JPH0135843B2 - - Google Patents
Info
- Publication number
- JPH0135843B2 JPH0135843B2 JP56170820A JP17082081A JPH0135843B2 JP H0135843 B2 JPH0135843 B2 JP H0135843B2 JP 56170820 A JP56170820 A JP 56170820A JP 17082081 A JP17082081 A JP 17082081A JP H0135843 B2 JPH0135843 B2 JP H0135843B2
- Authority
- JP
- Japan
- Prior art keywords
- titanium
- particle size
- compound
- mgo
- solid
- 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 organic acid esters Chemical class 0.000 claims description 37
- 239000002245 particle Substances 0.000 claims description 34
- 229910052749 magnesium Inorganic materials 0.000 claims description 32
- 239000011777 magnesium Substances 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 19
- 150000001336 alkenes Chemical class 0.000 claims description 13
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 230000000737 periodic effect Effects 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000002685 polymerization catalyst Substances 0.000 claims description 7
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 6
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 150000002170 ethers Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 33
- 239000000843 powder Substances 0.000 description 24
- 239000007787 solid Substances 0.000 description 19
- 239000010936 titanium Substances 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 17
- 150000003609 titanium compounds Chemical class 0.000 description 17
- 229910052719 titanium Inorganic materials 0.000 description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 15
- 239000007795 chemical reaction product Substances 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 14
- 150000003682 vanadium compounds Chemical class 0.000 description 14
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 13
- 230000005484 gravity Effects 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000011949 solid catalyst Substances 0.000 description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 11
- 238000007334 copolymerization reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 235000012245 magnesium oxide Nutrition 0.000 description 7
- 239000000155 melt Substances 0.000 description 7
- 150000002902 organometallic compounds Chemical class 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- JPUHCPXFQIXLMW-UHFFFAOYSA-N aluminium triethoxide Chemical compound CCO[Al](OCC)OCC JPUHCPXFQIXLMW-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000011343 solid material Substances 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002430 hydrocarbons Chemical group 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 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 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N Octyl butanoate Chemical compound CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- MMXKVMNBHPAILY-UHFFFAOYSA-N ethyl laurate Chemical compound CCCCCCCCCCCC(=O)OCC MMXKVMNBHPAILY-UHFFFAOYSA-N 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides 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
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 239000005049 silicon tetrachloride Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- UBZYKBZMAMTNKW-UHFFFAOYSA-J titanium tetrabromide Chemical compound Br[Ti](Br)(Br)Br UBZYKBZMAMTNKW-UHFFFAOYSA-J 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 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
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- AWFYPPSBLUWMFQ-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,6,7-tetrahydropyrazolo[4,3-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)NN=C2 AWFYPPSBLUWMFQ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-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
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- BDBNCVOMHKVOST-UHFFFAOYSA-K CCCCCO[Ti](Cl)(Cl)Cl Chemical compound CCCCCO[Ti](Cl)(Cl)Cl BDBNCVOMHKVOST-UHFFFAOYSA-K 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
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- FXTTXRHGRZVUAG-UHFFFAOYSA-N P.Cl.Cl.Cl.Cl.Cl Chemical compound P.Cl.Cl.Cl.Cl.Cl FXTTXRHGRZVUAG-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-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
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 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
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- DEFMLLQRTVNBOF-UHFFFAOYSA-K butan-1-olate;trichlorotitanium(1+) Chemical compound [Cl-].[Cl-].[Cl-].CCCCO[Ti+3] DEFMLLQRTVNBOF-UHFFFAOYSA-K 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- LKRBKNPREDAJJQ-UHFFFAOYSA-M chloro-di(propan-2-yl)alumane Chemical compound [Cl-].CC(C)[Al+]C(C)C LKRBKNPREDAJJQ-UHFFFAOYSA-M 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- UFCXHBIETZKGHB-UHFFFAOYSA-N dichloro(diethoxy)silane Chemical compound CCO[Si](Cl)(Cl)OCC UFCXHBIETZKGHB-UHFFFAOYSA-N 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- BEPAFCGSDWSTEL-UHFFFAOYSA-N dimethyl malonate Chemical compound COC(=O)CC(=O)OC BEPAFCGSDWSTEL-UHFFFAOYSA-N 0.000 description 1
- 150000002027 dodecanoic acid esters Chemical class 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 150000002148 esters Chemical class 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
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- NGAZZOYFWWSOGK-UHFFFAOYSA-N heptan-3-one Chemical compound CCCCC(=O)CC NGAZZOYFWWSOGK-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002680 magnesium 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
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 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
- 235000012254 magnesium hydroxide Nutrition 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
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical class [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 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
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method 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
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- BIEFSHWAGDHEIT-UHFFFAOYSA-J tetrabromovanadium Chemical compound [V+4].[Br-].[Br-].[Br-].[Br-] BIEFSHWAGDHEIT-UHFFFAOYSA-J 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 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
- ZLMGMVJGEULFPP-UHFFFAOYSA-J titanium(4+) trichloride phenoxide Chemical compound Cl[Ti](Cl)(Cl)OC1=CC=CC=C1 ZLMGMVJGEULFPP-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
- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 description 1
- YZVRVDPMGYFCGL-UHFFFAOYSA-N triacetyloxysilyl acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)OC(C)=O YZVRVDPMGYFCGL-UHFFFAOYSA-N 0.000 description 1
- ULIAPOFMBCCSPE-UHFFFAOYSA-N tridecan-7-one Chemical compound CCCCCCC(=O)CCCCCC ULIAPOFMBCCSPE-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
- RTAKQLTYPVIOBZ-UHFFFAOYSA-N tritert-butylalumane Chemical compound CC(C)(C)[Al](C(C)(C)C)C(C)(C)C RTAKQLTYPVIOBZ-UHFFFAOYSA-N 0.000 description 1
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Description
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äœã®èª¿è£œæ³ã«é¢ãããDETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a carrier for an olefin polymerization catalyst. In particular, the present invention relates to a method for preparing a carrier suitable for producing a polyolefin with good powder flowability.
