JP2009242788A - Rubber composition and tire using it - Google Patents
Rubber composition and tire using it Download PDFInfo
- Publication number
- JP2009242788A JP2009242788A JP2009053970A JP2009053970A JP2009242788A JP 2009242788 A JP2009242788 A JP 2009242788A JP 2009053970 A JP2009053970 A JP 2009053970A JP 2009053970 A JP2009053970 A JP 2009053970A JP 2009242788 A JP2009242788 A JP 2009242788A
- Authority
- JP
- Japan
- Prior art keywords
- group
- conjugated diene
- rubber composition
- diene polymer
- carbon atoms
- 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 114
- 239000005060 rubber Substances 0.000 title claims abstract description 113
- 239000000203 mixture Substances 0.000 title claims abstract description 93
- 229920000642 polymer Polymers 0.000 claims abstract description 115
- 150000001993 dienes Chemical class 0.000 claims abstract description 92
- 239000006229 carbon black Substances 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 15
- -1 diene compound Chemical class 0.000 claims description 70
- 125000004432 carbon atom Chemical group C* 0.000 claims description 48
- 239000010936 titanium Substances 0.000 claims description 47
- 229910052719 titanium Inorganic materials 0.000 claims description 46
- 229910052710 silicon Inorganic materials 0.000 claims description 44
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 38
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 28
- 238000009833 condensation Methods 0.000 claims description 25
- 230000005494 condensation Effects 0.000 claims description 25
- 125000002947 alkylene group Chemical group 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229910052718 tin Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 230000001588 bifunctional effect Effects 0.000 claims description 14
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 13
- 238000006460 hydrolysis reaction Methods 0.000 claims description 13
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 13
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 12
- 238000006482 condensation reaction Methods 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 229910052797 bismuth Inorganic materials 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229920002554 vinyl polymer Polymers 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 10
- 238000010511 deprotection reaction Methods 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 8
- 239000003505 polymerization initiator Substances 0.000 claims description 8
- 230000003014 reinforcing effect Effects 0.000 claims description 8
- 238000001179 sorption measurement Methods 0.000 claims description 7
- 239000011324 bead Substances 0.000 claims description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 6
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 239000010703 silicon Substances 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 4
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- JIDHFKQYRQEGCQ-UHFFFAOYSA-N 2-[diethoxy(methyl)silyl]-n,n-bis(trimethylsilyl)ethanamine Chemical compound CCO[Si](C)(OCC)CCN([Si](C)(C)C)[Si](C)(C)C JIDHFKQYRQEGCQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001339 alkali metal compounds Chemical class 0.000 claims description 3
- UJTGYJODGVUOGO-UHFFFAOYSA-N diethoxy-methyl-propylsilane Chemical compound CCC[Si](C)(OCC)OCC UJTGYJODGVUOGO-UHFFFAOYSA-N 0.000 claims description 3
- BUNFDZZVLUCBGM-UHFFFAOYSA-N 1,2,5-azadisilolidine Chemical compound C1C[SiH2]N[SiH2]1 BUNFDZZVLUCBGM-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- GLHRSDFTTICRBF-UHFFFAOYSA-N [2-(ethoxymethyl)azasilolidin-1-yl]-trimethylsilane Chemical compound CCOC[SiH]1CCCN1[Si](C)(C)C GLHRSDFTTICRBF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 241000255925 Diptera Species 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 claims 1
- 238000003795 desorption Methods 0.000 claims 1
- YQGOWXYZDLJBFL-UHFFFAOYSA-N dimethoxysilane Chemical compound CO[SiH2]OC YQGOWXYZDLJBFL-UHFFFAOYSA-N 0.000 claims 1
- 150000002739 metals Chemical class 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- 239000012855 volatile organic compound Substances 0.000 abstract description 25
- 238000004898 kneading Methods 0.000 abstract description 13
- 239000000446 fuel Substances 0.000 abstract description 12
- 238000002360 preparation method Methods 0.000 abstract description 5
- 241000872198 Serjania polyphylla Species 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 36
- 238000000034 method Methods 0.000 description 31
- 238000006116 polymerization reaction Methods 0.000 description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 229910001868 water Inorganic materials 0.000 description 26
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 25
- 235000019241 carbon black Nutrition 0.000 description 24
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 18
- 229910052744 lithium Inorganic materials 0.000 description 15
- 239000003607 modifier Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000003795 chemical substances by application Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 9
- 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 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 7
- 238000006011 modification reaction Methods 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- WZLRYEIJALOESF-UHFFFAOYSA-R 2-ethylhexane-1,3-diolate;hydron;titanium(4+) Chemical compound [H+].[H+].[H+].[H+].[Ti+4].CCCC([O-])C(CC)C[O-].CCCC([O-])C(CC)C[O-].CCCC([O-])C(CC)C[O-].CCCC([O-])C(CC)C[O-] WZLRYEIJALOESF-UHFFFAOYSA-R 0.000 description 6
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229940093858 ethyl acetoacetate Drugs 0.000 description 6
- 150000002642 lithium compounds Chemical class 0.000 description 6
- 125000005609 naphthenate group Chemical group 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- FZLHAQMQWDDWFI-UHFFFAOYSA-N 2-[2-(oxolan-2-yl)propan-2-yl]oxolane Chemical compound C1CCOC1C(C)(C)C1CCCO1 FZLHAQMQWDDWFI-UHFFFAOYSA-N 0.000 description 5
- 239000007983 Tris buffer Substances 0.000 description 5
- 230000003712 anti-aging effect Effects 0.000 description 5
- 150000007514 bases Chemical class 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 239000004636 vulcanized rubber Substances 0.000 description 5
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 208000012839 conversion disease Diseases 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 3
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- FJDQVJUXXNIHNB-UHFFFAOYSA-N lithium;pyrrolidin-1-ide Chemical compound [Li+].C1CC[N-]C1 FJDQVJUXXNIHNB-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 2
- KTXWGMUMDPYXNN-UHFFFAOYSA-N 2-ethylhexan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-].CCCCC(CC)C[O-] KTXWGMUMDPYXNN-UHFFFAOYSA-N 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000005370 alkoxysilyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- MTKOCRSQUPLVTD-UHFFFAOYSA-N butan-1-olate;titanium(2+) Chemical compound CCCCO[Ti]OCCCC MTKOCRSQUPLVTD-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical class [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pentene-2 Natural products CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000010734 process oil Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- ICNONUXPZBTVMH-CGKDLMRESA-L (9Z,12Z)-octadeca-9,12-dienoate oxygen(2-) zirconium(4+) Chemical compound [O-2].[Zr+4].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O ICNONUXPZBTVMH-CGKDLMRESA-L 0.000 description 1
- FHKLMBANUTXHKQ-LPPMGWMRSA-J (9Z,12Z)-octadeca-9,12-dienoate zirconium(4+) Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)O[Zr](OC(=O)CCCCCCC\C=C/C\C=C/CCCCC)(OC(=O)CCCCCCC\C=C/C\C=C/CCCCC)OC(=O)CCCCCCC\C=C/C\C=C/CCCCC FHKLMBANUTXHKQ-LPPMGWMRSA-J 0.000 description 1
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 1
- UKOVBLFUUCSBAW-GOJQJELCSA-L (Z)-octadec-9-enoate oxygen(2-) zirconium(4+) Chemical compound [O-2].[Zr+4].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O UKOVBLFUUCSBAW-GOJQJELCSA-L 0.000 description 1
- WGOMEMWEJIKLSU-UJUIXPSJSA-J (z)-octadec-9-enoate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O WGOMEMWEJIKLSU-UJUIXPSJSA-J 0.000 description 1
- JHQQFNSJNJARJJ-UJUIXPSJSA-J (z)-octadec-9-enoate;zirconium(4+) Chemical compound [Zr+4].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O JHQQFNSJNJARJJ-UJUIXPSJSA-J 0.000 description 1
- HIACAHMKXQESOV-UHFFFAOYSA-N 1,2-bis(prop-1-en-2-yl)benzene Chemical compound CC(=C)C1=CC=CC=C1C(C)=C HIACAHMKXQESOV-UHFFFAOYSA-N 0.000 description 1
- CORMBJOFDGICKF-UHFFFAOYSA-N 1,3,5-trimethoxy 2-vinyl benzene Natural products COC1=CC(OC)=C(C=C)C(OC)=C1 CORMBJOFDGICKF-UHFFFAOYSA-N 0.000 description 1
- UYMQPNRUQXPLCY-UHFFFAOYSA-N 1-(2-piperidin-1-ylethyl)piperidine Chemical compound C1CCCCN1CCN1CCCCC1 UYMQPNRUQXPLCY-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
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- IZUBVNGHMOTZBX-UHFFFAOYSA-N 2,2,2-tributoxyethyl 3-oxobutanoate;zirconium Chemical compound [Zr].CCCCOC(OCCCC)(OCCCC)COC(=O)CC(C)=O IZUBVNGHMOTZBX-UHFFFAOYSA-N 0.000 description 1
- IPKOJSMGLIKFLO-UHFFFAOYSA-N 2,2,5,5-tetramethyl-1,2,5-azadisilolidine Chemical compound C[Si]1(C)CC[Si](C)(C)N1 IPKOJSMGLIKFLO-UHFFFAOYSA-N 0.000 description 1
- YLYGKLVCLYXICU-UHFFFAOYSA-N 2-(chloro-ethoxy-methylsilyl)-n,n-bis(trimethylsilyl)ethanamine Chemical compound CCO[Si](C)(Cl)CCN([Si](C)(C)C)[Si](C)(C)C YLYGKLVCLYXICU-UHFFFAOYSA-N 0.000 description 1
- QICDJNHGLKPOES-UHFFFAOYSA-N 2-(chloro-methoxy-methylsilyl)-n,n-bis(trimethylsilyl)ethanamine Chemical compound CO[Si](C)(Cl)CCN([Si](C)(C)C)[Si](C)(C)C QICDJNHGLKPOES-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- ZPOBBCVISKKFBH-UHFFFAOYSA-N 2-[dimethoxy(methyl)silyl]-n,n-bis(trimethylsilyl)ethanamine Chemical compound CO[Si](C)(OC)CCN([Si](C)(C)C)[Si](C)(C)C ZPOBBCVISKKFBH-UHFFFAOYSA-N 0.000 description 1
- CZVSRHMBQDVNLW-UHFFFAOYSA-N 2-[dimethoxy(methyl)silyl]ethanamine Chemical compound CO[Si](C)(OC)CCN CZVSRHMBQDVNLW-UHFFFAOYSA-N 0.000 description 1
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 description 1
- WSKLLFWYPMAKEZ-UHFFFAOYSA-N 2-ethylbutanamide;lithium Chemical compound [Li].CCC(CC)C(N)=O WSKLLFWYPMAKEZ-UHFFFAOYSA-N 0.000 description 1
- GDKAXSGMPFSRJY-UHFFFAOYSA-J 2-ethylhexanoate;titanium(4+) Chemical compound [Ti+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O GDKAXSGMPFSRJY-UHFFFAOYSA-J 0.000 description 1
- OFYFURKXMHQOGG-UHFFFAOYSA-J 2-ethylhexanoate;zirconium(4+) Chemical compound [Zr+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O OFYFURKXMHQOGG-UHFFFAOYSA-J 0.000 description 1
- BWLBGMIXKSTLSX-UHFFFAOYSA-N 2-hydroxyisobutyric acid Chemical compound CC(C)(O)C(O)=O BWLBGMIXKSTLSX-UHFFFAOYSA-N 0.000 description 1
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 description 1
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 description 1
- IZXRSZNHUSJWIQ-UHFFFAOYSA-N 2-methylpropan-2-ol;titanium Chemical compound [Ti].CC(C)(C)O.CC(C)(C)O.CC(C)(C)O.CC(C)(C)O IZXRSZNHUSJWIQ-UHFFFAOYSA-N 0.000 description 1
- DTGZORBDGLEVNY-UHFFFAOYSA-N 2-propyloxolane Chemical compound CCCC1CCCO1 DTGZORBDGLEVNY-UHFFFAOYSA-N 0.000 description 1
- NZWCKRJQGFJYBJ-UHFFFAOYSA-N 3-(chloro-methoxy-methylsilyl)-n,n-bis(trimethylsilyl)propan-1-amine Chemical compound CO[Si](C)(Cl)CCCN([Si](C)(C)C)[Si](C)(C)C NZWCKRJQGFJYBJ-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical group CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- OBCIMLTXIKKCRS-UHFFFAOYSA-N 4-methylmorpholine;pyridine Chemical compound C1=CC=NC=C1.CN1CCOCC1 OBCIMLTXIKKCRS-UHFFFAOYSA-N 0.000 description 1
- RFVYQWYNYFCXQL-UHFFFAOYSA-N C1=CC=CC2=CC([Li])=CC=C21 Chemical compound C1=CC=CC2=CC([Li])=CC=C21 RFVYQWYNYFCXQL-UHFFFAOYSA-N 0.000 description 1
- PLEFTJLJRXNQHH-UHFFFAOYSA-N CC(C[Si](OC(C)N1[SiH2]CC[Si]1(C)C)(OCC)C)(C)C Chemical compound CC(C[Si](OC(C)N1[SiH2]CC[Si]1(C)C)(OCC)C)(C)C PLEFTJLJRXNQHH-UHFFFAOYSA-N 0.000 description 1
- FMKGEFJDGCCCKP-UHFFFAOYSA-N CCCCC(CC)C[Zr](CC(CC)CCCC)(CC(CC)CCCC)CC(CC)CCCC Chemical compound CCCCC(CC)C[Zr](CC(CC)CCCC)(CC(CC)CCCC)CC(CC)CCCC FMKGEFJDGCCCKP-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-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
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000004902 Softening Agent Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- IMNLDFWLNVKKGD-SWDNMTSISA-H [Al+3].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].[Al+3].C(CCCCCCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCCCCCC)(=O)[O-] Chemical compound [Al+3].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].C(CCCCCCC\C=C/CCCCCCCC)(=O)[O-].[Al+3].C(CCCCCCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCCCCCC)(=O)[O-].C(CCCCCCCCCCCCCCCCC)(=O)[O-] IMNLDFWLNVKKGD-SWDNMTSISA-H 0.000 description 1
- NTYDXFVCCCPXRG-UHFFFAOYSA-N [Li]C(C)(C)CC(C)(C)C Chemical compound [Li]C(C)(C)CC(C)(C)C NTYDXFVCCCPXRG-UHFFFAOYSA-N 0.000 description 1
- ZEDXYOJKIFJKHK-UHFFFAOYSA-N [Li]CCCCC1=CC=CC=C1 Chemical compound [Li]CCCCC1=CC=CC=C1 ZEDXYOJKIFJKHK-UHFFFAOYSA-N 0.000 description 1
- VBSKMKYTRASRSY-UHFFFAOYSA-N [Li]c1ccccc1CCCC Chemical compound [Li]c1ccccc1CCCC VBSKMKYTRASRSY-UHFFFAOYSA-N 0.000 description 1
- QGFLQSGGNUSMMV-UHFFFAOYSA-L [O--].[Ti+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O Chemical compound [O--].[Ti+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O QGFLQSGGNUSMMV-UHFFFAOYSA-L 0.000 description 1
- SWPNTWOFXXVNJH-UHFFFAOYSA-L [O--].[Ti+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O Chemical compound [O--].[Ti+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O SWPNTWOFXXVNJH-UHFFFAOYSA-L 0.000 description 1
- GJBIRLPKPPAPBH-UHFFFAOYSA-L [O--].[Zr+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O Chemical compound [O--].[Zr+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GJBIRLPKPPAPBH-UHFFFAOYSA-L 0.000 description 1
- SHZXIBKYGCQOJR-UHFFFAOYSA-L [O--].[Zr+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O Chemical compound [O--].[Zr+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O SHZXIBKYGCQOJR-UHFFFAOYSA-L 0.000 description 1
- WTTIGSUTVFXGJQ-GOJQJELCSA-L [O-2].[Ti+4].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O Chemical compound [O-2].[Ti+4].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O WTTIGSUTVFXGJQ-GOJQJELCSA-L 0.000 description 1
- NFXYFERCVXLLQX-CGKDLMRESA-L [O-2].[Ti+4].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O Chemical compound [O-2].[Ti+4].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O NFXYFERCVXLLQX-CGKDLMRESA-L 0.000 description 1
- MQKATURVIVFOQI-UHFFFAOYSA-N [S-][S-].[Li+].[Li+] Chemical compound [S-][S-].[Li+].[Li+] MQKATURVIVFOQI-UHFFFAOYSA-N 0.000 description 1
- SEDMZGQDIXKLPU-BGSQTJHASA-J [Ti+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O Chemical compound [Ti+4].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SEDMZGQDIXKLPU-BGSQTJHASA-J 0.000 description 1
- YCCVWBZTZTXXTG-LPPMGWMRSA-J [Ti+4].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O Chemical compound [Ti+4].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O YCCVWBZTZTXXTG-LPPMGWMRSA-J 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 1
- KMJRBSYFFVNPPK-UHFFFAOYSA-K aluminum;dodecanoate Chemical compound [Al+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O KMJRBSYFFVNPPK-UHFFFAOYSA-K 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010692 aromatic oil Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- NUMHJBONQMZPBW-UHFFFAOYSA-K bis(2-ethylhexanoyloxy)bismuthanyl 2-ethylhexanoate Chemical compound [Bi+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O NUMHJBONQMZPBW-UHFFFAOYSA-K 0.000 description 1
- IEBNUCVSDWFMDE-UHFFFAOYSA-N bis[2-(ethylamino)phenyl]methanone Chemical compound CCNC1=CC=CC=C1C(=O)C1=CC=CC=C1NCC IEBNUCVSDWFMDE-UHFFFAOYSA-N 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- BEQTZCISVVHICR-VLKMOBIUSA-K bis[[(9z,12z)-octadeca-9,12-dienoyl]oxy]alumanyl (9z,12z)-octadeca-9,12-dienoate Chemical compound [Al+3].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O BEQTZCISVVHICR-VLKMOBIUSA-K 0.000 description 1
- TWHQFSIEZNSVPD-VLKMOBIUSA-K bis[[(9z,12z)-octadeca-9,12-dienoyl]oxy]bismuthanyl (9z,12z)-octadeca-9,12-dienoate Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(=O)O[Bi](OC(=O)CCCCCCC\C=C/C\C=C/CCCCC)OC(=O)CCCCCCC\C=C/C\C=C/CCCCC TWHQFSIEZNSVPD-VLKMOBIUSA-K 0.000 description 1
- RHGQOMYDGHIKFH-GNOQXXQHSA-K bis[[(z)-octadec-9-enoyl]oxy]bismuthanyl (z)-octadec-9-enoate Chemical compound [Bi+3].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O RHGQOMYDGHIKFH-GNOQXXQHSA-K 0.000 description 1
- UQOQXWZPXFPRBR-UHFFFAOYSA-K bismuth dodecanoate Chemical compound [Bi+3].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O UQOQXWZPXFPRBR-UHFFFAOYSA-K 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- IMJGQTCMUZMLRZ-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C=CC(=C)C1=CC=CC=C1 IMJGQTCMUZMLRZ-UHFFFAOYSA-N 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- SMRTZQCUWYSWJR-UHFFFAOYSA-N chloro(ethoxy)silane Chemical compound CCO[SiH2]Cl SMRTZQCUWYSWJR-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- LEKSIJZGSFETSJ-UHFFFAOYSA-N cyclohexane;lithium Chemical compound [Li]C1CCCCC1 LEKSIJZGSFETSJ-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 239000003398 denaturant Substances 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- GRBFCEINWFRDOG-UHFFFAOYSA-K di(octadecanoyloxy)bismuthanyl octadecanoate Chemical compound [Bi+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GRBFCEINWFRDOG-UHFFFAOYSA-K 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- AMGXTMFXWTXVHS-UHFFFAOYSA-J dodecanoate titanium(4+) Chemical compound [Ti+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O AMGXTMFXWTXVHS-UHFFFAOYSA-J 0.000 description 1
