JPS6352654B2 - - Google Patents
Info
- Publication number
- JPS6352654B2 JPS6352654B2 JP10565779A JP10565779A JPS6352654B2 JP S6352654 B2 JPS6352654 B2 JP S6352654B2 JP 10565779 A JP10565779 A JP 10565779A JP 10565779 A JP10565779 A JP 10565779A JP S6352654 B2 JPS6352654 B2 JP S6352654B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- ethylene
- hydrogen
- solid product
- 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 163
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 104
- 239000005977 Ethylene Substances 0.000 claims description 104
- -1 polyethylene Polymers 0.000 claims description 92
- 239000012265 solid product Substances 0.000 claims description 92
- 229910052739 hydrogen Inorganic materials 0.000 claims description 77
- 239000001257 hydrogen Substances 0.000 claims description 77
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 72
- 229920000642 polymer Polymers 0.000 claims description 65
- 239000004698 Polyethylene Substances 0.000 claims description 49
- 229920000573 polyethylene Polymers 0.000 claims description 49
- 239000007789 gas Substances 0.000 claims description 42
- 239000003054 catalyst Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- 150000003623 transition metal compounds Chemical class 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 229920001296 polysiloxane Polymers 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 239000010936 titanium Substances 0.000 claims description 7
- 150000002736 metal compounds Chemical class 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
- 239000004711 α-olefin Substances 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- 150000008065 acid anhydrides Chemical class 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- 241000238413 Octopus Species 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052749 magnesium Inorganic materials 0.000 claims 1
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims 1
- 150000003682 vanadium compounds Chemical class 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 238000000034 method Methods 0.000 description 21
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 20
- 239000000843 powder Substances 0.000 description 19
- 239000011572 manganese Substances 0.000 description 17
- 239000000047 product Substances 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 239000000203 mixture Substances 0.000 description 12
- 238000000465 moulding Methods 0.000 description 12
- 238000000071 blow moulding Methods 0.000 description 11
- 230000005484 gravity Effects 0.000 description 11
- 150000002430 hydrocarbons Chemical group 0.000 description 11
- 239000000155 melt Substances 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 11
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 9
- 238000004080 punching Methods 0.000 description 7
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 5
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 5
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910001507 metal halide Inorganic materials 0.000 description 5
- 150000005309 metal halides Chemical class 0.000 description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- 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
- 241000251468 Actinopterygii Species 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000004677 hydrates Chemical class 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000011565 manganese chloride Substances 0.000 description 3
- 235000002867 manganese chloride Nutrition 0.000 description 3
- 229910000000 metal hydroxide Inorganic materials 0.000 description 3
- 150000004692 metal hydroxides Chemical class 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical class ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 241000251730 Chondrichthyes Species 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000005376 alkyl siloxane group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 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
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- 238000010101 extrusion blow moulding Methods 0.000 description 2
- 150000004665 fatty acids Chemical group 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229920006158 high molecular weight polymer Polymers 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 229940099607 manganese chloride Drugs 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
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical class ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 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
- 239000003643 water by type Chemical class 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class 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
- 125000006017 1-propenyl group Chemical group 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
- 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
- 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
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 229910019440 Mg(OH) Inorganic materials 0.000 description 1
- 229910026161 MgAl2O4 Inorganic materials 0.000 description 1
- 101100513612 Microdochium nivale MnCO gene Proteins 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910019213 POCl3 Inorganic materials 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-IGMARMGPSA-N Protium Chemical compound [1H] YZCKVEUIGOORGS-IGMARMGPSA-N 0.000 description 1
- 102100024864 REST corepressor 1 Human genes 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical class ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- ZQUQNMGBBXTGEW-UHFFFAOYSA-N [dimethyl-[methyl(diphenyl)silyl]oxysilyl]oxy-dimethyl-trimethylsilyloxysilane Chemical compound C=1C=CC=CC=1[Si](C)(O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C)C1=CC=CC=C1 ZQUQNMGBBXTGEW-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 229940071248 anisate Drugs 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- UADWUILHKRXHMM-ZDUSSCGKSA-N benzoflex 181 Natural products CCCC[C@H](CC)COC(=O)C1=CC=CC=C1 UADWUILHKRXHMM-ZDUSSCGKSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- LGSNSXWSNMARLH-UHFFFAOYSA-N butan-1-ol titanium Chemical compound C(CCC)O.[Ti].C(CCC)O LGSNSXWSNMARLH-UHFFFAOYSA-N 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- YCURFOQQPNHZAO-UHFFFAOYSA-N butyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OCCCC)=CC=CC2=C1 YCURFOQQPNHZAO-UHFFFAOYSA-N 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical class O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- DLRHRQTUCJTIIV-UHFFFAOYSA-N diethoxy(ethyl)alumane Chemical compound CC[O-].CC[O-].CC[Al+2] DLRHRQTUCJTIIV-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000005227 gel permeation chromatography Methods 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
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HMRROBKAACRWBP-UHFFFAOYSA-N methyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OC)=CC=CC2=C1 HMRROBKAACRWBP-UHFFFAOYSA-N 0.000 description 1
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-anisate Chemical compound COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- VECVSKFWRQYTAL-UHFFFAOYSA-N octyl benzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1 VECVSKFWRQYTAL-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 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
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N para-methoxy benzoic acid Natural products COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 description 1
- 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
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000002360 preparation method Methods 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
- 125000001725 pyrenyl group Chemical group 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
- 229910052596 spinel Inorganic materials 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 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
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Chemical class ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 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
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- 229940117958 vinyl acetate Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Polymerisation Methods In General (AREA)
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
重合体をつくる連続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、ジシクロベンタジエン
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（）と云うことが
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、更に研究を重ね
て本発明の連続多段重合法を完成するに到つた。
本発明の連続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0.1ないし3.0になるように
水素を供給すると共に、全エチレン供給量の30
〜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、１〜30Kg／cm2の圧力帯域に導き、溶媒に
溶解した水素の少なくとも一部分を分離し、分
離した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
フインを第１段および／または第２段重合系に供
給しエチレンとα―オレフインとの共重合体を製
造することができる。その場合、エチレンとα―
オレフインのモル数の総和と水素のモル比が上記
第１段および／または第２段のモル比となればよ
い。
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0.1ないし3.0の
範囲内に入るように、エチレンおよび水素を供給
することによつて調節される。この場合得られる
重合体の分子量は、平均分子量にして６×104〜
３×105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、上記１〜30Kg／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
とも一部分の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、
重合器上部に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
ル比は好ましくは１：1.0〜3.0であり、エチレン
供給量は全エチレン供給量の40〜60％、好ましく
は50％である。一方の第２段重合はエチレン対水
素のモル比は好ましくは１：0.001〜C.3、より好
ましくは１：0.005〜0.2であり、エチレン供給量
は全エチレン供給量の40〜60％、好ましくは50％
である。また、中空成形の場合、第１段重合は、
エチレン対水素のモル比は好ましくは１：1.0〜
3.0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。
本発明の多段連続重合は、通常複数個の重合器
を直列に連結するが、ある複数個の重合器を並列
（または一部を並列）に連結して第１段および／
または第２段重合系とすることも可能である。
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、例
えば、ブタン、ペンタン、ヘキサン、ヘプタン、
オクタン、灯油などが用いられる。
本発明の製造法に用いる触媒は、３価金属ハロ
ゲン化物と２価金属の水酸化物、酸化物、炭酸化
物、これらを含む複塩、または２価金属化合物の
水和物とを反応させて得られる固体生成物（）
と電子供与体化合物、第4a族または第5a族の遷
移金属化合物とから調製した遷移金属化合物を担
持させた最終の固体生成物（）と有機アルミニ
ウム化合物とを組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。
前記２価金属の水酸化物等（以下２価金属化合
物と云うことがある）としては、例えば、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挙
げられる。
固体生成物（）は、３価金属ハロゲン化物と
２価金属化合物とを反応させて得られる。この反
応させるために予めボールミルで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′は炭化水素基で
あり、更に詳しくは炭素数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。指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、プチル、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、例えばビニル、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、例えばシクロ
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、及びフエニ
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挙げる。
エーテルとしてはジエチルエーテル、ジプロピル
エーテル、ジブチルエーテル、ジ（イソアミル）
エーテル、エチレングリコールジメチルエーテ
ル、ジエチレングリコールジメチルエーテル、ジ
エチレングリコールジエチルエーテル、ジフエニ
ルエーテル、テトラヒドロフランなど、エステル
としては酢酸エチル、酢酸ブチル、酢酸アミル、
酪酸ビニル、酢酸ビニル、プロピオン酸メチル、
安息香酸メチル、安息香酸エチル、安息香酸プロ
ピル、安息香酸ブチル、安息香酸オクチル、安息
香酸２―エチルヘキシル、トルイル酸メチル、ト
ルイル酸エチル、トルイル酸ブチル、トルイル酸
２―エチルヘキシル、アニス酸メチル、アニス酸
エチル、アニス酸プロピル、ナフトエ酸メチル、
ナフトエ酸エチル、ナフトエ酸プロピル、ナフト
エ酸ブチル、ナフトエ酸２―エチルヘキシルな
ど、アルデヒドとしてはブチルアルデヒド、プロ
ピオンアルデヒド、ベンズアルデヒドなど、ケト
ンとしてはメチルエチルケトン、ジエチルケト
ン、アセチルアセトン、アセトフエノン、ベンゾ
フエノンなど、カルボン酸としては酢酸、プロピ
オン酸、安息香酸など、酸無水物としては無水酢
酸、無水酪酸、無水安息香酸など、酸アミドとし
てはホルムアミド、アセトアミド、ベンズアミド
など、アミンとしてはメチルアミン、ジメチルア
ミン、トリメチルアミン、アミルアミン、アニリ
ン、メチルアニリン、ピリジンなど、ニトリルと
してはアセトニトリル、プロピオニトリル、ベン
ゾニトリルなど、ホスフインとしてはトリエチル
ホスフイン、トリフエニルホスフインなど、チオ
エーテルとしてはジエチルスルフイド、ジフエニ
ルスルフイドなどが挙げられる。
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 continuous 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 dicyclobentadiene. 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, which produces a low-molecular polymer in the first stage and a high-molecular polymer in the second stage, at low temperatures and with a small amount of solvent. The purpose of this process is to obtain polyethylene with a wide molecular weight distribution. 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 (), an electron donor compound, and a solid product () prepared from a transition metal compound, and an organoaluminium compound, and after further research, the present invention was developed. We have completed a continuous multi-stage polymerization method. The method for producing polyethylene by continuous multi-stage polymerization of the present invention involves combining a trivalent metal halide and a divalent metal hydroxide, oxide, carbonate, a double salt containing these, or a hydrate of a divalent metal compound. A solid product obtained by the reaction (), an electron donor compound, a solid product supporting a transition metal compound prepared from a Group 4a or Group 5a transition metal compound (), and an organoaluminum compound. in the presence of a catalyst obtained by combining the above, in a saturated hydrocarbon solvent, in the presence of a gas phase, at a polymerization temperature of 50°C or more and 120°C or less, and a polymerization pressure of 5 to 70°C.
