JP2013227523A - Method of manufacturing vinyl cis-polybutadiene and vinyl cis-polybutadiene obtained by the same - Google Patents
Method of manufacturing vinyl cis-polybutadiene and vinyl cis-polybutadiene obtained by the same Download PDFInfo
- Publication number
- JP2013227523A JP2013227523A JP2013057296A JP2013057296A JP2013227523A JP 2013227523 A JP2013227523 A JP 2013227523A JP 2013057296 A JP2013057296 A JP 2013057296A JP 2013057296 A JP2013057296 A JP 2013057296A JP 2013227523 A JP2013227523 A JP 2013227523A
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- Japan
- Prior art keywords
- polymerization
- cis
- polybutadiene
- mol
- vinyl
- 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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- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 83
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims abstract description 67
- 229920002857 polybutadiene Polymers 0.000 title claims abstract description 63
- 239000005062 Polybutadiene Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 114
- 239000000178 monomer Substances 0.000 claims abstract description 47
- 150000001993 dienes Chemical class 0.000 claims abstract description 45
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000002896 organic halogen compounds Chemical class 0.000 claims abstract description 31
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 25
- 238000009835 boiling Methods 0.000 claims abstract description 14
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 24
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical group 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 abstract description 5
- 150000002367 halogens Chemical class 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 12
- MMEDJBFVJUFIDD-UHFFFAOYSA-N 2-[2-(carboxymethyl)phenyl]acetic acid Chemical compound OC(=O)CC1=CC=CC=C1CC(O)=O MMEDJBFVJUFIDD-UHFFFAOYSA-N 0.000 description 11
- 239000003426 co-catalyst Substances 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- -1 olefin compounds Chemical class 0.000 description 10
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 150000001869 cobalt compounds Chemical class 0.000 description 8
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- IAQRGUVFOMOMEM-ARJAWSKDSA-N cis-but-2-ene Chemical compound C\C=C/C IAQRGUVFOMOMEM-ARJAWSKDSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- IAQRGUVFOMOMEM-ONEGZZNKSA-N trans-but-2-ene Chemical compound C\C=C\C IAQRGUVFOMOMEM-ONEGZZNKSA-N 0.000 description 6
- 125000005234 alkyl aluminium group Chemical group 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 5
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 4
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-UHFFFAOYSA-N 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 235000010210 aluminium Nutrition 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 150000002222 fluorine compounds Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 150000002816 nickel compounds Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000691 measurement method Methods 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000005060 rubber Substances 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 2
- CJSBUWDGPXGFGA-UHFFFAOYSA-N 4-methylpenta-1,3-diene Chemical compound CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 2
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- QKFJKGMPGYROCL-UHFFFAOYSA-N phenyl isothiocyanate Chemical compound S=C=NC1=CC=CC=C1 QKFJKGMPGYROCL-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 2
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical compound C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- BOGRNZQRTNVZCZ-AATRIKPKSA-N (3e)-3-methylpenta-1,3-diene Chemical compound C\C=C(/C)C=C BOGRNZQRTNVZCZ-AATRIKPKSA-N 0.000 description 1
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-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
- BOGRNZQRTNVZCZ-UHFFFAOYSA-N 1,2-dimethyl-butadiene Natural products CC=C(C)C=C BOGRNZQRTNVZCZ-UHFFFAOYSA-N 0.000 description 1
- UVPKUTPZWFHAHY-UHFFFAOYSA-L 2-ethylhexanoate;nickel(2+) Chemical compound [Ni+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O UVPKUTPZWFHAHY-UHFFFAOYSA-L 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- SFXNZFATUMWBHR-UHFFFAOYSA-N 2-morpholin-4-yl-2-pyridin-3-ylacetonitrile Chemical compound C=1C=CN=CC=1C(C#N)N1CCOCC1 SFXNZFATUMWBHR-UHFFFAOYSA-N 0.000 description 1
- IGLWCQMNTGCUBB-UHFFFAOYSA-N 3-methylidenepent-1-ene Chemical compound CCC(=C)C=C IGLWCQMNTGCUBB-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 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
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ZDVDCDLBOLSVGM-UHFFFAOYSA-N [chloro(phenyl)methyl]benzene Chemical compound C=1C=CC=CC=1C(Cl)C1=CC=CC=C1 ZDVDCDLBOLSVGM-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000001361 allenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 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
- ZYSAVXVGWOCMMF-UHFFFAOYSA-N bromo formate Chemical compound BrOC=O ZYSAVXVGWOCMMF-UHFFFAOYSA-N 0.000 description 1
- IMJGQTCMUZMLRZ-UHFFFAOYSA-N buta-1,3-dien-2-ylbenzene Chemical compound C=CC(=C)C1=CC=CC=C1 IMJGQTCMUZMLRZ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- GAYAMOAYBXKUII-UHFFFAOYSA-L cobalt(2+);dibenzoate Chemical compound [Co+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAYAMOAYBXKUII-UHFFFAOYSA-L 0.000 description 1
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 description 1
- KYPVLDPQHIDKQJ-UHFFFAOYSA-N cobalt;ethyl 3-oxobutanoate Chemical compound [Co].CCOC(=O)CC(C)=O KYPVLDPQHIDKQJ-UHFFFAOYSA-N 0.000 description 1
- JUPWRUDTZGBNEX-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O JUPWRUDTZGBNEX-UHFFFAOYSA-N 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HRGXHRPMGDCKQM-UHFFFAOYSA-L dichlorocobalt;pyridine Chemical compound Cl[Co]Cl.C1=CC=NC=C1 HRGXHRPMGDCKQM-UHFFFAOYSA-L 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- 125000005594 diketone group Chemical class 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010077 mastication Methods 0.000 description 1
- 230000018984 mastication Effects 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
Description
本発明は、シス−１，４−ポリブタジエン及びシンジオタクチック−１，２−ポリブタジエンからなるビニル・シス−ポリブタジエンの製造方法及びそれによって得られたビニル・シス−ポリブタジエンに関する。 The present invention relates to a process for producing vinyl cis-polybutadiene comprising cis-1,4-polybutadiene and syndiotactic-1,2-polybutadiene and the vinyl cis-polybutadiene obtained thereby.
従来から、ビニル・シス−ポリブタジエンの製造は、ベンゼン、トルエン及びキシレンなどの炭化水素を主成分とする不活性有機溶媒中において、所定の触媒を用いて、１，３−ブタジエンを１，４−シス重合し、続いて、シンジオタクチック−１，２重合（以下、「１，２−ビニル重合」という場合がある。）する方法により行われている。 Conventionally, vinyl cis-polybutadiene has been produced by converting 1,3-butadiene into 1,4-butadiene using a predetermined catalyst in an inert organic solvent mainly containing hydrocarbons such as benzene, toluene and xylene. It is carried out by a method of carrying out cis polymerization and subsequently syndiotactic-1,2 polymerization (hereinafter sometimes referred to as “1,2-vinyl polymerization”).
例えば、特許文献１には、１，２−ビニル重合の際のハロゲン含有の有機アルミニウム化合物中のハロゲン原子のモル数と有機アルミニウム化合物のモル数の比を調整し、耐疲労性に優れたシス−１，４−ポリブタジエンとシンジオタクチック−１，２−ポリブタジエンからなる補強ポリブタジエンゴムを製造する方法が記載されている。また、例えば、特許文献２には、１，４−シス重合の際に二硫化炭素を存在させないことで、耐疲労性に優れた補強ポリブタジエンゴムを製造する方法が記載されている。このように、ビニル・シス−ポリブタジエンの製造においては、求めるゴムの性質に応じてあらゆる製造工程を調整することが求められる。 For example, in Patent Document 1, a ratio of the number of moles of halogen atoms and the number of moles of organoaluminum compound in a halogen-containing organoaluminum compound during 1,2-vinyl polymerization is adjusted to provide a cis having excellent fatigue resistance. A method for producing a reinforced polybutadiene rubber comprising -1,4-polybutadiene and syndiotactic-1,2-polybutadiene is described. For example, Patent Document 2 describes a method for producing a reinforced polybutadiene rubber having excellent fatigue resistance by not allowing carbon disulfide to be present during 1,4-cis polymerization. As described above, in the production of vinyl cis-polybutadiene, it is required to adjust every production process in accordance with the desired property of rubber.
ところで、ビニル・シス−ポリブタジエンは、その沸騰ｎ−ヘキサン不溶分（ＨＩ）の含有量により、様々な性質を変化させる。一般に、低ＨＩのビニル・シス−ポリブタジエンほど、ゴム組成物としたときに耐摩耗性、低発熱性に優れ、押出量が多く、生産性に優れる、などの特徴を有するようになる。 By the way, vinyl cis-polybutadiene changes various properties depending on the content of boiling n-hexane insoluble matter (HI). In general, vinyl cis-polybutadiene having a low HI has characteristics such as excellent abrasion resistance and low heat build-up when used as a rubber composition, a large amount of extrusion, and excellent productivity.
しかしながら、ビニル・シス−ポリブタジエンの製造において、ＨＩを低く調整することは容易ではなく、安定的にビニル・シス−ポリブタジエンを生産するための製造方法が望まれている。 However, in the production of vinyl cis-polybutadiene, it is not easy to adjust the HI low, and a production method for stably producing vinyl cis-polybutadiene is desired.
本発明は、上記問題点に鑑みてなされたものであり、容易にＨＩを低く調整することができ、生産性が良好で安定生産が可能なビニル・シス−ポリブタジエンの製造方法及びそれによって得られたビニル・シス−ポリブタジエンを提供することを目的とする。 The present invention has been made in view of the above-mentioned problems, and a method for producing vinyl cis-polybutadiene, which can easily adjust HI low, has good productivity and enables stable production, and is obtained thereby. It is an object of the present invention to provide vinyl cis-polybutadiene.
本発明者らは、以上の目的を達成するために、鋭意検討した結果、１，４−シス重合における水に対する有機アルミニウム及び有機ハロゲン化合物の全添加量、１，４−シス重合における有機アルミニウムと有機ハロゲン化合物の比率、原料となる共役ジエン系モノマーに対する１，２−ビニル重合における触媒の添加量、並びに１，４−シス重合及び１，２−ビニル重合において添加する全有機アルミニウムに対する１，２−ビニル重合における触媒の添加量を調整することにより、容易にＨＩを低く調整することができ、生産性が良好で安定生産が可能なビニル・シス−ポリブタジエンの製造方法を見出し、本発明に至った。 As a result of intensive studies to achieve the above object, the present inventors have found that the total amount of organoaluminum and organic halogen compound added to water in 1,4-cis polymerization, organoaluminum in 1,4-cis polymerization, and The ratio of the organic halogen compound, the amount of catalyst added in 1,2-vinyl polymerization relative to the conjugated diene monomer used as a raw material, and 1,2 relative to the total organoaluminum added in 1,4-cis polymerization and 1,2-vinyl polymerization -By adjusting the amount of catalyst added in vinyl polymerization, a method for producing vinyl cis-polybutadiene capable of easily adjusting HI to be low, having good productivity and enabling stable production has been found, and the present invention has been achieved. It was.
