KR100839759B1 - 4족 전이금속 화합물을 포함하는 촉매 조성물 및 이를이용한 폴리올레핀의 제조방법 - Google Patents
4족 전이금속 화합물을 포함하는 촉매 조성물 및 이를이용한 폴리올레핀의 제조방법 Download PDFInfo
- Publication number
- KR100839759B1 KR100839759B1 KR1020070000120A KR20070000120A KR100839759B1 KR 100839759 B1 KR100839759 B1 KR 100839759B1 KR 1020070000120 A KR1020070000120 A KR 1020070000120A KR 20070000120 A KR20070000120 A KR 20070000120A KR 100839759 B1 KR100839759 B1 KR 100839759B1
- Authority
- KR
- South Korea
- Prior art keywords
- carbon atoms
- group
- formula
- radical
- alkyl
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 79
- 239000003054 catalyst Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 40
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 25
- 229910052723 transition metal Inorganic materials 0.000 title claims description 11
- 150000003624 transition metals Chemical class 0.000 title claims description 11
- 150000003623 transition metal compounds Chemical class 0.000 claims abstract description 62
- 238000009826 distribution Methods 0.000 claims abstract description 13
- 230000009977 dual effect Effects 0.000 claims abstract description 11
- -1 Arylalkyl radicals Chemical class 0.000 claims description 130
- 125000004432 carbon atom Chemical group C* 0.000 claims description 126
- 150000001875 compounds Chemical class 0.000 claims description 95
- 125000000217 alkyl group Chemical group 0.000 claims description 41
- 125000003118 aryl group Chemical group 0.000 claims description 38
- 229910052736 halogen Inorganic materials 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 24
- 125000003342 alkenyl group Chemical group 0.000 claims description 23
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 16
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 16
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 150000001336 alkenes Chemical class 0.000 claims description 13
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 12
- 229910052752 metalloid Inorganic materials 0.000 claims description 12
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 claims description 8
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Chemical group 0.000 claims description 7
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- 125000003700 epoxy group Chemical group 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 125000000743 hydrocarbylene group Chemical group 0.000 claims description 7
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 claims description 6
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 claims description 6
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 6
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 claims description 6
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 6
- 150000005840 aryl radicals Chemical class 0.000 claims description 6
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 claims description 6
- 125000004437 phosphorous atom Chemical group 0.000 claims description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical group [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002841 Lewis acid Substances 0.000 claims description 4
- 229910052795 boron group element Inorganic materials 0.000 claims description 4
- 230000007935 neutral effect Effects 0.000 claims description 4
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical compound O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 claims description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group 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
- 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 claims description 2
- 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 claims description 2
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229940069096 dodecene Drugs 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
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- OLRJXMHANKMLTD-UHFFFAOYSA-N silyl Chemical compound [SiH3] OLRJXMHANKMLTD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 18
- 238000007334 copolymerization reaction Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 12
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 abstract description 9
- 238000002844 melting Methods 0.000 abstract description 6
- 230000008018 melting Effects 0.000 abstract description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002685 polymerization catalyst Substances 0.000 abstract description 3
- 230000002902 bimodal effect Effects 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract 1
- 238000005481 NMR spectroscopy Methods 0.000 description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 30
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000002904 solvent Substances 0.000 description 24
- 239000007787 solid Substances 0.000 description 23
- 239000012044 organic layer Substances 0.000 description 21
- 150000002736 metal compounds Chemical class 0.000 description 16
- 229920000642 polymer Polymers 0.000 description 14
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 12
- 239000005977 Ethylene Substances 0.000 description 12
- UBFBUNVAHZNDFD-UHFFFAOYSA-L [Cl-].[Cl-].CC=1C(C(=C(C=1)C)C)[Ti+2] Chemical compound [Cl-].[Cl-].CC=1C(C(=C(C=1)C)C)[Ti+2] UBFBUNVAHZNDFD-UHFFFAOYSA-L 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000003446 ligand Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- GEJUFTHBORQCNQ-UHFFFAOYSA-N phenylalumane Chemical compound [AlH2]c1ccccc1 GEJUFTHBORQCNQ-UHFFFAOYSA-N 0.000 description 9
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical compound [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 description 9
- JBALYHGVQNTMHI-UHFFFAOYSA-N 2-bromo-n-cyclohexylaniline Chemical compound BrC1=CC=CC=C1NC1CCCCC1 JBALYHGVQNTMHI-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 239000012190 activator Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000012230 colorless oil Substances 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 7
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 7
- 125000003368 amide group Chemical group 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- RCRFPHNGSDJXNZ-UHFFFAOYSA-N n-cyclohexyl-2-(2,3,5-trimethylcyclopenta-1,4-dien-1-yl)aniline Chemical compound CC1C=C(C)C(C=2C(=CC=CC=2)NC2CCCCC2)=C1C RCRFPHNGSDJXNZ-UHFFFAOYSA-N 0.000 description 6
- 229910052698 phosphorus Inorganic materials 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- ZOICEQJZAWJHSI-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boron Chemical compound [B]C1=C(F)C(F)=C(F)C(F)=C1F ZOICEQJZAWJHSI-UHFFFAOYSA-N 0.000 description 5
- LAKPILVQPVPULO-UHFFFAOYSA-N 2-(2-aminophenyl)-3,4-dimethylcyclopent-2-en-1-one Chemical compound CC1CC(=O)C(C=2C(=CC=CC=2)N)=C1C LAKPILVQPVPULO-UHFFFAOYSA-N 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- VIBIPXFOYXNBEO-UHFFFAOYSA-N n-cyclohexyl-4-methylaniline Chemical compound C1=CC(C)=CC=C1NC1CCCCC1 VIBIPXFOYXNBEO-UHFFFAOYSA-N 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 239000004711 α-olefin Substances 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 150000002466 imines Chemical class 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 125000000369 oxido group Chemical group [*]=O 0.000 description 4
- 125000002743 phosphorus functional group Chemical group 0.000 description 4
- 230000008569 process Effects 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
- DBQOUEWUAIHCNY-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)alumane Chemical compound Fc1c(F)c(F)c([AlH2])c(F)c1F DBQOUEWUAIHCNY-UHFFFAOYSA-N 0.000 description 3
- PYVIFKRYUHVUCF-UHFFFAOYSA-N 2,3,5-trimethylcyclopenta-1,3-diene Chemical compound CC1C=C(C)C(C)=C1 PYVIFKRYUHVUCF-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- DXQXWMYUGOTNGJ-UHFFFAOYSA-N [4-(trifluoromethyl)phenyl]boron Chemical compound [B]C1=CC=C(C(F)(F)F)C=C1 DXQXWMYUGOTNGJ-UHFFFAOYSA-N 0.000 description 3
- 239000002168 alkylating agent Substances 0.000 description 3
- 229940100198 alkylating agent Drugs 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 230000000704 physical effect Effects 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- GWUXLTRGPPIDJA-UHFFFAOYSA-N (4-methylphenyl)alumane Chemical compound CC1=CC=C([AlH2])C=C1 GWUXLTRGPPIDJA-UHFFFAOYSA-N 0.000 description 2
- VKMQKNJWQNCEQV-UHFFFAOYSA-N (4-methylphenyl)boron Chemical compound [B]C1=CC=C(C)C=C1 VKMQKNJWQNCEQV-UHFFFAOYSA-N 0.000 description 2
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 2
- LAMJVVUEZWMMDU-UHFFFAOYSA-N 2-bromo-n-cyclohexyl-4-methylaniline Chemical compound BrC1=CC(C)=CC=C1NC1CCCCC1 LAMJVVUEZWMMDU-UHFFFAOYSA-N 0.000 description 2
- OFPYNSLXBSMABT-UHFFFAOYSA-N 2-bromo-n-cyclohexyl-4-phenylaniline Chemical compound BrC1=CC(C=2C=CC=CC=2)=CC=C1NC1CCCCC1 OFPYNSLXBSMABT-UHFFFAOYSA-N 0.000 description 2
- SPKJZLMFVBBJAO-UHFFFAOYSA-N 2-bromo-n-pentan-3-ylaniline Chemical compound CCC(CC)NC1=CC=CC=C1Br SPKJZLMFVBBJAO-UHFFFAOYSA-N 0.000 description 2
- AOPBDRUWRLBSDB-UHFFFAOYSA-N 2-bromoaniline Chemical compound NC1=CC=CC=C1Br AOPBDRUWRLBSDB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000349731 Afzelia bipindensis Species 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- AGCYMXXIJOBNOQ-UHFFFAOYSA-N C1(CCCCC1)NC1=CC=C(CC2=CC=C(C=C2)NC2CCCCC2)C=C1.C1(CCCCC1)NC1=CC=C(CC2=CC=C(C=C2)NC2CCCCC2)C=C1 Chemical compound C1(CCCCC1)NC1=CC=C(CC2=CC=C(C=C2)NC2CCCCC2)C=C1.C1(CCCCC1)NC1=CC=C(CC2=CC=C(C=C2)NC2CCCCC2)C=C1 AGCYMXXIJOBNOQ-UHFFFAOYSA-N 0.000 description 2
- UHEXVMZIQRWBGV-UHFFFAOYSA-N CC1=C(C(=CC1C)C)C1=C(C=CC=C1)NC1CCCCC1.CC1=C(C(=CC1C)C)C1=C(C=CC=C1)NC1CCCCC1 Chemical compound CC1=C(C(=CC1C)C)C1=C(C=CC=C1)NC1CCCCC1.CC1=C(C(=CC1C)C)C1=C(C=CC=C1)NC1CCCCC1 UHEXVMZIQRWBGV-UHFFFAOYSA-N 0.000 description 2
- ABNCGYCFZDYTQP-UHFFFAOYSA-L CC1=C(C)C(C)=C(C)C1[Ti](Cl)Cl Chemical compound CC1=C(C)C(C)=C(C)C1[Ti](Cl)Cl ABNCGYCFZDYTQP-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LSEYWNQMVRWEOZ-UHFFFAOYSA-N NC1=C(C=CC=C1)C=1C(CC(C1C)C)=O.NC1=C(C=CC=C1)C=1C(CC(C1C)C)=O Chemical compound NC1=C(C=CC=C1)C=1C(CC(C1C)C)=O.NC1=C(C=CC=C1)C=1C(CC(C1C)C)=O LSEYWNQMVRWEOZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-O diethylammonium Chemical compound CC[NH2+]CC HPNMFZURTQLUMO-UHFFFAOYSA-O 0.000 description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical compound [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- JEYDKBGJAYTKLV-UHFFFAOYSA-N n-cyclohexyl-4-phenylaniline Chemical compound C1CCCCC1NC1=CC=C(C=2C=CC=CC=2)C=C1 JEYDKBGJAYTKLV-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-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
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 238000005292 vacuum distillation Methods 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
- JIJQAHZWDVEJJR-UHFFFAOYSA-N (2-methyl-5-oxocyclopenten-1-yl)boronic acid Chemical compound CC1=C(B(O)O)C(=O)CC1 JIJQAHZWDVEJJR-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000006023 1-pentenyl group Chemical group 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- PQHKNTLBXOTTOJ-UHFFFAOYSA-N 2-[2-(cyclohexylamino)-4-methylphenyl]-3,4-dimethylcyclopent-2-en-1-one Chemical compound CC1CC(=O)C(C=2C(=CC(C)=CC=2)NC2CCCCC2)=C1C PQHKNTLBXOTTOJ-UHFFFAOYSA-N 0.000 description 1
- VNRNPEVUBZSGHH-UHFFFAOYSA-N 2-[2-(tert-butylamino)-4-methylphenyl]-3,4-dimethylcyclopent-2-en-1-one Chemical compound CC1CC(=O)C(C=2C(=CC(C)=CC=2)NC(C)(C)C)=C1C VNRNPEVUBZSGHH-UHFFFAOYSA-N 0.000 description 1
- NOWDCHZXUDSRGY-UHFFFAOYSA-N 2-[4-chloro-2-(cyclohexylamino)phenyl]-3,4-dimethylcyclopent-2-en-1-one Chemical compound CC1CC(=O)C(C=2C(=CC(Cl)=CC=2)NC2CCCCC2)=C1C NOWDCHZXUDSRGY-UHFFFAOYSA-N 0.000 description 1
- WPWVMBLVSMSRCR-UHFFFAOYSA-N 2-bromo-3,4-dimethylcyclopent-2-en-1-one;ethene Chemical group C=C.CC1CC(=O)C(Br)=C1C WPWVMBLVSMSRCR-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 description 1
- 125000006024 2-pentenyl group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- SORYHJDKXCLYRR-UHFFFAOYSA-N 3,4-dimethyl-2-[4-methyl-2-(2-methylbutylamino)phenyl]cyclopent-2-en-1-one Chemical compound CCC(C)CNC1=CC(C)=CC=C1C1=C(C)C(C)CC1=O SORYHJDKXCLYRR-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000006027 3-methyl-1-butenyl group Chemical group 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- KIVYZWBTCVCAMG-UHFFFAOYSA-N 4-chloro-n-cyclohexylaniline Chemical compound C1=CC(Cl)=CC=C1NC1CCCCC1 KIVYZWBTCVCAMG-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 1
- KNNWNSVVTDKXHS-UHFFFAOYSA-N 4-methylaniline Chemical compound CC1=CC=C(N)C=C1.CC1=CC=C(N)C=C1 KNNWNSVVTDKXHS-UHFFFAOYSA-N 0.000 description 1
- SNBQPCHNLFUWQK-UHFFFAOYSA-N BrC=1C=C(CC2=CC(=C(C=C2)NC2CCCCC2)Br)C=CC1NC1CCCCC1.BrC=1C=C(CC2=CC(=C(C=C2)NC2CCCCC2)Br)C=CC1NC1CCCCC1 Chemical compound BrC=1C=C(CC2=CC(=C(C=C2)NC2CCCCC2)Br)C=CC1NC1CCCCC1.BrC=1C=C(CC2=CC(=C(C=C2)NC2CCCCC2)Br)C=CC1NC1CCCCC1 SNBQPCHNLFUWQK-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- SQCAYHQIZCAFJE-UHFFFAOYSA-N C(C)(C)(C)NC1=C(C=CC(=C1)C)C=1C(CC(C1C)C)=O.C(C)(C)(C)NC1=C(C=CC(=C1)C)C=1C(CC(C1C)C)=O Chemical compound C(C)(C)(C)NC1=C(C=CC(=C1)C)C=1C(CC(C1C)C)=O.C(C)(C)(C)NC1=C(C=CC(=C1)C)C=1C(CC(C1C)C)=O SQCAYHQIZCAFJE-UHFFFAOYSA-N 0.000 description 1
- PCDKVQGUSOAEJV-UHFFFAOYSA-N C(C)(C)(C)NC1=C(C=CC(=C1)C)C=1CCC(C1C)C Chemical compound C(C)(C)(C)NC1=C(C=CC(=C1)C)C=1CCC(C1C)C PCDKVQGUSOAEJV-UHFFFAOYSA-N 0.000 description 1
- LCVMJMDJBHJLHA-UHFFFAOYSA-N C(C)C(CNC1=C(C=CC(=C1)C)C=1C(CC(C1C)C)=O)C.C(C)C(CNC1=C(C=CC(=C1)C)C=1C(CC(C1C)C)=O)C Chemical compound C(C)C(CNC1=C(C=CC(=C1)C)C=1C(CC(C1C)C)=O)C.C(C)C(CNC1=C(C=CC(=C1)C)C=1C(CC(C1C)C)=O)C LCVMJMDJBHJLHA-UHFFFAOYSA-N 0.000 description 1
- ARCGVNSUOHUZDC-UHFFFAOYSA-N C1(=CC=CC=C1)C1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C.C1(=CC=CC=C1)NC1CCCCC1 Chemical compound C1(=CC=CC=C1)C1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C.C1(=CC=CC=C1)NC1CCCCC1 ARCGVNSUOHUZDC-UHFFFAOYSA-N 0.000 description 1
- PTXOMQYFRCQVFX-UHFFFAOYSA-N C1(CCCCC1)=NC1=CC=C(CC2=CC=C(C=C2)NC2CCCCC2)C=C1.C1(CCCCC1)=NC1=CC=C(CC2=CC=C(C=C2)NC2CCCCC2)C=C1 Chemical compound C1(CCCCC1)=NC1=CC=C(CC2=CC=C(C=C2)NC2CCCCC2)C=C1.C1(CCCCC1)=NC1=CC=C(CC2=CC=C(C=C2)NC2CCCCC2)C=C1 PTXOMQYFRCQVFX-UHFFFAOYSA-N 0.000 description 1
- ORVZUKKQYNMAQA-UHFFFAOYSA-N C1(CCCCC1)NC1=C(C=CC(=C1)C)C=1C(CC(C1C)C)=O.C1(CCCCC1)NC1=C(C=CC(=C1)C)C=1C(CC(C1C)C)=O Chemical compound C1(CCCCC1)NC1=C(C=CC(=C1)C)C=1C(CC(C1C)C)=O.C1(CCCCC1)NC1=C(C=CC(=C1)C)C=1C(CC(C1C)C)=O ORVZUKKQYNMAQA-UHFFFAOYSA-N 0.000 description 1
- FVCIZADRMUTMOZ-UHFFFAOYSA-N C1(CCCCC1)NC1=C(C=CC(=C1)C1=CC=CC=C1)C=1C(CC(C1C)C)=O.C1(CCCCC1)NC1=C(C=CC(=C1)C1=CC=CC=C1)C=1C(CC(C1C)C)=O Chemical compound C1(CCCCC1)NC1=C(C=CC(=C1)C1=CC=CC=C1)C=1C(CC(C1C)C)=O.C1(CCCCC1)NC1=C(C=CC(=C1)C1=CC=CC=C1)C=1C(CC(C1C)C)=O FVCIZADRMUTMOZ-UHFFFAOYSA-N 0.000 description 1
- NSEMZYRJJSDICF-UHFFFAOYSA-N C1(CCCCC1)NC1=C(C=CC(=C1)F)C=1C(CC(C1C)C)=O.C1(CCCCC1)NC1=C(C=CC(=C1)F)C=1C(CC(C1C)C)=O Chemical compound C1(CCCCC1)NC1=C(C=CC(=C1)F)C=1C(CC(C1C)C)=O.C1(CCCCC1)NC1=C(C=CC(=C1)F)C=1C(CC(C1C)C)=O NSEMZYRJJSDICF-UHFFFAOYSA-N 0.000 description 1
- LMZMGVYJPFRUIK-UHFFFAOYSA-N CC1=C(C(=CC1C)C)C1=C(C=CC=C1)N(CC)CCC.CC1=C(C(=CC1C)C)C1=C(C=CC=C1)N(CC)CCC Chemical compound CC1=C(C(=CC1C)C)C1=C(C=CC=C1)N(CC)CCC.CC1=C(C(=CC1C)C)C1=C(C=CC=C1)N(CC)CCC LMZMGVYJPFRUIK-UHFFFAOYSA-N 0.000 description 1
- ATUNXONANVNCIM-UHFFFAOYSA-N CC1=C(C(=CC1C)C)C1=C(C=CC=C1)NC(C)(C)C.CC1=C(C(=CC1C)C)C1=C(C=CC=C1)NC(C)(C)C Chemical compound CC1=C(C(=CC1C)C)C1=C(C=CC=C1)NC(C)(C)C.CC1=C(C(=CC1C)C)C1=C(C=CC=C1)NC(C)(C)C ATUNXONANVNCIM-UHFFFAOYSA-N 0.000 description 1
- WMDKPRIBMPCVFO-UHFFFAOYSA-N CC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C.C1(=CC=CC=C1)NC1CCCCC1 Chemical compound CC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C.C1(=CC=CC=C1)NC1CCCCC1 WMDKPRIBMPCVFO-UHFFFAOYSA-N 0.000 description 1
- ILFULCNZJPBKMH-UHFFFAOYSA-N CC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C.CC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C Chemical compound CC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C.CC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C ILFULCNZJPBKMH-UHFFFAOYSA-N 0.000 description 1
- LQIJNXGEFNBHCS-UHFFFAOYSA-N ClC1=CC(=C(C=C1)C=1C(CC(C1C)C)=O)NC1CCCCC1.ClC1=CC(=C(C=C1)C=1C(CC(C1C)C)=O)NC1CCCCC1 Chemical compound ClC1=CC(=C(C=C1)C=1C(CC(C1C)C)=O)NC1CCCCC1.ClC1=CC(=C(C=C1)C=1C(CC(C1C)C)=O)NC1CCCCC1 LQIJNXGEFNBHCS-UHFFFAOYSA-N 0.000 description 1
- ITSJZUAFZXCSHO-UHFFFAOYSA-N ClC1=CC(=C(C=C1)C=1CCC(C1C)C)NC1CCCCC1 Chemical compound ClC1=CC(=C(C=C1)C=1CCC(C1C)C)NC1CCCCC1 ITSJZUAFZXCSHO-UHFFFAOYSA-N 0.000 description 1
- FLMISJBNNWUWHV-UHFFFAOYSA-N ClC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C.C1(=CC=CC=C1)NC1CCCCC1 Chemical compound ClC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C.C1(=CC=CC=C1)NC1CCCCC1 FLMISJBNNWUWHV-UHFFFAOYSA-N 0.000 description 1
- ZFNVHFMMSMMCGT-UHFFFAOYSA-N ClC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C.ClC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C Chemical compound ClC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C.ClC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C ZFNVHFMMSMMCGT-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- IVJMHHIRHJEHHY-UHFFFAOYSA-N FC1=CC(=C(C=C1)C=1C(CC(C1C)C)=O)NC1CCCCC1.C(C=CCC)=O Chemical compound FC1=CC(=C(C=C1)C=1C(CC(C1C)C)=O)NC1CCCCC1.C(C=CCC)=O IVJMHHIRHJEHHY-UHFFFAOYSA-N 0.000 description 1
- CGHNXIZTAOKSOR-UHFFFAOYSA-N FC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C.C1(=CC=CC=C1)NC1CCCCC1 Chemical compound FC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C.C1(=CC=CC=C1)NC1CCCCC1 CGHNXIZTAOKSOR-UHFFFAOYSA-N 0.000 description 1
- LHORVNLVRPEUKL-UHFFFAOYSA-N FC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C.FC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C Chemical compound FC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C.FC1=CC(=C(C=C1)NC1CCCCC1)C1=C(C(C=C1C)C)C LHORVNLVRPEUKL-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- MYBJXSAXGLILJD-UHFFFAOYSA-N diethyl(methyl)alumane Chemical compound CC[Al](C)CC MYBJXSAXGLILJD-UHFFFAOYSA-N 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 238000007865 diluting Methods 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BXOUVIIITJXIKB-UHFFFAOYSA-N ethene;styrene Chemical compound C=C.C=CC1=CC=CC=C1 BXOUVIIITJXIKB-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- SHGOGDWTZKFNSC-UHFFFAOYSA-N ethyl(dimethyl)alumane Chemical compound CC[Al](C)C SHGOGDWTZKFNSC-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010410 layer 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
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002738 metalloids 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
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- NIRWGOMUADRKSA-UHFFFAOYSA-N n-cyclohexyl-4-fluoroaniline Chemical compound C1=CC(F)=CC=C1NC1CCCCC1 NIRWGOMUADRKSA-UHFFFAOYSA-N 0.000 description 1
- NTWCUQCYVRYLFL-UHFFFAOYSA-N n-ethyl-n-propyl-2-(2,3,5-trimethylcyclopenta-1,4-dien-1-yl)aniline Chemical compound CCCN(CC)C1=CC=CC=C1C1=C(C)C(C)C=C1C NTWCUQCYVRYLFL-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 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
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WNFSFUSCVXIYGN-UHFFFAOYSA-N phenylaluminum Chemical compound [Al]C1=CC=CC=C1 WNFSFUSCVXIYGN-UHFFFAOYSA-N 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
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000005648 substituted hydrocarbylene group Chemical group 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- NDUUEFPGQBSFPV-UHFFFAOYSA-N tri(butan-2-yl)alumane Chemical compound CCC(C)[Al](C(C)CC)C(C)CC NDUUEFPGQBSFPV-UHFFFAOYSA-N 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- CMHHITPYCHHOGT-UHFFFAOYSA-N tributylborane Chemical compound CCCCB(CCCC)CCCC CMHHITPYCHHOGT-UHFFFAOYSA-N 0.000 description 1
- PYLGJXLKFZZEBJ-UHFFFAOYSA-N tricyclopentylalumane Chemical compound C1CCCC1[Al](C1CCCC1)C1CCCC1 PYLGJXLKFZZEBJ-UHFFFAOYSA-N 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-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
- ZMPKTELQGVLZTD-UHFFFAOYSA-N tripropylborane Chemical compound CCCB(CCC)CCC ZMPKTELQGVLZTD-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
- WSITXTIRYQMZHM-UHFFFAOYSA-N tris(4-methylphenyl)alumane Chemical compound C1=CC(C)=CC=C1[Al](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 WSITXTIRYQMZHM-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/28—Titanium compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
-
- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/03—Multinuclear procatalyst, i.e. containing two or more metals, being different or not
-
- 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
- C08F2420/02—Cp or analog bridged to a non-Cp X anionic 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+
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Abstract
Description
Claims (14)
- a) 하기 화학식 2의 전이금속 화합물; 및b) 하기 화학식 3 내지 5로 표시되는 화합물로 이루어진 군으로부터 선택되는 적어도 하나의 조촉매 화합물을 포함하는 촉매 조성물:<화학식 2>상기 화학식 2에 있어서,R1 내지 R4 및 R7 내지 R10은 각각 독립적으로 수소 원자; 탄소수 1 내지 20의 알킬; 아릴; 실릴; 탄소수 2 내지 20의 알케닐; 알킬아릴; 아릴알킬 라디칼; 또는 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이며; R1 내지 R4 및 R7 내지 R10 중 적어도 2개는 탄소수 1 내지 20의 알킬 또는 아릴 라디칼을 포함하는 알킬리덴 라디칼에 의해 서로 연결되어 고리를 형성할 수 있고;R5 및 R11은 탄소수 1 내지 20의 알킬; 탄소수 3 내지 20의 씨클로알킬; 아릴; 실릴; 탄소수 2 내지 20의 알케닐; 알킬아릴; 아릴알킬; 또는 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이며;R6 및 R12는 각각 독립적으로 수소 원자; 할로겐 라디칼; 탄소수 1 내지 20의 알킬; 또는 아릴이고, R6과 R12는 서로 연결될 수 있으며;A 및 A'는 각각 독립적으로 질소 또는 인 원자이고;E는 두 개의 페닐렌 고리를 연결하는 공유 가교기(covalent bridging group)로서, 에폭시기; 에피티오기; 카르보닐기; 실란기; 디실란기; 치환되거나 치환되지 않은 탄소수 1 내지 60의 하이드로카르빌렌기; 또는 4B족, 5B족 또는 6B족 원소를 포함하는 치환되거나 치환되지 않은 탄소수 1 내지 60의 헤테로하이드로카르빌렌기이고;Q1 내지 Q4는 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 알킬아미도 라디칼; 아릴아미도 라디칼; 탄소수 1 내지 20의 알킬; 알케닐; 아릴; 알킬아릴; 아릴알킬; 또는 탄소수 1 내지 20의 알킬리덴 라디칼이며;M 은 4족 전이금속이고;<화학식 3>-[Al(R31)-O]a-상기 식에서, R31은 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 하이드로카르빌 라디칼; 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카르빌 라디칼이고;a는 2 이상의 정수이며;<화학식 4>J(R32)3상기 식에서, J는 알루미늄 또는 보론이고; R32는 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 하이드로카르빌 라디칼; 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카르빌 라디칼이며;<화학식 5>[L-H]+[Z(R33)4]- 또는 [L]+[Z(R33)4]-상기 식에서, L이 중성 또는 양이온성 루이스 산이고; H가 수소 원자이며; Z가 13족 원소이고; R33이 각각 독립적으로 1 이상의 수소 원자; 할로겐; 탄소수 1 내지 20의 하이드로카르빌; 또는 알콕시 또는 페녹시 라디칼로 치환된 탄소수 6 내지 20의 아릴 또는 알킬 라디칼이다.
- 삭제
- 청구항 1에 있어서, 상기 화학식 2의 화합물은 하기 화학식 7로 표시되는 것인 화합물인 것인 촉매 조성물:<화학식 7>상기 화학식 7에 있어서,R13 내지 R15 및 R17 내지 R19는 각각 독립적으로 수소 원자; 또는 탄소수 1 내지 20의 알킬; 아릴; 또는 실릴 라디칼이고;R16 및 R20은 각각 독립적으로 탄소수 1 내지 20의 알킬; 탄소수 3 내지 20의 씨클로알킬; 아릴; 실릴; 탄소수 2 지 20의 알케닐; 알킬아릴; 또는 아릴알킬 라디칼이며;Q5 내지 Q8은 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 알킬아미도 라디칼; 아릴아미도 라디칼; 또는 탄소수 1 내지 20의 알킬 라디칼이고;G는 에폭시기; 에피티오기; 카르보닐기; 산소 또는 질소 원자를 포함하는 치환기로 치환된 탄소수 1 내지 60의 헤테로하이드로카르빌렌기; 또는 -C(R21)2- (여기서, R21은 수소, 또는 탄소수 1 내지 20의 알킬; 아릴; 실릴; 탄소수 2 내지 20의 알케닐; 알킬아릴; 또는 아릴알킬임)이며;M은 4족 전이금속이다.
- a) 하기 화학식 2의 전이금속 화합물과 하기 화학식 3 또는 하기 화학식 4로 표시되는 화합물을 접촉시켜 혼합물을 얻는 단계; 및 b) 상기 a) 단계에서 얻은 혼합물에 하기 화학식 5의 화합물을 첨가하는 단계를 포함하는 촉매 조성물의 제조방법:<화학식 2>상기 화학식 2에 있어서,R1 내지 R4 및 R7 내지 R10은 각각 독립적으로 수소 원자; 탄소수 1 내지 20의 알킬; 아릴; 실릴; 탄소수 2 내지 20의 알케닐; 알킬아릴; 아릴알킬 라디칼; 또는 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이며; R1 내지 R4 및 R7 내지 R10 중 적어도 2개는 탄소수 1 내지 20의 알킬 또는 아릴 라디칼을 포함하는 알킬리덴 라디칼에 의해 서로 연결되어 고리를 형성할 수 있고;R5 및 R11은 탄소수 1 내지 20의 알킬; 탄소수 3 내지 20의 씨클로알킬; 아릴; 실릴; 탄소수 2 내지 20의 알케닐; 알킬아릴; 아릴알킬; 또는 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이며;R6 및 R12는 각각 독립적으로 수소 원자; 할로겐 라디칼; 탄소수 1 내지 20의 알킬; 또는 아릴이고, R6과 R12는 서로 연결될 수 있으며;A 및 A'는 각각 독립적으로 질소 또는 인 원자이고;E는 두 개의 페닐렌 고리를 연결하는 공유 가교기(covalent bridging group)로서, 에폭시기; 에피티오기; 카르보닐기; 실란기; 디실란기; 치환되거나 치환되지 않은 탄소수 1 내지 60의 하이드로카르빌렌기; 또는 4B족, 5B족 또는 6B족 원소를 포함하는 치환되거나 치환되지 않은 탄소수 1 내지 60의 헤테로하이드로카르빌렌기이고;Q1 내지 Q4는 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 알킬아미도 라디칼; 아릴아미도 라디칼; 탄소수 1 내지 20의 알킬; 알케닐; 아릴; 알킬아릴; 아릴알킬; 또는 탄소수 1 내지 20의 알킬리덴 라디칼이며;M 은 4족 전이금속이고;<화학식 3>-[Al(R31)-O]a-상기 식에서, R31은 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 하이드로카르빌 라디칼; 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카르빌 라디칼이고;a는 2 이상의 정수이며;<화학식 4>J(R32)3상기 식에서, J는 알루미늄 또는 보론이고; R32는 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 하이드로카르빌 라디칼; 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카르빌 라디칼이며;<화학식 5>[L-H]+[Z(R33)4]- 또는 [L]+[Z(R33)4]-상기 식에서, L이 중성 또는 양이온성 루이스 산이고; H가 수소 원자이며; Z가 13족 원소이고; R33이 각각 독립적으로 1 이상의 수소 원자; 할로겐; 탄소수 1 내지 20의 하이드로카르빌; 또는 알콕시 또는 페녹시 라디칼로 치환된 탄소수 6 내지 20의 아릴 또는 알킬 라디칼이다.
- 청구항 7에 있어서, 상기 전이금속 화합물 대비 상기 화학식 3 또는 화학식 4로 표시되는 화합물의 몰비는 1:2 내지 1:5,000 이고, 상기 a) 전이금속 화합물 대비 상기 화학식 5로 표시되는 화합물의 몰비는 1:1 내지 1:25인 것인 촉매 조성물의 제조방법.
- 하기 화학식 2의 전이금속 화합물과 하기 화학식 3으로 표시되는 화합물을 접촉시켜 혼합물을 얻는 단계를 포함하는 촉매 조성물의 제조방법:<화학식 2>상기 화학식 2에 있어서,R1 내지 R4 및 R7 내지 R10은 각각 독립적으로 수소 원자; 탄소수 1 내지 20의 알킬; 아릴; 실릴; 탄소수 2 내지 20의 알케닐; 알킬아릴; 아릴알킬 라디칼; 또는 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이며; R1 내지 R4 및 R7 내지 R10 중 적어도 2개는 탄소수 1 내지 20의 알킬 또는 아릴 라디칼을 포함하는 알킬리덴 라디칼에 의해 서로 연결되어 고리를 형성할 수 있고;R5 및 R11은 탄소수 1 내지 20의 알킬; 탄소수 3 내지 20의 씨클로알킬; 아릴; 실릴; 탄소수 2 내지 20의 알케닐; 알킬아릴; 아릴알킬; 또는 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이며;R6 및 R12는 각각 독립적으로 수소 원자; 할로겐 라디칼; 탄소수 1 내지 20의 알킬; 또는 아릴이고, R6과 R12는 서로 연결될 수 있으며;A 및 A'는 각각 독립적으로 질소 또는 인 원자이고;E는 두 개의 페닐렌 고리를 연결하는 공유 가교기(covalent bridging group)로서, 에폭시기; 에피티오기; 카르보닐기; 실란기; 디실란기; 치환되거나 치환되지 않은 탄소수 1 내지 60의 하이드로카르빌렌기; 또는 4B족, 5B족 또는 6B족 원소를 포함하는 치환되거나 치환되지 않은 탄소수 1 내지 60의 헤테로하이드로카르빌렌기이고;Q1 내지 Q4는 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 알킬아미도 라디칼; 아릴아미도 라디칼; 탄소수 1 내지 20의 알킬; 알케닐; 아릴; 알킬아릴; 아릴알킬; 또는 탄소수 1 내지 20의 알킬리덴 라디칼이며;M 은 4족 전이금속이고;<화학식 3>-[Al(R31)-O]a-상기 식에서, R31은 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 하이드로카르빌 라디칼; 또는 할로겐으로 치환된 탄소수 1 내지 20의 하이드로카르빌 라디칼이고;a는 2 이상의 정수이다.
- 청구항 9에 있어서, 상기 전이금속 화합물 대비 상기 화학식 3으로 표시되는 화합물의 몰비가 1:10 내지 1:10,000 인 것인 촉매 조성물의 제조방법.
- 하기 화학식 2의 전이금속 화합물과 하기 화학식 5로 표시되는 화합물을 접촉시켜 혼합물을 얻는 단계를 포함하는 촉매 조성물의 제조방법:<화학식 2>상기 화학식 2에 있어서,R1 내지 R4 및 R7 내지 R10은 각각 독립적으로 수소 원자; 탄소수 1 내지 20의 알킬; 아릴; 실릴; 탄소수 2 내지 20의 알케닐; 알킬아릴; 아릴알킬 라디칼; 또는 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이며; R1 내지 R4 및 R7 내지 R10 중 적어도 2개는 탄소수 1 내지 20의 알킬 또는 아릴 라디칼을 포함하는 알킬리덴 라디칼에 의해 서로 연결되어 고리를 형성할 수 있고;R5 및 R11은 탄소수 1 내지 20의 알킬; 탄소수 3 내지 20의 씨클로알킬; 아릴; 실릴; 탄소수 2 내지 20의 알케닐; 알킬아릴; 아릴알킬; 또는 하이드로카르빌로 치환된 14족 금속의 메탈로이드 라디칼이며;R6 및 R12는 각각 독립적으로 수소 원자; 할로겐 라디칼; 탄소수 1 내지 20의 알킬; 또는 아릴이고, R6과 R12는 서로 연결될 수 있으며;A 및 A'는 각각 독립적으로 질소 또는 인 원자이고;E는 두 개의 페닐렌 고리를 연결하는 공유 가교기(covalent bridging group)로서, 에폭시기; 에피티오기; 카르보닐기; 실란기; 디실란기; 치환되거나 치환되지 않은 탄소수 1 내지 60의 하이드로카르빌렌기; 또는 4B족, 5B족 또는 6B족 원소를 포함하는 치환되거나 치환되지 않은 탄소수 1 내지 60의 헤테로하이드로카르빌렌기이고;Q1 내지 Q4는 각각 독립적으로 할로겐 라디칼; 탄소수 1 내지 20의 알킬아미도 라디칼; 아릴아미도 라디칼; 탄소수 1 내지 20의 알킬; 알케닐; 아릴; 알킬아릴; 아릴알킬; 또는 탄소수 1 내지 20의 알킬리덴 라디칼이며;M 은 4족 전이금속이고;<화학식 5>[L-H]+[Z(R33)4]- 또는 [L]+[Z(R33)4]-상기 식에서, L이 중성 또는 양이온성 루이스 산이고; H가 수소 원자이며; Z가 13족 원소이고; R33이 각각 독립적으로 1 이상의 수소 원자; 할로겐; 탄소수 1 내지 20의 하이드로카르빌; 또는 알콕시 또는 페녹시 라디칼로 치환된 탄소수 6 내지 20의 아릴 또는 알킬 라디칼이다.
- 청구항 11에 있어서, 상기 전이금속 화합물 대비 상기 화학식 5로 표시되는 화합물의 몰비는 1:1 내지 1:25인 것인 촉매 조성물의 제조방법.
- 청구항 1 에 따른 촉매 조성물과 올레핀 단량체를 접촉시키는 단계를 포함하는 것을 특징으로 하는 이중 조성 분포를 가지는 폴리올레핀의 제조방법.
- 청구항 13에 있어서, 상기 올레핀 단량체는 에틸렌, 프로필렌, 1-부텐, 1-펜텐, 4-메틸-1-펜텐, 1-헥센, 1-헵텐, 1-옥텐, 1-데센, 1-운데센, 1-도데센, 1-테트라데센, 1-헥사데센, 1-아이토센, 노보넨, 노보나디엔, 에틸리덴노보넨, 페닐노보넨, 비닐노보넨, 디사이클로펜타디엔, 1,4-부타디엔, 1,5-펜타디엔, 1,6-헥사디엔, 스티렌, 알파-메틸스티렌, 디비닐벤젠 및 3-클로로메틸스티렌로 이루어진 군에서 선택되는 1종 또는 2종 이상을 포함하는 것인 폴리올레핀의 제조방법.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20050135900 | 2005-12-30 | ||
KR1020050135900 | 2005-12-30 | ||
KR1020060067117 | 2006-07-18 | ||
KR20060067117 | 2006-07-18 |
Publications (2)
Publication Number | Publication Date |
---|---|
KR20070072429A KR20070072429A (ko) | 2007-07-04 |
KR100839759B1 true KR100839759B1 (ko) | 2008-06-20 |
Family
ID=38228430
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1020070000120A KR100839759B1 (ko) | 2005-12-30 | 2007-01-02 | 4족 전이금속 화합물을 포함하는 촉매 조성물 및 이를이용한 폴리올레핀의 제조방법 |
KR1020070000115A KR100839758B1 (ko) | 2005-12-30 | 2007-01-02 | 전이금속 화합물 및 이의 제조 방법 |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR1020070000115A KR100839758B1 (ko) | 2005-12-30 | 2007-01-02 | 전이금속 화합물 및 이의 제조 방법 |
Country Status (8)
Country | Link |
---|---|
US (2) | US7678933B2 (ko) |
EP (2) | EP1966225B1 (ko) |
JP (2) | JP5090368B2 (ko) |
KR (2) | KR100839759B1 (ko) |
CN (1) | CN102558245A (ko) |
ES (2) | ES2428151T3 (ko) |
TW (2) | TWI336331B (ko) |
WO (2) | WO2007078133A1 (ko) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5090368B2 (ja) * | 2005-12-30 | 2012-12-05 | エルジー・ケム・リミテッド | 遷移金属化合物およびその製造方法 |
KR100874032B1 (ko) * | 2006-02-01 | 2008-12-17 | 주식회사 엘지화학 | 전이 금속 화합물을 포함하는 촉매 조성물 및 이를 이용한올레핀 중합 |
US10318981B2 (en) * | 2007-07-11 | 2019-06-11 | Joseph BOUS | System and method for conducting self-modifying semi-opaque sales |
EP2832739A1 (en) | 2013-08-01 | 2015-02-04 | Saudi Basic Industries Corporation | Bridged metallocene complex for olefin polymerization |
KR102546716B1 (ko) * | 2019-09-30 | 2023-06-23 | 주식회사 엘지화학 | 폴리프로필렌계 복합재 |
KR102516747B1 (ko) * | 2019-09-30 | 2023-04-03 | 주식회사 엘지화학 | 폴리프로필렌계 복합재 |
US11289056B2 (en) * | 2020-06-05 | 2022-03-29 | Michael Kevin Krobot | Interchangeable neck and bridge for a guitar |
Family Cites Families (33)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5427782A (en) * | 1977-08-04 | 1979-03-02 | Seiko Instr & Electronics Ltd | Semiconductor device and production of the same |
JPS5599954A (en) * | 1979-01-26 | 1980-07-30 | Sankyo Kagaku Kk | Synthesis of triphenylmethane dye |
JPS5727782A (en) * | 1980-07-29 | 1982-02-15 | Mitsui Toatsu Chem Inc | Colorant for pressure-sensitive, heat-sensitive recording paper |
US5055438A (en) * | 1989-09-13 | 1991-10-08 | Exxon Chemical Patents, Inc. | Olefin polymerization catalysts |
JPS644725A (en) * | 1987-06-29 | 1989-01-09 | Nippon Telegraph & Telephone | Organic nonlinear optical material |
EP0311899A3 (en) * | 1987-10-14 | 1990-06-27 | Air Products And Chemicals, Inc. | Alpha, beta-unsaturated alkenyl bis-aryldiamines for use in preparing cross-linkable condensation polymer |
JP2507773B2 (ja) * | 1988-03-22 | 1996-06-19 | 三井東圧化学株式会社 | フルオレン化合物の製造方法 |
NZ235032A (en) | 1989-08-31 | 1993-04-28 | Dow Chemical Co | Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component |
CN1029850C (zh) * | 1989-08-31 | 1995-09-27 | 陶氏化学公司 | 用于加成聚合的催化剂及其制备方法 |
US6686488B2 (en) | 1989-08-31 | 2004-02-03 | The Dow Chemical Company | Constrained geometry addition polymerization catalysts |
US5064802A (en) * | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
US6825369B1 (en) * | 1989-09-14 | 2004-11-30 | The Dow Chemical Company | Metal complex compounds |
PL166690B1 (pl) * | 1990-06-04 | 1995-06-30 | Exxon Chemical Patents Inc | Sposób wytwarzania polimerów olefin PL |
US5721185A (en) | 1991-06-24 | 1998-02-24 | The Dow Chemical Company | Homogeneous olefin polymerization catalyst by abstraction with lewis acids |
ES2111656T3 (es) | 1992-01-06 | 1998-03-16 | Dow Chemical Co | Composicion de catalizador mejorada. |
US5350723A (en) | 1992-05-15 | 1994-09-27 | The Dow Chemical Company | Process for preparation of monocyclopentadienyl metal complex compounds and method of use |
JP3672357B2 (ja) * | 1995-05-30 | 2005-07-20 | 三井化学株式会社 | 新規な遷移金属化合物および該遷移金属化合物からなるオレフィン重合用触媒成分 |
DE19624581C2 (de) | 1996-06-20 | 1999-02-04 | Targor Gmbh | Übergangsmetallverbindung und ein Verfahren zu ihrer Herstellung, sowie ihre Verwendung |
DK0933346T3 (da) * | 1996-07-31 | 2004-03-29 | Shionogi & Co | Nye p-terphenylforbindelser |
WO1999006412A1 (en) * | 1997-08-01 | 1999-02-11 | The Dow Chemical Company | Perfluoronaphthyl substituted boron containing catalyst activator |
EP1015462B1 (en) | 1997-09-15 | 2002-08-28 | The Dow Chemical Company | Bimetallic complexes and polymerization catalysts therefrom |
US6235917B1 (en) | 1998-08-28 | 2001-05-22 | The Dow Chemical Company | Dinuclear complexes and polymerization catalysts therefrom |
US6332023B1 (en) | 1998-06-04 | 2001-12-18 | Mci Communications Corporation | Method of and system for providing services in a communications network |
US6228790B1 (en) | 1998-06-29 | 2001-05-08 | Industrial Technology Research Institute | Dinuclear metallocene catalyst for preparing high molecular weight olefin polymer |
KR100354290B1 (ko) * | 1999-06-22 | 2002-09-28 | 주식회사 엘지화학 | 담지 메탈로센 촉매 및 이를 이용한 올레핀 중합 |
JP2003535097A (ja) | 2000-05-31 | 2003-11-25 | バーゼル、ポリオレフィン、ゲゼルシャフト、ミット、ベシュレンクテル、ハフツング | 遷移金属化合物の製造方法及び該化合物をオレフィンの重合に使用する方法 |
SG99905A1 (en) | 2000-06-21 | 2003-11-27 | Sumitomo Chemical Co | Transition metal compound, catalyst for addition polymerization, and process for producing addition polymer |
JP4094955B2 (ja) * | 2001-01-18 | 2008-06-04 | 塩野義製薬株式会社 | 置換アミノ基を有するテルフェニル化合物 |
ATE425172T1 (de) * | 2003-12-16 | 2009-03-15 | Basell Polyolefine Gmbh | Monocyclopentadienylkomplexe |
KR100789241B1 (ko) | 2005-07-08 | 2008-01-02 | 주식회사 엘지화학 | 전이금속 화합물, 이를 포함하는 촉매 조성물 및 이를이용한 올레핀 중합 |
US20070049711A1 (en) * | 2005-09-01 | 2007-03-01 | Chi-I Kuo | Catalyst compositions comprising support materials having an improved particle-size distribution |
JP5090368B2 (ja) * | 2005-12-30 | 2012-12-05 | エルジー・ケム・リミテッド | 遷移金属化合物およびその製造方法 |
KR100874032B1 (ko) * | 2006-02-01 | 2008-12-17 | 주식회사 엘지화학 | 전이 금속 화합물을 포함하는 촉매 조성물 및 이를 이용한올레핀 중합 |
-
2006
- 2006-12-29 JP JP2008548432A patent/JP5090368B2/ja active Active
- 2006-12-29 JP JP2008542255A patent/JP4988754B2/ja active Active
- 2006-12-29 WO PCT/KR2006/005907 patent/WO2007078133A1/en active Application Filing
- 2006-12-29 ES ES06835607T patent/ES2428151T3/es active Active
- 2006-12-29 US US12/087,215 patent/US7678933B2/en active Active
- 2006-12-29 EP EP06835608.8A patent/EP1966225B1/en active Active
- 2006-12-29 WO PCT/KR2006/005908 patent/WO2007078134A1/en active Application Filing
- 2006-12-29 US US12/087,216 patent/US7807762B2/en active Active
- 2006-12-29 TW TW095149921A patent/TWI336331B/zh active
- 2006-12-29 EP EP06835607.0A patent/EP1966223B1/en active Active
- 2006-12-29 TW TW095149903A patent/TWI342317B/zh active
- 2006-12-29 CN CN2011103749969A patent/CN102558245A/zh active Pending
- 2006-12-29 ES ES06835608.8T patent/ES2446926T3/es active Active
-
2007
- 2007-01-02 KR KR1020070000120A patent/KR100839759B1/ko active IP Right Grant
- 2007-01-02 KR KR1020070000115A patent/KR100839758B1/ko active IP Right Grant
Non-Patent Citations (1)
Title |
---|
Organometallics, 25, 2133-2134(2006).* |
Also Published As
Publication number | Publication date |
---|---|
JP4988754B2 (ja) | 2012-08-01 |
EP1966223A1 (en) | 2008-09-10 |
TWI336331B (en) | 2011-01-21 |
JP5090368B2 (ja) | 2012-12-05 |
US7678933B2 (en) | 2010-03-16 |
EP1966225A4 (en) | 2011-06-01 |
TW200745185A (en) | 2007-12-16 |
ES2428151T3 (es) | 2013-11-06 |
US20090005525A1 (en) | 2009-01-01 |
KR20070072428A (ko) | 2007-07-04 |
JP2009521527A (ja) | 2009-06-04 |
WO2007078133A1 (en) | 2007-07-12 |
EP1966225B1 (en) | 2013-12-25 |
US7807762B2 (en) | 2010-10-05 |
KR20070072429A (ko) | 2007-07-04 |
WO2007078134A1 (en) | 2007-07-12 |
EP1966223A4 (en) | 2011-06-01 |
US20090030221A1 (en) | 2009-01-29 |
ES2446926T3 (es) | 2014-03-10 |
KR100839758B1 (ko) | 2008-06-20 |
CN102558245A (zh) | 2012-07-11 |
TWI342317B (en) | 2011-05-21 |
JP2009517495A (ja) | 2009-04-30 |
EP1966223B1 (en) | 2013-08-14 |
EP1966225A1 (en) | 2008-09-10 |
TW200740835A (en) | 2007-11-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR100976131B1 (ko) | 전이금속 화합물의 제조 방법, 상기 방법으로 제조된전이금속 화합물 및 상기 전이금속 화합물을 포함하는 촉매조성물 | |
KR101685664B1 (ko) | 혼성 담지 촉매 및 이를 이용하는 올레핀계 중합체의 제조방법 | |
KR100839759B1 (ko) | 4족 전이금속 화합물을 포함하는 촉매 조성물 및 이를이용한 폴리올레핀의 제조방법 | |
KR20080076187A (ko) | 새로운 시클로펜타디에닐 리간드를 갖는 4족 전이금속화합물, 이의 제조방법 및 이를 이용한 올레핀계 중합체의제조방법 | |
KR100843603B1 (ko) | 전이금속 화합물, 이를 포함하는 촉매 조성물 및 이를이용한 올레핀 중합 | |
KR100789242B1 (ko) | 전이금속 화합물, 이를 포함하는 촉매 조성물 및 이를이용한 올레핀 중합 | |
KR20110009942A (ko) | 새로운 포스트 메탈로센형 전이금속 화합물 | |
KR101189194B1 (ko) | 새로운 전이금속 화합물 | |
KR100907429B1 (ko) | 전이금속 화합물, 이를 포함하는 촉매 조성물 및 이를이용한 올레핀 중합 | |
KR101217268B1 (ko) | 올레핀 중합용 촉매 조성물 및 이를 이용하여 제조된 올레핀 중합체 | |
KR20120024427A (ko) | 개선된 전이금속 촉매 조성물 및 이를 이용한 올레핀 중합체의 제조방법 | |
KR101601935B1 (ko) | 이핵 메탈로센 화합물, 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법 | |
KR101277292B1 (ko) | 내열성 및 탄성이 우수한 올레핀 중합체 및 그 제조 방법 | |
KR101077272B1 (ko) | 전이금속 화합물의 제조방법 | |
KR20050016737A (ko) | 올레핀 공중합체의 제조방법 | |
KR102065161B1 (ko) | 신규한 전이금속 화합물의 제조방법 | |
KR20160096445A (ko) | 촉매 조성물 및 이를 이용한 폴리올레핀의 제조방법 | |
KR101648554B1 (ko) | 촉매 조성물 및 이를 이용한 올레핀계 중합체의 제조방법 | |
KR20170068330A (ko) | 신규한 전이금속 화합물 | |
KR20170095033A (ko) | 신규한 전이금속 화합물 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A201 | Request for examination | ||
E902 | Notification of reason for refusal | ||
E902 | Notification of reason for refusal | ||
E701 | Decision to grant or registration of patent right | ||
GRNT | Written decision to grant | ||
FPAY | Annual fee payment |
Payment date: 20130410 Year of fee payment: 6 |
|
FPAY | Annual fee payment |
Payment date: 20140318 Year of fee payment: 7 |
|
FPAY | Annual fee payment |
Payment date: 20150416 Year of fee payment: 8 |
|
FPAY | Annual fee payment |
Payment date: 20160601 Year of fee payment: 9 |
|
FPAY | Annual fee payment |
Payment date: 20170328 Year of fee payment: 10 |
|
FPAY | Annual fee payment |
Payment date: 20180418 Year of fee payment: 11 |
|
FPAY | Annual fee payment |
Payment date: 20190401 Year of fee payment: 12 |