WO2009096545A1 - 新規ジウレタン化合物、その製造法およびそれを含有するアクリルゴム組成物 - Google Patents
新規ジウレタン化合物、その製造法およびそれを含有するアクリルゴム組成物 Download PDFInfo
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- WO2009096545A1 WO2009096545A1 PCT/JP2009/051622 JP2009051622W WO2009096545A1 WO 2009096545 A1 WO2009096545 A1 WO 2009096545A1 JP 2009051622 W JP2009051622 W JP 2009051622W WO 2009096545 A1 WO2009096545 A1 WO 2009096545A1
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- WIPO (PCT)
- Prior art keywords
- group
- acrylic rubber
- compound
- diurethane
- rubber composition
- Prior art date
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- 229920000800 acrylic rubber Polymers 0.000 title claims abstract description 73
- 229920000058 polyacrylate Polymers 0.000 title claims abstract description 73
- 150000001875 compounds Chemical class 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title abstract description 7
- 238000004073 vulcanization Methods 0.000 claims abstract description 82
- -1 diamine compound Chemical class 0.000 claims abstract description 76
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 22
- 125000003118 aryl group Chemical group 0.000 claims description 14
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 10
- 150000001412 amines Chemical class 0.000 claims description 9
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 7
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 7
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 7
- 125000002723 alicyclic group Chemical group 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 125000003700 epoxy group Chemical group 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 150000001336 alkenes Chemical group 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 5
- 125000001188 haloalkyl group Chemical group 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical group NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 2
- 125000006848 alicyclic heterocyclic group Chemical group 0.000 claims 1
- 238000004132 cross linking Methods 0.000 claims 1
- 230000006835 compression Effects 0.000 abstract description 9
- 238000007906 compression Methods 0.000 abstract description 9
- 230000005764 inhibitory process Effects 0.000 abstract 1
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 14
- OPNUROKCUBTKLF-UHFFFAOYSA-N 1,2-bis(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N\C(N)=N\C1=CC=CC=C1C OPNUROKCUBTKLF-UHFFFAOYSA-N 0.000 description 12
- 238000000465 moulding Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000001125 extrusion Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- XSQHUYDRSDBCHN-UHFFFAOYSA-N 2,3-dimethyl-2-propan-2-ylbutanenitrile Chemical compound CC(C)C(C)(C#N)C(C)C XSQHUYDRSDBCHN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 5
- 150000004984 aromatic diamines Chemical class 0.000 description 5
- 238000001746 injection moulding Methods 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- ILWJAOPQHOZXAN-UHFFFAOYSA-N 1,3-dithianyl Chemical group [CH]1SCCCS1 ILWJAOPQHOZXAN-UHFFFAOYSA-N 0.000 description 4
- HDIHOAXFFROQHR-UHFFFAOYSA-N 6-aminohexylcarbamic acid Chemical compound NCCCCCCNC(O)=O HDIHOAXFFROQHR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000005060 rubber Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 2
- HFCUBKYHMMPGBY-UHFFFAOYSA-N 2-methoxyethyl prop-2-enoate Chemical compound COCCOC(=O)C=C HFCUBKYHMMPGBY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006114 decarboxylation reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 125000004386 diacrylate group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- XJELOQYISYPGDX-UHFFFAOYSA-N ethenyl 2-chloroacetate Chemical compound ClCC(=O)OC=C XJELOQYISYPGDX-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- IRXSLJNXXZKURP-UHFFFAOYSA-N fluorenylmethyloxycarbonyl chloride Chemical compound C1=CC=C2C(COC(=O)Cl)C3=CC=CC=C3C2=C1 IRXSLJNXXZKURP-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000178 monomer Substances 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
- 150000003335 secondary amines Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 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
- 238000001721 transfer moulding Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- UTOVMEACOLCUCK-SNAWJCMRSA-N (e)-4-butoxy-4-oxobut-2-enoic acid Chemical compound CCCCOC(=O)\C=C\C(O)=O UTOVMEACOLCUCK-SNAWJCMRSA-N 0.000 description 1
- XLYMOEINVGRTEX-ONEGZZNKSA-N (e)-4-ethoxy-4-oxobut-2-enoic acid Chemical compound CCOC(=O)\C=C\C(O)=O XLYMOEINVGRTEX-ONEGZZNKSA-N 0.000 description 1
- 125000003088 (fluoren-9-ylmethoxy)carbonyl group Chemical group 0.000 description 1
- SASYHUDIOGGZCN-ARJAWSKDSA-N (z)-2-ethylbut-2-enedioic acid Chemical compound CC\C(C(O)=O)=C\C(O)=O SASYHUDIOGGZCN-ARJAWSKDSA-N 0.000 description 1
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- FUPAJKKAHDLPAZ-UHFFFAOYSA-N 1,2,3-triphenylguanidine Chemical compound C=1C=CC=CC=1NC(=NC=1C=CC=CC=1)NC1=CC=CC=C1 FUPAJKKAHDLPAZ-UHFFFAOYSA-N 0.000 description 1
- TUPIWWRTTIRPDS-UHFFFAOYSA-N 1,2-bis(hydroxymethyl)guanidine Chemical compound OCNC(=N)NCO TUPIWWRTTIRPDS-UHFFFAOYSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- ALVZNPYWJMLXKV-UHFFFAOYSA-N 1,9-Nonanediol Chemical compound OCCCCCCCCCO ALVZNPYWJMLXKV-UHFFFAOYSA-N 0.000 description 1
- SQZCAOHYQSOZCE-UHFFFAOYSA-N 1-(diaminomethylidene)-2-(2-methylphenyl)guanidine Chemical compound CC1=CC=CC=C1N=C(N)N=C(N)N SQZCAOHYQSOZCE-UHFFFAOYSA-N 0.000 description 1
- DNJRKFKAFWSXSE-UHFFFAOYSA-N 1-chloro-2-ethenoxyethane Chemical compound ClCCOC=C DNJRKFKAFWSXSE-UHFFFAOYSA-N 0.000 description 1
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- HILAYQUKKYWPJW-UHFFFAOYSA-N 1-dodecylguanidine Chemical compound CCCCCCCCCCCCN=C(N)N HILAYQUKKYWPJW-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- 125000000453 2,2,2-trichloroethyl group Chemical group [H]C([H])(*)C(Cl)(Cl)Cl 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-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
- QJFIXBNLKARINT-UHFFFAOYSA-N 2-(4-methylphenyl)sulfonylethanol Chemical compound CC1=CC=C(S(=O)(=O)CCO)C=C1 QJFIXBNLKARINT-UHFFFAOYSA-N 0.000 description 1
- JJRUAPNVLBABCN-UHFFFAOYSA-N 2-(ethenoxymethyl)oxirane Chemical compound C=COCC1CO1 JJRUAPNVLBABCN-UHFFFAOYSA-N 0.000 description 1
- MBEVSMZJMIQVBG-UHFFFAOYSA-N 2-(hydroxymethyl)guanidine Chemical compound NC(N)=NCO MBEVSMZJMIQVBG-UHFFFAOYSA-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
- LCZVSXRMYJUNFX-UHFFFAOYSA-N 2-[2-(2-hydroxypropoxy)propoxy]propan-1-ol Chemical compound CC(O)COC(C)COC(C)CO LCZVSXRMYJUNFX-UHFFFAOYSA-N 0.000 description 1
