JP2006169381A - Method for producing conjugated diene-based copolymer rubber - Google Patents
Method for producing conjugated diene-based copolymer rubber Download PDFInfo
- Publication number
- JP2006169381A JP2006169381A JP2004363990A JP2004363990A JP2006169381A JP 2006169381 A JP2006169381 A JP 2006169381A JP 2004363990 A JP2004363990 A JP 2004363990A JP 2004363990 A JP2004363990 A JP 2004363990A JP 2006169381 A JP2006169381 A JP 2006169381A
- Authority
- JP
- Japan
- Prior art keywords
- conjugated diene
- copolymer rubber
- compound
- producing
- diene copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 109
- 239000005060 rubber Substances 0.000 title claims abstract description 109
- 229920001577 copolymer Polymers 0.000 title claims abstract description 79
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 45
- 150000001993 dienes Chemical class 0.000 title abstract description 5
- -1 diene compound Chemical class 0.000 claims abstract description 105
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 47
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 45
- 239000000178 monomer Substances 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000003607 modifier Substances 0.000 claims abstract description 21
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 4
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 32
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 28
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 24
- 239000000377 silicon dioxide Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 11
- DIGKGWWSMMWBIZ-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]-n,n-bis(trimethylsilyl)propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN([Si](C)(C)C)[Si](C)(C)C DIGKGWWSMMWBIZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000003606 tin compounds Chemical class 0.000 claims description 6
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- JRFVCFVEJBDLDT-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]-n,n-bis(trimethylsilyl)propan-1-amine Chemical compound CO[Si](C)(OC)CCCN([Si](C)(C)C)[Si](C)(C)C JRFVCFVEJBDLDT-UHFFFAOYSA-N 0.000 claims description 3
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 claims description 3
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 claims description 3
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 3
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 claims description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 3
- FPKMSRRUOFZBQR-UHFFFAOYSA-N triphenoxymethylsilane Chemical compound O(C1=CC=CC=C1)C(OC1=CC=CC=C1)(OC1=CC=CC=C1)[SiH3] FPKMSRRUOFZBQR-UHFFFAOYSA-N 0.000 claims description 3
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims 1
- 238000005096 rolling process Methods 0.000 abstract description 16
- 238000004073 vulcanization Methods 0.000 abstract description 9
- 230000001747 exhibiting effect Effects 0.000 abstract description 2
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 239000003505 polymerization initiator Substances 0.000 description 9
- 229910007991 Si-N Inorganic materials 0.000 description 8
- 229910006294 Si—N Inorganic materials 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 229910052783 alkali metal Inorganic materials 0.000 description 7
- 150000001340 alkali metals Chemical class 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 6
- 239000004636 vulcanized rubber Substances 0.000 description 6
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000002480 mineral oil Substances 0.000 description 4
- 235000010446 mineral oil Nutrition 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 150000003112 potassium compounds Chemical class 0.000 description 4
- 239000010734 process oil Substances 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 229920003244 diene elastomer Polymers 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 150000002641 lithium Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 159000000001 potassium salts Chemical class 0.000 description 2
- 238000010092 rubber production Methods 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- QMGJMGFZLXYHCR-UHFFFAOYSA-N 1-(2-butoxypropoxy)butane Chemical compound CCCCOCC(C)OCCCC QMGJMGFZLXYHCR-UHFFFAOYSA-N 0.000 description 1
- IQXXEPZFOOTTBA-UHFFFAOYSA-N 1-benzylpiperazine Chemical compound C=1C=CC=CC=1CN1CCNCC1 IQXXEPZFOOTTBA-UHFFFAOYSA-N 0.000 description 1
- OUSXYCTXXLYBGJ-UHFFFAOYSA-N 1-ethenyl-2,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C=C)C(C(C)C)=C1 OUSXYCTXXLYBGJ-UHFFFAOYSA-N 0.000 description 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- IYSVFZBXZVPIFA-UHFFFAOYSA-N 1-ethenyl-4-(4-ethenylphenyl)benzene Chemical group C1=CC(C=C)=CC=C1C1=CC=C(C=C)C=C1 IYSVFZBXZVPIFA-UHFFFAOYSA-N 0.000 description 1
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 description 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- ZEBFPAXSQXIPNF-UHFFFAOYSA-N 2,5-dimethylpyrrolidine Chemical compound CC1CCC(C)N1 ZEBFPAXSQXIPNF-UHFFFAOYSA-N 0.000 description 1
- HNVIQLPOGUDBSU-UHFFFAOYSA-N 2,6-dimethylmorpholine Chemical compound CC1CNCC(C)O1 HNVIQLPOGUDBSU-UHFFFAOYSA-N 0.000 description 1
- IFNWESYYDINUHV-UHFFFAOYSA-N 2,6-dimethylpiperazine Chemical compound CC1CNCC(C)N1 IFNWESYYDINUHV-UHFFFAOYSA-N 0.000 description 1
- SDGKUVSVPIIUCF-UHFFFAOYSA-N 2,6-dimethylpiperidine Chemical compound CC1CCCC(C)N1 SDGKUVSVPIIUCF-UHFFFAOYSA-N 0.000 description 1
- FXRQXYSJYZPGJZ-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethenylbenzene Chemical compound CC(C)(C)OC=CC1=CC=CC=C1 FXRQXYSJYZPGJZ-UHFFFAOYSA-N 0.000 description 1
- TYENDWOHUUAIJH-UHFFFAOYSA-N 2-[(4-ethenylphenyl)methoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCC1=CC=C(C=C)C=C1 TYENDWOHUUAIJH-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- CTIFKKWVNGEOBU-UHFFFAOYSA-N 2-hexadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O CTIFKKWVNGEOBU-UHFFFAOYSA-N 0.000 description 1
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 description 1
- AQQPJNOXVZFTGE-UHFFFAOYSA-N 2-octadecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O AQQPJNOXVZFTGE-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- CDODDZJCEADUQQ-UHFFFAOYSA-N 3,3-dimethylpiperidine Chemical compound CC1(C)CCCNC1 CDODDZJCEADUQQ-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- VOSGLHJWGFISCM-UHFFFAOYSA-N 3-[ethoxy-methyl-(1-trimethylsilylethoxy)silyl]propan-1-amine Chemical compound NCCC[Si](C)(OCC)OC(C)[Si](C)(C)C VOSGLHJWGFISCM-UHFFFAOYSA-N 0.000 description 1
- LICHZOBEUWVYSY-UHFFFAOYSA-N 3-azabicyclo[3.2.2]nonane Chemical compound C1CC2CCC1CNC2 LICHZOBEUWVYSY-UHFFFAOYSA-N 0.000 description 1
- LIZKZVQBLDHKCY-UHFFFAOYSA-N 3-azaspiro[5.5]undecane Chemical compound C1CCCCC21CCNCC2 LIZKZVQBLDHKCY-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical compound CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- UDTHXSLCACXSKA-UHFFFAOYSA-N 3-tetradecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCCCC1=CC=CC(S(O)(=O)=O)=C1 UDTHXSLCACXSKA-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- JCQLPDZCNSVBMS-UHFFFAOYSA-N 5-phenylmethoxy-1h-indole Chemical compound C=1C=C2NC=CC2=CC=1OCC1=CC=CC=C1 JCQLPDZCNSVBMS-UHFFFAOYSA-N 0.000 description 1
- PNLYGADSOPWXOO-UHFFFAOYSA-N 8,8,8-trichlorooctyltin Chemical compound ClC(Cl)(Cl)CCCCCCC[Sn] PNLYGADSOPWXOO-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- SAIKULLUBZKPDA-UHFFFAOYSA-N Bis(2-ethylhexyl) amine Chemical compound CCCCC(CC)CNCC(CC)CCCC SAIKULLUBZKPDA-UHFFFAOYSA-N 0.000 description 1
- ZYSMGTWCQOWVHE-UHFFFAOYSA-N CC(C)(C)O[Ba] Chemical compound CC(C)(C)O[Ba] ZYSMGTWCQOWVHE-UHFFFAOYSA-N 0.000 description 1
- WAQAIDHIWUNFLP-UHFFFAOYSA-N CC(C)(C)O[Sr] Chemical compound CC(C)(C)O[Sr] WAQAIDHIWUNFLP-UHFFFAOYSA-N 0.000 description 1
- QXKOHICVGBUHGZ-UHFFFAOYSA-N CC(C)O[Ba] Chemical compound CC(C)O[Ba] QXKOHICVGBUHGZ-UHFFFAOYSA-N 0.000 description 1
- KKUZFMJIXIFTND-UHFFFAOYSA-N CCCCCC[Mg] Chemical compound CCCCCC[Mg] KKUZFMJIXIFTND-UHFFFAOYSA-N 0.000 description 1
- UWKKBEQZACDEBT-UHFFFAOYSA-N CCCC[Mg] Chemical compound CCCC[Mg] UWKKBEQZACDEBT-UHFFFAOYSA-N 0.000 description 1
- FMJFSSGHENXENQ-UHFFFAOYSA-N CCN([Ba])CC Chemical compound CCN([Ba])CC FMJFSSGHENXENQ-UHFFFAOYSA-N 0.000 description 1
- HYSGPFAWCHUDSR-UHFFFAOYSA-N CCO[Ba] Chemical compound CCO[Ba] HYSGPFAWCHUDSR-UHFFFAOYSA-N 0.000 description 1
- YSTSEMLRVJGMAC-UHFFFAOYSA-N CCO[Ca] Chemical compound CCO[Ca] YSTSEMLRVJGMAC-UHFFFAOYSA-N 0.000 description 1
- CBOGVHLUKOLNKK-UHFFFAOYSA-M CCS[Ba] Chemical compound CCS[Ba] CBOGVHLUKOLNKK-UHFFFAOYSA-M 0.000 description 1
- HDFZYMPEBPFGJN-UHFFFAOYSA-K CC[Sn+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O Chemical compound CC[Sn+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HDFZYMPEBPFGJN-UHFFFAOYSA-K 0.000 description 1
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-N Dicyclohexylamine Chemical compound C1CCCCC1NC1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-N 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- XRYGCVVVDCEPRL-UHFFFAOYSA-N n,1-dimethylpiperidin-4-amine Chemical compound CNC1CCN(C)CC1 XRYGCVVVDCEPRL-UHFFFAOYSA-N 0.000 description 1
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- CWOMTHDOJCARBY-UHFFFAOYSA-N n,n,3-trimethylaniline Chemical compound CN(C)C1=CC=CC(C)=C1 CWOMTHDOJCARBY-UHFFFAOYSA-N 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
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- IJJSYKQZFFGIEE-UHFFFAOYSA-N naphthalene;potassium Chemical compound [K].C1=CC=CC2=CC=CC=C21 IJJSYKQZFFGIEE-UHFFFAOYSA-N 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229960002446 octanoic acid Drugs 0.000 description 1
- 239000008041 oiling agent Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- LDIPVKABLDWRGC-UHFFFAOYSA-N phenylmethoxymethylbenzene;potassium Chemical compound [K].C=1C=CC=CC=1COCC1=CC=CC=C1 LDIPVKABLDWRGC-UHFFFAOYSA-N 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- ZRLVQFQTCMUIRM-UHFFFAOYSA-N potassium;2-methylbutan-2-olate Chemical compound [K+].CCC(C)(C)[O-] ZRLVQFQTCMUIRM-UHFFFAOYSA-N 0.000 description 1
- ZGJADVGJIVEEGF-UHFFFAOYSA-M potassium;phenoxide Chemical compound [K+].[O-]C1=CC=CC=C1 ZGJADVGJIVEEGF-UHFFFAOYSA-M 0.000 description 1
- WQKGAJDYBZOFSR-UHFFFAOYSA-N potassium;propan-2-olate Chemical compound [K+].CC(C)[O-] WQKGAJDYBZOFSR-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- BCMNMJSREMRSFP-UHFFFAOYSA-H trichloro(4-trichlorostannylbutyl)stannane Chemical compound Cl[Sn](Cl)(Cl)CCCC[Sn](Cl)(Cl)Cl BCMNMJSREMRSFP-UHFFFAOYSA-H 0.000 description 1
- BOEGBYDAWIJZGT-UHFFFAOYSA-N trichloromethyltin Chemical compound ClC(Cl)(Cl)[Sn] BOEGBYDAWIJZGT-UHFFFAOYSA-N 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
- Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は共役ジエン系共重合ゴムの製造方法、及びその製造方法により製造される共役ジエン系共重合ゴムに関し、更に詳しくは、加工性が良好であるとともに転がり抵抗の小さいゴム組成物を、従前の方法と同等の短い重合所要時間で製造可能な共役ジエン系共重合ゴムの製造方法、及びその製造方法により製造される共役ジエン系共重合ゴムに関する。 The present invention relates to a method for producing a conjugated diene copolymer rubber and a conjugated diene copolymer rubber produced by the production method. More specifically, a rubber composition having good processability and low rolling resistance has been conventionally used. The present invention relates to a process for producing a conjugated diene copolymer rubber that can be produced in a short polymerization time equivalent to the above method, and a conjugated diene copolymer rubber produced by the process.
