JPS6352659B2 - - Google Patents
Info
- Publication number
- JPS6352659B2 JPS6352659B2 JP17349680A JP17349680A JPS6352659B2 JP S6352659 B2 JPS6352659 B2 JP S6352659B2 JP 17349680 A JP17349680 A JP 17349680A JP 17349680 A JP17349680 A JP 17349680A JP S6352659 B2 JPS6352659 B2 JP S6352659B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- ethylene
- stage polymerization
- hydrogen
- compound
- 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 129
- -1 polyethylene Polymers 0.000 claims description 72
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 62
- 239000005977 Ethylene Substances 0.000 claims description 62
- 229920000642 polymer Polymers 0.000 claims description 52
- 239000012265 solid product Substances 0.000 claims description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims description 45
- 239000001257 hydrogen Substances 0.000 claims description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 42
- 239000004698 Polyethylene Substances 0.000 claims description 36
- 229920000573 polyethylene Polymers 0.000 claims description 36
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000007789 gas Substances 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 23
- 150000003623 transition metal compounds Chemical class 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 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
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- 150000002681 magnesium compounds Chemical class 0.000 claims 1
- 150000003682 vanadium compounds Chemical class 0.000 claims 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 150000002430 hydrocarbons Chemical group 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 238000004080 punching Methods 0.000 description 9
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 229910001507 metal halide Inorganic materials 0.000 description 6
- 150000005309 metal halides Chemical class 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 230000005484 gravity Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 238000000071 blow moulding Methods 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 description 4
- 150000004692 metal hydroxides Chemical class 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 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
- 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
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 239000004205 dimethyl polysiloxane Substances 0.000 description 3
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- 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 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-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
- 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
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000005376 alkyl siloxane group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons 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
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 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
- 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
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000010101 extrusion blow moulding Methods 0.000 description 2
- 150000004665 fatty acids Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 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
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000000395 magnesium oxide Substances 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
- 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
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 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
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 150000003609 titanium compounds Chemical class 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
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-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
- 239000003643 water by type Chemical class 0.000 description 2
- 239000008096 xylene Substances 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
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-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
- VCYDUTCMKSROID-UHFFFAOYSA-N 2,2,4,4,6,6-hexakis-phenyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VCYDUTCMKSROID-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
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000251730 Chondrichthyes Species 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
- 229910021586 Nickel(II) chloride Inorganic materials 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
- 229910021552 Vanadium(IV) chloride Inorganic materials 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
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 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
- 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
- LGSNSXWSNMARLH-UHFFFAOYSA-N butan-1-ol titanium Chemical compound C(CCC)O.[Ti].C(CCC)O LGSNSXWSNMARLH-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical class O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005336 cracking Methods 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
- DLRHRQTUCJTIIV-UHFFFAOYSA-N diethoxy(ethyl)alumane Chemical compound CC[O-].CC[O-].CC[Al+2] DLRHRQTUCJTIIV-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 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
- 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
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000004820 halides Chemical class 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
- 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 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 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
- 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
- 125000002496 methyl group Chemical group [H]C([H])([H])* 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
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- 150000002899 organoaluminium compounds Chemical class 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
- 239000002685 polymerization catalyst Substances 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
- 238000010298 pulverizing process Methods 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
- 230000035484 reaction time Effects 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
- 229910052596 spinel Inorganic materials 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 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
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 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
- 238000005406 washing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Description
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多段重合による製
造方法に関するものである。
本発明におけるポリエチレンとは、エチレンの
単独重合体のほかに、エチレンと共重合しうるほ
かの少量の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。
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
に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。
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。従来、前段（第１段）で
高分子側、後段（第２段）で低分子側をつくる多
段重合による製造方法として、特公昭46−11349
号、特開昭54−7488号、特開昭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価チタン化合物と有
機アルミニウム化合物の組合わせによる触媒を用
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方
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段重合系に流入し即ち充分
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。
一方、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（）と言う
ことがある）を担体とする触媒成分を研究してき
たが該固体生成物（）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（）と有
機アルミニウム化合物を組合わせた触媒を用いる
ことにより、従来の連続多段重合の欠点が解消さ
れることを見出し、種々の研究を重ねた結果、本
発明の製造方法を完成するに到つた。
すなわち、本発明の目的は、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多段重合において前記し
た従来の問題点が解消された製造方法を提供する
ことである。
本発明のポリエチレンの多段重合による製造方
法は、
ａ 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、第4a族または第5a族の遷移金属化合物と
から調製した遷移金属化合物を担持させた最終
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。
ｂ 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3.0をこえて7.0以下になるように
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。
本発明の製造方法は、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
ン対水素のモル比が１対0.001ないし0.5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
とによつて調節される。この場合得られる重合体
の分子量は、重量平均分子量にして２×105〜８
×105に相当する。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
た重合物はそのまゝ、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。その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70Kg／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3.0をこえて7.0以下の範
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する。第２段重合で得られる
重合体の分子量は、重量平均分子量にして1.5×
104〜６×104に相当する。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。
第１段重合および第２段重合の気相部のエチレ
ン対水素のモル比およびエチレンの供給量は最終
的に得られる重合体の用途によつて決定される。