すなわち本発明は、沸騰ｎ−ヘキサン不溶分（ＨＩ）が３〜９重量％であるビニル・シス−ポリブタジエンの製造方法であって、共役ジエン系モノマー及び溶媒を含む共役ジエン系モノマー溶液に水、第１の有機アルミニウム、有機ハロゲン化合物及び１，４重合触媒を添加して前記共役ジエン系モノマーを１，４−シス重合するシス重合工程（ａ）と、該シス重合工程（ａ）の後に第２の有機アルミニウム、二硫化炭素及び１，２重合触媒を添加して１，２−ビニル重合するビニル重合工程（ｂ）とを有し、（１）前記水１ｍｏｌに対する前記第１の有機アルミニウム及び前記有機ハロゲン化合物の全添加量が１．５〜３．０ｍｏｌであり、（２）前記第１の有機アルミニウムが非ハロゲン化有機アルミニウム化合物であり、前記非ハロゲン化有機アルミニウム化合物１ｍｏｌに対する前記有機ハロゲン化合物の添加量が１．５〜９．０ｍｏｌであり、（３）前記共役ジエン系モノマー１ｍｏｌに対する前記１，２重合触媒の添加量が０．１〜２．４μｍｏｌであり、（４）前記第１及び第２の有機アルミニウムからなる全有機アルミニウム１ｍｏｌに対する前記１，２重合触媒の添加量が０．０００１〜０．００３０ｍｏｌであることを特徴とするビニル・シス−ポリブタジエンの製造方法に関する。 That is, the present invention relates to a method for producing vinyl cis-polybutadiene having a boiling n-hexane insoluble content (HI) of 3 to 9% by weight, wherein water is added to a conjugated diene monomer solution containing a conjugated diene monomer and a solvent, A cis-polymerization step (a) for adding 1,4-cis polymerization of the conjugated diene monomer by adding a first organoaluminum, an organic halogen compound and a 1,4-polymerization catalyst, and a step after the cis-polymerization step (a) A vinyl polymerization step (b) in which 1,2-vinyl polymerization is carried out by adding 2 organoaluminum, carbon disulfide and 1,2 polymerization catalyst, and (1) the first organoaluminum with respect to 1 mol of the water and The total amount of the organohalogen compound is 1.5 to 3.0 mol, (2) the first organoaluminum is a nonhalogenated organoaluminum compound, and the nonhalogen The amount of the organohalogen compound added per mol of the organoaluminum compound is 1.5 to 9.0 mol, and (3) the amount of the 1,2 polymerization catalyst added per mol of the conjugated diene monomer is 0.1 to 2. (4) The vinyl cis characterized in that the addition amount of the 1,2 polymerization catalyst is 0.0001 to 0.0030 mol with respect to 1 mol of the total organoaluminum composed of the first and second organoaluminums. -It relates to a method for producing polybutadiene.
本発明に係るビニル・シス−ポリブタジエンの製造方法において、前記１，２重合触媒が、遷移金属触媒であることが好ましく、前記共役ジエン系モノマーが、１，３−ブタジエンであることが好ましい。 In the method for producing vinyl cis-polybutadiene according to the present invention, the 1,2 polymerization catalyst is preferably a transition metal catalyst, and the conjugated diene monomer is preferably 1,3-butadiene.
また、本発明は、上記記載のビニル・シス−ポリブタジエンの製造方法によって製造されたことを特徴とするビニル・シス−ポリブタジエンに関する。 The present invention also relates to a vinyl cis-polybutadiene produced by the above-described method for producing vinyl cis-polybutadiene.
以上のように、本発明によれば、容易にＨＩを低く調整することができ、生産性が良好で安定生産が可能なビニル・シス−ポリブタジエンの製造方法及びそれによって得られたビニル・シス−ポリブタジエンを提供することができる。 As described above, according to the present invention, a method for producing vinyl cis-polybutadiene capable of easily adjusting HI low, having good productivity and enabling stable production, and vinyl cis-obtained thereby. Polybutadiene can be provided.
本発明に係るビニル・シス−ポリブタジエンは、二段重合法によって製造できる。すなわち、シス重合工程（ａ）で１，４−シス重合を行い、そのまま重合を停止することなく、ビニル重合工程（ｂ）でシンジオタクチック−１，２重合を行うことによって、シス−１，４−ポリブタジエン中にシンジオタクチック−１，２−ポリブタジエン結晶を分散させたビニル・シス−ポリブタジエンが得られる。 The vinyl cis-polybutadiene according to the present invention can be produced by a two-stage polymerization method. That is, 1,4-cis polymerization is performed in the cis polymerization step (a), and syndiotactic-1,2 polymerization is performed in the vinyl polymerization step (b) without stopping the polymerization as it is. A vinyl cis-polybutadiene is obtained in which syndiotactic-1,2-polybutadiene crystals are dispersed in 4-polybutadiene.
（シス重合工程（ａ））
本発明に係るビニル・シス−ポリブタジエンにおいて、シス重合工程（ａ）は、共役ジエン系モノマー及び溶媒を含む共役ジエン系モノマー溶液に水、第１の有機アルミニウム、有機ハロゲン化合物及び１，４重合触媒を添加して前記共役ジエン系モノマーを１，４−シス重合する。
(Cis polymerization step (a))
In the vinyl cis-polybutadiene according to the present invention, the cis polymerization step (a) is carried out by adding water, a first organoaluminum, an organic halogen compound, and a 1,4 polymerization catalyst to a conjugated diene monomer solution containing a conjugated diene monomer and a solvent. Is added to perform 1,4-cis polymerization of the conjugated diene monomer.
シス重合工程（ａ）で使用する共役ジエン系モノマーとしては、１，３−ブタジエン、イソプレン、２−エチル−１，３−ブタジエン、２，３−ジメチルブタジエン、２−フェニル−１，３−ブタジエン、１，３−ペンタジエン、２−メチル−１，３−ペンタジエン、３−メチル−１，３−ペンタジエン、４−メチル−１，３−ペンタジエン、１，３−ヘキサジエン、２，４−ヘキサジエンが挙げられる。中でも、１，３−ブタジエンが好ましい。共役ジエン系モノマーは、１種を単独で用いてもよく、２種類以上を組み合わせて用いてもよい。
また、上記共役ジエン系モノマーは、共役ジエン系モノマー以外の他の共重合モノマーと組み合わせて使用してもよく、他の共重合モノマーとしては、スチレン、α−メチルスチレン等の芳香族ビニル化合物が挙げられる。他のモノマーは、１種を単独で用いてもよく、２種類以上を組み合わせて用いてもよい。
The conjugated diene monomer used in the cis polymerization step (a) includes 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, and 2-phenyl-1,3-butadiene. 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene It is done. Of these, 1,3-butadiene is preferred. As the conjugated diene monomer, one kind may be used alone, or two or more kinds may be used in combination.
The conjugated diene monomer may be used in combination with other copolymerization monomers other than the conjugated diene monomer. Examples of the other copolymerization monomers include aromatic vinyl compounds such as styrene and α-methylstyrene. Can be mentioned. Another monomer may be used individually by 1 type and may be used in combination of 2 or more type.
シス重合工程（ａ）において使用する溶媒としては、トルエン、ベンゼン及びキシレン等の芳香族炭化水素、ｎ−ヘキサン、ブタン、ヘプタン及びペンタン等の脂肪族炭化水素、シクロヘキサン及びシクロペンタン等の脂環族炭化水素、上記のオレフィン化合物及びシス−２−ブテン、トランス−２−ブテン等のオレフィン系炭化水素、ミネラルスピリット、ソルベントナフサ及びケロシン等の炭化水素系溶媒、並びに塩化メチレン等のハロゲン化炭化水素系溶媒などが挙げられる。また、１，３−ブタジエンモノマーのように共役ジエン系モノマーそのものを重合溶媒として用いてもよい。 Solvents used in the cis polymerization step (a) include aromatic hydrocarbons such as toluene, benzene and xylene, aliphatic hydrocarbons such as n-hexane, butane, heptane and pentane, and alicyclic groups such as cyclohexane and cyclopentane. Hydrocarbons, the above olefin compounds and olefinic hydrocarbons such as cis-2-butene and trans-2-butene, hydrocarbon solvents such as mineral spirits, solvent naphtha and kerosene, and halogenated hydrocarbons such as methylene chloride A solvent etc. are mentioned. Further, a conjugated diene monomer itself such as 1,3-butadiene monomer may be used as a polymerization solvent.
上記溶媒の中でも、シスおよびトランス−２−ブテンを主成分とし、１−ブテン、ｎ−ブタンなどを含む炭素数４の炭化水素混合物であるＣ４留分と、シクロペンタン、シクロヘキサン等の環状脂肪族炭化水素と、からなる混合溶媒が好ましく、環状脂肪族炭化水素の中では、安全性が高く、製造コストを抑える観点から、シクロヘキサンが特に好ましい。反応系中の共役ジエン系モノマーの濃度は１０〜６０重量％が好ましい。 Among the above solvents, cis and trans-2-butene as the main components, C4 fraction which is a C4 hydrocarbon mixture containing 1-butene, n-butane and the like, and cycloaliphatic such as cyclopentane and cyclohexane A mixed solvent consisting of hydrocarbons is preferred, and among the cycloaliphatic hydrocarbons, cyclohexane is particularly preferred from the viewpoint of high safety and reduced production costs. The concentration of the conjugated diene monomer in the reaction system is preferably 10 to 60% by weight.
シス重合工程（ａ）では、上記共役ジエン系モノマーと溶媒を混合して調整された共役ジエン系モノマー溶液に、水を加え、混合物中の水分の濃度を調整することが好ましい。水の添加量は、後述するように、第１の有機アルミニウム及び有機ハロゲン化合物の全添加量に応じて適宜調整することが好ましい。 In the cis polymerization step (a), it is preferable to adjust the concentration of water in the mixture by adding water to the conjugated diene monomer solution prepared by mixing the conjugated diene monomer and the solvent. As will be described later, the amount of water added is preferably adjusted as appropriate according to the total amount of the first organoaluminum and organic halogen compound added.
