WO2015046995A1 - Polyoléfine - Google Patents
Polyoléfine Download PDFInfo
- Publication number
- WO2015046995A1 WO2015046995A1 PCT/KR2014/009119 KR2014009119W WO2015046995A1 WO 2015046995 A1 WO2015046995 A1 WO 2015046995A1 KR 2014009119 W KR2014009119 W KR 2014009119W WO 2015046995 A1 WO2015046995 A1 WO 2015046995A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon atoms
- molecular weight
- polyolefin
- aryl
- formula
- Prior art date
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- 229920000098 polyolefin Polymers 0.000 title claims abstract description 63
- 238000009826 distribution Methods 0.000 claims abstract description 33
- 125000004432 carbon atom Chemical group C* 0.000 claims description 138
- 150000001875 compounds Chemical class 0.000 claims description 54
- 125000003118 aryl group Chemical group 0.000 claims description 29
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 24
- 239000005977 Ethylene Substances 0.000 claims description 23
- 125000000217 alkyl group Chemical group 0.000 claims description 23
- 239000004711 α-olefin Substances 0.000 claims description 22
- 239000012968 metallocene catalyst Substances 0.000 claims description 20
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- 150000002367 halogens Chemical class 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 125000003342 alkenyl group Chemical group 0.000 claims description 14
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 14
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 13
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 12
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910052796 boron Inorganic materials 0.000 claims description 12
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 125000003368 amide group Chemical group 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 6
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 6
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 6
- 238000010528 free radical solution polymerization reaction Methods 0.000 claims description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-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
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 125000005103 alkyl silyl group Chemical group 0.000 claims description 4
- 125000001118 alkylidene group Chemical group 0.000 claims description 4
- 125000005104 aryl silyl group Chemical group 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Chemical group 0.000 claims description 4
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- 229940069096 dodecene Drugs 0.000 claims description 3
- 125000000524 functional group Chemical group 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 239000002879 Lewis base Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052795 boron group element Inorganic materials 0.000 claims description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 2
- 229910052732 germanium Chemical group 0.000 claims description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052752 metalloid Inorganic materials 0.000 claims description 2
- 150000002738 metalloids Chemical class 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 2
- 230000000379 polymerizing effect Effects 0.000 claims description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims 2
- 150000001721 carbon Chemical group 0.000 claims 1
- 150000007527 lewis bases Chemical class 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- -1 1-nuxene Natural products 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 239000002904 solvent Substances 0.000 description 13
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 11
- 150000007523 nucleic acids Chemical class 0.000 description 11
- 102000039446 nucleic acids Human genes 0.000 description 11
- 108020004707 nucleic acids Proteins 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 9
- 230000007547 defect Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 7
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010924 continuous production Methods 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- VAMFXQBUQXONLZ-UHFFFAOYSA-N n-alpha-eicosene Natural products CCCCCCCCCCCCCCCCCCC=C VAMFXQBUQXONLZ-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VIMMECPCYZXUCI-MIMFYIINSA-N (4s,6r)-6-[(1e)-4,4-bis(4-fluorophenyl)-3-(1-methyltetrazol-5-yl)buta-1,3-dienyl]-4-hydroxyoxan-2-one Chemical compound CN1N=NN=C1C(\C=C\[C@@H]1OC(=O)C[C@@H](O)C1)=C(C=1C=CC(F)=CC=1)C1=CC=C(F)C=C1 VIMMECPCYZXUCI-MIMFYIINSA-N 0.000 description 2
