JP2013124369A - Conjugated diene rubber modified with polar silane, method and composition therefor - Google Patents
Conjugated diene rubber modified with polar silane, method and composition therefor Download PDFInfo
- Publication number
- JP2013124369A JP2013124369A JP2012234624A JP2012234624A JP2013124369A JP 2013124369 A JP2013124369 A JP 2013124369A JP 2012234624 A JP2012234624 A JP 2012234624A JP 2012234624 A JP2012234624 A JP 2012234624A JP 2013124369 A JP2013124369 A JP 2013124369A
- Authority
- JP
- Japan
- Prior art keywords
- conjugated diene
- diene rubber
- modified conjugated
- group
- oxygen
- 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
- 229920003244 diene elastomer Polymers 0.000 title claims abstract description 107
- 239000000203 mixture Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910000077 silane Inorganic materials 0.000 title abstract description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title description 2
- -1 alkoxy silane Chemical compound 0.000 claims abstract description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 26
- 239000001301 oxygen Substances 0.000 claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 claims abstract description 20
- 229910001413 alkali metal ion Inorganic materials 0.000 claims abstract description 14
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 13
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 30
- 229920001971 elastomer Polymers 0.000 claims description 25
- 239000005060 rubber Substances 0.000 claims description 25
- 150000001993 dienes Chemical class 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 23
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 230000008878 coupling Effects 0.000 claims description 8
- 238000010168 coupling process Methods 0.000 claims description 8
- 238000005859 coupling reaction Methods 0.000 claims description 8
- 125000001033 ether group Chemical group 0.000 claims description 7
- 125000000879 imine group Chemical group 0.000 claims description 7
- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims 1
- 238000003672 processing method Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 20
- 239000002904 solvent Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 14
- 239000003607 modifier Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- 238000001035 drying Methods 0.000 description 11
- 238000006011 modification reaction Methods 0.000 description 11
- 238000004073 vulcanization Methods 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 239000012744 reinforcing agent Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 238000005096 rolling process Methods 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004898 kneading Methods 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N Methyl ethyl ketone Natural products CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- VBKRXPZQAMBGCG-UHFFFAOYSA-N a805811 Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1.CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VBKRXPZQAMBGCG-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 239000003999 initiator Substances 0.000 description 3
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical compound CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- WXWYJCSIHQKADM-ZNAKCYKMSA-N (e)-n-[bis[[(e)-butan-2-ylideneamino]oxy]-ethenylsilyl]oxybutan-2-imine Chemical compound CC\C(C)=N\O[Si](O\N=C(/C)CC)(O\N=C(/C)CC)C=C WXWYJCSIHQKADM-ZNAKCYKMSA-N 0.000 description 2
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 description 2
- OIEANVCCDIRIDJ-UHFFFAOYSA-N 1-ethenyl-5-hexylnaphthalene Chemical compound C1=CC=C2C(CCCCCC)=CC=CC2=C1C=C OIEANVCCDIRIDJ-UHFFFAOYSA-N 0.000 description 2
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- GXDHCNNESPLIKD-UHFFFAOYSA-N 2-methylhexane Natural products CCCCC(C)C GXDHCNNESPLIKD-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Natural products O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-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
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- XIRPMPKSZHNMST-UHFFFAOYSA-N 1-ethenyl-2-phenylbenzene Chemical group C=CC1=CC=CC=C1C1=CC=CC=C1 XIRPMPKSZHNMST-UHFFFAOYSA-N 0.000 description 1
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical compound CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 description 1
- ZXHQLEQLZPJIFG-UHFFFAOYSA-N 1-ethoxyhexane Chemical group CCCCCCOCC ZXHQLEQLZPJIFG-UHFFFAOYSA-N 0.000 description 1
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical group CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 description 1
- CXBDYQVECUFKRK-UHFFFAOYSA-N 1-methoxybutane Chemical group CCCCOC CXBDYQVECUFKRK-UHFFFAOYSA-N 0.000 description 1
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 1
- LHXHDQJZVZUSBV-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(C(=C)C)=C.CC(C(=C)C)=C LHXHDQJZVZUSBV-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- MENUHMSZHZBYMK-UHFFFAOYSA-N 2-cyclohexylethenylbenzene Chemical compound C1CCCCC1C=CC1=CC=CC=C1 MENUHMSZHZBYMK-UHFFFAOYSA-N 0.000 description 1
- GUWMIMDSGCRWSR-UHFFFAOYSA-N 3-(ethoxymethyl)heptane Chemical group CCCCC(CC)COCC GUWMIMDSGCRWSR-UHFFFAOYSA-N 0.000 description 1
- SHUGUNYYEAYLKM-UHFFFAOYSA-N 3-(methoxymethyl)heptane Chemical group CCCCC(CC)COC SHUGUNYYEAYLKM-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Natural products CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Natural products CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- JJJUUMUJLGYXEG-UHFFFAOYSA-N C(CCC)C(C=C)=CCCCC.C(CCC)C(C=C)=CCCCC Chemical compound C(CCC)C(C=C)=CCCCC.C(CCC)C(C=C)=CCCCC JJJUUMUJLGYXEG-UHFFFAOYSA-N 0.000 description 1
- BHXSRLKYVPSYMQ-UHFFFAOYSA-N C=CC=C.C=CC=C Chemical group C=CC=C.C=CC=C BHXSRLKYVPSYMQ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- ICBJCVRQDSQPGI-UHFFFAOYSA-N Methyl hexyl ether Chemical group CCCCCCOC ICBJCVRQDSQPGI-UHFFFAOYSA-N 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 101710110820 Pesticin receptor Proteins 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- WXZIKFXSSPSWSR-UHFFFAOYSA-N [Li]CCCCC Chemical compound [Li]CCCCC WXZIKFXSSPSWSR-UHFFFAOYSA-N 0.000 description 1
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- KSGVXQNNSWGIIB-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C1(=CC=CC=C1)C(=C)C=C.C1(=CC=CC=C1)C(=C)C=C KSGVXQNNSWGIIB-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- BOTLEXFFFSMRLQ-UHFFFAOYSA-N cyclopentyloxycyclopentane Chemical compound C1CCCC1OC1CCCC1 BOTLEXFFFSMRLQ-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HCFAJYNVAYBARA-UHFFFAOYSA-N di-n-propyl ketone Natural products CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- PFCHFHIRKBAQGU-UHFFFAOYSA-N ethyl n-propyl ketone Natural products CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 description 1
- NGAZZOYFWWSOGK-UHFFFAOYSA-N ethyl-n-butyl-ketone Natural products CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- VNKYTQGIUYNRMY-UHFFFAOYSA-N methoxypropane Chemical group CCCOC VNKYTQGIUYNRMY-UHFFFAOYSA-N 0.000 description 1
- XNLICIUVMPYHGG-UHFFFAOYSA-N methyl n-propyl ketone Natural products CCCC(C)=O XNLICIUVMPYHGG-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical group CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 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
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- UCMSRHPIFRZHDO-UHFFFAOYSA-N penta-1,3-diene Chemical compound CC=CC=C.CC=CC=C UCMSRHPIFRZHDO-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 description 1
- 229960002447 thiram Drugs 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 239000012936 vulcanization activator Substances 0.000 description 1
- 238000009736 wetting Methods 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
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Tires In General (AREA)
Abstract
Description
本発明は共役ジエンゴムに関し、特に、アルコキシシランで変性した共役ジエンゴムに関する。 The present invention relates to a conjugated diene rubber, and more particularly to a conjugated diene rubber modified with an alkoxysilane.
溶液重合スチレンブタジエンゴム（ｓｏｌｕｔｉｏｎ Ｓｔｙｒｅｎｅ ｂｕｔａｄｉｅｎｅ ｒｕｂｂｅｒ、ＳＳＢＲ）はブタジエン及びスチレンのユニットから構成される。最初に米国Ｐｈｉｌｌｉｐｓ（フィリップス）社がロット式の製法を提示し、Ｆｉｒｅｓｔｏｎｅ（ファイヤストン）社が連続式のプロセスを開発して工業化生産を実現した。溶液重合スチレンブタジエンゴムは乳化重合スチレンブタジエンゴム（ｅｍｕｌｓｉｏｎ Ｓｔｙｒｅｎｅ ｂｕｔａｄｉｅｎｅ ｒｕｂｂｅｒ、ＥＳＢＲ）より機械性能及び転がり抵抗が優れているため、自動車工業及びその他ゴム製品により広く応用することが可能である。 Solution polymerized styrene butadiene rubber (SSBR) is composed of units of butadiene and styrene. First, Philips (Philips) of the United States presented a lot-type manufacturing method, and Firestone (Firestone) developed a continuous process to realize industrial production. Solution polymerized styrene butadiene rubber has better mechanical performance and rolling resistance than emulsion polymerized styrene butadiene rubber (ESBR), and can be widely applied to the automobile industry and other rubber products.
