WO2018093027A1 - Modifying agent, method for preparing same, and modified conjugated diene-based polymer comprising same - Google Patents
Modifying agent, method for preparing same, and modified conjugated diene-based polymer comprising same Download PDFInfo
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- WO2018093027A1 WO2018093027A1 PCT/KR2017/009721 KR2017009721W WO2018093027A1 WO 2018093027 A1 WO2018093027 A1 WO 2018093027A1 KR 2017009721 W KR2017009721 W KR 2017009721W WO 2018093027 A1 WO2018093027 A1 WO 2018093027A1
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- carbon atoms
- substituted
- unsubstituted
- formula
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- 229920000642 polymer Polymers 0.000 title claims abstract description 73
- 150000001993 dienes Chemical class 0.000 title claims abstract description 70
- 238000000034 method Methods 0.000 title claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 85
- 239000000126 substance Substances 0.000 claims abstract description 63
- 125000004432 carbon atom Chemical group C* 0.000 claims description 285
- 125000000524 functional group Chemical group 0.000 claims description 71
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 64
- 125000000217 alkyl group Chemical group 0.000 claims description 63
- 125000003118 aryl group Chemical group 0.000 claims description 63
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 49
- 125000000623 heterocyclic group Chemical group 0.000 claims description 48
- 125000000304 alkynyl group Chemical group 0.000 claims description 44
- 125000003342 alkenyl group Chemical group 0.000 claims description 40
- 125000003545 alkoxy group Chemical group 0.000 claims description 39
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 36
- 239000000178 monomer Substances 0.000 claims description 32
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 30
- 229910052805 deuterium Inorganic materials 0.000 claims description 30
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- -1 naphthyl sodium Chemical compound 0.000 claims description 21
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 125000001424 substituent group Chemical group 0.000 claims description 18
- 239000003607 modifier Substances 0.000 claims description 17
- 150000001721 carbon Chemical class 0.000 claims description 16
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 16
- 125000002947 alkylene group Chemical group 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 229920002554 vinyl polymer Polymers 0.000 claims description 14
- 125000005842 heteroatom Chemical group 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 12
- 150000002902 organometallic compounds Chemical class 0.000 claims description 12
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 11
- 239000000654 additive Substances 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 125000004434 sulfur atom Chemical group 0.000 claims description 9
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 8
- 125000004122 cyclic group Chemical group 0.000 claims description 8
- 239000003398 denaturant Substances 0.000 claims description 7
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 7
- 229910052717 sulfur Inorganic materials 0.000 claims description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 6
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 150000007514 bases Chemical class 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 125000005647 linker group Chemical group 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- 125000006735 (C1-C20) heteroalkyl group Chemical group 0.000 claims description 2
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 claims description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 claims description 2
- VSTXCZGEEVFJES-UHFFFAOYSA-N 1-cycloundecyl-1,5-diazacycloundec-5-ene Chemical compound C1CCCCCC(CCCC1)N1CCCCCC=NCCC1 VSTXCZGEEVFJES-UHFFFAOYSA-N 0.000 claims description 2
- UWKQJZCTQGMHKD-UHFFFAOYSA-N 2,6-di-tert-butylpyridine Chemical compound CC(C)(C)C1=CC=CC(C(C)(C)C)=N1 UWKQJZCTQGMHKD-UHFFFAOYSA-N 0.000 claims description 2
- ZFFBIQMNKOJDJE-UHFFFAOYSA-N 2-bromo-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(Br)C(=O)C1=CC=CC=C1 ZFFBIQMNKOJDJE-UHFFFAOYSA-N 0.000 claims description 2
- CSBDTEMAXHVRBB-UHFFFAOYSA-N 2-ethoxy-n,n-dimethylethanamine Chemical compound CCOCCN(C)C CSBDTEMAXHVRBB-UHFFFAOYSA-N 0.000 claims description 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 claims description 2
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 claims description 2
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 2
- BNHFWQQYLUPDOG-UHFFFAOYSA-N lithium;1,2,2,3-tetramethylpiperidine Chemical compound [Li].CC1CCCN(C)C1(C)C BNHFWQQYLUPDOG-UHFFFAOYSA-N 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 2
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 claims description 2
- NRUBUZBAZRTHHX-UHFFFAOYSA-N lithium;propan-2-ylazanide Chemical compound [Li+].CC(C)[NH-] NRUBUZBAZRTHHX-UHFFFAOYSA-N 0.000 claims description 2
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 claims description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 2
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims description 2
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- NUNQKTCKURIZQX-UHFFFAOYSA-N 2-(2-ethoxyethoxy)-2-methylpropane Chemical compound CCOCCOC(C)(C)C NUNQKTCKURIZQX-UHFFFAOYSA-N 0.000 claims 1
- ZATOFRITFRPYBT-UHFFFAOYSA-N C1=CC=C2C([Li])=CC=CC2=C1 Chemical compound C1=CC=C2C([Li])=CC=CC2=C1 ZATOFRITFRPYBT-UHFFFAOYSA-N 0.000 claims 1
- 150000004703 alkoxides Chemical class 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 34
- 239000003795 chemical substances by application Substances 0.000 abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 238000005096 rolling process Methods 0.000 abstract description 9
- 239000011256 inorganic filler Substances 0.000 abstract description 8
- 229910003475 inorganic filler Inorganic materials 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 230000001747 exhibiting effect Effects 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 55
- 239000005060 rubber Substances 0.000 description 55
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- 239000000203 mixture Substances 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 13
- 229920003048 styrene butadiene rubber Polymers 0.000 description 12
- 239000000945 filler Substances 0.000 description 11
- 238000004073 vulcanization Methods 0.000 description 10
- 244000043261 Hevea brasiliensis Species 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 9
- 229920003052 natural elastomer Polymers 0.000 description 9
- 229920001194 natural rubber Polymers 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 8
- 238000004898 kneading Methods 0.000 description 8
- 239000002174 Styrene-butadiene Substances 0.000 description 7
- 239000010734 process oil Substances 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 0 **(C(C[N+]([O-])=O)O*)O Chemical compound **(C(C[N+]([O-])=O)O*)O 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000005062 Polybutadiene Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000000704 physical effect Effects 0.000 description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 5
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 description 4
- 125000000739 C2-C30 alkenyl group Chemical group 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000003078 antioxidant effect Effects 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 230000020169 heat generation Effects 0.000 description 4
- 239000004636 vulcanized rubber Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 3
- 229920005549 butyl rubber Polymers 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000001976 improved effect Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 2
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 2
- 238000013329 compounding Methods 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
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000012763 reinforcing filler Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 125000005369 trialkoxysilyl group Chemical group 0.000 description 2
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- RRRXUCMQOPNVAT-UHFFFAOYSA-N 1-ethenyl-4-(4-methylphenyl)benzene Chemical compound C1=CC(C)=CC=C1C1=CC=C(C=C)C=C1 RRRXUCMQOPNVAT-UHFFFAOYSA-N 0.000 description 1
- OIEANVCCDIRIDJ-UHFFFAOYSA-N 1-ethenyl-5-hexylnaphthalene Chemical compound C1=CC=C2C(CCCCCC)=CC=CC2=C1C=C OIEANVCCDIRIDJ-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
- RCYNHSKTNNQPLT-UHFFFAOYSA-N 2-(1-ethoxyethoxy)-2-methylpropane Chemical compound CCOC(C)OC(C)(C)C RCYNHSKTNNQPLT-UHFFFAOYSA-N 0.000 description 1
- MENUHMSZHZBYMK-UHFFFAOYSA-N 2-cyclohexylethenylbenzene Chemical compound C1CCCCC1C=CC1=CC=CC=C1 MENUHMSZHZBYMK-UHFFFAOYSA-N 0.000 description 1
- DVNPFNZTPMWRAX-UHFFFAOYSA-N 2-triethoxysilylethanethiol Chemical compound CCO[Si](CCS)(OCC)OCC DVNPFNZTPMWRAX-UHFFFAOYSA-N 0.000 description 1
- LOSLJXKHQKRRFN-UHFFFAOYSA-N 2-trimethoxysilylethanethiol Chemical compound CO[Si](OC)(OC)CCS LOSLJXKHQKRRFN-UHFFFAOYSA-N 0.000 description 1
- YMXRPHMIOQYZOO-UHFFFAOYSA-N 3-(diethoxymethylsilyl)-N-[3-(diethoxymethylsilyl)propyl]-N-methylpropan-1-amine Chemical compound C(C)OC(OCC)[SiH2]CCCN(C)CCC[SiH2]C(OCC)OCC YMXRPHMIOQYZOO-UHFFFAOYSA-N 0.000 description 1
- LOOUJXUUGIUEBC-UHFFFAOYSA-N 3-(dimethoxymethylsilyl)propane-1-thiol Chemical compound COC(OC)[SiH2]CCCS LOOUJXUUGIUEBC-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- ZSFMFCWJHYPFPG-UHFFFAOYSA-N 3-triethoxysilylpropyl 2-methylthiirane-2-carboxylate Chemical compound CCO[Si](OCC)(OCC)CCCOC(=O)C1(C)CS1 ZSFMFCWJHYPFPG-UHFFFAOYSA-N 0.000 description 1
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- AKQWHIMDQYDQSR-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylthiirane-2-carboxylate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C1(C)CS1 AKQWHIMDQYDQSR-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 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 1
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 description 1
- ZSBKFEOSHGFEKJ-UHFFFAOYSA-N C1=CC=C2SC(SSSSCCC[SiH2]C(OC)OC)=NC2=C1 Chemical compound C1=CC=C2SC(SSSSCCC[SiH2]C(OC)OC)=NC2=C1 ZSBKFEOSHGFEKJ-UHFFFAOYSA-N 0.000 description 1
- SXLPVOKGQWNWFD-UHFFFAOYSA-N CCO[Si](CC[S+]=C(N(C)C)SSSSC(N(C)C)=[S+]CC[Si](OCC)(OCC)OCC)(OCC)OCC Chemical compound CCO[Si](CC[S+]=C(N(C)C)SSSSC(N(C)C)=[S+]CC[Si](OCC)(OCC)OCC)(OCC)OCC SXLPVOKGQWNWFD-UHFFFAOYSA-N 0.000 description 1
- ZZOXWBGGPBLVNQ-UHFFFAOYSA-N CN(C)C(SSSSC(N(C)C)=[S+]CCC[SiH2]C(OC)OC)=[S+]CCC[SiH2]C(OC)OC Chemical compound CN(C)C(SSSSC(N(C)C)=[S+]CCC[SiH2]C(OC)OC)=[S+]CCC[SiH2]C(OC)OC ZZOXWBGGPBLVNQ-UHFFFAOYSA-N 0.000 description 1
- SKFGZHGVWONCTD-UHFFFAOYSA-N CN(C)C(SSSSC(N(C)C)=[S+]CCC[Si](OC)(OC)OC)=[S+]CCC[Si](OC)(OC)OC Chemical compound CN(C)C(SSSSC(N(C)C)=[S+]CCC[Si](OC)(OC)OC)=[S+]CCC[Si](OC)(OC)OC SKFGZHGVWONCTD-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-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
- 239000004793 Polystyrene Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 229920006311 Urethane elastomer Polymers 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- WVUICGOYGDHVBH-ONEGZZNKSA-N [O-][N+](/C=C/c1ccc[o]1)=O Chemical compound [O-][N+](/C=C/c1ccc[o]1)=O WVUICGOYGDHVBH-ONEGZZNKSA-N 0.000 description 1
- PIAOLBVUVDXHHL-VOTSOKGWSA-N [O-][N+](/C=C/c1ccccc1)=O Chemical compound [O-][N+](/C=C/c1ccccc1)=O PIAOLBVUVDXHHL-VOTSOKGWSA-N 0.000 description 1
- WCNULONPFLBHQA-UHFFFAOYSA-N [O-][N+](CC(c(cc1)ccc1F)SCCCS)=O Chemical compound [O-][N+](CC(c(cc1)ccc1F)SCCCS)=O WCNULONPFLBHQA-UHFFFAOYSA-N 0.000 description 1
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- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229920003211 cis-1,4-polyisoprene Polymers 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 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
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 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
- 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 1
- GSYVJAOBRKCNOT-UHFFFAOYSA-N diethoxymethyl-[3-[3-(diethoxymethylsilyl)propyltetrasulfanyl]propyl]silane Chemical compound CCOC(OCC)[SiH2]CCCSSSSCCC[SiH2]C(OCC)OCC GSYVJAOBRKCNOT-UHFFFAOYSA-N 0.000 description 1
- 229960004132 diethyl ether Drugs 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920005558 epichlorohydrin rubber Polymers 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
- 238000011156 evaluation Methods 0.000 description 1
- ZONYXWQDUYMKFB-UHFFFAOYSA-N flavanone Chemical compound O1C2=CC=CC=C2C(=O)CC1C1=CC=CC=C1 ZONYXWQDUYMKFB-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000005246 galvanizing Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229920005555 halobutyl Polymers 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009413 insulation Methods 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 238000000465 moulding Methods 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
- 239000012454 non-polar solvent Substances 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
- 150000001282 organosilanes Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001084 poly(chloroprene) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000009864 tensile test Methods 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
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- ASAOXGWSIOQTDI-UHFFFAOYSA-N triethoxy-[2-(2-triethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CCO[Si](OCC)(OCC)CCSSSSCC[Si](OCC)(OCC)OCC ASAOXGWSIOQTDI-UHFFFAOYSA-N 0.000 description 1
- FBBATURSCRIBHN-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyldisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSCCC[Si](OCC)(OCC)OCC FBBATURSCRIBHN-UHFFFAOYSA-N 0.000 description 1
- VTHOKNTVYKTUPI-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSCCC[Si](OCC)(OCC)OCC VTHOKNTVYKTUPI-UHFFFAOYSA-N 0.000 description 1
- KLFNHRIZTXWZHT-UHFFFAOYSA-N triethoxy-[3-(3-triethoxysilylpropyltrisulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSCCC[Si](OCC)(OCC)OCC KLFNHRIZTXWZHT-UHFFFAOYSA-N 0.000 description 1
- QKJGTZOWMVHEHS-UHFFFAOYSA-N triethoxy-[3-(phenyltetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSSC1=CC=CC=C1 QKJGTZOWMVHEHS-UHFFFAOYSA-N 0.000 description 1
- JSXKIRYGYMKWSK-UHFFFAOYSA-N trimethoxy-[2-(2-trimethoxysilylethyltetrasulfanyl)ethyl]silane Chemical compound CO[Si](OC)(OC)CCSSSSCC[Si](OC)(OC)OC JSXKIRYGYMKWSK-UHFFFAOYSA-N 0.000 description 1
- JTTSZDBCLAKKAY-UHFFFAOYSA-N trimethoxy-[3-(3-trimethoxysilylpropyltetrasulfanyl)propyl]silane Chemical compound CO[Si](OC)(OC)CCCSSSSCCC[Si](OC)(OC)OC JTTSZDBCLAKKAY-UHFFFAOYSA-N 0.000 description 1
- PZJJKWKADRNWSW-UHFFFAOYSA-N trimethoxysilicon Chemical group CO[Si](OC)OC PZJJKWKADRNWSW-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000001993 wax Substances 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/25—Incorporating silicon atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/20—Incorporating sulfur atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/06—Butadiene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/06—Butadiene
Definitions
- the present invention relates to a modifier, and more particularly, a modifier excellent in interaction with rubber polymers and inorganic fillers, a method for preparing the same, and a functional group derived from the modifier, and having excellent workability, tensile strength, abrasion resistance, and rolling resistance. And a modified conjugated diene polymer having excellent wet road resistance.
- a method of reducing the hysteresis loss of the vulcanized rubber In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber.
- As an evaluation index of the vulcanized rubber a rebound elasticity of 50 ° C. to 80 ° C., tan ⁇ , Goodrich heat generation and the like are used. That is, a rubber material having a high resilience at the above temperature, or a small tan ⁇ and good rich heat generation is preferable.
- the greatest advantage of solution polymerization over emulsion polymerization is that the vinyl structure content and styrene content that define rubber properties can be arbitrarily controlled, and molecular weight and physical properties can be adjusted by coupling or modification. It can be adjusted. Therefore, it is easy to change the structure of the final prepared SBR or BR, and the movement of the chain ends can be reduced by the binding or modification of the chain ends, and the bonding strength with fillers such as silica or carbon black can be increased. It is widely used as a rubber material for tires.
- solution polymerization SBR When such a solution polymerization SBR is used as a rubber material for tires, by increasing the vinyl content in the SBR, the glass transition temperature of the rubber can be increased to not only control tire demand properties such as running resistance and braking force, but also increase the glass transition temperature. Proper adjustment can reduce fuel consumption.
- the solution polymerization SBR is prepared using an anionic polymerization initiator, and is used by binding or modifying the chain ends of the formed polymer using various modifiers. For example, US Pat. No.
- 4,397,994 discloses a technique in which the active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using alkyllithium, which is a monofunctional initiator, is bound using a binder such as a tin compound. It was.
- carbon black and silica are used as reinforcing fillers for tire treads, and when silica is used as reinforcing fillers, low hysteresis loss and wet road resistance are improved.
- the hydrophilic surface silica has a disadvantage of poor dispersibility due to low affinity with rubber compared to the hydrophobic surface carbon black, so that a separate silane coupler may be used to improve dispersibility or to impart a bond between silica and rubber. It is necessary to use a ring agent.
- a method of introducing a functional group having affinity or reactivity with silica to the rubber molecule terminal portion but the effect is not sufficient.
- Patent Document 1 US4397994 A
- the present invention has been made in order to solve the problems of the prior art, a modifier and a manufacturing method thereof having excellent dispersibility due to hydrogen bonding when combined with an inorganic filler, and modified therefrom excellent in workability, tensile strength, wear resistance,
- An object of the present invention is to provide a modified conjugated diene-based polymer having excellent rolling resistance and wet road resistance and a method for producing the same.
- the present invention provides a modifier comprising a compound represented by the following formula (1):
- R 1 is deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, substituted or Unsubstituted heteroalkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or substituted or unsubstituted hetero ring having 3 to 30 carbon atoms
- R 2 may be deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substitute
- R 4 and R 7 may be each independently an alkylene group having 1 to 10 carbon atoms
- R 5 , R 6 , R 8 and R 9 are each independently an alkyl group having 1 to 30 carbon atoms and carbon number It may be a cycloalkyl group of 5 to 30, or an aryl group of 6 to 30 carbon atoms
- m and n are each independently an integer selected from 0 to 3
- m + n ⁇ 1 one of the formula 1a or 1b
- m or n may each independently be an integer selected from 1 to 3.
- the present invention provides a method for preparing a denaturant comprising reacting a compound represented by Formula 2 with a compound represented by Formula 3:
- the present invention provides a modified conjugated diene-based polymer including the modifier-derived functional group and a method for producing the same.
- the hydrogen bond with the inorganic filler is included by including a functional group derived from the modifier at one end of the polymer. Due to this, the modified conjugated diene-based polymer having excellent interaction between the polymer and the inorganic filler can be prepared, and the modified conjugated diene-based polymer thus prepared has excellent processability, excellent tensile strength, wear resistance, rolling resistance, and wet road resistance. There is.
- the denaturing agent according to the present invention may include a compound represented by Formula 1 below:
- R 1 is deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, substituted or Unsubstituted heteroalkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or substituted or unsubstituted hetero ring having 3 to 30 carbon atoms
- R 2 may be deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substitute
- R 4 and R 7 may be each independently an alkylene group having 1 to 10 carbon atoms
- R 5 , R 6 , R 8 and R 9 are each independently an alkyl group having 1 to 30 carbon atoms and carbon number It may be a cycloalkyl group of 5 to 30, or an aryl group of 6 to 30 carbon atoms
- m and n are each independently an integer selected from 0 to 3
- m + n ⁇ 1 one of the formula 1a or 1b
- m or n may each independently be an integer selected from 1 to 3.
- R 1 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, substituted Or an unsubstituted C1-C20 heteroalkyl group, a substituted or unsubstituted C5-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C3-C20 hetero It may be a ring group, R 2 may be a functional group represented by the formula (1a), R 3 may be a functional group represented by the formula (1b), R 1 is substituted alkyl, alkenyl group, alkynyl group, heteroalkyl group, cyclo In the case of an alkyl group, an aryl group, or a heterocyclic group, the
- R 4 and R 7 may be each independently an alkylene group having 1 to 5 carbon atoms
- R 5 , R 6 , R 8 and R 9 are each independently an alkyl group having 1 to 20 carbon atoms and carbon number It may be a cycloalkyl group of 5 to 20, or an aryl group of 6 to 20 carbon atoms
- m and n may be each independently an integer selected from 1 to 3.
- the term 'substituted' may mean that the hydrogen of the functional group, the atomic group, or the compound is substituted with a specific substituent, and when the hydrogen of the functional group, the atomic group, or the compound is substituted with a specific substituent, the functional group, the atomic group, or the compound One or two or more substituents may be present, depending on the number of hydrogen present in the
- each substituent may be the same as or different from each other.
- the term 'alkyl group' may mean a monovalent aliphatic saturated hydrocarbon, and may be linear alkyl groups such as methyl, ethyl, propyl and butyl, and isopropyl, sec-butyl, tertiary, It may be meant to include all branched alkyl groups such as tert-butyl and neopentyl (neopentyl).
- alkylene group may refer to a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene and butylene.
- alkylsilyl group may be meant to include all monoalkylsilyl, dialkylsilyl and trialkylsilyl.
- alkenyl group' may refer to an alkyl group including one or two or more double bonds.
- alkynyl group' may refer to an alkyl group including one or two or more triple bonds.
- alkoxy group may include all functional groups, atomic groups, or compounds in which hydrogen at the end of an alkyl group is substituted with an oxygen atom, such as methoxy, ethoxy, propoxy and butoxy.
- heteroalkyl group may refer to an alkyl group in which carbon atoms (excluding terminal carbon atoms) in the alkyl group are substituted with one or more hetero atoms.
- cycloalkyl group may mean both cyclic saturated hydrocarbons or cyclic unsaturated hydrocarbons containing one or two or more unsaturated bonds.
- the term 'aryl group' may mean a cyclic aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded to each other. hydrocarbons) can be included.
- the term 'aralkyl group' may mean an alkyl group in which one or more aryl groups are necessarily substituted.
- heterocyclic group' may mean both a cycloalkyl group or an aryl group in which a carbon atom in a cycloalkyl group or an aryl group is substituted with one or more hetero atoms.
- the compound represented by Chemical Formula 1 may be a compound represented by Chemical Formulas 1-1 to 1-12.
- each R 13 is independently an alkyl group of 1 to 20, preferably a methyl group or an ethyl group.
- the compounds represented by the formula (1-1 to 1-12) are all represented as including a functional group of a trialkoxy silyl group, according to the present invention, the trialkoxy silyl group instead of alkyldimethoxysilyl, alkyldiethoxy As the silyl, dialkylmethoxysilyl and dialkylethoxysilyl groups and the like, it may be substituted with a substituted silyl functional group by appropriately combining the number of alkyl groups and alkoxy groups as necessary.
- the denaturing agent of the present invention includes a compound containing -NO 2 in a molecule, whereby hydrogen bonding is possible between a hydrogen atom bonded to -OH or the like present on the surface of an inorganic filler, particularly a silica-based filler, and an oxygen atom of -NO 2 .
- an inorganic filler particularly a silica-based filler
- an oxygen atom of -NO 2 oxygen atom of -NO 2
- the method of preparing a denaturant according to the present invention may include reacting a compound represented by Formula 2 with a compound represented by Formula 3 below:
- the compound represented by Chemical Formula 2 may be, for example, a compound represented by Chemical Formulas 2-1 to 2-6.
- the compound represented by Chemical Formula 3 may be a compound represented by Chemical Formula 3-1 or 3-6.
- R 13 in Formulas 3-1 to 3-6 are each independently an alkyl group of 1 to 20, preferably a methyl group or an ethyl group, and R 14 is each independently an alkyl group of 1 to 20, preferably a methyl group or an ethyl group to be.
- the alkoxysilyl group if necessary, such as triethoxysilyl, trimethoxysilyl, alkyldimethoxysilyl, alkyldiethoxysilyl, dialkylmethoxysilyl and dialkylethoxysilyl groups, etc. It may be substituted with a substituted silyl functional group in appropriate combination of numbers.
- the compounds represented by Chemical Formulas 3-1 to 3-6 may be compounds represented by the following Chemical Formulas 3-7 to 3-12, respectively.
