JPS6410526B2 - - Google Patents
Info
- Publication number
- JPS6410526B2 JPS6410526B2 JP10511880A JP10511880A JPS6410526B2 JP S6410526 B2 JPS6410526 B2 JP S6410526B2 JP 10511880 A JP10511880 A JP 10511880A JP 10511880 A JP10511880 A JP 10511880A JP S6410526 B2 JPS6410526 B2 JP S6410526B2
- Authority
- JP
- Japan
- Prior art keywords
- polymerization
- titanium
- compound
- catalyst
- ether
- 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
- -1 aluminum compound Chemical class 0.000 claims description 53
- 239000007787 solid Substances 0.000 claims description 35
- 239000003054 catalyst Substances 0.000 claims description 29
- 150000003609 titanium compounds Chemical class 0.000 claims description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- 150000003682 vanadium compounds Chemical class 0.000 claims description 13
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 10
- 239000005977 Ethylene Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 description 31
- 239000004698 Polyethylene Substances 0.000 description 29
- 229920000573 polyethylene Polymers 0.000 description 29
- 229920000642 polymer Polymers 0.000 description 23
- 239000000843 powder Substances 0.000 description 20
- 230000005484 gravity Effects 0.000 description 19
- 238000000498 ball milling Methods 0.000 description 16
- 239000010936 titanium Substances 0.000 description 16
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 229910052719 titanium Inorganic materials 0.000 description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 12
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 239000000155 melt Substances 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 230000037048 polymerization activity Effects 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 6
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000002902 organometallic compounds Chemical class 0.000 description 5
- 238000010298 pulverizing process Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- NMLLTHLOSVNFMY-UHFFFAOYSA-N 1-butoxy-3-methylbutane Chemical compound CCCCOCCC(C)C NMLLTHLOSVNFMY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- AQZGPSLYZOOYQP-UHFFFAOYSA-N Diisoamyl ether Chemical compound CC(C)CCOCCC(C)C AQZGPSLYZOOYQP-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical compound [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 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
- 230000006698 induction Effects 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- QCYFOZWGXKXDJA-UHFFFAOYSA-N 1-butoxyhexane Chemical compound CCCCCCOCCCC QCYFOZWGXKXDJA-UHFFFAOYSA-N 0.000 description 1
- HQUVLOKKTRUQNI-UHFFFAOYSA-N 1-ethoxy-3-methylbutane Chemical compound CCOCCC(C)C HQUVLOKKTRUQNI-UHFFFAOYSA-N 0.000 description 1
- PZHIWRCQKBBTOW-UHFFFAOYSA-N 1-ethoxybutane Chemical compound CCCCOCC PZHIWRCQKBBTOW-UHFFFAOYSA-N 0.000 description 1
- ZXHQLEQLZPJIFG-UHFFFAOYSA-N 1-ethoxyhexane Chemical compound CCCCCCOCC ZXHQLEQLZPJIFG-UHFFFAOYSA-N 0.000 description 1
- BPIUIOXAFBGMNB-UHFFFAOYSA-N 1-hexoxyhexane Chemical compound CCCCCCOCCCCCC BPIUIOXAFBGMNB-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-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
- RMGHERXMTMUMMV-UHFFFAOYSA-N 2-methoxypropane Chemical compound COC(C)C RMGHERXMTMUMMV-UHFFFAOYSA-N 0.000 description 1
- QJMYXHKGEGNLED-UHFFFAOYSA-N 5-(2-hydroxyethylamino)-1h-pyrimidine-2,4-dione Chemical compound OCCNC1=CNC(=O)NC1=O QJMYXHKGEGNLED-UHFFFAOYSA-N 0.000 description 1
- NTWOIGOPFDMZAE-UHFFFAOYSA-M CCO[Ti](Cl)(OCC)OCC Chemical compound CCO[Ti](Cl)(OCC)OCC NTWOIGOPFDMZAE-UHFFFAOYSA-M 0.000 description 1
- ZALOHOLPKHYYAX-UHFFFAOYSA-L CO[Ti](Cl)(Cl)OC Chemical compound CO[Ti](Cl)(Cl)OC ZALOHOLPKHYYAX-UHFFFAOYSA-L 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 1
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 1
- MGSCVPSSIVOYMY-UHFFFAOYSA-N [V+3].CC[O-].CC[O-].CC[O-] Chemical compound [V+3].CC[O-].CC[O-].CC[O-] MGSCVPSSIVOYMY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- WQAJKGNQVZTJAE-UHFFFAOYSA-M chloro(diethoxy)alumane Chemical compound [Cl-].CCO[Al+]OCC WQAJKGNQVZTJAE-UHFFFAOYSA-M 0.000 description 1
- CPGBHJOISIWUHQ-UHFFFAOYSA-M chloro-di(propan-2-yloxy)alumane Chemical compound CC(C)O[Al](Cl)OC(C)C CPGBHJOISIWUHQ-UHFFFAOYSA-M 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- AQEFLFZSWDEAIP-UHFFFAOYSA-N di-tert-butyl ether Chemical compound CC(C)(C)OC(C)(C)C AQEFLFZSWDEAIP-UHFFFAOYSA-N 0.000 description 1
- GCXKYQNCXYJOCU-UHFFFAOYSA-L dichloroalumanylium;propan-2-olate Chemical compound [Cl-].[Cl-].CC(C)O[Al+2] GCXKYQNCXYJOCU-UHFFFAOYSA-L 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 description 1
- UHSDHNXHBQDMMH-UHFFFAOYSA-L ethanolate;titanium(4+);dichloride Chemical compound CCO[Ti](Cl)(Cl)OCC UHSDHNXHBQDMMH-UHFFFAOYSA-L 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
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- ZEIWWVGGEOHESL-UHFFFAOYSA-N methanol;titanium Chemical compound [Ti].OC.OC.OC.OC ZEIWWVGGEOHESL-UHFFFAOYSA-N 0.000 description 1
- QZCOACXZLDQHLQ-UHFFFAOYSA-M methanolate titanium(4+) chloride Chemical compound [Cl-].[Ti+4].[O-]C.[O-]C.[O-]C QZCOACXZLDQHLQ-UHFFFAOYSA-M 0.000 description 1
- OKENUZUGNVCOMC-UHFFFAOYSA-K methanolate titanium(4+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].CO[Ti+3] OKENUZUGNVCOMC-UHFFFAOYSA-K 0.000 description 1
- LVLXTANMULARCV-UHFFFAOYSA-N methoxy-di(propan-2-yloxy)alumane Chemical compound CC(C)O[Al](OC)OC(C)C LVLXTANMULARCV-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- LTEDQKPGOZDGRZ-UHFFFAOYSA-L propan-2-olate;titanium(4+);dichloride Chemical compound Cl[Ti+2]Cl.CC(C)[O-].CC(C)[O-] LTEDQKPGOZDGRZ-UHFFFAOYSA-L 0.000 description 1
