WO2015056898A1 - 변성 공액 디엔계 중합체, 이의 제조방법, 및 이를 포함하는 고무 조성물 - Google Patents
변성 공액 디엔계 중합체, 이의 제조방법, 및 이를 포함하는 고무 조성물 Download PDFInfo
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- WO2015056898A1 WO2015056898A1 PCT/KR2014/008942 KR2014008942W WO2015056898A1 WO 2015056898 A1 WO2015056898 A1 WO 2015056898A1 KR 2014008942 W KR2014008942 W KR 2014008942W WO 2015056898 A1 WO2015056898 A1 WO 2015056898A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- conjugated diene
- independently
- formula
- modified conjugated
- polymer
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 164
- 150000001993 dienes Chemical class 0.000 title claims abstract description 159
- 229920001971 elastomer Polymers 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 239000005060 rubber Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 29
- 125000004432 carbon atom Chemical group C* 0.000 claims description 44
- 239000000178 monomer Substances 0.000 claims description 43
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 229920002554 vinyl polymer Polymers 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims description 20
- 150000002902 organometallic compounds Chemical class 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 125000002947 alkylene group Chemical group 0.000 claims description 13
- 239000011256 inorganic filler Substances 0.000 claims description 12
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- -1 R 23 Chemical compound 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 3
- 239000003607 modifier Substances 0.000 claims description 3
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 34
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 238000006116 polymerization reaction Methods 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 19
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 15
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Substances C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 7
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 6
- 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 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 6
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 238000004898 kneading Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000001294 propane Substances 0.000 description 5
- 239000013557 residual solvent Substances 0.000 description 5
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 0 CN(C)*N1C(*)N(C)*1 Chemical compound CN(C)*N1C(*)N(C)*1 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 2
- 239000003398 denaturant Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- VDNSZPNSUQRUMS-UHFFFAOYSA-N 1-cyclohexyl-4-ethenylbenzene Chemical compound C1=CC(C=C)=CC=C1C1CCCCC1 VDNSZPNSUQRUMS-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
- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 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
- NUNQKTCKURIZQX-UHFFFAOYSA-N 2-(2-ethoxyethoxy)-2-methylpropane Chemical compound CCOCCOC(C)(C)C NUNQKTCKURIZQX-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- CSBDTEMAXHVRBB-UHFFFAOYSA-N 2-ethoxy-n,n-dimethylethanamine Chemical compound CCOCCN(C)C CSBDTEMAXHVRBB-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
- UGWOAPBVIGCNOV-UHFFFAOYSA-N 5-ethenyldec-5-ene Chemical compound CCCCC=C(C=C)CCCC UGWOAPBVIGCNOV-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 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 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- 241000079947 Lanx Species 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
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000004450 alkenylene group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- SZAVVKVUMPLRRS-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].C[CH-]C SZAVVKVUMPLRRS-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 239000010421 standard material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
-
- 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
- C08C19/22—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
- C08C19/25—Incorporating silicon atoms into the molecule
-
- 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
Definitions
- the present invention relates to a modified conjugated diene-based polymer, a method for preparing the same, and a rubber composition including the same, wherein the modified conjugated diene-based polymer has excellent compatibility with inorganic fillers, processability, tensile strength, abrasion resistance, and wet road resistance, It relates to a preparation method thereof, and a rubber composition comprising the same.
- the tire tread was used in combination with an inorganic filler in order to reinforce the above physical properties in the conjugated diene rubber, but there was a problem in that the hysteresis loss was large or the dispersibility was inferior.
- the problem to be solved by the present invention is to provide a modified conjugated diene-based polymer excellent in compatibility with the inorganic filler and processability.
- Another object of the present invention is to provide a method for producing the modified conjugated diene polymer.
- Another object of the present invention is to provide a rubber composition excellent in exothermicity, tensile strength, wear resistance, low fuel consumption and wet road resistance, including the modified conjugated diene-based polymer.
- Another object of the present invention is to provide a rubber composition and a tire comprising the same.
- Another problem to be solved by the present invention is to provide a modifier used in the preparation of the modified conjugated diene-based polymer.
- a modified conjugated diene-based polymer represented by the following formula (1) is provided:
- R 1 , R 2 , and R 5 are each independently an alkylene group having 1 to 10 carbon atoms
- R 3 , R 4 , R 6, and R 7 are each independently an alkyl group having 1 to 10 carbon atoms
- R 8 is hydrogen or each independently an alkyl group having 1 to 10 carbon atoms
- P is a conjugated diene polymer chain
- P is a conjugated diene polymer chain
- a and c are each independently 0, 1, or 2
- b and d is each independently 1, 2, or 3
- a + b and c + d are each independently 1, 2, or 3
- A is or
- R 9 , R 10 , R 11 , and R 12 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.