- WDGXHWGCFUAELX-UHFFFAOYSA-J dodecanoate zirconium(4+) Chemical compound [Zr+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O WDGXHWGCFUAELX-UHFFFAOYSA-J 0.000 description 1
- 125000003438 dodecyl 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 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- UARGAUQGVANXCB-UHFFFAOYSA-N ethanol;zirconium Chemical compound [Zr].CCO.CCO.CCO.CCO UARGAUQGVANXCB-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- DECIPOUIJURFOJ-UHFFFAOYSA-N ethoxyquin Chemical compound N1C(C)(C)C=C(C)C2=CC(OCC)=CC=C21 DECIPOUIJURFOJ-UHFFFAOYSA-N 0.000 description 1
- 235000019285 ethoxyquin Nutrition 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000020169 heat generation Effects 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
- 230000001771 impaired effect Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 229920003049 isoprene rubber Polymers 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- XOXRRQOIDCIGAX-UHFFFAOYSA-N lithium ethyl(propyl)azanide Chemical compound [Li+].CCC[N-]CC XOXRRQOIDCIGAX-UHFFFAOYSA-N 0.000 description 1
- LHPXHKQJYVVXKC-UHFFFAOYSA-N lithium;benzyl(ethyl)azanide Chemical compound [Li+].CC[N-]CC1=CC=CC=C1 LHPXHKQJYVVXKC-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- IQEMUADSVZEVNV-UHFFFAOYSA-N lithium;cyclopentane Chemical compound [Li+].C1CC[CH-]C1 IQEMUADSVZEVNV-UHFFFAOYSA-N 0.000 description 1
- NVMMPHVQFFIBOS-UHFFFAOYSA-N lithium;dibutylazanide Chemical compound [Li+].CCCC[N-]CCCC NVMMPHVQFFIBOS-UHFFFAOYSA-N 0.000 description 1
- FHLMGEQZTIKOBY-UHFFFAOYSA-N lithium;didecylazanide Chemical compound [Li+].CCCCCCCCCC[N-]CCCCCCCCCC FHLMGEQZTIKOBY-UHFFFAOYSA-N 0.000 description 1
- AHNJTQYTRPXLLG-UHFFFAOYSA-N lithium;diethylazanide Chemical compound [Li+].CC[N-]CC AHNJTQYTRPXLLG-UHFFFAOYSA-N 0.000 description 1
- HOLCSXZMVPOUQR-UHFFFAOYSA-N lithium;dihexylazanide Chemical compound [Li+].CCCCCC[N-]CCCCCC HOLCSXZMVPOUQR-UHFFFAOYSA-N 0.000 description 1
- YDGSUPBDGKOGQT-UHFFFAOYSA-N lithium;dimethylazanide Chemical compound [Li+].C[N-]C YDGSUPBDGKOGQT-UHFFFAOYSA-N 0.000 description 1
- VZKVUHUYEOZDIY-UHFFFAOYSA-N lithium;dioctylazanide Chemical compound [Li+].CCCCCCCC[N-]CCCCCCCC VZKVUHUYEOZDIY-UHFFFAOYSA-N 0.000 description 1
- OWYFNXMEEFAXTO-UHFFFAOYSA-N lithium;dipropylazanide Chemical compound [Li+].CCC[N-]CCC OWYFNXMEEFAXTO-UHFFFAOYSA-N 0.000 description 1
- OKMANNMCASEBSW-UHFFFAOYSA-N lithium;methyl(2-phenylethyl)azanide Chemical compound [Li+].C[N-]CCC1=CC=CC=C1 OKMANNMCASEBSW-UHFFFAOYSA-N 0.000 description 1
- DWNRISLZVCBTRN-UHFFFAOYSA-N lithium;piperidin-1-ide Chemical compound [Li]N1CCCCC1 DWNRISLZVCBTRN-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
- 230000007774 longterm Effects 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([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])C([H])([H])[H] 0.000 description 1
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- KDPNWPBRHUJCIP-UHFFFAOYSA-L octadecanoate oxygen(2-) titanium(4+) Chemical compound [O-2].[Ti+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O KDPNWPBRHUJCIP-UHFFFAOYSA-L 0.000 description 1
- OXOUKWPKTBSXJH-UHFFFAOYSA-J octadecanoate;titanium(4+) Chemical compound [Ti+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O OXOUKWPKTBSXJH-UHFFFAOYSA-J 0.000 description 1
- VRQWWCJWSIOWHG-UHFFFAOYSA-J octadecanoate;zirconium(4+) Chemical compound [Zr+4].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O VRQWWCJWSIOWHG-UHFFFAOYSA-J 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
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 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
- 150000003141 primary amines Chemical class 0.000 description 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 description 1
- BCWYYHBWCZYDNB-UHFFFAOYSA-N propan-2-ol;zirconium Chemical compound [Zr].CC(C)O.CC(C)O.CC(C)O.CC(C)O BCWYYHBWCZYDNB-UHFFFAOYSA-N 0.000 description 1
- 239000002683 reaction inhibitor Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- CGRKYEALWSRNJS-UHFFFAOYSA-N sodium;2-methylbutan-2-olate Chemical compound [Na+].CCC(C)(C)[O-] CGRKYEALWSRNJS-UHFFFAOYSA-N 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- QAZLUNIWYYOJPC-UHFFFAOYSA-M sulfenamide Chemical compound [Cl-].COC1=C(C)C=[N+]2C3=NC4=CC=C(OC)C=C4N3SCC2=C1C QAZLUNIWYYOJPC-UHFFFAOYSA-M 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
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- HFDOCGSUMLRQPF-UHFFFAOYSA-N titanium;2,2,2-tributoxyethyl 3-oxobutanoate Chemical compound [Ti].CCCCOC(OCCCC)(OCCCC)COC(=O)CC(C)=O HFDOCGSUMLRQPF-UHFFFAOYSA-N 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-UHFFFAOYSA-N 0.000 description 1
- MDDPTCUZZASZIQ-UHFFFAOYSA-N tris[(2-methylpropan-2-yl)oxy]alumane Chemical compound [Al+3].CC(C)(C)[O-].CC(C)(C)[O-].CC(C)(C)[O-] MDDPTCUZZASZIQ-UHFFFAOYSA-N 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000004711 α-olefin 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
- Tires In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明は、ゴム組成物、それを用いたタイヤ及びそれらに用いる変性共役ジエン系重合体の製造方法に関する。更に詳しくは、本発明は、ゴム組成物調製における混練り時等において、揮発性有機化合物（ＶＯＣ）の発生量が少ない上、低発熱性（低燃費性）に優れるゴム組成物、該ゴム組成物を用いてなるタイヤ、及びそれらに用いられる変性共役ジエン系重合体の効果的な製造方法に関するものである。 The present invention relates to a rubber composition, a tire using the rubber composition, and a method for producing a modified conjugated diene polymer used in the rubber composition. More specifically, the present invention relates to a rubber composition that produces a small amount of volatile organic compound (VOC) during kneading in preparation of the rubber composition and is excellent in low heat buildup (low fuel consumption), and the rubber composition The present invention relates to an effective manufacturing method of tires using the products and modified conjugated diene polymers used in them.
近年、省エネルギー、省資源の社会的要請に伴い、自動車の燃料消費を節約するために、タイヤの耐久性の要求から、低ロス性・耐破壊性のゴム材料が多く望まれるようになってきた。
タイヤの転がり抵抗性能向上のために、低発熱性ゴム組成物を用いる手法が一般的になっており、その性能を発現するための技術として、充填材と相互作用を有する官能基を導入した変性重合体の利用は、極めて有効な手段である。
タイヤの転がり抵抗性能を向上させるために、補強用充填材を低減させる手法では、耐久性の悪化は免れないが、使用するポリマーに変性基を導入することによって、低ロス性と耐久性の両立を実現できることが分かっている。そして、ポリマーに導入される変性官能基の種類によっては、補強用充填材との相互作用が異なり、得られる性能も影響を受けることが知られている。
本発明者らの研究によると、第一アミノ基が導入された変性ポリマーは、カーボンブラックとの相互作用が極めて高く、低ロス性に優れるゴム組成物を与えることが分かった。この第一アミノ基のポリマーへの導入に関しては、例えば特許文献１に、第第一アミノ基及びアルコキシシリル基を有する共役ジエン重合体を含むゴム成分と、Ｎ2ＳＡが３０〜１００ｍ2／ｇのカーボンブラックを含有するゴム組成物が開示されている。
しかしながら、この技術においては、ポリマー中にアルコキシシリル基が残留するため、該ポリマー配合時において、アルコール分として大気中に放出されることが懸念され、作業環境等の環境衛生上の問題がある。
In recent years, with the social demands for energy and resource saving, in order to save the fuel consumption of automobiles, many demands for low loss and fracture resistant rubber materials have come to be demanded from the demand for tire durability. .
In order to improve the rolling resistance performance of tires, a technique using a low heat-generating rubber composition has become common, and as a technique for expressing the performance, modification by introducing a functional group that interacts with a filler The use of a polymer is a very effective means.
In order to improve the rolling resistance performance of tires, the method of reducing the filler for reinforcement does not prevent deterioration of durability, but by introducing a modifying group into the polymer used, both low loss and durability are achieved. It is known that can be realized. It is known that depending on the type of the modified functional group introduced into the polymer, the interaction with the reinforcing filler is different, and the obtained performance is also affected.
According to studies by the present inventors, it has been found that a modified polymer having a primary amino group introduced has a very high interaction with carbon black and gives a rubber composition excellent in low loss. Regarding introduction of this primary amino group into a polymer, for example, Patent Document 1 discloses a rubber component containing a conjugated diene polymer having a primary amino group and an alkoxysilyl group, and N 2 SA of 30 to 100 m 2 / g. A rubber composition containing the following carbon black is disclosed.
However, in this technique, since alkoxysilyl groups remain in the polymer, there is a concern that when the polymer is blended, alcohol may be released into the atmosphere, and there is a problem in environmental health such as a working environment.
本発明は、このような状況下で、ゴム組成物調製時における混練り時等において、揮発性有機化合物（ＶＯＣ）の発生量が少ない上、低発熱性（低燃費性）に優れるゴム組成物及び該ゴム組成物を用いたタイヤを提供することを目的とするものである。 Under such circumstances, the present invention provides a rubber composition that produces a small amount of volatile organic compound (VOC) during kneading at the time of preparation of the rubber composition and is excellent in low heat buildup (low fuel consumption). And a tire using the rubber composition.
本発明者らは、前記目的を達成するために鋭意研究を重ねた結果、下記の知見を得た。
分子鎖末端にケイ素原子が導入され、該ケイ素原子に１個の水酸基が直接に結合すると共に、第一アミノ基がアルキレン基を介して該ケイ素原子に結合してなる末端構造を有する変性共役ジエン系重合体、あるいはこの変性共役ジエン系重合体の２分子が、それぞれの上記水酸基を介して縮合した末端構造を有する変性共役ジエン系重合体は、末端にカーボンブラックとの相互作用が極めて高い第一アミノ基を有しており、特に大粒径カーボンブラックの配合において、低発熱性（低燃費性）に優れるゴム組成物を与えることを見出した。
また、上記変性共役ジエン系重合体は、分子鎖末端に導入されたケイ素原子に、加水分解性のヒドカルビルオキシ基が結合していないので、ゴム組成物調製における混練り時等において、該ヒドロカルビルオキシ基に由来するアルコールが発生することがなく、ＶＯＣの発生量が極めて少ないことを見出した。
更に、上記の変性共役ジエン系重合体は、活性末端を有する共役ジエン系重合体の該活性末端を、特定の方法により変性することにより、効率よく得ることができることを見出した。
本発明は、かかる知見に基づいて完成したものである。
As a result of intensive studies to achieve the above object, the present inventors have obtained the following knowledge.
A modified conjugated diene having a terminal structure in which a silicon atom is introduced at the end of a molecular chain, one hydroxyl group is directly bonded to the silicon atom, and a primary amino group is bonded to the silicon atom via an alkylene group The modified conjugated diene polymer having a terminal structure in which two molecules of the conjugated polymer or this modified conjugated diene polymer are condensed via the respective hydroxyl groups described above has an extremely high interaction with carbon black at the terminal. It has been found that a rubber composition having a single amino group and excellent in low heat build-up (low fuel consumption) is obtained particularly in the case of blending large particle size carbon black.
In addition, the modified conjugated diene-based polymer has no hydrolyzable hydrcarbyloxy group bonded to the silicon atom introduced into the molecular chain terminal. It has been found that alcohol derived from hydrocarbyloxy groups is not generated and the amount of VOC generated is extremely small.
Furthermore, it has been found that the above modified conjugated diene polymer can be obtained efficiently by modifying the active terminal of the conjugated diene polymer having an active terminal by a specific method.
The present invention has been completed based on such findings.
すなわち、本発明は、
（１）（Ａ）分子鎖末端が、下記一般式（１）で表される構造を有する変性共役ジエン系重合体（ａ−１）及び／又は下記一般式（２）で表される構造を有する変性共役ジエン系重合体（ａ−２）を含むゴム成分と、その１００質量部に対して、（Ｂ）チッ素吸着比表面積（Ｎ2ＳＡ）が２０〜１００ｍ2／ｇであるカーボンブラック１０〜１００質量部を含むことを特徴とするゴム組成物、
That is, the present invention
(1) (A) Modified conjugated diene polymer (a-1) having a structure represented by the following general formula (1) and / or a structure represented by the following general formula (2): Carbon black having a nitrogen adsorption specific surface area (N 2 SA) of 20 to 100 m 2 / g with respect to 100 parts by mass of the rubber component containing the modified conjugated diene polymer (a-2) having A rubber composition comprising 10 to 100 parts by mass,
（２）（Ａ）活性末端を有する共役ジエン系重合体の該活性末端に、１個のヒドロカルビルオキシ基と１個の反応性基とが直接にケイ素原子に結合し、かつ１個の保護された第一アミノ基がアルキレン基を介して該ケイ素原子に結合してなる２官能性ケイ素原子を含む化合物を反応させて変性したのち、加水分解反応及び脱保護反応を行うことにより得られる下記一般式（１）で表される末端構造を有する変性共役ジエン系重合体（ａ−１）を含むゴム成分と、そのゴム成分１００質量部に対して、（Ｂ）チッ素吸着比表面積（Ｎ2ＳＡ）が２０〜１００ｍ2／ｇであるカ−ボンブラック１０〜１００質量部を含むことを特徴とするゴム組成物、
（３）（Ａ）（ａ）活性末端を有する共役ジエン系重合体の該活性末端に、１個のヒドロカルビルオキシ基と１個の反応性基とが直接にケイ素原子に結合し、かつ１個の保護された第一アミノ基がアルキレン基を介して該ケイ素原子に結合してなる２官能性ケイ素原子を含む化合物を反応させて、変性を行う工程、（ｂ）チタン系、スズ系、アルミニウム系、ケイ素系、ジルコニウム系及びビスマス系の中から選ばれる少なくとも一種の縮合促進剤の存在下、前記の２官能性ケイ素原子を含む化合物が関与する縮合反応を行う工程、及び（ｃ）加水分解反応と脱保護反応とを行う工程を施すことにより得られる下記一般式（２）で表される変性共役ジエン系重合体（ａ−２）を含むゴム成分と、そのゴム成分１００質量部に対して、（Ｂ）チッ素吸着比表面積（Ｎ2ＳＡ）が２０〜１００ｍ2／ｇであるカ−ボンブラック１０〜１００質量部を含むことを特徴とするゴム組成物、
（４）活性末端を有する共役ジエン系重合体が、有機アルカリ金属化合物を重合開始剤とし、共役ジエン化合物単独、又は共役ジエン化合物と芳香族ビニル化合物をアニオン重合させて得られたものである上記（２）又は（３）に記載のゴム組成物、
（５）２官能性ケイ素原子を含む化合物が、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、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、Ｎ,Ｎ−ビス（トリメチルシリル）アミノエチルメチルジメトキシシラン、Ｎ,Ｎ−ビス（トリメチルシリル）アミノエチルメチルジエトキシシラン、１−トリメチルシリル−２−エトキシメチル−１−アザ−２−シラシクロペンタン及び３−（２，２，５，５−テトラメチル（１−アザ−２，５−ジシラシクロペンタン）−１−イル）プロピルメチルジエトキシシランの中から選ばれる少なくとも一種である上記（２）〜（４）のいずれかに記載のゴム組成物、
（６）（ｂ）工程で用いられる縮合促進剤が、チタン、スズ及びアルミニウムから選ばれる金属のアルコキシド、カルボン酸塩及びアセチルアセトナート錯塩、又はこれらの混合塩の中から選ばれる少なくとも一種である上記（３）〜（５）のいずれかに記載のゴム組成物、
（７）（Ａ）ゴム成分が、変性共役ジエン系重合体（ａ−１）及び／又は変性共役ジエン系重合体（ａ−２）を１０質量％以上の割合で含む上記（１）〜（６）のいずれかに記載のゴム組成物、
（８）（Ａ）ゴム成分が、変性共役ジエン系重合体（ａ−１）及び／又は変性共役ジエン系重合体（ａ−２）を５０質量％以上の割合で含む上記（７）に記載のゴム組成物、
（９）上記（１）〜（８）のいずれかに記載のゴム組成物を用いてなるタイヤ、及び
（１０）上記（１）〜（８）のいずれかに記載のゴム組成物をサイドウォール、サイド補強層及び／又はビードフィラーに用いてなるタイヤ
を提供するものである。
(2) (A) One hydrocarbyloxy group and one reactive group are directly bonded to the silicon atom at the active end of the conjugated diene polymer having an active end, and one protected The following general compounds obtained by reacting a compound containing a bifunctional silicon atom in which a primary amino group is bonded to the silicon atom via an alkylene group, followed by a hydrolysis reaction and a deprotection reaction For the rubber component containing the modified conjugated diene polymer (a-1) having a terminal structure represented by the formula (1) and 100 parts by mass of the rubber component, (B) nitrogen adsorption specific surface area (N 2 A rubber composition comprising 10 to 100 parts by mass of carbon black having a SA) of 20 to 100 m 2 / g,
(3) (A) (a) One hydrocarbyloxy group and one reactive group are directly bonded to the silicon atom at the active end of the conjugated diene polymer having an active end, and one A step of modifying by reacting a compound containing a bifunctional silicon atom in which the protected primary amino group is bonded to the silicon atom via an alkylene group, (b) titanium-based, tin-based, aluminum A step of performing a condensation reaction involving the above-mentioned compound containing a bifunctional silicon atom in the presence of at least one condensation accelerator selected from the group consisting of silicon, silicon, zirconium and bismuth, and (c) hydrolysis A rubber component containing a modified conjugated diene polymer (a-2) represented by the following general formula (2) obtained by performing a step of performing a reaction and a deprotection reaction, and 100 parts by mass of the rubber component (B) Ca nitrogen adsorption specific surface area (N 2 SA) is 20 to 100 m 2 / g - a rubber composition characterized by containing carbon black 10 to 100 parts by weight,
(4) The above conjugated diene polymer having an active end is obtained by anionic polymerization of a conjugated diene compound alone or a conjugated diene compound and an aromatic vinyl compound using an organic alkali metal compound as a polymerization initiator. (2) or the rubber composition according to (3),
(5) The compound containing a bifunctional silicon atom is N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, or N, N-bis (trimethylsilyl). Aminoethylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane, 1-trimethylsilyl-2-ethoxymethyl-1-aza-2-silacyclopentane and 3- (2,2,5,5) -Tetramethyl (1-aza-2,5-disilacyclopentane) -1-yl) propylmethyldiethoxysilane is at least one selected from the above (2) to (4) Rubber composition,
(6) The condensation accelerator used in step (b) is at least one selected from metal alkoxides, carboxylates and acetylacetonate complex salts selected from titanium, tin and aluminum, or mixed salts thereof. The rubber composition according to any one of (3) to (5) above,
(7) The above (1) to (A) in which the rubber component (A) contains the modified conjugated diene polymer (a-1) and / or the modified conjugated diene polymer (a-2) in a proportion of 10% by mass or more. 6) The rubber composition according to any one of
(8) (A) The rubber component is described in (7) above, in which the modified conjugated diene polymer (a-1) and / or the modified conjugated diene polymer (a-2) is contained in a proportion of 50% by mass or more. Rubber composition,
(9) A tire using the rubber composition according to any one of (1) to (8) above, and (10) a rubber composition according to any one of (1) to (8) above as a sidewall The present invention provides a tire used for a side reinforcing layer and / or a bead filler.
