JPH0346481B2 - - Google Patents
Info
- Publication number
- JPH0346481B2 JPH0346481B2 JP57019683A JP1968382A JPH0346481B2 JP H0346481 B2 JPH0346481 B2 JP H0346481B2 JP 57019683 A JP57019683 A JP 57019683A JP 1968382 A JP1968382 A JP 1968382A JP H0346481 B2 JPH0346481 B2 JP H0346481B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- catalyst component
- compound
- magnesium
- electron donor
- 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 - Lifetime
Links
- 239000010936 titanium Substances 0.000 claims description 50
- 239000003054 catalyst Substances 0.000 claims description 42
- 229910052719 titanium Inorganic materials 0.000 claims description 35
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 30
- 150000001875 compounds Chemical class 0.000 claims description 26
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 20
- 150000002681 magnesium compounds Chemical class 0.000 claims description 18
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 16
- 150000003609 titanium compounds Chemical class 0.000 claims description 16
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- 150000002148 esters Chemical class 0.000 claims description 12
- 239000011976 maleic acid Substances 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 11
- 239000011777 magnesium Substances 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid group Chemical group C(\C=C/C(=O)O)(=O)O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 150000002688 maleic acid derivatives Chemical class 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 5
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims 1
- 229920005604 random copolymer Polymers 0.000 claims 1
- -1 magnesium halide Chemical class 0.000 description 29
- 238000006116 polymerization reaction Methods 0.000 description 29
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 125000005234 alkyl aluminium group Chemical group 0.000 description 7
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 235000010210 aluminium Nutrition 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 229940018560 citraconate Drugs 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 5
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 5
- 150000002430 hydrocarbons Chemical group 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000011949 solid catalyst Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000003377 silicon compounds Chemical class 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 229920000576 tactic polymer Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YUXIBTJKHLUKBD-UHFFFAOYSA-N Dibutyl succinate Chemical compound CCCCOC(=O)CCC(=O)OCCCC YUXIBTJKHLUKBD-UHFFFAOYSA-N 0.000 description 2
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 description 2
- 229910010199 LiAl Inorganic materials 0.000 description 2
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- QCOAPBRVQHMEPF-UHFFFAOYSA-N bis(2-methylpropyl) butanedioate Chemical compound CC(C)COC(=O)CCC(=O)OCC(C)C QCOAPBRVQHMEPF-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 2
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 150000002366 halogen compounds Chemical class 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 150000003608 titanium Chemical class 0.000 description 2
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 1
- VMPGLVWHLGOGIQ-UHFFFAOYSA-N 2-(2-methylpropoxy)-2-oxoacetic acid Chemical compound CC(C)COC(=O)C(O)=O VMPGLVWHLGOGIQ-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- CDUJMDNHYLCBJI-UHFFFAOYSA-N C(CCC)[O-].C(CCC)[Al+2].C(CCC)[O-].C(CCC)[O-].C(CCC)[Al+2] Chemical compound C(CCC)[O-].C(CCC)[Al+2].C(CCC)[O-].C(CCC)[O-].C(CCC)[Al+2] CDUJMDNHYLCBJI-UHFFFAOYSA-N 0.000 description 1
- XBVQSAIISGFAAS-UHFFFAOYSA-N CC(C)O[Mg] Chemical compound CC(C)O[Mg] XBVQSAIISGFAAS-UHFFFAOYSA-N 0.000 description 1
- ZNEGVQGQHBETJB-UHFFFAOYSA-M CC=1C(=C(O[Mg])C=CC=1)C Chemical compound CC=1C(=C(O[Mg])C=CC=1)C ZNEGVQGQHBETJB-UHFFFAOYSA-M 0.000 description 1
- ZPHMYHCMBKTAND-UHFFFAOYSA-N CCCCC(CC)CO[Mg] Chemical compound CCCCC(CC)CO[Mg] ZPHMYHCMBKTAND-UHFFFAOYSA-N 0.000 description 1
- ZKCNZMISGOLOOY-UHFFFAOYSA-N CCCCCCCCO[Mg] Chemical compound CCCCCCCCO[Mg] ZKCNZMISGOLOOY-UHFFFAOYSA-N 0.000 description 1
- HIDWBDFPTDXCHL-UHFFFAOYSA-N CCCCO[Mg] Chemical compound CCCCO[Mg] HIDWBDFPTDXCHL-UHFFFAOYSA-N 0.000 description 1
- ZFAGXQVYYWOLNK-UHFFFAOYSA-N CCO[Mg] Chemical compound CCO[Mg] ZFAGXQVYYWOLNK-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- XLYMOEINVGRTEX-ARJAWSKDSA-N Ethyl hydrogen fumarate Chemical compound CCOC(=O)\C=C/C(O)=O XLYMOEINVGRTEX-ARJAWSKDSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 description 1
- JKRZOJADNVOXPM-UHFFFAOYSA-N Oxalic acid dibutyl ester Chemical compound CCCCOC(=O)C(=O)OCCCC JKRZOJADNVOXPM-UHFFFAOYSA-N 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
- UEKQGZQLUMSLNW-UHFFFAOYSA-N Propyl isome Chemical compound C1=C2C(C(=O)OCCC)C(C(=O)OCCC)C(C)CC2=CC2=C1OCO2 UEKQGZQLUMSLNW-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910010386 TiI4 Inorganic materials 0.000 description 1
- PZQBWGFCGIRLBB-NJYHNNHUSA-N [(2r)-2-[(2s,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-octadecanoyloxyethyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCCCCCCCCCCCC)[C@H]1OC[C@H](O)[C@H]1O PZQBWGFCGIRLBB-NJYHNNHUSA-N 0.000 description 1
- XFJNAOUAGWZUHZ-UHFFFAOYSA-M [Mg+]C.[O-]C1=CC=CC=C1 Chemical compound [Mg+]C.[O-]C1=CC=CC=C1 XFJNAOUAGWZUHZ-UHFFFAOYSA-M 0.000 description 1
- TZSQRHNPVPIZHV-UHFFFAOYSA-M [Mg]OC1=CC=CC=C1 Chemical compound [Mg]OC1=CC=CC=C1 TZSQRHNPVPIZHV-UHFFFAOYSA-M 0.000 description 1
- SZNWCVFYBNVQOI-UHFFFAOYSA-N [O-]CC.C(C)[Al+2].[O-]CC.[O-]CC.C(C)[Al+2] Chemical compound [O-]CC.C(C)[Al+2].[O-]CC.[O-]CC.C(C)[Al+2] SZNWCVFYBNVQOI-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GJRRTUSXQPXVES-UHFFFAOYSA-N bis(2-methylpropyl) oxalate Chemical compound CC(C)COC(=O)C(=O)OCC(C)C GJRRTUSXQPXVES-UHFFFAOYSA-N 0.000 description 1
