WO2016204457A1 - 폴리올레핀의 제조 방법 - Google Patents
폴리올레핀의 제조 방법 Download PDFInfo
- Publication number
- WO2016204457A1 WO2016204457A1 PCT/KR2016/006201 KR2016006201W WO2016204457A1 WO 2016204457 A1 WO2016204457 A1 WO 2016204457A1 KR 2016006201 W KR2016006201 W KR 2016006201W WO 2016204457 A1 WO2016204457 A1 WO 2016204457A1
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- Prior art keywords
- formula
- compound
- group
- carbon atoms
- metallocene
- Prior art date
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 55
- 239000012968 metallocene catalyst Substances 0.000 claims abstract description 35
- 238000009826 distribution Methods 0.000 claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 28
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 150000001336 alkenes Chemical class 0.000 claims abstract description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims description 115
- 239000003054 catalyst Substances 0.000 claims description 55
- 238000004519 manufacturing process Methods 0.000 claims description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 41
- -1 4,5,6,7-tetrahydro-1-indenyl Chemical group 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 14
- 125000003545 alkoxy group Chemical group 0.000 claims description 13
- 150000002367 halogens Chemical class 0.000 claims description 13
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 229910052723 transition metal Inorganic materials 0.000 claims description 12
- 150000003624 transition metals Chemical class 0.000 claims description 12
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 11
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 11
- 230000000379 polymerizing effect Effects 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical group 0.000 claims description 8
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 6
- 125000002947 alkylene group Chemical group 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000005018 aryl alkenyl group Chemical group 0.000 claims description 6
- 125000002102 aryl alkyloxo group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 5
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 4
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 4
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052732 germanium Inorganic materials 0.000 claims description 4
- VGRFVJMYCCLWPQ-UHFFFAOYSA-N germanium Chemical compound [Ge].[Ge] VGRFVJMYCCLWPQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 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 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims description 2
- HMDQPBSDHHTRNI-UHFFFAOYSA-N 1-(chloromethyl)-3-ethenylbenzene Chemical compound ClCC1=CC=CC(C=C)=C1 HMDQPBSDHHTRNI-UHFFFAOYSA-N 0.000 claims description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims description 2
- 229940069096 dodecene Drugs 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 2
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 2
- 125000003107 substituted aryl group Chemical group 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims 4
- 125000002524 organometallic group Chemical group 0.000 abstract description 6
- 229910004349 Ti-Al Inorganic materials 0.000 abstract description 3
- 229910004692 Ti—Al Inorganic materials 0.000 abstract description 3
- 239000003623 enhancer Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 42
- 230000000052 comparative effect Effects 0.000 description 38
- 239000012018 catalyst precursor Substances 0.000 description 29
- 230000003197 catalytic effect Effects 0.000 description 21
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 21
- 230000000694 effects Effects 0.000 description 20
- 150000007523 nucleic acids Chemical class 0.000 description 13
- 102000039446 nucleic acids Human genes 0.000 description 13
- 108020004707 nucleic acids Proteins 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 9
- 239000000654 additive Substances 0.000 description 9
- 229920000642 polymer Polymers 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 7
- 150000002902 organometallic compounds Chemical class 0.000 description 7
- 239000002243 precursor Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- RURFJXKOXIWFJX-UHFFFAOYSA-N (2,3,4,6-tetrafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C=C(F)C(F)=C1F RURFJXKOXIWFJX-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 150000004820 halides Chemical group 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 3
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- JNTPTNNCGDAGEJ-UHFFFAOYSA-N 6-chlorohexan-1-ol Chemical compound OCCCCCCCl JNTPTNNCGDAGEJ-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910007926 ZrCl Inorganic materials 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 125000005131 dialkylammonium group Chemical group 0.000 description 2