- R 1 , R 2 , and R 5 are each independently an alkylene group having 1 to 10 carbon atoms
- R 3 , R 4 , R 6 and R 7 are each independently an alkyl group having 1 to 10 carbon atoms
- R 8 is hydrogen or an alkyl group having 1 to 10 carbon atoms each independently
- a and c are each independently 0, 1, or 2
- A is , or
- R 9 , R 10 , R 11 , and R 12 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.
- a modified conjugated diene-based polymer rubber composition comprising 100 parts by weight of the modified conjugated diene-based polymer, and 0.1 to 200 parts by weight of an inorganic filler.
- a modifier for use in the preparation of the modified conjugated diene-based polymer is provided.
- a tire using the modified conjugated diene-based polymer rubber composition is provided.
- a modified conjugated diene-based polymer having excellent compatibility with the inorganic filler and improved processability by using a rubber composition comprising such modified conjugated diene-based polymer, exothermic Tires with excellent rolling resistance, low tensile resistance, abrasion resistance, low fuel consumption and wet road resistance can be provided.
- Figure 1 shows the size of the tensile test piece of the rubber composition prepared according to the present invention.
- Modified conjugated diene-based polymer according to an aspect of the present invention is represented by the formula (1):
- R 1 , R 2 , and R 5 are each independently an alkylene group having 1 to 10 carbon atoms
- R 3 , R 4 , R 6, and R 7 are each independently an alkyl group having 1 to 10 carbon atoms
- R 8 is hydrogen or each independently an alkyl group having 1 to 10 carbon atoms
- P is a conjugated diene polymer chain
- a and c are each independently 0, 1, or 2
- b and d are each independently 1, 2 , Or 3
- a + b and c + d are each independently 1, 2, or 3.
- A is a divalent linking group which may be connected to both nitrogen, and is an alkylene group.
- R 9 , R 10 , R 11 , and R 12 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.
- the modified conjugated diene-based polymer may have a number average molecular weight (Mn) of 1,000 to 2,000,000 g / mol, preferably 10,000 to 1,000,000 g / mol, more preferably 100,000 to 1,000,000 g / mol.
- Mn number average molecular weight
- the modification reaction may have the best or good physical properties.
- the modified conjugated diene-based polymer may have a molecular weight distribution (Mw / Mn) of 0.5 to 10, preferably 0.5 to 5, more preferably 1 to 4.
- Mw / Mn molecular weight distribution
- mixing with inorganic particles is excellent, so that physical properties may be improved, and workability may be greatly improved.
- the modified conjugated diene-based polymer may have a vinyl content of 10% by weight or more, preferably 15% by weight or more, more preferably 20 to 70% by weight.
- the vinyl content refers to the content of the monomer having a vinyl group, or the content of 1,2-added conjugated diene monomer rather than 1,4-addition based on 100% by weight of the conjugated diene monomer.
- the glass transition temperature of the polymer is increased to not only satisfy the properties required for the tire such as running resistance and braking force when applied to the tire, but also consume fuel. Has the effect of reducing
- the conjugated diene-based polymer chain represented by P in Formula 1 may be derived from a homopolymer of conjugated diene-based monomer or a copolymer of conjugated diene-based monomer and vinyl aromatic monomer.
- the conjugated diene polymer chain is a homopolymer having an alkali metal terminal obtained by polymerizing a conjugated diene monomer or a conjugated diene monomer and a vinyl aromatic monomer in a batch or continuous process in a hydrocarbon solvent in the presence of an organoalkali metal compound.
- a copolymer may be formed by reaction with a silyl group substituted with one or more alkoxy groups.
- the conjugated diene polymer chain is conjugated diene monomer.
- the polymer chain may include 0.0001 to 50% by weight, 10 to 40% by weight, or 20 to 40% by weight of the aromatic vinylic monomer based on a total of 100% by weight of the conjugated diene monomer and the vinyl aromatic monomer.
- the polymer chain consisting of the conjugated diene monomer and the vinyl aromatic monomer may be, for example, a random polymer chain.
- the conjugated diene monomer is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene and 2-phenyl-1,3- It may be at least one selected from the group consisting of butadiene.