- UFWRCRCDRAUAAO-UHFFFAOYSA-N bis(2-methylpropyl) pentanedioate Chemical compound CC(C)COC(=O)CCCC(=O)OCC(C)C UFWRCRCDRAUAAO-UHFFFAOYSA-N 0.000 description 1
- SWBJZPDGKVYSLT-UHFFFAOYSA-N bis(2-methylpropyl) propanedioate Chemical compound CC(C)COC(=O)CC(=O)OCC(C)C SWBJZPDGKVYSLT-UHFFFAOYSA-N 0.000 description 1
- MQKXWEJVDDRQKK-UHFFFAOYSA-N bis(6-methylheptyl) butanedioate Chemical compound CC(C)CCCCCOC(=O)CCC(=O)OCCCCCC(C)C MQKXWEJVDDRQKK-UHFFFAOYSA-N 0.000 description 1
- UTOVMEACOLCUCK-PLNGDYQASA-N butyl maleate Chemical compound CCCCOC(=O)\C=C/C(O)=O UTOVMEACOLCUCK-PLNGDYQASA-N 0.000 description 1
- OCFSGVNHPVWWKD-UHFFFAOYSA-N butylaluminum Chemical compound [Al].[CH2]CCC OCFSGVNHPVWWKD-UHFFFAOYSA-N 0.000 description 1
- QQHRHLXGCZWTDK-UHFFFAOYSA-L butylaluminum(2+);dibromide Chemical compound [Br-].[Br-].CCCC[Al+2] QQHRHLXGCZWTDK-UHFFFAOYSA-L 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229920005556 chlorobutyl Polymers 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- ISXDVFNOXYQPIA-UHFFFAOYSA-N dibutyl pentanedioate Chemical compound CCCCOC(=O)CCCC(=O)OCCCC ISXDVFNOXYQPIA-UHFFFAOYSA-N 0.000 description 1
- NFKGQHYUYGYHIS-UHFFFAOYSA-N dibutyl propanedioate Chemical compound CCCCOC(=O)CC(=O)OCCCC NFKGQHYUYGYHIS-UHFFFAOYSA-N 0.000 description 1
- VJRUISVXILMZSL-UHFFFAOYSA-M dibutylalumanylium;chloride Chemical compound CCCC[Al](Cl)CCCC VJRUISVXILMZSL-UHFFFAOYSA-M 0.000 description 1
- VTZJFPSWNQFPCQ-UHFFFAOYSA-N dibutylaluminum Chemical compound CCCC[Al]CCCC VTZJFPSWNQFPCQ-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- RFUDQCRVCDXBGK-UHFFFAOYSA-L dichloro(propyl)alumane Chemical compound [Cl-].[Cl-].CCC[Al+2] RFUDQCRVCDXBGK-UHFFFAOYSA-L 0.000 description 1
- AEVBUGHMKXBGBL-UHFFFAOYSA-N didecyl butanedioate Chemical compound CCCCCCCCCCOC(=O)CCC(=O)OCCCCCCCCCC AEVBUGHMKXBGBL-UHFFFAOYSA-N 0.000 description 1
- FFPZYKQFAKXVSW-UHFFFAOYSA-N didecyl pentanedioate Chemical compound CCCCCCCCCCOC(=O)CCCC(=O)OCCCCCCCCCC FFPZYKQFAKXVSW-UHFFFAOYSA-N 0.000 description 1
- YPTLFOZCUOHVFO-SREVYHEPSA-N diethyl (z)-2-methylbut-2-enedioate Chemical compound CCOC(=O)\C=C(\C)C(=O)OCC YPTLFOZCUOHVFO-SREVYHEPSA-N 0.000 description 1
- OUWSNHWQZPEFEX-UHFFFAOYSA-N diethyl glutarate Chemical compound CCOC(=O)CCCC(=O)OCC OUWSNHWQZPEFEX-UHFFFAOYSA-N 0.000 description 1
- HJXBDPDUCXORKZ-UHFFFAOYSA-N diethylalumane Chemical compound CC[AlH]CC HJXBDPDUCXORKZ-UHFFFAOYSA-N 0.000 description 1
- JJSGABFIILQOEY-UHFFFAOYSA-M diethylalumanylium;bromide Chemical compound CC[Al](Br)CC JJSGABFIILQOEY-UHFFFAOYSA-M 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- QMCVOSQFZZCSLN-QXMHVHEDSA-N dihexyl (z)-but-2-enedioate Chemical compound CCCCCCOC(=O)\C=C/C(=O)OCCCCCC QMCVOSQFZZCSLN-QXMHVHEDSA-N 0.000 description 1
- XEYHWMQDXTVNJW-UHFFFAOYSA-N dihexyl butanedioate Chemical compound CCCCCCOC(=O)CCC(=O)OCCCCCC XEYHWMQDXTVNJW-UHFFFAOYSA-N 0.000 description 1
- VIGLJKSIDLNMGH-UHFFFAOYSA-N dihexyl oxalate Chemical compound CCCCCCOC(=O)C(=O)OCCCCCC VIGLJKSIDLNMGH-UHFFFAOYSA-N 0.000 description 1
- MQXAJNXSULJYCY-UHFFFAOYSA-N dihexyl propanedioate Chemical compound CCCCCCOC(=O)CC(=O)OCCCCCC MQXAJNXSULJYCY-UHFFFAOYSA-N 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- WQEXBUQDXKPVHR-PLNGDYQASA-N dimethyl (z)-2-methylbut-2-enedioate Chemical compound COC(=O)\C=C(\C)C(=O)OC WQEXBUQDXKPVHR-PLNGDYQASA-N 0.000 description 1
- XTDYIOOONNVFMA-UHFFFAOYSA-N dimethyl pentanedioate Chemical compound COC(=O)CCCC(=O)OC XTDYIOOONNVFMA-UHFFFAOYSA-N 0.000 description 1
- TVWTZAGVNBPXHU-NXVVXOECSA-N dioctyl (z)-but-2-enedioate Chemical compound CCCCCCCCOC(=O)\C=C/C(=O)OCCCCCCCC TVWTZAGVNBPXHU-NXVVXOECSA-N 0.000 description 1
- KWABLUYIOFEZOY-UHFFFAOYSA-N dioctyl butanedioate Chemical compound CCCCCCCCOC(=O)CCC(=O)OCCCCCCCC KWABLUYIOFEZOY-UHFFFAOYSA-N 0.000 description 1
- PEJVLWCOQVHCAF-UHFFFAOYSA-N dioctyl oxalate Chemical compound CCCCCCCCOC(=O)C(=O)OCCCCCCCC PEJVLWCOQVHCAF-UHFFFAOYSA-N 0.000 description 1
- RXJJVYBGRFLCOX-UHFFFAOYSA-N dioctyl pentanedioate Chemical compound CCCCCCCCOC(=O)CCCC(=O)OCCCCCCCC RXJJVYBGRFLCOX-UHFFFAOYSA-N 0.000 description 1
- DTVMXQFQTCJMOR-UHFFFAOYSA-N dioctyl propanedioate Chemical compound CCCCCCCCOC(=O)CC(=O)OCCCCCCCC DTVMXQFQTCJMOR-UHFFFAOYSA-N 0.000 description 1
- YPLYFEUBZLLLIY-UHFFFAOYSA-N dipropan-2-yl butanedioate Chemical compound CC(C)OC(=O)CCC(=O)OC(C)C YPLYFEUBZLLLIY-UHFFFAOYSA-N 0.000 description 1
- ITHNIFCFNUZYLQ-UHFFFAOYSA-N dipropan-2-yl oxalate Chemical compound CC(C)OC(=O)C(=O)OC(C)C ITHNIFCFNUZYLQ-UHFFFAOYSA-N 0.000 description 1
- MSQKMFXJFBXZNQ-UHFFFAOYSA-N dipropan-2-yl pentanedioate Chemical compound CC(C)OC(=O)CCCC(=O)OC(C)C MSQKMFXJFBXZNQ-UHFFFAOYSA-N 0.000 description 1
- QRVSDVDFJFKYKA-UHFFFAOYSA-N dipropan-2-yl propanedioate Chemical compound CC(C)OC(=O)CC(=O)OC(C)C QRVSDVDFJFKYKA-UHFFFAOYSA-N 0.000 description 1
- SZHZCPHKDJWHNG-UHFFFAOYSA-N dipropyl butanedioate Chemical compound CCCOC(=O)CCC(=O)OCCC SZHZCPHKDJWHNG-UHFFFAOYSA-N 0.000 description 1
- HZHMMLIMOUNKCK-UHFFFAOYSA-N dipropyl oxalate Chemical compound CCCOC(=O)C(=O)OCCC HZHMMLIMOUNKCK-UHFFFAOYSA-N 0.000 description 1
- LWIWFCDNJNZEKB-UHFFFAOYSA-N dipropyl propanedioate Chemical compound CCCOC(=O)CC(=O)OCCC LWIWFCDNJNZEKB-UHFFFAOYSA-N 0.000 description 1
- CLPHAYNBNTVRDI-UHFFFAOYSA-N ditert-butyl propanedioate Chemical compound CC(C)(C)OC(=O)CC(=O)OC(C)(C)C CLPHAYNBNTVRDI-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-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
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- XLYMOEINVGRTEX-UHFFFAOYSA-N fumaric acid monoethyl ester Natural products CCOC(=O)C=CC(O)=O XLYMOEINVGRTEX-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- 235000019359 magnesium stearate Nutrition 0.000 description 1
- BSGVJBRWDNPHOR-UHFFFAOYSA-M magnesium;butan-1-olate;chloride Chemical compound [Mg+2].[Cl-].CCCC[O-] BSGVJBRWDNPHOR-UHFFFAOYSA-M 0.000 description 1
