JPS6366324B2 - - Google Patents
Info
- Publication number
- JPS6366324B2 JPS6366324B2 JP1397981A JP1397981A JPS6366324B2 JP S6366324 B2 JPS6366324 B2 JP S6366324B2 JP 1397981 A JP1397981 A JP 1397981A JP 1397981 A JP1397981 A JP 1397981A JP S6366324 B2 JPS6366324 B2 JP S6366324B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- ethylene
- hydrogen
- polymer
- stage polymerization
- 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 142
- -1 polyethylene Polymers 0.000 claims description 85
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 74
- 239000005977 Ethylene Substances 0.000 claims description 74
- 229920000642 polymer Polymers 0.000 claims description 66
- 229910052739 hydrogen Inorganic materials 0.000 claims description 55
- 239000001257 hydrogen Substances 0.000 claims description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 50
- 239000012265 solid product Substances 0.000 claims description 50
- 239000004698 Polyethylene Substances 0.000 claims description 44
- 229920000573 polyethylene Polymers 0.000 claims description 44
- 239000007789 gas Substances 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 28
- 150000003623 transition metal compounds Chemical class 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 229920001296 polysiloxane Polymers 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 150000004677 hydrates Chemical class 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 150000004649 carbonic acid derivatives 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 235000012254 magnesium hydroxide Nutrition 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 description 27
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 22
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 13
- 238000009826 distribution Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 238000004080 punching Methods 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 9
- 150000002430 hydrocarbons Chemical group 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000005484 gravity Effects 0.000 description 8
- 238000000465 moulding Methods 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000011777 magnesium Substances 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 description 5
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000000155 melt Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910001507 metal halide Inorganic materials 0.000 description 5
- 150000005309 metal halides Chemical class 0.000 description 5
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 125000001424 substituent group 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
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000000071 blow moulding Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- 125000002950 monocyclic group Chemical group 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 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
- 241000251468 Actinopterygii Species 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- FHUODBDRWMIBQP-UHFFFAOYSA-N Ethyl p-anisate Chemical compound CCOC(=O)C1=CC=C(OC)C=C1 FHUODBDRWMIBQP-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
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 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
- 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
- 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
- 238000007872 degassing Methods 0.000 description 2
- 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 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
- 229960001545 hydrotalcite Drugs 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 150000004679 hydroxides Chemical class 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
- 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
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 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
- 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
- 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
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [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
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 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
- 229910020068 MgAl 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
- 102100024864 REST corepressor 1 Human genes 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 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
- HJPOKQICBCJGHE-UHFFFAOYSA-J [C+4].[Cl-].[Cl-].[Cl-].[Cl-] Chemical compound [C+4].[Cl-].[Cl-].[Cl-].[Cl-] HJPOKQICBCJGHE-UHFFFAOYSA-J 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
- 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
- 125000004429 atom 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
- 230000015572 biosynthetic process Effects 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
- VJVUKRSEEMNRCM-UHFFFAOYSA-L butan-1-olate titanium(4+) dichloride Chemical compound [Cl-].[Cl-].CCCCO[Ti+2]OCCCC VJVUKRSEEMNRCM-UHFFFAOYSA-L 0.000 description 1
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical compound [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 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
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 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
- 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
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 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
- 239000007792 gaseous phase Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 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
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000001771 impaired effect Effects 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
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 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
- 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
- 150000002902 organometallic 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
- 239000002245 particle Substances 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- MVDYEFQVZNBPPH-UHFFFAOYSA-N pentane-2,3,4-trione Chemical compound CC(=O)C(=O)C(C)=O MVDYEFQVZNBPPH-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
- 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
- 239000000243 solution Substances 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
- 229910052720 vanadium Inorganic materials 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 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
- 239000003643 water by type Substances 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
系で低分子側重合体を、第２段重合系で高分子側
重合体をつくる多段重合法によるポリエチレンの
製造法に関する。
本発明におけるポリエチレンとは、エチレンの
単独重合体の他に、エチレンと共重合しうる他の
少量のα−オレフイン、例えば、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
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の方法がある
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。たとえば、担持型触媒成
分と有機金属化合物の組合せにより、第１段で低
分子側重合体をつくり、その後一たん重合系のガ
スを放出し、第２段で高分子側重合体をつくる連
続多段重合法が特開昭51−47079に開示されてい
る。該方法は、重合温度が120〜250℃の高温溶解
重合であること、重合体が溶解するに充分な溶媒
の使用が必要なため溶媒の使用量がかなり多いと
いう欠点がある。また、特公昭48−42716には、
第１段の重合終了後に、重合系を開放して気相の
ガスを放出し、新たに重合条件を設定しなおして
第２段の重合を行なう方法が開示されているが、
このような回分方式は重合生産性が著しく悪い。
本発明の目的は、これらの従来の問題点を解消
することであり、第一段で低分子重合体、第二段
で高分子重合体ををつくるポリエチレンの連続多
段重合を低温下、溶媒の少ない状態で行ない分子
量分布の広いポリエチレンを得ることである。
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来たが、
この固体生成物（）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み合せた触媒を用いるこ
とにより効果のあることを見出し、さらに研究を
重ねて本発明の多段重合法を完成するに到つた。
本発明の多段重合によるポリエチレンの製造法
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、第4a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固体生
成物（）と有機アルミニウム化合物とを組み
合わせて得られる触媒の存在下、飽和炭化水素
溶媒中、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５ないし70
Kg／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30〜90％のエチレンを供給して、第１段重
合を行い、
第１段重合終了後は、溶媒中に懸濁した重合
物を、１〜60Kg／cm2の圧力帯域に導き、気相部
より水素の少なくとも一部分は第１段重合系に
もどし、ついで該懸濁した重合物を気相が存在
する状態において、重合温度30℃以上100℃以
下、重合圧力５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、全エチレン量の10〜70％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。
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50℃以上120℃以下好ましくは70〜
100℃、重合圧力５ないし70Kg／cm2好ましくは10
ないし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
（Mw）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される。
第１段重合終了後は、溶媒中に懸濁した重合物
を、１〜60Kg／cm2の圧力帯域に導き、溶媒に溶解
した状態で第１段重合系を出た水素の少なくとも
一部分を該重合系外に抜出す。除去された水素は
少なくとも一部分は第１段重合系にもどし再利用
する。上記圧力の低い帯域は、通常各段の中間に
設けられるが、何れか一方の重合系に組込むこと
も可能である。第１段重合系と低圧力帯域との落
圧差は、第２段重合系で必要な水素量により決定
する。
大部分の水素を除去した溶媒に懸濁した重合物
を、移送ポンプなどの移送手段により、第２段重
合系に導く。新たに設定した重合温度30℃以上
100℃以下好ましくは40〜90℃、重合圧力５ない
