionally used. By using it, the polymerization reaction can be carried out efficiently in an aqueous medium, and even when used in combination with other polymerization initiators, temperature control and the like can be easily carried out.
[0061]
Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples, but the present invention is not limited thereto.
[0062]
【Example】
Example 1
2,2′-azobis (1-imino-1-methoxy-2-methylpropane) hydrochloric acid synthesized by introducing 32 g of hydrogen chloride into a suspension of 60 g of azobisisobutyronitrile, 28 g of methanol, and 270 ml of toluene 62 g of pyrrolidine was added to a toluene suspension of the salt and reacted at room temperature for 7 hours. After standing overnight, the crystals were collected by filtration and dried to obtain 50 g of light yellow crystals of 2,2′-azobis (2-methyl-1- (1-pyrrolidinyl) iminopropane hydrochloride.
Example 2
2,2'-Azobis (1-imino-1-methoxy-2-methylpropane) hydrochloride synthesized by introducing 32 g of hydrogen chloride into a suspension of azobisisobutyronitrile 60 g of methanol 28 g and toluene 270 ml The toluene suspension was neutralized with ammonia and filtered, and 62 g of pyrrolidine was added to the toluene solution of 2,2′-azobis (1-imino-1-methoxy-2-methylpropane) obtained by filtration and reacted for 7 hours. It was. After standing overnight, ethyl acetate was poured into the reaction solution, and the crystals were collected by filtration and dried to obtain 10 g of 2,2′-azobis (2-methyl-1- (1-pyrrolidinyl) iminopropane) pale yellow crystals. .
1H-NMR δ ppm (CD Three OD): 1.52 (12H, s, -CH Three ), 1.95 (8H, m, β-pyrrolidine ring), 3.50 (8H, m, α-pyrrolidine ring), 4.7 ppm (2H, br, = NH)
[0064]
Example 3
20 g of acrylamide was dissolved in 378 g of distilled water, heated to 70 ° C. in a nitrogen atmosphere, and then 2 ml of an aqueous solution in which 0.019 mol / L of the azoamidine compound hydrochloride obtained in Example 1 was dissolved was injected. The polymerization was carried out at A part of the reaction solution was sampled every predetermined time, methanol was added to precipitate the polymer to separate it, and it was dried to measure the polymerization rate for each time. The results are shown in Table 1.
[0065]
Comparative Example 1
Instead of the hydrochloride of the azoamidine compound obtained in Example 1, 2,2′-azobis (2-methylpropionamidine) hydrochloride (hereinafter, abbreviated as Comparative Compound 1), which is an existing representative azoamidine compound. The polymerization rate was measured in the same manner as in Example 3. The results are also shown in Table 1.
[0066]
Comparative Example 2
Instead of the hydrochloride of the azoamidine compound obtained in Example 1, 2,2′-azobis [N- (2-hydroxyethyl) -2-methylpropionamide] (hereinafter referred to as an existing representative azoamidine compound) The polymerization rate was measured in the same manner as in Example 3. The results are also shown in Table 1.
[0067]
[Table 1]
As is apparent from Table 1, when the polymerization rate of the azoamidine compound of the present invention when the polymerization temperature is 70 ° C. is compared with that of the existing comparative compounds 1 and 2, the polymerization rate is 10 when the polymerization time exceeds 4 hours. It turns out that it improves more than%.
[0069]
【The invention's effect】
As described above, the present invention provides a novel azoamidine compound having excellent solubility in solvents such as water and methanol, and the azoamidine compound has a 10-hour half-life temperature in water of 60 to 70 ° C. Yes, various monomers can be efficiently polymerized by using this in water-based polymerization.
Claims (6)
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