KR102384180B1 - Diene copolymer and method for preparing the same - Google Patents
Diene copolymer and method for preparing the same Download PDFInfo
- Publication number
- KR102384180B1 KR102384180B1 KR1020180002633A KR20180002633A KR102384180B1 KR 102384180 B1 KR102384180 B1 KR 102384180B1 KR 1020180002633 A KR1020180002633 A KR 1020180002633A KR 20180002633 A KR20180002633 A KR 20180002633A KR 102384180 B1 KR102384180 B1 KR 102384180B1
- Authority
- KR
- South Korea
- Prior art keywords
- conjugated diene
- monomer
- based monomer
- aromatic vinyl
- copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920001577 copolymer Polymers 0.000 title claims abstract description 64
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 163
- 150000001993 dienes Chemical class 0.000 claims abstract description 158
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 58
- 229920002554 vinyl polymer Polymers 0.000 claims description 58
- 229920000642 polymer Polymers 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 32
- 239000000945 filler Substances 0.000 claims description 20
- 229920005604 random copolymer Polymers 0.000 claims description 15
- 239000000654 additive Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 10
- 150000002902 organometallic compounds Chemical class 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 238000013329 compounding Methods 0.000 abstract description 9
- 229920001971 elastomer Polymers 0.000 description 59
- 239000005060 rubber Substances 0.000 description 59
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 34
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 25
- 230000000052 comparative effect Effects 0.000 description 19
- 239000000377 silicon dioxide Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 11
- 229920003048 styrene butadiene rubber Polymers 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000006229 carbon black Substances 0.000 description 10
- 238000009472 formulation Methods 0.000 description 10
- 238000004898 kneading Methods 0.000 description 10
- 244000043261 Hevea brasiliensis Species 0.000 description 9
- 238000004458 analytical method Methods 0.000 description 9
- 229920003052 natural elastomer Polymers 0.000 description 9
- 229920001194 natural rubber Polymers 0.000 description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- 239000002174 Styrene-butadiene Substances 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 7
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000010734 process oil Substances 0.000 description 7
- 239000006087 Silane Coupling Agent Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 239000005062 Polybutadiene Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000013016 damping Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- -1 naphthyl potassium Chemical compound 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 5
- OWRCNXZUPFZXOS-UHFFFAOYSA-N 1,3-diphenylguanidine Chemical compound C=1C=CC=CC=1NC(=N)NC1=CC=CC=C1 OWRCNXZUPFZXOS-UHFFFAOYSA-N 0.000 description 4
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 4
- 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 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 4
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 229920005549 butyl rubber Polymers 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000004636 vulcanized rubber Substances 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
- ZNRLMGFXSPUZNR-UHFFFAOYSA-N 2,2,4-trimethyl-1h-quinoline Chemical compound C1=CC=C2C(C)=CC(C)(C)NC2=C1 ZNRLMGFXSPUZNR-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- FZLHAQMQWDDWFI-UHFFFAOYSA-N 2-[2-(oxolan-2-yl)propan-2-yl]oxolane Chemical compound C1CCOC1C(C)(C)C1CCCO1 FZLHAQMQWDDWFI-UHFFFAOYSA-N 0.000 description 2
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-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
- 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
- 239000004793 Polystyrene Substances 0.000 description 2
- 229920006978 SSBR Polymers 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- DEQZTKGFXNUBJL-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)cyclohexanamine Chemical compound C1CCCCC1NSC1=NC2=CC=CC=C2S1 DEQZTKGFXNUBJL-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001195 polyisoprene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 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
- 230000008569 process Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000010421 standard material Substances 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- QPFMBZIOSGYJDE-QDNHWIQGSA-N 1,1,2,2-tetrachlorethane-d2 Chemical compound [2H]C(Cl)(Cl)C([2H])(Cl)Cl QPFMBZIOSGYJDE-QDNHWIQGSA-N 0.000 description 1
- ZWPUOFSQNASCII-UHFFFAOYSA-N 1-(2-ethoxyethoxy)butane Chemical group CCCCOCCOCC ZWPUOFSQNASCII-UHFFFAOYSA-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
- VVTGQMLRTKFKAM-UHFFFAOYSA-N 1-ethenyl-4-propylbenzene Chemical compound CCCC1=CC=C(C=C)C=C1 VVTGQMLRTKFKAM-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
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-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
- YRVRZDIWEXCJSX-UHFFFAOYSA-N 2-methyl-3-(3-triethoxysilylpropyl)thiirane-2-carboxylic acid Chemical compound CCO[Si](OCC)(OCC)CCCC1SC1(C)C(O)=O YRVRZDIWEXCJSX-UHFFFAOYSA-N 0.000 description 1
- HHZDRADWWVVISO-UHFFFAOYSA-N 2-methyl-3-(3-trimethoxysilylpropyl)thiirane-2-carboxylic acid Chemical compound CO[Si](OC)(OC)CCCC1SC1(C)C(O)=O HHZDRADWWVVISO-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
- 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
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-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
- ZATOFRITFRPYBT-UHFFFAOYSA-N C1=CC=C2C([Li])=CC=CC2=C1 Chemical compound C1=CC=C2C([Li])=CC=CC2=C1 ZATOFRITFRPYBT-UHFFFAOYSA-N 0.000 description 1
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- FSPIGXNLDXWYKZ-UHFFFAOYSA-N CCO[Si](CCC[S+]=C(N(C)C)SSSSC(N(C)C)=[S+]CCC[Si](OCC)(OCC)OCC)(OCC)OCC Chemical compound CCO[Si](CCC[S+]=C(N(C)C)SSSSC(N(C)C)=[S+]CCC[Si](OCC)(OCC)OCC)(OCC)OCC FSPIGXNLDXWYKZ-UHFFFAOYSA-N 0.000 description 1
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- 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
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 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
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- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- OUBMGJOQLXMSNT-UHFFFAOYSA-N N-isopropyl-N'-phenyl-p-phenylenediamine Chemical compound C1=CC(NC(C)C)=CC=C1NC1=CC=CC=C1 OUBMGJOQLXMSNT-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
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- NTYDXFVCCCPXRG-UHFFFAOYSA-N [Li]C(C)(C)CC(C)(C)C Chemical compound [Li]C(C)(C)CC(C)(C)C NTYDXFVCCCPXRG-UHFFFAOYSA-N 0.000 description 1
- SHJXVDAAVHAKFB-UHFFFAOYSA-N [Li]CCCCCCCCCC Chemical compound [Li]CCCCCCCCCC SHJXVDAAVHAKFB-UHFFFAOYSA-N 0.000 description 1
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- 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
- 229920000800 acrylic rubber Polymers 0.000 description 1
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- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
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- 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
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- 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
- 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
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- 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 group 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
- XWSQTXBRVIEOGT-UHFFFAOYSA-N triethoxy-[3-(tetrasulfanyl)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCSSSS XWSQTXBRVIEOGT-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
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
- C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
-
- 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
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- 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
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- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/21—Rubbery or elastomeric properties
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
본 발명은 우수한 배합물성을 가지면서 가공성이 개선된 공액디엔계 공중합체 및 이의 제조방법에 관한 것이다. 이에 따른 공액디엔계 공중합체는 화학식 1로 표시되는 바와 같이 방향족 비닐계 단량체와 공액디엔계 단량체 유래 랜덤 공중합 단위와 상기 랜던 공중합 단위 일 말단에 결합되어 있는 공액디엔계 단량체 유래 블록 중합 단위를 포함하되, 공액디엔계 단량체 유래 블록 중합 단위를 특정비율로 포함함으로써 인장특성 및 점탄성 특성과 같은 배합물성이 우수하면서 가공성이 개선될 수 있다.The present invention relates to a conjugated diene-based copolymer having excellent compounding properties and improved processability and a method for preparing the same. The conjugated diene-based copolymer according to this includes a random copolymerized unit derived from an aromatic vinylic monomer and a conjugated diene-based monomer and a block polymerized unit derived from a conjugated diene-based monomer bonded to one end of the random copolymerized unit as represented by Formula 1 , By including the block polymerization unit derived from the conjugated diene-based monomer in a specific ratio, compounding properties such as tensile properties and viscoelastic properties can be improved while processability can be improved.
Description
본 발명은 우수한 배합물성을 가지면서 가공성이 개선된 공액디엔계 공중합체 및 이의 제조방법에 관한 것이다.The present invention relates to a conjugated diene-based copolymer having excellent compounding properties and improved processability and a method for preparing the same.
최근 자동차에 대한 저연비화의 요구에 따라, 타이어용 고무 재료로서 주행저항이 적고, 내마모성, 인장 특성이 우수하며, 웨트 스키드 저항으로 대표되는 조정 안정성도 겸비한 공액디엔계 중합체가 요구되고 있다. In response to the recent demand for fuel economy reduction in automobiles, a conjugated diene-based polymer having low running resistance, excellent abrasion resistance and tensile properties, and adjustment stability typified by wet skid resistance is required as a rubber material for tires.
타이어의 주행저항을 감소시키기 위해서는 가황 고무의 히스테리시스 손실을 작게하는 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 또는 굿리치 발열이 작은 고무 재료가 바람직하다.In order to reduce the running resistance of the tire, there is a method of reducing the hysteresis loss of the vulcanized rubber, and rebound elasticity of 50°C to 80°C, Tan δ, Goodrich heat, etc. are used as evaluation indicators of the vulcanized rubber. That is, a rubber material having a large rebound elasticity at the above temperature or a small Tan δ or Goodrich heat generation is preferable.
히스테리시스 손실이 작은 고무 재료로서는, 천연 고무, 폴리이소프렌 고무 또는 폴리부타디엔 고무 등이 알려져 있지만, 이들은 웨트 스키드 저항성이 작은 문제가 있다. 이에 최근에는 스티렌-부타디엔 고무(이하, SBR이라 함) 또는 시스 함량이 조절된 부타디엔 고무(이하, Low Cis-BR이라 함)와 같은 공액디엔계 (공)중합체가 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 SBR 이나 Low Cis-BR 고무의 구조 변화가 용이하고, 사슬 말단의 결합이나 변성으로 사슬 말단의 움직임을 줄이고 실리카 또는 카본블랙 등의 충진제와의 결합력을 증가시킬 수 있어 용액 중합에 의한 SBR 고무가 타이어용 고무 재료로 많이 사용된다. 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, 연료소모를 줄일 수 있다. As a rubber material with a small hysteresis loss, natural rubber, polyisoprene rubber, polybutadiene rubber, etc. are known, but these have a problem of low wet skid resistance. Accordingly, recently, conjugated diene-based (co)polymers such as styrene-butadiene rubber (hereinafter referred to as SBR) or butadiene rubber with controlled cis content (hereinafter referred to as Low Cis-BR) have been manufactured by emulsion polymerization or solution polymerization. It is used as rubber for tires. Among them, the greatest advantage of solution polymerization compared to emulsion polymerization is that the content of vinyl structure and styrene content defining rubber properties can be arbitrarily adjusted, and molecular weight and physical properties can be adjusted by coupling or modification. that it can be adjusted. Therefore, it is easy to change the structure of the finally manufactured SBR or Low Cis-BR rubber, and it is possible to reduce the movement of the chain ends by bonding or modifying the chain ends and to increase the binding force with fillers such as silica or carbon black, so it is suitable for solution polymerization. SBR rubber is widely used as a rubber material for tires. When this solution-polymerized SBR is used as a rubber material for a tire, the glass transition temperature of the rubber is increased by increasing the vinyl content in the SBR, so that the required physical properties of the tire such as running resistance and braking force can be adjusted, and fuel consumption can be reduced. there is.
