JPS6352655B2 - - Google Patents
Info
- Publication number
- JPS6352655B2 JPS6352655B2 JP10753079A JP10753079A JPS6352655B2 JP S6352655 B2 JPS6352655 B2 JP S6352655B2 JP 10753079 A JP10753079 A JP 10753079A JP 10753079 A JP10753079 A JP 10753079A JP S6352655 B2 JPS6352655 B2 JP S6352655B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- ethylene
- solid product
- stage polymerization
- hydrogen
- 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 147
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 89
- 239000005977 Ethylene Substances 0.000 claims description 89
- -1 polyethylene Polymers 0.000 claims description 75
- 239000012265 solid product Substances 0.000 claims description 75
- 229920000642 polymer Polymers 0.000 claims description 56
- 229910052739 hydrogen Inorganic materials 0.000 claims description 53
- 239000001257 hydrogen Substances 0.000 claims description 53
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 51
- 239000004698 Polyethylene Substances 0.000 claims description 37
- 229920000573 polyethylene Polymers 0.000 claims description 37
- 239000007789 gas Substances 0.000 claims description 33
- 239000003054 catalyst Substances 0.000 claims description 27
- 238000004519 manufacturing process Methods 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 26
- 150000003623 transition metal compounds Chemical class 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 18
- 229920001296 polysiloxane Polymers 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 6
- 239000004711 α-olefin Substances 0.000 claims description 5
- 150000003609 titanium compounds Chemical class 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 2
- 239000000347 magnesium hydroxide Substances 0.000 claims description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 150000002681 magnesium compounds Chemical class 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- 238000000034 method Methods 0.000 description 18
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 17
- 239000011572 manganese Substances 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000203 mixture Substances 0.000 description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 150000002430 hydrocarbons Chemical group 0.000 description 11
- 239000000155 melt Substances 0.000 description 11
- 238000009826 distribution Methods 0.000 description 10
- 238000000465 moulding 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
- 238000000071 blow moulding Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 230000005484 gravity Effects 0.000 description 8
- 238000004080 punching Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 150000002736 metal compounds Chemical class 0.000 description 6
- 229910001507 metal halide Inorganic materials 0.000 description 6
- 150000005309 metal halides Chemical class 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 229910052719 titanium Inorganic materials 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 description 4
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 229910000000 metal hydroxide Inorganic materials 0.000 description 4
- 150000004692 metal hydroxides Chemical class 0.000 description 4
- 125000002950 monocyclic group Chemical group 0.000 description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 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
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910019440 Mg(OH) Inorganic materials 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 3
- 239000000395 magnesium oxide Substances 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
- 238000005406 washing Methods 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical class ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 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
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000005376 alkyl siloxane group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 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
- 239000011261 inert gas Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 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
- 239000002245 particle Substances 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
- 238000002360 preparation method Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HJUGFYREWKUQJT-UHFFFAOYSA-N tetrabromomethane Chemical compound BrC(Br)(Br)Br HJUGFYREWKUQJT-UHFFFAOYSA-N 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical class ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-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
- 229910052720 vanadium Inorganic materials 0.000 description 2
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 2
- 239000003643 water by type Chemical class 0.000 description 2
- 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
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- XOCOMEGNVMCRMP-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octaethyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound CC[Si]1(CC)O[Si](CC)(CC)O[Si](CC)(CC)O[Si](CC)(CC)O1 XOCOMEGNVMCRMP-UHFFFAOYSA-N 0.000 description 1
- VCYDUTCMKSROID-UHFFFAOYSA-N 2,2,4,4,6,6-hexakis-phenyl-1,3,5,2,4,6-trioxatrisilinane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VCYDUTCMKSROID-UHFFFAOYSA-N 0.000 description 1
- NOGFHTGYPKWWRX-UHFFFAOYSA-N 2,2,6,6-tetramethyloxan-4-one Chemical compound CC1(C)CC(=O)CC(C)(C)O1 NOGFHTGYPKWWRX-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- UADWUILHKRXHMM-UHFFFAOYSA-N 2-ethylhexyl benzoate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1 UADWUILHKRXHMM-UHFFFAOYSA-N 0.000 description 1
- 229940106004 2-ethylhexyl benzoate Drugs 0.000 description 1
- YBFYRBILSHBEHV-UHFFFAOYSA-N 2-ethylhexyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OCC(CC)CCCC)=CC=CC2=C1 YBFYRBILSHBEHV-UHFFFAOYSA-N 0.000 description 1
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 1
- 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
- 241000251730 Chondrichthyes Species 0.000 description 1
- MQVPFHBBKRCBOJ-UHFFFAOYSA-N ClCCCCO[Ti] Chemical compound ClCCCCO[Ti] MQVPFHBBKRCBOJ-UHFFFAOYSA-N 0.000 description 1
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 1
- 101000687448 Homo sapiens REST corepressor 1 Proteins 0.000 description 1
- 229910021025 KMgCl3 Inorganic materials 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 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
- 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
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 229940071248 anisate Drugs 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 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
- 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