- the vinyl aromatic monomers are, for example, styrene, ⁇ -methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4- (p-methylphenyl) styrene, and 1 It may be at least one selected from the group consisting of -vinyl-5-hexyl naphthalene, and as another example, may be styrene or ⁇ -methylstyrene.
- the modified conjugated diene-based polymer may have a Mooney viscosity of 40 or more, preferably 40 to 100, more preferably 45 to 90.
- Mooney viscosity has such a range, a modified conjugated diene polymer having excellent workability, compatibility, exothermicity, tensile strength, abrasion resistance, low fuel efficiency and wet road surface resistance can be prepared.
- Modified conjugated diene-based polymer according to an embodiment of the present invention may be represented by the following formula (2) or (3):
- R 15 , R 16 , R 18 , R 19 , R 22 , R 23 , R 25 , and R 26 are each independently an alkyl group having 1 to 5 carbon atoms
- R 13 , R 14 , R 17 , R 20 , R 21 , and R 24 are each independently an alkylene group having 1 to 5 carbon atoms
- P is a conjugated diene polymer chain
- a and c are each independently 0, 1, or 2
- b And d are each independently 1, 2, or 3
- a + b and c + d are each independently 1, 2, or 3.
- modified conjugated diene-based polymer may be represented by the following formula (4) or (5):
- P is a conjugated diene polymer chain
- a and c are each independently 0, 1, or 2
- b and d are each independently 1, 2, or 3
- a + b And c + d are each independently 1, 2, or 3.
- the modified conjugated diene-based polymer may be represented by the following formula (6) or formula (7):
- P is a conjugated diene polymer chain.
- R 1 , R 2 , and R 5 are each independently an alkylene group having 1 to 10 carbon atoms
- R 3 , R 4 , R 6, and R 7 are each independently an alkyl group having 1 to 10 carbon atoms
- R 8 is hydrogen or an alkyl group having 1 to 10 carbon atoms each independently
- a and c are each independently 0, 1, or 2
- A is , or
- R 9 , R 10 , R 11 , and R 12 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.
- conjugated diene monomer and the vinyl aromatic monomer are as described above.
- the solvent is not particularly limited as long as it is a solvent that can be applied to homopolymerization or copolymerization of conjugated diene monomers, and examples thereof include hydrocarbons or n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and It may be at least one selected from the group consisting of xylene.
- the organometallic compound may be at least one selected from the group consisting of an organoalkali metal compound, an organolithium compound, an organosodium compound, an organopotassium compound, an organorubidium compound, and an organocesium compound.
- the organometallic compound may be methyllithium, ethyllithium, isopropyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, n-decyllithium, tert-octylithium, phenyllithium, 1-naphthyl At least one selected from the group consisting of lithium, n-eicosilium, 4-butylphenyllithium, 4-tolyllithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium and 4-cyclopentyllithium have.
- the organometallic compound may be n-butyllithium, sec-butyllithium or a mixture thereof.
- the organometallic compound is a group consisting of naphthyl sodium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, sodium sulfonate, potassium sulfonate, lithium amide, sodium amide and potassium amide It may be one or more selected from, and may also be used in combination with other organometallic compounds.
- the organometallic compound may be used as 0.01 to 10 mmol, 0.05 to 5 mmol, 0.1 to 2 mmol or 0.1 to 1 mmol based on 100 g of the total monomer.
- an optimal conjugated diene-based polymer for preparing a modified conjugated diene-based polymer can be made.
- the molar ratio of the organometallic compound and the compound represented by Formula 8 is, for example, 1: 0.1 to 1:10, preferably 1: 0.3 to 1: 2. When the molar ratio satisfies this range, it is possible to give the modified reaction of optimal performance to the conjugated diene-based polymer.
- the active polymer having the metal end means a polymer in which a polymer anion and a metal cation are bonded.
- the modified conjugated diene-based polymer manufacturing method may be carried out by further adding a polar additive during the polymerization in the step (a).
- the reason why the polar additive is further added is that the polar additive controls the reaction rate of the conjugated diene monomer and the vinyl aromatic monomer.
- the polar additive may be a base or an ether, an amine or a mixture thereof, and specifically, tetrahydrofuran, ditetrahydroprilpropane, diethyl ether, cycloamyl ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether With diethylene glycol, dimethyl ether, tert-butoxyethoxyethane bis (2-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine It may be selected from the group consisting of, preferably ditetrahydropropylpropane, triethylamine or tetramethylethylenediamine.
- the polar additive may be used in 0.001 to 50 g, 0.001 to 10 g, 0.005 to 1 g, or 0.005 to 0.1 g based on a total of 100 g of the monomer to be added.