- FLALGSYYVIWTFQ-UHFFFAOYSA-K propan-2-olate;titanium(4+);trichloride Chemical compound [Cl-].[Cl-].[Cl-].CC(C)O[Ti+3] FLALGSYYVIWTFQ-UHFFFAOYSA-K 0.000 description 1
- ZYNMJJNWXVKJJV-UHFFFAOYSA-N propan-2-yloxybenzene Chemical compound CC(C)OC1=CC=CC=C1 ZYNMJJNWXVKJJV-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BIEFSHWAGDHEIT-UHFFFAOYSA-J tetrabromovanadium Chemical compound [V+4].[Br-].[Br-].[Br-].[Br-] BIEFSHWAGDHEIT-UHFFFAOYSA-J 0.000 description 1
- JYHZWKLCYKMFOD-UHFFFAOYSA-J tetraiodovanadium Chemical compound [V+4].[I-].[I-].[I-].[I-] JYHZWKLCYKMFOD-UHFFFAOYSA-J 0.000 description 1
- NLLZTRMHNHVXJJ-UHFFFAOYSA-J titanium tetraiodide Chemical compound I[Ti](I)(I)I NLLZTRMHNHVXJJ-UHFFFAOYSA-J 0.000 description 1
- DPNUIZVZBWBCPB-UHFFFAOYSA-J titanium(4+);tetraphenoxide Chemical compound [Ti+4].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 DPNUIZVZBWBCPB-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- WOZZOSDBXABUFO-UHFFFAOYSA-N tri(butan-2-yloxy)alumane Chemical compound [Al+3].CCC(C)[O-].CCC(C)[O-].CCC(C)[O-] WOZZOSDBXABUFO-UHFFFAOYSA-N 0.000 description 1
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- OBROYCQXICMORW-UHFFFAOYSA-N tripropoxyalumane Chemical compound [Al+3].CCC[O-].CCC[O-].CCC[O-] OBROYCQXICMORW-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
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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)
Description
【発明の詳細な説明】
本発明は新規な重合触媒によるポリオレフイン
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyolefin using a novel polymerization catalyst.
従来この種の技術分野においては、特公昭39−
12105号公報によりハロゲン化マグネシウムにチ
タン化合物などの遷移金属化合物を担持させた触
媒が知られており、さらにベルギー特許742112号
によりハロゲン化マグネシウムと四塩化チタンと
を共粉砕した触媒が知られている。 Conventionally, in this type of technical field, the
A catalyst in which a transition metal compound such as a titanium compound is supported on magnesium halide is known from Publication No. 12105, and a catalyst in which magnesium halide and titanium tetrachloride are co-pulverized is known from Belgian Patent No. 742112. .
しかしながらポリオレフインの製造上、触媒活
性はできるだけ高いことが望ましく、この観点か
らみると特公昭39−12105号記載の方法では重合
活性はまだ低く、ベルギー特許第742112号の方法
では重合活性は相当程度高くなつているがなお改
良が望まれる。 However, in the production of polyolefins, it is desirable for the catalyst activity to be as high as possible, and from this point of view, the method described in Japanese Patent Publication No. 39-12105 has a still low polymerization activity, while the method described in Belgian Patent No. 742112 has a considerably high polymerization activity. Although it is getting better, improvements are still desired.
またドイツ特許2137872号ではハロゲン化マグ
ネシウム、四塩化チタンおよびアルミナなどを共
粉砕することにより実質的にハロゲン化マグネシ
ウムの使用量を減らしているが、生産性の尺度と
も言える固体当りの活性の著しい増加は認められ
ずさらに高活性な触媒が望まれる。 Furthermore, in German Patent No. 2137872, the amount of magnesium halide used is substantially reduced by co-pulverizing magnesium halide, titanium tetrachloride, alumina, etc., but the activity per solid, which is a measure of productivity, is significantly increased. was not observed, and a catalyst with even higher activity is desired.
またポリオレフインの製造上生成ポリマーのか
さ比重はできるだけ高いことが生産性およびスラ
リーハンドリングの面から望ましい。この観点か
らみると前記特公昭39−12105号公報記載の方法
では生成ポリマーのかさ比重は低くかつ重合活性
も満足すべき状態ではなく、またベルギー特許
742112号の方法では重合活性は高いが生成ポリマ
ーのかさ比重は低いという欠点があり改良が望ま
れる。 Further, in the production of polyolefin, it is desirable that the bulk specific gravity of the polymer produced be as high as possible from the viewpoint of productivity and slurry handling. From this point of view, the method described in Japanese Patent Publication No. 39-12105 has a low bulk specific gravity and an unsatisfactory polymerization activity, and the Belgian patent
The method of No. 742112 has the drawback that although the polymerization activity is high, the bulk specific gravity of the resulting polymer is low, and improvements are desired.
本発明は上記の欠点を改良し、重合活性が高く
かつかさ比重の高いポリマーを高収率で得ること
ができ、かつ連続重合をきわめて容易に実施でき
る新規な重合触媒の製造方法ならびに該重合触媒
によるオレフインの重合、または共重合方法に関
するものであり、重合活性はきわめて高いため重
合時のモノマー分圧も低く、さらに生成ポリマー
のかさ比重が高いため、生産性を向上させること
ができ、また重合終了後の生成ポリマー中の触媒
残渣量はきわめて少量となり、したがつてポリオ
レフイン製造プロセスにおいて触媒除去工程が省
略できるためポリマー処理工程が簡素化され、全
体としてきわめて経済的なポリオレフインの製造
方法を提供するものである。 The present invention improves the above-mentioned drawbacks, provides a method for producing a novel polymerization catalyst that can obtain a polymer with high polymerization activity and high bulk specific gravity in high yield, and allows continuous polymerization to be carried out extremely easily, as well as a method for producing the polymerization catalyst. This method is related to the polymerization or copolymerization method of olefins.The polymerization activity is extremely high, so the monomer partial pressure during polymerization is low, and the bulk specific gravity of the resulting polymer is high, so it is possible to improve productivity. The amount of catalyst residue in the produced polymer after completion is extremely small, and therefore the catalyst removal step can be omitted in the polyolefin production process, simplifying the polymer treatment process and providing an extremely economical polyolefin production method as a whole. It is something.
本発明の方法では得られるポリマーのかさ比重
が大きいため単位溶媒当りのポリマー生成量が多
い。 In the method of the present invention, since the bulk specific gravity of the obtained polymer is large, the amount of polymer produced per unit solvent is large.
さらに本発明の長所をあげれば生成ポリマーの
粒径の観点からみてかさ比重が高いにもかかわら
ず、粗大粒子および50μ以下の微粒子が少ないた
め、連続重合反応が容易になり、かつポリマー処
理工程における遠心分離、および粉体輸送などの
ポリマー粒子の取り扱いが容易になることであ
る。 A further advantage of the present invention is that although the bulk specific gravity of the produced polymer is high in terms of particle size, there are few coarse particles and fine particles of 50μ or less, which facilitates continuous polymerization reactions and facilitates polymer processing. The handling of polymer particles, such as centrifugation and powder transport, is facilitated.