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- PWZFXELTLAQOKC-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide;tetrahydrate Chemical compound O.O.O.O.[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O PWZFXELTLAQOKC-UHFFFAOYSA-A 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- DLRHRQTUCJTIIV-UHFFFAOYSA-N diethoxy(ethyl)alumane Chemical compound CC[O-].CC[O-].CC[Al+2] DLRHRQTUCJTIIV-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 229940019778 diethylene glycol diethyl ether Drugs 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- RMTCVMQBBYEAPC-UHFFFAOYSA-K ethanolate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CCO[Ti+3] RMTCVMQBBYEAPC-UHFFFAOYSA-K 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- HQKSINSCHCDMLS-UHFFFAOYSA-N ethyl naphthalene-2-carboxylate Chemical compound C1=CC=CC2=CC(C(=O)OCC)=CC=C21 HQKSINSCHCDMLS-UHFFFAOYSA-N 0.000 description 1
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 1
- 210000000744 eyelid Anatomy 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 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
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 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
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WVWZECQNFWFVFW-UHFFFAOYSA-N methyl 2-methylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C WVWZECQNFWFVFW-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HMRROBKAACRWBP-UHFFFAOYSA-N methyl naphthalene-1-carboxylate Chemical compound C1=CC=C2C(C(=O)OC)=CC=CC2=C1 HMRROBKAACRWBP-UHFFFAOYSA-N 0.000 description 1
- DDIZAANNODHTRB-UHFFFAOYSA-N methyl p-anisate Chemical compound COC(=O)C1=CC=C(OC)C=C1 DDIZAANNODHTRB-UHFFFAOYSA-N 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 1
- VECVSKFWRQYTAL-UHFFFAOYSA-N octyl benzoate Chemical compound CCCCCCCCOC(=O)C1=CC=CC=C1 VECVSKFWRQYTAL-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- ZEYHEAKUIGZSGI-UHFFFAOYSA-N para-methoxy benzoic acid Natural products COC1=CC=C(C(O)=O)C=C1 ZEYHEAKUIGZSGI-UHFFFAOYSA-N 0.000 description 1
- 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
- 230000000379 polymerizing effect Effects 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
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 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
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-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
系で高分子側重合体を、第２段重合系で低分子側
重合体をつくるポリエチレンの連続多段重合によ
る製造法に関するものである。
本発明におけるポリエチレンとは、エチレンの
単独重合体の他に、エチレンと共重合しうる他の
少量のα―オレフイン、例えば、プロピレン、ブ
テン―１、ヘキセン―１，４―メチル―ペンテン
―１あるいはブタジエン、ジシクロペンタジエン
などのジエン類との共重合体をも含むものであ
る。
ポリエチレンの主要な用途である押出成形や中
空成形の分野では、高分子量（低メルトインデツ
クス）で、適切な強度を持ち、加工しやすいポリ
エチレンが要求されている。低メルトインデツク
スのポリエチレンは、強度はすぐれるが、成形時
流動性が劣るという欠点を有している。この問題
を解決する手段として、分子量分布を拡大する方
法がとられている。分子量分布の狭いポリエチレ
ンは、射出成形に適しているが、一方押出成形や
中空成形に使用されるポリエチレンとしては、分
子量分布の広いことが望ましい。分子量分布の狭
い重合体を中空成形した場合には、成形時の押出
圧力が過上昇し、成形不能になつたり、スジ、ア
バタの発生、メルトフラクチヤの発生などによ
り、製品の外観が著しく損われる。押出成形の場
合には、押出圧力の過上昇、成形の不安定性の増
大などにより、致命的な悪影響を受け、商品価値
を著しく低下させる。これらの諸問題を解決する
ために、重合体の分子量分布を広げることによ
り、加工上の生産性が向上し、外観のすぐれた製
品が得られる。
分子量分布を拡大する方法として、重合系への
第３成分の添加、触媒の一成分である有機アルミ
ニウ化合物の２種類の化合物の混合使用、多様な
重合活性点をもつ触媒の使用などが知られている
が、分子量分布の充分に広い重合体を製造するこ
とは必ずしも容易ではない。それに対して、分子
量分布巾を大巾に、しかも任意に調節する手段と
しては多段重合法が知られているが、その方法に
満足すべきものがない。従来、前段で高分子側後
段で低分子側をつくる多段重合による製造法とし
て、特公昭46―11349号、特開昭54―7488号、特
開昭54―32588号、が知られている。特公昭46―
11349号では、担体に担持することを必要としな
い３価チタン化合物と有機アルミニウム化合物の
組合せによる触媒を用いて、不活性溶媒中、圧力
10Kg／cm2（ゲージ圧）以下で重合する方法が示さ
れている。該方法は、担体を必要としない３価チ
タン化合物を使う点で触媒が限定されている上
に、開示された実施態様は、重合圧力が６Kg／cm2
（ゲージ圧）以下である。このような低い重合圧
力では重合体の生産性が著しく低く、しかも該方
法は非連続的な製造法であり、工業的に有利な連
続重合法については何ら具体的に記載されていな
い。特開昭54―7488では、担持型触媒を用いて、
第１段重合を、液充満の状態で行なわせることを
開示しているがこの方法は生成する重合体の分子
量を調節することが極めてむずかしい。特開昭54
―32588では、第１段重合器に強制的に不活性ガ
スを供給して全圧を高め、第１段重合で高分子側
重合体を第２段重合で低分子側重合体をつくるこ
とを開示しているが、供給された多量の不活性ガ
スが、消費または取除かれないまま第２段重合系
に流入即ち充分に低分子の重合体をつくるがむず
かしいという欠点を有している。
一方、本発明者らは、従来、３価金属ハロゲン
化物と２価金属の水酸化物、酸化物、炭酸化物、
これらを含む複塩、または２価金属化合物の水和
物との反応生成物（以下固体生成物（）と言う
ことがある）を担体とする触媒成分を研究して来
たが該固体生成物（）と電子供与体化合物と遷
移金属化合物から調製した固体生成物（）と有
機アルミニウム化合物を組み合せた触媒を用いる
ことにより、従来の連続多段重合の欠点が解消さ
れることを見出し、種々の研究を重ねた結果本発
明の製造法を完成するに到つた。
すなわち、本発明の目的は、第１段重合系で高
分子側重合体を、第２段重合系で低分子側重合体
をつくるポリエチレンの連続多段重合において前
記した従来の問題点が解消された製造法を提供す
ることである。
本発明のポリエチレンの連続多段重合による製
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、電子供与化合物
と、第4a族または第5a族の遷移金属化合物と
から調製した遷移金属化合物を担持させた最終
の固体生成物（）と有機アルミニウム化合物
とを組み合せて得られる触媒の存在下、飽和炭
化水素溶媒中、重合器の上部に気相が存在する
状態において、重合温度30℃以上100℃以下、
重合圧力11ないし70Kg／cm2の条件下で、重合器
気相部のエチレン対水素のモル比が１対0.001
ないし0.5になるように水素を供給すると共に、
全エチレン供給量の10ないし70％のエチレンを
供給して第１段重合を行ない。
続いて、溶媒に懸濁した重合物を第２段重合
系に移送し、飽和炭化水素溶媒中、重合器の上
部に気相が存在する状態において、重合温度50
℃以上120℃以下、重合圧力11ないし70Kg／cm2
の条件下で、重合器気相部のエチレン対水素の
モル比が１対0.1ないし3.0になるように水素を
供給すると共に、全エチレン供給量の30ないし
90％のエチレンを供給して第２段重合を行なう
ことを特徴とする。
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、重合度30℃以上100℃以下、好ましくは40〜
90℃、重合圧力11ないし70Kg／cm2好ましくは15〜
50Kg／cm2の条件下で第１段重合を行う。生成する
重合体の分子量は、重合器の気相部のエチレン対
水素のモル比が１対0.001ないし0.5の範囲内に入
るように、エチレンおよび水素を供給することに
よつて調節される。この場合得られる重合体の分
子量は、重量平均分子量にして２×105〜８×105
に相当する重合体の生成量は全エチレン供給量の
10ないし70％のエチレン供給で調節される。
つづいて第１段重合系で得られた溶媒に懸濁し
た重合物はそのまゝ、第２段重合系に移送する
が、必要に応じて水素、などの成分を分離して後
移送してもよい。その移送の方法は移送ポンプな
どの強制移送手段によつて行なう。第２段重合系
は新たに設定した重合条件下、すなわち重合温度
50℃以上120℃以下好ましくは70℃〜100℃重合圧
力11ないし70Kg／cm2好ましくは15〜50Kg／cm2、重
合器上部に気相部が存在する状態で重合を行な
う。生成する重合体の分子量は、気相部のエチレ
ン対水素のモル比が１対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
によつて調節する。第２段重合で得られる重合体
の分子量は、重量平均分子量にして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する。
第１段重合および第２段重合の気相部のエチレ
ン対水素のモル比およびエチレンの供給量は最終
的に得られる重合体の用途によつて決定される。
たとえば、フイルムに使用するポリエチレンを製
造する場合、第１段重合はエチレン対水素のモル
比は好ましくは１：0.001〜0.3、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。
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１：1.0〜3.0、より好ましくは１：1.5
〜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。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１：0.005〜0.5、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。一方第２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、より好ましくは１：1.2
〜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。
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、MgMl2O4、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
応を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の脂肪娘炭化水
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、ブチル、ペンチル、ヘキシル、オクチルなど
があり、分岐状の例としてイソプロピル、イソブ
チル、イソペンチル、イソヘキシル、イソオクチ
ル、２―メチルペンチル、３―メチルペンチル、
５―メチルヘキシルなどがある。不飽和炭化水素
基としてはアルケニル基、アルカジエニル基があ
り、不飽和結合を末端に有するものだけでなく内
