JP2013534934A - エチレンを選択的に重合させるための方法及びそのための触媒 - Google Patents
エチレンを選択的に重合させるための方法及びそのための触媒 Download PDFInfo
- Publication number
- JP2013534934A JP2013534934A JP2013511220A JP2013511220A JP2013534934A JP 2013534934 A JP2013534934 A JP 2013534934A JP 2013511220 A JP2013511220 A JP 2013511220A JP 2013511220 A JP2013511220 A JP 2013511220A JP 2013534934 A JP2013534934 A JP 2013534934A
- Authority
- JP
- Japan
- Prior art keywords
- tert
- butyl
- bis
- biphenyl
- trimethylpentan
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 184
- 239000003054 catalyst Substances 0.000 title claims abstract description 148
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 239000005977 Ethylene Substances 0.000 title claims abstract description 145
- 230000000379 polymerizing effect Effects 0.000 title claims abstract description 8
- 239000003446 ligand Substances 0.000 claims abstract description 391
- 239000000203 mixture Substances 0.000 claims abstract description 139
- 239000004711 α-olefin Substances 0.000 claims abstract description 127
- 239000012041 precatalyst Substances 0.000 claims abstract description 5
- -1 heterohydrocarbyl Chemical group 0.000 claims description 310
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 117
- 150000001336 alkenes Chemical class 0.000 claims description 79
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 78
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 72
- 125000005843 halogen group Chemical group 0.000 claims description 70
- 239000004698 Polyethylene Substances 0.000 claims description 65
- 229920000573 polyethylene Polymers 0.000 claims description 64
- 238000006116 polymerization reaction Methods 0.000 claims description 64
- 125000003118 aryl group Chemical group 0.000 claims description 53
- 125000004432 carbon atom Chemical group C* 0.000 claims description 43
- 125000002947 alkylene group Chemical group 0.000 claims description 42
- 229910052751 metal Inorganic materials 0.000 claims description 39
- 239000002184 metal Substances 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 125000001072 heteroaryl group Chemical group 0.000 claims description 38
- 125000001424 substituent group Chemical group 0.000 claims description 37
- 125000005842 heteroatom Chemical group 0.000 claims description 35
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 34
- 229920000642 polymer Polymers 0.000 claims description 30
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- DVZWQGLVEOWFOU-UHFFFAOYSA-N C[Hf]C Chemical compound C[Hf]C DVZWQGLVEOWFOU-UHFFFAOYSA-N 0.000 claims description 26
- 125000004429 atom Chemical group 0.000 claims description 23
- 125000000743 hydrocarbylene group Chemical group 0.000 claims description 23
- 230000009257 reactivity Effects 0.000 claims description 23
- 125000000129 anionic group Chemical group 0.000 claims description 17
- 150000003839 salts Chemical class 0.000 claims description 17
- 230000007935 neutral effect Effects 0.000 claims description 16
- KDUHDEJOJLPTMF-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=CC=C1Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC=C1)Cl)O Chemical compound C[Hf]C.C(CCOC1=C(C=CC=C1Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC=C1)Cl)O KDUHDEJOJLPTMF-UHFFFAOYSA-N 0.000 claims description 15
- OFEHDTNCQNYCLE-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=CC=C1C)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC=C1)C)O Chemical compound C[Hf]C.C(CCOC1=C(C=CC=C1C)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC=C1)C)O OFEHDTNCQNYCLE-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- OYFFSPILVQLRQA-UHFFFAOYSA-N 3,6-ditert-butyl-9h-carbazole Chemical compound C1=C(C(C)(C)C)C=C2C3=CC(C(C)(C)C)=CC=C3NC2=C1 OYFFSPILVQLRQA-UHFFFAOYSA-N 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- RAPRXJJCFWMXPA-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=C(C=C1Cl)F)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)F)Cl)O Chemical compound C[Hf]C.C(CCOC1=C(C=C(C=C1Cl)F)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)F)Cl)O RAPRXJJCFWMXPA-UHFFFAOYSA-N 0.000 claims description 10
- 125000005647 linker group Chemical group 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 9
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 7
- XMCTZPUHLDFEIC-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=C(C=C1CC)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)CC)O Chemical compound C[Hf]C.C(CCOC1=C(C=C(C=C1CC)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)CC)O XMCTZPUHLDFEIC-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 125000001624 naphthyl group Chemical group 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- BOTMOIOWIPYDLV-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=C(C=C1C)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)CC(C)(C)C)C(C)(C)CC(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)CC(C)(C)C)C(C)(C)CC(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)C)O Chemical compound C[Hf]C.C(CCOC1=C(C=C(C=C1C)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)CC(C)(C)C)C(C)(C)CC(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)CC(C)(C)C)C(C)(C)CC(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)C)O BOTMOIOWIPYDLV-UHFFFAOYSA-N 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 6
- XFWYFHMOQWZBAE-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=C(C=C1C)F)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)F)C)O Chemical compound C[Hf]C.C(CCOC1=C(C=C(C=C1C)F)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)F)C)O XFWYFHMOQWZBAE-UHFFFAOYSA-N 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- AMQUYNWUUVNGGS-UHFFFAOYSA-N C[Hf]C.C(CCCOC1=C(C=C(C=C1C)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)C)O Chemical compound C[Hf]C.C(CCCOC1=C(C=C(C=C1C)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)C)O AMQUYNWUUVNGGS-UHFFFAOYSA-N 0.000 claims description 4
- MFMLPUWUBHMKAI-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=C(C=C1C)C)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)C)C)O Chemical compound C[Hf]C.C(CCOC1=C(C=C(C=C1C)C)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)C)C)O MFMLPUWUBHMKAI-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- NDVOFOAQSGKYKE-UHFFFAOYSA-N 2-(3,6-ditert-butylcarbazol-9-yl)-6-[2-[3-[6-(3,6-ditert-butylcarbazol-9-yl)-2-(3,5-difluorophenyl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-3,5-difluorophenyl]-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)C(O)(OCCCOC=2C(=CC(F)=CC=2F)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)C=1C1=CC(F)=CC(F)=C1 NDVOFOAQSGKYKE-UHFFFAOYSA-N 0.000 claims description 3
- JPBBRFCSUUVAAK-UHFFFAOYSA-N 2-(3,6-ditert-butylcarbazol-9-yl)-6-[2-[3-[6-(3,6-ditert-butylcarbazol-9-yl)-2-(3,5-dimethylphenyl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-3,5-dimethylphenyl]-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC1=CC(C)=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)C)C(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCOC=2C(=CC(C)=CC=2C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 JPBBRFCSUUVAAK-UHFFFAOYSA-N 0.000 claims description 3
- LYJBGGGALRKOFN-UHFFFAOYSA-N 2-(3,6-ditert-butylcarbazol-9-yl)-6-[2-[3-[6-(3,6-ditert-butylcarbazol-9-yl)-2-(3-fluoro-5-methylphenyl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-5-fluoro-3-methylphenyl]-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC1=CC(F)=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)C)C(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCOC=2C(=CC(F)=CC=2C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 LYJBGGGALRKOFN-UHFFFAOYSA-N 0.000 claims description 3
- ILJGTSIJZIACFI-UHFFFAOYSA-N 2-(3,6-ditert-butylcarbazol-9-yl)-6-[3,5-dichloro-2-[3-[6-(3,6-ditert-butylcarbazol-9-yl)-2-(3,5-dichlorophenyl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]phenyl]-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)C(O)(OCCCOC=2C(=CC(Cl)=CC=2Cl)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)C=1C1=CC(Cl)=CC(Cl)=C1 ILJGTSIJZIACFI-UHFFFAOYSA-N 0.000 claims description 3