し70Kg／cm2好ましくは10〜50Kg／cm2の条件下で、
重合器上部の気相部が存在する状態で第２段重合
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0.001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。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、
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10〜70％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。
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１：3.0をこえて7.0以下好ましくは１：3.0
をこえて6.0であり、エチレン供給量は全エチレ
ン供給量の30〜90％、好ましくは40〜60％であ
る。一方の第２段重合はエチレン対水素のモル比
は好ましくは１：0.001〜0.3、より好ましくは
１：0.001〜0.2であり、エチレン供給量は全エチ
レン供給量の30〜90％、好ましくは40〜60％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3.0をこえて7.0以下であ
り、好ましくは１：3.0をこえて5.0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。第２段重合はエチレン対水素
のモル比は好ましくは１：0.005〜0.5、より好ま
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。
本発明の製造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、ヘプン、
オクタン、灯油などが用いられる。
本発明の製造法に用いる触媒は、３価金属ハロ
ゲン化物の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
ウム化合物とを組み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）が示されるが、
好ましくは、アルミニウムのハロゲン化物であ
る。
前記２価金属の水酸化物等（以下２価金属化合
物ということがある）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・2SiO2・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等があげ
られるが、好ましくはマグネシウムの前記化合物
である。
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（RoSR′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。
上記各一般式においてＲ，R′は炭素基であり、
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。
上記電子供与体化合物として具体例をあげる。
エーテル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、安怠香酸ブチル、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、アセチルケトン、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 a multi-stage polymerization method using a plurality of polymerization vessels to produce a low molecular weight polymer in the first stage polymerization system and a high molecular weight polymer in the second stage polymerization system. In the present invention, polyethylene means, in addition to a homopolymer of ethylene, a small amount 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 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. Methods to expand 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. For example, a continuous multi-stage polymerization method involves combining a supported catalyst component and an organometallic compound to produce a low-molecular polymer in the first stage, then releasing the polymerization gas, and producing a high-molecular polymer in the second stage. is disclosed in Japanese Patent Application Laid-Open No. 51-47079. This method has disadvantages in that it is a high-temperature dissolution polymerization with a polymerization temperature of 120 to 250°C, and that it requires the use of a sufficient amount of solvent to dissolve the polymer, so that the amount of solvent used is quite large. In addition, in the special public official publication 48-42716,
A method is disclosed in which after the first stage polymerization is completed, the polymerization system is opened to release gas in the gas phase, and the polymerization conditions are newly set to perform the second stage polymerization.
Such a batch method has extremely poor polymerization productivity. The purpose of the present invention is to solve these conventional problems, and to carry out the continuous multi-stage polymerization of polyethylene to produce a low-molecular polymer in the first stage and a high-molecular polymer in the second stage at low temperatures and in the absence of a solvent. It is possible to obtain polyethylene with a wide molecular weight distribution by carrying out the process in a small amount. The present inventors have conventionally developed reaction products (hereinafter referred to as I have been researching catalyst components that use solid products (sometimes referred to as ) as carriers.
It was discovered that it is effective to use a catalyst that combines this solid product (), a solid product () prepared from an electron donor compound and a transition metal compound, and an organoaluminum compound, and after further research, the present invention was developed. We have completed the multi-stage polymerization method. The method for producing polyethylene by multistage polymerization of the present invention involves 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. A combination of a solid product (2) obtained by carrying a transition metal compound prepared from an electron donor compound and a transition metal compound of group 4a or 5a and an organoaluminum compound. in the presence of a catalyst obtained from a saturated hydrocarbon solvent in the presence of a gas phase, at a polymerization temperature of 50°C or higher and 120°C or lower, and a polymerization pressure of 5 to 70°C.
Under conditions of Kg/ cm2 , 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 to 90% of the total ethylene supply amount is Ethylene is supplied to perform the first stage polymerization. After the first stage polymerization, the polymer suspended in the solvent is introduced into a pressure zone of 1 to 60 Kg/ cm2 , and at least hydrogen is removed from the gas phase. A portion is returned to the first stage polymerization system, and then the suspended polymer is placed in a polymerization vessel under the conditions of a polymerization temperature of 30°C to 100°C and a polymerization pressure of 5 to 70 kg/cm 2 in the presence of a gas phase. The molar ratio of ethylene to hydrogen in the gas phase is 1:
The second stage polymerization is carried out by supplying hydrogen in an amount of 0.001 to 0.5 and also supplying ethylene in an amount of 10 to 70% of the total ethylene amount. Further, if necessary, it can be supplied to the α-olefin first stage 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 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 the polymerization temperature is 50°C or higher and 120°C in a saturated hydrocarbon solvent with a gas phase present at the top of the polymerization vessel. Preferably 70~
100℃, polymerization pressure 5 to 70Kg/cm 2 preferably 10
The first stage polymerization is carried out under conditions of 50 to 50 kg/cm 2 . The molecular weight of the produced polymer is 7.0 because the molar ratio of ethylene to hydrogen in the gas phase of the polymerization vessel exceeds 1:3.0.
Adjustments are made by feeding ethylene and hydrogen to fall within the following ranges: in this case,
The molecular weight of the obtained polymer corresponds to 1.5×10 4 to 6×10 4 in terms of weight average molecular weight (Mw).
The amount of polymer produced is controlled by feeding 30 to 90% of the total ethylene feed. After the first stage polymerization is completed, the polymer suspended in the solvent is brought into a pressure zone of 1 to 60 kg/ cm2 , and at least a portion of the hydrogen that has exited the first stage polymerization system while dissolved in the solvent is removed. Extract it from the polymerization system. At least a portion of the removed hydrogen is returned to the first stage polymerization system for reuse. The above-mentioned low pressure zone is usually provided in the middle of each stage, but it can also be incorporated into either one of the polymerization systems. The drop pressure difference between the first stage polymerization system and the low pressure zone is determined by the amount of hydrogen required in the second stage polymerization system. The polymer suspended in the solvent from which most of the hydrogen has been removed is guided to the second stage polymerization system by a transfer means such as a transfer pump. Newly set polymerization temperature of 30℃ or higher
Under the conditions of 100℃ or less, preferably 40 to 90℃, and a polymerization pressure of 5 to 70Kg/ cm2 , preferably 10 to 50Kg/ cm2 ,
The second stage polymerization is carried out in the presence of a gas phase in the upper part of the polymerization vessel. The molecular weight of the resulting polymer is controlled by feeding ethylene and hydrogen such that the molar ratio of ethylene to hydrogen in the gas phase is within the range of 1:0.001 to 0.5. The molecular weight of the polymer obtained in the second stage polymerization is the weight average molecular weight,
It corresponds to 2×10 5 to 8×10 5 . The amount of polymer produced is controlled by feeding 10 to 70% of the total ethylene feed. 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. 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, in the first stage polymerization, the molar ratio of ethylene to hydrogen is greater than 1:3.0 and less than or equal to 7.0, preferably 1:3.0.