- YJCTUQFSSZSZPO-UHFFFAOYSA-L magnesium;chloride;phenoxide Chemical compound [Cl-].[Mg+]OC1=CC=CC=C1 YJCTUQFSSZSZPO-UHFFFAOYSA-L 0.000 description 1
- BJZBHTNKDCBDNQ-UHFFFAOYSA-L magnesium;dodecanoate Chemical compound [Mg+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BJZBHTNKDCBDNQ-UHFFFAOYSA-L 0.000 description 1
- KRTCPMDBLDWJQY-UHFFFAOYSA-M magnesium;ethanolate;chloride Chemical compound [Mg+2].[Cl-].CC[O-] KRTCPMDBLDWJQY-UHFFFAOYSA-M 0.000 description 1
- ZHLDMBMNKCIBQN-UHFFFAOYSA-M magnesium;methanolate;chloride Chemical compound [Cl-].CO[Mg+] ZHLDMBMNKCIBQN-UHFFFAOYSA-M 0.000 description 1
- CFXDAHURBQNVFG-UHFFFAOYSA-M magnesium;propan-2-olate;chloride Chemical compound [Mg+2].[Cl-].CC(C)[O-] CFXDAHURBQNVFG-UHFFFAOYSA-M 0.000 description 1
- 150000002689 maleic acids Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- OBRKWFIGZSMARO-UHFFFAOYSA-N propylalumane Chemical compound [AlH2]CCC OBRKWFIGZSMARO-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- DENFJSAFJTVPJR-UHFFFAOYSA-N triethoxy(ethyl)silane Chemical compound CCO[Si](CC)(OCC)OCC DENFJSAFJTVPJR-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical group CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
本発明は、オレフインの重合（以下、オレフイ
ンの共重合をも包含して用いることがある）によ
つて、オレフイン重合体（以下、オレフイン共重
合体を包含して用いることがある）を製造する方
法に関する。とくには、炭素数３以上のα−オレ
フインの重合に適用した場合、高立体規則性重合
体を高収量で得ることのできるオレフイン重合体
の製造方法に関する。さらには、炭素数３以上の
α−オレフインの重合において、重合に際して水
素等の分子量調節剤を用いて重合体のメルトイン
デツクスを変えても、重合体の立体規則性の低下
が少ないオレフインの重合が可能な方法に関す
る。
マグネシウム、チタン、ハロゲンおよび電子供
与体を必須成分とする固体触媒成分の製造方法に
ついてはすでに多くの提案があり、該固体触媒成
分を炭素数３以上のα−オレフインの重合に利用
するときに、高立体規則性重合体を高い触媒活性
で得ることが可能であることも知られている。し
かしながらその多くは、さらに活性や重合体の立
体規則性などにおいて一層の改良が望まれてい
る。
例えば重合後の後処理操作を施さずに高品質の
オレフイン重合体を得るためには、立体規則性重
合体の生成比率が非常に高く、しかも遷移金属当
たりの重合体収率が充分に大きくなくてはならな
い。従来諸提案の技術は、目的とする重合体の種
類によつては、上記観点において可成の水準にあ
ると言えるものもあるが、成形機の発錆に係わる
重合体中の残存ハロゲン含有量の点から見れば、
充分な性能を有していると言えるものは数少な
い。しかもその多くは、メルトインデツクスの大
きい重合体を製造するときには、収率や立体規則
性などの少なからざる低下をひき起こすという欠
点を有している。
本発明の目的とするところは、触媒活性の持続
性が優れ、単位触媒当りの重合活性や立体規則性
重合能の一層優れたオレフインの重合方法を提供
するにある。本発明の他の目的は高メルトインデ
ツクスの重合体の製造においても立体規則性指数
の低下傾向の少ない重合方法を提供するにある。
本発明の他の目的ならびに効果は以下の記載によ
り一層明らかとなろう。
本発明によれば、
〔Ａ〕 少なくとも(a)実質的に還元能を有しない
マグネシウム化合物、(b)チタン化合物及び(c)電
子供与体の三成分の相互反応によつて得られる
チタン、マグネシウム、ハロゲン及び電子供与
体を必須成分とするチタン触媒成分であつて、
該電子供与体が、マレイン酸及び置換マレイン
酸よりなる群から選ばれる不飽和カルボン酸と
直鎖脂肪族アルコールとのエステル又は炭素数
２ないし５の飽和直鎖ジカルボン酸のエステル
であるチタン触媒成分、
〔Ｂ〕 有機アルミニウム化合物触媒成分、及び
〔Ｃ〕 Si−Ｏ−Ｃ結合を有する有機ケイ素化合
物触媒成分
とから形成される触媒の存在下に、オレフイン
を重合もしくは共重合することを特徴とするオ
レフインの重合方法が提供される。
本発明で用いるチタン触媒成分(A)は、マグネシ
ウム、チタン、ハロゲン及び後記する特定の電子
供与体を必須成分とする高活性触媒成分である。
このチタン触媒成分(A)は、市販のハロゲン化マグ
ネシウムに比し、結晶性の低いハロゲン化マグネ
シウムを含み、その比表面積は、通常は約50m2／
ｇ以上、好適には約60ないし約800m2／ｇ、より
好ましくは約100ないし約400m2／ｇ程度のものが
よく、室温におけるヘキサン洗浄によつて実質的
にその組成が変ることがない。該チタン触媒成分
(A)において、ハロゲン／チタン（原子比）が約５
ないし約200、とくには約５ないし約100、後記電
子供与体／チタン（モル比）が約0.1ないし約10、
とくに約0.2ないし約６、マグネシウム／チタン
（原子比）が約２ないし約100、とくには約４ない
し約50程度のものが好ましい。該成分(A)はまた、
他の電子供与体、金属、元素、官能基などを含ん
でいてもよい。
このようなチタン触媒成分(A)は、例えばマグネ
シウム化合物（もしくはマグネシウム金属）、電
子供与体及びチタン化合物の相互接触によつて得
られるが、場合によつては、他の反応試剤、例え
ばケイ素、リン、アルミニウムなどの化合物を使
用することができる。
かかるチタン触媒成分(A)を製造する方法として
は、例えば、特開昭50−108385号、同50−126590
号、同51−20297号、同51−28189号、同51−
64586号、同51−92885号、同51−136625号、同52
−87489号、同52−100596号、同52−147688号、
同52−104593号、同53−2580号、同53−40093号、
同53−43094号、同55−135102号、同55−135103
号、同56−811号、同56−11908号、同56−18606
号などに開示された方法に準じて製造することが
できる。
これらチタン触媒成分(A)の製造方法の数例につ
いて、以下に簡単に述べる。
(1) マグネシウム化合物あるいはマグネシウム化
合物と電子供与体の錯化合物を、電子供与体、
粉砕助剤等の存在下又は不存在下、粉砕し又は
粉砕することなく、電子供与体及び／又は有機
アルミニウム化合物やハロゲン含有ケイ素化合
物のような反応助剤で予備処理し、又は予備処
理せずに得た固体と反応条件下に液相をなすチ
タン化合物と反応させる。但し、上記電子供与
体を少なくとも一回は使用する。
(2) 還元能を有しないマグネシウム化合物の液状
物と、液状チタン化合物を電子供与体の存在下
で反応させて固体状のチタン複合体を析出させ
る。
(3) (2)で得られるものに、チタン化合物を反応さ
せる。
(4) (1)や(2)で得られるものに電子供与体及びチタ
ン化合物を反応させる。
(5) マグネシウム化合物あるいはマグネシウム化
合物と電子供与体の錯化合物を、電子供与体、
粉砕助剤等の存在下又は不存在及びチタン化合
物の存在下に粉砕し、電子供与体及び／又は有
機アルミニウム化合物やハロゲン含有ケイ素化
合物のような反応助剤で予備処理し、又は予備
処理せずに得た固体をハロゲン又はハロゲン化
合物又は芳香族炭化水素で処理する。但し、上
記電子供与体を少なくとも一回は使用する。
(6) 前記化合物をハロゲン又はハロゲン化合物で
処理する。
これらの触媒成分の中では、触媒調製におい
て、液状のハロゲン化チタンを使用したものあ
るいはチタン化合物の作用時又は作用後におい
てハロゲン化炭化水素を使用したものがとくに
好ましい。
本発明のチタン触媒成分〔Ａ〕に含有されるべ
き電子供与体は、マレイン酸及び置換マレイン酸
から選ばれる不飽和ジカルボン酸、すなわち式
HOOCR1＝CR2COOH（R1，R2は水素又は置換基
を有する又は有しない任意の炭化水素基）で表わ
される不飽和ジカルボン酸と置換基を有する又は
有しない任意の直鎖脂肪族アルコールとのエステ
ルである。より具体的には、マレイン酸モノエチ
ル、マレイン酸ジエチル、マレイン酸ジｎ−プロ
ピル、マレイン酸モノｎ−ブチル、マレイン酸ジ
ｎ−ブチル、マレイン酸ジｎ−ヘキシル、マレイ
ン酸ジｎ−オクチル、マレイン酸ジｎ−デシル、
マレイン酸ジｎ−クロルブチル、シトラコン酸ジ
メチル、シトラコン酸ジエチル、シトラコン酸ジ
ｎ−プロピル、シトラコン酸ジｎ−ブチル、シト
ラコン酸モノｎ−ブチル、シトラコン酸ジｎ−ヘ
キシル、シトラコン酸ジｎ−オクチル、シトラコ
ン酸ジｎ−デシル、エチルマレイン酸ジエチル、
エチルマレイン酸ジｎ−プロピル、エチルマレイ
ン酸ジｎ−ブチル、エチルマレイン酸ジｎ−オク
チル、ジエチルマレイン酸ブチル、プロピルマレ
イン酸ジエチル、プロピルマレイン酸ジｎ−プロ
ピル、プロピルマレイン酸ジｎ−ブチル、プロピ
ルマレイン酸ジｎ−ヘキシル、プロピルマレイン
酸ジｎ−オクチル、ブチルマレイン酸ジエチル、
ブチルマレイン酸ジｎ−プロピル、ブチルマレイ
ン酸ジｎ−ブチルなどのエステルを挙げることが
できる。
これらの中では、マレイン酸及び置換マレイン
酸と炭素数２ないし10程度の直鎖アルコールとの
ジエステルが好ましく、とくにマレイン酸及び炭
素数１ないし４のアルキル基置換マレイン酸と炭
素数２ないし８の直鎖アルコールとのジエステル
が特に好ましい。
チタン触媒成分(A)に含有されるべき電子供与体
としてはまたは炭素数２ないし５の飽和直鎖ジカ
ルボン酸のエステルから選択することもできる。
このような化合物はシユウ酸、マロン酸、コハク
酸又はグルタル酸のエステルであつて、例えば、
シユウ酸ジメチル、シユウ酸ジメチル、シユウ酸
ジｎ−プロピル、シユウ酸ジiso−プロピル、シ
ユウ酸ジｎ−ブチル、シユウ酸モノiso−ブチル、
シユウ酸ジiso−ブチル、シユウ酸ジｎ−ヘキシ
ル、シユウ酸ジｎ−オクチル、シユウ酸ジiso−
オクチル、シユウ酸ジiso−デシル、マロン酸ジ
ｎ−プロピル、マロン酸ジiso−プロピル、マロ
ン酸ジｎ−ブチル、マロン酸ジiso−ブチル、マ
ロン酸ジtert−ブチル、マロン酸ジｎ−ヘキシ
ル、マロン酸ジｎ−オクチル、マロン酸ジiso−
オクチル、マロン酸ジiso−デシル、グルタル酸
ジメチル、グルタル酸ジエチル、グルタル酸ジｎ
−プロピル、グルタル酸ジiso−プロピル、グル
タル酸ジｎ−ブチル、グルタル酸ジiso−ブチル、
グルタル酸ジｎ−オクチル、グルタル酸ジiso−
オクチル、グルタル酸ジデシル、コハク酸ジエチ
ル、コハク酸ジエチル、コハク酸ジｎ−プロピ
ル、コハク酸ジiso−プロピル、コハク酸ジｎ−
ブチル、コハク酸ジiso−ブチル、コハク酸モノ
iso−ブチル、コハク酸ジｎ−オクチル、コハク
酸ジiso−オクチル、コハク酸ジｎ−ヘキシル、
コハク酸ジｎ−デシルなどのエステルを例示する
ことができる。これらの中では、前記飽和直鎖ジ
カルボン酸と炭素数３以上のアルコールのエステ
ル、中でも炭素数３ないし５の飽和直鎖ジカルボ
ン酸と炭素数３ないし10のアルコールのジエステ
ルを使用せるのが好ましい。
前記エステルは一種又は二種以上含有させるこ
とができる。
更に上記エステルをチタン触媒成分(A)に含有さ
せるに際し、必らずしも出発原料として、これら
を使用する必要はなく、チタン触媒成分(A)の調製
過程でこれら化合物に変化しうる化合物を用いて
該調製段階でこれら化合物に変換させてもよい。
又、上記化合物は、他の化合物、例えばアルミ
ニウム化合物、リン化合物、アミン化合物などと
の付加化合物の形で使用することもできる。
本発明において、前記〔Ａ〕固体チタン触媒成
分の調製に用いられるマグネシウム化合物は、還
元能を有しないマグネシウム化合物、すなわちマ
グネシウム−炭素結合やマグネシウム−水素結合
を有しないマグネシウム化合物が好ましく、これ