部に有するものも含み、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 continuous multi-stage polymerization, using a plurality of polymerization vessels to produce a high molecular weight polymer in the first stage polymerization system and a low molecular weight polymer in the second stage polymerization system. In the present invention, polyethylene means, in addition to a homopolymer of ethylene, a small amount of other α-olefins that can be copolymerized with ethylene, such as propylene, butene-1, hexene-1,4-methyl-pentene-1, or It also includes copolymers with dienes such as butadiene and dicyclopentadiene. In the fields of extrusion molding and blow molding, which are the main uses of polyethylene, polyethylene is required to have a high molecular weight (low melt index), appropriate strength, and easy processing. Polyethylene with a low melt index has excellent strength, but has the disadvantage of poor fluidity during molding. As a means to solve this problem, a method of expanding the molecular weight distribution has been adopted. Polyethylene with a narrow molecular weight distribution is suitable for injection molding, but it is desirable for polyethylene used in extrusion molding or blow molding to have a wide molecular weight distribution. When a polymer with a narrow molecular weight distribution is blow-molded, the extrusion pressure during molding increases excessively, making molding impossible, and the appearance of the product is significantly impaired due to the occurrence of streaks, avatars, and melt fractures. In the case of extrusion molding, an excessive increase in extrusion pressure, increased molding instability, etc. can have fatal adverse effects, significantly reducing commercial value. In order to solve these problems, by broadening the molecular weight distribution of the polymer, processing productivity can be improved and products with excellent appearance can be obtained. Known methods for expanding the molecular weight distribution include adding a third component to the polymerization system, using a mixture of two types of organic aluminum 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. Hitherto, Japanese Patent Publication Nos. 11349-1988, 7488-1988, and 32588-1988 are known as production methods using multi-stage polymerization in which a high molecular weight product is produced in the first stage and a low molecular weight product is produced in the second stage. Special Public Service 1977-
No. 11349 uses a catalyst consisting of a combination of a trivalent titanium compound and an organoaluminium compound that does not require support on a carrier, and is heated in an inert solvent under pressure.
A method of polymerizing at 10 kg/cm 2 (gauge pressure) or less is shown. The method is limited in catalysts in that it uses a trivalent titanium compound that does not require a carrier, and in the disclosed embodiment, the polymerization pressure is 6 Kg/cm 2
(gauge pressure) or less. At such a low polymerization pressure, the productivity of the polymer is extremely low, and the method is a discontinuous production method, and there is no specific description of an industrially advantageous continuous polymerization method. In JP-A-54-7488, using a supported catalyst,
Although it is disclosed that the first stage polymerization is carried out in a liquid-filled state, it is extremely difficult to control the molecular weight of the resulting polymer in this method. Unexamined Japanese Patent Publication 1973
-32588 discloses that by forcibly supplying an inert gas to the first stage polymerization vessel to increase the total pressure, a high molecular side polymer is produced in the first stage polymerization and a low molecular side polymer is produced in the second stage polymerization. However, it has the disadvantage that a large amount of the supplied inert gas flows into the second stage polymerization system without being consumed or removed, ie, it is difficult to produce a sufficiently low molecular weight polymer. On the other hand, the present inventors have conventionally discovered that trivalent metal halides and divalent metal hydroxides, oxides, carbonates,
We have been researching catalyst components using double salts containing these or reaction products (hereinafter sometimes referred to as solid products) with hydrates of divalent metal compounds as carriers. It was discovered that the drawbacks of conventional continuous multi-stage polymerization could be overcome by using a catalyst that combined a solid product () prepared from (), an electron donor compound, and a transition metal compound, and an organoaluminum compound, and various studies were conducted. As a result of repeated efforts, the manufacturing method of the present invention was completed. That is, an object of the present invention is to provide a production method that eliminates the above-mentioned conventional problems in the continuous multi-stage polymerization of polyethylene in which a high-molecular-weight polymer is produced in the first stage polymerization system and a low-molecular-weight polymer is produced in the second stage polymerization system. The goal is to provide the following. 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 donating compound, a final 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 a state where a gas phase exists at the top of the polymerization vessel, at a polymerization temperature of 30°C or more and 100°C or less,
Under polymerization pressure of 11 to 70 kg/ cm2 , the molar ratio of ethylene to hydrogen in the gas phase of the polymerizer is 1:0.001.
At the same time, hydrogen is supplied so that the amount of
The first stage polymerization is carried out by supplying 10 to 70% of the total amount of ethylene supplied. Subsequently, the polymer suspended in the solvent is transferred to the second stage polymerization system, and the polymerization temperature is increased to 50°C in a saturated hydrocarbon solvent with a gas phase present at the top of the polymerization vessel.
℃ or more and 120℃ or less, polymerization pressure 11 to 70Kg/cm 2
Under these conditions, hydrogen is supplied so that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization reactor is 1:0.1 to 3.0, and 30 to 30% of the total ethylene supply amount is
It is characterized in that the second stage polymerization is carried out by supplying 90% ethylene. In addition, if necessary, α-olefin may be supplied to the first and/or second stage polymerization system to combine with ethylene and α-olefin.
- Copolymers with olefins can be produced. In that case, the sum of the moles of ethylene and α-olefin and the molar ratio of hydrogen may be the molar ratio of the first stage and/or the second stage. In the production method of the present invention, polymerization is started by supplying a catalyst to the first stage polymerization system, and in a saturated hydrocarbon solvent in a state where a gas phase exists at the top of the polymerization vessel, the polymerization degree is 30°C or more and 100°C. Below, preferably 40~
90℃, polymerization pressure 11 to 70Kg/cm 2 preferably 15 to
The first stage polymerization is carried out under the condition of 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 1:0.001 to 0.5. The molecular weight of the polymer obtained in this case is 2×10 5 to 8×10 5 in weight average molecular weight.
The amount of polymer produced is equivalent to the amount of total ethylene supplied.