- Me is a methyl group and Et is an ethyl group.
- the molar ratio of the compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 3 is 0.5 to 2 mol of the compound represented by Chemical Formula 3 based on 1 mol of the compound represented by Chemical Formula 2. , 0.7 to 1.5 moles, or 0.9 to 1.1 moles.
- the molar ratio of the compound represented by Formula 2: the compound represented by Formula 3 may be 1: 0.5 to 1: 2, 1: 0.7 to 1: 1.5, or 1: 0.9 to 1: 1.1, and within this range The purity and yield are excellent at.
- the reaction may be carried out at a reaction temperature of 10 °C to 90 °C, 20 °C to 80 °C, or 20 °C to 60 °C, within this range the reaction rate is excellent, the product The purity and yield are excellent effects.
- the reaction may be carried out in the presence of a basic compound, in which case the proton of the compound represented by the formula (3) is removed by the basic compound, and then the double bond of the compound represented by the anionized X is represented by the formula (2).
- the basic compound may include methylamine, dimethylamine, triethylamine, tetramethylethylenediamine, lithiumdiisopropylamide, and 1,8-diazabicyclo. Consisting of 1,8-diazabicycloundec-7-ene, 2,6-di-tert-butylpyridine, and lithiumtetramethylpiperidine It may be at least one selected from the group.
- the modified conjugated diene-based polymer according to the present invention includes a repeating unit derived from a conjugated diene-based monomer, and may include a modifying agent-derived functional group including a compound represented by the following Formula 1 at one end.
- the conjugated diene-based monomer-derived repeating unit may mean a repeating unit formed when the conjugated diene-based monomer is polymerized, and the conjugated diene-based monomer may be, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene , Piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means halogen atom) It may be one or more selected.
- the modified conjugated diene-based copolymer may be, for example, a copolymer further comprising an aromatic vinyl monomer-derived repeating unit together with the repeating unit derived from the conjugated diene-based monomer.
- the aromatic vinyl monomer-derived repeating unit may mean a repeating unit formed by polymerization of an aromatic vinyl monomer, and the aromatic vinyl monomer may be, for example, styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, or 4-propyl. Styrene, 1-vinylnaphthalene, 4-
- It may be at least one selected from the group consisting of cyclohexyl styrene, 4- (p-methylphenyl) styrene and 1-vinyl-5-hexyl naphthalene.
- the modified conjugated diene-based polymer when the modified conjugated diene-based polymer is a copolymer including an aromatic vinyl monomer-derived repeating unit, the modified conjugated diene-based polymer may contain 50 to 95% by weight, 55 to 90% by weight, or 60 to 60% of the repeating unit derived from a conjugated diene monomer.
- 90 wt% may include 5 to 50 wt%, 10 to 45 wt%, or 10 to 40 wt% of an aromatic vinyl monomer-derived repeating unit, and has excellent rolling resistance, wet road resistance, and abrasion resistance within this range. It works.
- the copolymer may be a random copolymer, in this case there is an excellent balance between the physical properties.
- the random copolymer may mean that the repeating units constituting the copolymer are randomly arranged.
- the modified conjugated diene-based polymer may include a modification initiator-derived functional group containing a compound represented by the following formula (4) at the other end, in addition to one end containing a modifier-derived functional group comprising the compound represented by the formula (1) have.
- R 10 and R 11 are each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aralkyl group having 5 to 20 carbon atoms, or R 10 and R 11 These may combine with each other to form a saturated or unsaturated cyclic structure having 5 to 20 carbon atoms with adjacent N atoms, and when R 10 and R 11 form a cyclic structure, may have a branched structure, and R 12 It may be a single bond, an alkylene group having 1 to 20 carbon atoms, or one type of linking group selected from the group consisting of the following Chemical Formulas 5 to 7, and M may be an alkali metal.
- R 10 and R 11 may be each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 5 to 20 carbon atoms, and R is 12 may be a single bond, an alkylene group having 1 to 20 carbon atoms, or one linking group selected from the group consisting of Chemical Formulas 5 to 7, and M may be an alkali metal.
- R 10 and R 11 are each independently methyl, ethyl, propyl, butyl, octyl, cyclopropyl, cyclohexyl, 3-phenyl-1-propyl, isobutyl, decyl, heptyl or phenyl
- R 12 may be a single bond, an alkylene group having 2 to 16 carbon atoms, or one linking group selected from the group consisting of Chemical Formulas 3 to 5, and M may be Li.
- the modified initiator-derived functional group including the compound represented by Formula 4 is a polymer located at one end of the conjugated diene polymer corresponding to the polymerization initiation site. It can mean a functional group in the inside, there is an effect of improving the mechanical properties such as rolling resistance and wet road resistance, along with improving the dispersibility and processability of the conjugated diene-based polymer.
- the modified conjugated diene-based polymer according to an embodiment of the present invention has a number average molecular weight (Mn) of 10,000 g / mol to 2,000,000 g / mol, 50,000 g / mol to 1,800,000 g / mol, or 120,000 g / mol to 1,500,000 g / mol, the weight average molecular weight (Mw) may be 10,000 g / mol to 5,000,000 g / mol, 100,000 g / mol to 3,500,000 g / mol, or 120,000 g / mol to 2,000,000 g / mol, within this range Cloud resistance and wet road resistance is excellent effect.
- Mn number average molecular weight
- the modified conjugated diene-based polymer may have a molecular weight distribution (Mw / Mn) of 1.0 to 8.0, 1.0 to 4.0, or 1.0 to 3.5, there is an effect of excellent balance between physical properties within this range.
- Mw / Mn molecular weight distribution
- the modified conjugated diene-based polymer may have a monetary viscosity of 20 to 150 at 100 ° C., 20 to 150 at 140 ° C., and excellent workability and productivity within this range. .
- the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, 10% by weight or more, or 14% by weight to 70% by weight, and the glass transition temperature within this range can be adjusted to an appropriate range cloud It is effective in resistance, wet road resistance and low fuel efficiency.
- the vinyl content may refer to the content of 1,2-added conjugated diene-based monomers, not 1,4-addition, based on 100% by weight of the conjugated diene-based copolymer composed of a monomer having a vinyl group and an aromatic vinyl monomer. Can be.
- the terms 'derived repeating unit' and 'derived functional group' may refer to a component, a structure, or the substance itself derived from a substance.
- the modified conjugated diene-based polymer manufacturing method is to prepare an active polymer in which an organic metal is bonded by polymerizing a conjugated diene-based monomer, or an aromatic vinyl monomer and a conjugated diene-based monomer in a hydrocarbon solvent containing an organometallic compound. Step S1; And reacting with a denaturing agent including the active polymer and a compound represented by Formula 1 below (S2).
- the hydrocarbon solvent is not particularly limited, but may be, for example, one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene.
- the compound represented by Formula 1 may be used in an amount of 0.01 mmol to 10 mmol, 0.01 mmol to 5 mmol, or 0.02 mmol to 3 mmol, based on 100 g of the total monomer.
- the organometallic compound may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, or 0.1 mmol to 1 mmol, based on 100 g of the total monomer.
- the organometallic compound is, for example, methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naph Tilithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexylithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium , Lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.
- the organometallic compound may be a compound represented by Formula 4 below.
- the polymerization of the step (S1) may be carried out including a polar additive
- the polar additive may be added 0.001g to 50g, 0.001g to 10g, or 0.005g to 0.1g based on a total of 100g monomer. have.
- the polar additive is tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tert-butoxy ethoxyethane , Bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine, and may be one or more selected from the group consisting of triethylamine.
- It may be an amine or tetramethylethylenediamine, and may be the same as or different from the polar additives that may be added in the preparation of the amino silane-based compound, when the polar additives include conjugated diene monomer, or conjugated diene monomer and Compensating the difference in reaction rate when copolymerizing aromatic vinyl monomers By doing so, there is an effect of inducing the easy formation of a random copolymer.
- the polymerization of the step (S1) may be, for example, anionic polymerization, and specifically, may be living anion polymerization having an anion active site at the end of the polymerization by a growth polymerization reaction by anion.
- the polymerization of the step (S1) may be a temperature increase polymerization, isothermal polymerization or constant temperature polymerization (thermal insulation polymerization)
- the constant temperature polymerization may include the step of polymerization by the heat of reaction without the addition of heat after the addition of the organometallic compound optionally
- the temperature polymerization may mean a polymerization method in which the temperature is increased by optionally adding heat after the organometallic compound is added, and the isothermal polymerization is heat after adding the organometallic compound.
- the polymerization of the step (S1) may be carried out in a temperature range of -20 °C to 200 °C, 0 °C to 150 °C, or 10 °C to 120 °C for example.
- the active polymer prepared by the step (S1) may refer to a polymer in which a polymer anion and an organic metal cation are combined.
- the molar ratio of the modifier and the organometallic compound including the compound represented by Chemical Formula 1 is 1: 0.1 to 1:10, 1: 0.1 to 1: 5, or 1: 0.2 to 1: It can be 3, it is possible to carry out the modification performance of the optimum performance within this range, it is possible to obtain a conjugated diene-based polymer of high modification rate.
- the reaction of step (S2) is a modification reaction for introducing a functional group derived from the modifier into the active polymer, it may be to perform the reaction for 1 minute to 5 hours at 0 °C to 90 °C.
- the modified conjugated diene-based polymer manufacturing method may be performed by a batch polymerization (batch) or a continuous polymerization method comprising one or more reactors.
- the modified conjugated diene-based polymer manufacturing method may further include one or more steps of recovering and drying the solvent and the unreacted monomer, if necessary, following the step (S2) of the present invention.
- a rubber composition comprising the modified conjugated diene-based polymer.
- the rubber composition may include the modified conjugated diene-based polymer in an amount of 10 wt% or more, 10 wt% to 100 wt%, or 20 wt% to 90 wt%, and within this range, tensile strength, wear resistance, and the like. It is excellent in the mechanical properties of and excellent in the balance between each physical property.
- the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based polymer, wherein the rubber components may be included in an amount of 90% by weight or less based on the total weight of the rubber composition.
- the other rubber component may be included in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.
- the rubber component may be, for example, natural rubber or synthetic rubber, and specific examples include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber obtained by modifying or refining the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly (ethylene-co- Propylene), poly (styrene-co-butadiene), poly (styrene-co-isoprene), poly (styrene-co-isoprene-co-butadiene), poly (isoprene-co-butadiene), poly (ethylene-co-propylene Co-diene),
- the rubber composition may include, for example, 0.1 part by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer of the present invention.
- the filler may be, for example, a silica-based filler, and specific examples may be wet silica (silicate silicate), dry silica (silicate anhydrous), calcium silicate, aluminum silicate, colloidal silica, and the like.
- the wet silica may be the most compatible of the grip (wet grip).
- the rubber composition may further include a carbon black filler as needed.
- silica when silica is used as the filler, a silane coupling agent for improving reinforcement and low heat generation may be used together.
- the silane coupling agent may include bis (3-triethoxysilylpropyl) tetrasulfide.
- the compounding amount of the silane coupling agent is conventional.
- the silane coupling agent may be used in an amount of 1 part by weight to 20 parts by weight, or 5 parts by weight to 15 parts by weight with respect to 100 parts by weight of silica, and the effect as a coupling agent is within this range. While sufficiently exhibiting, there is an effect of preventing gelation of the rubber component.
- the rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and may further include a vulcanizing agent.
- the vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the rubber component, while ensuring the required elastic modulus and strength of the vulcanized rubber composition within this range and at the same time low fuel efficiency. Excellent effect.
- the rubber composition according to an embodiment of the present invention in addition to the above components, various additives commonly used in the rubber industry, specifically, vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scoring agents, zinc white, Stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.
- the vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG.
- a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG.
- Guanidine-based compounds such as (diphenylguanidine) may be used, and may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.
- the process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound, and when considering the tensile strength and abrasion resistance, when the aromatic process oil, hysteresis loss and low temperature characteristics are considered.
- Naphthenic or paraffinic process oils may be used.
- the process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and there is an effect of preventing a decrease in tensile strength and low heat generation (low fuel efficiency) of the vulcanized rubber within this range.
- the anti-aging agent is for example N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 6-ethoxy-2 , 2,4-trimethyl-1,2-dihydroquinoline, or a high temperature condensate of diphenylamine and acetone, and the like, and may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.
- the rubber composition according to an embodiment of the present invention may be obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc. by the compounding formulation, and has low heat resistance and abrasion resistance by a vulcanization process after molding. This excellent rubber composition can be obtained.
- a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc.
- the rubber composition may be used for tire members such as tire treads, under treads, sidewalls, carcass coated rubbers, belt coated rubbers, bead fillers, pancreapers, or bead coated rubbers, dustproof rubbers, belt conveyors, hoses, and the like. It may be useful for the production of various industrial rubber products.
- the present invention provides a tire manufactured using the rubber composition.
- the tire may include a tire or a tire tread.
- 0.1 mol (14.91 g) of the compound represented by the following Chemical Formula 2-1 was added to a 1L round bottom flask connected with a shrink line, and the water was removed under reduced pressure, and 500 ml of acetonitrile was added under an argon atmosphere.
- 0.1 mol (42.57 g) of the compound represented by Chemical Formula 3-7 and 10.12 g of triethylamine were added thereto, heated to 40 ° C., and stirred for 4 hours to obtain a compound represented by the following Chemical Formula 1-13.
- 1 H and 13 C nuclear magnetic resonance spectroscopy spectra were observed.
- 0.1 mol (14.91 g) of the compound represented by the following Chemical Formula 2-1 was added to a 1L round bottom flask connected by a shrink line, and the water was removed under reduced pressure. Then, 0.1 mol (of the compound represented by the following Chemical Formula 3-10 under an argon atmosphere) 23.84 g) was added thereto, and stirred at 25 ° C. for 1 hour to obtain a compound represented by the following Chemical Formula 1-14, and 1 H and 13 C nuclear magnetic resonance spectroscopic spectra were observed.
- Example 1 Except that 1.67g (4.3 mmol) of the compound represented by Formula 1-14 prepared in Preparation Example 2 was added instead of the compound represented by Formula 1-13 prepared in Preparation Example 1. , It was carried out in the same manner as in Example 1.
- Example 1 Except that 2.42g (4.3 mmol) of the compound represented by Formula 1-15 prepared in Preparation Example 3 was added instead of the compound represented by Formula 1-13 prepared in Preparation Example 1. , It was carried out in the same manner as in Example 1.
- Example 1 Except that 1.62g (4.3 mmol) of the compound represented by Formula 1-16 prepared in Preparation Example 4 was added instead of the compound represented by Formula 1-13 prepared in Preparation Example 1. , It was carried out in the same manner as in Example 1.
- Example 1 Except that 2.53g (4.3 mmol) of the compound represented by Formula 1-17 prepared in Preparation Example 5 was added instead of the compound represented by Formula 1-13 prepared in Preparation Example 1. , It was carried out in the same manner as in Example 1.
- Example 1 Except that 1.73g (4.3 mmol) of the compound represented by Formula 1-18 prepared in Preparation Example 6 was added instead of the compound represented by Formula 1-13 prepared in Preparation Example 1. , It was carried out in the same manner as in Example 1.
- Example 1 except that the compound represented by Formula 1-13 prepared in Preparation Example 1 was not added, it was carried out in the same manner as in Example 1.
- Example 1 In Example 1, except that 1.63 g (4.3 mmol) of bis (diethoxymethylsilylpropyl) -N-methylamine was added instead of the compound represented by Chemical Formula 1-13 prepared in Preparation Example 1, It carried out by the same method as Example 1.
- Example 1 2.30g (4.3 mmol) of N, N-bis (triethoxysilylpropyl) aminopropyl-1-imidazole was added instead of the compound represented by Chemical Formula 1-13 prepared in Preparation Example 1. Except that, it was carried out in the same manner as in Example 1.
- MWD weight average molecular weight
- MV pattern viscosity
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatohraph (GPC) analysis, and the molecular weight distribution (MWD, Mw / Mn) was calculated from the respective measured molecular weights.
- GPC gel permeation chromatohraph
- Mw molecular weight distribution
- the GPC used a combination of two PLgel Olexis (Polymer Laboratories Co.) column and one PLgel mixed-C (Polymer Laboratories Co.) column, all of the newly replaced column was a mixed bed column,
- the GPC standard material was calculated using polystyrene (PS) when calculating the molecular weight.
- the pattern viscosity (MV, (ML1 + 4, @ 100 °C) MU) was measured using a Rotor Speed 2 ⁇ 0.02 rpm, Large Rotorfmf at 100 °C using MV-2000 (ALPHA Technologies, Inc.), the sample used After leaving at room temperature (23 ⁇ 3 °C) for more than 30 minutes, 27 ⁇ 3 g was collected and filled into the die cavity, and platen was operated for 4 minutes.
- Each modified or unmodified styrene-butadiene copolymer of Examples and Comparative Examples was blended under the blending conditions shown in Table 2 below as a raw material rubber.
- the raw materials in Table 2 are each parts by weight based on 100 parts by weight of rubber.
- the rubber specimen is kneaded through the first stage kneading and the second stage kneading.
- a half-barrier mixer equipped with a temperature control device was used to prepare raw rubber (styrene-butadiene copolymer), filler, organosilane coupling agent, process oil, zincated, stearic acid, antioxidant, antioxidant, wax and The accelerator was kneaded.
- the temperature of the kneader was controlled to obtain a primary blend at a discharge temperature of 150 ° C.
- the first blend, sulfur and a vulcanization accelerator were added to the kneader, and a rubber specimen was prepared by a curing process at 150 ° C. for 20 minutes.
- Tensile properties were prepared in accordance with the tensile test method of ASTM 412 and measured the tensile strength at the cutting of the test piece and the tensile stress (300% modulus) at 300% elongation. Specifically, the tensile properties were measured at a rate of 50 cm / min at room temperature using a Universal Test Machin 4204 (Instron) tensile tester.
- Wear resistance of the rubber specimen prepared by using a DIN abrasion tester a load of 10 N is applied to a rotating drum (Drum) attached to the wear paper, the rubber specimen is moved in a direction perpendicular to the rotational direction of the drum, the wear loss
- the weight was measured and shown as an index on the basis of the loss weight of Comparative Example 2.
- the rotational speed of the drum is 40 rpm, and upon completion of the test the total travel distance of the specimen is 40 m. The smaller the index value of the loss weight, the better the wear resistance.
- Viscoelastic properties were measured by using a dynamic mechanical analyzer (TA Co., Ltd.) to determine the tan ⁇ by varying the strain at a frequency of 10 Hz and each measurement temperature (-60 ° C. to 60 ° C.) in a torsion mode. Payne effect is expressed as the difference between the minimum and maximum values at 0.28% to 40% strain.
- the lower the high temperature 60 [deg.] C tan ⁇ the lower the hysteresis loss, and the lower the running resistance (fuelability).
- the vulcanization characteristics (t90) were measured using MDF (moving die rheometer) for 50 minutes of vulcanization at 150 ° C., the MH (maximum torque) value and the time required until 90% quenching (t90).
- the modified conjugated diene-based polymer of the modified example according to the present invention is excellent in tensile properties, wear resistance, viscoelastic properties and vulcanization properties.
- the modified conjugated diene polymer of the embodiment modified with the modifying agent according to the present invention contains nitro groups in the modifying agent, so that the dispersibility is very excellent due to hydrogen bonding when combined with the inorganic filler
- Comparative Example 1 is an unmodified conjugated diene polymer
- the tensile, abrasion and viscoelastic properties were remarkably improved and further modified with an alkoxy silane-based modifier containing nitrogen atoms such as amine groups and imidazole groups, but not containing nitro groups.
- the viscoelastic properties were remarkably improved, and it was confirmed that rolling resistance, wet road resistance, and low running resistance were very excellent.
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Abstract
The present invention relates to a modifying agent and, more specifically, the present invention provides a modifying agent comprising a compound represented by chemical formula 1, a method for preparing the same, and a modified conjugated diene-based polymer comprising the same. In addition, the present invention provides: a modifying agent and a preparation method therefor, the modifying agent exhibiting excellent dispersion force by a hydrogen bond when mixed with an inorganic filler; and a modified conjugated diene-based polymer and a preparation method therefor, the modified conjugated diene-based polymer being obtained by modification using the modifying agent and having excellent processability, tensile strength, wear resistance, rolling resistance, and wet surface resistance.
Description
관련출원과의 상호인용Citation with Related Applications
본 출원은 2016년 11월 21일자 출원된 한국 특허 출원 제10-2016-0155265호 및 2017년 07월 26일자 출원된 한국 특허 출원 제10-2017-0094944호에 기초한 우선권의 이익을 주장하며, 해당 한국 특허 출원의 문헌에 개시된 모든 내용은 본 명세서의 일부로서 포함된다.This application claims the benefit of priority based on Korean Patent Application No. 10-2016-0155265, filed November 21, 2016 and Korean Patent Application No. 10-2017-0094944, filed July 26, 2017. All content disclosed in the literature of a Korean patent application is included as part of this specification.
기술분야Field of technology
본 발명은 변성제에 관한 것으로, 보다 상세하게는 고무 중합체 및 무기 충진제와 상호작용이 뛰어난 변성제 및 이의 제조방법과, 상기 변성제로부터 유래된 작용기를 포함함으로써 가공성이 우수하고, 인장강도, 내마모성, 구름저항 및 젖은 노면 저항성이 뛰어난 변성 공액디엔계 중합체에 관한 것이다.The present invention relates to a modifier, and more particularly, a modifier excellent in interaction with rubber polymers and inorganic fillers, a method for preparing the same, and a functional group derived from the modifier, and having excellent workability, tensile strength, abrasion resistance, and rolling resistance. And a modified conjugated diene polymer having excellent wet road resistance.
최근 자동차에 대한 저연비화의 요구에 따라, 타이어용 고무 재료로서 구름 저항이 적고, 내마모성, 인장 특성이 우수하며, 젖은 노면 저항성으로 대표되는 조정 안정성도 겸비한 공액디엔계 중합체가 요구되고 있다.Recently, in accordance with the demand for low fuel consumption for automobiles, there has been a demand for conjugated diene-based polymers having low rolling resistance, excellent wear resistance and tensile characteristics, and adjustment stability represented by wet road resistance as a rubber material for tires.
타이어의 구름 저항을 감소시키기 위해서는 가황 고무의 히스테리시스 손실을 작게 하는 방안이 있으며, 이러한 가황 고무의 평가 지표로서는 50 ℃ 내지 80 ℃의 반발탄성, tan δ, 굿리치 발열 등이 이용된다. 즉, 상기 온도에서의 반발탄성이 크거나 tan δ, 굿리치 발열이 작은 고무 재료가 바람직하다.In order to reduce the rolling resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber. As an evaluation index of the vulcanized rubber, a rebound elasticity of 50 ° C. to 80 ° C., tan δ, Goodrich heat generation and the like are used. That is, a rubber material having a high resilience at the above temperature, or a small tan δ and good rich heat generation is preferable.
히스테리시스 손실이 작은 고무 재료로서는, 천연 고무, 폴리이소프렌 고무 또는 폴리부타디엔 고무 등이 알려져 있지만, 이들은 젖은 노면 저항성이 작은 문제가 있다. 이에 최근에는 스티렌-부타디엔 고무(이하, SBR 이라 함) 또는 부타디엔 고무(이하, BR 이라 함)와 같은 공액디엔계 중합체 또는 공중합체가 유화중합이나 용액중합에 의해 제조되어 타이어용 고무로서 이용되고 있다. 이 중, 유화중합에 비해 용액중합이 갖는 최대의 장점은 고무 물성을 규정하는 비닐 구조 함량 및 스티렌 함량을 임의로 조절할 수 있고, 커플링(coupling)이나, 변성(modification) 등에 의해 분자량 및 물성 등을 조절할 수 있다는 점이다. 따라서, 최종 제조된 SBR이나 BR의 구조 변화가 용이하고, 사슬 말단의 결합이나 변성으로 사슬 말단의 움직임을 줄이고, 실리카 또는 카본블랙 등의 충진제와의 결합력을 증가시킬 수 있어 용액중합에 의한 SBR이 타이어용 고무 재료로 많이 사용된다.As a rubber material having a low hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber and the like are known, but these have a problem of low wet road resistance. Recently, conjugated diene-based polymers or copolymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber (hereinafter referred to as BR) have been produced by emulsion polymerization or solution polymerization and used as rubber for tires. . Among them, the greatest advantage of solution polymerization over emulsion polymerization is that the vinyl structure content and styrene content that define rubber properties can be arbitrarily controlled, and molecular weight and physical properties can be adjusted by coupling or modification. It can be adjusted. Therefore, it is easy to change the structure of the final prepared SBR or BR, and the movement of the chain ends can be reduced by the binding or modification of the chain ends, and the bonding strength with fillers such as silica or carbon black can be increased. It is widely used as a rubber material for tires.