그러나, SBR의 경우 주행저항이 적고, 내마모성, 인장특성 및 조정 안정성이이 우수하면서 가공성까지 좋은 특성을 가지기 어려우며, 고품질 타이어의 경우 상기의 기계적 물성(내마모성, 인장특성, 조정 안정성 등)뿐 아니라 가공성 또한 매우 중요한 특성으로 요구되고 있다. However, in the case of SBR, it is difficult to have good processability while having low running resistance, excellent abrasion resistance, tensile properties and adjustment stability. It is required as a very important characteristic.
따라서, 기본적인 타이어 요구 물성을 제공할 수 있을 뿐만 아니라 충진제와의 배합 용이성도 우수한, 즉 물성과 가공성이 균형있게 우수한 고무의 개발이 필요한 실정이다.Accordingly, there is a need to develop a rubber that can provide basic tire required physical properties and is excellent in compounding ease with a filler, that is, in a balanced way between physical properties and processability.
본 발명은 종래기술의 문제점을 해결하기 위하여 안출된 것으로, 우수한 배합물성을 가지면서 가공성이 개선된 공액디엔계 공중합체를 제공하는 것을 목적으로 한다. The present invention has been devised to solve the problems of the prior art, and an object of the present invention is to provide a conjugated diene-based copolymer having improved processability while having excellent compounding properties.
본 발명의 다른 목적은 상기 공액디엔계 공중합체의 제조방법을 제공하는 것이다. Another object of the present invention is to provide a method for preparing the conjugated diene-based copolymer.
상기의 과제를 해결하기 위하여, 본 발명은 하기 화학식 1로 표시되고, 공액디엔계 단량체 유래 블록 중합 단위를 5 중량% 초과, 30 중량% 이하로 포함하는 공액디엔계 공중합체를 제공한다:In order to solve the above problems, the present invention provides a conjugated diene-based copolymer represented by the following formula (1) and comprising more than 5% by weight and 30% by weight or less of a block polymerization unit derived from a conjugated diene-based monomer:
[화학식 1][Formula 1]
(SB)-B1 (SB)-B 1
상기 화학식 1에서, In Formula 1,
SB는 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 단위이고, B1은 공액디엔계 단량체 유래 블록 중합 단위이다. SB is a random copolymerized unit derived from an aromatic vinyl-based monomer and a conjugated diene-based monomer, and B 1 is a block-polymerized unit derived from a conjugated diene-based monomer.
또한, 본 발명은 탄화수소 용매 중에서, 유기금속 화합물 존재 하에 제1 공액디엔계 단량체 및 방향족 비닐계 단량체를 제1 중합하여 제1 중합물을 제조하는 단계(단계 1); 및 상기 제1 중합물에 제2 공액디엔계 단량체를 투입하고 제2 중합하는 단계(단계 2)를 포함하고, 상기 제2 공액디엔계 단량체는 하기 수학식 1을 만족하는 시점에 투입하는 것인 상기에 기재된 공액디엔계 공중합체의 제조방법을 제공한다:In addition, the present invention comprises the steps of preparing a first polymer by first polymerizing a first conjugated diene-based monomer and an aromatic vinyl-based monomer in the presence of an organometallic compound in a hydrocarbon solvent (step 1); and adding a second conjugated diene-based monomer to the first polymer and performing a second polymerization (step 2), wherein the second conjugated diene-based monomer is added at a time when the following Equation 1 is satisfied. It provides a method for producing a conjugated diene-based copolymer described in:
[수학식 1][Equation 1]
(a:b)=(c:d)(a:b)=(c:d)
상기 수학식 1에서, In Equation 1 above,
a:b는 제1 중합에서 제1 공액디엔계 단량체와 방향족 비닐계 단량체의 중량비이고, a: b is the weight ratio of the first conjugated diene-based monomer and the aromatic vinyl-based monomer in the first polymerization,
c:d는 제1 중합물 내에 제1 공액디엔계 단량체 유래 단위와 방향족 비닐계 단량체 유래 단위의 중량비이다.c:d is a weight ratio of the unit derived from the first conjugated diene-based monomer and the unit derived from the aromatic vinyl-based monomer in the first polymer.
본 발명에 따른 공액디엔계 공중합체는 화학식 1로 표시되는 바와 같이 방향족 비닐계 단량체와 공액디엔계 단량체 유래 랜덤 공중합 단위와 공액디엔계 단량체 유래 블록 중합 단위를 포함하되, 공액디엔계 단량체 유래 블록 중합 단위를 특정비율로 포함함으로써 인장특성 및 점탄성 특성과 같은 배합물성이 우수하면서 가공성이 개선될 수 있다. The conjugated diene-based copolymer according to the present invention includes a random copolymerized unit derived from an aromatic vinyl-based monomer and a conjugated diene-based monomer and a block-polymerized unit derived from a conjugated diene-based monomer as represented by Formula 1, but block polymerization derived from a conjugated diene-based monomer By including the unit in a specific ratio, processability can be improved while excellent compounding properties such as tensile properties and viscoelastic properties.
또한, 본 발명에 따른 공액디엔계 공중합체의 제조방법은 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 단위를 포함하는 제1 중합물을 제조하고, 특정시점에 공액디엔계 단량체를 상기 제1 중합물에 투입하여 중합시킴으로써 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 단위와 상기 랜덤 공중합 단위 일 말단에 공액디엔계 단량체 유래 블록 중합 단위가 결합된 구조의 공액디엔계 공중합체를 용이하게 제조할 수 있다.In addition, in the method for producing a conjugated diene-based copolymer according to the present invention, a first polymer comprising an aromatic vinyl-based monomer and a random copolymerized unit derived from a conjugated diene-based monomer is prepared, and the conjugated diene-based monomer is added to the first polymer at a specific time. By putting it into a polymer and polymerizing it, it is possible to easily prepare a conjugated diene-based copolymer having a structure in which a random copolymer unit derived from an aromatic vinyl monomer and a conjugated diene monomer and a block polymerization unit derived from a conjugated diene monomer are bonded to one end of the random copolymer unit. 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 help the understanding of the present invention.
본 명세서 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 present specification and claims should not be construed as being limited to ordinary or dictionary meanings, and the inventor may properly define the concept of the term in order to best describe his invention. Based on the principle that there is, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.
본 발명은 인장강도 및 점탄성 특성과 같은 배합물성이 우수하면서, 가공성이 개선된 공액디엔계 공중합체를 제공한다. The present invention provides a conjugated diene-based copolymer having improved processability while excellent in compounding properties such as tensile strength and viscoelastic properties.
본 발명의 일 실시예에 따른 상기 공액디엔계 공중합체는 하기 화학식 1로 표시되고, 공액디엔계 단량체 유래 블록 중합 단위를 5 중량% 초과, 30 중량% 이하로 포함하는 것을 특징으로 한다. The conjugated diene-based copolymer according to an embodiment of the present invention is represented by the following Chemical Formula 1, and it is characterized in that it contains more than 5% by weight and not more than 30% by weight of a block polymerization unit derived from a conjugated diene-based monomer.
[화학식 1][Formula 1]
(SB)-B1 (SB)-B 1
상기 화학식 1에서, In Formula 1,
SB는 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 단위이고, B1은 공액디엔계 단량체 유래 블록 중합 단위이다.SB is a random copolymerized unit derived from an aromatic vinyl-based monomer and a conjugated diene-based monomer, and B 1 is a block-polymerized unit derived from a conjugated diene-based monomer.
자동차에 대한 저연비화의 요구에 따라, 타이어용 고무 재료로서 주행저항이 적고, 내마모성, 인장 특성이 우수하며, 웨트 스키드 저항으로 대표되는 제동성도 겸비한 고무 재료가 요구되고 있으며, 이에 최근에는 고무의 구조 변화가 용이하고, 사슬 말단의 결합이나 변성으로 사슬 말단의 움직임을 줄이고 실리카 또는 카본블랙 등의 충진제와의 결합력을 증가시킬 수 있어 용액 중합에 의한 SBR 고무(이하, SSBR이라 한다)가 타이어용 고무 재료로 많이 사용된다. 이러한 SSBR은 유기금속 화합물 존재 하에, 방향족 비닐계 단량체와 공액디엔계 단량체를 중합하여 제조되는 랜덤 공중합체이나, 일반적으로 상기 두 단량체 간 반응속도 차이로 인해 중합체 쇄 말단에는 방향족 비닐계 단량체 블록 중합 단위가 형성되게 되며, 이 경우 가교 후 탄성물성이 저하되는 문제가 있다. 이에, 중합체 쇄 말단에 방향족 비닐계 단량체 블록 중합 단위 형성을 억제하기 위하여 랜덤화제(예컨대, 극성첨가제)를 투입하는 방안이 이용되고 있으나, 특정량 이상으로 투입량을 증가시키지 않으면 상기 방향족 비닐계 단량체 블록 중합 단위의 형성을 억제하기 어렵고, 랜덤화제 투입량이 증가하는 경우 제조된 공중합체 내 비닐 함량이 높아지고 반응속도가 지나치게 상승하여 중합된 고분자 사슬에 분지가 과도하게 증가되는 문제가 있다. 이러한 문제를 감소시키기 위하여 반응온도를 낮추거나 5% 이하(통상 2%)의 공액디엔계 단량체를 중합 말기에 별도로 투입하는 등 복잡한 공정성 조작이 요구되고 있으며, 이렇듯 방향족 비닐계 단량체 블록 중합 단위 형성을 억제하는 것은 쉽지 않다. In response to the demand for low fuel consumption for automobiles, a rubber material for tires that has low running resistance, excellent abrasion resistance and tensile properties, and also has braking performance typified by wet skid resistance is required as a rubber material for tires. SBR rubber by solution polymerization (hereinafter referred to as SSBR) is a tire rubber because it is easy to change, and it can reduce the movement of the chain ends by bonding or modifying the chain ends and increase the bonding strength with fillers such as silica or carbon black. It is widely used as a material. These SSBRs are random copolymers prepared by polymerizing an aromatic vinyl-based monomer and a conjugated diene-based monomer in the presence of an organometallic compound, but in general, due to a difference in reaction rate between the two monomers, an aromatic vinyl-based monomer block polymerization unit is located at the end of the polymer chain. is formed, and in this case, there is a problem in that elastic properties are deteriorated after crosslinking. Accordingly, a method of adding a randomizing agent (eg, a polar additive) is used to suppress the formation of a polymer unit of the aromatic vinyl-based monomer block at the end of the polymer chain, but unless the input amount is increased to a certain amount or more, the aromatic vinyl-based monomer block It is difficult to suppress the formation of polymerized units, and when the amount of the randomizing agent is increased, the vinyl content in the prepared copolymer increases and the reaction rate is excessively increased, so there is a problem in that branching in the polymerized polymer chain is excessively increased. In order to reduce this problem, a complicated process operation is required, such as lowering the reaction temperature or separately adding 5% or less (usually 2%) of the conjugated diene-based monomer at the end of polymerization. It is not easy to suppress.
이에, 본 발명은 방향족 비닐계 단량체와 공액디엔계 단량체 유래 랜덤 공중합 단위와 공액디엔계 단량체 유래 블록 중합 단위를 포함하되, 상기 공액디엔계 단량체 유래 블록 단위가 상기 랜덤 공중합 단위 일 말단에 결합된 구조를 갖는, 우수한 배합물성을 가지면서도 가공성이 크게 개선된 공액디엔계 공중합체를 제공한다. Accordingly, the present invention includes a random copolymer unit derived from an aromatic vinyl monomer and a conjugated diene monomer, and a block polymerization unit derived from a conjugated diene monomer, wherein the block unit derived from the conjugated diene monomer is bonded to one end of the random copolymer unit. To provide a conjugated diene-based copolymer having excellent compounding properties and greatly improved processability.