本発明によれば、アルキレン基を介して第一アミノ基が結合し、かつ加水分解性ヒドロカルビルオキシ基が結合していないケイ素原子が、分子鎖末端に導入された特定の末端構造を有する変性共役ジエン系重合体は、特に大粒径のカーボンブラックの配合において、低発熱性（低燃費性）に優れるゴム組成物及び該ゴム組成物を用いたタイヤを提供することができる。また、このゴム組成物は、加水分解性のヒドロカルビルオキシ基を含まないことから、混練り時等において、それに由来するアルコールの発生がなく、ＶＯＣの発生量を低く抑えることができる。
また、上記変性共役ジエン系重合体は、未変性共役ジエン系重合体の活性末端を特定の方法で変性することにより、効率よく製造することができる。
According to the present invention, a modified conjugate having a specific terminal structure in which a silicon atom to which a primary amino group is bonded via an alkylene group and a hydrolyzable hydrocarbyloxy group is not bonded is introduced to the molecular chain terminal. The diene polymer can provide a rubber composition excellent in low heat build-up (low fuel consumption) and a tire using the rubber composition, particularly when blended with carbon black having a large particle size. Moreover, since this rubber composition does not contain a hydrolyzable hydrocarbyloxy group, there is no generation of alcohol derived from it during kneading and the like, and the amount of VOC generated can be kept low.
The modified conjugated diene polymer can be efficiently produced by modifying the active terminal of the unmodified conjugated diene polymer by a specific method.
まず、本発明のゴム組成物について説明する。
［ゴム組成物］
本発明のゴム組成物は、（Ａ）変性共役ジエン系重合体（ａ−１）及び／又は変性共役ジエン系重合体（ａ−２）を含むゴム成分と、その１００質量部に対して、（Ｂ）チッ素吸着比表面積（Ｎ2ＳＡ）が２０〜１００ｍ2／ｇであるカーボンブラック１０〜１００質量部を含むことを特徴とする。
（変性共役ジエン系重合体（ａ−１））
本発明のゴム組成物において、（Ａ）成分のゴム成分に用いられる変性共役ジエン系重合体（ａ−１）は、分子鎖末端が、下記一般式（１）
First, the rubber composition of the present invention will be described.
[Rubber composition]
The rubber composition of the present invention comprises (A) a rubber component containing a modified conjugated diene polymer (a-1) and / or a modified conjugated diene polymer (a-2), and 100 parts by mass thereof. (B) nitrogen adsorption specific surface area (N 2 SA), characterized in that it contains carbon black from 10 to 100 parts by weight is 20 to 100 m 2 / g.
(Modified Conjugated Diene Polymer (a-1))
In the rubber composition of the present invention, the modified conjugated diene polymer (a-1) used for the rubber component (A) has a molecular chain terminal represented by the following general formula (1).
で表される構造を有している。
上記Ｒ1で表される炭素数１〜２０のヒドロカルビル基は、炭素数１〜２０のアルキル基、炭素数２〜２０のアルケニル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基等を挙げることができるが、これらの中で、炭素数１〜２０のアルキル基が好ましい。炭素数１〜２０のアルキル基は、直鎖状、分岐状、環状のいずれであってもよく、例えばメチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、各種ペンチル基、各種ヘキシル基、各種オクチル基、各種デシル基、各種ドデシル基、各種テトラデシル基、各種ヘキサデシル基、各種オクタデシル基、各種イコシル基、シクロペンチル基、シクロヘキシル基、メチルシクロペンチル基、シクロペンチルメチル基、メチルシクロヘキシル基、シクロヘキシルメチル基等を挙げることができる。これらの中で、原料の入手容易さ等の観点から、メチル基及びエチル基が好適である。
It has the structure represented by these.
The hydrocarbyl group having 1 to 20 carbon atoms represented by R 1 is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a 7 to 20 carbon atom. Although an aralkyl group etc. can be mentioned, Among these, a C1-C20 alkyl group is preferable. The alkyl group having 1 to 20 carbon atoms may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -Butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, various tetradecyl groups, various hexadecyl groups, various octadecyl groups, various icosyl groups, cyclopentyl group, cyclohexyl group And methylcyclopentyl group, cyclopentylmethyl group, methylcyclohexyl group, cyclohexylmethyl group and the like. Among these, a methyl group and an ethyl group are preferable from the viewpoint of availability of raw materials.
一方、Ｒ2は、炭素数１〜１２のアルキレン基であり、このアルキレン基は直鎖状、分岐状、環状のいずれであってもよく、その具体例としては、メチレン基、エチレン基、プロパン−１，３−ジイル基、ブタン−１，３−ジイル基、ブタン−１，４−ジイル基、ペンタン−１，３−ジイル基、ペンタン−１，５−ジイル基、ヘキサン−１，３−ジイル基、ヘキサン−１，６−ジイル基、ヘプタン−１，３−ジイル基、ヘプタン−１，７−ジイル基、オクタン−１，８−ジイル基、ノナン−１，９−ジイル基、デカン−１，１０−ジイル基、シクロペンタン−１，３−ジイル基、シクロヘキサン−１，４−ジイル基等が挙げられる。これらの中で、原料の入手容易さ及び性能等の観点から、エチレン基及びプロパン−１，３−ジイル基が好適である。
なお、−（ｐｏｌｙｍｅｒ）は共役ジエン系重合体のポリマー鎖である。
On the other hand, R 2 is an alkylene group having 1 to 12 carbon atoms, and this alkylene group may be linear, branched or cyclic, and specific examples thereof include a methylene group, an ethylene group, and propane. -1,3-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, pentane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,3- Diyl group, hexane-1,6-diyl group, heptane-1,3-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane- 1,10-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group and the like can be mentioned. Among these, an ethylene group and a propane-1,3-diyl group are preferable from the viewpoint of availability of raw materials and performance.
In addition,-(polymer) is a polymer chain of a conjugated diene polymer.
（変性共役ジエン系重合体（ａ−１）の製造）
前述した、分子鎖末端が前記一般式（１）で表される構造を有する変性共役ジエン系重合体（ａ−１）は、本発明の方法によれば、効率よく製造することができる。
本発明の変性共役ジエン系重合体（ａ−１）の製造方法は、活性末端を有する共役ジエン系重合体の該活性末端に、１個のヒドロカルビルオキシ基と１個の反応性基とが直接にケイ素原子に結合し、かつ１個の保護された第一アミノ基がアルキレン基を介して該ケイ素原子に結合してなる２官能性ケイ素原子を含む化合物を反応させて変性したのち、加水分解反応及び脱保護反応を行うことにより、上記一般式（１）で表される末端構造を有する変性共役ジエン系重合体（ａ−１）を得ることを特徴とする。
＜活性末端を有する共役ジエン系重合体＞
本発明の方法において用いられる活性末端を有する共役ジエン系重合体は、ジエン系モノマーを単独で、又は他のモノマーと共重合して得られるものであり、その製造方法については特に制限はなく、溶液重合法、気相重合法、バルク重合法のいずれも用いることができるが、特に溶液重合法が好ましい。また、重合形式は、回分式及び連続式のいずれであってもよい。
また、共役ジエン系重合体の分子中に存在する活性部位の金属はアルカリ金属及びアルカリ土類金属から選ばれる１種であることが好ましく、アルカリ金属が好ましく、特にリチウム金属が好ましい。
(Production of Modified Conjugated Diene Polymer (a-1))
The above-mentioned modified conjugated diene polymer (a-1) having a molecular chain terminal represented by the general formula (1) can be efficiently produced according to the method of the present invention.
In the process for producing the modified conjugated diene polymer (a-1) of the present invention, one hydrocarbyloxy group and one reactive group are directly attached to the active terminal of the conjugated diene polymer having an active terminal. And then modified by reacting with a compound containing a bifunctional silicon atom which is bonded to a silicon atom and one protected primary amino group is bonded to the silicon atom via an alkylene group. By performing the reaction and deprotection reaction, a modified conjugated diene polymer (a-1) having a terminal structure represented by the general formula (1) is obtained.
<Conjugated diene polymer having active terminal>
The conjugated diene polymer having an active terminal used in the method of the present invention is obtained by copolymerizing a diene monomer alone or with another monomer, and the production method is not particularly limited. Any of a solution polymerization method, a gas phase polymerization method and a bulk polymerization method can be used, but a solution polymerization method is particularly preferable. Moreover, any of a batch type and a continuous type may be sufficient as the superposition | polymerization form.
The active site metal present in the molecule of the conjugated diene polymer is preferably one selected from alkali metals and alkaline earth metals, preferably alkali metals, and particularly preferably lithium metal.
上記溶液重合法においては、例えば有機アルカリ金属化合物、特にリチウム化合物を重合開始剤とし、共役ジエン化合物単独又は共役ジエン化合物と芳香族ビニル化合物をアニオン重合させることにより、目的の重合体を製造することができる。
更には、ハロゲン含有モノマーを混在させ、ポリマー中のハロゲン原子を有機金属化合物によって活性化することも有効である。例えば、イソブチレン単位、パラメチルスチレン単位及びパラブロモメチルスチレン単位を含む共重合体の臭素部分をリチオ化して活性部位とすることも有効である。
In the solution polymerization method, for example, an organic alkali metal compound, particularly a lithium compound is used as a polymerization initiator, and a conjugated diene compound alone or a conjugated diene compound and an aromatic vinyl compound are anionically polymerized to produce a target polymer. Can do.
Furthermore, it is also effective to mix a halogen-containing monomer and activate a halogen atom in the polymer with an organometallic compound. For example, it is also effective to lithiate the bromine moiety of a copolymer containing an isobutylene unit, a paramethylstyrene unit and a parabromomethylstyrene unit to form an active site.
上記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、１．３−ペンタジエン、２，３−ジメチル−１，３−ブタジエン、２−フェニル−１，３−ブタジエン、１、３−ヘキサジエン等が挙げられる。これらは単独で用いてもよく、二種以上組み合わせて用いてもよいが、これらの中で、１，３−ブタジエン、イソプレン及び２，３−ジメチル−１，３−ブタジエンが特に好ましい。
また、これらの共役ジエン化合物との共重合に用いられる芳香族ビニル化合物としては、例えばスチレン、α−メチルスチレン、１−ビニルナフタレン、３−ビニルトルエン、エチルビニルベンゼン、ジビニルベンゼン、４−シクロへキシルスチレン、２，４，６−トリメチルスチレン等が挙げられる。これらは単独で用いてもよく、二種以上を組み合わせて用いてもよいが、これらの中で、スチレンが特に好ましい。
Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 1.3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-hexadiene, and the like. Is mentioned. These may be used singly or in combination of two or more. Among these, 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene are particularly preferable.
Examples of the aromatic vinyl compound used for copolymerization with these conjugated diene compounds include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-vinyltoluene, ethylvinylbenzene, divinylbenzene, and 4-cyclohexane. Xylstyrene, 2,4,6-trimethylstyrene and the like can be mentioned. These may be used alone or in combination of two or more, but among these, styrene is particularly preferred.
更に、単量体として共役ジエン化合物と芳香族ビニル化合物を用いて共重合を行う場合、それぞれ１，３−ブタジエン及びスチレンの使用が、単量体の入手の容易さ等の実用性面、及びアニオン重合特性がリビング性等の点で優れること等から、特に好適である。
また、溶液重合法を用いた場合には、溶媒中の単量体濃度は、好ましくは５〜５０質量％、より好ましくは１０〜３０質量％である。尚、共役ジエン化合物と芳香族ビニル化合物を用いて共重合を行う場合、仕込み単量体混合物中の芳香族ビニル化合物の含量は０〜５５質量％の範囲が好ましい。
Furthermore, when copolymerization is carried out using a conjugated diene compound and an aromatic vinyl compound as monomers, the use of 1,3-butadiene and styrene, respectively, makes practical use such as the availability of monomers, and The anionic polymerization characteristics are particularly preferable because of excellent living characteristics and the like.
When the solution polymerization method is used, the monomer concentration in the solvent is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. In addition, when copolymerizing using a conjugated diene compound and an aromatic vinyl compound, the content of the aromatic vinyl compound in the charged monomer mixture is preferably in the range of 0 to 55% by mass.
重合開始剤のリチウム化合物としては、特に制限はないが、ヒドロカルビルリチウム及びリチウムアミド化合物が好ましく用いられ、前者のヒドロカルビルリチウムを用いる場合には、重合開始末端にヒドロカルビル基を有し、かつ他方の末端が重合活性部位である共役ジエン系重合体が得られる。また、後者のリチウムアミド化合物を用いる場合には、重合開始末端に窒素含有基を有し、他方の末端が重合活性部位である共役ジエン系重合体が得られる。 The lithium compound of the polymerization initiator is not particularly limited, but hydrocarbyl lithium and lithium amide compounds are preferably used. When the former hydrocarbyl lithium is used, it has a hydrocarbyl group at the polymerization initiation terminal and the other terminal. A conjugated diene polymer having a polymerization active site is obtained. When the latter lithium amide compound is used, a conjugated diene polymer having a nitrogen-containing group at the polymerization initiation terminal and the other terminal being a polymerization active site is obtained.
上記ヒドロカルビルリチウムとしては、炭素数２〜２０のヒドロカルビル基を有するものが好ましく、例えばエチルリチウム、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−オクチルリチウム、ｎ−デシルリチウム、フェニルリチウム、２−ナフチルリチウム、２−ブチルーフェニルリチウム、4−フェニルーブチルリチウム、シクロへキシルリチウム、シクロペンチルリチウム、ジイソプロペニルベンゼンとブチルリチウムとの反応生成物等が挙げられるが、これらの中で、特にｎ−ブチルリチウムが好適である。 As the hydrocarbyl lithium, those having a hydrocarbyl group having 2 to 20 carbon atoms are preferable, for example, ethyl lithium, n-propyl lithium, isopropyl lithium, n-butyl lithium, sec-butyl lithium, tert-octyl lithium, n-decyl. Examples include lithium, phenyl lithium, 2-naphthyl lithium, 2-butyl-phenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, cyclopentyl lithium, a reaction product of diisopropenylbenzene and butyl lithium, and the like. Of these, n-butyllithium is particularly preferred.
一方、リチウムアミド化合物としては、例えばリチウムヘキサメチレンイミド、リチウムピロリジド、リチウムピぺリジド、リチウムへプタメチレンイミド、リチウムドデカメチレンイミド、リチウムジメチルアミド、リチウムジエチルアミド、リチウムジブチルアミド、リチウムジプロピルアミド、リチウムジへプチルアミド、リチウムジへキシルアミド、リチウムジオクチルアミド、リチウムジ−２−エチルへキシルアミド、リチウムジデシルアミド、リチウム−N−メチルピベラジド、リチウムエチルプロピルアミド、リチウムエチルブチルアミド、リチウムエチルベンジルアミド、リチウムメチルフェネチルアミド等が挙げられる。これらの中で、カーボンブラックに対する相互作用効果及び重合開始能の点から、リチウムヘキサメチレンイミド、リチウムピロリジド、リチウムピぺリジド、リチウムへプタメチレンイミド、リチウムドデカメチレンイミド等の環状リチウムアミドが好ましく、特にリチウムヘキサメチレンイミド及びリチウムピロリジドが好適である。 On the other hand, examples of the lithium amide compound include lithium hexamethylene imide, lithium pyrrolidide, lithium piperide, lithium heptamethylene imide, lithium dodecamethylene imide, lithium dimethyl amide, lithium diethyl amide, lithium dibutyl amide, lithium dipropyl amide, and lithium disulfide. Heptylamide, lithium dihexylamide, lithium dioctylamide, lithium di-2-ethylhexylamide, lithium didecylamide, lithium-N-methylpiverazide, lithium ethylpropylamide, lithium ethylbutyramide, lithium ethylbenzylamide, lithium methylphenethylamide, etc. Is mentioned. Among these, from the viewpoint of the interaction effect on carbon black and the ability of initiating polymerization, cyclic lithium amides such as lithium hexamethylene imide, lithium pyrrolidide, lithium piperidide, lithium heptamethylene imide, and lithium dodecamethylene imide are preferable. In particular, lithium hexamethylene imide and lithium pyrrolidide are suitable.
これらのリチウムアミド化合物は、一般に、第二アミンとリチウム化合物とから、予め調製したものを重合に使用することができるが、重合系中（ｉｎ−Ｓｉｔｕ）で調製することもできる。また、この重合開始剤の使用量は、好ましくは単量体１００g当たり、０．２〜２０ミリモルの範囲で選定される。
前記リチウム化合物を重合開始剤として用い、アニオン重合によって共役ジエン系重合体を製造する方法としては、特に制限はなく、従来公知の方法を用いることができる。
In general, these lithium amide compounds prepared from a secondary amine and a lithium compound can be used for polymerization, but can also be prepared in a polymerization system (in-situ). The amount of the polymerization initiator used is preferably selected in the range of 0.2 to 20 mmol per 100 g of monomer.
