JP5513338B2 - Butadiene polymer, process for producing the same, rubber composition and tire - Google Patents
Butadiene polymer, process for producing the same, rubber composition and tire Download PDFInfo
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- JP5513338B2 JP5513338B2 JP2010213893A JP2010213893A JP5513338B2 JP 5513338 B2 JP5513338 B2 JP 5513338B2 JP 2010213893 A JP2010213893 A JP 2010213893A JP 2010213893 A JP2010213893 A JP 2010213893A JP 5513338 B2 JP5513338 B2 JP 5513338B2
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- Prior art keywords
- butadiene
- component
- producing
- based polymer
- polymer
- 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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- 229920001971 elastomer Polymers 0.000 title description 46
- 239000005060 rubber Substances 0.000 title description 46
- 239000000203 mixture Substances 0.000 title description 35
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 title description 27
- 238000000034 method Methods 0.000 title description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 151
- 229920000642 polymer Polymers 0.000 claims description 52
- 239000003054 catalyst Substances 0.000 claims description 42
- 238000004519 manufacturing process Methods 0.000 claims description 37
- 239000000178 monomer Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 26
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 24
- 229910052779 Neodymium Inorganic materials 0.000 claims description 22
- -1 neodymium hydrocarbon Chemical class 0.000 claims description 21
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 19
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 19
- 239000002879 Lewis base Substances 0.000 claims description 18
- 150000002430 hydrocarbons Chemical group 0.000 claims description 18
- 150000007527 lewis bases Chemical class 0.000 claims description 18
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 150000007942 carboxylates Chemical class 0.000 claims description 8
- 229910001507 metal halide Inorganic materials 0.000 claims description 7
- 150000005309 metal halides Chemical class 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 150000002367 halogens Chemical class 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 5
- 239000002841 Lewis acid Substances 0.000 claims description 4
- 150000007517 lewis acids Chemical class 0.000 claims description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 150000002366 halogen compounds Chemical class 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- 238000004581 coalescence Methods 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 21
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000003795 chemical substances by application Substances 0.000 description 11
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 10
- 239000011521 glass Substances 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 229920002554 vinyl polymer Polymers 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910001868 water Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 6
- 230000003712 anti-aging effect Effects 0.000 description 6
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001993 dienes Chemical class 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 6
- GPNYZBKIGXGYNU-UHFFFAOYSA-N 2-tert-butyl-6-[(3-tert-butyl-5-ethyl-2-hydroxyphenyl)methyl]-4-ethylphenol Chemical compound CC(C)(C)C1=CC(CC)=CC(CC=2C(=C(C=C(CC)C=2)C(C)(C)C)O)=C1O GPNYZBKIGXGYNU-UHFFFAOYSA-N 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 4
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 238000001226 reprecipitation Methods 0.000 description 4
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 229940099607 manganese chloride Drugs 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 235000021317 phosphate Nutrition 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000005074 zinc chloride Nutrition 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 239000005968 1-Decanol Substances 0.000 description 2
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-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
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 description 2
- UZGARMTXYXKNQR-UHFFFAOYSA-K 7,7-dimethyloctanoate;neodymium(3+) Chemical compound [Nd+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O UZGARMTXYXKNQR-UHFFFAOYSA-K 0.000 description 2
- YPIFGDQKSSMYHQ-UHFFFAOYSA-N 7,7-dimethyloctanoic acid Chemical compound CC(C)(C)CCCCCC(O)=O YPIFGDQKSSMYHQ-UHFFFAOYSA-N 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 2
- 229910001626 barium chloride Inorganic materials 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 2
- VTZJFPSWNQFPCQ-UHFFFAOYSA-N dibutylaluminum Chemical compound CCCC[Al]CCCC VTZJFPSWNQFPCQ-UHFFFAOYSA-N 0.000 description 2
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 2
- JFICPAADTOQAMU-UHFFFAOYSA-L ethylaluminum(2+);dibromide Chemical compound CC[Al](Br)Br JFICPAADTOQAMU-UHFFFAOYSA-L 0.000 description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- ILPNRWUGFSPGAA-UHFFFAOYSA-N heptane-2,4-dione Chemical compound CCCC(=O)CC(C)=O ILPNRWUGFSPGAA-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 150000002798 neodymium compounds Chemical class 0.000 description 2
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 2
- GJYXGIIWJFZCLN-UHFFFAOYSA-N octane-2,4-dione Chemical compound CCCCC(=O)CC(C)=O GJYXGIIWJFZCLN-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000037048 polymerization activity Effects 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 description 1
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-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
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 description 1
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- VSKBCRUQHHGABO-UHFFFAOYSA-N [Al].[H][H].[H][H].[H][H] Chemical compound [Al].[H][H].[H][H].[H][H] VSKBCRUQHHGABO-UHFFFAOYSA-N 0.000 description 1
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- 238000004458 analytical method Methods 0.000 description 1
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- JUCWKFHIHJQTFR-UHFFFAOYSA-L beryllium iodide Chemical compound [Be+2].[I-].[I-] JUCWKFHIHJQTFR-UHFFFAOYSA-L 0.000 description 1
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- KZIUWSQALWALJH-UHFFFAOYSA-N bis(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)CP(O)(=O)CC(CC)CCCC KZIUWSQALWALJH-UHFFFAOYSA-N 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical class CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- TUBPQDOOWCNEEE-UHFFFAOYSA-N bis(4-nonylphenyl) hydrogen phosphate Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(O)(=O)OC1=CC=C(CCCCCCCCC)C=C1 TUBPQDOOWCNEEE-UHFFFAOYSA-N 0.000 description 1
- VXWHRXREMKFIFC-UHFFFAOYSA-N bis(4-nonylphenyl)phosphinic acid Chemical compound C1=CC(CCCCCCCCC)=CC=C1P(O)(=O)C1=CC=C(CCCCCCCCC)C=C1 VXWHRXREMKFIFC-UHFFFAOYSA-N 0.000 description 1
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- 125000001309 chloro group Chemical group Cl* 0.000 description 1
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- DZMKDJZCKIJKFW-UHFFFAOYSA-N di(octan-2-yl)phosphinic acid Chemical compound CCCCCCC(C)P(O)(=O)C(C)CCCCCC DZMKDJZCKIJKFW-UHFFFAOYSA-N 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
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- VJRUISVXILMZSL-UHFFFAOYSA-M dibutylalumanylium;chloride Chemical compound CCCC[Al](Cl)CCCC VJRUISVXILMZSL-UHFFFAOYSA-M 0.000 description 1
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- DXQYKFGICLVQFD-UHFFFAOYSA-N dioctan-2-yl hydrogen phosphate Chemical compound CCCCCCC(C)OP(O)(=O)OC(C)CCCCCC DXQYKFGICLVQFD-UHFFFAOYSA-N 0.000 description 1
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- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
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- XBKBZMOLSULOEA-UHFFFAOYSA-L methylaluminum(2+);dibromide Chemical compound C[Al](Br)Br XBKBZMOLSULOEA-UHFFFAOYSA-L 0.000 description 1
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- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
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- STMLQIACVZOCHU-UHFFFAOYSA-N octan-2-yl dihydrogen phosphate Chemical compound CCCCCCC(C)OP(O)(O)=O STMLQIACVZOCHU-UHFFFAOYSA-N 0.000 description 1
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- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
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- PFENPVAFZTUOOM-UHFFFAOYSA-N phenyl 3-oxobutanoate Chemical compound CC(=O)CC(=O)OC1=CC=CC=C1 PFENPVAFZTUOOM-UHFFFAOYSA-N 0.000 description 1
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- 239000010452 phosphate Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
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- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
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- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
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- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
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- 230000005070 ripening Effects 0.000 description 1
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- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
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- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- KXLQKNLVPVYVKX-UHFFFAOYSA-J tetrabromorhenium Chemical compound Br[Re](Br)(Br)Br KXLQKNLVPVYVKX-UHFFFAOYSA-J 0.000 description 1
- UXMRNSHDSCDMLG-UHFFFAOYSA-J tetrachlororhenium Chemical compound Cl[Re](Cl)(Cl)Cl UXMRNSHDSCDMLG-UHFFFAOYSA-J 0.000 description 1
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 238000000411 transmission spectrum Methods 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- ZIYNWDQDHKSRCE-UHFFFAOYSA-N tricyclohexylalumane Chemical compound C1CCCCC1[Al](C1CCCCC1)C1CCCCC1 ZIYNWDQDHKSRCE-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- GCZKMPJFYKFENV-UHFFFAOYSA-K triiodogold Chemical compound I[Au](I)I GCZKMPJFYKFENV-UHFFFAOYSA-K 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- RTAKQLTYPVIOBZ-UHFFFAOYSA-N tritert-butylalumane Chemical compound CC(C)(C)[Al](C(C)(C)C)C(C)(C)C RTAKQLTYPVIOBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Description
本発明は、ブタジエン系重合体及びその製造方法、並びにそれを用いたゴム組成物及びタイヤに関し、特にはシス-１,４結合含量が高いブタジエン系重合体の製造方法に関するものである。 The present invention relates to a butadiene polymer and a method for producing the same, and a rubber composition and a tire using the butadiene polymer, and particularly relates to a method for producing a butadiene polymer having a high cis-1,4 bond content.
従来、ブタジエン単量体から、該ブタジエン単量体単位のシス-１,４結合含量が高いポリブタジエンを合成するために、様々な触媒（主としてネオジム触媒）が検討されている。国際公開第２００５／０００９２１号（特許文献１）では、ネオジム化合物を触媒成分として用いることで、シス-１,４結合含量が98.0％以上で且つビニル結合含量が0.3％以下のブタジエン系重合体を合成できることが開示されている。また、特表２００５−５３０８７２号公報（特許文献２）では、ネオジム化合物に共役ジエン単量体を加えた触媒系を用いることで、シス-１,４結合含量が高いポリブタジエンを合成できることが開示されている。 Conventionally, various catalysts (mainly neodymium catalysts) have been studied in order to synthesize polybutadiene having a high cis-1,4 bond content of the butadiene monomer unit from the butadiene monomer. International Publication No. 2005/000921 (Patent Document 1) uses a neodymium compound as a catalyst component to provide a butadiene polymer having a cis-1,4 bond content of 98.0% or more and a vinyl bond content of 0.3% or less. It is disclosed that it can be synthesized. In addition, Japanese translation of PCT publication No. 2005-530872 (Patent Document 2) discloses that polybutadiene having a high cis-1,4 bond content can be synthesized by using a catalyst system in which a conjugated diene monomer is added to a neodymium compound. ing.