- the polar additive may be used in 0.001 to 10 g, 0.005 to 1 g, or 0.005 to 0.1 g based on a total of 1 mmol of the organometallic compound introduced.
- the polymerization of (a) may be, for example, anionic polymerization, and specifically, the polymerization of (a) may be a living anion polymerization that obtains active ends by growth reaction by anions.
- polymerization of (a) may be, for example, elevated temperature polymerization or constant temperature polymerization.
- the elevated temperature polymerization refers to a polymerization method including a step of raising the reaction temperature by adding heat optionally after adding the organometallic compound, and the constant temperature polymerization means a polymerization method in which no heat is optionally added after adding the organometallic compound. .
- the polymerization temperature of (a) may be, for example, -20 to 200 °C, 0 to 150 °C or 10 to 120 °C.
- the step (b) may be a step of injecting one or more, or two to three kinds of compounds represented by the formula (8).
- step (b) may be a step of reacting for 1 minute to 5 hours at 0 to 90 °C, for example.
- the modified conjugated diene-based polymer production method may be a batch polymerization (batch), or a continuous polymerization method including one or more reactors, for example.
- the compound of Formula 8 may be represented by, for example, the following Formula 9 or Formula 10:
- a and c are each independently 0, 1, or 2.
- a modified conjugated diene polymer prepared according to the above-described method for producing a modified conjugated diene polymer.
- the modified conjugated diene-based polymer may be represented by the following Chemical Formula 1.
- R 1 , R 2 , and R 5 are each independently an alkylene group having 1 to 10 carbon atoms
- R 3 , R 4 , R 6, and R 7 are each independently an alkyl group having 1 to 10 carbon atoms
- R 8 is hydrogen or each independently an alkyl group having 1 to 10 carbon atoms
- P is a conjugated diene polymer chain
- a and c are each independently 0, 1, or 2
- b and d are each independently 1, 2 , Or 3
- a + b and c + d are each independently 1, 2, or 3
- A is , or
- R 9 , R 10 , R 11 , and R 12 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.
- the modified conjugated diene polymer has a characteristic of viscoelasticity, and when measured at 10 Hz through DMA after silica blending, the Tan ⁇ value at 0 ° C. (Tan ⁇ at 0 ° C.) is, for example, 0.4 to 1 or 0.5 to 1 In this range, there is an effect that the road surface resistance or wetting resistance is significantly improved compared to the conventional invention.
- Tan ⁇ value (Tan ⁇ at 60 ° C.) at 60 ° C. may be, for example, 0.3 to 0.2, or 0.15 to 0.1, and within this range, the rolling resistance or rotational resistance (RR) is greatly improved as compared with the conventional invention. Effect.
- a modified conjugated diene-based polymer rubber composition comprising 100 parts by weight of the modified conjugated diene-based polymer, and 0.1 to 200 parts by weight of the inorganic filler.
- the inorganic filler may be, for example, 10 to 150 parts by weight, or 50 to 100 parts by weight.
- the inorganic filler may be at least one selected from the group consisting of silica-based fillers, carbon black, and mixtures thereof.
- silica-based fillers When the inorganic filler is a silica-based filler, dispersibility is greatly improved, and the hysteresis loss is greatly reduced by bonding the silica particles with the ends of the modified conjugated diene-based polymer of the present invention.
- the modified conjugated diene-based polymer rubber composition may further include another conjugated diene-based polymer.
- the other conjugated diene-based polymer may be styrene-butadiene rubber (SBR), butadiene rubber (BR), natural rubber, or a mixture thereof.
- SBR styrene-butadiene rubber
- BR butadiene rubber
- natural rubber or a mixture thereof.
- SBR may be, for example, solution styrene-butadiene rubber (SSBR).
- the modified conjugated diene-based polymer rubber composition may be one containing 20 to 100 parts by weight of the modified conjugated diene-based polymer and 0 to 80 parts by weight of the other conjugated diene-based polymer. have.
- the modified conjugated diene-based polymer rubber composition of the present invention may include 20 to 99 parts by weight of the modified conjugated diene-based polymer and 1 to 80 parts by weight of the other conjugated diene-based polymer.
- the modified conjugated diene-based polymer rubber composition of the present invention is 10 to 100 parts by weight of the modified conjugated diene-based polymer, 0 to 90 parts by weight of other conjugated diene-based polymer, 0 to 100 parts by weight of carbon black, silica 5 To 200 parts by weight and 2 to 20 parts by weight of the silane coupling agent.