シス重合工程（ａ）で使用する第１の有機アルミニウムは非ハロゲン化有機アルミニウム化合物であり、有機ハロゲン化合物と併用する。非ハロゲン化有機アルミニウム化合物のみではリニアリティーを高くする場合に生産性が悪く、有機ハロゲン化合物のみでは１，４−シス重合しないため好ましくない。両者を併用することで、生産性よく１，４−シス重合できるため好ましい。
非ハロゲン化有機アルミニウム化合物としては、例えば一般式ＡｌＲ３（但し、Ｒは炭素原子数１〜１０の炭化水素基である）により表わされるトリアルキルアルミニウムを用いることができる。トリアルキルアルミニウムの例としては、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、トリフェニルアルミニウム、トリ−ｐ−トリルアルミニウム、及びトリベンジルアルミニウムを挙げることができる。なお、トリアルキルアルミニウム内のアルキル基は、互いに同一でも、あるいは異なっていてもよい。この中でも特に、トリエチルアルミニウムが好ましい。また、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及びセスキエチルアルミニウムハイドライドなどの水素化有機アルミニウム化合物を用いることもできる。
The first organoaluminum used in the cis polymerization step (a) is a non-halogenated organoaluminum compound and is used in combination with the organohalogen compound. When only non-halogenated organoaluminum compounds are used, productivity is poor when increasing linearity, and only organic halogen compounds are not preferable because 1,4-cis polymerization is not performed. It is preferable to use both in combination because 1,4-cis polymerization can be performed with good productivity.
As the non-halogenated organoaluminum compound, for example, a trialkylaluminum represented by the general formula AlR 3 (wherein R is a hydrocarbon group having 1 to 10 carbon atoms) can be used. Examples of trialkylaluminums include trimethylaluminum, triethylaluminum, tri-n-propylaluminum, triisopropylaluminum, tri-n-butylaluminum, triisobutylaluminum, tripentylaluminum, trihexylaluminum, tricyclohexylaluminum, trioctyl Mention may be made of aluminum, triphenylaluminum, tri-p-tolylaluminum and tribenzylaluminum. The alkyl groups in the trialkylaluminum may be the same as or different from each other. Among these, triethylaluminum is particularly preferable. In addition, organic aluminum hydride compounds such as diethylaluminum hydride, diisobutylaluminum hydride and sesquiethylaluminum hydride can also be used.
有機ハロゲン化合物としては、ジアルキルアルミニウムクロライド、ジアルキルアルミニウムブロマイド、アルキルアルミニウムセスキクロライド、アルキルアルミニウムセスキブロマイド、及びアルキルアルミニウムジクロライドなどのハロゲン化有機アルミニウム化合物が挙げられる。上記ハロゲン化有機アルミニウム化合物のうち、ジメチルアルミニウムクロライド及びジエチルアルミニウムクロライドなどのジアルキルアルミニウムクロライド、セスキエチルアルミニウムクロライドなどのアルキルアルミニウムセスキクロライド、並びにエチルアルミニウムジクロライドなどのアルキルアルミニウムジクロライドが好ましく用いられ、ジメチルアルミニウムクロライド及びジエチルアルミニウムクロライドなどのジアルキルアルミニウムクロライドが特に好ましく用いられる。この中でも特に、ジエチルアルミニウムクロライドが好ましい。 Examples of the organic halogen compound include halogenated organoaluminum compounds such as dialkylaluminum chloride, dialkylaluminum bromide, alkylaluminum sesquichloride, alkylaluminum sesquibromide, and alkylaluminum dichloride. Of the halogenated organoaluminum compounds, dialkylaluminum chlorides such as dimethylaluminum chloride and diethylaluminum chloride, alkylaluminum sesquichlorides such as sesquiethylaluminum chloride, and alkylaluminum dichlorides such as ethylaluminum dichloride are preferably used, and dimethylaluminum chloride. And dialkylaluminum chlorides such as diethylaluminum chloride are particularly preferably used. Among these, diethyl aluminum chloride is particularly preferable.
また、有機ハロゲン化合物として、一般式ＲＸ（式中、Ｒは炭素数が１〜４０、好ましくは１〜２０の炭化水素基、Ｘはハロゲンを示す）で表されるハロゲン化アルキル化合物を用いることもできる。炭化水素基としては、アルキル基、アリール基、シクロアルキル基などが挙げられる。 Further, as the organic halogen compound, a halogenated alkyl compound represented by the general formula RX (wherein R represents a hydrocarbon group having 1 to 40 carbon atoms, preferably 1 to 20 carbon atoms, and X represents halogen) is used. You can also. Examples of the hydrocarbon group include an alkyl group, an aryl group, and a cycloalkyl group.
また、有機ハロゲン化合物として、一般式Ｒ１Ｒ２Ｒ３Ｃ−Ｘで表される有機ハロゲン化合物を用いることもできる。式中、Ｒ１は水素、アルキル基、アリール基、クロル置換アルキル基、アルコキシ基などであり、Ｒ２は水素、アルキル基、アリール基、クロル、ブロムなどであり、Ｒ３はアルキル基、アリール基、ビニル基、クロル、ブロムなどであり、Ｘはクロル、ブロムなどのハロゲンである。また、Ｒ２＋Ｒ３が酸素であってもよい。Ｒ１及びＲ２が水素である場合は、Ｒ３はアリール基であることが好ましい。上記のアルキル基は、飽和あるいは不飽和であってもよく、また、直鎖状、分岐状または環状のものであってもよく、脂肪族炭化水素基などが挙げられる。 In addition, as the organic halogen compound, an organic halogen compound represented by the general formula R 1 R 2 R 3 C—X can also be used. In the formula, R 1 is hydrogen, an alkyl group, an aryl group, a chloro-substituted alkyl group, an alkoxy group, R 2 is hydrogen, an alkyl group, an aryl group, chloro, bromo, etc., and R 3 is an alkyl group, aryl Group, vinyl group, chloro, bromo and the like, and X is halogen such as chloro, bromo and the like. R 2 + R 3 may be oxygen. When R 1 and R 2 are hydrogen, R 3 is preferably an aryl group. The alkyl group may be saturated or unsaturated, and may be linear, branched or cyclic, and examples thereof include an aliphatic hydrocarbon group.
具体的な化合物としては、メチル、エチル、ｉｓｏ−プロピル、ｉｓｏ−ブチル、ｔ−ブチル、フェニル、ベンジル、ベンゾイル、ベンジリデンなどのクロル化物またはブロム化物などが挙げられる。また、メチルクロロホルメート、ブロモホルメート、クロロジフェニルメタンまたはクロロトリフェニルメタンなどが挙げられる。 Specific examples of the compound include chlorinated or brominated compounds such as methyl, ethyl, iso-propyl, iso-butyl, t-butyl, phenyl, benzyl, benzoyl, and benzylidene. Further, methyl chloroformate, bromoformate, chlorodiphenylmethane, chlorotriphenylmethane, and the like can be given.
上記非ハロゲン化有機アルミニウム化合物１ｍｏｌに対する前記有機ハロゲン化合物の添加量は、１．５〜９．０ｍｏｌであり、２．０〜８．９ｍｏｌが好ましく、２．２〜８．８ｍｏｌが特に好ましい。上記範囲外では、重合活性が失活する可能性があるため好ましくない。 The amount of the organic halogen compound added to 1 mol of the non-halogenated organoaluminum compound is 1.5 to 9.0 mol, preferably 2.0 to 8.9 mol, and particularly preferably 2.2 to 8.8 mol. Outside the above range, the polymerization activity may be deactivated, which is not preferable.
上記第１の有機アルミニウム及び有機ハロゲン化合物の全添加量（上記非ハロゲン化有機アルミニウム化合物と有機ハロゲン化合物とを併用した合計の添加量）は、例えば、水、有機アルミニウム化合物及び可溶性コバルト化合物からなる触媒系を用いて１，４−シス重合する場合は、共役ジエン系モノマー１ｍｏｌ当たり０．１ｍｍｏｌ以上、特に０．５〜５０ｍｍｏｌであることが好ましい。また、例えば、ニッケル化合物、有機アルミニウム化合物及びフッ素化合物からなる触媒系を用いて１，４−シス重合する場合は、共役ジエン系モノマー１ｍｏｌ当たり１×１０−５〜１×１０−１ｍｏｌであることが好ましい。 The total addition amount of the first organoaluminum and the organic halogen compound (total addition amount using the non-halogenated organoaluminum compound and the organic halogen compound in combination) is composed of, for example, water, an organoaluminum compound, and a soluble cobalt compound. When 1,4-cis polymerization is performed using a catalyst system, it is preferably 0.1 mmol or more, particularly 0.5 to 50 mmol, per 1 mol of the conjugated diene monomer. For example, when 1,4-cis polymerization is performed using a catalyst system composed of a nickel compound, an organoaluminum compound, and a fluorine compound, the amount is 1 × 10 −5 to 1 × 10 −1 mol per mol of the conjugated diene monomer. It is preferable.
また、本発明においては、上記第１の有機アルミニウム及び有機ハロゲン化合物の全添加量と上記水の添加量とを調整することを特徴とする。上記第１の有機アルミニウム及び有機ハロゲン化合物の全添加量は、上記水１ｍｏｌ当たり、好ましくは１．５〜３．０ｍｏｌ、より好ましくは１．５５〜２．５ｍｏｌ、特に好ましくは１．６〜２．０ｍｏｌの範囲である。この範囲外では触媒活性が低下したり、シス−１，４構造含有率が低下したり、分子量が異常に低く又は高くなったりするため好ましくない。また、上記の範囲外では、重合時のゲルの発生を抑制することができず、このため重合槽などへのゲルの付着が起こり、さらに連続重合時間を延ばすことができないので好ましくない。 In the present invention, the total addition amount of the first organoaluminum and the organic halogen compound and the addition amount of the water are adjusted. The total amount of the first organoaluminum and the organic halogen compound added is preferably 1.5 to 3.0 mol, more preferably 1.55 to 2.5 mol, and particularly preferably 1.6 to 2 per 1 mol of the water. The range is 0.0 mol. Outside this range, the catalytic activity is lowered, the cis-1,4 structure content is lowered, and the molecular weight is abnormally low or high. Further, outside the above range, it is not preferable because the generation of gel at the time of polymerization cannot be suppressed, so that the gel adheres to the polymerization tank and the continuous polymerization time cannot be extended.
次いで、上記第１の有機アルミニウム及び有機ハロゲン化合物を添加した混合物に１，４重合触媒を添加して、共役ジエン系モノマーを１，４−シス重合する。１，４重合触媒としては、可溶性コバルト化合物、ニッケル化合物及びフッ素化合物等が挙げられるが、可溶性コバルト化合物が特に好ましい。 Subsequently, a 1,4 polymerization catalyst is added to the mixture to which the first organoaluminum and the organic halogen compound are added, and the conjugated diene monomer is subjected to 1,4-cis polymerization. Examples of the 1,4 polymerization catalyst include soluble cobalt compounds, nickel compounds, and fluorine compounds, and soluble cobalt compounds are particularly preferable.