There is no restriction | limiting in particular as a method of manufacturing a conjugated diene polymer by anionic polymerization using the said lithium compound as a polymerization initiator, A conventionally well-known method can be used.
具体的には、反応に不活性な有機溶剤、例えば脂肪族、脂環族、芳香族炭化水素化合物等の炭化水素系溶剤中において、共役ジエン化合物又は共役ジエン化合物と芳香族ビニル化合物を、前記リチウム化合物を重合開始剤として、所望により、用いられるランダマイザーの存在下にアニオン重合させることにより、目的の共役ジエン系重合体が得られる。 Specifically, in an organic solvent inert to the reaction, for example, a hydrocarbon solvent such as an aliphatic, alicyclic, or aromatic hydrocarbon compound, the conjugated diene compound or the conjugated diene compound and the aromatic vinyl compound are The desired conjugated diene polymer can be obtained by anionic polymerization in the presence of a randomizer to be used, if desired, using a lithium compound as a polymerization initiator.
前記炭化水素系溶剤としては、炭素数３〜８のものが好ましく、例えばプロパン、ｎ−ブタン、イソブタン、ｎ−ペンタン、イソペンタン、ｎ−ヘキサン、シクロヘキサン、プロペン、１−ブテン、イソブテン、トランス−２−ブテン、シス−２−ブテン、１−ペンテン、２−ペンテン、１−へキセン、２−へキセン、ベンゼン、トルエン、キシレン、エチルベンゼン等を挙げることができる。これらは単独で用いてもよく、二種以上を混合して用いてもよい。 The hydrocarbon solvent is preferably one having 3 to 8 carbon atoms, such as propane, n-butane, isobutane, n-pentane, isopentane, n-hexane, cyclohexane, propene, 1-butene, isobutene and trans-2. -Butene, cis-2-butene, 1-pentene, 2-pentene, 1-hexene, 2-hexene, benzene, toluene, xylene, ethylbenzene and the like. These may be used alone or in combination of two or more.
また、所望により用いられるランダマイザーとは共役ジエン系重合体のミクロ構造の制御、例えばブタジエン−スチレン共重合体におけるブタジエン部分の１，２結合、イソプレン重合体における３，４結合の増加等、あるいは共役ジエン化合物−芳香族ビニル化合物共重合体における単量体単位の組成分布の制御、例えばブタジエン−スチレン共重合体におけるブタジエン単位、スチレン単位のランダム化等の作用を有する化合物のことである。このランダマイザーとしては、特に制限はなく、従来ランダマイザーとして一般に使用されている公知の化合物の中から任意のものを適宜選択して用いることができる。具体的には、ジメトキシベンゼン、テトラヒドロフラン、ジメトキシエタン、ジ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、オキソラニルプロパンオリゴマー類［特に２，２−ビス（２−テトラヒドロフリル）−プロパンを含む物等］、トリエチルアミン、ピリジン、N−メチルモルホリン、N，N，N’，N’−テトラメチルエチレンジアミン、１，２−ジピぺリジノエタン等のエーテル類及び三級アミン類等を挙げることができる。また、カリウム−ｔ−アミレート、カリウム−ｔ−ブトキシド等のカリウム塩類、ナトリウム−ｔ−アミレート等のナトリウム塩類も用いることができる。
これらのランダマイザーは、一種を単独で用いてもよく、二種以上を組み合わせて用いてもよい。また、その使用量は、リチウム化合物１モル当たり、好ましくは０．０１〜１０００モル当量の範囲で選択される。
The randomizer used as desired is a control of the microstructure of the conjugated diene polymer, such as an increase in 1,2 bonds in the butadiene portion in the butadiene-styrene copolymer, an increase in 3,4 bonds in the isoprene polymer, or the like. It is a compound having an action of controlling the composition distribution of monomer units in a conjugated diene compound-aromatic vinyl compound copolymer, for example, randomizing butadiene units and styrene units in a butadiene-styrene copolymer. The randomizer is not particularly limited, and any one of known compounds generally used as a conventional randomizer can be appropriately selected and used. Specifically, dimethoxybenzene, tetrahydrofuran, dimethoxyethane, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, oxolanylpropane oligomers [especially those containing 2,2-bis (2-tetrahydrofuryl) -propane, etc.], triethylamine, pyridine N-methylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, ethers such as 1,2-dipiperidinoethane, and tertiary amines. Further, potassium salts such as potassium-t-amylate and potassium-t-butoxide, and sodium salts such as sodium-t-amylate can also be used.
One of these randomizers may be used alone, or two or more thereof may be used in combination. The amount used is preferably selected in the range of 0.01 to 1000 molar equivalents per mole of the lithium compound.
この重合反応における温度は、好ましくは０〜１５０℃、より好ましくは２０〜１３０℃の範囲で選定される。重合反応は、発生圧力下で行うことができるが、通常は単量体を実質的に液相に保つに十分な圧力で操作することが望ましい。すなわち、圧力は重合される個々の物質や、用いる重合媒体及び重合温度にもよるが、所望ならばより高い圧力を用いることができ、このような圧力は重合反応に関して不活性なガスで反応器を加圧する等の適当な方法で得られる。
この重合においては、重合開始剤、溶媒、単量体等、重合に関与する全ての原材料は、水、酸素、二酸化炭素、プロトン性化合物等の反応阻害物質を除去したものを用いることが望ましい。
尚、エラストマーとして重合体を得る場合は、得られる重合体又は共重合体の、示差熱分析法により求めたガラス転移温度（Ｔｇ）が−９５℃〜−１５℃であることが好ましい。ガラス転移温度を上記範囲にすることによって、粘度が高くなるのを抑え、取り扱いが容易な重合体を得ることができる。
The temperature in this polymerization reaction is preferably selected in the range of 0 to 150 ° C, more preferably 20 to 130 ° C. The polymerization reaction can be carried out under generated pressure, but it is usually desirable to operate at a pressure sufficient to keep the monomer in a substantially liquid phase. That is, the pressure depends on the particular material being polymerized, the polymerization medium used and the polymerization temperature, but higher pressures can be used if desired, such pressure being a gas that is inert with respect to the polymerization reaction. Can be obtained by an appropriate method such as pressurizing.
In this polymerization, it is desirable to use all raw materials involved in the polymerization, such as a polymerization initiator, a solvent, and a monomer, from which reaction inhibitors such as water, oxygen, carbon dioxide, and protic compounds have been removed.
In addition, when obtaining a polymer as an elastomer, it is preferable that the glass transition temperature (Tg) calculated | required by the differential thermal analysis method of the obtained polymer or copolymer is -95 degreeC--15 degreeC. By setting the glass transition temperature within the above range, it is possible to suppress the increase in viscosity and obtain a polymer that is easy to handle.
＜２官能性ケイ素原子を含む化合物＞
本発明においては、上記のようにして得られた共役ジエン系重合体の活性末端に、１個のヒドロカルビルオキシ基と、１個の反応性基とが直接にケイ素原子に結合し、かつ１個の保護された第一アミノ基がアルキレン基を介して該ケイ素原子に結合してなる２官能性ケイ素原子を含む化合物（以下、「変性剤」と称することがある。）を反応させて変性反応を行う。
当該変性剤としては、例えば一般式（３）、一般式（４）及び一般式（５）で表されるケイ素化合物を挙げることができる。
<Compound containing bifunctional silicon atom>
In the present invention, one hydrocarbyloxy group and one reactive group are directly bonded to a silicon atom at the active terminal of the conjugated diene polymer obtained as described above, and one A modification reaction by reacting a compound containing a bifunctional silicon atom in which the protected primary amino group is bonded to the silicon atom via an alkylene group (hereinafter sometimes referred to as “modifier”). I do.
As the said modifier | denaturant, the silicon compound represented, for example by General formula (3), General formula (4), and General formula (5) can be mentioned.
上記炭素数１〜２０のヒドロカルビル基については、前記一般式（１）におけるＲ1、一般式（２）におけるＲ3で説明したとおりである。また、Ｒ17で示される炭素数１〜１２のアルキレン基としては、メチレン基、エチレン基、プロパン−１，３−ジイル基、ブタン−１，３−ジイル基、ブタン−１，４−ジイル基、ペンタン−１，３−ジイル基、ペンタン−１，５−ジイル基、ヘキサン−１，３−ジイル基、ヘキサン−１，６−ジイル基、ヘプタン−１，３−ジイル基、ヘプタン−１，７−ジイル基、オクタン−１，８−ジイル基、ノナン−１，９−ジイル基、デカン−１，１０−ジイル基、シクロペンタン−１，３−ジイル基、シクロヘキサン−１，４−ジイル基等が挙げられる。
The hydrocarbyl groups of carbon number 1 to 20, R 1 in the general formula (1) is as described for R 3 in the general formula (2). Examples of the alkylene group having 1 to 12 carbon atoms represented by R 17 include a methylene group, an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, and a butane-1,4-diyl group. , Pentane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,3-diyl group, hexane-1,6-diyl group, heptane-1,3-diyl group, heptane-1, 7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1,10-diyl group, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group Etc.
当該変性剤における上記反応性基Ａ1、Ａ2がヒドロカルビルオキシ基である場合、当該変性剤としては、例えば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、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、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルメチルジメトキシシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルメチルジエトキシシラン、１−トリメチルシリル−２，２−エトキシメチル−１−アザ−２−シラシクロペンタン及び３−（２，２，５，５−テトラメチル（１−アザ−２，５−ジシラシクロペンタン）−１−イル）プロピルメチルジエトキシシラン等を挙げることができる。 When the reactive groups A 1 and A 2 in the modifier are hydrocarbyloxy groups, examples of the modifier include N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane and N, N-bis (trimethylsilyl). Aminopropylmethyldiethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminoethylmethyldiethoxysilane, 1-trimethylsilyl-2,2-ethoxymethyl-1-aza -2-silacyclopentane and 3- (2,2,5,5-tetramethyl (1-aza-2,5-disilacyclopentane) -1-yl) propylmethyldiethoxysilane .
また、上記反応性基Ａ1、Ａ2がハロゲン原子である場合、当該変性剤としては、例えばＮ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルメトキシクロロシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノプロピルメチルエトキシクロロシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルメチルメトキシクロロシラン、Ｎ，Ｎ−ビス（トリメチルシリル）アミノエチルメチルエトキシクロロシラン等が挙げられる。 When the reactive groups A 1 and A 2 are halogen atoms, examples of the modifier include N, N-bis (trimethylsilyl) aminopropylmethylmethoxychlorosilane, N, N-bis (trimethylsilyl) aminopropylmethyl. Examples include ethoxychlorosilane, N, N-bis (trimethylsilyl) aminoethylmethylmethoxychlorosilane, N, N-bis (trimethylsilyl) aminoethylmethylethoxychlorosilane, and the like.
当該変性剤の好ましいものとしては、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、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、１−トリメチルシリル−２，２−エトキシメチル−１−アザ−２−シラシクロペンタン、３−（２，２，５，５−テトラメチル（１−アザ−２，５−ジシラシクロペンタン−１−イル）プロピルメチルジエトキシシランである。 Preferred examples of the modifier include N, N-bis (trimethylsilyl) aminopropylmethyldimethoxysilane, N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane, 1-trimethylsilyl-2,2-ethoxymethyl-1 -Aza-2-silacyclopentane, 3- (2,2,5,5-tetramethyl (1-aza-2,5-disilacyclopentan-1-yl) propylmethyldiethoxysilane.
これらの変性剤は、１種単独で用いてもよく、２種以上組み合わせて用いてもよい。またこの変性剤は部分縮合物であってもよい。
ここで、部分縮合物とは、変性剤のＳｉ−ＯＲの一部（全部ではない）が縮合によりＳｉ−Ｏ−Ｓｉ結合したものをいう。
上記の変性反応においては、使用する共役ジエン系重合体は、少なくとも１０％のポリマー鎖がリビング性を有するものが好ましい。
These modifiers may be used alone or in combination of two or more. The modifier may be a partial condensate.
Here, the partial condensate refers to a product in which a part (but not all) of Si-OR as a modifier is Si-O-Si bonded by condensation.
In the above modification reaction, it is preferable that the conjugated diene polymer to be used has at least 10% of polymer chains having a living property.
当該変性剤による変性反応において、該変性剤の使用量は、好ましくは０．５〜２００ｍｍｏｌ／ｋｇ・共役ジエン系重合体である。同含有量は、更に好ましくは１〜１００ｍｍｏｌ／ｋｇ・共役ジエン系重合体であり、特に好ましくは２〜５０ｍｍｏｌ／ｋｇ・共役ジエン系重合体である。ここで、共役ジエン系重合体とは、製造時又は製造後、添加される老化防止剤等の添加剤を含まないポリマーのみの質量を意味する。変性剤の使用量を上記範囲にすることによって、カーボンブラックの分散性に優れ、加硫後の機械特性、耐摩耗性、低発熱性が改良される。
なお、上記変性剤の添加方法は、特に制限されず、一括して添加する方法、分割して添加する方法、あるいは、連続的に添加する方法等が挙げられるが、一括して添加する方法が好ましい。
In the modification reaction with the modifying agent, the amount of the modifying agent is preferably 0.5 to 200 mmol / kg · conjugated diene polymer. The content is more preferably 1 to 100 mmol / kg · conjugated diene polymer, and particularly preferably 2 to 50 mmol / kg · conjugated diene polymer. Here, the conjugated diene polymer means the mass of only a polymer that does not contain an additive such as an anti-aging agent added during or after the production. By making the usage-amount of a modifier into the said range, it is excellent in the dispersibility of carbon black, and the mechanical characteristics after a vulcanization, abrasion resistance, and low exothermic property are improved.
In addition, the addition method of the modifier is not particularly limited, and examples thereof include a batch addition method, a division addition method, a continuous addition method, and the like. preferable.
本発明においては、このようにして共役ジエン系重合体の活性末端に変性反応を施したのち、加水分解反応及び脱保護反応を行い、Ｓｉ原子に結合しているヒドロカルビルオキシ基又はハロゲン原子等の加水分解性官能基を水酸基に変換すると共に、保護されている第一アミノ基の脱保護を行って、遊離した第一アミンに変換する。
上記加水分解反応は、塩基性化合物と水とを加えて行うことが好ましい。塩基性化合物と水とを同時に加えても良いが、先に塩基性化合物又は塩基性化合物水溶液を重合反応系に加え、ｐＨが９〜１３、好ましくは１０〜１１になったことを確認してから、開始剤のＬｉモル量より過剰なモル量の水、例えば、２〜４倍のモル量の水を加え、加水分解が終了するまで、例えば、１０分〜数時間重合反応系を撹拌するのが良い。
前記塩基性化合物としては、水酸化ナトリウム、水酸化カリウム等の水酸化アルカリ金属がコスト面から好ましく、水酸化ナトリウムが特に好ましい。
このようにして、加水分解反応及び脱保護反応を終了後、２，６−ジ−ｔ−ブチル−ｐ−クレゾール（ＢＨＴ）のイソプロパノール溶液等を重合反応系に加えて、重合反応を停止する。
その後、水蒸気を吹き込んで溶剤の分圧を下げるスチームストリッピング等の脱溶媒処理や真空乾燥処理を施すことにより、分子鎖末端が、前記一般式（１）で表される構造を有する変性共役ジエン系重合体（ａ−１）が得られる。
In the present invention, after subjecting the active end of the conjugated diene polymer to a modification reaction in this way, a hydrolysis reaction and a deprotection reaction are carried out to obtain a hydrocarbyloxy group bonded to the Si atom, a halogen atom or the like. The hydrolyzable functional group is converted into a hydroxyl group, and the protected primary amino group is deprotected to convert it into a free primary amine.
The hydrolysis reaction is preferably performed by adding a basic compound and water. Basic compound and water may be added at the same time, but first add basic compound or basic compound aqueous solution to polymerization reaction system and confirm that pH is 9-13, preferably 10-11. Then, a molar amount of water more than the molar amount of Li of the initiator, for example, 2 to 4 times the molar amount of water is added, and the polymerization reaction system is stirred, for example, for 10 minutes to several hours until hydrolysis is completed. Is good.
As the basic compound, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferable from the viewpoint of cost, and sodium hydroxide is particularly preferable.
In this way, after completion of the hydrolysis reaction and deprotection reaction, an isopropanol solution of 2,6-di-t-butyl-p-cresol (BHT) or the like is added to the polymerization reaction system to stop the polymerization reaction.
Thereafter, a modified conjugated diene having a molecular chain terminal having a structure represented by the general formula (1) is obtained by performing a desolvation treatment such as steam stripping to reduce the partial pressure of the solvent by blowing water vapor or a vacuum drying treatment. A system polymer (a-1) is obtained.
（変性共役ジエン系重合体（ａ−２））
本発明のゴム組成物において、（Ａ）成分のゴム成分に用いられる変性共役ジエン系重合体（ａ−２）は分子鎖末端が、下記一般式（２）
(Modified Conjugated Diene Polymer (a-2))
In the rubber composition of the present invention, the modified conjugated diene polymer (a-2) used for the rubber component (A) has a molecular chain terminal represented by the following general formula (2).
で表される構造を有している。
上記Ｒ3で表される炭素数１〜２０のヒドロカルビル基及びＲ5のうちの炭素数１〜２０のヒドロカルビル基は、前記一般式（１）のＲ1で説明したとおりである。また、Ｒ4で表される炭素数１〜１２のアルキレン基は、前記一般式（１）のＲ2で説明したとおりである。
なお、−（ｐｏｌｙｍｅｒ）は共役ジエン系重合体のポリマー鎖である。
It has the structure represented by these.
The hydrocarbyl group having 1 to 20 carbon atoms represented by R 3 and the hydrocarbyl group having 1 to 20 carbon atoms out of R 5 are as described for R 1 in the general formula (1). Further, an alkylene group having 1 to 12 carbon atoms represented by R 4 are as described in the R 2 of the general formula (1).
In addition,-(polymer) is a polymer chain of a conjugated diene polymer.