- the modified conjugated diene-based polymer rubber composition of the present invention is 10 to 100 parts by weight of the modified conjugated diene-based polymer, 0 to 90 parts by weight of other conjugated diene-based polymer, 0 to 100 parts by weight of carbon black, silica 5 To 200 parts by weight and 2 to 20 parts by weight of the silane coupling agent, the sum of the weight of the modified conjugated diene-based polymer and other conjugated diene-based polymer may be 100 parts by weight.
- the modified conjugated diene-based polymer rubber composition of the present invention is 100 parts by weight of the polymer mixture comprising 10 to 99% by weight of the modified conjugated diene-based polymer and 1 to 90% by weight of the conjugated diene-based polymer It may include 1 to 100 parts by weight of black, 5 to 200 parts by weight of silica and 2 to 20 parts by weight of the silane coupling agent.
- the modified conjugated diene-based polymer rubber composition may further include 1 to 100 parts by weight of oil.
- the oil may be, for example, a mineral oil or a softener.
- the oil may be used in an amount of 10 to 100 parts by weight or 20 to 80 parts by weight based on 100 parts by weight of the conjugated diene-based copolymer, and exhibits good physical properties within this range, and further softens the rubber composition so that workability may be improved. Excellent effect.
- a denaturing agent is provided, which is a compound represented by the following formula (8).
- R 1 , R 2 , and R 5 are each independently an alkylene group having 1 to 10 carbon atoms
- R 3 , R 4 , R 6, and R 7 are each independently an alkyl group having 1 to 10 carbon atoms
- R 8 is hydrogen or an alkyl group having 1 to 10 carbon atoms each independently
- a and c are each independently 0, 1, or 2
- A is , or
- R 9 , R 10 , R 11 , and R 12 are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.
- the compound of Formula 8 may be represented by, for example, the following Formula 9 or Formula 10:
- a and c are each independently 0, 1, or 2.
- the tire or tire tread is manufactured using a rubber composition comprising a modified conjugated diene-based polymer having excellent compatibility with inorganic fillers and improved processability, thereby providing excellent rolling strength, wear resistance, and wet road resistance. It has the advantage of low resistance.
- 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 polymer.
- the analysis results of the modified conjugated diene-based polymer thus prepared are shown in Table 1 below.
- Three reactors were prepared, among which three reactors were used as polymerization reactors and three reactors were modified reactors.
- Styrene, 1,3-butadiene, and normal hexane from which impurities such as moisture were removed were mixed before entering the reactor at a rate of 1.788 kg / h, 4.477 kg / h, and 4.176 kg / h, respectively.
- the resulting mixed solution was continuously fed to a reactor 1, followed by 2,2-bis (2-oxoranyl) propane and n-butyllithium at a rate of 3.58 g / h and 39.57 mmol / h, respectively, as a polar additive.
- Furnace was supplied to the reactor 1 and the temperature inside the reactor was adjusted to 70 °C.
- the resulting polymer of the first reactor was continuously fed to the top of the second reactor and the temperature was maintained at 85 ° C. to proceed with the polymerization.
- the resulting polymer in the 2nd reactor was continuously fed to the top of the 3rd reactor, and N, N-Bis (triethoxysilyl propyl) aminopropyl-1-imidazole was continuously fed at a rate of 10.6 mmol / h and the modification was carried out. It was.
- a solution containing isopropyl alcohol and an antioxidant (wingstay-K) mixed at 8: 2 was added to the resulting polymer in a three-phase reactor at a rate of 32.5 g / h to terminate the polymerization reaction to obtain a polymer.
- TDAE oil treated distilled aromatic extract having a glass transition temperature in the range of about -44 to about -50 ° C.
- N-Bis (triethoxysilylpropyl) aminopropyl-1- (4,5-dihydro) imidazole was added instead of N, N-Bis (triethoxysilylpropyl) aminopropyl-1-imidazole used in Example 1 and reacted for 15 minutes. I was. Thereafter, the polymerization 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.
- BHT butylated hydroxytoluene
- 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 polymer.
- the analysis results of the modified conjugated diene-based polymer thus prepared are shown in Table 1 below.
- N, N-Bis (triethoxysilylpropyl) aminopropyl-1-imidazole was added and reacted for 15 minutes. Thereafter, the polymerization 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.
- BHT butylated hydroxytoluene
- 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 polymer.
- the analysis results of the modified conjugated diene-based polymer thus prepared are shown in Table 1 below.