近年の自動車の低燃費に対する要求が高まるにつれて、タイヤに使用するゴム材料の特性に対するニーズも増加している。共役ジエンゴムは低い転がり抵抗、優れた磨耗抵抗を備え、また耐スリップ性であるため操縦安定性に優れており、需要が高まっている。また、業界はタイヤのゴム組成物中にシリカコンパウンドまたはシリカコンパウンドとカーボンブラックとを補強剤として添加することを提示している。シリカコンパウンドまたはシリカコンパウンドとカーボンブラックとの混合物を含有するタイヤの表面は転がり抵抗が低く、耐スリップ性があり、操縦安定性により優れている。
共役ジエンゴムと補強剤との結合をより良好にするため、業界ではすでに多くの変性共役ジエンゴムの技術が生み出されている。特許文献１では、ＳＢＳブロック共重合体に用いるカップリング剤が開示されており、リチウム含有重合体をシラン含有カップリング剤と反応させて得られる重合体のカップリング率は９０％超であり、且つＳｉ−ＯＲ基が重合体中に存在しない。
As the demand for low fuel consumption of automobiles in recent years increases, the need for characteristics of rubber materials used for tires has also increased. Conjugated diene rubber has low rolling resistance, excellent wear resistance, and is slip resistant, so it has excellent handling stability and is in increasing demand. The industry also suggests adding a silica compound or silica compound and carbon black as a reinforcing agent to the rubber composition of the tire. The surface of a tire containing silica compound or a mixture of silica compound and carbon black has low rolling resistance, slip resistance, and excellent steering stability.
To improve the bond between conjugated diene rubber and reinforcing agent, many modified conjugated diene rubber technologies have already been created in the industry. Patent Document 1 discloses a coupling agent used for an SBS block copolymer, and a coupling rate of a polymer obtained by reacting a lithium-containing polymer with a silane-containing coupling agent is more than 90%, And Si-OR groups are not present in the polymer.
特許文献２では、２段階の変性の手順が開示されており、２種類の変性剤を使用することで、まずリチウム含有重合体のジエン重合体鎖末端をカップリング剤ＲｎＳｉＣｌ４−ｎまたはＲｎＳｎＣｌ４−ｎと反応させ、次にカップリング剤（Ｒ５Ｒ６Ｒ７−Ｓｉ−（ＣＨ２）ｎ−Ｎ−Ｒ８Ｒ９）と反応させて変性する。
特許文献３では、２種類の異なるシラン化合物によるリチウム含有スチレンブタジエンゴムの２段階変性が開示されている。また、特許文献４では、同一のシラン化合物によるリチウム含有スチレンブタジエンゴムの２段階変性が開示されている。
しかしながら、上述の先行技術で合成された変性共役ジエンゴムのプロセスはほとんどが複雑で難しく、実施が容易でないため、業界では先行技術で生じる問題を解決できる新しい共役ジエンゴム変性技術が必要とされている。
In Patent Document 2, a two-step modification procedure is disclosed. By using two kinds of modifiers, the diene polymer chain end of the lithium-containing polymer is first coupled to the coupling agent R n SiCl 4-n or is reacted with R n SnCl 4-n, then a coupling agent (R 5 R 6 R 7 -Si- (CH 2) n -N-R 8 R 9) is reacted to denatured.
Patent Document 3 discloses two-stage modification of lithium-containing styrene butadiene rubber with two different silane compounds. Patent Document 4 discloses two-stage modification of lithium-containing styrene butadiene rubber with the same silane compound.
However, since the processes of the modified conjugated diene rubber synthesized by the above prior art are mostly complicated and difficult and not easy to implement, there is a need in the industry for a new conjugated diene rubber modification technique that can solve the problems caused by the prior art.
本発明の目的は、アルコキシシランで変性した共役ジエンゴムの製造方法と、この方法で変性した共役ジエンゴム及びこの変性共役ジエンゴムを含む組成物とを提供することにある。 An object of the present invention is to provide a method for producing a conjugated diene rubber modified with alkoxysilane, a conjugated diene rubber modified by this method, and a composition containing the modified conjugated diene rubber.
一実施態様において、本発明の変性共役ジエンゴムの製造方法は、アルカリ金属イオンを含む共役ジエンゴムを提供する工程（ａ）と、前記アルカリ金属イオンを含む共役ジエンゴムをアルコキシシランと反応させ、前記変性共役ジエンゴムを生成する工程（ｂ）とを含み、前記アルコキシシランの構造式（Ｉ）が、 In one embodiment, the method for producing a modified conjugated diene rubber of the present invention comprises the step (a) of providing a conjugated diene rubber containing an alkali metal ion, the conjugated diene rubber containing the alkali metal ion is reacted with an alkoxysilane, and the modified conjugate. A step (b) of producing a diene rubber, wherein the structural formula (I) of the alkoxysilane is
一実施態様において、本発明の変性共役ジエンゴムの構造式は、 In one embodiment, the structural formula of the modified conjugated diene rubber of the present invention is:
本発明はその他の問題を解決するその他の特徴及び各種実施態様を含み、上述の特徴と合わせて、以下の実施形態で詳細に説明する。 The present invention includes other features and various embodiments that solve other problems, and will be described in detail in the following embodiments together with the features described above.
以下、本発明の最良の実施態様を説明する。本発明の内容を明確にするために、以下の説明では公知の部材、関連材料、及び関連処理技術について省略する場合がある。以下の説明は本発明の最良の実施態様を示すものであり、本発明の特許請求の範囲を限定するものではなく、その他、本発明の開示する要旨を逸脱せずに完成された変更または修正は、いずれも以下に述べる特許請求の範囲に含まれるものである。
重合反応：アルカリ金属イオンを含む共役ジエンゴムの調製
本発明のアルカリ金属イオンを含む共役ジエンゴムの製造方法は、好適な溶剤中で、アニオン重合法を利用して、有機アルカリ金属化合物を開始剤として共役ジエンモノマーまたは共役ジエンモノマー及びビニル芳香族炭化水素モノマーを重合し、アルカリ金属イオンを含む共役ジエンゴムを形成することを含む。
The best mode of the present invention will be described below. In order to clarify the contents of the present invention, in the following description, known members, related materials, and related processing techniques may be omitted. The following description shows the best mode of the present invention, and does not limit the scope of the claims of the present invention. Other changes or modifications completed without departing from the gist of the present invention are described below. Are included in the scope of the claims described below.
Polymerization Reaction: Preparation of Conjugated Diene Rubber Containing Alkali Metal Ions The method for producing a conjugated diene rubber containing alkali metal ions of the present invention is conjugated using an organic alkali metal compound as an initiator in a suitable solvent using an anionic polymerization method. Polymerizing a diene monomer or a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer to form a conjugated diene rubber containing alkali metal ions.
本発明の重合体は、共役ジエンモノマー重合体、または共役ジエンモノマー（例えばブタジエン（ｂｕｔａｄｉｅｎｅ）またはイソプレン（ｉｓｏｐｒｅｎｅ））とビニル芳香族炭化水素モノマー（例えばスチレン（Ｓｔｙｒｅｎｅ）またはメチルスチレン（ｍｅｔｈｙｌ Ｓｔｙｒｅｎｅ））の共重合体とすることができる。本発明の共役ジエンゴムの重合モノマーはブタジエン、イソプレン、及びスチレンに限定されず、上述のあらゆる好適な誘導体を本発明に用いることができる。例えば、共役ジエンモノマーは独立して、１，３−ブタジエン（１，３−ｂｕｔａｄｉｅｎｅ）、２，３−ジメチル−１，３−ブタジエン（２，３−ｄｉｍｅｔｈｙｌ−１，３−ｂｕｔａｄｉｅｎｅ）、３−ブチル−１，３−オクタジエン（３−ｂｕｔｙｌ−１，３−ｏｃｔａｄｉｅｎｅ）、イソプレン（ｉｓｏｐｒｅｎｅ）、１−メチルブタジエン（１−ｍｅｔｈｙｌｂｕｔａｄｉｅｎｅ）、２−フェニル−１，３−ブタジエン（２−ｐｈｅｎｙｌ−１，３−ｂｕｔａｄｉｅｎｅ）及びそれらの任意の組み合わせで構成される群から選択することができる。ビニル芳香族炭化水素モノマーは独立して、スチレン（Ｓｔｙｒｅｎｅ）、メチルスチレン（ｍｅｔｈｙｌｓｔｙｒｅｎｅ）及びそのあらゆる異性体、エチルスチレン（ｅｔｈｙｌｓｔｙｒｅｎｅ）及びそのあらゆる異性体、シクロヘキシルスチレン（ｃｙｃｌｏｈｅｘｙｌｓｔｙｒｅｎｅ）、ビニルビフェニル（ｖｉｎｙｌ ｂｉｐｈｅｎｙｌ）、１−ビニル−５−ヘキシルナフタレン（１−ｖｉｎｙｌ−５−ｈｅｘｙｌ ｎａｐｈｔｈａｌｅｎｅ）、ビニルナフタレン（ｖｉｎｙｌ ｎａｐｈｔｈａｌｅｎｅ）、ビニルアントラセン（ｖｉｎｙｌ ａｎｔｈｒａｃｅｎｅ）及びそれらの任意の組み合わせで構成される群から選択することができる。 The polymer of the present invention is a conjugated diene monomer polymer, or a conjugated diene monomer (eg, butadiene or isoprene) and a vinyl aromatic hydrocarbon monomer (eg, styrene or methyl styrene). It can be set as a copolymer. The polymerization monomer of the conjugated diene rubber of the present invention is not limited to butadiene, isoprene and styrene, and any suitable derivative described above can be used in the present invention. For example, the conjugated diene monomer is independently 1,3-butadiene (1,3-butadiene), 2,3-dimethyl-1,3-butadiene (2,3-dimethyl-1,3-butadiene), 3- Butyl-1,3-octadiene (3-butyl-1,3-octadiene), isoprene, 1-methylbutadiene (1-methylbutadiene), 2-phenyl-1,3-butadiene (2-phenyl-1, 3-butadiene) and any combination thereof. Vinyl aromatic hydrocarbon monomers are independently styrene, methylstyrene and any isomer thereof, ethylstyrene and any isomer thereof, cyclohexylstyrene, vinyl biphenyl. , 1-vinyl-5-hexylnaphthalene, vinyl naphthalene, vinyl anthracene, and any combination thereof may be selected from the group consisting of 1-vinyl-5-hexylnaphthalene, vinyl naphthalene, vinyl anthracene, and any combination thereof .