이러한 용액중합 SBR이 타이어용 고무 재료로 사용되는 경우, 상기 SBR 내의 비닐 함량을 증가시킴으로써 고무의 유리전이온도를 상승시켜 주행저항 및 제동력과 같은 타이어 요구 물성을 조절할 수 있을 뿐만 아니라, 유리전이온도를 적절히 조절함으로서 연료소모를 줄일 수 있다. 상기 용액중합 SBR은 음이온 중합 개시제를 사용하여 제조하며, 형성된 중합체의 사슬 말단을 여러 가지 변성제를 이용하여 결합시키거나, 변성시켜 사용되고 있다. 예를 들어, 미국특허 제4,397,994호에는 일관능성 개시제인 알킬리튬을 이용하여 비극성 용매 하에서 스티렌-부타디엔을 중합하여 얻어진 중합체의 사슬 말단의 활성 음이온을 주석화합물과 같은 결합제를 사용하여 결합시킨 기술을 제시하였다.When such a solution polymerization SBR is used as a rubber material for tires, by increasing the vinyl content in the SBR, the glass transition temperature of the rubber can be increased to not only control tire demand properties such as running resistance and braking force, but also increase the glass transition temperature. Proper adjustment can reduce fuel consumption. The solution polymerization SBR is prepared using an anionic polymerization initiator, and is used by binding or modifying the chain ends of the formed polymer using various modifiers. For example, US Pat. No. 4,397,994 discloses a technique in which the active anion at the chain end of a polymer obtained by polymerizing styrene-butadiene in a nonpolar solvent using alkyllithium, which is a monofunctional initiator, is bound using a binder such as a tin compound. It was.
한편, 타이어 트레드의 보강성 충진제로서 카본블랙 및 실리카 등이 사용되고 있는데, 보강성 충진제로서 실리카를 이용하는 경우 저히스테리시스 손실성 및젖은 노면 저항성이 향상된다는 장점이 있다. 그러나, 소수성 표면의 카본블랙 대비 친수성 표면의 실리카는 고무와의 친화성이 낮아 분산성이 나쁘다는 결점을 가지고 있어, 분산성을 개선시키거나 실리카-고무 간의 결합 부여를 행하기 위해 별도의 실란 커플링제를 사용할 필요가 있다. 이에, 고무 분자 말단부에 실리카와의 친화성이나 반응성을 갖는 관능기를 도입하는 방안이 이루어지고 있으나, 그 효과가 충분하지 않은 실정이다.On the other hand, carbon black and silica are used as reinforcing fillers for tire treads, and when silica is used as reinforcing fillers, low hysteresis loss and wet road resistance are improved. However, the hydrophilic surface silica has a disadvantage of poor dispersibility due to low affinity with rubber compared to the hydrophobic surface carbon black, so that a separate silane coupler may be used to improve dispersibility or to impart a bond between silica and rubber. It is necessary to use a ring agent. Thus, a method of introducing a functional group having affinity or reactivity with silica to the rubber molecule terminal portion, but the effect is not sufficient.
[선행기술문헌][Preceding technical literature]
[특허문헌][Patent Documents]
(특허문헌 1) US4397994 A(Patent Document 1) US4397994 A
본 발명은 상기 종래기술의 문제점을 해결하기 위하여 안출된 것으로, 무기 충진제와 배합 시 수소 결합으로 인해 우수한 분산력을 나타내는 변성제 및 이의 제조방법과, 이로부터 변성되어 가공성이 우수하고, 인장강도, 내마모성, 구름저항 및 젖은 노면 저항성이 뛰어난 변성 공액디엔계 중합체 및 이의 제조방법을 제공하는 것을 목적으로 한다.The present invention has been made in order to solve the problems of the prior art, a modifier and a manufacturing method thereof having excellent dispersibility due to hydrogen bonding when combined with an inorganic filler, and modified therefrom excellent in workability, tensile strength, wear resistance, An object of the present invention is to provide a modified conjugated diene-based polymer having excellent rolling resistance and wet road resistance and a method for producing the same.
상기의 과제를 해결하기 위한 본 발명의 일 실시예에 따르면, 본 발명은 하기 화학식 1로 표시되는 화합물을 포함하는 변성제를 제공한다:According to an embodiment of the present invention for solving the above problems, the present invention provides a modifier comprising a compound represented by the following formula (1):
[화학식 1][Formula 1]
상기 화학식 1에서, R1은 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기일 수 있고, R2는 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기, 또는 하기 화학식 1a로 표시되는 작용기일 수 있으며, R3는 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기, 또는 하기 화학식 1b로 표시되는 작용기일 수 있고, R1, R2 및 R3가 치환된 알킬기, 알킬실릴기, 알케닐기, 알카이닐기, 알콕시기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기인 경우, 치환된 알킬기, 알킬실릴기, 알케닐기, 알카이닐기, 알콕시기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기의 치환기는 중수소, 할로겐, 히드록시기, 니트로기, 시아노기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 30의 알카이닐기, 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 탄소수 5 내지 30의 시클로알킬기, 탄소수 6 내지 30의 아릴기, 및 탄소수 3 내지 30의 헤테로고리기로 이루어진 군으로부터 선택된 1종 이상일 수 있으며, X는 N, O 및 S 원자로 이루어진 군으로부터 선택된 1종의 헤테로 원자일 수 있고, X가 N인 경우 R2 및 R3 중 반드시 하나 이상은 하기 화학식 1a 또는 하기 화학식 1b로 표시되는 작용기일 수 있으며, X가 O 또는 S인 경우 R2 및 R3 중 하나의 작용기만 존재하되, R2가 존재하는 경우 R2는 하기 화학식 1a로 표시되는 작용기일 수 있고, R3가 존재하는 경우 R3는 하기 화학식 1b로 표시되는 작용기일 수 있으며,In Formula 1, R 1 is deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, substituted or Unsubstituted heteroalkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or substituted or unsubstituted hetero ring having 3 to 30 carbon atoms R 2 may be deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or Unsubstituted alkynyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, substituted or unsubstituted carbon A cycloalkyl group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, or a functional group represented by the following Formula 1a, and R 3 is Deuterium, substituted or unsubstituted C1-30 alkyl group, substituted or unsubstituted C1-30 alkylsilyl group, substituted or unsubstituted C2-30 alkenyl group, substituted or unsubstituted C2-30 An alkynyl group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, a substituted or unsubstituted carbon atom 6 It may be an aryl group of 30 to 30, or a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, or a functional group represented by the formula (1b), R 1 , R 2 And R 3 Is an alkyl group substituted, alkyl In case of silyl group, alkenyl group, alkynyl group, alkoxy group, heteroalkyl group, cycloalkyl group, aryl group, or heterocyclic group, substituted alkyl group, alkylsilyl group, alkenyl group, alkynyl group, alkoxy group, heteroalkyl group, cycloalkyl group, The substituent of the aryl group or the heterocyclic group is deuterium, halogen, hydroxy group, nitro group, cyano group, C1-30 alkyl group, C1-30 alkylsilyl group, C2-30 alkenyl group, C2-30 Alkynyl groups, alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 30 carbon atoms, cycloalkyl groups having 5 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, and heterocyclic groups having 3 to 30 carbon atoms may be at least one selected from the group consisting of, X is N, O or S atom may be a hetero atom selected from the group consisting of one kind of, when X is N R 2 and R 3 of the half When one or more may be an action represented by the following formula 1a or the formula 1b, but X is only present R 2 and R 3 one of the functional groups of the case of O or S, if the R 2 exist R 2 has the formula may be a functional group represented by 1a, if R 3 is present and R 3 is be an action represented by the following general formula 1b,
[화학식 1a][Formula 1a]
[화학식 1b][Formula 1b]
상기 화학식 1a 및 1b에서, R4 및 R7은 각각 독립적으로 탄소수 1 내지 10의 알킬렌기일 수 있고, R5, R6, R8 및 R9는 각각 독립적으로 탄소수 1 내지 30의 알킬기, 탄소수 5 내지 30의 시클로알킬기, 또는 탄소수 6 내지 30의 아릴기일 수 있으며, m 및 n은 각각 독립적으로 0 내지 3에서 선택된 정수이되, m+n ≥ 1일 수 있고, 상기 화학식 1a 또는 1b 중 하나의 작용기만 존재하는 경우, m 또는 n은 각각 독립적으로 1 내지 3에서 선택된 정수일 수 있다.In Formulas 1a and 1b, R 4 and R 7 may be each independently an alkylene group having 1 to 10 carbon atoms, and R 5 , R 6 , R 8 and R 9 are each independently an alkyl group having 1 to 30 carbon atoms and carbon number It may be a cycloalkyl group of 5 to 30, or an aryl group of 6 to 30 carbon atoms, m and n are each independently an integer selected from 0 to 3, m + n ≥ 1, one of the formula 1a or 1b When only functional groups are present, m or n may each independently be an integer selected from 1 to 3.
또한, 본 발명은 하기 화학식 2로 표시되는 화합물과 하기 화학식 3으로 표시되는 화합물을 반응시키는 단계를 포함하는 변성제 제조방법을 제공한다:In addition, the present invention provides a method for preparing a denaturant comprising reacting a compound represented by Formula 2 with a compound represented by Formula 3:
[화학식 2][Formula 2]
[화학식 3][Formula 3]
상기 화학식 2 및 3의 각 치환기에 대한 정의는 상기 화학식 1에서 정의한 바와 같다.Definitions of the substituents of Formulas 2 and 3 are as defined in Formula 1.
또한, 본 발명은 상기 변성제 유래 작용기를 포함하는 변성 공액디엔계 중합체 및 이의 제조방법을 제공한다.In addition, the present invention provides a modified conjugated diene-based polymer including the modifier-derived functional group and a method for producing the same.
본 발명에 따라, 무기 충진제와 배합 시 수소 결합으로 인해 우수한 분산력을 나타내는 변성제로 공액디엔계 중합체를 변성시키는 경우, 중합체의 일측 말단에 상기 변성제로부터 유래된 작용기를 포함함으로써, 무기 충진제와의 수소 결합으로 인해 중합체와 무기 충진제 간의 상호작용이 뛰어난 변성 공액디엔계 중합체의 제조가 가능하고, 이렇게 제조된 변성 공액디엔계 중합체는 가공성이 우수하고, 인장강도, 내마모성, 구름저항 및 젖은 노면 저항성이 뛰어난 효과가 있다.According to the present invention, when the conjugated diene-based polymer is modified with a modifier exhibiting excellent dispersibility due to hydrogen bonding when combined with the inorganic filler, the hydrogen bond with the inorganic filler is included by including a functional group derived from the modifier at one end of the polymer. Due to this, the modified conjugated diene-based polymer having excellent interaction between the polymer and the inorganic filler can be prepared, and the modified conjugated diene-based polymer thus prepared has excellent processability, excellent tensile strength, wear resistance, rolling resistance, and wet road resistance. There is.
이하, 본 발명에 대한 이해를 돕기 위하여 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail to aid in understanding the present invention.
본 발명의 설명 및 청구범위에서 사용된 용어나 단어는, 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여, 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in the description and claims of the present invention should not be construed as being limited to the ordinary or dictionary meanings, and the inventors should properly explain the concept of terms in order to explain their invention in the best way. Based on the principle that it can be defined, it should be interpreted as meaning and concept corresponding to the technical idea of the present invention.
본 발명에 따른 변성제는 하기 화학식 1로 표시되는 화합물을 포함할 수 있다:The denaturing agent according to the present invention may include a compound represented by Formula 1 below:
[화학식 1][Formula 1]
상기 화학식 1에서, R1은 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기일 수 있고, R2는 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기, 또는 하기 화학식 1a로 표시되는 작용기일 수 있으며, R3는 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기, 또는 하기 화학식 1b로 표시되는 작용기일 수 있고, R1, R2 및 R3가 치환된 알킬기, 알킬실릴기, 알케닐기, 알카이닐기, 알콕시기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기인 경우, 치환된 알킬기, 알킬실릴기, 알케닐기, 알카이닐기, 알콕시기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기의 치환기는 중수소, 할로겐, 히드록시기, 니트로기, 시아노기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 30의 알카이닐기, 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 탄소수 5 내지 30의 시클로알킬기, 탄소수 6 내지 30의 아릴기, 및 탄소수 3 내지 30의 헤테로고리기로 이루어진 군으로부터 선택된 1종 이상일 수 있으며, X는 N, O 및 S 원자로 이루어진 군으로부터 선택된 1종의 헤테로 원자일 수 있고, X가 N인 경우 R2 및 R3 중 반드시 하나 이상은 하기 화학식 1a 또는 하기 화학식 1b로 표시되는 작용기일 수 있으며, X가 O 또는 S인 경우 R2 및 R3 중 하나의 작용기만 존재하되, R2가 존재하는 경우 R2는 하기 화학식 1a로 표시되는 작용기일 수 있고, R3가 존재하는 경우 R3는 하기 화학식 1b로 표시되는 작용기일 수 있으며,In Formula 1, R 1 is deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, substituted or Unsubstituted heteroalkyl group having 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or substituted or unsubstituted hetero ring having 3 to 30 carbon atoms R 2 may be deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or Unsubstituted alkynyl group having 2 to 30 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, substituted or unsubstituted carbon A cycloalkyl group having 5 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, or a functional group represented by the following Formula 1a, and R 3 is Deuterium, substituted or unsubstituted C1-30 alkyl group, substituted or unsubstituted C1-30 alkylsilyl group, substituted or unsubstituted C2-30 alkenyl group, substituted or unsubstituted C2-30 An alkynyl group, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 5 to 30 carbon atoms, a substituted or unsubstituted carbon atom 6 It may be an aryl group of 30 to 30, or a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, or a functional group represented by the formula (1b), R 1 , R 2 And R 3 Is an alkyl group substituted, alkyl In case of silyl group, alkenyl group, alkynyl group, alkoxy group, heteroalkyl group, cycloalkyl group, aryl group, or heterocyclic group, substituted alkyl group, alkylsilyl group, alkenyl group, alkynyl group, alkoxy group, heteroalkyl group, cycloalkyl group, The substituent of the aryl group or the heterocyclic group is deuterium, halogen, hydroxy group, nitro group, cyano group, C1-30 alkyl group, C1-30 alkylsilyl group, C2-30 alkenyl group, C2-30 Alkynyl groups, alkoxy groups having 1 to 30 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 30 carbon atoms, cycloalkyl groups having 5 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, and heterocyclic groups having 3 to 30 carbon atoms may be at least one selected from the group consisting of, X is N, O or S atom may be a hetero atom selected from the group consisting of one kind of, when X is N R 2 and R 3 of the half When one or more may be an action represented by the following formula 1a or the formula 1b, but X is only present R 2 and R 3 one of the functional groups of the case of O or S, if the R 2 exist R 2 has the formula may be a functional group represented by 1a, if R 3 is present and R 3 is be an action represented by the following general formula 1b,
[화학식 1a][Formula 1a]
[화학식 1b][Formula 1b]
상기 화학식 1a 및 1b에서, R4 및 R7은 각각 독립적으로 탄소수 1 내지 10의 알킬렌기일 수 있고, R5, R6, R8 및 R9는 각각 독립적으로 탄소수 1 내지 30의 알킬기, 탄소수 5 내지 30의 시클로알킬기, 또는 탄소수 6 내지 30의 아릴기일 수 있으며, m 및 n은 각각 독립적으로 0 내지 3에서 선택된 정수이되, m+n ≥ 1일 수 있고, 상기 화학식 1a 또는 1b 중 하나의 작용기만 존재하는 경우, m 또는 n은 각각 독립적으로 1 내지 3에서 선택된 정수일 수 있다.In Formulas 1a and 1b, R 4 and R 7 may be each independently an alkylene group having 1 to 10 carbon atoms, and R 5 , R 6 , R 8 and R 9 are each independently an alkyl group having 1 to 30 carbon atoms and carbon number It may be a cycloalkyl group of 5 to 30, or an aryl group of 6 to 30 carbon atoms, m and n are each independently an integer selected from 0 to 3, m + n ≥ 1, one of the formula 1a or 1b When only functional groups are present, m or n may each independently be an integer selected from 1 to 3.
구체적인 예로, 상기 화학식 1에서, R1은 치환 또는 비치환된 탄소수 1 내지 20의 알킬기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 20의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 20의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 20의 헤테로고리기일 수 있고, R2는 하기 화학식 1a로 표시되는 작용기일 수 있으며, R3는 하기 화학식 1b로 표시되는 작용기일 수 있고, R1이 치환된 알킬기, 알케닐기, 알카이닐기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기인 경우, 치환된 알킬기, 알케닐기, 알카이닐기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기의 치환기는 중수소, 할로겐, 히드록시기, 니트로기, 시아노기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 30의 알카이닐기, 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 탄소수 5 내지 30의 시클로알킬기, 탄소수 6 내지 30의 아릴기, 및 탄소수 3 내지 30의 헤테로고리기로 이루어진 군으로부터 선택된 1종 이상일 수 있으며, X는 N, O 및 S 원자로 이루어진 군으로부터 선택된 1종의 헤테로 원자일 수 있고, X가 O 또는 S인 경우 R2 및 R3 중 하나의 작용기만 존재할 수 있으며,As a specific example, in Formula 1, R 1 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, substituted Or an unsubstituted C1-C20 heteroalkyl group, a substituted or unsubstituted C5-C20 cycloalkyl group, a substituted or unsubstituted C6-C20 aryl group, or a substituted or unsubstituted C3-C20 hetero It may be a ring group, R 2 may be a functional group represented by the formula (1a), R 3 may be a functional group represented by the formula (1b), R 1 is substituted alkyl, alkenyl group, alkynyl group, heteroalkyl group, cyclo In the case of an alkyl group, an aryl group, or a heterocyclic group, the substituted alkyl group, alkenyl group, alkynyl group, heteroalkyl group, cycloalkyl group, aryl group, or the substituent of the heterocyclic group may be deuterium, A halogen, a hydroxy group, a nitro group, a cyano group, an alkyl group having 1 to 30 carbon atoms, an alkylsilyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, Or a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heterocyclic group having 3 to 30 carbon atoms, and X is May be one hetero atom selected from the group consisting of N, O and S atoms, and when X is O or S, only one functional group of R 2 and R 3 may be present,
상기 화학식 1a 및 1b에서, R4 및 R7은 각각 독립적으로 탄소수 1 내지 5의 알킬렌기일 수 있고, R5, R6, R8 및 R9는 각각 독립적으로 탄소수 1 내지 20의 알킬기, 탄소수 5 내지 20의 시클로알킬기, 또는 탄소수 6 내지 20의 아릴기일 수 있으며, m 및 n은 각각 독립적으로 1 내지 3에서 선택된 정수일 수 있다.In Formulas 1a and 1b, R 4 and R 7 may be each independently an alkylene group having 1 to 5 carbon atoms, and R 5 , R 6 , R 8 and R 9 are each independently an alkyl group having 1 to 20 carbon atoms and carbon number It may be a cycloalkyl group of 5 to 20, or an aryl group of 6 to 20 carbon atoms, m and n may be each independently an integer selected from 1 to 3.
본 발명에서 용어 '치환'은 작용기, 원자단, 또는 화합물의 수소가 특정 치환기로 치환된 것을 의미할 수 있고, 작용기, 원자단, 또는 화합물의 수소가 특정 치환기로 치환되는 경우, 작용기, 원자단, 또는 화합물 내에 존재하는 수소의 개수에 따라 1개 또는 2개 이상의 복수의 치환기가 존재할 수 있으며, 복수의 치환기가As used herein, the term 'substituted' may mean that the hydrogen of the functional group, the atomic group, or the compound is substituted with a specific substituent, and when the hydrogen of the functional group, the atomic group, or the compound is substituted with a specific substituent, the functional group, the atomic group, or the compound One or two or more substituents may be present, depending on the number of hydrogen present in the
존재하는 경우, 각각의 치환기는 서로 동일할 수도 있고, 상이할 수도 있다.When present, each substituent may be the same as or different from each other.
본 발명에서 용어 '알킬기(alkyl group)'는 1가의 지방족 포화 탄화수소를 의미할 수 있고, 메틸, 에틸, 프로필 및 부틸 등의 선형 알킬기 및 이소프로필(isopropyl), 세크부틸(sec-butyl), 터셔리부틸(tert-butyl) 및 네오펜틸(neopentyl) 등의 분지형 알킬기를 모두 포함하는 의미일 수 있다.In the present invention, the term 'alkyl group' may mean a monovalent aliphatic saturated hydrocarbon, and may be linear alkyl groups such as methyl, ethyl, propyl and butyl, and isopropyl, sec-butyl, tertiary, It may be meant to include all branched alkyl groups such as tert-butyl and neopentyl (neopentyl).
본 발명에서 용어 '알킬렌기(alkylene group)'는 메틸렌, 에틸렌, 프로필렌 및 부틸렌 등과 같은 2가의 지방족 포화 탄화수소를 의미할 수 있다.In the present invention, the term "alkylene group" may refer to a divalent aliphatic saturated hydrocarbon such as methylene, ethylene, propylene and butylene.
본 발명에서 용어 '알킬실릴기(alkylsilyl group)'는 모노알킬실릴, 디알킬실릴 및 트리알킬실릴을 모두 포함하는 의미일 수 있다.In the present invention, the term "alkylsilyl group" may be meant to include all monoalkylsilyl, dialkylsilyl and trialkylsilyl.
본 발명에서 용어 '알케닐기(alkenyl group)'는 이중 결합을 1개 또는 2개 이상 포함하는 알킬기를 의미할 수 있다.In the present invention, the term 'alkenyl group' may refer to an alkyl group including one or two or more double bonds.
본 발명에서 용어 '알카이닐기(alkynyl group)'는 삼중 결합을 1개 또는 2개 이상 포함하는 알킬기를 의미할 수 있다.In the present invention, the term 'alkynyl group' may refer to an alkyl group including one or two or more triple bonds.
본 발명에서 용어 '알콕시기(alkoxy group)'는 메톡시, 에톡시, 프로폭시 및 부톡시 등과 같이 알킬기 말단의 수소가 산소 원자로 치환된 작용기, 원자단, 또는 화합물을 모두 포함하는 의미일 수 있다.In the present invention, the term "alkoxy group" may include all functional groups, atomic groups, or compounds in which hydrogen at the end of an alkyl group is substituted with an oxygen atom, such as methoxy, ethoxy, propoxy and butoxy.
본 발명에서 용어 '헤테로알킬기(heteroalkyl group)' 는 알킬기 내의 탄소 원자(말단의 탄소 원자는 제외)가 1개 이상의 헤테로 원자로 치환된 알킬기를 의미할 수 있다.As used herein, the term "heteroalkyl group" may refer to an alkyl group in which carbon atoms (excluding terminal carbon atoms) in the alkyl group are substituted with one or more hetero atoms.
본 발명에서 용어 '시클로알킬기(cycloalkyl group)'는 환형의 포화 탄화수소, 또는 불포화 결합을 1개 또는 2개 이상 포함하는 환형의 불포화 탄화수소를 모두 포함하는 의미일 수 있다.In the present invention, the term "cycloalkyl group" may mean both cyclic saturated hydrocarbons or cyclic unsaturated hydrocarbons containing one or two or more unsaturated bonds.
본 발명에서 용어 '아릴기(aryl group)'는 환형의 방향족 탄화수소를 의미할 수 있고, 또한 1개의 환이 형성된 단환 방향족 탄화수소(monocyclic aromatic hydrocarbon), 또는 2개 이상의 환이 결합된 다환 방향족 탄화수소(polycyclic aromatic hydrocarbon)을 모두 포함하는 의미일 수 있다.In the present invention, the term 'aryl group' may mean a cyclic aromatic hydrocarbon, and also a monocyclic aromatic hydrocarbon in which one ring is formed, or a polycyclic aromatic hydrocarbon in which two or more rings are bonded to each other. hydrocarbons) can be included.
본 발명에서 용어 '아르알킬기(aralkyl group)' 는 1개 이상의 아릴기가 반드시 치환된 알킬기를 의미할 수 있다.In the present invention, the term 'aralkyl group' may mean an alkyl group in which one or more aryl groups are necessarily substituted.