Kg/ cm2 , hydrogen is supplied so that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization reactor is 1:0.1 to 3.0, and 30% of the total ethylene supply amount is
The first stage polymerization is carried out by supplying ~90% ethylene. After the first stage polymerization, the polymer suspended in the solvent is brought to a pressure range of 1 to 30 kg/cm 2 and dissolved in the solvent. At least a portion of the separated hydrogen is returned to the first stage polymerization system, and the suspended polymer is then polymerized at a polymerization temperature of 30°C to 100°C in the presence of a gas phase. At a pressure of 5 to 70 kg/ cm2 , hydrogen is supplied so that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization vessel is 1 to 0.001 to 0.5,
The second stage polymerization is carried out by supplying 10 to 70% of the total ethylene amount. Further, if necessary, α-olefin can be supplied to the first and/or second stage polymerization system to produce a copolymer of ethylene and α-olefin. In that case, ethylene and α-
The sum of the moles of 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 controlled by supplying ethylene and hydrogen such that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization vessel is within the range of 1:0.1 to 3.0. The molecular weight of the polymer obtained in this case is 6×10 4 to 6×10 4 in terms of average molecular weight.
Equivalent to 3×10 5 . 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 introduced into the above pressure zone of 1 to 30 kg/ cm2 , and at least a portion of the hydrogen that has left the first stage polymerization system is dissolved in the solvent. Extracted 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 a state where a gas phase exists in the upper part of the polymerization vessel. The molecular weight of the resulting polymer is controlled by 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 preferably 1:1.0 to 3.0, and the ethylene feed rate is preferably 40 to 60% of the total ethylene feed rate. is 50%. On the other hand, in the second stage polymerization, the molar ratio of ethylene to hydrogen is preferably 1:0.001 to C.3, more preferably 1:0.005 to 0.2, and the amount of ethylene fed is 40 to 60% of the total amount of ethylene fed, preferably is 50%
It is. In addition, in the case of blow molding, the first stage polymerization is
The molar ratio of ethylene to hydrogen is preferably 1:1.0~
3.0, and the ethylene feed rate is 30-70%, preferably 50% of the total ethylene feed rate. In the second stage polymerization, the molar ratio of ethylene to hydrogen is preferably 1:
The ratio is 0.005 to 0.5, more preferably 1:0.01 to 0.4, and the amount of ethylene supplied is 30 to 70 of the total amount of ethylene supplied.
%, preferably 50%. 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 multi-stage continuous polymerization of the present invention, usually a plurality of polymerizers are connected in series, but a certain plurality of polymerizers are connected in parallel (or some of them are parallel) to form the first stage and/or
Alternatively, it is also possible to use a second stage polymerization system. 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, heptane,
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 the trivalent metal halide include aluminum trichloride (anhydrous) and iron trichloride (anhydrous). Examples of the divalent metal hydroxides (hereinafter sometimes referred to as divalent metal compounds) include Mg
Hydroxides like (OH) 2 , Ca(OH) 2 , Zn(OH) 2 , Mn(OH) 2 , oxides like MgO, CaO, ZnO, MnO , MgAl2O4 , Mg2SiO 4 , complex oxides containing divalent metals such as Mg6MnO8 , MgCO3 ,
Carbonates such as MnCO 3 , CaCO 3 , SnCl 2 .
2H2O , MgCl2・6H2O , NiCl2・6H2O ,
Halide hydrates such as MnCl2・4H2O , KMgCl3・6H2O , hydrates of double salts containing oxides and halides such as 8MgO・MgCl2・15H2O ,
Hydrates of double salts containing divalent metal oxides such as 3MgO・2SiO 2・2H 2 O, 3MgCO 3・Mg(OH) 2・
Hydrates of double salts of carbonates and hydroxides such as 3H 2 O, and waters of hydroxide carbonates containing divalent metals such as Mg 6 Al 2 (OH) 16 CO 3 4H 2 O Examples include Japanese products. The solid product () is obtained by reacting a trivalent metal halide and a divalent metal compound. In order to make this reaction happen, I used a ball mill in advance for 5 to 100 hours.
It is desirable to mix and grind for 1 to 10 hours using a vibrating mill to obtain a sufficiently mixed state. The mixing ratio of trivalent metal halide and divalent metal compound is
In terms of the atomic ratio of divalent metal to trivalent metal, an atomic ratio of 0.1 to 20 is usually sufficient, preferably 1 to 20.
The range is 10. The reaction temperature is usually 20-500℃,
Preferably it is 50-300°C. Reaction time is 30 minutes ~
If 50 hours is suitable and the reaction temperature is low, the reaction is allowed to proceed for a long time so that no unreacted trivalent metal remains. As an electron donor compound, ether (RO
-R'), ester (RCO 2 R'), aldehyde (RCHO), ketone (RCOR'), carboxylic acid (RCO 2 H), acid anhydride (R-CO 2 CO-R'), acid amide (RCONH 2 ) oxygenated electron donors such as
Nitrogen-containing electron donors such as amines ( RnNH3 - o , n=1-3), nitriles (RCN), phosphine ( RnPR'3 - o , n=1-3), phosphorus oxytrichloride (POCl3 ) ) 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 hydrocarbon groups, and more specifically, aliphatic hydrocarbons having 1 to 50 carbon atoms, unsaturated hydrocarbons, monocyclic hydrocarbon groups without substituents, and monocyclic hydrocarbon groups with substituents. There are monocyclic hydrocarbon groups, fused polycyclic hydrocarbon groups, etc. Examples of linear aliphatic hydrocarbon groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, and octyl, and branched examples include isopropyl, isobutyl, isopentyl, isohexyl, isooctyl, and 2-methyl. pentyl, 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,
Examples include isopropenyl, 1-propenyl, 2-butenyl, and 1,3-butadienyl. Monocyclic hydrocarbon groups include alicyclic and aromatic hydrocarbon groups, examples without substituents include alicyclic hydrocarbon groups such as cyclopropyl, cyclohexyl, 2-cyclopenten-1-yl, etc. , and phenyl group. Examples of substituents include tolyl,
Examples include xylyl, mesityl, cuyymyl, benzyl, diphenylmethyl, phenethyl, and styryl. Condensed polycyclic hydrocarbon groups include naphthyl, anthryl, phenanthryl, 2-indenyl, 1
- Includes pyrenyl. Specific examples will be given as the above electron donor compounds.