たとえば、フイルムに使用するポリエチレンを製
造する場合、第１段重合はエチレン対水素のモル
比は１：0.001〜0.3であり、好ましくは１：0.001
〜0.2である。エチレン供給量は全エチレン供給
量の40〜60％、好ましくは50％である。一方の第
２段重合は、エチレン対水素のモル比は１：3.0
〜7.0、好ましくは１：3.0〜6.0である。エチレン
供給量は全エチレン供給量の40〜60％、好ましく
は50％である。また、中空成形の場合、第１段重
合は、エチレン対水素のモル比は１：0.005〜
0.5、好ましくは１：0.01〜0.4であり、エチレン
供給量は全エチレン供給量の30〜70％、好ましく
は50％である。一方第２段重合はエチレン対水素
のモル比は１：3.0〜7.0、好ましくは１：3.0〜
5.0である。エチレン供給量は全エチレン供給量
の30〜70％、好ましくは50％である。
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段重合系にもすることも可能である。
本発明の多段重合は、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。
本発明の製造方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。
本発明の製造方法に用いる触媒は、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、第4a族または第5a族
の遷移金属化合物とから調製した遷移金属化合物
を担持させた最終の固体生成物（）と有機アル
ミニウム化合物とを組合わせて得られることが特
徴である。
３価金属ハロゲン化物としては、三塩化アルミ
ニウム（無水）、三塩化鉄（無水）が示される。
前記２価金属の水酸化物等（以下２価金属化合
物と言うことがある）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、Mg2SiO4、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、NiCl2・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・2SiO・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。
固体生成物（）は、３価金属ハロゲン化物と
２価金属化合物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。
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
は単独使用のほか、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。
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
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。不飽和炭化
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および芳香族炭化水
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―ビレニルなどがある。
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。
電子供与体化合物として用いることのできるポ
リシロキサンとしては、
一般式
The present invention relates to a method for producing polyethylene by multistage polymerization, using a plurality of polymerization vessels to produce a high molecular weight polymer in the first stage polymerization system and a low molecular weight polymer in the second stage polymerization system. In the present invention, polyethylene refers to ethylene homopolymers as well as small amounts of other α-olefins that can be copolymerized with ethylene, such as propylene, butene-1, hexene-1, 4-methyl-pentene-1, or It also includes copolymers with dienes such as butadiene and dicyclopentadiene. 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 on the other hand, polyethylene used for extrusion molding and blow molding is
It is desirable that the molecular weight distribution is wide. When blow molding a polymer with a narrow molecular weight distribution, the extrusion pressure during molding may rise excessively, making molding impossible, causing streaks,
The appearance of the product is significantly impaired due to the occurrence of 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. 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. Conventionally, as a manufacturing method using multi-stage polymerization, in which a high molecular side is produced in the first stage (first stage) and a low molecular side is produced in the second stage (second stage), there is
No., JP-A-54-7488, and JP-A-54-32588 are known. In Japanese Patent Publication No. 46-11349, a catalyst made of a combination of a trivalent titanium compound and an organoaluminium 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).
The method of polymerization is shown below. The method includes:
In addition to the catalyst being limited in that it uses a trivalent titanium compound that does not require support, the disclosed embodiments have a polymerization pressure of 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 Patent Publication No. 54-7488
discloses carrying out the first stage polymerization in a liquid-filled state using a supported catalyst, but with this method it is extremely difficult to control the molecular weight of the produced polymer. In JP-A-54-32588, the first
It is disclosed that an inert gas is forcibly supplied to the stage polymerization vessel to increase the total pressure, and a high molecular side polymer is produced in the first stage polymerization, and a low molecular side polymer is produced in the second stage polymerization, but the supply This method has the disadvantage that a large amount of the inert gas produced flows into the second stage polymerization system without being consumed or removed, which means that it is difficult to produce a sufficiently low molecular weight polymer. On the other hand, the present inventors have conventionally discovered that trivalent metal halides and divalent metal hydroxides, oxides, carbonates,
We have been researching catalyst components using double salts containing these or reaction products (hereinafter sometimes referred to as solid products) with hydrates of divalent metal compounds as carriers. We discovered that the drawbacks of conventional continuous multi-stage polymerization could be overcome by using a catalyst that combines a solid product () prepared from an electron donor compound and a transition metal compound with an organoaluminum compound, and conducted various research. As a result of repeated efforts, the manufacturing method of the present invention was completed. That is, an object of the present invention is to provide a production method in which the above-described conventional problems in multi-stage polymerization of polyethylene are solved, 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. It is to provide. The method for producing polyethylene by multistage polymerization of the present invention comprises: a. A trivalent metal halide and a divalent metal hydroxide, oxide, carbonate, a double salt containing these, or a hydrate of a divalent metal compound. The solid product obtained by the reaction (), the final solid product () supported on a transition metal compound prepared from an electron donor compound, a transition metal compound of group 4a or group 5a, and organoaluminum. In the presence of a catalyst obtained by combining a compound with a saturated hydrocarbon solvent, in a state where a gas phase exists in the upper part of a polymerization vessel, a polymerization temperature of 30°C or more and 100°C or less,
Under polymerization pressure of 11 to 70 kg/ cm2 , the molar ratio of ethylene to hydrogen in the gas phase of the polymerizer is 1:0.001.
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. b 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 in the presence of a gas phase at the top of 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 exceeds 1:3.0 and becomes 7.0 or less, and 30% of the total ethylene supply amount is
The second stage polymerization is carried out by supplying between 90% and 90% ethylene. In addition, if necessary, α-olefin may be supplied to the first and/or second stage polymerization system to combine with ethylene and α-olefin.
- Copolymers with olefins can be produced. In that case, the sum of the moles of ethylene and α-olefin and the molar ratio of hydrogen may be the molar ratio of the first stage and/or the second stage. In the production method of the present invention, polymerization is started by supplying a catalyst to the first stage polymerization system, and in a saturated hydrocarbon solvent in a state where a gas phase exists at the top of the polymerization vessel, the polymerization degree is 30°C or more and 100°C. 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 resulting polymer is controlled by supplying ethylene and hydrogen such that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization vessel is within the range of 1:0.001 to 0.5. The molecular weight of the polymer obtained in this case is 2×10 5 to 8 in terms of weight average molecular weight.
Equivalent to ×10 5 . The amount of polymer produced is regulated with an ethylene feed of 10 to 70% of the total ethylene feed. Subsequently, the polymer suspended in the solvent obtained in the first-stage polymerization system is transferred as is to the second-stage polymerization system, but if necessary, components such as hydrogen may be separated and transferred later. . The transfer method is performed by forced transfer means such as a transfer pump. The second stage polymerization system was developed under newly set polymerization conditions, i.e., at a polymerization temperature of 50
℃ to 120℃, preferably 70℃ to 1000℃, polymerization pressure 11 to 70Kg/ cm2 , preferably 15 to 50Kg/ cm2 ,
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 resulting polymer is controlled by supplying ethylene and hydrogen such that the molar ratio of ethylene to hydrogen in the gas phase is in the range of more than 1:3.0 and less than 7.0. The molecular weight of the polymer obtained in the second stage polymerization is 1.5 × weight average molecular weight.