重合を行うとき、有機リチウム化合物を開始剤として使用することが好適な選択であり、これにより分子鎖末端に炭素リチウムイオンを有するアルカリ金属イオン共役ジエンゴムが得られる。有機リチウム開始剤の具体的な例には、ｎ−プロピルリチウム、イソプロピルリチウム、ｎ−ブチルリチウム、ｓｅｃ−ブチルリチウム、ｔｅｒｔ−ブチルリチウム、ｎ−ペンチルリチウム、フェニルリチウム、トリルリチウム等が含まれ、ｎ−ブチルリチウムが好ましい。 When polymerizing, it is a preferred choice to use an organolithium compound as an initiator, thereby obtaining an alkali metal ion conjugated diene rubber having a carbon lithium ion at the end of the molecular chain. Specific examples of the organic lithium initiator include n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, n-pentyl lithium, phenyl lithium, tolyl lithium, and the like. n-Butyl lithium is preferred.
重合反応に用いる溶剤は、例えば不活性有機溶剤など、重合反応において反応に参与しない溶剤が適しており、このような溶剤には、ブタン、イソブタン、ペンタン、ｎ−ペンタン、イソペンタン、２,２,４−トリメチルペンタン、イソヘキサン、ｎ−ヘキサン、イソヘプタン、ｎ−ヘプタン、イソオクタン、ｎ−オクタンなどの脂肪族炭化水素化合物、またはシクロヘキサン、メチルシクロヘキサン、エチルシクロヘキサン、シクロペンタン、シクロヘプタン、メチルシクロペンタンなどの脂環式炭化水素類、またはベンゼン、トルエン、キシレン、エチルベンゼン、ジエチルベンゼン、プロピルベンゼンなどの芳香族炭化水素化合物を含み、本発明においてはシクロヘキサンが好適である。共役ジエンゴムの重合溶液濃度は一般に５％〜３５％であり、１０％〜３０％が好適である。一般的な状況下で、単純に不活性有機溶剤を溶剤として使用する場合、ビニル芳香族炭化水素または共役ジエンの重合速度が比較的遅く、かつ両者の重合反応性の差異が非常に大きいが、このとき極性溶剤を加える方法でこれを克服できる。本発明に適用する極性溶剤の具体的な例には、テトラヒドロフラン、ジエチルエーテル、シクロペンチルエーテル、ジプロピルエーテル、エチレングリコールジメチルエーテル、エチレングリコールモノメチルエーテル、ジエチレングリコール、ジメチルエーテル、エチルメチルエーテル等のエーテル化合物、テトラメチルエチレンジアミンが含まれ、テトラヒドロフラン及びジエチルエーテルが好適である。 As the solvent used for the polymerization reaction, a solvent that does not participate in the polymerization reaction, such as an inert organic solvent, is suitable. Examples of such a solvent include butane, isobutane, pentane, n-pentane, isopentane, 2,2, Aliphatic hydrocarbon compounds such as 4-trimethylpentane, isohexane, n-hexane, isoheptane, n-heptane, isooctane, n-octane, or cyclohexane, methylcyclohexane, ethylcyclohexane, cyclopentane, cycloheptane, methylcyclopentane, etc. Including the alicyclic hydrocarbons or aromatic hydrocarbon compounds such as benzene, toluene, xylene, ethylbenzene, diethylbenzene and propylbenzene, cyclohexane is preferred in the present invention. The concentration of the conjugated diene rubber in the polymerization solution is generally 5% to 35%, preferably 10% to 30%. Under ordinary circumstances, when an inert organic solvent is simply used as a solvent, the polymerization rate of vinyl aromatic hydrocarbon or conjugated diene is relatively slow, and the difference in polymerization reactivity between the two is very large. At this time, this can be overcome by adding a polar solvent. Specific examples of polar solvents applied to the present invention include tetrahydrofuran, diethyl ether, cyclopentyl ether, dipropyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether, diethylene glycol, dimethyl ether, ethyl methyl ether and other ether compounds, tetramethyl Ethylenediamine is included, and tetrahydrofuran and diethyl ether are preferred.
重合の開始温度は１０℃〜８０℃、最終温度は３０℃〜１５０℃とすることができ、温度の制御方法は断熱反応方式を使用でき、または恒温制御を採用するか、あるいは部分冷却方式を採用してもよい。
本発明の重合体中の共役ジエン／ビニル芳香族炭化水素の重量比は１００／０〜５０／５０であり、９５／５〜５５／４５が好ましく、８５／１５〜６０／４０がより好ましい。
本発明の各実施態様において、重合が完了した後でまだ変性剤と反応させていない重合体の初期数平均分子量（Ｍｉ）は８０ｋｇ／ｍｏｌｅ〜２０００ｋｇ／ｍｏｌｅ、好ましくは１００ｋｇ／ｍｏｌｅ〜１５００ｋｇ／ｍｏｌｅの間、より好ましくは１５０ｋｇ／ｍｏｌｅ〜１０００ｋｇ／ｍｏｌｅの間とする。数平均分子量の測定にはゲル浸透クロマトグラフィー（ｇｅｌ ｐｅｒｍｅａｔｉｏｎ ｃｈｒｏｍａｔｏｇｒａｐｈｙ、ＧＰＣ）を使用するが、これは当業者の常用する方法である。
変性反応：アルカリ金属イオンを含む共役ジエンゴムとアルコキシシランの反応
本発明の変性反応に使用する変性剤はアルコキシシランであり、構造式（Ｉ）
The starting temperature of the polymerization can be 10 ° C to 80 ° C, the final temperature can be 30 ° C to 150 ° C, the temperature control method can use an adiabatic reaction method, or adopt a constant temperature control, or a partial cooling method It may be adopted.
The weight ratio of conjugated diene / vinyl aromatic hydrocarbon in the polymer of the present invention is 100/0 to 50/50, preferably 95/5 to 55/45, and more preferably 85/15 to 60/40.
In each embodiment of the present invention, the initial number average molecular weight (Mi) of the polymer not yet reacted with the modifier after the polymerization is completed is 80 kg / mole to 2000 kg / mole, preferably 100 kg / mole to 1500 kg / mole. More preferably between 150 kg / mole and 1000 kg / mole. For the measurement of the number average molecular weight, gel permeation chromatography (GPC) is used, which is a method commonly used by those skilled in the art.
Modification Reaction: Reaction of Conjugated Diene Rubber Containing Alkali Metal Ion with Alkoxysilane The modifier used in the modification reaction of the present invention is alkoxysilane, and has the structural formula (I)
本発明の各実施態様において、Ｒ１、Ｒ２、Ｒ３の示すＣ２〜Ｃ１２の含酸素基はＣ２〜Ｃ１２のエーテル基が好適であり、Ｒ１、Ｒ２、Ｒ３は同一または異なる含酸素基とすることができる。エーテル基の好適な例は、一般式−ＣｍＨ２ｍ−Ｏ−ＣｎＨ２ｎ＋１で表され、ここでｍ及びｎは正の整数であり、かつｍ＋ｎ＝２〜１２である。Ｃ２〜Ｃ１２の含酸素基の好適な例は、ジメチルエーテル基（ＣＨ３−Ｏ−ＣＨ２−）、メトキシエトキシ基（ＣＨ３−Ｏ−Ｃ２Ｈ４−）、メチルプロピルエーテル基、メチル−ｎ−ブチルエーテル基、メチル−ｔｅｒｔ−ブチルエーテル基、メチル−n−ヘキシルエーテル基（ＣＨ３−Ｏ−Ｃ６Ｈ１２−）、ジエチルエーテル基、エチルメチルエーテル基（Ｃ２Ｈ５−Ｏ−ＣＨ２−）、エチルプロピルエーテル基（Ｃ２Ｈ５−Ｏ−Ｃ３Ｈ６−）、エチル−ｎ−ブチルエーテル基、エチル−ｔｅｒｔ−ブチルエーテル基、エチル−ｎ−ヘキシルエーテル基、メチル２−エチルヘキシルエーテル基（ＣＨ３−Ｏ−Ｃ４Ｈ８−ＣＨ（Ｃ２Ｈ５）−ＣＨ２−）、エチル２−エチルヘキシルエーテル基（Ｃ２Ｈ５−Ｏ−Ｃ４Ｈ８−ＣＨ（Ｃ２Ｈ５）−ＣＨ２−）などがあるが、ここで、−Ｃ２Ｈ４−Ｏ−ＣＨ３（メトキシエトキシ基）を特に好適な選択とする。 In embodiments of the present invention, oxygen-containing groups of the C 2 -C 12 indicated by R 1, R 2, R 3 is preferably an ether group of C 2 -C 12, R 1, R 2, R 3 is It can be the same or different oxygen-containing groups. Preferred examples of ether group is represented by the general formula -C m H 2m -O-C n H 2n + 1, where m and n are positive integers, and a m + n = 2 to 12. Suitable examples of the C 2 to C 12 oxygen-containing group include a dimethyl ether group (CH 3 —O—CH 2 —), a methoxyethoxy group (CH 3 —O—C 2 H 4 —), a methyl propyl ether group, methyl -n- butyl ether group, a methyl -tert- ether group, methyl -n- hexyl ether group (CH 3 -O-C 6 H 12 -), diethyl ether, ethyl methyl ether group (C 2 H 5 -O-CH 2 -), ethyl propyl ether group (C 2 H 5 -O-C 3 H 6 -), ethyl -n- butyl ether, ethyl -tert- butyl ether, ethyl -n- hexyl ether group, methyl 2-ethylhexyl ether group (CH 3 -O-C 4 H 8 -CH (C 2 H 5) -CH 2 -), ethyl 2-ethylhexyl ether group (C 2 H 5 - -C 4 H 8 -CH (C 2 H 5) -CH 2 -) but the like, where a particularly preferred choice of -C 2 H 4 -O-CH 3 ( methoxyethoxy group).
