JPS6352657B2 - - Google Patents
Info
- Publication number
- JPS6352657B2 JPS6352657B2 JP11060379A JP11060379A JPS6352657B2 JP S6352657 B2 JPS6352657 B2 JP S6352657B2 JP 11060379 A JP11060379 A JP 11060379A JP 11060379 A JP11060379 A JP 11060379A JP S6352657 B2 JPS6352657 B2 JP S6352657B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- solid product
- compound
- group
- ethylene
- 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
- 238000006116 polymerization reaction Methods 0.000 claims description 96
- 239000012265 solid product Substances 0.000 claims description 68
- -1 polyethylene Polymers 0.000 claims description 56
- 150000003623 transition metal compounds Chemical class 0.000 claims description 46
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 36
- 239000005977 Ethylene Substances 0.000 claims description 36
- 229920000642 polymer Polymers 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 29
- 239000001257 hydrogen Substances 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 23
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- 239000004698 Polyethylene Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 229920000573 polyethylene Polymers 0.000 claims description 17
- 150000003609 titanium compounds Chemical class 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 150000002367 halogens Chemical class 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 6
- 125000005287 vanadyl group Chemical group 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 150000002681 magnesium compounds Chemical class 0.000 claims 1
- 150000002899 organoaluminium compounds Chemical class 0.000 claims 1
- 150000002902 organometallic compounds Chemical class 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 13
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
- 150000002430 hydrocarbons Chemical group 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- 150000002736 metal compounds Chemical class 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 150000005309 metal halides Chemical class 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 150000003624 transition metals Chemical group 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 description 2
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010101 extrusion blow moulding Methods 0.000 description 2
- 150000004665 fatty acids Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 2
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 2
- 239000003643 water by type Chemical class 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- XOCOMEGNVMCRMP-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octaethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound CC[Si]1(CC)O[Si](CC)(CC)O[Si](CC)(CC)O[Si](CC)(CC)O1 XOCOMEGNVMCRMP-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- UADWUILHKRXHMM-UHFFFAOYSA-N 2-ethylhexyl benzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1 UADWUILHKRXHMM-UHFFFAOYSA-N 0.000 description 1
- 229940106004 2-ethylhexyl benzoate Drugs 0.000 description 1
- YBFYRBILSHBEHV-UHFFFAOYSA-N 2-ethylhexyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OCC(CC)CCCC)=CC=CC2=C1 YBFYRBILSHBEHV-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
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 1
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 1
- RASBDVLERRNNLJ-UHFFFAOYSA-N CCCCO[Ti] Chemical compound CCCCO[Ti] RASBDVLERRNNLJ-UHFFFAOYSA-N 0.000 description 1
- MQVPFHBBKRCBOJ-UHFFFAOYSA-N ClCCCCO[Ti] Chemical compound ClCCCCO[Ti] MQVPFHBBKRCBOJ-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- 101000687448 Homo sapiens REST corepressor 1 Proteins 0.000 description 1
- 229910021025 KMgCl3 Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- 102100024864 REST corepressor 1 Human genes 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ZQUQNMGBBXTGEW-UHFFFAOYSA-N [dimethyl-[methyl(diphenyl)silyl]oxysilyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C=1C=CC=CC=1[Si](C)(O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C)C1=CC=CC=C1 ZQUQNMGBBXTGEW-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005376 alkyl siloxane group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 229940071248 anisate Drugs 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- UADWUILHKRXHMM-ZDUSSCGKSA-N benzoflex 181 Natural products CCCC[C@H](CC)COC(=O)C1=CC=CC=C1 UADWUILHKRXHMM-ZDUSSCGKSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- LGSNSXWSNMARLH-UHFFFAOYSA-N butan-1-ol titanium Chemical compound C(CCC)O.[Ti].C(CCC)O LGSNSXWSNMARLH-UHFFFAOYSA-N 0.000 description 1
- APKYUQFPWXLNFH-UHFFFAOYSA-M butan-1-olate titanium(4+) chloride Chemical compound [Cl-].CCCCO[Ti+](OCCCC)OCCCC APKYUQFPWXLNFH-UHFFFAOYSA-M 0.000 description 1
- VJVUKRSEEMNRCM-UHFFFAOYSA-L butan-1-olate titanium(4+) dichloride Chemical compound [Cl-].[Cl-].CCCCO[Ti+2]OCCCC VJVUKRSEEMNRCM-UHFFFAOYSA-L 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YCURFOQQPNHZAO-UHFFFAOYSA-N butyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OCCCC)=CC=CC2=C1 YCURFOQQPNHZAO-UHFFFAOYSA-N 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical class O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- IFMWVBVPVXRZHE-UHFFFAOYSA-M chlorotitanium(3+);propan-2-olate Chemical compound [Cl-].[Ti+4].CC(C)[O-].CC(C)[O-].CC(C)[O-] IFMWVBVPVXRZHE-UHFFFAOYSA-M 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- RMTCVMQBBYEAPC-UHFFFAOYSA-K ethanolate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CCO[Ti+3] RMTCVMQBBYEAPC-UHFFFAOYSA-K 0.000 description 1
- DKQVJMREABFYNT-UHFFFAOYSA-N ethene Chemical group C=C.C=C DKQVJMREABFYNT-UHFFFAOYSA-N 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- HQKSINSCHCDMLS-UHFFFAOYSA-N ethyl naphthalene-2-carboxylate Chemical compound C1=CC=CC2=CC(C(=O)OCC)=CC=C21 HQKSINSCHCDMLS-UHFFFAOYSA-N 0.000 description 1
- MGDOJPNDRJNJBK-UHFFFAOYSA-N ethylaluminum Chemical compound [Al].C[CH2] MGDOJPNDRJNJBK-UHFFFAOYSA-N 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- HMRROBKAACRWBP-UHFFFAOYSA-N methyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OC)=CC=CC2=C1 HMRROBKAACRWBP-UHFFFAOYSA-N 0.000 description 1
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-anisate Chemical compound COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- VECVSKFWRQYTAL-UHFFFAOYSA-N octyl benzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1 VECVSKFWRQYTAL-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N para-methoxy benzoic acid Natural products COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- RLOWWWKZYUNIDI-UHFFFAOYSA-N phosphinic chloride Chemical compound ClP=O RLOWWWKZYUNIDI-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- JTQPTNQXCUMDRK-UHFFFAOYSA-N propan-2-olate;titanium(2+) Chemical compound CC(C)O[Ti]OC(C)C JTQPTNQXCUMDRK-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- DVFZYEJUWGWKLC-UHFFFAOYSA-N propyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OCCC)=CC=CC2=C1 DVFZYEJUWGWKLC-UHFFFAOYSA-N 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Description
【発明の詳細な説明】
本発明は、複数個の重合器を使い、第１段重合
系で高分子側重合体を、第２段重合系で低分子側
重合体をつくるポリエチレンの連続多段重合によ
る製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention is a process for producing polyethylene by continuous multi-stage polymerization using a plurality of polymerization vessels, producing a high-molecular-weight polymer in the first stage polymerization system and producing a low-molecular-weight polymer in the second stage polymerization system. It is about the method.
本発明におけるポリエチレンとは、エチレンの
単独重合体の他に、エチレンと共重合しうる他の
少量のα―オレフイン、たとえば、プロピレン、
ブテン―１、ヘキセン―１、４―メチル―ペンテ
ン―１あるいはブタンジエン、ジシクロペンタジ
エンなどのジエン類との共重合体をも含むもので
ある。 In the present invention, polyethylene refers to ethylene homopolymers as well as other small amounts of α-olefins that can be copolymerized with ethylene, such as propylene,
It also includes copolymers with dienes such as butene-1, hexene-1, 4-methyl-pentene-1, butane diene, and dicyclopentadiene.
ポリエチレンの主要な用途である押出成形や中
空成形の分野では、高分子量（低メルトインデツ
クス）で、適切な強度を持ち、加工しやすいポリ
エチレンが要求されている。低メルトインデツク
スのポリエチレンは、強度はすぐれるが、成形時
流動性が劣るという欠点を有している。この問題
を解決する手段として、分子量分布を拡大する方
法がとられている。分子量分布の狭いポリエチレ
ンは、射出成形に適しているが、一方押出成形や
中空成形に使用されるポリエチレンとしては、分
子量分布の広いことが望ましい。分子量分布の狭
い重合体を中空成形した場合には、成形時の押出
圧力が過上昇し、成形不能になつたり、スジ、ア
バタの発生、メルトフラクチヤの発生などによ
り、製品の外観が著しく損われる。押出成形の場
合には、押出圧力の過上昇、成形の不安定性の増
大などにより、致命的な悪影響を受け、商品価値
を著しく低下させる。これらの諸問題を解決する
ために、重合体の分子量分布を広げることによ
り、加工上の生産性が向上し、外観のすぐれた製
品が得られる。 In the fields of extrusion molding and blow molding, which are the main uses of polyethylene, polyethylene is required to have a high molecular weight (low melt index), appropriate strength, and easy processing. Polyethylene with a low melt index has excellent strength, but has the disadvantage of poor fluidity during molding. As a means to solve this problem, a method of expanding the molecular weight distribution has been adopted. Polyethylene with a narrow molecular weight distribution is suitable for injection molding, but it is desirable for polyethylene used in extrusion molding or blow molding to have a wide molecular weight distribution. When a polymer with a narrow molecular weight distribution is blow-molded, the extrusion pressure during molding increases excessively, making molding impossible, and the appearance of the product is significantly impaired due to the occurrence of streaks, avatars, and melt fractures. In the case of extrusion molding, an excessive increase in extrusion pressure, increased molding instability, etc. can have fatal adverse effects, significantly reducing commercial value. In order to solve these problems, by broadening the molecular weight distribution of the polymer, processing productivity can be improved and products with excellent appearance can be obtained.