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æãŸããŠããã Conventionally, in this type of technical field, many catalysts are known in which compounds of transition metals such as titanium or vanadium are supported on inorganic magnesium solids such as magnesium halides, magnesium oxides, and magnesium hydroxides. . However, in these known techniques, the obtained polymer particles generally have a small bulk specific gravity, a small average particle size, and a generally wide particle size distribution, so they have a large particulate powder portion, which reduces productivity and slurry. Improvements were strongly desired in terms of handling. Furthermore, when molding these polymers, problems such as generation of dust and reduction in efficiency during molding occur, so the above-mentioned increase in bulk specific gravity,
It was strongly desired to increase the average particle size and reduce the particulate powder portion.
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ããã®ã§ããã The present invention improves the above-mentioned drawbacks and provides a highly effective catalyst carrier that makes it possible to obtain a polymer with high bulk specific gravity, narrow particle size distribution, and excellent powder flowability with significantly less fine particulate portions of the polymer. It provides:
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ããããšãã§ããã That is, the present invention uses a liquid medium that dissolves a substance containing at least one component of magnesium dihalide (hereinafter abbreviated as magnesium halide) and that contains an oxide of a metal of group ~~ of the periodic table.
By gradually adding a saturated hydrocarbon (hereinafter referred to as an organic liquid compound) to at least one liquid medium selected from alcohols, organic acid esters, ketones, and ethers while maintaining the temperature at 10°C or less. The present invention relates to a method for producing a carrier for an olefin polymerization catalyst, which comprises depositing a carrier made of a substance having a precipitated particle size of 5 Όm or more. A titanium compound and/or a titanium compound and/or
Or, when olefin polymerization or copolymerization is carried out using a catalyst that combines a solid catalyst component supported with a vanadium compound and an organometallic compound,
The polymer yield per solid and the polymer yield per transition metal are significantly increased, thereby eliminating the need for a step for removing catalyst residues in the resulting polymer, and the resulting polymer powder has a high bulk specific gravity. It has a narrow particle size distribution, less particulate powder, good powder fluidity, and is not only easy to handle during polymerization operations but also has few troubles during molding, making it possible to produce polyolefins extremely advantageously. .
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åŸã€ãŠç²æ«æµåæ§ãããããŠè¯å¥œãšãªãã The present inventors previously filed a patent application for the case in which oxides of metals from Groups ~ of the periodic table do not coexist, but in the case of the present invention in which oxides of metals from Groups ~ of the periodic table coexist. The formation of irregularly shaped fine powder in the produced polymer is further reduced, the particle size distribution is further narrowed, and the bulk specific gravity is further improved.
Therefore, the powder fluidity is also extremely good.
以äžã«æ¬çºæã詳述ããã The present invention will be explained in detail below.
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液äœåªäœã«æº¶è§£ãããã In preparing the olefin polymerization catalyst carrier of the present invention, first, a substance containing at least one component of magnesium halide is dissolved in an organic liquid medium in which the substance can be dissolved.
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ããã The organic liquid medium for dissolving the substance containing at least one component of magnesium halide used at this time includes alcohols, esters, ethers, and ketones. Preferred specific examples include methanol, ethanol, and isopropanol. , butanol, pentanol, hexanol,
Alcohols such as octanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, methyl formate, ethyl formate, methyl acetate, ethyl acetate, butyl acetate, vinyl acetate, methyl acrylate, methyl methacrylate, octyl butyrate, ethyl laurate, lauric acid Esters such as octyl, methyl benzoate, ethyl benzoate, octyl paraoxybenzoate, dibutyl phthalate, dioctyl phthalate, dimethyl malonate, dimethyl maleate, diethyl maleate, dimethyl ether,
Examples include ethers such as diethyl ether, diisopropyl ether, dibutyl ether, diamyl ether, tetrahydrofuran, dioxane, and anisole, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone, dihexyl ketone, acetophenone, diphenyl ketone, and cyclohexanone. be able to.
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ã§ããã The substance containing magnesium halide as at least one component used in the present invention refers to magnesium halide or magnesium halide and another substance.
It is a reaction product with more than one kind of compound or a mixture thereof.
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ãã°ãã·ãŠã ã奜ãŸããã Magnesium halides include magnesium fluoride, magnesium chloride, magnesium bromide and magnesium iodide, with magnesium chloride being particularly preferred.
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äœãæ¬çºæã«ãããŠçšããããšãã§ããã Various known magnesium halide-containing carriers are used as the reaction product of magnesium halide and one or more other compounds. Specific examples of these include magnesium halide and Si
(OR) Reaction product with n X 4-n , Reaction product between magnesium halide and B(OR) o X 3-o , Reaction product between magnesium halide and Al(OR) o X 3-o , Halogen Reaction product of magnesium chloride and AlOX, reaction product of magnesium halide and compound having Al-O-C bond, reaction product of magnesium halide and aluminum chloride or aluminum chloride ether complex, magnesium halide and pentachloride Phosphorus, reaction product with phosphorus trichloride or phosphorus oxytrichloride, magnesium halide and dichloroethane,
Reaction products with organic halides such as trichlorobenzene, reaction products between magnesium halide and titanium oxyhalide, reaction products between magnesium halide and Si(OR) n X 4-n and Al(OR) o X 3-o reactant,
Magnesium halide, silicon tetrachloride and ROH
(In the formula,
R is a hydrocarbon residue having 1 to 20 carbon atoms, X is a halogen, and 0âŠmâŠ4, 0<nâŠ3). of course,
Other known halogenated magnesium-containing carriers can also be used in the present invention.
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奜ãŸããçšããããã There are no particular restrictions on the operation and conditions for dissolving the substance containing magnesium halide as at least one component, and the dissolution may be carried out, for example, at room temperature or by heating as appropriate. Although the concentration of the solution can be selected within a wide range, a range of 1 to 30% by weight is usually preferably used.
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溶解ãåŸãææ©æ¶²ç¶åªäœäžã§åå¿ãããŠãããã When using a reaction product of magnesium halide and another compound, these may be reacted in advance and then dissolved, or the reaction may be performed in an organic liquid medium in which the magnesium halide can be dissolved.
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ãã溶解æãããã¯æº¶è§£åŸã«æ·»å ããŠãããã There is no particular restriction on the timing of incorporating the oxide of a metal of group ~~ of the periodic table into the organic liquid medium. Alternatively, it may be added after dissolution.