本発明の各実施態様において、Ｒ１、Ｒ２、Ｒ３の示すＣ１〜Ｃ１２の含窒素基は好ましくはＣ１〜Ｃ１２のイミン基（ｉｍｉｎｅ）を含み、ここでＲ１、Ｒ２、Ｒ３は同一または異なる含窒素基である。イミン基の好適な例は、一般式（ＣnＨ２ｎ＋１）（ＣｍＨ２ｍ＋１）Ｃ＝Ｎ−で表されるものを用いることができ、ここでｍ＝０〜１０、ｎ＝１〜１１の整数である。含窒素基のイミン基の好適な例は、ジメチルケトンイミン基（（ＣＨ３）２Ｃ＝Ｎ−）、ジエチルケトンイミン基、ジプロピルケトンイミン基、ジ−ｎ−ブチルケトンイミン基、ジ−ｔｅｒｔ−ブチルケトンイミン基、メチルエチルケトンイミン基（ＣＨ３（ＣＨ２ＣＨ３）Ｃ＝Ｎ−）、メチルプロピルケトンイミン基、メチル−ｎ−ブチルケトンイミン基、メチル−ｔｅｒｔ−ブチルケトンイミン基、エチルプロピルケトンイミン基、エチル−ｎ−ブチルケトンイミン基、エチル−ｔｅｒｔ−ブチルケトンイミン基、フォルムアルデヒドイミン基（（ＣＨ３）ＣＨ＝Ｎ−）、アセトアルデヒドイミン基（（Ｃ２Ｈ５）ＣＨ＝Ｎ−）、プロピルアルデヒドイミン基（（Ｃ３Ｈ７）ＣＨ＝Ｎ−）、ジ−ｎ−ブチルケトンイミン基、ジ−ｔｅｒｔ−ブチルケトンイミン基などがあり、ここでメチルエチルケトンイミン基（−Ｎ＝Ｃ（ＣＨ２ＣＨ３）ＣＨ３）が特に好適な選択である。 In each embodiment of the present invention, the C 1 -C 12 nitrogen-containing group represented by R 1 , R 2 , R 3 preferably contains a C 1 -C 12 imine group, where R 1 , R 2 and R 3 are the same or different nitrogen-containing groups. Suitable examples of the imine group may include those represented by the general formula (C n H 2n + 1 ) (C m H 2m + 1 ) C═N—, where m = 0 to 10, n = 1 to 11 Is an integer. Preferable examples of the imine group of the nitrogen-containing group include dimethyl ketone imine group ((CH 3 ) 2 C═N—), diethyl ketone imine group, dipropyl ketone imine group, di-n-butyl ketone imine group, di- tert- butyl ketone imine group, methyl ethyl ketone imine group (CH 3 (CH 2 CH 3 ) C = N-), methyl propyl ketone imine group, methyl -n- butyl ketone imine group, methyl -tert- butyl ketone imine group, ethyl Propyl ketone imine group, ethyl-n-butyl ketone imine group, ethyl tert-butyl ketone imine group, formaldehyde imine group ((CH 3 ) CH═N—), acetaldehyde imine group ((C 2 H 5 ) CH═ N-), propyl aldehyde imine group ((C 3 H 7) CH = N-), di -n- butyl ketone imine group Include di -tert- butyl ketone imine group, wherein the methyl ethyl ketone imine group (-N = C (CH 2 CH 3) CH 3) is particularly preferred choice.
本発明の各実施態様において、Ｒ４はＣ１〜Ｃ１２のアルキル基、アルケニル基、アリール基、アルコキシ基で構成される群から選択され、その例にはメチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｔｅｒｔ−ブチル基、ヘキシル基、２−エチルヘキシル基、ビニル基（ｖｉｎｙｌ）、プロピルアルケニル基、ブチルアルケニル基、ヘキシルアルケニル基、フェニル基、トルエン基、エチルベンゼン基、キシレン基、プロピルベンゼン基、メチルアルコキシ基、エチルアルコキシ基、プロピルアルコキシ基、ｎ−ブチルアルコキシ基、イソブチルアルコキシ基があり、ここでＣＨ＝ＣＨ２（ビニル基）が特に好適な選択である。
変性反応の進行時、変性剤アルコキシシランはアルカリ金属イオンを含む共役ジエンゴムのジエン鎖末端と結合する。変性剤アルコキシシランのアルカリ金属イオン含有共役ジエンゴムに対するモル比は≧０.５であり、好ましくは≧０.６、より好ましくは≧０.７であるが、１０未満でなければならない。
上述の変性反応を経た共役ジエンゴムからは、直接溶剤が除去され、かつ水とは接触させない。この変性共役ジエンゴムのムーニー粘度は１０〜１５０であり、好ましくは１５〜１３０である。
In each embodiment of the present invention, R 4 is selected from the group consisting of C 1 to C 12 alkyl groups, alkenyl groups, aryl groups, alkoxy groups, examples of which include methyl, ethyl, propyl, Isopropyl group, n-butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, vinyl group (vinyl), propylalkenyl group, butylalkenyl group, hexylalkenyl group, phenyl group, toluene group, ethylbenzene group , xylene, propyl benzene group, methylalkoxy group, an ethyl alkoxy group, a propyl alkoxy group, n- butyl alkoxy group, there is isobutyl alkoxy group, wherein CH = CH 2 (vinyl group) is particularly preferred choice.
As the modification reaction proceeds, the modifier alkoxysilane binds to the diene chain end of the conjugated diene rubber containing alkali metal ions. The molar ratio of modifier alkoxysilane to alkali metal ion-containing conjugated diene rubber is ≧ 0.5, preferably ≧ 0.6, more preferably ≧ 0.7, but it must be less than 10.
The solvent is directly removed from the conjugated diene rubber that has undergone the above-described modification reaction, and is not brought into contact with water. This modified conjugated diene rubber has a Mooney viscosity of 10 to 150, preferably 15 to 130.
変性共役ジエンゴム
上述の変性反応を経た後、構造式（ＩＩ）の変性共役ジエンゴムを形成することができる。
Modified Conjugated Diene Rubber After undergoing the above-described modification reaction, a modified conjugated diene rubber of the structural formula (II) can be formed.
ここで、Ｄは共役ジエンモノマーまたは共役ジエンモノマーとビニル基芳香族モノマーから構成される重合体であり、Ｒ２、Ｒ３はそれぞれ独立してＣ２〜Ｃ１２の含酸素基及びＣ１〜Ｃ１２の含窒素基で構成される群から選択され、前記Ｃ２〜Ｃ１２の含酸素基はその炭素原子で直接前記アルコキシシランの酸素原子と結合され、前記Ｃ１〜Ｃ１２の含窒素基はその窒素原子で直接前記アルコキシシランの酸素原子と結合され、Ｒ４はＣ１〜Ｃ１２を含むアルキル基、アルケニル基、アリール基、アルコキシ基で構成される群から選択される。好適な実施態様において、Ｃ２〜Ｃ１２の含酸素基は一般式−ＣｍＨ２ｍ−Ｏ−ＣｎＨ２ｎ＋１で表されるエーテル基であり、ここでｍ及びｎは正の整数であり、かつｍ＋ｎ＝２〜１２である。ここで、特に−ＣＨ２ＣＨ２ＯＣＨ３で表される含酸素基が好適である。好適な実施態様において、Ｃ１〜Ｃ１２の含窒素基は、一般式（ＣｎＨ２ｎ＋１）（ＣｍＨ２ｍ＋１）Ｃ＝Ｎ−で表されるイミン基（ｉｍｉｎｅ ｇｒｏｕｐ）であり、ここでｍ＝０〜１０、ｎ＝１〜１１の整数であり、特に−Ｎ＝Ｃ（ＣＨ２ＣＨ３）ＣＨ３で表される含窒素基が好適である。Ｄ、Ｒ２、Ｒ３、Ｒ４の具体的な例については上述の重合及び変性反応の説明を参照できる。 Here, D is a polymer composed of a conjugated diene monomer or a conjugated diene monomer and a vinyl group aromatic monomer, and R 2 and R 3 are each independently an oxygen-containing group of C 2 to C 12 and C 1 to Selected from the group consisting of C 12 nitrogen-containing groups, wherein the C 2 -C 12 oxygen-containing groups are directly bonded to the oxygen atoms of the alkoxysilane at their carbon atoms, and the C 1 -C 12 nitrogen-containing groups The group is directly bonded to the oxygen atom of the alkoxysilane at the nitrogen atom, and R 4 is selected from the group consisting of an alkyl group containing C 1 to C 12 , an alkenyl group, an aryl group, and an alkoxy group. In a preferred embodiment, the C 2 to C 12 oxygen-containing group is an ether group represented by the general formula —C m H 2m —O—C n H 2n + 1 , wherein m and n are positive integers. And m + n = 2-12. Here, an oxygen-containing group represented by —CH 2 CH 2 OCH 3 is particularly preferable. In a preferred embodiment, the C 1 -C 12 nitrogen-containing group is an imine group represented by the general formula (C n H 2n + 1 ) (C m H 2m + 1 ) C═N—, A nitrogen-containing group represented by m = 0 to 10 and n = 1 to 11 and particularly represented by —N═C (CH 2 CH 3 ) CH 3 is preferred. For specific examples of D, R 2 , R 3 , and R 4 , the description of the polymerization and modification reaction described above can be referred to.