Ethers include diethyl ether, dipropyl ether, dibutyl ether, di(isoamyl)
Ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diphenyl ether, tetrahydrofuran, etc. Esters include ethyl acetate, butyl acetate, amyl acetate,
Vinyl butyrate, vinyl acetate, methyl propionate,
Methyl benzoate, ethyl benzoate, propyl benzoate, butyl benzoate, octyl benzoate, 2-ethylhexyl benzoate, methyl toluate, ethyl toluate, butyl toluate, 2-ethylhexyl toluate, methyl anisate, anisic acid Ethyl, propyl anisate, methyl naphthoate,
Ethyl naphthoate, propyl naphthoate, butyl naphthoate, 2-ethylhexyl naphthoate, etc. Aldehydes include butyraldehyde, propionaldehyde, benzaldehyde, etc. Ketones include methyl ethyl ketone, diethyl ketone, acetylacetone, acetophenone, benzophenone, etc. Carboxylic acids include Acetic acid, propionic acid, benzoic acid, etc. Acid anhydrides include acetic anhydride, butyric anhydride, benzoic anhydride, etc. Acid amides include formamide, acetamide, benzamide, etc. Amines include methylamine, dimethylamine, trimethylamine, amylamine, aniline , methylaniline, pyridine, etc. Nitriles include acetonitrile, propionitrile, benzonitrile, etc. Phosphines include triethylphosphine, triphenylphosphine, etc. Thioethers include diethyl sulfide, diphenyl sulfide, etc. . Polysiloxanes that can be used as electron donor compounds have the general formula
【式】（ｎ：３〜10000）で
表わされる鎖状又は環状のシロキサン重合物であ
り、各Ｒは、ケイ素に結合し得る同種又は異種の
残基をあらわすが、なかでも、水素、アルキル
基、アリール基等の炭化水素残基、ハロゲン、ア
ルコキシ基又はアリールオキシ基、脂肪酸残基等
の１種から成るもの及びこれらの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り、具体例
を示すとアルキルシロキサン重合物として、例え
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、
及びジメチルポリシロキサン〔Si（CH3）2O〕ｎ，
エチルポリシロキサン〔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
物又はハロアルキルシロキサン又はハロアリール
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事ができる。
これら種々のポリシロキサンは混合して用いる事
もできる。用いるポリシロキサンは液状である事
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、例えば四塩化チタン、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、次のような態様をとることができる。
(1) 固体生成物（）と電子供与体化合物と遷移
金属化合物とを同時に混合し、反応させる。
(2) 固体生成物（）と電子供与体化合物とを混
合し、次に遷移金属化合物を添加した後、反応
させる。
(3) 固体生成物（）と遷移金属化合物を混合
し、次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、次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、溶媒の存在下又は不存在下に
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。混合は撹拌しながら
行なうのが好ましい。混合後は撹拌しながら30〜
300℃、好ましくは50〜200℃で10分〜30時間反応
させる。
電子供与体化合物と遷移金属化合物とを混合
し、次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、予め室温（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（）を調製における混合、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、予
め、任意のまたは全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、四臭化炭素などのハロゲ
ン化炭化水素などが挙げられる。
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、公知触媒とは異なるもの
であり、重合活性が極めて高く、反応終了後、重
合体中の残触媒の除去工程、即ち脱灰工程をなく
すことが可能である。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。従つ
て、成形時流れ特性が良好で、成形時の樹脂圧力
が低く、高速成形が可能であり、メルトフラクチ
ヤが起きないために成形物の外観が良好である。
フイルム製造の場合、適度の強度および不透明性
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。Mw／Mn（Mw
は重量平均分子量、Mnは数平均分子量を表す。）
はWaters社製GPC―200型のゲルパーミユエーシ
ヨンクロマトグラフイーにより求めた。
重合体収率は、１時間、固体生成物（）１ｇ
当りのポリエチレンの収量ｇ（ｇ―重合体／ｇ―
（）．Hr）、または１時間、チタン原子1mmolあ
たりのポリエチレン収量ｇ（ｇ―重合体／mmol
―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
1000cm2に存在する直径50μm以上の粒状高分子物
質の個数を測定した。
中空成形は、中空成形機（55mmφ、50rpm、石
川島播磨製IPB―110）により、温度165〜175℃、
サイクルタイム３分間の条件下で内容積４のビ
ンを造つた。
耐ストレスクラツキング性（F50値）は、
ASTM―D1693に従つた。
実施例 １
(1) 遷移金属触媒成分の製造
水酸化マグネシウム76Kgと塩化アルミニウム
（無水）90Kgを、予め振動ミル中で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、次いで上記固体
生成物（）100Kgを加え、110℃に２時間反応さ
せた。反応終了後、常法に従い過を行ない、
液中に未反応四塩化チタンおよび未反応ポリシロ
キサンが検出されなくなるまで残つた固体生成物
をヘキサンで洗浄し、減圧乾燥後、固体生成物
（）を得た。固体生成物（）の１Kg中のチタ
ン原子は0.2molであつた。この固体生成物（）
を遷移金属触媒成分として使用した。
(2) エチレンの多段連続重合
内容積10の第１段重合器に、固体生成物
（）を１時間当り35mgチタン原子に換算して
0.007mmol）、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３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、80℃にお
いて、ブテン―１を５％（容量％）含むエチレン
を１時間当り360Nl、水素を重合器気相部のエチ
レン（ブテンを含む）対水素のモル比が１対1.5
になるように供給しつつ、全圧40Kg／cm2（ゲージ
圧）で連続的に第１段重合を行なつた。
第１段重合終了後、溶媒に懸濁した重合物を、
内圧２Kg／cm2（ゲージ圧）に保たれた脱ガス槽に
導き、ヘキサン中に溶解した水素などの大部分を
分離した。分離した水素およびエチレン（ブテン
を含む）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、75℃
において、エチレンを１時間当り340Nlの速度で
供給し、全圧40Kg／cm2（ゲージ圧）で連続的に第
２段重合を行なつた。第２段重合器気相部のエチ
レン対水素のモル比は１対0.06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102Kgを得た。重合体収率
は24.300ｇ―重合体／ｇ―（）・Hrであつた。
得られたポリエチレン粉末は、メルトインデツ
クス0.05、かさ比重0.40、密度0.950、ブテン含有
量2.5重量％、Mw／Mn25であつた。
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24Kg／Hrであ
つた。フイルムの打抜衝撃強度は140Kg―cm／mm、
ヘイズ値は77％、フイツシユアイは９個、表面状
態は良好で実用上問題のない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（ブテン含む）対水素
のモル比を１対0.14にすること以外は、実施例１
の(2)の第１段重合と同様にして、120時間連続的
に−段重合を行ない、実施例１と同じメルトイン
デツクス0.05の重合体粉末50Kgを得たが、Mw／
Mnが６であり、満足にフイルムを製造すること
はできなかつた。
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
0.15molであつた。該触媒成分を固体生成物
（）の替りに用い他は実施例１の(2)と同様にエ
チレンの多段連続重合を行ない、20Kgの重合体粉
末を得たが、Mw／Mnが10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所、フイル
ムにフイツシユアイが3000個であり、製膜性が安
定せず、打抜強度は70Kg―cm／mmで強度が不足
し、フイルムとして満足すべきものではなかつ
た。
実施例 ２
(1) 遷移金属触媒成分の製造
酸化マグネシウム75ｇと塩化アルミニウム（無
水）80ｇを、ボールミル中で24時間混合、粉砕
し、200℃で３時間加熱した後、冷却して粉砕し、
固体生成物（）を得た。
ヘプタン200ml中に、固体生成物（）150ｇ、
鎖状メチルエチルポリシロキサン100ｇ（粘度500
センチストークス）および四塩化チタン130ｇを
同時に加えて混合し、80℃に３時間反応させた。
その後は実施例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0.23mmolであつた。
(2) エチレンの多段連続重合
第１段重合器に、上記固体生成物（）を１時
間当り30mg、エチレンを１時間当り480Nl、水素
を重合器気相部のエチレン対水素のモル比が１対
1.2になるように供給し、第２段重合器に、70℃
において、エチレンを１時間当り200Nl供給し、
重合器気相部のエチレン対水素のモル比が１対
0.11になるように調節すること以外は、実施例１
と同様にエチレンの多段連続重合を行ない、150
時間の連続運転で127Kgの重合体粉末を得た。こ
のポリエチレンは、メルトインデツクス0.30、か
さ比重0.38、密度0.955、Mw／Mn22であり、中
空成形によりビンを成形した所、成形時の樹脂圧
が低く高速成形が可能であり、成形品の表面は良
好で、成形品の重量および偏肉のなさも満足すべ
きものであつた。
比較例 ３
重合器気相部のエチレン対水素のモル比を１対
0.7にすること以外は、実施例２の(2)の第１段重
合と同様にして150時間連続的に一段重合を行な
い、実施例２と同じメルトインデツクス0.30の重
合体粉末89Kgを得たが、Mw／Mnが６であり、
満足にビンを製造することはできなかつた。
比較例 ４
メチルエチルポリシロキサンを用いないこと以
外は、実施例２の(1)と同様にして遷移金属触媒成
分を得た。該触媒成分１ｇ中のチタン原子は0.16
ｍmolであつた。該触媒成分を固体生成物（）
の替りに用い他は実施例２の(2)と同様にエチレン
の多段連続重合を行ない、25Kgの重合体粉末を得
たが、Mw／Mnが10であつた。このポリエチレ
ンを用いて中空成形によりビンを成形した所、成
形品の表面がメルトフラクチヤにより滑らかさが
なく、偏肉が生じ、ビンとしては満足すべきもの
ではなかつた。
実施例 ３
塩化アルミニウム（無水）80ｇとヒドロタルサ
イト70ｇを、振動ミル中170℃に３時間加熱しな
がら、混合、粉砕、反応を同時に行なわせ固体生
成物（）を得た。
トルエン200ml中、四塩化チタン100ｇおよび固
体生成物（）100ｇを混合、続いて、ジ―ｎ―
ブチルエーテル130―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。
この固体生成物（）を用い、実施例１の(2)と
同様にエチレンの多段連続重合を行ない、102Kg
の重合体粉末を得た。メルトインデツクス0.03、
Mw／Mn24であり、実施例１と同様に満足すべ
きフイルムを製造することができた。
実施例 ４
塩化アルミニウム（無水）90Kgとマグネシアセ
メント110Kgをボールミル中で48時間混合、粉砕
し、250℃で２時間加熱した後、冷却して粉砕し、
固体生成物（）を得た。
キシレン200l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
（）を得た。固体生成物（）１Kg中のチタン
原子は0.25molであつた。
この固体生成物（）を用い、実施例２の(2)と
同様にエチレンの多段連続重合を行ない、127Kg
の重合体粉末を得た。メルトインデツクス
0.35Mw／Mn21であり、実施例２と同様に満足
すべきビンを製造することができた。
比較例 ５
特公昭52―13827号の方法に従い最終固体生成