본 발명에서 용어 '헤테로고리기(heterocyclic group)'는 시클로알킬기 또는 아릴기 내의 탄소 원자가 1개 이상의 헤테로 원자로 치환된 시클로알킬기 또는 아릴기를 모두 포함하는 의미일 수 있다.As used herein, the term 'heterocyclic group' may mean both a cycloalkyl group or an aryl group in which a carbon atom in a cycloalkyl group or an aryl group is substituted with one or more hetero atoms.
본 발명의 일 실시예에 따르면, 상기 화학식 1로 표시되는 화합물은 하기 화학식 1-1 내지 1-12로 표시되는 화합물일 수 있다.According to one embodiment of the present invention, the compound represented by Chemical Formula 1 may be a compound represented by Chemical Formulas 1-1 to 1-12.
[화학식 1-1][Formula 1-1]
[화학식 1-2][Formula 1-2]
[화학식 1-3][Formula 1-3]
[화학식 1-4][Formula 1-4]
[화학식 1-5][Formula 1-5]
[화학식 1-6][Formula 1-6]
[화학식 1-7][Formula 1-7]
[화학식 1-8][Formula 1-8]
[화학식 1-9][Formula 1-9]
[화학식 1-10][Formula 1-10]
[화학식 1-11][Formula 1-11]
[화학식 1-12][Formula 1-12]
상기 화학식 1-1 내지 1-12에서, R13는 각각 독립적으로 1 내지 20의 알킬기이며, 바람직하게는 메틸기 또는 에틸기이다.In Formulas 1-1 to 1-12, each R 13 is independently an alkyl group of 1 to 20, preferably a methyl group or an ethyl group.
한편, 상기 화학식 1-1 내지 1-12로 표시되는 화합물은 모두 트리알콕시실릴기의 작용기를 포함하는 것으로 표시되어 있지만, 본 발명에 따르면, 상기 트리알콕시실릴기는 대신 알킬디메톡시실릴, 알킬디에톡시실릴, 디알킬메톡시실릴 및 디알킬에톡시실릴기 등과 같이, 필요에 따라 알킬기와 알콕시기의 개수를 적절히 조합하여 치환된 실릴 작용기로 치환될 수 있다.On the other hand, the compounds represented by the formula (1-1 to 1-12) are all represented as including a functional group of a trialkoxy silyl group, according to the present invention, the trialkoxy silyl group instead of alkyldimethoxysilyl, alkyldiethoxy As the silyl, dialkylmethoxysilyl and dialkylethoxysilyl groups and the like, it may be substituted with a substituted silyl functional group by appropriately combining the number of alkyl groups and alkoxy groups as necessary.
본 발명의 변성제는, 분자 내에 -NO2를 포함 화합물을 포함함으로써, 무기 충진제, 특히 실리카계 충진제의 표면에 존재하는 -OH 등에 결합된 수소 원자와, -NO2의 산소 원자 간에 수소 결합이 가능하여, 충진제와 보다 강력한 상호 작용이 가능하고, 이에 따라 상기 변성제로부터 변성된 중합체와 충진제 간의 분산력이 증대되는 효과가 있다.The denaturing agent of the present invention includes a compound containing -NO 2 in a molecule, whereby hydrogen bonding is possible between a hydrogen atom bonded to -OH or the like present on the surface of an inorganic filler, particularly a silica-based filler, and an oxygen atom of -NO 2 . Thus, a stronger interaction with the filler is possible, thereby increasing the dispersibility between the polymer and the filler modified from the modifier.
본 발명에 따른 변성제 제조방법은 하기 화학식 2로 표시되는 화합물과 하기 화학식 3으로 표시되는 화합물을 반응시키는 단계를 포함할 수 있다:The method of preparing a denaturant according to the present invention may include reacting a compound represented by Formula 2 with a compound represented by Formula 3 below:
[화학식 2][Formula 2]
[화학식 3][Formula 3]
상기 화학식 2 및 3의 각 치환기에 대한 정의는 상기 화학식 1에서 정의한 바와 같다.Definitions of the substituents of Formulas 2 and 3 are as defined in Formula 1.
상기 화학식 2로 표시되는 화합물은 일례로 하기 화학식 2-1 내지 2-6으로 표시되는 화합물일 수 있다.The compound represented by Chemical Formula 2 may be, for example, a compound represented by Chemical Formulas 2-1 to 2-6.
[화학식 2-1][Formula 2-1]
[화학식 2-2][Formula 2-2]
[화학식 2-3][Formula 2-3]
[화학식 2-4][Formula 2-4]
[화학식 2-5][Formula 2-5]
[화학식 2-6][Formula 2-6]
또 다른 예로, 상기 화학식 3으로 표시되는 화합물은 하기 화학식 3-1 또는 3-6으로 표시되는 화합물일 수 있다.As another example, the compound represented by Chemical Formula 3 may be a compound represented by Chemical Formula 3-1 or 3-6.
[화학식 3-1][Formula 3-1]
[화학식 3-2][Formula 3-2]
[화학식 3-3][Formula 3-3]
[화학식 3-4][Formula 3-4]
[화학식 3-5][Formula 3-5]
[화학식 3-6][Formula 3-6]
상기 화학식 3-1 내지 3-6에서 R13은 각각 독립적으로 1 내지 20의 알킬기이며, 바람직하게는 메틸기 또는 에틸기이고, R14는 각각 독립적으로 1 내지 20의 알킬기이며, 바람직하게는 메틸기 또는 에틸기이다.R 13 in Formulas 3-1 to 3-6 are each independently an alkyl group of 1 to 20, preferably a methyl group or an ethyl group, and R 14 is each independently an alkyl group of 1 to 20, preferably a methyl group or an ethyl group to be.
구체적으로 상기 알콕시실릴기는, 트리에톡시실릴, 트리메톡시실릴, 알킬디메톡시실릴, 알킬디에톡시실릴, 디알킬메톡시실릴 및 디알킬에톡시실릴기 등과 같이, 필요에 따라 알킬기와 알콕시기의 개수를 적절히 조합하여 치환된 실릴 작용기로 치환될 수 있다.Specifically, the alkoxysilyl group, if necessary, such as triethoxysilyl, trimethoxysilyl, alkyldimethoxysilyl, alkyldiethoxysilyl, dialkylmethoxysilyl and dialkylethoxysilyl groups, etc. It may be substituted with a substituted silyl functional group in appropriate combination of numbers.
또 다른 예로, 상기 화학식 3-1 내지 3-6으로 표시되는 화합물은 각각 하기 화학식 3-7 내지 3-12로 표시되는 화합물 일 수 있다,As another example, the compounds represented by Chemical Formulas 3-1 to 3-6 may be compounds represented by the following Chemical Formulas 3-7 to 3-12, respectively.
[화학식 3-7][Formula 3-7]
[화학식 3-8][Formula 3-8]
[화학식 3-9][Formula 3-9]
[화학식 3-10][Formula 3-10]
[화학식 3-11][Formula 3-11]
[화학식 3-12][Formula 3-12]
상기 화학식 3-7 내지 3-12에서, Me는 메틸기이고, Et는 에틸기이다.In Formulas 3-7 to 3-12, Me is a methyl group and Et is an ethyl group.
한편, 상기 화학식 2로 표시되는 화합물과 상기 화학식 3으로 표시되는 화합물의 몰 비(화학식 2:화학식 3)는 화학식 2로 표시되는 화합물의 1몰을 기준으로 화학식 3으로 표시되는 화합물 0.5 내지 2몰, 0.7 내지 1.5 몰, 또는 0.9 내지 1.1 몰일 수 있다.Meanwhile, the molar ratio of the compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 3 (Formula 2: Chemical Formula 3) is 0.5 to 2 mol of the compound represented by Chemical Formula 3 based on 1 mol of the compound represented by Chemical Formula 2. , 0.7 to 1.5 moles, or 0.9 to 1.1 moles.
다시 말해서, 화학식 2로 표시되는 화합물:화학식 3으로 표시되는 화합물의 몰비는 1:0.5 내지 1:2, 1:0.7 내지 1:1.5, 또는 1:0.9 내지 1:1.1일 수 있고, 이 범위 내에서 순도와 수율이 우수한 효과가 있다.In other words, the molar ratio of the compound represented by Formula 2: the compound represented by Formula 3 may be 1: 0.5 to 1: 2, 1: 0.7 to 1: 1.5, or 1: 0.9 to 1: 1.1, and within this range The purity and yield are excellent at.
본 발명의 일 실시예에 따르면, 상기 반응은 10 ℃ 내지 90 ℃, 20 ℃ 내지 80 ℃, 또는 20 ℃ 내지 60 ℃의 반응 온도에서 실시될 수 있고, 이 범위 내에서 반응 속도가 우수하고, 생성물의 순도 및 수율이 우수한 효과가 있다.According to one embodiment of the invention, the reaction may be carried out at a reaction temperature of 10 ℃ to 90 ℃, 20 ℃ to 80 ℃, or 20 ℃ to 60 ℃, within this range the reaction rate is excellent, the product The purity and yield are excellent effects.
또 다른 예로, 상기 반응은 염기성 화합물의 존재 하에 실시될 수 있고, 이 경우 염기성 화합물에 의해 화학식 3으로 표시되는 화합물의 양성자가 제거된 후, 음이온화된 X가 화학식 2로 표시되는 화합물의 이중 결합에 첨가되는 첨가 반응을 수행함으로써, 반응 속도가 뛰어난 효과가 있다. 상기 염기성 화합물은 구체적인 예로, 메틸아민(methylamine), 디메틸아민(dimethylamine), 트리에틸아민(triethylamine), 테트라메틸에틸렌디아민(tetramethylethylenediamine), 리튬디이소프로필아마이드(lithiumdiisopropylamide), 1,8-디아자비시클로운데-7-센(1,8-diazabicycloundec-7-ene), 2,6-디-t-부틸피리딘(2,6-di-tert-butylpyridine), 리튬테트라메틸피페리딘(lithiumtetramethylpiperidine)으로 이루어진 군으로부터 선택된 1종 이상일 수 있다.As another example, the reaction may be carried out in the presence of a basic compound, in which case the proton of the compound represented by the formula (3) is removed by the basic compound, and then the double bond of the compound represented by the anionized X is represented by the formula (2). By carrying out the addition reaction added to, the reaction rate is excellent in effect. Specific examples of the basic compound may include methylamine, dimethylamine, triethylamine, tetramethylethylenediamine, lithiumdiisopropylamide, and 1,8-diazabicyclo. Consisting of 1,8-diazabicycloundec-7-ene, 2,6-di-tert-butylpyridine, and lithiumtetramethylpiperidine It may be at least one selected from the group.
본 발명에 따른 변성 공액디엔계 중합체는 공액디엔계 단량체 유래 반복 단위를 포함하고, 일측 말단에 하기 화학식 1로 표시되는 화합물을 포함하는 변성제 유래 작용기를 포함할 수 있다.The modified conjugated diene-based polymer according to the present invention includes a repeating unit derived from a conjugated diene-based monomer, and may include a modifying agent-derived functional group including a compound represented by the following Formula 1 at one end.
[화학식 1][Formula 1]
상기 화학식 1의 각 치환기에 대한 정의는 앞서 정의한 바와 같다.Definitions for each substituent of Formula 1 are as defined above.
상기 공액디엔계 단량체 유래 반복 단위는 공액디엔계 단량체가 중합 시 이루는 반복 단위를 의미할 수 있고, 상기 공액디엔계 단량체는 일례로 1,3-부타디엔, 2,3-디메틸-1,3-부타디엔, 피페릴렌, 3-부틸-1,3-옥타디엔, 이소프렌, 2-페닐-1,3-부타디엔 및 2-할로-1,3-부타디엔(할로는 할로겐 원자를 의미한다.)으로 이루어진 군으로부터 선택된 1종 이상일 수 있다.The conjugated diene-based monomer-derived repeating unit may mean a repeating unit formed when the conjugated diene-based monomer is polymerized, and the conjugated diene-based monomer may be, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene , Piperylene, 3-butyl-1,3-octadiene, isoprene, 2-phenyl-1,3-butadiene and 2-halo-1,3-butadiene (halo means halogen atom) It may be one or more selected.
한편, 상기 변성 공액디엔계 공중합체는 일례로 상기 공액디엔계 단량체 유래 반복 단위와 함께 방향족 비닐 단량체 유래 반복 단위를 더 포함하는 공중합체일 수 있다.The modified conjugated diene-based copolymer may be, for example, a copolymer further comprising an aromatic vinyl monomer-derived repeating unit together with the repeating unit derived from the conjugated diene-based monomer.
상기 방향족 비닐 단량체 유래 반복 단위는 방향족 비닐 단량체가 중합 시 이루는 반복 단위를 의미할 수 있고, 상기 방향족 비닐 단량체는 일례로 스티렌, α-메틸스티렌, 3-메틸스티렌, 4-메틸스티렌, 4-프로필스티렌, 1-비닐나프탈렌, 4-The aromatic vinyl monomer-derived repeating unit may mean a repeating unit formed by polymerization of an aromatic vinyl monomer, and the aromatic vinyl monomer may be, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, or 4-propyl. Styrene, 1-vinylnaphthalene, 4-
사이클로헥실스티렌, 4-(p-메틸페닐)스티렌 및 1-비닐-5-헥실나프탈렌으로 이루어진 군으로부터 선택된 1종 이상일 수 있다.It may be at least one selected from the group consisting of cyclohexyl styrene, 4- (p-methylphenyl) styrene and 1-vinyl-5-hexyl naphthalene.
상기 변성 공액디엔계 중합체가 방향족 비닐 단량체 유래 반복 단위를 포함하는 공중합체인 경우, 상기 변성 공액디엔계 중합체는 공액디엔계 단량체 유래 반복 단위를 50 내지 95 중량%, 55 내지 90 중량%, 혹은 60 내지 90 중량%로, 방향족 비닐 단량체 유래 반복 단위를 5 내지 50 중량%, 10 내지 45 중량%, 혹은 10 내지 40 중량%로 포함할 수 있고, 이 범위 내에서 구름 저항, 젖은 노면 저항성 및 내마모성이 우수한 효과가 있다.When the modified conjugated diene-based polymer is a copolymer including an aromatic vinyl monomer-derived repeating unit, the modified conjugated diene-based polymer may contain 50 to 95% by weight, 55 to 90% by weight, or 60 to 60% of the repeating unit derived from a conjugated diene monomer. 90 wt%, may include 5 to 50 wt%, 10 to 45 wt%, or 10 to 40 wt% of an aromatic vinyl monomer-derived repeating unit, and has excellent rolling resistance, wet road resistance, and abrasion resistance within this range. It works.
본 발명의 일 실시예에 따르면, 상기 공중합체는 랜덤 공중합체일 수 있고, 이 경우 각 물성 간의 밸런스가 우수한 효과가 있다. 상기 랜덤 공중합체는 공중합체를 이루는 반복 단위가 무질서하게 배열된 것을 의미할 수 있다.According to one embodiment of the invention, the copolymer may be a random copolymer, in this case there is an excellent balance between the physical properties. The random copolymer may mean that the repeating units constituting the copolymer are randomly arranged.
한편, 상기 변성 공액디엔계 중합체는 상기 화학식 1로 표시되는 화합물을 포함하는 변성제 유래 작용기를 포함하는 일측 말단 이외에, 타측 말단에 하기 화학식 4로 표시되는 화합물을 포함하는 변성 개시제 유래 작용기를 포함할 수 있다.On the other hand, the modified conjugated diene-based polymer may include a modification initiator-derived functional group containing a compound represented by the following formula (4) at the other end, in addition to one end containing a modifier-derived functional group comprising the compound represented by the formula (1) have.
[화학식 4][Formula 4]
상기 화학식 4에서, R10 및 R11은 각각 독립적으로 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 시클로알킬기 및 탄소수 5 내지 20의 아르알킬기로 이루어진 군으로부터 선택된 1종이거나, R10 및 R11이 서로 결합하여 인접한 N 원자와 함께 탄소수 5 내지 20의 포화 또는 불포화의 환상 구조를 형성할 수 있고, 상기 R10 및 R11이 환상 구조를 형성하는 경우, 분지 구조를 가질 수 있고, R12는 단일 결합, 탄소수 1 내지 20의 알킬렌기, 또는 하기 화학식 5 내지 7로 이루어진 군으로부터 선택된 1종의 연결기일 수 있으며, M은 알칼리 금속일 수 있다.In Formula 4, R 10 and R 11 are each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aralkyl group having 5 to 20 carbon atoms, or R 10 and R 11 These may combine with each other to form a saturated or unsaturated cyclic structure having 5 to 20 carbon atoms with adjacent N atoms, and when R 10 and R 11 form a cyclic structure, may have a branched structure, and R 12 It may be a single bond, an alkylene group having 1 to 20 carbon atoms, or one type of linking group selected from the group consisting of the following Chemical Formulas 5 to 7, and M may be an alkali metal.
[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
구체적인 예로, 상기 화학식 4에서, R10 및 R11은 각각 독립적으로 탄소수 1 내지 12의 알킬기, 탄소수 3 내지 14의 시클로알킬기 및 탄소수 5 내지 20의 아르알킬기로 이루어진 군으로부터 선택된 1종일 수 있고, R12는 단일 결합, 탄소수 1 내지 20의 알킬렌기, 또는 상기 화학식 5 내지 7로 이루어진 군으로부터 선택된 1종의 연결기일 수 있으며, M은 알칼리 금속일 수 있다.As a specific example, in Formula 4, R 10 and R 11 may be each independently selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 14 carbon atoms, and an aralkyl group having 5 to 20 carbon atoms, and R is 12 may be a single bond, an alkylene group having 1 to 20 carbon atoms, or one linking group selected from the group consisting of Chemical Formulas 5 to 7, and M may be an alkali metal.
보다 구체적인 예로, 상기 화학식 4에서, R10 및 R11은 각각 독립적으로 메틸, 에틸, 프로필, 부틸, 옥틸, 시클로프로필, 시클로헥실, 3-페닐-1-프로필, 이소부틸, 데실, 헵틸 또는 페닐일 수 있고, R12는 단일 결합, 탄소수 2 내지 16의 알킬렌기, 또는 상기 화학식 3 내지 5로 이루어진 군으로부터 선택된 1종의 연결기일 수 있으며, M은 Li일 수 있다.More specifically, in Formula 4, R 10 and R 11 are each independently methyl, ethyl, propyl, butyl, octyl, cyclopropyl, cyclohexyl, 3-phenyl-1-propyl, isobutyl, decyl, heptyl or phenyl R 12 may be a single bond, an alkylene group having 2 to 16 carbon atoms, or one linking group selected from the group consisting of Chemical Formulas 3 to 5, and M may be Li.
상기 화학식 4로 표시되는 화합물을 포함하는 변성 개시제 유래 작용기는 공액디엔계 중합체의 중합을 개시하기 위한 중합 개시제로서 변성 개시제를 이용하는 경우, 중합 개시 부위에 해당하는 공액디엔계 중합체의 일측 말단에 위치한 중합체 내의 작용기를 의미할 수 있고, 공액디엔계 중합체의 분산성, 가공성 개선과 함께, 구름 저항 및 젖은 노면 저항성 등의 기계적 물성을 향상시키는 효과가 있다.When the modified initiator is used as a polymerization initiator for initiating the polymerization of the conjugated diene polymer, the modified initiator-derived functional group including the compound represented by Formula 4 is a polymer located at one end of the conjugated diene polymer corresponding to the polymerization initiation site. It can mean a functional group in the inside, there is an effect of improving the mechanical properties such as rolling resistance and wet road resistance, along with improving the dispersibility and processability of the conjugated diene-based polymer.
본 발명의 일 실시예에 따른 상기 변성 공액디엔계 중합체는 수평균 분자량(Mn)이 10,000 g/mol 내지 2,000,000 g/mol, 50,000 g/mol 내지 1,800,000 g/mol, 또는 120,000 g/mol 내지 1,500,000 g/mol일 수 있고, 중량평균 분자량(Mw)이 10,000 g/mol 내지 5,000,000 g/mol, 100,000 g/mol 내지 3,500,000 g/mol, 또는 120,000 g/mol 내지 2,000,000 g/mol일 수 있고, 이 범위 내에서 구름 저항 및 젖은 노면 저항성이 우수한 효과가 있다. 또 다른 예로, 상기 변성 공액디엔계 중합체는 분자량 분포(Mw/Mn)가 1.0 내지 8.0, 1.0 내지 4.0, 또는 1.0 내지 3.5일 수 있고, 이 범위 내에서 물성 간의 물성 밸런스가 우수한 효과가 있다.The modified conjugated diene-based polymer according to an embodiment of the present invention has a number average molecular weight (Mn) of 10,000 g / mol to 2,000,000 g / mol, 50,000 g / mol to 1,800,000 g / mol, or 120,000 g / mol to 1,500,000 g / mol, the weight average molecular weight (Mw) may be 10,000 g / mol to 5,000,000 g / mol, 100,000 g / mol to 3,500,000 g / mol, or 120,000 g / mol to 2,000,000 g / mol, within this range Cloud resistance and wet road resistance is excellent effect. As another example, the modified conjugated diene-based polymer may have a molecular weight distribution (Mw / Mn) of 1.0 to 8.0, 1.0 to 4.0, or 1.0 to 3.5, there is an effect of excellent balance between physical properties within this range.
또 다른 예로, 상기 변성 공액디엔계 중합체는 무늬 점도(Mooney viscosity)가 100 ℃에서 20 내지 150일 수 있고, 140 ℃에서 20 내지 150일 수 있으며, 이 범위 내에서 가공성 및 생산성이 우수한 효과가 있다.As another example, the modified conjugated diene-based polymer may have a monetary viscosity of 20 to 150 at 100 ° C., 20 to 150 at 140 ° C., and excellent workability and productivity within this range. .
또한, 상기 변성 공액디엔계 중합체는 비닐 함량이 5 중량% 이상, 10 중량% 이상, 또는 14 중량% 내지 70 중량%일 수 있고, 이 범위 내에서 유리전이온도가 적절한 범위로 조절될 수 있어 구름 저항, 젖은 노면 저항성 및 저연비성이 우수한 효과가 있다. 여기에서, 상기 비닐 함량은 비닐기를 갖는 단량체와 방향족 비닐계 단량체로 이루어진 공액디엔계 공중합체 100 중량%에 대하여 1,4-첨가가 아닌 1,2-첨가된 공액디엔계 단량체의 함량을 의미할 수 있다.In addition, the modified conjugated diene-based polymer may have a vinyl content of 5% by weight or more, 10% by weight or more, or 14% by weight to 70% by weight, and the glass transition temperature within this range can be adjusted to an appropriate range cloud It is effective in resistance, wet road resistance and low fuel efficiency. Here, the vinyl content may refer to the content of 1,2-added conjugated diene-based monomers, not 1,4-addition, based on 100% by weight of the conjugated diene-based copolymer composed of a monomer having a vinyl group and an aromatic vinyl monomer. Can be.
한편, 본 발명에서 용어 '유래 반복 단위' 및 '유래 작용기'는 어떤 물질로부터 기인한 성분, 구조 또는 그 물질 자체를 나타내는 것일 수 있다.Meanwhile, in the present invention, the terms 'derived repeating unit' and 'derived functional group' may refer to a component, a structure, or the substance itself derived from a substance.
본 발명에 따른 변성 공액디엔계 중합체 제조방법은 유기 금속 화합물을 포함하는 탄화수소 용매 중에서, 공액디엔계 단량체, 또는 방향족 비닐계 단량체 및 공액디엔계 단량체를 중합하여 유기 금속이 결합된 활성 중합체를 제조하는 단계(S1); 및 상기 활성 중합체 및 하기 화학식 1로 표시되는 화합물을 포함하는 변성제와 반응시키는 단계(S2)를 포함할 수 있다.The modified conjugated diene-based polymer manufacturing method according to the present invention is to prepare an active polymer in which an organic metal is bonded by polymerizing a conjugated diene-based monomer, or an aromatic vinyl monomer and a conjugated diene-based monomer in a hydrocarbon solvent containing an organometallic compound. Step S1; And reacting with a denaturing agent including the active polymer and a compound represented by Formula 1 below (S2).
[화학식 1][Formula 1]
상기 화학식 1의 각 치환기에 대한 정의는 앞서 정의한 바와 같다.Definitions for each substituent of Formula 1 are as defined above.
