JPH0261961B2 - - Google Patents
Info
- Publication number
- JPH0261961B2 JPH0261961B2 JP21549282A JP21549282A JPH0261961B2 JP H0261961 B2 JPH0261961 B2 JP H0261961B2 JP 21549282 A JP21549282 A JP 21549282A JP 21549282 A JP21549282 A JP 21549282A JP H0261961 B2 JPH0261961 B2 JP H0261961B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- oxide
- butadiene
- ethylene
- mmol
- 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.)
- Expired
Links
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 60
- 239000003054 catalyst Substances 0.000 claims description 45
- -1 phosphorus compound Chemical class 0.000 claims description 45
- 239000012456 homogeneous solution Substances 0.000 claims description 22
- 239000000460 chlorine Substances 0.000 claims description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims description 20
- 239000011574 phosphorus Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 18
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 17
- 239000005977 Ethylene Substances 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- 150000002681 magnesium compounds Chemical class 0.000 claims description 13
- 150000001336 alkenes Chemical class 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 9
- 150000001993 dienes Chemical class 0.000 claims description 8
- 150000002430 hydrocarbons Chemical group 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000003609 titanium compounds Chemical class 0.000 claims description 7
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000010936 titanium Substances 0.000 description 41
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 25
- 238000000034 method Methods 0.000 description 19
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 239000002904 solvent Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 229910052719 titanium Inorganic materials 0.000 description 9
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- 229920001971 elastomer Polymers 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- HQMRIBYCTLBDAK-UHFFFAOYSA-M bis(2-methylpropyl)alumanylium;chloride Chemical compound CC(C)C[Al](Cl)CC(C)C HQMRIBYCTLBDAK-UHFFFAOYSA-M 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 229910003480 inorganic solid Inorganic materials 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229910019440 Mg(OH) Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000002897 diene group Chemical group 0.000 description 3
- 150000008282 halocarbons Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 229960002337 magnesium chloride Drugs 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 description 3
- 238000011282 treatment Methods 0.000 description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 2
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 description 2
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- YVBCULSIZWMTFY-UHFFFAOYSA-N 4-Heptanol Natural products CCCC(O)CCC YVBCULSIZWMTFY-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 238000004737 colorimetric analysis Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- QVKQJEWZVQFGIY-UHFFFAOYSA-N dipropyl hydrogen phosphate Chemical compound CCCOP(O)(=O)OCCC QVKQJEWZVQFGIY-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229940091250 magnesium supplement Drugs 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- XMNDMAQKWSQVOV-UHFFFAOYSA-N (2-methylphenyl) diphenyl phosphate Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C=CC=CC=1)OC1=CC=CC=C1 XMNDMAQKWSQVOV-UHFFFAOYSA-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
- KNKRKFALVUDBJE-UHFFFAOYSA-N 1,2-dichloropropane Chemical compound CC(Cl)CCl KNKRKFALVUDBJE-UHFFFAOYSA-N 0.000 description 1
- KIZGBMSFXOHDPW-UHFFFAOYSA-N 1-[bis(2-methylpropyl)phosphoryl]-2-methylpropane Chemical compound CC(C)CP(=O)(CC(C)C)CC(C)C KIZGBMSFXOHDPW-UHFFFAOYSA-N 0.000 description 1
- HRSRTFWJBHAXST-UHFFFAOYSA-N 1-[bis(2-methylpropyl)phosphoryloxy]-2-methylpropane Chemical compound CC(C)COP(=O)(CC(C)C)CC(C)C HRSRTFWJBHAXST-UHFFFAOYSA-N 0.000 description 1
- JPGXOMADPRULAC-UHFFFAOYSA-N 1-[butoxy(butyl)phosphoryl]oxybutane Chemical compound CCCCOP(=O)(CCCC)OCCCC JPGXOMADPRULAC-UHFFFAOYSA-N 0.000 description 1
- AATNZNJRDOVKDD-UHFFFAOYSA-N 1-[ethoxy(ethyl)phosphoryl]oxyethane Chemical compound CCOP(=O)(CC)OCC AATNZNJRDOVKDD-UHFFFAOYSA-N 0.000 description 1
- CNDHHGUSRIZDSL-UHFFFAOYSA-N 1-chlorooctane Chemical compound CCCCCCCCCl CNDHHGUSRIZDSL-UHFFFAOYSA-N 0.000 description 1
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 1
- GXYBSEVPLCHEBL-UHFFFAOYSA-N 1-dibutylphosphoryloxybutane Chemical compound CCCCOP(=O)(CCCC)CCCC GXYBSEVPLCHEBL-UHFFFAOYSA-N 0.000 description 1
- ZSSWXNPRLJLCDU-UHFFFAOYSA-N 1-diethylphosphorylethane Chemical compound CCP(=O)(CC)CC ZSSWXNPRLJLCDU-UHFFFAOYSA-N 0.000 description 1
- GQAXWUVTNDQEQR-UHFFFAOYSA-N 1-diethylphosphoryloxyethane Chemical compound CCOP(=O)(CC)CC GQAXWUVTNDQEQR-UHFFFAOYSA-N 0.000 description 1
- RKLTVCITGCXISI-UHFFFAOYSA-N 1-dioctylphosphoryloxyoctane Chemical compound CCCCCCCCOP(=O)(CCCCCCCC)CCCCCCCC RKLTVCITGCXISI-UHFFFAOYSA-N 0.000 description 1
- SNZSAFILJOCMFM-UHFFFAOYSA-N 1-dipropylphosphorylpropane Chemical compound CCCP(=O)(CCC)CCC SNZSAFILJOCMFM-UHFFFAOYSA-N 0.000 description 1
- HIAUUFZUTAVKRI-UHFFFAOYSA-N 1-oct-1-enoxyoct-1-ene Chemical compound CCCCCCC=COC=CCCCCCC HIAUUFZUTAVKRI-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- RNDNSYIPLPAXAZ-UHFFFAOYSA-N 2-Phenyl-1-propanol Chemical compound OCC(C)C1=CC=CC=C1 RNDNSYIPLPAXAZ-UHFFFAOYSA-N 0.000 description 1
- GEZGQQFKEOIGJS-UHFFFAOYSA-N 2-di(propan-2-yl)phosphorylpropane Chemical compound CC(C)P(=O)(C(C)C)C(C)C GEZGQQFKEOIGJS-UHFFFAOYSA-N 0.000 description 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 description 1
- NMVXHZSPDTXJSJ-UHFFFAOYSA-L 2-methylpropylaluminum(2+);dichloride Chemical compound CC(C)C[Al](Cl)Cl NMVXHZSPDTXJSJ-UHFFFAOYSA-L 0.000 description 1
- GOCVCBDBQYEFQD-UHFFFAOYSA-N 3-[[2-ethylhexoxy(2-ethylhexyl)phosphoryl]oxymethyl]heptane Chemical compound CCCCC(CC)COP(=O)(CC(CC)CCCC)OCC(CC)CCCC GOCVCBDBQYEFQD-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- YFTSCDTTWVSBLB-UHFFFAOYSA-N CCCCCCP(=O)CC Chemical compound CCCCCCP(=O)CC YFTSCDTTWVSBLB-UHFFFAOYSA-N 0.000 description 1