It corresponds to 10 4 to 6×10 4 . The amount of polymer produced is controlled by supplying ethylene at 30 to 90% of the total ethylene supply. The molar ratio of ethylene to hydrogen in the gas phase of the first stage polymerization and the second stage polymerization and the amount of ethylene supplied are determined depending on the intended use of the final polymer.
For example, when producing polyethylene for use in films, the molar ratio of ethylene to hydrogen in the first stage polymerization is 1:0.001 to 0.3, preferably 1:0.001.
~0.2. The ethylene feed rate is 40-60%, preferably 50% of the total ethylene feed rate. On the other hand, in the second stage polymerization, the molar ratio of ethylene to hydrogen was 1:3.0.
~7.0, preferably 1:3.0~6.0. The ethylene feed rate is 40-60%, preferably 50% of the total ethylene feed rate. In addition, in the case of blow molding, the molar ratio of ethylene to hydrogen in the first stage polymerization is 1:0.005 ~
0.5, preferably 1:0.01-0.4, and the ethylene feed rate is 30-70%, preferably 50% of the total ethylene feed rate. On the other hand, in the second stage polymerization, the molar ratio of ethylene to hydrogen is 1:3.0 to 7.0, preferably 1:3.0 to 7.0.
It is 5.0. The ethylene feed rate is 30-70%, preferably 50% of the total ethylene feed rate. 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. In the multistage polymerization of the present invention, a plurality of polymerization vessels are usually connected in series, but a certain plurality of polymerization vessels are connected in parallel (or some of them are parallel) to form the first and/or second stage polymerization system. It is also possible to do this. 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. The catalyst used in the production method of the present invention is produced by reacting a trivalent metal halide with a divalent metal hydroxide, oxide, carbonate, a double salt containing these, or a hydrate of a divalent metal compound. Combining the final solid product () supported with a transition metal compound prepared from the resulting solid product () and an electron donor compound, a group 4a or group 5a transition metal compound, and an organoaluminum compound. It is characterized by the fact that it can be obtained by Examples of the trivalent metal halide include aluminum trichloride (anhydrous) and iron trichloride (anhydrous). Examples of the divalent metal hydroxides (hereinafter sometimes referred to as divalent metal compounds) include Mg
Hydroxides like (OH) 2 , Ca(OH) 2 , Zn(OH) 2 , Mn(OH) 2 , oxides like MgO, CaO, ZnO, MnO , MgAl2O4 , Mg2SiO 4 , complex oxides containing divalent metals such as Mg6MnO8 , MgCO3 ,
Carbonates such as MnCO 3 , CaCO 3 , SnCl 2 .
2H2O , MgCl2・6H2O , NiCl2・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・2SiO・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. The solid product () is obtained by reacting a trivalent metal halide and a divalent metal compound. In order to carry out this reaction, use a ball mill in advance for 5 to 5 minutes.
It is desirable to mix and grind for 100 hours, or for 1 to 10 hours in a vibrating mill, to achieve a well-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. Suitable reaction time is 30 minutes to 50 hours, and if the reaction temperature is low,
The reaction is carried out for a long time so that no unreacted trivalent metal remains. As an electron donor compound, ether (RO
-R'), ester (RCO 2 R'), aldehyde (RCHO), ketone (RCOR'), carboxylic acid (RCO 2 H), acid anhydride (R-CO 2 CO-R'), acid amide (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. 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. Unsaturated hydrocarbon groups include alkenyl groups and alkadienyl groups, which 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 , 3-butadienyl, etc. 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 phenyl group. Some examples of substituents include tolyl, xylyl, mesityl, cuyumyl, benzyl, diphenylmethyl, phenethyl, styryl, and the like. Examples of the fused polycyclic hydrocarbon group include naphthyl, anthryl, phenanthryl, 2-indenyl, and 1-byrenyl. 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. . Polysiloxanes that can be used as electron donor compounds have the general formula