구체적으로, 본 발명의 일 실시예에 따른 상기 공액디엔계 공중합체는 화학식 1로 표시되는 구조를 가지되, 공액디엔계 단량체 유래 블록 중합 단위를 5 중량% 초과, 30 중량% 이하, 또는 10 중량% 이상 30 중량% 이하로 포함하는 것일 수 있다. 즉, 상기 공액디엔계 공중합체는 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 단위와 공액디엔계 단량체 유래 블록 중합 단위를 포함하되, 상기 공액디엔계 단량체 유래 블록 중합 단위가 상기 랜덤 공중합 단위의 적어도 일 말단 부위에 결합되어 있는 구조를 갖는 것일 수 있고, 이때 공액디엔계 단량체 유래 블록 중합 단위는 전체 공액디엔계 공중합체 100 중량% 대비 5 중량% 초과, 30 중량% 이하, 또는 10 중량% 내지 30 중량%로 상기 랜덤 공중합 단위에 결합되어 있는 것일 수 있다. 한편, 본 발명의 일 실시예에 따른 상기 공액디엔계 공중합체는 후술하는 제조방법에 의하여 제조됨으로써 상기의 구조를 가질 수 있는 것일 수 있다.Specifically, the conjugated diene-based copolymer according to an embodiment of the present invention has a structure represented by Formula 1, and contains more than 5% by weight, 30% by weight or less, or 10% by weight of a block polymerization unit derived from a conjugated diene-based monomer. % or more and 30 wt% or less may be included. That is, the conjugated diene-based copolymer includes a random copolymerized unit derived from an aromatic vinyl-based monomer and a conjugated diene-based monomer and a block polymerized unit derived from a conjugated diene-based monomer, wherein the block polymerized unit derived from the conjugated diene-based monomer is the random copolymer unit. It may have a structure bonded to at least one terminal site, and in this case, the block polymerization unit derived from the conjugated diene-based monomer is more than 5% by weight, 30% by weight or less, or 10% by weight to 100% by weight of the total conjugated diene-based copolymer. 30% by weight may be bound to the random copolymer unit. On the other hand, the conjugated diene-based copolymer according to an embodiment of the present invention may be one that can have the above structure by being prepared by a manufacturing method to be described later.
여기에서, 상기 화학식 1에서 SB로 표시된 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 단위는 방향족 비닐계 단량체 및 공액디엔계 단량체가 중합하여 형성하는 반복 단위를 나타내는 것으로, 방향족 비닐계 단량체 유래 단위와 공액디엔계 단량체 유래 단위를 포함할 수 있으며, 구체적으로는 방향족 비닐계 단량체 유래 단위 20 내지 45 중량% 및 공액디엔계 단량체 유래 단위 55 내지 80 중량%를 포함하는 것일 수 있다. Here, the random copolymerized unit derived from the aromatic vinyl-based monomer and the conjugated diene-based monomer represented by SB in Formula 1 represents a repeating unit formed by polymerization of the aromatic vinyl-based monomer and the conjugated diene-based monomer, and is a unit derived from the aromatic vinyl-based monomer. and a unit derived from a conjugated diene-based monomer, and specifically, may include 20 to 45% by weight of an aromatic vinyl-based monomer-derived unit and 55 to 80% by weight of a unit derived from a conjugated diene-based monomer.
또한, 상기 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 단위는 중량평균 분자량이 100,000 g/mol 내지 1,300,000 g/mol일 수 있고, 구체적으로는 200,000 g/mol 내지 1,000,000 g/mol 또는 300,000 g/mol 내지 800,000 g/mol일 수 있다. In addition, the random copolymerized unit derived from the aromatic vinyl-based monomer and the conjugated diene-based monomer may have a weight average molecular weight of 100,000 g/mol to 1,300,000 g/mol, and specifically 200,000 g/mol to 1,000,000 g/mol or 300,000 g/mol mol to 800,000 g/mol.
또한, 상기 화학식 1에서 B1으로 표시된 공액디엔계 단량체 유래 블록 중합 단위는 공액디엔계 단량체가 중합하여 형성하는 반복 단위를 나타내는 것으로, 중량평균 분자량이 10,000 g/mol 내지 500,000 g/mol일 수 있고, 구체적으로는 20,000 g/mol 내지 400,000 g/mol 또는 20,000 g/mol 내지 300,000 g/mol일 수 있다. In addition, the block polymerization unit derived from the conjugated diene-based monomer represented by B 1 in Formula 1 represents a repeating unit formed by polymerization of the conjugated diene-based monomer, and may have a weight average molecular weight of 10,000 g/mol to 500,000 g/mol, and , specifically 20,000 g/mol to 400,000 g/mol or 20,000 g/mol to 300,000 g/mol.
한편, 본 발명에서 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 할로겐원자를 의미한다)으로 이루어진 군에서 선택된 1종 이상일 수 있으며, 구체적으로는 1,3-부타디엔일 수 있다. Meanwhile, in the present invention, the conjugated diene-based monomer is, for example, 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, piperylene, 3-butyl-1,3-octadiene, isoprene, and 2-phenyl. It may be at least one member selected from the group consisting of -1,3-butadiene and 2-halo-1,3-butadiene (halo means a halogen atom), and specifically may be 1,3-butadiene.
또한, 상기 방향족 비닐계 단량체는 일례로 스티렌, α-메틸스티렌, 3-메틸스티렌, 4-메틸스티렌, 4-프로필스티렌, 1-비닐나프탈렌, 4-사이클로헥실스티렌, 4-(p-메틸페닐)스티렌 및 1-비닐-5-헥실나프탈렌으로 이루어진 군에서 선택된 1종 이상일 수 있으며, 구체적으로는 스티렌일 수 있다. In addition, the aromatic vinyl-based monomer is, for example, styrene, α-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 1-vinylnaphthalene, 4-cyclohexylstyrene, 4-(p-methylphenyl) It may be at least one selected from the group consisting of styrene and 1-vinyl-5-hexylnaphthalene, and specifically may be styrene.
또한, 본 발명의 일 실시예에 따른 상기 공액디엔계 공중합체는 하기 수학식 2로 나타내는 무니점도 차(△ MV)가 12 미만인 것일 수 있다. 구체적으로는, 상기 무니점도 차가 1 이상, 12 미만인 것일 수 있다. In addition, the conjugated diene-based copolymer according to an embodiment of the present invention may have a Mooney viscosity difference (Δ MV) represented by the following Equation 2 is less than 12. Specifically, the Mooney viscosity difference may be 1 or more and less than 12.
[수학식 2][Equation 2]
△ MV = CMV - PMV △ MV = CMV - PMV
상기 수학식 2에서, CMV(compound mooney viscosity)는 공액디엔계 공중합체, 충전제 및 가교제를 포함하는 배합물의 무니점도이고, PMV(polymer mooney viscosity)는 공액디엔계 공중합체의 무니점도이다. In Equation 2, compound mooney viscosity (CMV) is the Mooney viscosity of a formulation including the conjugated diene-based copolymer, a filler, and a crosslinking agent, and polymer mooney viscosity (PMV) is the Mooney viscosity of the conjugated diene-based copolymer.
이때, 상기 공액디엔계 공중합체는 무니점도가 30 이상, 구체적으로는 40 내지 150, 더욱 구체적으로는 40 내지 130일 수 있다. In this case, the conjugated diene-based copolymer may have a Mooney viscosity of 30 or more, specifically 40 to 150, and more specifically 40 to 130.
또한, 상기 무니점도 차는 공액디엔계 공중합체의 배합물성, 즉 충전제와의 배합 용이성을 나타내는 것으로 상기 무니점도 차가 적을수록 상기 공액디엔계 공중합체의 가공성이 우수함을 의미한다. In addition, the Mooney viscosity difference represents the compounding properties of the conjugated diene-based copolymer, that is, the ease of mixing with a filler, and the smaller the Mooney viscosity difference, the better the processability of the conjugated diene-based copolymer.
여기에서, 상기 배합물은 공액디엔계 공중합체와 충전제 및 가교제를 포함하는 혼합물인 것일 수 있고, 구체적으로는 후술하는 실험예 2, 1) 가교된 고무의 제조에 기재된 제2 배합물일 수 있다. 또한, 상기 무니점도는 Monsanto사 MV2000E의 Large Rotor를 사용하여 100℃ 및 Rotor Speed 2±0.02rpm의 조건에서 공액디엔계 공중합체 또는 배합물을 실온(23±5℃)에서 30분 이상 방치한 후 27±3g을 채취하여 다이 캐비티 내부에 채워 놓고 플래턴(Platen)을 작동시켜 토크를 인가하면서 측정하였다.Here, the formulation may be a mixture including a conjugated diene-based copolymer, a filler, and a crosslinking agent, and specifically, the second formulation described in Experimental Examples 2 and 1) Preparation of crosslinked rubber to be described later. In addition, the Mooney viscosity was measured after leaving the conjugated diene-based copolymer or formulation at room temperature (23±5° C.) for at least 30 minutes at 100° C. and a rotor speed of 2±0.02 rpm using a large rotor of Monsanto’s MV2000E. ±3g was collected and filled inside the die cavity, and the platen was operated to measure while applying the torque.
또한, 본 발명의 일 실시예에 따른 상기 공액디엔계 공중합체는 수평균분자량(Mn)이 100,000 g/mol 내지 1,000,000 g/mol, 구체적으로는 200,000 g/mol 내지 800,000 g/mol, 보다 구체적으로는 200,000 g/mol 내지 500,000 g/mol일 수 있고, 중량평균 분자량(Mw)이 100,000 g/mol 내지 1,800,000 g/mol, 구체적으로는 200,000 g/mol 내지 1,300,000 g/mol, 보다 구체적으로는 300,000 g/mol 내지 1,000,000 g/mol일 수 있으며, 분자량 분포(Mw/Mn)이 1.0 내지 3.0, 1.1 내지 2.5 또는 1.1 내지 2.0일 수 있다. In addition, the conjugated diene-based copolymer according to an embodiment of the present invention has a number average molecular weight (Mn) of 100,000 g/mol to 1,000,000 g/mol, specifically 200,000 g/mol to 800,000 g/mol, more specifically may be 200,000 g/mol to 500,000 g/mol, and a weight average molecular weight (Mw) of 100,000 g/mol to 1,800,000 g/mol, specifically 200,000 g/mol to 1,300,000 g/mol, more specifically 300,000 g It may be /mol to 1,000,000 g/mol, and the molecular weight distribution (Mw/Mn) may be 1.0 to 3.0, 1.1 to 2.5, or 1.1 to 2.0.
본 발명에서, 중량평균 분자량(Mw) 및 수평균 분자량(Mn)은 각각 겔 투과형 크로마토그래피(GPC)로 분석되는 폴리스티렌 환산 분자량이며, 분자량 분포(Mw/Mn)는 다분산성(polydispersity)이라고도 불리며, 중량평균 분자량(Mw)과 수평균 분자량(Mn)과의 비(Mw/Mn)로 계산하였다.In the present invention, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC), respectively, and the molecular weight distribution (Mw / Mn) is also called polydispersity, It was calculated as the ratio (Mw/Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn).
상기 공액디엔계 공중합체는 총 공중합체 중량 기준 비닐 함량이 10% 이상, 구체적으로는 15% 이상, 보다 구체적으로는 20% 내지 50%일 수 있고, 이 범위 내에서 중합체의 유리전이온도가 조절되어 타이어에 적용시 주행저항 및 제동력과 같은 타이어에 요구되는 물성을 만족시킬 수 있을 뿐만 아니라, 연료소모를 줄이는 효과가 있다. 이때 비닐 함량은 공액디엔계 공중합체 100 중량%에 대하여 1,4-첨가가 아닌 1,2-첨가된 공액디엔계 단량체의 함량을 의미할 수 있다.The conjugated diene-based copolymer may have a vinyl content of 10% or more, specifically 15% or more, and more specifically 20% to 50%, based on the total weight of the copolymer, and the glass transition temperature of the polymer is controlled within this range. When applied to a tire, it can satisfy the physical properties required for the tire, such as running resistance and braking force, as well as reduce fuel consumption. In this case, the vinyl content may mean the content of the 1,2-added conjugated diene-based monomer, not the 1,4-added, based on 100% by weight of the conjugated diene-based copolymer.