本発明の他の利点としては本発明の触媒を用い
て得られるポリエチレンは前記したようにかさ比
重が大きく、また所望のメルトインデツクスのポ
リマーを得るためには従来の方法に比べ水素濃度
が少なくて済みしたがつて重合時の全圧も比較的
小さくすることができ、経済性、生産性に及ぼす
効果も大きいことをあげることができる。 Another advantage of the present invention is that the polyethylene obtained using the catalyst of the present invention has a large bulk specific gravity as described above, and in order to obtain a polymer with a desired melt index, it requires a lower hydrogen concentration than conventional methods. Therefore, the total pressure during polymerization can be made relatively small, and the effects on economy and productivity are also great.
加えて本発明の触媒を用いてエチレンの重合を
行なつた場合、時間によるエチレン吸収速度の減
少が少ないことから少ない触媒量で長時間重合を
行なえることも利点としてあげることができる。 In addition, when ethylene is polymerized using the catalyst of the present invention, an advantage is that the ethylene absorption rate decreases little with time, so that the polymerization can be carried out for a long time with a small amount of catalyst.
更に、本発明の長所を挙げれば、本発明の触媒
を用いて得られるポリオレフインの分子量分布は
狭く、フイルム成形した場合における透明性が著
しくすぐれており、かつ耐衝撃強度も大きいとい
う利点を有していることである。 Furthermore, the advantages of the present invention are that the polyolefin obtained using the catalyst of the present invention has a narrow molecular weight distribution, extremely excellent transparency when formed into a film, and high impact strength. That is what we are doing.
本発明の触媒はこれらの多くの特徴を備え、か
つ前記の先行技術の欠点を改良した新規な触媒系
を提供するものであり、本発明の触媒を用いるこ
とによりこれら諸点を容易に達成できることは驚
くべきことと言わねばならない。 The catalyst of the present invention provides a novel catalyst system that has many of these features and improves the drawbacks of the prior art described above, and these points can be easily achieved by using the catalyst of the present invention. I must say it's surprising.
以下に本発明を具体的に説明する。すなわち、
本発明は
(1) ジハロゲン化マグネシウム（以下ハロゲン化
マグネシウムと称する）、
(2) 一般式Al（OR）oX3-o（ここでＲは炭素数１〜
24、好ましくは１〜12、最も好ましくは１〜
４、のアルキル基、アリール基及び／又はアラ
ルキル基、Ｘはハロゲン原子を示す。ｎは０＜
ｎ≦３である）で表わされる化合物、および、
(3) エーテル化合物
を共粉砕することにより得られる物質を固体担体
とし、該固体担体にチタン化合物またはチタン化
合物とバナジウム化合物を担持せしめた成分と有
機アルミニウム化合物（以下有機金属化合物と称
する）とを触媒として、エチレンを重合してポリ
エチレンを製造する方法に関する。 The present invention will be specifically explained below. That is,
The present invention comprises (1) magnesium dihalide (hereinafter referred to as magnesium halide), (2) general formula Al(OR ) o
24, preferably 1 to 12, most preferably 1 to 12
In the alkyl group, aryl group and/or aralkyl group of 4, X represents a halogen atom. n is 0<
n≦3), and (3) a component obtained by using a substance obtained by co-pulverizing an ether compound as a solid carrier, and supporting a titanium compound or a titanium compound and a vanadium compound on the solid carrier. The present invention relates to a method for producing polyethylene by polymerizing ethylene using an organoaluminum compound (hereinafter referred to as an organometallic compound) as a catalyst.
本発明に使用されるハロゲン化マグネシウムと
しては実質的に無水のものが用いられフツ化マグ
ネシウム、塩化マグネシウム、臭化マグネシウ
ム、ヨウ化マグネシウムおよびこれらの混合物が
あげられるがとくに塩化マグネシウムが好まし
い。 The magnesium halide used in the present invention is substantially anhydrous and includes magnesium fluoride, magnesium chloride, magnesium bromide, magnesium iodide, and mixtures thereof, with magnesium chloride being particularly preferred.
本発明に使用される一般式Al（OR）oX3-oで表
わされる化合物としては、アルミニウムトリメト
キシド、アルミニウムトリエトキシド、ジエトキ
シモノクロロアルミニウム、モノエトキシジクロ
ロアルミニウム、モノメトシジエトキシアルミニ
ウム、アルミニウムトリｎ―プロポキシド、アル
ミニウムトリイソプロポキシド、ジイソプロポキ
シモノクロロアルミニウム、モノイソプロポキシ
ジクロロアルミニウム、モノメトキシジイソプロ
ポキシアルミニウム、アルミニウムトリｎ―ブト
キシド、アルミニウムトリsec―ブトキシド、ア
ルミニウムトリｔ―ブトキシドがあげられるがと
くにアルミニウムトリメトキシド、アルミニウム
トリエトキシドが好ましい。 Examples of the compound represented by the general formula Al(OR ) o Aluminum tri-n-propoxide, aluminum triisopropoxide, diisopropoxymonochloroaluminum, monoisopropoxydichloroaluminum, monomethoxydiisopropoxyaluminum, aluminum tri-n-butoxide, aluminum trisec-butoxide, aluminum tri-t-butoxide Aluminum trimethoxide and aluminum triethoxide are particularly preferred.
本発明に使用されるエーテル化合物としては脂
肪族エーテル、環式エーテル、芳香族エーテル等
が挙げられ、具体的には、ジメチルエーテル、ジ
エチルエーテル、ジイソプロピルエーテル、ジｎ
―ブチルエーテル、ジｎ―アミルエーテル、ジイ
ソアミルエーテル、ジヘキシルエーテル、メチル
イソプロピルエーテル、メチルｔ―ブチルエーテ
ル、エチルイソプロピルエーテル、エチルｎ―ブ
チルエーテル、エチルイソアミルエーテル、エチ
ルｎ―ヘキシルエーテル、イソプロピルｔ―ブチ
ルエーテル、ｎ―ブチルイソアミルエーテル、ｎ
―ブチルイソアミルエーテル、ｎ―ブチルヘキシ
ルエーテル、テトラヒドロフラン、ジオキサン、
ジフエニルエーテル、エチルフエニルエーテル、
イソプロピルフエニルエーテルなどを挙げること
ができ、特に好ましくはジエチルエーテル、ジイ
ソプロピルエーテル、ジイソアミルエーテル、テ
トラヒドロフランを挙げることができる。 Ether compounds used in the present invention include aliphatic ethers, cyclic ethers, aromatic ethers, etc. Specifically, dimethyl ether, diethyl ether, diisopropyl ether, di-n
-Butyl ether, di-n-amyl ether, diisoamyl ether, dihexyl ether, methyl isopropyl ether, methyl t-butyl ether, ethyl isopropyl ether, ethyl n-butyl ether, ethyl isoamyl ether, ethyl n-hexyl ether, isopropyl t-butyl ether, n -butyl isoamyl ether, n
-Butyl isoamyl ether, n-butylhexyl ether, tetrahydrofuran, dioxane,
diphenyl ether, ethyl phenyl ether,
Examples include isopropylphenyl ether, and particularly preferred examples include diethyl ether, diisopropyl ether, diisoamyl ether, and tetrahydrofuran.