6.0, and the ethylene feed rate is 30-90%, preferably 40-60% of the total ethylene feed rate. On the other hand, in the second stage polymerization, the molar ratio of ethylene to hydrogen is preferably 1:0.001 to 0.3, more preferably 1:0.001 to 0.2, and the amount of ethylene fed is 30 to 90% of the total amount of ethylene fed, preferably 40%. ~60%. In addition, in the case of blow molding, in the first stage polymerization, the molar ratio of ethylene to hydrogen is more than 3.0 and less than 7.0, preferably more than 1:3.0 and 5.0, and the amount of ethylene supplied is less than the total amount of ethylene supplied. 30-70%, preferably 50%. In the second stage polymerization, the molar ratio of ethylene to hydrogen is preferably 1:0.005-0.5, more preferably 1:0.01-0.4, and the ethylene feed rate is 30-70%, preferably 50% of the total ethylene feed rate. be. 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 of the production method of the present invention may be a saturated hydrocarbon having 4 to 15 carbon atoms, such as butane, pentane, hexane, hepane,
Octane, kerosene, etc. are used. 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. Solid product obtained ()
and an electron donor compound, a transition metal compound of group 4a or group 5a. . Examples of trivalent metal halides include aluminum trichloride (anhydrous) and iron trichloride (anhydrous).
Preferred is an aluminum halide. 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, MgAl 2 O 4 , Mg 2 SiO 4 , complex oxides containing divalent metals such as Mg 6 MnO 8 , MgCO 3 ,
Carbonates such as MnCO 3 , CaCO 3 , SnCl 2
2H 2 O, MgCl 2・6H 2 O, NiCl 2・6H 2 O,
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 2・2H 2 O, 3MgCO 3・Mg(OH) 2・
Hydrations of double salts of carbonates and hydroxides such as 3H 2 O, and hydrates of hydroxide carbonates containing divalent metals such as Mg 6 Al 2 (OH) 16 CO 3 4H 2 O Among them, the above compound of magnesium is preferable. 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 (R-O
-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 thioethers (R o SR' 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 carbon groups,
More specifically, aliphatic hydrocarbons having 1 to 50 carbon atoms,
Examples include unsaturated hydrocarbons, monocyclic hydrocarbon groups without substituents, monocyclic hydrocarbon groups with substituents, and fused polycyclic hydrocarbon groups. 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,
Examples include 5-methylhexyl. 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 a 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-pyrenyl. 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,
Ethyl anisate, 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. , acetyl ketone, acetophenone, benzophenone, etc.; carboxylic acids such as acetic acid, propionic acid, benzoic acid; acid anhydrides such as acetic anhydride, butyric anhydride, benzoic anhydride; acid amides such as formamide, acetamide, benzamide, etc.; amines Examples include methylamine, dimethylamine, trimethylamine, amylamine, aniline, methylaniline, pyridine, etc.; examples of nitrile include acetonitrile, propionitrile,
Benzonitrile, etc.; Phosphines include triethylphosphine, triphenylphosphine, etc.;
Examples of thioethers include diethyl sulfide and diphenyl sulfide. 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
等の１種から成るものおよびこれらの２種以上
が、種種の比率で、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る。
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〕ｎ、エテルポリシクロシロキサン
〔SiH（C2H5）Ｏ〕ｎ、メチルエチルポリシロキ
サン〔Si（CH3）（C2H5）Ｏ〕ｎ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〔Si（C6H5）2O〕3、ジ
フエニルポリシロキサン〔Si（C6H5）2O〕ｎ、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（CH3）3、メチルフエニル
ポリシロキサン〔Si（CH3）（C6H5）Ｏ〕ｎ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等があげられ
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、つぎ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
において行うことができる。
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。混合は攪拌しながら
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、デカン等の脂肪族
炭化水素、ベンゼン、トルエン、キシレン、エチ
ルベンゼン、クメン等の芳香族炭化水素；クロル
ベンゼン、ジクロルベンゼン、トリクロルベンゼ
ン等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、四臭化炭素等のハ
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段重合系において低分子
側重合体、続いて、第２段重合系において高分子
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ることによ
り、120℃以下の低温重合（スラリー重合）を可
能ならしめたことである。そのため公知の連続高
温溶解重合に比べ、重合時溶媒の使用量が少ない
という経済性にすぐれていると共に、重合物を粉
体状で得ることができるという利点がある。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。本発明の他の特徴は、公知の連続高温溶解重
合に比べ、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。したがつて、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性を持ち、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
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スは
ASTM Ｄ−1238（Ｅ）に従つた。ｗ／ｎ（
ｗは重量平均分子量、ｎは数平均分子量を表
す。）はWaters社製GPC200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／ｍ−
（）・Hr）、または１時間、チタン原子１ｍmol
あたりのポリエチレン収量ｇ（ｇ−重合体／ｍ
mol−Ti.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−D781、ヘイズ値
はASTM−D1003、フイツシユアイはフイルム
100cm3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−D1693に従つた。
実施例 １
(1) 遷移金属化合物の製造
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0.3ｍmol、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、85℃において、エチレンを１時間当り
300Nl、水素を重合器気相部のエチレン対水素の
モル比が１対3.5になるように供給しつつ、連続
的に第１段重合を行なつた。このとき全圧は40
Kg／cm2（ゲージ圧）であつた。
第１段重合終了後、溶媒に懸濁した重合物を、
内圧1.0Kg／cm2（ゲージ圧）に保たれた内容積５
の脱ガス槽に導き、ヘキサン中に溶解した水素
やエチレンを分離し、分離された水素やエチレン