- BVKAPTYZTCULIA-UHFFFAOYSA-N 2-[5-chloro-2-[3-[2-(3-chloro-5-ethylphenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-3-ethylphenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CCC1=CC(Cl)=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)C)C(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCOC=2C(=CC(Cl)=CC=2CC)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 BVKAPTYZTCULIA-UHFFFAOYSA-N 0.000 claims description 3
- UNWJADNPKPBGHO-UHFFFAOYSA-N 2-[5-chloro-2-[3-[2-(3-chloro-5-methylphenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-3-methylphenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC1=CC(Cl)=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)C)C(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCOC=2C(=CC(Cl)=CC=2C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 UNWJADNPKPBGHO-UHFFFAOYSA-N 0.000 claims description 3
- UVYGDDKBSQIBQN-UHFFFAOYSA-N 2-[5-chloro-2-[4-[2-(3-chloro-5-methylphenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxybutoxy]-3-methylphenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC1=CC(Cl)=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)C)C(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCCOC=2C(=CC(Cl)=CC=2C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 UVYGDDKBSQIBQN-UHFFFAOYSA-N 0.000 claims description 3
- QTMLPDJTEQBSEH-UHFFFAOYSA-N 2-[5-tert-butyl-2-[3-[2-(3-tert-butyl-5-methylphenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-3-methylphenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)C1=CC(C)=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)C)C(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCOC=2C(=CC(=CC=2C)C(C)(C)C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 QTMLPDJTEQBSEH-UHFFFAOYSA-N 0.000 claims description 3
- AAEIDPIAKQIXCL-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=C(C=C1C(F)(F)F)F)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)F)C(F)(F)F)O Chemical compound C[Hf]C.C(CCOC1=C(C=C(C=C1C(F)(F)F)F)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)F)C(F)(F)F)O AAEIDPIAKQIXCL-UHFFFAOYSA-N 0.000 claims description 3
- JZEYXVORIHBKGF-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=C(C=C1C)C#N)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)C#N)C)O Chemical compound C[Hf]C.C(CCOC1=C(C=C(C=C1C)C#N)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)C#N)C)O JZEYXVORIHBKGF-UHFFFAOYSA-N 0.000 claims description 3
- RXNOTVYETBKSTP-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=C(C=C1C)C(C)(C)C)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)C(C)(C)C)C)O Chemical compound C[Hf]C.C(CCOC1=C(C=C(C=C1C)C(C)(C)C)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)C(C)(C)C)C)O RXNOTVYETBKSTP-UHFFFAOYSA-N 0.000 claims description 3
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 3
- WPBFHHFECZLFKW-UHFFFAOYSA-N 2-(3,6-ditert-butylcarbazol-9-yl)-6-[2-[3-[6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-2-(3-methoxy-5-methylphenyl)-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-5-methoxy-3-methylphenyl]-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound COC1=CC(C)=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)C)C(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCOC=2C(=CC(OC)=CC=2C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 WPBFHHFECZLFKW-UHFFFAOYSA-N 0.000 claims description 2
- VSOKDXMYVDRYAB-UHFFFAOYSA-N 2-(3,6-ditert-butylcarbazol-9-yl)-6-[2-[3-[6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-2-(3-methylphenyl)-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-3-methylphenyl]-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC1=CC=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)C)C(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCOC=2C(=CC=CC=2C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 VSOKDXMYVDRYAB-UHFFFAOYSA-N 0.000 claims description 2
- PNUKEFMZMLIEQX-UHFFFAOYSA-N 2-(3,6-ditert-butylcarbazol-9-yl)-6-[2-[3-[6-(3,6-ditert-butylcarbazol-9-yl)-2-(3,4-dimethylphenyl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-3,4-dimethylphenyl]-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C1=C(C)C(C)=CC=C1C(C1(O)OCCCOC=2C(=CC=C(C)C=2C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=CC(C(C)(C)CC(C)(C)C)=CC1N1C2=CC=C(C(C)(C)C)C=C2C2=CC(C(C)(C)C)=CC=C21 PNUKEFMZMLIEQX-UHFFFAOYSA-N 0.000 claims description 2
- MUJADVCLWQQCRA-UHFFFAOYSA-N 2-(3,6-ditert-butylcarbazol-9-yl)-6-[2-[3-[6-(3,6-ditert-butylcarbazol-9-yl)-2-[3-(dimethylamino)-5-methylphenyl]-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-5-(dimethylamino)-3-methylphenyl]-4-(2,4,4-trimethylpentan-2-yl)p Chemical compound CN(C)C1=CC(C)=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)C)C(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCOC=2C(=CC(=CC=2C)N(C)C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 MUJADVCLWQQCRA-UHFFFAOYSA-N 0.000 claims description 2
- HTVMMKFQMWYUDF-UHFFFAOYSA-N 2-(3-bromo-5-chlorophenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound OC=1C(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)=CC(C(C)(C)CC(C)(C)C)=CC=1C1=CC(Cl)=CC(Br)=C1 HTVMMKFQMWYUDF-UHFFFAOYSA-N 0.000 claims description 2
- BVCLQFKEAKREJO-UHFFFAOYSA-N 2-[3,6-bis(2,4,4-trimethylpentan-2-yl)carbazol-9-yl]-6-[2-[3-[6-[3,6-bis(2,4,4-trimethylpentan-2-yl)carbazol-9-yl]-2-(3-chloro-5-methylphenyl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-5-chloro-3-methylphenyl]-4-(2,4,4-tr Chemical compound CC1=CC(Cl)=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)CC(C)(C)C)C(C)(C)CC(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCOC=2C(=CC(Cl)=CC=2C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)CC(C)(C)C)C(C)(C)CC(C)(C)C)O)=C1 BVCLQFKEAKREJO-UHFFFAOYSA-N 0.000 claims description 2
- GPXCZALVTFKMSR-UHFFFAOYSA-N 2-[3-chloro-2-[3-[2-(3-chloro-5-fluorophenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-5-fluorophenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)C(O)(OCCCOC=2C(=CC(F)=CC=2Cl)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)C=1C1=CC(F)=CC(Cl)=C1 GPXCZALVTFKMSR-UHFFFAOYSA-N 0.000 claims description 2
- PIIFIVMLAVBAIH-UHFFFAOYSA-N 2-[3-chloro-2-[3-[2-(3-chlorophenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]phenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)C(O)(OCCCOC=2C(=CC=CC=2Cl)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)C=1C1=CC=CC(Cl)=C1 PIIFIVMLAVBAIH-UHFFFAOYSA-N 0.000 claims description 2
- NQDCOLRBHPXKRC-UHFFFAOYSA-N 2-[4-tert-butyl-2-[3-[2-(4-tert-butyl-3-chlorophenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-5-chlorophenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)C(O)(OCCCOC=2C(=CC(Cl)=C(C=2)C(C)(C)C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)C=1C1=CC=C(C(C)(C)C)C(Cl)=C1 NQDCOLRBHPXKRC-UHFFFAOYSA-N 0.000 claims description 2
- TZQCUWMDNRGOAB-UHFFFAOYSA-N 2-[4-tert-butyl-2-[3-[2-(4-tert-butylphenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]phenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)C(O)(OCCCOC=2C(=CC=C(C=2)C(C)(C)C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)C=1C1=CC=C(C(C)(C)C)C=C1 TZQCUWMDNRGOAB-UHFFFAOYSA-N 0.000 claims description 2
- IDYJSUFGBQWZRV-UHFFFAOYSA-N 2-[4-tert-butyl-2-[4-[2-(4-tert-butylphenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxybutoxy]phenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)C(O)(OCCCCOC=2C(=CC=C(C=2)C(C)(C)C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)C=1C1=CC=C(C(C)(C)C)C=C1 IDYJSUFGBQWZRV-UHFFFAOYSA-N 0.000 claims description 2
- PCOZIMPFYQULIA-UHFFFAOYSA-N 2-[5-chloro-2-[2-[2-(3-chloro-5-methylphenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxyethoxy]-3-methylphenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC1=CC(Cl)=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)C)C(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCOC=2C(=CC(Cl)=CC=2C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 PCOZIMPFYQULIA-UHFFFAOYSA-N 0.000 claims description 2
- PEPGGPNLVLPYCY-UHFFFAOYSA-N 2-[5-chloro-2-[3-[2-(3-chloro-5-fluorophenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-3-fluorophenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)C(O)(OCCCOC=2C(=CC(Cl)=CC=2F)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)C=1C1=CC(F)=CC(Cl)=C1 PEPGGPNLVLPYCY-UHFFFAOYSA-N 0.000 claims description 2