水接触反応
本発明の別の態様は、変性共役ジエンゴムを大量の水と接触させ、ムーニー粘度の安定性をより一層改善する。変性共役ジエンゴムと水との接触方法は、水蒸気ストリッピング（ｓｔｅａｍ ｓｔｒｉｐｐｉｎｇ）の方法またはその他適した方法を含む。水蒸気ストリッピングを例とすると、溶剤を含有する変性共役ジエンゴム溶液を水と接触させることができ、温度は１５０℃より低く制御し、ここで、変性共役ジエンゴム溶液中に含まれる溶剤に対する水の重量比は０.１以上とし、好ましくは０.５以上、より好ましくは１以上とし、かつｐＨを４〜１０の間にする。両者の接触時の温度は２０〜１５０℃とし、好ましくは３０〜１４０℃、より好ましくは４０〜１３０℃とする。両者の接触時間は５分間〜１０時間とし、好ましくは１０分間〜８時間、より好ましくは３０分間〜６時間とする。変性共役ジエンゴム溶液と水を接触させると同時に、または接触させた後、蒸気、電熱、熱気またはその他の熱源脱着溶剤を利用し、さらに例えば機械脱水、ベーキング乾燥またはエプロン乾燥（ａｐｒｏｎ ｄｒｙｅｒ）方式など既知の乾燥方法により処理するか、または、例えばゴムを１１０℃下でホットロール（ｈｏｔ ｒｏｌｌ）乾燥することができる。本発明の変性を経た共役ジエンゴムは、上述の水接触処理を経た後に測定したカップリング率が１０％〜９５％であり、好ましくは２０〜８０％、より好ましくは２５〜７５％、最も好ましくは３０〜７０％である。
上述の水接触処理を経て、溶剤除去及び乾燥を行った後の変性共役ジエンゴムのムーニー粘度は１５〜１５０であり、好ましくは２５〜１２０、より好ましくは３０〜１００である。
Water Contact Reaction Another aspect of the present invention is that the modified conjugated diene rubber is contacted with a large amount of water to further improve Mooney viscosity stability. Methods for contacting the modified conjugated diene rubber with water include steam stripping methods or other suitable methods. Taking steam stripping as an example, a modified conjugated diene rubber solution containing a solvent can be contacted with water and the temperature is controlled below 150 ° C., where the weight of water relative to the solvent contained in the modified conjugated diene rubber solution. The ratio is 0.1 or more, preferably 0.5 or more, more preferably 1 or more, and the pH is between 4 and 10. The temperature at the time of contact between the two is 20 to 150 ° C, preferably 30 to 140 ° C, more preferably 40 to 130 ° C. The contact time between them is 5 minutes to 10 hours, preferably 10 minutes to 8 hours, more preferably 30 minutes to 6 hours. At the same time as or after contacting the modified conjugated diene rubber solution with water, steam, electric heat, hot air or other heat source desorption solvent is used, and further known, for example, mechanical dehydration, baking drying, or apron drying method Or the rubber can be hot roll dried at 110 ° C., for example. The conjugated diene rubber having undergone the modification of the present invention has a coupling rate of 10% to 95%, preferably 20 to 80%, more preferably 25 to 75%, most preferably measured after the water contact treatment described above. 30-70%.
The Mooney viscosity of the modified conjugated diene rubber after solvent removal and drying through the water contact treatment described above is 15 to 150, preferably 25 to 120, and more preferably 30 to 100.
共役ジエンゴムの組成物
本発明の変性共役ジエンゴムは、他のゴム成分と混合して共役ジエンゴム組成物を形成することができる。他のゴム成分の具体的な例には、従来のスチレン−ブタジエン共重合体ゴム、ポリブタジエンゴム、ブタジエン−イソプレン共重合体ゴム、及びブチルゴムが含まれる。具体的な例としては、さらに天然ゴム、エチレン−プロピレン共重合体ゴム、及びエチレンオクテン共重合体ゴムが含まれる。上述の組成は２種類または多種類の形式の混合を応用できる。変性共役ジエンゴムを含む共役ジエンゴム組成物の組成は、全部のゴム成分の総量が１００重量部であるとき、変性共役ジエンゴムの含量が好ましくは少なくとも１０重量部、より好ましくは少なくとも２０重量部とすることができる。
Composition of Conjugated Diene Rubber The modified conjugated diene rubber of the present invention can be mixed with other rubber components to form a conjugated diene rubber composition. Specific examples of other rubber components include conventional styrene-butadiene copolymer rubber, polybutadiene rubber, butadiene-isoprene copolymer rubber, and butyl rubber. Specific examples further include natural rubber, ethylene-propylene copolymer rubber, and ethylene octene copolymer rubber. The above composition can be applied in two or more types of mixing. The composition of the conjugated diene rubber composition containing the modified conjugated diene rubber is such that when the total amount of all rubber components is 100 parts by weight, the content of the modified conjugated diene rubber is preferably at least 10 parts by weight, more preferably at least 20 parts by weight. Can do.
さらに、本発明の共役ジエンゴム組成物は添加剤を含有してもよい。添加剤の具体的な例には、例えば、硫黄などの加硫剤、例えばチアゾール系（ｔｈｉａｚｏｌｅ−ｂａｓｅｄ）加硫促進剤、チウラム系（ｔｈｉｕｒａｍ−ｂａｓｅｄ）加硫促進剤またはスルフェンアミド系（ｓｕｌｆｅｎａｍｉｄｅ−ｂａｓｅｄ）加硫促進剤などの加硫促進剤、例えばステアリン酸または酸化亜鉛などの加硫活性剤、 有機過酸化物、例えばシリカコンパウンドまたはカーボンブラックなどの補強剤、例えば炭酸カルシウムまたは滑石などの充填剤、シランカップリング剤、充填油、加工助剤、抗酸化剤、及び潤滑剤等が含まれる。
シリカコンパウンドを補強剤として本発明の共役ジエンゴム組成物に混合した実施態様において、全部のゴム成分の総量が１００重量部であるとき、シリカコンパウンドの含量は通常１０重量部〜２００重量部である。燃費の観点から見た場合、混合する量は少なくとも２０重量部が好ましく、かつ少なくとも３０重量部がより好ましい。補強効果の観点から見た場合、好ましくは１８０重量部を超過せず、より好ましくは１５０重量部を超過しない。シリカコンパウンドは非晶質合成シリカコンパウンドとすることができ、例えば可溶性珪酸塩（例えば珪酸ナトリウムまたは珪酸塩とアルミン酸塩との共沈物）の酸性化により得ることができる。一般に、このような沈殿シリカコンパウンドは当業者に公知である。合成シリカコンパウンド（沈殿シリカコンパウンド）のＢＥＴ比表面積は、窒素で測定し、例えば約５０〜約３００平方メートル／グラムの間の範囲とすることができ、また約１００〜約２５０平方メートル／グラムの間の範囲を選択してもよい。シリカコンパウンドは例えば約１００ｃｃ／ｇ〜約５００ｃｃ／ｇの間の範囲、より好ましくは約１２０ｃｃ／ｇ〜約３５０ｃｃ／ｇの間の範囲のフタル酸ジブチル（ｄｉｂｕｔｙｌｐｈｔｈａｌａｔｅ、ＤＢＰ）吸収値を有してもよい。その他各種商業的に市販されている合成シリカコンパウンドを本発明に使用することを考慮してもよく、例えばＨｉ−Ｓｉｌ（商標）型番２１０、２４３等のＰＰＧ Ｉｎｄｕｓｔｒｉｅｓ提供の商業的に市販されているシリカコンパウンド、例えば商品型番Ｚｅｏｓｉｌ １１６５ＭＰとＺｅｏｓｉｌ １６５ＧＲなどＲｈｏｄｉａ社提供の商業的に市販されているシリカコンパウンド、例えば商品型番ＶＮ２、ＶＮ３、７０００ＧＲ、９０００ＧＲなどのＥＶＯＮＩＫ社提供の商業的に市販されているシリカコンパウンド、及び例えば商品型番Ｚｅｏｐｏｌ ８７４５などのＨｕｂｅｒ提供の商業的に市販されているシリカコンパウンドを含み、またこれに限らない。
Furthermore, the conjugated diene rubber composition of the present invention may contain an additive. Specific examples of additives include, for example, vulcanizing agents such as sulfur, such as thiazole-based vulcanization accelerators, thiuram-based vulcanization accelerators, or sulfenamides. -Based) vulcanization accelerators such as vulcanization accelerators, for example vulcanization activators such as stearic acid or zinc oxide, organic peroxides such as silica compounds or reinforcing agents such as carbon black, such as calcium carbonate or talc Fillers, silane coupling agents, filler oils, processing aids, antioxidants, lubricants and the like are included.