近年の自動車に対する低燃費化要求に伴い、転がり抵抗が小さく、耐摩耗性、破壊特性に優れ、更にウェットスキッド抵抗に代表される操縦安定性をも兼ね備えたタイヤ用ゴム材料（ゴム組成物）を構成するのに好適な共役ジエン系ゴムの開発が望まれている。 Along with the recent demand for fuel efficiency reduction in automobiles, tire rubber materials (rubber compositions) that have low rolling resistance, excellent wear resistance and fracture characteristics, and also have handling stability typified by wet skid resistance. Development of conjugated diene rubbers suitable for construction is desired.
タイヤ用ゴム材料として、補強剤としてのシリカ又はシリカとカーボンブラックとの混合物を配合したゴム組成物を使用する方法が提案されている。シリカ又はシリカとカーボンブラックとの混合物を配合したタイヤトレッドは転がり抵抗が小さく、ウェットスキッド抵抗に代表される操縦安定性能が良好である。但し、一般的に、シリカを配合したゴム組成物は、カーボンブラックを配合したゴム組成物と比べて加工性に劣るという問題がある。 As a rubber material for tires, a method of using a rubber composition containing silica as a reinforcing agent or a mixture of silica and carbon black has been proposed. A tire tread blended with silica or a mixture of silica and carbon black has low rolling resistance and good steering stability performance typified by wet skid resistance. However, in general, a rubber composition containing silica is inferior in processability as compared with a rubber composition containing carbon black.
また、関連する従来技術として、共役ジエン化合物と芳香族ビニル化合物とを使用し、これらを共重合させた後、反応系に共役ジエン化合物を更に添加して共重合させ、次いで重合活性末端に適当なカップリング剤を反応させて共役ジエン系共重合ゴムを得る、共役ジエン系共重合ゴムの製造方法が開示されている（例えば、特許文献１，２参照）。この製造方法によれば、転がり抵抗の小さいゴム組成物を得るのに好適な共役ジエン系共重合ゴムを容易に製造することができる。 In addition, as a related prior art, a conjugated diene compound and an aromatic vinyl compound are used, and after copolymerizing them, a conjugated diene compound is further added to the reaction system for copolymerization, and then suitable for the polymerization active terminal. A method for producing a conjugated diene copolymer rubber is disclosed in which a conjugated diene copolymer rubber is obtained by reacting various coupling agents (see, for example, Patent Documents 1 and 2). According to this production method, a conjugated diene copolymer rubber suitable for obtaining a rubber composition having a small rolling resistance can be easily produced.
しかしながら、特許文献１において開示されている共役ジエン系共重合ゴムの製造方法によっては、得られるゴムの加工性が必ずしも良好であるとはいえない場合がある。このため、得られるゴムの加工性の改良を図る必要性があった。また、得られるゴムを加硫した場合、加硫後におけるゴム（加硫ゴム）の硬度が低下し易くなる傾向があるため、これを改良する製造方法の開発が求められている。更に、製造工程が複雑化すること回避し、生産コストを低減すること等を考慮すれば、重合にかかる時間を延長させることなく、従来と同等の所要時間で重合を完了させることができる製造方法の開発が求められている。
本発明は、このような従来技術の有する問題点に鑑みてなされたものであり、その課題とするところは、加工性が良好であるとともに加硫後においても十分な硬度を示し、転がり抵抗の小さいゴム組成物を得ることができる共役ジエン系共重合ゴムを、従前の方法と同等の短い重合所要時間で製造可能な共役ジエン系共重合ゴムの製造方法、及び加工性が良好であるとともに、転がり抵抗の小さいゴム組成物を得ることができる共役ジエン系共重合ゴムを提供することにある。 The present invention has been made in view of such problems of the prior art, and the problem is that the workability is good and the hardness is sufficient even after vulcanization, and the rolling resistance is low. A conjugated diene copolymer rubber capable of obtaining a small rubber composition can be produced in a short polymerization time equivalent to the conventional method, and the processability of the conjugated diene copolymer rubber is good, and the processability is good. An object of the present invention is to provide a conjugated diene copolymer rubber capable of obtaining a rubber composition having a low rolling resistance.
本発明者らは上記課題を達成すべく鋭意検討した結果、共役ジエン化合物、及び芳香族ビニル化合物等を共重合反応させつつ、重合転化率が所定の範囲内にある反応途中段階で、反応系に所定の多官能単量体等を添加して共重合反応を終了させ、次いで、変性剤を添加して反応させることによって、上記課題を達成することが可能であることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above-mentioned problems, the present inventors have carried out a copolymerization reaction of a conjugated diene compound, an aromatic vinyl compound, etc., while in the middle of the reaction when the polymerization conversion rate is within a predetermined range, The present inventors have found that the above-mentioned problems can be achieved by adding a predetermined polyfunctional monomer or the like to terminate the copolymerization reaction, and then adding a modifier to react. It came to be completed.
即ち、本発明によれば、以下に示す共役ジエン系共重合ゴムの製造方法、及びその製造方法により製造される共役ジエン系共重合ゴムが提供される。 That is, according to the present invention, the following conjugated diene copolymer rubber production method and conjugated diene copolymer rubber produced by the production method are provided.
［１］第一の共役ジエン化合物、及び第一の芳香族ビニル化合物を含有する反応系で共重合反応を開始させ、その後必要な場合に第二の共役ジエン化合物及び第二の芳香族ビニル化合物を添加し、前記共重合反応終了後、変性剤を添加して共役ジエン系共重合ゴムを得る共役ジエン系共重合ゴムの製造方法であって、重合転化率が３０％以上、９０％未満の範囲内にある反応途中段階で、前記反応系に第一の多官能単量体を添加する共役ジエン系共重合ゴムの製造方法。 [1] A copolymerization reaction is started in a reaction system containing a first conjugated diene compound and a first aromatic vinyl compound, and then, if necessary, a second conjugated diene compound and a second aromatic vinyl compound And after the completion of the copolymerization reaction, a modifier is added to obtain a conjugated diene copolymer rubber, wherein the polymerization conversion rate is 30% or more and less than 90%. A method for producing a conjugated diene copolymer rubber, wherein a first polyfunctional monomer is added to the reaction system in the middle of the reaction within a range.
［２］前記反応系に、前記第一の多官能単量体を連続的に添加する前記［１］に記載の共役ジエン系共重合ゴムの製造方法。 [2] The method for producing a conjugated diene copolymer rubber according to [1], wherein the first polyfunctional monomer is continuously added to the reaction system.
［３］第二の多官能単量体を更に含有する前記反応系で前記共重合反応を開始させる前記［１］又は［２］に記載の共役ジエン系共重合ゴムの製造方法。 [3] The method for producing a conjugated diene copolymer rubber according to [1] or [2], wherein the copolymerization reaction is started in the reaction system further containing a second polyfunctional monomer.
［４］前記第一の多官能単量体及び／又は前記第二の多官能単量体が、ジビニルベンゼンである前記［３］に記載の共役ジエン系共重合ゴムの製造方法。 [4] The method for producing a conjugated diene copolymer rubber according to [3], wherein the first polyfunctional monomer and / or the second polyfunctional monomer is divinylbenzene.
［５］前記第一の多官能単量体がジビニルベンゼンである場合に、反応途中段階で前記反応系に添加する前記ジビニルベンゼンの添加量が、前記第一の共役ジエン化合物、前記第二の共役ジエン化合物、前記第一の芳香族ビニル化合物、及び前記第二の芳香族ビニル化合物の合計の１００質量部に対して、０．００１〜１質量部である前記［４］に記載の共役ジエン系共重合ゴムの製造方法。 [5] When the first polyfunctional monomer is divinylbenzene, the amount of the divinylbenzene added to the reaction system during the reaction is such that the first conjugated diene compound and the second The conjugated diene according to [4], which is 0.001 to 1 part by mass with respect to 100 parts by mass of the total of the conjugated diene compound, the first aromatic vinyl compound, and the second aromatic vinyl compound. Of a copolymer rubber.
［６］前記第二の多官能単量体がジビニルベンゼンである場合に、前記反応系に含有される前記ジビニルベンゼンの含有量が、前記第一の共役ジエン化合物と前記第一の芳香族ビニル化合物の合計の１００質量部に対して、０〜１質量部である前記［４］又は［５］に記載の共役ジエン系共重合ゴムの製造方法。 [6] When the second polyfunctional monomer is divinylbenzene, the content of the divinylbenzene contained in the reaction system includes the first conjugated diene compound and the first aromatic vinyl. The method for producing a conjugated diene copolymer rubber according to [4] or [5], which is 0 to 1 part by mass with respect to 100 parts by mass of the total amount of the compounds.