【式】（ｎ：３〜10000）で
表わされる
鎖状又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又は異種の残基をあ
らわすが、なかでも、水素、アルキル基、アリー
ル基等の炭化水素残基、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
からな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。通常用いられるものは前記式中の各Ｒ
が炭化水素残基から成るものでありり、具体例を
示すとアルキルシロキサン重合物として、たとえ
ば、オクタメチルトリシロキサンCH3〔Si
（CH3）2O〕2Si（CH3）3、オクタエチルシクロテト
ラシロキサン〔Si（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〔Si（CH3）2O〕o、
エチルポリシクロシロキサン〔SiH（C2H5）Ｏ〕
ｏ、メチルエチルポリシロキサン〔Si（CH3）
（C2H5）Ｏ〕oなどの重合物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〔Si（C6H5）2O〕3、ジフエニルポリシロキサン
〔Si（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）3SiO〔Si（CH3）（C6H5）Ｏ〕2Si
（CCH3）3、メチルフエニルポリシロキサン〔Si
（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。このほかR1が
水素またはハロゲンでR2がアルキル基、アリー
ル基等の炭化水素残基であるアルキル水素シロキ
サン重合物またはハロアルキルシロキサンまたは
ハロアリールシロキサン重合物があげられる。ま
た、各Ｒがアルコキシ基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を用いる
ことができる。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。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。
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等であつ
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。
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。
(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。
(2) 固体生成物（）と電子供与体化合物とを混
合し、次に遷移金属化合物を添加した後、反応
させる。
(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。
(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。
いずれの方法も、溶媒の存在下または不存在下
において行なうことできる。
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−50℃〜＋30℃が適当であるが、最も普通には
室温（約20℃）で混合する。混合は撹拌しながら
行なうのが好ましい。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。
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。
反応終了後は常法により濾別し、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する。かくして固体生成物
（）を得る。
固体生成物（）の調製における混合、反応に
当つて、溶媒を用いることは必ずしも必要ではな
いが、均一に反応させることが好ましいので、あ
らかじめ、任意のまたはすべての上記成分を溶媒
に溶解または分散させておいて混合しても良い。
溶媒の使用量の合計は、上記各成分合計量の約10
倍（重量）以下で十分である。これら固体生成物
（）の調製に用いる溶媒としては、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。
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、エチルアルミニ
ウムジクロリドがあげられ、また、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
ムを用いることもできる。
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
媒の除去工程即ち脱灰工程をなくすことが可能で
ある。さらに加えるべき特徴は、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0.35〜0.45であり、粉末粒子の形
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。
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、比較例中のメルトインデツククスは
ASTM Ｄ―1238（Ｅ）に従つた。／
（は重量平均分子量、は数平均分子量を表
わす。）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。
重合体収率は、１時間、固体生成物（）１ｇ
当りのポリエチレンの収量ｇ（ｇ―重合体／ｇ―
（）・Hr）、または１時間、チタン（またはバナ
ジウム）原子1mmolあたりのポリエチレン収量
ｇ〔ｇ―重合体／mmol―Ti（またはＶ）・Hr〕
で示した。
フイルムは、インフレーシヨンフイルム成形機
（50mmφ、75rpm、プラコー社製）により、温度
180〜200℃の条件下で厚さ10μmのものを造つた。
製造時の溶融樹脂の吐出量をみた。得られたフイ
ルムの打抜衝撃強度はASTM Ｄ―781、ヘイズ
値はASTM Ｄ―1003、フイツシユアイは、フイ
ルム1000cm2に存在する直径50μm以上の粒状高分
子物質の個数を測定した。
中空成形は、中空成形機（55mmφ、50rpm、石
川島播磨製IPB―110）により、温度165〜175℃、
サイクルタイム３分間の条件下で内容積４のビ
ンを造つた。
耐ストレスクラツキング性（F50値）は、
ASTM Ｄ―1693に従つた。
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。
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、ついで上記固体
生成物（）100Kgを加え、110℃に２時間反応さ
せた。反応終了後、常法に従い濾過を行ない、濾
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残つた固体生成物
をヘキサンで洗浄し、減圧乾燥後、固体生成物
（）を得た。固体生成物（）の１Kg中のチタ
ン原子は0.2molであつた。この固体生成物（）
を遷移金属触媒成分として使用した。
(2) エチレンの多段連続重合
内容積10の第１段重合器に、上記固体生成物
（）を１時間当り35mg、トリエチルアルミニウ
ムを１時間当り0.35mmolおよびヘキサンを１時
間当り2.5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
330Nl、水素を重合器気相部のエチレン対水素の
モル比が１対0.006になるように供給しつつ、全
圧30Kg／cm2（ゲージ圧）で連続的に第１段重合を
行なつた。
続いて、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、重合器の液レベルが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350Nl、水素を重合器気相部のエチレン
（ブテンを含む）対水素のモル比が１対4.6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。
以上の多段重合を150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、ポリエチレン粉末125Kgを得た。重合体収率
は23800ｇ―重合体／ｇ―（）・Hr、119000ｇ
―重合体／mmol―Ti・Hrであつた。
このポリエチレンは、メルトインデツクス
0.04、かさ比重0.42、密度0.950ｇ／cm3、ブテン含
有量2.1重量％、／32であつた。
このポリエチレンを用いてフイルムを製造した
ところ、吐出量28Kg／Hrであつた。フイルムは、
打抜衝撃強度185Kg―cm／mm、ヘイズ81％、フイ
ツシユアイは４個で、実用上十分な性能のフイル
ムであつた。
比較例 １
重合器気相部のエチレン対水素のモル比を１対
0.17にし、80℃において、全圧40Kg／cm2（ゲージ
圧）で重合すること以外は、実施例１の第１段重
合の条件と同様にして、150時間連続的に一段重
合を行ない、メルトインデツクス0.04のポリエチ
レン59Kgを得た。しかし、このポリエチレンの
Mw／は６であつた。
このポリエチレンではフイルムを製造すること
はできなかつた。
比較例 ２
トルエン150中に、実施例１で得られた固体
生成物（）100Kgおよびジメチルポリシロキサ
ン100Kg（実施例１と同品）を加え、撹拌しなが
ら110℃に２時間反応させた後、未反応ポリシロ
キサンを除去しない状態で、四塩化チタン173Kg
を加え、更に110℃に２時間反応させた。その後
は実施例１と同様にして最終固体生成物を得た。
チタン原子の含有量は最終固体生成物１Kg中
0.14molであつた。
実施例１の固体生成物（）の代りに、この最
終固体生成物を１時間当り100mg、トリエチルア
ルミニウムを１時間当り0.6mmol供給すること以
外は実施例１と同様にして多段連続重合を行な
い、ポリエチレン122Kgを得た。重合体収率は
8100ｇ―重合体／ｇ（）・Hr、58000ｇ―重合
体／mmol―Ti・Hrであつた。
このポリエチレンはメルトインデツクス0.03、
かさ比重0.34、／16であつた。
フイルムを製造したところ、吐出量16Kg／Hr
であり流動性は不良であつた。フイルムの打抜衝
撃強度は100Kg―cm／mmで強度は不足し、フイツ
シユアイは100個でなお表面状態は良くなく、実
用に耐えるフイルムではなかつた。
比較例 ３
実施例において、エチレン１時間当り35Nl、
水素気相部のエチレン対水素が１対0.001になる
ように供給し、全圧10Kg／cm2（ゲージ圧）で第１
段重合を行ない、ブテン―１を２容量％含むエチ
レンを１時間当り640Nl、水素を気相部のエチレ
ン（ブテンを含む）対水素が１対1.8になるよう
に供給し、全圧40Kg／cm2（ゲージ圧）で第２段重
合を行なうこと以外は、実施例１と同様にしてエ
チレンの多段連続重合を行なつた。ポリエチレン
123Kgが得られた。
このポリエチレンは、メルトインデツクス
0.04、／12であつた。
このポリエチレンを用い、フイルムを製造した
ところ、吐出量13Kg／Hrであつた。フイルムの
打抜衝撃強度は55Kg―cm／mm、フイツシユアイは
750個もあり、実用に耐えるフイルムではなかつ
た。
実施例 ２
(1) 遷移金属触媒成分の製造
マグネシアセメント（3MgO・MgCl2・4H2O）
110ｇ塩化アルミニウム（無水）100ｇを回転ボー
ルミル中100℃に加熱しながら40時間反応させ、
固体生成物（）を得た。
キシレン200ml中に、オクタエチルシクロテト
ラシロキサン〔Si（C2H5）2O〕4150ｇ（粘度10セン
チストークス）およびオキシ三塩化バナジウム
120ｇを加え混合し、これに固体生成物（）100
ｇを加え、120℃に２時間反応させ、固体生成物
（）を得た。バナジウム含有量は固体生成物
（）１ｇ中0.18mmolであつた。
(2) エチレンの多段連続重合
内容積10の第１段重合器に、上記固体生成物
（）を１時間当り40mg、トリイソブチルアルミ
ニウムを１時間当り0.35mmolおよびヘキサンを
１時間当り2.5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、ブテン―１を５容量％
含むエチレンを１時間当り315Nl、水素を重合器
気相部のエチレン（ブテンを含む）対水素のモル
比が１対0.008になるように供給しつつ、全圧30
Kg／cm2（ゲージ圧）で連続的に第１段重合を行な
つた。
続いて、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、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、エチレンを１時間当り300Nl、新たに
トリイソブチルアルミニウムを１時間当り
0.1mmol、水素を重合器気相部のエチレン（第１
段重合器より導入されるブテン含む）対水素のモ
ル比が１対3.7になるように供給しつつ、全圧40
Kg／cm2（ゲージ圧）で第２段重合を行なつた。
以上の多段重合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、ポリエチレン粉末90Kgを得た。重合体収率
18800ｇ―重合体／ｇ―（）・Hr、104000ｇ―
重合体／mmol―Ｖ・Hrであつた。
このポリエチレンは、メルトインデツクス
0.05、ブテン含有量2.0重量％、かさ比重0.39、密
度0.949ｇ／cm2、／29であつた。
このポリエチレンを用いてフイルムを製造した
ところ、吐出量26.5Kg／Hrであつた。フイルム
は、打抜衝撃強度175Kg―cm／mm、ヘイズ値80％、
フイツシユアイは５個で、実用上十分な性能をも
つていた。
比較例 ４
実施例２において、ブテン―１を３容量％含む
エチレンを１時間当り495Nl、水素を気相部のエ
チレン（ブテン含む）対水素が１対0.02になるよ
うに供給し、全圧40Kg／cm2（ゲージ圧）で第１段
重合を行ない、エチレンを１時間当り120Nl、水
素を気相部のエチレン（ブテン含む）対水素のモ
ル比が１対4.2になるように供給し、全圧25Kg／
cm2（ゲージ圧）で第２段重合を行なうこと以外
は、実施例２と同様にしてエチレンの多段連続重
合を行ないポリエチレン91Kgを得た。
このポリエチレンは、メルトインデツククス
0.04、／14であつた。
このポリエチレンを用いてフイルムを製造した
ところ、吐出量12Kg／Hrであつた。フイルムは
打抜衝撃強度80Kg―cm／mm、フイツシユアイは
700個で実用に耐えるフイルムではなかつた。
実施例 ３
塩化アルミニウム（無水）80ｇとヒドロタルサ
イト70ｇ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。
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0.21mmolであつた。
実施例３で得た固体生成物（）を１時間当り
30mg、トリイソブチルアルミニウムを１時間当り
0.4mmol、ヘキサンを１時間当り２、エチレン
を１時間当り200Nl、水素を重合器気相部のエチ
レン対水素のモル比が１対0.05になるように供給
しつつ、全圧15Kg／cm2（ゲージ圧）で第１段重合
を行ない、続いて、エチレンを１時間当り
200Nl、水素を重合器気相部のエチレン対水素の
モル比が１対3.7になるように供給しつつ、全圧
25Kg／cm2（ゲージ圧）で第２段重合を行なうこと
以外は、実施例１と同様にして多段連続重合を行
ない、ポリエチレン72Kgを得た。重合体収率は
16000ｇ―重合体／ｇ―（）・Hr、76000ｇ―重
合体／mmol―Ti・Hrであつた。
このポリエチレンは、メルトインデツクス
0.25、かさ比重0.40、密度0.955ｇ／cm3、／
Mn27であつた。
このポリエチレンを用いて中空ビンを製造した
ところ、パリソンのドローダウンは小さく、成形
時メルトフラクチヤーを起こすことはなく、成形
品の表面はサメ肌現象も見られず、極めて良好で
あり、成形品１個の重量は280ｇで、偏肉もほと
んどなく、実用上十分な性能のピンであつた。It is a chain or cyclic siloxane polymer represented by the formula (n: 3 to 10000), and each R
represents the same or different types of residues that can bond to silicon, and among them, one type of hydrogen, hydrocarbon residues such as alkyl groups, aryl groups, halogens, alkoxy groups or aryloxy groups, fatty acid residues, etc. and compounds in which two or more of these are distributed and bonded within the molecule in various ratios are used. Those usually used are each R in the above formula.
is composed of hydrocarbon residues, and to give a specific example, as an alkylsiloxane polymer, for example, octamethyltrisiloxane CH 3 [Si
(CH 3 ) 2 O] 2 Si(CH 3 ) 3 , lower polymers such as octaethylcyclotetrasiloxane [Si(C 2 H 5 ) 2 O] 4, and dimethylpolysiloxane [Si(CH 3 ) 2 O] o ,
Ethylpolycyclosiloxane [SiH(C 2 H 5 ) O]
o , methylethylpolysiloxane [Si(CH 3 )
Alkylsiloxane polymers such as (C 2 H 5 )O] o , hexaphenylcyclotrisiloxane [Si(C 6 H 5 ) 2 O] 3 , diphenylpolysiloxane [Si(C 6 H 5 ) 2 O] o , and diphenyl octamethyltetrasiloxane (CH 3 ) 3 SiO [Si(CH 3 ) (C 6 H 5 )O] 2 Si
(CCH 3 ) 3 , methylphenylpolysiloxane [Si
Examples include alkylarylsiloxane polymers such as (CH 3 )(C 6 H 5 )O] o . Other examples include alkyl hydrogen siloxane polymers, haloalkyl siloxanes, or haloaryl siloxane polymers in which R 1 is hydrogen or halogen and R 2 is a hydrocarbon residue such as an alkyl group or an aryl group. Furthermore, polysiloxanes in which each R is an alkoxy group, an aryloxy group, or a fatty acid residue can be used. These various polysiloxanes can also be used in combination. It is desirable that the polysiloxane used is liquid, with a viscosity (at 25°C) of
10-10000 centistokes is suitable, preferably
It ranges from 10 to 1000 centistokes. Examples of transition metal compounds include titanium, vanadium halides, oxyhalides, alcoholates, alkoxyhalides, acetoxyhalides, etc., such as titanium tetrachloride, titanium tetrabromide, tetraethoxytitanium, tetrabutoxytitanium, monochlorobutoxytitanium, dichloro Examples include dibutoxytitanium, trichloromonoethoxytitanium, vanadium tetrachloride, vanadium oxytrichloride, and the like. As a specific method for preparing the solid product (2), the following embodiments can be adopted. (1) Simultaneously mix and react the solid product () with an electron donor compound and a transition metal compound. (2) Mix the solid product () and the electron donor compound, then add the transition metal compound and then react. (3) Mix the solid product () and the transition metal compound, then add the electron donor compound and react. (4) An electron donor compound and a transition metal compound are mixed, and then a solid product () is mixed into this mixture and reacted. Either method can be carried out in the presence or absence of a solvent. The mixing ratio of the solid product (), the electron donor compound and the transition metal compound is the solid product ()
For 100g, the electron donor compound is 10-10000g,
Preferably 20-5000g, transition metal compound 1-5000g
1000 g, preferably 10 to 500 g, and
The amount of the transition metal compound is 2 to 2000 g, preferably 5 to 500 g, per 100 g of the electron donor compound. Mixing is suitably carried out at -50°C to +30°C, but most commonly at room temperature (approximately 20°C). Preferably, the mixing is carried out with stirring. After mixing, stir while stirring for 30~
The reaction is carried out at 300°C, preferably 50 to 200°C, for 10 minutes to 30 hours. 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. After the reaction is completed, the mixture is filtered by a conventional method, washed repeatedly with a solvent to remove unreacted transition metal compounds and electron donor compounds, and dried. A solid product () is thus obtained. It is not always necessary to use a solvent during the mixing and reaction in the preparation of the solid product (), but it is preferable to react uniformly, so any or all of the above components may be dissolved or dispersed in a solvent in advance. You may leave it to mix.
The total amount of solvent used is approximately 10% of the total amount of each component above.
Less than double (weight) is sufficient. Solvents used for the preparation of these solid products () include hexane,
Aliphatic hydrocarbons such as heptane, octane, nonane, decane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene, tetrachloride Examples include carbon, chloroform, dichloroethane, trichloroethylene, tetrachloroethylene, and halogenated hydrocarbons such as carbon tetrabromide. Examples of organoaluminum compounds include trialkylaluminum such as triethylaluminum, triisobutylaluminum, and trihexylaluminum, dialkylaluminum monochloride such as diethylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and monoethoxydiethyl Aluminum, alkoxyalkyl aluminum such as diethoxymonoethyl aluminum can also be used. 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 stable multi-stage polymerization can be carried out for a long period of time with no or very little polymer adhesion to the walls of the polymerization vessel. The catalyst used in the present invention has extremely high polymerization activity, 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. A further feature to be added is that the polyethylene obtained has an extremely wide 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. In addition, the bulk specific gravity of the polyethylene powder obtained by the present invention is 0.35 to 0.45, and the shape of the powder particles is good, so the production efficiency is high per unit volume of the polymerization vessel and per hour, and the polymer powder is transported through pipes. It has the characteristics that the above-mentioned troubles occur less often and the powder can be easily granulated. Hereinafter, the features of the present invention will be specifically explained with reference to Examples. The melt index in Examples and Comparative Examples is
In accordance with ASTM D-1238(E). /
(Represents weight average molecular weight, represents number average molecular weight.) It was determined by gel permeation chromatography using GPC-200 manufactured by Waters. Polymer yield: 1 hour, 1 g of solid product ()
Yield of polyethylene per g (g-polymer/g-
()・Hr), or polyethylene yield g per mmol of titanium (or vanadium) atom per hour [g-polymer/mmol-Ti (or V)・Hr]
It was shown in The film is heated to a temperature of
A 10μm thick specimen was produced under conditions of 180-200℃.
The amount of molten resin discharged during manufacturing was observed. The punching impact strength of the obtained film was ASTM D-781, the haze value was ASTM D-1003, and the number of particulate polymeric substances with a diameter of 50 μm or more present in 1000 cm 2 of the film was measured. The blow molding was performed using a blow molding machine (55 mmφ, 50 rpm, IPB-110 manufactured by Ishikawajima Harima) at a temperature of 165 to 175°C.
A bottle with an internal volume of 4 was made under conditions of a cycle time of 3 minutes. Stress cracking resistance ( F50 value) is
In accordance with ASTM D-1693. 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.
Thereafter, it was cooled and pulverized to obtain a solid product (2). 173 kg of titanium tetrachloride and 100 kg of chain dimethylpolysiloxane (viscosity 100 centistokes) were added to 150 kg of toluene and mixed. Then, 100 kg of the above solid product (2) was added and reacted at 110°C for 2 hours. After the reaction is completed, filtration is performed according to a conventional method, and the remaining solid product is washed with hexane until unreacted titanium tetrachloride and unreacted polysiloxane are no longer detected in the filtrate. After drying under reduced pressure, the solid product () is removed. Obtained. The amount of titanium atoms in 1 kg of the solid product ( ) was 0.2 mol. This solid product ()
was used as the transition metal catalyst component. (2) Multistage continuous polymerization of ethylene To the first stage polymerization vessel with an internal volume of 10, the above solid product () was fed at a rate of 35 mg per hour, triethylaluminum at 0.35 mmol per hour, and hexane at a rate of 2.5 per hour. Then, while draining the contents of the polymerization vessel so as to maintain the liquid level in the polymerization vessel at 80%, ethylene was added per hour at 70°C.
The first stage polymerization was carried out continuously at a total pressure of 30 Kg/cm 2 (gauge pressure) while supplying 330 Nl and hydrogen such that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization reactor was 1:0.006. . Next, the entire amount of the polymer suspended in the solvent exiting the first-stage polymerization vessel is introduced into the second-stage polymerization vessel with an internal volume of 20% using a transfer pump, and polymerization is continued to maintain the liquid level in the polymerization vessel at 80%. While discharging the contents of the container, add 1 ethylene containing 5% by volume of butene-1 at 80°C.
While supplying hydrogen at a rate of 350Nl per hour so that the molar ratio of ethylene (including butene) to hydrogen in the gas phase of the polymerization reactor was 1:4.6, the process was carried out continuously at a total pressure of 40Kg/cm 2 (gauge pressure). A two-stage polymerization was performed. The above multi-stage polymerization was carried out continuously for 150 hours, but
The operation was extremely stable, and 125 kg of polyethylene powder was obtained after drying without deashing. Polymer yield is 23800g-polymer/g-()・Hr, 119000g
-Polymer/mmol-Ti/Hr. This polyethylene has melt index
0.04, bulk specific gravity 0.42, density 0.950 g/cm 3 , butene content 2.1% by weight, /32. When a film was manufactured using this polyethylene, the discharge rate was 28 kg/hr. The film is
The film had a punching impact strength of 185 kg-cm/mm, a haze of 81%, and 4 punching eyes, and had sufficient performance for practical use. Comparative Example 1 The molar ratio of ethylene to hydrogen in the gas phase of the polymerization vessel was set to 1:
0.17, the first stage polymerization was carried out continuously for 150 hours under the same conditions as the first stage polymerization in Example 1, except that the polymerization was carried out at 80°C and a total pressure of 40 kg/cm 2 (gauge pressure). 59 kg of polyethylene with an index of 0.04 was obtained. However, this polyethylene
Mw/ was 6. It was not possible to produce a film using this polyethylene. Comparative Example 2 100 kg of the solid product () obtained in Example 1 and 100 kg of dimethylpolysiloxane (same as Example 1) were added to 150 kg of toluene, and after reacting at 110°C for 2 hours with stirring, 173Kg of titanium tetrachloride without removing unreacted polysiloxane
was added, and the mixture was further reacted at 110°C for 2 hours. Thereafter, the final solid product was obtained in the same manner as in Example 1.
The content of titanium atoms in 1 kg of final solid product
It was 0.14mol. Multistage continuous polymerization was carried out in the same manner as in Example 1, except that instead of the solid product () of Example 1, 100 mg of this final solid product was supplied per hour, and 0.6 mmol of triethylaluminum was supplied per hour. 122 kg of polyethylene was obtained. The polymer yield is
8100g-polymer/g()・Hr, 58000g-polymer/mmol-Ti・Hr. This polyethylene has a melt index of 0.03,
The bulk specific gravity was 0.34, /16. When the film was manufactured, the discharge amount was 16Kg/Hr.
Therefore, the fluidity was poor. The punching impact strength of the film was 100 kg-cm/mm, which was insufficient, and even after 100 punches, the surface condition was not good, and the film was not suitable for practical use. Comparative Example 3 In the example, 35 Nl of ethylene per hour,
Hydrogen was supplied so that the ratio of ethylene to hydrogen in the gas phase was 1:0.001, and the first
Stage polymerization was carried out, and 640 Nl of ethylene containing 2% by volume of butene-1 was supplied per hour, and hydrogen was supplied at a ratio of ethylene (including butene) to hydrogen in the gas phase of 1:1.8, and the total pressure was 40 Kg/cm. Multistage continuous polymerization of ethylene was carried out in the same manner as in Example 1, except that the second stage polymerization was carried out at 2 (gauge pressure). polyethylene
123Kg was obtained. This polyethylene has melt index
It was 0.04, /12. When a film was manufactured using this polyethylene, the discharge rate was 13 kg/hr. The punching impact strength of the film is 55Kg-cm/mm.
There were 750 pieces, and it was not a film that could be used for practical purposes. Example 2 (1) Production of transition metal catalyst component Magnesia cement (3MgO・MgCl 2・4H 2 O)
110g aluminum chloride (anhydrous) 100g was heated to 100℃ in a rotating ball mill and reacted for 40 hours.
A solid product () was obtained. In 200 ml of xylene, 150 g of octaethylcyclotetrasiloxane [Si(C 2 H 5 ) 2 O] 4 (viscosity 10 centistokes) and vanadium oxytrichloride
Add 120g and mix, add solid product ()100
g was added thereto, and the mixture was reacted at 120°C for 2 hours to obtain a solid product (2). The vanadium content was 0.18 mmol in 1 g of solid product (). (2) Multistage continuous polymerization of ethylene Into a first stage polymerization vessel with an internal volume of 10, the above solid product () was added at a rate of 40 mg per hour, triisobutylaluminum at a rate of 0.35 mmol per hour, and hexane at a rate of 2.5 mmol per hour. Butene-1 was added to 5% by volume at 70°C while supplying and discharging the contents of the polymerization vessel to maintain the liquid level in the polymerization vessel at 80%.
While supplying ethylene containing 315Nl per hour and hydrogen such that the molar ratio of ethylene (including butene) to hydrogen in the gas phase of the polymerization reactor was 1:0.008, the total pressure was 30Nl per hour.
The first stage polymerization was carried out continuously at Kg/cm 2 (gauge pressure). Next, the entire amount of the polymer suspended in the solvent that came out of the first stage polymerization vessel was introduced into the second stage polymerization vessel with an internal volume of 20% using a transfer pump, so that the liquid level in the polymerization vessel was maintained at 80%. 80℃ while discharging the contents of the polymerization vessel.
300Nl of ethylene per hour and new triisobutylaluminum per hour.