- PDAXJVMXHHATAJ-UHFFFAOYSA-N CCCCO[PH2]=O Chemical compound CCCCO[PH2]=O PDAXJVMXHHATAJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- LXSJBQODTLCLTK-UHFFFAOYSA-N OCCCC[PH2]=O Chemical compound OCCCC[PH2]=O LXSJBQODTLCLTK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 229910010386 TiI4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- KZIUWSQALWALJH-UHFFFAOYSA-N bis(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)CP(O)(=O)CC(CC)CCCC KZIUWSQALWALJH-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- WCVSRFBEIOHADI-UHFFFAOYSA-N butoxy(butyl)phosphinic acid Chemical compound CCCCOP(O)(=O)CCCC WCVSRFBEIOHADI-UHFFFAOYSA-N 0.000 description 1
- YLYNVLJAZMTTIQ-UHFFFAOYSA-N butoxy(diethyl)alumane Chemical compound CCCC[O-].CC[Al+]CC YLYNVLJAZMTTIQ-UHFFFAOYSA-N 0.000 description 1
- BNMJSBUIDQYHIN-UHFFFAOYSA-N butyl dihydrogen phosphate Chemical compound CCCCOP(O)(O)=O BNMJSBUIDQYHIN-UHFFFAOYSA-N 0.000 description 1
- SHOVVTSKTTYFGP-UHFFFAOYSA-L butylaluminum(2+);dichloride Chemical compound CCCC[Al](Cl)Cl SHOVVTSKTTYFGP-UHFFFAOYSA-L 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- QZVALCYYGHPQRD-UHFFFAOYSA-N dibutan-2-yl hydrogen phosphate Chemical compound CCC(C)OP(O)(=O)OC(C)CC QZVALCYYGHPQRD-UHFFFAOYSA-N 0.000 description 1
- VJRUISVXILMZSL-UHFFFAOYSA-M dibutylalumanylium;chloride Chemical compound CCCC[Al](Cl)CCCC VJRUISVXILMZSL-UHFFFAOYSA-M 0.000 description 1
- LEFPWWWXFFNJAA-UHFFFAOYSA-N dicyclohexylphosphorylcyclohexane Chemical compound C1CCCCC1P(C1CCCCC1)(=O)C1CCCCC1 LEFPWWWXFFNJAA-UHFFFAOYSA-N 0.000 description 1
- QHAUASBJFFBWMY-UHFFFAOYSA-N didecyl hydrogen phosphate Chemical compound CCCCCCCCCCOP(O)(=O)OCCCCCCCCCC QHAUASBJFFBWMY-UHFFFAOYSA-N 0.000 description 1
- UWJCYVDGGSAERX-UHFFFAOYSA-N didodecylphosphinic acid Chemical compound CCCCCCCCCCCCP(O)(=O)CCCCCCCCCCCC UWJCYVDGGSAERX-UHFFFAOYSA-N 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 1
- PPQUYYAZSOKTQD-UHFFFAOYSA-M diethylalumanylium;iodide Chemical compound CC[Al](I)CC PPQUYYAZSOKTQD-UHFFFAOYSA-M 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- HUDSKKNIXMSHSZ-UHFFFAOYSA-N dihexyl hydrogen phosphate Chemical compound CCCCCCOP(O)(=O)OCCCCCC HUDSKKNIXMSHSZ-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- QRQUTSPLBBZERR-UHFFFAOYSA-M dioctylalumanylium;chloride Chemical compound CCCCCCCC[Al](Cl)CCCCCCCC QRQUTSPLBBZERR-UHFFFAOYSA-M 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- YEWZQCDRZRYAEB-UHFFFAOYSA-N ditert-butyl hydrogen phosphate Chemical compound CC(C)(C)OP(O)(=O)OC(C)(C)C YEWZQCDRZRYAEB-UHFFFAOYSA-N 0.000 description 1
- TVACALAUIQMRDF-UHFFFAOYSA-N dodecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCOP(O)(O)=O TVACALAUIQMRDF-UHFFFAOYSA-N 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- KCLVGLMRNKNKQB-UHFFFAOYSA-N hexoxy(hexyl)phosphinic acid Chemical compound CCCCCCOP(O)(=O)CCCCCC KCLVGLMRNKNKQB-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 1
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- HMQCZKVONBJPKW-UHFFFAOYSA-N octoxy(octyl)phosphinic acid Chemical compound CCCCCCCCOP(O)(=O)CCCCCCCC HMQCZKVONBJPKW-UHFFFAOYSA-N 0.000 description 1
- WRKCIHRWQZQBOL-UHFFFAOYSA-N octyl dihydrogen phosphate Chemical compound CCCCCCCCOP(O)(O)=O WRKCIHRWQZQBOL-UHFFFAOYSA-N 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- SOEVKJXMZBAALG-UHFFFAOYSA-N octylalumane Chemical compound CCCCCCCC[AlH2] SOEVKJXMZBAALG-UHFFFAOYSA-N 0.000 description 1
- RBLGTYCOUOIUNY-UHFFFAOYSA-L octylaluminum(2+);dichloride Chemical compound CCCCCCCC[Al](Cl)Cl RBLGTYCOUOIUNY-UHFFFAOYSA-L 0.000 description 1
- 150000002902 organometallic compounds Chemical group 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229940067107 phenylethyl alcohol Drugs 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
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- OHRVKCZTBPSUIK-UHFFFAOYSA-N tridodecyl phosphate Chemical compound CCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCC)OCCCCCCCCCCCC OHRVKCZTBPSUIK-UHFFFAOYSA-N 0.000 description 1
- XBEXIHMRFRFRAM-UHFFFAOYSA-N tridodecylalumane Chemical compound CCCCCCCCCCCC[Al](CCCCCCCCCCCC)CCCCCCCCCCCC XBEXIHMRFRFRAM-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- KENFVQBKAYNBKN-UHFFFAOYSA-N trihexadecyl phosphate Chemical compound CCCCCCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCC KENFVQBKAYNBKN-UHFFFAOYSA-N 0.000 description 1
- SFENPMLASUEABX-UHFFFAOYSA-N trihexyl phosphate Chemical compound CCCCCCOP(=O)(OCCCCCC)OCCCCCC SFENPMLASUEABX-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- FDGZUBKNYGBWHI-UHFFFAOYSA-N trioctadecyl phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(=O)(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC FDGZUBKNYGBWHI-UHFFFAOYSA-N 0.000 description 1
- WVPGXJOLGGFBCR-UHFFFAOYSA-N trioctyl phosphate Chemical compound CCCCCCCCOP(=O)(OCCCCCCCC)OCCCCCCCC WVPGXJOLGGFBCR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- OXFUXNFMHFCELM-UHFFFAOYSA-N tripropan-2-yl phosphate Chemical compound CC(C)OP(=O)(OC(C)C)OC(C)C OXFUXNFMHFCELM-UHFFFAOYSA-N 0.000 description 1
- RXPQRKFMDQNODS-UHFFFAOYSA-N tripropyl phosphate Chemical compound CCCOP(=O)(OCCC)OCCC RXPQRKFMDQNODS-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- SVETUDAIEHYIKZ-IUPFWZBJSA-N tris[(z)-octadec-9-enyl] phosphate Chemical compound CCCCCCCC\C=C/CCCCCCCCOP(=O)(OCCCCCCCC\C=C/CCCCCCCC)OCCCCCCCC\C=C/CCCCCCCC SVETUDAIEHYIKZ-IUPFWZBJSA-N 0.000 description 1
- CQXYINNETWHZTR-UHFFFAOYSA-N tritert-butyl phosphate Chemical compound CC(C)(C)OP(=O)(OC(C)(C)C)OC(C)(C)C CQXYINNETWHZTR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
本発明は高活性なチーグラー系触媒を用いてオ
レフインと共役ジエンを収率よく共重合させる方
法に関する。
エチレン/ブタジエン共重合の触媒として、例
えば特公昭47−15696号にTi(OBu)4/AlEt3系触
媒が、また特公昭49−26071号にTiCl4/Al(i−
Bu)3/カルボニル化合物系触媒が提案されてい
るが、これらの触媒系では触媒活性がTi原子1
g当り重合体100g以下と非常に低いものである。
さらに特公昭49−16784号公報にはMgCl2を電子
供与体の存在下四塩化チタンと加熱処理して得ら
れる固定触媒成分とトリアルキルアルミニウムよ
りなる触媒を用いてエチレンとブタジエンを共重
合させる方法が開示されている。この触媒活性は
30Kg/g−Ti・hrと高いものであるが、共重合
体中のジエン部分は2,3モル%以下と非常に低
いものである。
以上述べたようにオレフイン/共役ジエン共重
合体の製造方法は数多くの研究例が知られている
が、(1)重合温度が比較的高温であること(−20〜
150℃)、(2)触媒活性が高いこと、(3)共重合体中の
共役ジエンユニツトの割合を任意にコントロール
できること、(4)触媒調製が室温付近でできること
の実作業上望ましい4つの条件を同時に満足する
オレフイン/共役ジエン共重合体製造方法は未だ
に見い出されていない。
本発明者らは上記の条件を満たす共重合体の製
造方法を鋭意研究した結果次の製造方法を見い出
し、本発明に到達した。
本発明の共重合体を製造する方法を実施する為
に用いられる重合触媒の調製工程は添付の第1図
に示すフローチヤートに従つて行なわれ得る。し
かし、同図のフローチヤートは本発明の範囲を限
定するものではない。
本発明に従つて、有機溶媒の存在下又は不存在
下で調製された(A)含塩素マグネシウム化合物及び
P=O結合を有するリン化合物を含有する均一溶
液とチタン化合物とを接触させて得られる粉末及
び(B)有機アルミニウム化合物もしくは一般式
R2OH(R2は炭素数1〜20の炭化水素基)で表わ
されるアルコール性化合物で変性された有機アル
ミニウム化合物からなる触媒を用い、オレフイン
と共役ジエンとを共重合させることを特徴とする
オレフイン−共役ジエン共重合体の製造方法が提
供される。
以下に本発明を詳細に説明する。
先づ本発明で用いる触媒成分(A)について説明す
れば、含塩素マグネシウム化合物は具体的には