In the embodiment in which the silica compound is mixed with the conjugated diene rubber composition of the present invention as a reinforcing agent, when the total amount of all rubber components is 100 parts by weight, the content of the silica compound is usually 10 parts by weight to 200 parts by weight. From the viewpoint of fuel consumption, the amount to be mixed is preferably at least 20 parts by weight, and more preferably at least 30 parts by weight. From the viewpoint of the reinforcing effect, it preferably does not exceed 180 parts by weight, and more preferably does not exceed 150 parts by weight. The silica compound can be an amorphous synthetic silica compound and can be obtained, for example, by acidification of a soluble silicate (eg sodium silicate or a coprecipitate of silicate and aluminate). In general, such precipitated silica compounds are known to those skilled in the art. The BET specific surface area of synthetic silica compounds (precipitated silica compounds), measured with nitrogen, can range, for example, between about 50 to about 300 square meters / gram, and between about 100 to about 250 square meters / gram. A range may be selected. The silica compound may have a dibutyl phthalate (DBP) absorption value in the range of, for example, between about 100 cc / g and about 500 cc / g, more preferably between about 120 cc / g and about 350 cc / g. Good. Various other commercially available synthetic silica compounds may be considered for use in the present invention, such as those commercially available from PPG Industries, such as Hi-Sil ™ model numbers 210 and 243. Silica compounds, for example, commercially available silica compounds provided by Rhodia, such as product model number Zeosil 1165MP and Zeosil 165GR, for example, commercially available silica products provided by EVONIK, such as product model numbers VN2, VN3, 7000GR, 9000GR Including, but not limited to, compounds and commercially available silica compounds provided by Huber such as, for example, product model number Zeol 8745.
非シリカコンパウンドを補強剤として本発明の共役ジエンゴム組成物に混合した実施態様において、補強効果の観点から見た場合、全部のゴム成分の総量が１００重量部のとき、前記非シリカコンパウンド補強剤の含量は好ましくは１２０重量部を超過せず、かつより好ましくは１００重量部を超過しない。燃費の観点から見た場合、少なくとも１重量部が好ましく、かつ少なくとも３重量部がより好ましい。非シリカコンパウンド補強剤の好ましい具体的な例はカーボンブラックである。 In an embodiment in which a non-silica compound is mixed as a reinforcing agent with the conjugated diene rubber composition of the present invention, when viewed from the viewpoint of the reinforcing effect, when the total amount of all rubber components is 100 parts by weight, the non-silica compound reinforcing agent The content preferably does not exceed 120 parts by weight and more preferably does not exceed 100 parts by weight. From the viewpoint of fuel consumption, at least 1 part by weight is preferable, and at least 3 parts by weight is more preferable. A preferred specific example of a non-silica compound reinforcing agent is carbon black.
本発明の変性共役ジエンゴムと別のゴム成分、添加剤等を混合して共役ジエンゴム組成物を製造する方法は、例えばローラー、またはバンバリーミキサー（Ｂａｎｂｕｒｙ ｍｉｘｅｒ）、またはインターナルミキサーなどの従来のミキサーを使用して各組成成分を混練する方法とすることができる。混練の条件は、加硫剤または加硫促進剤を除き、添加剤、充填剤、シリカコンパウンド及び／またはその他の補強剤を混合するとき、混練温度は通常５０℃〜２００℃であり、８０℃〜１５０℃が好ましく、混練時間は通常３０秒〜３０分間であり、１分間〜３０分間が好ましい。加硫剤または加硫促進剤を混合するとき、混練温度は通常１００℃を超過せず、２５℃〜９０℃が好ましい。加硫剤または加硫促進剤の混合は、例えばプレス加硫（ｐｒｅｓｓ ｖｕｌｃａｎｉｚａｔｉｏｎ）を使用した加硫処理方式で行うことができる。加硫処理温度は通常１２０℃〜２００℃であり、１４０℃〜１８０℃が好ましい。 A method for producing a conjugated diene rubber composition by mixing the modified conjugated diene rubber of the present invention with another rubber component, an additive, etc. is performed using, for example, a roller, a Banbury mixer, or a conventional mixer such as an internal mixer. It can be used as a method of kneading each composition component. The kneading conditions are such that when the additive, filler, silica compound and / or other reinforcing agent are mixed, except for the vulcanizing agent or vulcanization accelerator, the kneading temperature is usually 50 ° C. to 200 ° C., 80 ° C. -150 degreeC is preferable, kneading | mixing time is 30 seconds-30 minutes normally, and 1 minute-30 minutes are preferable. When mixing a vulcanizing agent or a vulcanization accelerator, the kneading temperature usually does not exceed 100 ° C and is preferably 25 ° C to 90 ° C. Mixing of the vulcanizing agent or the vulcanization accelerator can be performed by, for example, a vulcanization method using press vulcanization. The vulcanization temperature is usually 120 ° C to 200 ° C, preferably 140 ° C to 180 ° C.
本発明の変性共役ジエンゴム及びその共役ジエンゴム組成物はタイヤ、靴底、床板材料、及び防振材料等に使用でき、かつ特にタイヤでの使用に適しており、タイヤ表面の転がり抵抗を抑え、耐スリップ性を促進し、操縦安定性及び信頼性を増進することができる。
以下、実施例を挙げて本発明の重合反応及び変性反応プロセスを詳細に説明する。
The modified conjugated diene rubber and the conjugated diene rubber composition of the present invention can be used for tires, shoe soles, floor board materials, vibration-proof materials, and the like, and are particularly suitable for use in tires. Slip properties can be promoted and steering stability and reliability can be improved.
Hereinafter, the polymerization reaction and the modification reaction process of the present invention will be described in detail with reference to examples.
実施例１
含酸素基
オートクレーブを準備し、初期容量約５リットルで窒素を充填した。２７５０グラムのシクロヘキサン、８２.５グラムのテトラヒドロフラン、１００グラムのスチレン及び３９０グラムの１,３−ブタジエンをオートクレーブ内に入れた。オートクレーブの内容物の温度が摂氏３０度に達したとき、３２５ミリグラム（５.０３ｍｍｏｌｅ）のｎ−ブチルリチウム（ｎ−ｂｕｔｙｌ ｌｉｔｈｉｕｍ）を添加して重合反応を開始した。重合反応は断熱状態下で行われた。重合反応がほぼ完了したとき、１０ｇの１,３−ブタジエンを加え、さらに約５分間重合反応させた。その後、２.８２ｇ（１０.０６ｍｍｏｌｅ）のビニルトリス（２−メトキシエトキシ）シラン（ｖｉｎｙｌ ｔｒｉｓ（２−ｍｅｔｈｏｘｙｅｔｈｏｘｙ）Ｓｉｌａｎｅ、以下Ｍ１という）を加え、約１５分間変性反応させた。続いて２,６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール（２,６−ｄｉ−ｔｅｒｔ−ｂｕｔｙｌ−ｐ−ｃｒｅｓｏｌ）を重合体溶液中に添加して反応を終止させた。この重合体溶液ゴムから溶剤を除去した後、１１０℃下でホットロール乾燥を行い、変性した共役ジエンゴムを得た。これを実施例１のゴムと定義する。実施例１の共役ジエンゴム−リチウムに対する変性剤（アルコキシシラン）のモル比、初期分子量（Ｍｉ）、及び得られた生成物の各種性質は表１に詳細に示す。
Example 1
An oxygen-containing autoclave was prepared and filled with nitrogen at an initial volume of about 5 liters. 2750 grams of cyclohexane, 82.5 grams of tetrahydrofuran, 100 grams of styrene and 390 grams of 1,3-butadiene were placed in the autoclave. When the temperature of the autoclave contents reached 30 degrees Celsius, 325 milligrams (5.03 mmole) of n-butyl lithium was added to initiate the polymerization reaction. The polymerization reaction was carried out under adiabatic conditions. When the polymerization reaction was almost completed, 10 g of 1,3-butadiene was added, and the polymerization reaction was further continued for about 5 minutes. Thereafter, 2.82 g (10.06 mmole) of vinyltris (2-methoxyethoxy) silane (2-methylethoxy) Silane (hereinafter referred to as M1) was added, and the modification reaction was performed for about 15 minutes. Subsequently, 2,6-di-tert-butyl-p-cresol (2,6-di-tert-butyl-p-cresol) was added to the polymer solution to terminate the reaction. After removing the solvent from the polymer solution rubber, hot roll drying was performed at 110 ° C. to obtain a modified conjugated diene rubber. This is defined as the rubber of Example 1. The molar ratio of the modifier (alkoxysilane) to the conjugated diene rubber-lithium in Example 1, the initial molecular weight (Mi), and various properties of the resulting product are detailed in Table 1.