可溶性コバルト化合物としては、上記溶媒又は液体共役ジエン系モノマーに可溶なものであるか、又は均一に分散できる、例えば、コバルト（ＩＩ）アセチルアセトナート及びコバルト（ＩＩＩ）アセチルアセトナートなどコバルトのβ−ジケトン錯体、コバルトアセト酢酸エチルエステル錯体のようなコバルトのβ−ケト酸エステル錯体、コバルトオクトエート、コバルトナフテネート及びコバルトベンゾエートなどの炭素数６以上の有機カルボン酸のコバルト塩、塩化コバルトピリジン錯体及び塩化コバルトエチルアルコール錯体などのハロゲン化コバルト錯体などが用いられる。可溶性コバルト化合物の添加量は、共役ジエン系モノマー１ｍｏｌ当たり０．００１ｍｍｏｌ以上、特に０．００５ｍｍｏｌ以上であることが好ましい。また、可溶性コバルト化合物に対する第１の有機アルミニウムのモル比（Ａｌ／Ｃｏ）は１０以上であり、特に５０以上であることが好ましい。 The soluble cobalt compound is soluble in the above solvent or liquid conjugated diene monomer, or can be uniformly dispersed, for example, cobalt β such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate. -Cobalt salts of organic carboxylic acids with 6 or more carbon atoms such as diketone complexes, cobalt β-keto acid ester complexes such as cobalt acetoacetic acid ethyl ester complex, cobalt octoate, cobalt naphthenate and cobalt benzoate, cobalt chloride pyridine complex And halogenated cobalt complexes such as cobalt chloride ethyl alcohol complex are used. The amount of the soluble cobalt compound added is preferably 0.001 mmol or more, particularly 0.005 mmol or more, per 1 mol of the conjugated diene monomer. The molar ratio (Al / Co) of the first organoaluminum to the soluble cobalt compound is 10 or more, and particularly preferably 50 or more.
ニッケル化合物としては、ニッケルの塩や錯体が好ましく用いられる。特に好ましいものとして、塩化ニッケル及び臭化ニッケルなどのハロゲン化ニッケル、硝酸ニッケルなどの無機酸のニッケル塩、オクチル酸ニッケル、酢酸ニッケル、ニッケルオクトエートなどの炭素原子数１〜１８のカルボン酸ニッケル、ナフテン酸ニッケル、マロン酸ニッケル、ニッケルのビスアセチルアセトナート及びトリスアセチルアセトネート、アセト酢酸エチルエステルなどのニッケル錯体、ハロゲン化ニッケルのトリアリールホスフィン錯体、トリアルキルホスフィン錯体、ピリジン錯体及びピコリン錯体等の有機塩基錯体、並びにエチルアルコール錯体などの各種錯体を挙げることができる。ニッケル化合物の添加量は、共役ジエン系モノマー１ｍｏｌ当たり１×１０−７〜１×１０−３ｍｏｌであることが好ましい。 As the nickel compound, a nickel salt or complex is preferably used. Particularly preferred are nickel halides such as nickel chloride and nickel bromide, nickel salts of inorganic acids such as nickel nitrate, nickel carboxylic acid having 1 to 18 carbon atoms such as nickel octylate, nickel acetate, nickel octoate, Nickel naphthenate, nickel malonate, nickel bisacetylacetonate and trisacetylacetonate, nickel complexes such as ethyl acetoacetate, nickel halide triarylphosphine complex, trialkylphosphine complex, pyridine complex and picoline complex Examples include organic base complexes and various complexes such as ethyl alcohol complexes. The addition amount of the nickel compound is preferably 1 × 10 −7 to 1 × 10 −3 mol per mol of the conjugated diene monomer.
フッ素化合物としては、三フッ化ホウ素のエーテル、アルコール、又はこれらの混合物の錯体、あるいはフッ化水素のエーテル、アルコール、又はこれらの錯体の混合物が好ましく用いられる。特に好ましいものとして、三フッ化ホウ素ジエチルエーテレート、三フッ化ホウ素ジブチルエーテレート、フッ化水素ジエチルエーテレート、及びフッ化水素ジブチルエーテレートを挙げることができる。フッ素化合物の添加量は、共役ジエン系モノマー１ｍｏｌ当たり１×１０−４〜１ｍｏｌであることが好ましい。 As the fluorine compound, boron trifluoride ether, alcohol, or a mixture of these mixtures, or hydrogen fluoride ether, alcohol, or a mixture of these complexes is preferably used. Particularly preferred are boron trifluoride diethyl etherate, boron trifluoride dibutyl etherate, hydrogen fluoride diethyl etherate, and hydrogen fluoride dibutyl etherate. The addition amount of the fluorine compound is preferably 1 × 10 −4 to 1 mol per mol of the conjugated diene monomer.
共役ジエン系モノマーを１，４−シス重合する温度は、０℃を超えて１００℃以下、好ましくは１０〜１００℃、さらに好ましくは２０〜１００℃である。重合時間は、１０分〜２時間の範囲が好ましい。また、１，４−シス重合後のポリマー濃度が５〜２６重量％となるように、１，４−シス重合を行うことが好ましい。重合は、重合槽（重合器）内にて溶液を攪拌混合して行う。重合に用いる重合槽としては、高粘度液攪拌装置付きの重合槽、例えば特公昭４０−２６４５号公報に記載された装置を用いることができる。 The temperature for the 1,4-cis polymerization of the conjugated diene monomer is more than 0 ° C and not more than 100 ° C, preferably 10 to 100 ° C, more preferably 20 to 100 ° C. The polymerization time is preferably in the range of 10 minutes to 2 hours. Moreover, it is preferable to perform 1,4-cis polymerization so that the polymer concentration after 1,4-cis polymerization is 5 to 26% by weight. The polymerization is carried out by stirring and mixing the solution in a polymerization tank (polymerizer). As a polymerization tank used for the polymerization, a polymerization tank equipped with a high-viscosity liquid stirring apparatus, for example, an apparatus described in JP-B-40-2645 can be used.
また、触媒成分の添加順序に特に制限はないが、水と第１の有機アルミニウムとをあらかじめ混合し、熟成して用いることが特に好ましい。熟成時間は０．１〜２４時間、熟成温度は０〜８０℃が好ましい。 The order of addition of the catalyst components is not particularly limited, but it is particularly preferable that water and the first organoaluminum are mixed in advance and aged. The aging time is preferably 0.1 to 24 hours, and the aging temperature is preferably 0 to 80 ° C.
１，４−シス重合時に、公知の分子量調節剤、例えばシクロオクタジエン、アレン、メチルアレン（１，２−ブタジエン）などの非共役ジエン類、又はエチレン、プロピレン、ブテン−１などのα−オレフィン類を使用することができる。また、重合時のゲルの生成をさらに抑制するため、公知のゲル化防止剤を使用することができる。 During 1,4-cis polymerization, known molecular weight regulators, for example, non-conjugated dienes such as cyclooctadiene, allene, methylallene (1,2-butadiene), or α-olefins such as ethylene, propylene, butene-1 Can be used. Moreover, in order to further suppress the production | generation of the gel at the time of superposition | polymerization, a well-known gelation inhibitor can be used.
１，４−シス重合で得られる共役ジエン系ポリマーのシス−１，４構造含有率は９０％以上、特に９５％以上であることが好ましい。ムーニー粘度（ＭＬ１＋４，１００℃、以下「ＭＬ１＋４」とする。）は１０〜１３０が好ましく、特に１５〜８０が好ましい。５％トルエン溶液粘度（Ｔｃｐ）は、２５〜４００であることが好ましい。また、１，４−シス重合で得られる共役ジエン系ポリマーは、実質的にゲル分を含有しないことが好ましい。 The cis-1,4 structure content of the conjugated diene polymer obtained by 1,4-cis polymerization is preferably 90% or more, particularly preferably 95% or more. The Mooney viscosity (ML 1 + 4 , 100 ° C., hereinafter referred to as “ML 1 + 4 ”) is preferably 10 to 130, and particularly preferably 15 to 80. The 5% toluene solution viscosity (Tcp) is preferably 25 to 400. Moreover, it is preferable that the conjugated diene type polymer obtained by 1, 4- cis-polymerization does not contain gel content substantially.
（ビニル重合工程（ｂ））
本発明に係るビニル・シス−ポリブタジエンの製造方法において、ビニル重合工程（ｂ）は、上記シス重合工程（ａ）で得られた重合反応混合物を用い、引き続きこの重合系で、第２の有機アルミニウム、二硫化炭素及び１，２重合触媒を添加して１，２−ビニル重合、特に好ましくは、シンジオタクチック−１，２重合する。その際に、得られた１，４−シス重合物には、さらに共役ジエン系モノマーを添加しても添加しなくてもよいが、生産性を高める観点から添加することが好ましい。添加する場合には、上記シス重合工程（ａ）で得られた重合反応混合物１００重量部当たり１〜５０重量部、好ましくは１〜２０重量部の共役ジエン系モノマーを添加することが好ましく、これにより、１，２−ビニル重合時の１，２−ポリブタジエンの収量を増大させることができる。
(Vinyl polymerization step (b))
In the method for producing vinyl cis-polybutadiene according to the present invention, the vinyl polymerization step (b) uses the polymerization reaction mixture obtained in the cis polymerization step (a), and in this polymerization system, the second organic aluminum is subsequently used. Then, carbon disulfide and a 1,2 polymerization catalyst are added to perform 1,2-vinyl polymerization, particularly preferably syndiotactic-1,2. At that time, the conjugated diene monomer may or may not be added to the obtained 1,4-cis polymer, but it is preferably added from the viewpoint of increasing productivity. When added, it is preferable to add 1 to 50 parts by weight, preferably 1 to 20 parts by weight of a conjugated diene monomer per 100 parts by weight of the polymerization reaction mixture obtained in the cis polymerization step (a). Thus, the yield of 1,2-polybutadiene during 1,2-vinyl polymerization can be increased.