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ãããšãã§ããããç¹ã«SiO2ãAl2O3ãSiO2ã»
Al2O3ãMgOã»Al2O3ã奜ãŸããã The oxides of groups 1 to 2 of the periodic table used in the present invention may be not only oxides of individual metals of groups 1 to 1 of the periodic table, but also double oxides of these metals, and of course may be mixtures thereof. Specific examples of these metal oxides include MgO, CaO,
ZnO , BaO2 , Ba2O3 , SiO2 , SnO3 , Al2O3 ,
MgOã»Al 2 O 3 , SiO 2ã»Al 2 O 3 , MgOã»SiO 2 ,
Examples include MgOã»CaOã»Al 2 O 3 , Al 2 O 3ã»CaO, etc., but especially SiO 2 , Al 2 O 3 , SiO 2ã»
Al 2 O 3 and MgO.Al 2 O 3 are preferred.
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å æ³ãããã§ãã€ãŠãããã The proportion of these metal oxides is 10g of a substance containing at least one component of magnesium halide.
The amount ranges from 0.1 to 500 g, preferably from 1 to 100 g, and more preferably from 2 to 50 g. The thus obtained substance containing at least one component of magnesium halide is dissolved in a liquid medium containing an oxide of a metal from Groups 1 to 10 of the Peripheral Table at temperatures below 10°C, for example from -80 to 10°C, preferably from -80°C to The temperature is maintained at 0°C, more preferably between -80°C and -20°C. Next, an organic liquid compound in which magnesium halide does not dissolve is gradually added to the liquid medium maintained at 10°C or lower. The organic liquid compound used at this time is
Various saturated hydrocarbon compounds such as pentane, hexane, heptane, octane, etc. are used. As for the rate of addition of the organic liquid compound, it is desirable to add it as slowly as possible, and by adding it as slowly as possible, a solid substance with a large particle size can be precipitated. Usually, a solution 1 containing a substance containing at least one component of magnesium halide
50 g or more, for example 50 to 5000 g, preferably 500 to 5000 g, of an organic liquid compound in which magnesium halide does not dissolve is added over 10 minutes or more, preferably 1 hour or more, for example 1 to 10 hours. As for the addition rate, it is desirable that the amount of organic liquid compound added per minute to solution 1 is 50 g or less, preferably 10 g or less, and most preferably 5 g or less. The addition method is not particularly limited and may be either a continuous addition method or a continuous addition method.
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ããã Among the solid substances thus precipitated, those with small particle sizes are not preferred, and those with a particle size of 5 ÎŒm or more are used as the carrier for the olefin polymerization catalyst targeted by the present invention. Particularly preferred is one of 10ÎŒ or more.
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±éåçšã®è§ŠåªãšããŠçšããã A titanium compound and/or a vanadium compound is supported on the carrier of the present invention thus prepared, and used in combination with an organometallic compound as a catalyst for polymerization or copolymerization of olefin.
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ãªãã10æéã®åŠçæéããããããšãã§ããã A method for supporting the titanium compound and/or vanadium compound on the carrier of the present invention includes, for example, bringing the carrier of the present invention into contact with the titanium compound and/or vanadium compound under heating in the presence or absence of an inert solvent. This can be done by combining both, preferably in the absence of a solvent.
This is carried out by heating to 50-300°C, preferably 100-150°C. Although the reaction time is not particularly limited, it is usually 5 minutes or more, and long-term contact may be allowed, although it is not necessary. For example, processing times can range from 5 minutes to 10 hours.
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ããšãéåžžè¡ãªãããã Titanium compound and/or used in the present invention
Alternatively, the amount of the vanadium compound may be used in excess, but it can usually be used in an amount of 0.001 to 50 times the weight of magnesium halide. Preferably, excess titanium compound and/or vanadium compound is removed by washing with a solvent after the mixing and heating treatment. After completion of the reaction, the means for removing the terminally reacted titanium compound and/or vanadium compound is not particularly limited, and may include washing the Ziegler catalyst several times with a solvent inert to the catalyst and evaporating the washing liquid under reduced pressure to obtain a solid powder. is usually done.
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ã®ç¯å²ããšãã«æãŸããã In addition, the amount of the titanium compound and/or vanadium compound to be supported is such that the titanium and/or vanadium content contained in the produced solid is 0.5 to 20.
It is most preferable to adjust the amount within a range of 1 to 10% by weight, and in order to obtain well-balanced activity per titanium and/or vanadium and activity per solid, a range of 1 to 10% by weight is particularly desirable.
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ãæããããã Examples of the titanium compound and/or vanadium compound used in the present invention include halides, alkoxy halides, alkoxides, and halogenated oxides of titanium and/or vanadium. 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, aryl or aralkyl groups;
X represents a halogen atom. n is 0âŠnâŠ4. ) is preferable, titanium tetrachloride,
Titanium tetrabromide, titanium tetraiodide, monomethoxytrichlorotitanium, dimethoxydichlorotitanium, trimethoxymonochlorotitanium, tetramethoxytitanium, monoethoxytrichlorotitanium, diethoxydichlorotitanium, triethoxymonochlorotitanium, tetraethoxytitanium, monoisopropoxy Trichlorotitanium, diisopropoxydichlorotitanium, triisopropoxymonochlorotitanium, tetraisopropoxytitanium, monobutoxytrichlorotitanium, dibutoxydichlorotitanium, monopentoxytrichlorotitanium, monophenoxytrichlorotitanium, diphenoxydichlorotitanium, triphenoxytitanium Examples include cymonochlorotitanium 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. It will be done. Also, the general formula Ti(OR) n X 4-n (where R
represents an alkyl group, aryl group or aralkyl group having 1 to 20 carbon atoms, 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, and tetraethoxyvanadium; Examples include trivalent vanadium compounds such as trivalent vanadium compounds, vanadium trichloride, and vanadium triethoxide.
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ãšãã§ããã As the organometallic compound used in the present invention, organometallic compounds of groups 1 to 10 of the periodic table, which are known as components of Ziegler's catalyst, can be used, but organoaluminum compounds and organozinc compounds are particularly preferred. Specific examples include the general formula R 3 Al,
R 2 AlX, RAlX 2 , R 2 AlOR, RAl(OR)X and
Organoaluminum compound of R 3 Al 2 2 Zn (however, R is an alkyl group having 1 to 20 carbon atoms and may be the same or different), and is represented by an organic zinc compound of triethylaluminum,
triisopropylaluminium, triisobutylaluminum, trisec-butylaluminum,
Examples include tri-tert-butylaluminum, trihexylaluminum, trioctylaluminum, diethylaluminum chloride, diisopropylaluminum chloride, ethylaluminum sesquichloride, diethylzinc, and mixtures thereof. The amount of the organometallic compound to be used is not particularly limited, but it can usually be used in an amount of 0.1 to 1000 times the amount of the titanium compound and/or vanadium compound.