- ZSQFTVCLWHQSPG-UHFFFAOYSA-N 2-[5-chloro-2-[3-[2-(3-chloro-5-propan-2-ylphenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-3-propan-2-ylphenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)C1=CC(Cl)=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)C)C(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCOC=2C(=CC(Cl)=CC=2C(C)C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 ZSQFTVCLWHQSPG-UHFFFAOYSA-N 0.000 claims description 2
- XFYYZWXKGVKKBJ-UHFFFAOYSA-N 2-[5-chloro-2-[4-[2-(3-chloro-5-methylphenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypentan-2-yloxy]-3-methylphenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC=1C=C(Cl)C=C(C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)C=1OC(C)CC(C)OC1(O)C(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)C=C(C(C)(C)CC(C)(C)C)C=C1C1=CC(C)=CC(Cl)=C1 XFYYZWXKGVKKBJ-UHFFFAOYSA-N 0.000 claims description 2
- VCVJFNYIUTXCPS-UHFFFAOYSA-N 2-[5-chloro-2-[5-[2-(3-chloro-5-methylphenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypentoxy]-3-methylphenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC1=CC(Cl)=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)C)C(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCCCOC=2C(=CC(Cl)=CC=2C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 VCVJFNYIUTXCPS-UHFFFAOYSA-N 0.000 claims description 2
- PXNMBOXULKKRPA-UHFFFAOYSA-N 2-[5-chloro-2-[6-[2-(3-chloro-5-methylphenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxyhexoxy]-3-methylphenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC1=CC(Cl)=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)C)C(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCCCCOC=2C(=CC(Cl)=CC=2C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 PXNMBOXULKKRPA-UHFFFAOYSA-N 0.000 claims description 2
- AMMGYHQCOPCVLQ-UHFFFAOYSA-N 2-[5-tert-butyl-2-[3-[2-(3-tert-butyl-5-chlorophenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-3-chlorophenyl]-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)C(O)(OCCCOC=2C(=CC(=CC=2Cl)C(C)(C)C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)C=1C1=CC(Cl)=CC(C(C)(C)C)=C1 AMMGYHQCOPCVLQ-UHFFFAOYSA-N 0.000 claims description 2
- IYBACNDBTLIVHR-UHFFFAOYSA-N 4-[3-[2-(3-cyano-5-methylphenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-3-[3-(3,6-ditert-butylcarbazol-9-yl)-2-hydroxy-5-(2,4,4-trimethylpentan-2-yl)phenyl]-5-methylbenzonitrile Chemical compound CC1=CC(C#N)=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)C)C(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCOC=2C(=CC(=CC=2C)C#N)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 IYBACNDBTLIVHR-UHFFFAOYSA-N 0.000 claims description 2
- FNPUWTQOFFPFAX-UHFFFAOYSA-N C[Hf]C.C(CCCCOC1=C(C=C(C=C1C)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)C)O Chemical compound C[Hf]C.C(CCCCOC1=C(C=C(C=C1C)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)C)O FNPUWTQOFFPFAX-UHFFFAOYSA-N 0.000 claims description 2
- IWVCZIWBZCSGOI-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=C(C=C1Br)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)Br)O Chemical compound C[Hf]C.C(CCOC1=C(C=C(C=C1Br)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)Br)O IWVCZIWBZCSGOI-UHFFFAOYSA-N 0.000 claims description 2
- AGINXMFXJNMGLY-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=C(C=C1C)C(F)(F)F)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)C(F)(F)F)C)O Chemical compound C[Hf]C.C(CCOC1=C(C=C(C=C1C)C(F)(F)F)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)C(F)(F)F)C)O AGINXMFXJNMGLY-UHFFFAOYSA-N 0.000 claims description 2
- ZESKUUDKBWTHBN-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=C(C=C1C)N(C)C)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)N(C)C)C)O Chemical compound C[Hf]C.C(CCOC1=C(C=C(C=C1C)N(C)C)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)N(C)C)C)O ZESKUUDKBWTHBN-UHFFFAOYSA-N 0.000 claims description 2
- FNFPHLGXSMYFRD-UHFFFAOYSA-N C[Hf]C.C(COC1=C(C=C(C=C1C)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)C)O Chemical compound C[Hf]C.C(COC1=C(C=C(C=C1C)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)C)O FNFPHLGXSMYFRD-UHFFFAOYSA-N 0.000 claims description 2
- NDCIXMBYGDHKOG-UHFFFAOYSA-N C[Hf]C.CC(CC(C)OC1=C(C=C(C=C1C)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)C)O Chemical compound C[Hf]C.CC(CC(C)OC1=C(C=C(C=C1C)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)C)O NDCIXMBYGDHKOG-UHFFFAOYSA-N 0.000 claims description 2
- QLARGBRQZCHYOW-UHFFFAOYSA-N C[Hf]C.C[Si](COC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)Cl)O)(COC1=C(C=C(C=C1Cl)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)C Chemical compound C[Hf]C.C[Si](COC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)Cl)O)(COC1=C(C=C(C=C1Cl)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)C QLARGBRQZCHYOW-UHFFFAOYSA-N 0.000 claims description 2
- COOXAWDWHWRVRD-UHFFFAOYSA-N C[Ti]C Chemical compound C[Ti]C COOXAWDWHWRVRD-UHFFFAOYSA-N 0.000 claims description 2
- VBMYBWBAVMRWJQ-UHFFFAOYSA-N C[Ti]C.C(CCOC1=C(C=C(C=C1Cl)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)Cl)O Chemical compound C[Ti]C.C(CCOC1=C(C=C(C=C1Cl)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)Cl)O VBMYBWBAVMRWJQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 claims description 2
- DWTDMFRATRTFLC-UHFFFAOYSA-N 2-(3,6-ditert-butylcarbazol-9-yl)-6-[2-[3-[6-(3,6-ditert-butylcarbazol-9-yl)-2-[3-fluoro-5-(trifluoromethyl)phenyl]-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-5-fluoro-3-(trifluoromethyl)phenyl]-4-(2,4,4-trimethylpentan-2- Chemical compound C=1C(C(C)(C)CC(C)(C)C)=CC(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)C(O)(OCCCOC=2C(=CC(F)=CC=2C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)C(F)(F)F)C=1C1=CC(F)=CC(C(F)(F)F)=C1 DWTDMFRATRTFLC-UHFFFAOYSA-N 0.000 claims 1
- IZQYFUIVSRIKCN-UHFFFAOYSA-N 2-(3,6-ditert-butylcarbazol-9-yl)-6-[3-methyl-5-(trifluoromethyl)phenyl]-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound FC(F)(F)C1=CC(C)=CC(C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 IZQYFUIVSRIKCN-UHFFFAOYSA-N 0.000 claims 1
- FHNTXWNJTHJPOQ-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=C(C=C1C)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=CC=C2C=2C=CC=CC12)O)OC1(C(=CC(=CC1N1C2=CC=CC=C2C=2C=CC=CC12)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)C)O Chemical compound C[Hf]C.C(CCOC1=C(C=C(C=C1C)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=CC=C2C=2C=CC=CC12)O)OC1(C(=CC(=CC1N1C2=CC=CC=C2C=2C=CC=CC12)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)C)O FHNTXWNJTHJPOQ-UHFFFAOYSA-N 0.000 claims 1
- UGVVIPAIDGTTNN-UHFFFAOYSA-N C[Zr]C Chemical compound C[Zr]C UGVVIPAIDGTTNN-UHFFFAOYSA-N 0.000 claims 1
- 239000000543 intermediate Substances 0.000 abstract description 39
- 238000005481 NMR spectroscopy Methods 0.000 description 155
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 119
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 96
- 238000004519 manufacturing process Methods 0.000 description 82
- 238000002360 preparation method Methods 0.000 description 80
- 239000000243 solution Substances 0.000 description 71
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 66
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 66
- 230000008569 process Effects 0.000 description 63
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 57
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 57
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 50
- 229920000098 polyolefin Polymers 0.000 description 48
- 229920001400 block copolymer Polymers 0.000 description 40
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 39
- 239000007787 solid Substances 0.000 description 39
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 38
- 239000000178 monomer Substances 0.000 description 34
- 239000002904 solvent Substances 0.000 description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 33