ビニル重合工程（ｂ）で添加する第２の有機アルミニウムとしては、一般式ＡｌＲ３により表される有機アルミニウム化合物が好ましく、具体的には、トリメチルアルミニウム、トリエチルアルミニウム、トリイソブチルアルミニウム、トリｎ−ヘキシルアルミニウム及びトリフェニルアルミニウムなどが好適である。上記有機アルミニウム化合物は、共役ジエン系モノマー１ｍｏｌ当たり０．１ｍｍｏｌ以上、特に０．５〜５０ｍｍｏｌが好ましい。なお、第２の有機アルミニウムとして、上記第１の有機アルミニウムの残部を用いることもできる。 The second organoaluminum added in the vinyl polymerization step (b) is preferably an organoaluminum compound represented by the general formula AlR 3 , specifically, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexyl. Aluminum and triphenylaluminum are preferred. The organoaluminum compound is preferably 0.1 mmol or more, particularly 0.5 to 50 mmol, per 1 mol of the conjugated diene monomer. Note that the remaining portion of the first organoaluminum can be used as the second organoaluminum.
二硫化炭素の濃度は、２０ｍｍｏｌ／Ｌ以下、特に好ましくは０．０１〜１０ｍｍｏｌ／Ｌである。二硫化炭素の代替として、公知のイソチオシアン酸フェニルやキサントゲン酸化合物を使用してもよい。水は、有機アルミニウム化合物と接触させた後、重合系に添加することが好ましい。水の添加量は、第２の有機アルミニウム１ｍｏｌ当たり０．１〜１．５ｍｏｌが好ましい。 The concentration of carbon disulfide is 20 mmol / L or less, particularly preferably 0.01 to 10 mmol / L. As an alternative to carbon disulfide, a known phenyl isothiocyanate or xanthate compound may be used. Water is preferably added to the polymerization system after contacting with the organoaluminum compound. The amount of water added is preferably 0.1 to 1.5 mol per mol of the second organoaluminum.
１，２重合触媒としては、遷移金属触媒であることが好ましく、特に、可溶性コバルト化合物を好適に用いることができる。可溶性コバルト化合物としては、上記１，４重合触媒として添加したものと同様のものが挙げられる。本発明に係るビニル・シス−ポリブタジエンの製造方法においては、前記共役ジエン系モノマー１ｍｏｌに対する１，２重合触媒の添加量が０．１〜２．４μｍｏｌの範囲内が好ましく、０．２〜２．３μｍｏｌがより好ましく、０．３〜２．２μｍｏｌが特に好ましい。遷移金属触媒の添加量が上記範囲より多いと、遷移金属触媒に対する共役ジエン系モノマーが少なくなるので、得られるシンジオタクチック−１，２構造が多く、且つ得られる樹脂成分の分子量が低くなってしまう。一方、シンジオタクチック−１，２構造の分子量を上げるという観点からすれば、遷移金属触媒の添加量は少なくても構わないが、上記範囲より少ない場合には得られる樹脂成分の収量が減ってしまう。上記共役ジエン系モノマー１ｍｏｌに対する１，２重合触媒の添加量は、１，２−ビニル重合の際にさらに共役ジエン系モノマーを添加した場合には、添加された共役ジエン系モノマーも含んだ共役ジエン系モノマー１ｍｏｌに対する１，２重合触媒の添加量とする。 As the 1,2 polymerization catalyst, a transition metal catalyst is preferable, and a soluble cobalt compound can be particularly preferably used. Examples of the soluble cobalt compound include the same compounds as those added as the 1,4 polymerization catalyst. In the method for producing vinyl cis-polybutadiene according to the present invention, the addition amount of the 1,2 polymerization catalyst with respect to 1 mol of the conjugated diene monomer is preferably in the range of 0.1 to 2.4 μmol, and preferably 0.2 to 2. 3 μmol is more preferable, and 0.3 to 2.2 μmol is particularly preferable. When the addition amount of the transition metal catalyst is more than the above range, the conjugated diene monomer with respect to the transition metal catalyst is decreased, so that the resulting syndiotactic-1,2 structure is large and the molecular weight of the obtained resin component is low. End up. On the other hand, from the viewpoint of increasing the molecular weight of the syndiotactic-1,2 structure, the addition amount of the transition metal catalyst may be small, but if it is less than the above range, the yield of the resin component obtained is reduced. End up. The addition amount of the 1,2 polymerization catalyst with respect to 1 mol of the conjugated diene monomer is such that, when a conjugated diene monomer is further added during 1,2-vinyl polymerization, the conjugated diene containing the added conjugated diene monomer. The addition amount of the 1,2 polymerization catalyst per 1 mol of the system monomer.
また、前記第１及び第２の有機アルミニウムからなる全有機アルミニウム１ｍｏｌに対する前記１，２重合触媒の添加量が０．０００１〜０．００３０ｍｏｌの範囲内が好ましく、０．０００２〜０．００２０ｍｏｌがより好ましく、０．０００３〜０．００１２ｍｏｌが特に好ましい。上記範囲外では、シンジオタクチック−１，２重合を制御することが困難なため好ましくない。本発明においては、上記共役ジエン系モノマー１ｍｏｌに対する１，２重合触媒の添加量の調整、及び上記第１及び第２の有機アルミニウムからなる全有機アルミニウム１ｍｏｌに対する１，２重合触媒の添加量の調整を行うことにより、容易に沸騰ｎ−ヘキサン不溶分（ＨＩ）を低く調整することができる。 Moreover, the addition amount of the said 1,2 polymerization catalyst with respect to 1 mol of all the organoaluminum which consists of said 1st and 2nd organoaluminum is within the range of 0.0001-0.0030 mol, 0.0002-0.0020 mol is more Preferably, 0.0003 to 0.0012 mol is particularly preferable. Outside the above range, it is difficult to control the syndiotactic-1,2 polymerization, which is not preferable. In the present invention, adjustment of the addition amount of the 1,2 polymerization catalyst with respect to 1 mol of the conjugated diene monomer and adjustment of the addition amount of the 1,2 polymerization catalyst with respect to 1 mol of the total organoaluminum composed of the first and second organic aluminums. The boiling n-hexane insoluble matter (HI) can be easily adjusted to a low level.
１，２−ビニル重合する温度は、−５〜１００℃が好ましく、特に−５〜８０℃が好ましい。重合時間は、１０分〜２時間の範囲が好ましい。１，２−ビニル重合後のポリマー濃度が９〜２９重量％となるように、１，２−ビニル重合を行うことが好ましい。重合は重合槽（重合器）内にて重合溶液を攪拌混合して行う。１，２−ビニル重合に用いる重合槽としては、１，２−ビニル重合中は更に高粘度となり、ポリマーが付着しやすいので、高粘度液攪拌装置付きの重合槽、例えば特公昭４０−２６４５号公報に記載された装置を用いることができる。 The temperature for 1,2-vinyl polymerization is preferably from -5 to 100 ° C, particularly preferably from -5 to 80 ° C. The polymerization time is preferably in the range of 10 minutes to 2 hours. It is preferable to carry out 1,2-vinyl polymerization so that the polymer concentration after 1,2-vinyl polymerization is 9 to 29% by weight. The polymerization is carried out by stirring and mixing the polymerization solution in a polymerization tank (polymerizer). As a polymerization tank used for 1,2-vinyl polymerization, the viscosity becomes higher during 1,2-vinyl polymerization and the polymer tends to adhere, so a polymerization tank equipped with a high-viscosity liquid stirring device, for example, Japanese Patent Publication No. 40-2645. The apparatus described in the publication can be used.
重合反応が所定の重合率に達した後、常法に従って公知の老化防止剤を添加することができる。老化防止剤としては、フェノール系の２，６−ジ−ｔ−ブチル−ｐ−クレゾール（ＢＨＴ）、リン系のトリノニルフェニルフォスファイト（ＴＮＰ）、並びに硫黄系の４，６−ビス（オクチルチオメチル）−ｏ−クレゾール及びジラウリル−３，３’−チオジプロピオネート（ＴＰＬ）などが挙げられる。これらを単独でも２種以上組み合わせて用いてもよく、老化防止剤の添加はビニル・シス−ポリブタジエン１００重量部に対して０．００１〜５重量部である。 After the polymerization reaction reaches a predetermined polymerization rate, a known anti-aging agent can be added according to a conventional method. Anti-aging agents include phenol-based 2,6-di-t-butyl-p-cresol (BHT), phosphorus-based trinonylphenyl phosphite (TNP), and sulfur-based 4,6-bis (octylthio). Methyl) -o-cresol and dilauryl-3,3′-thiodipropionate (TPL). These may be used singly or in combination of two or more, and the addition of the antioxidant is 0.001 to 5 parts by weight with respect to 100 parts by weight of vinyl cis-polybutadiene.
重合反応は、重合溶液にメタノール及びエタノールなどのアルコール、又は水などの極性溶媒を大量に投入する方法、塩酸及び硫酸などの無機酸、酢酸及び安息香酸などの有機酸、又は塩化水素ガスを重合溶液に導入する方法など、それ自体公知の方法を用いて停止する。次いで、通常の方法に従い、生成したビニル・シス−ポリブタジエンを分離、洗浄、続いて乾燥する。 For the polymerization reaction, a large amount of an alcohol such as methanol and ethanol or a polar solvent such as water is added to the polymerization solution, an inorganic acid such as hydrochloric acid and sulfuric acid, an organic acid such as acetic acid and benzoic acid, or a hydrogen chloride gas is polymerized. The reaction is stopped using a method known per se, such as a method of introducing the solution. The resulting vinyl cis-polybutadiene is then separated, washed and subsequently dried according to conventional methods.
また、本発明に係るビニル・シス−ポリブタジエンゴムの製造方法によって製造されたビニル・シス−ポリブタジエンの沸騰ｎ−ヘキサン不溶分（ＨＩ）は、３〜９重量％であり、３．４〜６．５重量％がより好ましい。上記範囲外では、耐摩耗性、低発熱性に劣り、押出量が少なく、加工性に劣るため好ましくない。一般に、ＨＩを低くすると生産性が低下してしまう問題があるが、本発明の製造方法によれば、上述のとおり、１，４−シス重合における水に対する有機アルミニウム及び有機ハロゲン化合物の全添加量、第１の有機アルミニウムと有機ハロゲン化合物の比率、原料となる共役ジエン系モノマーに対する１，２−ビニル重合における触媒の添加量、並びに１，４−シス重合及び１，２−ビニル重合において添加する全有機アルミニウムに対する１，２−ビニル重合における触媒の添加量を調整することにより、容易に低ＨＩへと調整したビニル・シス−ポリブタジエンゴムを生産性良く製造することが可能となる。
また、沸騰ｎ−ヘキサン可溶分は、ミクロ構造のシス−１，４構造が８０％以上が好ましい。
Further, the boiling n-hexane insoluble matter (HI) of vinyl cis-polybutadiene produced by the method for producing vinyl cis-polybutadiene rubber according to the present invention is 3 to 9% by weight, and 3.4 to 6. 5% by weight is more preferred. Outside the above range, it is not preferable because it is inferior in wear resistance and low exothermic property, has a small amount of extrusion, and is inferior in workability. In general, there is a problem that productivity decreases when HI is lowered. However, according to the production method of the present invention, as described above, the total amount of organoaluminum and organohalogen compounds added to water in 1,4-cis polymerization. The ratio of the first organoaluminum and the organic halogen compound, the amount of the catalyst added in 1,2-vinyl polymerization relative to the conjugated diene monomer used as a raw material, and the addition in 1,4-cis polymerization and 1,2-vinyl polymerization By adjusting the addition amount of the catalyst in 1,2-vinyl polymerization with respect to the total organoaluminum, it becomes possible to easily produce vinyl cis-polybutadiene rubber adjusted to low HI with high productivity.