［７］前記変性剤が、シリカと反応し得る化合物、又はスズ化合物と前記シリカと反応し得る化合物との混合物である前記［１］〜［６］のいずれかに記載の共役ジエン系共重合ゴムの製造方法。 [7] The conjugated diene copolymer according to any one of [1] to [6], wherein the modifier is a compound capable of reacting with silica or a mixture of a tin compound and a compound capable of reacting with silica. Rubber production method.
［８］前記シリカと反応し得る化合物が、ジブチルジクロロケイ素、メチルトリクロロケイ素、メチルジクロロケイ素、テトラクロロケイ素、トリエトキシメチルシラン、トリフェノキシメチルシラン、トリメトキシシラン、メチルトリエトキシシラン、４，５−エポキシヘプチルメチルジメトキシシラン、ビス（トリエトキシシリルプロピル）テトラサルファイド、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルジメトキシシラン、及びＮ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルジエトキシシランからなる群より選択される少なくとも一種である前記［７］に記載の共役ジエン系共重合ゴムの製造方法。 [8] The compound capable of reacting with silica is dibutyldichlorosilicon, methyltrichlorosilicon, methyldichlorosilicon, tetrachlorosilicon, triethoxymethylsilane, triphenoxymethylsilane, trimethoxysilane, methyltriethoxysilane, 4,5. -From the group consisting of epoxyheptylmethyldimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, and N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane The method for producing a conjugated diene copolymer rubber according to [7], which is at least one selected.
［９］前記第一の共役ジエン化合物及び／又は前記第二の共役ジエン化合物が、１，３−ブタジエンである前記［１］〜［８］のいずれかに記載の共役ジエン系共重合ゴムの製造方法。 [9] The conjugated diene copolymer rubber according to any one of [1] to [8], wherein the first conjugated diene compound and / or the second conjugated diene compound is 1,3-butadiene. Production method.
［１０］前記第一の芳香族ビニル化合物及び／又は前記第二の芳香族ビニル化合物が、スチレンである前記［１］〜［９］のいずれかに記載の共役ジエン系共重合ゴムの製造方法。 [10] The method for producing a conjugated diene copolymer rubber according to any one of [1] to [9], wherein the first aromatic vinyl compound and / or the second aromatic vinyl compound is styrene. .
［１１］前記［１］〜［１０］のいずれかに記載の共役ジエン系共重合ゴムの製造方法により製造される共役ジエン系共重合ゴム。 [11] A conjugated diene copolymer rubber produced by the method for producing a conjugated diene copolymer rubber according to any one of [1] to [10].
本発明の共役ジエン系共重合ゴムの製造方法によれば、加工性が良好であるとともに加硫後においても十分な硬度を示し、転がり抵抗の小さいゴム組成物を得ることができる共役ジエン系共重合ゴムを、従前の方法と同等の短い重合所要時間で製造可能である。 According to the method for producing a conjugated diene copolymer rubber of the present invention, a conjugated diene copolymer rubber that has good processability, exhibits sufficient hardness even after vulcanization, and can obtain a rubber composition having low rolling resistance. Polymerized rubber can be produced with a short polymerization time equivalent to the conventional method.
また、本発明の共役ジエン系共重合ゴムは、加工性が良好であるとともに加硫後においても十分な硬度を示し、転がり抵抗の小さいゴム組成物を得ることができるといった効果を奏するものである。 Further, the conjugated diene copolymer rubber of the present invention has an effect that the processability is good, the hardness is sufficient even after vulcanization, and a rubber composition having a low rolling resistance can be obtained. .
以下、本発明の実施の最良の形態について説明するが、本発明は以下の実施の形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲で、当業者の通常の知識に基づいて、以下の実施の形態に対し適宜変更、改良等が加えられたものも本発明の範囲に入ることが理解されるべきである。なお、本明細書において、単に「共役ジエン化合物」というときは、第一の共役ジエン化合物と第二の共役ジエン化合物のいずれをも意味する。また、単に「芳香族ビニル化合物」というときは、第一の芳香族ビニル化合物及び第二の芳香族ビニル化合物のいずれをも意味する。更に、単に「多官能単量体」というときは、第一の多官能単量体及び第二の多官能単量体のいずれをも意味する。 BEST MODE FOR CARRYING OUT THE INVENTION The best mode for carrying out the present invention will be described below, but the present invention is not limited to the following embodiment, and is based on the ordinary knowledge of those skilled in the art without departing from the gist of the present invention. It should be understood that modifications and improvements as appropriate to the following embodiments also fall within the scope of the present invention. In the present specification, the term “conjugated diene compound” means both the first conjugated diene compound and the second conjugated diene compound. The term “aromatic vinyl compound” means both the first aromatic vinyl compound and the second aromatic vinyl compound. Furthermore, when simply referred to as “polyfunctional monomer”, it means both the first polyfunctional monomer and the second polyfunctional monomer.
本発明の一実施形態は、第一の（Ａ）共役ジエン化合物、及び第一の（Ｂ）芳香族ビニル化合物を含有する反応系で共重合反応を開始させ、その後必要な場合に第二の（Ａ）共役ジエン化合物及び第二の（Ｂ）芳香族ビニル化合物を添加し、この共重合反応終了後、（Ｄ）変性剤を添加して共役ジエン系共重合ゴムを得る共役ジエン系共重合ゴムの製造方法であり、重合転化率が３０％以上、９０％未満の範囲内にある反応途中段階で、この反応系に第一の（Ｃ）多官能単量体を添加する共役ジエン系共重合ゴムの製造方法である。以下、その詳細について説明する。 One embodiment of the present invention starts a copolymerization reaction in a reaction system containing a first (A) conjugated diene compound and a first (B) aromatic vinyl compound, and then, if necessary, a second (A) Conjugated diene copolymer and second (B) aromatic vinyl compound are added, and after completion of this copolymerization reaction, (D) a modifier is added to obtain a conjugated diene copolymer rubber. This is a method for producing rubber, which is a conjugated diene copolymer in which a first (C) polyfunctional monomer is added to the reaction system in the middle of the reaction when the polymerization conversion is in the range of 30% or more and less than 90%. This is a method for producing polymer rubber. The details will be described below.
本実施形態の共役ジエン系共重合ゴムの製造方法では、先ず、第一の（Ａ）共役ジエン化合物、及び第一の（Ｂ）芳香族ビニル化合物を含有する反応系で共重合反応を開始させる。なお、この反応系に第二の（Ｃ）多官能単量体を更に含有させた状態で共重合反応を開始させることも好ましい。共重合反応は、所定の重合開始剤の存在下、適当な溶媒中で行われる。共重合反応の温度は、０〜１２０℃の範囲で行い、一定温度条件下でも上昇温度条件下でもよい。なお、重合方式は、バッチ重合方式、連続重合方式のいずれの方式でもよい。 In the method for producing a conjugated diene copolymer rubber of this embodiment, first, a copolymerization reaction is started in a reaction system containing the first (A) conjugated diene compound and the first (B) aromatic vinyl compound. . In addition, it is also preferable to start a copolymerization reaction in the state which further contains the 2nd (C) polyfunctional monomer in this reaction system. The copolymerization reaction is performed in a suitable solvent in the presence of a predetermined polymerization initiator. The temperature of the copolymerization reaction is performed in the range of 0 to 120 ° C., and may be a constant temperature condition or an elevated temperature condition. The polymerization method may be either a batch polymerization method or a continuous polymerization method.
定法に従って重合転化率をモニタリングし、重合転化率が３０％以上、９０％未満の範囲内、好ましくは３０〜７０％の範囲内、更に好ましくは３５〜６０％の範囲内にある反応途中段階で、反応系に第一の（Ｃ）多官能単量体を添加し、更に上述の条件と同様の条件で共重合反応を続行して終了させる。なお、必要な場合には、この反応系に第二の（Ａ）共役ジエン化合物や第二の（Ｂ）芳香族ビニル化合物を更に添加してもよい。 In the middle of the reaction, the polymerization conversion is monitored according to a conventional method, and the polymerization conversion is in the range of 30% or more and less than 90%, preferably in the range of 30 to 70%, more preferably in the range of 35 to 60%. The first (C) polyfunctional monomer is added to the reaction system, and the copolymerization reaction is continued under the same conditions as described above and terminated. If necessary, a second (A) conjugated diene compound or a second (B) aromatic vinyl compound may be further added to this reaction system.
重合転化率が３０％以上、９０％未満の範囲内にある反応途中段階で、反応系に第一の（Ｃ）多官能単量体を添加すると、得られるゴムの加工性が向上するとともに、従来と同等の所要時間で重合を終了させることができる。従って、製造工程が複雑化せず、生産コストの低減を図ることができる。なお、重合転化率が３０％未満の段階で反応系に第一の（Ｃ）多官能単量体を添加すると、得られるゴムの加工性が低下する。一方、重合転化率が９０％以上の段階で反応系に第一の（Ｃ）多官能単量体を添加すると、得られるゴムの加工性は良好であるが、重合反応が終了するまでに要する時間が増加する傾向にある。 When the first (C) polyfunctional monomer is added to the reaction system in the middle of the reaction when the polymerization conversion rate is in the range of 30% or more and less than 90%, the processability of the resulting rubber is improved, The polymerization can be completed in the same time required as before. Therefore, the manufacturing process is not complicated and the production cost can be reduced. If the first (C) polyfunctional monomer is added to the reaction system at a stage where the polymerization conversion is less than 30%, the processability of the resulting rubber is lowered. On the other hand, when the first (C) polyfunctional monomer is added to the reaction system at a stage where the polymerization conversion rate is 90% or more, the processability of the resulting rubber is good, but it is necessary until the polymerization reaction is completed. Time tends to increase.
反応系に第一の（Ｃ）多官能単量体を添加する方法としては、所定量の第一の（Ｃ）多官能単量体を一括して添加する方法や、連続的に添加する方法を挙げることができる。但し、本実施形態においては、連続的に添加することが、更に加工性の向上したゴムを得ることができるために好ましい。 As a method of adding the first (C) polyfunctional monomer to the reaction system, a method of adding a predetermined amount of the first (C) polyfunctional monomer all at once, or a method of adding continuously Can be mentioned. However, in this embodiment, it is preferable to add continuously because a rubber with further improved processability can be obtained.
次に、本実施形態の共役ジエン系共重合ゴムの製造方法で用られる各種の成分等について説明する。 Next, various components used in the method for producing a conjugated diene copolymer rubber according to this embodiment will be described.