分子量分布を拡大する方法として、重合系への
第３成分の添加、触媒の一成分である有機アルミ
ニウム化合物の２種類の化合物の混合使用、多様
な重合活性点をもつ触媒の使用などが知られてい
るが、分子量分布の充分に広い重合体を製造する
ことは必ずしも容易ではない。それに対して、分
子量分布巾を大巾に、しかも任意に調節する手段
としては多段重合法が知られているがその方法に
満足すべきものがない。 Known methods for expanding the molecular weight distribution include adding a third component to the polymerization system, using a mixture of two types of organoaluminum compounds that are one component of the catalyst, and using catalysts with various polymerization active sites. However, it is not always easy to produce a polymer with a sufficiently wide molecular weight distribution. On the other hand, a multi-stage polymerization method is known as a means for arbitrarily adjusting the molecular weight distribution width over a wide range, but this method is not satisfactory.
従来、前段で高分子側、後段で低分子側をつく
る多段重合による製造法として、特公昭46−
11349号、特開昭54−7488号、特公昭54−32588号
が、知られている。特公昭46−11349号では、担
体に担持することを必要としない３価のチタン化
合物と有機アルミニウム化合物の組合せによる触
媒を用いて、不活性溶媒中、圧力10Kg／cm2（ゲー
ジ圧）以下で重合する方法が示されている。該方
法は、担持を必要としない３価のチタン化合物を
使う点で触媒が限定されている上に、開示された
実施態様は、重合圧力が６Kg／cm2（ゲージ圧）以
下である。このような低い重合圧力では重合体の
生産性が著しく低く、しかも該方法は非連続的な
製造法であり、工業的に有利な連続重合法につい
ては何ら具体的に記載されていない。特開昭54−
7488では、担持型触媒を用いて、第１段重合を液
充満の状態で行なわせることを開示しているがこ
の方法は生成する重合体の分子量を調節すること
が極めてむずかしい。特開昭54−32588では、第
１段重合器に強制的に不活性ガスを供給して全圧
を高め、第１段重合で高分子側重合体を、第２段
重合で低分子側重合体をつくることを開示してい
るが、供給された多量の不活性ガスが、消費また
は取除かれないまま第２段重合系に流入し、充分
に低分子の重合体をつくるのがむずかしいという
欠点を有している。 Conventionally, a production method using multi-stage polymerization, in which the high molecular side is produced in the first stage and the low molecular side is produced in the latter stage, was developed in the 1970s.
No. 11349, Japanese Patent Publication No. 54-7488, and Japanese Patent Publication No. 54-32588 are known. In Japanese Patent Publication No. 46-11349, a catalyst consisting of a combination of a trivalent titanium compound and an organoaluminum compound, which does not need to be supported on a carrier, is used in an inert solvent at a pressure of 10 kg/cm 2 (gauge pressure) or less. A method of polymerizing is shown. This method is limited in terms of catalysts in that it uses trivalent titanium compounds that do not require support, and in the disclosed embodiments, the polymerization pressure is 6 kg/cm 2 (gauge pressure) or less. At such a low polymerization pressure, the productivity of the polymer is extremely low, and the method is a discontinuous production method, and there is no specific description of an industrially advantageous continuous polymerization method. Japanese Unexamined Patent Publication 1973-
No. 7488 discloses carrying out the first stage polymerization in a liquid-filled state using a supported catalyst, but this method makes it extremely difficult to control the molecular weight of the resulting polymer. In JP-A-54-32588, an inert gas is forcibly supplied to the first stage polymerization vessel to increase the total pressure, and the high molecular side polymer is produced in the first stage polymerization, and the low molecular side polymer is produced in the second stage polymerization. However, a large amount of the supplied inert gas flows into the second stage polymerization system without being consumed or removed, making it difficult to produce a sufficiently low molecular weight polymer. have.
本発明者らは、従来、３価金属ハロゲン化物と
２価金属の水酸化物、酸化物、炭酸化物、これら
を含む複塩、または２価金属化合物の水和物との
反応生成物（以下固体生成物（）ということが
ある）を担体とする触媒成分を研究してきた。ま
た、固体生成物（）と電子供与体化合物と遷移
金属化合物から調製した固体生成物（）はそれ
自体固体触媒成分として有機アルミニウム化合物
と組合せて、本発明者らにα―オレフイン重合触
媒に用いられている。（特願昭53−21246、同53−
21247）本発明者らは、上記触媒が多段重合に効
果あることを発見し、また、固体生成物（）
に、さらに特定の反応をさせると種々の効果があ
ることを見出し、さらに連続多段重合法の改良の
研究を重ねた結果、本発明に到達した。すなわ
ち、本発明は、第１段重合系で高分子側重合体
を、第２段重合系で低分子側重合体をつくるポリ
エチレンの連続多段重合法において、前記した従
来法の問題点を解決し分子量分布の広いポリエチ
レンを得ることを目的とするものである。 The present inventors have conventionally developed reaction products (hereinafter referred to as We have been researching catalyst components that use solid products (sometimes referred to as ) as supports. In addition, the solid product () prepared from the electron donor compound and the transition metal compound was itself used as a solid catalyst component in combination with an organoaluminum compound and used by the present inventors in an α-olefin polymerization catalyst. It is being (Patent application No. 53-21246, No. 53-
21247) The present inventors have discovered that the above catalyst is effective in multi-stage polymerization, and also produces a solid product ()
Furthermore, they discovered that various effects can be obtained by carrying out specific reactions, and as a result of further research into improving the continuous multi-stage polymerization method, they arrived at the present invention. That is, the present invention solves the problems of the conventional method described above in a continuous multi-stage polyethylene polymerization method in which a high-molecular-weight polymer is produced in the first stage polymerization system and a low-molecular-weight polymer is produced in the second stage polymerization system. The purpose is to obtain a wide range of polyethylene.
本発明のポリエチレンの連続多段重合による製
造方法は、
３価金属ハロゲン化物と２価金属の水酸化
物、酸化物、炭酸化物、これらを含む複塩、ま
たは２価金属化合物の水和物とを反応させて得
られる固体生成物（）と、電子供与体化合物
と、周期表ａ族またはａ族の遷移金属化合
物とから調製した固体生成物（）に、さら
に、（Ａ群）ハロゲンを含有したａ族または
Va族の遷移金属化合物（以下ハロゲン含有遷
移金属化合物という）および（Ｂ群）ハロゲン
を含有しないａ族またはVa族の遷移金属化
合物（以下ハロゲン非含有遷移金属化合物とい
う）のそれぞれの群より少なくとも１種ばれた
少なくとも２種の遷移金属化合物を反応させて
得られる最終の固体生成物（）と有機アルミ
ニウム化合物とを組合せて得られる触媒の存在
下飽和炭化水素溶媒中、重合器の上部に気相が
存在する状態において、重合温度30℃以上100
℃以下、重合圧力11ないし70Kg／cm2の条件下
で、重合器気相部のエチレン対水素のモル比が
１対0.001ないし0.5になるように水素供給する
と共に、全エチレン供給量の10ないし70％のエ
チレンを供給して第１段重合を行ない。 The method for producing polyethylene by continuous multi-stage polymerization of the present invention involves combining a trivalent metal halide and a divalent metal hydroxide, oxide, carbonate, a double salt containing these, or a hydrate of a divalent metal compound. A solid product () prepared from the solid product () obtained by the reaction, an electron donor compound, and a transition metal compound of Group A or Group A of the periodic table further contains (Group A) halogen. a group or
At least one member from each group of Group Va transition metal compounds (hereinafter referred to as halogen-containing transition metal compounds) and (group B) halogen-free Group A or Group Va transition metal compounds (hereinafter referred to as halogen-free transition metal compounds). A gas phase is added to the upper part of the polymerization vessel in a saturated hydrocarbon solvent in the presence of a catalyst obtained by combining the final solid product () obtained by reacting at least two seeded transition metal compounds with an organoaluminum compound. In the presence of
℃ or less and a polymerization pressure of 11 to 70 kg/cm 2 , hydrogen is supplied so that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization vessel is 1 to 0.001 to 0.5, and 10 to 10% of the total ethylene supply amount is The first stage polymerization was carried out by supplying 70% ethylene.
続いて、溶媒に懸濁した重合物を第２段重合
系に移送し、飽和炭化水素溶媒中、重合器の部
分に気相が存在する状態において、重合温度50
℃以上120℃以下、重合圧力11ないし70Kg／cm2
の条件下で、重合器気相部のエチレン対水素の
モル比が１対0.1ないし3.0になるように水素を
供給すると共に、全エチレン供給量の30ないし
90％のエチレンを供給して第２段重合を行なう
こと、
を特徴とする。また、必要に応じてα―オレフイ
ンを第１段および／または第２段重合系に供給し
エチレンとα―オレフインとの共重合体を製造す
ることができる。その場合、エチレンとα―オレ
フインのモル数の総和と水素のモル比が上記第１
段および／または第２段のモル比となればよい。 Subsequently, the polymer suspended in the solvent is transferred to the second stage polymerization system, and the polymerization temperature is increased to 50°C in a saturated hydrocarbon solvent with a gas phase present in the polymerization vessel.
℃ or more and 120℃ or less, polymerization pressure 11 to 70Kg/cm 2
Under these conditions, hydrogen is supplied so that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization reactor is 1:0.1 to 3.0, and 30 to 30% of the total ethylene supply amount is
The second stage polymerization is carried out by supplying 90% ethylene. Further, if necessary, α-olefin can be supplied to the first and/or second stage polymerization system to produce a copolymer of ethylene and α-olefin. In that case, the sum of the moles of ethylene and α-olefin and the molar ratio of hydrogen are
The molar ratio of the stage and/or the second stage may be satisfied.