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 150000004678 hydrides Chemical group 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 150000004714 phosphonium salts Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 1
- VNPQQEYMXYCAEZ-UHFFFAOYSA-N 1,2,3,4-tetramethylcyclopenta-1,3-diene Chemical compound CC1=C(C)C(C)=C(C)C1 VNPQQEYMXYCAEZ-UHFFFAOYSA-N 0.000 description 1
- XSBHWHZJHSUCOI-UHFFFAOYSA-N 1-[(2-methylpropan-2-yl)oxy]hexane Chemical compound CCCCCCOC(C)(C)C XSBHWHZJHSUCOI-UHFFFAOYSA-N 0.000 description 1
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical group CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-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
- DRHABPMHZRIRAH-UHFFFAOYSA-N 2,4,4,6,6-pentamethylhept-2-ene Chemical group CC(C)=CC(C)(C)CC(C)(C)C DRHABPMHZRIRAH-UHFFFAOYSA-N 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- VUGMARFZKDASCX-UHFFFAOYSA-N 2-methyl-N-silylpropan-2-amine Chemical compound CC(C)(C)N[SiH3] VUGMARFZKDASCX-UHFFFAOYSA-N 0.000 description 1
- UDMMZSJNHAWYKX-UHFFFAOYSA-N 4-phenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C(C=C2)CCC21C1=CC=CC=C1 UDMMZSJNHAWYKX-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- CGRVKSPUKAFTBN-UHFFFAOYSA-N N-silylbutan-1-amine Chemical compound CCCCN[SiH3] CGRVKSPUKAFTBN-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001793 charged compounds Polymers 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical class [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- HKUFIYBZNQSHQS-UHFFFAOYSA-O dioctadecylazanium Chemical compound CCCCCCCCCCCCCCCCCC[NH2+]CCCCCCCCCCCCCCCCCC HKUFIYBZNQSHQS-UHFFFAOYSA-O 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 229910021482 group 13 metal Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- CAKOOJUEUVRZLR-UHFFFAOYSA-N methyl(dioctadecyl)phosphane Chemical compound CCCCCCCCCCCCCCCCCCP(C)CCCCCCCCCCCCCCCCCC CAKOOJUEUVRZLR-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- OXQMIXBVXHWDPX-UHFFFAOYSA-N n,n,2-trimethylpropan-2-amine Chemical compound CN(C)C(C)(C)C OXQMIXBVXHWDPX-UHFFFAOYSA-N 0.000 description 1
- SRLHDBRENZFCIN-UHFFFAOYSA-N n,n-di(butan-2-yl)butan-2-amine Chemical compound CCC(C)N(C(C)CC)C(C)CC SRLHDBRENZFCIN-UHFFFAOYSA-N 0.000 description 1
- VFLWKHBYVIUAMP-UHFFFAOYSA-N n-methyl-n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCCCCCC VFLWKHBYVIUAMP-UHFFFAOYSA-N 0.000 description 1
- KUFYUMSBZMUWAN-UHFFFAOYSA-N n-methyl-n-tetradecyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCC KUFYUMSBZMUWAN-UHFFFAOYSA-N 0.000 description 1
- HSUGDXPUFCVGES-UHFFFAOYSA-N n-tetradecyltetradecan-1-amine Chemical compound CCCCCCCCCCCCCCNCCCCCCCCCCCCCC HSUGDXPUFCVGES-UHFFFAOYSA-N 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-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
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/02—Carriers therefor
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/647—Catalysts containing a specific non-metal or metal-free compound
- C08F4/649—Catalysts containing a specific non-metal or metal-free compound organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
Definitions
- the present invention is capable of both solution polymerization or slurry polymerization using an organometallic compound having a specific structure, and in the case of slurry polymerization, an additive for increasing the molecular weight is added without using an additional catalyst for supporting the organometallic compound.
- the present invention relates to a method for preparing polyolefin that exhibits more than the performance of conventional metallocene catalysts, and in particular, can easily increase the molecular weight of olefins.
- Metallocenes using Group 4 transition metals have been widely used in various organic catalysis reactions and various polymer reactions of olepin.
- the use of olefins for the reaction of polymers has been continuously studied in terms of the structure change in that it is a single active site catalyst, and thus, the catalyst activity, molecular weight, and molecular weight distribution, which are superior to conventional Ziegler-Natta catalysts, are controlled. It is easy to do so many industrial grand research has been done.
- Korean Patent Laid-Open Publication No. 2005-0117544 discloses a method of using a metallocene catalyst and a Thebes reagent during polymerization in order to prepare an ultra high molecular weight ethylene polymer of 1 million or more.
- the method focuses only on the preparation of ultra high molecular weight ethylene polymers, and for the polyethylene produced, its field of application and manufacturing process itself are extremely limited.
- the polymer according to the above method is an ultra high molecular weight polymer having a very narrow molecular weight distribution, there is a problem in that the workability is poor, the post-processing is difficult, and the market itself is also small.