또한, 본 발명은 상기 공액디엔계 공중합체의 제조방법을 제공한다. In addition, the present invention provides a method for producing the conjugated diene-based copolymer.
본 발명의 일 실시예에 따른 상기 제조방법은 탄화수소 용매 중에서, 유기금속 화합물 존재 하에 제1 공액디엔계 단량체 및 방향족 비닐계 단량체를 제1 중합하여 제1 중합물을 제조하는 단계(단계 1); 및 상기 제1 중합물에 제2 공액디엔계 단량체를 투입하고 제2 중합하는 단계(단계 2)를 포함하고, 상기 제2 공액디엔계 단량체는 하기 수학식 1을 만족하는 시점에 투입하는 것을 특징으로 한다. The manufacturing method according to an embodiment of the present invention comprises the steps of preparing a first polymer by first polymerizing a first conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon solvent in the presence of an organometallic compound (step 1); and adding a second conjugated diene-based monomer to the first polymer and performing a second polymerization (step 2), wherein the second conjugated diene-based monomer is added at a time when the following Equation 1 is satisfied. do.
[수학식 1][Equation 1]
(a:b)=(c:d)(a:b)=(c:d)
상기 수학식 1에서, In Equation 1 above,
a:b는 제1 중합에서 제1 공액디엔계 단량체와 방향족 비닐계 단량체의 중량비이고, a: b is the weight ratio of the first conjugated diene-based monomer and the aromatic vinyl-based monomer in the first polymerization,
c:d는 제1 중합물 내에 제1 공액디엔계 단량체 유래 단위와 방향족 비닐계 단량체 유래 단위의 중량비이다.c:d is a weight ratio of the unit derived from the first conjugated diene-based monomer and the unit derived from the aromatic vinyl-based monomer in the first polymer.
상기 단계 1은 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 단위를 포함하는 제1 중합물을 제조하기 위한 단계로, 탄화수소 용매 중에서 유기금속 화합물 존재 하에 제1 공액디엔계 단량체 및 방향족 비닐계 단량체를 제1 중합함으로써 수행할 수 있다. Step 1 is a step for preparing a first polymer comprising an aromatic vinyl-based monomer and a random copolymerized unit derived from a conjugated diene-based monomer, wherein the first conjugated diene-based monomer and the aromatic vinyl-based monomer are prepared in the presence of an organometallic compound in a hydrocarbon solvent. It can be carried out by first polymerization.
상기 탄화수소 용매는 특별히 제한하는 것은 아니나, 에컨대 n-펜탄, n-헥산, n-헵탄, 이소옥탄, 사이클로헥산, 톨루엔, 벤젠 및 크실렌으로 이루어진 군에서 선택된 1종 이상인 것일 수 있다. The hydrocarbon solvent is not particularly limited, but, for example, may be at least one selected from the group consisting of n-pentane, n-hexane, n-heptane, isooctane, cyclohexane, toluene, benzene and xylene.
상기 제1 공액디엔계 단량체는 앞서 정의한 공액디엔계 단량체와 같을 수 있고, 후술하는 제2 공액디엔계 단량체와 동일할 수 있다. 한편, 본 발명에서 제1 공액디엔계 단량체 및 제2 공액디엔계 단량체는 물질은 동일하나 제조방법 상 투입 시점의 차이를 명확히 나타내기 위하여 '제1' 및 '제2'로 구분한 것일 수 있다. The first conjugated diene-based monomer may be the same as the above-defined conjugated diene-based monomer, and may be the same as the second conjugated diene-based monomer to be described later. On the other hand, in the present invention, the first conjugated diene-based monomer and the second conjugated diene-based monomer have the same material, but may be divided into 'first' and 'second' in order to clearly indicate the difference in input timing in the manufacturing method. .
또한, 상기 방향족 비닐계 단량체는 앞서 정의한 바와 같을 수 있으며, 제1 공액디엔계 단량체, 제2 공액디엔계 단량체 및 방향족 비닐계 단량체의 사용량은 앞서 정의한 공액디엔계 공중합체를 제조할 수 있도록 적절히 조절하는 것일 수 있다. In addition, the aromatic vinyl-based monomer may be as defined above, and the amount of the first conjugated diene-based monomer, the second conjugated diene-based monomer and the aromatic vinyl-based monomer is appropriately adjusted so that the above-defined conjugated diene-based copolymer can be prepared. may be doing
상기 유기금속 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 있으며, 상기 유기금속 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, 나프틸칼륨, 리튬알콕사이드, 나트륨알콕사이드, 칼륨알콕사이드, 리튬술포네이트, 나트륨술포네이트, 칼륨술포네이트, 리튬아미드, 나트륨아미드, 칼류아미드 및 리튬 이소프로필아미드로 이루어진 군에서 선택된 1종 이상인 것일 수 있다. 구체적으로는 n-부틸리튬일 수 있다. 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, and the organometallic compound is, for example, methyl lithium; Ethyl lithium, propyl lithium, n-butyl lithium, s-butyl lithium, t-butyl lithium, hexyl lithium, n-decyl lithium, t-octyl lithium, phenyl lithium, 1-naphthyl lithium, n- eicosyl lithium, 4 -Butylphenyllithium, 4-tolylylithium, cyclohexyllithium, 3,5-di-n-heptylcyclohexyllithium, 4-cyclopentyllithium, naphthyl potassium, lithium alkoxide, sodium alkoxide, potassium alkoxide, lithium sulfonate, It may be at least one selected from the group consisting of sodium sulfonate, potassium sulfonate, lithium amide, sodium amide, caluamide and lithium isopropylamide. Specifically, it may be n-butyllithium.
상기 단계 1의 제1 중합은 극성 첨가제를 더 첨가하여 수행하는 것일 수 있으며, 상기 극성 첨가제는 단량체 총 100 g 대비 0.01 g 내지 2.0 g으로 첨가하는 것일 수 있다. 구체적으로는, 상기 극성 첨가제는 단량체 총 100 g 대비 0.05 g 내지 1.0 g, 더 구체적으로는 0.03 g 내지 0.5 g으로 첨가하는 것일 수 있다.The first polymerization in step 1 may be performed by further adding a polar additive, and the polar additive may be added in an amount of 0.01 g to 2.0 g based on 100 g of the total monomer. Specifically, the polar additive may be added in an amount of 0.05 g to 1.0 g, more specifically, 0.03 g to 0.5 g, based on 100 g of the total monomer.
상기 극성 첨가제는 테트라하이드로퓨란, 디테트라하이드로프릴프로판, 디에틸에테르, 시클로아말에테르, 디프로필에테르, 에틸렌디메틸에테르, 에틸렌디메틸에테르, 디에틸렌글리콜, 디메틸에테르, 3차 부톡시에톡시에탄 비스(3-디메틸아미노에틸)에테르, (디메틸아미노에틸)에틸에테르, 트리메틸아민, 트리에틸아민, 트리프로필아민 및 테트라메틸에틸렌디아민으로 이루어진 군으로부터 선택된 1종 이상인 것일 수 있다.The polar additive is tetrahydrofuran, ditetrahydroprilpropane, diethyl ether, cycloamal ether, dipropyl ether, ethylene dimethyl ether, ethylene dimethyl ether, diethylene glycol, dimethyl ether, tertiary butoxyethoxyethane bis ( It may be at least one selected from the group consisting of 3-dimethylaminoethyl) ether, (dimethylaminoethyl) ethyl ether, trimethylamine, triethylamine, tripropylamine, and tetramethylethylenediamine.
본 발명의 일 실시예에 따른 제조방법은 상기의 극성 첨가제를 사용함으로써 제1 공액디엔계 단량체 및 방향족 비닐계 단량체를 공중합시키는 경우 이들의 반응 속도 차이를 보완해줌으로써 랜덤 공중합체를 용이하게 형성할 수 있도록 유도할 수 있다.In the manufacturing method according to an embodiment of the present invention, when the first conjugated diene-based monomer and the aromatic vinyl-based monomer are copolymerized by using the polar additive, a random copolymer can be easily formed by compensating for a difference in their reaction rate. can be induced to do so.
상기 단계 1의 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 단계 1의 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 열을가하여 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.The polymerization in step 1 may be, for example, anionic polymerization, and as a specific example, living anionic polymerization having an anionic active site at the polymerization end by a growth polymerization reaction by an anion. In addition, the polymerization in step 1 may be an elevated temperature polymerization, isothermal polymerization, or constant temperature polymerization (adiabatic polymerization), wherein the constant temperature polymerization comprises the step of polymerizing by its own heat of reaction without optionally applying heat after adding an organometallic compound. It may mean a method, and the elevated temperature polymerization may refer to a polymerization method in which the temperature is increased by optionally applying heat after the organometallic compound is added, and the isothermal polymerization is performed by adding heat after adding the organometallic compound. It may refer to a polymerization method that maintains a constant temperature of the polymer by increasing heat or taking heat.
상기 제1 중합은 -20℃ 내지 150℃의 온도범위에서 수행하는 것일 수 있으며, 구체적으로는 0℃ 내지 120℃, 더욱 구체적으로는 50℃ 내지 100℃의 온도범위에서 수행하는 것일 수 있다.The first polymerization may be carried out in a temperature range of -20 °C to 150 °C, specifically 0 °C to 120 °C, more specifically 50 °C to 100 °C temperature range.
상기 단계 2는 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 단위 및 공액디엔계 단량체 유래 블록 중합 단위를 포함하되, 공액디엔계 단량체 유래 블록 중합 단위가 상기 랜덤 공중합체 단위 일 말단에 결합되어 있는 구조의 공액디엔계 공중합체를 제조하기 위한 단계로, 상기 제1 중합물에 제2 공액디엔계 단량체를 투입하고 제2 중합하여 수행할 수 있다.In step 2, a random copolymerized unit derived from an aromatic vinyl-based monomer and a conjugated diene-based monomer and a block polymerized unit derived from a conjugated diene-based monomer, wherein the block-polymerized unit derived from a conjugated diene-based monomer is bonded to one end of the random copolymer unit As a step for preparing a conjugated diene-based copolymer having a structure, it may be carried out by adding a second conjugated diene-based monomer to the first polymer and performing a second polymerization.
이때, 상기 제2 공액디엔계 단량체는 제1 공액디엔계 단량체 대비 7:1 내지 5:3(제1 공액디엔계 단량체:제2 공액디엔계 단량체)의 중량비가 되는 양으로 투입하는 것일 수 있다. In this case, the second conjugated diene-based monomer may be added in an amount that is a weight ratio of 7:1 to 5:3 (first conjugated diene-based monomer: second conjugated diene-based monomer) compared to the first conjugated diene-based monomer. .
한편, 상기 제2 공액디엔계 단량체는 상기 수학식 1을 만족하는 시점에 투입하는 것일 수 있다. Meanwhile, the second conjugated diene-based monomer may be added at a time point satisfying Equation 1 above.