らは還元能を有するマグネシウム化合物から誘導
されたものであつてもよい。このような還元能を
有しないマグネシウム化合物としては、塩化マグ
ネシウム、臭化マグネシウム、沃化マグネシウ
ム、弗化マグネシウムのようなハロゲン化マグネ
シウム；メトキシ塩化マグネシウム、エトキシ塩
化マグネシウム、イソプロポキシ塩化マグネシウ
ム、ブトキシ塩化マグネシウム、オクトキシ塩化
マグネシウムのようなアルコキシマグネシウムハ
ライド；フエノキシ塩化マグネシウム、メチルフ
エノキシ塩化マグネシウムのようなアリロキシマ
グネシウムハライド；エトキシマグネシウム、イ
ソプロポキシマグネシウム、ブトキシマグネシウ
ム、ｎ−オクトキシマグネシウム、２−エチルヘ
キソキシマグネシウムのようなアルコキシマグネ
シウム；フエノキシマグネシウム、ジメチルフエ
ノキシマグネシウムのようなアリロキシマグネシ
ウム；ラウリン酸マグネシウム、ステアリン酸マ
グネシウムのようなマグネシウムのカルボン酸塩
などを例示することができる。また、該マグネシ
ウム化合物は他の金属との錯化合物、複化合物あ
るいは他の金属化合物との混合物であつてもよ
い。さらにこれらの化合物の２種以上の混合物で
あつてもよい。これらの中でとくに好ましいマグ
ネシウム化合物は、ハロゲン含有マグネシウム化
合物、とりわけ塩化マグネシウム、アルコキシ塩
化マグネシウム、アリロキシ塩化マグネシウムで
ある。
本発明において、固体チタン触媒成分〔Ａ〕の
調製に用いられる(ii)チタン化合物としては種々あ
るが、通常Ti（OR）gX4-g（Ｒは炭化水素基、Ｘは
ハロゲン、０≦ｇ≦４）で示される４価のチタン
化合物が好適である。より具体的には、TiCl4、
TiBr4、TiI4などのテトラハロゲン化チタン；Ti
（OCH3）Cl3、Ti（OC2H5）Cl3、Ti（On−C4H9）
Cl3、Ti（OC2H5）Br3、Ti（OisoC4H9）Br3など
のトリハロゲン化アルコキシチタン；Ti
（OCH3）2Cl2、Ti（OC2H5）2Cl2、Ti（On−
C4H9）2Cl2、Ti（OC2H5）2Br2などのジハロゲン化
アルコキシチタン；Ti（OCH3）3Cl、Ti
（OC2H5）3Cl、Ti（On−C4H9）3Cl、Ti
（OC2H5）3Brなどのモノハロゲン化トリアルコキ
シチタン；Ti（OCH3）4、Ti（OC2H5）4、Ｔ（On−
C4H9）4などのテトラアルコキシチタンなどを例
示することができる。これらの中で好ましいもの
はハロゲン含有チタン化合物、とくにテトラハロ
ゲン化チタンであり、とくに好ましいのは四塩化
チタンである。
これらチタン化合物は単味で用いてよいし、混
合物の形で用いてもよい。あるいは炭化水素やハ
ロゲン化炭化水素などに希釈して用いてもよい。
チタン触媒成分(A)の調製において、チタン化合
物、マグネシウム化合物及び担持すべき電子供与
体、さらに必要に応じて使用されることのある他
の電子供与体、例えばアルコール、フエノール、
モノカルボン酸エステルなど、ケイ素化合物、ア
ルミニウム化合物などの使用量は、調製方法によ
つて異なり一概に規定できないが、例えばマグネ
シウム化合物１モル当り、担持すべき電子供与体
0.05ないし５モル、チタン化合物0.05ないし1000
モル程度の割合とすることができる。
本発明においては、以上のようにして得られる
固体触媒成分〔Ａ〕と、有機アルミニウム化合物
触媒成分〔Ｂ〕及びケイ素化合物〔Ｃ〕の組合せ
触媒を用いてオレフインの重合または共重合を行
う。
上記〔Ｂ〕成分としては、(i)少なくとも分子内
に１個のAl−炭素結合を有する有機アルミニウ
ム化合物、例えば一般式
R1mAl（OR2）nHpXq
（ここでR1およびR2は炭素原子、通常１ない
し15個、好ましくは１ないし４個を含む炭化水素
基で互いに同一でも異なつてもよい。Ｘはハロゲ
ン、ｍは０＜ｍ≦３、０≦ｎ＜３、ｐは０≦ｐ＜
３、ｑは０≦ｑ＜３の数であつて、しかもｍ＋ｎ
＋ｐ＋ｑ＝３である）で表わされる有機アルミニ
ウム化合物、
(ii) 一般式
M1AlR1 4
（ここでM1はLi，Na，Ｋであり、R1は前記と
同じ）で表わされる第族金属とアルミニウムと
の錯アルキル化物などを挙げることができる。
前記の(i)に属する有機アルミニウム化合物とし
ては、次のものを例示できる。一般式
R1mAl（OR2）3-n
（ここでR1およびR2は前記と同じ。ｍは好ま
しくは1.5≦ｍ≦３の数である。）、一般式
R1mAlX3-n
ここでR1は前記と同じ。Ｘはハロゲン、ｍは
好ましくは０＜ｍ＜３である。）、一般式
R1mAlH3-n
（ここでR1は前記と同じ。ｍは好ましくは２
≦ｍ＜３である。）、一般式
R1mAl（OR2）nXq
（ここでR1およびR2は前記と同じ。Ｘはハロ
ゲン、０＜ｍ≦３、０≦ｎ＜３、０≦ｑ＜３で、
ｍ＋ｎ＋ｑ＝である）で表わされるものなどを例
示できる。
(i)に属するアルミニウム化合物において、より
具体的にはトリエチルアルミニウム、トリブチル
アルミニウムなどのトリアルキルアルミニウム、
トリイソプレニルアルミニウムのようなトリアル
ケニルアルミニウム、ジエチルアルミニウムエト
キシド、ジブチルアルミニウムブトキシドなどの
ジアルキルアルミニウムアルコキシド、エチルア
ルミニウムセスキエトキシド、ブチルアルミニウ
ムセスキブトキシドなどのアルキルアルミニウム
セスキアルコキシドのほかに、R1 2.5Al（OR2）0.5
などで表わされる平均組成を有する部分的にアル
コキシ化されたアルキルアルミニウム、ジエチル
アルミニウムクロリド、ジブ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のような
ジアルキルアルミニウムハライド、エチルアルミ
ニウムセスキクロリド、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ブロミド
のようなアルキルアルミニウムセスキハライド、
エチルアルミニウムジクロリド、プロピルアルミ
ニウムジクロリド、ブチルアルミニウムジブロミ
ドなどのようなアルキルアルミニウムジハライド
などの部分的にハロゲン化されたアルキルアルミ
ニウム、ジエチルアルミニウムヒドリド、ジブチ
ルアルミニウムヒドリドなどのジアルキルアルミ
ニウムヒドリド、エチルアルミニウムジヒドリ
ド、プロピルアルミニウムジヒドリドなどのアル
キルアルミニウムジヒドリドなどの部分的に水素
化されたアルキルアルミニウム、エチルアルミニ
ウムエトキシクロリド、ブチルアルミニウムブト
キシクロリド、エチルアルミニウムエトキシブロ
ミドなどの部分的にアルコキシ化およびハロゲン
化されたアルキルアルミニウムである。
前記(ii)に属する化合物としては、LiAl
（C2H5）4、LiAl（C7H15）4などを例示できる。
また(i)に類似する化合物として酸素原子や窒素
原子を介して２以上のアルミニウムが結合した有
機アルミニウム化合物であつてもよい。このよう
な化合物として、例えば（C2H5）2AlOAl
（C2H5）2、（C4H9）2AlOAl（C4H9）2、
The present invention relates to the production of olefin polymers (hereinafter, the use may include olefin copolymers) by polymerization of olefins (hereinafter, the use may include olefin copolymerization). Regarding the method. In particular, the present invention relates to a method for producing an olefin polymer that can yield a highly stereoregular polymer in high yield when applied to the polymerization of an α-olefin having 3 or more carbon atoms. Furthermore, in the polymerization of α-olefins having 3 or more carbon atoms, even if the melt index of the polymer is changed using a molecular weight regulator such as hydrogen during polymerization, the stereoregularity of the polymer is not significantly reduced. Regarding the possible methods. There have already been many proposals regarding methods for producing solid catalyst components containing magnesium, titanium, halogen, and electron donors as essential components. It is also known that highly stereoregular polymers can be obtained with high catalytic activity. However, many of them require further improvement in terms of activity, stereoregularity, etc. of the polymer. For example, in order to obtain high-quality olefin polymers without post-polymerization post-treatment operations, the formation ratio of stereoregular polymers must be extremely high, and the polymer yield per transition metal must be sufficiently high. must not. Depending on the type of target polymer, some of the conventionally proposed technologies can be said to be at an acceptable level from the above viewpoint, but the residual halogen content in the polymer, which is related to rusting in molding machines, is From the point of view of
There are only a few that can be said to have sufficient performance. Moreover, most of them have the disadvantage that when producing a polymer with a large melt index, the yield and stereoregularity are considerably reduced. An object of the present invention is to provide a method for polymerizing olefins which has excellent sustainability of catalytic activity, and even better polymerization activity per unit catalyst and stereoregular polymerization ability. Another object of the present invention is to provide a polymerization method in which the stereoregularity index does not tend to decrease even in the production of high melt index polymers.
Other objects and effects of the present invention will become more apparent from the following description. According to the present invention, [A] titanium and magnesium obtained by the mutual reaction of at least three components: (a) a magnesium compound having substantially no reducing ability, (b) a titanium compound, and (c) an electron donor; , a titanium catalyst component containing a halogen and an electron donor as essential components,