- An object of the present invention is to provide a method for producing polyolefin using an organometallic complex of a specific structure exhibiting improved solubility, which can exhibit excellent effect even when used in a small amount as well as slurry polymerization, even when the solution polymerization. .
- another object of the present invention is to provide a method for producing a polyolefin that can improve the degradation of the polymerization catalyst performance, and more easily control the molecular weight distribution to produce a polymer that can exhibit a molecular weight distribution in various areas.
- the present invention provides a method for producing a polyolefin comprising the step of polymerizing an olefin monomer in the presence of a metallocene catalyst comprising a metallocene compound, a cocatalyst and a compound of formula (1) which is a molecular weight sensitizer.
- R 10 are each independently hydrogen, linear or branched alkyl having 1 to 10 carbon atoms, alkoxy or alkoxyalkyl,
- R u is a linear or branched alkylene group having 1 to 10 carbon atoms, or halogen
- Ri2 and R 13 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms, or halogen
- X is a halogen atom.
- Ri to Rio in Formula 1 may be at least one alkoxyalkyl having 1 to 10 carbon atoms.
- Ri to Rio is preferably at least one is alkoxyalkyl having 8 to 10 carbon atoms.
- R u may be an alkylene group having 4 to 10 carbon atoms
- R 12 and R 13 may each independently be an alkyl group having 4 to 10 carbon atoms.
- Formula 1 may be prepared by reacting the compound of Formula 2 and the organoaluminum compound of Formula 3 in a solvent.
- 3 ⁇ 4 to R 10 are each independently hydrogen, carbon number 1 Straight or branched chain alkyl, alkoxy or alkoxyalkyl of 10 to 10,
- X is halogen
- Rii, R12 and 3 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms or halogen, and at least one of R n , R12 and R 13 is a linear or branched alkyl group having 1 to 10 carbon atoms.
- the metallocene catalyst may further include a carrier.
- the metallocene catalyst may include a metallocene supported catalyst having a metallocene compound, a promoter, and a compound of Formula 1 supported on the promoter.
- Polymerizing the olefin monomer may include solution polymerization or slurry polymerization.
- the solution polymerization may include the step of solution polymerization of the olepan-based monomer in a solvent-containing reactor in the presence of a metallocene compound, a cocatalyst and a metallocene catalyst comprising a compound of formula (1).
- the compound of Formula 1 may be introduced into the reactor through a separate feed port during the polymerization of the olefin monomer.
- the slurry polymerization is a metallocene compound, a cocatalyst and a metallocene supported catalyst comprising a compound of the formula (1) supported on a carrier in one reactor, the olefin monomer in the reactor It may include the step of slurry polymerization while adding.
- the present invention specifically uses an organometallic complex containing a Ti-Al complex structure as a molecular weight regulator (ie, a molecular weight sensitizer), and by supporting it with a promoter on a carrier to prepare a metallocene catalyst, and then By using a strong catalyst for the polymerization of the olefin resin, ultra high molecular weight polyolefin having a wide molecular weight distribution and a very high molecular weight can be produced.
- the present invention provides the organometallic compound for solution polymerization as well as slurry polymerization due to improved solubility. Molecular weight distribution can be easily adjusted even if a small amount is added.
- the present invention can improve the performance degradation (activity and copolymerizability) of the polymerization catalyst.
- a supported catalyst in which the organometallic complex is immobilized on a carrier i ⁇ obi li zat ion
- a polyolefin having a higher molecular weight than that of a conventional metallocene catalyst without additional additives is added.
- the present invention can control the molecular weight distribution by using one metallocene catalyst.
- the meaning of "comprising” as used in the specification of the present invention embodies a specific characteristic, a region, an integer, a step, an operation, an element and / or a component, and another characteristic, an area, an integer, a step, an operation, an element and / It is not intended to exclude the presence or addition of components, which will be described in more detail with respect to the preparation method of the supported metallocene catalyst according to an embodiment of the present invention.
- a method for producing a polyolefin comprising the step of polymerizing an ollefin monomer in the presence of a metallocene compound, a cocatalyst and a metallocene catalyst comprising a compound of Formula 1 below.
- X is a halogen atom.