（Ａ）共役ジエン化合物
本実施形態の共役ジエン系共重合ゴムの製造方法で用いられる第一の共役ジエン化合物及び第二の共役ジエン化合物としては、例えば１，３−ブタジエン、イソプレン、２，３−ジメチル−１，３−ブタジエン、２−クロロ−１，３−ブタジエン、１，３−ペンタジエン、及びこれらの混合物等を挙げることができる。これらのうち、１，３−ブタジエンを用いることが好ましい。なお、第一の共役ジエン化合物と第二の共役ジエン化合物は、相互に同一であっても異なるものであってもよい。なお、本明細書において「第一の共役ジエン化合物」とは、重合開始時に存在させる共役ジエン化合物のことをいい、「第二の共役ジエン化合物」とは、重合開始後に添加する共役ジエン化合物のことをいう。第二の共役ジエン化合物は一種のみ添加してもよいし、二種以上添加してもよい。更に、第二の共役ジエン化合物は一回のみ添加してもよいし、二回以上添加してもよい。第二の共役ジエン化合物の添加方法は特に限定されないが、一括添加、分割添加、連続添加等の公知の方法を任意に適用することができる。但し、第二の共役ジエン化合物を、後述する第一の多官能性単量体の添加後、変性剤添加前（例えば直前）に添加することは、変性の効果を高めることができる点において好ましい。
(A) Conjugated diene compound Examples of the first conjugated diene compound and the second conjugated diene compound used in the method for producing a conjugated diene copolymer rubber according to this embodiment include 1,3-butadiene, isoprene, and 2,3. -Dimethyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1,3-pentadiene, and mixtures thereof. Of these, it is preferable to use 1,3-butadiene. The first conjugated diene compound and the second conjugated diene compound may be the same or different from each other. In the present specification, the “first conjugated diene compound” refers to a conjugated diene compound that is present at the start of polymerization, and the “second conjugated diene compound” refers to a conjugated diene compound that is added after the start of polymerization. That means. Only one kind of the second conjugated diene compound may be added, or two or more kinds thereof may be added. Furthermore, the second conjugated diene compound may be added only once, or may be added twice or more. Although the addition method of a 2nd conjugated diene compound is not specifically limited, Well-known methods, such as collective addition, divided addition, and continuous addition, can be applied arbitrarily. However, it is preferable to add the second conjugated diene compound after the addition of the first polyfunctional monomer described later and before the addition of the modifier (for example, immediately before), in that the effect of modification can be enhanced. .
（Ｂ）芳香族ビニル化合物
本実施形態の共役ジエン系共重合ゴムの製造方法で用いられる第一の芳香族ビニル化合物及び第二の芳香族ビニル化合物としては、例えばスチレン、２−メチルスチレン、３−メチルスチレン、４−メチルスチレン、α−メチルスチレン、２，４−ジメチルスチレン、２，４−ジイソプロピルスチレン、４−ｔｅｒｔ−ブチルスチレン、ｔｅｒｔ−ブトキシスチレン、ビニルベンジルジメチルアミン、（４−ビニルベンジル）ジメチルアミノエチルエーテル、Ｎ，Ｎ−ジメチルアミノエチルスチレン、ビニルピリジン、及びこれらの混合物等を挙げることができる。これらのうち、スチレンを用いることが好ましい。なお、第一の芳香族ビニル化合物と第二の芳香族ビニル化合物は、相互に同一であっても異なるものであってもよい。なお、本明細書において「第一の芳香族ビニル化合物」とは、重合開始時に存在させる芳香族ビニル化合物のことをいい、「第二の芳香族ビニル化合物」とは、重合開始後に添加する芳香族ビニル化合物のことをいう。第二の芳香族ビニル化合物は一種のみ添加してもよいし、二種以上添加してもよい。更に、第二の芳香族ビニル化合物は一回のみ添加してもよいし、二回以上添加してもよい。第二の芳香族ビニル化合物の添加方法は特に限定されないが、一括添加、分割添加、連続添加等の公知の方法を任意に適用することができる。但し、第二の芳香族ビニル化合物を、後述する第一の多官能性単量体の添加後、変性剤添加前（例えば直前）に添加することは、変性の効果を高めることができる点において好ましい。
(B) Aromatic vinyl compound Examples of the first aromatic vinyl compound and the second aromatic vinyl compound used in the method for producing the conjugated diene copolymer rubber of the present embodiment include styrene, 2-methylstyrene, and 3 -Methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl ) Dimethylaminoethyl ether, N, N-dimethylaminoethylstyrene, vinylpyridine, and mixtures thereof. Of these, styrene is preferably used. The first aromatic vinyl compound and the second aromatic vinyl compound may be the same or different from each other. In the present specification, the “first aromatic vinyl compound” refers to an aromatic vinyl compound that is present at the start of polymerization, and the “second aromatic vinyl compound” refers to an aromatic compound that is added after the start of polymerization. A group vinyl compound. Only one kind of the second aromatic vinyl compound may be added, or two or more kinds thereof may be added. Furthermore, the second aromatic vinyl compound may be added only once, or may be added twice or more. Although the addition method of a 2nd aromatic vinyl compound is not specifically limited, Well-known methods, such as collective addition, divided addition, and continuous addition, can be applied arbitrarily. However, the addition of the second aromatic vinyl compound after the addition of the first polyfunctional monomer, which will be described later, before the addition of the modifier (for example, immediately before) is in that the effect of modification can be enhanced. preferable.
（Ｃ）多官能単量体
本実施形態の共役ジエン系共重合ゴムの製造方法で用いられる第一の多官能単量体及び第二の多官能単量体としては、例えばジビニルベンゼン、ジビニルビフェニル、ジビニルナフタレン、及びこれらの混合物等を挙げることができる。これらのうち、ジビニルベンゼンを用いることが好ましい。なお、第一の多官能単量体と第二の多官能単量体は、相互に同一であっても異なるものであってもよい。第一の多官能単量体としてジビニルベンゼンを用いる場合に、反応途中段階で反応系に添加するジビニルベンゼンの添加量は、第一の共役ジエン化合物、第二の共役ジエン化合物、第一の芳香族ビニル化合物、及び第二の芳香族ビニル化合物の合計１００質量部に対して、０．００１〜１質量部であることが好ましく、０．００５〜０．１質量部であることが更に好ましく、０．００５〜０．０５質量部であることが特に好ましい。反応途中段階で反応系に添加するジビニルベンゼンの添加量が０．００１質量部未満であると、共重合体のベール形状の経時変化（コールドフロー）が起こり易くなる傾向にある。一方、１質量部超であると、共重合体のムーニー粘度の経時的上昇が顕著となる傾向にある。
(C) Polyfunctional monomer Examples of the first polyfunctional monomer and the second polyfunctional monomer used in the method for producing a conjugated diene copolymer rubber according to this embodiment include divinylbenzene and divinylbiphenyl. , Divinylnaphthalene, and mixtures thereof. Of these, divinylbenzene is preferably used. The first polyfunctional monomer and the second polyfunctional monomer may be the same or different from each other. When divinylbenzene is used as the first polyfunctional monomer, the amount of divinylbenzene added to the reaction system during the reaction is such that the first conjugated diene compound, second conjugated diene compound, first fragrance Is preferably 0.001 to 1 part by mass, more preferably 0.005 to 0.1 part by mass, with respect to 100 parts by mass of the total of the aromatic vinyl compound and the second aromatic vinyl compound, It is especially preferable that it is 0.005-0.05 mass part. When the amount of divinylbenzene added to the reaction system in the course of the reaction is less than 0.001 part by mass, the veil shape of the copolymer tends to change with time (cold flow). On the other hand, if it exceeds 1 part by mass, the Mooney viscosity of the copolymer tends to increase significantly with time.
また、第二の多官能単量体としてジビニルベンゼンを用いる場合に、反応系に最初から含有させるジビニルベンゼンの含有量は、第一の共役ジエン化合物と第一の芳香族ビニル化合物の合計の１００質量部に対して、０〜１質量部であることが好ましく、０〜０．５質量部であることが更に好ましく、０〜０．１質量部であることが特に好ましい。反応系に最初から含有させるジビニルベンゼンの含有量が１質量部超であると、共重合体の加工性が低下する傾向にある。 When divinylbenzene is used as the second polyfunctional monomer, the content of divinylbenzene contained in the reaction system from the beginning is 100, which is the total of the first conjugated diene compound and the first aromatic vinyl compound. It is preferably 0 to 1 part by mass, more preferably 0 to 0.5 part by mass, and particularly preferably 0 to 0.1 part by mass with respect to part by mass. When the content of divinylbenzene contained in the reaction system from the beginning is more than 1 part by mass, the processability of the copolymer tends to be lowered.
（Ｄ）変性剤
本実施形態の共役ジエン系共重合ゴムの製造方法で用いられる変性剤としては、シリカと反応し得る化合物、又はスズ化合物と前記シリカと反応し得る化合物との混合物を用いることが好ましい。シリカと反応し得る化合物は、ジブチルジクロロケイ素、メチルトリクロロケイ素、メチルジクロロケイ素、テトラクロロケイ素、トリエトキシメチルシラン、トリフェノキシメチルシラン、トリメトキシシラン、メチルトリエトキシシラン、４，５−エポキシヘプチルメチルジメトキシシラン、ビス（トリエトキシシリルプロピル）テトラサルファイド、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルジメトキシシラン、及びＮ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルジエトキシシランからなる群より選択される少なくとも一種であることが好ましい。これらのうち、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルジエトキシシラン（以下、「Ｓｉ−Ｎ変性剤」とも記す）を用いることが特に好ましい。
(D) Modifier As the modifier used in the method for producing a conjugated diene copolymer rubber of the present embodiment, a compound that can react with silica or a mixture of a tin compound and a compound that can react with silica is used. Is preferred. Compounds capable of reacting with silica are dibutyldichlorosilicon, methyltrichlorosilicon, methyldichlorosilicon, tetrachlorosilicon, triethoxymethylsilane, triphenoxymethylsilane, trimethoxysilane, methyltriethoxysilane, 4,5-epoxyheptylmethyl. At least selected from the group consisting of dimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, and N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane One type is preferred. Among these, it is particularly preferable to use N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane (hereinafter also referred to as “Si—N modifier”).
シリカと反応し得る化合物としてＳｉ−Ｎ変性剤、重合開始剤として後述するアルキルリチウムをそれぞれ使用する場合、Ｓｉ−Ｎ変性剤と、アルキルリチウムを構成するリチウム原子（Ｌｉ）のモル比は、（Ｓｉ−Ｎ変性剤）／（Ｌｉ）＝０．２〜１．０であることが好ましく、（Ｓｉ−Ｎ変性剤）／（Ｌｉ）＝０．３〜０．８であることが更に好ましい。（Ｓｉ−Ｎ変性剤）／（Ｌｉ）の値が０．２未満であると、転がり抵抗が悪化する傾向にある。一方、（Ｓｉ−Ｎ変性剤）／（Ｌｉ）の値が１．０超であると、未反応の変性剤が残留しコスト的に不利となる傾向にある。 When using a Si-N modifier as a compound capable of reacting with silica and an alkyl lithium described later as a polymerization initiator, the molar ratio between the Si-N modifier and the lithium atom (Li) constituting the alkyl lithium is ( (Si—N modifier) / (Li) = 0.2 to 1.0 is preferable, and (Si—N modifier) / (Li) = 0.3 to 0.8 is more preferable. When the value of (Si—N modifier) / (Li) is less than 0.2, the rolling resistance tends to deteriorate. On the other hand, when the value of (Si—N modifier) / (Li) exceeds 1.0, unreacted modifier remains and tends to be disadvantageous in cost.