物の調製を行ない、多段連続重合によりポリエチ
レンの製造を行なつた。
トルエン150ml中、実施例１で得られた固体生
成物（）100ｇを鎖状ジメチルポリシロキサン
100ｇ（実施例１と同品）と120℃で２時間反応さ
せた後、四塩化チタン173ｇを加え、110℃で２時
間反応させ、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１ｇ中0.14mmolであつた。
実施例１の固体生成物（）の代りにこの最終
固体生成物を用いること以外は、実施例１と同様
にエチレンの多段連続重合を行ない、Mw／Mn
が15のポリエチレンを得たがフイルムの性能は不
十分であつた。
比較例 ６
特公昭52―13827号の方法に従い、最終固体生
成物の調製を行ない、多段連続重合によりポリエ
チレンの製造を行なつた。
ヘプタン200ml中、実施例２で得られた固体生
成物（）150ｇを鎖状メチルエチルポリシロキ
サン100ｇと80℃で３時間反応させた後、メチル
エチルポリシロキサンを取除かない状態で、四塩
化チタン130ｇを加え、更に80℃に３時間反応さ
せ、その後は実施例２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
１ｇ中0.15mmolであつた。
実施例２において固体生成物（）の代りに、
この最終固体生成物を用いること以外は、実施例
２と同様にエチレンの多段連続重合を行ない、
100Kgの重合体粉末を得たが、Mw／Mnは14であ
つた。このポリエチレンを用いて中空成形したと
ころ、成形品の表面がメルトフラクチヤにより肌
荒れを生じ、偏肉も認められ、実用上不十分な性
能であつた。
比較例 ７
実施例３においてジ―ｎ―ブチルエーテルを用
いないこと以外は、実施例３と同様にして、最終
固体生成物を製造した。チタン含有量は最終固体
生成物１ｇ当り0.12mmolであつた。
この最終固体生成物を用い、実施例３と同様に
してエチレンの多段連続重合を行なつたが、得ら
れたポリエチレンのMw／Mnは11であり、フイ
ルムを製造することさえできなかつた。
比較例 ８
実施例４において酢酸ｎ―ブチルを用いないこ
と以外は、実施例４と同様にして最終固体生成物
を製造した。チタン含有量は最終固体生成物１ｇ
当り0.14mmolであつた。
この最終固体生成物を用い、実施例４と同様に
してエチレンの多段連続重合を行なつたが、得ら
れたポリエチレンのMw／Mnは９であり、中空
成形を行なつてもビンを製造することはできなか
つた。
実施例 ５
実施例１において、第１段重合の際トリイソブ
チルアルミニウムを１時間当り0.4mmol、ヘキサ
ンを１時間当り2.5の速度で供給し、85℃にお
いて、エチレンを１時間当り300Nl、水素を気相
部のエチレン対水素のモル比が１対2.8になるよ
うに供給し、第１段重合終了後は、分離した水素
およびエチレンをエチレン対水素のモル比が所定
比に保てるように循環再利用し、第２段重合にお
いては、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、
全圧30Kg／cm2（ゲージ圧）で行ない、気相部のエ
チレン（ブテン―１を含む）対水素のモル比を１
対0.02にすること以外は、実施例１と同様にエチ
レンの多段連続重合を行なつた。
ポリエチレン91Kgが得られ、メルトインデツク
ス0.04、かさ比重0.39、密度0.949、Mw／Mn27
であつた。製膜時の溶融樹脂の流動性は良好であ
り、製膜性も安定しており、打抜衝撃強度153Kg
―cm／mmで十分の強度を持ち、ヘイズ値79％で十
分な不透明感を持ち、フイツシユアイは５個で実
用上全く問題なく、表面状態は良好で、満足すべ
きフイルム性能であつた。
比較例 ９
実施例５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3.2
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―１を含む）対水素が１対0.04
になるように供給し、全圧40Kg／cm2で第２段重合
を行なうこと以外は実施例５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90Kgが得られ、メルトインデツク
ス0.03、Mw／Mn16であり、フイツシユアイが
650個もあり、打抜衝撃強度70Kg―cm／mmで強度
がかなり不足し、フイルムとして満足できるもの
は得られなかつた。
比較例 10
実施例５において、エチレンを１時間当り
380Nl、水素を気相部のエチレン対水素が１対2.8
になるように供給し、全圧40Kg／cm2（ゲージ圧）
で第１段重合を行ない、エチレンを１時間当り
30Nl、水素を気相部のエチレン対水素が１対
0.005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
５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85Kgが得られ、メルトインデツク
ス0.05、Mw／Mn12であり、フイツシユアイが
1000cm2当り700個もあり、フイルムの表面状態は
著しく不良であり、打抜衝撃強度40Kg―cm／mmで
強度も著しく不足し、フイルムとして満足できる
ものは得られなかつた。
実施例 ６
実施例２において、第１段重合の際、ヘキサン
を１時間当り２の速度で供給し、90℃におい
て、エチレンを１時間当り200Nl、水素を気相部
のエチレン対水素のモル比が１対1.7になるよう
に供給し、全圧20Kg／cm2（ゲージ圧）で行ない、
第１段重合終了後は、分離した水素およびエチレ
ンをエチレン対水素のモル比が所定比に保てるよ
うに循環再利用し、第２段重合においては65℃に
おいて、エチレンを１時間当り200Nlの速度で供
給し、全圧15Kg／cm2（ゲージ圧）で行ない、気相
部のエチレン対水素のモル比を１対0.08にするこ
と以外は、実施例２と同様にしてポリエチレンの
製造を行なつた。
ポリエチレン72Kgが得られ、メルトインデツク
ス0.25、かさ比重0.40、密度0.954、Mw／Mn24
であつた。中空成形されたビンは実用上全く問題
のなく、十分な性能を有していた。
実施例 ７
三塩化鉄（無水）70ｇと塩化マンガン
（MnCl2・4H2O）80ｇを、実施例１と同様に混
合、粉砕後反応させ、固体生成物（）を得た。
この固体生成物（）100ｇ、メチル水素ポリシ
ロキサン（粘度300センチストークス）100ｇ、四
塩化チタン100ｇおよびトルエン200mlを同時に混
合した後は、実施例１と同様に反応させ、固体生
成物（）を得た。チタン含有量は固体生成物
（）１ｇ当り0.42mmolであつた。
この固体生成物（）を用い、実施例６と同様
にエチレンの多段連続重合を行ない、ポリエチレ
ン70Kgを得た。メルトインデツクス0.36、かさ比
重0.36、密度0.956、Mw／Mn21であつた、中空
成形によりピンを製造したところ満足できる結果
を得た。
実施例 ８
三塩化鉄（無水）70ｇとヒドロマグネサイト
（3MgCO3・Mg（CH）2・3H2O）65ｇを振動ミル
中10時間混合、粉砕し、300℃に１時間加熱した
後、冷却して粉砕し、固体生成物（）を得た。
20℃に保たられたオクタン100ml中において、
固体生成物（）100ｇ、ｎ―ブチルアルデヒド
72ｇおよび四塩化バナジウム190ｇを同時に混合
し、その後、70℃に15時間反応させた。反応終了
後は実施例１を同様にして固体生成物（）を得
た。バナジウム含有量は固体生成物（）１ｇ当
り0.18mmolであつた。
この固体生成物（）を用い、実施例１におい
て第１段重合の際、プロピレンを３容量％含むエ
チレンを１時間当り300Nl、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
2.5になるように供給し、第１段重合終了後は、
分離した水素およびエチレン（プロピレンを含
む）を気相部のモル比が所定比に保てるように循
環再利用し第２段重合においてはプロピレンを３
容量％含むエチレンを１時間当り300Nl、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0.01になるように供給すること以外
は、実施例１と同様にエチレンの多段連続重合を
行なつた。
ポリエチレン86Kgが得られ、メルトインデツク
ス0.06、かさ比重0.41、密度0.951、Mw／Mn25
であつた。フイルム製膜時の溶融樹脂の流動性は
良好で、製膜性も安定しており、フイルムの打抜
衝撃強度150Kg―cm／mmで十分な強度を持ち、ヘ
イズ値79％で適度な不透明感であり、フイツシユ
アイは６個で全く問題なく、表面状態は良好で、
満足のできるフイルム性能であつた。
実施例 ９
内容積10の第１段重合器に実施例２の固体生
成物（）を１時間当り30mg、トリイソブチルア
ルミニウムを１時間当り0.4mmol、およびヘキサ
ンを１時間当り２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、80℃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2.3になるように供給しつつ、全
圧30Kg／cm2（ゲージ圧）で連続的に第１段重合を
行なつた。
第１段重合終了後、溶媒に懸濁した重合物を、
内圧２Kg／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、触媒は追加するこ
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、
エチレンを１時間当り300Nlの速度で供給し、全
圧20Kg／cm2（ゲージ圧）で連続的に第２段重合を
行なつた。第２段重合器気相部のエチレン対水素
のモル比は１対0.09になるように保つた。必要に
応じて水素を供給した。
以上の多段重合を150時間連続して行なつたが、
運転は極めて安定しており、脱灰をせず乾燥後、
ポリエチレン粉末107Kgを得た。重合体収率は
23.800ｇ―重合体／ｇ−（）・Hr、103000ｇ―
重合体／mmol―Ti・Hrであつた。
このポリエチレンは、メルトインデツクス
0.25、かさ比重0.41、密度0.955ｇ／cm2、Mw／
Mn25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事はなく、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、偏肉もほとん
どなく、実用上十分な性能のビンであつた。
比較例 11
重合器気相部のエチレン対水素のモル比を１対
0.6にすること以外は実施例９の第１段重合と同
様にして、150時間連続的に１段重合を行ない、
実施例９と同じのメルトインデツクス0.25のポリ
エチレン54Kgを得た。しかしこのポリエチレンの
Mw／Mnは６であつた。
中空成形によりビンは製造することはできなか
つた。
比較例 12
ヘプタン200ml中に、実施例２―(1)で得られた
固体生成物（）100ｇおよび鎖状メチルエチル
ポリシロキサン100ｇ（実施例２と同品）を加え、
撹拌しながら80℃に３時間反応させた後、未反応
ポリシロキサンを除去しない状態で四塩化チタン
130ｇを加え、更に80℃に３時間反応させた。そ
の後は実施例２―(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１
ｇ中、0.16mmolであつた。
実施例９の固体生成物（）の代りにこの最終
固体生成物を90mg使用し、トリイソブチルアルミ
ニウムを１時間当り0.8mmol供給すること以外は
実施例９と同様にして多段連続重合を行ないポリ
エチレン105Kgを得た。重合体収率は7800ｇ―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
0.28、かさ比重0.36、Mw／Mn13であつた。
中空ビンを製造したところ、成形品の表面がサ
メ肌をしていて外観が悪く、成形品１個の重量は
230ｇで不十分であり、偏肉現象もみられ、実用
に耐える性能のビンではなかつた。
実施例 10
(1) 遷移金属触媒成分の製造
塩化マンガン（MnCl2・4H2O）80ｇと三塩化
鉄（無水70）ｇを予め、振動ボールミル中２時間
混合、粉砕した後、120℃で６時間反応させ、固
体生成物（）を得た。
この固体生成物（）100ｇ、鎖状エチル水素
ポリシロキサン100ｇ（粘度100センチストーク
ス）、四塩化バナジウム100ｇおよびトルエン200
mlを同時に混合し、110℃に２時間反応させ、固
体生成物（）を得た。バナジウム含有量は固体
生成物（）１ｇ中0.15mmolであつた。
(2) エチレンの多段連続重合
上記固体生成物（）を１時間当り47mg、ピロ
ピレン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2.4になるように供
給し、85℃において行なうこと以外は実施例９と
同様にして第１段重合を行なつた。
脱ガス槽で分離した水素エチレンおよびプロピ
レンは第１段重合器気相部のモル比が所定比に保
てるように循環再利用した。
ブテン―１を２容量％含むエチレンを１時間当
り306Nl、気相部のエチレン（ブテンを含む）対
水素のモル比が１対0.1に保てるように必要に応
じて水素を供給し、75℃において行なうこと以外
は実施例９と同様にして第２段重合を行なつた。
以上の多段重合を120時間連続して行ないポリ
エチレン粉末90Kgを得る。重合体収率は16000ｇ
―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
0.23、かさ比重0.37、密度0.954ｇ／cm2、プロピレ
ンおよびブテン合計の含有量1.5重量％、Mw／
Mn25であつた。
中空成形により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
チヤーを起こす事もなく、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265ｇで十分であり、耐ストレスクラ
ツキング性は180Hrで問題なく、実用上十分な性
能のビンであつた。
比較例 13
重合器気相部のエチレン（プロピレンを含む）
対水素のモル比を１対0.18にすること以外は、実
施例10の第１段重合と同様にして、120時間連続
的に一段重合を行ない、メルトインデツクス0.27
のポリエチレン45Kgを得た。しかしこのポリエチ
レンMw／Mn7であつた。
中空成形によりビンをつくることはできなかつ
た。
比較例 14
トルエン200ml中に実施例10で得られた固体生
成物（）100ｇおよびエチル水素ポリシロキサ
ン100ｇ（実施例10と同品）を加え110℃に２時間
反応させた後、未反応ポリシロキサンを除去しな
い状態で、四塩化バナジウム100ｇを加え、更に
110℃に２時間反応させた。その後は実施例10と
同様にして最終固体生成物を得た。バナジウム原
子の含有量は最終固体生成物１ｇ中0.12mmolで
あつた。
実施例10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140mg、トリイソブチル