- Three reactors were prepared, among which three reactors were used as polymerization reactors and three reactors were modified reactors.
- styrene, 1,3-butadiene, and normal hexane from which impurities such as moisture were removed were mixed in advance before entering the reactor at 2.373 kg / h, 3.921 kg / h, and 4.196 kg / h, respectively.
- the resulting mixed solution was continuously fed to a reactor 1, followed by 2,2-bis (2-oxoranyl) propane and n-butyllithium at a rate of 3.58 g / h and 39.57 mmol / h, respectively, as a polar additive.
- Furnace was supplied to the reactor 1 and the temperature inside the reactor was adjusted to 70 °C.
- the resulting polymer of the first reactor was continuously fed to the top of the second reactor and the temperature was maintained at 85 ° C.
- the resulting polymer in the 2nd reactor was continuously fed to the top of the 3rd reactor, and N, N-Bis (triethoxysilyl propyl) aminopropyl-1-imidazole was continuously fed at a rate of 10.6 mmol / h and the modification was carried out. It was.
- a solution containing isopropyl alcohol and an antioxidant (wingstay-K) mixed at 8: 2 was added to the resulting polymer in a three-phase reactor at a rate of 32.5 g / h to terminate the polymerization reaction to obtain a polymer.
- TDAE oil treated distilled aromatic extract having a glass transition temperature in the range of about -44 to about -50 ° C.
- Table 2 shows the analysis results of the most unmodified conjugated diene-based polymer (5025-2HM grade, manufactured by Lanses Irish GmbH).
- a modified conjugated diene-based polymer was prepared in the same manner as in Example 1, except that 1.2 mmol of dimethylchlorosilane, a coupling agent, was added instead of N, N-Bis (triethoxysilylpropyl) aminopropyl-1-imidazole in Example 1. .
- the analysis results of the modified conjugated diene-based polymer thus prepared are shown in Table 2 below.
- Example 2 Except for adding 4,3 mmol of N, N-Bis (triethoxysilylpropyl) piperazine instead of N, N-Bis (triethoxysilylpropyl) aminopropyl-1-imidazole in Example 1, the modified conjugate was carried out in the same manner as in Example 1 The diene polymer was prepared. The analysis results of the modified conjugated diene-based polymer thus prepared are shown in Table 2 below.
- Mooney Viscosity ALPHA Technologies Inc. MV-2000 was used to preheat for 1 minute using two or more specimens weighing 15g and measured for 4 minutes at 100 °C.
- Mw Weight average molecular weight
- Mn number average molecular weight
- PDI molecular weight distribution
- the rubber composition of the conjugated diene-based polymer is kneaded through a total of first stage kneading and second stage kneading.
- a semi-barrier mixer equipped with a temperature controller is used to prepare raw rubber (conjugated diene polymer), filler, organosilane coupling agent, oil, galvanizing agent, stearic acid antioxidant, antioxidant, wax and accelerator. Kneaded. At this time, the temperature of the kneader was controlled, and the primary blend was obtained at the discharge temperature of 145-155 degreeC.
- Tan ⁇ was measured by changing the strain at a frequency of 10 Hz and each measurement temperature (-60 to 60 ° C.) in the torsion mode.
- the Payne effect is expressed as the difference between the minimum and maximum values at 0.28% to 40% of the strain.
- the smaller the Faye effect the better the dispersibility of the filler such as silica.
- the higher the low temperature 0 [deg.] C. Tan ⁇ the better the wet road surface resistance.
- the lower the high temperature 60 [deg.] C. Tan ⁇ the lower the hysteresis loss and the lower the rolling resistance of the tire, that is, the lower the fuel efficiency.
- Table 4 shows the physical properties of the vulcanized rubber.
- the Tan ⁇ value at 0 ° C. was higher than that of Comparative Preparation Example 2, so that the modified conjugated diene-based polymer of the present invention was applied to a tire.
- the rubber composition is included, it was confirmed that the resistance on the wet road surface was high.