本発明の製造法は、触媒を第１段重合系に供給
することにより重合を開始するが、飽和炭化水素
溶媒中、重合器上部に気相が存在する状態におい
て、重合温度30℃以上100℃以下、好ましくは40
〜90℃、重合圧力11ないし70Kg／cm2好ましくは15
〜50Kg／cm2の条件下で第１段重合を行なう。生成
する重合体の分子量は、重合器の気相部のエチレ
ン対水素のモルを供給することによつて調節され
る。重合体の生成量は全エチレン供給量の10ない
し70％のエチレン供給で調節される。つづいて、
第１段重合系で得られる溶媒に懸濁した重合物は
そのまま、第２段重合系に移送するが、必要に応
じて水素、などの成分を分離して後移送してもよ
い。移送の方法は移送ポンプなどの強制移送手段
によつて行なう。第２段重合系は新たに設定した
重合条件下、すなわち重合温度50℃以上120℃以
下好ましくは70℃〜1000℃、重合圧力11ないし70
Kg／cm2好ましくは15〜50Kg／cm2、重合器上部に気
相部が存在する状態で重合を行なう。生成する重
合体の分子量は、気相部のエチレン対水素のモル
比が１対0.1ないし3.0の範囲内に入るように、エ
チレンおよび水素を供給することによつて調節
し、重合体の生成量は全エチレン供給量の30〜90
％のエチレン供給で調節する。通常、第２段の分
子量は溶媒に溶解した水素のみで行なうが、新た
に供給することも可能である。 In the production method of the present invention, polymerization is started by supplying a catalyst to the first stage polymerization system, and the polymerization temperature is 30°C or more and 100°C in a saturated hydrocarbon solvent and in a state where a gas phase exists at the top of the polymerization vessel. Less than or equal to 40, preferably 40
~90℃, polymerization pressure 11 to 70Kg/ cm2 preferably 15
The first stage polymerization is carried out under conditions of ~50 Kg/cm 2 . The molecular weight of the polymer produced is controlled by feeding the moles of ethylene to hydrogen in the gas phase of the polymerizer. The amount of polymer produced is regulated with an ethylene feed of 10 to 70% of the total ethylene feed. Continuing,
The polymer suspended in the solvent obtained in the first stage polymerization system is transferred as it is to the second stage polymerization system, but if necessary, components such as hydrogen may be separated and then transferred. The transfer method is performed by forced transfer means such as a transfer pump. The second stage polymerization system is carried out under newly set polymerization conditions, namely, a polymerization temperature of 50°C to 120°C, preferably 70°C to 1000°C, and a polymerization pressure of 11 to 70°C.
Kg/cm 2 , preferably 15 to 50 Kg/cm 2 , and polymerization is carried out in a state where a gas phase exists in the upper part of the polymerization vessel. The molecular weight of the polymer produced is adjusted by supplying ethylene and hydrogen so that the molar ratio of ethylene to hydrogen in the gas phase is within the range of 1:0.1 to 3.0, and the amount of polymer produced is adjusted by supplying ethylene and hydrogen. is 30-90% of the total ethylene supply
Adjust with % ethylene supply. Usually, the second stage molecular weighting is carried out using only hydrogen dissolved in a solvent, but it is also possible to supply fresh hydrogen.
本発明の製造方法における触媒の供給は、通常
第１段重合系にのみなされるが、必要に応じて第
２段重合系にすることも可能である。 In the production method of the present invention, the catalyst is usually supplied only to the first stage polymerization system, but it can also be supplied to the second stage polymerization system if necessary.
本発明の多段連続重合は、通常複数個の重合器
を直列に連結するがある複数個の重合器を並列
（または一部を並列）に連結して第１段および／
または第２段重合系とすることも可能である。 In the multi-stage continuous polymerization of the present invention, a plurality of polymerization vessels are usually connected in series, but a plurality of polymerization vessels are connected in parallel (or some of them are parallel) to form the first stage and/or
Alternatively, it is also possible to use a second stage polymerization system.
本発明の製造法の重合に使用する溶媒として
は、炭素原子４〜15個から成る飽和炭化水素、た
とえば、ブタン、ペンタン、ヘキサン、ヘプタ
ン、オクタン、灯油などが用いられる。 The solvent used in the polymerization process of the present invention is a saturated hydrocarbon having 4 to 15 carbon atoms, such as butane, pentane, hexane, heptane, octane, kerosene, and the like.
本発明の製造方法に用いる触媒は、固体生成物
（）に、電子供与体化合物の存在下で、周期表
ａ族またはａ族の遷移金属化合物を反応させ
て得られた固体生成物（）に、さらに、（Ａ群）
ハロゲン含有遷移金属化合物および（Ｂ群）ハロ
ゲン非含有遷移金属化合物のそれぞれの群より少
なくとも１種選ばれた２種以上の遷移金属化合物
を反応させて得られた固体生成物（）と有機ア
ルミニウム化合物とを組合せることにより得られ
る。 The catalyst used in the production method of the present invention is a solid product () obtained by reacting a transition metal compound of Group A or Group A of the periodic table with a solid product () in the presence of an electron donor compound. , furthermore, (group A)
A solid product obtained by reacting two or more transition metal compounds selected from each of the halogen-containing transition metal compounds and (Group B) halogen-free transition metal compounds and an organoaluminum compound. It can be obtained by combining.
固体生成物（）は、３価金属ハロゲン化物と
２価金属の水酸化物、酸化物、炭酸化物、これら
含む複塩、または２価金属化合物の水和物（これ
らを２価金属化合物と総称）とを反応させて得ら
れる。この反応をさせるためにあらかじめボール
ミルで５〜100時間、振動ミルでは１〜10時間混
合、粉砕を行ない、十分混合された状態にするこ
とが望ましい。３価金属ハロゲン化物と２価金属
化合物の混合割合は、３価金属に対する２価金属
の原子比によつて示すと、通常0.1〜20で十分で
あり、好ましくは１〜10の範囲である。反応温度
は通常、20〜500℃、好ましくは50〜300℃であ
る。反応時間は30分〜50時間が適し、反応温度が
低い場合は、長時間反応させ、未反応の３価金属
が残らないように、反応を行なわせる。 The solid products () are trivalent metal halides, divalent metal hydroxides, oxides, carbonates, double salts containing these, or hydrates of divalent metal compounds (these are collectively referred to as divalent metal compounds). ) is obtained by reacting with In order to carry out this reaction, it is desirable to mix and pulverize in advance for 5 to 100 hours in a ball mill or 1 to 10 hours in a vibration mill to obtain a sufficiently mixed state. The mixing ratio of the trivalent metal halide and the divalent metal compound, expressed as the atomic ratio of the divalent metal to the trivalent metal, is usually in the range of 0.1 to 20, preferably in the range of 1 to 10. The reaction temperature is usually 20-500°C, preferably 50-300°C. A suitable reaction time is 30 minutes to 50 hours, and if the reaction temperature is low, the reaction is allowed to proceed for a long time so that no unreacted trivalent metal remains.
固体生成物（）の具体的な調製方法として
は、つぎのような態様をとることができる。 As a specific method for preparing the solid product (2), the following embodiments can be adopted.
(1) 固体生成物（）と電子供与体化合物と遷移
金属化合物とを同時に混合し、反応させる。(1) Simultaneously mix and react the solid product () with an electron donor compound and a transition metal compound.
(2) 固体生成物（）と電子供与体化合物とを混
合し、つぎに遷移金属化合物を添加した後、反
応させる。(2) Mix the solid product () and the electron donor compound, then add the transition metal compound and then react.
(3) 固体生成物（）と遷移金属化合物を混合
し、つぎに電子供与体化合物を添加した後、反
応させる。(3) Mix the solid product () and the transition metal compound, then add the electron donor compound and react.
(4) 電子供与体化合物と遷移金属化合物とを混合
し、つぎにこの混合物に固体生成物（）を混
合して反応させる。(4) An electron donor compound and a transition metal compound are mixed, and then a solid product () is mixed into this mixture and reacted.
いずれの方法も、溶媒存在下または不存在下に
おいて行うことができる。反応終了後は常法によ
り別し、溶媒で洗浄を繰返し、未反応遷移金属
化合物および電子供与体化合物を除去し乾燥して
固体生成物（）を得る。 Either method can be performed in the presence or absence of a solvent. After the reaction is completed, the mixture is separated by a conventional method, washed repeatedly with a solvent to remove unreacted transition metal compounds and electron donor compounds, and dried to obtain a solid product (2).
固体生成物（）の調製における固体生成物
（）、電子供与体化合物および遷移金属化合物の
混合割合は、固体生成物（）100ｇに対し、電
子供与体化合物は10〜10000ｇ、好ましくは20〜
5000ｇ、遷移金属化合物は１〜1000ｇ、好ましく
は10〜500ｇであつて、かつ、電子供与体化合物
100ｇに対し、遷移金属化合物２〜2000ｇ、好ま
しくは５〜500ｇである。混合は撹拌しながら行
なうのが好ましく、その温度は−50℃〜＋30℃が
適当であるが、最も普通には室温（約20℃）であ
る。混合後は撹拌しながら30〜300℃、好ましく
は50〜200℃で10分〜30時間反応させる。 The mixing ratio of the solid product (), electron donor compound and transition metal compound in the preparation of the solid product () is 10 to 10,000 g, preferably 20 to 10000 g of the electron donor compound per 100 g of the solid product ().
5000g, the transition metal compound is 1 to 1000g, preferably 10 to 500g, and the electron donor compound is
The transition metal compound is used in an amount of 2 to 2000 g, preferably 5 to 500 g, per 100 g. Mixing is preferably carried out with stirring, and the temperature is suitably between -50°C and +30°C, but most commonly at room temperature (about 20°C). After mixing, the mixture is reacted at 30 to 300°C, preferably 50 to 200°C, for 10 minutes to 30 hours while stirring.
電子供与体化合物と遷移金属化合物とを混合
し、つぎにこの混合物に固体生成物（）を混合
して反応させる場合は、電子供与体化合物と遷移
金属化合物との混合物は、固体生成物（）を混
合する前に、あらかじめ室温（約20℃）以上100
℃以下、好ましくは60℃以下の温度に、１分間〜
５時間経過させておいてもよい。 When an electron donor compound and a transition metal compound are mixed and then a solid product () is mixed with this mixture and reacted, the mixture of the electron donor compound and a transition metal compound is a solid product (). Before mixing, warm the mixture to room temperature (approximately 20℃) or above 100℃.
℃ or less, preferably 60℃ or less for 1 minute to
You may leave it for 5 hours.