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 2
- 229940106006 1-eicosene Drugs 0.000 description 2
- FIKTURVKRGQNQD-UHFFFAOYSA-N 1-eicosene Natural products CCCCCCCCCCCCCCCCCC=CC(O)=O FIKTURVKRGQNQD-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- SMBQBQBNOXIFSF-UHFFFAOYSA-N dilithium Chemical compound [Li][Li] SMBQBQBNOXIFSF-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229910021482 group 13 metal Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- JUJWROOIHBZHMG-RALIUCGRSA-N pyridine-d5 Chemical compound [2H]C1=NC([2H])=C([2H])C([2H])=C1[2H] JUJWROOIHBZHMG-RALIUCGRSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-O trimethylphosphanium Chemical compound C[PH+](C)C YWWDBCBWQNCYNR-UHFFFAOYSA-O 0.000 description 2
- 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 2
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 description 1
- 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 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
- 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
- BYHQTRFJOGIQAO-GOSISDBHSA-N 3-(4-bromophenyl)-8-[(2R)-2-hydroxypropyl]-1-[(3-methoxyphenyl)methyl]-1,3,8-triazaspiro[4.5]decan-2-one Chemical compound C[C@H](CN1CCC2(CC1)CN(C(=O)N2CC3=CC(=CC=C3)OC)C4=CC=C(C=C4)Br)O BYHQTRFJOGIQAO-GOSISDBHSA-N 0.000 description 1
- SKHRLNSNVBBGOG-UHFFFAOYSA-N 4,4,5,5-tetramethylcyclopent-2-yn-1-one Chemical compound CC1(C(C#CC1=O)(C)C)C SKHRLNSNVBBGOG-UHFFFAOYSA-N 0.000 description 1
- 241000349731 Afzelia bipindensis Species 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- LEUIHGAIKJLVHR-UHFFFAOYSA-N C(CCC)B(CCCC)CCCC.C(CC)B(CCC)CCC Chemical compound C(CCC)B(CCCC)CCCC.C(CC)B(CCC)CCC LEUIHGAIKJLVHR-UHFFFAOYSA-N 0.000 description 1
- PLGVIJOQDDMWAO-UHFFFAOYSA-N CCCCN(CCCC)CCCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F Chemical compound CCCCN(CCCC)CCCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F PLGVIJOQDDMWAO-UHFFFAOYSA-N 0.000 description 1
- HFEVWLDHPOCPTP-UHFFFAOYSA-N CCNCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F Chemical compound CCNCC.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F.FC(C(F)=C(C([Al+2])=C1F)F)=C1F HFEVWLDHPOCPTP-UHFFFAOYSA-N 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- 244000061458 Solanum melongena Species 0.000 description 1
- 229910010066 TiC14 Inorganic materials 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- SHPVKUQHCZKKRP-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCCCN(CCCC)CCCC SHPVKUQHCZKKRP-UHFFFAOYSA-N 0.000 description 1
- RPXNIXOOFOQCKJ-UHFFFAOYSA-N [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC Chemical compound [B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.[B+2]C(C(F)=C(C(F)=C1F)F)=C1F.CCNCC RPXNIXOOFOQCKJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000001273 butane Substances 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- ISEJRLXHKSHKPM-UHFFFAOYSA-N dimethyl(2-methylpropyl)alumane Chemical compound CC(C)C[Al](C)C ISEJRLXHKSHKPM-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- MWNKMBHGMZHEMM-UHFFFAOYSA-N dimethylalumanylium;ethanolate Chemical compound CCO[Al](C)C MWNKMBHGMZHEMM-UHFFFAOYSA-N 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- SKVWXDRVFXUPJX-UHFFFAOYSA-M lithium;carbamate Chemical compound [Li+].NC([O-])=O SKVWXDRVFXUPJX-UHFFFAOYSA-M 0.000 description 1
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BQBCXNQILNPAPX-UHFFFAOYSA-N methoxy(dimethyl)alumane Chemical compound [O-]C.C[Al+]C BQBCXNQILNPAPX-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000000369 oxido group Chemical group [*]=O 0.000 description 1
- 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 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052696 pnictogen Inorganic materials 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-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
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 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
- C08F4/42—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
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
-
- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
- C08F2420/00—Metallocene catalysts
- C08F2420/01—Cp or analog bridged to a non-Cp X neutral donor
-
- 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
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
Definitions
- the present invention relates to polyolefins, and more particularly, to polyolefins having a narrow molecular weight distribution and exhibiting a characteristic comonomer distribution.