- 239000011541 reaction mixture Substances 0.000 description 28
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 27
- 239000002685 polymerization catalyst Substances 0.000 description 27
- 125000000217 alkyl group Chemical group 0.000 description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 25
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 23
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 23
- 239000000460 chlorine Substances 0.000 description 22
- 235000019439 ethyl acetate Nutrition 0.000 description 22
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 22
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 22
- 230000002441 reversible effect Effects 0.000 description 22
- 150000001875 compounds Chemical class 0.000 description 21
- 238000003818 flash chromatography Methods 0.000 description 21
- 239000000741 silica gel Substances 0.000 description 21
- 229910002027 silica gel Inorganic materials 0.000 description 21
- 238000002425 crystallisation Methods 0.000 description 19
- 230000008025 crystallization Effects 0.000 description 19
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 19
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 18
- 239000003921 oil Substances 0.000 description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 18
- 239000012267 brine Substances 0.000 description 17
- 238000002390 rotary evaporation Methods 0.000 description 17
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 17
- 239000000126 substance Substances 0.000 description 17
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000000523 sample Substances 0.000 description 16
- 239000011734 sodium Substances 0.000 description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 150000003254 radicals Chemical class 0.000 description 15
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- 150000001721 carbon Chemical group 0.000 description 14
- 239000012986 chain transfer agent Substances 0.000 description 14
- 125000003636 chemical group Chemical group 0.000 description 14
- 229910052801 chlorine Inorganic materials 0.000 description 14
- 125000004093 cyano group Chemical group *C#N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 125000001309 chloro group Chemical group Cl* 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 13
- 125000000753 cycloalkyl group Chemical group 0.000 description 13
- 229910052731 fluorine Inorganic materials 0.000 description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 12
- 125000001153 fluoro group Chemical group F* 0.000 description 12
- 238000010348 incorporation Methods 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 12
- 229920002959 polymer blend Polymers 0.000 description 11
- 125000006239 protecting group Chemical group 0.000 description 11
- 238000012546 transfer Methods 0.000 description 11
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 11
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 125000002993 cycloalkylene group Chemical group 0.000 description 10
- 239000000706 filtrate Substances 0.000 description 10
- 125000000524 functional group Chemical group 0.000 description 10
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 10
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 229920006395 saturated elastomer Polymers 0.000 description 10
- DVVUCRMTAIIZLJ-UHFFFAOYSA-N 5-chloro-2-[3-(4-chloro-2-fluoro-6-iodophenoxy)propoxy]-1-fluoro-3-iodobenzene Chemical compound FC1=CC(Cl)=CC(I)=C1OCCCOC1=C(F)C=C(Cl)C=C1I DVVUCRMTAIIZLJ-UHFFFAOYSA-N 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 125000002015 acyclic group Chemical group 0.000 description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 9
- 125000001584 benzyloxycarbonyl group Chemical group C(=O)(OCC1=CC=CC=C1)* 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 9
- 238000004260 weight control Methods 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 8
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 125000004122 cyclic group Chemical group 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 239000003039 volatile agent Substances 0.000 description 8
- DNTJGBIQTKFVRH-UHFFFAOYSA-N 2,4-difluoro-6-iodophenol Chemical compound OC1=C(F)C=C(F)C=C1I DNTJGBIQTKFVRH-UHFFFAOYSA-N 0.000 description 7
- 150000001993 dienes Chemical class 0.000 description 7
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 7
- 230000003993 interaction Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000001294 propane Substances 0.000 description 7
- 230000002829 reductive effect Effects 0.000 description 7
- 125000006657 (C1-C10) hydrocarbyl group Chemical group 0.000 description 6
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 6
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 125000002619 bicyclic group Chemical group 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000012141 concentrate Substances 0.000 description 6
- 239000000284 extract Substances 0.000 description 6
- 125000004474 heteroalkylene group Chemical group 0.000 description 6
- 125000000592 heterocycloalkyl group Chemical group 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 150000001450 anions Chemical class 0.000 description 5
- 239000000010 aprotic solvent Substances 0.000 description 5
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 5
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920001903 high density polyethylene Polymers 0.000 description 5
- 239000004700 high-density polyethylene Substances 0.000 description 5
- 125000002950 monocyclic group Chemical group 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 125000006413 ring segment Chemical group 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 125000006736 (C6-C20) aryl group Chemical group 0.000 description 4
- VEFLKXRACNJHOV-UHFFFAOYSA-N 1,3-dibromopropane Chemical compound BrCCCBr VEFLKXRACNJHOV-UHFFFAOYSA-N 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- CKOMGKUZMFMLFG-UHFFFAOYSA-N 1-iodo-2-[3-(2-iodo-4-methoxy-6-methylphenoxy)propoxy]-5-methoxy-3-methylbenzene Chemical compound IC1=CC(OC)=CC(C)=C1OCCCOC1=C(C)C=C(OC)C=C1I CKOMGKUZMFMLFG-UHFFFAOYSA-N 0.000 description 4
- XQEHERLDCUVIQS-UHFFFAOYSA-N 2-iodo-4-methoxy-6-methylphenol Chemical compound COC1=CC(C)=C(O)C(I)=C1 XQEHERLDCUVIQS-UHFFFAOYSA-N 0.000 description 4
- QCEDDUSMBLCRNH-UHFFFAOYSA-N 4-chloro-2-ethylphenol Chemical compound CCC1=CC(Cl)=CC=C1O QCEDDUSMBLCRNH-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000013459 approach Methods 0.000 description 4
- 125000000732 arylene group Chemical group 0.000 description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 4
- 238000010511 deprotection reaction Methods 0.000 description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 150000002902 organometallic compounds Chemical class 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 235000009518 sodium iodide Nutrition 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 4
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 description 3
- 125000006651 (C3-C20) cycloalkyl group Chemical group 0.000 description 3
- DYEQHQNRKZJUCT-UHFFFAOYSA-N 1,2-dimethylidenecyclohexane Chemical compound C=C1CCCCC1=C DYEQHQNRKZJUCT-UHFFFAOYSA-N 0.000 description 3
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 3
- LKXHTGKMBHJBBI-UHFFFAOYSA-N 1-iodo-2-[3-(6-iodo-2,3-dimethylphenoxy)propoxy]-3,4-dimethylbenzene Chemical compound CC1=CC=C(I)C(OCCCOC=2C(=CC=C(C)C=2C)I)=C1C LKXHTGKMBHJBBI-UHFFFAOYSA-N 0.000 description 3
- NDNHZMBYUWUXRC-UHFFFAOYSA-N 1-tert-butyl-5-[3-(5-tert-butyl-4-chloro-2-iodophenoxy)propoxy]-2-chloro-4-iodobenzene Chemical compound C1=C(Cl)C(C(C)(C)C)=CC(OCCCOC=2C(=CC(Cl)=C(C=2)C(C)(C)C)I)=C1I NDNHZMBYUWUXRC-UHFFFAOYSA-N 0.000 description 3
- UMDKVOOEGYNMEB-UHFFFAOYSA-N 2,4-dichloro-6-iodophenol Chemical compound OC1=C(Cl)C=C(Cl)C=C1I UMDKVOOEGYNMEB-UHFFFAOYSA-N 0.000 description 3
- JVZUYKFIOZRDSK-UHFFFAOYSA-N 2-(2,3-dimethylphenoxy)oxane Chemical compound CC1=CC=CC(OC2OCCCC2)=C1C JVZUYKFIOZRDSK-UHFFFAOYSA-N 0.000 description 3
- KFPMSSWWZNDEAA-UHFFFAOYSA-N 2-(3-bromopropoxy)-5-chloro-1-iodo-3-methylbenzene Chemical compound CC1=CC(Cl)=CC(I)=C1OCCCBr KFPMSSWWZNDEAA-UHFFFAOYSA-N 0.000 description 3