MgCl2又はMg(OH)Clで、MgCl2は無水である
ことが好ましく、ボールミル粉砕、振動ミル粉砕
や錯化処理等の変性処理を施したものも用いるこ
とができる、またMg(OH)ClはMgCl2・6H2O
を高温で加熱することにより得られる。
P=O結合を有するリン化合物としては一般式
O=PR1m(OR2)n及び/又はO=P(OH)j
(OR3 k)R4 lで表わされる化合物が使用される
(但しR1、R2、R3、R4は炭素数1〜20の炭化水
素基、m,nは0〜3の整数でm+n=3、jは
1又は2、k,lは0〜2の整数でj+k+l=
3である)。具体的には下記のものが挙げられる。
トリメチルホスフエート、トリエチルホスフエ
ート、トリ−n−プロピルホスフエート、トリ−
イソ−プロピルホスフエート、トリ−n−ブチル
ホスフエート、トリ−i−ブチルホスフエート、
トリ−t−ブチルホスフエート、トリ−n−ヘキ
シルホスフエート、トリ−n−オクチルホスフエ
ート、トリ−2−エチル−ヘキシルホスフエー
ト、トリラウリルホスフエート、トリセチルホス
フエート、トリステアリルホスフエート、トリオ
レイルホスフエート、トリフエニルホスフエー
ト、トリトリル−ホスフエート、トリキシルホス
フエート、オクチルジフエニルホスフエート、ト
リルジフエニルホスフエート、キシリルジフエニ
ルホスフエート、エチル(ジエトキシ)ホスフイ
ンオキシド、n−プロピル(ジ−n−プロピルオ
キシ)ホスフインオキシド、n−ブチル(ジ−n
−ブトキシ)ホスフインオキシド、n−オクチル
(ジ−n−オクチルオキシ)ホスフインオキシド、
2−エチルヘキシル(ジ−2−エチルヘキシルオ
キシ)ホスフインオキシド、ジエチル(エトキ
シ)ホスフインオキシド、ジ−n−ブチル(n−
ブトキシ)ホスフインオキシド、ジイソブチル
(イソブトキシ)ホスフインオキシド、ジ−n−
オクチル(n−オクチルオキシ)ホスフインオキ
シド、ジ−2−エチルヘキシル(2−エチルヘキ
シルオキシ)ホスフインオキシド、トリエチルホ
スフインオキシド、トリ−n−プロピルホスフイ
ンオキシド、トリイソプロピルホスフインオキシ
ド、トリ−n−ブチルホスフインオキシド、トリ
イソブチルホスフインオキシド、トリ−n−オク
チルホスフインオキシド、トリ−2−エチルヘキ
シルホスフインオキシド、トリシクロヘキシルホ
スフインオキシド、トリフエニルホスフインオキ
シド、トリトリルホスフインオキシド、トリキシ
リルホスフインオキシド、モノヒドロキシジエト
キシホスフインオキシド、モノヒドロキシジプロ
ポキシホスフインオキシド、モノヒドロキシジ−
n−ブトキシホスフインオキシド、モノヒドロキ
シジ−sec−ブトキシホスフインオキシド、モノ
ヒドロキシジ−t−ブトキシホスフインオキシ
ド、モノヒドロキシジ−n−ヘキシルオキシホス
フインオキシド、モノヒドロキシジ−n−オクチ
ルオキシホスフインオキシド、モノヒドロキシジ
−2−エチルヘキシルオキシホスフインオキシ
ド、モノヒドロキシジ−n−デシルオキシホスフ
インオキシド、モノヒドロキシジ−n−ドデシル
ホスフインオキシド、モノヒドロキシ(n−ブチ
ル)n−ブトキシホスフインオキシド、モノヒド
ロキシ(n−ヘキシル)n−ヘキシルオキシホス
フインオキシド、モノヒドロキシ(n−オクチ
ル)n−オクチルオキシホスフインオキシド、モ
ノヒドロキシ(2−エチルヘキシル)2−エチル
ヘキシルホスフインオキシド、モノヒドロキシブ
チルホスフインオキシド、モノヒドロキシジ−2
−エチルヘキシルホスフインオキシド、ジヒドロ
キシモノブトキシホスフインオキシド、ジヒドロ
キシモノ−n−オクチルオキシホスフインオキシ
ド、ジヒドロキシモノ−2−エチルヘキシルオキ
シホスフインオキシド、ジヒドロキシモノ−n−
ドデシルオキシホスフインオキシド、ジヒドロキ
シブチルホスフインオキシド、ジヒドロキシ2−
エチルヘキシルホスフインオキシドなどがある。
含塩素マグネシウム化合物とリン化合物とを含
有する均一溶液は上記のリン化合物の中液状のリ
ン化合物を多量用いて調製することができ、また
リン化合物が固体又はワツクス状のときは有機溶
媒の存在下で調製することができる。有機溶媒と
しては炭化水素又はハロゲン化炭化水素が一種又
は二種以上用いられる。
これらの溶媒の具体例としてはn−ペンタン、
n−ヘキサン、n−ヘプタン、n−オクタン、イ
ソオクタン、n−デカン、石油エーテル、リグロ
イン、ケロシン、灯油、ベンゼン、トルエン、キ
シレン、シクロヘキサン、メチルシクロヘキサ
ン、メチレンクロリド、エチルクロリド、エチル
プロミド、1,2−ジクロルエタン、1,1−ジ
クロルエタン、n−ブチルクロリド、n−オクチ
ルクロリド、モノクロルシクロヘキサン、モノク
ロルベンゼン、o−ジクロルベンゼンなどが挙げ
られるがこれらの溶媒に限定されるものではな
い。
溶媒の存在下又は不存在下に含塩素マグネシウ
ム化合物1モルに対しリン化合物を1〜30モル、
好ましくは2〜10モル加えて−30゜〜120℃、好ま
しくは0〜60℃の温度で2分〜20時間、好ましく
は5分〜5時間撹拌することにより均一溶液を得
ることができる。更に、含塩素マグネシウム化合
物とリン化合物とを含有する溶液に四塩化チタン
をTi/Mg原子比が0.2〜2.0好ましくは0.1〜1.5の
範囲で添加することが望ましい。また、均一溶液
は多量の四塩化チタンに含塩素マグネシウム化合
物とリン化合物を添加することによつて調製する
こともできる。但しこの場合前記溶媒を共存させ
ると溶解が難しくなるので、これらの溶媒を共存
させないことが望ましい。
均一溶液の調製方法は別に限定されないが、例
えば次の如き方法があげられる:
(1) 炭化水素またはハロゲン化炭化水素溶媒の存
在下または不存在下に、含塩素マグネシウム化
合物1モルに1〜30モルのリン化合物を加えて
溶解した後、0.2〜2モルの四塩化チタンを添
加する方法、
(2) 含塩素マグネシウム化合物1モルと四塩化チ
タン0.2〜2モルを振動ミル、ボールミル等で
共粉砕した共粉砕物にリン化合物1〜30モルを
加えて溶解し、必要により前記溶媒で希釈する
方法、
(3) 含塩素マグネシウム化合物1モルと四塩化チ
タン0.2〜2モルとリン化合物1〜30モルと必
要により前記溶媒を加えて振動ミル、ボールミ
ル等で湿式粉砕し溶解する方法、
(4) 含塩素マグネシウム化合物1モルに四塩化チ
タン5〜1000モル加えて懸濁し、リン化合物2
〜10モル添加して多量の四塩化チタン中に溶解
する方法。
上記均一溶液と接触させるチタン化合物として
は一般式Ti(OR)oX4-o(ここで、RはC1〜12の炭化
水素、Xはハロゲン、n=0〜4である。)で表
わされるチタン化合物で、例えばTiCl4、TiBr4、
TiI4、Ti(OC2H5)Cl3、Ti(OC6H5)Cl3、Ti
(OC2H7)2Cl2、Ti(OC6H5)Cl2、Ti
(OC2H5)3Cl、Ti(OC2H5)4、Ti(OC6H11)4、
TiCl3、Ti(OC2H5)3、Ti(Oo−C4H9)3などを例
示することができる。
このうち三塩化チタン(TiCl3)又は四塩化チ
タン(TiCl4)が特に好ましい。
チタン化合物として三塩化チタンを使用する場
合三塩化チタンを含有する均一溶液とすることが
好ましく、このような溶液はジエチルエーテル、
ジ−n−プロピルエーテル、ジ−n−ブチルエー
テル、ビス(1−オクテニル)エーテル、アニソ
ール、ジフエニルエーテル等のエーテルあるいは
前述のP=O結合を有するリン化合物に三塩化チ
タンを溶解させることにより調製される。この
際、使用するエーテルあるいはリン化合物の量
は、チタン化合物とのモル比で表わしたときエー
テルまたはリン化合物/Ti=1.5〜20好ましくは
2.0〜10の範囲である。
また三塩化チタンは特開昭56−53112、同56−
53113、同56−59816、同56−59813、同56−
59814、同56−59815、同56−155021の公報に記載
した方法により調製した均一溶液を用いることが
できる。
触媒成分(A)の粉末を析出させる手段は例えば、
上記均一溶液に大過剰の四塩化チタンを滴下する
方法が挙げられる。析出時の温度は0〜200℃、
好ましくは20〜150℃である。
析出化剤としては、周期律表第族〜第族金
属の有機金属化合物又はチタン、パナジウム、ホ
ウ素、イオウ、スズ、ゲルマニウムなどのハロゲ
ン含有化合物である。たとえばTiCl4、TiCl3
(OC2H5)、TiCl3(O−n−C4H9)、Al(C5H5)
Cl2、Al2(C2H5)3Cl3などが挙げられる。
好ましくはチタンのハロゲン化物、有機アルミ
ニウミ化合物、特に好ましくはTiCl4である。
析出化剤の使用はチタン化合物および含塩素マ
グネシウム化合物を含む均一溶液中に含まれるエ
ーテルとリン化合物のモル数の和に対し1.0〜200
倍モル、好ましくは1.0〜100倍モルである。
この触媒成分(A)の粉末の析出化処理を行なう際
無機固体担体の存在下に行なうことができる。無
機固体担体としては表面積が50m2/g以上、好ま
しくは60m2/g以上、平均粒子径が200μ以下、
好ましくは150μ以下、平均細孔径が50Å以上、
好ましくは60Å以上の無機固体であり、シリカ、
アルミナ、セオライト、マグネシアなどが挙げら
れる。該無機固体担体の使用量は使用した含塩素
マグネシウム化合物1g当り0.5〜200g、好まし
くは1〜100gである。
上記のごとく調製した触媒成分(A)の粉末はペン
タン、ヘキサン、ヘプタン、ベンゼン、トルエン
などで十分洗浄した後、これらの溶媒の懸濁状態
で重合触媒として使用することが好ましい。
充分洗浄された触媒成分(A)の赤外線吸収スペク
トルをKBr錠剤法により測定すると、リン化合
物の特性吸収が認められた。
また、触媒成分(A)を含む前記溶媒の懸濁溶液を
水で分解した後、溶媒層のガスクロマトグラムを
測定し、リン化合物の存在量を定量することがで
きた。チタン含量は比色法により、マグネシウム
含量は原子吸光法により定量した。
触媒成分(A)のMg/Ti=0.5〜100(モル比)、好
ましくは0.5〜50(モル比)、リン化合物/Ti=
0.01〜2(モル比)、好ましくは0.05〜2(モル比)
の範囲である。
触媒成分(B)は有機アルミニウム化合物もしくは
有機アルミニウム化合物とアルコールとからなる
変成物が使用される。有機アルミニウム化合物は
一般式AlR1 nX3-n(R1は炭素数1〜20の炭化水素
基、Xはハロゲン、mは1,1.5,2または3)
で表わされる。例えば、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−ブチル
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、トリ−n−オク
チルアルミニウム、トリ−n−ドデシルアルミニ
ウム、ジエチルアルミニウムクロリド、ジエチル
アルミニウムブロミド、ジエチルアルミニウムア
イオダイド、ジ−n−ブチルアルミニウムクロリ
ド、ジイソブチルアルミニウムクロリド、ジ−n
−オクチルアルミニウムクロリド、エチルアルミ
ニウムセスキクロリド、イソブチルアルミニウム
セスキクロリド、エチルアルミニウムセスキクロ
リド、イソブチルアルミニウムセスキクロリド、
n−オクチルアルミニウムセスキクロリド、エチ
ルアルミニウムジクロリド、n−ブチルアルミニ
ウムジクロリド、イソブチルアルミニウムジクロ
リド、n−オクチルアルミニウムジクロリド、エ
チルアルミニウムジプロミド、ジエチルアルミニ
ウムモノエトキシド、ジエチルアルミニウムモノ
ブトキシドなどが挙げられるが、これらに限定さ
れるものではない。また2種以上の化合物を混合
して用いることもできる。
もしくは、触媒成分(B)として上記有機アルミニ
ウムを一般式R2OH(R2は炭素数1〜20の炭化水
素基)で表わされるアルコール性化合物で変性さ
せたものも用いられる。アルコール性化合物とし
ては例えば、メタノール、エタノール、n−ブタ
ノール、sec−ブタノール、t−ブタノール、フ
エノール、2−フエニルプロパノール、フエニル
エチルアルコール、2−メチルブタノール、ネオ
ペンチルアルコール、4−ヘプタノール、2−エ
チルヘキサノール、シクロヘキサノールなどが挙
げられる。
有機アルミニウム化合物とアルコール性化合物
との変成物は両者の混合割合(モル比)として
1:0.01〜1:2、好ましくは1:0.1〜1:1
であり、任意に各2種類以上のものを不活性溶媒
で希釈して用いることもできる。
重合用単量体のうち、オレフインとしては例え
ばエチレン、プロピレン、1−ブテン、1−ペン
テン、1−ヘキセン、4−メチル−1−ペンテ
ン、1−オクテンなどが挙げられる。
また共役ジエンとしては1,3−ブタジエン、
イソプレン、1,3−ペンタジエン、2,3−ジ
メチル−1,3−ブタジエンなどが挙げられる。
これらのオレフインと共役ジエンは各々任意の2
種類以上のものを任意の割合で混合して用いるこ
とができるが、好ましくはオレフインとしてはエ
チレンおよび又はプロピレン、共役ジエンとして
はブタジエンが好適に使用される。重合温度は通
常−20℃〜150℃、好ましくは0゜〜120℃である。
重合圧力は通常常圧から100Kg/cm2の範囲である。
共重合方法としては溶液重合、懸濁重合、塊状
重合のいづれでもとり得る。
重合溶媒としては炭化水素溶媒としてヘキサ
ン、ヘプタン、オクタン、灯油、ベンゼン、トル
エン、キシレン、シクロヘキサンなど、ハロゲン
化炭化水素溶媒としてメチレンクロライド、モノ
クロルエタン、1,1−ジクロルエタン、1,2
−ジクロルエタン、1,2−ジクロルプロパン、
モノクロルブタン、モノクロルベンゼンなどが挙
げられる。これらは単独あるいは2種以上を混合
して用いることができる。
共重合体の分子量は必要に応じて、水素を用い
ることにより任意に調節することができる。本発
明の方法によれば比較的高温で重合できること、
共重合体中のジエンユニツトが任意にコントロー
ルできるなどの利点がある。
次に実施例により本発明を更に具体的に説明す
る。
実施例中のエチレン、プロピレン、ブタジエ
ン、イソプレン等の共重合体中の単量体組成およ
びジエン部のミクロ構造は13C−NMRスペクト
ルにより求めた。
実施例 1
(1) 触媒成分A−1の調製:
十分に乾燥し、窒素置換した100mlのシユレ
ンクに回転子と無水の塩化マグネシウム1.0g
(10.5mmol)を入れる。さらに乾燥した2−
エチルヘキシル(ジ−2−エチルヘキシル)ホ
スフインオキシド13.2g(31.5mmol)を加え、
加熱すると無色透明の溶液を得る。これを40ml
のn−ヘキサンで希釈し、四塩化チタン19.9g