- Such an organometallic compound of the present invention as represented by the formula (1), specifically forms a Ti-Al complex structure in the structure. Since the solubility of the solvent is improved due to the specificity of the structure, it is possible to improve the catalyst performance even when using a small amount more than the conventional when the solution is added to the polymerization solution than when using other transition metals, the molecular weight control is more It has an easy effect. In addition, since the compound of Formula 1 may exhibit an effect of increasing the molecular weight even when using the same amount compared to the conventionally used Tebese reagents, it is possible to efficiently produce polyethylene.
- the present invention since the slurry polymerization is carried out while adding the catalyst on which the organometallic compound of Chemical Formula 1 is loaded into one reactor, and then olefin monomer is added thereto, the molecular weight distribution is wide and high molecular weight or ultra high molecular weight is simple. It was possible to prepare a polyolefin having a large amount. That is, the present invention is used for slurry polymerization in a state in which both the metallocene compound and the compound of formula 1 are supported on a carrier.
- the metallocene supported catalyst of the present invention is more effectively supported by the compound of Formula 1 than when the molecular weight modifier is added separately as before, and thus, the catalyst performance is improved by improving the structure.
- the compound of Formula 1 may be stably dissolved in an organic solvent used as a reaction medium or diluent and supplied to the reaction system.
- Ri to R 10 is alkyl or alkoxy
- the supported properties of the supported catalyst are enhanced, so that the action and effect are more uniform and excellent during the alkyl polymerization process without falling out of the compound in the solvent of the polymerization process. Can be expressed.
- Such Formula 1 may be prepared by reacting the compound of Formula 2 and the organoaluminum compound of Formula 3 in a solvent.
- 3 ⁇ 4 to R 10 are each independently hydrogen, linear or branched alkyl having 1 to 10 carbon atoms, alkoxy or alkoxyalkyl,
- X is halogen
- Rii, 12 and Ri3 are each independently a linear or branched alkyl group having 1 to 10 carbon atoms or halogen, and at least one of R u , R12 and 3 is linear or It is a C1-C10 alkyl group of a side chain. )
- the compound of Formula 2 and the compound of Formula 3 may have a molar ratio of about 1: 1 to 1: 3, or about 1: 1.5 to 1: 2.5, based on the molar ratio of Ti included in Formula 2 and aluminum included in Formula 3. Is preferably used. Most preferably, the molar ratio of the compound of Formula 2 and the compound of Formula 3, Ti contained in Formula 2, and aluminum included in Formula 3 is 1: 2.
- the preparation method of Chemical Formula 1 may proceed in a solvent, and the type of solvent is not particularly limited.
- the reaction solvent may be performed using a hydrocarbon solvent having 5 to 20 carbon atoms or an aromatic solvent having 6 to 20 carbon atoms under an inert atmosphere.
- the metallocene catalyst used for the olefin polymerization may further include a carrier well known in the art.
- the carrier may be selected from the group consisting of silica, silica-alumina and silica-magnesia.
- the metallocene catalyst according to one embodiment of the present invention may include the above-described metallocene compound, cocatalyst and the compound of Formula 1, and optionally the metallocene compound, the promoter and the compound of Formula 1 It may include a metallocene supported catalyst supported on the catalyst.
- the polyolefin when the compound of Formula 1 uses a metallocene supported catalyst supported on a carrier together with a metallocene compound, the polyolefin may be prepared by slurry polymerization.
- the polyolefin when the compound of Formula 1 is used separately, the polyolefin may be prepared by a solution polymerization method. Therefore, the step of polymerizing the olefin monomer may include solution polymerization or slurry polymerization. That is, the compound of Formula 1 may be used in a state of being supported on a carrier together with the metallocene compound described below, but may be separately added to the reaction vessel including the metallocene compound and the promoter in the reaction system during polymerization. It may be used in combination.
- the step of polymerizing the olefin monomer may include slurry polymerization. That is, in the present invention, the compound and the metallocene compound of Formula 1 are used in a form supported on a carrier, It is possible to prepare a polyolefin having a wide molecular weight distribution, excellent catalytic activity and various molecular weights without adding a separate additive during polymerization.
- the solution polymerization is a step of solution polymerization of the olefinic monomers in a solvent-containing reactor in the presence of a metallocene catalyst comprising a metallocene compound, a promoter and a compound of Formula 1 It may include.
- the compound of Formula 1 may be introduced into the reactor through a separate feed port during the polymerization of the olefin monomer.