そこで、本発明の目的は、既知の手法により得たブタジエン系重合体と比べて、ブタジエン単量体単位のシス-１,４結合含量が高いブタジエン系重合体を提供することにある。また、本発明の他の目的は、かかるブタジエン系重合体を含んでなり、耐摩耗性、耐亀裂成長性、耐オゾン劣化性及び作業性に優れたゴム組成物、及び該ゴム組成物を少なくとも何れかの部材に用いたタイヤを提供することにある。 Accordingly, an object of the present invention is to provide a butadiene polymer having a cis-1,4 bond content in a butadiene monomer unit higher than that of a butadiene polymer obtained by a known method. Another object of the present invention is to provide such a butadiene-based polymer, which is excellent in wear resistance, crack growth resistance, ozone deterioration resistance and workability, and at least the rubber composition. The object is to provide a tire used for any member.
本発明者らは、上記目的を達成するために鋭意検討した結果、特定の触媒系とアセチレン系炭化水素との存在下、ブタジエンを含む単量体を重合することで、シス-１,４結合含量が高いブタジエン系重合体が得られることを見出し、本発明を完成させるに至った。 As a result of diligent studies to achieve the above object, the present inventors have polymerized a monomer containing butadiene in the presence of a specific catalyst system and an acetylenic hydrocarbon to thereby obtain a cis-1,4 bond. The inventors have found that a butadiene polymer having a high content can be obtained, and have completed the present invention.
即ち、本発明のブタジエン系重合体の製造方法は、
(Ａ)成分：周期律表の原子番号５７〜７１の希土類元素含有化合物、又はこれらの化合物とルイス塩基との反応物、
(Ｂ)成分：下記一般式(I)：
ＡｌＲ1Ｒ2Ｒ3 ・・・ (I)
［式中、Ｒ1及びＲ2は、同一又は異なり、炭素数１〜１０の炭化水素基又は水素原子で、Ｒ3は炭素数１〜１０の炭化水素基であり、但し、Ｒ3は上記Ｒ1又はＲ2と同一又は異なっていてもよい］で表される有機アルミニウム化合物、並びに
(Ｃ)成分：ルイス酸、金属ハロゲン化物とルイス塩基との錯化合物、及び活性ハロゲンを含む有機化合物からなる群から選択される少なくとも一種のハロゲン化合物
からなる触媒系と炭素数が２〜１０で且つ三重結合を持つ不飽和炭化水素との存在下、少なくとも１,３−ブタジエンを含む単量体を重合することを特徴とする。
That is, the method for producing the butadiene polymer of the present invention includes:
Component (A): a rare earth element-containing compound having an atomic number of 57 to 71 in the periodic table, or a reaction product of these compounds with a Lewis base,
(B) component: The following general formula (I):
AlR 1 R 2 R 3 ... (I)
[Wherein, R 1 and R 2 are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R 3 is a hydrocarbon group having 1 to 10 carbon atoms, provided that R 3 represents the above And may be the same as or different from R 1 or R 2 ], and
Component (C): a catalyst system comprising at least one halogen compound selected from the group consisting of Lewis acids, complex compounds of metal halides and Lewis bases, and organic compounds containing active halogens, and having 2 to 10 carbon atoms A monomer containing at least 1,3-butadiene is polymerized in the presence of an unsaturated hydrocarbon having a triple bond.
本発明のブタジエン系重合体の製造方法の好適例においては、前記触媒系が、前記(Ａ)成分、前記(Ｂ)成分、前記(Ｃ)成分及び前記不飽和炭化水素の存在下で調製されてなる。 In a preferred embodiment of the method for producing a butadiene-based polymer of the present invention, the catalyst system is prepared in the presence of the component (A), the component (B), the component (C) and the unsaturated hydrocarbon. It becomes.
本発明のブタジエン系重合体の製造方法の他の好適例においては、前記不飽和炭化水素が、炭素原子鎖の末端に三重結合を持ち、１−ブチンであることが好ましい。 In another preferred embodiment of the method for producing a butadiene polymer of the present invention, the unsaturated hydrocarbon preferably has 1 to butyne with a triple bond at the end of the carbon atom chain.
本発明のブタジエン系重合体の製造方法は、１,３−ブタジエン100gに対し、前記不飽和炭化水素を0.01〜10mmol用いるのが好ましい。 In the method for producing a butadiene-based polymer of the present invention, 0.01 to 10 mmol of the unsaturated hydrocarbon is preferably used with respect to 100 g of 1,3-butadiene.
本発明のブタジエン系重合体の製造方法の他の好適例においては、前記(Ａ)成分における希土類元素含有化合物がネオジムの炭化水素溶媒に可溶な塩であり、ここで、前記(Ａ)成分は、ネオジムの分岐カルボン酸塩、又は該塩とルイス塩基との反応物であることが好ましい。 In another preferred embodiment of the method for producing a butadiene-based polymer of the present invention, the rare earth element-containing compound in the component (A) is a salt soluble in a neodymium hydrocarbon solvent, wherein the component (A) Is preferably a neodymium branched carboxylate or a reaction product of the salt and a Lewis base.
また、本発明のブタジエン系重合体は、上記の方法によって得られたことを特徴とし、更に、本発明のゴム組成物は、該ブタジエン系重合体を含むことを特徴とし、また更に、本発明のタイヤは、該ゴム組成物をタイヤのいずれかの部材に用いたことを特徴とする。 The butadiene polymer of the present invention is obtained by the above method, and the rubber composition of the present invention further includes the butadiene polymer, and further, the present invention. This tire is characterized in that the rubber composition is used for any member of the tire.
本発明によれば、特定の触媒系とアセチレン系炭化水素との存在下、ブタジエンを含む単量体を重合することで、シス-１,４結合含量が高いブタジエン系重合体を提供することができる。また、かかるブタジエン系重合体を含んでなり、耐摩耗性、耐亀裂成長性、耐オゾン劣化性及び作業性に優れたゴム組成物、及び該ゴム組成物を少なくとも何れかの部材に用いたタイヤを提供することができる。 According to the present invention, it is possible to provide a butadiene polymer having a high cis-1,4 bond content by polymerizing a monomer containing butadiene in the presence of a specific catalyst system and an acetylene hydrocarbon. it can. Also, a rubber composition comprising such a butadiene-based polymer and having excellent wear resistance, crack growth resistance, ozone deterioration resistance and workability, and a tire using the rubber composition as at least any member Can be provided.
以下に、本発明のブタジエン系重合体の製造方法を詳細に説明する。本発明のブタジエン系重合体の製造方法は、以下に詳述する(Ａ)成分、(Ｂ)成分及び(Ｃ)成分からなる触媒系と炭素数が２〜１０で且つ三重結合を持つ不飽和炭化水素との存在下、少なくとも１,３-ブタジエンを含む単量体を重合することを特徴とする。 Below, the manufacturing method of the butadiene-type polymer of this invention is demonstrated in detail. The method for producing a butadiene-based polymer of the present invention comprises a catalyst system comprising the components (A), (B) and (C), which will be described in detail below, and an unsaturated group having 2 to 10 carbon atoms and having a triple bond. It is characterized in that a monomer containing at least 1,3-butadiene is polymerized in the presence of a hydrocarbon.
本発明のブタジエン系重合体の製造方法に使用する触媒系の（Ａ）成分は、周期律表の原子番号５７〜７１の希土類元素を含有する化合物、又はこれらの化合物とルイス塩基との反応物である。ここで、原子番号５７〜７１の希土類元素の中でも、ネオジム、プラセオジウム、セリウム、ランタン、ガドリニウム等、又はこれらの混合物が好ましく、ネオジムが特に好ましい。 The component (A) of the catalyst system used in the method for producing a butadiene polymer of the present invention is a compound containing a rare earth element having an atomic number of 57 to 71 in the periodic table, or a reaction product of these compounds with a Lewis base. It is. Here, among the rare earth elements having atomic numbers 57 to 71, neodymium, praseodymium, cerium, lanthanum, gadolinium, or the like, or a mixture thereof is preferable, and neodymium is particularly preferable.
上記希土類元素含有化合物としては、炭化水素溶媒に可溶な塩が好ましく、具体的には、上記希土類元素のカルボン酸塩、アルコキサイド、β−ジケトン錯体、リン酸塩及び亜リン酸塩が挙げられ、これらの中でも、カルボン酸塩及びリン酸塩が好ましく、カルボン酸塩が特に好ましい。ここで、炭化水素溶媒としては、ブタン、ペンタン、ヘキサン、ヘプタン等の炭素数４〜１０の飽和脂肪族炭化水素、シクロペンタン、シクロヘキサン等の炭素数５〜２０の飽和脂環式炭化水素、１−ブテン、２−ブテン等のモノオレフィン類、ベンゼン、トルエン、キシレン等の芳香族炭化水素、塩化メチレン、クロロホルム、トリクロロエチレン、パークロロエチレン、１，２−ジクロロエタン、クロロベンゼン、ブロモベンゼン、クロロトルエン等のハロゲン化炭化水素が挙げられる。 The rare earth element-containing compound is preferably a salt soluble in a hydrocarbon solvent, and specifically includes the rare earth element carboxylates, alkoxides, β-diketone complexes, phosphates and phosphites. Of these, carboxylates and phosphates are preferable, and carboxylates are particularly preferable. Here, examples of the hydrocarbon solvent include saturated aliphatic hydrocarbons having 4 to 10 carbon atoms such as butane, pentane, hexane and heptane, saturated alicyclic hydrocarbons having 5 to 20 carbon atoms such as cyclopentane and cyclohexane, -Monoolefins such as butene, 2-butene, aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform, trichloroethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, chlorotoluene, etc. A halogenated hydrocarbon is mentioned.