また、スズ化合物としては、例えばテトラクロロスズ、テトラブロムスズ、トリクロロブチルスズ、トリクロロメチルスズ、トリクロロオクチルスズ、ジブロムジメチルスズ、ジクロロジメチルスズ、ジクロロジブチルスズ、ジクロロジオクチルスズ、１，２−ビス（トリクロロスタニル）エタン、１，２−ビス（メチルジクロロスタニルエタン）、１，４−ビス（トリクロロスタニル）ブタン、１，４−ビス（メチルジクロロスタニル）ブタン、エチルスズトリステアレート、ブチルスズトリスオクタノエート、ブチルスズトリスステアレート、ブチルスズトリスラウレート、ジブチルスズビスオクタノエート、ジブチルスズビスステアレート、ジブチルスズビスラウレート等を好適例として挙げることができる。これらのうち、テトラクロロスズ（ＳｎＣｌ4）を用いることが特に好ましい。 Examples of the tin compound include tetrachlorotin, tetrabromotin, trichlorobutyltin, trichloromethyltin, trichlorooctyltin, dibromodimethyltin, dichlorodimethyltin, dichlorodibutyltin, dichlorodioctyltin, 1,2-bis (trichloro Stanyl) ethane, 1,2-bis (methyldichlorostannylethane), 1,4-bis (trichlorostannyl) butane, 1,4-bis (methyldichlorostannyl) butane, ethyltin tristearate, butyltin Preferred examples include trisoctanoate, butyltin tristearate, butyltin trislaurate, dibutyltin bisoctanoate, dibutyltin bisstearate, dibutyltin bislaurate, and the like. Of these, it is particularly preferable to use tetrachlorotin (SnCl 4 ).
スズ化合物としてテトラクロロスズ（ＳｎＣｌ4）、重合開始剤として後述するアルキルリチウムをそれぞれ使用する場合、テトラクロロスズ（ＳｎＣｌ4）と、アルキルリチウムを構成するリチウム原子（Ｌｉ）のモル比は、（ＳｎＣｌ4）／（Ｌｉ）＝０〜０．２であることが好ましく、（ＳｎＣｌ4）／（Ｌｉ）＝０〜０．１７５であることが更に好ましい。一方、（ＳｎＣｌ4）／（Ｌｉ）の値が０．２超であると、Ｓｉ−Ｎ変性剤の結合量が低下して転がり抵抗が悪化する傾向にある。 When tetrachlorotin (SnCl 4 ) is used as the tin compound and alkyl lithium described later as the polymerization initiator is used, the molar ratio of tetrachlorotin (SnCl 4 ) to the lithium atom (Li) constituting the alkyl lithium is ( SnCl 4 ) / (Li) = 0 to 0.2 is preferable, and (SnCl 4 ) / (Li) = 0 to 0.175 is more preferable. On the other hand, if the value of (SnCl 4 ) / (Li) is more than 0.2, the bonding amount of the Si—N modifier tends to decrease and rolling resistance tends to deteriorate.
（Ｅ）その他の成分等
共重合反応の重合開始剤としては、例えば有機アルカリ金属や有機アルカリ土類金属等を使用することができる。有機アルカリ金属、有機アルカリ土類金属等としては、例えばｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム、ｔ−ブチルリチウム等のアルキルリチウム、１，４−ジリチオブタン等のアルキレンジリチウム、フェニルリチウム、スチルベンリチウム、リチウムナフタレン等の有機リチウム化合物、ナトリウムナフタレン、カリウムナフタレン、ｎ−ブチルマグネシウム、ｎ−ヘキシルマグネシウム、エトキシカルシウム、ステアリン酸カルシウム、ｔ−ブトキシストロンチウム、エトキシバリウム、イソプロポキシバリウム、エチルメルカプトバリウムｔ−ブトキシバリウム、フェノキシバリウム、ジエチルアミノバリウム、ステアリン酸バリウム等を挙げることができる。これらの中で、ｎ−ブチルリチウム、ｓｅｃ−ブチルリチウムが更に好ましい。
(E) Other components etc. As a polymerization initiator of a copolymerization reaction, an organic alkali metal, an organic alkaline earth metal, etc. can be used, for example. Examples of the organic alkali metal and organic alkaline earth metal include alkyllithium such as n-butyllithium, sec-butyllithium and t-butyllithium, alkylenedilithium such as 1,4-dilithiobutane, phenyllithium, stilbenelithium, Organolithium compounds such as lithium naphthalene, sodium naphthalene, potassium naphthalene, n-butylmagnesium, n-hexylmagnesium, ethoxycalcium, calcium stearate, t-butoxystrontium, ethoxybarium, isopropoxybarium, ethylmercaptobarium t-butoxybarium, Mention may be made of phenoxybarium, diethylaminobarium, barium stearate and the like. Of these, n-butyllithium and sec-butyllithium are more preferable.
また、上述した有機アルカリ金属を所定の第２級アミン化合物又は第３級アミン化合物と反応させ、得られた反応生成物を重合開始剤として共重合反応に使用することもできる。第２級アミン化合物又は第３級アミン化合物と反応させる有機アルカリ金属としては、有機リチウム化合物が好ましく、ｎ−ブチルリチウム、ｓｅｃ−ブチルリチウムが更に好ましい。 Moreover, the organic alkali metal mentioned above can be made to react with a predetermined | prescribed secondary amine compound or a tertiary amine compound, and the obtained reaction product can also be used for a copolymerization reaction as a polymerization initiator. As the organic alkali metal to be reacted with the secondary amine compound or the tertiary amine compound, an organic lithium compound is preferable, and n-butyl lithium and sec-butyl lithium are more preferable.
有機アルカリ金属と反応させる第２級アミン化合物としては、例えばジメチルアミン、ジエチルアミン、ジプロピルアミン、ジ−ｎ−ブチルアミン、ジ−ｓｅｃ−ブチルアミン、ジペンチルアミン、ジヘキシルアミン、ジ−ｎ−オクチルアミン、ジ−（２−エチルヘキシル）アミン、ジシクロヘキシルアミン、Ｎ−メチルベンジルアミン、ジアリルアミン、モルホリン、ピペラジン、２，６−ジメチルモルホリン、２，６−ジメチルピペラジン、１−エチルピペラジン、２−メチルピペラジン、１−ベンジルピペラジン、ピペリジン、３，３−ジメチルピペリジン、２，６−ジメチルピペリジン、１−メチル−４−（メチルアミノ）ピペリジン、２，２，６，６−テトラメチルピペリジン、ピロリジン、２，５−ジメチルピロリジン、アゼチジン、ヘキサメチレンイミン、ヘプタメチレンイミン、５−ベンジルオキシインドール、３−アザスピロ［５．５］ウンデカン、３−アザビシクロ［３．２．２］ノナン、カルバゾール等を挙げることができる。 Secondary amine compounds to be reacted with the organic alkali metal include, for example, dimethylamine, diethylamine, dipropylamine, di-n-butylamine, di-sec-butylamine, dipentylamine, dihexylamine, di-n-octylamine, di- -(2-ethylhexyl) amine, dicyclohexylamine, N-methylbenzylamine, diallylamine, morpholine, piperazine, 2,6-dimethylmorpholine, 2,6-dimethylpiperazine, 1-ethylpiperazine, 2-methylpiperazine, 1-benzyl Piperazine, piperidine, 3,3-dimethylpiperidine, 2,6-dimethylpiperidine, 1-methyl-4- (methylamino) piperidine, 2,2,6,6-tetramethylpiperidine, pyrrolidine, 2,5-dimethylpyrrolidine Azechi Emissions, hexamethyleneimine, heptamethyleneimine, 5-benzyloxyindole, 3-azaspiro [5.5] undecane, 3-azabicyclo [3.2.2] nonane may be mentioned carbazole.
また、有機アルカリ金属と反応させる第３級アミン化合物としては、例えばＮ，Ｎ−ジメチル−ｏ−トルイジン、Ｎ，Ｎ−ジメチル−ｐ−トルイジン、Ｎ，Ｎ−ジメチル−ｍ−トルイジン、α−ピコリン、β−ピコリン、γ−ピコリン、ベンジルジメチルアミン、ベンジルジエチルアミン、ベンジルジプロピルアミン、ベンジルジブチルアミン、（ｏ−メチルベンジル）ジメチルアミン、（ｍ−メチルベンジル）ジメチルアミン、（ｐ−メチルベンジル）ジメチルアミン、Ｎ，Ｎ−テトラメチレン−ｏ−トルイジン、Ｎ，Ｎ−ヘプタメチレン−ｏ−トルイジン、Ｎ，Ｎ−ヘキサメチレン−ｏ−トルイジン、Ｎ，Ｎ−トリメチレンベンジルアミン、Ｎ，Ｎ−テトラメチレンベンジルアミン、Ｎ，Ｎ−ヘキサメチレンベンジルアミン、Ｎ，Ｎ−テトラメチレン（ｏ−メチルベンジル）アミン、Ｎ，Ｎ−テトラメチレン（ｐ−メチルベンジル）アミン、Ｎ，Ｎ−ヘキサメチレン（ｏ−メチルベンジル）アミン、Ｎ，Ｎ−ヘキサメチレン（ｐ−メチルベンジル）アミン等を挙げることができる。 Examples of the tertiary amine compound to be reacted with the organic alkali metal include N, N-dimethyl-o-toluidine, N, N-dimethyl-p-toluidine, N, N-dimethyl-m-toluidine, and α-picoline. , Β-picoline, γ-picoline, benzyldimethylamine, benzyldiethylamine, benzyldipropylamine, benzyldibutylamine, (o-methylbenzyl) dimethylamine, (m-methylbenzyl) dimethylamine, (p-methylbenzyl) dimethyl Amine, N, N-tetramethylene-o-toluidine, N, N-heptamethylene-o-toluidine, N, N-hexamethylene-o-toluidine, N, N-trimethylenebenzylamine, N, N-tetramethylene Benzylamine, N, N-hexamethylenebenzylamine, N, N-teto Methylene (o-methylbenzyl) amine, N, N-tetramethylene (p-methylbenzyl) amine, N, N-hexamethylene (o-methylbenzyl) amine, N, N-hexamethylene (p-methylbenzyl) amine Etc.