は、第１段重合器気相部のエチレン対水素が所定
比に保てるように循環再利用した。
脱ガス槽を出た重合物スラリーは、内容積10
の第２段重合器に全量導入し、水素および触媒を
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、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の速度で供給し、連続的に第２
段重合を行なつた。このとき30Kg／cm2（ゲージ
圧）であつた。第２段重合器気相部のエチレン
（ブテンを含む）対水素のモル比は１対0.01であ
つた。
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、ポリエチレン粉末91Kgを得た。重合体収率は
21700ｇ二重合体／ｇ−（）・Hr、108000ｇ−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、ブテン含有量２重量％、かさ比重0.41、密
度0.950ｇ／cm2、／30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、溶融樹脂の吐出量は27Kg／Hrで流動
性は良好であり、製膜状態も安定していた。フイ
ルムの打抜衝撃強度は180Kg−cm／mmで十分な強
度であり、ヘイズ値は81％で適度の不透明感を持
ち、フイツシユアイは４個で極めて少なかつた。
フイルムの表面は滑らかで良好であり、極めてす
ぐれたフイルム性能であつた。
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
0.16にすること以外は、実施例１の第１段重合の
条件と同様にして、120時間連続的に一段重合を
行ない、メルトインデツクス0.05のポリエチレン
43Kgを得た。しかしこのポリエチレンは／
Mnは６であつた。
このポリエチレンはフイルムを製造することが
できなかつた。
比較例 ２
ジメチルポリシロキサンを用いないこと以外
は、実施例１の(1)と同様にして遷移金属触媒成分
を得た。該触媒成分１Kg中のチタン原子は0.15ｍ
molであつた。実施例１において、固体生成物
（）の代りに該触媒成分を１時間当り250mg、ト
リエチルアルミニウムを１時間当り1.5ｍmolを
供給すること以外は同様にして多段連絡重合を行
なつたが、重合開始後50時間経過して第２段重合
器壁にポリマーが付着し始め、72時間経過して第
１段重合器壁にもポリマー付着がみられ、得られ
るポリマー中に塊状のポリマーがみられるなど運
転は不安定なものであつた。ポリエチレン87Kgを
得た。重合体収率は2900ｇ−重合体／ｇ−（）・
Hr、19000ｇ−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0.05、
かさ比重0.25、／13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で溶融樹脂の流動性は
極めて悪く、製膜状態も不安定であつた。フイル
ムの打抜衝撃強度80Kg−cm／mmで強度は不足し、
フイツシユアイは450個で表面状態は極めて悪く、
実用に耐えるフイルムではなかつた。
比較例 ３
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、攪拌しなが
ら110℃に２時間反応させた後、未反応ジメチル
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、さらに118℃で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90Kgを得た。重合体収率は7500
ｇ−重合体／ｇ−（）・Hr、54000ｇ−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
であり流動性は悪かつた。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 ４
実施例１において、エチレンを１時間当り
120Nl、水素を気相部のエチレン対水素が１対4.0
になるように供給し、全圧25Kg／cm2（ゲージ圧）
で第１段重合を行ない、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（ブテンを含む）対水素が１対0.05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
チレンが91Kg得られた。
このポリエチレンは、メルトインデツクス
0.03、／16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13／Kg／Hrであつた。フイルム
の打抜衝撃強度85Kg−cm／mm、フイツシユアイは
600個もあり、実用に耐えるフイルムではなかつ
た。
比較例 ５
実施例１において、エチレンを１時間当り
570Nl、水素を気相部のエチレン対水素が１対1.6
になるように供給して、第１段重合を行ない、エ
チレンを１時間当り30Nl、水素を気相部のエチ
レン対水素のモル比が１対0.002になるように供
給し、全圧10Kg／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。ポリエチレンが85Kg
得られた。
このポリエチレンは、メルトインデツクス
0.05、／13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50Kg−cm／mm、フイツシユアイは
800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
ヒドロタルサイト（Mg6Al2（OH）16CO3・
4H2O）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。
トルエン200ml中、トリクロルモノブトキシチ
タン150ｇおよび固体生成物（）100ｇを混合、
続いて、鎖状メチル水素ポリシロキサン150ｇ
（粘度300センチストークス）を加え、100℃に４
時間反応させた。その後は実施例１−(1)と同様に
洗浄し、固体生成物（）を得た。タン原子の含
有量は固体生成物（）１ｇ中0.24ｍmolであつ
た。
(2) エチレンの多段重合
上記固体生成物（）を１時間当り30mg、プロ
ピレンを２容量％含むエチレンを１時間当り
306Nl、水素を気相部のエチレン（プロピレンを
含む）対水素のモル比が１対3.3になるように供
給しつつ、90℃において行なうこと以外は実施例
１と同様にして第１段重合を行なつた。
以下は実施例１と同様に行い、続いて、プロピ
レンを１容量％およびブテン−１を３容量％含む
エチレンを１時間当り313Nl、水素を気相部のエ
チレン（プロピレンとブテンを含む）対水素のモ
ル比が１対0.009になるように供給しつつ、65℃
において行なうこと以外は実施例１と同様にして
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、ポリエチレン粉末
112Kgを得た。その重合体収率は24900ｇ−重合
体／ｇ−（）・Hr、104000ｇ−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0.40、密度0.948ｇ／cm2・プロピレ
ンおよびブテン合計の含有量1.8重量％、／
Mn28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、フイルム製造時の吐出量は27Kg／Hr
であつた。フイルムの打抜衝撃強度165Kg−cm／
mm、ヘイズ値80％、フイツシユアイは８個、表面
状態は良好で、極めてすぐれたフイルム性能であ
つた。
実施例 ３
(1) 遷移金属触媒成分の製造
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。
(2) エチレンの多段重合
実施例１において、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の代りに
トリイソブチルアルミニウム0.4ｍmol、ブテン
−１を５容量％含むエチレンを１時間当り315Nl
の速度で供給し、第１段重合器の気相部のエチレ
ン（ブテンを含む）対水素のモル比を１対4.5と
すること以外は同様にして第１段重合を行ない、
脱ガス槽で分離された水素、エチレンおよびブテ
ンは、第１段重合器気相部のエチレン対水素が所
定比に保てるように循環再利用し、また、エチレ
ンを１時間当り300Nlの速度で供給し、第２段重
合器気相部のエチレン対水素のモル比を１対
0.005とすること以外は同様にして第２段重合を
行ない、その他は実施例１と同様にして多段重合
を行なつた。ポリエチレン85Kgが得られた。重合
体収率は20200ｇ−重合体／ｇ−（）・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2.2重量％、かさ比重0.38、密
度0.949ｇ／cm3、／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、溶融樹脂の吐出量は28Kg／Hrで流動性
は良好であり、製膜状態も安定していた。フイル
ムの打抜衝撃強度185Kg−cm／mm、ヘイズ値82％、
フイツシユアイ５個、表面状態は良好で、極めて
すぐれたフイルム性能であつた。
実施例 ４
(1) 遷移金属触媒成分の製造
塩化アルミニウム（無水）90ｇ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。
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時間反応させた。そ
の後は実施例１と同様に洗浄し、固体生成物
（）１Kg中のチタン原子は0.25molであつた。
(2) エチレンの多段重合
実施例１において、上記(1)で得られた固体生成
物（）を１時間当り30mg、トリエチルアルミニ
ウムの代りにトリイソブチルアルミニウム0.4ｍ
mol、ヘキサンを１時間当り２の速度で供給
し、80℃において、第１段重合器気相部のエチレ
ン対水素のモル比を１対3.6とすること以外は同
様にして第１段重合を行ない、また、エチレンを
１時間当り300Nの速度で供給し、第２段重合
器気相部のエチレン対水素のモル比を１対0.08と
すること以外は、同様にして第２段重合を行な
い、その他は実施例１と同様にして連続多段重合
を行なつた。ポリエチレン81Kgが得られた。重合
体収率は22.500ｇ−重合体／ｇ−（）・Hrであ
つた。
このポリエチレンは、メルトインデツクス
0.24、かさ比重0.39、密度0.953ｇ／cm3、／
Mn26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、サメ
肌現象も見られず、成形品の表面は極めて良好で
あり、成形品１個の重量は280ｇで適量であり、
偏肉もほとんどなく、実用上十分な性能のビンで
あつた。
実施例 ５
内容積10の第１段重合器に、実施例２で得ら
れた固体生成物（）を１時間当り30mg、トリエ
チルアルミニウムを１時間当り0.3ｍmolおよび
ヘキサンを１時間当り２の速度で供給し、エチ
レンを１時間当り200N、水素を重合器の気相
部のエチレン対水素のモル比が１：５となるよう
に供給しつつ、連続的に第１段重合を行なつた。
このとき全圧は38Kg／cm2であつた。
第２段重合を、65℃において、ブテン−１を５
％（容量％）含むエチレンを１時間当り300N、
ヘキサンを１時間当り１の速度で供給し、連続
的に行なつた。気相部より50Nのガスを抜き出
し、第１段重合器に循環再利用した。このとき第
２段重合器の全圧は16Kg／cm2で、気相部のエチレ
ン対水素のモル比は１対0.08であつた。
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、第２段重合器より排
出した重合物スラリーを脱灰せず別乾燥後、メ
ルトインデツクス0.06、かさ比重0.40、密度
0.951、分子量分布／26の重合体粉末69Kg
を安定して得ることができた。
このポリエチレン粉末を用いてフイルムを製造
したところ、溶融樹脂の吐出量は25Kg／Hrであ
つた。フイルムの打抜き衝撃強度は155Kg−cm／
mm、ヘイズ値は79％、フイツシユアイは５個、表