상기 탄화수소 용매는 특별히 제한되는 것은 아니나, 예컨대 n-펜탄, n-헥산, n-헵탄, 이소옥탄, 사이클로 헥산, 톨루엔, 벤젠 및 크실렌으로 이루어진 군으로부터 선택된 1종 이상인 것일 수 있다.The hydrocarbon solvent is not particularly limited, but may be, for example, one or more selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene.
본 발명의 일 실시예에 따르면, 상기 화학식 1로 표시되는 화합물은 단량체 총 100 g을 기준으로 0.01 mmol 내지 10 mmol, 0.01 mmol 내지 5 mmol, 또는 0.02 mmol 내지 3 mmol의 양으로 사용할 수 있다.According to an embodiment of the present invention, the compound represented by Formula 1 may be used in an amount of 0.01 mmol to 10 mmol, 0.01 mmol to 5 mmol, or 0.02 mmol to 3 mmol, based on 100 g of the total monomer.
본 발명의 일 실시예에 따르면, 상기 유기 금속 화합물은 단량체 총 100 g을 기준으로 0.01 mmol 내지 10 mmol, 0.05 mmol 내지 5 mmol, 0.1 mmol 내지 2 mmol, 또는 0.1 mmol 내지 1 mmol로 사용할 수 있다.According to an embodiment of the present invention, the organometallic compound may be used in an amount of 0.01 mmol to 10 mmol, 0.05 mmol to 5 mmol, 0.1 mmol to 2 mmol, or 0.1 mmol to 1 mmol, based on 100 g of the total monomer.
상기 유기 금속 화합물은 일례로 메틸리튬, 에틸리튬, 프로필리튬, n-부틸리튬, s-부틸리튬, t-부틸리튬, 헥실리튬, n-데실리튬, t-옥틸리튬, 페닐리튬, 1-나프틸리튬, n-에이코실리튬, 4-부틸페닐리튬, 4-톨릴리튬, 사이클로헥실리튬, 3,5-디-n-헵틸사이클로헥실리튬, 4-사이클로펜틸리튬, 나프틸나트륨, 나프틸칼륨, 리튬 알콕사이드, 나트륨 알콕사이드, 칼륨 알콕사이드, 리튬 술포네이트, 나트륨 술포네이트, 칼륨 술포네이트, 리튬 아미드, 나트륨 아미드, 칼륨아미드 및 리튬 이소프로필아미드로 이루어진 군으로부터 선택된 1종 이상일 수 있다.The organometallic compound is, for example, methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octyllithium, phenyllithium, 1-naph Tilithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexylithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium , Lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide.
또 다른 예로, 상기 유기 금속 화합물은 하기 화학식 4로 표시되는 화합물일 수 있다.As another example, the organometallic compound may be a compound represented by Formula 4 below.
[화학식 4][Formula 4]
상기 화학식 4에서, 각 치환기에 대한 정의는 앞서 정의한 바와 같다.In Formula 4, the definition of each substituent is as defined above.
한편, 상기 (S1) 단계의 중합은 극성 첨가제를 포함하여 실시될 수 있고, 상기 극성 첨가제는 단량체 총 100g을 기준으로 0.001g 내지 50g, 0.001g 내지 10g, 또는 0.005g 내지 0.1g의 첨가할 수 있다. 또한, 상기 극성 첨가제는 테트라하이드로퓨란, 디테트라하이드로퓨릴프로판, 디에틸에테르, 시클로아말에테르, 디프로필에테르, 에틸렌디메틸에테르, 에틸렌디메틸에테르, 디에틸글리콜, 디메틸에테르, 3차 부톡시에톡시에탄, 비스(3-디메틸아미노에틸)에테르, (디메틸아미노에틸)에틸에테르, 트리메틸아민, 트리에틸아민, 트리프로필아민 및 테트라메틸에틸렌디아민으로 이루어진 군으로부터 선택된 1종 이상일 수 있고, 바람직하게는 트리에틸아민 또는 테트라메틸에틸렌디아민일 수 있으며, 상기 아미노 실란계 화합물의 제조 시 투입될 수 있는 극성 첨가제와 동일하거나 상이할 수 있고, 상기 극성 첨가제를 포함하는 경우 공액디엔계 단량체, 또는 공액디엔계 단량체 및 방향족 비닐계 단량체를 공중합시키는 경우 이들의 반응 속도 차이를 보완해줌으로써 랜덤 공중합체를 용이하게 형성할 수 있도록 유도하는 효과가 있다.On the other hand, the polymerization of the step (S1) may be carried out including a polar additive, the polar additive may be added 0.001g to 50g, 0.001g to 10g, or 0.005g to 0.1g based on a total of 100g monomer. have. In addition, the polar additive is tetrahydrofuran, ditetrahydrofuryl propane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tert-butoxy ethoxyethane , Bis (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine and tetramethylethylenediamine, and may be one or more selected from the group consisting of triethylamine. It may be an amine or tetramethylethylenediamine, and may be the same as or different from the polar additives that may be added in the preparation of the amino silane-based compound, when the polar additives include conjugated diene monomer, or conjugated diene monomer and Compensating the difference in reaction rate when copolymerizing aromatic vinyl monomers By doing so, there is an effect of inducing the easy formation of a random copolymer.
상기 (S1) 단계의 중합은 일례로 음이온 중합일 수 있고, 구체적인 예로 음이온에 의한 성장 중합 반응에 의해 중합 말단에 음이온 활성 부위를 갖는 리빙 음이온 중합일 수 있다. 또한, 상기 (S1) 단계의 중합은 승온 중합, 등온 중합 또는 정온 중합(단열 중합)일 수 있고, 상기 정온 중합은 유기 금속 화합물을 투입한 이후 임의로 열을 가하지 않고 자체 반응열로 중합시키는 단계를 포함하는 중합방법을 의미할 수 있고, 상기 승온 중합은 상기 유기 금속 화합물을 투입한 이후 임의로 열을 가하여 온도를 증가시키는 중합방법을 의미할 수 있으며, 상기 등온 중합은 상기 유기 금속 화합물을 투입한 이후 열을 가하여 열을 증가시키거나 열을 뺏어 중합물의 온도를 일정하게 유지하는 중합방법을 의미할 수 있다. 또한, 상기 (S1) 단계의 중합은 일례로 상기 중합은 -20 ℃ 내지 200 ℃, 0 ℃ 내지 150 ℃, 또는 10 ℃ 내지 120 ℃의 온도범위에서 실시될 수 있다.The polymerization of the step (S1) may be, for example, anionic polymerization, and specifically, may be living anion polymerization having an anion active site at the end of the polymerization by a growth polymerization reaction by anion. In addition, the polymerization of the step (S1) may be a temperature increase polymerization, isothermal polymerization or constant temperature polymerization (thermal insulation polymerization), the constant temperature polymerization may include the step of polymerization by the heat of reaction without the addition of heat after the addition of the organometallic compound optionally The temperature polymerization may mean a polymerization method in which the temperature is increased by optionally adding heat after the organometallic compound is added, and the isothermal polymerization is heat after adding the organometallic compound. By adding to increase the heat or take the heat may mean a polymerization method for maintaining a constant temperature of the polymer. In addition, the polymerization of the step (S1) may be carried out in a temperature range of -20 ℃ to 200 ℃, 0 ℃ to 150 ℃, or 10 ℃ to 120 ℃ for example.
상기 (S1) 단계에 의해 제조된 활성 중합체는 중합체 음이온과 유기 금속 양이온이 결합된 중합체를 의미할 수 있다.The active polymer prepared by the step (S1) may refer to a polymer in which a polymer anion and an organic metal cation are combined.
본 발명의 일 실시예에 따르면, 상기 화학식 1로 표시되는 화합물을 포함하는 변성제와 유기 금속 화합물의 몰비는 1:0.1 내지 1:10, 1:0.1 내지 1:5, 또는 1:0.2 내지 1:3일 수 있고, 이 범위 내에서 최적 성능의 변성 반응을 수행할 수 있어, 고변성률의 공액디엔계 중합체를 수득할 수 있다.According to an embodiment of the present invention, the molar ratio of the modifier and the organometallic compound including the compound represented by Chemical Formula 1 is 1: 0.1 to 1:10, 1: 0.1 to 1: 5, or 1: 0.2 to 1: It can be 3, it is possible to carry out the modification performance of the optimum performance within this range, it is possible to obtain a conjugated diene-based polymer of high modification rate.
상기 (S2) 단계의 반응은 활성 중합체에 상기 변성제로부터 유래된 작용기를 도입시키기 위한 변성 반응으로, 0 ℃ 내지 90 ℃에서 1분 내지 5시간 동안 반응을 수행하는 것일 수 있다.The reaction of step (S2) is a modification reaction for introducing a functional group derived from the modifier into the active polymer, it may be to perform the reaction for 1 minute to 5 hours at 0 ℃ to 90 ℃.
또한, 본 발명의 일 실시예에 따르면, 상기 변성 공액디엔계 중합체 제조방법은 회분식(배치식) 또는 1종 이상의 반응기를 포함하는 연속식 중합방법에 의하여 수행하는 것일 수 있다.In addition, according to one embodiment of the present invention, the modified conjugated diene-based polymer manufacturing method may be performed by a batch polymerization (batch) or a continuous polymerization method comprising one or more reactors.
상기 변성 공액디엔계 중합체 제조방법은 일례로 본 발명의 상기 (S2) 단계에 이어서, 필요에 따라 용매 및 미반응 단량체 회수 및 건조 단계들 중 1 이상의 단계를 더 포함할 수 있다.The modified conjugated diene-based polymer manufacturing method may further include one or more steps of recovering and drying the solvent and the unreacted monomer, if necessary, following the step (S2) of the present invention.
본 발명에 따르면 상기의 변성 공액디엔계 중합체를 포함하는 고무 조성물이 제공된다.According to the present invention there is provided a rubber composition comprising the modified conjugated diene-based polymer.
상기 고무 조성물은 상기 변성 공액디엔계 중합체를 10 중량% 이상, 10 중량% 내지 100 중량%, 또는 20 중량% 내지 90 중량%의 양으로 포함하는 것일 수 있고, 이 범위 내에서 인장 강도, 내마모성 등의 기계적 물성이 우수하고, 각 물성 간의 밸런스가 뛰어난 효과가 있다.The rubber composition may include the modified conjugated diene-based polymer in an amount of 10 wt% or more, 10 wt% to 100 wt%, or 20 wt% to 90 wt%, and within this range, tensile strength, wear resistance, and the like. It is excellent in the mechanical properties of and excellent in the balance between each physical property.
또한, 상기 고무 조성물은 상기 변성 공액디엔계 중합체 외에 필요에 따라 다른 고무 성분을 더 포함할 수 있고, 이 때 상기 고무 성분은 고무 조성물 총 중량에 대하여 90 중량% 이하의 함량으로 포함될 수 있다. 구체적인 예로 상기 다른 고무 성분은 상기 변성 공액디엔계 중합체 100 중량부에 대하여 1 중량부 내지 900 중량부로 포함되는 것일 수 있다.In addition, the rubber composition may further include other rubber components as needed in addition to the modified conjugated diene-based polymer, wherein the rubber components may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. As a specific example, the other rubber component may be included in an amount of 1 part by weight to 900 parts by weight based on 100 parts by weight of the modified conjugated diene-based polymer.
상기 고무 성분은 일례로 천연고무 또는 합성고무일 수 있으며, 구체적인 예로 시스-1,4-폴리이소프렌을 포함하는 천연고무(NR); 상기 일반적인 천연고무를 변성 또는 정제한, 에폭시화 천연고무(ENR), 탈단백 천연고무(DPNR), 수소화 천연고무 등의 변성 천연고무; 스티렌-부타디엔 공중합체(SBR), 폴리부타디엔(BR), 폴리이소프렌(IR), 부틸고무(IIR), 에틸렌-프로필렌 공중합체, 폴리이소부틸렌-코-이소프렌, 네오프렌, 폴리(에틸렌-코-프로필렌), 폴리(스티렌-코-부타디엔), 폴리(스티렌-코-이소프렌), 폴리(스티렌-코-이소프렌-코-부타디엔), 폴리(이소프렌-코-부타디엔), 폴리(에틸렌-코-프로필렌-코-디엔), 폴리설파이드 고무, 아크릴 고무, 우레탄 고무, 실리콘 고무, 에피클로로히드린 고무, 부틸 고무, 할로겐화 부틸 고무 등과 같은 합성고무일 수 있으며, 이들 중 어느 하나 또는 둘 이상의 혼합물이 사용될 수 있다.The rubber component may be, for example, natural rubber or synthetic rubber, and specific examples include natural rubber (NR) including cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber obtained by modifying or refining the general natural rubber; Styrene-butadiene copolymer (SBR), polybutadiene (BR), polyisoprene (IR), butyl rubber (IIR), ethylene-propylene copolymer, polyisobutylene-co-isoprene, neoprene, poly (ethylene-co- Propylene), poly (styrene-co-butadiene), poly (styrene-co-isoprene), poly (styrene-co-isoprene-co-butadiene), poly (isoprene-co-butadiene), poly (ethylene-co-propylene Co-diene), polysulfide rubber, acrylic rubber, urethane rubber, silicone rubber, epichlorohydrin rubber, butyl rubber, halogenated butyl rubber, etc., and any one or a mixture of two or more thereof may be used. have.
상기 고무 조성물은 일례로 본 발명의 변성 공액디엔계 중합체 100 중량부에 대하여 0.1 중량부 내지 200 중량부, 또는 10 중량부 내지 120 중량부의 충진제를 포함하는 것일 수 있다. 상기 충진제는 일례로 실리카계 충진제일 수 있고, 구체적인 예로 습식 실리카(함수규산), 건식 실리카(무수규산), 규산칼슘, 규산알루미늄 또는 콜로이드 실리카 등일 수 있으며, 바람직하게는 파괴 특성의 개량 효과 및 웨트 그립성(wet grip)의 양립 효과가 가장 뛰어난 습식 실리카일 수 있다. 또한, 상기 고무 조성물은 필요에 따라 카본블랙계 충진제를 더 포함할 수 있다. The rubber composition may include, for example, 0.1 part by weight to 200 parts by weight, or 10 parts by weight to 120 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene polymer of the present invention. The filler may be, for example, a silica-based filler, and specific examples may be wet silica (silicate silicate), dry silica (silicate anhydrous), calcium silicate, aluminum silicate, colloidal silica, and the like. The wet silica may be the most compatible of the grip (wet grip). In addition, the rubber composition may further include a carbon black filler as needed.
또 다른 예로, 상기 충전제로 실리카가 사용되는 경우 보강성 및 저발열성 개선을 위한 실란 커플링제가 함께 사용될 수 있고, 구체적인 예로 상기 실란 커플링제는 비스(3-트리에톡시실릴프로필)테트라술피드, 비스(3-트리에톡시실릴프로필)트리술피드, 비스(3-트리에톡시실릴프로필)디술피드, 비스(2-트리에톡시실릴에틸)테트라술피드, 비스(3-트리메톡시실릴프로필)테트라술피드, 비스(2-트리메톡시실릴에틸)테트라술피드, 3-머캅토프로필트리메톡시실란, 3-머캅토프로필트리에톡시실란, 2-머캅토에틸트리메톡시실란, 2-머캅토에틸트리에톡시실란, 3-트리메톡시실릴프로필-N,N-디메틸티오카르바모일테트라술피드, 3-트리에톡시실릴프로필-N,N-디메틸티오카르바모일테트라술피드, 2-트리에톡시실릴에틸-N,N-디메틸티오카르바모일테트라술피드, 3-트리메톡시실릴프로필벤조티아졸릴테트라술피드, 3-트리에톡시실릴프로필벤졸릴테트라술피드, 3-트리에톡시실릴프로필메타크릴레이트모노술피드, 3-트리메톡시실릴프로필메타크릴레이트모노술피드, 비스(3-디에톡시메틸실릴프로필)테트라술피드, 3-머캅토프로필디메톡시메틸실란, 디메톡시메틸실릴프로필-N,N-디메틸티오카르바모일테트라술피드 또는 디메톡시메틸실릴프로필벤조티아졸릴테트라술피드 등일 수 있으며, 이들 중 어느 하나 또는 둘 이상의 혼합물이 사용될 수 있다. 바람직하게는 보강성 개선 효과를 고려할 때 비스(3-트리에톡시실릴프로필)폴리술피드 또는 3-트리메톡시실릴프로필벤조티아질테트라술피드일 수 있다.As another example, when silica is used as the filler, a silane coupling agent for improving reinforcement and low heat generation may be used together. As a specific example, the silane coupling agent may include bis (3-triethoxysilylpropyl) tetrasulfide. , Bis (3-triethoxysilylpropyl) trisulfide, bis (3-triethoxysilylpropyl) disulfide, bis (2-triethoxysilylethyl) tetrasulfide, bis (3-trimethoxysilyl Propyl) tetrasulfide, bis (2-trimethoxysilylethyl) tetrasulfide, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-triethoxysilylpropyl-N, N-dimethylthiocarbamoyl tetrasulfate Feed, 2-triethoxysilylethyl-N, N-dimethylthiocarbamoyl tetrasulfide, 3-trime Sisilylpropylbenzothiazolyl tetrasulfide, 3-triethoxysilylpropylbenzolyl tetrasulfide, 3-triethoxysilylpropyl methacrylate monosulfide, 3-trimethoxysilylpropyl methacrylate monosulfide , Bis (3-diethoxymethylsilylpropyl) tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N, N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzo Thiazolyltetrasulfide, and the like, and any one or a mixture of two or more thereof may be used. Preferably, considering the reinforcing improvement effect, it may be bis (3-triethoxysilylpropyl) polysulfide or 3-trimethoxysilylpropylbenzothiazyl tetrasulfide.
또한, 본 발명의 일 실시예에 따른 상기 고무 조성물은, 고무 성분으로서 활성 부위에 실리카와의 친화성이 높은 작용기가 도입된 변성 공액디엔계 중합체가 사용되고 있기 때문에, 실란 커플링제의 배합량은 통상의 경우보다 저감될 수 있고, 이에 따라, 상기 실란 커플링제는 실리카 100 중량부에 대하여 1 중량부 내지 20 중량부, 또는 5 중량부 내지 15 중량부로 사용될 수 있으며, 이 범위 내에서 커플링제로서의 효과가 충분히 발휘되면서도 고무 성분의 겔화를 방지하는 효과가 있다.In addition, in the rubber composition according to one embodiment of the present invention, since a modified conjugated diene-based polymer having a functional group having high affinity with silica is introduced as the rubber component, the compounding amount of the silane coupling agent is conventional. The silane coupling agent may be used in an amount of 1 part by weight to 20 parts by weight, or 5 parts by weight to 15 parts by weight with respect to 100 parts by weight of silica, and the effect as a coupling agent is within this range. While sufficiently exhibiting, there is an effect of preventing gelation of the rubber component.
본 발명의 일 실시예에 따른 상기 고무 조성물은 황 가교성일 수 있고, 가황제를 더 포함할 수 있다. 상기 가황제는 구체적으로 황 분말일 수 있고, 고무 성분 100 중량부에 대하여 0.1 중량부 내지 10 중량부로 포함될 수 있으며, 이 범위 내에서 가황 고무 조성물의 필요한 탄성률 및 강도를 확보함과 동시에 저연비성이 뛰어난 효과가 있다.The rubber composition according to an embodiment of the present invention may be sulfur crosslinkable, and may further include a vulcanizing agent. The vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 parts by weight to 10 parts by weight with respect to 100 parts by weight of the rubber component, while ensuring the required elastic modulus and strength of the vulcanized rubber composition within this range and at the same time low fuel efficiency. Excellent effect.
본 발명의 일 실시예에 따른 상기 고무 조성물은 상기한 성분들 외에, 통상 고무 공업계에서 사용되는 각종 첨가제, 구체적으로는 가황 촉진제, 공정유, 가소제, 노화 방지제, 스코치 방지제, 아연화(zinc white), 스테아르산, 열경화성 수지, 또는 열가소성 수지 등을 더 포함할 수 있다.The rubber composition according to an embodiment of the present invention, in addition to the above components, various additives commonly used in the rubber industry, specifically, vulcanization accelerators, process oils, plasticizers, anti-aging agents, anti-scoring agents, zinc white, Stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.
상기 가황 촉진제는 일례로 M(2-머캅토벤조티아졸), DM(디벤조티아질디술피드), CZ(N-시클로헥실-2-벤조티아질술펜아미드) 등의 티아졸계 화합물, 혹은 DPG(디페닐구아니딘) 등의 구아니딘계 화합물이 사용될 수 있고, 고무 성분 100 중량부에 대하여 0.1 중량부 내지 5 중량부로 포함될 수 있다.The vulcanization accelerator is, for example, a thiazole-based compound such as M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazylsulfenamide), or DPG. Guanidine-based compounds such as (diphenylguanidine) may be used, and may be included in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the rubber component.
상기 공정유는 고무 조성물 내에서 연화제로서 작용하는 것으로, 일례로 파라핀계, 나프텐계, 또는 방향족계 화합물일 수 있고, 인장 강도 및 내마모성을 고려할 때 방향족계 공정유가, 히스테리시스 손실 및 저온 특성을 고려할 때 나프텐계 또는 파라핀계 공정유가 사용될 수 있다. 상기 공정유는 일례로 고무 성분 100 중량부에 대하여 100 중량부 이하의 함량으로 포함될 수 있고, 이 범위 내에서 가황 고무의 인장 강도, 저발열성(저연비성)의 저하를 방지하는 효과가 있다.The process oil acts as a softener in the rubber composition, and may be, for example, a paraffinic, naphthenic, or aromatic compound, and when considering the tensile strength and abrasion resistance, when the aromatic process oil, hysteresis loss and low temperature characteristics are considered. Naphthenic or paraffinic process oils may be used. For example, the process oil may be included in an amount of 100 parts by weight or less based on 100 parts by weight of the rubber component, and there is an effect of preventing a decrease in tensile strength and low heat generation (low fuel efficiency) of the vulcanized rubber within this range.
상기 노화방지제는 일례로 N-이소프로필-N'-페닐-p-페닐렌디아민, N-(1,3-디메틸부틸)-N'-페닐-p-페닐렌디아민, 6-에톡시-2,2,4-트리메틸-1,2-디히드로퀴놀린, 또는 디페닐아민과 아세톤의 고온 축합물 등일 수 있고, 고무 성분 100 중량부에 대하여 0.1 중량부 내지 6 중량부로 사용될 수 있다.The anti-aging agent is for example N-isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 6-ethoxy-2 , 2,4-trimethyl-1,2-dihydroquinoline, or a high temperature condensate of diphenylamine and acetone, and the like, and may be used in an amount of 0.1 to 6 parts by weight based on 100 parts by weight of the rubber component.
본 발명의 일 실시예에 따른 상기 고무 조성물은 상기 배합 처방에 의해 밴버리 믹서, 롤, 인터널 믹서 등의 혼련기를 사용하여 혼련함으로써 수득될 수 있고, 성형 가공 후 가황 공정에 의해 저발열성이며 내마모성이 우수한 고무 조성물이 수득될 수 있다.The rubber composition according to an embodiment of the present invention may be obtained by kneading using a kneading machine such as a Banbury mixer, a roll, an internal mixer, etc. by the compounding formulation, and has low heat resistance and abrasion resistance by a vulcanization process after molding. This excellent rubber composition can be obtained.
이에 따라 상기 고무 조성물은 타이어 트레드, 언더 트레드, 사이드 월, 카카스 코팅 고무, 벨트 코팅 고무, 비드 필러, 췌이퍼, 또는 비드 코팅 고무 등의 타이어의 각 부재나, 방진고무, 벨트 컨베이어, 호스 등의 각종 공업용 고무 제품의 제조에 유용할 수 있다.Accordingly, the rubber composition may be used for tire members such as tire treads, under treads, sidewalls, carcass coated rubbers, belt coated rubbers, bead fillers, pancreapers, or bead coated rubbers, dustproof rubbers, belt conveyors, hoses, and the like. It may be useful for the production of various industrial rubber products.
아울러, 본 발명은 상기 고무 조성물을 이용하여 제조된 타이어를 제공한다.In addition, the present invention provides a tire manufactured using the rubber composition.
상기 타이어는 타이어 또는 타이어 트레드를 포함하는 것일 수 있다.The tire may include a tire or a tire tread.
이하, 실시예에 의하여 본 발명을 더욱 상세하게 설명하고자 한다. 그러나, 하기 실시예는 본 발명을 예시하기 위한 것으로 이들 만으로 본 발명의 범위가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited only to these.