- a metallocene supported catalyst comprising a metallocene compound, a cocatalyst, and a compound of Formula 1 supported on a carrier is added to one reactor, and then the reactor It may include the step of slurry polymerization while adding an olefinic monomer to.
- the metallocene compound included in the metallocene catalyst may be any one or more selected from compounds represented by the following Chemical Formulas 4 to 6.
- M 1 is a Group 4 transition metal
- Z 1 is a halogen atom, C1 to C20 alkyl, C2 to C10 ' alkenyl, C7 to C40 alkylaryl, C7 to C40 arylalkyl, C6 to C20 aryl, Substituted or unsubstituted C1 to C20 alkylidene, substituted or unsubstituted amino group, C2 to C20 alkylalkoxy, or C7 to C40 arylalkoxy; n is 1 or 0;
- n 1 or 0;
- Cp 5 is any one selected from the group consisting of cyclopentadienyl, indenyl, 4, 5, 6, 7-tetrahydro-1-indenyl and fluorenyl radicals, which are May be substituted with a hydrocarbon having 1 to 20 carbon atoms;
- R e is hydrogen, C1 to C20 alkyl, C1 to C10 alkoxy, C2 to C20 alkoxyalkyl, C6 to C20 aryl, C6 to C10 aryloxy, C2 to C20 alkenyl, C7 to C40 alkylaryl Arylalkyl of C7 to C40, arylalkenyl of C8 to C40, or alkynyl of C2 to C10;
- J is any one selected from the group consisting of NR f , 0, PR f and S, wherein R f is C1 to C20 alkyl, aryl, substituted alkyl or substituted aryl.
- the metallocene compound is a high molecular weight olefin-based copolymer having a high SCB content, at the same time including only one selected from the compounds represented by Formulas 4 to 6, and at the same time has a wide molecular weight distribution, not only excellent physical properties but also processability Excellent olefin polymers can be prepared.
- a promoter supported together with a carrier for activating the metallocene compound is an organometallic compound containing a Group 13 metal, and polymerizes an olefin under a general metallocene catalyst. If it can be used when it is not particularly limited.
- n is an integer of 2 or more.
- T + is a + monovalent polyatomic ion
- ⁇ is boron in +3 oxidation state
- Q is independently a hydride group, a dialkylamido group, a halide group, an alkoxide group, an aryl oxide group, Selected from the group consisting of hydrocarbyl groups, halocarbyl groups and halo-substituted hydrocarbyl groups, wherein Q has up to 20 carbons, but at less than one position Q is a halide group.
- the promoter of Formula 7 may be an alkylaluminoxane compound having a repeating unit bonded in a linear, circular, or reticular form. Specific examples of such a promoter include methylaluminoxane (MA0), ethylaluminoxane, and isobutyl. Aluminoxane, butyl aluminoxane, etc. are mentioned.
- the borate-based promoter of Formula 8 may be a borate-based compound in the form of a trisubstituted ammonium salt, or a dialkyl ammonium salt, a trisubstituted phosphonium salt.
- C 2 promoter examples include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenyl Borate, methyltetracyclooctadecylammonium tetraphenylborate, ⁇ , ⁇ -dimethylaniline tetraphenylborate, ⁇ , ⁇ -diethylaninynium tetraphenylborate, ⁇ , ⁇ -dimethyl (2,4,6-trimethylaniyl titanium) tetraphenylborate, trimethylammonium tetrakis (penta flow oro-phenyl) borate, methyl-di-tetradecyl ammonium t
- the mass ratio of the total transition metal to the carrier included in the metallocene compound may be 1:10 to 1: 1.
- the carrier and the metallocene compound are included in the mass ratio, an optimal shape can be exhibited.
- the mass ratio of the promoter compound to the carrier may be from 1: 1 to 1: 100.
- the mass ratio of the metallocene compound may be 10: 1 to 1:10, preferably 5: 1 to 1: 5.
- silica, silica-alumina, silica-magnesia, etc., dried at a high temperature may be used, and these are usually oxides, carbonates, such as Na 2 0, K 2 C0 3) BaS0 4> and Mg (N0 3 ) 2 , Sulfate, and nitrate components.
- the drying temperature of the carrier is preferably about 200 to 800 ° C., more preferably about 300 to 600 ° C., most preferably about 300 to 400 ° C.