상기 수학식 1에서, a:b는 제1 중합에서 제1 공액디엔계 단량체와 방향족 비닐계 단량체의 중량비, 즉 제1 중합에서 사용된 제1 공액디엔계 단량체의 사용량(a)과 방향족 비닐계 단량체의 사용량(b)의 중량비를 나타내는 것이고, c:d는 제1 중합물 내에 제1 공액디엔계 단량체 유래 단위와 방향족 비닐계 단량체 유래 단위의 중량비, 즉, 제1 중합물 내 방향족 비닐계 단량체와 공액디엔계 단량체 유래 랜덤 공중합 단위를 구성하는 방향족 비닐계 단량체 유래 단위의 비율(c)과 공액디엔계 단량체 유래 단위의 비율(d)의 중량비를 나타내는 것일 수 있다.In Equation 1, a:b is the weight ratio of the first conjugated diene-based monomer and the aromatic vinyl-based monomer in the first polymerization, that is, the amount of the first conjugated diene-based monomer used in the first polymerization (a) and the aromatic vinyl-based monomer. It represents the weight ratio of the amount of the monomer used (b), c:d is the weight ratio of the unit derived from the first conjugated diene-based monomer and the unit derived from the aromatic vinyl-based monomer in the first polymer, that is, the aromatic vinyl-based monomer and the conjugate of the first polymer. It may represent a weight ratio of the ratio (c) of the units derived from the aromatic vinyl-based monomer and the ratio (d) of the units derived from the conjugated diene-based monomer constituting the diene-based monomer-derived random copolymerization unit.
여기에서, 상기 수학식 1은 제1 중합에 사용된 제1 공액디엔계 단량체와 방향족 비닐계 단량체의 중합 전환율을 나타내는 것으로, 수학식 1을 만족한다는 것은 상기 제1 공액디엔계 단량체와 방향족 비닐계 단량체가 중합에 모두 참여하여 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 단위로 전환되었음을 나타내는 것일 수 있다. 구체적으로, 통상 방향족 비닐계 단량체는 공액디엔계 단량체 대비 반응속도가 느리며, 따라서 공액디엔계 단량체가 방향족 비닐계 단량체 보다 빠르게 소진되어 중합 사슬로 전환된다. 따라서 중합 반응 이후 중합물 내 공액디엔계 단량체 유래 단위와 방향족 비닐계 단량체 유래 단위의 비율이 초기 중합 반응에 사용된 공액디엔계 단량체와 방향족 비닐계 단량체의 비율과 동일해지는 시점은 방향족 비닐계 단량체가 중합에 모두 사용되어 소진된 시점일 수 있다. 즉, 상기 수학식 1을 만족하는 시점은 방향족 비닐계 단량체의 중합 전환율이 100%인 시점일 수 있고, 구체적으로는 오차범위(-3%)까지 포함하는 97% 내지 100%인 시점일 수 있다.Here, Equation 1 represents the polymerization conversion rate of the first conjugated diene-based monomer and the aromatic vinyl-based monomer used in the first polymerization, and satisfying Equation 1 means that the first conjugated diene-based monomer and the aromatic vinyl-based monomer are satisfied. It may indicate that all of the monomers participate in polymerization and are converted into random copolymerized units derived from aromatic vinyl-based monomers and conjugated diene-based monomers. Specifically, in general, the aromatic vinyl-based monomer has a slower reaction rate than the conjugated diene-based monomer, and therefore the conjugated diene-based monomer is consumed faster than the aromatic vinyl-based monomer and is converted into a polymer chain. Therefore, after the polymerization reaction, when the ratio of the unit derived from the conjugated diene monomer and the unit derived from the aromatic vinyl monomer in the polymer becomes the same as the ratio of the conjugated diene monomer and the aromatic vinyl monomer used in the initial polymerization reaction, the aromatic vinyl monomer is polymerized. It may be a point in time when it is all used up and exhausted. That is, the time point satisfying Equation 1 may be a time point at which the polymerization conversion rate of the aromatic vinyl-based monomer is 100%, and specifically may be a time point of 97% to 100% including an error range (-3%). .
이때, 상기 c:d는 중합 중, 반응기에서 중합물을 채취하여 NMR 분석을 통해 확인하였다. At this time, the c: d was confirmed through NMR analysis by collecting the polymer from the reactor during polymerization.
한편, 제2 중합은 제1 중합과 동일한 조건을 유지하면서 수행하는 것일 수 있다. Meanwhile, the second polymerization may be performed while maintaining the same conditions as the first polymerization.
아울러, 본 발명은 상기 변성 공액디엔계 중합체를 포함하는 고무 조성물을 제공한다.In addition, the present invention provides a rubber composition comprising the modified conjugated diene-based polymer.
상기 고무 조성물은 변성 공액디엔계 중합체를 0.1 중량% 내지 100 중량%, 구체적으로는 20 중량% 내지 90 중량%로 포함하는 것일 수 있다.The rubber composition may include 0.1 wt% to 100 wt% of the modified conjugated diene-based polymer, specifically 20 wt% to 90 wt%.
또한, 상기 고무 조성물은 상기 변성 공액디엔계 중합체 외에 필요에 따라 다른 고무 성분을 더 포함할 수 있으며, 이때 상기 고무 성분은 고무 조성물 총 중량에 대하여 90 중량% 이하의 함량으로 포함될 수 있다. 구체적으로는 상기 변성 공액디엔계 공중합체 100 중량부에 대하여 1 중량부 내지 90 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 component may be included in an amount of 90% by weight or less based on the total weight of the rubber composition. Specifically, it may be included in an amount of 1 part by weight to 90 parts by weight based on 100 parts by weight of the modified conjugated diene-based copolymer.
상기 고무 성분은 천연고무 또는 합성고무일 수 있으며, 예컨대 상기 고무 성분은 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 natural rubber or synthetic rubber, for example, the rubber component may include natural rubber (NR) containing cis-1,4-polyisoprene; Modified natural rubbers such as epoxidized natural rubber (ENR), deproteinized natural rubber (DPNR), and hydrogenated natural rubber that are modified or refined of 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. may be synthetic rubbers, and any one or mixture of two or more thereof may be used. there is.
또한, 상기 고무 조성물은 변성 공액디엔계 중합체 100 중량부에 대하여 0.1 중량부 내지 200 중량부의 충진제를 포함하는 것일 수 있으며, 구체적으로는 0.1 중량부 내지 150 중량부의 충진제를 포함하는 것일 수 있다. 상기 충진제는 실리카계 충진제, 카본블랙계 충진제 또는 이들 조합인 것일 수 있다.In addition, the rubber composition may include 0.1 parts by weight to 200 parts by weight of a filler based on 100 parts by weight of the modified conjugated diene-based polymer, and specifically, it may include 0.1 parts by weight to 150 parts by weight of the filler. The filler may be a silica-based filler, a carbon black-based filler, or a combination thereof.
상기 카본블랙계 충진제는 특별히 제한하는 것은 아니나, 예컨대 질소 흡착 비표면적(N2SA, JIS K 6217-2:2001에 준거해서 측정함)이 20 ㎡/g 내지 250 ㎡/g인 것일 수 있다. 또, 상기 카본블랙은 디부틸프탈레이트 흡유량(DBP)이 80 cc/100g 내지 200 cc/100g인 것일 수 있다. 상기 카본블랙의 질소흡착 비표면적이 250 m2/g을 초과하면 고무 조성물의 가공성이 저하될 우려가 있고, 20 m2/g 미만이면 카본블랙에 의한 보강 성능이 미미할 수 있다. 또한, 상기 카본블랙의 DBP 흡유량이 200 cc/100g을 초과하면 고무 조성물의 가공성이 저하될 우려가 있고, 80 cc/100g 미만이면 카본블랙에 의한 보강 성능이 미미할 수 있다. The carbon black-based filler is not particularly limited, but may have, for example, a nitrogen adsorption specific surface area (N 2 SA, measured in accordance with JIS K 6217-2:2001) of 20 m 2 /g to 250 m 2 /g. In addition, the carbon black may have a dibutyl phthalate oil absorption (DBP) of 80 cc/100g to 200 cc/100g. When the nitrogen adsorption specific surface area of the carbon black exceeds 250 m 2 /g, the processability of the rubber composition may decrease, and if it is less than 20 m 2 /g, the reinforcing performance by the carbon black may be insignificant. In addition, when the DBP oil absorption amount of the carbon black exceeds 200 cc/100g, there is a fear that the processability of the rubber composition is reduced, and when it is less than 80 cc/100g, the reinforcing performance by the carbon black may be insignificant.
또한, 상기 실리카는 특별히 제한하는 것은 아니나, 예컨대 습식 실리카(함수규산), 건식 실리카(무수규산), 규산칼슘, 규산알루미늄 또는 콜로이드 실리카 등일 수 있다. 구체적으로는, 상기 실리카는 파괴 특성의 개량 효과 및 웨트 그립성(wet grip)의 양립 효과가 가장 현저한 습실 실리카일 수 있다. 또한, 상기 실리카는 질소흡착 비표면적(nitrogen surface area per gram, N2SA)이 120 ㎡/g 내지 180 ㎡/g이고, CTAB(cetyl trimethyl ammonium bromide) 흡착 비표면적이 100 ㎡/g 내지 200 ㎡/g일 수 있다. 상기 실리카의 질소흡착 비표면적이 120 ㎡/g 미만이면 실리카에 의한 보강 성능이 저하될 우려가 있고, 180 ㎡/g을 초과하면 고무 조성물의 가공성이 저하될 우려가 있다. 또한, 상기 실리카의 CTAB 흡착 비표면적이 100 ㎡/g 미만이면 충진제인 실리카에 의한 보강 성능이 저하될 우려가 있고, 200 ㎡/g을 초과하면 고무 조성물의 가공성이 저하될 우려가 있다.In addition, the silica is not particularly limited, but may be, for example, wet silica (hydrous silicic acid), dry silica (silicic anhydride), calcium silicate, aluminum silicate or colloidal silica. Specifically, the silica may be wet silica having the most remarkable effect of improving fracture properties and coexisting effects of wet grip. In addition, the silica has a nitrogen adsorption specific surface area (nitrogen surface area per gram, N 2 SA) of 120 m / g to 180 m / g, and a cetyl trimethyl ammonium bromide (CTAB) adsorption specific surface area of 100 m / g to 200 m It can be /g. If the nitrogen adsorption specific surface area of the silica is less than 120 m 2 /g, there is a fear that the reinforcing performance by silica may be lowered, and if it exceeds 180 m / g, there is a fear that the processability of the rubber composition may decrease. In addition, if the CTAB adsorption specific surface area of the silica is less than 100 m 2 /g, the reinforcing performance by the silica filler may decrease, and if it exceeds 200 m / g, the processability of the rubber composition may decrease.
한편, 상기 충진제로서 실리카가 사용될 경우 보강성 및 저발열성 개선을 위해 실란 커플링제가 함께 사용될 수 있다. On the other hand, when silica is used as the filler, a silane coupling agent may be used together to improve reinforcement and low heat generation.
상기 실란 커플링제로는 구체적으로 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 등을 들 수 있으며, 이들 중 어느 하나 또는 둘 이상의 혼합물이 사용될 수 있다. 보다 구체적으로는 보강성 개선 효과를 고려할 때 상기 실란 커플링제는 비스(3-트리에톡시실릴프로필)폴리술피드 또는 3-트리메톡시실릴프로필벤조티아질테트라술피드일 수 있다.Specifically, the silane coupling agent is bis(3-triethoxysilylpropyl)tetrasulfide, bis(3-triethoxysilylpropyl)trisulfide, bis(3-triethoxysilylpropyl)disulfide, bis (2-triethoxysilylethyl)tetrasulfide, bis(3-trimethoxysilylpropyl)tetrasulfide, bis(2-trimethoxysilylethyl)tetrasulfide, 3-mercaptopropyltrimethoxysilane , 3-mercaptopropyltriethoxysilane, 2-mercaptoethyltrimethoxysilane, 2-mercaptoethyltriethoxysilane, 3-trimethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfur Feed, 3-triethoxysilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide, 2-triethoxysilylethyl-N,N-dimethylthiocarbamoyltetrasulfide, 3-trimethoxysilyl Propylbenzothiazolyltetrasulfide, 3-triethoxysilylpropylbenzolyltetrasulfide, 3-triethoxysilylpropylmethacrylate monosulfide, 3-trimethoxysilylpropylmethacrylate monosulfide, bis (3-diethoxymethylsilylpropyl)tetrasulfide, 3-mercaptopropyldimethoxymethylsilane, dimethoxymethylsilylpropyl-N,N-dimethylthiocarbamoyltetrasulfide or dimethoxymethylsilylpropylbenzothiazolyl tetrasulfide and the like, and any one or a mixture of two or more thereof may be used. More specifically, in consideration of the reinforcing improvement effect, the silane coupling agent may be bis(3-triethoxysilylpropyl)polysulfide or 3-trimethoxysilylpropylbenzothiazyltetrasulfide.