- VIDNBQNODXBIKD-UHFFFAOYSA-N 2-(4-methoxy-2-methylphenoxy)oxane Chemical compound CC1=CC(OC)=CC=C1OC1OCCCC1 VIDNBQNODXBIKD-UHFFFAOYSA-N 0.000 description 3
- WFWSREBPXRRQQR-UHFFFAOYSA-N 2-(4-methoxyphenoxy)oxane Chemical compound C1=CC(OC)=CC=C1OC1OCCCC1 WFWSREBPXRRQQR-UHFFFAOYSA-N 0.000 description 3
- SAUZMXWWQSEZCV-UHFFFAOYSA-N 2-bromo-4-tert-butyl-6-chlorophenol Chemical compound CC(C)(C)C1=CC(Cl)=C(O)C(Br)=C1 SAUZMXWWQSEZCV-UHFFFAOYSA-N 0.000 description 3
- KSYHPGHAMBDJLG-UHFFFAOYSA-N 2-bromo-5-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(Br)C(O)=C1 KSYHPGHAMBDJLG-UHFFFAOYSA-N 0.000 description 3
- QWEAJCDNFQMPOD-UHFFFAOYSA-N 2-iodo-1-(methoxymethoxy)-4-(2,4,4-trimethylpentan-2-yl)benzene Chemical compound COCOC1=CC=C(C(C)(C)CC(C)(C)C)C=C1I QWEAJCDNFQMPOD-UHFFFAOYSA-N 0.000 description 3
- VDEDIYDCJTUMNX-UHFFFAOYSA-N 3,6-ditert-butyl-9-[2-(oxan-2-yloxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-(2,4,4-trimethylpentan-2-yl)phenyl]carbazole Chemical compound C1CCCOC1OC=1C(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)=CC(C(C)(C)CC(C)(C)C)=CC=1B1OC(C)(C)C(C)(C)O1 VDEDIYDCJTUMNX-UHFFFAOYSA-N 0.000 description 3
- ODVREDGIWSDQFD-UHFFFAOYSA-N 3-(4-methylphenyl)sulfonyloxypropyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCCCOS(=O)(=O)C1=CC=C(C)C=C1 ODVREDGIWSDQFD-UHFFFAOYSA-N 0.000 description 3
- OXVSFVHTIMKLHR-UHFFFAOYSA-N 4-chloro-2-(1-hydroxypropan-2-yl)phenol Chemical compound OCC(C)C1=CC(Cl)=CC=C1O OXVSFVHTIMKLHR-UHFFFAOYSA-N 0.000 description 3
- SJSWZIGQCMAPBV-UHFFFAOYSA-N 4-chloro-2-fluoro-6-iodophenol Chemical compound OC1=C(F)C=C(Cl)C=C1I SJSWZIGQCMAPBV-UHFFFAOYSA-N 0.000 description 3
- XLGCDJBIFRLTJZ-UHFFFAOYSA-N 4-chloro-2-iodo-6-methylphenol Chemical compound CC1=CC(Cl)=CC(I)=C1O XLGCDJBIFRLTJZ-UHFFFAOYSA-N 0.000 description 3
- CZIPXDZTLVWDFZ-UHFFFAOYSA-N 4-chloro-2-iodo-6-propan-2-ylphenol Chemical compound CC(C)C1=CC(Cl)=CC(I)=C1O CZIPXDZTLVWDFZ-UHFFFAOYSA-N 0.000 description 3
- JBEWAUJIUYSHQH-UHFFFAOYSA-N 4-chloro-2-propan-2-ylphenol Chemical compound CC(C)C1=CC(Cl)=CC=C1O JBEWAUJIUYSHQH-UHFFFAOYSA-N 0.000 description 3
- CCTDLMVZOUPXEC-UHFFFAOYSA-N 4-tert-butyl-1-[3-(4-tert-butyl-2-methylphenoxy)propoxy]-2-methylbenzene Chemical compound CC1=CC(C(C)(C)C)=CC=C1OCCCOC1=CC=C(C(C)(C)C)C=C1C CCTDLMVZOUPXEC-UHFFFAOYSA-N 0.000 description 3
- AERBUFODZUOUIU-UHFFFAOYSA-N 5-chloro-2-[3-(4-chloro-2-iodo-6-methylphenoxy)propoxy]-1-iodo-3-methylbenzene Chemical compound CC1=CC(Cl)=CC(I)=C1OCCCOC1=C(C)C=C(Cl)C=C1I AERBUFODZUOUIU-UHFFFAOYSA-N 0.000 description 3
- SOTXSJYMVOCNAJ-UHFFFAOYSA-N 5-chloro-2-[3-(4-chloro-2-iodo-6-propan-2-ylphenoxy)propoxy]-1-iodo-3-propan-2-ylbenzene Chemical compound CC(C)C1=CC(Cl)=CC(I)=C1OCCCOC1=C(I)C=C(Cl)C=C1C(C)C SOTXSJYMVOCNAJ-UHFFFAOYSA-N 0.000 description 3
- DNGHOKOPSOJZFU-UHFFFAOYSA-N 5-chloro-2-[3-(4-chloro-2-iodophenoxy)propoxy]-1-iodo-3-methylbenzene Chemical compound CC1=CC(Cl)=CC(I)=C1OCCCOC1=CC=C(Cl)C=C1I DNGHOKOPSOJZFU-UHFFFAOYSA-N 0.000 description 3
- TWDSAKRIFDXKES-UHFFFAOYSA-N 5-chloro-2-[4-(4-chloro-2-iodo-6-methylphenoxy)butoxy]-1-iodo-3-methylbenzene Chemical compound CC1=CC(Cl)=CC(I)=C1OCCCCOC1=C(C)C=C(Cl)C=C1I TWDSAKRIFDXKES-UHFFFAOYSA-N 0.000 description 3
- COYVTCLXNSGLFE-UHFFFAOYSA-N 5-tert-butyl-2-iodophenol Chemical compound CC(C)(C)C1=CC=C(I)C(O)=C1 COYVTCLXNSGLFE-UHFFFAOYSA-N 0.000 description 3
- DDBWAWMMQWKMJG-UHFFFAOYSA-N 5-tert-butyl-4-chloro-2-iodophenol Chemical compound CC(C)(C)C1=CC(O)=C(I)C=C1Cl DDBWAWMMQWKMJG-UHFFFAOYSA-N 0.000 description 3
- WVMDQTZMUAFNGA-UHFFFAOYSA-N 6-iodo-2,3-dimethylphenol Chemical compound CC1=CC=C(I)C(O)=C1C WVMDQTZMUAFNGA-UHFFFAOYSA-N 0.000 description 3
- CJGDFSDTJBDUCN-UHFFFAOYSA-N 9-[2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl]carbazole Chemical compound COCOC1=CC=C(C(C)(C)CC(C)(C)C)C=C1N1C2=CC=CC=C2C2=CC=CC=C21 CJGDFSDTJBDUCN-UHFFFAOYSA-N 0.000 description 3
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 3
- XAVABQFAFYDGTE-UHFFFAOYSA-N C[Hf]C.C(CCOC1=C(C=C(C=C1C(C)C)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)C(C)C)O Chemical compound C[Hf]C.C(CCOC1=C(C=C(C=C1C(C)C)Cl)C=1C(=C(C=C(C1)C(C)(CC(C)(C)C)C)N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)O)OC1(C(=CC(=CC1N1C2=CC=C(C=C2C=2C=C(C=CC12)C(C)(C)C)C(C)(C)C)C(C)(CC(C)(C)C)C)C1=CC(=CC(=C1)Cl)C(C)C)O XAVABQFAFYDGTE-UHFFFAOYSA-N 0.000 description 3
- 238000004566 IR spectroscopy Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910019093 NaOCl Inorganic materials 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000007844 bleaching agent Substances 0.000 description 3
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 3
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 125000004404 heteroalkyl group Chemical group 0.000 description 3
- 125000000593 indol-1-yl group Chemical group [H]C1=C([H])C([H])=C2N([*])C([H])=C([H])C2=C1[H] 0.000 description 3
- 125000003387 indolinyl group Chemical group N1(CCC2=CC=CC=C12)* 0.000 description 3
- 125000001041 indolyl group Chemical group 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 150000007527 lewis bases Chemical group 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 3
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 2
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 description 2
- 125000006645 (C3-C4) cycloalkyl group Chemical group 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- VQOXUMQBYILCKR-UHFFFAOYSA-N 1-Tridecene Chemical compound CCCCCCCCCCCC=C VQOXUMQBYILCKR-UHFFFAOYSA-N 0.000 description 2
- ANZIRKFZCCTRGU-UHFFFAOYSA-N 1-bromo-2-[3-(2-bromo-4-tert-butyl-6-chlorophenoxy)propoxy]-5-tert-butyl-3-chlorobenzene Chemical group BrC1=CC(C(C)(C)C)=CC(Cl)=C1OCCCOC1=C(Cl)C=C(C(C)(C)C)C=C1Br ANZIRKFZCCTRGU-UHFFFAOYSA-N 0.000 description 2
- QHIYRSRWEUCPMX-UHFFFAOYSA-N 1-bromo-2-[3-(2-bromo-4-tert-butyl-6-methylphenoxy)propoxy]-5-tert-butyl-3-methylbenzene Chemical compound CC1=CC(C(C)(C)C)=CC(Br)=C1OCCCOC1=C(C)C=C(C(C)(C)C)C=C1Br QHIYRSRWEUCPMX-UHFFFAOYSA-N 0.000 description 2
- LCUJBUXMQHUUMH-UHFFFAOYSA-N 1-bromo-2-[3-(2-bromo-5-tert-butylphenoxy)propoxy]-4-tert-butylbenzene Chemical compound CC(C)(C)C1=CC=C(Br)C(OCCCOC=2C(=CC=C(C=2)C(C)(C)C)Br)=C1 LCUJBUXMQHUUMH-UHFFFAOYSA-N 0.000 description 2
- PPBXRVJCQZNXRK-UHFFFAOYSA-N 1-bromo-2-[4-(2-bromo-5-tert-butylphenoxy)butoxy]-4-tert-butylbenzene Chemical compound CC(C)(C)C1=CC=C(Br)C(OCCCCOC=2C(=CC=C(C=2)C(C)(C)C)Br)=C1 PPBXRVJCQZNXRK-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- ADOBXTDBFNCOBN-UHFFFAOYSA-N 1-heptadecene Chemical compound CCCCCCCCCCCCCCCC=C ADOBXTDBFNCOBN-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- VOPSPNLGQLBTNP-UHFFFAOYSA-N 1-iodo-2-[3-(2-iodo-4,6-dimethylphenoxy)propoxy]-3,5-dimethylbenzene Chemical compound IC1=CC(C)=CC(C)=C1OCCCOC1=C(C)C=C(C)C=C1I VOPSPNLGQLBTNP-UHFFFAOYSA-N 0.000 description 2
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 2
- PJLHTVIBELQURV-UHFFFAOYSA-N 1-pentadecene Chemical compound CCCCCCCCCCCCCC=C PJLHTVIBELQURV-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- QWBBPBRQALCEIZ-UHFFFAOYSA-N 2,3-dimethylphenol Chemical compound CC1=CC=CC(O)=C1C QWBBPBRQALCEIZ-UHFFFAOYSA-N 0.000 description 2
- ORXUNBLSAFVHAY-UHFFFAOYSA-N 2-(3,6-ditert-butylcarbazol-9-yl)-6-[3-fluoro-5-(trifluoromethyl)phenyl]-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound OC=1C(N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)=CC(C(C)(C)CC(C)(C)C)=CC=1C1=CC(F)=CC(C(F)(F)F)=C1 ORXUNBLSAFVHAY-UHFFFAOYSA-N 0.000 description 2
- SNKLPZOJLXDZCW-UHFFFAOYSA-N 2-Methyl-4-(1,1-dimethylethyl) phenol Natural products CC1=CC(C(C)(C)C)=CC=C1O SNKLPZOJLXDZCW-UHFFFAOYSA-N 0.000 description 2
- AVACKPMKMKQZIL-UHFFFAOYSA-N 2-[3-(2,4-difluoro-6-iodophenoxy)propoxy]-1,5-difluoro-3-iodobenzene Chemical compound IC1=CC(F)=CC(F)=C1OCCCOC1=C(F)C=C(F)C=C1I AVACKPMKMKQZIL-UHFFFAOYSA-N 0.000 description 2