固体生成物（）は、固体生成物（）に、
（Ａ群）ａ族またはａ族のハロゲン含有遷移
金属化合物、および（Ｂ群）ａ族またはａ族
のハロゲン非含有遷移金属化合物のそれぞれの群
から少なくとも１種選定された少なくとも合計２
種の遷移金属化合物を反応させて得られる。（Ａ
群）より少なくとも１種、（Ｂ群）より少なくと
も１種の遷移金属化合物を選んで用いれば良く、
従つて同一の群から２種以上の遷移金属化合物を
選んで他の群から選んだものと共に用いることも
本発明の範囲に包含される。 Solid product () is converted into solid product (),
(Group A) a group a or a halogen-containing transition metal compound; and (group B) a group a or a group a halogen-free transition metal compound.
It is obtained by reacting various transition metal compounds. (A
At least one transition metal compound from group B) and at least one transition metal compound from group B may be selected and used.
Therefore, it is also within the scope of the present invention to select two or more transition metal compounds from the same group and use them together with compounds selected from other groups.
固体生成物（）と（Ａ群）、（Ｂ群）のそれぞ
れから選ばれた遷移金属化合物〔以下これらをそ
れぞれ（Ａ群）遷移金属化合物、（Ｂ群）遷移金
属化合物ということがあり、一つの群より２種以
上の遷移金属化合物が選ばれるときはそのすべて
を包含する〕を反応させる具体的な方法として
は、
(1) （Ａ群）遷移金属化合物と（Ｂ群）遷移金属
化合物の混合物に、固体生成物（）を加えて
加熱する。 The solid product () and a transition metal compound selected from each of (Group A) and (Group B) [hereinafter these may be referred to as (Group A) transition metal compound and (Group B) transition metal compound, respectively; (1) (Group A) transition metal compound and (Group B) transition metal compound Add the solid product () to the mixture and heat.
(2) 固体生成物（）に（Ａ群）遷移金属化合物
を混合した後、（Ｂ群）遷移金属化合物を加え
て加熱する。(2) After mixing the transition metal compound (group A) with the solid product (), the transition metal compound (group B) is added and heated.
(3) 固体生成物（）に（Ａ群）遷移金属化合物
を加熱反応させ、引続いて（Ｂ群）遷移金属化
合物を加え加熱する。(3) A transition metal compound (group A) is heated to react with the solid product (), and then a transition metal compound (group B) is added and heated.
などの諸方法をあげることができる。いずれの反
応方法も、溶媒を存在させても、させなくても行
なうことができる。上記反応の終了後は常法によ
り別し、脂肪族炭化水素、芳香族炭化水素等の
溶媒で常温または好ましくは60℃以上にて洗浄し
て未反応の遷移金属化合物を除去し、乾燥して、
固体生成物（）を得る。There are various methods such as. Both reaction methods can be carried out with or without the presence of a solvent. After the above reaction is completed, it is separated by a conventional method, washed with a solvent such as an aliphatic hydrocarbon or an aromatic hydrocarbon at room temperature or preferably at 60°C or higher to remove unreacted transition metal compounds, and dried. ,
A solid product () is obtained.
（Ａ群）（Ｂ群）各遷移金属化合物の使用量
（一つの群より２種以上使用する場合はその合計
量）の割合は、（Ａ群）遷移金属化合物に含有さ
れる遷移金属原子数の（Ｂ群）遷移金属化合物の
それに対する比（以下単に遷移金属原子比と云
う）として10／１〜１／10、好ましくは５／１〜
１／５である。固体生成物（）と遷移金属化合
物の総重量の割合は、固体生成物（）100ｇに
対して、１〜1000ｇで十分である。反応温度は30
〜500℃、好ましくは50〜300℃であり、反応時間
は10分〜５〜50時間、好ましくは30分〜10時間で
ある。溶媒を使用する場合は、固体生成物（）
100ｇに対し、０〜1000mlで十分である。かくし
て、固体生成物（）に遷移金属化合物が担持さ
れる。 (Group A) (Group B) The ratio of the usage amount of each transition metal compound (if two or more types from one group are used, the total amount) is the number of transition metal atoms contained in the (Group A) transition metal compound. The ratio of (group B) transition metal compound to that (hereinafter simply referred to as transition metal atomic ratio) is 10/1 to 1/10, preferably 5/1 to
It is 1/5. It is sufficient that the ratio of the total weight of the solid product () to the transition metal compound is 1 to 1000 g per 100 g of the solid product (). The reaction temperature is 30
The temperature is 500°C to 300°C, and the reaction time is 10 minutes to 5 to 50 hours, preferably 30 minutes to 10 hours. If a solvent is used, the solid product ()
0 to 1000 ml is sufficient for 100 g. The transition metal compound is thus supported on the solid product ().
本発明の触媒は、上記方法で得られた固体生成
物（）と有機アルミニウム化合物とを組合せる
ことによつて得られる。 The catalyst of the present invention is obtained by combining the solid product () obtained by the above method with an organoaluminum compound.
３価金属ハロゲン化物てとしては、三塩化アル
ミニウム（無水）、三塩化鉄（無水）が示される。
２価金属の水酸化物としては、たとえば、Mg
（OH）2、Ca（OH）2、Zn（OH）2、Mn（OH）2のよ
うな水酸化物、MgO、CaO、ZnO、MnOのよう
な酸化物、MgAl2O4、Mg2SlO4、Mg6MnO8のよ
うな２価金属を含む複酸化物、MgCO3、
MnCO3、CaCO3、のような炭酸化物、SnCl2・
2H2O、MgCl2・6H2O、NlCl2・6H2O、
MnCl2・4H2O、KMgCl3・6H2Oのようなハロゲ
ン化物水和物、8MgO・MgCl2・15H2Oのような
酸化物とハロゲン化物を含む複塩の水和物、
3MgO・2SlO2・2H2Oのような２価金属の酸化物
を含む複塩の水和物、3MgCO3・Mg（OH）2・
3H2Oのような炭酸化物と水酸化物の複塩の水和
物、および、Mg6Al2（OH）16CO3・4H2Oのよう
な２価金属を含む水酸化炭酸化物の水和物などが
あげられる。 Examples of trivalent metal halides include aluminum trichloride (anhydrous) and iron trichloride (anhydrous).
Examples of divalent metal hydroxides include Mg
Hydroxides like (OH) 2 , Ca(OH) 2 , Zn(OH) 2 , Mn(OH) 2 , oxides like MgO, CaO, ZnO, MnO , MgAl2O4 , Mg2SlO 4 , complex oxides containing divalent metals such as Mg6MnO8 , MgCO3 ,
Carbonates such as MnCO 3 , CaCO 3 , SnCl 2 .
2H2O , MgCl2・6H2O , NlCl2・6H2O ,
Halide hydrates such as MnCl2・4H2O , KMgCl3・6H2O , hydrates of double salts containing oxides and halides such as 8MgO・MgCl2・15H2O ,
Hydrates of double salts containing divalent metal oxides such as 3MgO・2SlO 2・2H 2 O, 3MgCO 3・Mg(OH) 2・
Hydrates of double salts of carbonates and hydroxides such as 3H 2 O, and waters of hydroxide carbonates containing divalent metals such as Mg 6 Al 2 (OH) 16 CO 3 4H 2 O Examples include Japanese food.
電子供与体化合物としては、エーテル（Ｒ―Ｏ
―R′） エステル（RCO2R′）、アルデヒド
（RCHO）、ケトン（RCOR′）、カルボン酸
（RCO2H）、酸無水物（Ｒ―CO2CO―R′）、酸ア
ミド（RCONH2）のような含酸素電子供与体、
アミン（RnNH3-o、ｎ＝１〜３）、ニトリル
（RCN）などのような含窒素電子供与体、ホスフ
イン（RnPR′3-o、ｎ＝１〜３）、オキシ三塩化リ
ン（POCl3）のような含リン電子供与体、チオエ
ーテル（RnSR′2-o、ｎ＝１〜２）などの含イオ
ウ電子供与体が用いられる。これらの電子供与体
は単独使用の他、２以上を混合しても用いること
ができるし、また電子供与体に化合物としてポリ
シロキサンを用いることもできる。 As an electron donor compound, ether (RO
-R') Esters (RCO 2 R'), aldehydes (RCHO), ketones (RCOR'), carboxylic acids (RCO 2 H), acid anhydrides (R-CO 2 CO-R'), acid amides (RCONH 2 ), oxygenated electron donors such as
Nitrogen-containing electron donors such as amines (RnNH 3-o , n=1-3), nitriles (RCN), phosphine (RnPR′ 3-o , n=1-3), phosphorus oxytrichloride (POCl 3 ) and sulfur-containing electron donors such as thioether (RnSR' 2-o , n=1 to 2) are used. These electron donors can be used alone or in combination of two or more, and polysiloxane can also be used as a compound for the electron donor.
上記各一般式においてＲ，R′は炭化水素基で
あり、さらに詳しくは炭素数１〜50の脂肪族炭化
水素、不飽和炭化水素、置換基のない単環式炭化
水素基、置換基のある単環式炭化水素基、縮合多
環式炭化水素基などがある。脂肪族炭化水素基と
しては、直鎖状の例としてメチル、エチル、プロ
ピル、ブチル、ペンチル、ヘキシル、オクチルな
どがあり、分岐状の例としてイソプロピル、イソ
ブチル、イソペンチル、イソヘキシル、イソオク
クチル、２―メチルペンチル、３―メチルペンチ
ル、５―メチルヘキシルなどがある。飽和炭化水
素基としてはアルケニル基、アルカジエニル基が
あり、不飽和結合を末端に有するものだけでなく
内部に有するものも含み、たとえばビニル、アリ
ル、イソプロペニル、１―プロペニル、２―ブテ
ニル、１，３―ブタジエニルなどがある。単環式
炭化水素基としては脂環式及び芳香族炭化水素基
が含まれ、置換基のない例としては、たとえばシ
クロプロピル、シクロヘキシル、２―シクロペン
テン―１―イルなどの脂環式炭化水素基、および
フエニル基がある。置換基のある例としてはトル
イル、キシリル、メシチル、キユミル、ベンジ
ル、ジフエニルメチル、フエネチル、スチリルな
どがある。縮合多環式炭化水素基としてはナフチ
ル、アントリル、フエナントリル、２―インデニ
ル、１―ピレニルなどがある。 In each of the above general formulas, R and R' are hydrocarbon groups, and more specifically, aliphatic hydrocarbons having 1 to 50 carbon atoms, unsaturated hydrocarbons, monocyclic hydrocarbon groups without substituents, and monocyclic hydrocarbon groups with substituents. There are monocyclic hydrocarbon groups, fused polycyclic hydrocarbon groups, etc. Examples of linear aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl, and branched examples include isopropyl, isobutyl, isopentyl, isohexyl, isooctyl, and 2-methylpentyl. , 3-methylpentyl, 5-methylhexyl, etc. Saturated hydrocarbon groups include alkenyl groups and alkadienyl groups, and include not only those with terminal unsaturated bonds but also those with internal unsaturated bonds, such as vinyl, allyl, isopropenyl, 1-propenyl, 2-butenyl, 1, Examples include 3-butadienyl. Monocyclic hydrocarbon groups include alicyclic and aromatic hydrocarbon groups, examples without substituents include alicyclic hydrocarbon groups such as cyclopropyl, cyclohexyl, 2-cyclopenten-1-yl, etc. , and a phenyl group. Some examples of substituents include tolyl, xylyl, mesityl, cuyumyl, benzyl, diphenylmethyl, phenethyl, styryl, and the like. Examples of fused polycyclic hydrocarbon groups include naphthyl, anthryl, phenanthryl, 2-indenyl, and 1-pyrenyl.