The boiling n-hexane soluble content is preferably 80% or more of the microstructure cis-1,4 structure.
本発明に係るビニル・シス−ポリブタジエンの製造方法によって製造されたビニル・シス−ポリブタジエンのシンジオタクチック−１，２重合体の融点は１００〜２２０℃が好ましく、１７０〜２１０℃が特に好ましい。 The melting point of the vinyl cis-polybutadiene syndiotactic-1,2 polymer produced by the method for producing vinyl cis-polybutadiene according to the present invention is preferably from 100 to 220 ° C, particularly preferably from 170 to 210 ° C.
また、沸騰ｎ−ヘキサン可溶分の５重量％トルエン溶液粘度（Ｔｃｐ）と１００℃におけるムーニー粘度（ＭＬ１＋４）との比（Ｔｃｐ／ＭＬ１＋４）は、２．１以下であることが好ましく、１．０〜２．１であることがより好ましく、１．５〜２．０５が特に好ましい。 Further, the ratio (T cp / ML 1 + 4 ) of 5 wt% toluene solution viscosity (T cp ) of boiling n-hexane solubles to Mooney viscosity (ML 1 + 4 ) at 100 ° C. is 2.1 or less. Preferably, it is 1.0 to 2.1, more preferably 1.5 to 2.05.
また、ＲＰＡ２０００型試験機（アルファテクノロジーズ社製）を用いてＬＡＯＳ測定方法により測定した長鎖分岐指数（ＬＣＢ Ｉｎｄｅｘ）は、４．１０〜５．９０が好ましく、４．３０〜５．７０がより好ましく、４．５０〜５．５０が特に好ましい。ＲＰＡ２０００型試験機（アルファテクノロジーズ社製）を用いてＬＡＯＳ測定方法により測定した長鎖分岐指数（ＬＣＢ Ｉｎｄｅｘ）とは、溶解ポリマーのダイナミック特性において、近似した特徴を持つ長鎖分岐（ＬＣＢ）と分子量分布の挙動から、分子量分布による影響を取り除いたより正確な長鎖分岐の指数を示す。なお、ＬＣＢ Ｉｎｄｅｘの詳細については、“FT-Rheology, a Tool to Quantify Long Chain Branching (LCB) in Natural Rubber and its Effect on Mastication, Mixing Behaviour and Final Properties.”（Henri G. Burhin, Alpha Technologies, UK 15 Rue du Culot B-1435 Hevillers, Belgium）などを参照することができる。ＬＣＢ Ｉｎｄｅｘが４．１０未満では、配合時の混練機での発熱量が大きくなり、ヤケ問題や連続生産が困難であり、５．９０を超えると配合物を押し出した際のスウェルが大きくなり、寸法安定性が劣るため好ましくない。 Further, the long chain branching index (LCB Index) measured by the LAOS measurement method using an RPA2000 type tester (manufactured by Alpha Technologies) is preferably 4.10 to 5.90, more preferably 4.30 to 5.70. Preferably, it is 4.50 to 5.50. The long chain branching index (LCB Index) measured by the LAOS measurement method using an RPA2000 type tester (manufactured by Alpha Technologies) is the long chain branching (LCB) having an approximate characteristic in the dynamic characteristics of the dissolved polymer and the molecular weight. From the distribution behavior, a more accurate index of long-chain branching is shown by removing the influence of molecular weight distribution. For details of LCB Index, see “FT-Rheology, a Tool to Quantify Long Chain Branching (LCB) in Natural Rubber and its Effect on Mastication, Mixing Behavior and Final Properties.” (Henri G. Burhin, Alpha Technologies, UK 15 Rue du Culot B-1435 Hevillers, Belgium). If the LCB Index is less than 4.10, the amount of heat generated in the kneading machine at the time of blending becomes large, and the burning problem and continuous production are difficult. If it exceeds 5.90, the swell when extruding the blend increases. Since dimensional stability is inferior, it is not preferable.
また、シンジオタクチック−１，２−ポリブタジエン（ＳＰＢ）による補強効果は、補強ポリブタジエンゴム（すなわち、得られたビニル・シス−ポリブタジエン）のムーニー粘度と沸騰ｎ−ヘキサン可溶分のムーニー粘度の差（ΔＭＬ１＋４）を沸騰ｎ−ヘキサン不溶分（ＨＩ）の量で割った値（ΔＭＬ１＋４／ＨＩ）で表すことができる。すなわち、ΔＭＬ１＋４／ＨＩが大きいほど補強効果が高いことを示す。しかしながら、補強性が高すぎると粘度が高くなりすぎ、加工性に悪影響を及ぼすため好ましくない。 Further, the reinforcing effect of syndiotactic-1,2-polybutadiene (SPB) is the difference between the Mooney viscosity of the reinforced polybutadiene rubber (that is, the obtained vinyl cis-polybutadiene) and the Mooney viscosity of the boiling n-hexane soluble component. (ΔML 1 + 4 ) can be represented by a value (ΔML 1 + 4 / HI) divided by the amount of boiling n-hexane insoluble matter (HI). That is, it shows that a reinforcement effect is so high that (DELTA) ML1 + 4 / HI is large. However, if the reinforcing property is too high, the viscosity becomes too high, which adversely affects workability.
さらにまた、剛性率（Ｇ＊）は、２５０〜５００ｋＰａが好ましく、２６０〜４９０ｋＰａがより好ましい。この数値が２５０ｋＰａより低いとＳＰＢの補強が得られず、例えばコールドフロー性等が悪くなる。一方、この数値が５００ｋＰａより高くなると弾性率が高く加工性が劣る。 Furthermore, the rigidity (G *) is preferably 250 to 500 kPa, and more preferably 260 to 490 kPa. When this numerical value is lower than 250 kPa, SPB reinforcement cannot be obtained, and, for example, cold flow properties are deteriorated. On the other hand, if this value is higher than 500 kPa, the elastic modulus is high and the workability is poor.
以下、本発明を実施例に基づいて具体的に説明するが、これらは本発明の目的を限定するものではない。なお、各物性の測定方法は次のとおりである。 EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, these do not limit the objective of this invention. In addition, the measuring method of each physical property is as follows.
（１）ムーニー粘度（ＭＬ１＋４）：ＪＩＳ Ｋ６３００に準じて１００℃で測定した。なお、表３中「１，４−シス重合後ＭＬ１＋４」は、沸騰ｎ−ヘキサン可溶分のムーニー粘度を測定した。
（２）沸騰ｎ−ヘキサン不溶分（ＨＩ）：示差走査熱量計（ＤＳＣ）により測定した融解熱量から、あらかじめ作成した融解熱量と実測のＨＩとの検量線を用いて算出した。実測ＨＩは、２ｇのビニル・シス−ポリブタジエンを２００ｍｌのｎ−ヘキサンで４時間ソックスレー抽出した後の抽出残部の重量％である。
（３）ＳＰＢ融点（Ｔｍ）：示差走査熱量計（ＤＳＣ）による吸熱曲線のピーク温度により決定した。
（４）沸騰ｎ−ヘキサン可溶分の５％トルエン溶液粘度（Ｔｃｐ）：沸騰ｎ−ヘキサン可溶分を５％になるようにトルエンに溶解して、キャノンフェンスケ粘度計を用いて２５℃で測定した。
（５）長鎖分岐指数（ＬＣＢ Ｉｎｄｅｘ）：ＲＰＡ２０００型試験機（アルファテクノロジーズ社製）を用いてＬＡＯＳ測定方法により測定した。
(1) Mooney viscosity (ML 1 + 4 ): measured at 100 ° C. according to JIS K6300. In Table 3, “ML 1 + 4 after 1,4-cis polymerization” was measured for Mooney viscosity of boiling n-hexane soluble matter.
(2) Boiling n-hexane insoluble matter (HI): Calculated from a calorific value measured with a differential scanning calorimeter (DSC) using a calibration curve between the heat of fusion prepared in advance and the measured HI. The measured HI is the weight% of the remainder after Soxhlet extraction of 2 g of vinyl cis-polybutadiene with 200 ml of n-hexane for 4 hours.
(3) SPB melting point (Tm): determined by the peak temperature of the endothermic curve by a differential scanning calorimeter (DSC).
(4) Viscosity of 5% toluene solution soluble in boiling n-hexane (T cp ): Dissolved in toluene so that the boiling n-hexane soluble content is 5%, and using a Canon Fenske viscometer Measured at ° C.
(5) Long chain branching index (LCB Index): Measured by the LAOS measurement method using an RPA2000 type tester (manufactured by Alpha Technologies).
（６）押出し生産性Ｉｎｄｅｘ：経験則から導き出した以下の計算式よりゴム組成物での押出し生産性を算出し、比較例２を指数１００として算出した。 (6) Extrusion productivity Index: Extrusion productivity in the rubber composition was calculated from the following calculation formula derived from an empirical rule, and Comparative Example 2 was calculated with an index of 100.
（７）ＶＣＲ生産性：収量を使用した重合触媒及びモノマーで除した値とし、比較例２を指数１００として算出した。
（８）剛性指数（Ｇ＊）：１００℃において、Ａｌｐｈａ Ｔｅｃｈｎｏｌｏｇｉｅｓ Ｍｏｏｎｅｙ ｖｉｓｃｏｍｅｔｅｒを用いて、周波数１００ｃｐｍ、歪み２．７９％の条件下にて５分間のウォームアップを行った後、同一温度条件下、歪１０％、２〜２５０ｃｐｍの周波数掃引で行った実験より得た。Ｇ＊は、周波数２５０ｃｐｍにおけるＧ＊の数値である。
(7) VCR productivity: The yield was calculated by dividing the yield by the polymerization catalyst and monomer used, and Comparative Example 2 was calculated with an index of 100.
(8) Rigidity index (G *): At 100 ° C., using Alpha Technologies Mooney viscometer, after warming up for 5 minutes at a frequency of 100 cpm and a strain of 2.79%, It was obtained from an experiment conducted with a frequency sweep of 10% strain and 2 to 250 cpm. G * is a numerical value of G * at a frequency of 250 cpm.