本実施形態においては、エーテル化合物及び／又は第３級アミン化合物を反応系中に含有させることが、得られる共役ジエン系共重合ゴムの共役ジエン部分のミクロ構造（ビニル結合含量）を調整することができるために好ましい。エーテル化合物としては、例えばジエチルエーテル、ジ−ｎ−ブチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル、ジエチレングリコールジメチルエーテル、プロピレングリコールジメチルエーテル、プロピレングリコールジエチルエーテル、プロピレングリコールジブチルエーテル、テトラヒドロフラン、２，２−（ビステトラヒドロフルフリル）プロパン、ビステトラヒドロフルフリルホルマール、テトラヒドロフルフリルアルコールのメチルエーテル、テトラヒドロフルフリルアルコールのエチルエーテル、テトラヒドロフルフリルアルコールのブチルエーテル、α−メトキシテトラヒドロフラン、ジメトキシベンゼン、ジメトキシエタン等を挙げることができる。また、第３級アミン化合物としては、例えばトリエチルアミン、ピリジン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、ジピペリジノエタン、Ｎ，Ｎ−ジエチルエタノールアミンのメチルエーテル、Ｎ，Ｎ−ジエチルエタノールアミンのエチルエーテル、Ｎ，Ｎ−ジエチルエタノールアミンのブチルエーテル等を挙げることができる。 In this embodiment, the inclusion of an ether compound and / or a tertiary amine compound in the reaction system adjusts the microstructure (vinyl bond content) of the conjugated diene portion of the resulting conjugated diene copolymer rubber. It is preferable because Examples of the ether compound include diethyl ether, di-n-butyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, tetrahydrofuran, and 2,2- (bis Tetrahydrofurfuryl) propane, bistetrahydrofurfuryl formal, methyl ether of tetrahydrofurfuryl alcohol, ethyl ether of tetrahydrofurfuryl alcohol, butyl ether of tetrahydrofurfuryl alcohol, α-methoxytetrahydrofuran, dimethoxybenzene, dimethoxyethane, etc. it can. Examples of the tertiary amine compound include triethylamine, pyridine, N, N, N ′, N′-tetramethylethylenediamine, dipiperidinoethane, methyl ether of N, N-diethylethanolamine, N, N— Examples include ethyl ether of diethylethanolamine, butyl ether of N, N-diethylethanolamine, and the like.
本実施形態において使用することができる溶媒として、炭化水素溶媒を挙げることができる。この炭化水素溶媒としては、例えばペンタン、ヘキサン、ヘプタン、オクタン、メチルシクロペンタン、シクロヘキサン、ベンゼン、トルエン、キシレン等を挙げることができる。これらのうち、シクロヘキサン、又はヘプタンが好ましい。 A hydrocarbon solvent can be mentioned as a solvent which can be used in this embodiment. Examples of the hydrocarbon solvent include pentane, hexane, heptane, octane, methylcyclopentane, cyclohexane, benzene, toluene, xylene and the like. Of these, cyclohexane or heptane is preferred.
本実施形態においては、重合開始剤とともにカリウム化合物を反応系に添加することもできる。重合開始剤とともにカリウム化合物を反応系に添加すると、使用される重合開始剤の反応性を向上させることができ、得られる共役ジエン系共重合ゴム中に導入される芳香族ビニル化合物をランダムに配列させることができ、又は芳香族ビニル化合物の単連鎖を形成させることができる。カリウム化合物としては、例えばカリウムイソプロポキシド、カリウム−ｔ−ブトキシド、カリウム−ｔ−アミロキシド、カリウム−ｎ−ヘプタオキシド、カリウムベンジルオキシド等のカリウムアルコキシド、カリウムフェノキシド、イソバレリアン酸、カプリル酸、ラウリル酸、パルミチン酸、ステアリン酸、オレイン酸、リノレイン酸、安息香酸、フタル酸、２−エチルヘキサン酸等のカリウム塩、ドデシルベンゼンスルホン酸、テトラデシルベンゼンスルホン酸、ヘキサデシルベンゼンスルホン酸、オクタデシルベンゼンスルホン酸等の有機スルホン酸のカリウム塩、亜リン酸ジエチル、亜リン酸ジイソプロピル、亜リン酸ジフェニル、亜リン酸ジブチル、亜リン酸ジラウリル等の有機亜リン酸部分エステルのカリウム塩等を挙げることができる。 In this embodiment, a potassium compound can also be added to a reaction system with a polymerization initiator. When a potassium compound is added to the reaction system together with the polymerization initiator, the reactivity of the polymerization initiator used can be improved, and the aromatic vinyl compound introduced into the resulting conjugated diene copolymer rubber is randomly arranged. Or a single chain of an aromatic vinyl compound can be formed. Examples of the potassium compound include potassium isopropoxide, potassium t-butoxide, potassium t-amyloxide, potassium alkoxide such as potassium n-heptaoxide and potassium benzyl oxide, potassium phenoxide, isovaleric acid, caprylic acid and lauric acid. , Potassium salts such as palmitic acid, stearic acid, oleic acid, linolenic acid, benzoic acid, phthalic acid, 2-ethylhexanoic acid, dodecylbenzenesulfonic acid, tetradecylbenzenesulfonic acid, hexadecylbenzenesulfonic acid, octadecylbenzenesulfonic acid Examples of potassium salts of organic phosphites such as diethyl phosphite, diisopropyl phosphite, diphenyl phosphite, dibutyl phosphite, dilauryl phosphite, etc. Door can be.
上記のカリウム化合物は、重合開始剤として用いるアルカリ金属又はアルカリ土類金属１グラム原子当量につき、必要に応じて０．５モルまで添加することが好ましい。０．５モル超であると、重合活性が低下して生産性が低下したり、また、変性剤によって重合活性末端を変性させる反応を行う際の変性効率が低下することがある。 The potassium compound is preferably added up to 0.5 mol as required per 1 gram atomic equivalent of an alkali metal or alkaline earth metal used as a polymerization initiator. If it exceeds 0.5 mol, the polymerization activity may decrease and the productivity may decrease, and the modification efficiency may be decreased when a reaction for modifying the polymerization active terminal with a modifier is performed.
上述してきたようにして得られる共役ジエン系共重合ゴムを含有する反応系（重合反応溶液）中から、通常の溶液重合法において用いられる方法によって目的とする共役ジエン系共重合ゴムを単離することができる。具体的には、先ず、溶液状態の反応系に安定剤等を添加した後、必要に応じて芳香族系プロセスオイル、ナフテン系プロセスオイル等の伸展油や、重量平均分子量が１５万以下の液状ポリマー（又はこの液状ポリマーの溶液）を添加する。次いで、直接乾燥法やスチームストリッピング法によって溶剤と分離して洗浄し、真空乾燥機、熱風乾燥機やロール等で乾燥することにより、共役ジエン系共重合ゴムを単離することができる。 From the reaction system (polymerization reaction solution) containing the conjugated diene copolymer rubber obtained as described above, the target conjugated diene copolymer rubber is isolated by a method used in a normal solution polymerization method. be able to. Specifically, first, a stabilizer or the like is added to the reaction system in a solution state, and then an extension oil such as an aromatic process oil or a naphthenic process oil or a liquid having a weight average molecular weight of 150,000 or less as necessary. Add the polymer (or a solution of this liquid polymer). Next, the conjugated diene copolymer rubber can be isolated by separating and washing with a solvent by a direct drying method or a steam stripping method, and drying with a vacuum dryer, a hot air dryer or a roll.
次に、本発明の共役ジエン系共重合ゴムの一実施形態について説明する。本実施形態の共役ジエン系共重合ゴムは、上述してきた本発明の実施形態である共役ジエン系共重合ゴムの製造方法により製造されたものである。従って、加工性が良好であり、また、加硫後においても十分な硬度を示し、転がり抵抗の小さいゴム組成物を得ることができるといった効果を奏するものである。 Next, an embodiment of the conjugated diene copolymer rubber of the present invention will be described. The conjugated diene copolymer rubber of this embodiment is produced by the above-described method for producing a conjugated diene copolymer rubber which is an embodiment of the present invention. Therefore, it is possible to obtain a rubber composition having good processability and exhibiting sufficient hardness even after vulcanization and having a low rolling resistance.
本実施形態の共役ジエン系共重合ゴムのムーニー粘度（ＭＬ1+4，１００℃）は、２０〜２００の範囲であることが好ましく、３５〜１００の範囲であることが更に好ましい。ムーニー粘度（ＭＬ1+4，１００℃）が２０未満であると、破壊強度、耐摩耗性、及び低ヒステリシスロス性が低下する傾向にある。一方、ムーニー粘度（ＭＬ1+4，１００℃）が２００超であると、加工性が低下する傾向にある。 The Mooney viscosity (ML 1 + 4 , 100 ° C.) of the conjugated diene copolymer rubber of this embodiment is preferably in the range of 20 to 200, and more preferably in the range of 35 to 100. When the Mooney viscosity (ML 1 + 4 , 100 ° C.) is less than 20, the fracture strength, wear resistance, and low hysteresis loss tend to be reduced. On the other hand, when the Mooney viscosity (ML 1 + 4 , 100 ° C.) is more than 200, processability tends to decrease.
なお、ムーニー粘度（ＭＬ1+4，１００℃）が１００超である共役ジエン系共重合ゴムもそれ単独では加工性が十分ではない場合もあるが、芳香族系プロセスオイル、ナフテン系プロセスオイル等の伸展油や、重量平均分子量が１５万以下の液状ポリマーを添加することで、ムーニー粘度（ＭＬ1+4，１００℃）を１００以下とし、十分な加工性を確保することができる。用いられる伸展油としては、ジエン系ゴムに通常用いられる伸展油や軟化剤であれば特に制限されないが、鉱物油系の伸展油が好ましい。一般的に、鉱物油の伸展油は、芳香族系オイル、脂環族系オイル、及び脂肪族系オイルの混合物であり、これらの混合割合によって芳香族系、脂環族系、脂肪族系と分類されているが、本実施形態においてはいずれのものも使用することができる。なかでも、粘度比重恒数（Ｖ．Ｇ．Ｃ．値）が０．９００〜１．０４９の芳香族系鉱物油（アロマティックオイル）、又は０．８００〜０．８９９の脂肪族系鉱物油（ナフテニックオイル）が、低ヒステリシス性／ウェットスキッド抵抗の点から好ましい。 In addition, conjugated diene copolymer rubber having Mooney viscosity (ML 1 + 4 , 100 ° C.) exceeding 100 may not have sufficient processability by itself, but aromatic process oil, naphthene process oil, etc. By adding an extender oil or a liquid polymer having a weight average molecular weight of 150,000 or less, the Mooney viscosity (ML 1 + 4 , 100 ° C.) can be made 100 or less, and sufficient processability can be secured. The extending oil to be used is not particularly limited as long as it is an extending oil or softening agent usually used for diene rubbers, but a mineral oil-based extending oil is preferable. In general, the extension oil of mineral oil is a mixture of aromatic oil, alicyclic oil, and aliphatic oil, and depending on the mixing ratio of these, aromatic, alicyclic, aliphatic Although classified, any one can be used in the present embodiment. Among them, an aromatic mineral oil having a viscosity specific gravity constant (VGC value) of 0.900 to 1.049, or an aliphatic mineral oil having a viscosity of 0.800 to 0.899. (Naphthenic oil) is preferable from the viewpoint of low hysteresis / wet skid resistance.