- SUBSTITUTE SHEET (RULE 26) Compounds listed in the above figure have a phosphorus (1), ethylene or propylene (2), methylidene (3) and methylene ( 4 ) bridges instead of the CGC-structured silicon bridges, but ethylene polymerization or ethylene and alphalephine are introduced, respectively. When applied to the copolymerization did not show excellent results in terms of polymerization activity and co-polymerization performance compared to CGC.
- the present invention uses a metallocene catalyst to control the distribution of comonomers according to the molecular weight.
- the present invention controls the distribution of comonomers according to the molecular weight by using a metallocene catalyst.
- Eggplant is to provide a polyolefin.
- One aspect of the present invention for achieving the above object provides a polyolefin having a molecular weight distribution of 1.5 to 3, the branch gradient number (BGN) value of 0.01 to 1.0 calculated by the following formula (1):
- the low molecular weight grain content means the grain content at the left boundary of 80%, except for the left and right ends 10% of the total area (branch content of 2 or more carbon atoms per 1,000 carbons, unit: 1,000 C).
- the high molecular weight side branch content means the content of the branch at the right boundary.
- the polyolefins of the present invention can be used in various fields, such as household articles, automobiles, shock absorbers, which alone or blended with other polymers, requiring high laminar strength and elasticity.
- FIG. 1 is a graph showing the results of GPC-FTIR measurement of the polyolefin of Example 1.
- FIG. 2 is a graph showing the results of GPC-FTIR measurement of polyolefin of Example 2.
- FIG. 3 is a graph showing the results of GPC-FTIR measurement of polyolefin of Comparative Example 1.
- first and second are used to describe various components, and the terms are used only for the purpose of distinguishing one component from other components.
- the molecular weight distribution is 1.5 to 3, and the BGN (Branch gradient number) value calculated by the following Equation 1 provides 0.01 to 1.0 polyolefin.
- Branch Gradient Number (BGN) High Molecular Weight Side Branch Content-Low Molecular Weight
- BGN branch gradient number
- SCB short carbon branch
- LCB long carbon branch
- the BGN (Branch gradient number) value is measured by using the GPC-FTIR equipment to measure the molecular weight, molecular weight distribution, and defect content at the same time continuously, and log-log (w / w) of the molecular weight (Molecular weight, Mw) as the x-axis.
- the molecular weight distribution curve is plotted using the logarithmic molecular weight distribution (dwt / dlog Mw) as the y-axis, the low-molecular weight content of the low-molecular weight defect is determined at the left boundary of 80% except for the left and right ends 10% of the total area.
- the content (unit: dog / 1,000C), and the high molecular weight side branch content means the value calculated according to the following formula 1 as the content of the defect at the right boundary of the middle 80%.
- the content of the grains is to mean the content of two or more carbon atoms per 1,000 carbons.
- the BGN value is positive, it means that the low content of grains is low in the low molecular weight region according to the molecular weight distribution curve for the logarithm of the molecular weight, and that the side branch content is relatively high in the high molecular weight region.
- the value is negative (-), it means a structure that has a high content of grains in a low molecular weight region and a relatively low content of grains in a high molecular weight region.
- the polyolefin of the present invention has a BGN value measured and calculated in the same manner as 0.01 to 1.0, or about 0.01 to about 0.9, or about 0.01 to about 0.5, or about 0.01 to about 0.2, or about 0.01 to about 0.1, or From about 0.03 to about 0.1. That is, the polyolefin of the present invention has a low branched content in the low molecular weight region, a relatively high branched content in the high molecular weight region, and the slope thereof is within the above-described range.
- the physical properties of the polyolefin can be optimized to achieve high impact strength and good mechanical properties. This results in high layer strength and good mechanical properties when compounded with other polymers such as polypropylene resins. Can be achieved.