チタン化合物またはチタン化合物とバナジウム
化合物としては、これら金属のハロゲン化物、ア
ルコキシハロゲン化物、アルコキシド、ハロゲン
化酸化物等を挙げることができる。チタン化合物
としては４価のチタン化合物と３価のチタン化合
物が好適であり、４価のチタン化合物としては具
体的には一般式Ti（OR）oX4-o（ここでＲは炭素数
１〜20のアルキル基、アリール基またはアラルキ
ル基を示し、Ｘはハロゲン原子を示す。ｎは０≦
ｎ≦４である。）で示されるものが好ましく、四
塩化チタン、四臭化チタン、四ヨウ化チタン、モ
ノメトキシトリクロロチタン、ジメトキシジクロ
ロチタン、トリメトキシモノクロロチタン、テト
ラメトキシチタン、モノエトキシトリクロロチタ
ン、ジエトキシジクロロチタン、トリエトキシモ
ノクロロチタン、テトラエトキシチタン、モノイ
ソプロポキシトリクロロチタン、ジイソプロポキ
シジクロロチタン、トリイソプロポキシモノクロ
ロチタン、テトライソプロポキシチタン、モノブ
トキシトリクロロチタン、ジブトキシジクロロチ
タン、モノベントキシトリクロロチタン、モノフ
エノキシトリクロロチタン、ジフエノキシジクロ
ロチタン、トリフエノキシモノクロロチタン、テ
トラフエノキシチタン等を挙げることができる。
３価のチタン化合物としては、四塩化チタン、四
臭化チタン等の四ハロゲン化チタンを水素、アル
ミニウム、チタンあるいは周期律表〜族金属
の有機金属化合物により還元して得られる三ハロ
ゲン化チタンが挙げられる。また一般式Ti（OR）
nX4-n（ここでＲは炭素数１〜20のアルキル基、
アリール基またはアラルキル基を示し、Ｘはハロ
ゲン原子を示す。ｍは０＜ｍ＜４である。）で示
される４価のハロゲン化アルコキシチタンを周期
律表〜族金属の有機金属化合物により還元し
て得られる３価のチタン化合物が挙げられる。バ
ナジウム化合物としては、四塩化バナジウム、四
臭化バナジウム、四ヨウ化バナジウムの如き４価
のバナジウム化合物、オキシ三塩化バナジウム、
オルソアルキルバナデートの如き５価のバナジウ
ム化合物、三塩化バナジウム、バナジウムトリエ
トキシドの如き３価のバナジウム化合物が挙げら
れる。 Examples of the titanium compound or the titanium compound and vanadium compound include halides, alkoxy halides, alkoxides, and halogenated oxides of these metals. Preferred titanium compounds are tetravalent titanium compounds and trivalent titanium compounds, and specific examples of tetravalent titanium compounds include the general formula Ti(OR) o X 4-o (where R is 1 carbon number) ~20 alkyl group, aryl group or aralkyl group, X represents a halogen atom, n is 0≦
n≦4. ) are preferred, and titanium tetrachloride, titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, Triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxytrichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monobentoxytrichlorotitanium, monophenol Examples include citrichlorotitanium, diphenoxydichlorotitanium, triphenoxymonochlorotitanium, and tetraphenoxytitanium.
Examples of trivalent titanium compounds include titanium trihalides obtained by reducing titanium tetrahalides such as titanium tetrachloride and titanium tetrabromide with hydrogen, aluminum, titanium, or organometallic compounds of group metals of the periodic table. Can be mentioned. Also general formula Ti(OR)
n X 4-n (where R is an alkyl group having 1 to 20 carbon atoms,
It represents an aryl group or an aralkyl group, and X represents a halogen atom. m is 0<m<4. ) A trivalent titanium compound obtained by reducing a tetravalent alkoxy titanium halide represented by the following formula with an organometallic compound of a group metal of the periodic table is exemplified. Examples of vanadium compounds include tetravalent vanadium compounds such as vanadium tetrachloride, vanadium tetrabromide, vanadium tetraiodide, vanadium oxytrichloride,
Examples include pentavalent vanadium compounds such as orthoalkylvanadate, trivalent vanadium compounds such as vanadium trichloride, and vanadium triethoxide.
本発明をさらに効果的にするため、チタン化合
物をバナジウム化合物を併用するときのＶ／Ti
モル比は２／１〜0.01／１の範囲が好ましい。 In order to make the present invention even more effective, when a titanium compound is used in combination with a vanadium compound, V/Ti
The molar ratio is preferably in the range of 2/1 to 0.01/1.
本発明に用いる有機金属化合物の例としては一
般式R3Al、K2AlX、RAlX2、R2AlOR、RAl
（OR）ＸおよびR3Al2X3の有機アルミニウム化合
物（ただしＲは炭素数１〜20のアルキル基または
アリール基、Ｘはハロゲン原子を示し、Ｒは同一
でもまた異なつてもよい）、具体的な例としては
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、トリオクチ
ルアルミニウム、ジエチルアルミニウム、エチル
アルミニウムセスキクロリドおよびこれらの混合
物等があげられる。 Examples of organometallic compounds used in the present invention include general formulas R 3 Al, K 2 AlX, RAlX 2 , R 2 AlOR, RAl
(OR) Organoaluminum compounds of X and R 3 Al 2 X 3 (R is an alkyl group or aryl group having 1 to 20 carbon atoms, Examples include triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum, ethylaluminum sesquichloride, and mixtures thereof.
本発明において、有機金属化合物の使用量はと
くに制限されないが通常遷移金属化合物に対して
0.1〜1000モル倍使用することができる。 In the present invention, the amount of the organometallic compound used is not particularly limited, but is usually
It can be used in amounts of 0.1 to 1000 moles.
本発明において、(1)ハロゲン化マグネシウム、
(2)一般式Al（OR）oX3-oで表わされる化合物、お
よび(3)エーテル化合物の共粉砕は、不活性ガス雰
囲気中で行なうべきであり、また湿気はできる限
り避けるべきである。 In the present invention, (1) magnesium halide,
Co-pulverization of (2) a compound represented by the general formula Al(OR) o X 3-o and (3) an ether compound should be performed in an inert gas atmosphere, and moisture should be avoided as much as possible. .