以下、本発明を実施例に基づいて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。なお、実施例、比較例中の「部」及び「％」は、特に断らない限り質量基準である。また、各種物性値の測定方法、及び評価方法を以下に示す。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the examples and comparative examples, “parts” and “%” are based on mass unless otherwise specified. Moreover, the measuring method and evaluation method of various physical property values are shown below.
［結合スチレン含量（％）］：２７０ＭＨｚ1Ｈ−ＮＭＲによって求めた。 [Bound Styrene Content (%)]: Determined by 270 MHz 1 H-NMR.
［（ブタジエン部分の）ビニル含量（％）］：２７０ＭＨｚ1Ｈ−ＮＭＲによって求めた。 [Vinyl content (% of butadiene moiety)]: Determined by 270 MHz 1 H-NMR.
［変性反応前ピーク分子量］：ゲルパーミエーションクロマトグラフィー（ＧＰＣ）（ＨＬＣ−８１２０ＧＰＣ（商品名（東ソー社製）））を使用して得られたＧＰＣ曲線の、多官能単量体、シリカと反応し得る化合物、及びスズ化合物との反応により分子量が増加したポリマーを除いたポリマー部分に相当する山の部分の頂点に相当する保持時間から、ポリスチレン換算で求めた。 [Peak molecular weight before denaturation reaction]: Reaction with polyfunctional monomer and silica of GPC curve obtained by using gel permeation chromatography (GPC) (HLC-8120GPC (trade name (manufactured by Tosoh Corporation))) It was determined in terms of polystyrene from the retention time corresponding to the apex of the peak portion corresponding to the polymer portion excluding the polymer that could be obtained and the polymer whose molecular weight increased due to the reaction with the tin compound.
［ムーニー粘度（ＭＬ1+4，１００℃）］：ＪＩＳ Ｋ６３００に準拠し、Ｌローターを使用して、予熱１分、ローター作動時間４分、温度１００℃の条件で求めた。 [Mooney viscosity (ML 1 + 4 , 100 ° C.)]: Measured according to JIS K6300 using an L rotor under conditions of preheating 1 minute, rotor operating time 4 minutes, and temperature 100 ° C.
［加硫ゴムの物性評価・測定］：
（ｉ）［ロール加工性（シート肌）］：硫黄と加硫促進剤を除いて行う練り（「Ａ練り」ともいう）後の配合ゴムをロールに通してシートとし、光沢を目視で観察した。以下に示す基準に従って評価した。
◎：極めて良好
○：良好
△：普通
×：悪い
××：極めて悪い
[Evaluation and measurement of physical properties of vulcanized rubber]:
(I) [Roll processability (sheet skin)]: The compounded rubber after kneading (also referred to as “A kneading”) excluding sulfur and the vulcanization accelerator was passed through a roll to form a sheet, and the gloss was visually observed. . Evaluation was performed according to the following criteria.
◎: Extremely good ○: Good △: Normal ×: Poor ××: Extremely bad
（ｉｉ）［配合ムーニー粘度］：加硫前の配合ゴムを測定用試料とし、ＪＩＳ Ｋ６３００に準拠し、Ｌローターを使用して、予熱１分、ローター作動時間４分、温度１００℃の条件で測定した。指数で表示し、数値が大きいほど加工性が良好である。 (Ii) [Mixed Mooney Viscosity]: Using a compounded rubber before vulcanization as a measurement sample, in accordance with JIS K6300, using an L rotor, preheating 1 minute, rotor operating time 4 minutes, temperature 100 ° C. It was measured. Expressed as an index, the larger the value, the better the workability.
（ｉｉｉ）［７０℃ｔａｎδ］：加硫ゴムを測定用試料とし、動的スペクトロメーター（米国レオメトリックス社製）を使用し、引張動歪０．７％、角速度１００ラジアン毎秒、７０℃の条件で測定した。指数で表示し、数値が大きいほど転がり抵抗性が小さく良好である。 (Iii) [70 ° C. tan δ]: Using vulcanized rubber as a measurement sample, using a dynamic spectrometer (manufactured by Rheometrics, USA), tensile dynamic strain 0.7%, angular velocity 100 radians per second, 70 ° C. Measured with Expressed as an index, the larger the value, the smaller the rolling resistance and the better.
（ｉｖ）［０℃ｔａｎδ］：加硫ゴムを測定用試料とし、動的スペクトロメーター（米国レオメトリックス社製）を使用し、引張動歪０．１４％、角速度１００ラジアン毎秒、０℃の条件で測定した。指数で表示し、数値が大きいほどウェットスキッド抵抗性が大きく良好である。 (Iv) [0 ° C. tan δ]: Using vulcanized rubber as a measurement sample, using a dynamic spectrometer (manufactured by Rheometrics, USA), tensile dynamic strain 0.14%, angular velocity 100 radians per second, 0 ° C. Measured with Expressed as an index, the larger the value, the greater the wet skid resistance.
（ｖ）［ＤＩＮ摩耗試験］：加硫ゴムを測定用試料とし、ＤＩＮ摩耗試験機（東洋精機社製）を使用し、ＪＩＳ Ｋ６２６４に準拠し、荷重１０Ｎで２５℃にて測定した。指数で表示し、数値が大きいほど耐摩耗性が良好である。 (V) [DIN abrasion test]: A vulcanized rubber was used as a measurement sample, and a DIN abrasion tester (manufactured by Toyo Seiki Co., Ltd.) was used. Expressed as an index, the larger the value, the better the wear resistance.
（実施例１）
窒素置換された内容積５リットルのオートクレーブ反応器に、シクロヘキサン２５００ｇ、テトラヒドロフラン２５ｇ、スチレン１３５ｇ、１，３−ブタジエン３５５ｇを仕込んだ。反応器内容物の温度を１０℃に調整した後、ｎ−ブチルリチウム３１５ｍｇを添加して重合を開始した。重合は断熱条件で実施し、最高温度は８５℃に達した。重合転化率が３５％に達した時点で、ジビニルベンゼン（純度５５％）０．０７０ｇ（ｍ−、ｐ−ジビニルベンゼンとして、反応初期段階に仕込んだスチレン及び１，３−ブタジエンの合計１００部に対して０．０１４部に相当）を、重合転化率が５５％に達するまで連続的に添加しつつ、重合を継続させた。重合転化率が９９％に達した時点（重合開始から２６分経過）で、１，３−ブタジエン１０ｇを２分間で追加し、次いで、テトラクロロスズ４９ｍｇを追加し、その１分後に、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルジエトキシシラン１０２５ｍｇを加えて１５分間反応を行った。反応後の重合体溶液に、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾールを添加した。次いで、スチームストリッピングにより脱溶媒を行い、１１０℃に調温された熱ロールで乾燥することにより共重合ゴム（実施例１）を得た。得られた共重合ゴムの各種物性値等を表１に示す。
Example 1
An autoclave reactor with an internal volume of 5 liters purged with nitrogen was charged with 2500 g of cyclohexane, 25 g of tetrahydrofuran, 135 g of styrene, and 355 g of 1,3-butadiene. After adjusting the temperature of the reactor contents to 10 ° C., 315 mg of n-butyllithium was added to initiate polymerization. The polymerization was carried out under adiabatic conditions and the maximum temperature reached 85 ° C. When the polymerization conversion rate reached 35%, 0.070 g of divinylbenzene (purity 55%) (m-, p-divinylbenzene was used as a total of 100 parts of styrene and 1,3-butadiene charged in the initial stage of the reaction. The polymerization was continued while continuously adding until the polymerization conversion reached 55%. When the polymerization conversion rate reached 99% (26 minutes after the start of polymerization), 10 g of 1,3-butadiene was added over 2 minutes, and then 49 mg of tetrachlorotin was added. 1025 mg of N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane was added and the reaction was carried out for 15 minutes. 2,6-Di-tert-butyl-p-cresol was added to the polymer solution after the reaction. Subsequently, the solvent was removed by steam stripping, and the copolymer rubber (Example 1) was obtained by drying with a hot roll adjusted to 110 ° C. Table 1 shows various physical property values of the obtained copolymer rubber.
（実施例２）
重合転化率が３５％に達した時点で、ジビニルベンゼン（純度５５％）０．０７０ｇ（ｍ−、ｐ−ジビニルベンゼンとして、反応初期段階に仕込んだスチレン及び１，３−ブタジエンの合計１００部に対して０．０１４部に相当）を一括して添加すること以外は、前述の実施例１と同様にして共重合ゴム（実施例２）を得た。得られた共重合ゴムの各種物性値等を表１に示す。
(Example 2)
When the polymerization conversion rate reached 35%, 0.070 g of divinylbenzene (purity 55%) (m-, p-divinylbenzene was used as a total of 100 parts of styrene and 1,3-butadiene charged in the initial stage of the reaction. Copolymer rubber (Example 2) was obtained in the same manner as in Example 1 except that it was added in a batch. Table 1 shows various physical property values of the obtained copolymer rubber.
（実施例３）
重合転化率が３５％に達した時点で、ジビニルベンゼン（純度５５％）０．０７０ｇ（ｍ−、ｐ−ジビニルベンゼンとして、反応初期段階に仕込んだスチレン及び１，３−ブタジエンの合計１００部に対して０．０１４部に相当）を、重合転化率が８８％に達するまで連続的に添加すること以外は、前述の実施例１と同様にして共重合ゴム（実施例３）を得た。得られた共重合ゴムの各種物性値等を表１に示す。
(Example 3)
When the polymerization conversion rate reached 35%, 0.070 g of divinylbenzene (purity 55%) (m-, p-divinylbenzene was used as a total of 100 parts of styrene and 1,3-butadiene charged in the initial stage of the reaction. Copolymer rubber (Example 3) was obtained in the same manner as in Example 1 except that it was continuously added until the polymerization conversion reached 88%. Table 1 shows various physical property values of the obtained copolymer rubber.
（比較例１）
溶液重合スチレン−ブタジエンゴム（ＪＳＲ社製、商品名「ＳＬ５６３」）を比較例１とした。
(Comparative Example 1)
Solution polymerization styrene-butadiene rubber (trade name “SL563” manufactured by JSR Corporation) was used as Comparative Example 1.