(105mmol)を滴下し、黄色の微粉末を生成し
た。これを一夜熟成後、上澄液を除去し、さら
にn−ヘキサン80mlで洗浄した。この操作を6
回繰り返した後、n−ヘキサンを加え50mlのス
ラリー溶液としこれを重合触媒とした。
(2) エチレンとブタジエンとの共重合:
回転子を入れたステンレス製オートクレーブ
を真空ラインに接続し10-3トールで30分間十分
に乾燥し、窒素で常圧に戻した。
その後窒素気流下でn−ヘキサン20mlを入
れ、前記(1)で調製した触媒成分(A)のn−ヘキサ
ンスラリーをチタン原子換算で0.032mmol添
加し、さらにトリイソブチルアルミニウム
0.128mmolを加えた。
この反応容器を液体窒素、温度下で冷却脱気
後ブタジエン6.9g(164mmol)とエチレン4.6
g(164mmol)とを導入後、50℃で1時間撹
拌放置した。反応終了後常圧に戻し老化防止剤
入りの多量のメタノールを加え十分に洗浄し、
減圧乾燥して白色粉末状の重合体を6.3g得た。
触媒活性は4.1Kg/g・Ti・hrであつた。
得られた重合体の13C−NMRスペクトルを
求めたところエチレン含量81モルパーセントで
あり、ブタジエン部のミクロ構造はトランス−
1.4構造68パーセント、シス−1.4構造16パーセ
ント、ビニル構造16%であつた。
実施例 2
トリイソブチルアルミニウムを1.28mmol用い
た以外は実施例1と同様にエチレンとブタジエン
を重合させたところ白色粉末重合体5.7gを得た。
触媒活性は3.7Kg/g・Ti・hrであつた。又エチ
レン含量は45モルパーセントであつた。
実施例 3
実施例1のトリイソブチルアルミニウムの代り
にジイソブチルアルミニウムクロリド・0.128m
molを用いた以外は実施例1と同様にエチレンと
ブタジエンとを共重合させたところ白色粉末重合
体3.8gを得た。触媒活性は2.5Kg/g・Ti・hrで
あつた。エチレン含量は72モル%であつた。
実施例 4
実施例2のエチレンの代りにプロピレン6.9g
(164mmol)を用いた以外は実施例2と同様にプ
ロピレンとブタジエンを重合させた。
この結果白色ゴム状の重合体3.5gを得た。触
媒活性は2.3Kg/g・Ti・hrであつた。この重合
体の13C−NMRスペクトルを求めたところプロ
ピレン含量43モルパーセントであり、ブタジエン
部のミクロ構造はトランス−1.4構造78パーセン
ト、シス−1.4構造8パーセント、ビニル構造14
パーセントであつた。
実施例 5
実施例1のエチレンの代りにプロピレン6.9g
(164mmol)、トリイソブチルアルミニウムの代
りにジイソブチルアルミニウムクロリド1.28m
molを用い、重合温度を90℃とした以外は実施例
1と同様にプロピレンとブタジエンを重合させ
た。
この結果白色ポリマー5.4gを得た。触媒活性
は3.5Kg/g・Ti・hrであつた。又プロピレン含
量は32モルパーセントであつた。
実施例 6
実施例1のトリイソブチルアルミニウムの代り
にジイソブチルアルミニウムクロリド1.28m
mol、重合温度90℃、モノマーとしてブタジエン
4.4g(82mmol)、エチレン2.3g(82mmol)、
プロピレン6.9g(164mmoI)を用いた以外は実
施例1と同様に重合し白色ゴム状重合体5.4gを
得た。触媒活性は3.5Kg/g・Ti・hrであつた。
共重合体中のエチレンとプロピレン、ブタジエ
ンの組成はそれぞれ43モルパーセント、34モルパ
ーセント、23モルパーセントであつた。共重合体
中のブタジエン部のミクロ構造はトランス−1.4
構造35パーセント、シス−1.4構造52パーセント、
ビニル構造13パーセントであつた。
GPC分析によると数平均分子量42000、重量平
均分子量354000であつた。
実施例 7
実施例6の重合温度を50゜、重合時間を15分、
トルエン量を40mlにした以外は実施例6と同様に
エチレン、プロピレン、ブタジエンを重合し、白
色ゴム状重合体5.9gを得た。触媒活性は15.4
Kg/g・Ti・hrであつた。
共重合体中のエチレン、プロピレン、ブタジエ
ンの組成は37モルパーセント、41モルパーセン
ト、22モルパーセントであり、ブタジエン部のミ
クロ構造にトランス−1.4構造32パーセント、シ
ス−1.4構造59パーセント、ビニル構造9パーセ
ントであつた。
GPC分析によると数平均分子量25000重量平均
分子量213000であつた。
実施例 8
触媒成分(A)は実施例1と同様に調製された。触
媒成分(B)は次の示す方法によつて調製した。
十分に乾燥したシユレンクを窒素置換した後ジ
イソブチルアルミニウムクロリド1.2mmolを入
れ、t−ブタノール0.24mmolを滴下し触媒成分
(B)とした。
触媒成分(A)をチタン換算量で0.03mmol分取
し、上記方法で調製した触媒成分(B)を全量滴下し
た。さらにこれら触媒成分(A)と触媒成分(B)とを全
量ステンレス製オートクレーブに入れ液体窒素温
度下で冷却脱気し、エチレン4.6g(164mmol)
とブタジエン8,8g(164mmol)を導入し、
50℃で15分間撹拌放置し、白色重合体5.0g得た。
触媒活性は13.9Kg/g・Ti・hrであつた。共重合
体中のエチレンとブタジエンの組成は82モルパー
セント及び18モルパーセントであつた。
実施例 9
実施例8の条件でモノマーとしてエチレン2.3
g(84mmol)、プロピレン6.9g(164mmol)、
ブタジエン4.4g(84mmol)を用いた以外は実
施例8と同様にエチレン、プロピレン、ブタジエ
ンを重合させた。
この結果白色ゴム状重合体5.4gを得た。触媒
活性は15.0Kg/g・Ti・hrであつた。共重合体中
のエチレン/プロピレン/ブタジエンのモル比は
28/33/39であつた。DSC分析によるとTgは−
58℃でTmは約40゜〜約100℃の幅広いピークを示
した。
実施例 10
実施例8のt−ブタノールの量を0.36mmolと
した以外は同様にエチレン、プロピレン、ブタジ
エンを重合させた。
この結果白色ゴム状共重合体4.1gを得た。触
媒活性は11.4Kg/g・Ti・hrであつた。又共重合
体のエチレン/プロピレン/ブタジエンのモル比
は27/39/34であつた。DSC分析によるとTgは
−58℃でTmは約40〜100℃の幅広いピークを示
めた。
実施例 11
実施例8のブタジエンの代りにイソプレンを用
いた以外は同様にエチレン、プロピレン、イソプ
レンを重合させた。
この結果白色ゴム状重合体2.2gを得た。触媒
活性は6.1Kg/g・Ti・hrとなる。
実施例 12
(1) 触媒成分A−2の調製
窒素気流下に300mlのフラスコに100gの塩化
マグネシウム・6水塩を入れ、300℃に加熱し
た。一度均一な溶液になり、さらに加熱すると
白色の固体が生成した。窒素気流下で粉砕した
後、減圧下に300℃で10時間加熱して、Mg
(OH)Clの粉末を得た。
充分乾燥し、窒素置換した100mlのフラスコ
に、回転子とMg(OH)Cl1g(13mmol)を入
れた。モレキユラーシーブスで乾燥した2−エ
チルヘキシル(ジ−2−エチルヘキシルオキ
シ)ホスフインオキシド36mmolを加え、130
℃に加熱した。この状態ではMg(OH)Clは溶
解しないが、このフラスコに四塩化チタン13m
molを添加すると、褐色の均一溶液が得られ
た。この均一溶液をさらに130℃で2時間加熱
を続けた。
充分乾燥し、窒素置換した別の100mlのフラ
スコに回転子を入れ乾燥したn−ヘキサン60ml
と四塩化チタン13mmolを入れ、湯浴にて60℃
に保つた。この溶液をはげしく撹拌しながら前
記のマグネシウム、チタン、リンを含む均一溶
液をゆつくりと滴下した。直ちに黄色の微粉末
固体複合体が生成した。60℃で2時間撹拌を続
けた。撹拌を止めて黄色微粉末固体を析出さ
せ、上澄液を別した。新たに、乾燥したn−
ヘキサン60mlを加え30分間撹拌し洗浄した。こ
の洗浄操作を6回繰り返した。黄白色の微粉末
固体を得た。n−ヘキサンを加えて全量を50ml
にした。この微粉末固体複合体スラリー中のチ
タン濃度は0.024mol/であり、Mg/Ti=
10.5(モル比)であつた。
(2) エチレン、プロピレンとブタジエンの共重
合:
上記触媒成分A−2をチタン換算量で0.03m
mol分取し、実施例9と同様の方法でエチレ
ン、プロピレンとブタジエンを共重合し、ゴム
状ポリマー2.8gを得た。触媒活性は7.8Kg/
g・Ti・hrであつた。
実施例 13〜15
(1) 触媒成分A−3、A−4、A−5の調製:
充分乾燥し、窒素置換した100mlのフラスコ
に回転子と無水の塩化マグネシウム1g(10.5
mmol)を入れる。モレキユラーシーブスで乾
燥した表1記載の溶媒の所定量と表1記載のリ
ン化合物の21mmolを加え、室温で20分間撹拌
すると塩化マグネシウムは完全に溶解し、無色
透明な均一溶液を得た。
この均一溶液に四塩化チタン1.16ml(10.5m
mol)を加え30分間静置した。黄色の透明均一
溶液となつた。この溶液を撹拌しながら四塩化
チタン12mlを徐々に加えると黄色の微粉末が生
成した。2時間撹拌を続けたのち、黄色の微粉
末固体複合体を析出させ、上澄を別した。新
たに乾燥したn−ヘキサン80mlを加え30分間撹
拌し洗浄した。この洗浄操作を6回繰り返し
た。黄白色の微粉末固体複合体を得た。n−ヘ
キサンを加えて全量を50mlのスラリーにした。
The present invention relates to a method for copolymerizing an olefin and a conjugated diene in good yield using a highly active Ziegler catalyst. As a catalyst for ethylene/butadiene copolymerization, for example, a Ti(OBu) 4 /AlEt 3 catalyst was disclosed in Japanese Patent Publication No. 47-15696, and a TiCl 4 /Al(i-
Bu) 3 /carbonyl compound-based catalysts have been proposed, but in these catalyst systems the catalytic activity is limited to 1 Ti atom.
The amount of polymer per gram is very low, less than 100g.
Furthermore, Japanese Patent Publication No. 49-16784 describes a method for copolymerizing ethylene and butadiene using a fixed catalyst component obtained by heat-treating MgCl 2 with titanium tetrachloride in the presence of an electron donor and a catalyst consisting of trialkylaluminium. is disclosed. This catalytic activity is
Although it is high at 30 kg/g-Ti.hr, the diene portion in the copolymer is very low at 2.3 mol% or less. As mentioned above, there are many research examples of methods for producing olefin/conjugated diene copolymers; however, (1) the polymerization temperature is relatively high (from -20 to
(150℃), (2) high catalytic activity, (3) ability to control the proportion of conjugated diene units in the copolymer, and (4) ability to prepare the catalyst at around room temperature. A method for producing an olefin/conjugated diene copolymer that is simultaneously satisfactory has not yet been found. The present inventors have conducted extensive research into methods for producing a copolymer that satisfies the above conditions, and as a result, have discovered the following production method and have arrived at the present invention. The process for preparing the polymerization catalyst used to carry out the method for producing the copolymer of the present invention can be carried out according to the flowchart shown in the attached FIG. 1. However, the flowchart in the figure is not intended to limit the scope of the present invention. According to the present invention, a titanium compound is obtained by contacting a homogeneous solution containing (A) a chlorine-containing magnesium compound and a phosphorus compound having a P=O bond prepared in the presence or absence of an organic solvent. Powder and (B) organoaluminum compound or general formula