- PTJDGKYFJYEAOK-UHFFFAOYSA-N 2-butoxyethyl prop-2-enoate Chemical compound CCCCOCCOC(=O)C=C PTJDGKYFJYEAOK-UHFFFAOYSA-N 0.000 description 1
- WHBAYNMEIXUTJV-UHFFFAOYSA-N 2-chloroethyl prop-2-enoate Chemical compound ClCCOC(=O)C=C WHBAYNMEIXUTJV-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- NWIIFBPIDORBCY-UHFFFAOYSA-N 2-methylprop-2-enoic acid;propane-1,2,3-triol;prop-2-enoic acid Chemical compound OC(=O)C=C.CC(=C)C(O)=O.OCC(O)CO NWIIFBPIDORBCY-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- QRJZGVVKGFIGLI-UHFFFAOYSA-N 2-phenylguanidine Chemical compound NC(=N)NC1=CC=CC=C1 QRJZGVVKGFIGLI-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- JHUUPUMBZGWODW-UHFFFAOYSA-N 3,6-dihydro-1,2-dioxine Chemical compound C1OOCC=C1 JHUUPUMBZGWODW-UHFFFAOYSA-N 0.000 description 1
- UACBZRBYLSMNGV-UHFFFAOYSA-N 3-ethoxypropyl prop-2-enoate Chemical compound CCOCCCOC(=O)C=C UACBZRBYLSMNGV-UHFFFAOYSA-N 0.000 description 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 description 1
- WPSWDCBWMRJJED-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propan-2-yl]phenol;oxirane Chemical compound C1CO1.C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 WPSWDCBWMRJJED-UHFFFAOYSA-N 0.000 description 1
- KMKWGXGSGPYISJ-UHFFFAOYSA-N 4-[4-[2-[4-(4-aminophenoxy)phenyl]propan-2-yl]phenoxy]aniline Chemical compound C=1C=C(OC=2C=CC(N)=CC=2)C=CC=1C(C)(C)C(C=C1)=CC=C1OC1=CC=C(N)C=C1 KMKWGXGSGPYISJ-UHFFFAOYSA-N 0.000 description 1
- 125000006281 4-bromobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Br)C([H])([H])* 0.000 description 1
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 1
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 description 1
- CBNJYSMAGBOTFG-UHFFFAOYSA-N 6-aminohexylcarbamic acid;carbamic acid;hexane-1,6-diamine Chemical compound NC(O)=O.NCCCCCCN.NCCCCCCNC(O)=O CBNJYSMAGBOTFG-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
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- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- QGRPEBYUVHSYDR-UHFFFAOYSA-N CC(=C)C(O)=O.OCC(O)COOC(=O)C=C Chemical compound CC(=C)C(O)=O.OCC(O)COOC(=O)C=C QGRPEBYUVHSYDR-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Natural products OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
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- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
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- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 102100030090 Probable ATP-dependent RNA helicase DHX58 Human genes 0.000 description 1
- 101710144666 Probable ATP-dependent RNA helicase DHX58 Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- LINDOXZENKYESA-UHFFFAOYSA-N TMG Natural products CNC(N)=NC LINDOXZENKYESA-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N Tetraethylene glycol, Natural products OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- CGBYBGVMDAPUIH-UHFFFAOYSA-N acide dimethylmaleique Natural products OC(=O)C(C)=C(C)C(O)=O CGBYBGVMDAPUIH-UHFFFAOYSA-N 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- HAMNKKUPIHEESI-UHFFFAOYSA-N aminoguanidine Chemical compound NNC(N)=N HAMNKKUPIHEESI-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- NIVZHWNOUVJHKV-UHFFFAOYSA-N bethanidine Chemical compound CN\C(=N/C)NCC1=CC=CC=C1 NIVZHWNOUVJHKV-UHFFFAOYSA-N 0.000 description 1
- 125000000319 biphenyl-4-yl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000000490 cinnamyl group Chemical group C(C=CC1=CC=CC=C1)* 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 description 1
- 125000004186 cyclopropylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- ANEDZEVDORCLPM-UHFFFAOYSA-N ethyl 1,3-dithiane-2-carboxylate Chemical compound CCOC(=O)C1SCCCS1 ANEDZEVDORCLPM-UHFFFAOYSA-N 0.000 description 1
- 229920006229 ethylene acrylic elastomer Polymers 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000003818 flash chromatography Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 125000003827 glycol group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- ZHDTXTDHBRADLM-UHFFFAOYSA-N hydron;2,3,4,5-tetrahydropyridin-6-amine;chloride Chemical compound Cl.NC1=NCCCC1 ZHDTXTDHBRADLM-UHFFFAOYSA-N 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 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
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- SINFYWWJOCXYFD-UHFFFAOYSA-N methoxymethyl prop-2-enoate Chemical compound COCOC(=O)C=C SINFYWWJOCXYFD-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 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 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 125000001209 o-nitrophenyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])[N+]([O-])=O 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- 125000006503 p-nitrobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1[N+]([O-])=O)C([H])([H])* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- VMBJJCDVORDOCF-UHFFFAOYSA-N prop-2-enyl 2-chloroacetate Chemical compound ClCC(=O)OCC=C VMBJJCDVORDOCF-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010058 rubber compounding Methods 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/12—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C317/18—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/20—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/08—Six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/02—Ortho- or ortho- and peri-condensed systems
- C07C2603/04—Ortho- or ortho- and peri-condensed systems containing three rings
- C07C2603/06—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members
- C07C2603/10—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings
- C07C2603/12—Ortho- or ortho- and peri-condensed systems containing three rings containing at least one ring with less than six ring members containing five-membered rings only one five-membered ring
- C07C2603/18—Fluorenes; Hydrogenated fluorenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/205—Compounds containing groups, e.g. carbamates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Definitions
- the present invention relates to a novel diurethane compound, a process for producing the same, and an acrylic rubber composition containing the same. More specifically, the present invention relates to a diurethane compound used as a novel vulcanizing agent for a crosslinkable group-containing acrylic rubber, a production method thereof, and an acrylic rubber composition containing the same.
- Carboxyl group-containing acrylic rubber is a non-halogen acrylic rubber with excellent heat resistance, compression set resistance, non-corrosion to metals, and environmental considerations among acrylic rubbers.