- the polyolefin of the present invention may have a range of about 20 to about 120 carbon atoms, preferably about 50 to about 100 carbon atoms per 1,000 carbon atoms.
- the polyolefins of the invention also have a range 3 ⁇ 4 ⁇ in which the molecular weight distribution (weight average molecular weight / number average molecular weight) is from about 1.0 to about 3.0, or from about 1.5 to about 3.0, or from about 1.5 to about 2.8, or from about 2.0 to about 18.
- the polyolefin of the present invention may exhibit high layer strength by having a very narrow molecular weight distribution.
- the polyolefin has a melt flow index (Ml) measured at 190 ° C. and a 2.16 kg load condition in accordance with ASTM D1238 of about 0.1 to about 2000 g / 10 min, preferably about 0.1 to about 1000 g / 10 min, Preferably about 0.1 to 500 g / 10min, but is not limited thereto.
- Ml melt flow index
- melt flow rate ratio (MFRR) of the polyolefin may be about 5 to about 15, preferably about 6 to about 13, but is not limited thereto.
- density of the polyolefin can be about 0.85 to about 0.91 g cc, preferably about 0.86 to about 0.91 g / cc, more preferably about 0.86 to about 0.90 g / cc, but is not limited thereto. It is not.
- the physical properties may be more optimized to achieve high laminar strength and good mechanical properties.
- the polyolefin which concerns on this invention is a copolymer of ethylene which is an olefinic monomer, and an alpha olefin comonomer.
- Alpha olefins having 3 or more carbon atoms may be used as the alpha olefin copolymer.
- Alpha olefins having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 4 -methylxopentene, 1'nucleene, 1-heptene, 1'octene, ⁇ decene, 1-undecene, 1-dodecene and 1- Tetradecene, 1-nuxadecene, 1-octadecene, or 1-eicosene.
- Ateo a copolymer of said ethylene and alpha-olefin comonomer on, alpha eulre content of the pins co-monomer is from about 5 to about 70 parts by weight 0/0, preferably from about 5 to about 60 Increased 0 /., And more preferably About 10 to about 50 weight%.
- the weight average molecular weight of the polyolefin according to the present invention may be about 10,000 to about 500,000 g / mol, preferably about 20,000 to about 200,000 g / m, but is not limited thereto.
- the polyolefin according to the present invention has excellent layer strength when mixed with other polymers, and can be used in various fields such as household articles, automobiles, layer absorbers, and the like.
- Polyolefins according to the present invention having the above characteristics can be obtained by copolymerization with ethylene and alpha olepin using a common metallocene compound including two metallocene compounds of different structures as catalysts,
- the polyolefin may have a molecular weight distribution and a BGN value as described above. More specifically, the polyolefin of the present invention, the first metallocene compound represented by the formula (1); And in the presence of a common metallocene catalyst comprising a second metallocene compound represented by the formula (2), it can be obtained by combining the ethylene and alpha olepin comonomer.
- R1 and R2 may be the same as or different from each other, and each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylsilyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Or a metalloid of a Group 4 metal substituted with hydrocarbyl; R 1 and R 2 or two R 2 may be connected to each other by an alkylidine including an alkyl having 1 to 20 carbon atoms or an aryl functional group having 6 to 20 carbon atoms to form a ring;
- R3, 3 'and R3 may be the same or different from each other, and each independently Hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an amido group; Two or more of said R3, R3 ', and R3 "may be linked to each other to form an aliphatic ring or an aromatic ring;
- CY is a substituted or unsubstituted aliphatic or aromatic ring, and the substituents substituted in CY are halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an alkyl amido group having 1 to 20 carbon atoms; An aryl amido group having 6 to 20 carbon atoms, and when there are a plurality of substituents, two or more substituents in the substituents may be linked to each other to form an aliphatic or aromatic ring;
- Ml is a Group 4 transition metal
- Q1 and Q2 may be the same as or different from each other, and each independently halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkyl amido having 1 to 20 carbon atoms; Aryl amido having 6 to 20 carbon atoms; Or alkylidene having 1 to 20 carbon atoms.