It is characterized by copolymerizing an olefin and a conjugated diene using a catalyst made of an organoaluminum compound modified with an alcoholic compound represented by R 2 OH (R 2 is a hydrocarbon group having 1 to 20 carbon atoms). A method for producing an olefin-conjugated diene copolymer is provided. The present invention will be explained in detail below. First, to explain the catalyst component (A) used in the present invention, the chlorine-containing magnesium compound is specifically
MgCl 2 or Mg(OH)Cl, MgCl 2 is preferably anhydrous, and those subjected to modification treatments such as ball milling, vibration milling, and complexing treatment can also be used. is MgCl 2 6H 2 O
obtained by heating at high temperature. Phosphorus compounds having a P=O bond have the general formula O=PR 1 m(OR 2 )n and/or O=P(OH) j
(OR 3 k ) A compound represented by R 4 l is used (where R 1 , R 2 , R 3 , and R 4 are hydrocarbon groups having 1 to 20 carbon atoms, and m and n are integers of 0 to 3. m+n=3, j is 1 or 2, k, l are integers from 0 to 2, and j+k+l=
3). Specifically, the following can be mentioned. Trimethyl phosphate, triethyl phosphate, tri-n-propyl phosphate, tri-
Iso-propyl phosphate, tri-n-butyl phosphate, tri-i-butyl phosphate,
Tri-t-butyl phosphate, tri-n-hexyl phosphate, tri-n-octyl phosphate, tri-2-ethyl-hexyl phosphate, trilauryl phosphate, tricetyl phosphate, tristearyl phosphate, trio Leyl phosphate, triphenyl phosphate, tritolyl phosphate, trixyl phosphate, octyl diphenyl phosphate, tolyl diphenyl phosphate, xylyl diphenyl phosphate, ethyl (diethoxy) phosphine oxide, n-propyl (di -n-propyloxy)phosphine oxide, n-butyl(di-n
-butoxy)phosphine oxide, n-octyl (di-n-octyloxy)phosphine oxide,
2-Ethylhexyl(di-2-ethylhexyloxy)phosphine oxide, diethyl(ethoxy)phosphine oxide, di-n-butyl(n-
butoxy)phosphine oxide, diisobutyl(isobutoxy)phosphine oxide, di-n-
Octyl(n-octyloxy)phosphine oxide, di-2-ethylhexyl(2-ethylhexyloxy)phosphine oxide, triethylphosphine oxide, tri-n-propylphosphine oxide, tri-isopropylphosphine oxide, tri-n- Butylphosphine oxide, triisobutylphosphine oxide, tri-n-octylphosphine oxide, tri-2-ethylhexylphosphine oxide, tricyclohexylphosphine oxide, triphenylphosphine oxide, tritolylphosphine oxide, trixylphosphine oxide monooxide, monohydroxydiethoxyphosphine oxide, monohydroxydipropoxyphosphine oxide, monohydroxydipropoxyphosphine oxide,
n-butoxyphosphine oxide, monohydroxydi-sec-butoxyphosphine oxide, monohydroxydi-t-butoxyphosphine oxide, monohydroxydi-n-hexyloxyphosphine oxide, monohydroxydi-n-octyloxyphosphine oxide monooxide, monohydroxydi-2-ethylhexyloxyphosphine oxide, monohydroxydi-n-decyloxyphosphine oxide, monohydroxydi-n-dodecylphosphine oxide, monohydroxy(n-butyl)n-butoxyphosphine oxide, monohydroxy (n-hexyl) n-hexyloxyphosphine oxide, monohydroxy (n-octyl) n-octyloxyphosphine oxide, monohydroxy (2-ethylhexyl) 2-ethylhexylphosphine oxide, monohydroxybutylphosphine oxide inoxide, monohydroxydi-2
-Ethylhexylphosphine oxide, dihydroxymonobutoxyphosphine oxide, dihydroxymono-n-octyloxyphosphine oxide, dihydroxymono-2-ethylhexyloxyphosphine oxide, dihydroxymono-n-
Dodecyloxyphosphine oxide, dihydroxybutylphosphine oxide, dihydroxy 2-
Examples include ethylhexylphosphine oxide. A homogeneous solution containing a chlorine-containing magnesium compound and a phosphorus compound can be prepared using a large amount of the above-mentioned liquid phosphorus compound, or when the phosphorus compound is solid or waxy, it can be prepared in the presence of an organic solvent. It can be prepared with As the organic solvent, one or more hydrocarbons or halogenated hydrocarbons are used. Specific examples of these solvents include n-pentane,
n-hexane, n-heptane, n-octane, isooctane, n-decane, petroleum ether, ligroin, kerosene, kerosene, benzene, toluene, xylene, cyclohexane, methylcyclohexane, methylene chloride, ethyl chloride, ethyl bromide, 1,2- Examples include dichloroethane, 1,1-dichloroethane, n-butyl chloride, n-octyl chloride, monochlorocyclohexane, monochlorobenzene, o-dichlorobenzene, etc., but are not limited to these solvents. 1 to 30 moles of phosphorus compound per mole of chlorine-containing magnesium compound in the presence or absence of a solvent,
A homogeneous solution can be obtained by adding preferably 2 to 10 mol and stirring at a temperature of -30° to 120°C, preferably 0 to 60°C, for 2 minutes to 20 hours, preferably 5 minutes to 5 hours. Furthermore, it is desirable to add titanium tetrachloride to the solution containing the chlorine-containing magnesium compound and the phosphorus compound at a Ti/Mg atomic ratio in the range of 0.2 to 2.0, preferably 0.1 to 1.5. A homogeneous solution can also be prepared by adding a chlorine-containing magnesium compound and a phosphorus compound to a large amount of titanium tetrachloride. However, in this case, if the above-mentioned solvents are allowed to coexist, dissolution becomes difficult, so it is desirable not to coexist these solvents. The method for preparing a homogeneous solution is not particularly limited, but examples include the following methods: (1) In the presence or absence of a hydrocarbon or halogenated hydrocarbon solvent, 1 to 30% of the chlorine-containing magnesium compound is added to 1 mole of the compound. A method in which 0.2 to 2 moles of titanium tetrachloride is added after adding and dissolving 1 mole of a phosphorus compound, (2) Co-pulverization of 1 mole of a chlorine-containing magnesium compound and 0.2 to 2 moles of titanium tetrachloride using a vibration mill, ball mill, etc. A method of adding 1 to 30 moles of a phosphorus compound to the co-pulverized product, dissolving it, and diluting it with the above solvent if necessary, (3) 1 mole of a chlorine-containing magnesium compound, 0.2 to 2 moles of titanium tetrachloride, and 1 to 30 moles of a phosphorus compound. (4) 5 to 1,000 moles of titanium tetrachloride are added to 1 mole of the chlorine-containing magnesium compound and suspended, and the phosphorus compound 2 is dissolved.
A method of adding ~10 mol and dissolving it in a large amount of titanium tetrachloride. The titanium compound to be brought into contact with the homogeneous solution is represented by the general formula Ti (OR)oX4 -o (where R is a C1-12 hydrocarbon, titanium compounds such as TiCl 4 , TiBr 4 ,
TiI4 , Ti ( OC2H5 ) Cl3 , Ti( OC6H5 ) Cl3 , Ti