上記希土類元素のカルボン酸塩としては、下記一般式(II)：
(Ｒ4−ＣＯ2)3Ｍ ・・・ (II)
（式中、Ｒ4は炭素数１〜２０の炭化水素基で、Ｍは周期律表の原子番号５７〜７１の希土類元素である）で表される化合物が挙げられる。ここで、Ｒ4は、飽和又は不飽和でもよく、アルキル基及びアルケニル基が好ましく、直鎖状、分岐状及び環状のいずれでもよい。また、カルボキシル基は、１級、２級又は３級の炭素原子に結合している。該カルボン酸塩として、具体的には、オクタン酸、２−エチルヘキサン酸、オレイン酸、ネオデカン酸、ステアリン酸、安息香酸、ナフテン酸、バーサチック酸［シェル化学（株）製の商品名であって、カルボキシル基が３級炭素原子に結合しているカルボン酸］等の塩が挙げられ、これらの中でも、２−エチルヘキサン酸、ネオデカン酸、ナフテン酸、バーサチック酸の塩が好ましい。
As the rare earth element carboxylate, the following general formula (II):
(R 4 -CO 2 ) 3 M (II)
(Wherein, R 4 is a hydrocarbon group having 1 to 20 carbon atoms, and M is a rare earth element having an atomic number of 57 to 71 in the periodic table). Here, R 4 may be saturated or unsaturated, is preferably an alkyl group or an alkenyl group, and may be linear, branched or cyclic. The carboxyl group is bonded to a primary, secondary or tertiary carbon atom. Specific examples of the carboxylate include octanoic acid, 2-ethylhexanoic acid, oleic acid, neodecanoic acid, stearic acid, benzoic acid, naphthenic acid, versatic acid [trade names of Shell Chemical Co., Ltd. , A carboxylic acid in which a carboxyl group is bonded to a tertiary carbon atom] and the like. Among these, salts of 2-ethylhexanoic acid, neodecanoic acid, naphthenic acid, and versatic acid are preferable.
上記希土類元素のアルコキサイドとしては、下記一般式(III)：
(Ｒ5Ｏ)3Ｍ ・・・ (III)
（式中、Ｒ5は炭素数１〜２０の炭化水素基で、Ｍは周期律表の原子番号５７〜７１の希土類元素である）で表される化合物が挙げられる。Ｒ5Ｏで表されるアルコキシ基としては、２−エチル−ヘキシルアルコキシ基、オレイルアルコキシ基、ステアリルアルコキシ基、フェノキシ基、ベンジルアルコキシ基等が挙げられる。これらの中でも、２−エチル−ヘキシルアルコキシ基、ベンジルアルコキシ基が好ましい。
As the rare earth element alkoxide, the following general formula (III):
(R 5 O) 3 M (III)
(Wherein, R 5 is a hydrocarbon group having 1 to 20 carbon atoms, and M is a rare earth element having an atomic number of 57 to 71 in the periodic table). The alkoxy group represented by R 5 O, 2-ethyl - hexyl alkoxy group, oleyl alkoxy group, stearyl alkoxy group, phenoxy group, and benzylalkoxy group. Among these, a 2-ethyl-hexylalkoxy group and a benzylalkoxy group are preferable.
上記希土類元素のβ−ジケトン錯体としては、上記希土類元素のアセチルアセトン錯体、ベンゾイルアセトン錯体、プロピオニトリルアセトン錯体、バレリルアセトン錯体、エチルアセチルアセトン錯体等が挙げられる。これらの中でも、アセチルアセトン錯体、エチルアセチルアセトン錯体が好ましい。 Examples of the rare earth element β-diketone complex include the rare earth element acetylacetone complex, benzoylacetone complex, propionitrileacetone complex, valerylacetone complex, and ethylacetylacetone complex. Among these, an acetylacetone complex and an ethylacetylacetone complex are preferable.
上記希土類元素のリン酸塩及び亜リン酸塩としては、上記希土類元素と、リン酸ビス（２−エチルヘキシル）、リン酸ビス（１−メチルヘプチル）、リン酸ビス（ｐ−ノニルフェニル）、リン酸ビス（ポリエチレングリコール−ｐ−ノニルフェニル）、リン酸（１−メチルヘプチル）（２−エチルヘキシル）、リン酸（２−エチルヘキシル）（ｐ−ノニルフェニル）、２−エチルヘキシルホスホン酸モノ−２−エチルヘキシル、２−エチルヘキシルホスホン酸モノ−ｐ−ノニルフェニル、ビス（２−エチルヘキシル）ホスフィン酸、ビス（１−メチルヘプチル）ホスフィン酸、ビス（ｐ−ノニルフェニル）ホスフィン酸、（１−メチルヘプチル）（２−エチルヘキシル）ホスフィン酸、（２−エチルヘキシル）（ｐ−ノニルフェニル）ホスフィン酸等との塩が挙げられ、これらの中でも、上記希土類元素と、リン酸ビス（２−エチルヘキシル）、リン酸ビス（１−メチルヘプチル）、２−エチルヘキシルホスホン酸モノ−２−エチルヘキシル、ビス（２−エチルヘキシル）ホスフィン酸との塩が好ましい。 Examples of the rare earth element phosphate and phosphite include the rare earth element, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl phosphate), bis (p-nonylphenyl) phosphate, phosphorus Acid bis (polyethylene glycol-p-nonylphenyl), phosphoric acid (1-methylheptyl) (2-ethylhexyl), phosphoric acid (2-ethylhexyl) (p-nonylphenyl), 2-ethylhexylphosphonic acid mono-2-ethylhexyl 2-ethylhexylphosphonic acid mono-p-nonylphenyl, bis (2-ethylhexyl) phosphinic acid, bis (1-methylheptyl) phosphinic acid, bis (p-nonylphenyl) phosphinic acid, (1-methylheptyl) (2 -Ethylhexyl) phosphinic acid, (2-ethylhexyl) (p-nonylphenyl) phosphine Among these, the rare earth elements, bis (2-ethylhexyl) phosphate, bis (1-methylheptyl) phosphate, mono-2-ethylhexyl 2-ethylhexylphosphonate, bis A salt with (2-ethylhexyl) phosphinic acid is preferred.
上記希土類元素含有化合物の中でも、ネオジムのリン酸塩、及びネオジムのカルボン酸塩が更に好ましく、特にネオジムの２−エチルヘキサン酸塩、ネオジムのネオデカン酸塩、ネオジムのバーサチック酸塩等のネオジムの分岐カルボン酸塩が最も好ましい。 Among the rare earth element-containing compounds, neodymium phosphate and neodymium carboxylate are more preferable, and in particular, neodymium branching such as neodymium 2-ethylhexanoate, neodymium neodecanoate, neodymium versatate, etc. Carboxylate is most preferred.
また、(Ａ)成分は、上記希土類元素含有化合物とルイス塩基との反応物でもよい。該反応物は、ルイス塩基によって、希土類元素含有化合物の溶剤への溶解性が向上しており、また、長期間安定に貯蔵することができる。上記希土類元素含有化合物を溶剤に容易に可溶化させるため、また、長期間安定に貯蔵するために用いられるルイス塩基は、希土類元素1モル当り0〜30モル、好ましくは1〜10モルの割合で、両者の混合物として、又は予め両者を反応させた生成物として用いられる。ここで、ルイス塩基としては、アセチルアセトン、テトラヒドロフラン、ピリジン、Ｎ,Ｎ−ジメチルホルムアミド、チオフェン、ジフェニルエーテル、トリエチルアミン、有機リン化合物、１価又は２価のアルコールが挙げられる。 The component (A) may be a reaction product of the rare earth element-containing compound and a Lewis base. The reaction product has improved solubility of the rare earth element-containing compound in the solvent due to the Lewis base, and can be stably stored for a long period of time. In order to easily solubilize the rare earth element-containing compound in a solvent and to store stably for a long period of time, the Lewis base is used in a proportion of 0 to 30 mol, preferably 1 to 10 mol, per mol of rare earth element. Or as a mixture of the two or as a product obtained by reacting both in advance. Here, examples of the Lewis base include acetylacetone, tetrahydrofuran, pyridine, N, N-dimethylformamide, thiophene, diphenyl ether, triethylamine, an organic phosphorus compound, and a monovalent or divalent alcohol.
以上に述べた(Ａ)成分としての希土類元素含有化合物又はこれらの化合物とルイス塩基との反応物は、１種単独で使用することも、２種以上を混合して用いることもできる。 The rare earth element-containing compound as the component (A) described above or the reaction product of these compounds and a Lewis base can be used singly or in combination of two or more.
本発明のブタジエン系重合体の製造方法に使用する触媒系の(Ｂ)成分は、下記一般式(I)：
ＡｌＲ1Ｒ2Ｒ3・・・ (I)
（式中、Ｒ1及びＲ2は、同一又は異なり、炭素数１〜１０の炭化水素基又は水素原子で、Ｒ3は炭素数１〜１０の炭化水素基であり、但し、Ｒ3は上記Ｒ1又はＲ2と同一又は異なっていてもよい）で表される有機アルミニウム化合物である。式(I)の有機アルミニウム化合物としては、トリメチルアルミニウム、トリエチルアルミニウム、トリ−ｎ−プロピルアルミニウム、トリイソプロピルアルミニウム、トリ−ｎ−ブチルアルミニウム、トリイソブチルアルミニウム、トリ−ｔ−ブチルアルミニウム、トリペンチルアルミニウム、トリヘキシルアルミニウム、トリシクロヘキシルアルミニウム、トリオクチルアルミニウム；水素化ジエチルアルミニウム、水素化ジ−ｎ−プロピルアルミニウム、水素化ジ−ｎ−ブチルアルミニウム、水素化ジイソブチルアルミニウム、水素化ジヘキシルアルミニウム、水素化ジイソヘキシルアルミニウム、水素化ジオクチルアルミニウム、水素化ジイソオクチルアルミニウム；エチルアルミニウムジハイドライド、ｎ−プロピルアルミニウムジハイドライド、イソブチルアルミニウムジハイドライド等が挙げられ、これらの中でも、トリエチルアルミニウム、トリイソブチルアルミニウム、水素化ジエチルアルミニウム、水素化ジイソブチルアルミニウムが好ましい。以上に述べた(Ｂ)成分としての有機アルミニウム化合物は、１種単独で使用することも、２種以上を混合して用いることもできる。
The component (B) of the catalyst system used in the method for producing a butadiene polymer of the present invention is represented by the following general formula (I):
AlR 1 R 2 R 3 ... (I)
(In the formula, R 1 and R 2 are the same or different, and are a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R 3 is a hydrocarbon group having 1 to 10 carbon atoms, provided that R 3 is the above. And may be the same as or different from R 1 or R 2 . Examples of organoaluminum compounds of formula (I) include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-t-butylaluminum, tripentylaluminum, Trihexyl aluminum, tricyclohexyl aluminum, trioctyl aluminum; diethyl aluminum hydride, di-n-propyl aluminum hydride, di-n-butyl aluminum hydride, diisobutyl aluminum hydride, dihexyl aluminum hydride, diisohexyl hydride Aluminum, dioctyl aluminum hydride, diisooctyl aluminum hydride; ethyl aluminum dihydride, n-propyl aluminum diha Doraido, include isobutyl aluminum dihydride and the like, among these, triethylaluminum, triisobutylaluminum, hydrogenated diethylaluminum, hydrogenated diisobutylaluminum are preferred. The organoaluminum compound as the component (B) described above can be used singly or as a mixture of two or more.
本発明のブタジエン系重合体の製造方法に使用する触媒系の(Ｃ)成分は、ルイス酸、金属ハロゲン化物とルイス塩基との錯化合物、及び活性ハロゲンを含む有機化合物からなる群から選択される少なくとも一種のハロゲン化合物である。 The component (C) of the catalyst system used in the method for producing a butadiene-based polymer of the present invention is selected from the group consisting of Lewis acids, complex compounds of metal halides and Lewis bases, and organic compounds containing active halogens. It is at least one halogen compound.
上記ルイス酸は、ルイス酸性を有し、炭化水素に可溶である。具体的には、二臭化メチルアルミニウム、二塩化メチルアルミニウム、二臭化エチルアルミニウム、二塩化エチルアルミニウム、二臭化ブチルアルミニウム、二塩化ブチルアルミニウム、臭化ジメチルアルミニウム、塩化ジメチルアルミニウム、臭化ジエチルアルミニウム、塩化ジエチルアルミニウム、臭化ジブチルアルミニウム、塩化ジブチルアルミニウム、セスキ臭化メチルアルミニウム、セスキ塩化メチルアルミニウム、セスキ臭化エチルアルミニウム、セスキ塩化エチルアルミニウム、二塩化ジブチルスズ、三臭化アルミニウム、三塩化アンチモン、五塩化アンチモン、三塩化リン、五塩化リン、四塩化スズ、四塩化ケイ素等が例示できる。これらの中でも、塩化ジエチルアルミニウム、セスキ塩化エチルアルミニウム、二塩化エチルアルミニウム、臭化ジエチルアルミニウム、セスキ臭化エチルアルミニウム、及び二臭化エチルアルミニウムが好ましい。また、トリエチルアルミニウムと臭素の反応生成物のようなアルキルアルミニウムとハロゲンの反応生成物を用いることもできる。 The Lewis acid has Lewis acidity and is soluble in hydrocarbons. Specifically, methyl aluminum dibromide, methyl aluminum dichloride, ethyl aluminum dibromide, ethyl aluminum dichloride, butyl aluminum dibromide, butyl aluminum dichloride, dimethyl aluminum bromide, dimethyl aluminum chloride, diethyl bromide Aluminum, diethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide, ethylaluminum sesquichloride, dibutyltin dichloride, aluminum tribromide, antimony trichloride, Examples include antimony pentachloride, phosphorus trichloride, phosphorus pentachloride, tin tetrachloride, and silicon tetrachloride. Among these, diethylaluminum chloride, sesquiethylaluminum chloride, ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide, and ethylaluminum dibromide are preferable. Alternatively, a reaction product of an alkylaluminum and a halogen such as a reaction product of triethylaluminum and bromine can be used.
上記金属ハロゲン化物とルイス塩基との錯化合物を構成する金属ハロゲン化物としては、塩化ベリリウム、臭化ベリリウム、ヨウ化ベリリウム、塩化マグネシウム、臭化マグネシウム、ヨウ化マグネシウム、塩化カルシウム、臭化カルシウム、ヨウ化カルシウム、塩化バリウム、臭化バリウム、ヨウ化バリウム、塩化亜鉛、臭化亜鉛、ヨウ化亜鉛、塩化カドミウム、臭化カドミウム、ヨウ化カドミウム、塩化水銀、臭化水銀、ヨウ化水銀、塩化マンガン、臭化マンガン、ヨウ化マンガン、塩化レニウム、臭化レニウム、ヨウ化レニウム、塩化銅、ヨウ化銅、塩化銀、臭化銀、ヨウ化銀、塩化金、ヨウ化金、臭化金等が挙げられ、これらの中でも、塩化マグネシウム、塩化カルシウム、塩化バリウム、塩化マンガン、塩化亜鉛、塩化銅が好ましく、塩化マグネシウム、塩化マンガン、塩化亜鉛、塩化銅が特に好ましい。 Examples of the metal halide constituting the complex compound of the above metal halide and Lewis base include beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, calcium chloride, calcium bromide, iodine. Calcium chloride, barium chloride, barium bromide, barium iodide, zinc chloride, zinc bromide, zinc iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, manganese chloride, Manganese bromide, manganese iodide, rhenium chloride, rhenium bromide, rhenium iodide, copper chloride, copper iodide, silver chloride, silver bromide, silver iodide, gold chloride, gold iodide, gold bromide, etc. Of these, magnesium chloride, calcium chloride, barium chloride, manganese chloride, zinc chloride, and copper chloride are preferred. , Magnesium chloride, manganese chloride, zinc chloride, copper chloride being particularly preferred.
また、上記金属ハロゲン化物とルイス塩基との錯化合物を構成するルイス塩基としては、リン化合物、カルボニル化合物、窒素化合物、エーテル化合物、アルコール等が好ましい。具体的には、リン酸トリブチル、リン酸トリ−２−エチルヘキシル、リン酸トリフェニル、リン酸トリクレジル、トリエチルホスフィン、トリブチルホスフィン、トリフェニルホスフィン、ジエチルホスフィノエタン、ジフェニルホスフィノエタン、アセチルアセトン、ベンゾイルアセトン、プロピオニトリルアセトン、バレリルアセトン、エチルアセチルアセトン、アセト酢酸メチル、アセト酢酸エチル、アセト酢酸フェニル、マロン酸ジメチル、マロン酸ジエチル、マロン酸ジフェニル、酢酸、オクタン酸、２−エチル−ヘキサン酸、オレイン酸、ステアリン酸、安息香酸、ナフテン酸、バーサチック酸、トリエチルアミン、Ｎ,Ｎ−ジメチルアセトアミド、テトラヒドロフラン、ジフェニルエーテル、２−エチル−ヘキシルアルコール、オレイルアルコール、ステアリルアルコール、フェノール、ベンジルアルコール、１−デカノール、ラウリルアルコール等が挙げられ、これらの中でも、リン酸トリ−２−エチルヘキシル、リン酸トリクレジル、アセチルアセトン、２−エチルヘキサン酸、バーサチック酸、２−エチルヘキシルアルコール、１−デカノール、ラウリルアルコールが好ましい。 Moreover, as a Lewis base which comprises the complex compound of the said metal halide and a Lewis base, a phosphorus compound, a carbonyl compound, a nitrogen compound, an ether compound, alcohol, etc. are preferable. Specifically, tributyl phosphate, tri-2-ethylhexyl phosphate, triphenyl phosphate, tricresyl phosphate, triethylphosphine, tributylphosphine, triphenylphosphine, diethylphosphinoethane, diphenylphosphinoethane, acetylacetone, benzoylacetone , Propionitrile acetone, valeryl acetone, ethyl acetylacetone, methyl acetoacetate, ethyl acetoacetate, phenyl acetoacetate, dimethyl malonate, diethyl malonate, diphenyl malonate, acetic acid, octanoic acid, 2-ethyl-hexanoic acid, olein Acid, stearic acid, benzoic acid, naphthenic acid, versatic acid, triethylamine, N, N-dimethylacetamide, tetrahydrofuran, diphenyl ether, 2-ethyl-hexyl alcohol, Examples include oleyl alcohol, stearyl alcohol, phenol, benzyl alcohol, 1-decanol, and lauryl alcohol. Among these, tri-2-ethylhexyl phosphate, tricresyl phosphate, acetylacetone, 2-ethylhexanoic acid, versatic acid, 2 -Ethylhexyl alcohol, 1-decanol and lauryl alcohol are preferred.
上記ルイス塩基は、上記金属ハロゲン化物1モル当り、0.01〜30モル、好ましくは0.5〜10モルの割合で反応させる。このルイス塩基との反応物を使用すると、ポリマー中に残存する金属を低減することができる。 The Lewis base is reacted at a ratio of 0.01 to 30 mol, preferably 0.5 to 10 mol, per 1 mol of the metal halide. When the reaction product with the Lewis base is used, the metal remaining in the polymer can be reduced.
上記活性ハロゲンを含む有機化合物としては、ベンジルクロライド等が挙げられる。 Examples of the organic compound containing the active halogen include benzyl chloride.
本発明のブタジエン系重合体の製造方法に使用する触媒系には、上記(Ａ)〜(Ｃ)成分の他に、更に(Ｄ)成分として、有機アルミニウムオキシ化合物、所謂アルミノキサンを添加してもよい。ここで、該アルミノキサンとしては、メチルアルミノキサン、エチルアルミノキサン、プロピルアルミノキサン、ブチルアルミノキサン、クロロアルミノキサン等が挙げられる。(Ｄ)成分としてアルミノキサンを加えることで、分子量分布がシャープになり、触媒としての活性も向上する。 In addition to the above components (A) to (C), an organic aluminum oxy compound, so-called aluminoxane may be added as a component (D) to the catalyst system used in the method for producing a butadiene polymer of the present invention. Good. Here, examples of the aluminoxane include methylaluminoxane, ethylaluminoxane, propylaluminoxane, butylaluminoxane, chloroaluminoxane and the like. By adding aluminoxane as the component (D), the molecular weight distribution becomes sharp and the activity as a catalyst is improved.