- M 2 is a Group 4 transition metal
- Q3 and Q4 may be the same or different from each other, and each independently halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Carbon number 1 Alkyl amido of from 20 to 20; Aryl amido having 6 to 20 carbon atoms; Or alkylidene having 1 to 20 carbon atoms;
- R4 to R10 may be the same as or different from each other, and each independently hydrogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylsilyl having 1 to 20 carbon atoms, arylsilyl having 6 to 20 carbon atoms; Or alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms;
- B is carbon, silicon, or germanium, and is a bridge that binds a cyclopentadienyl-based ligand and JR10 zy by a covalent bond;
- J is a periodic table group 15 element or group 16 element
- z is the oxidation number of the element J
- y is the bond number of the J element
- n is an integer of 0-10.
- the polymerization reaction of the ethylene and alpha olefin comonomer may be made at about 130 to about 250 ° C, preferably about 140 to about 200 ° C.
- the activity of the catalyst may be maintained even in a high temperature synthesis process of 130 ° C. or higher, so that the active point of the catalyst in the synthesis reaction of the polyolefin is 2 Make it ideal.
- the metallocene catalyst for synthesizing the high-density pleurepine is generally not used in the solution polymerization step of applying a high reaction resistance due to its low activity in the high temperature region, but the second metallocene compound of Chemical Formula 2 is represented by Chemical Formula 1 When mixed with the first metallocene compound of the excellent catalytic activity can be exhibited even in a high temperature region of 130 ° C or more.
- reaction reaction of the ethylene and alpha olefin comonomer may be carried out in a continuous solution polymerization process, bulk polymerization process, suspension polymerization process or emulsion polymerization process. It may proceed, but preferably by solution polymerization reaction in a single reactor.
- polyolefin can be synthesized in a single reactor even though two different metallocene catalysts are used, and thus a simple manufacturing process can be configured to reduce process time and cost.
- first metallocene compound of Formula 1 include, but are not limited to, the compound of Formula 3 or Formula 4.
- R1, R2, Q1, Q2 and Ml are the same as defined in Formula 1, and R11 may be the same as or different from each other, and each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or amido group; Two or more of the R 11 may be connected to each other to form an aliphatic ring or an aromatic ring.
- R1, R2, Q1, Q2 and Ml are the same as defined in Formula 1, and R12 may be the same or different from each other, and each independently hydrogen; halogen; Alkyl having 1 to 20 carbon atoms; Alkenyl having 2 to 20 carbon atoms; Aryl having 6 to 20 carbon atoms; Alkylaryl having 7 to 20 carbon atoms; Arylalkyl having 7 to 20 carbon atoms; Alkoxy having 1 to 20 carbon atoms; Aryloxy having 6 to 20 carbon atoms; Or an amido group; Two or more of the R 12 may be connected to each other to form an aliphatic ring or an aromatic ring.
- R2 may be each independently hydrogen or methyl group
- Q1 or Q2 may be the same or different from each other, and each independently may be a methyl group : dimethylamido group or chloride group.
- Specific examples of the second metallocene compound of Chemical Formula 2 may include a compound of the following chemical formula, but are not limited thereto.
- the common metallocene catalyst in the method for preparing the polyolefin, may further include a cocatalyst compound in addition to the first and second metallocene compounds described above.
- the cocatalyst compound includes a Group 13 metal of the periodic table, and may be at least one selected from the group consisting of a compound of Formula 5, a compound of Formula 6, and a compound of Formula 7.