アルミニウムを１時間当り0.96mmol供給するこ
と以外は実施例10と同様にして多段連続重合を行
ないポリエチレン粉末88Kgを得た。重合体収率は
5200ｇ―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
0.30、かさ比重0.34、Mw／Mn13であつた。
中空成形をしたところ、成形品の表面がサメ肌
をしていた外観が悪く、成形品１個の重量は225
ｇで不十分であり、偏肉現象もみられ、実用に耐
える性能のビンではなかつた。It is a chain or cyclic siloxane polymer represented by the formula (n: 3 to 10,000), and each R represents the same or different type of residue that can be bonded to silicon, including hydrogen and an 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; specific examples include alkylsiloxane polymers such as octamethyltrisiloxane CH 3 [Si
(CH 3 ) 2 O] 2 Si(CH 3 ) 3 , lower polymers such as octaethylcyclotetrasiloxane [Si(C 2 H 5 ) 2 O] 4 ,
and dimethylpolysiloxane [Si(CH 3 ) 2 O]n,
Ethylpolysiloxane [SiH (C 2 H 5 ) O] n, Methyl ethyl polysiloxane [Si (CH 3 ) (C 2 H 5 )
Alkylsiloxane polymers such as polymers such as O]n, hexaphenylcyclotrisiloxane [Si(C 6 H 5 ) 2 O] 3 , diphenylpolysiloxane [Si
Arylsiloxane polymers such as (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 ,
Methylphenylpolysiloxane [Si(CH 3 )
Examples include alkylarylsiloxane polymers such as (C 6 H 5 )O]n. 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. Further, 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, with a viscosity (at 25° C.) suitably in the range 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, acetoxyhalides, etc., such as titanium tetrachloride, titanium tetrabromide, tetraethoxytitanium, tetrabutoxytitanium, monochlorobutoxytitanium, dichloro Examples include dibutoxytitanium, trichloromonoethoxytitanium, vanadium tetrachloride, vanadium oxytrichloride, and the like. As a specific method for preparing the solid product (2), the following embodiments can be adopted. (1) Simultaneously mix and react the solid product () with an electron donor compound and a transition metal compound. (2) Mix the solid product () and the electron donor compound, then add the transition metal compound and then react. (3) Mix the solid product () and the transition metal compound, then add the electron donor compound and then react. (4) Mixing an electron donor compound and a transition metal compound, and then mixing and reacting the solid product () with this mixture. 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). Preferably, the mixing is carried out with stirring. After mixing, stir 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 and reacted with this mixture, the mixture of the electron donor compound and a transition metal compound is a solid product (). Before mixing, heat the mixture to room temperature (approximately 20℃) or above and below 100℃,
Preferably, the temperature may be kept at 60° C. or lower for 1 minute to 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 necessarily necessary to use a solvent during mixing and reaction in preparing the solid product (), but it is preferable to react uniformly, so any or all of the above components may be dissolved or dispersed in a solvent in advance. You may leave it to mix. 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. These solid products ()
Solvents used for the preparation include aliphatic hydrocarbons such as hexane, heptane, octane, nonane, and decane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, and cumene, chlorobenzene, dichlorobenzene, trichlorobenzene, etc. halogenated aromatic hydrocarbons, carbon tetrachloride, chloroform, dichloroethane, trichloroethylene,
Examples include halogenated hydrocarbons such as tetrachlorethylene 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. By doing so,
This enabled 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 is different from known catalysts and has extremely high polymerization activity, making it possible to eliminate the step of removing the residual catalyst in the polymer, that is, the deashing step, after the reaction is completed. 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 fish eyes, a smooth film surface, and stable moldability over a long period of time. In addition, the bulk specific gravity of the polyethylene powder obtained by the present invention is 0.35 to 0.45, and the shape of the powder particles is good, so the production efficiency per unit volume of the polymerization vessel and per hour is high, and the piping of the polymer powder is It has the characteristics that there are no transportation problems and the powder can be easily granulated. Hereinafter, the features of the present invention will be specifically explained with reference to Examples. The melt index in Examples and Comparative Examples is
In accordance with ASTM D-1238(E). Mw/Mn (Mw
represents the weight average molecular weight, and Mn represents the number average molecular weight. )
was determined using GPC-200 gel permeation chromatography manufactured by Waters. Polymer yield: 1 hour, 1 g of solid product ()
Yield of polyethylene per g (g-polymer/g-
(). Hr), or polyethylene yield in g per mmol of titanium atom per hour (g-polymer/mmol
- 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 1000 cm 2 was measured. The blow molding was performed using a blow molding machine (55 mmφ, 50 rpm, IPB-110 manufactured by Ishikawajima Harima) at a temperature of 165 to 175°C.
A bottle with an internal volume of 4 was made under conditions of a cycle time of 3 minutes. Stress cracking resistance ( F50 value) is
In accordance with ASTM-D1693. Example 1 (1) Production of transition metal catalyst component 76 kg of magnesium hydroxide and 90 kg of aluminum chloride (anhydrous) were mixed in advance in a vibration mill for 5 hours.
After pulverizing, the mixture was reacted at 150°C for 5 hours. Thereafter, it was cooled and pulverized to obtain a solid product (2). 173 kg of titanium tetrachloride and 100 kg of chain dimethylpolysiloxane (viscosity 100 centistokes) were added to 150 kg of toluene and mixed. Then, 100 kg of the above solid product (2) was added and reacted at 110° C. for 2 hours. After the reaction is 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 continuous polymerization of ethylene In the first stage polymerization vessel with an internal volume of 10, the solid product () was converted into 35mg titanium atoms per hour.
0.007 mmol), triethylaluminum was fed at a rate of 0.3 mmol per hour and hexane was fed at a rate of 3 mmol per hour, and the contents of the polymerization vessel were discharged to maintain the liquid level in the polymerization vessel at 80% at 80°C. , 360 Nl per hour of ethylene containing 5% (volume %) butene-1, and hydrogen at a molar ratio of ethylene (including butene) to hydrogen in the gas phase of the polymerizer of 1:1.5.