（実施例１）
表１及び２に示す配合で、ビニル・シス−ポリブタジエンを作製した。具体的には、内容量１．５Ｌのオートクレーブに、予めモレキュラーシーブスで脱水処理したシクロヘキサン、１，３−ブタジエン、シスおよびトランス−２−ブテンを主成分とするＣ４留分の重量比が３７／３２／３１となるよう調整した混合溶液６００ｍＬを入れ、窒素置換した。この溶液に水１．０２ｍｍｏｌを加えて３０分間攪拌後、１，５−シクロオクタジエン７．６８ｍｍｏｌ、トリエチルアルミニウム（ＴＥＡ：有機ハロゲン化合物）０．４２ｍｍｏｌおよびジエチルアルミニウムクロライド（ＤＥＡＣ：第１有機Ａｌ）１．８ｍｍｏｌを加えて５分間攪拌した。溶液を６０℃にしてコバルトオクトエート（１，４重合Ｃｏ触媒）５．５μｍｏｌを加えて２０分間１，４−シス重合を行った。その後、トリエチルアルミニウム（ＴＥＡ：第２有機Ａｌ）２．７ｍｍｏｌを加えて６０℃とし、水１．２０ｍｍｏｌを加えて５分間攪拌後、コバルトオクトエート（１，２重合Ｃｏ触媒）０．００１８ｍｍｏｌを加えて２分間攪拌し、さらに、二硫化炭素０．１５ｍｍｏｌを加えることで、２０分間シンジオタクチック−１，２重合を行った。所定時間経過後、４，６−ビス（オクチルチオメチル）−ｏ−クレゾールを含むメタノールを加えて重合を停止し、重合物を回収、乾燥してビニル・シス−ポリブタジエンを得た。得られたビニル・シス−ポリブタジエンのＨＩは、３．８重量％であった。その他の結果は表３に示した。なお、表１及び２は、全ての単位をｍｏｌ／Ｌに換算した値を示した。
Example 1
Vinyl cis-polybutadiene was prepared with the formulations shown in Tables 1 and 2. Specifically, the weight ratio of the C4 fraction mainly composed of cyclohexane, 1,3-butadiene, cis and trans-2-butene dehydrated in advance with molecular sieves in an autoclave having an internal volume of 1.5 L is 37 / The mixed solution 600mL adjusted so that it might become 32/31 was put, and nitrogen substitution was carried out. After adding 1.02 mmol of water to this solution and stirring for 30 minutes, 7.68 mmol of 1,5-cyclooctadiene, 0.42 mmol of triethylaluminum (TEA: organohalogen compound) and diethylaluminum chloride (DEAC: first organic Al) 1.8 mmol was added and stirred for 5 minutes. The solution was brought to 60 ° C., and 5.5 μmol of cobalt octoate (1,4-polymerization Co catalyst) was added to carry out 1,4-cis polymerization for 20 minutes. Thereafter, 2.7 mmol of triethylaluminum (TEA: second organic Al) was added to 60 ° C., 1.20 mmol of water was added and stirred for 5 minutes, and then 0.0018 mmol of cobalt octoate (1,2 polymerization Co catalyst) was added. The mixture was stirred for 2 minutes, and 0.15 mmol of carbon disulfide was further added to carry out syndiotactic-1,2 polymerization for 20 minutes. After a predetermined time, methanol containing 4,6-bis (octylthiomethyl) -o-cresol was added to terminate the polymerization, and the polymer was recovered and dried to obtain vinyl cis-polybutadiene. The resulting vinyl cis-polybutadiene had a HI of 3.8% by weight. The other results are shown in Table 3. Tables 1 and 2 show values obtained by converting all units to mol / L.
（実施例２）
シンジオタクチック−１，２重合の際に追加するコバルトオクトエートを０．００４８ｍｍｏｌとした以外は、実施例１と同様にしてビニル・シス−ポリブタジエンを得た。得られたビニル・シス−ポリブタジエンのＨＩは、５．６重量％であった。その他の結果は表３に示した。
(Example 2)
Vinyl cis-polybutadiene was obtained in the same manner as in Example 1 except that the cobalt octoate added during syndiotactic-1,2 polymerization was changed to 0.0048 mmol. The resulting vinyl cis-polybutadiene had a HI of 5.6% by weight. The other results are shown in Table 3.
（比較例１）
表１及び２に示す配合で、ビニル・シス−ポリブタジエンを作製した。具体的には、内容量１．５Ｌのオートクレーブに、予めモレキュラーシーブスで脱水処理したシクロヘキサン、１，３−ブタジエン、シスおよびトランス−２−ブテンを主成分とするＣ４留分の重量比が３７／３２／３１となるよう調整した混合溶液１０００ｍＬを入れ、窒素置換した。この溶液に水２．００ｍｍｏｌを加えて３０分間攪拌後、１，５−シクロオクタジエン１２．２ｍｍｏｌ、トリエチルアルミニウム（ＴＥＡ：有機ハロゲン化合物）０．７０ｍｍｏｌおよびジエチルアルミニウムクロライド（ＤＥＡＣ：第１有機Ａｌ）２．３０ｍｍｏｌを加えて５分間攪拌した。溶液を６０℃にしてコバルトオクトエート（１，４重合Ｃｏ触媒）４．３μｍｏｌを加えて２０分間１，４−シス重合を行った。その後、トリエチルアルミニウム（ＴＥＡ：第２有機Ａｌ）３．９ｍｍｏｌを加えて６０℃とし、５分間攪拌後、コバルトオクトエート（１，２重合Ｃｏ触媒）０．０４３ｍｍｏｌを加えて２分間攪拌し、さらに、二硫化炭素０．２５ｍｍｏｌを加えることで、２０分間シンジオタクチック−１，２重合を行った。所定時間経過後、４，６−ビス（オクチルチオメチル）−ｏ−クレゾールを含むメタノールを加えて重合を停止し、重合物を回収、乾燥してビニル・シス−ポリブタジエンを得た。得られたビニル・シス−ポリブタジエンのＨＩは、１３．８重量％であった。その他の結果は表３に示した。
(Comparative Example 1)
Vinyl cis-polybutadiene was prepared with the formulations shown in Tables 1 and 2. Specifically, the weight ratio of the C4 fraction mainly composed of cyclohexane, 1,3-butadiene, cis and trans-2-butene dehydrated in advance with molecular sieves in an autoclave having an internal volume of 1.5 L is 37 / 1000 mL of a mixed solution adjusted to 32/31 was added, and the atmosphere was replaced with nitrogen. After adding 2.00 mmol of water to this solution and stirring for 30 minutes, 12.2-mmol of 1,5-cyclooctadiene, 0.70 mmol of triethylaluminum (TEA: organic halogen compound) and diethylaluminum chloride (DEAC: first organic Al) 2.30 mmol was added and stirred for 5 minutes. The solution was brought to 60 ° C. and 4.3 μmol of cobalt octoate (1,4-polymerization Co catalyst) was added, and 1,4-cis polymerization was carried out for 20 minutes. Thereafter, 3.9 mmol of triethylaluminum (TEA: second organic Al) was added to 60 ° C., and the mixture was stirred for 5 minutes. Then, 0.043 mmol of cobalt octoate (1,2 polymerization Co catalyst) was added, and the mixture was stirred for 2 minutes. By adding 0.25 mmol of carbon disulfide, syndiotactic-1,2 polymerization was carried out for 20 minutes. After a predetermined time, methanol containing 4,6-bis (octylthiomethyl) -o-cresol was added to terminate the polymerization, and the polymer was recovered and dried to obtain vinyl cis-polybutadiene. The resulting vinyl cis-polybutadiene had a HI of 13.8% by weight. The other results are shown in Table 3.
（比較例２）
シンジオタクチック−１，２重合の際に追加するコバルトオクトエートを０．００６ｍｍｏｌとした以外は、実施例１と同様にしてビニル・シス−ポリブタジエンゴムを得た。得られたビニル・シス−ポリブタジエンのＨＩは、６．７重量％であった。その他の結果は表３に示した。
(Comparative Example 2)
A vinyl cis-polybutadiene rubber was obtained in the same manner as in Example 1 except that the amount of cobalt octoate added during syndiotactic-1,2 polymerization was 0.006 mmol. The resulting vinyl cis-polybutadiene had a HI of 6.7% by weight. The other results are shown in Table 3.
（比較例３）
内容量１．５Ｌのオートクレーブに、予めモレキュラーシーブスで脱水処理したシクロヘキサン、１，３−ブタジエン、シスおよびトランス−２−ブテンを主成分とするＣ４留分の重量比が４５／３０／２５となるよう調整した混合溶液６００ｍＬを入れ、窒素置換した。この溶液に水１．７４ｍｍｏｌを加えて３０分間攪拌後、１，５−シクロオクタジエン４．８ｍｍｏｌ、ジエチルアルミニウムクロライド（ＤＥＡＣ：第１有機Ａｌ）０．９６ｍｍｏｌ及びトリエチルアルミニウム（ＴＥＡ：有機ハロゲン化合物）０．９６ｍｍｏｌを加えて５分間攪拌した。溶液を６０℃にしてコバルトオクトエート（１，４重合Ｃｏ触媒）４．８μｍｏｌを加えて２０分間１，４−シス重合を行った。その後、トリエチルアルミニウム（ＴＥＡ：第２有機Ａｌ）２．７ｍｍｏｌを加えて６０℃とし、水１．２ｍｍｏｌを加えて５分間攪拌後、コバルトオクトエート（１，２重合Ｃｏ触媒）０．００６ｍｍｏｌを加えて２分間攪拌し、さらに、二硫化炭素０．１５ｍｍｏｌを加えることで、２０分間シンジオタクチック−１，２重合を行った。所定時間経過後、４，６−ビス（オクチルチオメチル）−ｏ−クレゾールを含むメタノールを加えて重合を停止し、重合物を回収、乾燥してビニル・シス−ポリブタジエンを得た。得られたビニル・シス−ポリブタジエンのＴｃｐ／ＭＬ１＋４は、２．１６であった。その他の結果は表３に示した。
(Comparative Example 3)
The weight ratio of the C4 fraction mainly composed of cyclohexane, 1,3-butadiene, cis and trans-2-butene dehydrated in advance in molecular sieves in an autoclave having an internal volume of 1.5 L is 45/30/25. Then, 600 mL of the mixed solution prepared as described above was added and purged with nitrogen. 1.74 mmol of water was added to this solution and stirred for 30 minutes. Then, 4.8 mmol of 1,5-cyclooctadiene, 0.96 mmol of diethylaluminum chloride (DEAC: first organic Al) and triethylaluminum (TEA: organohalogen compound) 0.96 mmol was added and stirred for 5 minutes. The solution was brought to 60 ° C., 4.8 μmol of cobalt octoate (1,4 polymerization Co catalyst) was added, and 1,4-cis polymerization was carried out for 20 minutes. Thereafter, 2.7 mmol of triethylaluminum (TEA: second organic Al) was added to 60 ° C., 1.2 mmol of water was added and stirred for 5 minutes, and then 0.006 mmol of cobalt octoate (1,2 polymerization Co catalyst) was added. The mixture was stirred for 2 minutes, and 0.15 mmol of carbon disulfide was further added to carry out syndiotactic-1,2 polymerization for 20 minutes. After a predetermined time, methanol containing 4,6-bis (octylthiomethyl) -o-cresol was added to terminate the polymerization, and the polymer was recovered and dried to obtain vinyl cis-polybutadiene. The resulting vinyl cis-polybutadiene had a Tcp / ML 1 + 4 of 2.16. The other results are shown in Table 3.