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枩床ã觊åªã®ã¢ã«æ¯ãªã©ã®éåæ¡ä»¶ãå€ããããš
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ã®å€æ®µéã®éååå¿ãäœãæ¯éãªãå®æœã§ããã 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.
â, and 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.
æ¬çºæã®æ¹æ³ã¯ãã°ã©ãŒè§Šåªã§éåã§ãããã¹
ãŠã®ãªã¬ãã€ã³ã®éåã«é©çšå¯èœã§ãããç¹ã«ç
çŽ æ°ïŒã12ã®Î±âãªã¬ãã€ã³ã奜ãŸãããããšã
ã°ãšãã¬ã³ããããã¬ã³ãïŒâããã³ãããã»ã³
âïŒãïŒâã¡ãã«ãã³ãã³âïŒããªã¯ãã³âïŒãª
ã©ã®Î±âãªã¬ãã€ã³é¡ã®åç¬éåããã³ãšãã¬ã³
ãšãããã¬ã³ããšãã¬ã³ãšïŒâããã³ããšãã¬ã³
ãšããã»ã³âïŒããšãã¬ã³ãšïŒâã¡ãã«ãã³ãã³
âïŒããšãã¬ã³ãšãªã¯ãã³âïŒããããã¬ã³ãšïŒ
âããã³ã®å
±éåãªã©ã«å¥œé©ã«äœ¿çšãããã The method of the present invention is applicable to the polymerization of all olefins that can be polymerized with Ziegler's catalyst, and α-olefins having 2 to 12 carbon atoms are particularly preferred, such as ethylene, propylene, 1-butene, hexene-1,4-methyl Homopolymerization of α-olefins such as pentene-1 and octene-1, and ethylene and propylene, ethylene and 1-butene, ethylene and hexene-1, ethylene and 4-methylpentene-1, ethylene and octene-1, propylene and 1
- Suitable for use in copolymerization of butene, etc.
ãŸããããªãªã¬ãã€ã³ã®æ¹è³ªãç®çãšããå Žå
ã®ãžãšã³ãšã®å
±éåã奜ãŸããè¡ãããããã®æ
䜿çšããããžãšã³ååç©ã®äŸãšããŠã¯ãã¿ãžãš
ã³ãïŒïŒïŒâãããµãžãšã³ããšããªãã³ãã«ãã«
ãã³ããžã·ã¯ããã³ã¿ãžãšã³çãæããããšãã§
ããã Copolymerization with dienes is also preferably carried out for the purpose of modifying polyolefins. Examples of diene compounds used at this time include butadiene, 1,4-hexadiene, ethylidenenorbornene, dicyclopentadiene, and the like.
以äžã«å®æœäŸãã®ã¹ããããããã¯æ¬çºæãå®
æœããããã®èª¬æçšã®ãã®ã§ãã€ãŠæ¬çºæã¯ãã
ãã«å¶éããããã®ã§ã¯ãªãã 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.
å®æœäŸ ïŒ
(a) æ
äœã®èª¿è£œ
ç¡æ°Žã®å¡©åãã°ãã·ãŠã 10ïœãã¢ã«ãããŠã
ããªãšããã·ãïŒïœããã³äºé
žåã±ã€çŽ 10ïœã
ããã©ããããã©ã³200mläžã«å ãã100âã§ïŒ
æéå ç±ããåŸãâ60âã«ä¿ã¡ããããµã³200ml
ãæ¹æäžã«30åãããŠåŸã
ã«æ·»å ããŠåºäœç©è³ª
ãæåºãããã次ã«ãäžæŸã¿æ¶²ãé€å»ããã®
ã¡ãæžå§äžã«100âã§ïŒæé也ç¥ãè¡ããå¹³å
ç²åŸ60ÎŒã®åºäœåŠäœãåŸããExample 1 (a) Preparation of carrier 10 g of anhydrous magnesium chloride, 5 g of aluminum triethoxide and 10 g of silicon dioxide were added to 200 ml of tetrahydrofuran and heated at 100°C for 10 g.
After heating for an hour, keep at -60â and 200ml of hexane.
was gradually added over 30 minutes with stirring to precipitate a solid material. Next, after removing the supernatant liquid, drying was performed at 100° C. for 1 hour under reduced pressure to obtain a solid carrier having an average particle size of 60 Όm.
(b) 觊åªæåã®è£œé
åèšã®åºäœæ
äœïŒïœããã³åå¡©åãã¿ã³0.5
mlããããµã³40mläžã«å ãããããµã³éæµäžã«
ïŒæéåå¿ãè¡ã€ãã次ã«äžæŸã¿æ¶²ãé€å»ãã
ã®ã¡ãæŽæ¶²ã«åå¡©åãã¿ã³ãæ€åºãããªããªã
ãŸã§ãããµã³ã§æŽæµãç¹°ãè¿ããåºäœè§Šåªæå
ãåŸããåºäœè§ŠåªæåïŒïœåœããã«ã¯22mgã®ã
ã¿ã³ãå«ãŸããŠããã(b) Production of catalyst components 2 g of the above solid support and 0.5 titanium tetrachloride
ml was added to 40 ml of hexane, and the reaction was carried out for 1 hour under reflux of hexane. Next, after removing the supernatant liquid, washing was repeated with hexane until no titanium tetrachloride was detected in the washing liquid, thereby obtaining a solid catalyst component. Each gram of solid catalyst component contained 22 mg of titanium.
(c) éå
æ°çžéåè£
眮ãšããŠã¯ã¹ãã³ã¬ã¹è£œãªãŒãã¯
ã¬ãŒããçšããããã¯ãŒãæµé調ç¯åšããã³ä¹Ÿ
åŒãµã€ã¯ãã³ã§ã«ãŒããã€ããããªãŒãã¯ã¬ãŒ
ãã¯ãžã€ã±ããã«æž©æ°Žãæµãããšã«ãã枩床ã
調ç¯ããã(c) Polymerization A stainless steel autoclave was used as the gas phase polymerization apparatus, a loop was created with a blower, a flow rate regulator, and a dry cyclone, and the temperature of the autoclave was adjusted by flowing hot water through the jacket.