本発明において、固体担体にチタン化合物また
はチタン化合物とバナジウム化合物を担持する方
法としては、固体担体を不活性な溶媒の存在下ま
たは不存在下に、チタン化合物またはチタン化合
物とバナジウム化合物に加熱下に接触させること
により行なうことができ、好ましくは、溶媒の不
存在下に両者を、50〜300℃、好ましくは100〜
150℃に加熱することにより行なうのが便利であ
る。反応時間はとくに限定はされないが通常は５
分以上であり、必要ではないが長時間接触させる
ことは差支えない。たとえば５分ないし10時間の
処理時間をあげることができる。もちろん、この
処理は酸素、および水分を絶つた不活性ガス雰囲
気下で行なわれるべきである。反応終了後未反応
の遷移金属化合物を取り除く手段はとくに限定さ
れるものではなく、チグラー触媒に不活性な溶媒
で数回洗浄し洗液を減圧条件下で蒸発させ固体粉
末を得ることができる。しかしより望ましい方法
としては必要量のチタン化合物またはチタン化合
物とバナジウム化合物を(1)ハロゲン化マグネシウ
ム、(2)一般式Al（OR）oX3-oで表わされる化合物、
および(3)エーテル化合物との共存下に同時に共粉
砕するか、あるいは(1)ハロゲン化マグネシウム、
(2)一般式Al（OR）oX3-oで表わされる化合物、お
よび(3)エーテル化合物を共粉砕し、しかる後チタ
ン化合物またはチタン化合物とバナジウム化合物
を加え更に共粉砕して、固体担体にチタン化合物
またはチタン化合物とバナジウム化合物を担持さ
せる。もちろん共粉砕操作は不活性ガス雰囲気中
で行なうべきであり、また湿気はできる限り避け
るべきである。 In the present invention, as a method for supporting a titanium compound or a titanium compound and a vanadium compound on a solid support, the solid support is heated to a titanium compound or a titanium compound and a vanadium compound in the presence or absence of an inert solvent. This can be carried out by bringing them into contact, preferably at 50 to 300°C, preferably at 100 to 300°C, in the absence of a solvent.
This is conveniently carried out by heating to 150°C. The reaction time is not particularly limited, but is usually 5
Although it is not necessary, there is no problem with contacting for a long time. For example, processing times can range from 5 minutes to 10 hours. Of course, this treatment should be carried out under an inert gas atmosphere free of oxygen and moisture. The means for removing unreacted transition metal compounds after completion of the reaction is not particularly limited, and a solid powder can be obtained by washing the Ziegler catalyst several times with an inert solvent and evaporating the washings under reduced pressure. However, a more desirable method is to combine the necessary amounts of a titanium compound or a titanium compound and a vanadium compound with (1) magnesium halide, (2) a compound represented by the general formula Al(OR) o X 3-o ,
and (3) simultaneous co-pulverization in the presence of an ether compound, or (1) magnesium halide,
(2) A compound represented by the general formula Al(OR ) o supports a titanium compound or a titanium compound and a vanadium compound. Of course, the co-grinding operation should be carried out in an inert gas atmosphere and moisture should be avoided as much as possible.
ハロゲン化マグネシウムと一般式Al（OR）o
X3-oで表わされる化合物との混合割合は、アル
ミニウム化合物の量が余りにも少なすぎてもまた
逆にあまりにも多すぎても重合活性は低下する傾
向にありMg／Alモル比が１／0.01〜１／１の範
囲内であり、好ましくは１／0.05〜１／0.5の範
囲が高活性の触媒の製造のために望ましい。 Magnesium halide and general formula Al(OR) o
The mixing ratio with the compound represented by X 3-o is such that polymerization activity tends to decrease if the amount of the aluminum compound is too small or too large; The ratio is within the range of 0.01 to 1/1, preferably 1/0.05 to 1/0.5 for producing a highly active catalyst.
本発明において、エーテル化合物の使用量は余
り多すぎてもまた少なすぎても添加効果は望め
ず、通常ハロゲン化マグネシウム100ｇに対して
0.1〜50ｇ、好ましくは0.5〜10ｇの範囲内であ
る。 In the present invention, if the amount of the ether compound used is too large or too small, no effect can be expected.
It is in the range of 0.1-50g, preferably 0.5-10g.
また担持させるチタン化合物またはチタン化合
物とバナジウム化合物の量は生成固体中に含まれ
るチタンとバナジウムが0.5〜10重量％の範囲内
になるように調節するのが最も好ましく、バラン
スの良いチタンとバナジウム当りの活性、固体当
りの活性を得るためには１〜８重量％の範囲がと
くに望ましい。 It is most preferable to adjust the amount of the titanium compound or titanium compound and vanadium compound to be supported so that the titanium and vanadium contained in the produced solid are within the range of 0.5 to 10% by weight. The range of 1 to 8% by weight is particularly desirable in order to obtain an activity of 1 to 8% by weight.
共粉砕に用いる装置はとくに限定はされないが
通常ボールミル、振動ミル、ロツドミル、衝撃ミ
ルなどが使用されその粉砕方式に応じての混合順
序、粉砕時間、粉砕温度などの条件は特に限定さ
れるものではなく当業者にとつて容易に定められ
るものである。通常０℃〜200℃好ましくは20℃
〜100℃の温度で0.5時間〜30時間共粉砕すること
により本発明の触媒を製造することができる。 The equipment used for co-pulverization is not particularly limited, but usually a ball mill, vibration mill, rod mill, impact mill, etc. are used, and there are no particular restrictions on the conditions such as mixing order, grinding time, grinding temperature, etc. depending on the grinding method. It can be easily determined by a person skilled in the art. Usually 0℃~200℃ Preferably 20℃
The catalyst of the invention can be prepared by co-milling at a temperature of ~100°C for 0.5 to 30 hours.
本発明の触媒を使用してのオレフインの重合は
スラリー重合、溶液重合または気相重合にて行う
ことができ、重合反応は通常のチグラー型触媒に
よるオレフイン重合反応と同様にして行なわれ
る。すなわち反応はすべて実質的に酸素、水など
を絶つた状態で不活性炭化水素の存在下、あるい
は不存在下で行なわれる。オレフインの重合条件
は温度は20ないし120℃好ましくは50ないし100℃
であり、圧力は常圧ないし70Kg／cm2、好ましくは
２ないし60Kg／cm2である。分子量の調節は重合温
度、触媒のモル比などの重合条件を変えることに
よつてもある程度調節できるが重合系中に水素を
添加することにより効果的に行なわれる。もちろ
ん、本発明の触媒を用いて、水素濃度、重合温度
など重合条件の異なつた２段階ないしそれ以上の
多段階の重合反応も何ら支障なく実施できる。 Olefin polymerization using the catalyst of the present invention can be carried out by slurry polymerization, solution polymerization or gas phase polymerization, and the polymerization reaction is carried out in the same manner as the olefin polymerization reaction using a conventional Ziegler type catalyst. That is, all reactions are carried out in the presence or absence of inert hydrocarbons, substantially deprived of oxygen, water, and the like. Polymerization conditions for olefin include temperature of 20 to 120°C, preferably 50 to 100°C.
The pressure is normal pressure to 70 kg/cm 2 , preferably 2 to 60 kg/cm 2 . Although the molecular weight can be adjusted to some extent by changing polymerization conditions such as polymerization temperature and catalyst molar ratio, it is effectively carried out by adding hydrogen to the polymerization system. Of course, using the catalyst of the present invention, a two-step or more multi-step polymerization reaction with different polymerization conditions such as hydrogen concentration and polymerization temperature can be carried out without any problem.
本発明の方法はエチレンを重合するものである
が、エチレンにチグラー触媒で重合できる他のオ
レフイン類を共重合することも可能である。 Although the method of the present invention is for polymerizing ethylene, it is also possible to copolymerize ethylene with other olefins that can be polymerized with a Ziegler catalyst.
以下に実施例をのべるが、これらは本発明を実
施するための説明用のものであつて本発明はこれ
らに制限されるものではない。 Examples will be described below, but these are for illustrative purposes to carry out the present invention, and the present invention is not limited thereto.
実施例 １
(a) 触媒成分の製造
１／２インチ直径を有するステンレススチー
ル製ボールが25コ入つた内容積400mlのステン
レススチール製ポツトに市販の無水塩化マグネ
シウム10ｇ、アルミニウムトリエトキシド1.9
ｇ、および四塩化チタン2.1ｇを入れ窒素雰囲
気下、室温で16時間ボールミリングを行なつ
た。ついでテトラヒドロフラン0.7ｇを加えさ
らに16時間ボールミリングを行なつた。ボール
ミリング後得られた固体粉末１ｇには38mgのチ
タンが含まれていた。Example 1 (a) Preparation of catalyst components 10 g of commercially available anhydrous magnesium chloride and 1.9 g of aluminum triethoxide were placed in a 400 ml stainless steel pot containing 25 1/2 inch diameter stainless steel balls.
g and 2.1 g of titanium tetrachloride were added, and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere. Then, 0.7 g of tetrahydrofuran was added and ball milling was continued for an additional 16 hours. 1 g of solid powder obtained after ball milling contained 38 mg of titanium.
(b) 重 合
２のステンレススチール製誘導撹拌機付き
オートクレーブを窒素置換しヘキサン1000mlを
入れ、トリエチルアルミニウム１ミリモルおよ
び前記の固体粉末10mgを加え撹拌しながら90℃
に昇温した。ヘキサンの蒸気圧で系は２Kg／
cm2．Ｇになるが水素を全圧が5.2Kg／cm2．Ｇに
なるまで張り込み、ついでエチレンを全圧が10
Kg／cm2．Ｇになるまで張り込んで重合を開始し
た。全圧が10Kg／cm2．Ｇになるようにエチレン
を連続的に導入し１時間重合を行なつた。重合
終了後重合体スラリーをビーカーに移し、ヘキ
サンを減圧除去し、メルトインデツクス2.1、
かさ比重0.33の白色ポリエチレン153ｇを得た。
触媒活性は83900ｇポリエチレン／gTi.hr.
C2H4圧、3190ｇポリエチレン／ｇ固体、hr.
C2H4圧でありかさ比重の高いポリエチレンが
きわめて高活性に得られた。またこの重合体を
ASTM―D1238―65Tの方法により190℃で荷
重2.16Kgおよび10Kgのメルトインデツクスを測
定したところ分子量分布の広さを示すFR値は
7.5であり、分子量分布は非常に狭かつた。(b) Polymerization The stainless steel autoclave equipped with an induction stirrer from step 2 was purged with nitrogen, 1000 ml of hexane was added thereto, 1 mmol of triethylaluminum and 10 mg of the above solid powder were added, and the temperature was heated at 90°C with stirring.
The temperature rose to . At the vapor pressure of hexane, the system is 2Kg/
cm2 ． G, but the total pressure of hydrogen is 5.2Kg/cm 2 . G, then add ethylene until the total pressure is 10
Kg/ cm2 . The mixture was tensioned until the temperature reached G and polymerization was started. Total pressure is 10Kg/cm 2 . Ethylene was continuously introduced so that G was obtained, and polymerization was carried out for 1 hour. After polymerization, the polymer slurry was transferred to a beaker, hexane was removed under reduced pressure, and the melt index was 2.1.
153 g of white polyethylene with a bulk specific gravity of 0.33 was obtained.
Catalytic activity is 83900g polyethylene/gTi.hr.
C 2 H 4 pressure, 3190g polyethylene/g solids, hr.
Polyethylene with high bulk specific gravity and C 2 H 4 pressure was obtained with extremely high activity. Also, this polymer
When the melt index was measured at 190℃ with a load of 2.16Kg and 10Kg using the ASTM-D1238-65T method, the FR value, which indicates the breadth of the molecular weight distribution, was
7.5, and the molecular weight distribution was very narrow.
比較例 １
実施例１に記したボールミルポツトに無水塩化
マグネシウム10ｇ、アルミニウムトリエトキシド
2.1ｇ、および四塩化チタン2.0ｇを入れ窒素雰囲
気下、室温で16時間ボールミリングを行なつた。
ボールミリング後得られた固体粉末１ｇには35mg
のチタンが含まれていた。Comparative Example 1 10 g of anhydrous magnesium chloride and aluminum triethoxide were placed in the ball mill pot described in Example 1.
2.1 g of titanium tetrachloride and 2.0 g of titanium tetrachloride were added, and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere.
1g of solid powder obtained after ball milling contains 35mg
contained titanium.
上記の固体粉末10mgを使用し実施例１と同様の
操作で１時間重合を行ないメルトインデツクス
2.0、かさ比重0.30の白色ポリエチレン131ｇを得
た。触媒活性は73800ｇポリエチレン／gTi.hr.
C2H4圧、2730ｇポリエチレン／ｇ固体、hr.C2H4
圧であつた。得られた重合体のFR値は8.3であつ
た。 Using 10 mg of the above solid powder, polymerization was carried out for 1 hour in the same manner as in Example 1 to obtain a melt index.
2.0, and 131 g of white polyethylene with a bulk specific gravity of 0.30 was obtained. Catalytic activity is 73800g polyethylene/gTi.hr.
C 2 H 4 pressure, 2730g polyethylene/g solids, hr.C 2 H 4
It was hot under pressure. The obtained polymer had an FR value of 8.3.