ポリシロキサンは一般式〔（―R1R2SlO）―o（ｎ
＝３〜10000）〕で表わされる鎖状または環状のシ
ロキサン重合物であり、各Ｒは、ケイ素に結合し
得る同種または異種の残基をあらわすが、なかで
も、水素、アルキル基、アリール基などの炭化水
素残基、ハロゲン、アルコキシ基またはアリール
オキシ基、脂肪酸残基などの１種から成るものお
よびこれらの２種以上が、種々の比率で、分子内
に分布結合しているものなどが用いられる。用い
るポリシロキサンは液状であることが望ましく、
粘度（25℃）は10〜10000センチストークスが適
し、好ましくは、10〜1000センチストークスの範
囲である。 Polysiloxane has the general formula [(-R 1 R 2 SlO)- o (n
= 3 to 10,000)], where each R represents the same or different type of residue that can be bonded to silicon, including hydrogen, an alkyl group, an aryl group, etc. Hydrocarbon residues, halogens, alkoxy groups or aryloxy groups, fatty acid residues, etc., and those in which two or more of these groups are distributed and bonded within the molecule in various ratios are used. It will be done. It is desirable that the polysiloxane used be in liquid form;
The viscosity (at 25° C.) is suitably in the range of 10 to 10,000 centistokes, preferably in the range of 10 to 1,000 centistokes.
上記電子供与体化合物として具体例をあげる。
エーテルとしてはジエチルエーテル、ジプロピル
エーテル、ジブチルエーテル、ジ（イソアミル）
エーテル、エチレングリコールジメチルエーテ
ル、ジエチレングリコールジメチルエーテル、ジ
エチレングリコールジエチルエーテル、ジフエニ
ルエーテル、テトラヒドロフランなど、エステル
としては酢酸エチル、酢酸ブチル、酢酸アミル、
酪酸ビニル、酢酸ビニル、プロピオン酸メチル、
安息香酸メチル、安息香酸エチル、安息香酸プロ
ピル、安息香酸ブチル、安息香酸オクチル、安息
香酸２―エチルヘキシル、トルイル酸メチル、ト
ルイル酸エチル、トルイル酸ブチル、トルイル酸
２―エチルヘキシル、アニス酸メチル、アニス酸
エチル、アニス酸プロピル、ナフトエ酸メチル、
ナフトエ酸エチル、ナフトエ酸プロピル、ナフト
エ酸ブチル、ナフトエ酸２―エチルヘキシルな
ど、アルデヒドとしてはブチルアルデヒド、プロ
ピオンアルデヒド、ベンズアルデヒドなど、ケト
ンとしてはメチルエチルケトン、ジエチルケト
ン、アセチルアセトン、アセトフエノン、ベンゾ
フエノンなど、カルボン酸としては酢酸、プロピ
オン酸、安息香酸など、酸無水物としては無水酢
酸、無水酪酸、無水安息香酸など、酸アミドとし
てはホルムアミド、アセトアミド、ベンズアミド
など、アミンとしてはメチルアミン、ジメチルア
ミン、トリメチルアミン、アミルアミン、アニリ
ン、メチルアニリン、ピリジンなど、ニトリルと
してはアセトニトリル、プロピオニトリル、ベン
ゾニトリルなど、ホスフインとしてはトリエチル
ホスフイン、トリフエニルホスフインなど、チオ
エーテルとしてはジエチルスルフイド、ジフエニ
ルスルフイドなどがあげられる。また、ポリシロ
キサンとしては、オクタメチルトリシロキサン
CH3〔Sl（CH3）2O〕2Sl（CH3）3、オクタエチルシク
ロテトラシロキサン〔Sl（C2H5）2O〕4などの低級
重合物、およびジメチルポリシロキサン〔Sl
（CH3）2O〕o、エチルポリシクロシロキサン〔SlH
（C2H5）Ｏ〕o、メチルエチルポリシロキサン〔Sl
（CH3）（C2H5）Ｏ〕oなどの重合物などのアルキ
ルシロキサン重合物、またヘキサフエニルシクロ
トリシロキサン〔Sl（C6H5）2O〕3、ジフエニルポ
リシロキサン〔Sl（C6H5）2O〕o、などのアリール
シロキサン重合物、またジフエニルオクタメチル
テトラシロキサン（CH3）3SlO〔Sl（CH3）（C6H5）
Ｏ〕2Sl（CH3）3、メチルフエニルポリシロキサン
〔Sl（CH3）（C6H5）Ｏ〕oなどのアルキルアリール
シロキサン重合物などが示される。この他アルキ
ル水素シロキサン重合物、ハロアルキルシロキサ
ン、ハロアリールシロキサン重合物、各Ｒがアル
コキシまたはアリールオキシ基または脂肪酸残基
であるポリシロキサンなどがあげられる。また、
これら種々のポリシロキサンは混合して用いるこ
ともできる。 Specific examples of the above electron donor compounds are given below.
Ethers include diethyl ether, dipropyl ether, dibutyl ether, di(isoamyl)
Ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diphenyl ether, tetrahydrofuran, etc. Esters include ethyl acetate, butyl acetate, amyl acetate,
Vinyl butyrate, vinyl acetate, methyl propionate,
Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, butyl toluate, 2-ethylhexyl toluate, methyl anisate, anisic acid Ethyl, propyl anisate, methyl naphthoate,
Ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, etc. Aldehydes include butyraldehyde, propionaldehyde, benzaldehyde, etc. Ketones include methyl ethyl ketone, diethyl ketone, acetylacetone, acetophenone, benzophenone, etc. Carboxylic acids include Acetic acid, propionic acid, benzoic acid, etc. Acid anhydrides include acetic anhydride, butyric anhydride, benzoic anhydride, etc. Acid amides include formamide, acetamide, benzamide, etc. Amines include methylamine, dimethylamine, trimethylamine, amylamine, aniline , methylaniline, pyridine, etc. Nitriles include acetonitrile, propionitrile, benzonitrile, etc. Phosphines include triethylphosphine, triphenylphosphine, etc. Thioethers include diethyl sulfide, diphenyl sulfide, etc. . In addition, as polysiloxane, octamethyltrisiloxane
Lower polymers such as CH 3 [Sl(CH 3 ) 2 O] 2 Sl(CH 3 ) 3 , octaethylcyclotetrasiloxane [Sl(C 2 H 5 ) 2 O] 4 , and dimethylpolysiloxane [Sl
( CH3 ) 2O 〕 o , ethylpolycyclosiloxane〔SlH
(C 2 H 5 )O] o , methylethylpolysiloxane [Sl
Alkylsiloxane polymers such as (CH 3 ) ( C 2 H 5 ) O ] Arylsiloxane polymers such as (C 6 H 5 ) 2 O] o , and diphenyl octamethyltetrasiloxane (CH 3 ) 3 SlO [Sl(CH 3 ) (C 6 H 5 )
Examples include alkylarylsiloxane polymers such as O] 2 Sl(CH 3 ) 3 and methylphenylpolysiloxane [Sl(CH 3 )(C 6 H 5 )O] o . Other examples include alkyl hydrogen siloxane polymers, haloalkyl siloxanes, haloaryl siloxane polymers, and polysiloxanes in which each R is an alkoxy or aryloxy group or a fatty acid residue. Also,
These various polysiloxanes can also be used in combination.
遷移金属化合物としてはチタン、バナジウムの
ハライド、オキシハライド、アルコレート、アル
コキシハライド、アセトキシハライドなどであつ
て、たとえば四塩化チタン、四臭化チタン、テト
ラエトキシチタン、テトラブトキシチタン、モノ
クロロブトキシチタン、ジクロロジブトキシチタ
ン、トリクロロモノエトキシチタン、四塩化バナ
ジウム、オキシ三塩化バナジウムなどがあげられ
る。 Examples of transition metal compounds include titanium, vanadium halides, oxyhalides, alcoholates, alkoxyhalides, and acetoxyhalides, such as titanium tetrachloride, titanium tetrabromide, tetraethoxytitanium, tetrabutoxytitanium, monochlorobutoxytitanium, and dichloro Examples include dibutoxytitanium, trichloromonoethoxytitanium, vanadium tetrachloride, vanadium oxytrichloride, and the like.
（Ａ群）のハロゲン含有遷移金属化合物として
は、チタン、バナジウムのハライド、オキシハラ
イド、アルコキシハライド、アセトキシハライド
などの化合物、たとえば、四塩化チタン、四臭化
チタン、トリクロルモノイソプロポシチタン、ジ
クロルジイソプツポキシチタン、モノクロルトリ
イソプロポキシチタン、トリクロルモノブトキシ
チタン、ジクロルジブトキシチタン、モノクロル
トリブトキシチタン、四塩化バナジウム、オキシ
三塩化バナジウムなどがある。 (Group A) halogen-containing transition metal compounds include compounds such as titanium, vanadium halides, oxyhalides, alkoxyhalides, and acetoxyhalides, such as titanium tetrachloride, titanium tetrabromide, titanium trichloromonoisoproposite, and Examples include diisopropoxytitanium, monochlorotriisopropoxytitanium, trichlormonobutoxytitanium, dichlorodibutoxytitanium, monochlorotributoxytitanium, vanadium tetrachloride, vanadium oxytrichloride, and the like.