（変性共役ジエン系重合体（ａ−２）の製造）
前述した、分子鎖末端が前記一般式（２）で表される構造を有する変性共役ジエン系重合体（ａ−２）は、本発明の方法によれば、効率よく製造することができる。
本発明の変性共役ジエン系重合体（ａ−２）の製造方法は、（ａ）活性末端を有する共役ジエン系重合体の該活性末端に、１個のヒドロカルビルオキシ基と１個の反応性基とが直接にケイ素原子に結合し、かつ１個の保護された第一アミノ基がアルキレン基を介して該ケイ素原子に結合してなる２官能性ケイ素原子を含む化合物を反応させて、変性を行う工程、（ｂ）チタン系、スズ（錫）系、アルミニウム系、ケイ素系、ジルコニウム系及びビスマス系の中から選ばれる少なくとも一種の縮合促進剤の存在下、前記の２官能性ケイ素原子を含む化合物が関与する縮合反応を行う工程、及び（ｃ）加水分解反応と脱保護反応とを行う工程を施し、前記一般式（２）で表される変性共役ジエン系重合体（ａ−２）を得ることを特徴とする。
この変性共役ジエン系重合体（ａ−２）の製造方法においては、（ａ）工程の変性反応工程までは、前述の変性共役ジエン系重合体（ａ−１）の製造方法における変性反応と同様であるが、当該製造方法においては、（ａ）工程の変性反応工程後、（ｂ）工程として、縮合促進剤の存在下、（ａ）工程で使用した２官能性ケイ素原子を含む化合物が関与する縮合反応を行う工程を施す。
(Production of Modified Conjugated Diene Polymer (a-2))
The above-mentioned modified conjugated diene polymer (a-2) having the structure represented by the general formula (2) at the molecular chain terminal can be efficiently produced according to the method of the present invention.
The process for producing the modified conjugated diene polymer (a-2) according to the present invention comprises: (a) one hydrocarbyloxy group and one reactive group at the active end of the conjugated diene polymer having an active end. Is directly bonded to a silicon atom, and a compound containing a bifunctional silicon atom in which one protected primary amino group is bonded to the silicon atom via an alkylene group is reacted to modify (B) including the above-mentioned bifunctional silicon atom in the presence of at least one condensation accelerator selected from titanium, tin (tin), aluminum, silicon, zirconium and bismuth. Subjecting the modified conjugated diene polymer (a-2) represented by the general formula (2) to a step of performing a condensation reaction involving a compound, and (c) a step of performing a hydrolysis reaction and a deprotection reaction. It is characterized by obtaining.
In the production method of the modified conjugated diene polymer (a-2), the modification reaction step in the step (a) is the same as the modification reaction in the production method of the modified conjugated diene polymer (a-1). However, in the production method, after the modification reaction step in step (a), as the step (b), a compound containing a bifunctional silicon atom used in step (a) is involved in the presence of a condensation accelerator. A step of performing a condensation reaction is performed.
＜縮合促進剤＞
この（ｂ）工程においては、縮合促進剤として、チタン系、スズ系、アルミニウム系、ケイ素系、ジルコニウム系及びビスマス系の中から選ばれる少なくとも一種の金属化合物が好ましい。より具体的には、チタン系として、四価のチタンのアルコキシド、カルボン酸塩及びアセチルアセトナート錯塩、又はこれらの混合塩等が好適に挙げられ、スズ系として、二価のスズのジカルボン酸｛特に、ビス（ヒドロカルビルカルボン酸）塩｝や、四価のスズのジヒドロカルビルスズのジカルボン酸塩｛ビス（ヒドロカルビルカルボン酸）｝塩を含む）、ビス（β−ジケトネート）、アルコキシハライド、モノカルボン酸塩ヒドロキシド等を好適に挙げられる。スズに結合したヒドロカルビル基としては炭素数が４以上のものが望ましく、炭素数４から炭素数８のものが特に好ましい。
また、アルミニウム系として、三価のアルミニウムのアルコキシド、カルボン酸塩及びアセチルアセトナート錯塩又はこれらの混合塩等が好適に挙げられる。
以上より、縮合促進剤として、チタン、スズ及びアルミニウムから選ばれる金属のアルコキシド、カルボン酸塩及びアセチルアセトナート錯塩、又はこれらの混合塩の中から選ばれる少なくとも一種が好適である。
<Condensation accelerator>
In the step (b), at least one metal compound selected from titanium, tin, aluminum, silicon, zirconium and bismuth is preferred as the condensation accelerator. More specifically, tetravalent titanium alkoxides, carboxylates and acetylacetonate complex salts, or mixed salts thereof are preferably cited as titanium-based, and divalent tin dicarboxylic acid { In particular, bis (hydrocarbyl carboxylic acid) salt}, divalent carboxylic acid tin dicarboxylate {including bis (hydrocarbyl carboxylic acid)} salt), bis (β-diketonate), alkoxy halide, monocarboxylic acid Preferred examples include salt hydroxide. The hydrocarbyl group bonded to tin preferably has 4 or more carbon atoms, and particularly preferably has 4 to 8 carbon atoms.
Further, preferred examples of the aluminum system include trivalent aluminum alkoxides, carboxylates and acetylacetonate complex salts, or mixed salts thereof.
From the above, as the condensation accelerator, at least one selected from metal alkoxides, carboxylates and acetylacetonate complex salts selected from titanium, tin and aluminum, or mixed salts thereof is preferable.
上述の縮合促進剤の内、チタン系が特に好適であり、チタン（Ｔｉ）のアルコキシド、カルボン酸塩及びアセチルアセトナート錯塩が好ましく用いられる。
具体的な縮合促進剤としては、テトラキス（２−エチル−１，３−ヘキサンジオラト）チタン、テトラキス（２−メチル−１，３−ヘキサンジオラト）チタン、テトラキス（２−プロピル−１，３−ヘキサンジオラト）チタン、テトラキス（２−ブチル−１，３−ヘキサンジオラト）チタン、テトラキス（１，３−ヘキサンジオラト）チタン、テトラキス（１，３−ペンタンジオラト）チタン、テトラキス（２−メチル−１，３−ペンタンジオラト）チタン、テトラキス（２−エチル−１，３−ペンタンジオラト）チタン、テトラキス（２−プロピル−１，３−ペンタンジオラト）チタン、テトラキス（２−ブチル−１，３−ペンタンジオラト）チタン、テトラキス（１，３−ヘプタンジオラト）チタン、テトラキス（２−メチル−１，３−ヘプタンジオラト）チタン、テトラキス（２−エチル−１，３−ヘプタンジオラト）チタン、テトラキス（２−プロピル−１，３−ヘプタンジオラト）チタン、テトラキス（２−ブチル−１，３−ヘプタンジオラト）チタン、テトラキス（２−エチルヘキソキシ）チタン、テトラメトキシチタン、テトラエトキシチタン、テトラ−ｎ−プロポキシチタン、テトライソプロポキシチタン、テトラ−ｎ−ブトキシチタン、テトラ−ｎ−ブトキシチタンオリゴマー、テトライソブトキシチタン、テトラ−ｓｅｃ−ブトキシチタン、テトラ−ｔｅｒｔ−ブトキシチタン、ビス（オレート）ビス（２−エチルヘキサノエート）チタン、チタンジプロポキシビス（トリエタノールアミネート）、チタンジブトキシビス（トリエタノールアミネート）、チタントリブトキシステアレート、チタントリプロポキシステアレート、チタントリプロポキシアセチルアセトネート、チタンジプロポキシビス（アセチルアセトネート）、チタントリプロポキシ（エチルアセトアセテート）、チタンプロポキシアセチルアセトネートビス（エチルアセトアセテート）、チタントリブトキシアセチルアセトネート、チタンジブトキシビス（アセチルアセトネート）、チタントリブトキシエチルアセトアセテート、チタンブトキシアセチルアセトネートビス（エチルアセトアセテート）、チタンテトラキス（アセチルアセトネート）、チタンジアセチルアセトネートビス（エチルアセトアセテート）、ビス（２−エチルヘキサノエート）チタンオキサイド、ビス（ラウレート）チタンオキサイド、ビス（ナフテネート）チタンオキサイド、ビス（ステアレート）チタンオキサイド、ビス（オレエート）チタンオキサイド、ビス（リノレート）チタンオキサイド、テトラキス（２−エチルヘキサノエート）チタン、テトラキス（ラウレート）チタン、テトラキス（ナフテネート）チタン、テトラキス（ステアレート）チタン、テトラキス（オレエート）チタン、テトラキス（リノレート）チタン、チタンジ−ｎ−ブトキサイド（ビス−２，４−ペンタンジオネート）、チタンオキサイドビス（テトラメチルヘプタンジオネート）、チタンオキサイドビス（ペンタンジオネート）、チタンテトラ（ラクテート）などが挙げられる。中でも、テトラキス（２−エチル−１，３−ヘキサンジオラト）チタン、テトラキス（２−エチルヘキソキシ）チタン、チタンジ−ｎ−ブトキサイド（ビス−２，４−ペンタンジオネート）が好ましい。
Of the above-mentioned condensation accelerators, titanium is particularly preferred, and titanium (Ti) alkoxides, carboxylates and acetylacetonate complex salts are preferably used.
Specific condensation accelerators include tetrakis (2-ethyl-1,3-hexanediolato) titanium, tetrakis (2-methyl-1,3-hexanediolato) titanium, tetrakis (2-propyl-1,3). -Hexanediolato) titanium, tetrakis (2-butyl-1,3-hexanediolato) titanium, tetrakis (1,3-hexanediolato) titanium, tetrakis (1,3-pentanediolato) titanium, tetrakis (2 -Methyl-1,3-pentanediolato) titanium, tetrakis (2-ethyl-1,3-pentanediolato) titanium, tetrakis (2-propyl-1,3-pentanediolato) titanium, tetrakis (2-butyl) -1,3-pentanediolato) titanium, tetrakis (1,3-heptanediolato) titanium, tetrakis (2-methyl-1,3- Butanediolato) titanium, tetrakis (2-ethyl-1,3-heptanediolato) titanium, tetrakis (2-propyl-1,3-heptanediolato) titanium, tetrakis (2-butyl-1,3-heptanediolato) titanium, tetrakis (2- Ethylhexoxy) titanium, tetramethoxy titanium, tetraethoxy titanium, tetra-n-propoxy titanium, tetraisopropoxy titanium, tetra-n-butoxy titanium, tetra-n-butoxy titanium oligomer, tetraisobutoxy titanium, tetra-sec-butoxy titanium , Tetra-tert-butoxytitanium, bis (oleate) bis (2-ethylhexanoate) titanium, titanium dipropoxybis (triethanolamate), titanium dibutoxybis (triethanolamate), tita Tributoxy systemate, titanium tripropoxy systemate, titanium tripropoxyacetylacetonate, titanium dipropoxybis (acetylacetonate), titanium tripropoxy (ethylacetoacetate), titanium propoxyacetylacetonatebis (ethylacetoacetate), titanium Tributoxyacetylacetonate, titanium dibutoxybis (acetylacetonate), titanium tributoxyethylacetoacetate, titaniumbutoxyacetylacetonatebis (ethylacetoacetate), titanium tetrakis (acetylacetonate), titanium diacetylacetonatebis (ethyl) Acetoacetate), bis (2-ethylhexanoate) titanium oxide, bis (laurate) titanium oxide, bis (naphthenate) ) Titanium oxide, bis (stearate) titanium oxide, bis (oleate) titanium oxide, bis (linoleate) titanium oxide, tetrakis (2-ethylhexanoate) titanium, tetrakis (laurate) titanium, tetrakis (naphthenate) titanium, tetrakis (Stearate) titanium, tetrakis (oleate) titanium, tetrakis (linoleate) titanium, titanium di-n-butoxide (bis-2,4-pentanedionate), titanium oxide bis (tetramethylheptanedionate), titanium oxide bis ( Pentanedionate), titanium tetra (lactate) and the like. Among these, tetrakis (2-ethyl-1,3-hexanediolato) titanium, tetrakis (2-ethylhexoxy) titanium, and titanium di-n-butoxide (bis-2,4-pentanedionate) are preferable.
また、スズ系の具体的な縮合促進剤として、例えば、２−エチルヘキサン酸スズ｛[ＣＨ3(ＣＨ2)3ＣＨ(Ｃ2Ｈ5)ＣＯ2]2Ｓｎ（二価）｝が挙げられる。
アルミニウム系の具体的な縮合促進剤として、例えば、トリエトキシアルミニウム、トリ−ｎ−プロポキシアルミニウム、トリイソプロポキシアルミニウム、トリ−ｎ−ブトキシアルミニウム、トリ−ｓｅｃ−ブトキシアルミニウム、トリ−ｔｅｒｔ−ブトキシアルミニウム、アルミニウムジブトキシステアレート、アルミニウムジブトキシアセチルアセトネート、アルミニウムブトキシビス（アセチルアセトネート）、アルミニウムジブトキシエチルアセトアセテート、アルミニウムトリス（アセチルアセトネート）、アルミニウムトリス（エチルアセトアセテート）、トリス（２−エチルヘキサノエート）アルミニウム、トリス（ラウレート）アルミニウム、トリス（ナフテネート）アルミニウム、トリス（ステアレート）アルミニウム、トリス（オレエート）アルミニウム、トリス（リノレート）アルミニウム等が挙げられる。
Moreover, as a specific tin-based condensation accelerator, for example, tin 2-ethylhexanoate {[CH 3 (CH 2 ) 3 CH (C 2 H 5 ) CO 2 ] 2 Sn (divalent)} can be mentioned. .
Specific aluminum-based condensation accelerators include, for example, triethoxyaluminum, tri-n-propoxyaluminum, triisopropoxyaluminum, tri-n-butoxyaluminum, tri-sec-butoxyaluminum, tri-tert-butoxyaluminum, Aluminum dibutoxy systemate, aluminum dibutoxyacetylacetonate, aluminum butoxybis (acetylacetonate), aluminum dibutoxyethylacetoacetate, aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), tris (2-ethyl) Hexanoate) aluminum, tris (laurate) aluminum, tris (naphthenate) aluminum, tris (stearate) aluminum Tris (oleate) aluminum, tris (linolate) aluminum, and the like.
また、ビスマス系の具体的な縮合促進剤として、例えば、トリス（２−エチルヘキサノエート）ビスマス、トリス（ラウレート）ビスマス、トリス（ナフテネート）ビスマス、トリス（ステアレート）ビスマス、トリス（オレエート）ビスマス、トリス（リノレート）ビスマス等が挙げられる。
ジルコニウム系の具体的な縮合促進剤として、例えば、テトラ−ｎ−プロポキシジルコニウム、テトライソプロポキシジルコニウム、テトラ−ｎ−ブトキシジルコニウム、テトラ−ｓｅｃ−ブトキシジルコニウム、テトラ−ｔｅｒｔ−ブトキシジルコニウム、テトラ（２−エチルヘキシル）ジルコニウム、ジルコニウムトリブトキシステアレート、ジルコニウムトリブトキシアセチルアセトネート、ジルコニウムジブトキシビス（アセチルアセトネート）、ジルコニウムトリブトキシエチルアセトアセテート、ジルコニウムブトキシアセチルアセトネートビス（エチルアセトアセテート）、ジルコニウムテトラキス（アセチルアセトネート）、ジルコニウムジアセチルアセトネートビス（エチルアセトアセテート）、ビス（２−エチルヘキサノエート）ジルコニウムオキサイド、ビス（ラウレート）ジルコニウムオキサイド、ビス（ナフテネート）ジルコニウムオキサイド、ビス（ステアレート）ジルコニウムオキサイド、ビス（オレエート）ジルコニウムオキサイド、ビス（リノレート）ジルコニウムオキサイド、テトラキス（２−エチルヘキサノエート）ジルコニウム、テトラキス（ラウレート）ジルコニウム、テトラキス（ナフテネート）ジルコニウム、テトラキス（ステアレート）ジルコニウム、テトラキス（オレエート）ジルコニウム、テトラキス（リノレート）ジルコニウム、テトラエトキシジルコニウム等が挙げられる。
Further, as specific bismuth-based condensation accelerators, for example, tris (2-ethylhexanoate) bismuth, tris (laurate) bismuth, tris (naphthenate) bismuth, tris (stearate) bismuth, tris (oleate) bismuth , Tris (linoleate) bismuth and the like.
Specific examples of the zirconium-based condensation accelerator include tetra-n-propoxyzirconium, tetraisopropoxyzirconium, tetra-n-butoxyzirconium, tetra-sec-butoxyzirconium, tetra-tert-butoxyzirconium, tetra (2- Ethylhexyl) zirconium, zirconium tributoxy systemate, zirconium tributoxyacetylacetonate, zirconium dibutoxybis (acetylacetonate), zirconium tributoxyethylacetoacetate, zirconium butoxyacetylacetonatebis (ethylacetoacetate), zirconium tetrakis (acetyl) Acetonate), zirconium diacetylacetonate bis (ethyl acetoacetate), bis (2-ethylhexa) Ate) zirconium oxide, bis (laurate) zirconium oxide, bis (naphthenate) zirconium oxide, bis (stearate) zirconium oxide, bis (oleate) zirconium oxide, bis (linoleate) zirconium oxide, tetrakis (2-ethylhexanoate) Zirconium, tetrakis (laurate) zirconium, tetrakis (naphthenate) zirconium, tetrakis (stearate) zirconium, tetrakis (oleate) zirconium, tetrakis (linoleate) zirconium, tetraethoxyzirconium and the like can be mentioned.
本発明における縮合反応には、前記縮合促進剤と水とを組み合わせて用いる。水としては、単体やアルコール等の溶液、炭化水素溶媒中の分散ミセル等の形態が好適に用いられるほか、必要ならば固体表面の吸着水や水和物の水和水等の、反応系中で水を放出し得る化合物が潜在的に含んだ水分も有効に用いることができる。従って吸着水を持つ固体や、水和物等、容易に水を放出することができる化合物を前記縮合促進剤と併用することも好ましい態様として挙げられる。 In the condensation reaction in the present invention, the condensation accelerator and water are used in combination. Water is preferably used in the form of a solution such as a simple substance or alcohol, or a dispersed micelle in a hydrocarbon solvent, and if necessary, in the reaction system such as adsorbed water on the solid surface or hydrated water of hydrate. Water that is potentially contained in a compound capable of releasing water can also be used effectively. Accordingly, it is also preferable to use a compound that can easily release water, such as a solid having adsorbed water or a hydrate, in combination with the condensation accelerator.
前記縮合促進剤と水は、反応系に別々に投入しても、使用直前に混合して混合物として投入してもよいが、混合物の長期保存は金属化合物の分解を招くので好ましくない。
尚、水の反応系中への投入は、アルコール等の水と相溶性のある有機溶媒の溶液としてもよいし、種々の化学工学的手法を用いて水を直接炭化水素溶液中に注入・分散させても良い。また、水は縮合反応終了後に、スチームストリッピング等により加えても良い。
The condensation accelerator and water may be added separately to the reaction system or mixed immediately before use as a mixture, but long-term storage of the mixture is not preferable because it causes decomposition of the metal compound.
In addition, water may be charged into the reaction system as a solution of an organic solvent compatible with water such as alcohol, or water is directly injected and dispersed in the hydrocarbon solution using various chemical engineering techniques. You may let them. Water may be added by steam stripping or the like after completion of the condensation reaction.