제조예Production Example
제조예 1: 화학식 1-13으로 표시되는 화합물의 제조Preparation Example 1 Preparation of Compound Represented by Chemical Formula 1-13
쉬링크 라인이 연결된 1L 둥근바닥플라스크에 하기 화학식 2-1로 표시되는 화합물 0.1 mol (14.91 g)을 넣고 감압하여 수분을 완전히 제거한 후, 아르곤 분위기 하에서 아세토니트릴(acetonitrile) 500 ml를 넣은 후, 하기 화학식 3-7으로 표시되는 화합물 0.1 mol (42.57 g)과 트리에틸아민(triethylamine) 10.12 g을 투입하고, 40 ℃로 가열하고, 4시간 동안 교반시켜, 하기 화학식 1-13으로 표시되는 화합물을 수득하고, 1H 및 13C 핵자기 공명 분광학적 스펙트럼을 관찰하였다.0.1 mol (14.91 g) of the compound represented by the following Chemical Formula 2-1 was added to a 1L round bottom flask connected with a shrink line, and the water was removed under reduced pressure, and 500 ml of acetonitrile was added under an argon atmosphere. 0.1 mol (42.57 g) of the compound represented by Chemical Formula 3-7 and 10.12 g of triethylamine were added thereto, heated to 40 ° C., and stirred for 4 hours to obtain a compound represented by the following Chemical Formula 1-13. And 1 H and 13 C nuclear magnetic resonance spectroscopy spectra were observed.
[화학식 2-1][Formula 2-1]
[화학식 3-7][Formula 3-7]
[화학식 1-13][Formula 1-13]
1H NMR (CDCl3, 500 MHz) δ 7.27-7.36 (m, 5H), 4.81 (d, 2H), 3.83-3.92 (m, 13H), 2.43 (m, 4H), 1.33 (m, 4H), 1.21 (t, 18H), 0.56 (t, 4H). 1 H NMR (CDCl 3 , 500 MHz) δ 7.27-7.36 (m, 5H), 4.81 (d, 2H), 3.83-3.92 (m, 13H), 2.43 (m, 4H), 1.33 (m, 4H), 1.21 (t, 18H), 0.56 (t, 4 H).
13C NMR (CDCl3, 500 MHz) δ 137.4, 128.8, 128.8, 128.4, 128.4, 127.2, 82.1, 64.7, 58.4, 58.4, 58.4, 58.4, 58.4, 58.4, 56.5, 56.5, 23.9, 23.9, 18.4, 18.4, 18.4, 18.4, 18.4, 18.4, 14.4, 14.4. 13 C NMR (CDCl 3 , 500 MHz) δ 137.4, 128.8, 128.8, 128.4, 128.4, 127.2, 82.1, 64.7, 58.4, 58.4, 58.4, 58.4, 58.4, 58.4, 56.5, 56.5, 23.9, 23.9, 18.4, 18.4 , 18.4, 18.4, 18.4, 18.4, 14.4, 14.4.
제조예 2: 화학식 1-14로 표시되는 화합물의 제조Preparation Example 2 Preparation of Compound Represented by Chemical Formula 1-14
쉬링크 라인이 연결된 1L 둥근바닥플라스크에 하기 화학식 2-1로 표시되는 화합물 0.1 mol (14.91 g)을 넣고 감압하여 수분을 완전히 제거한 후, 아르곤 분위기 하에서 하기 화학식 3-10으로 표시되는 화합물 0.1 mol (23.84 g)을 투입하고, 25 ℃에서, 1시간 동안 교반시켜, 하기 화학식 1-14로 표시되는 화합물을 수득하고, 1H 및 13C 핵자기 공명 분광학적 스펙트럼을 관찰하였다.0.1 mol (14.91 g) of the compound represented by the following Chemical Formula 2-1 was added to a 1L round bottom flask connected by a shrink line, and the water was removed under reduced pressure. Then, 0.1 mol (of the compound represented by the following Chemical Formula 3-10 under an argon atmosphere) 23.84 g) was added thereto, and stirred at 25 ° C. for 1 hour to obtain a compound represented by the following Chemical Formula 1-14, and 1 H and 13 C nuclear magnetic resonance spectroscopic spectra were observed.
[화학식 2-1][Formula 2-1]
[화학식 3-10][Formula 3-10]
[화학식 1-14][Formula 1-14]
1H NMR (CDCl3, 500 MHz) δ 7.20-7.30 (m, 5H), 5.11 (d, 2H), 3.8-3.9 (m, 7H), 2.60 (m, 2H), 1.62 (m, 2H), 1.21 (t, 9H), 0.56 (t, 2H). 1 H NMR (CDCl 3 , 500 MHz) δ 7.20-7.30 (m, 5H), 5.11 (d, 2H), 3.8-3.9 (m, 7H), 2.60 (m, 2H), 1.62 (m, 2H), 1.21 (t, 9H), 0.56 (t, 2 H).
13C NMR (CDCl3, 500 MHz) δ 139.0, 128.7, 128.7, 128.6, 128.6, 84.4, 58.4, 58.4, 58.4, 41.1, 32.5, 18.4, 18.4, 18.4, 17.1, 15.6. 13 C NMR (CDCl 3 , 500 MHz) δ 139.0, 128.7, 128.7, 128.6, 128.6, 84.4, 58.4, 58.4, 58.4, 41.1, 32.5, 18.4, 18.4, 18.4, 17.1, 15.6.
제조예 3: 화학식 1-15로 표시되는 화합물의 제조Preparation Example 3 Preparation of Compound Represented by Chemical Formula 1-15
상기 제조예 1에서, 쉬링크 라인이 연결된 1L 둥근바닥플라스크에 화학식 2-1로 표시되는 화합물 대신, 하기 화학식 2-3으로 표시되는 화합물 0.1 mol (13.91 g)을 넣은 것을 제외하고는 상기 제조예 1과 동일한 방법으로 제조하고, 1H 및 13C 핵자기 공명 분광학적 스펙트럼을 관찰하였다.In Preparation Example 1, except that 0.1 mol (13.91 g) of the compound represented by the following Chemical Formula 2-3 was added to the 1L round bottom flask connected to the shrink line, instead of the compound represented by the following Chemical Formula 2-1. Prepared in the same manner as 1, and observed 1 H and 13 C nuclear magnetic resonance spectroscopy spectra.
[화학식 2-3][Formula 2-3]
[화학식 3-7][Formula 3-7]
[화학식 1-15][Formula 1-15]
1H NMR (CDCl3, 500 MHz) δ 7.32 (m, 1H), 6.39-6.43 (m, 2H), 4.74-4.82 (m, 2H), 4.39 (t, 1H), 3.83-3.92 (m, 12H), 2.43 (m, 4H), 1.35 (m, 4H), 1.21 (t, 18H), 0.56 (t, 4H). 1 H NMR (CDCl 3 , 500 MHz) δ 7.32 (m, 1H), 6.39-6.43 (m, 2H), 4.74-4.82 (m, 2H), 4.39 (t, 1H), 3.83-3.92 (m, 12H ), 2.43 (m, 4H), 1.35 (m, 4H), 1.21 (t, 18H), 0.56 (t, 4H).
13C NMR (CDCl3, 500 MHz) δ 151.1, 141.5, 110.0, 109.2, 80.3, 65.9, 58.4, 58.4, 58.4, 58.4, 58.4, 58.4, 54.1, 54.1, 22.3, 22.3, 18.4, 18.4, 18.4, 18.4, 18.4, 18.4, 14.4, 14.4. 13 C NMR (CDCl 3 , 500 MHz) δ 151.1, 141.5, 110.0, 109.2, 80.3, 65.9, 58.4, 58.4, 58.4, 58.4, 58.4, 58.4, 54.1, 54.1, 22.3, 22.3, 18.4, 18.4, 18.4, 18.4 , 18.4, 18.4, 14.4, 14.4.
제조예 4: 화학식 1-16으로 표시되는 화합물의 제조Preparation Example 4 Preparation of Compound Represented by Chemical Formula 1-16
상기 제조예 2에서, 쉬링크 라인이 연결된 1L 둥근바닥플라스크에 화학식 2-1로 표시되는 화합물 대신, 하기 화학식 2-3으로 표시되는 화합물 0.1 mol (13.91 g)을 넣은 것을 제외하고는 상기 제조예 2와 동일한 방법으로 제조하고, 1H 및 13C 핵자기 공명 분광학적 스펙트럼을 관찰하였다.In Preparation Example 2, except that 0.1 mol (13.91 g) of the compound represented by the following Chemical Formula 2-3 was added to the 1L round bottom flask connected to the shrink line, instead of the compound represented by the Chemical Formula 2-1, Prepared in the same manner as 2, 1 H and 13 C nuclear magnetic resonance spectroscopy spectra were observed.
[화학식 2-3][Formula 2-3]
[화학식 3-10][Formula 3-10]
[화학식 1-16][Formula 1-16]
1H NMR (CDCl3, 500 MHz) δ 7.49 (d, 1H), 6.33 (t, 1H), 6.11 (d, 1H), 4.95-5.1 (m, 2H), 4.00 (m, 1H), 3.83 (m, 6H), 2.60 (m, 2H), 1.62 (m, 2H), 1.21 (t, 9H), 0.56 (t, 2H). 1 H NMR (CDCl 3 , 500 MHz) δ 7.49 (d, 1H), 6.33 (t, 1H), 6.11 (d, 1H), 4.95-5.1 (m, 2H), 4.00 (m, 1H), 3.83 ( m, 6H), 2.60 (m, 2H), 1.62 (m, 2H), 1.21 (t, 9H), 0.56 (t, 2H).
13C NMR (CDCl3, 500 MHz) δ 151.8, 141.5, 110.0, 107.2, 82.6, 58.4, 58.4, 58.4, 42.3, 30.1, 18.4, 18.4, 18.4, 16.5, 15.6. 13 C NMR (CDCl 3 , 500 MHz) δ 151.8, 141.5, 110.0, 107.2, 82.6, 58.4, 58.4, 58.4, 42.3, 30.1, 18.4, 18.4, 18.4, 16.5, 15.6.
제조예 5: 화학식 1-17로 표시되는 화합물의 제조Preparation Example 5 Preparation of Compound Represented by Chemical Formula 1-17
상기 제조예 1에서, 쉬링크 라인이 연결된 1L 둥근바닥플라스크에 화학식 2-1로 표시되는 화합물 대신, 하기 화학식 2-4로 표시되는 화합물 0.1 mol (16.32 g)을 넣은 것을 제외하고는 상기 제조예 1과 동일한 방법으로 제조하고, 1H 및 13C 핵자기 공명 분광학적 스펙트럼을 관찰하였다.In Preparation Example 1, except that 0.1 mol (16.32 g) of the compound represented by the following Chemical Formula 2-4 was added to the 1L round bottom flask connected with the shrink line, instead of the compound represented by the chemical formula 2-1, Prepared in the same manner as 1, and observed 1 H and 13 C nuclear magnetic resonance spectroscopy spectra.
[화학식 2-4][Formula 2-4]
[화학식 3-7][Formula 3-7]
[화학식 1-17][Formula 1-17]
1H NMR (CDCl3, 500 MHz) δ 7.06-7.15 (m,4H), 4.66-4.92 (m, 2H), 3.83-3.90 (m, 13H), 2.43 (m, 4H), 2.19 (s, 3H), 1.95 (m, 4H), 1.21 (t, 18H), 0.56 (t, 4H). 1 H NMR (CDCl 3 , 500 MHz) δ 7.06-7.15 (m, 4H), 4.66-4.92 (m, 2H), 3.83-3.90 (m, 13H), 2.43 (m, 4H), 2.19 (s, 3H ), 1.95 (m, 4H), 1.21 (t, 18H), 0.56 (t, 4H).
13C NMR (CDCl3, 500 MHz) δ136.9, 134.4, 128.7, 128.7, 127.2, 127.2, 82.1, 64.7, 58.4, 58.4, 58.4, 58.4, 58.4, 58.4, 56.5, 56.5, 23.9, 23.9, 21.3, 18.4, 18.4, 18.4, 18.4, 18.4, 18.4, 14.4, 14.4. 13 C NMR (CDCl 3 , 500 MHz) δ 136.9, 134.4, 128.7, 128.7, 127.2, 127.2, 82.1, 64.7, 58.4, 58.4, 58.4, 58.4, 58.4, 58.4, 56.5, 56.5, 23.9, 23.9, 21.3, 18.4, 18.4, 18.4, 18.4, 18.4, 18.4, 14.4, 14.4.
제조예 6: 화학식 1-18로 표시되는 화합물의 제조Preparation Example 6 Preparation of Compound Represented by Chemical Formula 1-18
상기 제조예 2에서, 쉬링크 라인이 연결된 1L 둥근바닥플라스크에 화학식 2-1로 표시되는 화합물 대신, 하기 화학식 2-4로 표시되는 화합물 0.1 mol (16.32 g)을 넣은 것을 제외하고는 상기 제조예 2와 동일한 방법으로 제조하고, 1H 및 13C 핵자기 공명 분광학적 스펙트럼을 관찰하였다.In Preparation Example 2, except that 0.1 mol (16.32 g) of the compound represented by the following Chemical Formula 2-4 was added to the 1L round bottom flask connected by the shrink line, instead of the compound represented by the chemical formula 2-1, Prepared in the same manner as 2, 1 H and 13 C nuclear magnetic resonance spectroscopy spectra were observed.
[화학식 2-4][Formula 2-4]
[화학식 3-10][Formula 3-10]
[화학식 1-18][Formula 1-18]
1H NMR (CDCl3, 500 MHz) δ 7.06-7.15 (m,4H), 4.66-4.91 (m, 2H), 3.80-3.88 (m, 7H), 2.60 (m, 2H), 2.34 (s, 3H), 1.62 (m, 2H), 1.21 (t, 9H), 0.56 (t, 2H). 1 H NMR (CDCl 3 , 500 MHz) δ 7.06-7.15 (m, 4H), 4.66-4.91 (m, 2H), 3.80-3.88 (m, 7H), 2.60 (m, 2H), 2.34 (s, 3H ), 1.62 (m, 2H), 1.21 (t, 9H), 0.56 (t, 2H).
13C NMR (CDCl3, 500 MHz) δ136.8, 136.0, 128.9, 128.9, 127.3, 127.3, 84.4, 58.4, 58.4, 58.4, 41.1, 32.5, 21.3, 18.4, 18.4, 18.4, 17.1, 15.6. 13 C NMR (CDCl 3 , 500 MHz) δ 136.8, 136.0, 128.9, 128.9, 127.3, 127.3, 84.4, 58.4, 58.4, 58.4, 41.1, 32.5, 21.3, 18.4, 18.4, 18.4, 17.1, 15.6.
실시예Example
실시예 1Example 1
20L 오토클레이브 반응기에 스티렌 270g, 1,3-부타디엔 710g 및 노말헥산 5,000g, 극성첨가제로 디테트라하이드로퓨릴프로판 0.9 g을 넣은 후 반응기 내부온도를 40 ℃로 승온하였다. 반응기 내부 온도가 40 ℃에 도달했을 때, n-부틸리튬 4.3mmol을 반응기에 투입하여 단열 승온 반응을 진행시켰다. 단열 승온 반응이 끝난 다음 20 여분 경과 후 1,3-부타디엔 20g을 투입하여 중합체의 말단을 부타디엔으로 캡핑(capping)하였다. 5 분 후 상기 제조예 1에서 제조된 화학식 1-13으로 표시되는 화합물 2.47g (4.3 mmol)을 투입하고, 15분 간 반응시켰다. 이 후 에탄올을 이용하여 중합반응을 정지시키고, 산화방지제인 BHT(부틸레이티드하이드록시톨루엔)가 헥산에 0.3 중량% 녹아있는 용액 45ml를 첨가하였다. 그 결과 얻어진 중합물을 스팀으로 가열된 온수에 넣고 교반하여 용매를 제거한 다음, 롤 건조하여 잔량의 용매 와 물을 제거하여, 변성 공액디엔계 중합체를 제조하였다. 이렇게 제조된 변성 공액디엔계 중합체에 대한 분석 결과는 하기 표 1에 나타내었다.Into a 20L autoclave reactor, 270 g of styrene, 710 g of 1,3-butadiene, 5,000 g of normal hexane, and 0.9 g of ditetrahydrofurylpropane were added as a polar additive, and the temperature inside the reactor was raised to 40 ° C. When the internal temperature of the reactor reached 40 ° C., 4.3 mmol of n-butyllithium was added to the reactor to perform an adiabatic heating reaction. 20 g of 1,3-butadiene was added after 20 minutes after the adiabatic heating reaction was completed, and the ends of the polymer were capped with butadiene. After 5 minutes, 2.47 g (4.3 mmol) of the compound represented by Chemical Formula 1-13 prepared in Preparation Example 1 were added thereto, and reacted for 15 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 45 ml of a solution in which 0.3 wt% of BHT (butylated hydroxytoluene), an antioxidant, was dissolved in hexane was added. The resulting polymer was placed in hot water heated with steam, stirred to remove the solvent, and then dried in rolls to remove residual solvent and water to prepare a modified conjugated diene-based polymer. The analysis results of the modified conjugated diene-based polymer thus prepared are shown in Table 1 below.
실시예 2Example 2
상기 실시예 1에서, 상기 제조예 1에서 제조된 화학식 1-13으로 표시되는 화합물 대신 상기 제조예 2에서 제조된 화학식 1-14로 표시되는 화합물을 1.67g (4.3 mmol) 투입한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하였다.In Example 1, except that 1.67g (4.3 mmol) of the compound represented by Formula 1-14 prepared in Preparation Example 2 was added instead of the compound represented by Formula 1-13 prepared in Preparation Example 1. , It was carried out in the same manner as in Example 1.
실시예 3Example 3
상기 실시예 1에서, 상기 제조예 1에서 제조된 화학식 1-13으로 표시되는 화합물 대신 상기 제조예 3에서 제조된 화학식 1-15로 표시되는 화합물을 2.42g (4.3 mmol) 투입한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하였다.In Example 1, except that 2.42g (4.3 mmol) of the compound represented by Formula 1-15 prepared in Preparation Example 3 was added instead of the compound represented by Formula 1-13 prepared in Preparation Example 1. , It was carried out in the same manner as in Example 1.
실시예 4Example 4
상기 실시예 1에서, 상기 제조예 1에서 제조된 화학식 1-13으로 표시되는 화합물 대신 상기 제조예 4에서 제조된 화학식 1-16으로 표시되는 화합물을 1.62g (4.3 mmol) 투입한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하였다.In Example 1, except that 1.62g (4.3 mmol) of the compound represented by Formula 1-16 prepared in Preparation Example 4 was added instead of the compound represented by Formula 1-13 prepared in Preparation Example 1. , It was carried out in the same manner as in Example 1.
실시예 5Example 5
상기 실시예 1에서, 상기 제조예 1에서 제조된 화학식 1-13으로 표시되는 화합물 대신 상기 제조예 5에서 제조된 화학식 1-17로 표시되는 화합물을 2.53g (4.3 mmol) 투입한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하였다.In Example 1, except that 2.53g (4.3 mmol) of the compound represented by Formula 1-17 prepared in Preparation Example 5 was added instead of the compound represented by Formula 1-13 prepared in Preparation Example 1. , It was carried out in the same manner as in Example 1.
실시예 6Example 6
상기 실시예 1에서, 상기 제조예 1에서 제조된 화학식 1-13으로 표시되는 화합물 대신 상기 제조예 6에서 제조된 화학식 1-18로 표시되는 화합물을 1.73g (4.3 mmol) 투입한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하였다.In Example 1, except that 1.73g (4.3 mmol) of the compound represented by Formula 1-18 prepared in Preparation Example 6 was added instead of the compound represented by Formula 1-13 prepared in Preparation Example 1. , It was carried out in the same manner as in Example 1.
비교예 1Comparative Example 1
상기 실시예 1에서, 상기 제조예 1에서 제조된 화학식 1-13으로 표시되는 화합물을 투입하지 않은 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하였다.In Example 1, except that the compound represented by Formula 1-13 prepared in Preparation Example 1 was not added, it was carried out in the same manner as in Example 1.
비교예 2Comparative Example 2
상기 실시예 1에서, 상기 제조예 1에서 제조된 화학식 1-13으로 표시되는 화합물 대신 비스(디에톡시메틸실릴프로필)-N-메틸아민을 1.63g (4.3 mmol) 투입한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하였다.In Example 1, except that 1.63 g (4.3 mmol) of bis (diethoxymethylsilylpropyl) -N-methylamine was added instead of the compound represented by Chemical Formula 1-13 prepared in Preparation Example 1, It carried out by the same method as Example 1.
비교예 3Comparative Example 3
상기 실시예 1에서, 상기 제조예 1에서 제조된 화학식 1-13로 표시되는 화합물 대신 N,N-비스(트리에톡시실릴프로필)아미노프로필-1-이미다졸을 2.30g (4.3 mmol) 투입한 것을 제외하고는, 상기 실시예 1과 동일한 방법으로 실시하였다.In Example 1, 2.30g (4.3 mmol) of N, N-bis (triethoxysilylpropyl) aminopropyl-1-imidazole was added instead of the compound represented by Chemical Formula 1-13 prepared in Preparation Example 1. Except that, it was carried out in the same manner as in Example 1.
실험예Experimental Example
실험예 1Experimental Example 1
상기 실시예 및 비교예에서 제조된 각 변성 또는 미변성 공액디엔계 중합체에 대하여 각각 중량평균분자량(Mw, X103g/mol), 수평균분자량(Mn, X103g/mol), 분자량 분포(MWD) 및 무늬 점도(MV)를 각각 측정하였다. 결과를 하기 표 1에 나타내었다.The weight average molecular weight (Mw, X10 3 g / mol), number average molecular weight (Mn, X10 3 g / mol), and molecular weight distribution of each modified or unmodified conjugated diene-based polymer prepared in Examples and Comparative Examples, respectively ( MWD) and pattern viscosity (MV) were measured, respectively. The results are shown in Table 1 below.
상기 중량평균분자량(Mw), 수평균분자량(Mn)은 GPC(Gel permeation chromatohraph) 분석을 통하여 측정하였으며, 분자량 분포(MWD, Mw/Mn)는 측정된 상기 각 분자량으로부터 계산하여 얻었다. 구체적으로, 상기 GPC는 PLgel Olexis(Polymer Laboratories 社) 컬럼 두 자루와 PLgel mixed-C(Polymer Laboratories 社) 컬럼 한 자루를 조합하여 사용하고, 새로 교체한 컬럼은 모두 mixed bed 타입의 컬럼을 사용하였으며, 분자량 계산시 GPC 기준물질(Standard material)은 PS(polystyrene)을 사용하여 실시하였다.The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatohraph (GPC) analysis, and the molecular weight distribution (MWD, Mw / Mn) was calculated from the respective measured molecular weights. Specifically, the GPC used a combination of two PLgel Olexis (Polymer Laboratories Co.) column and one PLgel mixed-C (Polymer Laboratories Co.) column, all of the newly replaced column was a mixed bed column, The GPC standard material was calculated using polystyrene (PS) when calculating the molecular weight.
상기 무늬 점도(MV, (ML1+4, @100℃) MU)는 MV-2000(ALPHA Technologies 社)를 이용하여 100 ℃에서 Rotor Speed 2±0.02 rpm, Large Rotorfmf 사용하여 측정하였으며, 이때 사용된 시료는 실온(23±3 ℃)에서 30분 이상 방치한 후 27±3 g을 채취하여 다이 캐비티 내부에 채워 놓고 Platen을 작동시켜 4분 동안 측정하였다.The pattern viscosity (MV, (ML1 + 4, @ 100 ℃) MU) was measured using a Rotor Speed 2 ± 0.02 rpm, Large Rotorfmf at 100 ℃ using MV-2000 (ALPHA Technologies, Inc.), the sample used After leaving at room temperature (23 ± 3 ℃) for more than 30 minutes, 27 ± 3 g was collected and filled into the die cavity, and platen was operated for 4 minutes.
| 구분division | Mw(X103g/mol)Mw (X10 3 g / mol) | Mn(X103g/mol)Mn (X10 3 g / mol) | MWDMWD | MVMV |
| 실시예 1Example 1 | 566566 | 391391 | 1.41.4 | 9090 |
| 실시예 2Example 2 | 456456 | 317317 | 1.41.4 | 6969 |
| 실시예 3Example 3 | 566566 | 392392 | 1.41.4 | 9090 |
| 실시예 4Example 4 | 455455 | 315315 | 1.41.4 | 6868 |
| 실시예 5Example 5 | 559559 | 388388 | 1.41.4 | 9191 |
| 실시예 6Example 6 | 459459 | 317317 | 1.41.4 | 6969 |
| 비교예 1Comparative Example 1 | 258258 | 239239 | 1.11.1 | 4343 |
| 비교예 2Comparative Example 2 | 390390 | 301301 | 1.31.3 | 6868 |
| 비교예 3Comparative Example 3 | 553553 | 384384 | 1.41.4 | 8888 |
실험예 2Experimental Example 2
상기 실시예 및 비교예에서 제조된 각 변성 또는 미변성 공액디엔계 공중합체를 포함하는 고무 조성물 및 이로부터 제조된 성형품의 물성을 비교분석하기 위하여, 인장특성, 내마모성 및 젖은 노면 저항성을 각각 측정하여 그 결과를 하기 표 3에 나타내었다.In order to compare and analyze the physical properties of the rubber composition and the molded article prepared from each modified or unmodified conjugated diene copolymer prepared in Examples and Comparative Examples, by measuring the tensile properties, wear resistance and wet road resistance The results are shown in Table 3 below.