Add 0.1 mmol of hydrogen to ethylene (first
While supplying hydrogen at a molar ratio of 1:3.7 (including butene introduced from the stage polymerizer), the total pressure was 40
The second stage polymerization was carried out at Kg/cm 2 (gauge pressure). The above multi-stage polymerization was carried out continuously for 120 hours, but
The operation was extremely stable, and 90 kg of polyethylene powder was obtained after drying without deashing. Polymer yield
18800g-Polymer/g-()・Hr, 104000g-
Polymer/mmol-V.Hr. This polyethylene has melt index
0.05, butene content 2.0% by weight, bulk specific gravity 0.39, density 0.949 g/cm 2 , /29. When a film was manufactured using this polyethylene, the discharge rate was 26.5 kg/Hr. The film has a punching impact strength of 175 kg-cm/mm, a haze value of 80%,
There were five fisheyes, and they had sufficient performance for practical use. Comparative Example 4 In Example 2, 495 Nl of ethylene containing 3% by volume of butene-1 was supplied per hour, hydrogen was supplied so that the ratio of ethylene (including butene) to hydrogen in the gas phase was 1:0.02, and the total pressure was 40 kg. The first stage polymerization was carried out at /cm 2 (gauge pressure), and ethylene was supplied at 120 Nl per hour, and hydrogen was supplied so that the molar ratio of ethylene (including butene) to hydrogen in the gas phase was 1:4.2. Pressure 25Kg/
Multistage continuous polymerization of ethylene was carried out in the same manner as in Example 2 except that the second stage polymerization was carried out at cm 2 (gauge pressure) to obtain 91 kg of polyethylene. This polyethylene is melt indexed
It was 0.04, /14. When a film was manufactured using this polyethylene, the discharge rate was 12 kg/hr. The film has a punching impact strength of 80Kg-cm/mm, and the punching eye has a punching impact strength of 80Kg-cm/mm.
At 700 pieces, it was not a film that could withstand practical use. Example 3 80 g of aluminum chloride (anhydrous) and 70 g of hydrotalcite were heated at 170° C. for 3 hours in a vibrating mill while mixing, pulverizing, and reacting simultaneously to obtain a solid product (). 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 the mixture was reacted at 100°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 0.21 mmol. The solid product obtained in Example 3 () per hour
30mg triisobutylaluminum per hour
While supplying 0.4 mmol of hexane per hour, 200 Nl of ethylene per hour, and hydrogen such that the molar ratio of ethylene to hydrogen in the gas phase of the polymerizer was 1:0.05, the total pressure was 15 Kg/cm 2 ( The first stage polymerization was carried out at
While supplying 200Nl of hydrogen such that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization reactor was 1:3.7, the total pressure was increased.
Multistage continuous polymerization was carried out in the same manner as in Example 1, except that the second stage polymerization was carried out at 25 kg/cm 2 (gauge pressure), and 72 kg of polyethylene was obtained. The polymer yield is
16000g-polymer/g-()・Hr, 76000g-polymer/mmol-Ti・Hr. This polyethylene has a melt index
0.25, bulk specific gravity 0.40, density 0.955g/cm 3 , /
It was Mn27. When a hollow bottle was manufactured using this polyethylene, the drawdown of the parison was small, no melt fracture occurred during molding, and the surface of the molded product was extremely good with no shark skin phenomenon. Each pin weighed 280 g, had almost no uneven thickness, and had sufficient performance for practical use.
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)
存在下、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
方法において ａ 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、チタンまたはバナジウム
化合物とから調製した化合物を担持させた最終
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 ｂ 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
エチレン対水素のモル比が１対3.0をこえて7.0
以下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項記載の製造方法。 ３ 固体生成物（）が固体生成物（）100ｇ
に対し電子供与体化合物20〜1000ｇ、遷移金属化
合物は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。 ４ 電子供与体化合物がポリシロキサンである特
許請求の範囲第１項、第２項または第３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、ケトンもしくは酸無水物である特許
請求の範囲第１項、第２項または第４項記載の製
造方法。[Claims] 1 Using a Ziegler type catalyst in the presence of a solvent and hydrogen, using multiple polymerization vessels, a high molecular side polymer is produced in the first stage polymerization system, and a low molecular side polymer is produced in the second stage polymerization system. In a method for producing polyethylene by continuous multi-stage polymerization, a aluminum halide and [(hydroxide, oxide, carbonate of magnesium, double salt containing these) or hydrate of a magnesium compound]
A solid product () obtained by reacting with
In the presence of a catalyst obtained by combining an organoaluminum compound with the final solid product (2) supported by a compound prepared from an electron donor compound and a titanium or vanadium compound, in a saturated hydrocarbon solvent, a polymerization vessel is prepared. in the presence of a gas phase at the top of the polymerization temperature of 30°C or more and 100°C or less,
Under polymerization pressure of 11 to 70 kg/ cm2 , the molar ratio of ethylene to hydrogen in the gas phase of the polymerizer is 1:0.001.
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 b. Next, the polymer suspended in the solvent is transferred to the second stage polymerization system, and is heated in a polymerization vessel in a saturated hydrocarbon solvent. In the presence of a gas phase at the top of the polymerization temperature of 50
℃ or more and 120℃ or less, polymerization pressure 11 to 70Kg/cm 2
Under these conditions, the molar ratio of ethylene to hydrogen in the gas phase of the polymerization reactor exceeds 1:3.0 to 7.0.
A method for producing polyethylene by multistage polymerization, characterized in that hydrogen is supplied in the following amount, and ethylene is supplied in an amount of 30 to 90% of the total amount of ethylene supplied to carry out the second stage polymerization. 2. The production 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. Method. 3 Solid product () is 100g of solid product ()
The production method according to claim 1, wherein the electron donor compound is 20 to 1000 g and the transition metal compound is 10 to 500 g, and the transition metal compound is 30 to 500 g per 100 g of the electron donor compound. . 4. The manufacturing method according to claim 1, 2 or 3, wherein the electron donor compound is polysiloxane. 5 The electron donor compound is an ether, an ester,
The manufacturing method according to claim 1, 2 or 4, which is an aldehyde, ketone or acid anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17349680A JPS5798510A (en) | 1980-12-09 | 1980-12-09 | Production of polyethylene by multistage polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17349680A JPS5798510A (en) | 1980-12-09 | 1980-12-09 | Production of polyethylene by multistage polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5798510A JPS5798510A (en) | 1982-06-18 |
| JPS6352659B2 true JPS6352659B2 (en) | 1988-10-19 |
Family
ID=15961585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17349680A Granted JPS5798510A (en) | 1980-12-09 | 1980-12-09 | Production of polyethylene by multistage polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5798510A (en) |
-
1980
- 1980-12-09 JP JP17349680A patent/JPS5798510A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5798510A (en) | 1982-06-18 |
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