前記縮合促進剤の使用量としては、該縮合促進剤のモル数が、反応系内に存在するヒドロカルビルオキシ基総量に対するモル比として、０．１〜１０となることが好ましく、０．５〜５が特に好ましい。縮合促進剤の使用量を上記範囲にすることによって縮合反応が効率よく進行する。
また、水のモル数は、反応系内に存在するヒドロカルビオキシシリル基の総量に対するモル比として、共に０．１以上が好ましい。上限は目的や反応条件によっても異なるが、縮合処理以前の段階で重合体活性部位に結合されたヒドロカルビオキシシリル基の量に対して０．５から３モル当量の有効な水が存在することが好ましい。
また、該縮合促進剤を用いた縮合反応は２０℃以上の温度で行うことが好ましく、更には３０〜１２０℃の範囲が好ましい。反応時間としては、０．５分〜１０時間、好ましくは０．５分〜５時間、より好ましくは０．５〜１２０分程度、３〜６０分の範囲が更に好ましい。
なお、縮合反応時の反応系の圧力は、通常、０．０１〜２０ＭＰａ、好ましくは０．０５〜１０ＭＰａである。
As the use amount of the condensation accelerator, the number of moles of the condensation accelerator is preferably 0.1 to 10 as the molar ratio with respect to the total amount of hydrocarbyloxy groups present in the reaction system, preferably 0.5 to 5 Is particularly preferred. By setting the use amount of the condensation accelerator within the above range, the condensation reaction proceeds efficiently.
Further, the number of moles of water is preferably 0.1 or more as a molar ratio to the total amount of hydrocarboxysilyl groups present in the reaction system. The upper limit depends on the purpose and reaction conditions, but there should be 0.5 to 3 molar equivalents of effective water based on the amount of hydrocarboxysilyl groups bound to the polymer active site before the condensation treatment. Is preferred.
The condensation reaction using the condensation accelerator is preferably performed at a temperature of 20 ° C. or higher, and more preferably in the range of 30 to 120 ° C. The reaction time is 0.5 minutes to 10 hours, preferably 0.5 minutes to 5 hours, more preferably about 0.5 to 120 minutes, and further preferably 3 to 60 minutes.
In addition, the pressure of the reaction system at the time of condensation reaction is 0.01-20 Mpa normally, Preferably it is 0.05-10 Mpa.
本発明においては、 縮合反応の形式については特に制限はなく、バッチ式反応器を用いても、多段連続式反応器等の装置を用いて連続式で行ってもよい。また、この縮合反応と脱溶媒を同時に行っても良い。
このようにして縮合反応を行ったのち、（ｃ）工程として、加水分解反応と脱保護反応を行う。この加水分解反応と脱保護反応は、前述した変性共役ジエン系重合体（ａ−１）の製造における説明と同様にして実施することができる。
（ｃ）工程の加水分解反応と脱保護反応を終了後前述の変性共役ジエン系重合体（ａ−１）の場合と同様に、２，６−ジ−ｔ−ブチル−ｐ−クレゾール（ＢＨＴ）のイソプロパノール溶液等を重合反応系に加えて、重合反応を停止する。その後、スチームストリッピング等の脱溶媒処理や、熱ロール乾燥、真空乾燥等の乾燥処理を施すことにより分子鎖末端が、前記一般式（２）で表される構造を有する変性共役ジエン系重合体（ａ−２）が得られる。
In the present invention, the type of the condensation reaction is not particularly limited, and it may be carried out using a batch reactor or a continuous system using an apparatus such as a multistage continuous reactor. Moreover, you may perform this condensation reaction and a desolvent simultaneously.
After performing the condensation reaction in this way, a hydrolysis reaction and a deprotection reaction are performed as step (c). This hydrolysis reaction and deprotection reaction can be carried out in the same manner as described above for the production of the modified conjugated diene polymer (a-1).
(C) After completion of the hydrolysis reaction and deprotection reaction in the step, as in the case of the modified conjugated diene polymer (a-1), 2,6-di-t-butyl-p-cresol (BHT) The isopropanol solution or the like is added to the polymerization reaction system to stop the polymerization reaction. Thereafter, a modified conjugated diene polymer having a structure in which the molecular chain terminal is represented by the general formula (2) by performing a solvent removal treatment such as steam stripping, or a drying treatment such as hot roll drying or vacuum drying. (A-2) is obtained.
（（Ａ）ゴム成分）
本発明のゴム組成物における（Ａ）ゴム成分は、前述した製造方法により得られる、分子鎖末端が、前記一般式（１）で表される変性共役ジエン系重合体（ａ−１）を一種用いてもよいし、二種以上組み合わせて用いてもよく、また、前記一般式（２）で表される変性共役ジエン系重合体（ａ−２）を一種用いてもよいし、二種以上組み合わせて用いてもよい。あるいは、変性共役ジエン系重合体（ａ−１）一種以上と変性共役ジエン系重合体（ａ−２）一種以上とを組み合わせて用いてもよい。
当該（Ａ）ゴム成分中の変性共役ジエン系重合体（ａ−１）及び／又は（ａ−２）の含有量は、１０質量％以上が好ましく、５０質量％以上がより好ましい。変性共役ジエン系重合体の含有量が１０質量％以上であれば、本発明の効果が良好に発揮される。
((A) rubber component)
The rubber component (A) in the rubber composition of the present invention is a kind of the modified conjugated diene polymer (a-1) obtained by the above-described production method and having a molecular chain terminal represented by the general formula (1). It may be used, may be used in combination of two or more, and may be one kind of modified conjugated diene polymer (a-2) represented by the general formula (2), or two or more kinds. You may use it in combination. Alternatively, one or more modified conjugated diene polymers (a-1) and one or more modified conjugated diene polymers (a-2) may be used in combination.
The content of the modified conjugated diene polymer (a-1) and / or (a-2) in the rubber component (A) is preferably 10% by mass or more, and more preferably 50% by mass or more. When the content of the modified conjugated diene polymer is 10% by mass or more, the effect of the present invention is exhibited well.
なお、本発明のゴム組成物に用いる変性共役ジエン系重合体（ａ−１）及び／又は（ａ−２）と併用される他のゴム成分としては、天然ゴム、合成イソプレンゴム、ブタジエンゴム、スチレン−ブタジエンゴム、エチレン−α−オレフィン共重合ゴム、エチレン−α−オレフィン−ジエン共重合ゴム、アクリロニトリル−ブタジエン共重合ゴム、クロロブレンゴム、ハロゲン化ブチルゴム及びこれらの混合物等が挙げられる。また、その一部が多官能型、例えば四塩化スズ、四塩化珪素のような変性剤を用いることにより分岐構造を有しているものでもよい。 As other rubber components used in combination with the modified conjugated diene polymer (a-1) and / or (a-2) used in the rubber composition of the present invention, natural rubber, synthetic isoprene rubber, butadiene rubber, Examples thereof include styrene-butadiene rubber, ethylene-α-olefin copolymer rubber, ethylene-α-olefin-diene copolymer rubber, acrylonitrile-butadiene copolymer rubber, chlorobrene rubber, halogenated butyl rubber, and mixtures thereof. Further, some of them may have a branched structure by using a polyfunctional type, for example, a modifier such as tin tetrachloride or silicon tetrachloride.
本発明のゴム組成物に用いる変性共役ジエン系重合体（ａ−１）及び（ａ−２）は、重量平均分子量（Ｍｗ）が５０×１０3〜１，０００×１０3であることが好ましく、１００×１０3〜６００×１０3であることが更に好ましい。また、分子量分布（Ｍｗ／Ｍｎ）が５以下であることが好ましく、３以下であることがより好ましい。変性共役ジエン系重合体の重量平均分子量を前記範囲内にすることによって加硫物の弾性率の低下、ヒステリシスロスの上昇を抑えて優れた耐破壊特性を得るとともに、変性共役ジエン系重合体を含むゴム組成物の優れた混練作業性が得られる。また、変性共役ジエン系重合体の分子量分布を前記範囲内にすることで変性共役ジエン系重合体をゴム組成物に配合しても、ゴム組成物の作業性を低下させることがなく、混練りが容易で、ゴム組成物の物性を十分に向上させることができる。
ここで、重量平均分子量（Ｍｗ）及び分子量分布は、ＧＰＣ［東ソー製、ＨＬＣ−８０２０］により検出器として屈折計を用いて測定し、単分散ポリスチレンを標準としたポリスチレン換算で示した。なお、カラムはＧＭＨＸＬ［東ソー製］で、溶離液はテトラヒドロフランである。
The modified conjugated diene polymers (a-1) and (a-2) used in the rubber composition of the present invention preferably have a weight average molecular weight (Mw) of 50 × 10 3 to 1,000 × 10 3. 100 × 10 3 to 600 × 10 3 is more preferable. Moreover, it is preferable that molecular weight distribution (Mw / Mn) is 5 or less, and it is more preferable that it is 3 or less. By setting the weight average molecular weight of the modified conjugated diene polymer within the above range, the elastic modulus of the vulcanizate is reduced and the increase in hysteresis loss is suppressed to obtain excellent fracture resistance, and the modified conjugated diene polymer is Excellent kneading workability of the rubber composition to be contained can be obtained. Further, even if the modified conjugated diene polymer is blended with the rubber composition by making the molecular weight distribution of the modified conjugated diene polymer within the above range, the workability of the rubber composition is not lowered and kneading is performed. And the physical properties of the rubber composition can be sufficiently improved.
Here, the weight average molecular weight (Mw) and the molecular weight distribution were measured by GPC [manufactured by Tosoh Corporation, HLC-8020] using a refractometer as a detector, and were shown in terms of polystyrene using monodisperse polystyrene as a standard. The column is GMHXL [manufactured by Tosoh] and the eluent is tetrahydrofuran.
また、本発明のゴム組成物に用いる変性共役ジエン系重合体（ａ−１）及び（ａ−２）は、共役ジエン部のビニル結合含有量が、ゴム組成物の耐久性向上の観点から、５０％以下であることが好ましく、３０％以下であることがより好ましい。
なお、ビニル結合含有量は、赤外法（モレロ法）により求めた。
The modified conjugated diene polymers (a-1) and (a-2) used in the rubber composition of the present invention have a vinyl bond content in the conjugated diene part from the viewpoint of improving the durability of the rubber composition. It is preferably 50% or less, and more preferably 30% or less.
The vinyl bond content was determined by an infrared method (Morello method).
社団法人 日本ゴム協会は、揮発性有機化合物（ＶＯＣ）の発生を現行の６５％に低減させることを目標としている。従って、本発明のゴム組成物は、下記の方法で測定した揮発性有機化合物（ＶＯＣ）の発生量が現行の６５％以下であることが好ましく、５０％以下であることが更に好ましく、３５％以下であることが特に好ましい。このＶＯＣの発生量が現行の６５％を超えると押出し工程においてゴム材料に気泡が発生するおそれがあり、また環境に対する負荷が大きくなり、好ましくない。
＜ＶＯＣ測定方法＞
１５％ｎ−ブタノール及び８５％トルエンからなる溶媒中の０．２Ｎトルエンスルホン酸／０．２４Ｎ水からなるシロキサン加水分解試薬で試料を処理し、未加硫ゴム組成物中に残留する［ＥｔＯＳｉ］からのエタノールの化学量論的量をヘッドスペース／ガスクロマトグラフィーにより測定する。
The Japan Rubber Association aims to reduce the generation of volatile organic compounds (VOC) to the current 65%. Therefore, in the rubber composition of the present invention, the amount of volatile organic compound (VOC) generated by the following method is preferably 65% or less, more preferably 50% or less, and more preferably 35%. It is particularly preferred that If the amount of VOC generated exceeds the current 65%, bubbles may be generated in the rubber material in the extrusion process, and the burden on the environment increases, which is not preferable.
<VOC measurement method>
The sample was treated with a siloxane hydrolysis reagent consisting of 0.2N toluenesulfonic acid / 0.24N water in a solvent consisting of 15% n-butanol and 85% toluene and remained in the unvulcanized rubber composition [EtOSi] The stoichiometric amount of ethanol from is measured by headspace / gas chromatography.
（カーボンブラック）
本発明のゴム組成物においては、前記（Ａ）ゴム成分１００質量部に対して、（Ｂ）窒素吸着比表面積（Ｎ2ＳＡ）が２０〜１００ｍ2／ｇであるカーボンブラックを、１０〜１００質量部の割合で用いる。
本発明のゴム組成物に用いられる変性共役ジエン系重合体（ａ−１）及び（ａ−２）は、分子鎖末端に遊離の第一アミノ基を有しており、この第一アミノ基は、特にＮ2ＳＡが１００ｍ2／ｇ以下のカーボンブラックに対して、極めて高い相互作用を示し、低発熱性能（低燃費性能）に優れるゴム組成物を与えるが、Ｎ2ＳＡが１００ｍ2／ｇを超えるカーボンブラックに対しては、効果が充分に発揮されない。またＮ2ＳＡが２０ｍ2／ｇ未満では補強性が不足し、充分な耐久性が得られない。該Ｎ2ＳＡは、好ましくは２０〜９５ｍ2／ｇであり、より好ましくは
２５〜９０ｍ2／ｇである。なお、このＮ2ＳＡは、ＪＩＳ Ｋ ６２１７−２：２００１に準拠して測定される値である。
このようなカーボンブラックとしては、例えばＨＡＦ、ＦＥＦ、ＧＰＦ、ＳＲＦ、Ｎ３３９、ＩＩＳＡＦ−ＨＳ（Ｎ２８５）等が挙げられる。
（Ａ）ゴム成分１００質量部に対し、当該カーボンブラックの含有量が１０質量部未満では充分な補強効果が得られず、１００質量部を超えると混練りや押出しが困難となる。好ましいカーボンブラックの含有量は２０〜８０質量部であり、より好ましくは３０〜７０質量部である。
(Carbon black)
In the rubber composition of the present invention, (B) a carbon black having a nitrogen adsorption specific surface area (N 2 SA) of 20 to 100 m 2 / g with respect to 100 parts by mass of the (A) rubber component is 10 to 100. Used in the ratio of parts by mass.
The modified conjugated diene polymers (a-1) and (a-2) used in the rubber composition of the present invention have a free primary amino group at the end of the molecular chain. In particular, carbon black having N 2 SA of 100 m 2 / g or less gives a rubber composition exhibiting extremely high interaction and excellent in low heat generation performance (low fuel consumption performance), but N 2 SA is 100 m 2 / g. The effect is not sufficiently exhibited for carbon blacks exceeding. If N 2 SA is less than 20 m 2 / g, the reinforcing property is insufficient and sufficient durability cannot be obtained. The N 2 SA is preferably 20 to 95 m 2 / g, more preferably 25 to 90 m 2 / g. The N 2 SA is a value measured according to JIS K 6217-2: 2001.
Examples of such carbon black include HAF, FEF, GPF, SRF, N339, IISAF-HS (N285), and the like.
(A) If the carbon black content is less than 10 parts by mass with respect to 100 parts by mass of the rubber component, a sufficient reinforcing effect cannot be obtained, and if it exceeds 100 parts by mass, kneading and extrusion become difficult. The content of carbon black is preferably 20 to 80 parts by mass, more preferably 30 to 70 parts by mass.
（その他配合成分）
本発明のゴム組成物は、硫黄架橋性であることが好ましく、加硫剤として硫黄が好適に用いられる。その使用量としては、ゴム成分１００質量部に対し、硫黄分（硫黄及び硫黄供与剤の硫黄分の合計量）を０．１〜１０質量部配合することが好ましい。この範囲であれば、加硫ゴム組成物の必要な弾性率及び強度を確保すると共に低燃費性を得ることができるからである。この観点から、硫黄分を０．５〜５質量部配合することが更に好ましい。
(Other ingredients)
The rubber composition of the present invention is preferably sulfur crosslinkable, and sulfur is suitably used as a vulcanizing agent. As the amount used, it is preferable to blend 0.1 to 10 parts by mass of sulfur (total amount of sulfur and sulfur donors) with respect to 100 parts by mass of the rubber component. This is because within this range, the necessary elastic modulus and strength of the vulcanized rubber composition can be ensured and fuel efficiency can be obtained. In this respect, it is more preferable to blend 0.5 to 5 parts by mass of the sulfur content.
本発明のゴム組成物には、本発明の目的が損なわれない範囲で、所望により、通常ゴム工業界で用いられる各種薬品、例えば硫黄以外の加硫剤、加硫促進剤、プロセス油、可塑剤、老化防止剤、スコーチ防止剤、亜鉛華、ステアリン酸、熱硬化性樹脂、熱可塑性樹脂等を含有させることができる。 In the rubber composition of the present invention, various chemicals usually used in the rubber industry, for example, vulcanizing agents other than sulfur, vulcanization accelerators, process oils, plastics, and the like are used as long as the object of the present invention is not impaired. Agent, anti-aging agent, anti-scorch agent, zinc white, stearic acid, thermosetting resin, thermoplastic resin and the like can be contained.
本発明で使用できる加硫促進剤は、特に限定されるものではないが、例えば、Ｍ（２−メルカプトベンゾチアゾール）、ＤＭ（ジベンゾチアジルジスルフィド）、ＣＺ（Ｎ−シクロヘキシル−２−ベンゾチアジルスルフェンアミド）等のチアゾール系、あるいはＤＰＧ（ジフェニルグアニジン）等のグアニジン系の加硫促進剤等を挙げることができ、その使用量は、ゴム成分１００質量部に対し、０．１〜５．０質量部が好ましく、更に好ましくは０．２〜３．０質量部である。 The vulcanization accelerator that can be used in the present invention is not particularly limited, and examples thereof include M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), and CZ (N-cyclohexyl-2-benzothiazyl). Sulfenamide) and other guanidine vulcanization accelerators such as DPG (diphenylguanidine) can be used, and the amount used is 0.1-5. 0 mass part is preferable, More preferably, it is 0.2-3.0 mass part.
また、本発明のゴム組成物で使用できる軟化剤として用いるプロセス油としては、例えば、パラフィン系、ナフテン系、アロマチック系等を挙げることができる。引張強度、耐摩耗性を重視する用途にはアロマチック系が、ヒステリシスロス、低温特性を重視する用途にはナフテン系又はパラフィン系が用いられる。その使用量は、ゴム成分１００質量部に対して、０〜１００質量部が好ましく、１００質量部以下であれば加硫ゴムの引張強度、低発熱性(低燃費性)が悪化するのを抑制することができる。 Examples of the process oil used as a softening agent that can be used in the rubber composition of the present invention include paraffinic, naphthenic, and aromatic oils. Aromatics are used for applications that emphasize tensile strength and wear resistance, and naphthenic or paraffinic systems are used for applications that emphasize hysteresis loss and low-temperature characteristics. The amount used is preferably 0 to 100 parts by mass with respect to 100 parts by mass of the rubber component, and if it is 100 parts by mass or less, the deterioration of the tensile strength and low heat build-up (low fuel consumption) of the vulcanized rubber is suppressed. can do.