（比較例４）
内容量１．５Ｌのオートクレーブに、予めモレキュラーシーブスで脱水処理したシクロヘキサン、１，３−ブタジエン、シスおよびトランス−２−ブテンを主成分とするＣ４留分の重量比が２５／３０／４５となるよう調整した混合溶液６００ｍＬを入れ、窒素置換した。この溶液に水１．２８ｍｍｏｌを加えて３０分間攪拌後、１，５−シクロオクタジエン６．３６ｍｍｏｌ、ジエチルアルミニウムクロライド（ＤＥＡＣ：第１有機Ａｌ）１．８ｍｍｏｌを加えて５分間攪拌した。溶液を６０℃にしてコバルトオクトエート（１，４重合Ｃｏ触媒）４．４４μｍｏｌを加えて２０分間１，４−シス重合を行った。その後、トリエチルアルミニウム（ＴＥＡ：第２有機Ａｌ）２．７ｍｍｏｌを加えて６０℃とし、水１．２ｍｍｏｌを加えて５分間攪拌後、コバルトオクトエート（１，２重合Ｃｏ触媒）０．０２５８ｍｍｏｌを加えて２分間攪拌し、さらに、二硫化炭素０．１５ｍｍｏｌを加えることで、２０分間シンジオタクチック−１，２重合を行った。所定時間経過後、４，６−ビス（オクチルチオメチル）−ｏ−クレゾールを含むメタノールを加えて重合を停止し、重合物を回収、乾燥してビニル・シス−ポリブタジエンを得た。得られたビニル・シス−ポリブタジエンのＴｃｐ／ＭＬ１＋４は、２．１７であった。その他の結果は表３に示した。
(Comparative Example 4)
The weight ratio of the C4 fraction mainly composed of cyclohexane, 1,3-butadiene, cis and trans-2-butene, dehydrated with molecular sieves in advance in an autoclave with an internal volume of 1.5 L is 25/30/45. Then, 600 mL of the mixed solution prepared as described above was added and purged with nitrogen. 1.28 mmol of water was added to this solution and stirred for 30 minutes, and then 6.36 mmol of 1,5-cyclooctadiene and 1.8 mmol of diethylaluminum chloride (DEAC: first organic Al) were added and stirred for 5 minutes. The solution was heated to 60 ° C. and 4.44 μmol of cobalt octoate (1,4-polymerization Co catalyst) was added to carry out 1,4-cis polymerization for 20 minutes. Thereafter, 2.7 mmol of triethylaluminum (TEA: second organic Al) was added to 60 ° C., 1.2 mmol of water was added and stirred for 5 minutes, and then 0.0258 mmol of cobalt octoate (1,2 polymerization Co catalyst) was added. The mixture was stirred for 2 minutes, and 0.15 mmol of carbon disulfide was further added to carry out syndiotactic-1,2 polymerization for 20 minutes. After a predetermined time, methanol containing 4,6-bis (octylthiomethyl) -o-cresol was added to terminate the polymerization, and the polymer was recovered and dried to obtain vinyl cis-polybutadiene. The resulting vinyl cis-polybutadiene had a Tcp / ML 1 + 4 of 2.17. The other results are shown in Table 3.
以上より、水に対する第１有機Ａｌと有機ハロゲン化合物の全添加量、第１有機Ａｌに対する有機ハロゲン化合物の添加量、１，３−ブタジエンに対する１，２−重合Ｃｏ触媒の添加量、並びに第１及び第２有機Ａｌの合計有機Ａｌに対する１，２−重合Ｃｏ触媒の添加量を調整することで、容易にＨＩを低く調整することができ、生産性よく安定的に低ＨＩのビニル・シス−ポリブタジエンが得られることが分かる。 From the above, the total addition amount of the first organic Al and the organic halogen compound to water, the addition amount of the organic halogen compound to the first organic Al, the addition amount of the 1,2-polymerization Co catalyst to 1,3-butadiene, and the first By adjusting the amount of the 1,2-polymerization Co catalyst added to the total organic Al of the second organic Al, the HI can be easily adjusted to a low level, and the vinyl cis- It can be seen that polybutadiene is obtained.
Claims (4)
共役ジエン系モノマー及び溶媒を含む共役ジエン系モノマー溶液に水、第１の有機アルミニウム、有機ハロゲン化合物及び１，４重合触媒を添加して前記共役ジエン系モノマーを１，４−シス重合するシス重合工程（ａ）と、
該シス重合工程（ａ）の後に第２の有機アルミニウム、二硫化炭素及び１，２重合触媒を添加して１，２−ビニル重合するビニル重合工程（ｂ）とを有し、
（１）前記水１ｍｏｌに対する前記第１の有機アルミニウム及び前記有機ハロゲン化合物の全添加量が１．５〜３．０ｍｏｌであり、
（２）前記第１の有機アルミニウムが非ハロゲン化有機アルミニウム化合物であり、前記非ハロゲン化有機アルミニウム化合物１ｍｏｌに対する前記有機ハロゲン化合物の添加量が１．５〜９．０ｍｏｌであり、
（３）前記共役ジエン系モノマー１ｍｏｌに対する前記１，２重合触媒の添加量が０．１〜２．４μｍｏｌであり、
（４）前記第１及び第２の有機アルミニウムからなる全有機アルミニウム１ｍｏｌに対する前記１，２重合触媒の添加量が０．０００１〜０．００３０ｍｏｌであることを特徴とするビニル・シス−ポリブタジエンの製造方法。 A method for producing vinyl cis-polybutadiene having a boiling n-hexane insoluble content (HI) of 3 to 9% by weight, comprising:
Cis polymerization in which water, first organoaluminum, organic halogen compound and 1,4 polymerization catalyst are added to a conjugated diene monomer solution containing a conjugated diene monomer and a solvent to 1,4-cis polymerize the conjugated diene monomer. Step (a);
A vinyl polymerization step (b) in which a second organoaluminum, carbon disulfide and a 1,2 polymerization catalyst are added after the cis polymerization step (a) to polymerize 1,2-vinyl;
(1) The total addition amount of the first organoaluminum and the organohalogen compound with respect to 1 mol of the water is 1.5 to 3.0 mol,
(2) The first organoaluminum is a non-halogenated organoaluminum compound, and the amount of the organohalogen compound added relative to 1 mol of the non-halogenated organoaluminum compound is 1.5 to 9.0 mol,
(3) The addition amount of the 1,2 polymerization catalyst with respect to 1 mol of the conjugated diene monomer is 0.1 to 2.4 μmol,
(4) Production of vinyl cis-polybutadiene, wherein the addition amount of the 1,2 polymerization catalyst is 0.0001 to 0.0030 mol with respect to 1 mol of total organoaluminum composed of the first and second organoaluminums. Method.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017132956A (en) * | 2016-01-29 | 2017-08-03 | 宇部興産株式会社 | Vinyl-cis-polybutadiene rubber and method for producing the same |
| WO2020116367A1 (en) * | 2018-12-03 | 2020-06-11 | 宇部興産株式会社 | Polybutadiene and method for producing same |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0448815B2 (en) * | 1984-09-19 | 1992-08-07 | Ube Industries | |
| JPH07188341A (en) * | 1993-11-09 | 1995-07-25 | Polysar Rubber Corp | Production of cis-1,4-polybutadiene with reduced gel formation |
| JP2000044633A (en) * | 1998-07-31 | 2000-02-15 | Ube Ind Ltd | Production of new vinyl-cis-butadiene rubber and vinyl- cis-butadiene rubber composition |
| JP2001294614A (en) * | 2000-04-13 | 2001-10-23 | Ube Ind Ltd | Polybutadiene and method for producing the same |
| JP2004083851A (en) * | 2002-06-24 | 2004-03-18 | Ube Ind Ltd | Method for producing conjugated diene polymer |
| JP2004244427A (en) * | 2003-02-10 | 2004-09-02 | Ube Ind Ltd | Polybutadiene composition and its production process |
| JP2010235865A (en) * | 2009-03-31 | 2010-10-21 | Ube Ind Ltd | Method of producing reinforced polybutadiene rubber |
-
2013
- 2013-03-19 JP JP2013057296A patent/JP5447708B2/en active Active
- 2013-03-22 MY MYPI2013001007A patent/MY160311A/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0448815B2 (en) * | 1984-09-19 | 1992-08-07 | Ube Industries | |
| JPH07188341A (en) * | 1993-11-09 | 1995-07-25 | Polysar Rubber Corp | Production of cis-1,4-polybutadiene with reduced gel formation |
| JP2000044633A (en) * | 1998-07-31 | 2000-02-15 | Ube Ind Ltd | Production of new vinyl-cis-butadiene rubber and vinyl- cis-butadiene rubber composition |
| JP2001294614A (en) * | 2000-04-13 | 2001-10-23 | Ube Ind Ltd | Polybutadiene and method for producing the same |
| JP2004083851A (en) * | 2002-06-24 | 2004-03-18 | Ube Ind Ltd | Method for producing conjugated diene polymer |
| JP2004244427A (en) * | 2003-02-10 | 2004-09-02 | Ube Ind Ltd | Polybutadiene composition and its production process |
| JP2010235865A (en) * | 2009-03-31 | 2010-10-21 | Ube Ind Ltd | Method of producing reinforced polybutadiene rubber |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017132956A (en) * | 2016-01-29 | 2017-08-03 | 宇部興産株式会社 | Vinyl-cis-polybutadiene rubber and method for producing the same |
| WO2020116367A1 (en) * | 2018-12-03 | 2020-06-11 | 宇部興産株式会社 | Polybutadiene and method for producing same |
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