Adjusted with 10 to 70% ethylene feed. Next, the polymer suspended in the solvent obtained in the first stage polymerization system is transferred as it is to the second stage polymerization system, but if necessary, components such as hydrogen may be separated and then transported. Good too. The transfer method is performed by forced transfer means such as a transfer pump. The second stage polymerization system is under newly set polymerization conditions, i.e., polymerization temperature.
Polymerization is carried out at a polymerization pressure of 50°C to 120°C, preferably 70°C to 100°C, 11 to 70 kg/cm 2 , preferably 15 to 50 kg/cm 2 , and a gas phase in the upper part of the polymerization vessel. The molecular weight of the resulting polymer is controlled by supplying ethylene and hydrogen such that the molar ratio of ethylene to hydrogen in the gas phase is within the range of 1:0.1 to 3.0. The molecular weight of the polymer obtained in the second stage polymerization is 6×10 4 to 3 in terms of weight average molecular weight.
Equivalent to ×10 5 . The amount of polymer produced is controlled by supplying ethylene at 30 to 90% of the total ethylene supply. The molar ratio of ethylene to hydrogen in the gas phase of the first stage polymerization and the second stage polymerization and the amount of ethylene supplied are determined depending on the intended use of the final polymer.
For example, when producing polyethylene for use in films, the molar ratio of ethylene to hydrogen in the first stage polymerization is preferably 1:0.001 to 0.3, more preferably 1:0.005 to 0.2, and the amount of ethylene supplied is the total ethylene supply. 40-60% of the amount, preferably 50%.
On the other hand, in the second stage polymerization, the molar ratio of ethylene to hydrogen is preferably 1:1.0 to 3.0, more preferably 1:1.5.
~3.0, and the ethylene feed rate is 40-60%, preferably 50% of the total ethylene feed rate. In the case of blow molding, in the first stage polymerization, the molar ratio of ethylene to hydrogen is preferably 1:0.005 to 0.5, more preferably 1:0.01 to 0.4, and the ethylene supply amount is 30 to 30 of the total ethylene supply amount. 70%, preferably 50%. On the other hand, in the second stage polymerization, the molar ratio of ethylene to hydrogen is preferably 1:1.0 to 3.0, more preferably 1:1.2.
~3.0, and the ethylene feed rate is 30-70%, preferably 50% of the total ethylene feed rate. In the production method of the present invention, the catalyst is usually supplied only to the first stage polymerization system, but it can also be supplied to the second stage polymerization system, if necessary. In the 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 , MgMl2O4 , 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 carry out this reaction, we 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、
エチルポリシクロシロキサン〔SiH（C2H5）Ｏ〕
ｎ，メチルエチルポリシロキサン〔Si（CH3）
（C2H5）Ｏ〕ｎなどの重合物などのアルキルシロ
キサン重合物、またヘキサフエニルシクロトリシ
ロキサン〔Si（C6H5）2O〕3，ジフエニルポリシロ
キサン〔Si（C6H5）2O〕ｎ，などのアリールシロ
キサン重合物、またジフエニルオクタメチルテト
ラシロキサン（CH3）3SiO〔Si（CH3）（C6H5）Ｏ〕
2Si（CH3）3，メチルフエニルポリシロキサン〔Si
（CH3）（C6H5）Ｏ〕ｎなどのアルキルアリール
シロキサン重合物などが示される。この他R1が
水素またはハロゲンでR2がアルキル基、アリー
ル基等の炭化水素残基であるアルキル水素シロキ
サン重合物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１〜1000
ｇ、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給体
化合物を除去し乾燥する。かくして固体生成物
（）を得る。
固体生成物（）の調製における混合、反応に
当つて、溶媒を用いることは必ずしも必要ではな
いが、均一に反応させることが好ましいので、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段重合系において高分子
側重合体、続いて、第２段重合系において低分子
側重合体を製造する連続多段重合法において、本
発明に示した特殊な重合触媒を用い、重合器上部
に気相部を存在させ、気相部のエチレン対水素の
モル比を規制することにより、分子量および生成
量の調節を極めて容易ならしめたことである。本
発明は、公知の連続多段スラリー重合法に比べ、
第１段および第２段重合系の重合体の分子量およ
び生成量の調節が極めて容易であるという特徴を
有している。また、本発明の重合においては、重
合器壁への重合体付着が全くないか極めて少なく
長時間安定した多段重合を行なうことができると
いう特徴がある。本発明に使用する触媒は、重合
活性が極めて高く、反応終了後、重合体中の残触
媒の除去工程即ち脱灰工程をなくすことが可能で
ある。更に加えるべき特徴は、得られるポリエチ
レンの分子量分布が極めて広いことである。従つ
て、成形時流れ特性が良好で、成形時の樹脂圧力
が低く、高速成形が可能であり、メルトフラクチ
ヤが起きないために成形物の外観が良好である。
フイルム製造の場合、適度の強度および不透明感
を持ち、フイツシユアイが見られず、フイルム表
面が滑らかで、成形性が長時間安定している。ま
た、本発明により得られるポリエチレン粉末のか
さ比重は0.35〜0.45であり、粉体粒子の形状が良
好なことにより、重合器の容積当り、時間当りの
生産効率が大きく、重合物粉体の配管輸送上のト
ラブル発生が少なく、粉体の造粒も容易であると
いう特徴をもつている。
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わ
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
物質の固数を測定した。
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0.35mmolおよびヘキサンを１時間当り４
の速度で供給し、重合器内の液レベルが80％に保
てるように重合器内容物を排出しながら、70℃に
おいて、エチレンを１時間当り350Nl、水素を重
合器気相部のエチレン対水素のモル比が１対0.05
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段重合器を出た溶媒に懸濁した重合物を、
移送ポンプにより、内容積20の第２段重合器に
全量導入し、ヘキサンおよび触媒を追加すること
なく、重合器内の液レベルが80％に保てるように
重合器内容物を排出しながら、80℃において、ブ
テン―１を５容量％含むエチレンを１時間当り
370Nl、水素を重合器気相部のエチレン対水素の
モル比が１対1.6になるように供給しつつ、全圧
40Kg／cm2（ゲージ圧）で連続的に第２段重合を行
なつた。
以上の多段重合を120時間連続して行なつたが
運転は極めて安定しており、脱灰をせずに乾燥後
メルトインデツクス0.05、かさ比重0.40、密度、
0.950、分子量分布Mw／Mn25の重合体粉末105
Kgを得た。このポリエチレンを用いてフイルムを
製造した所、製膜時の溶融樹脂の流動性は良好で
あり、製膜性は安定しており、打抜衝撃強度145
Kg／mmで適度の強度およびヘイズ値77％の適度の
不透明感を持ち、フイツシユアイは９個で実用上
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 １
重合器気相部のエチレン対水素のモル比を１対
0.15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時間連続的に一段重合を行
ない、メルトインデツクス0.05の重合体粉末51Kg
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、フイツシユアイは
450個であり、製膜性が安定せず、打抜強度は70
Kg―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、エチレンを１時間あたり、
210Nl、水素を重合器気相部のエチレン対水素の
モル比が１対0.1になるように供給し、第２段重
合器に、エチレンを１時間当り495Nl、水素を重
合器気相部のエチレン対水素のモル比が１対1.3
になるように供給すること以外は、実施例１と同
様にエチレンの多段連続重合を行ない、150時間
の連続運転で130Kgの重合体粉末を得た。このポ