- Demand for sealing materials is increasing.
- the scorch time tends to be shorter than the vulcanization speed, that is, if the vulcanization speed is increased, the scorch time is too short, and if the vulcanization speed is decreased, the scorch time tends to be longer.
- the scorch time is short, the flow of the dough is deteriorated, and molding failure occurs. If the vulcanization speed is slowed, the molding time becomes longer, leading to an increase in cost. This means that the formability is inferior from the ideal of high vulcanization speed and long scorch time.
- vulcanization molding method of acrylic rubber generally, mold molding (injection molding, compression molding, transfer molding, etc.) and extrusion molding are used, and at present, the vulcanization speed at the time of molding and the scorch time are balanced. Therefore, there are the following two vulcanization system flows. (1) Aliphatic diamine (vulcanizing agent) / guanidine (vulcanizing accelerator) (2) Aromatic diamine (vulcanizing agent) / guanidine (vulcanizing accelerator)
- the aliphatic diamine vulcanization system used mainly for mold molding applications that prioritize the vulcanization speed is more than the aromatic diamine vulcanization system for extrusion applications that mainly prioritizes scorch time (t5: 10 minutes or more)
- Aromatic diamine vulcanization system with fast vulcanization speed but short scorch time, while longer scorch time than aliphatic diamine vulcanization system (4,4'-diaminodiphenyl ether, 2,2-bis [ 4- (4-aminophenoxy) phenyl] propane, methylenedianiline, and the like are disadvantageous in that the vulcanization rate is slow.
- a vulcanization system that enables high-speed vulcanization and can achieve both non-scorch has not yet been found.
- hexamethylenediamine carbamate (6-aminohexylcarbamic acid) H 3 N + (CH 2 ) 6 NHCOO - is a carboxyl group. It is widely used for the vulcanization of acrylic rubber containing chlorine and acrylic rubber containing chlorine group, and the vulcanization reaction is performed by applying heat to this vulcanizing agent compound, so that the protective group of amino group of hexamethylenediamine is 100 ° C.
- hexamethylene diamine Pyrolysis decarboxylation from nearby becomes hexamethylenediamine, which reacts with a carboxyl group or the like, which is a crosslinkable functional group in acrylic rubber, so that the vulcanization reaction proceeds. For this reason, there is a disadvantage that the scorch time is short (inferior to the scorch stability).
- hexamethylene diamine is used as a carbonate is that hexamethylene diamine is highly hygroscopic and easily vaporized, and is difficult to handle.
- carboxyl group-containing acrylic rubber includes carboxyl group-containing ethylene acrylic rubber (DuPont product Boemac G), specific carboxyl group-containing acrylic rubber (Electrochemical Industrial Products ER), etc., and these carboxyl group-containing acrylic rubbers There is also a problem that rubber has a short scorch time.
- the object of the present invention is to contain a diurethane compound used as a novel vulcanizing agent for a crosslinkable group-containing acrylic rubber, a method for producing the same, and a vulcanizing agent to improve the delay of the vulcanization rate due to scorch suppression, That is, an acrylic rubber composition that achieves both good vulcanization speed possessed by aliphatic diamine and good scorch stability possessed by aromatic diamine, and also satisfies the vulcanization properties of the vulcanizate, particularly compression set resistance. It is to provide.
- R 2 SO 2 ) m (CH 2 ) n OCONHR 1 NHCOO (CH 2 ) n (SO 2 ) m R 2
- R 1 is a C 1 to C 20 linear or branched divalent aliphatic alkylene group, divalent alicyclic cycloalkylene group or divalent aromatic group
- R 2 has a carbamate structure. Is a group that can be decomposed by the action of a basic vulcanization accelerator to generate a diamine, n is 0, 1 or 2, and m is 0 or 1.
- Such a diurethane compound is obtained by reacting a diamine compound represented by the general formula H 2 NR 1 NH 2 with a chloroformate compound represented by the general formula ClCOO (CH 2 ) n (SO 2 ) m R 2 , or It is produced by reacting a diisocyanate compound represented by OCNR 1 NCO with a hydroxyl group-containing compound represented by the general formula R 2 (SO 2 ) m (CH 2 ) n OH.
- This diurethane compound is blended with a polyamine-crosslinkable group-containing acrylic rubber together with a basic vulcanization accelerator to form an acrylic rubber composition.
- the acrylic rubber composition according to the present invention is an acrylic rubber composition containing a vulcanization system comprising a diurethane compound which is a novel compound and a basic vulcanization accelerator, and is a normal vulcanizing agent for carboxyl group-containing acrylic rubber Unlike the case where the vulcanization reaction by thermal decomposition proceeds by thermal decomposition, the vulcanization reaction proceeds due to the decomposition action by the basic vulcanization accelerator added at the same time as the diurethane compound. Even if a diurethane compound is used as an agent, vulcanization does not proceed at all unless a basic vulcanization accelerator is used in combination.
- a diurethane compound used as a vulcanizing agent alone is stable without being thermally decomposed even at 180 ° C., but is deprotected in the presence of a basic vulcanization accelerator, and hexamethylenediamine is generated to cause a vulcanization reaction. Make it progress. As a result, it was possible to perform short-time injection molding that could not be realized with conventional diamine vulcanization systems, and aliphatic diamine vulcanization systems could not be used in terms of scorching, and aromatic diamine vulcanization systems were used. Enables high-speed vulcanization (short-time vulcanization) and high-temperature extrusion of products for extrusion molding. Note that the scorch time t5 (125 ° C.) required for extrusion molding must be 10 minutes or more, and this requirement is also satisfied.
- the diurethane compound represented by can be synthesized by the following reaction. (1) H 2 NR 1 NH 2 + 2ClCOO (CH 2 ) n (SO 2 ) m R 2 (chloroformate compound) (2) OCNR 1 NCO + 2R 2 (SO 2 ) m (CH 2 ) n OH (Hydroxyl-containing compound)
- R 1 is a C 1 to C 20 linear or branched divalent aliphatic alkylene group, divalent alicyclic cycloalkyl group or divalent aromatic group.
- alkyl group examples include Examples of the divalent aromatic group include Preferably, a C 4 to C 10 linear alkylene group is used.
- R 2 is a group capable of being decomposed by the action of a basic vulcanization accelerator to generate a diamine when having a carbamate structure.
- Specific examples include C 1 to C 20 alkyl groups, alkoxyl groups, haloalkyl groups.
- Olefin group, aryl group or aralkyl group, fluorenyl-containing group, S-containing group, Si-containing group, N-containing group or P-containing group, S-containing group or N-containing group is aromatic or alicyclic heterocyclic Can be a group.