更に、本発明のゴム組成物で使用できる老化防止剤としては、例えば３Ｃ（Ｎ−イソプロピル−Ｎ’−フェニル−ｐ−フェニレンジアミン、６Ｃ［Ｎ−（１，３−ジメチルブチル）−Ｎ’−フェニル−ｐ−フェニレンジアミン］、ＡＷ（６−エトキシ−２，２，４−トリメチル−１，２−ジヒドロキノリン）、ジフェニルアミンとアセトンの高温縮合物等を挙げることができる。その使用量は、ゴム成分１００質量部に対して、０．１〜６．０質量部が好ましく、更に好ましくは０．３〜５．０質量部である。 Furthermore, examples of the anti-aging agent that can be used in the rubber composition of the present invention include 3C (N-isopropyl-N′-phenyl-p-phenylenediamine, 6C [N- (1,3-dimethylbutyl) -N′- Phenyl-p-phenylenediamine], AW (6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline), high-temperature condensate of diphenylamine and acetone, etc. The amount used is rubber. 0.1-6.0 mass parts is preferable with respect to 100 mass parts of components, More preferably, it is 0.3-5.0 mass parts.
［ゴム組成物の調製、タイヤの作製］
本発明のゴム組成物は、前記配合処方により、バンバリーミキサー、ロール、インターナルミキサー等の混練り機を用いて混練りすることによって得られ、成形加工後、加硫を行い、例えばタイヤ、特に、空気入りタイヤのサイドウォール、サイド補強層やビードフィラー等として用いられる。
本発明のタイヤは、本発明のゴム組成物をサイドウォール、サイド補強層やビードフィラー等に用いて通常の空気入りタイヤ又はランフラットタイヤ等の製造方法によって製造される。すなわち、前記のように各種薬品を含有させた本発明のゴム組成物が未加硫の段階で各部材に加工され、タイヤ成形機上で通常の方法により貼り付け成形され、生タイヤが成形される。この生タイヤを加硫機中で加熱加圧して、タイヤが得られる。
このようにして得られた本発明のタイヤは、通常走行時の転がり抵抗性を軽減し低燃費性を向上させたものとなる。また、ランフラットタイヤのサイド補強層やビードフィラーに用いれば、通常走行時の低燃費性に加えて、ランフラット耐久性をも向上させたものとなる。
[Preparation of rubber composition, preparation of tire]
The rubber composition of the present invention is obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer or the like according to the above compounding prescription, vulcanizing after molding, for example, tires, particularly It is used as a sidewall of a pneumatic tire, a side reinforcing layer, a bead filler, and the like.
The tire of the present invention is produced by a method for producing a normal pneumatic tire, a run flat tire, or the like using the rubber composition of the present invention as a sidewall, a side reinforcing layer, a bead filler, or the like. That is, as described above, the rubber composition of the present invention containing various chemicals is processed into each member at an unvulcanized stage, pasted and molded by a normal method on a tire molding machine, and a raw tire is molded. The The green tire is heated and pressed in a vulcanizer to obtain a tire.
The tire of the present invention thus obtained has reduced rolling resistance during normal running and improved fuel efficiency. Moreover, if it is used for the side reinforcing layer or bead filler of the run flat tire, run flat durability is improved in addition to low fuel consumption during normal driving.
次に、本発明を実施例により更に詳細に説明するが、本発明は、これらの例によってなんら限定されるものではない。
なお、加硫ゴム組成物の３％動的損失正接（ｔａｎδ）及び未加硫ゴム組成物からの揮発性有機化合物（ＶＯＣ）量は、下記の方法に従って測定した。
（１）３％動的損失正接（ｔａｎδ）
粘弾性測定装置（レオメトリックス社製）を使用し、温度６０℃、歪み３％、周波数１５Ｈｚでｔａｎδを測定した。比較例３、５又は６のｔａｎδを１００として下記式により指数表示した。指数値が小さい程、低発熱性であり、ヒステリシスロスが小さいことを示す。
３％ｔａｎδ指数＝｛（供試加硫ゴム組成物の３％ｔａｎδ）／（比較例３、５又は６の加硫ゴム組成物の３％ｔａｎδ）｝×１００
（２）未加硫ゴム組成物からのＶＯＣ発生量
上述のＶＯＣ測定方法により、未加硫ゴム組成物のＶＯＣ発生量を測定した。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The 3% dynamic loss tangent (tan δ) of the vulcanized rubber composition and the amount of volatile organic compound (VOC) from the unvulcanized rubber composition were measured according to the following methods.
(1) 3% dynamic loss tangent (tan δ)
Using a viscoelasticity measuring device (Rheometrics), tan δ was measured at a temperature of 60 ° C., a strain of 3%, and a frequency of 15 Hz. The tan δ of Comparative Example 3, 5 or 6 was taken as 100, and indexed by the following formula. A smaller index value indicates a lower exothermic property and a smaller hysteresis loss.
3% tan δ index = {(3% tan δ of the test vulcanized rubber composition) / (3% tan δ of the vulcanized rubber composition of Comparative Example 3, 5 or 6)} × 100
(2) VOC generation amount from unvulcanized rubber composition VOC generation amount of the unvulcanized rubber composition was measured by the above-described VOC measurement method.
製造例１ 変性ＢＲ−ａの製造
窒素置換された５Ｌオートクレーブに、窒素下、シクロヘキサン１．４ｋｇ、１，３−ブタジエン２５０ｇ、２，２−ジテトラヒドロフリルプロパン０．０２８５ｍｍｏｌをシクロヘキサン溶液として注入し、これに２．８５ｍｍｏｌのｎ−ブチルリチウム（ＢｕＬｉ）を加えた後、撹拌装置を備えた５０℃温水浴中で４．５時間重合を行った。１，３−ブタジエンの反応転化率は、ほぼ１００％であった。次に、この重合体溶液を温度６０℃に保ち、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を２．８５ｍｍｏｌ添加し、１５分間反応させた後、重合体溶液を温度６０℃に保ったままテトラキス（２−エチル−１，３−ヘキサンジオラト）チタン２．８５ｍｍｏｌ加え更に１５分間撹拌し反応させた。その後、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．３ｇを含むメタノール溶液に抜き取り、重合停止させた後、スチームストリッピングにより脱溶媒し、１１０℃のロールで乾燥して、変性ＢＲ−ａを得た。
Production Example 1 Production of Modified BR-a Into a nitrogen-substituted 5 L autoclave, 1.4 kg of cyclohexane, 250 g of 1,3-butadiene, and 0.0285 mmol of 2,2-ditetrahydrofurylpropane were injected as a cyclohexane solution under nitrogen. After adding 2.85 mmol of n-butyllithium (BuLi) to this, polymerization was carried out for 4.5 hours in a 50 ° C. warm water bath equipped with a stirrer. The reaction conversion of 1,3-butadiene was almost 100%. Next, this polymer solution was kept at a temperature of 60 ° C., 2.85 mmol of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane was added and reacted for 15 minutes, and then the polymer solution was brought to a temperature of 60 ° C. While keeping it, 2.85 mmol of tetrakis (2-ethyl-1,3-hexanediolato) titanium was added and further stirred for 15 minutes to react. Thereafter, the solution was taken out in a methanol solution containing 1.3 g of 2,6-di-tert-butyl-p-cresol, and after the polymerization was stopped, the solvent was removed by steam stripping, and dried with a roll at 110 ° C. -A was obtained.
製造例２ 変性ＢＲ−ｂの製造
製造例１において、テトラキス（２−エチル−１，３−ヘキサンジオラト）チタン２．８５ｍｍｏｌの代わりに、２−エチルヘキサン酸スズ２．８５ｍｍｏｌを用いた以外は、製造例１と同様にして、変性ＢＲ−ｂを得た。
Production Example 2 Production of Modified BR-b In Production Example 1, 2.85 mmol of tin 2-ethylhexanoate was used instead of 2.85 mmol of tetrakis (2-ethyl-1,3-hexanediolato) titanium. In the same manner as in Production Example 1, modified BR-b was obtained.
製造例３ 変性ＢＲ−ｃの製造
製造例１において、テトラキス（２−エチル−１，３−ヘキサンジオラト）チタン２．８５ｍｍｏｌの代わりに、トリス（ステアレート）アルミニウム２．８５ｍｍｏｌを用いた以外は、製造例１と同様にして、変性ＢＲ−ｃを得た。
Production Example 3 Production of Modified BR-c In Production Example 1, 2.85 mmol of tris (stearate) aluminum was used instead of 2.85 mmol of tetrakis (2-ethyl-1,3-hexanediolato) titanium. In the same manner as in Production Example 1, modified BR-c was obtained.
製造例４ 変性ＢＲ−ｄの製造
窒素置換された５Ｌオートクレーブに、窒素下、シクロヘキサン１．４ｋｇ、１，３−ブタジエン２５０ｇ、２，２−ジテトラヒドロフリルプロパン０．０２８５ｍｍｏｌをシクロヘキサン溶液として注入し、これに２．８５ｍｍｏｌのｎ−ブチルリチウム（ＢｕＬｉ）を加えた後、撹拌装置を備えた５０℃温水浴中で４．５時間重合を行った。１，３−ブタジエンの反応転化率は、ほぼ１００％であった。次に、この重合体溶液を温度６０℃に保ち、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を２．８５ｍｍｏｌ添加し、３０分間反応させた後、重合反応系に、１規定の水酸化ナトリウム（ＮａＯＨ）水溶液を少しずつ加え、ｐＨ１０．５になった段階で、水をリチウム（Ｌｉ）対比３倍のモル量加え、３０分間撹拌した。その後、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．３ｇを含むメタノール溶液に抜き取り、重合停止させた後、スチームストリッピングにより脱溶媒し、１１０℃のロールで乾燥して、変性ＢＲ−ｄを得た。
Production Example 4 Production of Modified BR-d Into a nitrogen-substituted 5 L autoclave, 1.4 kg of cyclohexane, 250 g of 1,3-butadiene, and 0.0285 mmol of 2,2-ditetrahydrofurylpropane were injected as a cyclohexane solution under nitrogen. After adding 2.85 mmol of n-butyllithium (BuLi) to this, polymerization was carried out for 4.5 hours in a 50 ° C. warm water bath equipped with a stirrer. The reaction conversion of 1,3-butadiene was almost 100%. Next, this polymer solution was kept at a temperature of 60 ° C., 2.85 mmol of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane was added, and the mixture was reacted for 30 minutes. A sodium hydroxide (NaOH) aqueous solution was added little by little, and when the pH reached 10.5, water was added in a molar amount 3 times that of lithium (Li), and the mixture was stirred for 30 minutes. Thereafter, the solution was taken out in a methanol solution containing 1.3 g of 2,6-di-tert-butyl-p-cresol, and after the polymerization was stopped, the solvent was removed by steam stripping, and dried with a roll at 110 ° C. -D was obtained.
製造例５ 変性ＢＲ−ｅの製造
窒素置換された５Ｌオートクレーブに、窒素下、シクロヘキサン１．４ｋｇ、１，３−ブタジエン２５０ｇ、２，２−ジテトラヒドロフリルプロパン０．０２８５ｍｍｏｌをシクロヘキサン溶液として注入し、これに２．８５ｍｍｏｌのｎ−ブチルリチウム（ＢｕＬｉ）を加えた後、撹拌装置を備えた５０℃温水浴中で４．５時間重合を行った。１，３−ブタジエンの反応転化率は、ほぼ１００％であった。次に、この重合体溶液を温度６０℃に保ち、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を２．８５ｍｍｏｌ添加し、３０分間反応させた。その後、２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．３ｇを含むメタノール溶液に抜き取り、重合停止させた後、スチームストリッピングにより脱溶媒し、１１０℃のロールで乾燥して、変性ＢＲ−ｅを得た。
Production Example 5 Production of Modified BR-e Into a nitrogen-substituted 5 L autoclave, 1.4 kg of cyclohexane, 250 g of 1,3-butadiene, and 0.0285 mmol of 2,2-ditetrahydrofurylpropane were injected as a cyclohexane solution under nitrogen. After adding 2.85 mmol of n-butyllithium (BuLi) to this, polymerization was carried out for 4.5 hours in a 50 ° C. warm water bath equipped with a stirrer. The reaction conversion of 1,3-butadiene was almost 100%. Next, this polymer solution was kept at a temperature of 60 ° C., and 2.85 mmol of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane was added and reacted for 30 minutes. Thereafter, the solution was taken out in a methanol solution containing 1.3 g of 2,6-di-tert-butyl-p-cresol, and after the polymerization was stopped, the solvent was removed by steam stripping, and dried with a roll at 110 ° C. -E was obtained.
製造例６ 変性ＢＲ−ｆの製造
製造例５において、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２．８５ｍｍｏｌの代わりに、４，４'−ビス（ジエチルアミノ）ベンゾフェノン２．８５ｍｍｏｌを用いた以外は、製造例５と同様にして、変性ＢＲ−ｆを得た。
Production Example 6 Production of Modified BR-f In Production Example 5, 2.85 mmol of 4,4′-bis (diethylamino) benzophenone was used instead of 2.85 mmol of N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane. A modified BR-f was obtained in the same manner as in Production Example 5 except that.
製造例７ 未変性ＢＲ−ｇの製造
窒素置換された５Ｌオートクレーブに、窒素下、シクロヘキサン１．４ｋｇ、１，３−ブタジエン２５０ｇ、２，２−ジテトラヒドロフリルプロパン０．０２８５ｍｍｏｌをシクロヘキサン溶液として注入し、これに２．８５ｍｍｏｌのｎ−ブチルリチウム（ＢｕＬｉ）を加えた後、撹拌装置を備えた５０℃温水浴中で４．５時間重合を行った。１，３−ブタジエンの反応転化率は、ほぼ１００％であった。この重合体溶液を２，６−ジ−ｔｅｒｔ−ブチル−ｐ−クレゾール１．３ｇ含むメタノール溶液に抜き取り、重合停止させた後、スチームストリッピングにより脱溶媒し、１１０℃のロールで乾燥して未変性ＢＲ−ｇを得た。
Production Example 7 Production of Unmodified BR-g Into a nitrogen-substituted 5 L autoclave, 1.4 kg of cyclohexane, 250 g of 1,3-butadiene, and 0.0285 mmol of 2,2-ditetrahydrofurylpropane were injected as a cyclohexane solution under nitrogen. Then, 2.85 mmol of n-butyllithium (BuLi) was added thereto, followed by polymerization in a 50 ° C. warm water bath equipped with a stirrer for 4.5 hours. The reaction conversion of 1,3-butadiene was almost 100%. This polymer solution was taken out in a methanol solution containing 1.3 g of 2,6-di-tert-butyl-p-cresol, and after the polymerization was stopped, the solvent was removed by steam stripping, and dried with a roll at 110 ° C. Modified BR-g was obtained.
実施例１〜５及び比較例１〜６
表１の第１練りステージの配合組成に従って、各成分を混練りしたのち、これに、第２練りステージに示す種類と量の各成分を配合して、実施例１〜５及び比較例１〜６の１１種類のゴム組成物を調製した。これら１１種類の未加硫ゴム組成物のＶＯＣ発生量を測定した。
更に、これら１１種類の未加硫ゴム組成物を１６５℃、１５分間加硫した後、３％動的損失正接（ｔａｎδ）を測定した。結果を表２〜４に示す。
Examples 1-5 and Comparative Examples 1-6
After kneading each component according to the blend composition of the first kneading stage in Table 1, the components of the type and amount shown in the second kneading stage are blended into the components, and Examples 1 to 5 and Comparative Examples 1 to 5 are blended. 6 11 types of rubber compositions were prepared. VOC generation amounts of these 11 kinds of unvulcanized rubber compositions were measured.
Furthermore, after 11 types of these unvulcanized rubber compositions were vulcanized at 165 ° C. for 15 minutes, 3% dynamic loss tangent (tan δ) was measured. The results are shown in Tables 2-4.
１）ＢＲ：製造例１〜６で得られた変性ＢＲ−ａ〜ｆ及び製造例７で得られた未変性ＢＲ−ｇである。
２）天然ゴム：ＲＳＳ＃３
３）カーボンブラック：
(イ) 表２記載のＮ2ＳＡが４２ｍ2／ｇであるものは、カーボンブラックＦＥＦ、東海カーボン株式会社製、商標「シーストＳＯ」。
(ロ) 表３記載のＮ2ＳＡが１１８ｍ2／ｇであるものは、カーボンブラックＩＳＡＦ、東海カーボン株式会社製、商標「シースト６」。
(ハ) 表４記載のＮ2ＳＡが９７ｍ2／ｇであるものは、カーボンブラックＩＩＳＡＦ−ＨＳ（Ｎ２８５）、三菱化学株式会社製、商標「ダイアブラックＩＩ」。
４）老化防止剤６Ｃ：Ｎ−（１，３−ジメチルブチル）−Ｎ’−フェニル−ｐ−フェニレンジアミン、大内新興化学工業社製、商標「ノクラック６Ｃ」
５）老化防止剤ＲＤ：２，２，４−トリメチル−１，２−ジヒドロキノリン重合物、大内新興化学工業社製、商標「ノクラック２２４」
６）加硫促進剤ＣＢＳ：Ｎ−シクロヘキシル−２−ベンゾチアジルスルフェンアミド、大内新興化学工業社製、商標「ノクセラーＣＺ」
７）加硫促進剤ＭＢＴＳ：ジベンゾチアジルジスルフィド、大内新興化学工業社製、商標「ノクセラーＤＭ」
1) BR: modified BR-a to f obtained in Production Examples 1 to 6 and unmodified BR-g obtained in Production Example 7.
2) Natural rubber: RSS # 3
3) Carbon black:
(A) N 2 SA listed in Table 2 is 42 m 2 / g is carbon black FEF, manufactured by Tokai Carbon Co., Ltd., trademark “SEAST SO”.
(B) N 2 SA listed in Table 3 is 118 m 2 / g is carbon black ISAF, manufactured by Tokai Carbon Co., Ltd., trademark “SEAST 6”.
(C) N 2 SA described in Table 4 is 97 m 2 / g is carbon black IISAF-HS (N285), manufactured by Mitsubishi Chemical Corporation, and trade name “Dia Black II”.
4) Anti-aging agent 6C: N- (1,3-dimethylbutyl) -N′-phenyl-p-phenylenediamine, manufactured by Ouchi Shinsei Chemical Co., Ltd., trademark “NOCRACK 6C”
5) Anti-aging agent RD: 2,2,4-trimethyl-1,2-dihydroquinoline polymer, manufactured by Ouchi Shinsei Chemical Co., Ltd., trademark “NOCRACK 224”
6) Vulcanization accelerator CBS: N-cyclohexyl-2-benzothiazylsulfenamide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trademark “Noxeller CZ”
7) Vulcanization accelerator MBTS: Dibenzothiazyl disulfide, manufactured by Ouchi Shinsei Chemical Industry Co., Ltd., trademark “Noxeller DM”
１）Ｘ：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
２）Ｙ：２，２'−ジエチルアミノベンゾフェノン
３）チタン系：テトラキス（２−エチル−１，３−ヘキサンジオラト）チタン
４）スズ系：２−エチルヘキサン酸スズ
５）アルミニウム系：トリス（ステアレート）アルミニウム
６）ＶＯＣ：揮発性有機化合物
1) X: N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane 2) Y: 2,2′-diethylaminobenzophenone 3) Titanium system: Tetrakis (2-ethyl-1,3-hexanediolato) titanium 4 ) Tin series: Tin 2-ethylhexanoate 5) Aluminum series: Tris (stearate) aluminum 6) VOC: Volatile organic compounds
１）、３）及び６）は、いずれも表２の注と同じ。
1), 3) and 6) are all the same as the notes in Table 2.