リエチレンは、メルトインデツクス0.30、かさ比
重0.38、密度0.955、Mw／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
0.8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時間連続的に第１段重合の
みを行ない。メルトインデツクス0.30の重合体粉
末38Kg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
0.16mmol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なかつ
た。
実施例 ３
塩化アルミニウム（無水）80ｇとヒドロタルサ
イト70ｇを、振動ミル中170℃に３時間加熱しな
がら、混合、粉砕、反応を同時に行なわせ、固体
生成物（）を得た。
トルエン200ml中、四塩化チタン100ｇおよび固
体生成物（）100ｇを混合、続いて、ジ―ｎ―
ブチルエーテル130ｇを加え、100℃に３時間反応
させた。その後は実施例１と同様に洗浄し、固体
生成物（）を得た。固体生成物（）１ｇ中の
チタン原子は0.21mmolであつた。
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、105Kg
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200中、固体生成物（）100Kgおよ
び酢酸ｎ―ブチル60Kgを混合、続いて、四塩化チ
タン100Kgを加え、120℃に２時間反応させた。そ
の後は実施例１と同様に洗浄し、固体生成物
（）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、130Kg
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。このポリエチレ
ンを用いて実施例１と同様にフイルムを製造した
が、打抜強度は100Kg―cm／mm以下であり、フイ
ツシユアイは150個でフイルムとしての商品価値
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、85Kg
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によりビンを
製造した所、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、ブテン
を５容量％含むエチレンを１時間当り315Nl、水
素を気相部のエチレン（ブテンを含む）対水素の
モル比が１対0.01になるように供給し、全圧を25
Kg／cm2（ゲージ圧）で行ない、第２段重合におい
ては、85℃において、ブテン―１を５容量％含む
エチレンを１時間当り300Nl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
3.0にすること以外は、実施例１と同様にエチレ
ンの多段連続重合およびフイルムの製造を行なつ
た。
ポリエチレン90Kgが得られ、メルトインデツク
ス0.04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、製膜性も安しており、打抜衝撃強度152Kg―
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、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
チレン対水素が１対0.04になるように供給し、全
圧35Kg／cm2（ゲージ圧）で第１段重合を行ない、
エチレンを１時間当り120Nl、水素を気相部のエ
チレン対水素が１対3.0になるように供給し、全
圧25Kg／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
30Nl、水素を気相部のエチレン対水素が１対
0.003になるように供給し、全圧８Kg／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570Nl、水素を気相部のエチレン対水素が１
対2.9になるように供給し、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82Kg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
1000個以上もあり、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、65℃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0.07になるよう
に供給し、全圧15Kg／cm2（ゲージ圧）で行ない、
第２段重合においては、90℃においては、エチレ
ンを１時間当り200Nlの速度で供給し、全圧25
Kg／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2.0にすること以外は、実
施例２と同様にしてポリエチレンおよび中空ビン
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を塩化マンガン
（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。実施
例２と同様に中空成形によりビンを製造し、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（OH）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―ブチルアルデビド
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と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0.008になるように供給し、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2.8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およびフイルムの製造を行な
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。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
(1) 遷移金属触媒成分の製造
ヒドロマグネサイト（3MgCO3・Mg（OH）2・
3H2O）65ｇと三塩化鉄（無水）70ｇを振動ミル
中10時間混合、粉砕し、300℃に１時間反応させ、
固体生成物（）を得た。
ｏ―ジクロルベンゼン150ml中に、鎖状ジ―ｎ
―ブチルポリシロキサン200ｇ（粘度1000センチ
ストークス）および固体生成物（）100ｇを加
え混合し、これに四塩化チタン200ｇを加え、160
℃に３時間反応させ、固体生成物（）を得た。
チタン含有量は固体生成物（）１ｇ中
0.20mmolであつた。
(2) エチレンの多段連続重合
内容積10の第１段重合器に、上記固体生成物
（）を１時間当り35mg、トリエチルアルミニウ
ムを１時間当り0.35mmolおよびヘキサンを１時
間当り２、の速度で供給し、重合器内の液レベ
ルが80％に保てるように重合器内容物を排出しな
がら、70℃において、ブテン―１を３容量％含む
エチレンを11時間当り310Nl、水素を重合器気相
部のエチレン（ブテンを含む）対水素のモル比が
１対0.05になるように供給しつつ、全圧20Kg／cm2
（ゲージ圧）で連続的に第１段重合を行なつた。
続いて、第１段重合器を出た溶媒に懸濁した重
合物を、移送ポンプにより内容積20の第２段重
合器に全量導入し、重合器内の液レベルが80％に
保てるように重合器内容物を排出しながら、85℃
において、エチレンを１時間当り300Nl、新たに
トリエチルアルミニウムを追加することなく、水
素を重合器気相部のエチレン（第１段重合器より
導入されるブテンを含む）対水素のモル比が１対
3.0になるように供給しつつ、全圧35Kg／cm2（ゲ
ージ圧）で連続的に第２段重合を行なつた。
以上の多段重合を150時間連続して行なつたが、
運転は極めて安定しており、脱灰をせずに乾燥
後、ポリエチレン粉末111Kgを得た。重合体収率
は21100ｇ―重合体／ｇ―（）・Hr、106000ｇ
―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
0.30、かさ比重0.38、密度0.956ｇ／cm2、ブテン含
有量1.2重量％、Mw／Mn26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275ｇで十分
であり、偏肉もほとんどなく、耐ストレスクラツ
キング性（F50値）は170Hrで問題なく、実用上
十分な性能のビンであつた。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,
Ethylpolycyclosiloxane [SiH(C 2 H 5 ) O]
n, methylethylpolysiloxane [Si(CH 3 )
Alkylsiloxane polymers such as (C 2 H 5 )O]n, hexaphenylcyclotrisiloxane [Si(C 6 H 5 ) 2 O] 3 , diphenylpolysiloxane [Si(C 6 H Arylsiloxane polymers such as 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
Examples include alkylarylsiloxane polymers such as (CH 3 )(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. Also,
Polysiloxanes in which each R is an alkoxy group or an aryloxy group or a fatty acid residue can be used. These various polysiloxanes can also be used in combination. It is desirable that the polysiloxane used be in liquid form, with a viscosity (at 25°C) of 10 to 10,000.
centistokes is suitable, preferably 10 to 1000
centistokes range. 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) An electron donor compound and a transition metal compound are mixed, and then a solid organism () is mixed with this mixture and reacted. Both methods can be carried out in the presence or absence of a solvent. The mixing ratio of solid organism (), electron donor compound and transition metal compound is 100g of solid organism ()
In contrast, the electron donor compound weighs 10 to 10,000 g, preferably 20 to 5,000 g, and the transition metal compound weighs 1 to 1,000 g.
g, preferably 10 to 500 g, and 2 to 5 g of the transition metal compound per 100 g of the electron donor compound.
2000g, preferably 5-500g. The mixture is-
Mixing is most commonly carried out at room temperature (approximately 20°C), although temperatures of 50°C to +30°C are suitable. Preferably, the mixing is carried out with stirring. 30~300 while stirring after mixing.
℃, preferably 50 to 200℃ 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. Although it is not necessarily necessary to use a solvent during the mixing and reaction in the preparation of the solid product (2), 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 tetrachloroethylene and carbon tetrabromide. Examples of organoaluminum compounds include trialkylaluminum such as triethylaluminum, triisobutylaluminum, and trihexylaluminum, dialkylaluminum monochloride such as diethylaluminum monochloride, ethylaluminum sesquichloride, ethylaluminum dichloride, and monoethoxydiethyl Aluminum, alkoxyalkyl aluminum such as diethoxymonoethyl aluminum can also be used. A feature of the present invention is that the special polymerization catalyst shown in the present invention is used in a continuous multi-stage polymerization method in which a high molecular side polymer is produced in the first stage polymerization system, and then a low molecular side polymer is produced in the second stage polymerization system. By providing a gas phase in the upper part of the polymerization vessel and regulating the molar ratio of ethylene to hydrogen in the gas phase, the molecular weight and production amount can be extremely easily controlled. Compared to the known continuous multi-stage slurry polymerization method, the present invention has the following advantages:
It is characterized in that it is extremely easy to control the molecular weight and production amount of the polymer in the first and second stage polymerization systems. Furthermore, the polymerization of the present invention is characterized in that stable multi-stage polymerization can be carried out for a long period of time with no or very little polymer adhesion to the walls of the polymerization vessel. The catalyst used in the present invention has extremely high polymerization activity, and it is possible to eliminate the step of removing the residual catalyst in the polymer, that is, the deashing step after the reaction is completed. A further feature to be added is that the resulting polyethylene has an extremely wide molecular weight distribution. Therefore, the flow characteristics during molding are good, the resin pressure during molding is low, high-speed molding is possible, and the appearance of the molded product is good because melt fracture does not occur.
In the case of film production, it has appropriate strength and opacity, no visible fissures, a smooth film surface, and stable moldability over a long period of time. In addition, the bulk specific gravity of the polyethylene powder obtained by the present invention is 0.35 to 0.45, and the shape of the powder particles is good, so the production efficiency per unit volume of the polymerization vessel and per hour is high, and the piping of the polymer powder is It has the characteristics of less trouble during transportation and easy granulation of powder. 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 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 number of solid particles of granular polymeric substances with a diameter of 50 μm or more present in 1000 cm 2 of the film was measured. The blow molding was performed using a blow molding machine (55 mmφ, 50 rpm, IPB-110 manufactured by Ishikawajima Harima) at a temperature of 165 to 175°C.
A bottle with an internal volume of 4 was made under conditions of a cycle time of 3 minutes. Stress cracking resistance ( F50 value) is
In accordance with ASTM-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 completed, filtration is carried out according to a conventional 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
0.007 mmol), triethylaluminum 0.35 mmol per hour and hexane 4 per hour
While discharging the contents of the polymerization vessel so as to maintain the liquid level in the polymerization vessel at 80%, at 70°C, ethylene was supplied at a rate of 350Nl per hour, and hydrogen was supplied at a rate of 350Nl per hour in the gas phase of the polymerization vessel. The molar ratio of is 1:0.05
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. The polymer suspended in the solvent exiting the first stage polymerization vessel is
The entire amount was introduced into the second-stage polymerization vessel with an internal volume of 20% using a transfer pump, and the content of the polymerization vessel was discharged to maintain the liquid level in the polymerization vessel at 80% without adding hexane or catalyst. ℃, ethylene containing 5% by volume of butene-1 per hour.
370Nl, while supplying hydrogen such that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization reactor was 1 to 1.6, while increasing the total pressure.
The second stage polymerization was carried out continuously at 40 kg/cm 2 (gauge pressure). The above multi-stage polymerization was carried out continuously for 120 hours, and the operation was extremely stable, and after drying without deashing, the melt index was 0.05, the bulk specific gravity was 0.40, the density was
0.950, polymer powder 105 with molecular weight distribution Mw/Mn25
Got Kg. When a film was manufactured using this polyethylene, the fluidity of the molten resin during film formation was good, the film formability was stable, and the punching impact strength was 145.
It had a suitable strength in terms of Kg/mm and a moderate opacity with a haze value of 77%, and had a good surface condition with no practical problems, with 9 fixation eyes, and had satisfactory film performance. Comparative Example 1 The molar ratio of ethylene to hydrogen in the gas phase of the polymerization vessel was set to 1:
One-stage polymerization was carried out continuously for 120 hours in the same manner as the first-stage polymerization in (2) of Example 1, except that the melt index was 0.15, and 51 kg of polymer powder with a melt index of 0.05 was obtained.
However, the Mw/Mn was 6 and it was not possible to produce a film 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 amount of titanium atoms in 1 kg of the catalyst component was 0.15 mol. Using the catalyst component instead of the solid product (2), multistage continuous polymerization of ethylene was carried out in the same manner as in Example 1 (2), and 20 kg of polymer powder was obtained.
Mw/Mn was 10. The company that produced the film using this polyethylene,
450 pieces, film formability is unstable, and punching strength is 70
The strength was insufficient at Kg-cm/mm, and the film was not satisfactory. 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 organism was 0.23 mmol. (2) Multi-stage continuous polymerization of ethylene: Add ethylene to the first stage polymerization vessel per hour.
210Nl and hydrogen were supplied so that the molar ratio of ethylene to hydrogen in the gas phase of the polymerizer was 1:0.1, and 495Nl of ethylene was supplied per hour to the second stage polymerizer, and hydrogen was added to the ethylene in the gas phase of the polymerizer per hour. Molar ratio of hydrogen to 1:1.3
Multi-stage continuous polymerization of ethylene was carried out in the same manner as in Example 1, except that the polymer was supplied in such a manner that 130 kg of polymer powder was obtained in 150 hours of continuous operation. 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:
Only the first 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 ratio was set to 0.8. Although 38 kg of polymer powder with a melt index of 0.30 was obtained, the Mw/Mn was 6, and bottles could not be manufactured 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
It was 0.16 mmol. Multistage continuous polymerization of ethylene was carried out in the same manner as in Example 2 (2) except that the catalyst component was used in place of the solid product (2), and 25 kg of polymer powder was obtained, except that Mw/Mn was 10. Ta. When this polyethylene was used for blow molding, 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 vibration mill while mixing, pulverizing, and reacting simultaneously to obtain a solid product (). Mix 100 g of titanium tetrachloride and 100 g of solid product () in 200 ml of toluene, followed by
130 g of butyl ether was added and the mixture was reacted at 100°C for 3 hours. Thereafter, washing was performed in the same manner as in Example 1 to obtain a solid product (2). The amount of titanium atoms in 1 g of the solid product ( ) was 0.21 mmol. Using this solid product (2), multistage continuous polymerization of ethylene was carried out in the same manner as in Example 1 (2), and 105 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. 100 kg of solid product (200) and 60 kg of n-butyl acetate were mixed in xylene 200, followed by adding 100 kg of titanium tetrachloride and reacting at 120°C for 2 hours. Thereafter, 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 130 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. 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. Example 1 except that this final solid product is used in place of the solid product () in Example 1.