A titanium catalyst component in which the electron donor is an ester of an unsaturated carboxylic acid selected from the group consisting of maleic acid and substituted maleic acid and a linear aliphatic alcohol, or an ester of a saturated linear dicarboxylic acid having 2 to 5 carbon atoms. , characterized in that the olefin is polymerized or copolymerized in the presence of a catalyst formed from [B] an organoaluminum compound catalyst component and [C] an organosilicon compound catalyst component having a Si-O-C bond. A method for polymerizing olefins is provided. The titanium catalyst component (A) used in the present invention is a highly active catalyst component containing magnesium, titanium, halogen, and a specific electron donor described below as essential components.
This titanium catalyst component (A) contains magnesium halide with lower crystallinity than commercially available magnesium halides, and its specific surface area is usually about 50 m 2 /
It is preferably about 60 to about 800 m 2 /g, more preferably about 100 to about 400 m 2 /g, and its composition is not substantially changed by washing with hexane at room temperature. The titanium catalyst component
In (A), halogen/titanium (atomic ratio) is approximately 5
from about 200, particularly from about 5 to about 100, with an electron donor/titanium (molar ratio) of from about 0.1 to about 10,
In particular, those having a magnesium/titanium (atomic ratio) of about 0.2 to about 6, about 2 to about 100, particularly about 4 to about 50 are preferred. The component (A) also includes:
It may also contain other electron donors, metals, elements, functional groups, etc. Such a titanium catalyst component (A) can be obtained, for example, by mutual contact of a magnesium compound (or magnesium metal), an electron donor and a titanium compound, but optionally with other reactants, such as silicon, Compounds such as phosphorus and aluminum can be used. As a method for producing such a titanium catalyst component (A), for example, JP-A-50-108385 and JP-A-50-126590 are used.
No. 51-20297, No. 51-28189, No. 51-
No. 64586, No. 51-92885, No. 51-136625, No. 52
-87489, 52-100596, 52-147688,
No. 52-104593, No. 53-2580, No. 53-40093,
No. 53-43094, No. 55-135102, No. 55-135103
No. 56-811, No. 56-11908, No. 56-18606
It can be manufactured according to the method disclosed in No. Some examples of methods for producing these titanium catalyst components (A) will be briefly described below. (1) A magnesium compound or a complex compound of a magnesium compound and an electron donor,
Grinding or not grinding, with or without grinding aids, pretreated with electron donors and/or reaction aids such as organoaluminum compounds and halogen-containing silicon compounds, or without pretreatment. The solid obtained is reacted with a titanium compound that forms a liquid phase under reaction conditions. However, the above electron donor is used at least once. (2) A liquid magnesium compound that does not have reducing ability and a liquid titanium compound are reacted in the presence of an electron donor to precipitate a solid titanium complex. (3) React the material obtained in (2) with a titanium compound. (4) React the material obtained in (1) or (2) with an electron donor and a titanium compound. (5) A magnesium compound or a complex compound of a magnesium compound and an electron donor,
Grinding in the presence or absence of grinding aids etc. and in the presence of titanium compounds, pre-treated with electron donors and/or reaction aids such as organoaluminum compounds and halogen-containing silicon compounds, or without pre-treatment. The solid obtained is treated with a halogen or a halogen compound or an aromatic hydrocarbon. However, the above electron donor is used at least once. (6) Treating the compound with a halogen or a halogen compound. Among these catalyst components, those using liquid titanium halides or those using halogenated hydrocarbons during or after the action of the titanium compound in catalyst preparation are particularly preferred. The electron donor to be contained in the titanium catalyst component [A] of the present invention is an unsaturated dicarboxylic acid selected from maleic acid and substituted maleic acid, that is, an unsaturated dicarboxylic acid of the formula
HOOCR 1 = CR 2 COOH (R 1 and R 2 are hydrogen or any hydrocarbon group with or without a substituent) and any linear aliphatic alcohol with or without a substituent It is an ester of More specifically, monoethyl maleate, diethyl maleate, di-n-propyl maleate, mono-n-butyl maleate, di-n-butyl maleate, di-n-hexyl maleate, di-n-octyl maleate, maleic acid. acid di-n-decyl,
Di-n-chlorobutyl maleate, dimethyl citraconate, diethyl citraconate, di-n-propyl citraconate, di-n-butyl citraconate, mono-n-butyl citraconate, di-n-hexyl citraconate, di-n-octyl citraconate, di-n-decyl citraconate, diethyl ethyl maleate,
Di-n-propyl ethyl maleate, di-n-butyl ethyl maleate, di-n-octyl ethyl maleate, butyl diethyl maleate, diethyl propyl maleate, di-n-propyl propyl maleate, di-n-butyl propyl maleate, Di-n-hexyl propyl maleate, di-n-octyl propyl maleate, diethyl butyl maleate,
Esters such as di-n-propyl butyl maleate and di-n-butyl butyl maleate can be mentioned. Among these, diesters of maleic acid and substituted maleic acid with linear alcohols having about 2 to 10 carbon atoms are preferred, and in particular maleic acid and diesters of substituted maleic acid and substituted maleic acids with alkyl groups having 1 to 4 carbon atoms and linear alcohols having about 2 to 8 carbon atoms are preferable. Particular preference is given to diesters with straight-chain alcohols. The electron donor to be contained in the titanium catalyst component (A) can also be selected from esters of saturated linear dicarboxylic acids having 2 to 5 carbon atoms.