１）、３）及び６）は、いずれも表２の注と同じ。
1), 3) and 6) are all the same as the notes in Table 2.
表２から分かるように、変性ＢＲ−ａ〜ｄは、変性剤として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を用いており、これらを用いた実施例１〜４の未加硫ゴム組成物は、変性剤として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を用いているが、縮合促進剤を加えず、加水分解処理もしていない変性ＢＲ−ｅを用いた比較例１の未加硫ゴム組成物と比較して、ＶＯＣ発生量が少ない。
また、表２から分かるように、本発明の製造方法により得られる変性共役ジエン系重合体を用いた実施例１〜４のゴム組成物は、比較例１〜３のゴム組成物と比較して、３％ｔａｎδ指数が低く、低発熱性に優れる。
そして、表２〜４を比較すれば、同一の変性ＢＲ−ａを同じ量用いても、カーボンブラックのＮ2ＳＡが１００ｍ2／ｇを超える表３の比較例４のゴム組成物は、未変性ＢＲ−ｇを用いたゴム組成物対比で、３％ｔａｎδの値の低下が少なく、カーボンブラックのＮ2ＳＡが１００ｍ2／ｇを超えると変性ＢＲの効果が充分に発揮されないことが理解される。
As can be seen from Table 2, modified BR-a to d use N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane as a modifier, and unvulcanized examples 1 to 4 using these. The rubber composition uses N, N-bis (trimethylsilyl) aminopropylmethyldiethoxysilane as a modifying agent, but uses a modified BR-e that does not contain a condensation accelerator and is not hydrolyzed. Compared with 1 unvulcanized rubber composition, the amount of VOC generation is small.
Further, as can be seen from Table 2, the rubber compositions of Examples 1 to 4 using the modified conjugated diene polymer obtained by the production method of the present invention are compared with the rubber compositions of Comparative Examples 1 to 3. 3% tan δ index is low, and low heat build-up is excellent.
And comparing Tables 2-4, even if the same amount of the same modified BR-a is used, the rubber composition of Comparative Example 4 in Table 3 in which N 2 SA of carbon black exceeds 100 m 2 / g is not It is understood that the reduction in the value of 3% tan δ is small in comparison with the rubber composition using the modified BR-g, and the effect of the modified BR is not sufficiently exhibited when the N 2 SA of the carbon black exceeds 100 m 2 / g. The
本発明のゴム組成物は、その調製における混練り時等において、揮発性有機化合物（ＶＯＣ）の発生量が少ない上、低発熱性（低燃費性）に優れ、例えばサイドウォール、サイド補強層やビードフィラー等のタイヤ部材として好適に用いられる。 The rubber composition of the present invention has a small amount of volatile organic compound (VOC) generated at the time of kneading and the like, and is excellent in low heat buildup (low fuel consumption). For example, a sidewall, a side reinforcing layer, It is suitably used as a tire member such as a bead filler.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009053970A JP5473360B2 (en) | 2008-03-10 | 2009-03-06 | Rubber composition and tire using the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008060256 | 2008-03-10 | ||
| JP2008060256 | 2008-03-10 | ||
| JP2009053970A JP5473360B2 (en) | 2008-03-10 | 2009-03-06 | Rubber composition and tire using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2009242788A true JP2009242788A (en) | 2009-10-22 |
| JP5473360B2 JP5473360B2 (en) | 2014-04-16 |
Family
ID=41305042
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009053970A Active JP5473360B2 (en) | 2008-03-10 | 2009-03-06 | Rubber composition and tire using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5473360B2 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011030833A1 (en) * | 2009-09-09 | 2011-03-17 | 株式会社ブリヂストン | Modifying agent, method for producing modified conjugated diene polymer using modifying agent, and modified conjugated diene polymer |
| WO2011129425A1 (en) * | 2010-04-16 | 2011-10-20 | 旭化成ケミカルズ株式会社 | Process for producing modified conjugated diene polymer, modified conjugated diene polymer, and composition of modified conjugated diene polymer |
| WO2012043829A1 (en) | 2010-10-01 | 2012-04-05 | 株式会社ブリヂストン | Rubber composition and method of producing same, and tire |
| JP2013053293A (en) * | 2011-08-31 | 2013-03-21 | Tsrc Corp | Process for producing conjugated diene rubber, and composition of the rubber |
| US8816014B2 (en) | 2009-10-02 | 2014-08-26 | Asahi Kasei Chemicals Corporation | Method for producing modified conjugated diene-based polymer, modified conjugated diene-based polymer, and modified conjugated diene-based polymer composition |
| JP2015520789A (en) * | 2013-04-25 | 2015-07-23 | エルジー・ケム・リミテッド | Method for continuously producing modified conjugated diene polymer, polymer obtained therefrom and rubber composition containing the same |
| JP2015529736A (en) * | 2012-09-14 | 2015-10-08 | トリンゼオ ヨーロッパ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Aminosilane modified polymer |
| KR20150121820A (en) * | 2014-04-22 | 2015-10-30 | 한국타이어 주식회사 | Rubber composition of sidewall insert for run flat tire and tire manufactured by using the same |
| KR20160042037A (en) * | 2013-08-09 | 2016-04-18 | 꽁빠니 제네날 드 에따블리세망 미쉘린 | Modified diene elastomer comprising a diene elastomer coupled by an aminoalkoxysilane compound and having an amine function at the chain end, and rubber composition comprising same |
| KR20160042952A (en) * | 2013-08-08 | 2016-04-20 | 꽁빠니 제네날 드 에따블리세망 미쉘린 | Diene elastomer modified by coupling having silanol functions, synthesis method for same and rubber composition comprising it |
| CN111630075A (en) * | 2017-12-15 | 2020-09-04 | 株式会社普利司通 | Functionalized polymer, method for preparing the same and rubber composition containing the same |
| JP2020530060A (en) * | 2017-12-05 | 2020-10-15 | エルジー・ケム・リミテッド | Modified conjugated diene polymer and rubber composition containing it |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102026826B (en) * | 2008-03-10 | 2015-01-14 | 株式会社普利司通 | Method for producing modified conjugated diene polymer/copolymer, modified conjugated diene polymer/copolymer, and rubber composition and tier using the same |
Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10316800A (en) * | 1997-05-07 | 1998-12-02 | Michelin & Cie | Rubber composition |
| JPH11255843A (en) * | 1998-03-13 | 1999-09-21 | Hiroshi Okamoto | Rubber containing silanol |
| JP2002103912A (en) * | 2000-07-24 | 2002-04-09 | Bridgestone Corp | Pneumatic tire |
| WO2003046020A1 (en) * | 2001-11-27 | 2003-06-05 | Bridgestone Corporation | Conjugated diene polymer, process for its production and rubber compositions containing the same |
| JP2003246817A (en) * | 2001-03-26 | 2003-09-05 | Jsr Corp | Hydrogenated modified polymer, process for producing it and composition comprising it |
| WO2003087171A1 (en) * | 2002-04-12 | 2003-10-23 | Bridgestone Corporation | Process for producing modified polymer, modified polymer obtained by the process, and rubber composition |
| JP2004168903A (en) * | 2002-11-20 | 2004-06-17 | Jsr Corp | Conjugated diolefin (co)polymer rubber, method for producing the same (co)polymer rubber, rubber composition and tire |
| JP2004168904A (en) * | 2002-11-20 | 2004-06-17 | Jsr Corp | Conjugated diolefin copolymer rubber, method for producing the same copolymer rubber, rubber composition and tire |
| JP2005008870A (en) * | 2003-05-22 | 2005-01-13 | Jsr Corp | Method for producing modified conjugated diene-based polymer and rubber composition |
| WO2005087814A1 (en) * | 2004-03-15 | 2005-09-22 | Jsr Corporation | Conjugated-diolefin (co)polymer rubber and process for producing the same |
| WO2006101025A1 (en) * | 2005-03-18 | 2006-09-28 | Jsr Corporation | Process for producing modified polymer, modified polymer obtained by the process, and rubber composition thereof |
| WO2006112450A1 (en) * | 2005-04-15 | 2006-10-26 | Bridgestone Corporation | Modified conjugated diene copolymer, rubber compositions and tires |
| WO2007034785A1 (en) * | 2005-09-22 | 2007-03-29 | Asahi Kasei Chemicals Corporation | Conjugated diene polymer and process for production thereof |
| WO2007040252A1 (en) * | 2005-10-05 | 2007-04-12 | Jsr Corporation | Process for producing modified conjugated diene polymer, modified conjugated diene polymer obtained by the process, and rubber composition containing the same |
| WO2009113546A1 (en) * | 2008-03-10 | 2009-09-17 | 株式会社ブリヂストン | Method for producing modified conjugated diene polymer/copolymer, modified conjugated diene polymer/copolymer, and rubber composition and tier using the same |
-
2009
- 2009-03-06 JP JP2009053970A patent/JP5473360B2/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10316800A (en) * | 1997-05-07 | 1998-12-02 | Michelin & Cie | Rubber composition |
| JPH11255843A (en) * | 1998-03-13 | 1999-09-21 | Hiroshi Okamoto | Rubber containing silanol |
| JP2002103912A (en) * | 2000-07-24 | 2002-04-09 | Bridgestone Corp | Pneumatic tire |
| JP2003246817A (en) * | 2001-03-26 | 2003-09-05 | Jsr Corp | Hydrogenated modified polymer, process for producing it and composition comprising it |
| WO2003046020A1 (en) * | 2001-11-27 | 2003-06-05 | Bridgestone Corporation | Conjugated diene polymer, process for its production and rubber compositions containing the same |
| WO2003087171A1 (en) * | 2002-04-12 | 2003-10-23 | Bridgestone Corporation | Process for producing modified polymer, modified polymer obtained by the process, and rubber composition |
| JP2004168903A (en) * | 2002-11-20 | 2004-06-17 | Jsr Corp | Conjugated diolefin (co)polymer rubber, method for producing the same (co)polymer rubber, rubber composition and tire |
| JP2004168904A (en) * | 2002-11-20 | 2004-06-17 | Jsr Corp | Conjugated diolefin copolymer rubber, method for producing the same copolymer rubber, rubber composition and tire |
| JP2005008870A (en) * | 2003-05-22 | 2005-01-13 | Jsr Corp | Method for producing modified conjugated diene-based polymer and rubber composition |
| WO2005087814A1 (en) * | 2004-03-15 | 2005-09-22 | Jsr Corporation | Conjugated-diolefin (co)polymer rubber and process for producing the same |
| WO2006101025A1 (en) * | 2005-03-18 | 2006-09-28 | Jsr Corporation | Process for producing modified polymer, modified polymer obtained by the process, and rubber composition thereof |
| WO2006112450A1 (en) * | 2005-04-15 | 2006-10-26 | Bridgestone Corporation | Modified conjugated diene copolymer, rubber compositions and tires |
| WO2007034785A1 (en) * | 2005-09-22 | 2007-03-29 | Asahi Kasei Chemicals Corporation | Conjugated diene polymer and process for production thereof |
| WO2007040252A1 (en) * | 2005-10-05 | 2007-04-12 | Jsr Corporation | Process for producing modified conjugated diene polymer, modified conjugated diene polymer obtained by the process, and rubber composition containing the same |
| WO2009113546A1 (en) * | 2008-03-10 | 2009-09-17 | 株式会社ブリヂストン | Method for producing modified conjugated diene polymer/copolymer, modified conjugated diene polymer/copolymer, and rubber composition and tier using the same |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5952560B2 (en) * | 2009-09-09 | 2016-07-13 | 株式会社ブリヂストン | Modifier, method for producing modified conjugated diene polymer using the modifier, and modified conjugated diene polymer |
| US9394321B2 (en) | 2009-09-09 | 2016-07-19 | Bridgestone Corporation | Modifying agent, method for producing modified conjugated diene polymer using modifying agent, and modified conjugated diene polymer |
| WO2011030833A1 (en) * | 2009-09-09 | 2011-03-17 | 株式会社ブリヂストン | Modifying agent, method for producing modified conjugated diene polymer using modifying agent, and modified conjugated diene polymer |
| JPWO2011030833A1 (en) * | 2009-09-09 | 2013-02-07 | 株式会社ブリヂストン | Modifier, method for producing modified conjugated diene polymer using the modifier, and modified conjugated diene polymer |
| US8816014B2 (en) | 2009-10-02 | 2014-08-26 | Asahi Kasei Chemicals Corporation | Method for producing modified conjugated diene-based polymer, modified conjugated diene-based polymer, and modified conjugated diene-based polymer composition |
| JPWO2011129425A1 (en) * | 2010-04-16 | 2013-07-18 | 旭化成ケミカルズ株式会社 | Method for producing modified conjugated diene polymer, modified conjugated diene polymer, and modified conjugated diene polymer composition |
| JP5584288B2 (en) * | 2010-04-16 | 2014-09-03 | 旭化成ケミカルズ株式会社 | Process for producing modified conjugated diene polymer, and modified conjugated diene polymer composition |
| US9644046B2 (en) | 2010-04-16 | 2017-05-09 | Asahi Kasei Chemicals Corporation | Method for producing modified conjugated diene-based polymer, modified conjugated diene-based polymer, and modified conjugated diene-based polymer composition |
| US9193807B2 (en) | 2010-04-16 | 2015-11-24 | Asahi Kasei Chemicals Corporation | Method for producing modified conjugated diene-based polymer, modified conjugated diene-based polymer, and modified conjugated diene-based polymer composition |
| WO2011129425A1 (en) * | 2010-04-16 | 2011-10-20 | 旭化成ケミカルズ株式会社 | Process for producing modified conjugated diene polymer, modified conjugated diene polymer, and composition of modified conjugated diene polymer |
| WO2012043829A1 (en) | 2010-10-01 | 2012-04-05 | 株式会社ブリヂストン | Rubber composition and method of producing same, and tire |
| JP2013053293A (en) * | 2011-08-31 | 2013-03-21 | Tsrc Corp | Process for producing conjugated diene rubber, and composition of the rubber |
| JP2015529736A (en) * | 2012-09-14 | 2015-10-08 | トリンゼオ ヨーロッパ ゲゼルシャフト ミット ベシュレンクテル ハフツング | Aminosilane modified polymer |
| US10253158B2 (en) | 2013-04-25 | 2019-04-09 | Lg Chem, Ltd. | Method for continuously preparing modified conjugated diene polymers, polymers obtained from the method, and rubber composition comprising the same |
| JP2015520789A (en) * | 2013-04-25 | 2015-07-23 | エルジー・ケム・リミテッド | Method for continuously producing modified conjugated diene polymer, polymer obtained therefrom and rubber composition containing the same |
| KR20160042952A (en) * | 2013-08-08 | 2016-04-20 | 꽁빠니 제네날 드 에따블리세망 미쉘린 | Diene elastomer modified by coupling having silanol functions, synthesis method for same and rubber composition comprising it |
| KR102266575B1 (en) | 2013-08-08 | 2021-06-21 | 꽁빠니 제네날 드 에따블리세망 미쉘린 | Diene elastomer modified by coupling having silanol functions, synthesis method for same and rubber composition comprising it |
| KR20160042037A (en) * | 2013-08-09 | 2016-04-18 | 꽁빠니 제네날 드 에따블리세망 미쉘린 | Modified diene elastomer comprising a diene elastomer coupled by an aminoalkoxysilane compound and having an amine function at the chain end, and rubber composition comprising same |
| KR102237021B1 (en) | 2013-08-09 | 2021-04-09 | 꽁빠니 제네날 드 에따블리세망 미쉘린 | Modified diene elastomer comprising a diene elastomer coupled by an aminoalkoxysilane compound and having an amine function at the chain end, and rubber composition comprising same |
| KR101635382B1 (en) | 2014-04-22 | 2016-07-04 | 한국타이어 주식회사 | Rubber composition of sidewall insert for run flat tire and tire manufactured by using the same |
| KR20150121820A (en) * | 2014-04-22 | 2015-10-30 | 한국타이어 주식회사 | Rubber composition of sidewall insert for run flat tire and tire manufactured by using the same |
| JP2020530060A (en) * | 2017-12-05 | 2020-10-15 | エルジー・ケム・リミテッド | Modified conjugated diene polymer and rubber composition containing it |
| CN111630075A (en) * | 2017-12-15 | 2020-09-04 | 株式会社普利司通 | Functionalized polymer, method for preparing the same and rubber composition containing the same |
| US11807704B2 (en) | 2017-12-15 | 2023-11-07 | Bridgestone Corporation | Functionalized polymer, process for preparing and rubber compositions containing the functionalized polymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5473360B2 (en) | 2014-04-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5473360B2 (en) | Rubber composition and tire using the same | |
| JP5914572B2 (en) | tire | |
| JP5611585B2 (en) | Process for producing modified conjugated diene polymer, modified conjugated diene polymer, and rubber composition | |
| JP5756248B2 (en) | tire | |
| JP4159993B2 (en) | Method for producing modified polymer, modified polymer and rubber composition obtained by the method | |
| JP6085077B2 (en) | Rubber composition and tire using the same | |
| WO2009113499A1 (en) | Rubber composition for tire base rubber composition, and pneumatic tire made using said rubber composition | |
| WO2010126144A1 (en) | Tire | |
| EP2266819A1 (en) | Method for producing modified conjugated diene polymer/copolymer, modified conjugated diene polymer/copolymer, and rubber composition and tier using the same | |
| JP5451167B2 (en) | Modified low molecular weight conjugated diene polymer | |
| WO2009133888A1 (en) | Process for production of modified conjugated diene copolymer, modified conjugated diene copolymer produced by the process, rubber composition, and tire | |
| WO2008050851A1 (en) | Process for producing modified polymer, modified polymer obtained by the process, and rubber composition containing the same | |
| JPWO2009084667A1 (en) | tire | |
| JPWO2011030833A1 (en) | Modifier, method for producing modified conjugated diene polymer using the modifier, and modified conjugated diene polymer | |
| JP2011057946A (en) | Rubber composition and tire using the same | |
| JP5663146B2 (en) | Process for producing modified conjugated diene polymer, modified conjugated diene polymer, rubber composition, pneumatic tire | |
| WO2017104423A1 (en) | Rubber composition and tire | |
| JP2009242769A (en) | Rubber composition and tire using it, and modified conjugated diene polymer and its production method | |
| JP4944376B2 (en) | Rubber composition, method for producing the same, and tire | |
| JP2009280807A (en) | Rubber composition and tire using the same | |
| JP2010185053A (en) | Tire | |
| JP2009263536A (en) | Pneumatic tire | |
| JP2009263479A (en) | Rubber composition and tire using the same | |
| JP5512933B2 (en) | Method for producing modified conjugated diene copolymer, modified conjugated diene copolymer obtained by the method, rubber composition and tire | |
| JP2009280804A (en) | Rubber composition for tire and tire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20120227 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A132 Effective date: 20131001 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20140107 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20140204 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5473360 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |