JPH04154819A - Production of conjugated diene polymer - Google Patents
Production of conjugated diene polymerInfo
- Publication number
- JPH04154819A JPH04154819A JP27938590A JP27938590A JPH04154819A JP H04154819 A JPH04154819 A JP H04154819A JP 27938590 A JP27938590 A JP 27938590A JP 27938590 A JP27938590 A JP 27938590A JP H04154819 A JPH04154819 A JP H04154819A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- acid
- carboxylic acid
- acid compound
- earth metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 19
- 150000001993 dienes Chemical class 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 16
- -1 Lewis acid compound Chemical class 0.000 claims abstract description 82
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 28
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000002841 Lewis acid Substances 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 5
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims abstract description 5
- 238000012662 bulk polymerization Methods 0.000 claims abstract description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000009826 distribution Methods 0.000 abstract description 7
- 229920001971 elastomer Polymers 0.000 abstract description 7
- 239000005060 rubber Substances 0.000 abstract description 7
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 6
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 abstract description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002989 phenols Chemical class 0.000 abstract description 5
- 229960002446 octanoic acid Drugs 0.000 abstract description 3
- 239000005635 Caprylic acid (CAS 124-07-2) Substances 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 description 19
- 150000003839 salts Chemical class 0.000 description 18
- 238000000034 method Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 12
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- OBETXYAYXDNJHR-SSDOTTSWSA-M (2r)-2-ethylhexanoate Chemical compound CCCC[C@@H](CC)C([O-])=O OBETXYAYXDNJHR-SSDOTTSWSA-M 0.000 description 7
- IGFHQQFPSIBGKE-UHFFFAOYSA-N 4-nonylphenol Chemical compound CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001206 Neodymium Chemical class 0.000 description 6
- 239000007822 coupling agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000006085 branching agent Substances 0.000 description 5
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000037048 polymerization activity Effects 0.000 description 4
- 150000002909 rare earth metal compounds Chemical class 0.000 description 4
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002905 metal composite material Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-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
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 2
- XDOFQFKRPWOURC-UHFFFAOYSA-N 16-methylheptadecanoic acid Chemical compound CC(C)CCCCCCCCCCCCCCC(O)=O XDOFQFKRPWOURC-UHFFFAOYSA-N 0.000 description 2
- HNRMPXKDFBEGFZ-UHFFFAOYSA-N 2,2-dimethylbutane Chemical compound CCC(C)(C)C HNRMPXKDFBEGFZ-UHFFFAOYSA-N 0.000 description 2
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001218 Thorium Chemical class 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 2
- SHOVVTSKTTYFGP-UHFFFAOYSA-L butylaluminum(2+);dichloride Chemical compound CCCC[Al](Cl)Cl SHOVVTSKTTYFGP-UHFFFAOYSA-L 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- BYLOHCRAPOSXLY-UHFFFAOYSA-N dichloro(diethyl)silane Chemical compound CC[Si](Cl)(Cl)CC BYLOHCRAPOSXLY-UHFFFAOYSA-N 0.000 description 2
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 2
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 2
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-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
- 230000001747 exhibiting effect Effects 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical group 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 150000003463 sulfur Chemical class 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- XYHKNCXZYYTLRG-UHFFFAOYSA-N 1h-imidazole-2-carbaldehyde Chemical compound O=CC1=NC=CN1 XYHKNCXZYYTLRG-UHFFFAOYSA-N 0.000 description 1
- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 description 1
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 1
- WCASXYBKJHWFMY-NSCUHMNNSA-N 2-Buten-1-ol Chemical compound C\C=C\CO WCASXYBKJHWFMY-NSCUHMNNSA-N 0.000 description 1
- RFCQDOVPMUSZMN-UHFFFAOYSA-N 2-Naphthalenethiol Chemical compound C1=CC=CC2=CC(S)=CC=C21 RFCQDOVPMUSZMN-UHFFFAOYSA-N 0.000 description 1
- QUSTYFNPKBDELJ-UHFFFAOYSA-N 2-Pentanethiol Chemical compound CCCC(C)S QUSTYFNPKBDELJ-UHFFFAOYSA-N 0.000 description 1
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 description 1
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 description 1
- UOBYKYZJUGYBDK-UHFFFAOYSA-N 2-naphthoic acid Chemical compound C1=CC=CC2=CC(C(=O)O)=CC=C21 UOBYKYZJUGYBDK-UHFFFAOYSA-N 0.000 description 1
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- 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 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M 3-Methylbutanoic acid Natural products CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- PWHHTYJQSMSOEC-UHFFFAOYSA-N 3-methylcyclohexanethiol Chemical compound CC1CCCC(S)C1 PWHHTYJQSMSOEC-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VIZORQUEIQEFRT-UHFFFAOYSA-N Diethyl adipate Chemical compound CCOC(=O)CCCCC(=O)OCC VIZORQUEIQEFRT-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 239000005639 Lauric acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- PQLAYKMGZDUDLQ-UHFFFAOYSA-K aluminium bromide Chemical compound Br[Al](Br)Br PQLAYKMGZDUDLQ-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- UIJGNTRUPZPVNG-UHFFFAOYSA-N benzenecarbothioic s-acid Chemical compound SC(=O)C1=CC=CC=C1 UIJGNTRUPZPVNG-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- DAMJCWMGELCIMI-UHFFFAOYSA-N benzyl n-(2-oxopyrrolidin-3-yl)carbamate Chemical compound C=1C=CC=CC=1COC(=O)NC1CCNC1=O DAMJCWMGELCIMI-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N beta-methyl-butyric acid Natural products CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- NZIXICKPQWIFAU-UHFFFAOYSA-K bromo(dimethyl)alumane;dibromo(methyl)alumane Chemical compound C[Al](C)Br.C[Al](Br)Br NZIXICKPQWIFAU-UHFFFAOYSA-K 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- HYZXMVILOKSUKA-UHFFFAOYSA-K chloro(dimethyl)alumane;dichloro(methyl)alumane Chemical compound C[Al](C)Cl.C[Al](Cl)Cl HYZXMVILOKSUKA-UHFFFAOYSA-K 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical compound SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 description 1
- VJRUISVXILMZSL-UHFFFAOYSA-M dibutylalumanylium;chloride Chemical compound CCCC[Al](Cl)CCCC VJRUISVXILMZSL-UHFFFAOYSA-M 0.000 description 1
- VTZJFPSWNQFPCQ-UHFFFAOYSA-N dibutylaluminum Chemical compound CCCC[Al]CCCC VTZJFPSWNQFPCQ-UHFFFAOYSA-N 0.000 description 1
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N dimethyl-butadiene Natural products CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 1
- ZGMHEOLLTWPGQX-UHFFFAOYSA-M dimethylalumanylium;bromide Chemical compound C[Al](C)Br ZGMHEOLLTWPGQX-UHFFFAOYSA-M 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- ROORDVPLFPIABK-UHFFFAOYSA-N diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- ZSRQBQCAUQRBPS-UHFFFAOYSA-N naphthalen-2-ylmethanethiol Chemical compound C1=CC=CC2=CC(CS)=CC=C21 ZSRQBQCAUQRBPS-UHFFFAOYSA-N 0.000 description 1
- SEXOVMIIVBKGGM-UHFFFAOYSA-N naphthalene-1-thiol Chemical compound C1=CC=C2C(S)=CC=CC2=C1 SEXOVMIIVBKGGM-UHFFFAOYSA-N 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 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
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000011191 terminal modification Methods 0.000 description 1
- TUNFSRHWOTWDNC-HKGQFRNVSA-N tetradecanoic acid Chemical compound CCCCCCCCCCCCC[14C](O)=O TUNFSRHWOTWDNC-HKGQFRNVSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- MEBRQLCKPRKBOH-UHFFFAOYSA-K trichloro(ethyl)stannane Chemical compound CC[Sn](Cl)(Cl)Cl MEBRQLCKPRKBOH-UHFFFAOYSA-K 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
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は高いシス１，４結合金率と狭い分子量分布とを
有し、優れたゴム特性を示す共役ジエン類重合体を、極
めて高効率に製造する方法に関するものである。Detailed Description of the Invention [Industrial Field of Application] The present invention provides a highly efficient method for producing conjugated diene polymers having a high cis-1,4 bond content and narrow molecular weight distribution and exhibiting excellent rubber properties. The present invention relates to a method for manufacturing the same.
高い１，４−シス結合金率を有する共役ジエン類重合体
の製造方法としては、既に多数の方法が公知である。特
にニッケル、コバルト、チタン等の遷移金属化合物を主
成分とする複合触媒を用いて得られるブタジェン重合体
は、一般にはシス結合金率が９０％を越えるものであり
、リチウム基材触媒による低シスブタジェン重合体とと
もに工業的に製造され、各種用途に広く使用されている
。Many methods are already known for producing conjugated diene polymers having a high 1,4-cis bond content. In particular, butadiene polymers obtained using composite catalysts containing transition metal compounds such as nickel, cobalt, and titanium as main components generally have a cis bond content of more than 90%; It is produced industrially together with polymers and is widely used for various purposes.
高シスブタジェン重合体を製造する他の方法として、希
土類金属化合物を主成分とする複合触媒を用いる方法も
知られている。この場合得られるブタジェン重合体は、
遷移金属触媒によって得られる高シスブタジェン重合体
に比較して、粘着性に優れるといった特長を有するとさ
れている。As another method for producing high-cis butadiene polymers, a method using a composite catalyst containing a rare earth metal compound as a main component is also known. The butadiene polymer obtained in this case is
It is said to have superior adhesiveness compared to high-cis butadiene polymers obtained using transition metal catalysts.
（Ｋａｕｔｓｃｈｕｋ ｕｎｄ Ｇｕｍｍｉ Ｋｕｎｓ
ｔｓｔｏｆｆｅ、第２２巻、２９３真、１９６９年刊行
）しかし、この種の複合触媒の主成分である希土類金属
化合物あるいはこれらの複合触媒系全体の重合溶媒等に
対する溶解性は十分でなく、不均一に成ることもあって
、その触媒活性は不十分なものであった。また、得られ
るブタジェン重合体の分子量分布は広いものとなり、そ
れ故、弾性特性等のゴム性能も一般の高シスブタジェン
ゴムに比較して特に優れるというものではなかった。(Kautschuk und Gummi Kuns
(Tstoffe, Vol. 22, 293, published in 1969) However, the solubility of the rare earth metal compound, which is the main component of this type of composite catalyst, or the entire composite catalyst system in the polymerization solvent, etc. is not sufficient, and it is unevenly distributed. Therefore, the catalytic activity was insufficient. Furthermore, the molecular weight distribution of the obtained butadiene polymer was wide, and therefore the rubber properties such as elastic properties were not particularly superior compared to general high-cis butadiene rubbers.
これらの希土類金属を主成分とする複合触媒の欠点を改
良すべく種々の試みも既になされている。Various attempts have already been made to improve the drawbacks of composite catalysts containing these rare earth metals as main components.
例えば重合触媒を重合系への添加に先立ち、少量の共役
ジエンの存在下に予備反応し、活性を向上させる方法（
特公昭４７−１４７２９号公報）、複合触媒の主成分で
ある希土類金属化合物として、希土類金属のアルコラー
ドを用いる方法、ネオジムのフェノール塩を用いる方法
あるいはネオジムの特定された３級カルボン酸塩を用い
て複合触媒の溶解性を改善した方法（特開昭５４−４０
８９０号公報、特開昭６０−１０８４０８号公報、特開
昭５５−６６９０３号公報）等が知られている。For example, a method of pre-reacting a polymerization catalyst in the presence of a small amount of conjugated diene before adding it to a polymerization system to improve its activity (
(Japanese Patent Publication No. 47-14729), a method using a rare earth metal Alcolade, a method using a phenol salt of neodymium, or a method using a specified tertiary carboxylate of neodymium as the rare earth metal compound that is the main component of the composite catalyst. Method for improving the solubility of composite catalysts (JP-A-54-40)
890, JP-A-60-108408, JP-A-55-66903), etc. are known.
またさらに、希土類金属のカルボン酸塩とアセチルアセ
トン等のルイス塩基との反応生成物を主成分とする複合
触媒を用いることによって、炭化水素溶媒に対する重合
触媒の溶解性を改善し、高い重合活性が達成できること
が開示されている。Furthermore, by using a composite catalyst whose main component is a reaction product of a rare earth metal carboxylate and a Lewis base such as acetylacetone, the solubility of the polymerization catalyst in hydrocarbon solvents is improved and high polymerization activity is achieved. It is disclosed what can be done.
（特開昭５８−１７０９号公報）
〔発明が解決すべき課題〕
上述の如く、希土類金属化合物を主成分とする複合触媒
、特に希土類金属のカルボン酸塩化合物を主成分とする
複合触媒によって、高いシス含率の共役ジエン重合体が
得られることは既に知られている。しかし、高い触媒活
性を達成するためには、予備反応もしくは触媒μ）成等
の特殊な操作を必要とするものである。工業的には、こ
の予備反応もしくは触媒熟成等の操作は、生産プロセス
を複雑化するものであり、生産効率の低下、生産コスト
の上昇等の問題を来すものとなり、解決が求められるも
のであった。またさらに、その重合活性についてもさら
なる改善が求められるとごろであった。(Unexamined Japanese Patent Publication No. 58-1709) [Problems to be Solved by the Invention] As mentioned above, a composite catalyst containing a rare earth metal compound as a main component, particularly a composite catalyst containing a rare earth metal carboxylate compound as a main component, It is already known that conjugated diene polymers with high cis content can be obtained. However, in order to achieve high catalytic activity, special operations such as preliminary reactions or catalyst μ) formation are required. Industrially, operations such as pre-reaction or catalyst ripening complicate the production process, leading to problems such as reduced production efficiency and increased production costs, which need to be resolved. there were. Moreover, further improvements in the polymerization activity have been required.
本発明者は、上述の問題を解決するために鋭意検討した
結果、希土類金属のカルボン酸塩化合物の一部の酸基を
、カルボン酸よりも酸性度が低く、かつ水分等の非存在
下に希土類金属と安定な塩を作り得る程度に十分な酸性
度を有する他の有機酸基で置換することによって、得ら
れる希土類金属の複合塩が重合触媒等に対する溶解性に
優れ、これを用いる複合触媒は予備反応もしくは触媒熟
成等の特殊な操作を必要とせずに、極めて高い触媒活性
を達成できることを見い出し本発明に到達したものであ
る。As a result of intensive studies to solve the above-mentioned problems, the present inventors have determined that some acid groups of rare earth metal carboxylate compounds have lower acidity than carboxylic acids and in the absence of moisture etc. By substituting with other organic acid groups having sufficient acidity to form stable salts with rare earth metals, the resulting composite salt of rare earth metals has excellent solubility in polymerization catalysts, etc., and composite catalysts using this salt The present invention was achieved by discovering that extremely high catalytic activity can be achieved without requiring special operations such as pre-reaction or catalyst ripening.
本発明によって達成される優れた作用効果、即ち希土類
金属複合塩の重合溶媒等に対する優れた溶解性および複
合開始剤としての高い重合活性は、驚くべきことに希土
類金属の複合塩を構成するカルボン酸の希土類金属塩お
よび他の有機酸化合物の希土類金属塩を、それぞれ別途
に重合系に添加することによっては全く達成されるもの
ではなく、本発明の提供する特定の複合塩を用いること
によって初めて達成されるものである。The excellent effects achieved by the present invention, namely, the excellent solubility of the rare earth metal composite salt in polymerization solvents and the high polymerization activity as a composite initiator, are surprisingly due to the carboxylic acid constituting the rare earth metal composite salt. This cannot be achieved at all by separately adding rare earth metal salts of organic acid compounds and rare earth metal salts of other organic acid compounds to the polymerization system, but can be achieved for the first time by using the specific composite salt provided by the present invention. It is something that will be done.
即ち、本発明は共役ジエン類を塊状重合又は炭化水素溶
媒中で溶液重合するに際し、（ａ）希土類金属のカルボ
ン酸化合物及び他の有機酸化合物との複合塩化合物、（
ｂ）有機アルミニウム化合物及び（ｃ）ハロゲン含有ル
イス酸化合物から成る複合触媒を存在させることを特徴
とする共役ジエン類重合体の製造方法を提供するもので
ある。That is, when carrying out bulk polymerization or solution polymerization of conjugated dienes in a hydrocarbon solvent, the present invention provides (a) a complex salt compound of a rare earth metal with a carboxylic acid compound and another organic acid compound;
The present invention provides a method for producing a conjugated diene polymer, characterized in that a composite catalyst comprising b) an organoaluminum compound and (c) a halogen-containing Lewis acid compound is present.
ここに、希土類金属のカルボン酸化合物及び他の有機酸
化合物との複合塩化合物とは、一般式ＬｎＡ、Ｂ２又は
ＬｎＡ２Ｂ、で表すことができ、Ｌｎは希土類金属であ
り、Ａはカルボン酸化合物の酸基、Ｂは、対応するカル
ボン酸の酸性度より低い、カルボン酸以外の有機酸化合
物の酸基を示す。Here, the complex salt compound of a rare earth metal with a carboxylic acid compound and another organic acid compound can be represented by the general formula LnA, B2 or LnA2B, where Ln is a rare earth metal and A is a carboxylic acid compound. The acid group B represents an acid group of an organic acid compound other than a carboxylic acid, which has a lower acidity than the corresponding carboxylic acid.
複合触媒の成分（ａ）を構成する希土類金属とは原子番
号５７から７１の元素であり、好ましくは原子番号５７
から６０の元素であり、最も好ましい金属はネオジムで
ある。用いることのできる希土類金属は希土類金属相互
の混合物であっても、また少量の６一
他の金属を含むものであっても当然構わない。The rare earth metal constituting component (a) of the composite catalyst is an element with an atomic number of 57 to 71, preferably an element with an atomic number of 57.
60 elements, the most preferred metal being neodymium. Of course, the rare earth metals that can be used may be mixtures of rare earth metals or may contain small amounts of other metals.
また、カルボン酸化合物に置換しうる他の有機酸化合物
は、具体的な酸性度を示す数値としての２５°Ｃ１水中
の酸解離指数ｐＫａが５以上が好ましく、より好ましく
は５〜２０の範囲、特に好ましくは８〜１２の範囲の酸
性度を有する有機酸化合物から選ぶことができる。ここ
で言う有機酸とは広く希土類金属と塩を作り得る有機化
合物を指すものである。この範囲にある具体的有機酸化
合物の種類としてはフェノール、アルコールおよびその
イオウ同族体を挙げることができる。置換する有機酸化
合物の酸性度がｐＫａ ５より強いと、本発明の特徴で
ある高い触媒活性が十分発揮されにくい場合がある。ま
た置換する有機酸化合物の酸性度がｐＫａ２０より弱い
と、希土類金属複合塩化合物の製造時もしくは貯蔵時の
安定性が低下する場合がある。Further, the other organic acid compound that can be substituted for the carboxylic acid compound preferably has an acid dissociation index pKa in 25° C. water of 5 or more, more preferably in the range of 5 to 20, as a numerical value indicating specific acidity. Particularly preferably, it can be selected from organic acid compounds having an acidity in the range of 8 to 12. The term "organic acid" as used herein broadly refers to organic compounds that can form salts with rare earth metals. Specific organic acid compounds within this range include phenols, alcohols, and their sulfur analogs. If the acidity of the organic acid compound to be substituted is stronger than pKa 5, the high catalytic activity that is a feature of the present invention may be difficult to fully exhibit. Furthermore, if the acidity of the organic acid compound to be substituted is weaker than pKa20, the stability of the rare earth metal complex salt compound during production or storage may decrease.
カルボン酸化合物と置換し得る特に好ましい有機酸化合
物の種類はフェノール化合物である。Particularly preferred types of organic acid compounds that can be substituted for carboxylic acid compounds are phenolic compounds.
これらの希土類金属の複合塩化合物は、例えば対応する
カルボン酸化合物のナトリウム塩と対応する他の有機酸
化合物のナトリウム塩との混合物を、希土類金属の塩酸
塩と、アルコールもしくはアセトン等の溶媒中で反応さ
せることによって容易に得ることができる。These rare earth metal complex salt compounds can be produced by, for example, preparing a mixture of the corresponding sodium salt of a carboxylic acid compound and the corresponding sodium salt of another organic acid compound with a rare earth metal hydrochloride in a solvent such as alcohol or acetone. It can be easily obtained by reaction.
複合触媒の成分（ａ）を構成するカルボン酸化合物類は
、下記の一般式（Ｉ）で表されるカルボン酸化合物およ
びそのイオウ同族体である。The carboxylic acid compounds constituting component (a) of the composite catalyst are a carboxylic acid compound represented by the following general formula (I) and its sulfur homolog.
Ｒ’−Ｃ−ＬＨ・・・・・・・・・・・・・・・・・・
・・・・・・・・・ （１）ＩＩ
ここにＲ１は炭素数３〜３０、好ましくは４から２０の
範囲の脂肪族炭化水素基、脂環族炭化水素基、または炭
素数６〜３０、好ましくは７〜２０の範囲のアルキル置
換芳香族炭化水素基を表す。R'-C-LH・・・・・・・・・・・・・・・
(1) II Here, R1 is an aliphatic hydrocarbon group having 3 to 30 carbon atoms, preferably 4 to 20 carbon atoms, an alicyclic hydrocarbon group, or an alicyclic hydrocarbon group having 6 to 30 carbon atoms. , preferably represents an alkyl-substituted aromatic hydrocarbon group in the range of 7 to 20.
Ｌは酸素もしくはイオウ原子を示す。この好ましい具体
例としては、イソ吉草酸、カプリル酸、オクタン酸、ラ
ウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸
、イソステアリン酸、オレイン酸、リノール酸、シクロ
ペンクンカルボン酸、ナフテン酸、エチルヘキサン酸、
ビバール酸、バーサチック酸（シェル化学から販売され
るＣＩＯモノカルボン酸の異性体の混合物から構成され
る合成酸）、フェニル酢酸、安息香酸、２−ナフトエ酸
、ヘキサンチオール酸、２，２−ジメチルブタンチオン
酸、デカンチオン酸、テトラデカンチオン酸、千オ安息
香酸等が挙げられる。L represents an oxygen or sulfur atom. Preferred specific examples include isovaleric acid, caprylic acid, octanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, cyclopencune carboxylic acid, naphthenic acid, and ethylhexanoic acid. ,
Bivalic acid, versatic acid (synthetic acid composed of a mixture of isomers of CIO monocarboxylic acids sold by Shell Chemical), phenylacetic acid, benzoic acid, 2-naphthoic acid, hexanethiolic acid, 2,2-dimethylbutane Examples include thionic acid, decanethionic acid, tetradecanethionic acid, and thiobenzoic acid.
アルコール、フェノール化合物およびそのイオウ同族体
は、一般式（ＩＩ）で表される。Alcohols, phenolic compounds and their sulfur analogs are represented by general formula (II).
Ｒ”−ＬＨ・・・・・・・・・・・・・・・・・・・・
・・・・・・・ （ＩＩ）ここにＲ２は炭素数２〜３０
、好ましくは４から２０の範囲の脂肪族炭化水素基、脂
環族炭化水素基、または炭素数６〜３０、好ましくは７
〜２０の範囲のアルキル置換芳香族炭化水素基を表す。R”-LH・・・・・・・・・・・・・・・・・・
・・・・・・・・・ (II) Here, R2 has 2 to 30 carbon atoms.
, preferably an aliphatic hydrocarbon group in the range of 4 to 20, an alicyclic hydrocarbon group, or a carbon number of 6 to 30, preferably 7
represents an alkyl-substituted aromatic hydrocarbon group in the range of ~20.
Ｌは酸素もしくはイオウ原子を表す。具体例としては、
エチルアルコール、ｎ−プロピルアルコール、１ｓｏ−
プロピルアルコール、ｔｅｒｔ−ブチルアルコール、ｔ
ｅｒｔ−アミルアルコール、ｎ−へキシアルコール、シ
クロヘキシアルコール、アリルアルコール、２−ブテニ
ルアルコール、３−へキセニルアルコール、２．５−デ
カジェニルアルコール、ベンジルアルコール、フェノー
ル、カテコール、１−ナフトール、２−ナフトール、２
，６−シーｔｅｒｔ−ブチルフェノール、２，６−シー
ｔｅｒｔ−ブチル−４−メチルフェノール、２．４．６
−トリーｔｅｒ ｔ−ブチルフェノール、４−フェニル
フェノール、エタンチオール、１−ブタンチオール、２
−ペンタンチオール、２−１ｓｏ＝ブタンチオール、チ
オフェノール、２−ナフタレンチオール、シクロヘキサ
ンチオール、３−メチルシクロヘキサンチオール、２−
ナフタレンチオール、ベンゼンメタンチオール、２−ナ
フタレンメタンチオール等が挙げられる。L represents an oxygen or sulfur atom. As a specific example,
Ethyl alcohol, n-propyl alcohol, 1so-
Propyl alcohol, tert-butyl alcohol, t
ert-amyl alcohol, n-hexyl alcohol, cyclohexy alcohol, allyl alcohol, 2-butenyl alcohol, 3-hexenyl alcohol, 2,5-decajenyl alcohol, benzyl alcohol, phenol, catechol, 1-naphthol , 2-naphthol, 2
, 6-tert-butylphenol, 2,6-tert-butyl-4-methylphenol, 2.4.6
-Treeter t-butylphenol, 4-phenylphenol, ethanethiol, 1-butanethiol, 2
-pentanethiol, 2-1so=butanethiol, thiophenol, 2-naphthalenethiol, cyclohexanethiol, 3-methylcyclohexanethiol, 2-
Examples include naphthalenethiol, benzenemethanethiol, 2-naphthalenemethanethiol, and the like.
本発明の複合触媒の成分（ａ）は希土類金属のカルボン
酸化合物および他の有機酸化合物との複合塩化合物単独
であることが好ましい。しかし、一部希土類金属のカル
ボン酸化合物もしくは他の有機酸化合物単独の塩を不純
物として含むものであっても構わない。しかし、この場
合でも複合塩化合物が少なくとも５０モル％、好ましく
は７５モル％以上、特に好ましくは８５％以上含まれな
ければ本発明の目的を十分達成できない。Component (a) of the composite catalyst of the present invention is preferably a single complex salt compound of a rare earth metal carboxylic acid compound and another organic acid compound. However, it may contain a portion of a rare earth metal carboxylic acid compound or a salt of another organic acid compound alone as an impurity. However, even in this case, the object of the present invention cannot be fully achieved unless the complex salt compound is contained in an amount of at least 50 mol %, preferably 75 mol % or more, particularly preferably 85 mol % or more.
またさらに、未反応の有機酸化合物を不純物として、本
発明の目的を損なわない範囲で含むものであっても構わ
ないことは当然である。Furthermore, it goes without saying that unreacted organic acid compounds may be contained as impurities within a range that does not impair the object of the present invention.
本発明の複合触媒を構成する成分（ｂ）である有機アル
ミニウム化合物は、一般式（Ｉ［［）で表される。The organoaluminum compound which is the component (b) constituting the composite catalyst of the present invention is represented by the general formula (I[[).
へｘＲニー、 Ｈ，・・・・・・・・・町・・町・・（
ＩＩＩ）ここにＲ３は炭素数１〜２０、好ましくは２が
ら８の範囲の脂肪炭化水素基、脂環族炭化水素基、また
は炭素数６〜２０、好ましくは６〜１２の範囲のアルキ
ル置換芳香族炭化水素基を表す。ｎは０．１または２、
好ましくは０または１であり、■は水素原子を示す。HexR knee, H,... Town... Town... (
III) Here, R3 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms, preferably 2 to 8 carbon atoms, an alicyclic hydrocarbon group, or an alkyl-substituted aromatic group having 6 to 20 carbon atoms, preferably 6 to 12 carbon atoms. represents a group hydrocarbon group. n is 0.1 or 2,
Preferably it is 0 or 1, and ■ represents a hydrogen atom.
好ましい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、トリイソプロ
ピルアルミニウム、トリイソブチルアルミニウム、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、ジエチルアルミニウムハイドライド、ジイソブチル
アルミニウムハイドライド、エチルアルミニウムシバイ
ドライド、イソブチルアルミニウムシバイドライド等が
挙げられ、特に好ましいものはトリエチルアルミニウム
、トリイソブチルアルミニウム、ジエチルアルミニウム
ハイドライド、ジイソブチルアルモニウムハイドライド
である。これらは２種以上の混合物であっても良い。Preferred organoaluminum compounds include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, trihexylaluminum, tricyclohexylaluminum, diethylaluminum hydride, diisobutylaluminum hydride, ethylaluminum sibide, isobutylaluminum sibide, and the like. Particularly preferred are triethylaluminum, triisobutylaluminum, diethylaluminum hydride, and diisobutylalmonium hydride. These may be a mixture of two or more types.
本発明の複合触媒を構成する成分（ｃ）であるハロゲン
含有ルイス酸化合物は、■ｂ、ＴＶｂまたはｖｂに属す
る元素、好ましくはアルミニウム元素のハイドライドな
いしは有機金属ハライドが挙げられ、ハライドとしては
塩素または臭素が好ましい。これらの化合物の例として
は、メチルアルミニウムジクロライド、メチルアルミニ
ウムジクロライド、エチルアルミニウムジブロマイド、
エチルアルミニウムジクロライド、ブチルアルミニウム
ジクロライド、ブチルアルミニウムジクロライド、ジメ
チルアルミニウムブロマイド、ジメチルアルミニウムク
ロライド、ジエチルアルミニウムブロマイド、ジエチル
アルミニウムクロライド、ジブチルアルミニウムブロマ
イド、ジブチルアルミニウムクロライド、メチルアルミ
ニウムセスキブロマイド、メチルアルミニウムセスキク
ロライド、エチルアルミニウムセスキブロマイド、エチ
ルアルミニウムセスキクロライド、ジブチル錫、ジクロ
ライド、アルミニウムトリブロマイド、三塩化アンチモ
ン、五塩化アンチモン、三塩化リン、五塩化リン及び四
塩化錫があり、特に好ましいものとしてジエチルアルミ
ニウムクロライド、エチルアルミニウムセスキクロライ
ド、エチルアルミニウムジクロライド、ジエチルアルミ
ニウムブロマイド、エチルアルミニウムセスキブロマイ
ド及びエチルアルミニウムジブロマイドが挙げられる。The halogen-containing Lewis acid compound which is the component (c) constituting the composite catalyst of the present invention includes a hydride or organometallic halide of an element belonging to (b), TVb or vb, preferably aluminum element, and the halide is chlorine or organometallic halide. Bromine is preferred. Examples of these compounds include methylaluminum dichloride, methylaluminum dichloride, ethylaluminum dibromide,
Ethylaluminum dichloride, butylaluminum dichloride, butylaluminum dichloride, dimethylaluminum bromide, dimethylaluminum chloride, diethylaluminum bromide, diethylaluminum chloride, dibutylaluminum bromide, dibutylaluminum chloride, methylaluminum sesquibromide, methylaluminum sesquichloride, ethylaluminum sesquibromide , ethylaluminum sesquichloride, dibutyltin, dichloride, aluminum tribromide, antimony trichloride, antimony pentachloride, phosphorus trichloride, phosphorus pentachloride, and tin tetrachloride, and particularly preferred are diethylaluminum chloride, ethylaluminum sesquichloride, Mention may be made of ethylaluminum dichloride, diethylaluminum bromide, ethylaluminum sesquibromide and ethylaluminum dibromide.
本発明の製造方法において使用される複合触媒の各成分
の量もしくは組成比は、その目的によって異なるものと
なる。一般には共役ジエン類単量体１００ ｇあたり、
成分（ａ）の使用量は０．０１〜１０ミリモルであり、
好ましくは０．０５〜Ｉミリモルの範囲で使用できる。The amount or composition ratio of each component of the composite catalyst used in the production method of the present invention varies depending on the purpose. Generally, per 100 g of conjugated diene monomer,
The amount of component (a) used is 0.01 to 10 mmol,
It can be used preferably in a range of 0.05 to 1 mmol.
また一般には成分（ｂ）の使用量は成分（ａ）に対する
モル比で表し、（ｂ）／（ａ）＝ｘ〜１００、好ましく
は５〜５０の範囲で使用できる。さらに成分（ｃ）の使
用モル量はその分子中に含まれるハロゲン原子数で異な
るものとなり、成分（ａ）１モルに対するハロゲン原子
数で表し、一般にはハロゲン族子／（ａ）−１〜６、好
ましくは２〜４の範囲で使用できる。Generally, the amount of component (b) to be used is expressed as a molar ratio to component (a), and can be used in the range of (b)/(a)=x to 100, preferably 5 to 50. Furthermore, the molar amount of component (c) used varies depending on the number of halogen atoms contained in the molecule, and is expressed as the number of halogen atoms per mole of component (a), and is generally expressed as the number of halogen atoms/(a)-1 to 6 , preferably in the range of 2 to 4.
本発明の製造方法によって用いることのできる単量体と
しては、ブタジェン、イソプレン、ピペリレン、ジメチ
ルブタジェン等の炭素数４〜Ｂの範囲の共役ジエン化合
物あるいはその混合物から選ぶことができ、最も好まし
い単量体はブタジェンである。またスチレン等のビニル
芳香族炭化水素化合物共存下に重合もしくはビニル芳香
族化合物と共重合することも可能である。The monomer that can be used in the production method of the present invention can be selected from conjugated diene compounds having 4 to B carbon atoms such as butadiene, isoprene, piperylene, dimethylbutadiene, etc., or mixtures thereof, and the most preferred monomers are The polymer is butadiene. It is also possible to polymerize in the coexistence of a vinyl aromatic hydrocarbon compound such as styrene or to copolymerize with a vinyl aromatic compound.
本発明の製造方法は、塊状重合もしくは溶液重合法によ
って実施される。溶液重合法を用いる場合に使用できる
重合溶媒としては、ｎ＝ペンタン、ｎ−ヘキサン、ｎ−
へブタン、シクロヘキサン、ベンゼン、トルエン等の沸
点が２００°Ｃ以下の脂肪族炭化水素、脂環族炭化水素
または芳香族炭化水素が好ましい。重合溶媒はこれらの
２成分の混合物であっても当然構わない。また、メチレ
ンクロライドやクロルベンゼン等のハロゲン化炭化水素
やケトン化合物やエーテル化合物、トリアルキルアミ−
１４＝
ン化合物等の非プロトン性の極性有機溶媒を少量含むこ
とも可能であり、条件により複合触媒の重合溶媒への溶
解性ひいては重合活性をさらに改善できる。The production method of the present invention is carried out by bulk polymerization or solution polymerization. Polymerization solvents that can be used when using the solution polymerization method include n=pentane, n-hexane, n-
Preferred are aliphatic hydrocarbons, alicyclic hydrocarbons, or aromatic hydrocarbons having a boiling point of 200°C or less, such as hebutane, cyclohexane, benzene, and toluene. Of course, the polymerization solvent may be a mixture of these two components. In addition, halogenated hydrocarbons such as methylene chloride and chlorobenzene, ketone compounds, ether compounds, and trialkyl amide
It is also possible to contain a small amount of an aprotic polar organic solvent such as a 14= compound, and depending on the conditions, the solubility of the composite catalyst in the polymerization solvent and thus the polymerization activity can be further improved.
本発明の製造方法における重合温度は、−３０〜１５０
°Ｃ１好ましくは１０〜１２０ ’Ｃ１特に好ましくは
３０〜１００°Ｃで実施される。重合反応形式は回分法
あるいは連続法のいずれにおいても利用できる。The polymerization temperature in the production method of the present invention is -30 to 150
C1 is preferably carried out at 10-120' C1, particularly preferably 30-100°C. The polymerization reaction format can be either a batch method or a continuous method.
また、重合に先立って、共役ジエン単量体の共存下ある
いは非共存下に、触媒成分の一部の組合せ、あるいは全
てを予備反応あるいは熟成することも本発明の製造方法
においては可能である。これらの操作の条件によっては
触媒活性が向上し、得られるポリマーの分子量分布が狭
くなる等のさらなる効果を達成することができる。Further, in the production method of the present invention, it is also possible to pre-react or ripen some or all of the catalyst components in the presence or absence of a conjugated diene monomer prior to polymerization. Depending on the conditions of these operations, further effects such as improved catalyst activity and narrower molecular weight distribution of the resulting polymer can be achieved.
重合反応が所定の重合率を達成した後、必要により公知
の末端変性剤もしくは末端分岐化剤、さらには重合停止
剤、重合体安定剤を反応系に加え、共役ジエン類重合体
の製造における公知の脱溶媒、乾燥操作、例えばスチー
ムストリッピング乾燥、加熱乾燥等により重合体を回収
できる。After the polymerization reaction has achieved a predetermined polymerization rate, if necessary, a known terminal modifier or terminal branching agent, as well as a polymerization terminator and a polymer stabilizer are added to the reaction system, and a known terminal modification agent or terminal branching agent, as well as a polymerization terminator and a polymer stabilizer are added to the reaction system. The polymer can be recovered by removing the solvent and drying operations such as steam stripping drying, heat drying, etc.
末端変性剤は、共役ジエン類のアニオン重合技術で公知
の各種末端変性剤から選ぶことができる。The terminal modifier can be selected from various terminal modifiers known in the art of anionic polymerization of conjugated dienes.
具体的な例は、例えば下記の公知資料により知ることが
できる。Specific examples can be found, for example, from the following publicly known materials.
特開昭６２−１４９７０８号公報
特開昭６２−１５６１０４号公報
特開昭６２−１６１８４４号公報
特開昭６３−３０４１号公報
特開昭６２−２２８５２号公報
末端分岐化剤も、一般に共役シエンナ！１のアニオン重
合技術で公知の末端分岐化剤から選ぶことができる。こ
の例としてはマルチエポキシド、マルチイソシアネート
、マルチイミン、マルチアルデヒド、マルチケトン、マ
ルチ酸無水物、マルチエステル、モノエステル、マルチ
ハライド、−ｔｗ化炭素および二酸化炭素が挙げられる
。特に好ましいカップリング剤はテトラクロルシラン、
トリクロルモノメチルシラン、トリクロルモノエチルシ
ラン、ジクロルジエチルシラン等のマルチハロゲン化硅
素化合物、テトラクロルスズ、トリクし１ルモノメチル
スズ、トリクロルモノエチルスズ等のマルチハロゲン化
スズ化合物、炭酸ジフェニル、アジピン酸ジエチル等の
エステル化合物である。JP-A-62-149708 JP-A-62-156104 JP-A-62-161-844 JP-A-63-3041 JP-A-62-22852 The terminal branching agent is also generally a conjugated sienna! The terminal branching agent can be selected from known terminal branching agents in the anionic polymerization technique of No.1. Examples include multiepoxides, multiisocyanates, multiimines, multialdehydes, multiketones, multianhydrides, multiesters, monoesters, multihalides, -twized carbons, and carbon dioxide. Particularly preferred coupling agents are tetrachlorosilane,
Multihalogenated silicon compounds such as trichloromonomethylsilane, trichloromonoethylsilane, dichlorodiethylsilane, multihalogenated tin compounds such as tetrachlortin, trichlormonomethyltin, trichloromonoethyltin, diphenyl carbonate, diethyl adipate. It is an ester compound such as.
カップリング剤の使用量は使用有機金属に当量の使用が
最大枝分れに最適の量と考えられる。しかし所望のカッ
プリング度によって、いかなる範囲のカップリング剤ｈ
ｉ゛も使用できる。−・般には有機アルミニウムあたり
０．１〜１．５当計のカップリング剤量で使用する。カ
ップリング剤は単独もしくは不活性炭化水素溶媒として
添加することができる。またカップリング剤は一度に、
分割してまたは連続的に添加できる。カンプリング反応
はその反応性によっても異なるが、辿常重合温度に近い
温度で、数分から数時間行う。The amount of coupling agent used is considered to be the optimum amount for maximum branching if the amount is equivalent to the organic metal used. However, depending on the degree of coupling desired, any range of coupling agents h
i゛ can also be used. - Generally, the coupling agent is used in an amount of 0.1 to 1.5 equivalents per organic aluminum. The coupling agent can be added alone or as an inert hydrocarbon solvent. In addition, the coupling agent is
Can be added in portions or continuously. Campling reactions vary depending on their reactivity, but are usually carried out at a temperature close to the polymerization temperature for several minutes to several hours.
重合停止剤は、水もしくはプロトン性の極性有機化合物
から選ぶことができる。後者の例としては、各＋ｍのア
ルコール、フェノール、カルボン酸化合物を挙げること
ができる。The polymerization terminator can be selected from water or a protic polar organic compound. Examples of the latter include alcohol, phenol, and carboxylic acid compounds of each +m.
また重合体安定剤は公知の共役ジエン頻重合体の安定剤
、酸化防止剤から選ぶことかできる。The polymer stabilizer can be selected from known stabilizers for conjugated diene polypolymers and antioxidants.
安定剤、酸化防止剤の特に好ましい例としては２．６−
シーｔｅｒｔ−ブチル−４−メチルフェノール、トリー
ノニルフェニルホスフェート、フェニル−β−ナフチル
アミン、ＮＮ′−ジアルキル−ジフェニルアミン、Ｎ−
アルキル−ジフェニルアミン等が挙げられる。Particularly preferred examples of stabilizers and antioxidants include 2.6-
Tert-butyl-4-methylphenol, trinonylphenyl phosphate, phenyl-β-naphthylamine, NN'-dialkyl-diphenylamine, N-
Examples include alkyl-diphenylamine.
本発明により得られた重合体は、その優れたゴム特性を
生かす各種用途、例えは必要により他の合成ゴムあるい
は天然ゴムと混合し、ｌ・レッド、カーカス、ザイドウ
ォール、ビード部等のタイヤ各部位への利用、あるいは
ホース、窓枠、ベルト、防振ゴム、自動車部品の原料ゴ
ム等の工業用品への利用、さらには耐衝撃性ポリスチレ
ン、ＡＢＳ樹脂等の樹脂強化剤として利用することによ
って優れた性能、効果を達成できる。The polymer obtained according to the present invention can be used in various applications that take advantage of its excellent rubber properties, for example, by mixing it with other synthetic rubber or natural rubber, if necessary, to apply it to tires such as l/red, carcass, zydwall, and bead parts. It is excellent for use in industrial parts such as hoses, window frames, belts, anti-vibration rubber, raw rubber for automobile parts, and as a reinforcing agent for resins such as impact-resistant polystyrene and ABS resin. It is possible to achieve better performance and effects.
以下に実施例を示し、本発明を具体的に説明するが、本
発明の範囲はこれらの実施例に限定されるものではない
。EXAMPLES The present invention will be specifically explained below with reference to Examples, but the scope of the present invention is not limited to these Examples.
実施例１〜３及び比較例１〜３
（１）複合塩化合物調製
本実施例において用いた複合触媒の成分（ａ）である一
般式Ｌｎへ＋Ｉ３ｚもしくはＬｎＡ２Ｂ＋に対応する希
土類金属の複合塩は下記に示す手法により調製した。Examples 1 to 3 and Comparative Examples 1 to 3 (1) Preparation of composite salt compound The rare earth metal composite salt corresponding to the general formula Ln+I3z or LnA2B+, which is the component (a) of the composite catalyst used in this example, is as follows. It was prepared by the method shown in .
ここに、Ｌｎはネオジム金属、八は２−エチルヘキサン
酸の酸基、Ｂはｐ−ノニルフェノールの酸基である。Here, Ln is neodymium metal, 8 is the acid group of 2-ethylhexanoic acid, and B is the acid group of p-nonylphenol.
複合塩はそれぞれの組成に対応する組成比の塩化ランタ
ンのアセトン？容？夜と、２−エチルヘキサン酸のすト
リウム塩とｐ−ノニルフェノールのすトリウム塩との混
合物のアセトン溶液とを、撹拌下に混合、反応し、その
後乾燥することによって調製した。得られた複合塩は、
テトラヒドロフランを展開溶媒として液クロマトグラフ
イーによって成分分析することができる。これらは、各
々に不純物として２−エチルヘキサン酸のネオジム塩、
ｐ−ノニルフェノールのネオジム塩および目標以外のＬ
ｎＡ 、 Ｂ２もしくはＬｎＡ２Ｂ、に対応する複合塩
を一部含むものであった。Is the composite salt acetone of lanthanum chloride with a composition ratio corresponding to each composition? Yong? It was prepared by mixing and reacting a mixture of a thorium salt of 2-ethylhexanoic acid and a thorium salt of p-nonylphenol with an acetone solution under stirring, followed by drying. The obtained complex salt is
Component analysis can be performed by liquid chromatography using tetrahydrofuran as a developing solvent. These each contain neodymium salt of 2-ethylhexanoic acid as an impurity,
Neodymium salt of p-nonylphenol and L other than the target
It contained a part of a complex salt corresponding to nA, B2 or LnA2B.
得られた複合塩の成分純度ばＬｎＡｚＢ＋に対応する複
合塩においては純度８６％、ＬｎＡ１Ｂ２に対応する複
合塩においては純度８８％であった。The component purity of the obtained complex salt was 86% for the complex salt corresponding to LnAzB+, and 88% for the complex salt corresponding to LnA1B2.
（２）重合反応
十分に乾燥した１００ｍＲ耐圧ガラスボトルを打栓し、
乾燥窒素で内部を十分パージした。６０ｇの１゜３−ブ
タジェンを含む４００ｇのシクロヘキザン混液をボトル
内に注入した後、表−１に記載の２−エチルヘキサン酸
とｐ−ノニルフェノールを同じく表−１記載の組成で配
位子とするネオジウムの複合塩化合物０．１２ミリモル
、トリイソブチルアルミニウム３．６ ミリモル、さら
にエチルアルミニウムセスキクロリドをＣ１／Ｎｄ’＝
３元素比になる如く添加し、６５°Ｃで２時間重合を
行った。重合後、ＢＩＴ （２，６−ビス（ｔ−ブチル
）−４−メチルフェノール〕の１０ｗｔ％のメタノール
／シクロヘキサン混合溶液１０滅で反応を停止させ、さ
らに大量のメタノールで重合体を分離させ、５０°Ｃで
真空乾燥した。(2) Polymerization reaction A sufficiently dried 100mR pressure-resistant glass bottle is capped,
The interior was thoroughly purged with dry nitrogen. After injecting 400 g of a cyclohexane mixture containing 60 g of 1゜3-butadiene into a bottle, 2-ethylhexanoic acid and p-nonylphenol listed in Table 1 were mixed with a ligand in the same composition as listed in Table 1. 0.12 mmol of neodymium complex salt compound, 3.6 mmol of triisobutylaluminum, and further ethylaluminum sesquichloride at C1/Nd'=
They were added so that the ratio of the three elements would be achieved, and polymerization was carried out at 65°C for 2 hours. After the polymerization, the reaction was stopped by adding a 10 wt% methanol/cyclohexane mixed solution of BIT (2,6-bis(t-butyl)-4-methylphenol) to 10 ml, and then the polymer was separated with a large amount of methanol to 50 ml. Vacuum dried at °C.
実施例１は上記の複合塩調製によって得られたＬｎＡ２
Ｂ、に対応する複合塩、実施例３はＬｎＡ、Ｂ２に対応
する複合塩、さらに実施例２は両者を等モルに成る如く
用いた。Example 1 is LnA2 obtained by the above complex salt preparation.
A complex salt corresponding to LnA and B2 was used in Example 3, and a complex salt corresponding to LnA and B2 was used in Example 2 in equimolar amounts.
比較例１，２は、それぞれ２−エチルヘキサン酸のネオ
ジム塩、ｐ−ノニルフェノールのネオジム塩を単独で用
いた例である。比較例３ば、２−エチルヘキサン酸のネ
オジム塩、ｐ−ノニルフェノールのネオジム塩を等モル
量、全量が０．１２ミリモルに成る如く、順次添加した
例である。Comparative Examples 1 and 2 are examples in which neodymium salt of 2-ethylhexanoic acid and neodymium salt of p-nonylphenol were used alone, respectively. Comparative Example 3 is an example in which neodymium salt of 2-ethylhexanoic acid and neodymium salt of p-nonylphenol were sequentially added in equimolar amounts such that the total amount was 0.12 mmol.
このようにして得られた重合体の収率、■、４−シス含
率、分子量分布、ムーニー粘度を表−１に示す。The yield, ■, 4-cis content, molecular weight distribution, and Mooney viscosity of the polymer thus obtained are shown in Table 1.
（３）分析方法
１）シス含率は赤外分光光度計を用いて測定し、モレロ
法にてデーター処理して求めた。(3) Analysis method 1) The cis content was measured using an infrared spectrophotometer and was determined by data processing using the Morello method.
２）分子量分布はゲルパーミェーションクロマトグラフ
ィーを用い、Ｔ肝（テトラヒドロフラン）を展開溶剤と
して分析した。2) Molecular weight distribution was analyzed using gel permeation chromatography using T liver (tetrahydrofuran) as a developing solvent.
実施例４〜６及び比較例４
実施例４〜５は、カルボン酸とともにネオジムの複合塩
化合物を構成するための他の有機酸に、ｐ−ノニルフェ
ノールに代えて表−２記載の、２，６−ジ−５ｅｃ−ブ
チルフェノール、イソアミルアルコール、ｔｅｒｔ−ド
デカンチオールを用いる外は実施例１と同様に実施した
。また比較例３は、複合塩化合物を構成するための他の
有機酸の酸性度が、カルボン酸の酸性度を越える有機酸
化合物であるドデシルベンゼンスルホン酸を用いる外は
実施例１と同様に実施した。結果を表−２に示す。Examples 4 to 6 and Comparative Example 4 In Examples 4 to 5, in place of p-nonylphenol, 2, 6, and The same procedure as in Example 1 was carried out except that -di-5ec-butylphenol, isoamyl alcohol, and tert-dodecanethiol were used. Comparative Example 3 was carried out in the same manner as Example 1, except that dodecylbenzenesulfonic acid, which is an organic acid compound whose acidity exceeds that of carboxylic acid, was used to form the complex salt compound. did. The results are shown in Table-2.
以下余白
実施例７〜９
実施例７〜９は、２−エチルヘキサン酸に代えて表−３
記載のカルボン酸化合物を用いる外は実施例１と同様に
実施した。結果を表−３に示す。Below are blank spaces Examples 7 to 9 Examples 7 to 9 are shown in Table 3 in place of 2-ethylhexanoic acid.
Example 1 was carried out in the same manner as in Example 1, except that the carboxylic acid compound described above was used. The results are shown in Table-3.
以下余白
一２６〜
実施例ＩＯ〜Ｉ２
実施例１０〜１２は、１〜リイソブチルアルミニウムに
代えて表−４記載の有機アルミニウムを、同表記載の世
相いる外は実施例１と同様に実施した。Margin below - 26 - Examples IO - I2 Examples 10 - 12 were carried out in the same manner as in Example 1, except that organic aluminum listed in Table 4 was used in place of 1 - lysobutylaluminum, except for the circumstances listed in the same table. .
結果を表−４に示す。The results are shown in Table 4.
以下余白
実施例１３〜１５
実施例１３〜１５は、エヂルアルミニウムセスキクロリ
ドに代えて、表−５のハロゲン含有ルイス酸を、同表記
載の世相いる外は実施例１と同様に実施した。結果を表
〜５に示す。Examples 13 to 15 Examples 13 to 15 were carried out in the same manner as in Example 1, except that the halogen-containing Lewis acid shown in Table 5 was used in place of edylaluminum sesquichloride, except for the circumstances described in the same table. The results are shown in Table 5.
以下余白
＝２９−
〔発明の効果］
本発明は高いシス１，４結合金率と狭い分子量分布とを
有し、優れたゴム特性を示す共役ジエン類重合体を、極
めて高効率に製造する方法である。The following margin = 29- [Effects of the Invention] The present invention provides a method for producing, with extremely high efficiency, a conjugated diene polymer having a high cis-1,4 bond ratio and a narrow molecular weight distribution and exhibiting excellent rubber properties. It is.
特許出願人 旭化成工業株式会社Patent applicant: Asahi Kasei Industries, Ltd.
Claims (1)
重合するに際し、 （ａ）希土類金属のカルボン酸化合物及び他の有機酸化
合物との複合塩化合物、 （ｂ）有機アルミニウム化合物及び （ｃ）ハロゲン含有ルイス酸化合物 から成る複合触媒を存在させることを特徴とする共役ジ
エン類重合体の製造方法。 ここに、希土類金属のカルボン酸化合物及び他の有機酸
化合物との複合塩化合物とは、一般式ＬｎＡ＿１Ｂ＿２
又はＬｎＡ＿２Ｂ＿１で表すことができ、Ｌｎは希土類
金属であり、Ａはカルボン酸化合物の酸基、Ｂは、対応
するカルボン酸の酸性度より低い、カルボン酸以外の有
機酸化合物の酸基を示す[Claims] 1. When carrying out bulk polymerization or solution polymerization of conjugated dienes in a hydrocarbon solvent, (a) a complex salt compound of a rare earth metal with a carboxylic acid compound and another organic acid compound; (b) an organic aluminum compound; A method for producing a conjugated diene polymer, comprising the presence of a composite catalyst comprising a compound and (c) a halogen-containing Lewis acid compound. Here, the complex salt compound of a rare earth metal with a carboxylic acid compound and other organic acid compounds has the general formula LnA_1B_2
Or it can be represented by LnA_2B_1, where Ln is a rare earth metal, A is an acid group of a carboxylic acid compound, and B is an acid group of an organic acid compound other than carboxylic acid, which has lower acidity than the corresponding carboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2279385A JPH0791340B2 (en) | 1990-10-19 | 1990-10-19 | Method for producing conjugated gen polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2279385A JPH0791340B2 (en) | 1990-10-19 | 1990-10-19 | Method for producing conjugated gen polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04154819A true JPH04154819A (en) | 1992-05-27 |
| JPH0791340B2 JPH0791340B2 (en) | 1995-10-04 |
Family
ID=17610406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2279385A Expired - Fee Related JPH0791340B2 (en) | 1990-10-19 | 1990-10-19 | Method for producing conjugated gen polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0791340B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6255416B1 (en) | 1998-05-13 | 2001-07-03 | Jsr Corporation | Method of producing conjugated diene polymers |
| US7294680B2 (en) | 1997-03-05 | 2007-11-13 | Jsr Corporation | Method of producing conjugated diene polymers with narrow molecular weight distribution and polymer produced |
| JP2009013420A (en) * | 2001-02-28 | 2009-01-22 | Bridgestone Corp | Continuous process for producing conjugated diene polymer having narrow molecular weight distribution and product therefrom |
| FR2944800A1 (en) * | 2009-04-28 | 2010-10-29 | Michelin Soc Tech | CATALYTIC SYSTEMS BASED ON A RARE-EARTH COMPLEX FOR STEREOSPECIFIC POLYMERIZATION OF CONJUGATED DIENES |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61268705A (en) * | 1985-05-15 | 1986-11-28 | エニ−ケム・エラストメ−リ・エセ・ピ・ア | Production of butadiene polymer or copolymer |
-
1990
- 1990-10-19 JP JP2279385A patent/JPH0791340B2/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61268705A (en) * | 1985-05-15 | 1986-11-28 | エニ−ケム・エラストメ−リ・エセ・ピ・ア | Production of butadiene polymer or copolymer |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7294680B2 (en) | 1997-03-05 | 2007-11-13 | Jsr Corporation | Method of producing conjugated diene polymers with narrow molecular weight distribution and polymer produced |
| US6255416B1 (en) | 1998-05-13 | 2001-07-03 | Jsr Corporation | Method of producing conjugated diene polymers |
| JP2009013420A (en) * | 2001-02-28 | 2009-01-22 | Bridgestone Corp | Continuous process for producing conjugated diene polymer having narrow molecular weight distribution and product therefrom |
| FR2944800A1 (en) * | 2009-04-28 | 2010-10-29 | Michelin Soc Tech | CATALYTIC SYSTEMS BASED ON A RARE-EARTH COMPLEX FOR STEREOSPECIFIC POLYMERIZATION OF CONJUGATED DIENES |
| WO2010125072A1 (en) * | 2009-04-28 | 2010-11-04 | Societe De Technologie Michelin | Catalytic systems made of a complex of rare earths for stereospecific polymerisation of conjugated dienes |
| US20120123070A1 (en) * | 2009-04-28 | 2012-05-17 | Societe De Technologie Michelin | Catalytic Systems Made of a Complex of Rare Earths For Stereospecific Polymerisation Of Conjugated Dienes |
| US8946368B2 (en) | 2009-04-28 | 2015-02-03 | Compagnie Generale Des Etablissements | Catalytic systems made of a complex of rare earths for stereospecific polymerisation of conjugated dienes |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0791340B2 (en) | 1995-10-04 |
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