面状態は良好で実用上好ましいものであつた。A chain or cyclic siloxane polymer represented by the formula (n: 3 to 10,000), in which each R represents the same or different type of residue that can be bonded to silicon, and among them, hydrogen, alkyl group , hydrocarbon residues such as aryl groups, halogens, alkoxy groups or aryloxy groups, fatty acid residues, etc., and two or more of these groups are distributed and bonded within the molecule in various ratios. things are used. Those commonly used are those in which each R in the above formula consists of a hydrocarbon residue.
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
Polymers such as (CH 3 ) 2 O]n, etherpolycyclosiloxane [SiH(C 2 H 5 )O]n, methylethylpolysiloxane [Si(CH 3 )(C 2 H 5 )O]n, etc. Alkylsiloxane polymers, arylsiloxane polymers such as hexaphenylcyclotrisiloxane [Si(C 6 H 5 ) 2 O] 3 , diphenylpolysiloxane [Si(C 6 H 5 ) 2 O]n, and Diphenyl octamethyltetrasiloxane (CH 3 ) 3 SiO [Si
(CH 3 )(C 6 H 5 )O] 2 Si(CH 3 ) 3 , alkylarylsiloxane polymers such as methylphenylpolysiloxane [Si(CH 3 )(C 6 H 5 )O]n, etc. It will be done. 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. The polysiloxane used is desirably liquid and has a viscosity (at 25° C.) of 10 to 10,000 centistokes, preferably in the range of 10 to 1,000 centistokes. Examples of transition metal compounds include titanium, vanadium halides, oxyhalides, alcoholates, alkoxyhalides, and acetoxyhalides, such as titanium tetrachloride, titanium tetrabromide, tetraethoxytitanium, tetrabutoxytitanium, monochlorobutoxytitanium, Examples include dichlorodibutoxytitanium, 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. Both methods 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). Mixing is preferably 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 separated 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 in 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 also mix it. It is sufficient that the total amount of solvent used is about 10 times (by weight) or less the total amount of each of the above components. 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 carbon,
Examples include halogenated hydrocarbons such as chloroform, dichloroethane, trichloroethylene, tetrachloroethylene, and 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 low-molecular-weight polymer is produced in the first stage polymerization system, and then a high-molecular-weight polymer is produced in the second stage polymerization system. This made it possible to perform low-temperature polymerization (slurry polymerization) below 120°C. Therefore, compared to known continuous high-temperature melt polymerization, this method is economically advantageous in that less solvent is used during polymerization, and the polymer can be obtained in powder form. 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 has extremely high polymerization activity, and it is possible to eliminate the step of removing the remaining catalyst in the polymer after the reaction, that is, the step of deashing. Another feature of the present invention is that the resulting polyethylene has a much broader molecular weight distribution than conventional continuous high temperature melt polymerizations. 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, and a smooth film surface.
Formability is stable for a long time. In addition, the bulk specific gravity of the polyethylene powder obtained by the present invention is 0.35~
0.45, 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, there is no trouble in piping transportation of polymer powder, and it is easy to granulate the powder. It has the characteristic of being Hereinafter, the features of the present invention will be specifically explained with reference to Examples. The melt index in Examples and Comparative Examples is
According to ASTM D-1238(E). w/n(
w represents the weight average molecular weight, and n represents the number average molecular weight. ) was determined using GPC200 gel permeation chromatography manufactured by Waters. Polymer yield: 1 hour, 1 g of solid product ()
Yield of polyethylene per g (g-polymer/m-
()・Hr) or 1 hour, 1 mmol of titanium atoms
Polyethylene yield per g (g-polymer/m
mol-Ti.Hr). 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-D781, the haze value was ASTM-D1003, and the film was
The number of particulate polymeric substances with a diameter of 50 μm or more existing in 100 cm 3 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
According to ASTM-D1693. Example 1 (1) Production of transition metal compound 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 (). 173 kg of titanium tetrachloride and 100 kg of linear 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 complete, evaporate according to the usual method,
The remaining solid product was washed with hexane until unreacted titanium tetrachloride and unreacted polysiloxane were no longer detected in the solution, and after drying under reduced pressure, a solid product () was 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 polymerization of ethylene In a first stage polymerization vessel with an internal volume of 10, 35 mg of the above solid product () per hour, 0.3 mmol of triethylaluminum per hour, and 1 hexane were added per hour.
Ethylene was fed at a rate of 2.5 per hour at 85°C, while discharging the contents of the polymerization vessel to maintain the liquid level in the polymerization vessel at 80%.
The first stage polymerization was carried out continuously while supplying 300 Nl of hydrogen such that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization vessel was 1:3.5. At this time, the total pressure is 40
Kg/cm 2 (gauge pressure). After the first stage polymerization, the polymer suspended in the solvent is
Internal volume 5 maintained at internal pressure 1.0Kg/cm 2 (gauge pressure)
The hydrogen and ethylene dissolved in the hexane were separated, and the separated hydrogen and ethylene were recycled and reused to maintain a predetermined ratio of ethylene to hydrogen in the gas phase of the first stage polymerizer. . The polymer slurry leaving the degassing tank has an internal volume of 10
The entire amount was introduced into the second stage polymerization vessel, and the contents were heated to 70°C while draining the contents of the polymerization vessel to maintain the liquid level in the polymerization vessel at 80% without adding hydrogen or catalyst.
, ethylene containing 5% by volume of butene-1 was fed at a rate of 315 Nl per hour, and the second
A stepwise polymerization was carried out. At this time, the pressure was 30Kg/cm 2 (gauge pressure). The molar ratio of ethylene (including butene) to hydrogen in the gas phase of the second stage polymerizer was 1:0.01. The above multi-stage polymerization was carried out continuously for 120 hours, but
The operation was extremely stable, and 91 kg of polyethylene powder was obtained after drying without deashing. The polymer yield is
21,700 g of polymer/g-()·Hr and 108,000 g of polymer/mmol-Ti·Hr. This polyethylene has melt index
0.04, butene content 2% by weight, bulk specific gravity 0.41, density 0.950 g/cm 2 , /30. When a film was manufactured using this polyethylene, the discharge rate of the molten resin was 27 kg/hr, the fluidity was good, and the film forming state was stable. The punching impact strength of the film was 180 kg-cm/mm, which was sufficient, the haze value was 81%, and it had a moderate opacity, and there were only 4 eyes, which was extremely small.
The surface of the film was smooth and good, and the film performance was extremely excellent. Comparative Example 1 The molar ratio of ethylene to hydrogen in the gas phase of the polymerization vessel was set to 1:
One-stage polymerization was carried out continuously for 120 hours under the same conditions as the first-stage polymerization in Example 1, except that the melt index was 0.16, and polyethylene with a melt index of 0.05 was obtained.
Obtained 43Kg. However, this polyethylene/
Mn was 6. This polyethylene could not be made into a film. Comparative Example 2 A transition metal catalyst component was obtained in the same manner as in Example 1 (1) except that dimethylpolysiloxane was not used. The titanium atom in 1 kg of the catalyst component is 0.15m
It was hot in mol. Multistage catalytic polymerization was carried out in the same manner as in Example 1 except that 250 mg of the catalyst component was supplied per hour and 1.5 mmol of triethylaluminum was supplied per hour instead of the solid product (), but the polymerization did not start. After 50 hours, polymer began to adhere to the wall of the second stage polymerization vessel, and after 72 hours, polymer adhesion was also observed on the wall of the first stage polymerization vessel, and lumps of polymer were observed in the obtained polymer. Driving was unstable. 87 kg of polyethylene was obtained. The polymer yield is 2900g-polymer/g-()・
Hr, 19000g-polymer/mmol-Ti.Hr. This polyethylene has a melt index of 0.05,
The bulk specific gravity was 0.25, /13. When a film was manufactured using this polyethylene, the fluidity of the molten resin was extremely poor at a discharge rate of 12 kg/hr, and the film formation state was also unstable. The punching impact strength of the film is 80Kg-cm/mm, which is insufficient.
There are 450 fisheyes, and the surface condition is extremely poor.
The film was not suitable for practical use. Comparative Example 3 100Kg of the solid product obtained in Example 1 and 100Kg of dimethylpolysiloxane (same product as Example 1) were added to 150% toluene, and after reacting at 110°C for 2 hours with stirring, 173 kg of titanium tetrachloride was added without removing unreacted dimethylpolysiloxane, and the mixture was further reacted at 118°C for 2 hours. Thereafter, the final solid product was obtained in the same manner as in Example 1. The content of titanium atoms was 0.14 mol per 1 kg of the final solid product. Multistage continuous polymerization was carried out in the same manner as in Example 1, except that 100 mg of this final solid product was supplied per hour instead of the solid product () of Example 1, and 0.6 mmol of triethylaluminum was supplied per hour. Gained 90Kg. Polymer yield is 7500
g-polymer/g-()・Hr, 54000g-polymer/
It was mmol-Ti.Hr. This polyethylene has melt index
0.03, bulk specific gravity 0.34, /16. When the film was manufactured, the discharge amount was 16Kg/Hr.
Therefore, liquidity 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 4 In Example 1, ethylene per hour
120Nl, ethylene to hydrogen in the gas phase is 1:4.0
The total pressure is 25Kg/cm 2 (gauge pressure).
The first stage polymerization was carried out at 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 40 kg/cm 2 (gauge pressure). 91Kg of polyethylene was obtained. This polyethylene has melt index
It was 0.03, /16. When a film was produced using this polyethylene, the discharge rate was 13/Kg/Hr. The punching impact strength of the film is 85Kg-cm/mm.
There were 600 of them, and the film was not of any practical use. Comparative Example 5 In Example 1, ethylene per hour
570Nl, ethylene to hydrogen in the gas phase is 1:1.6
Ethylene was supplied at 30Nl per hour, hydrogen was supplied at a molar ratio of ethylene to hydrogen of 1:0.002 in the gas phase, and the total pressure was 10Kg/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). 85kg of polyethylene
Obtained. This polyethylene has melt index
It was 0.05, /13. When a film was manufactured using this polyethylene, the discharge rate was 13 kg/hr. The punching impact strength of the film is 50Kg-cm/mm, and the punching impact strength of the film is 50Kg-cm/mm.
There were 800 pieces, and it was not a film that could be used for practical purposes. Example 2 (1) Production of transition metal catalyst component Hydrotalcite (Mg 6 Al 2 (OH) 16 CO 3・
4H 2 O) 70g and aluminum chloride (anhydrous) 80g
was heated at 170° C. for 3 hours in a vibrating mill while mixing, grinding and reaction were carried out simultaneously to obtain a solid product (). Mix 150 g of trichloromonobutoxytitanium and 100 g of solid product () in 200 ml of toluene,
Next, 150g of linear methylhydrogen polysiloxane
(viscosity 300 centistokes) and heated to 100℃
Allowed time to react. Thereafter, it was washed in the same manner as in Example 1-(1) to obtain a solid product (2). The content of tan atoms was 0.24 mmol in 1 g of the solid product (). (2) Multi-stage polymerization of ethylene 30 mg of the above solid product () per hour, ethylene containing 2% by volume of propylene per hour
The first stage polymerization was carried out in the same manner as in Example 1, except that 306Nl and hydrogen were supplied so that the molar ratio of ethylene (including propylene) to hydrogen in the gas phase was 1:3.3, and the polymerization was carried out at 90°C. I did it. The following procedure was carried out in the same manner as in Example 1. Subsequently, ethylene containing 1% by volume of propylene and 3% by volume of butene-1 was added at 313 Nl per hour, and hydrogen was added to the gaseous phase of ethylene (including propylene and butene) to hydrogen. at 65°C while supplying at a molar ratio of 1:0.009.
The second stage polymerization was carried out in the same manner as in Example 1, except that the second stage polymerization was carried out in the same manner as in Example 1. The above multi-stage polymerization was carried out continuously for 150 hours, but
Operation is extremely stable and polyethylene powder
Obtained 112Kg. The polymer yield is 24900g-polymer/g-()・Hr, 104000g-polymer/mmol
-It was Ti・Hr. This polyethylene has melt index
0.03, bulk specific gravity 0.40, density 0.948g/ cm2 , total content of propylene and butene 1.8% by weight, /
It was Mn28. When a film was manufactured using this polyethylene, the discharge amount during film manufacturing was 27Kg/Hr.
It was hot. Film punching impact strength 165Kg-cm/
mm, haze value of 80%, number of fixation eyes was 8, the surface condition was good, and the film performance was extremely excellent. Example 3 (1) Production of transition metal catalyst component 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 produce a solid product ( ) was obtained. Mixing 100 g of titanium tetrachloride and 100 g of solid product () in 200 ml of toluene, followed by di-n-
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. (2) Multistage polymerization of ethylene In Example 1, the above solid product () was
35 mg per hour, 0.4 mmol of triisobutyl aluminum instead of triethyl aluminum, 315 Nl per hour of ethylene containing 5% by volume of butene-1.
The first stage polymerization was carried out in the same manner except that the molar ratio of ethylene (including butene) to hydrogen in the gas phase of the first stage polymerization vessel was 1:4.5.
The hydrogen, ethylene, and butene separated in the degassing tank are recycled and reused to maintain a predetermined ratio of ethylene to hydrogen in the gas phase of the first stage polymerizer, and ethylene is supplied at a rate of 300 Nl per hour. The molar ratio of ethylene to hydrogen in the gas phase of the second stage polymerization vessel was set to 1:1.
A second stage polymerization was carried out in the same manner as in Example 1 except that the concentration was set to 0.005, and a multistage polymerization was carried out in the same manner as in Example 1. 85 kg of polyethylene was obtained. The polymer yield was 20200 g-polymer/g-().Hr. This polyethylene has melt index
0.05, butene content 2.2% by weight, bulk specific gravity 0.38, density 0.949g/cm 3 , /32. When a film was manufactured using this polyethylene, the discharge rate of the molten resin was 28 kg/hr, the fluidity was good, and the film forming state was stable. Film punching impact strength 185Kg-cm/mm, haze value 82%,
There were 5 fish eyes, the surface condition was good, and the film performance was extremely excellent. Example 4 (1) Production of transition metal catalyst component 90 g 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. 100 kg of the solid product (200) 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. Thereafter, it was washed in the same manner as in Example 1, and the amount of titanium atoms in 1 kg of the solid product () was 0.25 mol. (2) Multistage polymerization of ethylene In Example 1, 30 mg of the solid product ( ) obtained in (1) above was added per hour, and 0.4 m of triisobutylaluminum was added instead of triethylaluminum.
The first stage polymerization was carried out in the same manner except that hexane was supplied at a rate of 2 mol per hour and the molar ratio of ethylene to hydrogen in the gas phase of the first stage polymerizer was 1:3.6 at 80°C. The second stage polymerization was carried out in the same manner except that ethylene was supplied at a rate of 300 N per hour and the molar ratio of ethylene to hydrogen in the gas phase of the second stage polymerization vessel was 1:0.08. Continuous multi-stage polymerization was carried out in the same manner as in Example 1 except for the following. 81 kg of polyethylene was obtained. The polymer yield was 22.500 g-polymer/g-().Hr. This polyethylene has melt index
0.24, bulk specific gravity 0.39, density 0.953g/cm 3 , /
It was Mn26. When a hollow bottle was manufactured using this polyethylene, the drawdown of the parison was small, no melt fracture occurred during molding, no shark skin phenomenon was observed, and the surface of the molded product was extremely good. The weight of one piece is 280g, which is a suitable amount.
There was almost no uneven thickness, and the bottle had sufficient performance for practical use. Example 5 Into a first stage polymerization vessel having an internal volume of 10, 30 mg of the solid product obtained in Example 2 () per hour, 0.3 mmol of triethylaluminum per hour, and hexane at a rate of 2 per hour were added. The first stage polymerization was carried out continuously while ethylene was supplied at 200 N per hour and hydrogen was supplied so that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization vessel was 1:5.
At this time, the total pressure was 38 Kg/cm 2 . The second stage polymerization was carried out at 65°C with 5% butene-1.
% (volume %) of ethylene containing 300N per hour,
Hexane was fed at a rate of 1 per hour and was continuous. 50N of gas was extracted from the gas phase and recycled to the first stage polymerization vessel. At this time, the total pressure in the second stage polymerization vessel was 16 kg/cm 2 and the molar ratio of ethylene to hydrogen in the gas phase was 1:0.08. The above multi-stage polymerization was carried out continuously for 120 hours, but
The operation is extremely stable, and after drying the polymer slurry discharged from the second stage polymerization vessel separately without deashing, the melt index is 0.06, the bulk specific gravity is 0.40, and the density is
0.951, molecular weight distribution/26 polymer powder 69Kg
was obtained stably. When a film was manufactured using this polyethylene powder, the amount of molten resin discharged was 25 kg/hr. The punching impact strength of the film is 155Kg-cm/
mm, the haze value was 79%, the number of fish eyes was 5, and the surface condition was good and preferred for practical use.
第１図は、本発明を説明するためのフローシー
トである。
FIG. 1 is a flow sheet for explaining the present invention.
Claims (1)
存在下、複数個の重合器を使い第１段重合系で低
分子側重合体を、第２段重合系で高分子側重合体
をつくる連続多段重合によるポリエチレンの製造
法において、 アルミニウムの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、Ti化合物とから調製した遷移金属化
合物を担持させた固体生成物（）と有機アル
ミニウム化合物とを組み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５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30〜90
％のエチレンを供給して、第１段重合を行な
い、 第１段重合終了後は、溶媒中に懸濁した重合
物を、１〜60Kg／cm2の圧力帯域に導き、気相部
より水素の少なくとも一部分は第１段重合系に
もどし、ついで該懸濁した重合物を気相が存在
する状態において、重合温度30℃以上100℃以
下、重合圧力５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、全エチレン量の10〜70％のエチレンを供
給して、第２段重合を行なうこと、 を特徴とする多段重合によるポリエチレンの製造
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が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（）項記載の製造法。 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項の製造
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３項記載の製造
法。[Claims] 1 Using a Ziegler type catalyst in the presence of a solvent and hydrogen, using multiple polymerization vessels, a low molecular weight polymer is produced in the first stage polymerization system, and a high molecular side polymer is produced in the second stage polymerization system. In the method for producing polyethylene by continuous multistage polymerization, solids obtained by reacting aluminum halides with magnesium hydroxides, oxides, carbonates, double salts containing these, or hydrates of divalent metal compounds. in a saturated hydrocarbon solvent in the presence of a catalyst obtained by combining an organic aluminum compound with a solid product () supporting a transition metal compound prepared from the product (), an electron donor compound, and a Ti compound; In the presence of a gas phase in the upper part of the polymerization vessel, under the conditions of a polymerization temperature of 50°C to 120°C and a polymerization pressure of 5 to 70 kg/cm 2 , the molar ratio of ethylene to hydrogen in the gas phase of the polymerization vessel is 1:3.0. In addition to supplying hydrogen so that the amount exceeds 7.0 and becomes 30 to 90% of the total ethylene supply amount.
% of ethylene is supplied to perform the first stage polymerization. After the first stage polymerization, the polymer suspended in the solvent is introduced into a pressure zone of 1 to 60 Kg/ cm2 , and hydrogen is extracted from the gas phase. At least a portion of the polymer is returned to the first stage polymerization system, and then the suspended polymer is treated in the presence of a gas phase at a polymerization temperature of 30° C. or more and 100° C. or less and a polymerization pressure of 5 to 70 kg/cm 2 . The molar ratio of ethylene to hydrogen in the gas phase of the polymerizer is 1:
A method for producing polyethylene by multistage polymerization, characterized by supplying hydrogen at a concentration of 0.001 to 0.5, and supplying ethylene in an amount of 10 to 70% of the total ethylene amount to carry out second stage polymerization. 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. Manufacturing method. 3 Solid product () is 100g of solid product ()
20 to 1000 g of the electron donor compound and 10 to 500 g of the transition metal compound, and 30 to 500 g of the transition metal compound per 100 g of the electron donor compound. Law. 4. The manufacturing method according to claim 1, 2 or 3, wherein the electron donor compound is polysiloxane. 5. The production method according to claim 1, 2 or 3, wherein the electron donor compound is an ether, ester, aldehyde, ketone or acid anhydride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1397981A JPS57128707A (en) | 1981-02-02 | 1981-02-02 | Preparation of polyethylene by multistage polymerization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1397981A JPS57128707A (en) | 1981-02-02 | 1981-02-02 | Preparation of polyethylene by multistage polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57128707A JPS57128707A (en) | 1982-08-10 |
| JPS6366324B2 true JPS6366324B2 (en) | 1988-12-20 |
Family
ID=11848335
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1397981A Granted JPS57128707A (en) | 1981-02-02 | 1981-02-02 | Preparation of polyethylene by multistage polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57128707A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03121927A (en) * | 1989-10-06 | 1991-05-23 | Nissan Motor Co Ltd | Detachable hatch roof for automobile |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0780938B2 (en) * | 1985-12-28 | 1995-08-30 | 三井石油化学工業株式会社 | METHOD FOR PRODUCING POLYOLEFIN WITH IMPROVED FISH EYE EYE LEVEL |
| KR101359287B1 (en) * | 2003-12-19 | 2014-02-10 | 바젤 폴리올레핀 게엠베하 | Process for the (co)polymerization of ethylene |
| EP2414406A1 (en) * | 2009-04-02 | 2012-02-08 | Total Petrochemicals Research Feluy | Method for optimizing energy consumption in an extrusion process |
| EP3293206B1 (en) * | 2016-09-12 | 2019-10-23 | Thai Polyethylene Co., Ltd. | Multimodal polyethylene pipe |
| HUE047431T2 (en) * | 2016-09-12 | 2020-04-28 | Thai Polyethylene Co Ltd | Multimodal polyethylene pipe |
| EP3293214B1 (en) * | 2016-09-12 | 2019-12-25 | Thai Polyethylene Co., Ltd. | High performances multimodal ultra high molecular weight polyethylene |
| EP3749707A1 (en) | 2018-02-05 | 2020-12-16 | ExxonMobil Chemical Patents Inc. | Enhanced processability of lldpe by addition of ultra-high molecular weight high density polyethylene |
-
1981
- 1981-02-02 JP JP1397981A patent/JPS57128707A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03121927A (en) * | 1989-10-06 | 1991-05-23 | Nissan Motor Co Ltd | Detachable hatch roof for automobile |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57128707A (en) | 1982-08-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4923935A (en) | Process for producing polyethylene of ultrahigh molecular weight | |
| US7504464B2 (en) | Process for control of polymer fines in a gas-phase polymerization | |
| RU2120448C1 (en) | Method of preparing ethylene-olefin copolymers having higher processibility, and composition based on low- density linear polyethylene copolymer and propylene in particle form | |
| JPS6042806B2 (en) | Copolymer manufacturing method | |
| JPS6366324B2 (en) | ||
| JPS6226321B2 (en) | ||
| JPS6352651B2 (en) | ||
| CN112625155B (en) | Preparation method of polypropylene | |
| JPS6352654B2 (en) | ||
| JPS5825362B2 (en) | Method for producing α-olefin polymer | |
| GB2033911A (en) | Preparation of ethylene-propylene copolymers | |
| JPS6352650B2 (en) | ||
| JP3311780B2 (en) | Method for producing olefin polymer | |
| JPS6352655B2 (en) | ||
| JPS6352659B2 (en) | ||
| JPS6352656B2 (en) | ||
| JPS6352657B2 (en) | ||
| US3781253A (en) | Process for the preparation of ethylene polymer or copolymer | |
| US4260723A (en) | Method for producing olefin polymers | |
| US4324875A (en) | Method for producing olefin polymers | |
| US4403081A (en) | Method for producing α-olefin polymers | |
| KR840000371B1 (en) | Process for producing polyethylene by continuous multi-stage polymerization | |
| JPS63142008A (en) | Production of ethylene-olefin copolymer | |
| JPS5834811A (en) | Polymerization of ethylene | |
| EP0024881B1 (en) | Process for producing polyethylene by continuous multi-stage polymerization and moulded articles made from the product |