- R 2 group examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a diisopropylmethyl group, a tertiary butyl group, a tertiary amyl group, a cyclobutyl group, a cyclohexyl group, a cycloheptyl group, and a cyclopropylmethyl group.
- Chain or alicyclic alkyl group such as, methoxy, ethoxy, propoxy, butoxy, phenoxy, 4-methylphenoxy and other alkoxyl groups, 2,2,2-trichloroethyl group, 1,1-dimethyl-2-bromoethyl group Haloalkyl groups such as 1,1-dimethyl-2,2-dibromoethyl group, 1,1-dimethyl-2,2,2-trichloroethyl group, vinyl group, allyl group, 1-isopropylallyl group, cinnamyl group, Olefin group such as 4-nitrocinnamyl group, phenyl group, m-nitrophenyl group, o-nitrophenyl group, 3,4-dimethoxy-6-nitrobenzyl group, phenyl (o-nitrophenyl) Til, benzyl, p-methoxybenzyl, 3,5-dimethoxybenzyl, p-decyloxybenzyl,
- a diamine compound such as hexamethylenediamine melted in a hot water bath, 1,4-dioxane, and an aqueous sodium carbonate solution as a neutralizing agent are used.
- the mixture is cooled to about 0 to 2 ° C., and a 1,4-dioxane solution of a chloroformate compound that is stoichiometrically more than twice the mole of the diamine compound is added to the reactor at a temperature of 5 ° C.
- the mixture is dropped at a dropping rate so as not to exceed, and stirred for about several hours after completion of the dropping under room temperature conditions.
- water is added to the reaction mixture, and the precipitated solid is separated by filtration.
- the hydroxyl group-containing compound and the diisocyanate compound are reacted in an organic solvent such as toluene and dioxane while stirring at about 75 to 110 ° C. and then cooled, and the insoluble part is removed. It is produced by filtering.
- the obtained diurethane compound is blended with a polyvalent amine crosslinkable group-containing acrylic rubber together with a basic vulcanization accelerator to form an acrylic rubber composition.
- a polyvalent amine crosslinkable group-containing acrylic rubber an acrylic rubber using a polyvalent amine such as a carboxyl group-containing acrylic rubber, an epoxy group-containing acrylic rubber, and a chlorine group-containing acrylic rubber as a vulcanizing agent is preferably used.
- a diamine vulcanized type carboxyl group-containing acrylic rubber is used.
- the carboxyl group-containing acrylic rubber at least one of an alkyl acrylate having an alkyl group having 1 to 8 carbon atoms and an alkoxyalkyl acrylate having an alkoxyalkyl group having 2 to 8 carbon atoms and a carboxyl group-containing unsaturated compound are used. A polymerized one is used.
- alkyl acrylate examples include methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, and methacrylates corresponding thereto.
- the longer the chain length of the alkyl group the more advantageous in terms of cold resistance, but disadvantageous in oil resistance, and the shorter the chain length, the opposite tendency is seen, from the balance of oil resistance and cold resistance.
- alkoxyalkyl acrylate for example, methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, n-butoxyethyl acrylate, ethoxypropyl acrylate, etc. are used, preferably 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate is used. It is done.
- Alkoxyalkyl acrylates and alkyl acrylates can be used alone, but preferably the former is used in a proportion of 60 to 0% by weight and the latter is used in a proportion of 40 to 100% by weight when the alkoxyalkyl acrylate is copolymerized. Has a good balance between oil resistance and cold resistance, but when it is copolymerized at a higher ratio, normal properties and heat resistance tend to decrease.
- carboxyl group-containing unsaturated compounds include monoalkyl esters of maleic acid or fumaric acid methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, etc., itaconic acid or methyl citraconic acid, ethyl, propyl, isopropyl, n- Examples thereof include monoalkyl esters such as butyl and isobutyl, preferably maleic acid mono n-butyl ester, fumaric acid monoethyl ester, and fumaric acid mono n-butyl ester. In addition to these, unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid are also used.
- carboxyl group-containing unsaturated compounds are used in such a copolymerization ratio as to occupy about 0.5 to 10% by weight, preferably about 1 to 7% by weight in the carboxyl group-containing acrylic elastomer. Insufficient vulcanization results in deterioration of compression set value. On the other hand, if the copolymerization ratio is increased, scorching becomes easier. The copolymerization reaction is carried out so that the polymerization conversion rate is 90% or more. Therefore, the weight ratio of each charged monomer is almost the copolymer composition weight ratio of the produced copolymer.
- carboxyl group-containing acrylic elastomer other copolymerizable ethylenically unsaturated monomers such as styrene, ⁇ -methylstyrene, vinyl toluene, vinyl naphthalene, (meth) acrylonitrile, acrylic acid amide, vinyl acetate, Cyclohexyl acrylate, benzyl acrylate, 2-hydroxyethyl acrylate, 4-hydroxybutyl acrylate, ethylene, propylene, piperylene, butadiene, isoprene, pentadiene, and the like can be copolymerized in a proportion of about 50% by weight or less.
- styrene ⁇ -methylstyrene
- vinyl toluene vinyl naphthalene
- (meth) acrylonitrile acrylic acid amide
- vinyl acetate Cyclohexyl acrylate
- benzyl acrylate 2-hydroxyethyl acrylate
- a polyfunctional (meth) acrylate or oligomer having a glycol residue in the side chain such as ethylene glycol, propylene glycol, 1,4- Di (meth) acrylates of alkylene glycols such as butanediol, 1,6-hexanediol, 1,9-nonanediol, di (meth) acrylates such as neopentyl glycol, tetraethylene glycol, tripropylene glycol, polypropylene glycol, bisphenol A ethylene oxide adduct diacrylate, dimethylol tricyclodecane diacrylate, glycerin methacrylate acrylate, 3-acryloyloxyglycerin monomethacrylate and the like can be further copolymerized and used.
- an epoxy group-containing unsaturated compound such as vinyl glycidyl ether, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, etc.
- a copolymer obtained by copolymerization at a copolymerization ratio of about 0.5 to 10% by weight, preferably about 1 to 5% by weight in the acrylic elastomer contained is used.
- a chlorine group-containing unsaturated compound such as chloroethyl vinyl ether, chloroethyl acrylate, vinyl benzyl chloride, vinyl chloroacetate
- a copolymer obtained by copolymerizing allyl chloroacetate or the like at a copolymerization ratio of about 0.1 to 15% by weight, preferably about 0.3 to 5% by weight, in the chlorine group-containing acrylic rubber is used.
- these chlorine group-containing unsaturated compounds those obtained by copolymerizing vinyl chloroacetate or the like form an active chlorine group-containing acrylic rubber.