- VEHDPCXTYVFOPR-UHFFFAOYSA-N 2-carbazol-9-yl-6-[2-[3-[6-carbazol-9-yl-2-(3-chloro-5-methylphenyl)-1-hydroxy-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-5-chloro-3-methylphenyl]-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC1=CC(Cl)=CC(C=2C(C(N3C4=CC=CC=C4C4=CC=CC=C43)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCOC=2C(=CC(Cl)=CC=2C)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=CC=C3C3=CC=CC=C32)O)=C1 VEHDPCXTYVFOPR-UHFFFAOYSA-N 0.000 description 2
- KUDRANMELYZFGK-UHFFFAOYSA-N 2-iodo-4,6-dimethylphenol Chemical compound CC1=CC(C)=C(O)C(I)=C1 KUDRANMELYZFGK-UHFFFAOYSA-N 0.000 description 2
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 2
- WJQOZHYUIDYNHM-UHFFFAOYSA-N 2-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC=C1O WJQOZHYUIDYNHM-UHFFFAOYSA-N 0.000 description 2
- 238000005084 2D-nuclear magnetic resonance Methods 0.000 description 2
- FDPBHFOYBSWJBR-UHFFFAOYSA-N 4-chloro-2-ethyl-6-iodophenol Chemical compound CCC1=CC(Cl)=CC(I)=C1O FDPBHFOYBSWJBR-UHFFFAOYSA-N 0.000 description 2
- CZDDHJXSYYUEPT-UHFFFAOYSA-N 4-fluoro-2-iodo-6-(trifluoromethyl)phenol Chemical compound OC1=C(I)C=C(F)C=C1C(F)(F)F CZDDHJXSYYUEPT-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 2
- HJMDAVVPDXRYRT-UHFFFAOYSA-N 5-chloro-2-[3-(4-chloro-2-ethyl-6-iodophenoxy)propoxy]-1-ethyl-3-iodobenzene Chemical compound CCC1=CC(Cl)=CC(I)=C1OCCCOC1=C(I)C=C(Cl)C=C1CC HJMDAVVPDXRYRT-UHFFFAOYSA-N 0.000 description 2
- NRZLMVMAZOJHAP-UHFFFAOYSA-N 5-fluoro-2-[3-(4-fluoro-2-iodo-6-methylphenoxy)propoxy]-1-iodo-3-methylbenzene Chemical compound CC1=CC(F)=CC(I)=C1OCCCOC1=C(C)C=C(F)C=C1I NRZLMVMAZOJHAP-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- OWYWGLHRNBIFJP-UHFFFAOYSA-N Ipazine Chemical compound CCN(CC)C1=NC(Cl)=NC(NC(C)C)=N1 OWYWGLHRNBIFJP-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 241000183024 Populus tremula Species 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical group [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 2
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical group [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 125000005037 alkyl phenyl group Chemical group 0.000 description 2
- 239000000538 analytical sample Substances 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 238000006254 arylation reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004266 aziridin-1-yl group Chemical group [H]C1([H])N(*)C1([H])[H] 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013058 crude material Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- 238000000113 differential scanning calorimetry Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000007345 electrophilic aromatic substitution reaction Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- FCZCIXQGZOUIDN-UHFFFAOYSA-N ethyl 2-diethoxyphosphinothioyloxyacetate Chemical compound CCOC(=O)COP(=S)(OCC)OCC FCZCIXQGZOUIDN-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000004254 isoquinolin-1-yl group Chemical group [H]C1=C([H])C2=C([H])C([H])=C([H])C([H])=C2C(*)=N1 0.000 description 2
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 229910001507 metal halide Inorganic materials 0.000 description 2
- 150000005309 metal halides Chemical class 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- 238000000238 one-dimensional nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 125000001979 organolithium group Chemical group 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 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 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- XQYMIMUDVJCMLU-UHFFFAOYSA-N phenoxyperoxybenzene Chemical compound C=1C=CC=CC=1OOOC1=CC=CC=C1 XQYMIMUDVJCMLU-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000004611 spectroscopical analysis Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 125000005717 substituted cycloalkylene group Chemical group 0.000 description 2
- 239000003760 tallow Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- FRDZGSBXKJXGNR-HTQZYQBOSA-N (1r,2r)-2-n,2-n-dimethylcyclohexane-1,2-diamine Chemical compound CN(C)[C@@H]1CCCC[C@H]1N FRDZGSBXKJXGNR-HTQZYQBOSA-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
- 125000006747 (C2-C10) heterocycloalkyl group Chemical group 0.000 description 1
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 description 1
- QVLAWKAXOMEXPM-DICFDUPASA-N 1,1,1,2-tetrachloro-2,2-dideuterioethane Chemical compound [2H]C([2H])(Cl)C(Cl)(Cl)Cl QVLAWKAXOMEXPM-DICFDUPASA-N 0.000 description 1
- QVLAWKAXOMEXPM-UHFFFAOYSA-N 1,1,1,2-tetrachloroethane Chemical class ClCC(Cl)(Cl)Cl QVLAWKAXOMEXPM-UHFFFAOYSA-N 0.000 description 1
- 125000004605 1,2,3,4-tetrahydroisoquinolinyl group Chemical group C1(NCCC2=CC=CC=C12)* 0.000 description 1
- 125000004607 1,2,3,4-tetrahydroquinolinyl group Chemical group N1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000003626 1,2,4-triazol-1-yl group Chemical group [*]N1N=C([H])N=C1[H] 0.000 description 1
- XBJHZEUYCYYCLK-UHFFFAOYSA-N 1,2-dimethylidenecyclopentane Chemical compound C=C1CCCC1=C XBJHZEUYCYYCLK-UHFFFAOYSA-N 0.000 description 1
- 125000004509 1,3,4-oxadiazol-2-yl group Chemical group O1C(=NN=C1)* 0.000 description 1
- 125000004521 1,3,4-thiadiazol-2-yl group Chemical group S1C(=NN=C1)* 0.000 description 1
- SOZLNIPBRVQUOG-UHFFFAOYSA-N 1,3-dibromopentane Chemical group CCC(Br)CCBr SOZLNIPBRVQUOG-UHFFFAOYSA-N 0.000 description 1
- CTDOPUVVTOMREJ-UHFFFAOYSA-N 1,3-dimethylidenecyclohexane Chemical compound C=C1CCCC(=C)C1 CTDOPUVVTOMREJ-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- IBODDUNKEPPBKW-UHFFFAOYSA-N 1,5-dibromopentane Chemical group BrCCCCCBr IBODDUNKEPPBKW-UHFFFAOYSA-N 0.000 description 1
- MDMTWWABYVCEOM-UHFFFAOYSA-N 1,5-dichloro-2-[3-(2,4-dichloro-6-iodophenoxy)propoxy]-3-iodobenzene Chemical compound IC1=CC(Cl)=CC(Cl)=C1OCCCOC1=C(Cl)C=C(Cl)C=C1I MDMTWWABYVCEOM-UHFFFAOYSA-N 0.000 description 1
- SGRHVVLXEBNBDV-UHFFFAOYSA-N 1,6-dibromohexane Chemical group BrCCCCCCBr SGRHVVLXEBNBDV-UHFFFAOYSA-N 0.000 description 1
- QCVSDCHNBNFJDQ-UHFFFAOYSA-N 1-(4-chloro-2-hydroxyphenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1O QCVSDCHNBNFJDQ-UHFFFAOYSA-N 0.000 description 1
- XTGCUDZCCIRWHL-UHFFFAOYSA-N 1-(5-chloro-2-hydroxyphenyl)ethanone Chemical compound CC(=O)C1=CC(Cl)=CC=C1O XTGCUDZCCIRWHL-UHFFFAOYSA-N 0.000 description 1
- 125000004173 1-benzimidazolyl group Chemical group [H]C1=NC2=C([H])C([H])=C([H])C([H])=C2N1* 0.000 description 1
- KNJUWQJGEGGMOA-UHFFFAOYSA-N 1-bromo-4-tert-butyl-2-propoxybenzene Chemical compound BrC1=C(OCCC)C=C(C=C1)C(C)(C)C KNJUWQJGEGGMOA-UHFFFAOYSA-N 0.000 description 1
- JWMKUKRBNODZFA-UHFFFAOYSA-N 1-ethoxy-2-methylbenzene Chemical compound CCOC1=CC=CC=C1C JWMKUKRBNODZFA-UHFFFAOYSA-N 0.000 description 1
- HKCQYAPIHRALPY-UHFFFAOYSA-N 1-methyl-2-propoxybenzene Chemical compound CCCOC1=CC=CC=C1C HKCQYAPIHRALPY-UHFFFAOYSA-N 0.000 description 1
- 125000004214 1-pyrrolidinyl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- DEPDDPLQZYCHOH-UHFFFAOYSA-N 1h-imidazol-2-amine Chemical compound NC1=NC=CN1 DEPDDPLQZYCHOH-UHFFFAOYSA-N 0.000 description 1
- WEOIMVGRKQBCKD-UHFFFAOYSA-N 2,3-dimethylidenebicyclo[2.2.2]octane Chemical compound C1CC2CCC1C(=C)C2=C WEOIMVGRKQBCKD-UHFFFAOYSA-N 0.000 description 1
- KUZOHDYKJXNCSI-UHFFFAOYSA-N 2,4-dibromopentane Chemical group CC(Br)CC(C)Br KUZOHDYKJXNCSI-UHFFFAOYSA-N 0.000 description 1
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical compound OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- NVWVWEWVLBKPSM-UHFFFAOYSA-N 2,4-difluorophenol Chemical compound OC1=CC=C(F)C=C1F NVWVWEWVLBKPSM-UHFFFAOYSA-N 0.000 description 1
- KUFFULVDNCHOFZ-UHFFFAOYSA-N 2,4-xylenol Chemical compound CC1=CC=C(O)C(C)=C1 KUFFULVDNCHOFZ-UHFFFAOYSA-N 0.000 description 1
- NMXLXQGHBSPIDR-UHFFFAOYSA-N 2-(2-methylpropyl)oxaluminane Chemical compound CC(C)C[Al]1CCCCO1 NMXLXQGHBSPIDR-UHFFFAOYSA-N 0.000 description 1
- DXTSOKMMCFCQEB-UHFFFAOYSA-N 2-(3,6-ditert-butylcarbazol-9-yl)-6-[2-[3-[6-(3,6-ditert-butylcarbazol-9-yl)-1-hydroxy-2-[3-methyl-5-(trifluoromethyl)phenyl]-4-(2,4,4-trimethylpentan-2-yl)cyclohexa-2,4-dien-1-yl]oxypropoxy]-3-methyl-5-(trifluoromethyl)phenyl]-4-(2,4,4-trimethylpentan-2- Chemical compound FC(F)(F)C1=CC(C)=CC(C=2C(C(N3C4=CC=C(C=C4C4=CC(=CC=C43)C(C)(C)C)C(C)(C)C)C=C(C=2)C(C)(C)CC(C)(C)C)(O)OCCCOC=2C(=CC(=CC=2C)C(F)(F)F)C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 DXTSOKMMCFCQEB-UHFFFAOYSA-N 0.000 description 1
- ZLBKAUWLVWHMRO-UHFFFAOYSA-N 2-(3-chloro-5-methylphenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC1=CC(Cl)=CC(C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 ZLBKAUWLVWHMRO-UHFFFAOYSA-N 0.000 description 1
- AFIHSECJZCZCES-UHFFFAOYSA-N 2-(3-chloro-5-propan-2-ylphenyl)-6-(3,6-ditert-butylcarbazol-9-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)C1=CC(Cl)=CC(C=2C(=C(C=C(C=2)C(C)(C)CC(C)(C)C)N2C3=CC=C(C=C3C3=CC(=CC=C32)C(C)(C)C)C(C)(C)C)O)=C1 AFIHSECJZCZCES-UHFFFAOYSA-N 0.000 description 1
- QTLLJEKQHSHZBV-UHFFFAOYSA-N 2-[2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenoxy]oxane Chemical compound IC1=CC(C(C)(C)CC(C)(C)C)=CC=C1OC1OCCCC1 QTLLJEKQHSHZBV-UHFFFAOYSA-N 0.000 description 1
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- BINAYPRCRGPNHS-UHFFFAOYSA-N 2-iodo-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(I)=C1 BINAYPRCRGPNHS-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000389 2-pyrrolyl group Chemical group [H]N1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- UOSAHZRDELKPHL-UHFFFAOYSA-N 3,6-ditert-butyl-9-[2-(methoxymethoxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl]carbazole Chemical compound COCOC1=CC=C(C(C)(C)CC(C)(C)C)C=C1N1C2=CC=C(C(C)(C)C)C=C2C2=CC(C(C)(C)C)=CC=C21 UOSAHZRDELKPHL-UHFFFAOYSA-N 0.000 description 1
- ABMRGRMWIYEOLT-UHFFFAOYSA-N 3,6-ditert-butyl-9-[2-(oxan-2-yloxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl]carbazole Chemical compound C12=CC=C(C(C)(C)C)C=C2C2=CC(C(C)(C)C)=CC=C2N1C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OC1CCCCO1 ABMRGRMWIYEOLT-UHFFFAOYSA-N 0.000 description 1
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- BOXGGSPOSRTPTH-UHFFFAOYSA-N 3-methylidenebicyclo[2.2.2]octane Chemical compound C1CC2C(=C)CC1CC2 BOXGGSPOSRTPTH-UHFFFAOYSA-N 0.000 description 1
- CYEKUDPFXBLGHH-UHFFFAOYSA-N 3-tert-Butylphenol Chemical compound CC(C)(C)C1=CC=CC(O)=C1 CYEKUDPFXBLGHH-UHFFFAOYSA-N 0.000 description 1
- MRWWWZLJWNIEEJ-UHFFFAOYSA-N 4,4,5,5-tetramethyl-2-propan-2-yloxy-1,3,2-dioxaborolane Chemical compound CC(C)OB1OC(C)(C)C(C)(C)O1 MRWWWZLJWNIEEJ-UHFFFAOYSA-N 0.000 description 1
- ZKMUKBBWORLNLA-UHFFFAOYSA-N 4-chloro-2-fluorophenol Chemical compound OC1=CC=C(Cl)C=C1F ZKMUKBBWORLNLA-UHFFFAOYSA-N 0.000 description 1
- RHPUJHQBPORFGV-UHFFFAOYSA-N 4-chloro-2-methylphenol Chemical compound CC1=CC(Cl)=CC=C1O RHPUJHQBPORFGV-UHFFFAOYSA-N 0.000 description 1
- RNOVGJWJVRESAA-UHFFFAOYSA-N 4-fluoro-2-(trifluoromethyl)phenol Chemical compound OC1=CC=C(F)C=C1C(F)(F)F RNOVGJWJVRESAA-UHFFFAOYSA-N 0.000 description 1
- AIJQYPOGTRNCHQ-UHFFFAOYSA-N 4-fluoro-2-iodo-6-methylphenol Chemical compound CC1=CC(F)=CC(I)=C1O AIJQYPOGTRNCHQ-UHFFFAOYSA-N 0.000 description 1
- GKQDDKKGDIVDAG-UHFFFAOYSA-N 4-fluoro-2-methylphenol Chemical compound CC1=CC(F)=CC=C1O GKQDDKKGDIVDAG-UHFFFAOYSA-N 0.000 description 1
- MNVMYTVDDOXZLS-UHFFFAOYSA-N 4-methoxyguaiacol Natural products COC1=CC=C(O)C(OC)=C1 MNVMYTVDDOXZLS-UHFFFAOYSA-N 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- PRLINSMUYJWPBL-UHFFFAOYSA-N 4-tert-butyl-2-chlorophenol Chemical compound CC(C)(C)C1=CC=C(O)C(Cl)=C1 PRLINSMUYJWPBL-UHFFFAOYSA-N 0.000 description 1
- CGFUVIGKEIAWFG-UHFFFAOYSA-N 5-chloro-2-[2-(4-chloro-2-iodo-6-methylphenoxy)ethoxy]-1-iodo-3-methylbenzene Chemical compound CC1=CC(Cl)=CC(I)=C1OCCOC1=C(C)C=C(Cl)C=C1I CGFUVIGKEIAWFG-UHFFFAOYSA-N 0.000 description 1
- XOGYKECMMMACIU-UHFFFAOYSA-N 7,7-dimethyl-2,3-dimethylidenebicyclo[2.2.1]heptane Chemical compound C1CC2C(=C)C(=C)C1C2(C)C XOGYKECMMMACIU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- 101100167062 Caenorhabditis elegans chch-3 gene Proteins 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- GHINKMVTNAIWDE-UHFFFAOYSA-N ClC1=CC(=C(OCCC)C(=C1)I)F Chemical compound ClC1=CC(=C(OCCC)C(=C1)I)F GHINKMVTNAIWDE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910004373 HOAc Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-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
- 238000006069 Suzuki reaction reaction Methods 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- GKKWWKGQDPXNFT-UHFFFAOYSA-N [3,6-ditert-butyl-9-[2-(oxan-2-yloxy)-5-(2,4,4-trimethylpentan-2-yl)phenyl]-2h-carbazol-3-yl]boronic acid Chemical compound C12=CC=C(C(C)(C)C)C=C2C2=CC(C(C)(C)C)(B(O)O)CC=C2N1C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OC1CCCCO1 GKKWWKGQDPXNFT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 125000005098 aryl alkoxy carbonyl group Chemical group 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 238000006758 bulk electrolysis reaction Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- KIZFHUJKFSNWKO-UHFFFAOYSA-M calcium monohydroxide Chemical compound [Ca]O KIZFHUJKFSNWKO-UHFFFAOYSA-M 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 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
- RLPXAKVDWHODPX-UHFFFAOYSA-N cyclohexane;ethene Chemical compound C=C.C1CCCCC1 RLPXAKVDWHODPX-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 125000006547 cyclononyl group Chemical group [H]C1([H])C([H])([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
- 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
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 125000004639 dihydroindenyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N dimethylacetone Natural products CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 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
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- XXUJMEYKYHETBZ-UHFFFAOYSA-N ethyl 4-nitrophenyl ethylphosphonate Chemical compound CCOP(=O)(CC)OC1=CC=C([N+]([O-])=O)C=C1 XXUJMEYKYHETBZ-UHFFFAOYSA-N 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 150000002258 gallium Chemical class 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 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
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000003037 imidazol-2-yl group Chemical group [H]N1C([*])=NC([H])=C1[H] 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000003427 indacenyl group Chemical group 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 229940030980 inova Drugs 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000004552 isoquinolin-4-yl group Chemical group C1=NC=C(C2=CC=CC=C12)* 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- NSPJNIDYTSSIIY-UHFFFAOYSA-N methoxy(methoxymethoxy)methane Chemical compound COCOCOC NSPJNIDYTSSIIY-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 125000004170 methylsulfonyl group Chemical group [H]C([H])([H])S(*)(=O)=O 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KVKFRMCSXWQSNT-UHFFFAOYSA-N n,n'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- VFLWKHBYVIUAMP-UHFFFAOYSA-N n-methyl-n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCCCCCC VFLWKHBYVIUAMP-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- UMRZSTCPUPJPOJ-KNVOCYPGSA-N norbornane Chemical compound C1C[C@H]2CC[C@@H]1C2 UMRZSTCPUPJPOJ-KNVOCYPGSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- NOUWNNABOUGTDQ-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2+] NOUWNNABOUGTDQ-UHFFFAOYSA-N 0.000 description 1
- 125000003145 oxazol-4-yl group Chemical group O1C=NC(=C1)* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- ZVJXTEDWOZFOQQ-UHFFFAOYSA-N phenol;hydrate Chemical group O.OC1=CC=CC=C1.OC1=CC=CC=C1 ZVJXTEDWOZFOQQ-UHFFFAOYSA-N 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- UYWQUFXKFGHYNT-UHFFFAOYSA-N phenylmethyl ester of formic acid Natural products O=COCC1=CC=CC=C1 UYWQUFXKFGHYNT-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000003880 polar aprotic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 125000004307 pyrazin-2-yl group Chemical group [H]C1=C([H])N=C(*)C([H])=N1 0.000 description 1
- 125000004353 pyrazol-1-yl group Chemical group [H]C1=NN(*)C([H])=C1[H] 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000246 pyrimidin-2-yl group Chemical group [H]C1=NC(*)=NC([H])=C1[H] 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 125000004159 quinolin-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C([H])C(*)=NC2=C1[H] 0.000 description 1