（Ｂ群）のハロゲン非含有の遷移金属化合物と
しては、チタン、バナジウムのアルコキシド、た
とえば、オルトチタン酸テトラメチル（テトラメ
トキシチタン）、オルトチタン酸テトラエチル
（テトラエトキシチタン）、オルトチタン酸テトラ
イソプロピル（テトライソプロポキシチタン）、
オルトチタン酸テトラｎ―ブチル（テトラ―ｎ―
ブトキシチタン）などのオルトチタン酸テトラア
ルキル（テトラアルコキシチタン）、バナジルト
リエチラート（VO（OC2H5）3）、バナジルトリイ
ソプロピラート（VO（OCH（CH3）2）3）、バナジ
ルトリｎ―ブチラート（VO（OC4H9）3）などの
バナジルトリアルコラートがある。（Ｂ群）の化
合物として一般式RO―〔Tl（OR）2―Ｏ―〕nＲで表
わされるポリチタン酸エステルを用いることがで
きる。（式中、ｍは２以上の整数、好ましくは２
〜10、Ｒはアルキル基、アリール基またはアラル
キル基を示し、すべてのＲが同一種類の基である
必要はない。Ｒの炭素数は１〜10が好ましいが、
特に制限されるものではない、また、アルコキシ
基の一部が水酸基であつてもよい。）具体的には、
ポリチタン酸メチル、ポリチタン酸エチル、ポリ
チタン酸イソプロピル、ポリチタン酸ｎ―プロピ
ル、ポリチタン酸ｎ―ブチル、ポリチタン酸ｎ―
ヘキシルなどがある。 (Group B) halogen-free transition metal compounds include alkoxides of titanium and vanadium, such as tetramethyl orthotitanate (tetramethoxytitanium), tetraethyl orthotitanate (tetraethoxytitanium), and tetraisopropyl orthotitanate ( tetraisopropoxy titanium),
Tetra-n-butyl orthotitanate (tetra-n-
tetraalkyl orthotitanate (tetraalkoxytitanium) such as butoxytitanium), vanadyl triethylate (VO(OC 2 H 5 ) 3 ), vanadyl triisopropylate (VO(OCH(CH 3 ) 2 ) 3 ), vanadyl trin -There are vanadyl trialcholates such as butyrate (VO(OC 4 H 9 ) 3 ). As the compound of (Group B), a polytitanate ester represented by the general formula RO-[Tl(OR) 2 -O-] nR can be used. (In the formula, m is an integer of 2 or more, preferably 2
~10, R represents an alkyl group, an aryl group, or an aralkyl group, and all R's do not need to be the same type of group. The number of carbon atoms in R is preferably 1 to 10, but
There are no particular limitations, and a portion of the alkoxy group may be a hydroxyl group. )in particular,
Methyl polytitanate, ethyl polytitanate, isopropyl polytitanate, n-propyl polytitanate, n-butyl polytitanate, n- polytitanate
Hexyl etc.
有機アルミニウム化合物としては、トリエチル
アルミニウム、トリイソブチルアルミニウム、ト
リヘキシルアルミニウムなどのトリアルキルアル
ミニウム、ジエチルアルミニウムモノクロリドな
どのジアルキルアルミニウムモノクロリド、エチ
ルアルミニウムセスキクロリドなどの他に、モノ
エトキシジエチルアルミニウム、ジエトキシモノ
エチルアルミニウムなどのアルコキシアルキルア
ルミニウムがある。 Examples of organic aluminum compounds include trialkylaluminum such as triethylaluminum, triisobutylaluminum, and trihexylaluminum, dialkylaluminum monochloride such as diethylaluminum monochloride, and ethylaluminum sesquichloride, as well as monoethoxydiethylaluminum, diethoxymonochloride, etc. There are alkoxyalkylaluminums such as ethylaluminum.
本発明の触媒調製において反応時や反応後の洗
滌などに使用する溶媒としては、ヘキサン、ヘプ
タン、オクタン、ノナン、デカンなどの脂肪族炭
化水素、ベンゼン、トルエン、キシレン、エチル
ベンゼン、クメンなどの芳香族炭化水素、クロル
ベンゼン、ジクロルベンゼン、トリクロルベンゼ
ンなどのハロゲン化芳香族炭化水素、四塩化炭
素、クロロホルム、ジクロルエタン、トリクロル
エチレン、テトラクロルエチレン、四臭化炭素な
どのハロゲン化炭化水素などがあげられる。 In the catalyst preparation of the present invention, solvents used during the reaction and for washing after the reaction include aliphatic hydrocarbons such as hexane, heptane, octane, nonane, and decane, and aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cumene. Examples include hydrocarbons, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene, and halogenated hydrocarbons such as carbon tetrachloride, chloroform, dichloroethane, trichlorethylene, tetrachlorethylene, and carbon tetrabromide. .
本発明の特徴は、第１段重合系において高分子
側重合体、続いて、第２段重合系において低分子
側重合体を製造する連続多段重合法において、本
発明に示した特殊な重合触媒を用い、重合器上部
に気相部を存在させ、気相部のエチレン対水素の
モル比を規制することにより、分子量および生成
量の調節を極めて容易ならしめたことである。本
発明は、公知の連続多段スラリー重合法に比べ、
第１段および第２段重合系の重合体の分子量およ
び生成量の調節が極めて容易であるという特徴を
有している。また、本発明の重合においては、重
合器壁への重合体付着が全くないか極めて少な
く、長時間安定した多段重合を行なうことができ
るという特徴がある。本発明に使用する触媒は、
重合活性が極めて高く、反応終了後、重合体中の
残触媒の除去工程すなわち脱灰工程をなくすこと
が可能である。 A feature of the present invention is that the special polymerization catalyst shown in the present invention is used in a continuous multi-stage polymerization method in which a high molecular side polymer is produced in the first stage polymerization system, and then a low molecular side polymer is produced in the second stage polymerization system. By providing a gas phase in the upper part of the polymerization vessel and regulating the molar ratio of ethylene to hydrogen in the gas phase, the molecular weight and production amount can be extremely easily controlled. Compared to the known continuous multi-stage slurry polymerization method, the present invention has the following advantages:
It is characterized in that it is extremely easy to control the molecular weight and production amount of the polymer in the first and second stage polymerization systems. Furthermore, the polymerization of the present invention is characterized in that there is no or very little polymer adhesion to the walls of the polymerization vessel, and stable multi-stage polymerization can be carried out for a long period of time. The catalyst used in the present invention is
The polymerization activity is extremely high, and it is possible to eliminate the step of removing the residual catalyst in the polymer, that is, the deashing step after the reaction is completed.
本発明の他の特徴は、得られるポリエチレンの
分子量分布が極めて広いことである。従つて、成
形時流れ特性が良好で、成形時の樹脂圧力が低
く、高速成形が可能であり、メルトフラクチヤが
起きないために成形物の外観が良好である。フイ
ルム製造の場合、適度の強度および不透明感を持
ち、フイツシユアイが見られず、フイルム表面が
滑らかで、成形性が長時間安定している。また、
本発明により得られるポリエチレン粉末のかさ比
重は0.35〜0.43であり、粉体粒子の形状が良好な
ことにより、重合器の容積当り、時間当りの生産
効率が大きく、重合物粉体の配管輸送上のトラブ
ル発生が少なく、粉体の造粒も容易であるという
特徴をもつている。 Another feature of the invention is that the resulting polyethylene has a very broad molecular weight distribution. Therefore, the flow characteristics during molding are good, the resin pressure during molding is low, high-speed molding is possible, and the appearance of the molded product is good because melt fracture does not occur. In the case of film production, it has appropriate strength and opacity, no visible fissures, a smooth film surface, and stable moldability over a long period of time. Also,
The bulk specific gravity of the polyethylene powder obtained by the present invention is 0.35 to 0.43, and the shape of the powder particles is good, so the production efficiency per unit volume of the polymerization vessel and per hour is high, and it is easy to transport the polymer powder through pipes. It is characterized by having fewer troubles and easy granulation of powder.
以下、実施例により本発明の特徴を具体的に説
明する。実施例中、メルトインデツクスは
ASTM Ｄ―1238(E)に従つた。MW／MN（MWは重
量平均分子量であり、MNは数平均分子量であ
る。）はWaters社製GPC―200型のゲルパーミユ
エーシヨンクロマトグラフイーにより求めた。 Hereinafter, the features of the present invention will be specifically explained with reference to Examples. In the examples, the melt index is
In accordance with ASTM D-1238(E). M W /M N (M W is the weight average molecular weight, and M N is the number average molecular weight) was determined by gel permeation chromatography using GPC-200 manufactured by Waters.
実施例 １
(1) 遷移金属触媒成分の製造
水酸化マグネシウム76Kgと塩化アルミニウム
（無水）90Kgをあらかじめ振動ミル中で５時間混
合、粉砕した後、150℃で５時間反応させた。そ
の後冷却し、微粉砕を行ない、固体生成物（）
を得た。Example 1 (1) Production of transition metal catalyst component 76 kg of magnesium hydroxide and 90 kg of aluminum chloride (anhydrous) were mixed in advance in a vibration mill for 5 hours, pulverized, and then reacted at 150°C for 5 hours. After that, it is cooled and pulverized to produce a solid product ().
I got it.
トルエン150中に、四塩化チタン173Kgおよび
鎖状ジメチルポリシロキサン（粘度100センチス
トークス）100Kgを加え混合し、次いで、上記固
体生成物（）100Kgを加え、110℃に２時間反応
させた。反応終了後、常法に従い過を行ない、
液中に未反応四塩化チタンおよび未反応ポリシ
ロキサンが検出されなくなるまで固体生成物をヘ
キサンで洗浄し、減圧乾燥後、固体生成物（）
を得た。 173 kg of titanium tetrachloride and 100 kg of linear dimethylpolysiloxane (viscosity 100 centistokes) were added to 150 kg of toluene and mixed. Next, 100 kg of the above solid product (2) was added and reacted at 110°C for 2 hours. After the reaction is complete, evaporate according to the usual method,
The solid product is washed with hexane until unreacted titanium tetrachloride and unreacted polysiloxane are no longer detected in the liquid, and after drying under reduced pressure, the solid product ()
I got it.