80âã«èª¿ç¯ãããªãŒãã¯ã¬ãŒãã«äžèšåºäœè§Š
åªæåã50mgïŒhrãããã³ããªãšãã«ã¢ã«ãã
ãŠã ãïŒïœmolïŒhrã®é床ã§äŸçµŠãããŸãããª
ãŒãã¯ã¬ãŒãæ°çžäžã®ããã³âïŒïŒãšãã¬ã³æ¯
ïŒã¢ã«æ¯ïŒã0.28ã«ãããã«æ°ŽçŽ ãå
šå§ã®15ïŒ
ãšãªãããã«èª¿æŽããªããåã
ã®ã¬ã¹ãäŸçµŠ
ãããã€ããã¯ãŒã«ããç³»å
ã®ã¬ã¹ã埪ç°ãã
ãŠå
šå§ã10KgïŒcm2ã»ïŒ§ã«ä¿ã€ããã«ããŠéåã
è¡ãªã€ããçæãããšãã¬ã³å
±éåäœã¯ããæ¯
é0.40ãã¡ã«ãã€ã³ããã¯ã¹ïŒMIïŒ0.85ãå¯åºŠ
0.9211ã§ãã€ãã The above solid catalyst component was fed to an autoclave adjusted to 80°C at a rate of 50 mg/hr and triethylaluminum at a rate of 5 mmol/hr, and the butene-1/ethylene ratio (molar ratio) in the gas phase of the autoclave was set to 0.28. Furthermore, hydrogen is added to 15% of the total pressure.
Polymerization was carried out by supplying each gas while adjusting the following, and by circulating the gas in the system using a blower to maintain the total pressure at 10 kg/cm 2 ·G. The produced ethylene copolymer has a bulk specific gravity of 0.40, a melt index (MI) of 0.85, and a density
It was 0.9211.
ãŸã觊åªæŽ»æ§ã¯341000ïœå
±éåäœïŒïœTiãš
ããããŠé«æŽ»æ§ã§ãã€ãã Furthermore, the catalyst activity was extremely high at 341,000 g copolymer/g Ti.
10æéã®é£ç¶é転ã®ã®ã¡ãªãŒãã¯ã¬ãŒãã解
æŸããå
éšã®ç¹æ€ãè¡ãªã€ããå
å£ããã³æ¹æ
æ©ã«ã¯å
šãããªããŒã¯ä»çããŠããããããã
ã§ãã€ãã After 10 hours of continuous operation, the autoclave was opened and the interior was inspected, but the inner walls and stirrer were clean with no polymer attached at all.
åŸãããããªããŒç²æ«ã®å¹³åç²åŸã¯1000ÎŒãš
倧ããããŸããç²åŸ200Ό以äžã®åŸ®ç²ã¯0.2ïŒ
ãš
å°ãªãã€ãã The average particle size of the obtained polymer powder was as large as 1000ÎŒ, and the amount of fine powder with a particle size of 200ÎŒ or less was as low as 0.2%.
å®æœäŸ ïŒ
ç¡æ°Žå¡©åãã°ãã·ãŠã 10ïœãã¢ã«ãããŠã ããª
ãšããã·ãïŒïœãããã©ãšããã·ã·ã©ã³ïŒïœãã
ã³äºé
žåã±ã€çŽ 10ïœãé
¢é
žãšãã«200mläžã«å ã
100âã§ïŒæéå ç±ããåŸãâ30âã«ä¿ã¡ããããµ
ã³200mlãæ¹æäžã«30åãããŠåŸã
ã«æ·»å ããŠåº
äœç©è³ªãæåºãããå¹³åç²åŸ55ÎŒã®åºäœæ
äœãåŸ
ããExample 2 10 g of anhydrous magnesium chloride, 3 g of aluminum triethoxide, 2 g of tetraethoxysilane and 10 g of silicon dioxide were added to 200 ml of ethyl acetate.
After heating at 100°C for 1 hour, the temperature was maintained at -30°C, and 200ml of hexane was gradually added over 30 minutes with stirring to precipitate a solid substance, thereby obtaining a solid support with an average particle size of 55Ό.
äžèšåºäœæ
äœãçšããããšãé€ããŠã¯ãå®æœäŸ
ïŒãšåæ§ã®æ¹æ³ã§åºäœè§ŠåªæåïŒãã¿ã³æ
æéïŒ
25mgïŒïœïŒã補é ããå®æœäŸïŒãšåæ§ã®æ¹æ³ã§ãš
ãã¬ã³ãšããã³âïŒã®å
±éåãè¡ã€ãã The solid catalyst component (amount of titanium supported:
25 mg/g) and copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1.
çæå
±éåäœã¯ãããæ¯é0.42ãã¡ã«ãã€ã³ã
ãã¯ã¹0.72ãå¯åºŠ0.9206ã§ããããŸã觊åªæŽ»æ§ã¯
322500ïœå
±éåäœïŒïœTiãšããããŠé«æŽ»æ§ã§ã
ã€ãã The resulting copolymer has a bulk specific gravity of 0.42, a melt index of 0.72, a density of 0.9206, and a catalytic activity of
The activity was extremely high at 322,500g copolymer/gTi.
åŸãããããªããŒç²æ«ã®å¹³åç²åŸã¯950ÎŒãšå€§
ããããŸãç²åŸ200Ό以äžã®åŸ®ç²ã¯0.3ïŒ
ãšå°ãªã
ã€ãã The average particle size of the obtained polymer powder was as large as 950ÎŒ, and the amount of fine powder with a particle size of 200ÎŒ or less was as low as 0.3%.