- the drying temperature of the carrier is less than about 200 ° C, the moisture is too much to react with the surface of the carrier and the promoter reacts, and when it exceeds about 800 ° C, the surface area decreases as the pores of the carrier surface merge, It is not preferable because many hydroxyl groups are lost and only siloxane groups are left, resulting in a decrease in reaction space with the promoter.
- the amount of hydroxy groups on the surface of the carrier is preferably about 0.1 to 10 kPa / g, more preferably about 0.5 to 1 mmol / g.
- the amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions for preparing the carrier or by drying conditions such as temperature, time, vacuum or spray drying. If the amount of the hydroxyl group is less than about 0.01 mmol / g, the reaction space with the cocatalyst is small, and if the amount of the hydroxyl group is greater than about 10 GPa ol / g, it is due to moisture other than the hydroxyl group present on the surface of the carrier particle. It is not preferable because there is possibility.
- the mass ratio of the total transition metal to the carrier included in the metallocene compound may be about 1: 10 to 1: 1,000.
- the carrier and the metallocene compound are included in the mass ratio, the optimum shape can be exhibited.
- organoaluminum compounds for removing water in the reactor are further added, the polymerization reaction may proceed in the presence thereof.
- organoaluminum compounds include trialkylaluminum, dialkylaluminum halides, alkylaluminum dihalides, aluminumdialkyl hydrides or alkylaluminum sesquihalides, and more specific examples thereof include AKC 2 3/4.
- Such organoaluminum compounds may be continuously introduced into the reactor and may be introduced at a rate of about 0.1 to 10 moles per kilogram of reaction medium introduced into the reactor for proper water removal.
- the olefinic monomers may be ethylene, alpha- olefins, cyclic olefins, diene olefins or triene olefins having two or more double bonds.
- the polymerization reaction may be carried out by homopolymerization with one olefin monomer or copolymerization with two or more monomers using one continuous slurry polymerization reaction reactor, a loop slurry reactor, a gas phase reactor, or a solution reaction reactor.
- a high molecular weight or ultra high molecular weight polyolefin can be obtained having a weight average molecular weight of about 100,000 to about 3,000,000 g / mol, or about 100,000 to about 2,000,000 g / mol, which has a molecular weight distribution.
- PDI, Mw / Mn may be about 2 to about 20, or about 3 to about 15.
- the molecular weight distribution can be controlled using one metallocene catalyst, and in particular, a relatively wide molecular weight distribution and very high Ultra high molecular weight polyolefins having a molecular weight can be produced.
- t-butyl -0- (C3 ⁇ 4) 6 -C 5 H 5 was dissolved in THF at -78 ° C, n-BuLi was slowly added, and then heated to silver and reacted for 8 hours. The solution was again added slowly to a suspension solution of ZrCl 4 (THF) 2 (1.7 g, 4.5 mmol) / THF (30 mL) at -78 ° C and reacted further for 6 hours at room temperature. All volatiles were dried in vacuo and the resulting oily liquid material was filtered off by addition of a nucleic acid solvent. The filtered solution was vacuum dried and nucleic acid was added to induce precipitate at low temperature (-2CTC).
- THF ZrCl 4
- reaction temperature was maintained at 50 ° C.
- 25 6-t-buthoxyhexyl chloride was added to the reactor at a rate of 5 mL / min using a feeding pump.
- 6-t-butoxynuclear chloride was added, it was observed that the reaction temperature increased by about 4 to 5 degrees. Subsequently, the mixture was stirred for 12 hours while adding 6-t-secondary nucleus chloride.
- the reaction mixture was stirred for 12 hours while slowly raising the temperature to room temperature.
- TiCl 3 (THF) 3 (10 ⁇ l ol) was rapidly added to the dilithium salt of a ligand of ⁇ 78 ° C. synthesized in THF solution. The reaction solution was slowly stirred for 12 hours at room temperature at -78 ° C.
- the reaction product was filtered under a Schlenk glass filter to remove salts, and then the filtered solution was residue-dried to remove all solvents. After 0 ⁇ , the nucleic acid was added to the resultant from which the solvent was removed to induce precipitation at low temperature (-20 ° C.).
- the measured 3 ⁇ 4 NMR data of [t-Bu-0 (CH 2 ) 6 -C 5 H 4 ] 2 TiCl 2 obtained were as follows.
- the supported catalyst was prepared by supporting the catalyst precursor (1) of Preparation Example 1 and the compound of Preparation Example Ktether® E) on a carrier.