The first stage polymerization was carried out continuously at a total pressure of 40 Kg/cm 2 (gauge pressure) while supplying the polymer so as to achieve the following. After the first stage polymerization, the polymer suspended in the solvent is
The mixture was introduced into a degassing tank maintained at an internal pressure of 2 kg/cm 2 (gauge pressure), and most of the hydrogen and other substances dissolved in hexane were separated. The separated hydrogen and ethylene (including butene) were recycled and reused so as 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 reactor, and the temperature was raised to 75°C while draining the contents of the polymerization reactor to maintain the liquid level in the reactor at 80% without adding hydrogen or catalyst.
Ethylene was supplied at a rate of 340 Nl per hour, and the second stage polymerization was carried out continuously at a total pressure of 40 Kg/cm 2 (gauge pressure). The molar ratio of ethylene to hydrogen in the gas phase of the second stage polymerizer was 1:0.06. The above multi-stage polymerization was carried out continuously for 120 hours, but
The operation was extremely stable, and 102 kg of polyethylene powder was obtained after drying without deashing. The polymer yield was 24.300 g-polymer/g-()·Hr. The obtained polyethylene powder had a melt index of 0.05, a bulk specific gravity of 0.40, a density of 0.950, a butene content of 2.5% by weight, and an Mw/Mn of 25. When a film was manufactured using this polyethylene powder, the amount of molten resin discharged was 24 kg/hr. The punching impact strength of the film is 140Kg-cm/mm,
The film had a haze value of 77%, 9 fixation eyes, a good surface condition, and no problems in practical use. Comparative Example 1 Example 1 except that the molar ratio of ethylene (including butene) to hydrogen in the gas phase of the polymerization reactor was set to 1:0.14.
In the same manner as the first stage polymerization in (2), one-stage polymerization was carried out continuously for 120 hours to obtain 50 kg of polymer powder with the same melt index of 0.05 as in Example 1, but with Mw/
Mn was 6, and a film could not be produced satisfactorily. 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 atoms in 1 kg of the catalyst component are
It was 0.15mol. Multistage continuous polymerization of ethylene was carried out in the same manner as in Example 1 (2) except that the catalyst component was used in place of the solid product (2), and 20 kg of polymer powder was obtained, except that Mw/Mn was 10. Ta. When a film was manufactured using this polyethylene, the film had 3000 fissure eyes, the film formability was unstable, and the punching strength was 70 kg-cm/mm, which was insufficient, and the film was not satisfactory. Ta. Example 2 (1) Production of transition metal catalyst component 75 g of magnesium oxide and 80 g of aluminum chloride (anhydrous) were mixed in a ball mill for 24 hours, pulverized, heated at 200°C for 3 hours, cooled and pulverized,
A solid product () was obtained. 150 g of solid product () in 200 ml of heptane,
100g linear methylethylpolysiloxane (viscosity 500
centistokes) and 130 g of titanium tetrachloride were added at the same time, mixed, and reacted at 80° 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 0.23 mmol. (2) Multistage continuous polymerization of ethylene In the first stage polymerization vessel, 30 mg of the above solid product () was added per hour, ethylene was added to 480 Nl per hour, and hydrogen was added to the polymerization vessel at a molar ratio of ethylene to hydrogen in the gas phase of 1. versus
1.2 to the second stage polymerization vessel at 70℃.
, 200Nl of ethylene was supplied per hour,
The molar ratio of ethylene to hydrogen in the gas phase of the polymerizer is 1:
Example 1 except for adjusting to 0.11
Perform multistage continuous polymerization of ethylene in the same manner as 150
127Kg of polymer powder was obtained in continuous operation for hours. This polyethylene has a melt index of 0.30, bulk specific gravity of 0.38, density of 0.955, and Mw/Mn22.When molded into a bottle by blow molding, the resin pressure during molding is low and high-speed molding is possible, and the surface of the molded product is The weight and thickness of the molded product were also satisfactory. Comparative Example 3 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 150 hours in the same manner as the first-stage polymerization in (2) of Example 2, except that the melt index was 0.7, and 89 kg of polymer powder with the same melt index as in Example 2 of 0.30 was obtained. But Mw/Mn is 6,
It was not possible to manufacture the bottles satisfactorily. Comparative Example 4 A transition metal catalyst component was obtained in the same manner as in Example 2 (1) except that methylethylpolysiloxane was not used. The titanium atoms in 1 g of the catalyst component are 0.16
It was mmol. The catalyst component is converted into a solid product ()
Multistage continuous polymerization of ethylene was carried out in the same manner as in Example 2 (2) except that 25 kg of polymer powder was obtained, but the Mw/Mn was 10. When a bottle was molded by blow molding using this polyethylene, the surface of the molded product lacked smoothness due to melt fracture, and uneven thickness occurred, making it unsatisfactory as a bottle. Example 3 80 g of aluminum chloride (anhydrous) and 70 g of hydrotalcite were heated at 170° C. for 3 hours in a vibrating mill while mixing, pulverizing, and reacting simultaneously to obtain a solid product (). Mix 100 g of titanium tetrachloride and 100 g of solid product () in 200 ml of toluene, followed by
Butyl ether 130- was added and reacted at 100°C for 3 hours. Thereafter, washing was carried out 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. Using this solid product (2), multistage continuous polymerization of ethylene was carried out in the same manner as in Example 1 (2), and 102 kg
A polymer powder was obtained. Melt index 0.03,
Mw/Mn was 24, and as in Example 1, a satisfactory film could be produced. Example 4 90 kg of aluminum chloride (anhydrous) and 110 kg of magnesia cement were mixed in a ball mill for 48 hours, pulverized, heated at 250°C for 2 hours, cooled and pulverized,
A solid product () was obtained. In 200 liters of xylene, 100 kg of solid product () and 60 kg of n-butyl acetate were mixed, then 100 kg of titanium tetrachloride was added and reacted at 120°C for 2 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 kg of the solid product ( ) was 0.25 mol. Using this solid product (2), multistage continuous polymerization of ethylene was carried out in the same manner as in Example 2 (2), and 127 kg
A polymer powder was obtained. melt index
It was 0.35 Mw/Mn21, and as in Example 2, a satisfactory bottle could be manufactured. Comparative Example 5 A final solid product was prepared according to the method disclosed in Japanese Patent Publication No. 52-13827, and polyethylene was produced by multistage continuous polymerization. In 150 ml of toluene, add 100 g of the solid product () obtained in Example 1 to linear dimethylpolysiloxane.
After reacting with 100g (same product as in Example 1) at 120°C for 2 hours, 173g of titanium tetrachloride was added and reacted at 110°C for 2 hours, and then the same procedure as in Example 1 was carried out to obtain the final solid product. Ta. The content of titanium atoms was 0.14 mmol in 1 g of the final solid product. Multistage continuous polymerization of ethylene was carried out in the same manner as in Example 1, except that this final solid product was used in place of the solid product () of Example 1, and Mw/Mn
Although a polyethylene of 15 was obtained, the performance of the film was insufficient. Comparative Example 6 A final solid product was prepared according to the method disclosed in Japanese Patent Publication No. 52-13827, and polyethylene was produced by multistage continuous polymerization. After reacting 150 g of the solid product () obtained in Example 2 with 100 g of linear methylethylpolysiloxane at 80°C for 3 hours in 200 ml of heptane, titanium tetrachloride was added without removing the methylethylpolysiloxane. 130 g was added and the reaction was further carried out at 80° C. for 3 hours, after which the final solid product was obtained in the same manner as in Example 2. The content of titanium atoms was 0.15 mmol in 1 g of the final solid product. In Example 2, instead of the solid product (),
Multistage continuous polymerization of ethylene was carried out in the same manner as in Example 2 except that this final solid product was used,
100 kg of polymer powder was obtained, and Mw/Mn was 14. When blow molding was performed using this polyethylene, the surface of the molded product became rough due to melt fracture, uneven thickness was observed, and the performance was insufficient for practical use. Comparative Example 7 A final solid product was prepared in the same manner as in Example 3, except that di-n-butyl ether was not used in Example 3. The titanium content was 0.12 mmol/g of final solid product. Using this final solid product, multistage continuous polymerization of ethylene was carried out in the same manner as in Example 3, but the Mw/Mn of the obtained polyethylene was 11, and it was not even possible to produce a film. Comparative Example 8 A final solid product was produced in the same manner as in Example 4, except that n-butyl acetate was not used in Example 4. Titanium content is 1g of final solid product
The amount was 0.14 mmol. Using this final solid product, multistage continuous polymerization of ethylene was carried out in the same manner as in Example 4, but the Mw/Mn of the obtained polyethylene was 9, and bottles could be manufactured even if blow molding was performed. I couldn't do that. Example 5 In Example 1, triisobutylaluminum was supplied at a rate of 0.4 mmol per hour and hexane was supplied at a rate of 2.5 per hour during the first stage polymerization, and ethylene was supplied at a rate of 300 Nl per hour and hydrogen was supplied in gas at 85°C. The phase is supplied so that the molar ratio of ethylene to hydrogen is 1 to 2.8, and after the completion of the first stage polymerization, the separated hydrogen and ethylene are recycled and reused so that the molar ratio of ethylene to hydrogen is maintained at the specified ratio. However, in the second stage polymerization, ethylene containing 5% by volume of butene-1 was supplied at a rate of 315 Nl per hour at 70°C.
The process was carried out at a total pressure of 30 kg/cm 2 (gauge pressure), and the molar ratio of ethylene (including butene-1) to hydrogen in the gas phase was 1.