1) 고무 시편의 제조1) Preparation of Rubber Specimen
실시예 및 비교예의 각 변성 또는 미변성 스티렌-부타디엔 공중합체를 원료 고무로 하여 하기 표 2에 나타낸 배합 조건으로 배합하였다. 표 2 내의 원료는 고무 100 중량부 기준에 대한 각 중량부이다.Each modified or unmodified styrene-butadiene copolymer of Examples and Comparative Examples was blended under the blending conditions shown in Table 2 below as a raw material rubber. The raw materials in Table 2 are each parts by weight based on 100 parts by weight of rubber.
| 구분division | 원료Raw material | 함량(중량부)Content (parts by weight) |
| 제1단 혼련1st stage kneading | 고무Rubber | 100100 |
| 실리카Silica | 7070 | |
| 커플링제Coupling agent | 11.211.2 | |
| 공정유Process oil | 2525 | |
| 아연화제Galvanizing agent | 33 | |
| 스테아르산Stearic acid | 22 | |
| 산화 방지제Antioxidant | 22 | |
| 노화 방지제Anti aging agents | 22 | |
| 왁스Wax | 1One | |
| 고무촉진제Rubber accelerator | 1.751.75 | |
| 제2단 혼련2nd stage kneading | 황sulfur | 1.51.5 |
| 가황촉진제Vulcanization accelerator | 22 |
구체적으로 상기 고무시편은 제1단 혼련 및 제2단 혼련을 통해 혼련된다. 제1단 혼련에서는 온도제어장치를 부속한 반바리 믹서를 사용하여 원료 고무(스티렌-부타디엔 공중합체), 충진제, 유기실란 커플링제, 공정유, 아연화, 스테아르산, 산화 방지제, 노화 방지제, 왁스 및 촉진제를 혼련하였다. 이 때, 혼련기의 온도를 제어하고, 150 ℃의 배출온도에서 1차 배합물을 얻었다. 제2단 혼련에서는 상기 1차 배합물을 실온까지 냉각한 후, 혼련기에 1차 배합물, 황 및 가황촉진제를 가하고, 150 ℃에서 20분간 큐어링 공정을 거쳐 고무시편을 제조하였다.Specifically, the rubber specimen is kneaded through the first stage kneading and the second stage kneading. In the first stage kneading, a half-barrier mixer equipped with a temperature control device was used to prepare raw rubber (styrene-butadiene copolymer), filler, organosilane coupling agent, process oil, zincated, stearic acid, antioxidant, antioxidant, wax and The accelerator was kneaded. At this time, the temperature of the kneader was controlled to obtain a primary blend at a discharge temperature of 150 ° C. In the second stage kneading, after cooling the first blend to room temperature, the first blend, sulfur and a vulcanization accelerator were added to the kneader, and a rubber specimen was prepared by a curing process at 150 ° C. for 20 minutes.
2) 인장특성2) tensile properties
인장특성은 ASTM 412의 인장시험법에 준하여 각 시험편을 제조하고 상기 시험편의 절단시의 인장강도 및 300% 신장시의 인장응력(300% 모듈러스)를 측정하였다. 구체적으로, 인장특성은 Universal Test Machin 4204(Instron 社) 인장 시험기를 이용하여 실온에서 50 cm/min의 속도로 측정하였다. Tensile properties were prepared in accordance with the tensile test method of ASTM 412 and measured the tensile strength at the cutting of the test piece and the tensile stress (300% modulus) at 300% elongation. Specifically, the tensile properties were measured at a rate of 50 cm / min at room temperature using a Universal Test Machin 4204 (Instron) tensile tester.
3) 내마모성3) wear resistance
상기 제조된 고무시편의 내마모성을 DIN 마모 시험기를 이용하여, 마모지가 붙여진 회전 드럼(Drum)에 10 N의 하중을 부가하고, 고무 시편을 드럼의 회전 방향의 직각 방향으로 이동시킨 후, 마모된 손실무게량을 측정하였고, 비교예 2의 손실무게량을 기준으로 지수화하여 나타내었다. 드럼의 회전 속도는 40 rpm이고, 시험 완료 시 시편의 총 이동 거리는 40 m이다. 손실무게량의 지수값이 작을수록 내마모성이 우수한 것을 나타낸다.Wear resistance of the rubber specimen prepared by using a DIN abrasion tester, a load of 10 N is applied to a rotating drum (Drum) attached to the wear paper, the rubber specimen is moved in a direction perpendicular to the rotational direction of the drum, the wear loss The weight was measured and shown as an index on the basis of the loss weight of Comparative Example 2. The rotational speed of the drum is 40 rpm, and upon completion of the test the total travel distance of the specimen is 40 m. The smaller the index value of the loss weight, the better the wear resistance.
4) 점탄성 특성4) viscoelastic properties
점탄성 특성은 동적 기계 분석기(TA 社)를 이용하여 비틀림 모드로 주파수 10 Hz, 각 측정온도(-60℃~60℃)에서 변형을 변화시켜 tan δ를 측정하였다. 페인 효과(Payne effect)는 변형 0.28% 내지 40%에서의 최소값과 최대값의 차이로 나타내었다. 저온 0 ℃ tan δ가 높은 것일수록 젖은 노면저항성이 우수하고, 고온 60℃ tan δ가 낮을수록 히스테리시스 손실이 적고, 저주행저항성(연비성)이 우수함을 나타낸다.Viscoelastic properties were measured by using a dynamic mechanical analyzer (TA Co., Ltd.) to determine the tan δ by varying the strain at a frequency of 10 Hz and each measurement temperature (-60 ° C. to 60 ° C.) in a torsion mode. Payne effect is expressed as the difference between the minimum and maximum values at 0.28% to 40% strain. The higher the low temperature 0 [deg.] C tan δ, the better the wet road surface resistance. The lower the high temperature 60 [deg.] C tan δ, the lower the hysteresis loss, and the lower the running resistance (fuelability).
5) 가류특성5) Vulcanization Characteristics
가류특성(t90)은 MDF(moving die rheometer)를 이용하여 150 ℃에서 50분 동안의 가류 시, MH(최대토크) 값 및 90 % 가류될 때까지의 소요시간(t90)을 측정하였다.The vulcanization characteristics (t90) were measured using MDF (moving die rheometer) for 50 minutes of vulcanization at 150 ° C., the MH (maximum torque) value and the time required until 90% quenching (t90).
| 구분division | 인장특성Tensile Properties | 내마모성Wear resistance | 점탄성Viscoelastic | 가류특성Vulcanization Characteristics | ||
| 300 % 모듈러스(kgf/cm2)300% modulus (kgf / cm 2 ) | 인장강도 (kgf/cm2)Tensile Strength (kgf / cm 2 ) | IndexIndex | tan δ@0℃tan δ @ 0 ℃ | tan δ@60℃tan δ @ 60 ℃ | t90(분)t90 (minutes) | |
| 실시예 1Example 1 | 155155 | 177177 | 9999 | 1.1231.123 | 0.0940.094 | 21.521.5 |
| 실시예 2Example 2 | 154154 | 175175 | 9999 | 1.1261.126 | 0.0990.099 | 21.621.6 |
| 실시예 3Example 3 | 155155 | 177177 | 100100 | 1.1351.135 | 0.0890.089 | 21.921.9 |
| 실시예 4Example 4 | 156156 | 176176 | 100100 | 1.1391.139 | 0.0910.091 | 21.821.8 |
| 실시예 5Example 5 | 155155 | 176176 | 101101 | 1.1221.122 | 0.0950.095 | 21.721.7 |
| 실시예 6Example 6 | 154154 | 177177 | 9999 | 1.1251.125 | 0.1000.100 | 21.521.5 |
| 비교예 1Comparative Example 1 | 121121 | 148148 | 9090 | 0.8010.801 | 0.1310.131 | 22.022.0 |
| 비교예 2Comparative Example 2 | 151151 | 177177 | 100100 | 0.9980.998 | 0.1080.108 | 21.721.7 |
| 비교예 3Comparative Example 3 | 156156 | 174174 | 9999 | 1.0031.003 | 0.1090.109 | 21.921.9 |
상기 표 3에 나타낸 바와 같이, 본 발명에 따른 변성제로 변성된 실시예의 변성 공액디엔계 중합체는 인장특성, 내마모성, 점탄성 특성 및 가류특성이 뛰어난 것을 확인할 수 있었다.As shown in Table 3, it was confirmed that the modified conjugated diene-based polymer of the modified example according to the present invention is excellent in tensile properties, wear resistance, viscoelastic properties and vulcanization properties.
특히, 본 발명에 따른 변성제로 변성된 실시예의 변성 공액디엔계 중합체는 변성제 내에 니트로기를 함유함으로써, 무기 충진제와 배합 시 수소 결합으로 인해 분산력 매우 우수하여, 미변성 공액디엔계 중합체인 비교예 1에 비해, 인장특성, 내마모성 및 점탄성 특성이 현저히 개선되었고, 나아가 아민기, 이미다졸기 등의 질소 원자를 함유하되, 니트로기를 포함하지 않는 알콕시 실란계 변성제를 통해 변성을 실시한 비교예 2 및 3의 경우와 비교할 때에도, 점탄성 특성이 현저히 개선되어, 구름저항, 젖은 노면 저항성 및 저주행저항성이 매우 뛰어난 것을 확인할 수 있었다.In particular, the modified conjugated diene polymer of the embodiment modified with the modifying agent according to the present invention contains nitro groups in the modifying agent, so that the dispersibility is very excellent due to hydrogen bonding when combined with the inorganic filler, in Comparative Example 1 is an unmodified conjugated diene polymer Compared to Comparative Examples 2 and 3, the tensile, abrasion and viscoelastic properties were remarkably improved and further modified with an alkoxy silane-based modifier containing nitrogen atoms such as amine groups and imidazole groups, but not containing nitro groups. Compared with, the viscoelastic properties were remarkably improved, and it was confirmed that rolling resistance, wet road resistance, and low running resistance were very excellent.
Claims (20)
- 하기 화학식 1로 표시되는 화합물을 포함하는 변성제:Modifiers comprising a compound represented by the following formula (1):[화학식 1][Formula 1]
상기 화학식 1에서,In Chemical Formula 1,R1은 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기이고,R 1 is deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkanyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number 1 A heteroalkyl group of 30 to 30, a substituted or unsubstituted cycloalkyl group of 5 to 30 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic group of 3 to 30 carbon atoms,R2는 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기, 또는 하기 화학식 1a로 표시되는 작용기이며,R 2 is deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon atoms Alkynyl group of 2 to 30, substituted or unsubstituted alkoxy group of 1 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group of 5 to 30 carbon atoms, substituted or unsubstituted An aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, or a functional group represented by the following Formula 1a,R3는 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기, 또는 하기 화학식 1b로 표시되는 작용기이고,R 3 is deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon atom Alkynyl group of 2 to 30, substituted or unsubstituted alkoxy group of 1 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group of 5 to 30 carbon atoms, substituted or unsubstituted An aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, or a functional group represented by the following Formula 1b,R1, R2 및 R3가 치환된 알킬기, 알킬실릴기, 알케닐기, 알카이닐기, 알콕시기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기인 경우, 치환된 알킬기, 알킬실릴기, 알케닐기, 알카이닐기, 알콕시기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기의 치환기는 중수소, 할로겐, 히드록시기, 니트로기, 시아노기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 30의 알카이닐기, 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 탄소수 5 내지 30의 시클로알킬기, 탄소수 6 내지 30의 아릴기, 및 탄소수 3 내지 30의 헤테로고리기로 이루어진 군으로부터 선택된 1종 이상이며,When R 1 , R 2 and R 3 are substituted alkyl, alkylsilyl, alkenyl, alkynyl, alkoxy, heteroalkyl, cycloalkyl, aryl or heterocyclic groups, substituted alkyl, alkylsilyl, alke Substituents for the alkyl group, the alkynyl group, the alkoxy group, the heteroalkyl group, the cycloalkyl group, the aryl group, or the heterocyclic group are deuterium, halogen, hydroxy group, nitro group, cyano group, alkyl group having 1 to 30 carbon atoms, alkylsilyl having 1 to 30 carbon atoms A group, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, and 6 to 6 carbon atoms At least one selected from the group consisting of an aryl group of 30 and a heterocyclic group having 3 to 30 carbon atoms,X는 N, O 및 S 원자로 이루어진 군으로부터 선택된 1종의 헤테로 원자이고,X is one hetero atom selected from the group consisting of N, O and S atoms,X가 N인 경우 R2 및 R3 중 반드시 하나 이상은 하기 화학식 1a 또는 하기 화학식 1b로 표시되는 작용기이며,When X is N, at least one of R 2 and R 3 is a functional group represented by the following Formula 1a or 1b,X가 O 또는 S인 경우 R2 및 R3 중 하나의 작용기만 존재하되, R2가 존재하는 경우 R2는 하기 화학식 1a로 표시되는 작용기이고, R3가 존재하는 경우 R3는 하기 화학식 1b로 표시되는 작용기이며,But X is O or there is only S in case R 2 and R 3 one of the functional groups of, and R 2 is the functional group represented by the following formula (1a) if R 2 is present, when the R 3 present R 3 has the formula 1b Is a functional group represented by[화학식 1a][Formula 1a]
[화학식 1b][Formula 1b]
상기 화학식 1a 및 1b에서,In Chemical Formulas 1a and 1b,R4 및 R7은 각각 독립적으로 탄소수 1 내지 10의 알킬렌기이고,R 4 and R 7 are each independently an alkylene group having 1 to 10 carbon atoms,R5, R6, R8 및 R9는 각각 독립적으로 탄소수 1 내지 30의 알킬기, 탄소수 5 내지 30의 시클로알킬기, 또는 탄소수 6 내지 30의 아릴기이며,R 5 , R 6 , R 8 and R 9 are each independently an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,m 및 n은 각각 독립적으로 0 내지 3에서 선택된 정수이되, m+n ≥ 1이고,m and n are each independently an integer selected from 0 to 3, wherein m + n ≥ 1,상기 화학식 1a 또는 1b 중 하나의 작용기만 존재하는 경우, m 또는 n은 각각 독립적으로 1 내지 3에서 선택된 정수이다.When only one functional group of Formula 1a or 1b is present, m or n are each independently an integer selected from 1 to 3. - 제1항에 있어서,The method of claim 1,상기 화학식 1에서,In Chemical Formula 1,R1은 치환 또는 비치환된 탄소수 1 내지 20의 알킬기, 치환 또는 비치환된 탄소수 2 내지 20의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 20의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 20의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 20의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 20의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 20의 헤테로고리기이고,R 1 is a substituted or unsubstituted C1-C20 alkyl group, a substituted or unsubstituted C2-C20 alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, a substituted or unsubstituted C1-C20 Heteroalkyl group, a substituted or unsubstituted cycloalkyl group having 5 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms,R2는 상기 화학식 1a로 표시되는 작용기이며,R 2 is a functional group represented by Formula 1a,R3는 상기 화학식 1b로 표시되는 작용기이고,R 3 is a functional group represented by Formula 1b,R1이 치환된 알킬기, 알케닐기, 알카이닐기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기인 경우, 치환된 알킬기, 알케닐기, 알카이닐기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기의 치환기는 중수소, 할로겐, 히드록시기, 니트로기, 시아노기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 30의 알카이닐기, 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 탄소수 5 내지 30의 시클로알킬기, 탄소수 6 내지 30의 아릴기, 및 탄소수 3 내지 30의 헤테로고리기로 이루어진 군으로부터 선택된 1종 이상이며,When R 1 is a substituted alkyl group, alkenyl group, alkynyl group, heteroalkyl group, cycloalkyl group, aryl group, or heterocyclic group, substituted alkyl group, alkenyl group, alkynyl group, heteroalkyl group, cycloalkyl group, aryl group, or heterocyclic ring The substituent of the group is deuterium, halogen, hydroxy group, nitro group, cyano group, alkyl group of 1 to 30 carbon atoms, alkylsilyl group of 1 to 30 carbon atoms, alkenyl group of 2 to 30 carbon atoms, alkynyl group of 2 to 30 carbon atoms, 1 carbon atom 1 type selected from the group consisting of an alkoxy group having 30 to 30, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, and a heterocyclic group having 3 to 30 carbon atoms That's it,X는 N, O 및 S 원자로 이루어진 군으로부터 선택된 1종의 헤테로 원자이고,X is one hetero atom selected from the group consisting of N, O and S atoms,X가 O 또는 S인 경우 R2 및 R3 중 하나의 작용기만 존재하며,When X is O or S, only one functional group of R 2 and R 3 is present,상기 화학식 1a 및 1b에서,In Chemical Formulas 1a and 1b,R4 및 R7은 각각 독립적으로 탄소수 1 내지 5의 알킬렌기이고,R 4 and R 7 are each independently an alkylene group having 1 to 5 carbon atoms,R5, R6, R8 및 R9는 각각 독립적으로 탄소수 1 내지 20의 알킬기, 탄소수 5 내지 20의 시클로알킬기, 또는 탄소수 6 내지 20의 아릴기이며,R 5 , R 6 , R 8 and R 9 are each independently an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms,m 및 n은 각각 독립적으로 1 내지 3에서 선택된 정수인 변성제.m and n are each independently an integer selected from 1-3.
- 제1항에 있어서,The method of claim 1,상기 화학식 1로 표시되는 화합물은 하기 화학식 1-1 내지 1-12로 표시되는 화합물로 이루어진 군으로부터 선택된 1종인 변성제.The compound represented by Chemical Formula 1 is a denaturant selected from the group consisting of compounds represented by the following Chemical Formulas 1-1 to 1-12.[화학식 1-1][Formula 1-1]
[화학식 1-2][Formula 1-2]
[화학식 1-3][Formula 1-3]
[화학식 1-4][Formula 1-4]
[화학식 1-5][Formula 1-5]
[화학식 1-6][Formula 1-6]
[화학식 1-7][Formula 1-7]
[화학식 1-8][Formula 1-8]
[화학식 1-9][Formula 1-9]
[화학식 1-10][Formula 1-10]
[화학식 1-11][Formula 1-11]
[화학식 1-12][Formula 1-12]
상기 화학식 1-1 내지 1-12에서, R13은 각각 독립적으로 1 내지 20의 알킬기이다.In Formulas 1-1 to 1-12, each R 13 independently represents an alkyl group of 1 to 20. - 제3항에 있어서,The method of claim 3,상기 R13은 각각 독립적으로 에틸기 또는 메틸기인 것을 특징으로 하는 변성제.The R 13 are each independently an ethyl group or a methyl group.
- 하기 화학식 2로 표시되는 화합물과 하기 화학식 3으로 표시되는 화합물을 반응시키는 단계를 포함하는 변성제 제조방법:A method for preparing a denaturant comprising reacting a compound represented by Formula 2 with a compound represented by Formula 3 below:[화학식 2][Formula 2]
[화학식 3][Formula 3]
상기 화학식 2 및 3에서,In Chemical Formulas 2 and 3,R1은 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기이고,R 1 is deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkanyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number 1 A heteroalkyl group of 30 to 30, a substituted or unsubstituted cycloalkyl group of 5 to 30 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic group of 3 to 30 carbon atoms,R2는 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기, 또는 하기 화학식 1a로 표시되는 작용기이며,R 2 is deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon atoms Alkynyl group of 2 to 30, substituted or unsubstituted alkoxy group of 1 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group of 5 to 30 carbon atoms, substituted or unsubstituted An aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, or a functional group represented by the following Formula 1a,R3는 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기, 또는 하기 화학식 1b로 표시되는 작용기이고,R 3 is deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon atom Alkynyl group of 2 to 30, substituted or unsubstituted alkoxy group of 1 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group of 5 to 30 carbon atoms, substituted or unsubstituted An aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, or a functional group represented by the following Formula 1b,R1, R2 및 R3가 치환된 알킬기, 알킬실릴기, 알케닐기, 알카이닐기, 알콕시기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기인 경우, 치환된 알킬기, 알킬실릴기, 알케닐기, 알카이닐기, 알콕시기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기의 치환기는 중수소, 할로겐, 히드록시기, 니트로기, 시아노기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 30의 알카이닐기, 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 탄소수 5 내지 30의 시클로알킬기, 탄소수 6 내지 30의 아릴기, 및 탄소수 3 내지 30의 헤테로고리기로 이루어진 군으로부터 선택된 1종 이상이며,When R 1 , R 2 and R 3 are substituted alkyl, alkylsilyl, alkenyl, alkynyl, alkoxy, heteroalkyl, cycloalkyl, aryl or heterocyclic groups, substituted alkyl, alkylsilyl, alke Substituents for the alkyl group, the alkynyl group, the alkoxy group, the heteroalkyl group, the cycloalkyl group, the aryl group, or the heterocyclic group are deuterium, halogen, hydroxy group, nitro group, cyano group, alkyl group having 1 to 30 carbon atoms, alkylsilyl having 1 to 30 carbon atoms A group, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, and 6 to 6 carbon atoms At least one selected from the group consisting of an aryl group of 30 and a heterocyclic group having 3 to 30 carbon atoms,X는 N, O 및 S 원자로 이루어진 군으로부터 선택된 1종의 헤테로 원자이고,X is one hetero atom selected from the group consisting of N, O and S atoms,X가 N인 경우 R2 및 R3 중 반드시 하나 이상은 하기 화학식 1a 또는 하기 화학식 1b로 표시되는 작용기이며,When X is N, at least one of R 2 and R 3 is a functional group represented by the following Formula 1a or 1b,X가 O 또는 S인 경우 R2 및 R3 중 하나의 작용기만 존재하되, R2가 존재하는 경우 R2는 하기 화학식 1a로 표시되는 작용기이고, R3가 존재하는 경우 R3는 하기 화학식 1b로 표시되는 작용기이며,But X is O or there is only S in case R 2 and R 3 one of the functional groups of, and R 2 is the functional group represented by the following formula (1a) if R 2 is present, when the R 3 present R 3 has the formula 1b Is a functional group represented by[화학식 1a][Formula 1a]
[화학식 1b][Formula 1b]
상기 화학식 1a 및 1b에서,In Chemical Formulas 1a and 1b,R4 및 R7은 각각 독립적으로 탄소수 1 내지 10의 알킬렌기이고,R 4 and R 7 are each independently an alkylene group having 1 to 10 carbon atoms,R5, R6, R8 및 R9는 각각 독립적으로 탄소수 1 내지 30의 알킬기, 탄소수 5 내지 30의 시클로알킬기, 또는 탄소수 6 내지 30의 아릴기이며,R 5 , R 6 , R 8 and R 9 are each independently an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,m 및 n은 각각 독립적으로 0 내지 3에서 선택된 정수이되, m+n ≥ 1이고,m and n are each independently an integer selected from 0 to 3, wherein m + n ≥ 1,상기 화학식 1a 또는 1b 중 하나의 작용기만 존재하는 경우, m 또는 n은 각각 독립적으로 1 내지 3에서 선택된 정수이다.When only one functional group of Formula 1a or 1b is present, m or n are each independently an integer selected from 1 to 3. - 제5항에 있어서,The method of claim 5,상기 화학식 2로 표시되는 화합물과 상기 화학식 3으로 표시되는 화합물의 몰 비(화학식 2:화학식 3)는 1:0.5 내지 1:2인 변성제 제조방법.A molar ratio of the compound represented by Chemical Formula 2 and the compound represented by Chemical Formula 3 (Formula 2: Formula 3) is 1: 0.5 to 1: 2.