- a supported metallocene catalyst was prepared in the same manner as in Preparation Example 4, except that 0.5 mmol of the catalyst precursor of Preparation Example 1 and 0.5 mmol of the compound Ktether Eli E) of Example 1 were supported on the support. .
- a supported metallocene catalyst was prepared in the same manner as in Preparation Example 4, except that Ktether ⁇ E) 0.25 ⁇ was supported.
- a supported metallocene catalyst was prepared in the same manner as in Preparation Example 4, except that 0.5 mmol of the catalyst precursor (2) of Preparation Example 2 and 0.05 ⁇ l ol of the compound Ktether MWE of Example 1 were supported on the support.
- a supported metallocene catalyst was prepared in the same manner as in Preparation Example 4, except that 1 (tether LEY E) 0.15 Pa was supported.
- a supported metallocene catalyst was prepared in the same manner as in Preparation Example 4, except that 0.5 mm of the catalyst precursor (2) of Preparation Example 2 and 0.25 K of the compound Ktether X E) of Example 1 were supported on the support.
- the supported metallocene catalyst was prepared by supporting only the catalyst precursor (1) of Preparation Example 1 on a carrier.
- Silica (SYL0P0L 948, manufactured by Grace Davi Sioi) was dehydrated under vacuum at a temperature of 400 ° C. for 12 hours.
- a supported catalyst was prepared in the same manner as in Comparative Preparation Example 1, except that only the catalyst precursor (2) of Preparation Example 2 was supported on the support instead of the catalyst precursor (1) of Preparation Example 1.
- the catalyst precursor (1) (20 ⁇ 1) was put in a plastic, 20 mL of toluene was added and stirred to prepare an ImM catalyst solution.
- Two 300 mL Andrew bars were prepared, assembled with an impeller part, and replaced with argon in the glove box.
- the glove box-treated Andrew bar was placed inside (a small amount of TMA was prescribed), each with 180 mL of toluene and 10 mL of MA0 (10 wt% toluene) solution.
- Comparative Example 3 A polyolefin was prepared in the same manner as in Comparative Example 1 except for using 3 ⁇ 4 using the catalyst precursor (2) of Preparation Example 2 instead of the catalyst precursor (1) of Preparation Example 1.
- the polyolefin was prepared in the same manner as in Comparative Example 1, except that Compound Ktether MWE of Preparation Example 3 was added to the reaction vessel through another line so as to be 0.1 mol% based on 1% ol of the catalyst precursor.
- Compound Ktether MWE of Preparation Example 3 was added to the reaction vessel through another line so as to be 0.1 mol% based on 1% ol of the catalyst precursor.
- the compound Ktether MWE of Preparation Example 3 was additionally supplied to the reaction vessel through another line so that the catalyst precursor (2) became 0.1 mol% based on 1 ⁇ ol. Except for producing a polyolefin in the same manner as in Comparative Example 1.
- the polyolefin was prepared in the same manner as in Example 2, except that Compound Ktether MWE of Preparation Example 3 was additionally supplied to the reactor via another line such that the catalyst precursor (2) was 0.05 mol% based on 1 ⁇ ol. Prepared.
- the effect of increasing the molecular weight in solution polymerization is insignificant.
- the effect of increasing the molecular weight was very large.
- the present invention can exhibit an excellent effect even if the amount of the tether E is reduced.
- Comparative Example 1 had a low molecular weight and narrow molecular weight distribution of the polyolefin even though the catalytic activity was similar to the present application.
- Comparative Example 2 was intended to widen the molecular weight distribution using the Thebes reagent as an additive, but was lower than Example 2 of the present application, and the molecular weight of polyolefin was also low. And although the molecular weight of the polyolefin was comparative example 3 high, the molecular weight distribution became narrower.
- Comparative Example 4 showed a high molecular weight, but the catalyst activity was too low and the molecular weight distribution was narrow.
- the polymerization was carried out in a 2 L metal alloy reactor which was thermostatically equipped with a mechanical stirrer and used at high pressure.
- the supported catalysts of Comparative Preparation Examples 1 and 2 were used, and Compound 1 of Preparation Example 3 was supplied to the reactor through another line during polymerization.
- Tevec reagent (C 5 3 ⁇ 4) 2 TiCH 2 ClAl (CH 3 ) 2 ) is additionally supplied to the reaction vessel. By polymerization.