(OC 2 H 7 ) 2 Cl 2 , Ti (OC 6 H 5 )Cl 2 , Ti
( OC2H5 ) 3Cl , Ti ( OC2H5 ) 4 , Ti ( OC6H11 ) 4 ,
Examples include TiCl3 , Ti( OC2H5 ) 3 , Ti( Oo - C4H9 ) 3 , and the like. Among these, titanium trichloride (TiCl 3 ) or titanium tetrachloride (TiCl 4 ) is particularly preferred. When titanium trichloride is used as the titanium compound, it is preferable to prepare a homogeneous solution containing titanium trichloride, and such a solution may be prepared using diethyl ether,
Prepared by dissolving titanium trichloride in an ether such as di-n-propyl ether, di-n-butyl ether, bis(1-octenyl) ether, anisole, diphenyl ether, or the above-mentioned phosphorus compound having a P=O bond. be done. At this time, the amount of ether or phosphorus compound used is preferably ether or phosphorus compound/Ti=1.5 to 20 when expressed in molar ratio with the titanium compound.
It ranges from 2.0 to 10. In addition, titanium trichloride is disclosed in JP-A-56-53112 and JP-A-56-53112.
53113, 56-59816, 56-59813, 56-
Homogeneous solutions prepared by the methods described in Publications No. 59814, No. 56-59815, and No. 56-155021 can be used. The means for precipitating the powder of the catalyst component (A) is, for example,
A method may be mentioned in which a large excess of titanium tetrachloride is dropped into the above homogeneous solution. The temperature during precipitation is 0 to 200℃,
Preferably it is 20-150°C. The precipitating agent is an organometallic compound of a group metal to group metal of the periodic table, or a halogen-containing compound such as titanium, panadium, boron, sulfur, tin, or germanium. For example TiCl 4 , TiCl 3
(OC 2 H 5 ), TiCl 3 (O-n-C 4 H 9 ), Al (C 5 H 5 )
Examples include Cl 2 , Al 2 (C 2 H 5 ) 3 Cl 3 . Preferred are titanium halides, organic aluminum compounds, and particularly preferred are TiCl 4 . The amount of precipitating agent used is 1.0 to 200 per the sum of the moles of ether and phosphorus compound contained in a homogeneous solution containing a titanium compound and a chlorine-containing magnesium compound.
It is twice the molar amount, preferably 1.0 to 100 times the molar amount. This precipitation treatment of the catalyst component (A) powder can be carried out in the presence of an inorganic solid carrier. The inorganic solid carrier has a surface area of 50 m 2 /g or more, preferably 60 m 2 /g or more, and an average particle size of 200 μ or less,
Preferably 150 μ or less, average pore diameter 50 Å or more,
Preferably an inorganic solid with a diameter of 60 Å or more, such as silica,
Examples include alumina, theolite, and magnesia. The amount of the inorganic solid carrier used is 0.5 to 200 g, preferably 1 to 100 g, per 1 g of the chlorine-containing magnesium compound used. The powder of catalyst component (A) prepared as described above is preferably washed sufficiently with pentane, hexane, heptane, benzene, toluene, etc., and then used as a polymerization catalyst in a suspended state in these solvents. When the infrared absorption spectrum of the thoroughly washed catalyst component (A) was measured by the KBr tablet method, characteristic absorption of phosphorus compounds was observed. Further, after decomposing the suspension solution of the solvent containing the catalyst component (A) with water, the gas chromatogram of the solvent layer was measured, and the amount of the phosphorus compound present could be determined. The titanium content was determined by a colorimetric method, and the magnesium content was determined by an atomic absorption method. Mg/Ti of catalyst component (A) = 0.5 to 100 (molar ratio), preferably 0.5 to 50 (molar ratio), phosphorus compound/Ti =
0.01-2 (molar ratio), preferably 0.05-2 (molar ratio)
is within the range of As the catalyst component (B), an organoaluminum compound or a modified product consisting of an organoaluminum compound and an alcohol is used. The organoaluminum compound has the general formula AlR 1 n
It is expressed as For example, trimethylaluminum, triethylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminium, tri-n-dodecylaluminum, diethylaluminium chloride, diethylaluminum bromide, diethylaluminium iodide, di-n-butylaluminum chloride, diisobutylaluminum chloride, di-n
-octylaluminum chloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride, ethylaluminum sesquichloride, isobutylaluminum sesquichloride,
Examples include n-octylaluminum sesquichloride, ethylaluminum dichloride, n-butylaluminum dichloride, isobutylaluminum dichloride, n-octylaluminum dichloride, ethylaluminum dipromide, diethylaluminum monoethoxide, diethylaluminum monobutoxide, etc. It is not limited. Moreover, two or more kinds of compounds can also be used as a mixture. Alternatively, as the catalyst component (B), the organic aluminum modified with an alcoholic compound represented by the general formula R 2 OH (R 2 is a hydrocarbon group having 1 to 20 carbon atoms) may also be used. Examples of alcoholic compounds include methanol, ethanol, n-butanol, sec-butanol, t-butanol, phenol, 2-phenylpropanol, phenylethyl alcohol, 2-methylbutanol, neopentyl alcohol, 4-heptanol, -Ethylhexanol, cyclohexanol, etc. The mixed ratio (mole ratio) of the modified product of an organoaluminum compound and an alcoholic compound is 1:0.01 to 1:2, preferably 1:0.1 to 1:1.
Two or more of each type can be optionally diluted with an inert solvent and used. Among the monomers for polymerization, examples of the olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 1-octene. In addition, the conjugated diene is 1,3-butadiene,
Examples include isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, and the like.
These olefins and conjugated dienes can each be any 2
More than one type of olefin can be mixed and used in any ratio, but ethylene and/or propylene is preferably used as the olefin, and butadiene is preferably used as the conjugated diene. The polymerization temperature is usually -20°C to 150°C, preferably 0° to 120°C.
Polymerization pressure usually ranges from normal pressure to 100 kg/cm 2 . The copolymerization method may be solution polymerization, suspension polymerization, or bulk polymerization. Hydrocarbon solvents such as hexane, heptane, octane, kerosene, benzene, toluene, xylene, and cyclohexane are used as polymerization solvents, and methylene chloride, monochloroethane, 1,1-dichloroethane, 1,2 as halogenated hydrocarbon solvents.