또한, 상기 실란 커플링제는 충진제 100 중량부에 대하여 1 중량부 내지 20 중량부로 사용될 수 있다. 상기한 범위로 사용될 때, 커플링제로서의 효과가 충분히 발휘되면서도 고무 성분의 겔화를 방지할 수 있다. 보다 구체적으로는 상기 실란 커플링제는 실리카 100 중량부에 대하여 5 중량부 내지 15 중량부로 사용될 수 있다.In addition, the silane coupling agent may be used in an amount of 1 to 20 parts by weight based on 100 parts by weight of the filler. When used in the above range, it is possible to prevent gelation of the rubber component while sufficiently exhibiting the effect as a coupling agent. More specifically, the silane coupling agent may be used in an amount of 5 to 15 parts by weight based on 100 parts by weight of silica.
또한, 본 발명에 따른 일 실시예에 따른 고무 조성물은 황 가교성일 수 있으며, 이에 따라 가황제를 더 포함할 수 있다.In addition, the rubber composition according to an embodiment according to the present invention may be crosslinkable with sulfur, and thus may further include a vulcanizing agent.
상기 가황제는 구체적으로 황분말일 수 있으며, 고무 성분 100 중량부에 대하여 0.1 중량부 내지 10 중량부로 포함될 수 있다. 상기 함량범위로 포함될 때, 가황 고무 조성물의 필요한 탄성률 및 강도를 확보할 수 있으며, 동시에 저연비성을 얻을 수 있다.The vulcanizing agent may be specifically sulfur powder, and may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the rubber component. When included in the above content range, it is possible to secure the required elastic modulus and strength of the vulcanized rubber composition, and at the same time to obtain low fuel economy.
또한, 본 발명에 따른 일 실시예에 따른 고무 조성물은 상기한 성분들 외에, 통상 고무 공업계에서 사용되는 각종 첨가제, 구체적으로는 가황 촉진제, 공정오일, 가소제, 노화 방지제, 스코치 방지제, 아연화(zincoxide), 스테아르산, 열경화성 수지, 또는 열가소성 수지 등을 더 포함할 수 있다.In addition, the rubber composition according to an embodiment of the present invention includes, in addition to the above components, various additives commonly used in the rubber industry, specifically, a vulcanization accelerator, a process oil, a plasticizer, an anti-aging agent, an anti-scorch agent, zinc oxide , stearic acid, a thermosetting resin, or a thermoplastic resin may be further included.
상기 가황 촉진제는 특별히 한정되는 것은 아니며, 구체적으로는 M(2-머캅토벤조티아졸), DM(디벤조티아질디술피드), CZ(N-시클로헥실-2-벤조티아질술펜아미드) 등의 티아졸계 화합물, 혹은 DPG(디페닐구아니딘) 등의 구아니딘계 화합물이 사용될 수 있다. 상기 가황 촉진제는 고무 성분 100 중량부에 대하여 0.1 중량부 내지 5 중량부로 포함될 수 있다.The vulcanization accelerator is not particularly limited, and specifically, M (2-mercaptobenzothiazole), DM (dibenzothiazyl disulfide), CZ (N-cyclohexyl-2-benzothiazyl sulfenamide), etc. A thiazole-based compound of , or a guanidine-based compound such as DPG (diphenylguanidine) may be used. The vulcanization accelerator may be included in an amount of 0.1 parts by weight to 5 parts by weight based on 100 parts by weight of the rubber component.
또한, 상기 공정오일은 고무 조성물내 연화제로서 작용하는 것으로, 구체적으로는 파라핀계, 나프텐계, 또는 방향족계 화합물일 수 있으며, 보다 구체적으로는 인장 강도 및 내마모성을 고려할 때 방향족계 공정오일이, 히스테리시스 손실 및 저온 특성을 고려할 때 나프텐계 또는 파라핀계 공정오일이 사용될 수 있다. 상기 공정오일은 고무 성분 100 중량부에 대하여 100 중량부 이하의 함량으로 포함될 수 있으며, 상기 함량으로 포함될 때, 가황 고무의 인장 강도, 저발열성(저연비성)의 저하를 방지할 수 있다.In addition, the process oil acts as a softener in the rubber composition. Specifically, it may be a paraffinic, naphthenic, or aromatic compound. More specifically, in consideration of tensile strength and abrasion resistance, the aromatic process oil is Considering the loss and low temperature characteristics, 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.
또한, 상기 노화방지제로는 구체적으로 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 등을 들 수 있다. 상기 노화방지제는 고무 성분 100 중량부에 대하여 0.1 중량부 내지 6 중량부로 사용될 수 있다.In addition, the antioxidant is specifically N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6- and oxy-2,2,4-trimethyl-1,2-dihydroquinoline, or a high-temperature condensate of diphenylamine and acetone. The antioxidant 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 고무 조성물은 상기 배합 처방에 의해 밴버리 믹서, 롤, 인터널 믹서 등의 혼련기를 사용하여 혼련함으로써 수득될 수 있으며, 또 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 can be obtained by kneading using a kneader such as a Banbury mixer, a roll, or an internal mixer according to the above formulation, and also has low heat generation and wear resistance by a vulcanization process after molding processing. 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, 췌퍼, 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 each member of the tire, such as a tire tread, under tread, sidewall, carcass coated rubber, belt coated rubber, bead filler, chumper, or bead coated rubber, vibration proof rubber, belt conveyor, hose, etc. It may be useful in the manufacture of various industrial rubber products.
상기 고무 조성물을 이용하여 제조된 성형품은 타이어 또는 타이어 트레드를 포함하는 것일 수 있다.A molded article manufactured using the rubber composition may include a tire or a tire tread.
이하, 실시예 및 실험예에 의하여 본 발명을 더욱 상세하게 설명하고자 한다. 그러나, 하기 실시예 및 실험예는 본 발명을 예시하기 위한 것으로 이들 만으로 본 발명의 범위가 한정되는 것은 아니다. 또한, 이하 실시예 및 비교예에서 회분식 중합(batch type 중합)을 통한 일 예시만을 보였으나, 이는 본 발명을 예시하기 위한 것일 뿐 본 발명의 범위가 회분식 중합에만 한정되는 것은 아니다. Hereinafter, the present invention will be described in more detail by way of Examples and Experimental Examples. However, the following Examples and Experimental Examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto. In addition, although only one example through batch polymerization is shown in the following Examples and Comparative Examples, this is only for illustrating the present invention, and the scope of the present invention is not limited to batch polymerization.
실시예 1Example 1
20L 오토클레이브 반응기에 스티렌 160 g, 1,3-부타디엔 560 g 및 n-헥산 4,533 g, 극성 첨가제로 2,2-디(2-테트라하이드로퓨릴)프로판 6.53 mmol을 넣은 후 반응기 내부온도를 75℃로 승온하였다. 반응기 내부 온도가 75℃에 도달했을 때, n-부틸리튬 3.75 mmol을 반응기에 투입하여 30분 동안 제1 단열 승온 반응을 진행시켰다. 여기에 1,3- 부타디엔 80 g을 투입하여 75℃를 유지하면서 30분 동안 제2 단열 승온 반응을 진행시켰다. 이때, 제2 단열 승온 반응에서, 1,3-부타디엔은 제1 단열 승온 반응 이후 반응기에서 중합물을 채취하여 NMR분석을 실시한 후, 제1 단열 승온 반응시 사용된 스티렌과 1,3-부타디엔의 중량비와 NMR로 분석된 스티렌 유래 단위와 1,3-부타디엔 유래 단위의 중량비가 동일한 것을 확인하고 투입하였다(스티렌의 중합 전환율 100%인 시점). 이후 에탄올을 이용하여 중합반응을 정지시키고, 산화방지제인 BHT(부틸레이티드하이드록시톨루엔) 1.0 중량부를 첨가하였다. 그 결과 얻어진 중합물을 스팀 스트리핑으로 용매를 제거한 다음, 롤 건조하여 잔량의 용매 와 물을 제거하여, 공액디엔계 공중합체를 제조하였다.In a 20L autoclave reactor, 160 g of styrene, 560 g of 1,3-butadiene and 4,533 g of n-hexane, and 6.53 mmol of 2,2-di(2-tetrahydrofuryl)propane as a polar additive were added, and then the temperature inside the reactor was increased to 75°C. was heated to When the internal temperature of the reactor reached 75° C., 3.75 mmol of n-butyllithium was added to the reactor, and the first adiabatic temperature rising reaction was performed for 30 minutes. 80 g of 1,3-butadiene was added thereto, and a second adiabatic temperature increasing reaction was performed for 30 minutes while maintaining 75°C. At this time, in the second adiabatic temperature increasing reaction, 1,3-butadiene is obtained by collecting a polymer from the reactor after the first adiabatic temperature increasing reaction, performing NMR analysis, and then the weight ratio of styrene and 1,3-butadiene used in the first adiabatic temperature increasing reaction It was confirmed that the weight ratio of the styrene-derived unit and the 1,3-butadiene-derived unit analyzed by NMR and the NMR was the same, and was added (when the polymerization conversion rate of styrene was 100%). Thereafter, the polymerization reaction was stopped using ethanol, and 1.0 parts by weight of BHT (butylated hydroxytoluene), an antioxidant, was added. The resulting polymer was removed by steam stripping to remove the solvent, and then roll-dried to remove the residual amount of solvent and water to prepare a conjugated diene-based copolymer.
실시예 2Example 2
실시예 1에서, 제1 단열 승온 반응 시 1,3-부타디엔을 400 g으로 사용하고, 제2 단열 승온 반응 시 1,3-부타디엔을 240 g으로 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 공액디엔계 공중합체를 제조하였다(스티렌의 중합 전환율 99.8%). The same method as in Example 1, except that in Example 1, 400 g of 1,3-butadiene was used in the first adiabatic temperature increase reaction and 240 g of 1,3-butadiene was used in the second adiabatic temperature increase reaction. Conjugated diene-based copolymer was prepared through (99.8% polymerization conversion of styrene).
비교예 1Comparative Example 1
20L 오토클레이브 반응기에 스티렌 160 g, 1,3-부타디엔 640 g 및 n-헥산 4,533 g, 극성 첨가제로 2,2-디(2-테트라하이드로퓨릴)프로판 6.53 mmol을 넣은 후 반응기 내부온도를 75℃로 승온하였다. 반응기 내부 온도가 75℃에 도달했을 때, n-부틸리튬 3.75 mmol을 반응기에 투입하여 30분 동안 제1 단열 승온 반응을 진행시켰다. 이후 에탄올을 이용하여 중합반응을 정지시키고, 산화방지제인 BHT(부틸레이티드하이드록시톨루엔) 1.0 중량부를 첨가하였다. 그 결과 얻어진 중합물을 스팀 스트리핑으로 용매를 제거한 다음, 롤 건조하여 잔량의 용매 와 물을 제거하여, 공액디엔계 공중합체를 제조하였다.In a 20L autoclave reactor, 160 g of styrene, 640 g of 1,3-butadiene and 4,533 g of n-hexane, and 6.53 mmol of 2,2-di(2-tetrahydrofuryl)propane as a polar additive were added, and then the temperature inside the reactor was increased to 75°C. was heated to When the internal temperature of the reactor reached 75° C., 3.75 mmol of n-butyllithium was added to the reactor, and the first adiabatic temperature rising reaction was performed for 30 minutes. Thereafter, the polymerization reaction was stopped using ethanol, and 1.0 parts by weight of BHT (butylated hydroxytoluene), an antioxidant, was added. The resulting polymer was removed by steam stripping to remove the solvent, and then roll-dried to remove the residual amount of solvent and water to prepare a conjugated diene-based copolymer.