実施例 ２
実施例１に記したボールミルポツトに無水塩化
マグネシウム10ｇへ、アルミニウムトリエトキシ
ド2.2ｇおよび四塩化チタン2.1ｇ入れ窒素雰囲気
下、室温で16時間ボールミリングを行なつた。つ
いでジイソプロピルエーテル0.7ｇを添加してさ
らに窒素雰囲気下、室温で16時間ボールミリング
を行なつた。ボールミリング後得られた固体粉末
１ｇには37mgのチタンが含まれていた。Example 2 10 g of anhydrous magnesium chloride, 2.2 g of aluminum triethoxide and 2.1 g of titanium tetrachloride were placed in the ball mill pot described in Example 1, and ball milling was carried out at room temperature under a nitrogen atmosphere for 16 hours. Then, 0.7 g of diisopropyl ether was added, and ball milling was further carried out at room temperature for 16 hours under a nitrogen atmosphere. 1 g of solid powder obtained after ball milling contained 37 mg of titanium.
上記の固体粉末10mgを使用し実施例１と同様の
操作で１時間重合を行ないメルトインデツクス
1.8、かさ比重0.32の白色ポリエチレン135ｇを得
た。触媒活性は76000ｇポリエチレン／gTi.hr.
C2H4圧、2810ｇポリエチレン／ｇ固体、hr.C2H4
圧であつた。得られた重合体のFR値は7.6であつ
た。 Using 10 mg of the above solid powder, polymerization was carried out for 1 hour in the same manner as in Example 1 to obtain a melt index.
1.8, and 135 g of white polyethylene with a bulk specific gravity of 0.32 was obtained. Catalytic activity is 76000g polyethylene/gTi.hr.
C 2 H 4 pressure, 2810g polyethylene/g solids, hr.C 2 H 4
It was hot under pressure. The obtained polymer had an FR value of 7.6.
実施例 ３
実施例１に記したボールミルポツトに無水塩化
マグネシウム10ｇ、アルミニウムトリエトキシド
2.2ｇおよび四塩化チタン２ｇ入れ窒素雰囲気下、
室温で16時間ボールミリングを行なつた。ついで
ジエチルエーテル0.7ｇを添加してさらに窒素雰
囲気下、室温で16時間ボールミリングを行なつ
た。ボールミリング後得られた固体粉末１ｇには
37mgのチタンが含まれていた。Example 3 10 g of anhydrous magnesium chloride and aluminum triethoxide were placed in the ball mill pot described in Example 1.
2.2g and 2g of titanium tetrachloride under nitrogen atmosphere.
Ball milling was performed at room temperature for 16 hours. Then, 0.7 g of diethyl ether was added, and ball milling was further carried out at room temperature for 16 hours under a nitrogen atmosphere. For 1 g of solid powder obtained after ball milling,
Contains 37mg of titanium.
上記の固体粉末10mgを使用し実施例１と同様の
操作で１時間重合を行ないメルトインデツクス
1.9、かさ比重0.35の白色ポリエチレン168ｇを得
た。触媒活性は94600ｇポリエチレン／gTi.hr.
C2H4圧、3500ｇポリエチレン／ｇ固体、hr.C2H4
圧であつた。得られた重合体のFR値は7.3であつ
た。 Using 10 mg of the above solid powder, polymerization was carried out for 1 hour in the same manner as in Example 1 to obtain a melt index.
168 g of white polyethylene with a bulk specific gravity of 0.35 was obtained. Catalytic activity is 94600g polyethylene/gTi.hr.
C 2 H 4 pressure, 3500g polyethylene/g solids, hr.C 2 H 4
It was hot under pressure. The FR value of the obtained polymer was 7.3.
実施例 ４
実施例１に記したボールミルポツトに無水塩化
マグネシウム10ｇ、ジエトキシアルミニウムモノ
クロリド2.1ｇおよび四塩化チタン２ｇを入れ窒
素雰囲気下、室温で16時間ボールミリングを行な
つた。ついでジエチルエーテル0.7ｇを加えさら
に16時間ボールミリングを行なつた。ボールミリ
ング後得られた固体粉末１ｇには39mgのチタンが
含まれていた。Example 4 10 g of anhydrous magnesium chloride, 2.1 g of diethoxyaluminum monochloride and 2 g of titanium tetrachloride were placed in the ball mill pot described in Example 1, and ball milling was carried out at room temperature under a nitrogen atmosphere for 16 hours. Then, 0.7 g of diethyl ether was added and ball milling was carried out for an additional 16 hours. 1 g of solid powder obtained after ball milling contained 39 mg of titanium.
上記の固体粉末10mgを使用し実施例１と同様の
操作で１時間重合を行ないメルトインデツクス
2.3、かさ比重0.33の白色ポリエチレン179ｇを得
た。触媒活性は95600ｇポリエチレン／gTi.hr.
C2H4圧、3730ｇポリエチレン／ｇ固体、hr.C2H4
圧であつた。得られた重合体のFR値は7.5であつ
た。 Using 10 mg of the above solid powder, polymerization was carried out for 1 hour in the same manner as in Example 1 to obtain a melt index.
2.3, and 179 g of white polyethylene with a bulk specific gravity of 0.33 was obtained. Catalyst activity is 95600g polyethylene/gTi.hr.
C 2 H 4 pressure, 3730g polyethylene/g solids, hr.C 2 H 4
It was hot under pressure. The FR value of the obtained polymer was 7.5.
実施例 ５
実施例１に記したボールミルポツトに無水塩化
マグネシウム10ｇ、アルミニウムトリエトキシド
1.9ｇ、テトラヒドロフラン0.7ｇ、および四塩化
チタン2.1ｇを入れ窒素雰囲気下、室温で16時間
ボールミリングを行なつた。ボールミリング後得
られた固体粉末１ｇには37mgのチタンが含まれて
いた。Example 5 10 g of anhydrous magnesium chloride and aluminum triethoxide were placed in the ball mill pot described in Example 1.
1.9 g of titanium tetrachloride, 0.7 g of tetrahydrofuran, and 2.1 g of titanium tetrachloride were added, and ball milling was performed at room temperature for 16 hours under a nitrogen atmosphere. 1 g of solid powder obtained after ball milling contained 37 mg of titanium.
上記の固体粉末10mgを使用し実施例１と同様の
操作で１時間重合を行ないメルトインデツクス
2.1、かさ比重0.31の白色ポリエチレン144ｇを得
た。触媒活性は81100ｇポリエチレンgTi.hr.
C2H4圧、3000ｇポリエチレン／ｇ固体、hr.C2H4
圧であつた。得られた重合体のFR値は7.7であつ
た。 Using 10 mg of the above solid powder, polymerization was carried out for 1 hour in the same manner as in Example 1 to obtain a melt index.
2.1, and 144 g of white polyethylene with a bulk specific gravity of 0.31 was obtained. Catalytic activity is 81100g polyethylene gTi.hr.
C 2 H 4 pressure, 3000g polyethylene/g solids, hr.C 2 H 4
It was hot under pressure. The obtained polymer had an FR value of 7.7.