- R13 is a halogen radical, a hydrocarbyl radical having 1 to 20 carbon atoms, or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen, c is an integer of 2 or more,
- D is aluminum or boron
- R14 is hydrocarbyl having 1 to 20 carbon atoms or hydrocarbyl having 1 to 20 carbon atoms substituted with halogen
- L is a neutral or cationic Lewis base
- H is a hydrogen atom
- Z is a Group 13 element
- E may be the same or different from each other, and each independently one or more hydrogen atoms is halogen, hydrocarbon having 1 to 20 carbon atoms, alkoxy or Or an aryl group having 6 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms unsubstituted or substituted with phenoxy.
- a compound represented by the above formula (V) may, for example, such as methyl aluminoxane (MAO), ethyl aluminoxane, isobutyl aluminoxane, butyl aluminoxane may be.
- MAO methyl aluminoxane
- ethyl aluminoxane ethyl aluminoxane
- isobutyl aluminoxane isobutyl aluminoxane
- butyl aluminoxane may be.
- alkyl metal compound represented by the formula (6) for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tripropyl aluminum,.
- Examples of the compound represented by the formula (7) include triethylammonium tetraphenylboron, tributylammonium tetraphenylboron, trimethylammonium tetraphenylboron, tripropylammonium tetraphenylboron, and trimethylammonium tetra (P).
- Tripropylammonium tetraphenylaluminum trimethylammonium tetra ( ⁇ -rylryl) aluminum, tripropylammonium tetra ( ⁇ -rylryl) aluminum, triethylammonium tetra ( ⁇ , ⁇ -dimethylphenyl) aluminum, tributylammonium Tetra ( ⁇ -trifluoromethylphenyl) aluminum, trimethylammonium tetra ( ⁇ - trifluoromethylphenyl) aluminum, tributylammonium tetrapentafluorophenylaluminum, ⁇ , ⁇ -diethylanilinium tetraphenylaluminum, ⁇ , ⁇ - diethylanilinium tetraphenylaluminum, ⁇ , ⁇ - diethylanilinium tetrapentafluorophenylaluminum,
- Triphenylphosphonium tetraphenylaluminum Trimethylphosphonium tetraphenylaluminum, triphenylcarbonium tetraphenylboron, triphenylcarbonium tetraphenylaluminum, triphenylcarbonium tetra ( ⁇ -trifluoromethylphenyl) boron,
- Triphenylcarbonium tetrapentafluorophenylboron and the like Triphenylcarbonium tetrapentafluorophenylboron and the like.
- the content of the promoter is the amount of the first and second metallocene compound
- the molar ratio of the Group 13 metals to Group 4 metals may be about 1 to about 10,000, preferably about 1 to about 1,000, more preferably about 1 to about 500. remind If the molar ratio is less than 1, the effect of the addition of the promoter is insignificant. If the molar ratio exceeds 10,000, the excess alkyl group, which does not participate in the reaction and the residual alkyl group, rather inhibits the catalytic reaction and may act as a catalyst poison. This may cause a problem that excess aluminum or boron will remain in the polymer.
- a hydrocarbon solvent such as pentane, nucleic acid, heptane, or an aromatic solvent such as benzene or toluene may be used as the reaction solvent, but is not necessarily limited thereto, and may be used in the art. Any solvent can be used.
- the common metallocene catalyst is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms suitable for an olefin polymerization process, for example, pentane, nucleic acid, heptane, nonane, decane, and isomers thereof. It can be injected by dissolving or diluting with aromatic hydrocarbon solvents such as and toluene and benzene, and hydrocarbon solvents substituted with chlorine atoms such as dichloromethane and chlorobenzene.
- the solvent used herein is preferably used by removing a small amount of water or air that acts as a catalyst poison by treating a small amount of alkylaluminum, and may be carried out by further using a promoter.
- a polyolefin satisfying the above-described physical properties may be manufactured. Copolymerization with alpha olefins when using a mixed metallocene catalyst is particularly induced by the second metallocene compound that makes the high molecular weight moiety, which enables the production of high performance polyolefins in which alpha olefin comonomers are concentrated on the high molecular weight chain side. do.