å®æœäŸ ïŒ
ç¡æ°Žå¡©åãã°ãã·ãŠã 10ïœãã¢ã«ãããŠã ããª
ãšããã·ãïŒïœããžãšããã·ãžã¯ããã·ã©ã³ïŒ
ïœãããã©ãããã·ã·ã©ã³ïŒïœããã³ã¢ã«ãã15
ïœãé
¢é
žãšãã«200mläžã«å ã100âã§ïŒæéå ç±
ããåŸãâ30âã«ä¿ã¡ããããµã³200mlãæ¹æäžã«
30åãããŠåŸã
ã«æ·»å ããŠåºäœç©è³ªãæåºããã
å¹³åç²åŸ50ÎŒã®åºäœæ
äœãåŸããExample 3 10 g of anhydrous magnesium chloride, 2 g of aluminum triethoxide, 2 g of diethoxydichlorosilane
g, 1 g of tetrabutoxysilane and 15 alumina
Add g to 200ml of ethyl acetate and heat at 100â for 1 hour, then keep at -30â and add 200ml of hexane with stirring.
Add gradually over 30 minutes to precipitate solid material,
A solid support with an average particle size of 50Ό was obtained.
äžèšåºäœæ
äœãçšããããšãé€ããŠã¯ãå®æœäŸ
ïŒãšåæ§ã®æ¹æ³ã§åºäœè§ŠåªæåïŒãã¿ã³æ
æéïŒ
18mgïŒïœïŒã補é ããå®æœäŸïŒãšåæ§ã®æ¹æ³ã§ãš
ãã¬ã³ãšããã³âïŒã®å
±éåãè¡ã€ãã The solid catalyst component (amount of titanium supported:
Copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1.
çæå
±éåäœã¯ãããæ¯é0.41ãã¡ã«ãã€ã³ã
ãã¯ã¹0.95ãå¯åºŠ0.9200ã§ããããŸã觊åªæŽ»æ§ã¯
311000ïœå
±éåäœïŒïœTiãšããããŠé«æŽ»æ§ã§ã
ã€ãã The resulting copolymer has a bulk specific gravity of 0.41, a melt index of 0.95, a density of 0.9200, and a catalytic activity of
The activity was extremely high at 311,000g copolymer/gTi.
åŸãããããªããŒç²æ«ã®å¹³åç²åŸã¯900ÎŒãšå€§
ããããŸãç²åŸ200Ό以äžã®åŸ®ç²ã¯0.4ïŒ
ãšå°ãªã
ã€ãã The average particle size of the obtained polymer powder was as large as 900ÎŒ, and the amount of fine powder with a particle size of 200ÎŒ or less was as low as 0.4%.
å®æœäŸ ïŒ
ã¢ã«ãã15ïœãå«æããé
¢é
žãšãã«200mläžã«ã
ç¡æ°Žå¡©åãã°ãã·ãŠã 10ïœããã³ããã©ã¢ã»ãã
ã·ã·ã©ã³ãå ãã100âã§ïŒæéå ç±ããåŸãâ30
âã«ä¿ã¡ããããµã³200mlãæ¹æäžã«30åãããŠ
åŸã
ã«æ·»å ããŠåºäœç©è³ªãæåºãããå¹³åç²åŸ
53ÎŒã®åºäœæ
äœãåŸããExample 4 In 200 ml of ethyl acetate containing 15 g of alumina,
After adding 10 g of anhydrous magnesium chloride and tetraacetoxysilane and heating at 100°C for 1 hour, -30
â, 200 ml of hexane was gradually added over 30 minutes under stirring to precipitate the solid material, and the average particle size was determined.
A solid support of 53Ό was obtained.
äžèšåºäœæ
äœãçšããããšãé€ããŠã¯ãå®æœäŸ
ïŒãšåæ§ã®æ¹æ³ã§åºäœè§ŠåªæåïŒãã¿ã³æ
æéïŒ
13mgïŒïœïŒã補é ããå®æœäŸïŒãšåæ§ã®æ¹æ³ã§ãš
ãã¬ã³ãšããã³âïŒã®å
±éåãè¡ã€ãã The solid catalyst component (amount of titanium supported:
Copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1.
çæå
±éåäœã¯ãããæ¯é0.39ãã¡ã«ãã€ã³ã
ãã¯ã¹1.1ãå¯åºŠ0.9216ã§ããããŸã觊åªæŽ»æ§ã¯
323000ïœå
±éåäœïŒïœTiãšããããŠé«æŽ»æ§ã§ã
ã€ãã The resulting copolymer has a bulk specific gravity of 0.39, a melt index of 1.1, a density of 0.9216, and a catalytic activity of
The activity was extremely high at 323,000g copolymer/gTi.
åŸãããããªããŒç²æ«ã®å¹³åç²åŸã¯950ÎŒãšå€§
ããããŸãç²åŸ200Ό以äžã®åŸ®ç²ã¯0.3ïŒ
ãšå°ãªã
ã€ãã The average particle size of the obtained polymer powder was as large as 950ÎŒ, and the amount of fine powder with a particle size of 200ÎŒ or less was as low as 0.3%.
å®æœäŸ ïŒ
ç¡æ°Žå¡©åãã°ãã·ãŠã 10ïœãããã©ã€ãœããã
ãã·ãã¿ã³ïŒïœãåå¡©åã±ã€çŽ ïŒïœããã³
MgOã»Al2O315ïœããžãšãã«ãšãŒãã«200mläžã«
å ãã100âã§ïŒæéå ç±ããåŸãâ30âã«ä¿ã¡ã
ãããµã³200mlãæ¹æäžã«30åãããŠåŸã
ã«æ·»å
ããŠãåºäœç©è³ªãæåºãããå¹³åç²åŸ45ÎŒã®åºäœ
æ
äœãåŸããExample 5 10 g of anhydrous magnesium chloride, 4 g of tetraisopropoxy titanium, 2 g of silicon tetrachloride, and
Add 15 g of MgO.Al 2 O 3 to 200 ml of diethyl ether, heat at 100°C for 1 hour, then keep at -30°C,
200 ml of hexane was gradually added over 30 minutes with stirring to precipitate a solid substance, yielding a solid support with an average particle size of 45 ÎŒm.
äžèšåºäœæ
äœãçšãåå¡©åãã¿ã³ã®ä»£ããã«ã
ãã©ã€ãœããããã·ãã¿ã³ã䜿çšããããšãé€ã
ãŠã¯ãå®æœäŸïŒãšåæ§ã®æ¹æ³ã§åºäœè§ŠåªæåïŒã
ã¿ã³æ
æéïŒ15mgïŒïœïŒã補é ããå®æœäŸïŒãšå
æ§ã®æ¹æ³ã§ãšãã¬ã³ãšããã³âïŒã®å
±éåãè¡ã€
ãã A solid catalyst component (titanium supported amount: 15 mg/g) was produced in the same manner as in Example 1, except for using the above solid carrier and using tetraisopropoxy titanium instead of titanium tetrachloride. Copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1.