（比較例２）
窒素置換された内容積５リットルのオートクレーブ反応器に、シクロヘキサン２５００ｇ、テトラヒドロフラン２５ｇ、スチレン１３５ｇ、１，３−ブタジエン３５５ｇ、ジビニルベンゼン（純度５５質量％）０．０２８ｇ（ｍ−、ｐ−ジビニルベンゼンとして、反応初期段階に仕込んだスチレン及び１，３−ブタジエンの合計１００部に対して０．００６部に相当）を仕込んだ。反応器内容物の温度を２０℃に調整した後、ｎ−ブチルリチウム３１５ｍｇを添加して重合を開始した。重合は断熱条件で実施し、最高温度は８５℃に達した。重合転化率が９９％に達した時点（重合開始から２６分経過）で１，３−ブタジエン１０ｇを２分間で追加し、次いでテトラクロロスズ４９ｍｇを追加した、その１分後に、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルジエトキシシラン１０２５ｍｇを加えて、更に１５分間反応を行った。反応後の重合体溶液に、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾールを添加した。次いで、スチームストリッピングにより脱溶媒を行い、１１０℃に調温された熱ロールで乾燥することにより共重合ゴム（比較例２）を得た。得られた共重合ゴムの各種物性値等を表１に示す。
(Comparative Example 2)
Into an autoclave reactor with an internal volume of 5 liters purged with nitrogen, cyclohexane 2500 g, tetrahydrofuran 25 g, styrene 135 g, 1,3-butadiene 355 g, divinylbenzene (purity 55 mass%) 0.028 g (m-, p-divinylbenzene as , Equivalent to 0.006 parts with respect to 100 parts in total of styrene and 1,3-butadiene charged in the initial stage of reaction). After adjusting the temperature of the reactor contents to 20 ° C., 315 mg of n-butyllithium was added to initiate polymerization. The polymerization was carried out under adiabatic conditions and the maximum temperature reached 85 ° C. When the polymerization conversion reached 99% (26 minutes after the start of polymerization), 10 g of 1,3-butadiene was added over 2 minutes, and then 49 mg of tetrachlorotin was added. One minute later, N, N— Bis (trimethylsilyl) aminopropylmethyldiethoxysilane (1025 mg) was added, and the reaction was further continued for 15 minutes. 2,6-Di-tert-butyl-p-cresol was added to the polymer solution after the reaction. Subsequently, the solvent was removed by steam stripping, and the copolymer rubber (Comparative Example 2) was obtained by drying with a hot roll adjusted to 110 ° C. Table 1 shows various physical property values of the obtained copolymer rubber.
（比較例３）
重合転化率が１５％に達した時点で、ジビニルベンゼン（純度５５％）０．０７０ｇ（ｍ−、ｐ−ジビニルベンゼンとして、反応初期段階に仕込んだスチレン及び１，３−ブタジエンの合計１００部に対して０．０１４部に相当）を、重合転化率が３５％に達するまで連続的に添加すること以外は、前述の実施例１と同様にして共重合ゴム（比較例３）を得た。得られた共重合ゴムの各種物性値等を表１に示す。
(Comparative Example 3)
When the polymerization conversion rate reached 15%, 0.070 g of divinylbenzene (purity 55%) (m-, p-divinylbenzene was used as a total of 100 parts of styrene and 1,3-butadiene charged in the initial stage of the reaction. Copolymer rubber (Comparative Example 3) was obtained in the same manner as in Example 1 except that it was continuously added until the polymerization conversion reached 35%. Table 1 shows various physical property values of the obtained copolymer rubber.
（ゴム組成物（加硫物）の調製）
表２に示す「ゴム組成物の配合処方」に従って、２５０ｍｌラボプラストミルを使用して調製したゴム組成物を加硫した。なお、Ａ練りは１００℃×５０ｒｐｍで約３分間行い、その際のダンプの計器温度は約１４０℃、実温度は約１５０℃であった。また、Ａ練り後の配合ゴムに硫黄と加硫促進剤を追加してから行う練り（「Ｂ練り」ともいう）は、７０℃×６０ｒｐｍで１分間行った。得られた加硫ゴムの加工性、転がり抵抗性、ウェットスキッド抵抗性、及び耐摩耗性を評価した。結果を表３に示す。
(Preparation of rubber composition (vulcanized product))
The rubber composition prepared using a 250 ml lab plast mill was vulcanized in accordance with “rubber composition formula” shown in Table 2. In addition, A kneading was performed at 100 ° C. × 50 rpm for about 3 minutes, and the instrument temperature of the dump at that time was about 140 ° C., and the actual temperature was about 150 ° C. The kneading after adding sulfur and the vulcanization accelerator to the compounded rubber after Kneading (also referred to as “B kneading”) was performed at 70 ° C. × 60 rpm for 1 minute. The processability, rolling resistance, wet skid resistance, and wear resistance of the obtained vulcanized rubber were evaluated. The results are shown in Table 3.
表１に示すように、実施例１〜３の第一段重合所要時間は、比較例１，２の第一段重合所要時間と同等の短さであり、短時間で重合反応を終了できることが判明した。また、表３に示すように、比較例２では転がり抵抗性、ウェットスキッド抵抗性、及び耐摩耗性が良好である反面、加工性が低下している。しかし、実施例１〜３では、転がり抵抗性、ウェットスキッド抵抗性、及び耐摩耗性が比較例２と同様に良好であるとともに、加工性がより改善され、良好なものとなっていることが明らかとなった。なお、ジビニルベンゼンの添加方法が連続である場合（実施例１，３）と一括である場合（実施例２）とを比較すると、連続で添加した場合の方が、より加工性の良好なゴム組成物を得ることができる。 As shown in Table 1, the time required for the first stage polymerization in Examples 1 to 3 is as short as the time required for the first stage polymerization in Comparative Examples 1 and 2, and the polymerization reaction can be completed in a short time. found. Moreover, as shown in Table 3, in Comparative Example 2, although rolling resistance, wet skid resistance, and wear resistance are good, workability is low. However, in Examples 1 to 3, the rolling resistance, wet skid resistance, and wear resistance are as good as those in Comparative Example 2, and the workability is further improved and is good. It became clear. In addition, when the addition method of divinylbenzene is continuous (Examples 1 and 3) and the case of batch addition (Example 2), rubber with better processability is obtained when the addition method is continuous. A composition can be obtained.
本発明の共役ジエン系共重合ゴムは、自動車用タイヤトレッド、サイドウォール、カーカス等のタイヤ用のゴム組成物を構成するゴムとして、或いはベルト、ホース、防振ゴム、履き物等の、その他の工業用品用のゴム組成物を構成するゴムとして好適に用いることができる。 The conjugated diene copolymer rubber of the present invention is used as a rubber constituting a rubber composition for tires such as automobile tire treads, sidewalls and carcass, or in other industries such as belts, hoses, anti-vibration rubbers and footwear. It can be suitably used as a rubber constituting a rubber composition for articles.
Claims (11)
重合転化率が３０％以上、９０％未満の範囲内にある反応途中段階で、前記反応系に第一の多官能単量体を添加する共役ジエン系共重合ゴムの製造方法。 The copolymerization reaction is started in the reaction system containing the first conjugated diene compound and the first aromatic vinyl compound, and then the second conjugated diene compound and the second aromatic vinyl compound are added if necessary. , After completion of the copolymerization reaction, a method for producing a conjugated diene copolymer rubber to obtain a conjugated diene copolymer rubber by adding a modifier,
A method for producing a conjugated diene copolymer rubber, wherein a first polyfunctional monomer is added to the reaction system in the course of a reaction in which a polymerization conversion rate is within a range of 30% or more and less than 90%.
反応途中段階で前記反応系に添加する前記ジビニルベンゼンの添加量が、前記第一の共役ジエン化合物、前記第二の共役ジエン化合物、前記第一の芳香族ビニル化合物、及び前記第二の芳香族ビニル化合物の合計の１００質量部に対して、０．００１〜１質量部である請求項４に記載の共役ジエン系共重合ゴムの製造方法。 When the first polyfunctional monomer is divinylbenzene,
The amount of the divinylbenzene added to the reaction system during the reaction is such that the first conjugated diene compound, the second conjugated diene compound, the first aromatic vinyl compound, and the second aromatic The method for producing a conjugated diene copolymer rubber according to claim 4, wherein the content is 0.001 to 1 part by mass with respect to 100 parts by mass of the total vinyl compound.
前記反応系に含有される前記ジビニルベンゼンの含有量が、前記第一の共役ジエン化合物と前記第一の芳香族ビニル化合物の合計の１００質量部に対して、０〜１質量部である請求項４又は５に記載の共役ジエン系共重合ゴムの製造方法。 When the second polyfunctional monomer is divinylbenzene,
The content of the divinylbenzene contained in the reaction system is 0 to 1 part by mass with respect to 100 parts by mass as a total of the first conjugated diene compound and the first aromatic vinyl compound. 6. A process for producing a conjugated diene copolymer rubber as described in 4 or 5.
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| JP2004363990A JP4736416B2 (en) | 2004-12-16 | 2004-12-16 | Method for producing conjugated diene copolymer rubber |
| CA002576167A CA2576167C (en) | 2004-08-06 | 2005-07-21 | Process for producing conjugated diene copolymer rubber |
| EP05766333.8A EP1783143B1 (en) | 2004-08-06 | 2005-07-21 | Process for producing conjugated diene copolymer rubber |
| US11/573,308 US7427651B2 (en) | 2004-08-06 | 2005-07-21 | Process for producing conjugated diene copolymer rubber |
| KR1020077003675A KR101157295B1 (en) | 2004-08-06 | 2005-07-21 | Process for producing conjugated diene copolymer rubber |
| PCT/JP2005/013414 WO2006013732A1 (en) | 2004-08-06 | 2005-07-21 | Process for producing conjugated diene copolymer rubber |
| TW094126079A TWI375680B (en) | 2004-08-06 | 2005-08-01 | Method for producing conjugated diene type copolymerized rubber |
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| JP2009132907A (en) * | 2007-11-07 | 2009-06-18 | Jsr Corp | Method for manufacturing hydrogenated conjugated diene-based polymerization rubber, hydrogenated conjugated diene-based polymerization rubber, composition comprising the same and rubber-molded article |
| US8258332B2 (en) | 2007-06-18 | 2012-09-04 | Bridgestone Corporation | Polymers functionalized with halosilanes containing an amino group |
| JP2014122357A (en) * | 2008-03-10 | 2014-07-03 | Bridgestone Corp | Method for manufacturing a modified conjugated diene (co)polymer, method for manufacturing a modified conjugated (co)polymer-containing rubber composition, and pneumatic tire using a rubber composition manufactured by the manufacturing method |
| JP2015044996A (en) * | 2013-08-28 | 2015-03-12 | ザ・グッドイヤー・タイヤ・アンド・ラバー・カンパニーＴｈｅ Ｇｏｏｄｙｅａｒ Ｔｉｒｅ ＆ Ｒｕｂｂｅｒ Ｃｏｍｐａｎｙ | Functionalized polymer, rubber composition and pneumatic tire |
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| US8258332B2 (en) | 2007-06-18 | 2012-09-04 | Bridgestone Corporation | Polymers functionalized with halosilanes containing an amino group |
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| JP2015044996A (en) * | 2013-08-28 | 2015-03-12 | ザ・グッドイヤー・タイヤ・アンド・ラバー・カンパニーＴｈｅ Ｇｏｏｄｙｅａｒ Ｔｉｒｅ ＆ Ｒｕｂｂｅｒ Ｃｏｍｐａｎｙ | Functionalized polymer, rubber composition and pneumatic tire |
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