実施例 ６
２ステンレススチール製誘導撹拌機付きオー
トクレーブを窒素置換し乾燥した高密度ポリエチ
レンペレツト50ｇを入れ、ついで実施例１で使用
した触媒成分20mg、およびトリエチルアルミニウ
ム１ミリモルを加え、撹拌しながら80℃まで加温
した。つぎに水素を３Kg／cm2・Ｇになるまでフイ
ードし、ついでエチレン、およびブテン―１をフ
イードして全圧を８Kg／cm2・Ｇになるように保ち
ながら重合を行なつた。このときオートクレーブ
中のブテン―１とエチレンのモル比を0.11になる
ようにコントロールした。重合を２時間行なつた
のち生成重合体、およびペレツトの混合物を回収
し、ふるい分けして生成重合体を得た。生成重合
体のメルトインデツクスは1.8、密度は0.9302で
あり、FR値は7.1できわめて分布の狭いものであ
つた。Example 6 2 Into a stainless steel autoclave equipped with an induction stirrer, 50 g of dried high-density polyethylene pellets was placed under nitrogen atmosphere, and then 20 mg of the catalyst component used in Example 1 and 1 mmol of triethylaluminum were added, and the mixture was heated to 80 g with stirring. Warmed to ℃. Next, hydrogen was fed until the pressure reached 3 kg/cm 2 ·G, and then ethylene and butene-1 were fed to carry out polymerization while maintaining the total pressure at 8 kg/cm 2 ·G. At this time, the molar ratio of butene-1 and ethylene in the autoclave was controlled to be 0.11. After polymerization was carried out for 2 hours, a mixture of the produced polymer and pellets was collected and sieved to obtain the produced polymer. The produced polymer had a melt index of 1.8, a density of 0.9302, and an FR value of 7.1, with an extremely narrow distribution.
実施例 ７
実施例１において、四塩化チタン2.1ｇに代え
て、モノブトキシトリクロロチタン2.4ｇを用い
たことを除いては実施例１と同様の操作で触媒成
分を合成し、固体粉末１ｇ当たり37mgのチタンを
含有する固体粉末を得た。Example 7 A catalyst component was synthesized in the same manner as in Example 1, except that 2.4 g of monobutoxytrichlorotitanium was used instead of 2.1 g of titanium tetrachloride, and 37 mg per 1 g of solid powder was synthesized. A solid powder containing titanium was obtained.
上記の固体粉末10mgを使用し、実施例１と同様
の操作で１時間重合を行いメルトインデツクス
2.3、かさ比重0.35の白色ポリエチレン135ｇを得
た。触媒活性は76000ｇポリエチレン／gTi.hr.
C2H4圧、2810ｇポリエチレン／ｇ固体．hr.C2H4
圧であり、かさ比重の高いポリエチレンがきわめ
て高活性に得られた。また、この重合体のF.R.値
は7.3であり、分子量分布は非常に狭かつた。 Using 10 mg of the above solid powder, polymerization was carried out for 1 hour in the same manner as in Example 1, and the melt index was
2.3, and 135 g of white polyethylene with a bulk specific gravity of 0.35 was obtained. Catalytic activity is 76000g polyethylene/gTi.hr.
C 2 H 4 pressure, 2810g polyethylene/g solids. hr.C 2 H 4
Polyethylene with high bulk specific gravity and extremely high activity was obtained. Furthermore, the FR value of this polymer was 7.3, and the molecular weight distribution was extremely narrow.
実施例 ８
実施例１において、四塩化チタン2.1ｇに代え
て、四塩化チタン2.1ｇおよびVO（OC2H5）30.5ｇ
を用いたことを除いては実施例１と同様の操作で
触媒成分を合成し、固体粉末１ｇ当たりのチタン
および９mgのバナジウムを含有する固体粉末を得
た。Example 8 In Example 1, 2.1 g of titanium tetrachloride and 0.5 g of VO(OC 2 H 5 ) 3 were used instead of 2.1 g of titanium tetrachloride.
A catalyst component was synthesized in the same manner as in Example 1, except that a solid powder containing titanium and 9 mg of vanadium per gram of solid powder was obtained.
上記の固体粉末10mgを使用し、実施例１と同様
の操作で１時間重合を行いメルトインデツクス
2.2、かさ比重0.36の白色ポリエチレン126ｇを得
た。触媒活性は71000ｇポリエチレン／gTi・hr.
C2H4圧、2630ｇポリエチレン／ｇ固体．hr.C2H4
圧であり、かさ比重の高いポリエチレンが極めて
高活性に得られた。また、この重合体のF.R.値は
7.3であり、分子量分布は非常に狭かつた。 Using 10 mg of the above solid powder, polymerization was carried out for 1 hour in the same manner as in Example 1, and the melt index was
2.2, and 126 g of white polyethylene with a bulk specific gravity of 0.36 was obtained. Catalytic activity is 71000g polyethylene/gTi・hr.
C 2 H 4 pressure, 2630g polyethylene/g solids. hr.C 2 H 4
Polyethylene with high bulk specific gravity and extremely high activity was obtained. Also, the FR value of this polymer is
7.3, and the molecular weight distribution was very narrow.
第１図は本発明のオレフイン重合における触媒
調製の一例を示すフローチヤート図面である。
FIG. 1 is a flowchart showing an example of catalyst preparation in olefin polymerization of the present invention.
Claims (1)
とバナジウム化合物を担持せしめた成分と有機ア
ルミニウム化合物とを触媒としてエチレンを重合
してポリオレフインを製造する方法において、該
固体担体が (1) ジハロゲン化マグネシウム、 (2) 一般式Al（OR）oX3-o（ここでＲは炭素数１〜
24のアルキル基、アリール基及び／又はアラル
キル基、Ｘはハロゲン原子を示す。ｎは０＜ｎ
≦３である）で表わされる化合物および (3) エーテル化合物 を共粉砕することにより得られる物質からなるこ
とを特徴とするポリオレフインの製造方法。[Claims] 1. A method for producing polyolefin by polymerizing ethylene using a component in which a titanium compound or a titanium compound and a vanadium compound are supported on a solid carrier and an organic aluminum compound as a catalyst, wherein the solid carrier comprises (1) Magnesium dihalide, (2) General formula Al (OR) o X 3-o (where R has 1 to 1 carbon atoms
24 alkyl, aryl and/or aralkyl groups; X represents a halogen atom; n is 0<n
≦3) and (3) an ether compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10511880A JPS5730709A (en) | 1980-08-01 | 1980-08-01 | Preparation of polyolefin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10511880A JPS5730709A (en) | 1980-08-01 | 1980-08-01 | Preparation of polyolefin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5730709A JPS5730709A (en) | 1982-02-19 |
| JPS6410526B2 true JPS6410526B2 (en) | 1989-02-22 |
Family
ID=14398897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10511880A Granted JPS5730709A (en) | 1980-08-01 | 1980-08-01 | Preparation of polyolefin |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5730709A (en) |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55116905A (en) * | 1978-08-25 | 1980-09-08 | Errut Prod Ltd | Flat cutting device |
-
1980
- 1980-08-01 JP JP10511880A patent/JPS5730709A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5730709A (en) | 1982-02-19 |
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