Perform multistage continuous polymerization of ethylene in the same manner as Mw/
Polyethylene with Mn of 15 was obtained. A film was produced using this polyethylene in the same manner as in Example 1, but the punching strength was less than 100 kg-cm/mm, the number of punches was 150, and the commercial value 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. Example 2 except that this final solid product is used in place of the solid product () in Example 2.
In the same way, multistage continuous polymerization of ethylene was carried out, and 85Kg
A polymer powder with Mw/Mn of 14 was obtained.
When a bottle was manufactured by blow molding 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 produced 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, during the first stage polymerization, triisobutylaluminum was supplied at a rate of 0.4 mmol per hour, hexane was supplied at a rate of 2.5 mmol per hour, and ethylene containing 5% by volume of butene was supplied at a rate of 315 Nl per hour. Hydrogen was supplied so that the molar ratio of ethylene (including butene) to hydrogen in the gas phase was 1:0.01, and the total pressure was reduced to 25
In the second stage polymerization, ethylene containing 5% by volume of butene-1 was fed at a rate of 300 Nl per hour at 85°C, and the total pressure was 30 kg/cm 2 (gauge pressure). pressure), and the molar ratio of ethylene (including butene-1) to hydrogen in the gas phase is 1:1.
Multistage continuous polymerization of ethylene and film production were carried out in the same manner as in Example 1, except that the polymerization rate was 3.0. 90 kg of polyethylene was obtained, with a melt index of 0.04, bulk specific gravity of 0.39, density of 0.949, and Mw/Mn of 27. The fluidity of the molten resin during film formation is good, the film formability is also low, and the punching impact strength is 152Kg.
The film had sufficient strength in terms of cm/mm, 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, 495 Nl of ethylene containing 3% by volume of butene-1 was supplied per hour, hydrogen was supplied so that the ratio of ethylene to hydrogen in the gas phase was 1:0.04, and the total pressure was 35 Kg/cm 2 ( The first stage polymerization is carried out at (gauge pressure),
The same procedure as in Example 5 was carried out, except that ethylene was supplied at 120 Nl per hour and hydrogen was supplied at a ratio of ethylene to hydrogen in the gas phase of 1:3.0, and the second stage polymerization was carried out at a total pressure of 25 kg/ cm2 . Multi-stage continuous polymerization of ethylene was carried out. 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.
30Nl, 1 pair of hydrogen and ethylene in the gas phase
0.003, and the first stage polymerization was carried out at a total pressure of 8 kg/cm 2 (gauge pressure). Ethylene was supplied at 570 Nl per hour, and hydrogen was supplied at a ratio of ethylene to hydrogen in the gas phase of 1.
Multi-stage continuous polymerization of ethylene was carried out in the same manner as in Example 5, except that the second stage polymerization was carried out by supplying ethylene at a ratio of 2.9 to 2.9. 82 kg of polyethylene was obtained, the melt index was 0.05, Mw/Mn was 12, and the fish eye was
There were more than 1,000 pieces, and the surface condition of the film was extremely poor, and the punching impact strength was 40 kg-cm/mm, which was extremely insufficient, so that 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 65°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 1:0.07, and the total pressure was 15Kg/cm 2 (gauge pressure).
In the second stage polymerization, at 90°C, ethylene was fed at a rate of 200 Nl per hour, and the total pressure was 25
Polyethylene and hollow bottles were produced in the same manner as in Example 2, except that the reaction was carried out at Kg/cm 2 (gauge pressure) and the molar ratio of ethylene to hydrogen in the gas phase was 1:2.0. 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 ground 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, 100 g of titanium tetrachloride, and 200 ml of toluene, the mixture was reacted in the same manner as in Example 1 to obtain a solid product (). 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. The melt index was 0.36, the bulk specific gravity was 0.36, the density was 0.956, and Mw/Mn was 21. A bottle was manufactured by blow molding in the same manner as in Example 2, and satisfactory results were obtained. Example 8 70 g of iron trichloride (anhydrous) and 65 g of hydromagnesite (3MgCO 3・Mg(OH) 2・3H 2 O) were mixed in a vibrating mill for 10 hours, ground, 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-butyraldebide
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 () 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 (), in 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 in the gas phase by mol of ethylene (including propylene) to hydrogen. The ratio is 1
In the second stage polymerization, ethylene containing 3% by volume of propylene was supplied at 300 Nl per hour, and hydrogen was supplied at a molar ratio of ethylene (including propylene) to hydrogen in the gas phase of 1 to 2.8. The multistage continuous polymerization of ethylene and the production of a film were carried out in the same manner as in Example 1, except that the ethylene was supplied in such a manner that 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,
The film formability is also stable, and the punching impact strength of the film is
Sufficient strength at 150Kg-cm/mm, haze value 79
%, it has a moderate opacity, and the eyelid is 6
There were no problems at all, the surface condition was good, and the film performance was satisfactory. Example 9 (1) Production of transition metal catalyst component Hydromagnesite (3MgCO 3・Mg(OH) 2・
3H 2 O) 65g and 70g of iron trichloride (anhydrous) were mixed and ground in a vibrating mill for 10 hours, and reacted at 300℃ for 1 hour.
A solid product () was obtained. In 150 ml of o-dichlorobenzene, chain di-n
- Add and mix 200 g of butyl polysiloxane (viscosity 1000 centistokes) and 100 g of solid product (), add 200 g of titanium tetrachloride,
C. for 3 hours to obtain a solid product ().
Titanium content in 1g of solid product ()
It was 0.20 mmol. (2) Multistage continuous polymerization of ethylene Into the first stage polymerization vessel with an internal volume of 10, the above solid product () was added at a rate of 35 mg per hour, triethylaluminum at 0.35 mmol per hour, and hexane at a rate of 2 per hour. While discharging the contents of the polymerization vessel to maintain the liquid level in the polymerization vessel at 80%, at 70°C, 310Nl of ethylene containing 3% by volume of butene-1 was added to the polymerization vessel per 11 hours, and hydrogen was added to the polymerization vessel gas phase. While supplying so that the molar ratio of ethylene (including butene) to hydrogen is 1:0.05, the total pressure is 20Kg/cm 2
The first stage polymerization was carried out continuously at (gauge pressure). Next, the entire amount of the polymer suspended in the solvent that came out of the first stage polymerization vessel was introduced into the second stage polymerization vessel with an internal volume of 20% using a transfer pump, so that the liquid level in the polymerization vessel was maintained at 80%. 85℃ while discharging the contents of the polymerization vessel.