- Example 7 (carrier / 0.5-8.8 977,120 6.1 catalyst precursor (1))
- Catalytic precursor (2) In Table 2, Examples 5 to 10 of the present invention, according to the use of a metallocene catalyst having a formula (1) in one reactor during slurry polymerization, without using a separate additive in the reaction vessel, Comparative Example 5 Compared to 10, it can be seen that the polyolefin having a wide range of molecular weight and high molecular weight as well as exhibiting various catalytic activities. Therefore, the present invention can more effectively support the formula (1) on the carrier than the conventional, it is possible to improve the performance of the metallocene supported catalyst, thereby providing a polymer having a molecular weight distribution of various zones.
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Abstract
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Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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JP2017543357A JP6511151B2 (ja) | 2015-06-15 | 2016-06-10 | ポリオレフィンの製造方法 |
US15/552,658 US10870712B2 (en) | 2015-06-15 | 2016-06-10 | Method for preparing polyolefin |
EP16811870.1A EP3246343A4 (en) | 2015-06-15 | 2016-06-10 | Method for preparing polyolefin |
CN201680015862.9A CN107406536B (zh) | 2015-06-15 | 2016-06-10 | 制备聚烯烃的方法 |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113039217A (zh) * | 2019-09-27 | 2021-06-25 | 株式会社Lg化学 | 混杂负载型催化剂和使用该催化剂制备聚烯烃的方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20080104331A (ko) * | 2006-02-22 | 2008-12-02 | 셰브론 필립스 케미컬 컴퍼니 엘피 | 바이모달 고분자의 중합을 위한 이중 메탈로센 촉매 |
KR20130019793A (ko) * | 2011-08-18 | 2013-02-27 | 주식회사 엘지화학 | 폴리올레핀 수지의 제조방법 |
KR20140071142A (ko) * | 2012-12-03 | 2014-06-11 | 대림산업 주식회사 | 성형성 및 기계적 물성이 우수한 멀티모달 폴리올레핀 수지 제조를 위한 촉매 조성물 및 이를 이용한 중합 방법 |
JP2014185287A (ja) * | 2013-03-25 | 2014-10-02 | Japan Polypropylene Corp | プロピレン−エチレン共重合体樹脂組成物並びにフィルム |
KR20150059125A (ko) * | 2013-11-21 | 2015-05-29 | 주식회사 엘지화학 | 폴리올레핀의 제조 방법 및 이로부터 제조된 폴리올레핀 |
-
2016
- 2016-06-10 WO PCT/KR2016/006201 patent/WO2016204457A1/ko active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR20080104331A (ko) * | 2006-02-22 | 2008-12-02 | 셰브론 필립스 케미컬 컴퍼니 엘피 | 바이모달 고분자의 중합을 위한 이중 메탈로센 촉매 |
KR20130019793A (ko) * | 2011-08-18 | 2013-02-27 | 주식회사 엘지화학 | 폴리올레핀 수지의 제조방법 |
KR20140071142A (ko) * | 2012-12-03 | 2014-06-11 | 대림산업 주식회사 | 성형성 및 기계적 물성이 우수한 멀티모달 폴리올레핀 수지 제조를 위한 촉매 조성물 및 이를 이용한 중합 방법 |
JP2014185287A (ja) * | 2013-03-25 | 2014-10-02 | Japan Polypropylene Corp | プロピレン−エチレン共重合体樹脂組成物並びにフィルム |
KR20150059125A (ko) * | 2013-11-21 | 2015-05-29 | 주식회사 엘지화학 | 폴리올레핀의 제조 방법 및 이로부터 제조된 폴리올레핀 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3246343A4 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113039217A (zh) * | 2019-09-27 | 2021-06-25 | 株式会社Lg化学 | 混杂负载型催化剂和使用该催化剂制备聚烯烃的方法 |
CN113039217B (zh) * | 2019-09-27 | 2023-05-12 | 株式会社Lg化学 | 混杂负载型催化剂和使用该催化剂制备聚烯烃的方法 |
US11993665B2 (en) | 2019-09-27 | 2024-05-28 | Lg Chem, Ltd. | Hybrid supported catalyst and method of preparing polyolefin using the same |
US12006378B2 (en) | 2019-09-27 | 2024-06-11 | Lg Chem, Ltd. | Polyethylene and its chlorinated polyethylene |
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