本発明で使用する触媒系の各成分の量又は組成比は、その目的又は必要性に応じて適宜選択される。このうち、(Ａ)成分は、１,３−ブタジエン100gに対し、0.00001〜1.0ミリモル用いるのが好ましく、0.0001〜0.5ミリモル用いるのが更に好ましい。(Ａ)成分の使用量が0.00001ミリモル未満では、重合活性が低くなり、1.0ミリモルを超えると、触媒濃度が高くなり、脱灰工程が必要となる。また、(Ａ)成分と(Ｂ)成分の割合は、モル比で、(Ａ)成分：(Ｂ)成分が1：1〜1：700、好ましくは1：3〜1：500である。更に、(Ａ)成分と(Ｃ)成分中のハロゲンの割合は、モル比で、1：0.1〜1：30、好ましくは1：0.2〜1：15、更に好ましくは1：2.0〜1：5.0である。また、(Ｄ)成分中のアルミニウムと(Ａ)成分との割合は、モル比で、1：1〜700：1、好ましくは3：1〜500：1である。これらの触媒量または構成成分比の範囲外では、高活性な触媒として作用せず、または、触媒残渣を除去する工程が必要になるため好ましくない。また、上記の(Ａ)〜(Ｃ)成分以外に、重合体の分子量を調節する目的で、水素ガスを共存させて重合反応を行ってもよい。 The amount or composition ratio of each component of the catalyst system used in the present invention is appropriately selected according to its purpose or necessity. Of these, the component (A) is preferably used in an amount of 0.00001 to 1.0 mmol, more preferably 0.0001 to 0.5 mmol, per 100 g of 1,3-butadiene. When the amount of component (A) used is less than 0.00001 mmol, the polymerization activity is low, and when it exceeds 1.0 mmol, the catalyst concentration increases and a deashing step is required. Moreover, the ratio of (A) component and (B) component is molar ratio, and (A) component: (B) component is 1: 1-1: 700, Preferably it is 1: 3-1: 500. Furthermore, the ratio of the halogen in the component (A) and the component (C) is in a molar ratio of 1: 0.1 to 1:30, preferably 1: 0.2 to 1:15, more preferably 1: 2.0 to 1: 5.0. It is. Further, the ratio of aluminum to the component (A) in the component (D) is 1: 1 to 700: 1, preferably 3: 1 to 500: 1 in terms of molar ratio. Outside the range of these catalyst amounts or component ratios, it is not preferable because it does not act as a highly active catalyst or requires a step of removing the catalyst residue. In addition to the above components (A) to (C), the polymerization reaction may be carried out in the presence of hydrogen gas for the purpose of adjusting the molecular weight of the polymer.
触媒成分として、上記の(Ａ)成分、(Ｂ)成分、(Ｃ)成分以外に、必要に応じて、１,３−ブタジエン等の共役ジエン単量体を少量、具体的には、(Ａ)成分の化合物1モル当り0〜1000モルの割合で用いてもよい。触媒成分としての１,３−ブタジエン等の共役ジエン単量体は必須ではないが、これを併用すると、触媒活性が一段と向上する利点がある。 As a catalyst component, in addition to the above components (A), (B), and (C), a small amount of a conjugated diene monomer such as 1,3-butadiene, if necessary, specifically (A ) Component may be used at a ratio of 0 to 1000 moles per mole of the compound. A conjugated diene monomer such as 1,3-butadiene as a catalyst component is not essential, but when used in combination, there is an advantage that the catalytic activity is further improved.
上記触媒の製造は、例えば、溶媒に(Ａ)成分〜(Ｃ)成分を溶解させ、さらに必要に応じて、１，３−ブタジエンを反応させることによる。その際、各成分の添加順序は、特に限定されず、更に(Ｄ)成分としてアルミノキサンを添加してもよい。重合活性の向上、重合開始誘導期間の短縮の観点からは、これら各成分を、予め混合して、反応させ、熟成させることが好ましい。ここで、熟成温度は、0〜100℃であり、20〜80℃が好ましい。0℃未満では、充分に熟成が行われず、100℃を超えると、触媒活性の低下や、分子量分布の広がりが起こる。また、熟成時間は、特に制限なく、重合反応槽に添加する前にライン中で接触させることでも熟成でき、通常は、0.5分以上あれば充分であり、数日間は安定である。 The production of the catalyst is, for example, by dissolving the components (A) to (C) in a solvent and further reacting 1,3-butadiene as necessary. In that case, the addition order of each component is not specifically limited, Furthermore, you may add aluminoxane as (D) component. From the viewpoint of improving the polymerization activity and shortening the polymerization initiation induction period, it is preferable that these components are mixed in advance, reacted and aged. Here, the aging temperature is 0 to 100 ° C, preferably 20 to 80 ° C. When the temperature is less than 0 ° C, ripening is not sufficiently performed, and when the temperature exceeds 100 ° C, the catalytic activity is lowered and the molecular weight distribution is widened. The aging time is not particularly limited, and can be ripened by contacting in the line before adding to the polymerization reaction tank. Usually, 0.5 minutes or more is sufficient and stable for several days.
また、本発明のブタジエン系重合体の製造方法は、１,３−ブタジエンを含む単量体を重合させる際に、上記触媒系と共に、炭素数が２〜１０で且つ三重結合を持つ不飽和炭化水素（以下、アセチレン系炭化水素ともいう）が存在することを必要とする。該不飽和炭化水素は、重合を進行させるための触媒成分とは異なるが、該不飽和炭化水素を用いることで、１,３-ブタジエン単量体単位のシス-１,４構造への選択性が向上し、シス-１,４結合含量が大幅に増加する。 The method for producing a butadiene-based polymer of the present invention comprises unsaturated carbonization having a carbon number of 2 to 10 and a triple bond together with the catalyst system when a monomer containing 1,3-butadiene is polymerized. Hydrogen (hereinafter also referred to as acetylenic hydrocarbon) needs to be present. The unsaturated hydrocarbon is different from the catalyst component for proceeding the polymerization, but by using the unsaturated hydrocarbon, selectivity to the cis-1,4 structure of the 1,3-butadiene monomer unit And the cis-1,4 bond content is greatly increased.
本発明のブタジエン系重合体の製造方法に使用するアセチレン系炭化水素は、炭素数が２〜１０で且つ三重結合を持つ化合物であり、ここで、三重結合は、炭素原子鎖の末端に位置するのが好ましい。また、上記アセチレン系炭化水素は、直鎖状及び分岐状のいずれでもよく、三重結合の他に二重結合を有してもよい。具体的には、アセチレン、プロピン（メチルアセチレン）、１−ブチン（エチルアセチレン）、ビニルアセチレン等のアセチレン類が例示できる。また、本発明で使用するアセチレン系炭化水素の量は、その目的又は必要性に応じて適宜選択されるが、１,３-ブタジエン100gに対し、0.01〜10mmolであるのが好ましい。該アセチレン系炭化水素の使用量が１,３-ブタジエン100gに対して0.01mmol未満では、選択性の向上効果が低くなり、一方、10mmolを超えると、ブタジエン系重合体の収率が低下する。 The acetylene hydrocarbon used in the method for producing a butadiene polymer of the present invention is a compound having 2 to 10 carbon atoms and a triple bond, wherein the triple bond is located at the end of the carbon atom chain. Is preferred. The acetylene hydrocarbon may be either linear or branched, and may have a double bond in addition to a triple bond. Specific examples include acetylenes such as acetylene, propyne (methylacetylene), 1-butyne (ethylacetylene), and vinylacetylene. The amount of the acetylene hydrocarbon used in the present invention is appropriately selected according to the purpose or necessity thereof, but is preferably 0.01 to 10 mmol with respect to 100 g of 1,3-butadiene. When the amount of the acetylenic hydrocarbon used is less than 0.01 mmol with respect to 100 g of 1,3-butadiene, the effect of improving the selectivity is lowered. On the other hand, when it exceeds 10 mmol, the yield of the butadiene polymer is lowered.
本発明のブタジエン系重合体の製造方法においては、例えば、触媒系を含む溶媒中にアセチレン系炭化水素を加えてもよいが、触媒系を調製する前にアセチレン系炭化水素を加えることが好ましい。即ち、上記触媒系は、(Ａ)成分、(Ｂ)成分、(Ｃ)成分及びアセチレン系炭化水素の存在下で調製されることが好ましく、これにより、シス-１,４構造への選択性を更に向上させることができる。 In the method for producing a butadiene-based polymer of the present invention, for example, acetylene-based hydrocarbons may be added to a solvent containing a catalyst system, but acetylene-based hydrocarbons are preferably added before preparing the catalyst system. That is, the catalyst system is preferably prepared in the presence of the component (A), the component (B), the component (C), and the acetylenic hydrocarbon, whereby the selectivity to the cis-1,4 structure is achieved. Can be further improved.
本発明のブタジエン系重合体の製造方法に使用する単量体は、少なくとも１,３−ブタジエンを含み、１,３−ブタジエンと共重合可能なその他の単量体を含んでもよい。ここで、１,３−ブタジエンと共重合可能なその他の単量体としては、例えば、炭素数５〜８の共役ジエン単量体、芳香族ビニル単量体等が挙げられ、これらの中でも、炭素数５〜８の共役ジエン単量体が好ましい。上記炭素数５〜８の共役ジエン単量体としては、２−メチル−１，３−ブタジエン、２，３−ジメチル−１，３−ブタジエン、１，３−ペンタジエン、１，３−ヘキサジエン等が挙げられる。上記芳香族ビニル単量体としては、スチレン、ｐ−メチルスチレン、α−メチルスチレン、ビニルナフタレン等が挙げられる。 The monomer used in the method for producing a butadiene polymer of the present invention contains at least 1,3-butadiene and may contain other monomers copolymerizable with 1,3-butadiene. Here, examples of other monomers copolymerizable with 1,3-butadiene include conjugated diene monomers having 5 to 8 carbon atoms, aromatic vinyl monomers, and the like. Among these, A conjugated diene monomer having 5 to 8 carbon atoms is preferred. Examples of the conjugated diene monomer having 5 to 8 carbon atoms include 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Can be mentioned. Examples of the aromatic vinyl monomer include styrene, p-methylstyrene, α-methylstyrene, and vinylnaphthalene.
上記ブタジエン系重合体の製造は、溶液重合で行うことが好ましい。ここで、溶液重合の場合、重合溶媒としては、不活性の有機溶媒を用いる。不活性の有機溶媒としては、ブタン、ペンタン、ヘキサン、ヘプタン等の炭素数４〜１０の飽和脂肪族炭化水素、シクロペンタン、シクロヘキサン等の炭素数５〜２０の飽和脂環式炭化水素、１−ブテン、２−ブテン等のモノオレフィン類、ベンゼン、トルエン、キシレン等の芳香族炭化水素、塩化メチレン、クロロホルム、四塩化炭素、トリクロロエチレン、パークロロエチレン、１，２−ジクロロエタン、クロロベンゼン、ブロモベンゼン、クロロトルエン等のハロゲン化炭化水素が挙げられる。これらの中でも、炭素数５〜６の脂肪族炭化水素、脂環式炭化水素が特に好ましい。これらの溶媒は、１種単独で使用してもよく、２種以上を混合して使用してもよい。 The production of the butadiene-based polymer is preferably performed by solution polymerization. Here, in the case of solution polymerization, an inert organic solvent is used as the polymerization solvent. Examples of the inert organic solvent include saturated aliphatic hydrocarbons having 4 to 10 carbon atoms such as butane, pentane, hexane and heptane, saturated alicyclic hydrocarbons having 5 to 20 carbon atoms such as cyclopentane and cyclohexane, 1- Monoolefins such as butene and 2-butene, aromatic hydrocarbons such as benzene, toluene and xylene, methylene chloride, chloroform, carbon tetrachloride, trichloroethylene, perchloroethylene, 1,2-dichloroethane, chlorobenzene, bromobenzene, chloro And halogenated hydrocarbons such as toluene. Among these, a C5-C6 aliphatic hydrocarbon and alicyclic hydrocarbon are especially preferable. These solvents may be used alone or in combination of two or more.