- the polyolefin production can be carried out by solution polymerization, for example, can be carried out according to the conventional method while continuously supplying ethylene and alpha olefin comonomer at a constant ratio.
- the alpha olephine comonomer is, for example, propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-nucleene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-nuxadecene, 1-octadecene or 1-eicosene may be used.
- the present invention is not limited thereto.
- the polymerization temperature when copolymerizing alpha olefin as a comonomer with the common metallocene catalyst may range from about 130 to about 250 ° C., preferably from about 140 to about 200 ° C.
- the activity of the catalyst can be maintained even in a high temperature synthesis process of 130 ° C. or higher, so that the catalyst in the synthesis reaction of polyolefin Let the active point of be at least 2.
- the metallocene catalyst for synthesizing high-density polyolefin is not generally used in the solution thickening step of applying a high reaction temperature because of its low activity in the high temperature region, but the second metallocene compound of Formula 2 is When mixed with the first metallocene compound, excellent catalytic activity may be exhibited even in a high temperature region of 130 ° C or higher.
- the polymerization pressure is preferably performed at about 1 to about 150 bar, more preferably about 1 to about 120 bar, most preferably about 10 to about 120 bar.
- the polymerization reaction of the ethylene and the alpha olefin pin comonomer can control the physical properties of the polyolefin prepared by adjusting the content of the second metallocene compound.
- the common metallocene catalyst includes a second metallocene compound in a relatively low content. More specifically, the second metallocene compound is more than 0 mol% to less than about 50 mol%, preferably about 5 to about 30 mol%, based on the total amount of the first and second metallocene compounds, More preferably from about 5 to about 25 mol%.
- the second metallocene compound is included in such a content ratio, it is possible to provide a polyolefin having a narrow molecular weight distribution but having a BGN value in the above-described range.
- 1,2,3,4-tetrahydroquinoline 13.08 g, 98.24 mmol
- diethyl ether 150 mL
- the shield tank was immersed in a -78 ° C. low temperature bath made of dry ice and acetone and stirred for 30 minutes.
- n-BuLi n-butyllithium, 39.3 mL, 2.5M, 98.24 mmol
- the flask was stirred for 2 hours, the flask was cooled to room temperature while removing the generated butane gas.
- the flask was again immersed in a -78 ° C low temperature bath to lower the silver and added CO 2 gas. As the carbon dioxide gas was added, the slurry disappeared and became a transparent solution. The flask was connected to a bubbler to raise the temperature to room temperature while removing carbon dioxide gas. Thereafter, excess C0 2 gas and solvent were removed under vacuum. The flask was transferred to a dry box, pentane was added thereto, stirred vigorously, and filtered to obtain lithium carbamate of a white solid compound. The white solid compound is coordinated with diethyl ether. The yield is 100%.
- 6-t-buthoxyhexane was confirmed by ⁇ -NMR, and the Grignard reaction proceeded well from 6-t-butoxynucleic acid. .
- 6-t-buthoxyhexyl magnesium chloride was synthesized.
- the 2 L autoclave continuous process reactor was charged with nucleic acid solvent (5.38 kg / h) and 1-butene (0.82 kg / h), then the temperature at the top of the reactor was preheated to 160 ° C.
- Triisobutylaluminum compound (0.05 mmol / min)
- the first metallocene compound obtained above (0.45 ⁇ / ⁇ )
- the crab 2 metallocene compound 0.05 ⁇ / min
- dimethylanilinium tetrakis prenta Florophenyl
- ethylene (0.87 kg / h) was introduced into the autoclave reactor and maintained at 160 ° C. for 30 minutes or more in a continuous process at a pressure of 89 bar, followed by copolymerization to obtain a copolymer.
- the remaining ethylene gas was removed and the polymer solution was dried in a vacuum oven for at least 12 hours, and then physical properties were measured.