Multistage continuous polymerization of ethylene was carried out in the same manner as in Example 1, except that the ratio was set to 0.02. 91 kg of polyethylene was obtained, melt index 0.04, bulk specific gravity 0.39, density 0.949, Mw/Mn27
It was hot. The fluidity of the molten resin during film formation is good, the film formability is stable, and the punching impact strength is 153 kg.
- It had sufficient strength in cm/mm, had sufficient opacity with a haze value of 79%, had no practical problems with 5 fixation eyes, had a good surface condition, and had satisfactory film performance. Comparative Example 9 In Example 5, ethylene per hour
120Nl, hydrogen in the gas phase ethylene to hydrogen 1:3.2
The total pressure is 25Kg/cm 2 (gauge pressure).
The first stage polymerization was carried out using ethylene containing 3% by volume of butene-1 at 495 Nl per hour, and hydrogen in the gas phase at a ratio of ethylene (including butene-1) to hydrogen at 1:0.04.
Multistage continuous polymerization of ethylene was carried out in the same manner as in Example 5, except that the second stage polymerization was carried out at a total pressure of 40 kg/cm 2 . 90 kg of polyethylene was obtained, the melt index was 0.03, Mw/Mn was 16, and the fish eye was
There were 650 pieces, and the punching impact strength was 70 kg-cm/mm, which was quite insufficient in strength, and it was not possible to obtain a film that was satisfactory. Comparative Example 10 In Example 5, ethylene was added per hour.
380Nl, ethylene to hydrogen in the gas phase is 1:2.8
The total pressure is 40Kg/cm 2 (gauge pressure).
The first stage polymerization was carried out at a rate of ethylene per hour.
30Nl, 1 pair of hydrogen and ethylene in the gas phase
Multistage continuous polymerization of ethylene was carried out in the same manner as in Example 5, except that the second stage polymerization was carried out at a total pressure of 10 Kg/cm 2 (gauge pressure). 85 kg of polyethylene was obtained, the melt index was 0.05, Mw/Mn was 12, and the fish eye was
There were as many as 700 pieces per 1000 cm 2 , and the surface condition of the film was extremely poor.The punching impact strength was 40 kg-cm/mm, which was extremely insufficient, and a satisfactory film could not be obtained. Example 6 In Example 2, during the first stage polymerization, hexane was supplied at a rate of 2 per hour, and at 90°C, ethylene was supplied at 200 Nl per hour, and hydrogen was supplied at a molar ratio of ethylene to hydrogen in the gas phase. was supplied at a ratio of 1:1.7, and the total pressure was 20Kg/cm 2 (gauge pressure).
After the first stage polymerization is completed, the separated hydrogen and ethylene are recycled and reused to maintain the molar ratio of ethylene to hydrogen at a predetermined ratio.In the second stage polymerization, ethylene is added at a rate of 200 Nl per hour at 65°C. Polyethylene was produced in the same manner as in Example 2, except that the process was carried out at a total pressure of 15 Kg/cm 2 (gauge pressure) and the molar ratio of ethylene to hydrogen in the gas phase was 1:0.08. Ta. 72 kg of polyethylene was obtained, melt index 0.25, bulk specific gravity 0.40, density 0.954, Mw/Mn24
It was hot. The blow-molded bottle had no practical problems and had sufficient performance. Example 7 70 g of iron trichloride (anhydrous) and 80 g of manganese chloride (MnCl 2 .4H 2 O) were mixed and pulverized in the same manner as in Example 1, and then reacted to obtain a solid product ( ).
After simultaneously mixing 100 g of this solid product (), 100 g of methylhydrogen polysiloxane (viscosity 300 centistokes), 100 g of titanium tetrachloride, and 200 ml of toluene, the reaction was carried out in the same manner as in Example 1 to obtain the solid product (). Ta. The titanium content was 0.42 mmol/g of solid product. Using this solid product (2), multistage continuous polymerization of ethylene was carried out in the same manner as in Example 6 to obtain 70 kg of polyethylene. A pin with a melt index of 0.36, bulk specific gravity of 0.36, density of 0.956, and Mw/Mn of 21 was manufactured by blow molding, and satisfactory results were obtained. Example 8 70 g of iron trichloride (anhydrous) and 65 g of hydromagnesite (3MgCO 3・Mg (CH) 2・3H 2 O) were mixed in a vibrating mill for 10 hours, pulverized, heated to 300°C for 1 hour, and then cooled. The solid product () was obtained by grinding. In 100ml of octane kept at 20℃,
100 g of solid product (), n-butyraldehyde
72 g and 190 g of vanadium tetrachloride were simultaneously mixed and then reacted at 70° C. for 15 hours. After the reaction was completed, a solid product (2) was obtained in the same manner as in Example 1. The vanadium content was 0.18 mmol/g of solid product. Using this solid product (), during the first stage polymerization in Example 1, ethylene containing 3% by volume of propylene was added at 300 Nl per hour, and hydrogen was added at a molar ratio of ethylene (including propylene) to hydrogen in the gas phase. 1 pair
After the first stage polymerization,
The separated hydrogen and ethylene (including propylene) are recycled and recycled so that the molar ratio in the gas phase can be maintained at a predetermined ratio, and in the second stage polymerization, propylene is
Ethylene was produced in multiple stages in the same manner as in Example 1, except that ethylene containing % by volume was supplied at 300 Nl per hour and hydrogen was supplied so that the molar ratio of ethylene (including propylene) to hydrogen in the gas phase was 1:0.01. Continuous polymerization was carried out. 86 kg of polyethylene was obtained, melt index 0.06, bulk specific gravity 0.41, density 0.951, Mw/Mn25
It was hot. The fluidity of the molten resin during film formation is good, and the film formability is stable.The punching impact strength of the film is 150Kg-cm/mm, which is sufficient strength, and the haze value is 79%, giving a moderate opacity. There are 6 fisheyes, no problems at all, and the surface condition is good.
The film performance was satisfactory. Example 9 30 mg of the solid product of Example 2 () per hour, 0.4 mmol of triisobutylaluminum per hour, and hexane were fed to a first stage polymerization reactor with an internal volume of 10 at a rate of 2 per hour. , while discharging the contents of the polymerization vessel so as to maintain the liquid level in the polymerization vessel at 80%, at 80°C, ethylene was added at 300 Nl per hour, and hydrogen was added at a molar ratio of ethylene to hydrogen in the gas phase of the polymerization vessel of 1. The first stage polymerization was carried out continuously at a total pressure of 30 Kg/cm 2 (gauge pressure) while feeding at a ratio of 2.3 to 2.3. After the first stage polymerization, the polymer suspended in the solvent is
Internal volume 5 maintained at an internal pressure of 2Kg/cm 2 (gauge pressure)
The hydrogen and ethylene dissolved in hexane were separated, and the separated hydrogen and ethylene were recycled and reused so as 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, without adding any catalyst, and at 70℃ while draining the contents of the polymerization vessel so as to maintain the liquid level in the polymerization vessel at 80%.
Ethylene was supplied at a rate of 300 Nl per hour, and the second stage polymerization was carried out continuously at a total pressure of 20 Kg/cm 2 (gauge pressure). The molar ratio of ethylene to hydrogen in the gas phase of the second stage polymerizer was maintained at 1:0.09. Hydrogen was supplied as needed. The above multi-stage polymerization was carried out continuously for 150 hours, but
The operation is extremely stable, and after drying without deashing,
107 kg of polyethylene powder was obtained. The polymer yield is
23.800g-Polymer/g-()・Hr, 103000g-
Polymer/mmol-Ti・Hr. This polyethylene has a melt index
0.25, bulk specific gravity 0.41, density 0.955g/cm 2 , Mw/
It was Mn25. 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, the surface of the molded product was extremely good, and the molded product Each bottle weighed 280g, had almost no uneven thickness, and had sufficient performance for practical use. Comparative Example 11 The molar ratio of ethylene to hydrogen in the gas phase of the polymerization reactor was set to 1:
The first stage polymerization was carried out continuously for 150 hours in the same manner as the first stage polymerization of Example 9 except that the polymerization was adjusted to 0.6.
54 kg of polyethylene having a melt index of 0.25 as in Example 9 was obtained. However, this polyethylene
Mw/Mn was 6. Bottles could not be manufactured by blow molding. Comparative Example 12 In 200 ml of heptane, add 100 g of the solid product () obtained in Example 2-(1) and 100 g of linear methylethyl polysiloxane (same product as Example 2),
After reacting at 80℃ for 3 hours with stirring, titanium tetrachloride was added without removing unreacted polysiloxane.