上記ブタジエン系重合体の製造は、25℃以下の重合温度で行うのが好ましく、10〜-78℃で行うのが更に好ましい。重合温度が25℃を超えると、重合反応を充分に制御することができず、生成したブタジエン系重合体のシス−１，４結合含量が低下するおそれがあり、ビニル結合含量が上昇してしまう。 The butadiene-based polymer is preferably produced at a polymerization temperature of 25 ° C. or less, more preferably from 10 to −78 ° C. When the polymerization temperature exceeds 25 ° C., the polymerization reaction cannot be sufficiently controlled, and the cis-1,4 bond content of the produced butadiene polymer may decrease, and the vinyl bond content increases. .
上記ブタジエン系重合体の製造は、回分式及び連続式のいずれで行ってもよい。また、上記ブタジエン系重合体の製造において、上記希土類元素化合物系触媒及び重合体を失活させないために、重合の反応系内に酸素、水、炭酸ガス等の失活作用のある化合物の混入を極力なくすような配慮が必要である。 The butadiene polymer may be produced either batchwise or continuously. In addition, in the production of the butadiene-based polymer, in order not to deactivate the rare earth element compound-based catalyst and the polymer, mixing of a deactivating compound such as oxygen, water, carbon dioxide gas in the polymerization reaction system. Consideration to eliminate as much as possible is necessary.
次に、本発明のブタジエン系重合体を詳細に説明する。本発明のブタジエン系重合体は、１,３−ブタジエン単量体単位を含み、上述の方法によって得られることを特徴とし、１,３−ブタジエン単量体単位のシス-１,４結合含量が非常に高い。なお、本発明では、ブタジエン系重合体中の１,３−ブタジエン単量体単位のミクロ構造は、ビニル結合含量の測定精度が高いことで知られるフーリエ変換赤外分光法（ＦＴ−ＩＲ法）により測定する。 Next, the butadiene polymer of the present invention will be described in detail. The butadiene-based polymer of the present invention includes a 1,3-butadiene monomer unit and is obtained by the above-described method, and has a cis-1,4 bond content of the 1,3-butadiene monomer unit. Very expensive. In the present invention, the microstructure of the 1,3-butadiene monomer unit in the butadiene polymer is Fourier transform infrared spectroscopy (FT-IR method), which is known to have high measurement accuracy of vinyl bond content. Measure with
＜ＦＴ−ＩＲによるミクロ構造の分析法＞
同一セルの二硫化炭素をブランクとして、5mg/mLの濃度に調製したブタジエン系重合体の二硫化炭素溶液のＦＴ−ＩＲ透過率スペクトルを測定し、該スペクトルの1130cm-1付近の山ピーク値をａ、967cm-1付近の谷ピーク値をｂ、911cm-1付近の谷ピーク値をｃ、736cm-1付近の谷ピーク値をｄとしたとき、下記行列式(IV)：
(シス−１,４結合含量)＝ｅ／(ｅ＋ｆ＋ｇ)×100（％） ・・・ (V)
(トランス−１,４結合含量)＝ｆ／(ｅ＋ｆ＋ｇ)×100（％） ・・・ (VI)
(ビニル結合含量)＝ｇ／(ｅ＋ｆ＋ｇ)×100（％） ・・・ (VII)
に従ってシス−１,４結合含量、トランス−１,４結合含量及びビニル結合含量を求める。なお、上記スペクトルの1130cm-1付近の山ピーク値ａはベースラインを、967cm-1付近の谷ピーク値ｂはトランス−１,４結合を、911cm-1付近の谷ピーク値ｃはビニル結合を、736cm-1付近の谷ピーク値ｄはシス−１,４結合を示す。
<Analysis method of microstructure by FT-IR>
Using the carbon disulfide in the same cell as a blank, measure the FT-IR transmittance spectrum of a carbon disulfide solution of a butadiene-based polymer prepared at a concentration of 5 mg / mL, and calculate the peak peak value near 1130 cm -1 of the spectrum. a, when the valley peak value b in the vicinity of 967 cm -1, a valley peak value c near 911 cm -1, a valley peak value around 736cm -1 was d, the following matrix equation (IV):
(Cis-1,4 bond content) = e / (e + f + g) × 100 (%) (V)
(Trans-1,4 bond content) = f / (e + f + g) × 100 (%) (VI)
(Vinyl bond content) = g / (e + f + g) × 100 (%) (VII)
To determine the cis-1,4 bond content, trans-1,4 bond content and vinyl bond content. In the above spectrum, the peak value a near 1130 cm −1 is the baseline, the valley peak value b near 967 cm −1 is the trans-1,4 bond, and the valley peak value c near 911 cm −1 is the vinyl bond. The valley peak value d near 736 cm −1 indicates a cis-1,4 bond.
本発明のブタジエン系重合体は、シス−１,４結合含量が98.0％以上であるのが好ましい。シス−１,４結合含量が98.0％未満であるブタジエン系重合体は、伸張結晶性が不充分で、ゴム組成物の耐摩耗性、耐亀裂成長性及び耐オゾン劣化性を向上させる効果が小さい。 The butadiene polymer of the present invention preferably has a cis-1,4 bond content of 98.0% or more. A butadiene-based polymer having a cis-1,4 bond content of less than 98.0% has insufficient stretch crystallinity, and has little effect of improving the wear resistance, crack growth resistance and ozone deterioration resistance of the rubber composition. .
本発明のブタジエン系重合体は、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）との比（Ｍｗ／Ｍｎ）、即ち分子量分布（Ｍｗ／Ｍｎ）が1.6〜3.5であるのが好ましく、1.6〜2.7であるのが更に好ましい。ここで、重量平均分子量（Ｍｗ）と数平均分子量（Ｍｎ）とは、ゲルパーミエーションクロマトグラフィー（ＧＰＣ）により測定したポリスチレン換算の値である。ブタジエン系重合体の分子量分布（Ｍｗ／Ｍｎ）が1.6未満では、該ブタジエン系重合体を含むゴム組成物の作業性が悪化するため、混練りが困難となり、ゴム組成物の物性を十分に向上できない場合がある。また、ブタジエン系重合体の分子量分布が3.5を超えると、ゴム組成物の未加硫粘度が改良される割にはヒステリシスロス等のゴム物性の低下が大きくなり好ましくない。 The butadiene polymer of the present invention preferably has a weight average molecular weight (Mw) to number average molecular weight (Mn) ratio (Mw / Mn), that is, a molecular weight distribution (Mw / Mn) of 1.6 to 3.5. More preferably, it is -2.7. Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values in terms of polystyrene measured by gel permeation chromatography (GPC). If the molecular weight distribution (Mw / Mn) of the butadiene polymer is less than 1.6, the workability of the rubber composition containing the butadiene polymer is deteriorated, so that kneading becomes difficult, and the physical properties of the rubber composition are sufficiently improved. There are cases where it is not possible. On the other hand, when the molecular weight distribution of the butadiene-based polymer exceeds 3.5, the rubber properties such as hysteresis loss are greatly deteriorated although the unvulcanized viscosity of the rubber composition is improved.
本発明のブタジエン系重合体は、数平均分子量（Ｍｎ）が100,000〜500,000であるのが好ましく、150,000〜300,000であるのが更に好ましい。ブタジエン系重合体の数平均分子量が100,000未満では、加硫物の弾性率が低下し、ヒステリシスロスが上昇し、更に耐摩耗性が悪化するため好ましくなく、500,000を超えると、該ブタジエン系重合体を含むゴム組成物の作業性が悪化して、混練りが困難となり、ゴム組成物の物性を十分に向上させることができない。 The butadiene-based polymer of the present invention preferably has a number average molecular weight (Mn) of 100,000 to 500,000, more preferably 150,000 to 300,000. If the number average molecular weight of the butadiene-based polymer is less than 100,000, the elastic modulus of the vulcanizate is decreased, the hysteresis loss is increased, and the wear resistance is further deteriorated. The workability of the rubber composition containing, deteriorates, making kneading difficult, and the physical properties of the rubber composition cannot be sufficiently improved.
本発明のブタジエン系重合体は、１,３−ブタジエン単量体単位が80〜100質量％で、１,３−ブタジエンと共重合可能なその他の単量体単位が20〜0質量％であるのが好ましい。重合体中の１,３−ブタジエン単量体単位含量が80質量％未満では、重合体全体に対する１,４−シス結合含量が低下する為、本発明の効果が発現しにくくなる。なお、本発明のブタジエン系重合体は、１,３−ブタジエン単量体のみからなるのが特に好ましく、即ち、ポリブタジエンゴム（ＢＲ）であるのが特に好ましい。ここで、１,３−ブタジエンと共重合可能なその他の単量体としては、上述した単量体が挙げられる。 In the butadiene-based polymer of the present invention, the 1,3-butadiene monomer unit is 80 to 100% by mass, and the other monomer unit copolymerizable with 1,3-butadiene is 20 to 0% by mass. Is preferred. When the 1,3-butadiene monomer unit content in the polymer is less than 80% by mass, the 1,4-cis bond content with respect to the whole polymer is lowered, and thus the effect of the present invention is hardly exhibited. The butadiene-based polymer of the present invention is particularly preferably composed of only 1,3-butadiene monomer, that is, particularly preferably polybutadiene rubber (BR). Here, examples of the other monomer copolymerizable with 1,3-butadiene include the monomers described above.
次に、本発明のゴム組成物を詳細に説明する。本発明のゴム組成物は、上述したブタジエン系重合体をゴム成分として含むことを特徴とする。上記ブタジエン系重合体をゴム組成物に配合することで、ゴム組成物の耐摩耗性、耐亀裂成長性及び耐オゾン劣化性を大幅に向上させることができる。また、かかる特性の向上効果を十分に確保するため、該ゴム組成物を構成するゴム成分は、上記ブタジエン系重合体を１０質量％以上含むのが好ましい。なお、本発明のゴム組成物には、ゴム成分として、上記ブタジエン系重合体の他、天然ゴム（ＮＲ）、ポリイソプレンゴム（ＩＲ）等のゴム成分を併用することができる。 Next, the rubber composition of the present invention will be described in detail. The rubber composition of the present invention is characterized by containing the butadiene-based polymer described above as a rubber component. By blending the butadiene-based polymer into the rubber composition, the wear resistance, crack growth resistance and ozone deterioration resistance of the rubber composition can be greatly improved. In order to sufficiently secure the effect of improving such characteristics, the rubber component constituting the rubber composition preferably contains 10% by mass or more of the butadiene-based polymer. In the rubber composition of the present invention, a rubber component such as natural rubber (NR) and polyisoprene rubber (IR) can be used in combination with the butadiene-based polymer as a rubber component.