Such compounds are esters of oxalic acid, malonic acid, succinic acid or glutaric acid, e.g.
Dimethyl oxalate, dimethyl oxalate, di-n-propyl oxalate, diiso-propyl oxalate, di-n-butyl oxalate, monoiso-butyl oxalate,
Diiso-butyl oxalate, di-n-hexyl oxalate, di-n-octyl oxalate, diiso- oxalate
Octyl, diiso-decyl oxalate, di-n-propyl malonate, diiso-propyl malonate, di-n-butyl malonate, diiso-butyl malonate, di-tert-butyl malonate, di-n-hexyl malonate , di-n-octyl malonate, di-iso- malonate
Octyl, diisodecyl malonate, dimethyl glutarate, diethyl glutarate, di-glutarate
-propyl, diiso-propyl glutarate, di-n-butyl glutarate, diiso-butyl glutarate,
Di-n-octyl glutarate, di-iso- glutarate
Octyl, didecyl glutarate, diethyl succinate, diethyl succinate, di-n-propyl succinate, diiso-propyl succinate, di-n-succinate
Butyl, diisobutyl succinate, monosuccinate
iso-butyl, di-n-octyl succinate, diiso-octyl succinate, di-n-hexyl succinate,
Examples include esters such as di-n-decyl succinate. Among these, it is preferable to use an ester of the saturated linear dicarboxylic acid and an alcohol having 3 or more carbon atoms, especially a diester of a saturated linear dicarboxylic acid having 3 to 5 carbon atoms and an alcohol having 3 to 10 carbon atoms. One or more types of the above esters can be contained. Furthermore, when incorporating the above-mentioned esters into the titanium catalyst component (A), it is not necessary to use them as starting materials, and compounds that can be converted into these compounds during the preparation process of the titanium catalyst component (A) are not necessarily used as starting materials. may be used to convert these compounds during the preparation step. The above compounds can also be used in the form of addition compounds with other compounds such as aluminum compounds, phosphorus compounds, and amine compounds. In the present invention, the magnesium compound used in the preparation of the solid titanium catalyst component [A] is preferably a magnesium compound that does not have reducing ability, that is, a magnesium compound that does not have a magnesium-carbon bond or a magnesium-hydrogen bond. It may be derived from a magnesium compound having the ability. Magnesium compounds without such reducing ability include magnesium halides such as magnesium chloride, magnesium bromide, magnesium iodide, and magnesium fluoride; methoxymagnesium chloride, ethoxymagnesium chloride, isopropoxymagnesium chloride, and butoxymagnesium chloride. , alkoxymagnesium halides such as octoxymagnesium chloride; allyloxymagnesium halides such as phenoxymagnesium chloride, methylphenoxymagnesium chloride; such as ethoxymagnesium, isopropoxymagnesium, butoxymagnesium, n-octoxymagnesium, 2-ethylhexoxymagnesium Examples include alkoxymagnesium such as phenoxymagnesium, allyloxymagnesium such as dimethylphenoxymagnesium, and magnesium carboxylate such as magnesium laurate and magnesium stearate. Further, the magnesium compound may be a complex compound with other metals, a composite compound, or a mixture with other metal compounds. Furthermore, it may be a mixture of two or more of these compounds. Among these, particularly preferred magnesium compounds are halogen-containing magnesium compounds, particularly magnesium chloride, alkoxymagnesium chloride, and allyloxymagnesium chloride. In the present invention, there are various titanium compounds (ii) used for preparing the solid titanium catalyst component [A], but usually Ti(OR) g X 4-g (R is a hydrocarbon group, X is a halogen, 0≦ A tetravalent titanium compound represented by g≦4) is suitable. More specifically, TiCl4 ,
Titanium tetrahalides such as TiBr4 , TiI4 ; Ti
( OCH3 ) Cl3 , Ti ( OC2H5 ) Cl3 , Ti(On− C4H9 )
Trihalogenated alkoxytitanium such as Cl3 , Ti( OC2H5 ) Br3 , Ti( OisoC4H9 ) Br3 ; Ti
(OCH 3 ) 2 Cl 2 , Ti (OC 2 H 5 ) 2 Cl 2 , Ti (On−
Dihalogenated alkoxy titanium such as C4H9 ) 2Cl2 , Ti( OC2H5 ) 2Br2 ; Ti( OCH3 ) 3Cl , Ti
(OC 2 H 5 ) 3 Cl, Ti (On−C 4 H 9 ) 3 Cl, Ti
Monohalogenated trialkoxytitanium such as (OC 2 H 5 ) 3 Br; Ti(OCH 3 ) 4 , Ti(OC 2 H 5 ) 4 , T(On−
Examples include tetraalkoxytitanium such as C 4 H 9 ) 4 . Preferred among these are halogen-containing titanium compounds, particularly titanium tetrahalide, and particularly preferred is titanium tetrachloride. These titanium compounds may be used alone or in the form of a mixture. Alternatively, it may be used after being diluted with a hydrocarbon or halogenated hydrocarbon. In preparing the titanium catalyst component (A), a titanium compound, a magnesium compound, an electron donor to be supported, and other electron donors that may be used as necessary, such as alcohol, phenol,
The amount of monocarboxylic acid ester, silicon compound, aluminum compound, etc. to be used varies depending on the preparation method and cannot be unconditionally specified, but for example, the amount of the electron donor to be supported per 1 mole of magnesium compound
0.05 to 5 mol, titanium compound 0.05 to 1000
The proportion can be on the order of moles. In the present invention, olefin polymerization or copolymerization is carried out using a combination catalyst of the solid catalyst component [A] obtained as described above, an organoaluminum compound catalyst component [B], and a silicon compound [C]. As the above [B] component, (i) an organoaluminum compound having at least one Al-carbon bond in the molecule, for example, a compound having the general formula R 1 mAl(OR 2 )nHpXq (where R 1 and R 2 are carbon atoms , usually 1 to 15 hydrocarbon groups, preferably 1 to 4 hydrocarbon groups, which may be the same or different from each other. X is halogen, m is 0<m≦3, 0≦n<3, p is 0≦p <
3. q is a number of 0≦q<3, and m+n
+p+q=3); (ii) Group metals represented by the general formula M 1 AlR 1 4 (where M 1 is Li, Na, K, and R 1 is the same as above); Examples include complex alkylated products of aluminum and aluminum. Examples of the organoaluminum compounds that belong to (i) above include the following. General formula R 1 mAl(OR 2 ) 3-n (where R 1 and R 2 are the same as above. m is preferably a number of 1.5≦m≦3), general formula R 1 mAlX 3-n where and R 1 is the same as above. X is halogen, and m is preferably 0<m<3. ), general formula R 1 mAlH 3-n (where R 1 is the same as above, m is preferably 2
≦m<3. ), general formula R 1 mAl(OR 2 )nXq (where R 1 and R 2 are the same as above, X is halogen, 0<m≦3, 0≦n<3, 0≦q<3,
Examples include those represented by m+n+q=. Among the aluminum compounds belonging to (i), more specifically, trialkyl aluminum such as triethyl aluminum and tributyl aluminum,
Besides trialkenylaluminum such as triisoprenylaluminum, dialkylaluminum alkoxide such as diethylaluminum ethoxide, dibutylaluminum butoxide, alkylaluminum sesquialkoxide such as ethylaluminum sesquiethoxide, butylaluminum sesquibutoxide, R 1 2 . 5 Al( OR2 ) 0.5
Partially alkoxylated alkyl aluminum halides, such as diethylaluminum chloride, dibutyl aluminum chloride, diethylaluminium bromide, ethyl aluminum sesquichloride, butyl aluminum sesquichloride, ethyl aluminum sesquibromide, etc., with an average composition of alkyl aluminum sesquihalides, such as