130g was added and the reaction was further carried out at 80°C for 3 hours. Thereafter, the final solid product was obtained in the same manner as in Example 2-(1). The content of titanium atoms is the final solid product 1
It was 0.16 mmol in g. Multistage continuous polymerization was carried out in the same manner as in Example 9, except that 90 mg of this final solid product was used instead of the solid product () of Example 9, and 0.8 mmol of triisobutylaluminum was supplied per hour, to produce 105 kg of polyethylene. I got it. The polymer yield was 7800 g-polymer/g-().Hr. This polyethylene has melt index
0.28, bulk specific gravity 0.36, and Mw/Mn13. When a hollow bottle was manufactured, the surface of the molded product had a shark-skinned appearance, which made it look bad, and the weight of one molded product was
230g was insufficient, and there was also a phenomenon of uneven thickness, so the bottle did not have a performance that could withstand practical use. Example 10 (1) Production of transition metal catalyst component Manganese chloride (MnCl 2 4H 2 O) 80 g and iron trichloride (anhydrous 70 g) were mixed in advance in a vibrating ball mill for 2 hours, pulverized, and heated at 120°C for 6 hours. After reacting for an hour, a solid product () was obtained. 100 g of this solid product (), 100 g of linear ethylhydrogen polysiloxane (viscosity 100 centistokes), 100 g of vanadium tetrachloride and 200 g of toluene.
ml were mixed simultaneously and reacted at 110°C for 2 hours to obtain a solid product (). The vanadium content was 0.15 mmol in 1 g of solid product (). (2) Multistage continuous polymerization of ethylene 47 mg of the above solid product () per hour, ethylene containing 2% by volume of propylene per hour
306Nl and hydrogen were supplied so that the molar ratio of ethylene (including propylene) to hydrogen in the gas phase was 1:2.4, and the first stage polymerization was carried out in the same manner as in Example 9, except that it was carried out at 85°C. Summer. The hydrogen ethylene and propylene separated in the degassing tank were recycled and reused so that the molar ratio in the gas phase of the first stage polymerizer was maintained at a predetermined ratio. Ethylene containing 2% by volume of butene-1 was supplied at 306Nl per hour, and hydrogen was supplied as necessary to maintain the molar ratio of ethylene (including butene) to hydrogen in the gas phase at 1:0.1, at 75°C. The second stage polymerization was carried out in the same manner as in Example 9 except for the following. The above multistage polymerization was carried out continuously for 120 hours to obtain 90 kg of polyethylene powder. Polymer yield is 16000g
-Polymer/g()・Hr. This polyethylene has melt index
0.23, bulk specific gravity 0.37, density 0.954g/cm 2 , total content of propylene and butene 1.5% by weight, Mw/
It was Mn25. When a bottle was manufactured by blow molding, 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 the bottle was 265 g, which was sufficient, and the stress cracking resistance was 180 hours without any problems, indicating that the bottle had sufficient performance for practical use. Comparative Example 13 Ethylene (including propylene) in the gas phase of the polymerization reactor
One-stage polymerization was carried out continuously for 120 hours in the same manner as the first-stage polymerization in Example 10, except that the molar ratio of hydrogen to 1:0.18, and the melt index was 0.27.
45 kg of polyethylene was obtained. However, this polyethylene Mw/Mn7. It was not possible to make bottles by blow molding. Comparative Example 14 100 g of the solid product () obtained in Example 10 and 100 g of ethylhydrogen polysiloxane (same as Example 10) were added to 200 ml of toluene, and the unreacted polysiloxane was reacted at 110°C for 2 hours. Add 100g of vanadium tetrachloride without removing it, and then
The reaction was carried out at 110°C for 2 hours. Thereafter, the final solid product was obtained in the same manner as in Example 10. The content of vanadium atoms was 0.12 mmol in 1 g of the final solid product. Multistage continuous polymerization was carried out in the same manner as in Example 10, except that 140 mg of this final solid product was supplied per hour instead of the solid product () of Example 10, and 0.96 mmol of triisobutylaluminum was supplied per hour. 88Kg of powder was obtained. The polymer yield is
It was 5200g-polymer/g-()・Hr. This polyethylene has a melt index
0.30, bulk specific gravity 0.34, and Mw/Mn13. When hollow molding was performed, the surface of the molded product had a shark-skinned appearance, and the weight of one molded product was 225.
g was insufficient, uneven thickness was observed, and the bottle did not have a performance that could withstand practical use.
第１図は、本発明の製造法に係る触媒のフロー
チヤートである。
FIG. 1 is a flowchart of the catalyst according to the production method of the present invention.
Claims (1)
存在下、複数個の重合器を使い第１段重合系で低
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、 (i) ３価の鉄またはアルミニウムのハロゲン化物
とマグネシウムまたはマンガンの水酸化物、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（）と電子供与化合物と、チタン
またはバナジウムの化合物とから調製した遷移
金属化合物を担持させたこ固体生成物（）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0.1ないし3.0になるように
水素を供給すると共に、全エチレン供給量の30
〜90％のエチレンを供給して、第１段重合を行
ない、 (ii) 第１段重合終了後は、溶媒中に懸濁した重合
物を、１〜30Kg／cm2の圧力帯域に導き、溶媒に
溶解した水素の少なくとも一部分を分離し、分
離した水素の少なくとも一部分は第１段重合系
にもどし、 (iii) 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、 を特徴とする連続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（）1000ｇ
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１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 multi-stage polymerization, (i) trivalent iron or aluminum halide and magnesium or manganese hydroxide, oxide, carbonate, or double salt containing these;
A solid product obtained by reacting a hydrate of a valent metal compound (), an electron donating compound, and a transition metal compound prepared from a titanium or vanadium compound supported on an octopus solid product () and an organoaluminum compound in the presence of a catalyst obtained by combining the above, in a saturated hydrocarbon solvent, in the presence of a gas phase at the top of the polymerization vessel, at a polymerization temperature of 50°C or higher and 120°C or lower, and a polymerization pressure of 5 to 70°C.
Kg/ cm2 , hydrogen is supplied so that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization reactor is 1:0.1 to 3.0, and 30% of the total ethylene supply amount is
The first stage polymerization is carried out by supplying ~90% ethylene; (ii) After the first stage polymerization is completed, the polymer suspended in the solvent is brought into a pressure zone of 1 to 30 Kg/ cm2 ; At least a portion of the hydrogen dissolved in the solvent is separated, at least a portion of the separated hydrogen is returned to the first stage polymerization system, and (iii) the suspended polymer is then heated to a polymerization temperature of 30° C. in the presence of a gas phase. Under the conditions of 100°C or less and a polymerization pressure of 5 to 70 kg/cm 2 , hydrogen is supplied so that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization vessel is 1:0.001 to 0.5,
A method for producing polyethylene by continuous multistage polymerization, characterized by supplying ethylene in an amount of 10 to 70% of the total ethylene amount to perform 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 1000g of solid product ()
The manufacturing method according to claim 1, wherein the electron donor compound is 20 to 1000 g and the transition metal compound is 10 to 500 g, and the transition metal compound is 30 to 500 g per 100 g of the electron donor compound. . 4. The manufacturing method according to claim 1, 2 or 3, wherein the electron donor compound is polysiloxane. 5 The electron donor compound is an ether, an ester,
The production method according to claim 1, 2 or 3, which is an aldehyde, ketone or acid anhydride.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10565779A JPS5632505A (en) | 1979-08-20 | 1979-08-20 | Production of polyethylene by continuous multistage polymerization |
| DE8080302878T DE3064828D1 (en) | 1979-08-20 | 1980-08-20 | Process for producing polyethylene by continuous multi-stage polymerization and moulded articles made from the product |
| EP19800302878 EP0024881B1 (en) | 1979-08-20 | 1980-08-20 | Process for producing polyethylene by continuous multi-stage polymerization and moulded articles made from the product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10565779A JPS5632505A (en) | 1979-08-20 | 1979-08-20 | Production of polyethylene by continuous multistage polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5632505A JPS5632505A (en) | 1981-04-02 |
| JPS6352654B2 true JPS6352654B2 (en) | 1988-10-19 |
Family
ID=14413505
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10565779A Granted JPS5632505A (en) | 1979-08-20 | 1979-08-20 | Production of polyethylene by continuous multistage polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5632505A (en) |
Families Citing this family (6)
| 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 |
| JPH075763U (en) * | 1993-06-30 | 1995-01-27 | 佳子 村上 | Laminated card |
| BE1011333A3 (en) * | 1997-08-20 | 1999-07-06 | Solvay | Method of composition ethylene polymers. |
| US8080699B2 (en) * | 2009-08-28 | 2011-12-20 | Chemtura Corporation | Two-stage process and system for forming high viscosity polyalphaolefins |
| KR101141494B1 (en) * | 2007-09-05 | 2012-05-03 | 에스케이이노베이션 주식회사 | Ethylene copolymer having multiple pitch in molecular weight distribution and the method of preparing the same |
| CN113480683B (en) * | 2021-06-04 | 2022-12-27 | 中国神华煤制油化工有限公司 | Polymerization switching process for producing polyethylene |
-
1979
- 1979-08-20 JP JP10565779A patent/JPS5632505A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5632505A (en) | 1981-04-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4923935A (en) | Process for producing polyethylene of ultrahigh molecular weight | |
| 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 | |
| Sailors et al. | History of polyolefins | |
| US4105847A (en) | Method for polymerization of ethylene | |
| US3200173A (en) | Process for preparing blends of polypropylene with copolymers of ethylene and propylene | |
| JPS6352651B2 (en) | ||
| JPS6352654B2 (en) | ||
| JPS6366324B2 (en) | ||
| US4076922A (en) | Method for producing ethylene polymers | |
| JPS6352655B2 (en) | ||
| JPS5825362B2 (en) | Method for producing α-olefin polymer | |
| JP3311780B2 (en) | Method for producing olefin polymer | |
| JPS6352656B2 (en) | ||
| US3781253A (en) | Process for the preparation of ethylene polymer or copolymer | |
| JPS6352659B2 (en) | ||
| US4260723A (en) | Method for producing olefin polymers | |
| JPS6352657B2 (en) | ||
| JPS63142008A (en) | Production of ethylene-olefin copolymer | |
| JPH07103176B2 (en) | Method for producing polyethylene by multistage polymerization | |
| US4324875A (en) | Method for producing olefin polymers | |
| JPH0531563B2 (en) | ||
| EP0024881B1 (en) | Process for producing polyethylene by continuous multi-stage polymerization and moulded articles made from the product | |
| KR840000371B1 (en) | Method for producing polyethylene by continuous multistage polymerization | |
| JPH011709A (en) | Method for producing polyethylene by multistage polymerization | |
| JPS5834811A (en) | Ethylene polymerization method |