本発明のゴム組成物は、上記ゴム成分100質量部に対して充填剤10質量部以上を配合してなるのが好ましい。充填剤を10質量部以上含むことで、ゴム組成物の補強性がより一層向上する。ここで、充填剤としては、カーボンブラック、シリカ等が挙げられる。 The rubber composition of the present invention is preferably formed by blending 10 parts by mass or more of a filler with 100 parts by mass of the rubber component. By containing 10 parts by mass or more of the filler, the reinforcing property of the rubber composition is further improved. Here, examples of the filler include carbon black and silica.
また、本発明のゴム組成物は、硫黄架橋性であるのが好ましい。ゴム組成物が硫黄で架橋された加硫ゴムは、タイヤ部材として十分な強度を有する。なお、本発明のゴム組成物は、耐摩耗性に優れるためタイヤのトレッドとして好適であり、また、耐亀裂成長性及び耐オゾン劣化性に優れるためタイヤのサイドウォールとしても好適である。また、作業性に優れるため、混練りが容易で、高い物性を発現することができる。 Further, the rubber composition of the present invention is preferably sulfur crosslinkable. Vulcanized rubber obtained by crosslinking a rubber composition with sulfur has sufficient strength as a tire member. The rubber composition of the present invention is suitable as a tire tread because of excellent abrasion resistance, and is also suitable as a sidewall of a tire because of excellent crack growth resistance and ozone degradation resistance. Moreover, since it is excellent in workability | operativity, kneading | mixing is easy and can express a high physical property.
上記ゴム組成物には、上述のゴム成分、充填剤の他、加硫剤、加硫促進剤、老化防止剤、スコーチ防止剤、軟化剤、酸化亜鉛、ステアリン酸、シランカップリング剤等のゴム業界で通常使用される配合剤を、本発明の目的を害しない範囲内で適宜選択し配合することができる。これら配合剤は、市販品を好適に使用することができる。なお、上記ゴム組成物は、ゴム成分に、必要に応じて適宜選択した各種配合剤を配合して、混練り、熱入れ、押出等することにより製造することができる。 In addition to the rubber components and fillers described above, the rubber composition includes rubbers such as vulcanizing agents, vulcanization accelerators, anti-aging agents, anti-scorching agents, softening agents, zinc oxide, stearic acid, and silane coupling agents. A compounding agent usually used in the industry can be appropriately selected and blended within a range not impairing the object of the present invention. As these compounding agents, commercially available products can be suitably used. In addition, the said rubber composition can be manufactured by mix | blending the various compounding agent suitably selected as needed with the rubber component, kneading | mixing, heating, extrusion, etc.
次に、本発明のタイヤを詳細に説明する。本発明のタイヤは、上述したゴム組成物を該タイヤのいずれかの部材に用いたことを特徴とし、耐摩耗性、耐亀裂成長性及び耐オゾン劣化性に優れる。本発明のタイヤは、上記ゴム組成物を何れかの部材に用いる限り特に制限はなく、該部材としては、トレッド、サイドウォール等が挙げられ、通常の方法で製造することができる。 Next, the tire of the present invention will be described in detail. The tire of the present invention is characterized by using the rubber composition described above for any member of the tire, and is excellent in wear resistance, crack growth resistance and ozone deterioration resistance. The tire of the present invention is not particularly limited as long as the rubber composition is used for any member, and examples of the member include a tread, a sidewall and the like, and can be manufactured by a usual method.
以下に、実施例を挙げて本発明を更に詳しく説明するが、本発明は下記の実施例に何ら限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples.
＜重合体製造例１＞
（触媒溶液Ａの調製）
乾燥及び窒素置換された容積100mLのゴム栓付きガラスビンに、順次、ブタジエンのシクロヘキサン溶液（ブタジエン濃度：2.35Ｍ）7.64ml、ネオジムネオデカノエートのシクロヘキサン溶液（ネオジム濃度：0.56Ｍ）0.53mL、メチルアルミノキサン（ＭＡＯ）［東ソーファインケム製ＰＭＡＯ］のトルエン溶液（アルミニウム濃度：2.74Ｍ）9.31mL、水素化ジイソブチルアルミニウム［関東化学製］のヘキサン溶液（0.95Ｍ）6.63mLを投入し、室温で2分間熟成した後、塩化ジエチルアルミニウム［関東化学製］のヘキサン溶液（0.98Ｍ）1.22mLを加え、室温で時折撹拌しながら15分間熟成した。こうして得られた触媒溶液Ａ中のネオジム濃度は、0.012Ｍ（mol/L）であった。
<Polymer Production Example 1>
(Preparation of catalyst solution A)
In a glass bottle with a rubber stopper with a volume of 100 mL that has been dried and purged with nitrogen, 7.64 mL of cyclohexane solution of butadiene (butadiene concentration: 2.35 M), 0.53 mL of cyclohexane solution of neodymium neodecanoate (neodymium concentration: 0.56 M), methyl Aluminoxane (MAO) [PMAO manufactured by Tosoh Finechem] in toluene solution (aluminum concentration: 2.74M) 9.31mL, diisobutylaluminum hydride [manufactured by Kanto Chemical Co., Ltd.] in hexane (0.95M) 6.63mL, and aged at room temperature for 2 minutes Then, 1.22 mL of a hexane solution (0.98 M) of diethylaluminum chloride [manufactured by Kanto Chemical Co., Inc.] was added, and aged for 15 minutes with occasional stirring at room temperature. The neodymium concentration in the catalyst solution A thus obtained was 0.012 M (mol / L).
（重合体Ａの製造）
乾燥及び窒素置換された容積約1Lのゴム栓付きガラスビンに、乾燥精製された１,３−ブタジエンのシクロヘキサン溶液及び乾燥シクロヘキサンをそれぞれ投入し、ブタジエンのシクロヘキサン溶液（ブタジエン濃度：11質量％）35gが投入された状態とした。次に、上記のようにして調製した触媒溶液Ａ2.36mL（ネオジム換算で11.8mmol）を加え、50℃の水浴中で1時間重合を行った。引き続き、老化防止剤２,２'−メチレン−ビス(４−エチル−６−ｔ−ブチルフェノール)（ＮＳ−５）のイソプロパノール溶液（ＮＳ−５濃度：5質量％）2mLを加えて反応を停止させ、更に、微量のＮＳ−５を含むイソプロパノール溶液中で再沈澱させた後、常法にて乾燥して、重合体Ａを得た。
(Production of polymer A)
A glass bottle with a rubber stopper with a volume of about 1L that has been dried and nitrogen-substituted is charged with a dry-purified cyclohexane solution of 1,3-butadiene and dry cyclohexane, respectively, and 35 g of a butadiene cyclohexane solution (butadiene concentration: 11% by mass) It was in the state of being thrown in. Next, 2.36 mL of catalyst solution A prepared as described above (11.8 mmol in terms of neodymium) was added, and polymerization was performed in a water bath at 50 ° C. for 1 hour. Subsequently, the reaction was stopped by adding 2 mL of an isopropanol solution (NS-5 concentration: 5% by mass) of the anti-aging agent 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5). Further, after reprecipitation in an isopropanol solution containing a small amount of NS-5, the polymer A was obtained by drying in a conventional manner.
＜重合体製造例２＞
（重合体Ｂの製造）
乾燥及び窒素置換された容積約1Lのゴム栓付きガラスビンに、ブタジエンのシクロヘキサン溶液（ブタジエン濃度：11質量％）35gと１-ブチンのシクロヘキサン溶液（１-ブチン濃度：1質量％）0.03gを投入し、10℃の水浴中で十分に冷却した。次に、上記のようにして調製した触媒溶液Ａ2.36mL（ネオジム換算で11.8mmol）を加え、50℃の水浴中で1時間重合を行った。引き続き、老化防止剤２,２'−メチレン−ビス(４−エチル−６−ｔ−ブチルフェノール)（ＮＳ−５）のイソプロパノール溶液（ＮＳ−５濃度：5質量％）2mLを加えて反応を停止させ、更に、微量のＮＳ−５を含むイソプロパノール溶液中で再沈澱させた後、常法にて乾燥して、重合体Ｂを得た。
<Polymer Production Example 2>
(Production of polymer B)
A glass bottle with a rubber stopper with a volume of about 1L that has been dried and substituted with nitrogen is charged with 35g of butadiene in cyclohexane (butadiene concentration: 11% by mass) and 0.03g of 1-butyne in cyclohexane (1-butyne concentration: 1% by mass). And sufficiently cooled in a 10 ° C. water bath. Next, 2.36 mL of catalyst solution A prepared as described above (11.8 mmol in terms of neodymium) was added, and polymerization was performed in a water bath at 50 ° C. for 1 hour. Subsequently, the reaction was stopped by adding 2 mL of an isopropanol solution (NS-5 concentration: 5% by mass) of the anti-aging agent 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5). Furthermore, after reprecipitating in an isopropanol solution containing a trace amount of NS-5, it was dried by a conventional method to obtain a polymer B.