çæå
±éåäœã¯ãããæ¯é0.41ãã¡ã«ãã€ã³ã
ãã¯ã¹1.0ãå¯åºŠ0.9219ã§ããããŸã觊åªæŽ»æ§ã¯
207000ïœå
±éåäœïŒïœTiãšããããŠé«æŽ»æ§ã§ã
ã€ãã The resulting copolymer has a bulk specific gravity of 0.41, a melt index of 1.0, a density of 0.9219, and a catalytic activity of
The activity was extremely high at 207,000g copolymer/gTi.
åŸãããããªããŒç²æ«ã®å¹³åç²åŸã¯870ÎŒãšå€§
ããããŸãç²åŸ200Ό以äžã®åŸ®ç²ã¯0.5ïŒ
ãšå°ãªã
ã€ãã The average particle size of the obtained polymer powder was as large as 870ÎŒ, and the amount of fine powder with a particle size of 200ÎŒ or less was as low as 0.5%.
å®æœäŸ ïŒ
ç¡æ°Žå¡©åãã°ãã·ãŠã 10ïœããã³å¡©åã¢ã«ãã
ãŠã ã»ãžãšãã«ãšãŒãã©ãŒãé¯äœïŒïœãçªçŽ äžã§
16æéããŒã«ããªã³ã°ãè¡ã€ããåŸãããåå¿ç
æç©ãããã©ããããã©ã³200mläžã«æº¶è§£ãããã
ãã®æº¶æ¶²ã«äºé
žåã±ã€çŽ 10ïœãå ããåŸãâ70â
ã«ä¿ã¡ããããµã³200mlãæ¹æäžã«30åãããŠ
åŸã
ã«æ·»å ããŠåºäœç©è³ªãæåºãããå¹³åç²åŸ
46ÎŒã®åºäœæ
äœãåŸããExample 6 10 g of anhydrous magnesium chloride and 1 g of aluminum chloride diethyl etherate complex were added under nitrogen.
Ball milling took place for 16 hours. The resulting reaction product was dissolved in 200 ml of tetrahydrofuran.
After adding 10 g of silicon dioxide to this solution, -70â
200 ml of hexane was gradually added over 30 minutes under stirring to precipitate the solid material, and the average particle size was
A 46Ό solid support was obtained.
äžèšåºäœæ
äœãçšããããšãé€ããŠã¯ãå®æœäŸ
ïŒãšåæ§ã®æ¹æ³ã§åºäœè§ŠåªæåïŒãã¿ã³æ
æéïŒ
21mgïŒïœïŒã補é ããå®æœäŸïŒãšåæ§ã®æ¹æ³ã§ãš
ãã¬ã³ãšããã³âïŒã®å
±éåãè¡ã€ãã The solid catalyst component (amount of titanium supported:
21 mg/g) and copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1.
çæå
±éåäœã¯ãããæ¯é0.43ãã¡ã«ãã€ã³ã
ãã¯ã¹0.80ãå¯åºŠ0.9223ã§ããããŸã觊åªæŽ»æ§ã¯
190000ïœå
±éåäœïŒgTiãšããããŠé«æŽ»æ§ã§ãã€
ãã The resulting copolymer has a bulk specific gravity of 0.43, a melt index of 0.80, a density of 0.9223, and a catalytic activity of
The activity was extremely high at 190,000g copolymer/gTi.
åŸãããããªããŒç²æ«ã®å¹³åç²åŸã¯890ÎŒãšå€§
ããããŸãç²åŸ200Ό以äžã®åŸ®ç²ã¯0.5ïŒ
ãšå°ãªã
ã€ãã The average particle size of the obtained polymer powder was as large as 890ÎŒ, and the amount of fine powder with a particle size of 200ÎŒ or less was as low as 0.5%.
å®æœäŸ ïŒ
ç¡æ°Žã®å¡©åãã°ãã·ãŠã 10ïœãã¢ã«ãããŠã ã
ãªãšããã·ãïŒïœããã³äºé
žåã±ã€çŽ 10ïœãã¢ã»
ãã³300mläžã«å ãã100âã§ïŒæéå ç±ããåŸã
â60âã«ä¿ã¡ããããµã³300mlãæ¹æäžã«30åã
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äžæŸã¿æ¶²ãé€å»ããã®ã¡ãæžå§äžã«100âã§ïŒæ
é也ç¥ãè¡ããå¹³åç²åŸ60ÎŒã®åºäœæ
äœãåŸããExample 7 10 g of anhydrous magnesium chloride, 5 g of aluminum triethoxide and 10 g of silicon dioxide were added to 300 ml of acetone, heated at 100° C. for 1 hour, and then
While maintaining the temperature at â60° C., 300 ml of hexane was gradually added over 30 minutes with stirring to precipitate a solid substance. Next, after removing the supernatant liquid, drying was performed at 100° C. for 1 hour under reduced pressure to obtain a solid carrier with an average particle size of 60 ÎŒm.
äžèšåºäœæ
äœãçšããããšãé€ããŠã¯ãå®æœäŸ
ïŒãšåæ§ã®æ¹æ³ã§åºäœè§ŠåªæåïŒãã¿ã³æ
æéïŒ
24mgïŒïœïŒã補é ããå®æœäŸïŒãšåæ§ã®æ¹æ³ã§ãš
ãã¬ã³ãšããã³âïŒã®å
±éåãè¡ã€ãã The solid catalyst component (amount of titanium supported:
24 mg/g) and copolymerization of ethylene and butene-1 was carried out in the same manner as in Example 1.
çæå
±éåäœã¯ãããæ¯é0.39ãã¡ã«ãã€ã³ã
ãã¯ã¹0.90ãå¯åºŠ0.9222ã§ããããŸã觊åªæŽ»æ§ã¯
315000ïœå
±éåäœïŒïœTiãšããããŠé«æŽ»æ§ã§ã
ã€ãã The resulting copolymer has a bulk specific gravity of 0.39, a melt index of 0.90, a density of 0.9222, and a catalytic activity of
The activity was extremely high at 315,000g copolymer/gTi.