비교예 2Comparative Example 2
실시예 1에서, 제2 단열 승온 반응에서 1,3-부타디엔을 제1 단열 승온 반응시 사용된 스티렌과 1,3-부타디엔의 중량비 대비 NMR로 분석된 스티렌 유래 단위와 1,3-부타디엔 유래 단위의 중량비가 동일해지기 전에 투입한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 공액디엔계 공중합체를 제조하였다(스티렌의 중합 전환율 96%).In Example 1, the styrene-derived unit and 1,3-butadiene-derived unit analyzed by NMR compared to the weight ratio of styrene and 1,3-butadiene used in the first adiabatic temperature increasing reaction for 1,3-butadiene in the second adiabatic temperature increasing reaction A conjugated diene-based copolymer was prepared in the same manner as in Example 1, except that it was added before the weight ratio of the styrene became the same (the polymerization conversion rate of styrene was 96%).
비교예 3Comparative Example 3
실시예 1에서, 제1 단열 승온 반응 시 1,3-부타디엔을 240 g으로 사용하고, 제2 단열 승온 반응 시 1,3-부타디엔을 400 g으로 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 공액디엔계 공중합체를 제조하였다.The same method as in Example 1, except that in Example 1, 240 g of 1,3-butadiene was used in the first adiabatic temperature increase reaction, and 400 g of 1,3-butadiene was used in the second adiabatic temperature increase reaction. A conjugated diene-based copolymer was prepared through
비교예 4Comparative Example 4
실시예 1에서, 제1 단열 승온 반응 시 1,3-부타디엔을 600 g으로 사용하고, 제2 단열 승온 반응 시 1,3-부타디엔을 40 g으로 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통하여 공액디엔계 공중합체를 제조하였다.The same method as in Example 1, except that in Example 1, 600 g of 1,3-butadiene was used in the first adiabatic temperature increasing reaction and 40 g of 1,3-butadiene was used in the second adiabatic temperature increasing reaction. A conjugated diene-based copolymer was prepared through
실험예 1Experimental Example 1
상기 실시예 및 비교예에서 제조된 각 공액디엔계 공중합체의 미세구조 분석, 매크로 구조 분석 및 분자량 특성을 측정하였다. 결과를 하기 표 1에 나타내었다.Microstructure analysis, macro structure analysis and molecular weight characteristics of each conjugated diene-based copolymer prepared in Examples and Comparative Examples were measured. The results are shown in Table 1 below.
1) 미세구조 분석 1) Microstructure analysis
미세구조 분석 Varian VNMRS 500 Mhz NMR을 이용하여 측정하였으며, 용매로는 1,1,2,2-테트라클로로에탄 D2(Cambridge Isotope 社)를 사용하였다.Microstructure analysis was measured using Varian VNMRS 500 Mhz NMR, and 1,1,2,2-tetrachloroethane D2 (Cambridge Isotope) was used as a solvent.
2) 매크로 구조 분석2) Macro structure analysis
매크로 구조 분석은 무니점도와 감쇠시간(decay time) 분석으로 실시하였다.Macro structure analysis was performed by Mooney viscosity and decay time analysis.
무니점도는 MV-2000E(Monsanto 社)를 이용하여 rotor speed 2±0.02 rpm, Large Rotor를 사용하여 ML(1+4 at 100℃)를 측정하였다. 이때 시료는 실온(23±3℃)에서 30분 이상 방치한 후 27±3 g을 채취하여 Die Cavity 내부에 채워 넣고 Platen을 작동시켜 측정하였다.Mooney viscosity was measured using MV-2000E (Monsanto Co., Ltd.), rotor speed 2±0.02 rpm, and ML (1+4 at 100°C) using a large rotor. At this time, the sample was left at room temperature (23±3℃) for more than 30 minutes, and then 27±3 g was collected, filled in the die cavity, and measured by operating the platen.
감쇠시간(decay time)은 상기 무니점도 측정 완료 후 rotor가 멈춘 상태에서 2분간 Die Cavity 내부에 시료를 그대로 두고 시간 경과에 따른 torque 값의 감소 정도로 측정하였으며, 무니점도에 해당하는 torque 값에서 80%가 감소한(즉 20%의 torque 값) torque 값을 나타낸 시점을 감쇠시간으로 기록하였다. 이때, 감쇠시간이 클수록 공액디엔계 공중합체의 탄성이 우수함을 나타낸다. 한편, 감쇠시간의 증가는 공중합체 내 분자사슬 증가에 의해 나타나는 것으로 상기 감쇠시간이 적절한 수치로 증가하는 경우에는 가공성이 개선되어 충진제 분산 등에 긍정적인 영향을 미치게되나, 지나치게 증가하는 경우에는 가교 후에도 다수의 분자사슬 자유말단이 잔류하고 있어 오히려 주행 저항성에 부정적인 영향을 미치게 된다. 따라서, 이러한 특성을 반영하여, 감쇠시간은 2 분을 넘지 않는 것이 바람직할 수 있다.Decay time was measured by the degree of decrease in torque value over time by leaving the sample in the die cavity for 2 minutes with the rotor stopped after completing the Mooney viscosity measurement, and 80% from the torque value corresponding to Mooney viscosity The point at which the torque value decreased (that is, the torque value of 20%) was recorded as the damping time. At this time, the greater the damping time, the better the elasticity of the conjugated diene-based copolymer. On the other hand, the increase in the damping time is indicated by an increase in the molecular chain in the copolymer. When the damping time is increased to an appropriate value, the processability is improved, which has a positive effect on the dispersion of the filler, etc., but if it is excessively increased, many The free end of the molecular chain remains, which has a negative effect on driving resistance. Therefore, reflecting these characteristics, it may be preferable that the decay time does not exceed 2 minutes.
3) 분자량 특성3) molecular weight characteristics
상기 각 공중합체에 대한 분자량 특성은 중량평균 분자량(Mw), 수평균 분자량(Mn) 및 분자량 분포(Mw/Mn)을 측정하여 비교하였다.The molecular weight characteristics of each of the copolymers were compared by measuring the weight average molecular weight (Mw), the number average molecular weight (Mn), and the molecular weight distribution (Mw/Mn).
구체적으로, 각 공중합체를 40℃ 조건 하에서 테트라히드로퓨란(THF)에 30분간 녹인 후 겔 투과 크로마토 그래피(GPC: gel permeation chromatography)에 적재하여 흘려주었다. 이때, 칼럼은 폴리머 라보레토리즈사(Polymer Laboratories)의 상품명 PLgel Olexis 칼럼 두 자루와 PLgel mixed-C 칼럼 한 자루를 조합 사용하였다. 또 새로 교체한 칼럼은 모두 혼합상(mixed bed) 타입의 칼럼을 사용하였으며, 겔 투과 크로마토그래피 표준 물질(GPC STandard material)로서 폴리스티렌(Polystyrene)을 사용하였다. Specifically, each copolymer was dissolved in tetrahydrofuran (THF) for 30 minutes under a condition of 40° C., and then loaded and flowed through gel permeation chromatography (GPC). In this case, as the column, two PLgel Olexis columns manufactured by Polymer Laboratories and one PLgel mixed-C column were used in combination. In addition, all of the newly replaced columns used a mixed bed type column, and polystyrene was used as a gel permeation chromatography standard material (GPC STandard material).
(SM, wt%)styrene
(SM, wt%)
(ML(1+4) @ 100℃)Mooney Viscosity (PMV)
(ML(1+4) @ 100℃)
실험예 2Experimental Example 2
상기 실시예 및 비교예의 각 공중합체를 포함하는 고무 조성물 및 이로부터 제조된 성형품의 물성을 비교분석하기 위하여, 무니점도, 점탄성 특성 및 인장강도를 측정하였다. 결과를 하기 표 3에 나타내었다. In order to comparatively analyze the physical properties of the rubber composition including the copolymers of Examples and Comparative Examples and molded articles prepared therefrom, Mooney viscosity, viscoelastic properties, and tensile strength were measured. The results are shown in Table 3 below.
1) 가교된 고무의 제조1) Preparation of cross-linked rubber
각 가교된 고무는 제1단 혼련과 제2단 혼련과정을 거쳐 제조하였으며, 제1단 혼련과 제2단 혼련과정에서 사용된 물질은 하기 표 2에 나타내었다. 이때, 공중합체를 제외한 물질의 사용량은 공중합체 100 중량부를 기준으로 하여 나타낸 것이다. Each cross-linked rubber was manufactured through the first-stage kneading and second-stage kneading processes, and the materials used in the first-stage kneading and second-stage kneading processes are shown in Table 2 below. In this case, the amount of the material excluding the copolymer is shown based on 100 parts by weight of the copolymer.
제1단 혼련에서는 온도제어장치를 부속한 Inter-meshing 타입 반바리믹서를 사용하여 상기 각 공중합체, 충전제, 공정오일(process oil), 노화방지제, 산화아연(ZnO), 스테아린산(stearic acid), 왁스 및 산화방지제를 배합하여 제1단 혼련하였다. 이때, 제1단 혼련은 Rotor 회전수를 증가시켜 내부 온도를 150로 승온시키고 260초 동안 온도를 유지시켜 실시하여 제1 배합물을 얻었다. 제2단 혼련에서는 상기 제1 배합물을 실온까지 냉각한 후 혼련기에 고무 촉진제, 황분말 및 가황촉진제를 첨가하고 40의 150초 동안 50 rpm으로 마일드하게 믹싱한 후 70℃의 롤을 이용하여 시트 형태의 고무인 제2 배합물을 얻었다. 이후, 160℃ 프레스에서 각 제2 배합물을 t'90시간의 1.3배를 곱한 시간만큼 열을 가하여 각 가교된 고무를 제조하였다. In the first stage kneading, each copolymer, filler, process oil, antioxidant, zinc oxide (ZnO), stearic acid, The wax and antioxidant were blended and kneaded in the first stage. At this time, the first stage kneading was carried out by increasing the number of rotations of the rotor to raise the internal temperature to 150 and maintaining the temperature for 260 seconds to obtain a first formulation. In the second stage kneading, after cooling the first compound to room temperature, a rubber accelerator, sulfur powder and vulcanization accelerator are added to the kneader, and after mild mixing at 50 rpm for 150 seconds of 40 ° C., a sheet form using a roll at 70 ° C. A second formulation was obtained which is a rubber of Thereafter, each second compound was heated in a press at 160° C. for a time multiplied by 1.3 times t'90 hours to prepare each cross-linked rubber.