, the molar ratio of ethylene (including butene introduced from the first stage polymerizer) to hydrogen in the gas phase of the polymerizer was 1 to 300 Nl per hour, without adding new triethylaluminum.
The second stage polymerization was carried out continuously at a total pressure of 35 Kg/cm 2 (gauge pressure) while supplying the polymer so that the total pressure was 35 Kg/cm 2 (gauge pressure). The above multi-stage polymerization was carried out continuously for 150 hours, but
The operation was extremely stable, and 111 kg of polyethylene powder was obtained after drying without deashing. Polymer yield is 21100g-polymer/g-()・Hr, 106000g
-Polymer/mmol-Ti/Hr. This polyethylene has a melt index
0.30, bulk specific gravity 0.38, density 0.956 g/cm 2 , butene content 1.2% by weight, and Mw/Mn 26. When bottles were manufactured by blow molding using this polyethylene, the drawdown of the parison was small, no melt fracture occurred during molding, no shark skin phenomenon was observed, and the surface of the molded product was extremely good. The weight of one molded product was sufficient at 275 g, there was almost no uneven thickness, and the stress cracking resistance ( F50 value) was 170 hours without any problems, indicating that the bottle had sufficient performance for practical use.
第１図は、本発明の製造法に係る触媒のフロー
チヤートである。
FIG. 1 is a flowchart of the catalyst according to the production method of the present invention.
Claims (1)
存在下、複数個の重合器を使い第１段重合系で高
分子側重合体を、第２段重合系で低分子側重合体
をつくるポリエチレンの連続多段重合による製造
法において、 (i) 三価の鉄またはアルミニウムのハロゲン化物
とマグネシウムの水酸化物、酸化物、炭酸化
物、これらを含む複塩、またはマグネシウム化
合物の水和物とを反応させて得られる固体生成
物（）と電子供与体化合物と、チタン化合物
とから調製したチタン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触媒の存在下、飽和
炭化水素溶媒中、重合器の上部に気相が存在す
る状態において、重合温度30℃以上100℃以下、
重合圧力11ないし70Kg／cm2の条件下で、重合器
気相部のエチレン対水素のモル比が１対0.001
ないし0.5になるように水素を供給すると共に、
全エチレン供給量の10ないし70％のエチレンを
供給して、第１段重合を行ない、 (ii) 続いて、溶媒に懸濁した重合物を第２段重合
系に移送し、飽和炭化水素溶媒中、重合器の上
部に気相が存在する状態において、重合温度50
℃以上120℃以下、重合圧力11ないし70Kg／cm2
の条件下で、重合器気相部のエチレン対水素の
エチレン対水素のモル比が１対0.1ないし3.0に
なるように水素を供給すると共に、全エチレン
供給量の30ないし90％のエチレンを供給して第
２段重合を行なうことを特徴とするポリエチレ
ンの連続多段重合による製造法。 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
範囲第１項の製造法。 ３ 固体生成物（）が固体生成物（）100ｇ
に対し電子供与体化合物が20〜1000ｇ、遷移金属
化合物は10〜500ｇであつて、かつ電子供与体化
合物100ｇに対し遷移金属化合物30〜500ｇで調製
した特許請求の範囲第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４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４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 high molecular side polymer is produced in the first stage polymerization system, and a low molecular side polymer is produced in the second stage polymerization system. In the method for producing polyethylene by continuous multi-stage polymerization, (i) trivalent iron or aluminum halide and magnesium hydroxide, oxide, carbonate, double salt containing these, or hydrate of magnesium compound; The presence of a catalyst obtained by combining the solid product () obtained by reacting the solid product () with the electron donor compound and the final solid product () supported on the titanium compound prepared from the titanium compound and the organoaluminum compound. Below, in a saturated hydrocarbon solvent, in a state where a gas phase exists at the top of the polymerization vessel, the polymerization temperature is 30°C or more and 100°C or less,
Under polymerization pressure of 11 to 70 kg/ cm2 , the molar ratio of ethylene to hydrogen in the gas phase of the polymerizer is 1:0.001.
At the same time, hydrogen is supplied so that the amount of
The first stage polymerization is carried out by supplying 10 to 70% of the total amount of ethylene supplied, (ii) The polymer suspended in the solvent is then transferred to the second stage polymerization system, and a saturated hydrocarbon solvent is added. In a state where a gas phase exists at the top of the polymerization vessel, the polymerization temperature is 50℃.
℃ or more and 120℃ or less, polymerization pressure 11 to 70Kg/cm 2
Under these conditions, hydrogen is supplied so that the molar ratio of ethylene to hydrogen in the gas phase of the polymerization reactor is 1:0.1 to 3.0, and ethylene is supplied in an amount of 30 to 90% of the total ethylene supply amount. A method for producing polyethylene by continuous multi-stage polymerization, characterized in that a second stage polymerization is carried out. 2. The production method 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. 3 Solid product () is 100g 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 4, wherein the electron donor compound is polysiloxane. 5 The electron donor compound is an ether, an ester,
The manufacturing method according to claim 1, 2 or 4, which is an aldehyde, ketone or acid anhydride.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10753079A JPS5632507A (en) | 1979-08-23 | 1979-08-23 | 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 |
|---|---|---|---|
| JP10753079A JPS5632507A (en) | 1979-08-23 | 1979-08-23 | Production of polyethylene by continuous multistage polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5632507A JPS5632507A (en) | 1981-04-02 |
| JPS6352655B2 true JPS6352655B2 (en) | 1988-10-19 |
Family
ID=14461520
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10753079A Granted JPS5632507A (en) | 1979-08-20 | 1979-08-23 | Production of polyethylene by continuous multistage polymerization |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5632507A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5893742A (en) * | 1981-12-01 | 1983-06-03 | Showa Denko Kk | Thermoforming resin composition |
| JPH062776B2 (en) * | 1984-12-21 | 1994-01-12 | 日本石油株式会社 | Method for producing ultra high molecular weight polyethylene |
| DE3723526A1 (en) * | 1987-07-16 | 1989-01-26 | Hoechst Ag | METHOD FOR PRODUCING A POLYOLEFIN WITH A WIDE MOLE WEIGHT DISTRIBUTION |
| WO2022107690A1 (en) | 2020-11-17 | 2022-05-27 | 旭化成株式会社 | Polyethylene powder and molded body |
| KR20240078753A (en) * | 2022-11-28 | 2024-06-04 | 한화토탈에너지스 주식회사 | Polyethylene resin for secondary battery separator, method of manufacturing the same, and secondary battery separator and secondary battery including the same |
-
1979
- 1979-08-23 JP JP10753079A patent/JPS5632507A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5632507A (en) | 1981-04-02 |
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