Partially halogenated alkylaluminiums such as alkylaluminum dihalides such as ethylaluminum dichloride, propylaluminum dichloride, butylaluminum dibromide etc., dialkylaluminum hydrides such as diethylaluminum hydride, dibutylaluminum hydride, ethylaluminum dihydride, Partially hydrogenated alkyl aluminums such as alkyl aluminum dihydrides such as propyl aluminum dihydride, partially alkoxylated and halogenated alkyl aluminums such as ethyl aluminum ethoxy chloride, butyl aluminum butoxy chloride, ethyl aluminum ethoxy bromide It is. Compounds belonging to (ii) above include LiAl
Examples include (C 2 H 5 ) 4 and LiAl(C 7 H 15 ) 4 . Further, as a compound similar to (i), it may be an organic aluminum compound in which two or more aluminum atoms are bonded via an oxygen atom or a nitrogen atom. Examples of such compounds include (C 2 H 5 ) 2 AlOAl
(C 2 H 5 ) 2 , (C 4 H 9 ) 2 AlOAl(C 4 H 9 ) 2 ,
内容積２のオートクレーブに精製ヘキサン
750mlを装入し、室温プロピレン雰囲気下トリエ
チルアルミニウム0.75mmol、ジフエニルジメト
キシシラン0.075mmol及び前記触媒成分〔Ａ〕を
チタン原子換算で0.015mmol装入した、水素200
mlを導入した後70℃に昇温し、２時間重合を行つ
た。重合中の圧力は７Kg／cm2Ｇに保つた。重合終
了後、生成重合体を含むスラリーを過し、白色
粉末状重合体と液相部に分離した。乾燥後の白色
粉末状重合体の収量は190ｇであり、沸とうｎ−
ヘプタンによる抽出残率は96.7％、MIは11、そ
の見掛密度は0.36ｇ／mlであつた。一方、液相部
の濃縮により溶媒可溶性重合体3.3ｇを得た。し
たがつて活性は12900ｇ−PP／mmol−Tiであ
り、トータルIIは95.1％であつた。
実施例 ２，３，４，５，６，７，８，９
〔触媒成分〔Ａ〕の調製〕
実施例１において、マレイン酸ジｎブチル6.9
mlを表１に示す化合物及び量に変えた以外は実施
例１に示した方法に従い触媒成分〔Ａ〕を調製し
た。該触媒成分の組成及び比表面積を表１に示し
た。
〔プロピレン重合〕
実施例１において、トリエチルアルミニウム
0.75mmol及びジフエニルジメトキシシラン
0.075mmolをそれぞれトリエチルアルミニウム
2.5mmol及びジフエニルジメトキシシラン
0.25mmolに変え、更に重合時間を２時間から４
時間に変えた以外は実施例１に示した方法に従い
プロピレンの重合を行なつた。結果を表１に示し
た。
実施例 10
〔触媒成分〔Ａ〕の調製〕
無水塩化マグネシウム20ｇ、マレイン酸ジｎ−
ブチル6.9mlおよび粉砕助剤としてシリコン油
（信越化学社製TSS−451、20cs）を窒素雰囲気中
直径15mmのステンレス鋼（SUS−32）製ボール
2.8Kgを収容した内容積800ml、内直径100mmのス
テンレス鋼（SUS−32）製ボールミル容器に装
入し、衝撃の加速度7Gで24時間接触させる。得
られた共粉砕物15ｇを四塩化チタン150ml中に懸
濁させ、110℃で２時間撹拌下に接触した後、固
体部を過によつて採取し、洗液中に遊離の四塩
化チタンが検出されなくなるまで精製ヘキサンで
充分洗浄後乾燥し、触媒成分〔Ａ〕を得る。該成
分は原子換算でチタン2.4重量％、塩素62.0重量
％、マグネシウム20.0重量％であり、また、その
比表面積は192m2／ｇであつた。
〔プロピレン重合〕
実施例２と同様な方法によりプロピレン重合を
行なつた。結果を表１に示した。
実施例 11
〔触媒成分〔Ａ〕の精製〕
内容積２の高速撹拌装置（特殊機化工業製）
を十分N2置換したのち、精製灯油700ml、市販
MgCl210ｇ、エタノール24.2ｇおよび商品名エマ
ゾール20（花王アトラス社製、ソルビタンジステ
アレート）３ｇを入れ、系を撹拌下に昇温し、
120℃にて800rpmで30分撹拌した。高速撹拌下、
内径５mmのテフロン製チユーブを用いて、あらか
じめ−10℃に冷却された精製灯油１を張り込ん
で２ガラスフラスコ（撹拌機付）に移液した。
生成固体を過により採取し、ヘキサンで十分洗
浄したのち担体を得た。
該担体7.5ｇを室温で150mlの四塩化チタン中に
懸濁させた後120℃に撹拌下昇温した。昇温途中
80℃でコハク酸ジｎブチル1.5mlを添加した。120
℃２時間の撹拌混合の後、固体部を過により採
取し、再び150mlの四塩化チタンに懸濁させ、再
度120℃２時間の撹拌混合を行なつた。更に該反
応物より反応固体物を過にて採取し、十分な量
の精製ヘキサンにて洗浄する事により、固体触媒
成分〔Ａ〕を得た。該成分は原子換算でチタン
2.0重量％、塩素66.0重量％、マグネシウム21.0重
量％であり、またその比表面積は240m2／ｇであ
つた。
〔プロピレン重合〕
実施例２と同様な方法によりプロピレン重合を
行なつた。結果を表１に示した。
実施例 12
〔触媒成分〔Ａ〕の調製〕
実施例11において、コハク酸ジｎ−ブチルをコ
ハク酸ジiso−ブチルに変えた以外は実施例11と
同様な方法で触媒成分〔Ａ〕を調製した。該触媒
成分の組成及び比表面積を表１に示した。
〔プロピレン重合〕
実施例２と同様な方法によりプロピレン重合を
行なつた。結果を表１に示した。
Purified hexane in an autoclave with an internal volume of 2
750 ml of hydrogen was charged, 0.75 mmol of triethylaluminum, 0.075 mmol of diphenyldimethoxysilane, and 0.015 mmol of the catalyst component [A] in terms of titanium atoms were charged under a propylene atmosphere at room temperature.
ml was introduced, the temperature was raised to 70°C, and polymerization was carried out for 2 hours. The pressure during polymerization was maintained at 7 kg/cm 2 G. After the polymerization was completed, the slurry containing the produced polymer was filtered and separated into a white powdery polymer and a liquid phase. The yield of white powdered polymer after drying was 190 g, and the yield was 190 g.
The extraction residue rate with heptane was 96.7%, the MI was 11, and the apparent density was 0.36 g/ml. On the other hand, 3.3 g of a solvent-soluble polymer was obtained by concentrating the liquid phase. Therefore, the activity was 12900 g-PP/mmol-Ti and the total II was 95.1%. Example 2, 3, 4, 5, 6, 7, 8, 9 [Preparation of catalyst component [A]] In Example 1, di-n-butyl maleate 6.9
Catalyst component [A] was prepared according to the method shown in Example 1, except that ml was changed to the compound and amount shown in Table 1. The composition and specific surface area of the catalyst components are shown in Table 1. [Propylene polymerization] In Example 1, triethylaluminum
0.75mmol and diphenyldimethoxysilane
0.075mmol each of triethylaluminum
2.5mmol and diphenyldimethoxysilane
Change the amount to 0.25 mmol and further increase the polymerization time from 2 hours to 4 hours.
Polymerization of propylene was carried out according to the method shown in Example 1, except that the time was changed. The results are shown in Table 1. Example 10 [Preparation of catalyst component [A]] 20 g of anhydrous magnesium chloride, di-maleic acid
Add 6.9 ml of butyl and silicone oil (TSS-451, 20 cs, manufactured by Shin-Etsu Chemical Co., Ltd.) as a grinding aid to a stainless steel (SUS-32) ball with a diameter of 15 mm in a nitrogen atmosphere.
The product was placed in a stainless steel (SUS-32) ball mill container with an internal volume of 800 ml and an internal diameter of 100 mm containing 2.8 kg, and was left in contact for 24 hours with an impact acceleration of 7 G. 15 g of the obtained co-pulverized material was suspended in 150 ml of titanium tetrachloride, and after contacting with stirring at 110°C for 2 hours, the solid part was collected by filtration, and free titanium tetrachloride was found in the washing liquid. The catalyst component [A] is obtained by thoroughly washing with purified hexane until it is no longer detected and then drying. The components were 2.4% by weight of titanium, 62.0% by weight of chlorine, and 20.0% by weight of magnesium in terms of atoms, and the specific surface area was 192 m 2 /g. [Propylene Polymerization] Propylene polymerization was carried out in the same manner as in Example 2. The results are shown in Table 1. Example 11 [Purification of catalyst component [A]] High-speed stirring device with internal volume 2 (manufactured by Tokushu Kika Kogyo)
After sufficiently replacing with N 2 , 700ml of refined kerosene, commercially available.
10 g of MgCl 2 , 24.2 g of ethanol, and 3 g of Emazol 20 (trade name, manufactured by Kao Atlas Co., Ltd., sorbitan distearate) were added, and the temperature of the system was raised while stirring.
The mixture was stirred at 120° C. and 800 rpm for 30 minutes. Under high speed stirring,
Using a Teflon tube with an inner diameter of 5 mm, refined kerosene 1 previously cooled to -10°C was charged and transferred to a 2-glass flask (equipped with a stirrer).
The produced solid was collected by filtration and thoroughly washed with hexane to obtain a carrier. After suspending 7.5 g of the carrier in 150 ml of titanium tetrachloride at room temperature, the temperature was raised to 120° C. with stirring. During temperature rise
At 80° C. 1.5 ml of di-n-butyl succinate was added. 120
After stirring and mixing for 2 hours at 120°C, the solid portion was collected by filtration, suspended again in 150 ml of titanium tetrachloride, and stirring and mixing was performed again at 120°C for 2 hours. Further, a reaction solid was collected from the reaction product by filtration and washed with a sufficient amount of purified hexane to obtain a solid catalyst component [A]. The component is titanium in terms of atoms.