(50 wt% 카본블랙+50 wt% 비스(3-트리에톡시실릴프로필테트라술판))Z50S (Degussa)
(50 wt% carbon black + 50 wt% bis(3-triethoxysilylpropyltetrasulfane))
(폴리머라이즈드 2,2,4-트리메틸-1,2-디하이드로퀴놀린)RD (Flexsys)
(Polymerized 2,2,4-trimethyl-1,2-dihydroquinoline)
(N-1,3-디메틸부틸-N'-페닐-p-페닐렌디아민)6PPD (Flexsys)
(N-1,3-dimethylbutyl-N'-phenyl-p-phenylenediamine)
(디페닐구아니딘)DPG (Flexsys)
(diphenylguanidine)
(N-t-부틸-2-벤조티아질술폰아미드)CZ (Flexsys)
(Nt-Butyl-2-benzothiazylsulfonamide)
2) 무니점도2) Mooney viscosity
무니점도는 상기 가교된 고무 시편 제조 중에 제조된 각 제2 배합물을 이용하여 측정하였다. 구체적으로는 MV-2000E(Monsanto 社)를 이용하여 Rotor speed 2±0.02 rpm, Large Rotor를 사용하여 100℃에서 ML(1+4)를 측정하였다. 이때 시료는 실온(23±3℃)에서 30분 이상 방치한 후 27±3 g을 채취하여 Die Cavity 내부에 채워 넣고 Platen을 작동시켜 측정하였다. Mooney viscosity was measured using each of the second formulations prepared during the preparation of the cross-linked rubber specimen. Specifically, ML (1+4) was measured at 100° C. using a MV-2000E (Monsanto Co., Ltd.) with a rotor speed of 2±0.02 rpm and a large rotor. At this time, the sample was left at room temperature (23±3℃) for more than 30 minutes, and then 27±3 g was collected, filled in the die cavity, and measured by operating the platen.
3) 인장특성3) Tensile properties
인장특성은 ASTM 412의 인장시험법에 준하여 각 시험편을 제조하고 상기 시험편의 절단시의 인장강도, 300% 신장시의 인장응력(300% 모듈러스) 및 신율(%)를 측정하였다. 구체적으로, 인장특성은 Universal Test Machine 4204(Instron 社) 인장 시험기를 이용하여 실온에서 50 cm/min의 속도로 측정하여 인장강도 및 300% 신장시의 인장응력 값을 얻었다. For tensile properties, each test piece was prepared according to the tensile test method of ASTM 412, and the tensile strength at the time of cutting the test piece, tensile stress (300% modulus) and elongation (%) at 300% elongation were measured. Specifically, tensile properties were measured at room temperature at a speed of 50 cm/min using a Universal Test Machine 4204 (Instron Co., Ltd.) tensile tester to obtain tensile strength and tensile stress values at 300% elongation.
4) 점탄성 특성4) Viscoelastic properties
상기 제조된 각 가교된 고무의 주행 저항성(Rolling ResisTance, 60℃ Tan δ) 및 젖은 노면 저항성(wet grip, 0℃ Tan δ)를 측정하였다. The rolling resistance (Rolling Resistance, 60°C Tan δ) and wet grip (0°C Tan δ) of each crosslinked rubber prepared above were measured.
구체적으로, Explexor 500N(Gabo 社, 독일)를 이용하여 Frequency 10 Hz, Static Strain 3.5%, Dynamic Strain 3%에서 각 측정온도(0~70)에서 2 ℃/min으로 승온하면서 temperature sweep 모드로 측정하였다. 각 결과값은 비교예 1의 값을 100으로 하여 지수화(백분율, %)로 나타내었다.Specifically, using an Explexor 500N (Gabo, Germany), it was measured in a temperature sweep mode while raising the temperature to 2 ℃/min at each measurement temperature (0 to 70) at a frequency of 10 Hz, static strain 3.5%, and dynamic strain 3%. . Each result value was expressed as an index (percentage, %) with the value of Comparative Example 1 being 100.
(가공성)Mooney viscosity
(Processability)
(kgf/cm2)The tensile strength
(kgf/cm 2 )
(Index, %)Tan δ at 0
(Index, %)
(Index, %)Tan δ at 60
(Index, %)
상기 표 3에 나타난 바와 같이, 본 발명의 일 실시예에 따른 실시예 1 및 실시예 2가 비교예 1 내지 비교예 4 대비 인장특성, 점탄성 특성 및 가공성이 균형있게 우수한 것을 확인하였다. As shown in Table 3, it was confirmed that Examples 1 and 2 according to an embodiment of the present invention were superior in tensile properties, viscoelastic properties and workability compared to Comparative Examples 1 to 4 in a well-balanced manner.
한편, 비교예 3의 경우 실시예나 다른 비교예 대비 가공성이 향상되고 0℃에서의 Tan δ 값이 크게 증가하였으나, 60℃에서의 Tan δ 값이 급격하게 감소되어 가공성, 인장특성 및 점탄성 특성이 균형을 이루지 못하였다. 이는, 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 블록의 적어도 일 말단에 위치하는 공액디엔계 단량체 유래 중합 블록의 비율이 증가함에 따라 가공성이 향상될 수는 있으나, 특정비율을 초과하는 경우 공중합체 내 분자사슬이 과도하게 증가할 수 있고 이에 주행 저항성이 급격히 저하되는 등 물성 균형을 깨뜨릴 수 있음을 나타내는 것이다(표 1 및 감쇠시간 참고).On the other hand, in the case of Comparative Example 3, the workability was improved and the Tan δ value at 0° C. was greatly increased compared to the Examples and other comparative examples, but the Tan δ value at 60° C. was sharply decreased to balance the workability, tensile properties and viscoelastic properties. did not achieve This may improve processability as the ratio of the polymer block derived from the conjugated diene monomer positioned at at least one end of the random copolymer block derived from the aromatic vinyl monomer and the conjugated diene monomer increases, but when it exceeds a specific ratio, the This indicates that the molecular chain in the coalescing may be excessively increased, which may break the balance of physical properties, such as a sharp decrease in driving resistance (refer to Table 1 and damping time).
Claims (11)
[화학식 1]
(SB)-B1
상기 화학식 1에서,
SB는 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 블록이고, B1은 공액디엔계 단량체 유래 중합 블록이며,
상기 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 블록은 방향족 비닐계 단량체 유래 단위 20 중량% 내지 45 중량% 및 공액디엔계 단량체 유래 단위 55 중량% 내지 80 중량%를 포함하고,,
상기 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 블록 내 공액디엔계 단량체 유래 단위와 공액디엔계 단량체 유래 블록 중합 단위는 7:1 내지 5:3의 중량비를 갖는다.
A conjugated diene-based copolymer represented by the following formula (1) and comprising more than 5 wt% and 30 wt% or less of a polymer block derived from a conjugated diene-based monomer:
[Formula 1]
(SB)-B 1
In Formula 1,
SB is a random copolymer block derived from an aromatic vinyl-based monomer and a conjugated diene-based monomer, B 1 is a polymerized block derived from a conjugated diene-based monomer,
The random copolymer block derived from the aromatic vinyl-based monomer and the conjugated diene monomer comprises 20 wt% to 45 wt% of an aromatic vinyl-based monomer-derived unit and 55 wt% to 80 wt% of a unit derived from a conjugated diene-based monomer,
In the random copolymer block derived from the aromatic vinyl monomer and the conjugated diene monomer, the unit derived from the conjugated diene monomer and the unit derived from the conjugated diene monomer and the block polymerized unit derived from the conjugated diene monomer have a weight ratio of 7:1 to 5:3.
상기 공액디엔계 공중합체는 공액디엔계 단량체 유래 중합 블록을 10 중량% 이상, 30 중량% 이하로 포함하는 것인 공액디엔계 공중합체.
The method according to claim 1,
The conjugated diene-based copolymer is a conjugated diene-based copolymer comprising a polymer block derived from a conjugated diene-based monomer in an amount of 10 wt% or more and 30 wt% or less.
상기 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 블록은 중량평균 분자량이 100,000 g/mol 내지 1,300,000 g/mol인 것인 공액디엔계 공중합체.
The method according to claim 1,
The random copolymer block derived from the aromatic vinyl-based monomer and the conjugated diene-based monomer has a weight average molecular weight of 100,000 g/mol to 1,300,000 g/mol.
상기 공액디엔계 단량체 유래 중합 블록은 중량평균 분자량이 10,000 g/mol 내지 500,000 g/mol인 것인 공액디엔계 공중합체.
The method according to claim 1,
The conjugated diene-based monomer-derived polymerization block has a weight average molecular weight of 10,000 g/mol to 500,000 g/mol.
상기 공액디엔계 공중합체는 하기 수학식 2로 나타내는 무니점도 차(△ MV)가 12 미만인 공액디엔계 공중합체:
[수학식 2]
△ MV = CMV - PMV
상기 수학식 2에서 CMV는 공액디엔계 공중합체, 충전제 및 가교제를 포함하는 배합물의 무니점도이고, PMV는 공액디엔계 공중합체의 무니점도이다.
The method according to claim 1,
The conjugated diene-based copolymer is a conjugated diene-based copolymer having a Mooney viscosity difference (Δ MV) of less than 12 represented by the following Equation 2:
[Equation 2]
△ MV = CMV - PMV
In Equation 2, CMV is the Mooney viscosity of the blend including the conjugated diene-based copolymer, the filler, and the crosslinking agent, and PMV is the Mooney viscosity of the conjugated diene-based copolymer.
2) 상기 제1 중합물에 제2 공액디엔계 단량체를 투입하고 제2 중합하는 단계를 포함하고,
상기 제2 공액디엔계 단량체는 하기 수학식 1를 만족하는 시점에 투입하고
상기 제2 공액디엔계 단량체는 제1 공액디엔계 단량체 대비 7:1 내지 5:3(제1 공액디엔계 단량체:제2 공액디엔계 단량체)의 중량비가 되는 양으로 투입하는 것인,
하기 화학식 1로 표시되고 공액디엔계 단량체 유래 중합 블록을 5 중량% 초과 30 중량% 이하로 포함하는 공액디엔계 공중합체의 제조방법:
[수학식 1]
(a:b)=(c:d)
상기 수학식 1에서,
a:b는 제1 중합에서 제1 공액디엔계 단량체와 방향족 비닐계 단량체의 중량비이고,
c:d는 제1 중합물 내에 제1 공액디엔계 단량체 유래 단위와 방향족 비닐계 단량체 유래 단위의 중량비이며,
[화학식 1]
(SB)-B1
상기 화학식 1에서,
SB는 방향족 비닐계 단량체 및 공액디엔계 단량체 유래 랜덤 공중합 블록이고, B1은 공액디엔계 단량체 유래 중합 블록이다.
1) preparing a first polymer by first polymerizing a first conjugated diene-based monomer and an aromatic vinyl-based monomer in a hydrocarbon solvent in the presence of an organometallic compound; and
2) adding a second conjugated diene-based monomer to the first polymer and performing a second polymerization;
The second conjugated diene-based monomer is added at a time point satisfying Equation 1 below,
The second conjugated diene-based monomer is added in an amount that is a weight ratio of 7:1 to 5:3 (first conjugated diene-based monomer: second conjugated diene-based monomer) compared to the first conjugated diene-based monomer,
A method for producing a conjugated diene-based copolymer represented by the following formula (1) and comprising more than 5% by weight and not more than 30% by weight of a polymerization block derived from a conjugated diene-based monomer:
[Equation 1]
(a:b)=(c:d)
In Equation 1 above,
a: b is the weight ratio of the first conjugated diene-based monomer and the aromatic vinyl-based monomer in the first polymerization,
c: d is the weight ratio of the unit derived from the first conjugated diene-based monomer and the unit derived from the aromatic vinyl-based monomer in the first polymer,
[Formula 1]
(SB)-B 1
In Formula 1,
SB is a random copolymer block derived from an aromatic vinyl monomer and a conjugated diene monomer, and B 1 is a polymerization block derived from a conjugated diene monomer.
상기 단계 1)의 제1 중합은 극성 첨가제의 존재 하에 수행하는 것인 공액디엔계 공중합체의 제조방법.
9. The method of claim 8,
The first polymerization of step 1) is a method for producing a conjugated diene-based copolymer is carried out in the presence of a polar additive.
상기 극성 첨가제는 단량체 총 100 g 대비 0.01 g 내지 2.0 g으로 첨가하는 것인 공액디엔계 공중합체의 제조방법.9. The method of claim 8,
The polar additive is a method for producing a conjugated diene-based copolymer to be added in an amount of 0.01 g to 2.0 g based on 100 g of the total monomer.
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