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Abstract
Description
구분 | 실시예 | |||||
High vinyl | High styrene | |||||
1 | 2 | 3 | 4 | 5 | ||
시료 | A | B | C | D | E | |
n-부틸리튬(mmol/h) | 4mmol | 39.6 | 4mmol | 4mmol | 39.6 | |
극성첨가제(g/h) | 0.86g | 3.58 | 0.86g | 0.86g | 3.58 | |
변성제(mmol/h) | a | 4.3mmol | 10.6 | - | 4.3mmol | 10.6 |
b | - | - | 4.3mmol | - | - | |
오일 | 종류 | - | TDAE | - | - | TDAE |
phr | - | 25 | - | - | 25 | |
무니점도(MV) | 88 | 77 | 85 | 83 | 75 | |
NMR(%) | SM | 27 | 27 | 27 | 36 | 36 |
Vinyl | 41 | 43 | 41 | 26 | 27 | |
GPC(x104) | Mp | 25 | - | 25 | 25 | - |
Mn | 38 | 47 | 38 | 39 | 47 | |
Mw | 55 | 164 | 55 | 55 | 144 | |
PDI | 1.4 | 3.5 | 1.4 | 1.4 | 3.1 |
구분 | 비교예 | ||||
1 | 2 | 3 | 4 | ||
시료 | F | G | H | I | |
n-부틸리튬(mmol) | - | - | 4 | 4 | |
극성첨가제(g) | - | - | 0.86 | 0.86 | |
변성제(mmol) | c | - | - | 1.2 | - |
d | - | - | - | 4.3 | |
오일 | 종류 | TDAE | RAE | - | - |
phr | 37.5 | 37.5 | - | - | |
무니점도(MV) | 61 | 53 | 64 | 66 | |
NMR(%) | SM | 26 | 36 | 27 | 29 |
Vinyl | 50 | 26 | 43 | 41 | |
GPC(x104) | Mp | - | - | - | 25 |
Mn | 39 | 33 | 31 | 34 | |
Mw | 69 | 94 | 50 | 45 | |
PDI | 1.8 | 2.8 | 1.2 | 1.3 |
구분 | 물질 | 함량(단위 : phr) |
제1 단 혼련 | 고무 | 137.5 |
실리카 | 70.0 | |
커플링제 | 11.2 | |
오일 | - | |
아연화제 | 3.0 | |
스테아르산 | 2.0 | |
산화방지제 | 2.0 | |
노화방지제 | 2.0 | |
왁스 | 1.0 | |
제2 단 혼련 | 고무촉진제 | 1.75 |
황 | 1.5 | |
가황촉진제 | 2.0 | |
총 중량 | 234.0 |
구분 | 시험예1 | 시험예2 | 시험예3 | 시험예4 | 시험예5 | 비교시험예1 | 비교시험예2 | 비교시험예3 | 비교시험예4 |
시료 | 제조예1 | 제조예2 | 제조예3 | 제조예4 | 제조예5 | 비교제조예1 | 비교제조예2 | 비교제조예3 | 비교제조예4 |
300% 모듈러스(㎏f/㎠) | 132 | 122 | 130 | 130 | 117 | 98 | 105 | 104 | 127 |
인장강도(㎏f/㎠) | 213 | 193 | 202 | 203 | 187 | 161 | 177 | 168 | 161 |
Tan δ at 0℃ | 0.967 | 0.915 | 0.902 | 0.978 | 0.917 | 0.647 | 0.766 | 0.542 | 0.803 |
Tan δ at 60℃ | 0.101 | 0.108 | 0.106 | 0.110 | 0.119 | 0.133 | 0.142 | 0.115 | 0.109 |
60 ℃ ΔG’(페이니 효과) | 0.29 | 0.30 | 0.30 | 0.29 | 0.31 | 0.56 | 0.45 | 0.74 | 0.35 |
Claims (22)
- 하기 화학식 1로 표시되는 변성 공액 디엔계 중합체:[화학식 1]상기 화학식 1에서, R1, R2, 및 R5 는 각각 독립적으로 탄소수 1 내지 10의 알킬렌기이고, R3, R4, R6 및 R7은 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, R8은 수소 또는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, P는 공액 디엔계 중합체 사슬이고, a 및 c는 각각 독립적으로 0, 1, 또는 2이고, b 및 d는 각각 독립적으로 1, 2, 또는 3이고, a+b 및 c+d는 각각 독립적으로 1, 2, 또는 3이고, A는 , 또는 이고, R9, R10, R11, 및 R12는 각각 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기이다.
- 청구항 1에 있어서,상기 화학식 1은 하기 화학식 2 또는 화학식 3으로 표시되는 것을 특징으로 하는 변성 공액 디엔계 중합체:[화학식 2][화학식 3]상기 화학식 2 및 화학식 3에서, R15, R16, R18, R19, R22, R23, R25, 및 R26 은 각각 독립적으로 탄소수 1 내지 5의 알킬기이고, R13, R14, R17, R20, R21, 및 R24 는 각각 독립적으로 탄소수 1 내지 5의 알킬렌기이고, P는 공액 디엔계 중합체 사슬이고, a 및 c는 각각 독립적으로 0, 1, 또는 2이고, b 및 d는 각각 독립적으로 1, 2, 또는 3이고, a+b 및 c+d는 각각 독립적으로 1, 2, 또는 3이다.