2.0% by weight, 66.0% by weight of chlorine, and 21.0% by weight of magnesium, and its specific surface area was 240m 2 /g. [Propylene Polymerization] Propylene polymerization was carried out in the same manner as in Example 2. The results are shown in Table 1. Example 12 [Preparation of catalyst component [A]] Catalyst component [A] was prepared in the same manner as in Example 11 except that di-n-butyl succinate was changed to diiso-butyl succinate. did. The composition and specific surface area of the catalyst components are shown in Table 1. [Propylene Polymerization] Propylene polymerization was carried out in the same manner as in Example 2. The results are shown in Table 1.
【表】【table】
【表】
実施例 13，14，15，16，17，18，19
実施例１に記載の固体触媒成分〔Ａ〕を用い、
重合時に添加するトリエチルアルミニウム
0.75mmolを2.51mmolに、又ジフエニルジメトキ
シシラン0.075mmolをフエニルトリエトキシシラ
ン0.25mmol、ビニルトリメトキシシラン
0.30mmolメチルトリメトキシシラン0.45mmol、
テトラエトキシシラン0.30mmol、エチルトリエ
トキシシラン0.25mmol、ビニルトリエトキシシ
ラン0.25mmol、メチルフエニルジメトキシシラ
ン0.25mmolに更に重合時間２時間を４時間に変
えた以外は実施例１と同様にしてプロピレン重合
を行なつた。重合結果を表２に示した。[Table] Examples 13, 14, 15, 16, 17, 18, 19 Using the solid catalyst component [A] described in Example 1,
Triethylaluminum added during polymerization
0.75mmol to 2.51mmol, and 0.075mmol of diphenyldimethoxysilane to 0.25mmol of phenyltriethoxysilane, vinyltrimethoxysilane
0.30mmol methyltrimethoxysilane 0.45mmol,
Propylene polymerization was carried out in the same manner as in Example 1, except that 0.30 mmol of tetraethoxysilane, 0.25 mmol of ethyltriethoxysilane, 0.25 mmol of vinyltriethoxysilane, and 0.25 mmol of methylphenyldimethoxysilane were added, and the polymerization time was changed from 2 hours to 4 hours. I did this. The polymerization results are shown in Table 2.
【表】【table】
【表】
実施例 20，21，22
実施例１に記載の固体触媒成分〔Ａ〕を用い、
重合時添加する水素量を400ml、800ml、1600mlに
変えた以外は実施例13と同様にしてプロピレン重
合を行なつた。重合結果は表３に示した。[Table] Examples 20, 21, 22 Using the solid catalyst component [A] described in Example 1,
Propylene polymerization was carried out in the same manner as in Example 13, except that the amount of hydrogen added during polymerization was changed to 400 ml, 800 ml, and 1600 ml. The polymerization results are shown in Table 3.
【表】
比較例
特開昭55−36203号公報に記載の実施例１に従
いチタン触媒成分を調製した。このチタン触媒成
分を使用し、ジフエニルジメトキシシランをメチ
ルトリエトキシシランに代えた以外は実施例１に
示した方法に従いプロピレンの重合を行つた。重
合結果を表４に示す。[Table] Comparative Example A titanium catalyst component was prepared according to Example 1 described in JP-A-55-36203. Using this titanium catalyst component, propylene was polymerized according to the method shown in Example 1, except that diphenyldimethoxysilane was replaced with methyltriethoxysilane. The polymerization results are shown in Table 4.
図１は、本発明の方法に使用する触媒の調製工
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 catalyst used in the method of the present invention.
Claims (1)
ないマグネシウム化合物、(b)チタン化合物及び
(c)電子供与体の三成分の相互反応によつて得ら
れるチタン、マグネシウム、ハロゲン及び電子
供与体を必須成分とするチタン触媒成分であつ
て、該電子供与体が、マレイン酸及び置換マレ
イン酸よりなる群から選ばれる不飽和カルボン
酸と直鎖脂肪族アルコールとのエステル又は炭
素数２ないし５の飽和直鎖ジカルボン酸のエス
テルであるチタン触媒成分、 〔Ｂ〕 有機アルミニウム化合物触媒成分、 及び 〔Ｃ〕 Si−Ｏ−Ｃ結合を有する有機ケイ素化合
物触媒成分、 とから形成される触媒の存在下に、オレフイン
を重合もしくは共重合することを特徴とするオ
レフイン系重合体（ただし、プロピレン含有率
40ないし90モル％、結晶化度40重量％以下のプ
ロピレンと炭素数４以上のα−オレフインとの
ランダム共重合体を除く）の製造方法。[Scope of Claims] 1 [A] At least (a) a magnesium compound having substantially no reducing ability, (b) a titanium compound, and
(c) A titanium catalyst component containing titanium, magnesium, halogen, and an electron donor as essential components obtained by mutual reaction of three components of an electron donor, wherein the electron donor is maleic acid and substituted maleic acid. a titanium catalyst component which is an ester of an unsaturated carboxylic acid and a linear aliphatic alcohol selected from the group consisting of, or an ester of a saturated linear dicarboxylic acid having 2 to 5 carbon atoms; [B] an organoaluminum compound catalyst component; C] An olefin-based polymer characterized by polymerizing or copolymerizing an olefin in the presence of a catalyst formed from an organosilicon compound catalyst component having a Si-O-C bond (however, the propylene content
(excluding random copolymers of propylene with a crystallinity of 40 to 90 mol% and a crystallinity of 40% by weight or less and an α-olefin having 4 or more carbon atoms).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1968382A JPS58138708A (en) | 1982-02-12 | 1982-02-12 | Polymerization of olefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1968382A JPS58138708A (en) | 1982-02-12 | 1982-02-12 | Polymerization of olefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58138708A JPS58138708A (en) | 1983-08-17 |
| JPH0346481B2 true JPH0346481B2 (en) | 1991-07-16 |
Family
ID=12006028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1968382A Granted JPS58138708A (en) | 1982-02-12 | 1982-02-12 | Polymerization of olefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58138708A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100341040B1 (en) * | 1994-08-18 | 2002-11-23 | 칫소가부시키가이샤 | High Rigidity Propylene-Ethylene Block Copolymer Composition and Its Manufacturing Method |
| US6071846A (en) * | 1995-04-24 | 2000-06-06 | Tokuyama Corporation | Olefin polymerization catalyst and a polyolefin production method |
| JP3355864B2 (en) * | 1995-04-24 | 2002-12-09 | チッソ株式会社 | Continuous production of high-rigidity propylene / ethylene block copolymer |
| JP4970653B2 (en) * | 1998-12-25 | 2012-07-11 | 東邦チタニウム株式会社 | Solid catalyst component and catalyst for propylene polymerization |
| CN100415778C (en) | 2001-09-13 | 2008-09-03 | 巴塞尔聚烯烃意大利有限公司 | Components and catalysts for the polymerization of olefins |
| JP4031656B2 (en) | 2002-03-14 | 2008-01-09 | バセル ポリオレフィン イタリア エス．アール．エル． | Polypropylene resin composition and film thereof |
| US9562119B2 (en) * | 2010-05-25 | 2017-02-07 | W. R. Grace & Co.-Conn. | Ethylene polymerization catalysts |
| US11162050B2 (en) | 2016-12-27 | 2021-11-02 | Mitsui Chemicals, Inc. | Lubricating oil composition, viscosity modifier for lubricating oil, and additive composition for lubricating oil |
| EP4023737A4 (en) | 2019-08-29 | 2023-08-30 | Mitsui Chemicals, Inc. | Lubricating oil composition |
| WO2023171433A1 (en) * | 2022-03-11 | 2023-09-14 | 東邦チタニウム株式会社 | Solid catalyst ingredient for olefin polymerization, method for producing solid catalyst ingredient for olefin polymerization, catalyst for olefin polymerization, method for producing olefin polymer, and olefin polymer |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52151691A (en) * | 1975-11-21 | 1977-12-16 | Montedison Spa | #-olefin polymerization catalyst |
| JPS53104687A (en) * | 1977-02-25 | 1978-09-12 | Mitsui Petrochem Ind Ltd | Preparation of propylene-ethylene elastic copolymer |
| JPS5536203A (en) * | 1978-09-05 | 1980-03-13 | Asahi Chem Ind Co Ltd | Catalyst for polymerization of olefin |
| JPS58138720A (en) * | 1982-02-12 | 1983-08-17 | Mitsui Petrochem Ind Ltd | Preparation of propylene random copolymer |
-
1982
- 1982-02-12 JP JP1968382A patent/JPS58138708A/en active Granted
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52151691A (en) * | 1975-11-21 | 1977-12-16 | Montedison Spa | #-olefin polymerization catalyst |
| JPS53104687A (en) * | 1977-02-25 | 1978-09-12 | Mitsui Petrochem Ind Ltd | Preparation of propylene-ethylene elastic copolymer |
| JPS5536203A (en) * | 1978-09-05 | 1980-03-13 | Asahi Chem Ind Co Ltd | Catalyst for polymerization of olefin |
| JPS58138720A (en) * | 1982-02-12 | 1983-08-17 | Mitsui Petrochem Ind Ltd | Preparation of propylene random copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58138708A (en) | 1983-08-17 |
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