トルエン200中に、四塩化チタン87Kgおよび
オルトチタン酸テトライソプロピル65Kgを加え混
合し、次いで、上記固体生成物（）100Kgを加
え、90℃で１時間、その後、120℃で２時間反応
させた。反応終了後、常法により液中にチタン
化合物が検出されなくなるまでヘキサンで洗浄を
繰返した後、減圧乾燥を行ない、固体生成物
（）を得た。固体生成物（）１Kg中のチタン
原子は2.2molであつた。 87 kg of titanium tetrachloride and 65 kg of tetraisopropyl orthotitanate were added and mixed in 200 g of toluene, and then 100 kg of the above solid product (2) was added and reacted at 90°C for 1 hour and then at 120°C for 2 hours. After the reaction was completed, washing was repeated with hexane by a conventional method until no titanium compound was detected in the solution, followed by drying under reduced pressure to obtain a solid product (). The amount of titanium atoms in 1 kg of the solid product ( ) was 2.2 mol.
(2) エチレンの多段連続重合
内容積10の第１段重合器に、固体生成物
（）を１時間当りチタン原子に換算して
0.09mmol、トリエチルアルミニウムを１時間当
り0.4mmolおよびヘキサンを１時間当り４の速
度で供給し、重合器内の液レベルが80％に保てる
ように重合器内容物を排出しながら、70℃におい
て、エチレンを１時間当り350Nl、水素を重合器
気相部のエチレン対水素のモル比が１対0.06にな
るように供給しつつ、全圧40Kg／cm2（ゲージ圧）
で連続的に第１段重合を行なつた。(2) Multistage continuous polymerization of ethylene In the first stage polymerization vessel with an internal volume of 10, the solid product () was converted into titanium atoms per hour.
0.09 mmol of triethylaluminum, 0.4 mmol of triethylaluminum per hour, and hexane of 4 mmol per hour were supplied at 70°C while discharging the contents of the polymerization vessel to maintain the liquid level in the polymerization vessel at 80%. While supplying ethylene at 350Nl per hour and hydrogen at a molar ratio of ethylene to hydrogen in the gas phase of the polymerization reactor of 1:0.06, the total pressure was 40Kg/cm 2 (gauge pressure).
The first stage polymerization was carried out continuously.
第１段重合器を出た溶媒に懸濁した重合物を、
移送ポンプにより、内容積20の第２段重合器に
全量導入し、ヘキサンおよび触媒を追加すること
なく、重合器内の液レベルが80％に保てるように
重合器内容物を排出しながら、80℃において、ブ
テン―１を５容量％含むエチレンを１時間当り
370Nl、水素を重合器気相部のエチレン対水素の
モル比が１対1.7になるように供給しつつ、全圧
40Kg／cm2（ゲージ圧）で連続的に第２段重合を行
なつた。 The polymer suspended in the solvent exiting the first stage polymerization vessel is
The entire amount was introduced into the second-stage polymerization vessel with an internal volume of 20% using a transfer pump, and the content of the polymerization vessel was discharged to maintain the liquid level in the polymerization vessel at 80% without adding hexane or catalyst. ℃, ethylene containing 5% by volume of butene-1 per hour.
370Nl, while supplying hydrogen such that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization reactor was 1:1.7, while increasing the total pressure.
The second stage polymerization was carried out continuously at 40 kg/cm 2 (gauge pressure).
以上の多段重合を120時間連続して行なつたが、
運転は極めて安定しており、脱灰をせずに乾燥
後、メルトインデツクス0.05、かさ比重0.40、密
度0.950、分子量分布MW／MN29の重合体粉体104
Kgを得た。このポリエチレンを用いてフイルムを
製造した所、製膜性は安定しており、フイルムが
適度の強度および不透明感を持ち、フイツシユア
イは見られず、表面状態は良好で、満足すべきも
のでああつた。 The above multi-stage polymerization was carried out continuously for 120 hours, but
The operation is extremely stable, and after drying without deashing, the polymer powder 104 has a melt index of 0.05, a bulk specific gravity of 0.40, a density of 0.950, and a molecular weight distribution of M W /M N of 29.
Got Kg. When a film was produced using this polyethylene, the film-forming property was stable, the film had appropriate strength and opacity, no stickiness was observed, and the surface condition was satisfactory.
実施例 ２
(1) 遷移金属触媒成分の製造
酸化マグネシウム75ｇと塩化アルミニウム（無
水）80ｇを、ボールミル中で24時間混合、粉砕し
200℃で３時間加熱した後、冷却して粉砕し、固
体生成物（）を得た。Example 2 (1) Production of transition metal catalyst component 75 g of magnesium oxide and 80 g of aluminum chloride (anhydrous) were mixed in a ball mill for 24 hours and ground.
After heating at 200°C for 3 hours, the mixture was cooled and ground to obtain a solid product ().
ヘプタン200ml中に、固体生成物（）150ｇ、
鎖状メチルエチルポリシロキサン80ｇ（粘度500
センチストークス）および四塩化チタン130ｇを
同時に加えて混合し、80℃に３時間反応させた。
その後は、ヘキサン洗浄を行ない、固体生成物
（）を得た。 150 g of solid product () in 200 ml of heptane,
Chain methylethyl polysiloxane 80g (viscosity 500
centistokes) and 130 g of titanium tetrachloride were added at the same time, mixed, and reacted at 80° C. for 3 hours.
After that, washing with hexane was performed to obtain a solid product (2).
トルエン400ml中に、固体生成物（）100ｇお
よび四塩化チタン87ｇを加え混合し、ついで、ポ
リチタン酸イソプロピル（５量体）47ｇを加え、
110℃に３時間反応させた。その後は実施例１と
同様に洗浄し、固体生成物（）を得た。固体生
成物（）１ｇ中のチタン原子は2.1mmolであつ
た。 In 400 ml of toluene, 100 g of the solid product () and 87 g of titanium tetrachloride were added and mixed, then 47 g of isopropyl polytitanate (pentamer) was added,
The reaction was carried out at 110°C for 3 hours. Thereafter, washing was performed in the same manner as in Example 1 to obtain a solid product (2). The amount of titanium atoms in 1 g of the solid product ( ) was 2.1 mmol.
(2) エチレンの多段連続重合
第１段重合器に、エチレンを１時間当り
210Nl、水素を重合器気相部のエチレ対水素のモ
ル比が１対0.15になるように供給し、第２段重合
器に、エチレンを１時間当り495Nl、水素を重合
器気相部のエチレン対水素のモル比が１対1.4に
なるように供給すること以外は、実施例１と同様
にエチレンの多段連続重合を行ない、150時間の
連続運転で130Kgの重合体粉末を得た。このポリ
エチレンは、メルトインデツクス0.30、かさ比重
0.38、密度0.955、MW／MN26であり、中空成形
によりビンを成形した所、成形時の樹脂圧が低く
高速成形が可能であり、成形品の表面は良好で、
成形品の重量および偏肉のなさも満足すべきもの
であつた。(2) Multistage continuous polymerization of ethylene Ethylene is added per hour to the first stage polymerization vessel.
210Nl, hydrogen was supplied to the polymerizer gas phase so that the molar ratio of ethylene to hydrogen was 1:0.15, and 495Nl of ethylene was supplied per hour to the second stage polymerizer, and hydrogen was supplied to the ethylene reactor in the gas phase of the polymerizer. Multi-stage continuous polymerization of ethylene was carried out in the same manner as in Example 1, except that the molar ratio of hydrogen to hydrogen was 1:1.4, and 130 kg of polymer powder was obtained in 150 hours of continuous operation. This polyethylene has a melt index of 0.30 and a bulk specific gravity of
0.38, density 0.955, M W /M N 26, and when the bottle was molded by blow molding, the resin pressure during molding was low and high speed molding was possible, and the surface of the molded product was good.
The weight and thickness of the molded product were also satisfactory.
実施例 ３
ヒドロタルサイト70ｇと塩化アルミニウム（無
水）80ｇを、振動ミル中170℃に３時間加熱しな
がら、混合、粉砕、反応を同時に行なわせ、固体
生成物（）を得た。Example 3 70 g of hydrotalcite and 80 g of aluminum chloride (anhydrous) were mixed, pulverized, and reacted simultaneously while heating at 170° C. for 3 hours in a vibrating mill to obtain a solid product ().
トルエン200ml中、四塩化チタン100ｇおよび固
体生成物（）100ｇを混合、続いて、ジ―ｎ―
ブチルエーテル130ｇを加え、100℃に３時間反応
させ、ヘキサン洗浄後、固体生成物（）を得
た。 Mix 100 g of titanium tetrachloride and 100 g of solid product () in 200 ml of toluene, followed by
130 g of butyl ether was added and reacted at 100° C. for 3 hours, and after washing with hexane, a solid product () was obtained.
キシレン400ml中、固体生成物（）100ｇおよ
び四塩化チタン114ｇ加え混合し、80℃に３時間
反応させた後、オルトチタン酸テトラｎ―ブチル
58ｇを加え130℃に２時間反応させた。その後は
実施例１と同様に洗浄し、固体生成物（）を得
た。固体生成物（）１ｇ中のチタン原子は
1.9mmolであつた。 In 400 ml of xylene, 100 g of solid product () and 114 g of titanium tetrachloride were added and mixed, and after reacting at 80°C for 3 hours, tetra-n-butyl orthotitanate was added.
58g was added and reacted at 130°C for 2 hours. Thereafter, washing was performed in the same manner as in Example 1 to obtain a solid product (2). Titanium atoms in 1g of solid product () are
It was 1.9 mmol.