実施例２から５
含酸素基
実施例２から実施例５の工程は実施例１の工程を参照し、いずれも同様の溶剤及び反応物を使用するが、各反応物の含量のみ反応条件が異なる。各実施例の反応条件、例えば変性剤（アルコキシシラン）の共役ジエンゴム−リチウムに対するモル比、初期分子量（Ｍｉ）、及び得られた生成物の各種性質は表１に詳細に示す。
Examples 2 to 5
Oxygen-containing groups The processes of Examples 2 to 5 refer to the process of Example 1, and all use the same solvent and reactant, but the reaction conditions differ only in the content of each reactant. The reaction conditions for each example, such as the molar ratio of modifier (alkoxysilane) to conjugated diene rubber-lithium, initial molecular weight (Mi), and various properties of the resulting product are detailed in Table 1.
実施例６
含窒素基
オートクレーブを準備し、初期容量約５リットルで窒素を充填した。２７５０グラムのシクロヘキサン、８２.５グラムのテトラヒドロフラン、１００グラムのスチレン及び３９０グラムの１,３−ブタジエンをオートクレーブ内に入れた。オートクレーブの内容物の温度が摂氏３０度に達したとき、３２５ミリグラム（５.０３ｍｍｏｌｅ）のｎ−ブチルリチウム（ｎ−ｂｕｔｙｌ ｌｉｔｈｉｕｍ）を添加して重合反応を開始した。重合反応は断熱状態下で行われた。重合反応がほぼ完了したとき、１０ｇの１,３−ブタジエンを加え、さらに約５分間重合反応させた。その後（５.０３ｍｍｏｌｅ）のビニルトリス（メチルエチルケトキシム）シラン（Ｖｉｎｙｌ ｔｒｉｓ（ｍｅｔｈｙｌｅｔｈｙｌｋｅｔｏｘｉｍｅ） ｓｉｌａｎｅ、以下Ｍ２という）を加え、約１５分間変性反応させた。続いて２,６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール（２,６−ｄｉ−ｔｅｒｔ−ｂｕｔｙｌ−ｐ−ｃｒｅｓｏｌ）を重合体溶液中に添加して反応を終止させた。この重合体溶液ゴムから溶剤を除去した後、１１０℃下でホットロール乾燥を行い、変性した共役ジエンゴムを得た。これを実施例６のゴムと定義する。実施例６の変性剤（アルコキシシラン）の共役ジエンゴム−リチウムに対するモル比、初期分子量（Ｍｉ）、及び得られた産物の各種性質は表２に詳細に示す。
Example 6
A nitrogen-containing autoclave was prepared and filled with nitrogen at an initial volume of about 5 liters. 2750 grams of cyclohexane, 82.5 grams of tetrahydrofuran, 100 grams of styrene and 390 grams of 1,3-butadiene were placed in the autoclave. When the temperature of the autoclave contents reached 30 degrees Celsius, 325 milligrams (5.03 mmole) of n-butyl lithium was added to initiate the polymerization reaction. The polymerization reaction was carried out under adiabatic conditions. When the polymerization reaction was almost completed, 10 g of 1,3-butadiene was added, and the polymerization reaction was further continued for about 5 minutes. Thereafter, (5.03 mmole) of vinyltris (methylethylketoxime) silane (Vinyl tris (methylethylketoxime) silane, hereinafter referred to as M2) was added, and a denaturation reaction was performed for about 15 minutes. Subsequently, 2,6-di-tert-butyl-p-cresol (2,6-di-tert-butyl-p-cresol) was added to the polymer solution to terminate the reaction. After removing the solvent from the polymer solution rubber, hot roll drying was performed at 110 ° C. to obtain a modified conjugated diene rubber. This is defined as the rubber of Example 6. The molar ratio of the modifier (alkoxysilane) of Example 6 to conjugated diene rubber-lithium, the initial molecular weight (Mi), and various properties of the resulting product are detailed in Table 2.
実施例７から９
含窒素基
実施例７から実施例９の工程は実施例６の工程を参照し、いずれも同様の溶剤及び反応物を使用するが、各反応物の含量のみ反応条件が異なる。各実施例の反応条件、例えば変性剤（アルコキシシラン）の共役ジエンゴム−リチウムに対するモル比、初期分子量（Ｍｉ）、及び得られた産物の各種性質は後付の表２に詳細に示す。
Examples 7 to 9
Nitrogen-containing groups The processes of Example 7 to Example 9 refer to the process of Example 6, and all use the same solvent and reactant, but the reaction conditions differ only in the content of each reactant. The reaction conditions for each example, for example, the molar ratio of modifier (alkoxysilane) to conjugated diene rubber-lithium, initial molecular weight (Mi), and various properties of the resulting product are detailed in Table 2 below.
比較実施例１
重合反応工程は実施例１と同じである。変性反応時、１.０５g（５.０３ｍｍｏｌｅ）のテトラエトキシシラン（ｔｅｔｒａｅｔｈｏｘｙｓｉｌａｎｅ、ＴＥＯＳ）で実施例１のアルコキシシランを代替し、約１０分間反応させた。続いて、２,６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール（２,６−ｄｉ−ｔｅｒｔ−ｂｕｔｙｌ−ｐ−ｃｒｅｓｏｌ）を重合体溶液中に添加して反応を終止させた。この重合体溶液ゴムから溶剤を除去した後、１１０℃下でホットロール乾燥を行い、変性した共役ジエンゴムを得た。これを比較実施例１のゴムと定義する。比較実施例１の変性剤（アルコキシシラン）の共役ジエンゴム−リチウムに対するモル比、初期分子量（Ｍｉ）、及び得られた生成物の各種性質は表１に詳細に示す。
Comparative Example 1
The polymerization reaction process is the same as in Example 1. During the modification reaction, 1.05 g (5.03 mmole) of tetraethoxysilane (tetraethoxysilane, TEOS) was substituted for the alkoxysilane of Example 1 and allowed to react for about 10 minutes. Subsequently, 2,6-di-tert-butyl-p-cresol (2,6-di-tert-butyl-p-cresol) was added to the polymer solution to terminate the reaction. After removing the solvent from the polymer solution rubber, hot roll drying was performed at 110 ° C. to obtain a modified conjugated diene rubber. This is defined as the rubber of Comparative Example 1. The molar ratio of the modifier (alkoxysilane) of Comparative Example 1 to conjugated diene rubber-lithium, the initial molecular weight (Mi), and various properties of the resulting product are detailed in Table 1.
比較実施例２及び３
比較実施例２及び３の工程は比較実施例１の工程を参照し、反応物の種類が主に異なる。比較実施例１で使用した変性剤はテトラエトキシシラン（ｔｅｔｒａｅｔｈｏｘｙｓｉｌａｎｅ、ＴＥＯＳ）であり、比較実施例２で使用した変性剤はテトラメトキシシラン（ｔｅｔｒａｍｅｔｈｏｘｙｓｉｌａｎｅ、ＴＭＯＳ）であり、比較実施例３で使用した変性剤はメチルトリメトキシシラン（ｔｒｉｍｅｔｈｏｘｙ（ｍｅｔｈｙｌ）ｓｉｌａｎｅ、以下略してＴＭＯＭＳ）である。各比較実施例の変性剤の共役ジエンゴム−リチウムに対するモル比、初期分子量（Ｍｉ）等の反応条件、及び得られた生成物の各種性質は表１に詳細に示す。
Comparative Examples 2 and 3
The processes of Comparative Examples 2 and 3 refer to the process of Comparative Example 1, and the types of reactants are mainly different. The modifier used in Comparative Example 1 was tetraethoxysilane (tetraethoxysilane, TEOS), and the modifier used in Comparative Example 2 was tetramethoxysilane (tetramethoxysilane, TMOS), and the modifier used in Comparative Example 3 was used. The agent is methyltrimethoxysilane (trimethyl (methyl) silane, hereinafter abbreviated as TMOMS). Table 1 shows in detail the reaction conditions such as the molar ratio of the modifier of each comparative example to the conjugated diene rubber-lithium, the initial molecular weight (Mi), and the properties of the resulting product.
以下、本発明の上述の各実施例から得られる共役ジエンゴムの組成物から製造した硫化シートフィルムの損失正接を測定する方法について説明する。
１００重量部の各実施例のゴム、７８.４重量部のシリカコンパウンド（商品名Ｕｌｔｒａｓｉｌ ７０００ＧＲ、ＥＶＯＮＩＫ社製造）、６.９重量部のシランカップリング剤（商品名Ｓｉ６９、ＥＶＯＮＩＫ社製造）、５０.０重量部の充填油（ＴＤＡＥ、ＩＲＰＣ社製造）、１.５重量部の抗酸化剤（商品名Ａｎｔｉｇｅｎｅ ３Ｃ）、２重量部のステアリン酸、２重量部の酸化亜鉛、１.５重量部のロウ、１.４重量部の硫黄、及び２重量部の加硫促進剤（商品名ＣＺとＤ各１重量部）を混練して組成物を形成した。この組成物は２つのローラー装置によりシートフィルムに成型することができ、このシートフィルムを１６０℃まで加熱し、４５分間維持して加硫を行い、加硫シートフィルムを得た。
加硫シートフィルムの６０℃での損失正接（ｌｏｓｓ ｔａｎｇｅｎｔ、ｔａｎδ（６０℃））は、粘弾性計を使用して測定することができ、測定条件は応力１％、周波数１０Ｈｚとする。例えば、比較実施例を標準とし、比較実施例１を１００％とすると、各実施例において値が高いほど、省エネ効果に優れていることになる。加硫シートフィルムの０℃での損失正接（ｔａｎδ（０℃））は、粘弾性計を使用して測定でき、測定条件は応力０.５％、周波数１０Ｈｚとする。例えば、比較実施例を標準とし、比較実施例１を１００％とすると、実施例の値が高いほど、ブレーキグリップ力の安全効果が優れていることになる。各実施例の加硫シートフィルムで得られた損失正接を表１及び表２に示す。
Hereinafter, a method for measuring the loss tangent of the sulfide sheet film produced from the conjugated diene rubber composition obtained from each of the above examples of the present invention will be described.