-dichloroethane, 1,2-dichloropropane,
Examples include monochlorobutane and monochlorobenzene. These can be used alone or in combination of two or more. The molecular weight of the copolymer can be arbitrarily adjusted by using hydrogen, if necessary. According to the method of the present invention, polymerization can be performed at relatively high temperatures;
It has the advantage that the diene units in the copolymer can be controlled arbitrarily. Next, the present invention will be explained in more detail with reference to Examples. The monomer composition and the microstructure of the diene moiety in the copolymers of ethylene, propylene, butadiene, isoprene, etc. in the Examples were determined by 13 C-NMR spectroscopy. Example 1 (1) Preparation of catalyst component A-1: A rotor and 1.0 g of anhydrous magnesium chloride were placed in a 100 ml Schlenk that had been thoroughly dried and purged with nitrogen.
(10.5 mmol). Further dried 2-
Add 13.2 g (31.5 mmol) of ethylhexyl (di-2-ethylhexyl) phosphine oxide,
Upon heating, a clear and colorless solution is obtained. 40ml of this
19.9 g of titanium tetrachloride diluted with n-hexane
(105 mmol) was added dropwise to produce a yellow fine powder. After aging this overnight, the supernatant liquid was removed and further washed with 80 ml of n-hexane. Do this operation 6
After repeating this process several times, n-hexane was added to prepare 50 ml of slurry solution, which was used as a polymerization catalyst. (2) Copolymerization of ethylene and butadiene: A stainless steel autoclave containing a rotor was connected to a vacuum line, thoroughly dried at 10 -3 Torr for 30 minutes, and returned to normal pressure with nitrogen. Thereafter, 20 ml of n-hexane was added under a nitrogen stream, and 0.032 mmol of the n-hexane slurry of the catalyst component (A) prepared in (1) above was added in terms of titanium atoms.
0.128 mmol was added. This reaction vessel was cooled and degassed under liquid nitrogen temperature, and then 6.9 g (164 mmol) of butadiene and 4.6 g of ethylene were added.
g (164 mmol) was introduced, and the mixture was left stirring at 50° C. for 1 hour. After the reaction, return to normal pressure, add a large amount of methanol containing anti-aging agent, and wash thoroughly.
After drying under reduced pressure, 6.3 g of a white powdery polymer was obtained.
The catalyst activity was 4.1 Kg/g·Ti·hr. The 13 C-NMR spectrum of the obtained polymer revealed that the ethylene content was 81 mol percent, and the microstructure of the butadiene moiety was trans-
The composition was 68% 1.4 structure, 16% cis-1.4 structure, and 16% vinyl structure. Example 2 Ethylene and butadiene were polymerized in the same manner as in Example 1 except that 1.28 mmol of triisobutylaluminum was used, and 5.7 g of a white powder polymer was obtained.
The catalyst activity was 3.7 Kg/g・Ti・hr. Also, the ethylene content was 45 mole percent. Example 3 Diisobutylaluminum chloride 0.128m instead of triisobutylaluminum in Example 1
Ethylene and butadiene were copolymerized in the same manner as in Example 1 except that mol was used, and 3.8 g of a white powder polymer was obtained. The catalyst activity was 2.5Kg/g・Ti・hr. The ethylene content was 72 mol%. Example 4 Propylene 6.9g instead of ethylene in Example 2
Propylene and butadiene were polymerized in the same manner as in Example 2 except that (164 mmol) was used. As a result, 3.5 g of a white rubbery polymer was obtained. The catalyst activity was 2.3 Kg/g·Ti·hr. The 13 C-NMR spectrum of this polymer revealed that the propylene content was 43 mol percent, and the microstructure of the butadiene moiety was 78 percent trans-1.4 structure, 8 percent cis-1.4 structure, and 14 vinyl structure.
It was a percentage. Example 5 6.9g of propylene instead of ethylene in Example 1
(164 mmol), 1.28 m of diisobutyl aluminum chloride instead of triisobutyl aluminum
Propylene and butadiene were polymerized in the same manner as in Example 1, except that mol was used and the polymerization temperature was 90°C. As a result, 5.4 g of white polymer was obtained. The catalyst activity was 3.5Kg/g・Ti・hr. Also, the propylene content was 32 mole percent. Example 6 1.28m of diisobutylaluminum chloride instead of triisobutylaluminum in Example 1
mol, polymerization temperature 90℃, butadiene as monomer
4.4g (82mmol), ethylene 2.3g (82mmol),
Polymerization was carried out in the same manner as in Example 1 except that 6.9 g (164 mmol) of propylene was used to obtain 5.4 g of a white rubbery polymer. The catalyst activity was 3.5Kg/g・Ti・hr. The compositions of ethylene, propylene, and butadiene in the copolymer were 43 mole percent, 34 mole percent, and 23 mole percent, respectively. The microstructure of the butadiene moiety in the copolymer is trans-1.4
35% structure, 52% cis-1.4 structure,
The vinyl structure was 13%. According to GPC analysis, the number average molecular weight was 42,000 and the weight average molecular weight was 354,000. Example 7 The polymerization temperature of Example 6 was 50°, the polymerization time was 15 minutes,
Ethylene, propylene, and butadiene were polymerized in the same manner as in Example 6, except that the amount of toluene was changed to 40 ml, and 5.9 g of a white rubbery polymer was obtained. Catalytic activity is 15.4
It was Kg/g・Ti・hr. The compositions of ethylene, propylene, and butadiene in the copolymer are 37 mol percent, 41 mol percent, and 22 mol percent, and the microstructure of the butadiene part includes 32 percent trans-1.4 structure, 59 percent cis-1.4 structure, and 9 vinyl structure. It was a percentage. According to GPC analysis, the number average molecular weight was 25,000 and the weight average molecular weight was 213,000. Example 8 Catalyst component (A) was prepared in the same manner as in Example 1. Catalyst component (B) was prepared by the method shown below. After thoroughly drying Schülenk, the atmosphere was replaced with nitrogen, 1.2 mmol of diisobutylaluminum chloride was added, and 0.24 mmol of t-butanol was added dropwise to remove the catalyst component.
(B). 0.03 mmol of catalyst component (A) was collected in terms of titanium, and the entire amount of catalyst component (B) prepared by the above method was added dropwise. Furthermore, these catalyst components (A) and catalyst components (B) were placed in a stainless steel autoclave and cooled and degassed under liquid nitrogen temperature, yielding 4.6 g (164 mmol) of ethylene.
and 8.8 g (164 mmol) of butadiene were introduced,
The mixture was left stirring at 50°C for 15 minutes to obtain 5.0 g of a white polymer.
The catalyst activity was 13.9 Kg/g·Ti·hr. The composition of ethylene and butadiene in the copolymer was 82 mole percent and 18 mole percent. Example 9 Ethylene 2.3 as a monomer under the conditions of Example 8
g (84 mmol), propylene 6.9 g (164 mmol),
Ethylene, propylene, and butadiene were polymerized in the same manner as in Example 8 except that 4.4 g (84 mmol) of butadiene was used. As a result, 5.4 g of a white rubbery polymer was obtained. The catalyst activity was 15.0 Kg/g・Ti・hr. The molar ratio of ethylene/propylene/butadiene in the copolymer is
It was 28/33/39. According to DSC analysis, Tg is −
At 58°C, Tm showed a broad peak ranging from about 40° to about 100°C. Example 10 Ethylene, propylene, and butadiene were polymerized in the same manner as in Example 8 except that the amount of t-butanol was changed to 0.36 mmol. As a result, 4.1 g of a white rubbery copolymer was obtained. The catalyst activity was 11.4 Kg/g・Ti・hr. The molar ratio of ethylene/propylene/butadiene in the copolymer was 27/39/34. DSC analysis showed a broad peak with a Tg of -58°C and a Tm of about 40-100°C. Example 11 Ethylene, propylene, and isoprene were polymerized in the same manner as in Example 8 except that isoprene was used instead of butadiene. As a result, 2.2 g of a white rubbery polymer was obtained. The catalytic activity is 6.1Kg/g・Ti・hr. Example 12 (1) Preparation of catalyst component A-2 100 g of magnesium chloride hexahydrate was placed in a 300 ml flask under a nitrogen stream and heated to 300°C. Once a homogeneous solution was obtained, a white solid formed upon further heating. After grinding under a nitrogen stream, it was heated at 300°C for 10 hours under reduced pressure to produce Mg.
(OH)Cl powder was obtained. A rotor and 1 g (13 mmol) of Mg(OH)Cl were placed in a thoroughly dried 100 ml flask that had been purged with nitrogen. Add 36 mmol of 2-ethylhexyl (di-2-ethylhexyloxy)phosphine oxide dried with molecular sieves,
heated to ℃. Although Mg(OH)Cl does not dissolve in this state, 13 m of titanium tetrachloride is added to this flask.
Upon addition of mol, a brown homogeneous solution was obtained. This homogeneous solution was further heated at 130°C for 2 hours. Add 60 ml of n-hexane to another 100 ml flask that has been thoroughly dried and purged with nitrogen.
Add 13 mmol of titanium tetrachloride and heat at 60℃ in a hot water bath.
I kept it. While vigorously stirring this solution, the above homogeneous solution containing magnesium, titanium, and phosphorus was slowly added dropwise. A yellow finely powdered solid complex was immediately formed. Stirring was continued for 2 hours at 60°C. Stirring was stopped to precipitate a yellow fine powder solid, and the supernatant liquid was separated. Freshly dried n-
60 ml of hexane was added and stirred for 30 minutes for washing. This washing operation was repeated six times. A yellowish white finely powdered solid was obtained. Add n-hexane and bring the total volume to 50ml
I made it. The titanium concentration in this fine powder solid composite slurry is 0.024 mol/Mg/Ti=
The molar ratio was 10.5. (2) Copolymerization of ethylene, propylene and butadiene: 0.03 m of the above catalyst component A-2 in terms of titanium.