åŸãããããªããŒç²æ«ã®å¹³åç²åŸã¯950ÎŒãšå€§
ããããŸãç²åŸ20Ό以äžã®åŸ®ç²ã¯0.2ïŒ
ãšå°ãªãã€
ãã The average particle size of the obtained polymer powder was as large as 950ÎŒ, and the amount of fine powder with a particle size of 20ÎŒ or less was as low as 0.2%.
å®æœäŸ ïŒ
å®æœäŸïŒãšåæ§ãªåºäœè§Šåªæåããã³è£
眮ãçš
ãã80âã«èª¿ç¯ãããªãŒãã¯ã¬ãŒãã«åºäœè§Šåªæ
åã50mgïŒhrãããã³ããªãšãã«ã¢ã«ãããŠã ã
ïŒããªã¢ã«ïŒhrã®é床ã§äŸçµŠãããŸãããããã¬
ã³ãäŸçµŠãããã€ããã¯ãŒã«ããç³»å
ã®ã¬ã¹ã埪
ç°ãããŠå
šå§ã10KgïŒcm2ã»ïŒ§ã«ä¿ã€ããã«ããŠé
åãè¡ã€ããçæãããããã¬ã³éåäœã¯ããæ¯
é0.44ãšç²åæ§ç¶ã«ãããããŸãã觊åªæŽ»æ§ã¯
118000ïœéåäœïŒïœTiãšããããŠé«æŽ»æ§ã§ãã€
ããExample 8 Using the same solid catalyst component and equipment as in Example 1, the solid catalyst component was supplied at a rate of 50 mg/hr and triethylaluminum at a rate of 5 mmol/hr to an autoclave adjusted to 80°C, and propylene was supplied at a rate of 5 mmol/hr. The polymerization was carried out while maintaining the total pressure at 10 kg/cm 2 ·G by circulating the gas in the system using a blower. The produced propylene polymer has excellent particle properties with a bulk specific gravity of 0.44, and has a high catalytic activity.
The activity was extremely high at 118,000g polymer/gTi.
第ïŒå³ã¯æ¬çºæã®ãªã¬ãã€ã³éå觊åªæ
äœã®è£œ
é æ¹æ³åã³ãããå«ããªã¬ãã€ã³éå觊åªã®è£œé
æ¹æ³ã瀺ããããŒãã€ãŒãå³ã§ããã
FIG. 1 is a flowchart showing a method for producing an olefin polymerization catalyst carrier and a method for producing an olefin polymerization catalyst containing the same according to the present invention.
Claims (1)
åãšããç©è³ªã溶解ãããã€åšæåŸè¡šç¬¬ãæ
éå±ã®é žåç©ãå«æããã¢ã«ã³ãŒã«é¡ãææ©é žãš
ã¹ãã«é¡ãã±ãã³é¡ããã³ãšãŒãã«é¡ããéžã°ã
ãå°ãªããšãäžçš®ã®æ¶²äœåªäœã10â以äžã®æž©åºŠã«
ä¿ã¡ã該液äœåªäœã«é£œåçåæ°ŽçŽ ãåŸã ã«æ·»å ã
ãããšã«ããç²åŸ5Ό以äžã®ç©è³ªãããªãæ äœã
æåºãããããšãç¹åŸŽãšãããªã¬ãã€ã³éå觊åª
çšæ äœã®è£œé æ¹æ³ã ïŒ åšæåŸè¡šç¬¬ãæéå±ã®é žåç©ãMgOã
CaOãZnOãBaOãSiO2ãSnO2ãAl2O3ã
MgOã»Al2O3ãSiO2ã»Al2O3ãMgOã»SiO2ã
MgOã»CaOã»Al2O3ãããã³Al2O3ã»CaOãããª
ã矀ããéžã°ããå°ãªããšãäžçš®é¡ã®é žåç©ã§ã
ãããšãç¹åŸŽãšããç¹èš±è«æ±ã®ç¯å²ç¬¬ïŒé ã«èšèŒ
ã®è£œé æ¹æ³ã[Scope of Claims] 1. A substance selected from alcohols, organic acid esters, ketones, and ethers that dissolves a substance containing at least one component of magnesium dihalide and contains an oxide of a metal of Groups 1 to 1 of the periodic table. An olefin polymerization catalyst characterized in that at least one liquid medium is maintained at a temperature of 10°C or less, and a saturated hydrocarbon is gradually added to the liquid medium to precipitate a carrier consisting of a substance with a particle size of 5ÎŒ or more. Method for manufacturing carrier. 2 The oxides of metals from groups ~ of the periodic table are MgO,
CaO, ZnO, BaO, SiO2 , SnO2 , Al2O3 ,
MgOã»Al 2 O 3 , SiO 2ã»Al 2 O 3 , MgOã»SiO 2 ,
The manufacturing method according to claim 1, characterized in that the oxide is at least one type of oxide selected from the group consisting of MgO.CaO.Al 2 O 3 and Al 2 O 3.CaO.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17082081A JPS5874704A (en) | 1981-10-27 | 1981-10-27 | Carrier for olefin polymerization catalyst |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP17082081A JPS5874704A (en) | 1981-10-27 | 1981-10-27 | Carrier for olefin polymerization catalyst |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS5874704A JPS5874704A (en) | 1983-05-06 |
JPH0135843B2 true JPH0135843B2 (en) | 1989-07-27 |
Family
ID=15911932
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP17082081A Granted JPS5874704A (en) | 1981-10-27 | 1981-10-27 | Carrier for olefin polymerization catalyst |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS5874704A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS58109507A (en) * | 1981-12-23 | 1983-06-29 | Toho Titanium Co Ltd | Production of catalytic component for olefin polymerization |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4965999A (en) * | 1972-09-13 | 1974-06-26 | ||
JPS5238590A (en) * | 1975-09-18 | 1977-03-25 | Montedison Spa | Catalyst component for polymerizing olefin into spherical form |
-
1981
- 1981-10-27 JP JP17082081A patent/JPS5874704A/en active Granted
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4965999A (en) * | 1972-09-13 | 1974-06-26 | ||
JPS5238590A (en) * | 1975-09-18 | 1977-03-25 | Montedison Spa | Catalyst component for polymerizing olefin into spherical form |
Also Published As
Publication number | Publication date |
---|---|
JPS5874704A (en) | 1983-05-06 |
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