- LG Chem's LLDPE (product name: SN318) prepared with a Ziegler-Natta catalyst was prepared. Comparative Example 2
- BGN Branch gradient number: In the GPC-FTIR measurement result, the log value (log Mw) of the molecular weight (Mw) is the X-axis, and the molecular weight distribution (dwt / dlog Mw) is y for the log value.
- the content of low molecular weight side branches is 80% at the left boundary, except for the left and right ends 10% of the total area.
- the amount of grains was determined as the amount of grains at the right boundary of 80%, and the BGN value was obtained by calculating the value of the following formula (1). [Expression i] '
- FIGS. 1 to 4 GPC-FTIR measurement results of the polyolefins of Examples 1 and 2 and Comparative Examples 1 and 2 are shown in FIGS. 1 to 4, respectively.
- the content of the carbon content of 2 or more carbon atoms at the left boundary point (point A) and the carbon content of 2 or more carbon atoms at the right boundary point (point B) in the middle 80% region of the molecular weight distribution curve area By measuring the content it can be seen that the BGN value calculated according to 1 has a positive value.
- the polyolefin of Comparative Example 1 had a negative BGN value of ⁇ 0.14 and a molecular weight distribution exceeded 3.
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Abstract
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CN201480048452.5A CN105518034B (zh) | 2013-09-30 | 2014-09-29 | 聚烯烃 |
EP14849825.6A EP3037441B1 (fr) | 2013-09-30 | 2014-09-29 | Polyoléfine |
JP2016545698A JP6407291B2 (ja) | 2013-09-30 | 2014-09-29 | ポリオレフィン |
ES14849825T ES2966662T3 (es) | 2013-09-30 | 2014-09-29 | Poliolefina |
US15/021,149 US9701768B2 (en) | 2013-09-30 | 2014-09-29 | Polyolefin |
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JP2019515097A (ja) * | 2016-04-27 | 2019-06-06 | ハンファ ケミカル コーポレーション | 混成担持メタロセン触媒を用いた高密度エチレン系重合体及び製造方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4547551A (en) * | 1982-06-22 | 1985-10-15 | Phillips Petroleum Company | Ethylene polymer blends and process for forming film |
US5064802A (en) | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
KR960010734B1 (ko) * | 1991-06-07 | 1996-08-07 | 후지쓰 가부시끼가이샤 | 메모리 셀 캐패시터를 구비한 반도체 메모리장치 및 그의 제조방법 |
JP2003507538A (ja) * | 1999-08-19 | 2003-02-25 | ボレアリス テクノロジー オイ | 容器製造方法 |
KR20050088087A (ko) * | 2002-11-27 | 2005-09-01 | 보레알리스 테크놀로지 오와이. | 폴리에틸렌 조성물로서의 용도 |
-
2014
- 2014-09-29 WO PCT/KR2014/009119 patent/WO2015046995A1/fr active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4547551A (en) * | 1982-06-22 | 1985-10-15 | Phillips Petroleum Company | Ethylene polymer blends and process for forming film |
US5064802A (en) | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
KR960010734B1 (ko) * | 1991-06-07 | 1996-08-07 | 후지쓰 가부시끼가이샤 | 메모리 셀 캐패시터를 구비한 반도체 메모리장치 및 그의 제조방법 |
JP2003507538A (ja) * | 1999-08-19 | 2003-02-25 | ボレアリス テクノロジー オイ | 容器製造方法 |
KR20050088087A (ko) * | 2002-11-27 | 2005-09-01 | 보레알리스 테크놀로지 오와이. | 폴리에틸렌 조성물로서의 용도 |
Non-Patent Citations (1)
Title |
---|
CHEM. REV., vol. 103, 2003, pages 283 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019515097A (ja) * | 2016-04-27 | 2019-06-06 | ハンファ ケミカル コーポレーション | 混成担持メタロセン触媒を用いた高密度エチレン系重合体及び製造方法 |
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