100 parts by weight of rubber of each example, 78.4 parts by weight of silica compound (trade name Ultrasil 7000GR, manufactured by EVONIK), 6.9 parts by weight of silane coupling agent (trade names Si69, manufactured by EVONIK), 50 0.0 parts by weight of filler oil (TDAE, manufactured by IRPC), 1.5 parts by weight of antioxidant (trade name Antigene 3C), 2 parts by weight of stearic acid, 2 parts by weight of zinc oxide, 1.5 parts by weight No. 1 wax, 1.4 parts by weight of sulfur, and 2 parts by weight of a vulcanization accelerator (trade names CZ and 1 part by weight of D each) were kneaded to form a composition. This composition can be formed into a sheet film by two roller devices, and this sheet film is heated to 160 ° C. and maintained for 45 minutes to vulcanize to obtain a vulcanized sheet film.
The loss tangent (loss tangent, tan δ (60 ° C.)) at 60 ° C. of the vulcanized sheet film can be measured using a viscoelasticity meter, and the measurement conditions are a stress of 1% and a frequency of 10 Hz. For example, when the comparative example is standard and the comparative example 1 is 100%, the higher the value in each example, the better the energy saving effect. The loss tangent (tan δ (0 ° C.)) at 0 ° C. of the vulcanized sheet film can be measured using a viscoelastic meter, and the measurement conditions are a stress of 0.5% and a frequency of 10 Hz. For example, assuming that the comparative example is a standard and the comparative example 1 is 100%, the higher the value of the example, the better the safety effect of the brake grip force. Tables 1 and 2 show loss tangents obtained from the vulcanized sheet films of the respective examples.
以上のアクロン摩耗率は耐磨耗性、ｔａｎδ（摂氏０度）は濡れた路面でのグリップ力、ｔａｎδ（摂氏６０度）は転がり抵抗性をそれぞれ表し、三者の個別の数値が高いほど優れている。 The above Akron wear rate is wear resistance, tan δ (0 degree Celsius) is the grip force on wet road surface, tan δ (60 degree Celsius) is rolling resistance, and the higher the individual values of the three, the better ing.
表１及び表２において、ムーニー粘度ＭＶ（ＭＬ１＋４，１００℃）は予熱１分間、且つ１００℃を４分間持続した条件下で測定された。ムーニー粘度測定時点は、変性反応が完了し、溶剤を除去した後（直接溶剤除去後と記載）、水蒸気ストリッピングと機械乾燥後（水蒸気ストリッピングと乾燥後と記載）、９０℃で相対湿度８０％及び４０時間の保管試験後（保管試験後と記載）である。表１において、ＭＶ（水蒸気ストリッピングと乾燥後）とＭＶ（保管試験後）の数値を比較するとほぼ等しく、ムーニー粘度の安定性の改善が示されている。カップリング率（Ｃｏｕｐｌｉｎｇ Ｒａｔｉｏ（Ｃ／Ｒ％））はゲル浸透クロマトグラフィー（ＧＰＣ）及び屈折率検出器で測定され、分子量がカップリングする前の分子量より高い重合体が全部の重合体に占める割合であり、測定時にテトラヒドロフラン（ｔｅｔｒａｈｙｄｒｏｆｕｒａｎ）を移動相（ｍｏｂｉｌｅ ｐｈａｓｅ）とする。カップリング率の測定時点は、変性反応が完了した後の重合体溶液状態（重合体溶液と記載）、水蒸気ストリッピングと機械乾燥後（水蒸気ストリッピングと乾燥後と記載）である。その他の特性は当業者の常用する技術で試験を行うことができ、例えばスチレン含量、ビニル基含量はフーリエ変換赤外分光光度計（ＦＴＩＲ）で測定できる。アクロン磨耗（Ａｋｒｏｎ ａｂｒａｓｉｏｎ）率で示される耐磨耗性にはアクロン磨耗試験機を使用でき、荷重６ポンド、回転数３３００における磨耗量を測定する。指数が高いほど磨耗量が少ないことを表す。 In Tables 1 and 2, Mooney viscosity MV (ML 1 + 4 , 100 ° C.) was measured under conditions of preheating for 1 minute and 100 ° C. for 4 minutes. The Mooney viscosity was measured at the time when the modification reaction was completed and the solvent was removed (described as direct solvent removal), after steam stripping and mechanical drying (described as steam stripping and after drying), and at 90 ° C. and a relative humidity of 80 % And after 40 hours storage test (described as after storage test). In Table 1, when comparing the numerical values of MV (after steam stripping and drying) and MV (after storage test), the stability of Mooney viscosity is improved. Coupling ratio (Coupling Ratio (C / R%)) is measured by gel permeation chromatography (GPC) and a refractive index detector, and the ratio of the polymer whose molecular weight is higher than the molecular weight before coupling to the total polymer Tetrahydrofuran is used as a mobile phase at the time of measurement. The measurement point of the coupling rate is the state of the polymer solution after the modification reaction is completed (described as a polymer solution), after steam stripping and mechanical drying (described as steam stripping and after drying). Other characteristics can be tested by techniques commonly used by those skilled in the art. For example, the styrene content and vinyl group content can be measured with a Fourier transform infrared spectrophotometer (FTIR). For the abrasion resistance indicated by the Akron abrasion rate, an Akron abrasion tester can be used, and the amount of abrasion at a load of 6 pounds and a rotational speed of 3300 is measured. The higher the index, the less the amount of wear.
実施例１〜５は表１においてアクロン摩耗率（Ｉｄｅｘ）、ｔａｎδ（摂氏０度）及びｔａｎδ（摂氏６０度）のいずれも比較例１〜３より高く、耐磨耗性、転がり抵抗性、濡れた路面でのグリップ性能の向上が示されている。
実施例６〜９は表２においてアクロン摩耗率（Ｉｄｅｘ）、ｔａｎδ（摂氏０度）及びｔａｎδ（摂氏６０度）のいずれも比較例４より高く、耐磨耗性、転がり抵抗性、濡れた路面でのグリップ性能の向上が示されている。
本発明について好適な実施態様を挙げて上述のように開示したが、上述の説明は本発明を制限するものではなく、当業者が本発明の要旨を逸脱しない範囲で変更や修正を行うことが可能であるため、本発明の保護範囲は特許請求の範囲の定義に準じる。
In Examples 1 to 5, in Table 1, all of Akron wear rate (Idex), tan δ (0 degree Celsius) and tan δ (60 degree Celsius) are higher than Comparative Examples 1 to 3, and wear resistance, rolling resistance, and wetting The improvement of grip performance on the road surface is shown.
In Examples 6 to 9, in Table 2, all of Akron wear rate (Idex), tan δ (0 degree Celsius), and tan δ (60 degree Celsius) are higher than those of Comparative Example 4, and wear resistance, rolling resistance, wet road surface The improvement in grip performance is shown.
Although the present invention has been disclosed as described above with reference to preferred embodiments, the above description does not limit the present invention, and those skilled in the art can make changes and modifications without departing from the spirit of the present invention. Therefore, the protection scope of the present invention is in accordance with the definition of the claims.
Claims (28)
アルカリ金属イオンを含む共役ジエンゴムを提供する工程（ａ）と、
前記アルカリ金属イオンを含む共役ジエンゴムをアルコキシシランと反応させ、前記変性共役ジエンゴムを生成する工程（ｂ）とを含み、前記アルコキシシランが構造式（Ｉ）
Providing a conjugated diene rubber comprising alkali metal ions (a);
Reacting the conjugated diene rubber containing the alkali metal ion with an alkoxysilane to produce the modified conjugated diene rubber, wherein the alkoxysilane has the structural formula (I)
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| WO1995021202A1 (en) * | 1994-02-01 | 1995-08-10 | Asahi Kasei Kogyo Kabushiki Kaisha | Novel modified polymer containing cyclic molecular structure unit |
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| JP2006137858A (en) * | 2004-11-12 | 2006-06-01 | Yokohama Rubber Co Ltd:The | Conjugative diene base polymer and rubber composition containing the same |
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| JPH0790007A (en) * | 1993-09-20 | 1995-04-04 | Sumitomo Rubber Ind Ltd | Silane-modified diene rubber, vulcanized rubber composition and production of silane-modified diene rubber |
| WO1995021202A1 (en) * | 1994-02-01 | 1995-08-10 | Asahi Kasei Kogyo Kabushiki Kaisha | Novel modified polymer containing cyclic molecular structure unit |
| JP2005120259A (en) * | 2003-10-17 | 2005-05-12 | Shin Etsu Chem Co Ltd | Room-temperature-curable organopolysiloxane composition |
| JP2006137858A (en) * | 2004-11-12 | 2006-06-01 | Yokohama Rubber Co Ltd:The | Conjugative diene base polymer and rubber composition containing the same |
| WO2009072650A1 (en) * | 2007-12-07 | 2009-06-11 | Bridgestone Corporation | Tire |
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