この固体生成物（）を用い、実施例１の(2)と
同様にエチレンの多段連続重合を行ない、104Kg
の重合体粉末を得た。メルトインデツクス0.03、
MW／MN27であり、実施例１と同様に満足すべき
フイルムを製造することができた。 Using this solid product (2), multistage continuous polymerization of ethylene was carried out in the same manner as in Example 1 (2), and 104 kg
A polymer powder was obtained. Melt index 0.03,
M W /M N was 27, and a satisfactory film could be produced in the same manner as in Example 1.
実施例 ４
塩化アルミニウム（無水）90Kgとマグネシアセ
メント110Kgをボールミル中で48時間混合、粉砕
し、250℃で２時間加熱した後、冷却して粉砕し、
固体生成物（）を得た。Example 4 90 kg of aluminum chloride (anhydrous) and 110 kg of magnesia cement were mixed in a ball mill for 48 hours, pulverized, heated at 250°C for 2 hours, cooled and pulverized,
A solid product () was obtained.
キシレン200中、固体生成物（）100Kgおよ
び酢酸ｎ―ブチル60Kgを混合、続いて、四塩化チ
タン100Kgを加え、120℃に２時間反応させ、ヘキ
サン洗浄後、固体生成物（）を得た。 100 kg of solid product () and 60 kg of n-butyl acetate were mixed in xylene 200, followed by adding 100 kg of titanium tetrachloride and reacting at 120° C. for 2 hours. After washing with hexane, solid product () was obtained.
トルエン400中、固体生成物（）100Kgおよ
びポリチタン酸ｎ―ブチル84Kgを加え混合し、つ
いで、四塩化チタン174Kgを加え、120℃に２時間
反応させた。その後は実施例１と同様に洗浄し、
固体生成物（）を得た。固体生成物（）１Kg
のチタン原子は1.8molであつた。 In 400 g of toluene, 100 kg of the solid product () and 84 kg of n-butyl polytitanate were added and mixed, and then 174 kg of titanium tetrachloride was added and reacted at 120° C. for 2 hours. After that, wash in the same manner as in Example 1,
A solid product () was obtained. Solid product () 1Kg
The amount of titanium atoms was 1.8 mol.
この固体生成物（）を用い、実施例２の(2)と
同様にエチレンの多段連続重合をない、130Kgの
重合体粉末を得た。メルトインデツクス0.35、
MW／MN24であり、実施例２と同様に満足すべき
ビン製造することができた。 Using this solid product (2), 130 kg of polymer powder was obtained in the same manner as in Example 2 (2) without the multistage continuous polymerization of ethylene. Melt index 0.35,
M W /M N was 24, and a satisfactory bottle could be manufactured in the same manner as in Example 2.
第１図は、本発明の製造法に係る触媒のフロー
チヤートである。
FIG. 1 is a flowchart of the catalyst according to the production method of the present invention.
Claims (1)
媒成分とを組合せて得られる触媒、溶媒および水
素の存在下、ポリエチレンを連続多段重合によつ
て製造する方法において、 (i) アルミニウムハロゲン化物とマグネシウムの
水酸化物、酸化物、炭酸化物、これらを含む複
塩、またはマグネシウム化合物の水和物とを反
応させて得られる固体生成物（）と、電子供
与体化合物と、チタン化合物とから調製した固
体生成物（）に、さらに（Ａ群）ハロゲンを
含有したチタン化合物（以下ハロゲン含有チタ
ン化合物という）および（Ｂ群）ハロゲンを含
有しないチタン化合物（以下ハロゲン非含有チ
タン化合物という）のそれぞれの群より少なく
とも１種選ばれた少なくとも２種のチタン化合
物を反応させて得られる最終の固体生成物
（）と有機アルミニウム化合物とを組合わせ
ることにより得られる触媒の存在下、飽和炭化
水素溶媒中、重合器の上部に気相が存在する状
態において、重合温度30℃以上、100℃以下、
重合圧力11ないし70Kg／cm2の条件下で、重合器
気相部のエチレン対水素のモル比が１対000.1
ないし0.5になるように水素を供給すると共に、
全エチレン供給量の10ないし70％のエチレンを
供給して、第１段重合を行ない、 (ii) 続いて、溶媒に懸濁した重合物を第２段重合
系に移送し、飽和炭化水素溶媒中、重合器の上
部に気相が存在する状態において、重合温度50
℃以上120℃以下、重合圧力11ないし70Kg／cm2
の条件下で、重合器気相部のエチレン対水素の
モル比が１対0.1ないし3.0になるように水素を
供給すると共に、全エチレン供給量の30ないし
90％のエチレンを供給して第２段重合を行なう
こと を特徴とするポリエチレンの連続多段重合による
製造方法。 ２ 少量のα―オレフインを第１段重合系およ
び／または第２段重合系に供給して、エチレンと
の共重合体を製造することを特徴とする特許請求
の範囲第１項記載のポリエチレンの製造方法。 ３ ハロゲン含有チタン化合物はチタンのハライ
ド、オキシハライド、アルコキシハライド、また
はアセトキシハライドである特許請求の範囲第１
項に記載の製造方法。 ４ ハロゲン非含有チタン化合物はチタンのアル
コキシド、オルトチタン酸テトラアルキル（テト
ラアルコキシチタン）、バナジルトリアルコラー
ト、またはポリチタン酸エステルである特許請求
の範囲第１項に記載の製造方法。 ５ 電子供与体化合物がエーテル、エステル、ア
ルデヒド、ケトン、酸無水物もしくはポリシロキ
サンである特許請求の範囲第１項記載の製造方
法。 ６ 固体生成物（）が固体生成物（）100ｇ
に対し電子供与体化合物が20〜1000ｇ、チタン化
合物は10〜500ｇであつて、かつ電子供与体化合
物100ｇに対しチタン化合物30〜500ｇで調製した
特許請求の範囲第１項に記載の製造方法。 ７ 固体生成物（）が（Ａ群）ハロゲン含有チ
タン化合物と（Ｂ群）ハロゲン非含有チタン化合
物のそれぞれに含有するチタン原子数の比が10／
１〜１／10の範囲にあり、かつ両化合物の合計量
が固体生成物（）100ｇに対して、１〜1000ｇ
を使用し、反応温度30〜500℃で反応させて得ら
れた特許請求の範囲第１項に記載の製造方法。[Scope of Claims] 1. A method for producing polyethylene by continuous multistage polymerization in the presence of a catalyst obtained by combining a transition metal compound catalyst component and an organometallic compound catalyst component, a solvent, and hydrogen, comprising: (i) aluminum A solid product obtained by reacting a halide with a magnesium hydroxide, oxide, carbonate, a double salt containing these, or a hydrate of a magnesium compound, an electron donor compound, and a titanium compound. Further, (Group A) a titanium compound containing a halogen (hereinafter referred to as a halogen-containing titanium compound) and (Group B) a titanium compound that does not contain a halogen (hereinafter referred to as a halogen-free titanium compound) to the solid product prepared from (). In the presence of a catalyst obtained by combining an organoaluminium compound with the final solid product obtained by reacting at least two titanium compounds selected from each group of In a solvent, in a state where a gas phase exists at the top of the polymerization vessel, the polymerization temperature is 30°C or higher and 100°C or lower,
Under polymerization pressure of 11 to 70 kg/ cm2 , the molar ratio of ethylene to hydrogen in the gas phase of the polymerizer is 1:000.1.
At the same time, hydrogen is supplied so that the amount of
The first stage polymerization is carried out by supplying 10 to 70% of the total amount of ethylene supplied, (ii) The polymer suspended in the solvent is then transferred to the second stage polymerization system, and a saturated hydrocarbon solvent is added. In a state where a gas phase exists at the top of the polymerization vessel, the polymerization temperature is 50℃.
℃ or more and 120℃ or less, polymerization pressure 11 to 70Kg/cm 2
Under these conditions, hydrogen is supplied so that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization reactor is 1:0.1 to 3.0, and 30 to 30% of the total ethylene supply amount is
A method for producing polyethylene by continuous multistage polymerization, characterized in that the second stage polymerization is carried out by supplying 90% ethylene. 2. Polyethylene according to claim 1, characterized in that a small amount of α-olefin is supplied to the first stage polymerization system and/or the second stage polymerization system to produce a copolymer with ethylene. Production method. 3. Claim 1, wherein the halogen-containing titanium compound is a titanium halide, oxyhalide, alkoxyhalide, or acetoxyhalide.
The manufacturing method described in section. 4. The production method according to claim 1, wherein the halogen-free titanium compound is a titanium alkoxide, tetraalkyl orthotitanate (tetraalkoxytitanium), vanadyl trialcholate, or polytitanate. 5. The manufacturing method according to claim 1, wherein the electron donor compound is an ether, ester, aldehyde, ketone, acid anhydride, or polysiloxane. 6 Solid product () is 100g of solid product ()
The manufacturing method according to claim 1, wherein the amount of the electron donor compound is 20 to 1000 g and the titanium compound is 10 to 500 g, and the amount of the titanium compound is 30 to 500 g per 100 g of the electron donor compound. 7 The ratio of the number of titanium atoms contained in each of the halogen-containing titanium compound (Group A) and the halogen-free titanium compound (Group B) in the solid product () is 10/
1 to 1/10, and the total amount of both compounds is 1 to 1000 g per 100 g of solid product ().
The manufacturing method according to claim 1, obtained by reacting at a reaction temperature of 30 to 500°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11060379A JPS5634713A (en) | 1979-08-30 | 1979-08-30 | Preparation of polyethylene by continuous multistage polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11060379A JPS5634713A (en) | 1979-08-30 | 1979-08-30 | Preparation of polyethylene by continuous multistage polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5634713A JPS5634713A (en) | 1981-04-07 |
| JPS6352657B2 true JPS6352657B2 (en) | 1988-10-19 |
Family
ID=14540023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11060379A Granted JPS5634713A (en) | 1979-08-30 | 1979-08-30 | Preparation of polyethylene by continuous multistage polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5634713A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60184908U (en) * | 1984-05-18 | 1985-12-07 | 三井造船株式会社 | reinforced structure |
-
1979
- 1979-08-30 JP JP11060379A patent/JPS5634713A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5634713A (en) | 1981-04-07 |
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