＜重合体製造例３＞
（触媒溶液Ｃの調製）
乾燥及び窒素置換された容積100mLのゴム栓付きガラスビンに、順次、ブタジエンのシクロヘキサン溶液（ブタジエン濃度：2.35Ｍ）3.82ml、１−ブチンのシクロヘキサン溶液（ブチン濃度：0.14Ｍ）33.23mL、ネオジムネオデカノエートのシクロヘキサン溶液（ネオジム濃度：0.56Ｍ）0.27mL、メチルアルミノキサン（ＭＡＯ）［東ソーファインケム製ＰＭＡＯ］のトルエン溶液（アルミニウム濃度：2.74Ｍ）4.65mL、水素化ジイソブチルアルミニウム［関東化学製］のヘキサン溶液（0.95Ｍ）3.32mLを投入し、室温で2分間熟成した後、塩化ジエチルアルミニウム［関東化学製］のヘキサン溶液（0.98Ｍ）0.61mLを加え、室温で時折撹拌しながら15分間熟成した。こうして得られた触媒溶液Ｃ中のネオジム濃度は、0.003Ｍ（mol/L）であった。
<Polymer Production Example 3>
(Preparation of catalyst solution C)
In a glass bottle with a rubber stopper with a volume of 100 mL that has been dried and purged with nitrogen, 3.82 mL of butadiene in cyclohexane (butadiene concentration: 2.35 M), 33.23 mL of 1-butyne in cyclohexane (butyne concentration: 0.14 M), neodymium neodeca 0.27mL of noate in cyclohexane (neodymium concentration: 0.56M), 4.65mL of toluene solution (aluminum concentration: 2.74M) in methylaluminoxane (MAO) [PMAO manufactured by Tosoh Finechem], hexane in diisobutylaluminum hydride [manufactured by Kanto Chemical] After adding 3.32 mL of the solution (0.95 M) and aging at room temperature for 2 minutes, 0.61 mL of hexane solution (0.98 M) of diethylaluminum chloride [manufactured by Kanto Chemical Co., Inc.] was added, and aging was performed for 15 minutes with occasional stirring. The neodymium concentration in the catalyst solution C thus obtained was 0.003 M (mol / L).
（重合体Ｃの製造）
乾燥及び窒素置換された容積約1Lのゴム栓付きガラスビンに、乾燥精製された１,３−ブタジエンのシクロヘキサン溶液及び乾燥シクロヘキサンをそれぞれ投入し、ブタジエンのシクロヘキサン溶液（ブタジエン濃度：11質量％）35gが投入された状態とし、次に、上記のようにして調製した触媒溶液Ｃ9.26mL（ネオジム換算で0.028mmol）を加え、50℃の水浴中で1時間重合を行った。引き続き、老化防止剤２,２'−メチレン−ビス(４−エチル−６−ｔ−ブチルフェノール)（ＮＳ−５）のイソプロパノール溶液（ＮＳ−５濃度：5質量％）2mLを加えて反応を停止させ、更に、微量のＮＳ−５を含むイソプロパノール溶液中で再沈澱させた後、常法にて乾燥して、重合体Ｃを得た。
(Production of polymer C)
A glass bottle with a rubber stopper with a volume of about 1L that has been dried and nitrogen-substituted is charged with a dry-purified cyclohexane solution of 1,3-butadiene and dry cyclohexane, respectively, and 35 g of a butadiene cyclohexane solution (butadiene concentration: 11% by mass) Next, 9.26 mL of catalyst solution C prepared as described above (0.028 mmol in terms of neodymium) was added, and polymerization was performed in a 50 ° C. water bath for 1 hour. Subsequently, the reaction was stopped by adding 2 mL of an isopropanol solution (NS-5 concentration: 5% by mass) of the anti-aging agent 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5). Furthermore, after reprecipitation in an isopropanol solution containing a small amount of NS-5, the polymer C was obtained by drying in a conventional manner.
＜重合体製造例４＞
（触媒溶液Ｄの調製）
乾燥及び窒素置換された容積100mLのゴム栓付きガラスビンに、順次、ネオジムネオデカノエートのシクロヘキサン溶液（ネオジム濃度：0.56Ｍ）0.27mL、トリイソブチルアルミニウムのトルエン溶液（アルミニウム濃度：1.03Ｍ）4.22mLを投入し、室温で2分間熟成した後、塩化ジエチルアルミニウム［関東化学製］のヘキサン溶液（0.98Ｍ）0.92mLを加え、室温で時折撹拌しながら15分間熟成した。こうして得られた触媒溶液Ｄ中のネオジム濃度は、0.012Ｍ（mol/L）であった。
<Polymer Production Example 4>
(Preparation of catalyst solution D)
In a glass bottle with a rubber stopper with a volume of 100 mL that has been dried and replaced with nitrogen, 0.27 mL of a neodymium neodecanoate cyclohexane solution (neodymium concentration: 0.56 M), and a toluene solution of triisobutylaluminum (aluminum concentration: 1.03 M) in sequence 4.22 mL Was added, and the mixture was aged at room temperature for 2 minutes. Then, 0.92 mL of a hexane solution (0.98M) of diethylaluminum chloride [manufactured by Kanto Chemical Co., Inc.] was added, and the mixture was aged at room temperature with occasional stirring for 15 minutes. The neodymium concentration in the catalyst solution D thus obtained was 0.012 M (mol / L).
（重合体Ｄの製造）
乾燥及び窒素置換された容積約1Lのゴム栓付きガラスビンに、乾燥精製された１,３−ブタジエンのシクロヘキサン溶液及び乾燥シクロヘキサンをそれぞれ投入し、ブタジエンのシクロヘキサン溶液（ブタジエン濃度：11質量％）35gが投入された状態とし、次に、上記のようにして調製した触媒溶液Ｄ5.32mL（ネオジム換算で0.063mmol）を加え、50℃の水浴中で2時間重合を行った。引き続き、老化防止剤２,２'−メチレン−ビス(４−エチル−６−ｔ−ブチルフェノール)（ＮＳ−５）のイソプロパノール溶液（ＮＳ−５濃度：5質量％）2mLを加えて反応を停止させ、更に、微量のＮＳ−５を含むイソプロパノール溶液中で再沈澱させた後、常法にて乾燥して、重合体Ｄを得た。
(Production of polymer D)
A glass bottle with a rubber stopper with a volume of about 1L that has been dried and nitrogen-substituted is charged with a dry-purified cyclohexane solution of 1,3-butadiene and dry cyclohexane, respectively, and 35 g of a butadiene cyclohexane solution (butadiene concentration: 11% by mass) Next, 5.32 mL (0.063 mmol in terms of neodymium) of the catalyst solution D prepared as described above was added, and polymerization was performed in a 50 ° C. water bath for 2 hours. Subsequently, the reaction was stopped by adding 2 mL of an isopropanol solution (NS-5 concentration: 5% by mass) of the anti-aging agent 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5). Furthermore, after reprecipitation in an isopropanol solution containing a small amount of NS-5, the polymer D was obtained by drying in a conventional manner.
＜重合体製造例５＞
（重合体Ｅの製造）
乾燥及び窒素置換された容積約1Lのゴム栓付きガラスビンに、ブタジエンのシクロヘキサン溶液（ブタジエン濃度：11質量％）35gと１-ブチンのシクロヘキサン溶液（１-ブチン濃度：1質量％）0.03gを投入し、次に、上記のようにして調製した触媒溶液Ｄ5.32mL（ネオジム換算で0.063mmol）を加え、50℃の水浴中で2時間重合を行った。引き続き、老化防止剤２,２'−メチレン−ビス(４−エチル−６−ｔ−ブチルフェノール)（ＮＳ−５）のイソプロパノール溶液（ＮＳ−５濃度：5質量％）2mLを加えて反応を停止させ、更に、微量のＮＳ−５を含むイソプロパノール溶液中で再沈澱させた後、常法にて乾燥して、重合体Ｅを得た。
<Polymer Production Example 5>
(Production of polymer E)
A glass bottle with a rubber stopper with a volume of about 1L that has been dried and substituted with nitrogen is charged with 35g of butadiene in cyclohexane (butadiene concentration: 11% by mass) and 0.03g of 1-butyne in cyclohexane (1-butyne concentration: 1% by mass). Next, 5.32 mL (0.063 mmol in terms of neodymium) of the catalyst solution D prepared as described above was added, and polymerization was performed in a 50 ° C. water bath for 2 hours. Subsequently, the reaction was stopped by adding 2 mL of an isopropanol solution (NS-5 concentration: 5% by mass) of the anti-aging agent 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) (NS-5). Furthermore, after reprecipitation in an isopropanol solution containing a small amount of NS-5, the polymer E was obtained by drying in a conventional manner.
以上のようにして得られたポリブタジエンゴム（重合体Ａ〜Ｅ）の特性を表１に示す。なお、ミクロ構造の分析は、上述したＦＴ−ＩＲ法で行った。また、数平均分子量（Ｍｎ）、重量平均分子量（Ｍｗ）及び分子量分布（Ｍｗ／Ｍｎ）は、ＧＰＣ［東ソー製、ＨＬＣ−８０２０］により検出器として屈折計を用いて測定し、単分散ポリスチレンを標準としたポリスチレン換算で示した。なお、カラムはＧＭＨＸＬ［東ソー製］で、溶離液はテトラヒドロフランである。 Table 1 shows the characteristics of the polybutadiene rubber (polymers A to E) obtained as described above. The microstructure was analyzed by the above-described FT-IR method. The number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were measured using a refractometer as a detector by GPC [manufactured by Tosoh Corporation, HLC-8020]. Shown in standard polystyrene conversion. The column is GMHXL [manufactured by Tosoh] and the eluent is tetrahydrofuran.
Claims (7)
(Ｂ)成分：下記一般式(Ｉ)：
ＡｌＲ１Ｒ２Ｒ３ ・・・ (Ｉ)
［式中、Ｒ１及びＲ２は、同一又は異なり、炭素数１〜１０の炭化水素基又は水素原子で、Ｒ３は炭素数１〜１０の炭化水素基であり、但し、Ｒ３は上記Ｒ１又はＲ２と同一又は異なっていてもよい］で表される有機アルミニウム化合物、並びに
(Ｃ)成分：ルイス酸、金属ハロゲン化物とルイス塩基との錯化合物、及び活性ハロゲンを含む有機化合物からなる群から選択される少なくとも一種のハロゲン化合物
からなる触媒系と炭素数が２〜１０で且つ三重結合を持つ不飽和炭化水素との存在下、少なくとも１,３−ブタジエンを含む単量体を重合することを特徴とするブタジエン系重合体の製造方法。 Component (A): a rare earth element-containing compound having an atomic number of 57 to 71 in the periodic table, or a reaction product of these compounds with a Lewis base,
Component (B): The following general formula (I):
AlR 1 R 2 R 3 (I)
[Wherein, R 1 and R 2 are the same or different and each represents a hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom, and R 3 is a hydrocarbon group having 1 to 10 carbon atoms, provided that R 3 represents the above And may be the same as or different from R 1 or R 2 ], and
Component (C): a catalyst system comprising at least one halogen compound selected from the group consisting of Lewis acids, complex compounds of metal halides and Lewis bases, and organic compounds containing active halogens, and having 2 to 10 carbon atoms A method for producing a butadiene-based polymer comprising polymerizing a monomer containing at least 1,3-butadiene in the presence of an unsaturated hydrocarbon having a triple bond.
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