Mol fractions were collected, and ethylene, propylene, and butadiene were copolymerized in the same manner as in Example 9 to obtain 2.8 g of a rubbery polymer. Catalytic activity is 7.8Kg/
It was g・ti・hr. Examples 13 to 15 (1) Preparation of catalyst components A-3, A-4, and A-5: A rotor and 1 g (10.5
mmol). A predetermined amount of the solvent shown in Table 1 dried with molecular sieves and 21 mmol of the phosphorus compound shown in Table 1 were added, and the mixture was stirred at room temperature for 20 minutes. Magnesium chloride was completely dissolved to obtain a colorless and transparent homogeneous solution. Add 1.16ml (10.5ml) of titanium tetrachloride to this homogeneous solution.
mol) was added and left to stand for 30 minutes. It became a yellow transparent homogeneous solution. 12 ml of titanium tetrachloride was gradually added to this solution while stirring, producing a yellow fine powder. After continued stirring for 2 hours, a yellow fine powder solid complex was precipitated and the supernatant was separated. 80 ml of freshly dried n-hexane was added and stirred for 30 minutes for washing. This washing operation was repeated six times. A yellow-white finely powdered solid composite was obtained. N-hexane was added to make a 50 ml slurry.
【表】
(2) 上記の方法で調製した触媒成分A−3ないし
A−5を用いた以外は実施例9と同様の方法で
エチレン、プロピレン、ブタジエンを共重合
し、得られた重合体収量をそれぞれ表1に示し
た。
実施例 16
(1) 触媒成分A−6の調製:
充分に乾燥し、窒素置換した300mlのフラス
コに、乾燥したパラジウムカーボン粉末(パラ
ジウム含量5%)1gと乾燥した1,2−ジク
ロルエタン200mlと四塩化チタン11ml(100m
mol)を仕込み、ついで撹拌下にn−ブチルエ
ーテル34ml(200mmol)を添加した〔エーテ
ル/Ti=2.0(モル比)〕。フラスコを20℃に保
ち、水素を0.2/mmの速度で8時間吹き込ん
だ。黄黒色の溶液が生成した。この溶液を窒素
下で過し、粉末状のパラジウムカーボンを
別した。液は均一な黄黒色の溶液であつた。
この均一溶液を酸化還元滴定法により分析した
ところ、四塩化チタンの還元率は、ほぼ100%
であつた。1,2−ジクロルエタンを加えて稀
釈した。生成した三塩化チタンの濃度
0.4mol/に調整した。
また充分乾燥し、窒素置換した1000mlのフラ
スコに無水の粉末状塩化マグネシウム25g
(0.262mol)を入れ、ジ(2−エチル−ヘキシ
ルオキシ)(2−エチルヘキシル)ホスフイン
オキシド360ml(0.787mol)を加えて撹拌下に
溶解した。n−ヘキサンを加えて全量を524ml
(MgCl2で0.50mol/)とした。
300mlのフラスコに上記の塩化マグネシウム
を含む均一溶液20ml(MgCl2で10mmol)を入
れた。次に前記の三塩化チタン溶液25ml(10m
mol)を加えた。さらにn−ヘキサン145mlを
加えた。緑色の均一溶液が得られた。
このように生成した均一溶液に析出化剤とし
て四塩化チタン10mlを撹拌下にゆつくり滴下す
ると、濃緑色の微粉末固体が生成した。1時間
撹拌した後微粉末固体を析出させた。上澄は黒
色均一溶液であつた。上澄を別し、新たなn
−ヘキサン200mlを加えて微粉末固体を洗浄し
た。この操作を6回繰り返えした。n−ヘキサ
ンを加えて、全量を200mlとし微黄緑色の微粉
末固体のn−ヘキサン懸濁液を得た。Ti濃度
を比色分析により求めたところ0.011mol/
であつた。Mg/Ti(モル比)=4.5であつた。
(2) エチレンとプロピレン、ブタジエンとの共重
合:
上記触媒成分A−6をチタン換算量で0.03m
mol分取し触媒として用いた以外は実施例9と
同様にエチレンとプロピレン、ブタジエンとの
共重合を行ない、ゴム状重合体6.2gを得た。
触媒活性は17.3Kg/g・Ti・hrであつた。[Table] (2) Polymer yield obtained by copolymerizing ethylene, propylene, and butadiene in the same manner as in Example 9 except that catalyst components A-3 to A-5 prepared by the above method were used. are shown in Table 1. Example 16 (1) Preparation of catalyst component A-6: In a thoroughly dried 300 ml flask that was purged with nitrogen, 1 g of dried palladium carbon powder (palladium content 5%), 200 ml of dried 1,2-dichloroethane, and Titanium chloride 11ml (100m
mol), and then 34 ml (200 mmol) of n-butyl ether was added while stirring [ether/Ti=2.0 (mole ratio)]. The flask was kept at 20°C, and hydrogen was bubbled in at a rate of 0.2/mm for 8 hours. A yellow-black solution formed. The solution was filtered under nitrogen to separate the powdered palladium on carbon. The liquid was a homogeneous yellow-black solution.
When this homogeneous solution was analyzed by redox titration method, the reduction rate of titanium tetrachloride was found to be almost 100%.
It was hot. It was diluted by adding 1,2-dichloroethane. Concentration of titanium trichloride produced
The amount was adjusted to 0.4 mol/. In addition, 25 g of anhydrous powdered magnesium chloride was placed in a 1000 ml flask that had been thoroughly dried and purged with nitrogen.
(0.262 mol) and 360 ml (0.787 mol) of di(2-ethyl-hexyloxy)(2-ethylhexyl)phosphine oxide were added and dissolved under stirring. Add n-hexane to bring the total volume to 524ml
(0.50 mol/MgCl 2 ). A 300 ml flask was charged with 20 ml of the homogeneous solution containing magnesium chloride (10 mmol in MgCl 2 ). Next, 25 ml (10 m
mol) was added. Furthermore, 145 ml of n-hexane was added. A green homogeneous solution was obtained. When 10 ml of titanium tetrachloride as a precipitating agent was slowly added dropwise to the homogeneous solution thus produced while stirring, a dark green fine powder solid was produced. After stirring for 1 hour, a finely powdered solid was precipitated. The supernatant was a black homogeneous solution. Separate the supernatant and create a new n
- 200 ml of hexane was added to wash the finely powdered solid. This operation was repeated six times. N-hexane was added to bring the total volume to 200 ml to obtain an n-hexane suspension of a slightly yellow-green fine powder solid. The Ti concentration was determined by colorimetric analysis and was 0.011mol/
It was hot. Mg/Ti (molar ratio) was 4.5. (2) Copolymerization of ethylene, propylene, and butadiene: 0.03 m of the above catalyst component A-6 in terms of titanium.
Copolymerization of ethylene, propylene, and butadiene was carried out in the same manner as in Example 9, except that the mol fraction was used as a catalyst, and 6.2 g of a rubbery polymer was obtained.
The catalyst activity was 17.3 Kg/g·Ti·hr.
第1図は本発明の製造方法を実施する為に用い
られる重合触媒の調製工程を示すフローチヤート
である。
FIG. 1 is a flowchart showing the steps for preparing a polymerization catalyst used to carry out the production method of the present invention.
Claims (1)
(A)含塩素マグネシウム化合物及びP=O結合を有
するリン化合物を含有する均一溶液とチタン化合
物とを接触させて得られる粉末及び(B)有機アルミ
ニウム化合物もしくは一般式R2OH(R2は炭素数
1〜20の炭化水素基)で表わされるアルコール性
化合物で変性された有機アルミニウム化合物から
なる触媒を用い、オレフインと共役ジエンとを共
重合させることを特徴とするオレフイン−共役ジ
エン共重合体の製造方法。 2 オレフインがエチレン及び/又はプロピレン
であり共役ジエンがブタジエンである特許請求の
範囲第1項の製造方法。[Claims] 1. Prepared in the presence or absence of an organic solvent
(A) Powder obtained by contacting a titanium compound with a homogeneous solution containing a chlorine-containing magnesium compound and a phosphorus compound having a P=O bond, and (B) an organoaluminum compound or a compound with the general formula R 2 OH (R 2 is carbon An olefin-conjugated diene copolymer characterized in that an olefin and a conjugated diene are copolymerized using a catalyst made of an organoaluminum compound modified with an alcoholic compound represented by a hydrocarbon group of numbers 1 to 20. Production method. 2. The manufacturing method according to claim 1, wherein the olefin is ethylene and/or propylene and the conjugated diene is butadiene.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21549282A JPS59108008A (en) | 1982-12-10 | 1982-12-10 | Production of olefin-conjugated diene copolymer |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21549282A JPS59108008A (en) | 1982-12-10 | 1982-12-10 | Production of olefin-conjugated diene copolymer |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59108008A JPS59108008A (en) | 1984-06-22 |
JPH0261961B2 true JPH0261961B2 (en) | 1990-12-21 |
Family
ID=16673275
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21549282A Granted JPS59108008A (en) | 1982-12-10 | 1982-12-10 | Production of olefin-conjugated diene copolymer |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59108008A (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SG71754A1 (en) * | 1997-02-13 | 2000-04-18 | Sumitomo Chemical Co | Copolymer and copolymer composition |
US7888542B2 (en) | 2005-12-12 | 2011-02-15 | Neste Oil Oyj | Process for producing a saturated hydrocarbon component |
US7998339B2 (en) | 2005-12-12 | 2011-08-16 | Neste Oil Oyj | Process for producing a hydrocarbon component |
US8053614B2 (en) | 2005-12-12 | 2011-11-08 | Neste Oil Oyj | Base oil |
JP5557642B2 (en) * | 2010-07-30 | 2014-07-23 | 株式会社ブリヂストン | Copolymer of conjugated diene compound and non-conjugated olefin |
JP5961483B2 (en) * | 2012-08-20 | 2016-08-02 | 株式会社ブリヂストン | Method for producing copolymer |
-
1982
- 1982-12-10 JP JP21549282A patent/JPS59108008A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS59108008A (en) | 1984-06-22 |
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