- 청구항 1에 있어서,상기 변성 공액 디엔계 중합체는 1,000 내지 2,000,000 g/mol의 수평균분자량(Mn)을 가지는 것을 특징으로 하는 변성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 변성 공액 디엔계 중합체는 0.5 내지 10의 분자량 분포(Mw/Mn)를 가지는 것을 특징으로 하는 변성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 변성 공액 디엔계 중합체는, 비닐 함량이 10 중량% 이상인 것을 특징으로 하는 변성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 공액 디엔계 중합체 사슬은 공액 디엔계 단량체의 단독 중합체 또는 공액 디엔계 단량체와 비닐 방향족 단량체의 공중합체로부터 유래된 것을 특징으로 하는 변성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 변성 공액 디엔계 중합체는, 공액 디엔계 단량체와 방향족 비닐계 단량체를 합한 총 100 중량%를 기준으로 방향족 비닐계 단량체가 0.0001 내지 50 중량%로 포함된 것을 특징으로 하는 변성 공액 디엔계 중합체.
- 청구항 1에 있어서,상기 변성 공액 디엔계 중합체는 40 이상의 무니점도를 갖는 것을 특징으로 하는 변성 공액 디엔계 중합체.
- (a) 공액 디엔계 단량체, 또는 공액 디엔계 단량체와 비닐 방향족 단량체를 용매 하에서 유기금속 화합물을 이용하여 중합시켜 금속 말단을 갖는 활성 중합체를 형성하는 단계; 및(b) 상기 활성 중합체에 하기 화학식 8로 표시되는 화합물을 투입하여 변성시키는 단계를 포함하는 변성 공액 디엔계 중합체의 제조방법:[화학식 8]
- 청구항 11에 있어서,상기 유기금속 화합물은, 상기 단량체 총 100 g을 기준으로 0.01 내지 10 mmol로 사용되는 것을 특징으로 하는 변성 공액 디엔계 중합체의 제조방법.
- 청구항 11에 있어서,상기 유기금속 화합물과 상기 화학식 8로 표시되는 화합물의 몰비는 1: 0.1 내지 1: 10인 것을 특징으로 하는 변성 공액 디엔계 중합체의 제조방법.
- 청구항 11에 있어서,상기 (a) 단계에서 극성첨가제가 더 투입되는 것을 특징으로 하는 변성 공액 디엔계 중합체의 제조방법.
- 청구항 16에 있어서,상기 극성첨가제는 상기 유기금속 화합물 총 1 mmol을 기준으로 0.001 내지 10 g으로 투입되는 것을 특징으로 하는 변성 공액 디엔계 중합체의 제조방법.
- 청구항 11 내지 청구항 17 중 어느 한 항의 변성 공액 디엔계 중합체의 제조방법에 따라 제조되어 하기 화학식 1로 표시되는 변성 공액 디엔계 중합체:[화학식 1]상기 화학식 1에서, R1, R2, 및 R5 는 각각 독립적으로 탄소수 1 내지 10의 알킬렌기이고, R3, R4, R6 및 R7은 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, R8은 수소 또는 각각 독립적으로 탄소수 1 내지 10의 알킬기이고, P는 공액 디엔계 중합체 사슬이고, a 및 c는 각각 독립적으로 0, 1, 또는 2이고, b 및 d는 각각 독립적으로 1, 2, 또는 3이고, a+b 및 c+d는 각각 독립적으로 1, 2, 또는 3이고, A는 , 또는 이고, R9, R10, R11, 및 R12는 각각 독립적으로 수소, 또는 탄소수 1 내지 10의 알킬기이다.
- 청구항 1 내지 청구항 10 중 어느 한 항의 변성 공액 디엔계 중합체 100 중량부, 및 무기 충진제 0.1 내지 200 중량부를 포함하는 변성 공액 디엔계 중합체 고무 조성물.
- 청구항 19에 있어서,상기 무기 충진제는 실리카계 충진제, 카본 블랙 및 이들의 혼합물로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 변성 공액 디엔계 중합체 고무 조성물.
- 청구항 19의 변성 공액 디엔계 중합체 고무 조성물을 포함하는 타이어 또는 타이어 트레드.
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