- 제5항에 있어서,The method of claim 5,상기 반응은 10 ℃ 내지 90 ℃의 반응 온도에서 실시되는 것인 변성제 제조방법.The reaction is a method of producing a denaturant is carried out at a reaction temperature of 10 ℃ to 90 ℃.
- 제5항에 있어서,The method of claim 5,상기 반응은 염기성 화합물의 존재 하에 실시되는 것인 변성제 제조방법.Wherein the reaction is carried out in the presence of a basic compound.
- 제8항에 있어서,The method of claim 8,상기 염기성 화합물은 메틸아민(methylamine), 디메틸아민(dimethylamine), 트리에틸아민(triethylamine), 테트라메틸에틸렌디아민(tetramethylethylenediamine), 리튬디이소프로필아마이드(lithiumdiisopropylamide), 1,8-디아자비시클로운데-7-센(1,8-diazabicycloundec-7-ene), 2,6-디-t-부틸피리딘(2,6-di-tert-butylpyridine), 리튬테트라메틸피페리딘(lithiumtetramethylpiperidine)으로 이루어진 군으로부터 선택된 1종 이상인 변성제 제조방법.The basic compound is methylamine (dimethylamine), dimethylamine (dimethylamine), triethylamine (triethylamine), tetramethylethylenediamine, lithium diisopropylamide, 1,8- diazabicyclo unde-7 Selected from the group consisting of 1,8-diazabicycloundec-7-ene, 2,6-di-tert-butylpyridine, and lithiumtetramethylpiperidine 1 or more types of denaturant production method.
- 공액디엔계 단량체 유래 반복 단위를 포함하고, 일측 말단에 하기 화학식 1로 표시되는 화합물을 포함하는 변성제 유래 작용기를 포함하는 변성 공액디엔계 중합체:Modified conjugated diene-based polymer comprising a repeating unit derived from a conjugated diene-based monomer, comprising a modifier-derived functional group comprising a compound represented by the following formula (1) at one end:[화학식 1][Formula 1]
상기 화학식 1에서,In Chemical Formula 1,R1은 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기이고,R 1 is deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkanyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number 1 A heteroalkyl group of 30 to 30, a substituted or unsubstituted cycloalkyl group of 5 to 30 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic group of 3 to 30 carbon atoms,R2는 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기, 또는 하기 화학식 1a로 표시되는 작용기이며,R 2 is deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon atoms Alkynyl group of 2 to 30, substituted or unsubstituted alkoxy group of 1 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group of 5 to 30 carbon atoms, substituted or unsubstituted An aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, or a functional group represented by the following Formula 1a,R3는 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기, 또는 하기 화학식 1b로 표시되는 작용기이고,R 3 is deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon atom Alkynyl group of 2 to 30, substituted or unsubstituted alkoxy group of 1 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group of 5 to 30 carbon atoms, substituted or unsubstituted An aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, or a functional group represented by the following Formula 1b,R1, R2 및 R3가 치환된 알킬기, 알킬실릴기, 알케닐기, 알카이닐기, 알콕시기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기인 경우, 치환된 알킬기, 알킬실릴기, 알케닐기, 알카이닐기, 알콕시기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기의 치환기는 중수소, 할로겐, 히드록시기, 니트로기, 시아노기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 30의 알카이닐기, 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 탄소수 5 내지 30의 시클로알킬기, 탄소수 6 내지 30의 아릴기, 및 탄소수 3 내지 30의 헤테로고리기로 이루어진 군으로부터 선택된 1종 이상이며,When R 1 , R 2 and R 3 are substituted alkyl, alkylsilyl, alkenyl, alkynyl, alkoxy, heteroalkyl, cycloalkyl, aryl or heterocyclic groups, substituted alkyl, alkylsilyl, alke Substituents for the alkyl group, the alkynyl group, the alkoxy group, the heteroalkyl group, the cycloalkyl group, the aryl group, or the heterocyclic group are deuterium, halogen, hydroxy group, nitro group, cyano group, alkyl group having 1 to 30 carbon atoms, alkylsilyl having 1 to 30 carbon atoms A group, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, and 6 to 6 carbon atoms At least one selected from the group consisting of an aryl group of 30 and a heterocyclic group having 3 to 30 carbon atoms,X는 N, O 및 S 원자로 이루어진 군으로부터 선택된 1종의 헤테로 원자이고,X is one hetero atom selected from the group consisting of N, O and S atoms,X가 N인 경우 R2 및 R3 중 반드시 하나 이상은 하기 화학식 1a 또는 하기 화학식 1b로 표시되는 작용기이며,When X is N, at least one of R 2 and R 3 is a functional group represented by the following Formula 1a or 1b,X가 O 또는 S인 경우 R2 및 R3 중 하나의 작용기만 존재하되, R2가 존재하는 경우 R2는 하기 화학식 1a로 표시되는 작용기이고, R3가 존재하는 경우 R3는 하기 화학식 1b로 표시되는 작용기이며,But X is O or there is only S in case R 2 and R 3 one of the functional groups of, and R 2 is the functional group represented by the following formula (1a) if R 2 is present, when the R 3 present R 3 has the formula 1b Is a functional group represented by[화학식 1a][Formula 1a]
[화학식 1b][Formula 1b]
상기 화학식 1a 및 1b에서,In Chemical Formulas 1a and 1b,R4 및 R7은 각각 독립적으로 탄소수 1 내지 10의 알킬렌기이고,R 4 and R 7 are each independently an alkylene group having 1 to 10 carbon atoms,R5, R6, R8 및 R9는 각각 독립적으로 탄소수 1 내지 30의 알킬기, 탄소수 5 내지 30의 시클로알킬기, 또는 탄소수 6 내지 30의 아릴기이며,R 5 , R 6 , R 8 and R 9 are each independently an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,m 및 n은 각각 독립적으로 0 내지 3에서 선택된 정수이되, m+n ≥ 1이고,m and n are each independently an integer selected from 0 to 3, wherein m + n ≥ 1,상기 화학식 1a 또는 1b 중 하나의 작용기만 존재하는 경우, m 또는 n은 각각 독립적으로 1 내지 3에서 선택된 정수이다.When only one functional group of Formula 1a or 1b is present, m or n are each independently an integer selected from 1 to 3. - 공액디엔계 단량체 유래 반복 단위를 포함하고, 일측 말단에 하기 화학식 1로 표시되는 화합물을 포함하는 변성제 유래 작용기를 포함하며, 타측 말단에 하기 화학식 4로 표시되는 변성 개시제 유래 작용기를 포함하는 변성 공액디엔계 중합체:A modified conjugated diene comprising a conjugated diene-based monomer-derived repeating unit, a denaturant-derived functional group containing a compound represented by the following formula (1) at one end, and a modified initiator-derived functional group represented by the following formula (4) at the other end System polymers:[화학식 1][Formula 1]
상기 화학식 1에서,In Chemical Formula 1,R1은 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기이고,R 1 is deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkanyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number 1 A heteroalkyl group of 30 to 30, a substituted or unsubstituted cycloalkyl group of 5 to 30 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic group of 3 to 30 carbon atoms,R2는 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기, 또는 하기 화학식 1a로 표시되는 작용기이며,R 2 is deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon atoms Alkynyl group of 2 to 30, substituted or unsubstituted alkoxy group of 1 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group of 5 to 30 carbon atoms, substituted or unsubstituted An aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, or a functional group represented by the following Formula 1a,R3는 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기, 또는 하기 화학식 1b로 표시되는 작용기이고,R 3 is deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon atom Alkynyl group of 2 to 30, substituted or unsubstituted alkoxy group of 1 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group of 5 to 30 carbon atoms, substituted or unsubstituted An aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, or a functional group represented by the following Formula 1b,R1, R2 및 R3가 치환된 알킬기, 알킬실릴기, 알케닐기, 알카이닐기, 알콕시기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기인 경우, 치환된 알킬기, 알킬실릴기, 알케닐기, 알카이닐기, 알콕시기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기의 치환기는 중수소, 할로겐, 히드록시기, 니트로기, 시아노기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 30의 알카이닐기, 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 탄소수 5 내지 30의 시클로알킬기, 탄소수 6 내지 30의 아릴기, 및 탄소수 3 내지 30의 헤테로고리기로 이루어진 군으로부터 선택된 1종 이상이며,When R 1 , R 2 and R 3 are substituted alkyl, alkylsilyl, alkenyl, alkynyl, alkoxy, heteroalkyl, cycloalkyl, aryl or heterocyclic groups, substituted alkyl, alkylsilyl, alke Substituents for the alkyl group, the alkynyl group, the alkoxy group, the heteroalkyl group, the cycloalkyl group, the aryl group, or the heterocyclic group are deuterium, halogen, hydroxy group, nitro group, cyano group, alkyl group having 1 to 30 carbon atoms, alkylsilyl having 1 to 30 carbon atoms A group, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, and 6 to 6 carbon atoms At least one selected from the group consisting of an aryl group of 30 and a heterocyclic group having 3 to 30 carbon atoms,X는 N, O 및 S 원자로 이루어진 군으로부터 선택된 1종의 헤테로 원자이고,X is one hetero atom selected from the group consisting of N, O and S atoms,X가 N인 경우 R2 및 R3 중 반드시 하나 이상은 하기 화학식 1a 또는 하기 화학식 1b로 표시되는 작용기이며,When X is N, at least one of R 2 and R 3 is a functional group represented by the following Formula 1a or 1b,X가 O 또는 S인 경우 R2 및 R3 중 하나의 작용기만 존재하되, R2가 존재하는 경우 R2는 하기 화학식 1a로 표시되는 작용기이고, R3가 존재하는 경우 R3는 하기 화학식 1b로 표시되는 작용기이며,But X is O or there is only S in case R 2 and R 3 one of the functional groups of, and R 2 is the functional group represented by the following formula (1a) if R 2 is present, when the R 3 present R 3 has the formula 1b Is a functional group represented by[화학식 1a][Formula 1a]
[화학식 1b][Formula 1b]
상기 화학식 1a 및 1b에서,In Chemical Formulas 1a and 1b,R4 및 R7은 각각 독립적으로 탄소수 1 내지 10의 알킬렌기이고,R 4 and R 7 are each independently an alkylene group having 1 to 10 carbon atoms,R5, R6, R8 및 R9는 각각 독립적으로 탄소수 1 내지 30의 알킬기, 탄소수 5 내지 30의 시클로알킬기, 또는 탄소수 6 내지 30의 아릴기이며,R 5 , R 6 , R 8 and R 9 are each independently an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,m 및 n은 각각 독립적으로 0 내지 3에서 선택된 정수이되, m+n ≥ 1이고,m and n are each independently an integer selected from 0 to 3, wherein m + n ≥ 1,상기 화학식 1a 또는 1b 중 하나의 작용기만 존재하는 경우, m 또는 n은 각각 독립적으로 1 내지 3에서 선택된 정수이며,When only one functional group of Formula 1a or 1b is present, m or n are each independently an integer selected from 1 to 3,[화학식 4][Formula 4]
상기 화학식 4에서,In Chemical Formula 4,R10 및 R11은 각각 독립적으로 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 시클로알킬기 및 탄소수 5 내지 20의 아르알킬기로 이루어진 군으로부터 선택된 1종이거나, R10 및 R11이 서로 결합하여 인접한 N 원자와 함께 탄소수 5 내지 20의 포화 또는 불포화의 환상 구조를 형성하고, 상기 R10 및 R11이 환상 구조를 형성하는 경우, 분지 구조를 가질 수 있고,R 10 and R 11 are each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aralkyl group having 5 to 20 carbon atoms, or R 10 and R 11 are bonded to each other When together with the N atom to form a saturated or unsaturated cyclic structure of 5 to 20 carbon atoms, and when R 10 and R 11 form a cyclic structure, it may have a branched structure,R12는 단일 결합, 탄소수 1 내지 20의 알킬렌기, 또는 하기 화학식 5 내지 7로 이루어진 군으로부터 선택된 1종의 연결기이며,R 12 is a single bond, an alkylene group having 1 to 20 carbon atoms, or one linking group selected from the group consisting of the following Chemical Formulas 5 to 7,M은 알칼리 금속이다.M is an alkali metal.[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
- 제10항 또는 제11항에 있어서,The method according to claim 10 or 11, wherein상기 변성 공액디엔계 중합체는 방향족 비닐 단량체 유래 반복 단위를 더 포함하는 것인 변성 공액디엔계 중합체.The modified conjugated diene polymer is a modified conjugated diene polymer further comprising a repeating unit derived from an aromatic vinyl monomer.
- 제10항 또는 제11항에 있어서,The method according to claim 10 or 11, wherein상기 변성 공액디엔계 중합체는 수평균 분자량(Mn)이 10,000 g/mol 내지 2,000,000 g/mol인 변성 공액디엔계 중합체.The modified conjugated diene polymer is a modified conjugated diene polymer having a number average molecular weight (Mn) of 10,000 g / mol to 2,000,000 g / mol.
- 제10항 또는 제11항에 있어서,The method according to claim 10 or 11, wherein상기 변성 공액디엔계 중합체는 분자량 분포(Mw/Mn)가 1.0 내지 8.0인 변성 공액디엔계 중합체.The modified conjugated diene polymer is a modified conjugated diene polymer having a molecular weight distribution (Mw / Mn) of 1.0 to 8.0.
- 유기 금속 화합물을 포함하는 탄화수소 용매 중에서, 공액디엔계 단량체, 또는 방향족 비닐계 단량체 및 공액디엔계 단량체를 중합하여 유기 금속이 결합된 활성 중합체를 제조하는 단계(S1); 및In the hydrocarbon solvent comprising an organometallic compound, a step of polymerizing the conjugated diene monomer, or an aromatic vinyl monomer and the conjugated diene monomer to prepare an active polymer in which the organic metal is bonded (S1); And상기 활성 중합체 및 하기 화학식 1로 표시되는 화합물을 포함하는 변성제를 반응시키는 단계(S2)를 포함하는 변성 공액디엔계 중합체 제조방법:Method of producing a modified conjugated diene-based polymer comprising the step (S2) of reacting a modifier comprising the active polymer and a compound represented by the formula (1):[화학식 1][Formula 1]
상기 화학식 1에서,In Chemical Formula 1,R1은 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기이고,R 1 is deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkanyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number 1 A heteroalkyl group of 30 to 30, a substituted or unsubstituted cycloalkyl group of 5 to 30 carbon atoms, a substituted or unsubstituted aryl group of 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic group of 3 to 30 carbon atoms,R2는 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기, 또는 하기 화학식 1a로 표시되는 작용기이며,R 2 is deuterium, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or unsubstituted carbon atoms Alkynyl group of 2 to 30, substituted or unsubstituted alkoxy group of 1 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group of 5 to 30 carbon atoms, substituted or unsubstituted An aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, or a functional group represented by the following Formula 1a,R3는 중수소, 치환 또는 비치환된 탄소수 1 내지 30의 알킬기, 치환 또는 비치환된 탄소수 1 내지 30의 알킬실릴기, 치환 또는 비치환된 탄소수 2 내지 30의 알케닐기, 치환 또는 비치환된 탄소수 2 내지 30의 알카이닐기, 치환 또는 비치환된 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 치환 또는 비치환된 탄소수 5 내지 30의 시클로알킬기, 치환 또는 비치환된 탄소수 6 내지 30의 아릴기, 또는 치환 또는 비치환된 탄소수 3 내지 30의 헤테로고리기, 또는 하기 화학식 1b로 표시되는 작용기이고,R 3 is deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon atom Alkynyl group of 2 to 30, substituted or unsubstituted alkoxy group of 1 to 30 carbon atoms, substituted or unsubstituted heteroalkyl group of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group of 5 to 30 carbon atoms, substituted or unsubstituted An aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 3 to 30 carbon atoms, or a functional group represented by the following Formula 1b,R1, R2 및 R3가 치환된 알킬기, 알킬실릴기, 알케닐기, 알카이닐기, 알콕시기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기인 경우, 치환된 알킬기, 알킬실릴기, 알케닐기, 알카이닐기, 알콕시기, 헤테로알킬기, 시클로알킬기, 아릴기, 또는 헤테로고리기의 치환기는 중수소, 할로겐, 히드록시기, 니트로기, 시아노기, 탄소수 1 내지 30의 알킬기, 탄소수 1 내지 30의 알킬실릴기, 탄소수 2 내지 30의 알케닐기, 탄소수 2 내지 30의 알카이닐기, 탄소수 1 내지 30의 알콕시기, 치환 또는 비치환된 탄소수 1 내지 30의 헤테로알킬기, 탄소수 5 내지 30의 시클로알킬기, 탄소수 6 내지 30의 아릴기, 및 탄소수 3 내지 30의 헤테로고리기로 이루어진 군으로부터 선택된 1종 이상이며,When R 1 , R 2 and R 3 are substituted alkyl, alkylsilyl, alkenyl, alkynyl, alkoxy, heteroalkyl, cycloalkyl, aryl or heterocyclic groups, substituted alkyl, alkylsilyl, alke Substituents for the alkyl group, the alkynyl group, the alkoxy group, the heteroalkyl group, the cycloalkyl group, the aryl group, or the heterocyclic group are deuterium, halogen, hydroxy group, nitro group, cyano group, alkyl group having 1 to 30 carbon atoms, alkylsilyl having 1 to 30 carbon atoms A group, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, and 6 to 6 carbon atoms At least one selected from the group consisting of an aryl group of 30 and a heterocyclic group having 3 to 30 carbon atoms,X는 N, O 및 S 원자로 이루어진 군으로부터 선택된 1종의 헤테로 원자이고,X is one hetero atom selected from the group consisting of N, O and S atoms,X가 N인 경우 R2 및 R3 중 반드시 하나 이상은 하기 화학식 1a 또는 하기 화학식 1b로 표시되는 작용기이며,When X is N, at least one of R 2 and R 3 is a functional group represented by the following Formula 1a or 1b,X가 O 또는 S인 경우 R2 및 R3 중 하나의 작용기만 존재하되, R2가 존재하는 경우 R2는 하기 화학식 1a로 표시되는 작용기이고, R3가 존재하는 경우 R3는 하기 화학식 1b로 표시되는 작용기이며,But X is O or there is only S in case R 2 and R 3 one of the functional groups of, and R 2 is the functional group represented by the following formula (1a) if R 2 is present, when the R 3 present R 3 has the formula 1b Is a functional group represented by[화학식 1a][Formula 1a]
[화학식 1b][Formula 1b]
상기 화학식 1a 및 1b에서,In Chemical Formulas 1a and 1b,R4 및 R7은 각각 독립적으로 탄소수 1 내지 10의 알킬렌기이고,R 4 and R 7 are each independently an alkylene group having 1 to 10 carbon atoms,R5, R6, R8 및 R9는 각각 독립적으로 탄소수 1 내지 30의 알킬기, 탄소수 5 내지 30의 시클로알킬기, 또는 탄소수 6 내지 30의 아릴기이며,R 5 , R 6 , R 8 and R 9 are each independently an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms,m 및 n은 각각 독립적으로 0 내지 3에서 선택된 정수이되, m+n ≥ 1이고,m and n are each independently an integer selected from 0 to 3, wherein m + n ≥ 1,상기 화학식 1a 또는 1b 중 하나의 작용기만 존재하는 경우, m 또는 n은 각각 독립적으로 1 내지 3에서 선택된 정수이다.When only one functional group of Formula 1a or 1b is present, m or n are each independently an integer selected from 1 to 3. - 제15항에 있어서,The method of claim 15,상기 유기 금속 화합물은 단량체 총 100 g을 기준으로 0.01 mmol 내지 10 mmol로 사용하는 것인 변성 공액디엔계 중합체 제조방법.The organometallic compound is a modified conjugated diene-based polymer manufacturing method of using 0.01 mmol to 10 mmol based on a total of 100 g of the monomer.
- 제15항에 있어서,The method of claim 15,상기 유기 금속 화합물은 메틸리튬, 에틸리튬, 프로필리튬, n-부틸리튬, s-부틸리튬, t-부틸리튬, 헥실리튬, n-데실리튬, t-옥틸리튬, 페닐리튬, 1-나프틸리튬, n-에이코실리튬, 4-부틸페닐리튬, 4-톨릴리튬, 사이클로헥실리튬, 3,5-디-n-헵틸사이클로헥실리튬, 4-사이클로펜틸리튬, 나프틸나트륨, 나프틸칼륨, 리튬 알콕사이드, 나트륨 알콕사이드, 칼륨 알콕사이드, 리튬 술포네이트, 나트륨 술포네이트, 칼륨 술포네이트, 리튬 아미드, 나트륨 아미드, 칼륨아미드 및 리튬 이소프로필아미드로 이루어진 군으로부터 선택된 1종 이상인 것인 변성 공액디엔계 중합체 제조방법.The organometallic compound is methyllithium, ethyllithium, propyllithium, n-butyllithium, s-butyllithium, t-butyllithium, hexyllithium, n-decyllithium, t-octylithium, phenyllithium, 1-naphthyllithium , n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl sodium, naphthyl potassium, lithium Method for producing a modified conjugated diene-based polymer which is at least one selected from the group consisting of alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, potassium amide and lithium isopropylamide. .
- 제15항에 있어서,The method of claim 15,상기 유기 금속 화합물은 하기 화학식 4로 표시되는 화합물인 변성 공액디엔계 중합체 제조방법:The organometallic compound is a modified conjugated diene-based polymer manufacturing method of the compound represented by the following formula (4):[화학식 4][Formula 4]
상기 화학식 4에서,In Chemical Formula 4,R10 및 R11은 각각 독립적으로 탄소수 1 내지 20의 알킬기, 탄소수 3 내지 20의 시클로알킬기 및 탄소수 5 내지 20의 아르알킬기로 이루어진 군으로부터 선택된 1종이거나, R10 및 R11이 서로 결합하여 인접한 N 원자와 함께 탄소수 5 내지 20의 포화 또는 불포화의 환상 구조를 형성하고, 상기 R10 및 R11이 환상 구조를 형성하는 경우, 분지 구조를 가질 수 있고,R 10 and R 11 are each independently selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, and an aralkyl group having 5 to 20 carbon atoms, or R 10 and R 11 are bonded to each other When together with the N atom to form a saturated or unsaturated cyclic structure of 5 to 20 carbon atoms, and when R 10 and R 11 form a cyclic structure, it may have a branched structure,R12는 단일 결합, 탄소수 1 내지 20의 알킬렌기, 또는 하기 화학식 5 내지 7로 이루어진 군으로부터 선택된 1종의 연결기이며,R 12 is a single bond, an alkylene group having 1 to 20 carbon atoms, or one linking group selected from the group consisting of the following Chemical Formulas 5 to 7,M은 알칼리 금속이다.M is an alkali metal.[화학식 5][Formula 5]
[화학식 6][Formula 6]
[화학식 7][Formula 7]
- 제15항에 있어서,The method of claim 15,상기 (S1) 단계의 중합은 극성 첨가제를 포함하여 실시되는 것인 변성 공액디엔계 중합체 제조방법.The polymerization of step (S1) is a modified conjugated diene-based polymer manufacturing method that is carried out including a polar additive.
- 제19항에 있어서,The method of claim 19,상기 극성 첨가제는 테트라하이드로퓨란, 디테트라하이드로퓨릴프로판, 디에틸에테르, 시클로아말에테르, 디프로필에테르, 에틸렌디메틸에테르, 에틸렌디메틸에테르, 디에틸글리콜, 디메틸에테르, 3차 부톡시에톡시에탄, 비스(3-디메틸아미노에틸)에테르, (디메틸아미노에틸)에틸에테르, 트리메틸아민, 트리에틸아민, 트리프로필아민 및 테트라메틸에틸렌디아민으로 이루어진 군으로부터 선택된 1종 이상인 변성 공액디엔계 중합체 제조방법.The polar additives include tetrahydrofuran, ditetrahydrofurylpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethyl glycol, dimethyl ether, tert-butoxyethoxyethane, bis A method for producing a modified conjugated diene polymer, which is at least one selected from the group consisting of (3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine.
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| JP2018517316A JP6778260B2 (en) | 2016-11-21 | 2017-09-05 | A modifier, a method for producing the same, and a modified conjugated diene polymer containing the same. |
| EP17837928.5A EP3348587B1 (en) | 2016-11-21 | 2017-09-05 | Modifying agent and modified conjugated diene-based polymer comprising the same |
| CN201780003064.9A CN108368195B (en) | 2016-11-21 | 2017-09-05 | Modifier, method for producing the same, and modified conjugated diene polymer containing the same |
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