- the diurethane compound as a vulcanizing agent is used in a proportion of about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight, per 100 parts by weight of these polyvalent amine crosslinkable group-containing acrylic elastomers. If the proportion of the vulcanizing agent used is less than this, vulcanization becomes insufficient, and sufficient physical properties cannot be obtained in terms of tensile strength, compression set, and the like. On the other hand, if it is used at a higher ratio, it will cause a decrease in elongation at break and a deterioration in compression set.
- a basic vulcanization accelerator is used in combination with the diurethane compound vulcanizing agent.
- a basic vulcanization accelerator a guanidine compound, 1,8-diazabicyclo [5.4.0] undecene-7, 1,5-diazabicyclo [4.3.0] nonene-5, or the like is used.
- a mixture of 1,8-diazabicyclo [5.4.0] undecene-7 and silica can be used, and actually, Safic Alcan product Vulcofac ACT55 and the like are used.
- guanidine examples include guanidine or its substitutes such as aminoguanidine, 1,1,3,3-tetramethylguanidine, n-dodecylguanidine, methylolguanidine, dimethylolguanidine, 1-phenylguanidine, 1,3-diphenylguanidine, 1,3-di-o-tolylguanidine, triphenylguanidine, 1-benzyl-2,3-dimethylguanidine, cyanoguanidine, etc. are used, and 1,6-guanidinohexane, guanylurea, biguanide, 1-o -Tolyl biguanide is also used.
- guanidine or its substitutes such as aminoguanidine, 1,1,3,3-tetramethylguanidine, n-dodecylguanidine, methylolguanidine, dimethylolguanidine, 1-phenylguanidine, 1,3-diphenylguanidine, 1,3-d
- Guanidine as a basic vulcanization accelerator is used in an amount of about 0.1 to 10 parts by weight, preferably about 0.3 to 6 parts by weight, based on 100 parts by weight of an acrylic rubber containing a polyvalent amine crosslinkable group. 0.01 to 1 part by weight, preferably about 0.03 to 0.5 part by weight is used. Further, the mixture of 1,8-diazabicyclo [5.4.0] undecene-7 and silica is about 0.1 to 10 parts by weight, preferably about 0.2 to 5 parts by weight, per 100 parts by weight of the polyamine-crosslinkable group-containing acrylic rubber. It is used in the ratio. If the addition ratio of the basic vulcanization accelerator is too small, the vulcanization does not proceed even when the diurethane compound vulcanizing agent is used, whereas the scorch used at a higher ratio is not preferable.
- the diurethane compound of the present invention is not decomposed at 100 ° C., which is the temperature at which the conventionally used deprotection reaction of hexamethylenediamine carbamate proceeds, but is decomposed by the action of a basic vulcanization accelerator.
- a derivative in which the amino group of hexamethylenediamine is protected with a 9-fluorenylmethyloxycarbonyl group [Fmoc] is used alone as a vulcanizing agent [HMDA-Fmoc]
- HMDA-Fmoc vulcanizing agent
- decarboxylation of hexamethylenediamine carbamate The vulcanization does not proceed at the temperature, and the vulcanization proceeds by the action of the basic vulcanization accelerator to generate hexamethylenediamine. Accordingly, by appropriately adjusting the blending amount of the basic vulcanization accelerator, it is possible to realize high-speed vulcanization and scorch resistance while maintaining desired vulcanized physical properties.
- the reaction mechanism is considered as follows.
- reaction mechanism of the diurethane compound [HMDA-Dmoc] disubstituted with the [2- (1,3-dithianyl) methyl] group is considered to be as shown in the following formula.
- Preparation of acrylic rubber composition includes inorganic fillers such as carbon black and silica that are generally used as carboxyl group-containing acrylic rubber and rubber compounding agents, lubricants, anti-aging agents, and other necessary compounding agents such as Banbury mixers. After being kneaded by a closed type kneader, a vulcanizing agent and a vulcanization accelerator are added and mixed using an open roll. The prepared acrylic rubber composition is generally vulcanized by press vulcanization at about 150 to 200 ° C. for about 1 to 60 minutes, and if necessary, oven vulcanized at about 150 to 200 ° C. for about 1 to 10 hours. Done.
- inorganic fillers such as carbon black and silica that are generally used as carboxyl group-containing acrylic rubber and rubber compounding agents, lubricants, anti-aging agents, and other necessary compounding agents such as Banbury mixers.
- a vulcanizing agent and a vulcanization accelerator are added and mixed using an open roll.
- Example 1 In a 500 ml four-necked flask equipped with a thermometer, a dropping funnel and a stirrer, 5.42 g (46.6 mmol) of hexamethylenediamine (Wako Pure Chemical Industries, Ltd.) previously melted in a hot water bath at 50 ° C., 1, 160 ml of 4-dioxane (Tokyo Kasei product) and 124 ml of 10% by weight sodium carbonate (Wako Pure Chemical Industries, Ltd.) aqueous solution were charged in this order and cooled to 0 ° C.
- Example 2 In a 200-ml three-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 2- (p-toluenesulfonyl) ethanol HOCH 2 CH 2 SO 2 (pC 6 H 4 ) CH 3 11.91 g (59.7 mmol), 5.00 g (29.4 mmol) of hexamethylene diisocyanate and 100 ml of toluene were charged, and the reactor was heated to 80 ° C. and stirred for 8 hours.
- 2- (p-toluenesulfonyl) ethanol HOCH 2 CH 2 SO 2 (pC 6 H 4 ) CH 3 11.91 g (59.7 mmol)
- 5.00 g (29.4 mmol) of hexamethylene diisocyanate and 100 ml of toluene were charged, and the reactor was heated to 80 ° C. and stirred for 8 hours.
- Example 3 (1) Into a 5 L round bottom flask was charged 2L of tertiary butyl methyl ether and 253.3 g (1.2 mol) of a crude product of 2- (ethoxycarbonyl) -1,3-dithiane synthesized by a known method. Further, 148.2 g (3.9 mol) of NaBH 4 was charged. A dropping funnel was attached to this round-bottomed flask, and 650 ml of methanol was charged therein, and the dropping was performed over 3 hours or more at room temperature. After the dropping was completed, the mixture was stirred at 40 to 45 ° C. for 5 hours.
- the components other than the vulcanizing agent and the vulcanization accelerator were kneaded with a Banbury mixer, and then the vulcanizing agent and the vulcanization accelerator were added using an open roll.
- the acrylic rubber composition thus prepared was vulcanized by press vulcanization at 180 ° C. for 8 minutes and oven vulcanization at 175 ° C. for 4 hours.
- Example 5 In Example 4, the amount of 1,3-di-o-tolylguanidine was changed to 1 part by weight.
- Example 6 In Example 4, the amount of 1,3-di-o-tolylguanidine was changed to 2 parts by weight.
- Example 7 In Example 6, 1.75 parts by weight of HMDA-Tsec was used instead of HMDA-Fmoc.
- Example 8 In Example 7, the amount of 1,3-di-o-tolylguanidine was changed to 4 parts by weight.
- Example 9 In Example 4, 1 part by weight of a mixture of 1,8-diazabicyclo [5.4.0] undecene-7 and silica (Vulcofac ACT55 manufactured by Safic Alcan) was used instead of 1,3-di-o-tolylguanidine. It was.
- Example 10 In Example 4, 0.28 parts by weight of 1,8-diazabicyclo [5.4.0] undecene-7 was used in place of 1,3-di-o-tolylguanidine.
- Example 11 In Example 4, the following components were used.
- Example 12 In Example 4, the following components were used.
- Example 13 instead of the epoxy group-containing acrylic rubber, the same amount of active chlorine group-containing acrylic rubber (Unimatec product Noxtite PA-402K) was used.
- Example 14 In Example 12, instead of the epoxy group-containing acrylic rubber, the same amount of chlorine group-containing acrylic rubber (Unimatec product Noxtite PA-212) was used, and the amount of HMDA-Fmoc was changed to 2.25 parts by weight.
- Example 6 0.5 part by weight of hexamethylenediamine carbamate (Unimatec Cheminox AC-6) was used in place of HMDA-Fmoc.
- Example 6 Comparative Example 2 In Example 6, 0.5 parts by weight of 4,4-diaminodiphenyl ether was used in place of HMDA-Fmoc.
- Comparative Example 3 In Comparative Example 1, 1,3-di-o-tolylguanidine was not used.
- Example 9 0.5 part by weight of hexamethylenediamine carbamate (Cheminox AC-6) was used in place of HMDA-Fmoc.
- Example 10 Comparative Example 7 In Example 10, 0.5 parts by weight of hexamethylenediamine carbamate (Cheminox AC-6) was used instead of HMDA-Fmoc.
- Example 8 Comparative Example 8 In Example 11, 1.25 parts by weight of hexamethylenediamine carbamate (Cheminox AC-6) was used in place of HMDA-Fmoc.
- Example 15 The acrylic rubber composition was prepared and vulcanized in the same manner as in Example 4 using the above components.
- Example 16 In Example 15, the amount of 1,3-di-o-tolylguanidine was changed to 4 parts by weight.
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Abstract
Description
(1) 脂肪族ジアミン(加硫剤)/グアニジン(加硫促進剤)
(2) 芳香族ジアミン(加硫剤)/グアニジン(加硫促進剤)
R2(SO2)m(CH2)nOCONHR1NHCOO(CH2)n(SO2)mR2
(ここで、R1はC1~C20の直鎖状または分岐状の2価脂肪族アルキレン基、2価脂環式シクロアルキレン基または2価芳香族基であり、R2はカーバメート構造としたとき、塩基性加硫促進剤の作用で分解し、ジアミンを発生させ得る基であり、nは0、1または2であり、mは0または1である)で表わされるジウレタン化合物が提供される。
R2(SO2)m(CH2)nOCONHR1NHCOO(CH2)n(SO2)mR2
で表わされるジウレタン化合物は、次のような反応によって合成することができる。
(1) H2NR1NH2+2ClCOO(CH2)n(SO2)mR2 (クロロホーメート化合物)
(2) OCNR1NCO+2R2(SO2)m(CH2)nOH (水酸基含有化合物)
等が挙げられ、2価芳香族基としては例えば
等が挙げられるが、好ましくはC4~C10の直鎖状アルキレン基が用いられる。
温度計、滴下ロートおよび攪拌機を備えた内容量500mlの四口フラスコ中に、予め50℃の湯浴で溶融しておいたヘキサメチレンジアミン(和光純薬製品)5.42g(46.6ミリモル)、1,4-ジオキサン(東京化成製品)160mlおよび10重量%炭酸ナトリウム(和光純薬製品)水溶液124mlをこの順序で仕込み、0℃迄冷却した。
ClCOOCH2-R (R:9-フルオレニル基)
24.8g(93.2ミリモル)を1,4-ジオキサン120mlに溶解させた溶液を、滴下ロートから反応器中の温度が5℃を超えないような滴下速度で滴下し、滴下終了後室温条件下で6時間攪拌した。反応終了後、反応混合物に水200mlを加え、析出した固体をろ別した。
1H NMR:(a)4.2ppm (t 2H)
(b)4.4ppm (d 4H)
(c)3.2ppm (q 4H)
(d)1.5ppm (m 4H)
(e)1.3ppm (m 4H)
Aromatic H:7.2-7.8ppm (m 16H)
FT-IR:3335cm-1:第2級アミンのN-H伸縮振動
1686cm-1:ウレタン結合由来のC=O伸縮振動
温度計、環流冷却管および攪拌機を備えた内容量200mlの三口フラスコ中に、2-(p-トルエンスルホニル)エタノール HOCH2CH2SO2(p-C6H4)CH3 11.91g(59.7ミリモル)、ヘキサメチレンジイソシアネート5.00g(29.4ミリモル)およびトルエン100mlを仕込み、反応器を80℃に加温し、8時間攪拌した。
1H NMR:(a)2.45ppm (s 6H)
(b),(c)7.2-7.8ppm (m 8H)
(d)3.4ppm (t 4H)
(e)4.4ppm (t 4H)
(f)3.1ppm (q 4H)
(g)1.6ppm (m 4H)
(h)1.3ppm (m 4H)
FT-IR:3339cm-1:第2級アミンのN-H伸縮振動
1693cm-1:ウレタン結合由来のC=O伸縮振動
1322,1142cm-1:スルホン結合(-SO2-)
(1)内容量5Lの丸底フラスコ中に、第3ブチルメチルエーテル2Lおよび既知の方法により合成した2-(エトキシカルボニル)-1,3-ジチアンの粗生成物253.3g(1.2モル)を仕込み、さらにNaBH4 148.2g(3.9モル)を仕込んだ。この丸底フラスコに滴下ロートを取り付け、ここにメタノール650mlを仕込み、室温条件下で3時間以上かけて滴下を行い、滴下終了後40~45℃で5時間攪拌した。
1H NMR:
(a)2.0ppm (m 2H)
(b)2.8ppm (m 4H)
(c)3.9ppm (t 1H)
(d)3.8ppm (d 2H)
(e)3.0ppm (br 1H)
1H NMR:
(a)2.0ppm (m 4H)
(b)2.8ppm (m 8H)
(c)4.1ppm (t 2H)
(d)4.4ppm (d 4H)
(e)4.9ppm (br 2H)
(f)3.2ppm (m 4H)
(g)1.5ppm (m 4H)
(h)1.3ppm (m 4H)
ムーニー・スコーチ試験:JIS K6300-1準拠(125℃)
MLminは、t5の値(単位:分)は長い程成形時の生地ヤケ
の懸念が少なく、ヤケに起因する不良が少ない
一般には、t5の値が10分以上であれば、射出成形、圧縮
成形、押出成形でのヤケに起因する不良が少なくなる
加硫試験:JIS K6300-2準拠(180℃、12分間)
東洋精機製ロータレスレオメーターRLR-3使用
加硫速度の評価は、加硫試験のtc10、tc90およびME(MH-ML)で判断
でき、tc10およびtc90が短くかつMEが大きい程加硫速度は速い
常態値:JIS K6251、JIS K6253準拠
圧縮永久歪:JIS K6262準拠(150℃または175℃、70時間)
実施例4において、1,3-ジ-o-トリルグアニジン量が1重量部に変更された。
実施例4において、1,3-ジ-o-トリルグアニジン量が2重量部に変更された。
実施例6において、HMDA-Fmocの代りに、1.75重量部のHMDA-Tsecが用いられた。
実施例7において、1,3-ジ-o-トリルグアニジン量が4重量部に変更された。
実施例4において、1,3-ジ-o-トリルグアニジンの代りに、1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7とシリカとの混合物(Safic Alcan社製Vulcofac ACT55)が1重量部用いられた。
実施例4において、1,3-ジ-o-トリルグアニジンの代りに、1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7が0.2重量部用いられた。
実施例12において、エポキシ基含有アクリルゴムの代りに、同量の活性塩素基含有アクリルゴム(ユニマテック製品ノックスタイトPA-402K)が用いられた。
実施例12において、エポキシ基含有アクリルゴムの代りに、同量の塩素基含有アクリルゴム(ユニマテック製品ノックスタイトPA-212)が用いられ、HMDA-Fmoc量が2.25重量部に変更された。
実施例6において、HMDA-Fmocの代りに、0.5重量部のヘキサメチレンジアミンカーバメート(ユニマテック製品ケミノックスAC-6)が用いられた。
実施例6において、HMDA-Fmocの代りに、0.5重量部の4,4-ジアミノジフェニルエーテルが用いられた。
比較例1において、1,3-ジ-o-トリルグアニジンが用いられなかった。
実施例4において、1,3-ジ-o-トリルグアニジンが用いられなかった。
実施例7において、1,3-ジ-o-トリルグアニジンが用いられなかった。
実施例9において、HMDA-Fmocの代りに、0.5重量部のヘキサメチレンジアミンカーバメート(ケミノックスAC-6)が用いられた。
実施例10において、HMDA-Fmocの代りに、0.5重量部のヘキサメチレンジアミンカーバメート(ケミノックスAC-6)が用いられた。
実施例11において、HMDA-Fmocの代りに、1.25重量部のヘキサメチレンジアミンカーバメート(ケミノックスAC-6)が用いられた。
実施例15において、1,3-ジ-o-トリルグアニジン量が4重量部に変更された。
実施例15において、1,3-ジ-o-トリルグアニジンが用いられなかった。
(1)比較例9では、180℃でレオメーターの測定を行ったが加硫トルクは上がらず、加硫は進行しなかった。このことから、実施例3(2)で得られた生成物は180℃では熱分解しないことが分かる。
(2)また、実施例15~16は、1,3-ジ-o-トリルグアニジンのような塩基性化合物が存在する場合、ビスカーバメート構造が分解し、ヘキサメチレンジアミンが発生することを証明している。
Claims (18)
- 一般式 R2(SO2)m(CH2)nOCONH-R1-NHCOO(CH2)n(SO2)mR2
(ここで、R1はC1~C20の直鎖状または分岐状の2価脂肪族アルキレン基、2価脂環式シクロアルキレン基または2価芳香族基であり、R2はカーバメート構造としたとき、塩基性加硫促進剤の作用で分解し、ジアミンを発生させ得る基であり、nは0、1または2であり、mは0または1である)で表わされるジウレタン化合物。 - R2がC1~C20のアルキル基、アルコキシル基、ハロアルキル基、オレフィン基、アリール基またはアラルキル基、フルオレニル含有基、S含有基、Si含有基、N含有基またはP含有基である請求項1記載のジウレタン化合物。
- S含有基またはN含有基が芳香族または脂環式の複素環式基である請求項2記載のジウレタン化合物。
- 一般式 H2NR1NH2(ここで、R1はC1~C20の直鎖状または分岐状構造の2価の脂肪族アルキレン基、2価の脂環式シクロアルキル基または2価芳香族基である)で表わされるジアミン化合物に、一般式 ClCOO(CH2)n(SO2)mR2(ここで、R2はC1~C20のアルキル基、アルコキシル基、ハロアルキル基、オレフィン基、アリール基またはアラルキル基、フルオレニル含有基、S含有基、Si含有基、N含有基またはP含有基であり、nは0、1または2であり、mは0または1である)で表わされるクロロホーメート化合物を反応させることを特徴とする請求項1記載のジウレタン化合物の製造法。
- 一般式 OCNR1NCO(ここで、R1はC1~C20の直鎖状または分岐状構造の2価の脂肪族アルキレン基、2価の脂環式シクロアルキル基または2価芳香族基である)で表わされるジイソシアネート化合物に、一般式 R2(SO2)m(CH2)nOH(ここで、R2はC1~C20のアルキル基、アルコキシル基、ハロアルキル基、オレフィン基、アリール基またはアラルキル基、フルオレニル含有基、S含有基、Si含有基、N含有基またはP含有基であり、nは0、1または2であり、mは0または1である)で表わされる水酸基含有化合物を反応させることを特徴とする請求項1記載のジウレタン化合物の製造法。
- 多価アミン架橋性基含有アクリルゴム、加硫剤としての請求項1記載のジウレタン化合物および塩基性加硫促進剤を含有してなるアクリルゴム組成物。
- 多価アミン架橋性基含有アクリルゴムがカルボキシル基含有アクリルゴム、エポキシ基含有アクリルゴムまたは塩素基含有アクリルゴムである請求項9記載のアクリルゴム組成物。
- 多価アミン架橋性基含有アクリルゴム100重量部当り、加硫剤としてのジウレタン化合物が0.1~10重量部、塩基性加硫促進剤としてのグアニジン化合物が0.1~10重量部の割合で用いられた請求項9記載のアクリルゴム組成物。
- 多価アミン架橋性基含有アクリルゴム100重量部当り、加硫剤としてのジウレタン化合物が0.1~10重量部、塩基性加硫促進剤としての1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7または1,5-ジアザビシクロ〔4.3.0〕ノネン-5が0.01~1重量部の割合で用いられた請求項9記載のアクリルゴム組成物。
- 多価アミン架橋性基含有アクリルゴム100重量部当り、加硫剤としてのジウレタン化合物が0.1~10重量部、塩基性加硫促進剤としての1,8-ジアザビシクロ〔5.4.0〕ウンデセン-7とシリカとの混合物が0.1~10重量部の割合で用いられた請求項9記載のアクリルゴム組成物。
- 請求項9記載のアクリルゴム組成物から型成形された加硫成形品。
- 請求項9記載のアクリルゴム組成物から押出成形された加硫成形品。
Priority Applications (4)
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CN2009801037621A CN101932556B (zh) | 2008-01-30 | 2009-01-30 | 二氨基甲酸酯化合物、其制造方法及含有其的丙烯酸橡胶组合物 |
JP2009520723A JP4883178B2 (ja) | 2008-01-30 | 2009-01-30 | 新規ジウレタン化合物、その製造法およびそれを含有するアクリルゴム組成物 |
EP09706856.3A EP2243770B1 (en) | 2008-01-30 | 2009-01-30 | Novel diurethane compound, process for producing the same, and acrylic rubber composition containing the same |
US12/919,718 US8288483B2 (en) | 2008-01-30 | 2009-01-30 | Diurethane compound, process for producing the same, and acrylic rubber composition containing the same |
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US (1) | US8288483B2 (ja) |
EP (1) | EP2243770B1 (ja) |
JP (2) | JP4883178B2 (ja) |
KR (1) | KR101269895B1 (ja) |
CN (1) | CN101932556B (ja) |
WO (1) | WO2009096545A1 (ja) |
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WO2010072465A1 (de) * | 2008-12-15 | 2010-07-01 | Contitech Schlauch Gmbh | Vulkanisierbare kautschukmischung, insbesondere auf basis acm oder aem, und vulkanisat, insbesondere ein schlauchmaterial |
WO2012117849A1 (ja) | 2011-02-28 | 2012-09-07 | Nok株式会社 | アクリルゴム組成物 |
CN103224678A (zh) * | 2013-03-29 | 2013-07-31 | 浙江固耐橡塑科技有限公司 | 一种丙烯酸酯橡胶复合材料 |
WO2016052335A1 (ja) * | 2014-09-29 | 2016-04-07 | 日本ゼオン株式会社 | ゴム架橋物 |
WO2019003917A1 (ja) * | 2017-06-29 | 2019-01-03 | Nok株式会社 | 架橋アクリルゴム成形体の製造方法、アクリルゴム組成物およびシール材 |
WO2020105536A1 (ja) | 2018-11-20 | 2020-05-28 | ユニマテック株式会社 | 新規カルバミン酸エステル化合物およびそれを含有するアクリルゴム組成物 |
WO2022049872A1 (ja) | 2020-09-03 | 2022-03-10 | ユニマテック株式会社 | フェノチアジン誘導体およびアクリルゴム組成物 |
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WO2023021832A1 (ja) | 2021-08-18 | 2023-02-23 | ユニマテック株式会社 | 架橋性アクリルゴム組成物 |
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Cited By (19)
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WO2010072465A1 (de) * | 2008-12-15 | 2010-07-01 | Contitech Schlauch Gmbh | Vulkanisierbare kautschukmischung, insbesondere auf basis acm oder aem, und vulkanisat, insbesondere ein schlauchmaterial |
WO2012117849A1 (ja) | 2011-02-28 | 2012-09-07 | Nok株式会社 | アクリルゴム組成物 |
JP5229430B2 (ja) * | 2011-02-28 | 2013-07-03 | Nok株式会社 | アクリルゴム組成物 |
CN103384700A (zh) * | 2011-02-28 | 2013-11-06 | Nok株式会社 | 丙烯酸橡胶组合物 |
CN103384700B (zh) * | 2011-02-28 | 2015-02-11 | Nok株式会社 | 丙烯酸橡胶组合物 |
US9062188B2 (en) | 2011-02-28 | 2015-06-23 | Nok Corporation | Acrylic rubber composition |
CN103224678A (zh) * | 2013-03-29 | 2013-07-31 | 浙江固耐橡塑科技有限公司 | 一种丙烯酸酯橡胶复合材料 |
CN103224678B (zh) * | 2013-03-29 | 2015-09-02 | 浙江固耐橡塑科技有限公司 | 一种丙烯酸酯橡胶复合材料 |
WO2016052335A1 (ja) * | 2014-09-29 | 2016-04-07 | 日本ゼオン株式会社 | ゴム架橋物 |
JPWO2016052335A1 (ja) * | 2014-09-29 | 2017-07-13 | 日本ゼオン株式会社 | ゴム架橋物 |
WO2019003917A1 (ja) * | 2017-06-29 | 2019-01-03 | Nok株式会社 | 架橋アクリルゴム成形体の製造方法、アクリルゴム組成物およびシール材 |
JPWO2019003917A1 (ja) * | 2017-06-29 | 2020-04-23 | Nok株式会社 | 架橋アクリルゴム成形体の製造方法、アクリルゴム組成物およびシール材 |
WO2020105536A1 (ja) | 2018-11-20 | 2020-05-28 | ユニマテック株式会社 | 新規カルバミン酸エステル化合物およびそれを含有するアクリルゴム組成物 |
US11932644B2 (en) | 2018-11-20 | 2024-03-19 | Unimatec Co., Ltd. | Carbamate ester compound and acrylic rubber composition containing the same |
WO2022049958A1 (ja) * | 2020-09-02 | 2022-03-10 | ユニマテック株式会社 | アクリルエラストマー共重合体およびその架橋性組成物 |
JPWO2022049958A1 (ja) * | 2020-09-02 | 2022-03-10 | ||
JP7253119B2 (ja) | 2020-09-02 | 2023-04-05 | ユニマテック株式会社 | アクリルエラストマー共重合体およびその架橋性組成物 |
WO2022049872A1 (ja) | 2020-09-03 | 2022-03-10 | ユニマテック株式会社 | フェノチアジン誘導体およびアクリルゴム組成物 |
WO2022059290A1 (ja) * | 2020-09-15 | 2022-03-24 | ユニマテック株式会社 | ゴム組成物 |
Also Published As
Publication number | Publication date |
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JP5240238B2 (ja) | 2013-07-17 |
CN101932556B (zh) | 2013-08-14 |
EP2243770A1 (en) | 2010-10-27 |
EP2243770A4 (en) | 2012-01-18 |
US20110040043A1 (en) | 2011-02-17 |
CN101932556A (zh) | 2010-12-29 |
KR20100120666A (ko) | 2010-11-16 |
EP2243770B1 (en) | 2015-02-25 |
JP4883178B2 (ja) | 2012-02-22 |
US8288483B2 (en) | 2012-10-16 |
JP2010235955A (ja) | 2010-10-21 |
KR101269895B1 (ko) | 2013-05-31 |
JPWO2009096545A1 (ja) | 2011-05-26 |
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