- 125000004549 quinolin-4-yl group Chemical group N1=CC=C(C2=CC=CC=C12)* 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000012453 solvate Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical compound C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- 125000001981 tert-butyldimethylsilyl group Chemical group [H]C([H])([H])[Si]([H])(C([H])([H])[H])[*]C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- SFLXUZPXEWWQNH-UHFFFAOYSA-K tetrabutylazanium;tribromide Chemical compound [Br-].[Br-].[Br-].CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC.CCCC[N+](CCCC)(CCCC)CCCC SFLXUZPXEWWQNH-UHFFFAOYSA-K 0.000 description 1
- 125000003039 tetrahydroisoquinolinyl group Chemical group C1(NCCC2=CC=CC=C12)* 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000000147 tetrahydroquinolinyl group Chemical group N1(CCCC2=CC=CC=C12)* 0.000 description 1
- 125000004523 tetrazol-1-yl group Chemical group N1(N=NN=C1)* 0.000 description 1
- 125000004299 tetrazol-5-yl group Chemical group [H]N1N=NC(*)=N1 0.000 description 1
- WROMPOXWARCANT-UHFFFAOYSA-N tfa trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F.OC(=O)C(F)(F)F WROMPOXWARCANT-UHFFFAOYSA-N 0.000 description 1
- 125000000437 thiazol-2-yl group Chemical group [H]C1=C([H])N=C(*)S1 0.000 description 1
- 125000004496 thiazol-5-yl group Chemical group S1C=NC=C1* 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000004044 trifluoroacetyl group Chemical group FC(C(=O)*)(F)F 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical group CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Classifications
-
- 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
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
-
- 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
- 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
- C08F4/64003—Titanium, zirconium, hafnium or compounds thereof the metallic compound containing a multidentate ligand, i.e. a ligand capable of donating two or more pairs of electrons to form a coordinate or ionic bond
- C08F4/64168—Tetra- or multi-dentate ligand
- C08F4/64186—Dianionic ligand
- C08F4/64193—OOOO
-
- 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
-
- 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+
-
- 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
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- 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
- C08F210/14—Monomers containing five or more carbon atoms
-
- 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
- C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
- C08F2500/03—Narrow molecular weight distribution, i.e. Mw/Mn < 3
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Indole Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
本発明の取り組む問題には、α−オレフィンの存在下でエチレンを選択的に重合する新規な方法及び触媒を提供することが含まれる。
構成成分(a)の前記金属−リガンド錯体は、式(I)の1つ又はそれ以上の金属−リガンド錯体であり:
Mは、各々独立に、+2、+3、又は+4の形式酸化状態である、チタン、ジルコニウム、又はハフニウムであり;
nは、0〜3の整数であり(この際、nが0である場合、Xは存在しない)(すなわち、(X)nは存在しない);
各々のXは、独立に、中性、一価アニオン性(monoanionic)、又は二価アニオン性(dianionic)である単座リガンドであるか;あるいは、2つのXは、一緒に、中性、一価アニオン性、又は二価アニオン性である二座リガンドを形成し;
X及びnは、式(I)の金属−リガンド錯体が、全体的に中性であるような方法で選ばれ;
各々のZは、独立に、O、S、Nヒドロカルビル、又はPヒドロカルビルあり;
Lは、ヒドロカルビレン又はヘテロヒドロカルビレンであり、前記ヒドロカルビレンは、(Lが結合している)式(I)中のZ原子を結合する1−炭素原子〜6−炭素原子のリンカー主鎖(1-carbon atom to 6-carbon atom linker backbone)を含む部分を有し、前記ヘテロヒドロカルビレンは、式(I)中のZ原子を結合する1−原子〜6−原子のリンカー主鎖を含む部分を有し、前記ヘテロヒドロカルビレンの前記1−原子〜6−原子のリンカー主鎖の各々の原子は、独立に、炭素原子又はヘテロ原子であり、各々のヘテロ原子は、独立に、O、S、S(O)、S(O)2、Si(RC)2、Ge(RC)2、P(RP)、又はN(RN)であり、独立に、各々のRCは、非置換(C1−C18)ヒドロカルビルであるか、又は2つのRCは、一緒に(C2−C19)アルキレンを形成し(例えば、前記2つのRCは、それらが両方とも結合しているケイ素原子と一緒に、3員〜20員のシラシクロアルキルを形成する)、各々のRPは、非置換(C1−C18)ヒドロカルビルであり;かつ、各々のRNは、非置換(C1−C18)ヒドロカルビル、水素原子であるか又は存在しない(例えば、Nを含有するヘテロアリールにおいて見られるように、Nが、−N=を含む場合に存在しない);
R1a、R2a、R1b、及びR2bのうちの少なくとも1つは、独立に、ヒドロカルビル、ヘテロヒドロカルビル、又はハロゲン原子であり;かつ、R1a、R2a、R1b、及びR2bのうちのその他のものの各々は、独立に、水素原子、ヒドロカルビル、ヘテロヒドロカルビル、又はハロゲン原子であり;
R3a、R4a、R3b、R4b、R6c、R7c、R8c、R6d、R7d、及びR8dの各々は、独立に、水素原子;ヒドロカルビル;ヘテロヒドロカルビル;又はハロゲン原子であり;
R5c及びR5dの各々は、独立に、アリール又はヘテロアリールであり;
上述のアリール、ヘテロアリール、ヒドロカルビル、ヘテロヒドロカルビル、ヒドロカルビレン、及びヘテロヒドロカルビレン基の各々は、独立に、非置換であるか又は1つ若しくはそれ以上の置換基RSで置換され(RSによる過置換までを含む);かつ
各々のRSは、独立に、ハロゲン原子、ポリフルオロ置換(つまり、1つ又はそれ以上の置換基RSの1つが、2つ又はそれ以上のフルオロ置換基を表す、それは形式的には、置換された基の非置換形の2個又はそれ以上の水素原子をそれぞれ置換する)、パーフルオロ置換(つまり、1つのRSが、その結果置換される、置換された基の非置換形の炭素結合水素原子(すなわちH−C)と同数のフルオロ置換基を表す)、非置換(C1−C18)アルキル、F3C−、FCH2O−、F2HCO−、F3CO−、R3Si−、R3Ge−、RO−、RS−、RS(O)−、RS(O)2−、R2P−、R2N−、R2C=N−、NC−、RC(O)O−、ROC(O)−、RC(O)N(R)−、又はR2NC(O)−であるか、あるいは、RSの2つは、一緒に非置換(C1−C18)アルキレンを形成し、各々のRは、独立に、非置換(C1−C18)アルキルである);
前記構成成分(b)の前記活性化共触媒が、1つ若しくはそれ以上の活性化共触媒、又はその反応生成物を含み、前記式(I)の1つ又はそれ以上の金属−リガンド錯体のモルの総数の、前記1つ又はそれ以上の活性化共触媒のモルの総数に対する比は、1:10,000〜100:1であり;
接触段階が、オレフィン重合条件下で実施され(後述)、非重合α−オレフィンの存在下で高濃度の(rich)ポリエチレン(例えば、(C3−C40)α−オレフィン)を作製し;かつ
前記方法が、反応性の鎖を(インサイチューで)形成し、エチレン残留物(residual)を含む第1の反応性の鎖末端にエチレン(モノマー)を添加することに対する反応速度定数k11;エチレン残留物を含む第2の反応性の鎖末端にα−オレフィン(コモノマー)を添加することに対する反応速度定数k12;及び、14よりも大きい、好ましくは20以上のk12で除算したk11に等しい反応性比r1(すなわち、r1=k11/k12≧20)により特徴づけることができる。r1を決定するために、オレフィン重合条件は、少なくとも摂氏140度(℃)の重合温度を含むことが好ましい。好ましくは、r1を決定するための重合温度は、高くても190℃である。後述の(C3−C40)α−オレフィンの存在下でのエチレンの選択重合のための一般手順が、r1を決定するために好ましい。
本発明の一部の実施形態は、少なくとも実施形態の様々な特徴を説明する助けとなる、添付の図面(類)に関して本明細書に記載される。
(b)各々のDは、1,2,3,4,5,6,7,8−オクタヒドロアントラセン−9−イルである;
(c)各々のDは、9H−カルボゾール(carbozol)−9−イルである;又は
(d)各々のDは、3,5−ビス(1,1−ジメチルエチル)フェニルである;
(f)各々のEは、メトキシである。
(a)〜(f)のリガンドは、それぞれ、米国特許出願公開第2006/0025548A1号のリガンドLL102、LL103、LL104、LL105、LL133、及びLL144と同じである。
式中、Rp2及びRp1は、それぞれコモノマー及びモノマーの重合速度であり、F2及びF1は共重合体中の各々のモル分率である。F1+F2=1であるので、本発明者らはこの方程式を以下のように再構成することができる。
すべての溶媒及び試薬は、商業的供給源より入手し、別に指定される場合を除いて入手したまま使用した。ヘキサン溶媒は、活性アルミナのカラム、それに続いて、アルミナ上のQ5酸化銅のカラム(Cu−0226 Sは、BASF Corporationの子会社Engelhardより入手)に通して精製する。テトラヒドロフラン(THF)及びジエチルエーテルは、活性アルミナのカラムに通して精製する。すべての金属−リガンド錯体は、Vacuum Atmospheres不活性雰囲気グローブボックス中で、乾燥窒素雰囲気下で合成及び貯蔵する。NMRスペクトルは、300メガヘルツ(MHz)Varian INOVAスペクトロメーターで記録する。化学シフトは、テトラメチルシランに対して百万分率で(δ)報告し、重水素化溶媒中の残留プロトンを基準にする。
13C NMR(101 MHz, CDCl3) δ 142.17(s), 137.96(s), 123.45(s), 123.28(s), 116.11(s), 109.97(s), 34.73(s), 32.09(s).
13C{1H} NMR(CDCl3) δ 152.21, 144.52, 135.56, 128.03, 114.17, 85.36, 56.92, 38.01, 32.43, 31.90および31.64.
GCMS(m/e): 332(M+).
13C{1H} NMR(C6D6) δ 154.47, 145.69, 137.49, 127.40, 114.45, 95.12, 87.32, 56.98, 56.03, 38.11, 32.55.
13C{1H} NMR(CDCl3) δ 151.37, 144.89, 142.16, 139.87, 127.85, 126.81, 126.63, 123.34, 122.99, 116.34, 116.03, 109.45, 95.13, 57.00, 56.07, 38.25, 34.70, 32.40, 32.07, 31.84, 31.57.
13C{1H} NMR(CDCl3) δ 153.27, 145.49, 136.98, 127.08, 114.44, 96.72, 87.09, 61.69, 56.91, 37.95, 32.33, 31.81, 31.52, 31.44, 30.26, 25.27, 18.36.
13C{1H} NMR(CDCl3) δ 150.96, 144.22, 142.07, 140.02, 127.49, 126.60, 126.56, 123.14, 123.12, 122.96, 116.37, 115.88, 115.72, 110.18, 109.52, 97.02, 61.56, 57.03, 38.23, 34.69, 32.41, 32.07, 31.86, 31.72, 31.50, 29.98, 25.06, 17.61.
13C{1H} NMR(126 MHz, CDCl3) δ155.88(dd, J = 245.8, 11.1 Hz), 148.90(dd, J = 247.0, 12.4 Hz), 140.77(d, J = 18.5 Hz), 120.44(dd, J = 24.9, 4.0 Hz), 104.93(dd, J = 26.8, 22.7 Hz), 83.27(dd, J = 10.4, 1.5 Hz).
19F NMR(282 MHz) δ -118.84(m), -128.95(m).
GCMS(m/e): 256(M+).
13C{1H} NMR(126 MHz, CDCl3) δ158.02(dd, J = 249.1, 11.9 Hz), 154.04(dd, J = 253.9, 12.7 Hz), 143.75(dd, J = 12.4, 4.1 Hz), 121.02(dd, J = 24.5, 3.6 Hz), 105.65(dd, J = 26.3, 23.8 Hz), 91.46(dd, J = 10.4, 2.4 Hz), 71.17(d, J = 4.8 Hz), 30.89(s).
19F NMR(282 MHz, CDCl3) δ -114.45(m), -121.09, m).
GCMS(m/e): 552(M+).
GCMS(m/e): 289(M+).
1H NMR(CDCl3) δ 7.67(d, J = 2.5 Hz, 2H), 7.38(d, J = 2.5 Hz, 2H), 4.26(t, J = 6.5 Hz, 4H)および2.47(クインテット, J = 6.5 Hz, 2H).
13C{1H} NMR(CDCl3) δ 153.75, 137.08, 130.43, 130.23, 127.89, 92.82, 70.79および31.00.
1H NMR(CDCl3) δ 7.43(dd, J = 0.55および2.5 Hz, 1H), 7.06(d, J = 2.5 Hz, 1H), 5.23(s, 1H)および2.26(s, 3H).
13C{1H} NMR(CDCl3) δ 151.70, 134.28, 131.11, 125.88, 125.55, 85.34および17.22.
GCMS(m/e): 268(M+).
1H NMR(CDCl3) δ 7.59(d, J = 2.4 Hz, 2H), 7.14(d, J = 2.4 Hz, 2H), 4.09(t, J = 6.5 Hz, 4H), 2.44(クインテット, J = 6.5 Hz, 2H)および2.32( s, 6H).
13C{1H} NMR(CDCl3) δ156.01,136.21, 133.26, 131.32, 129.81, 92.24, 70.07, 31.05, 17.20.
GCMS(m/e): 577(M+).
製法20:1,3−ビス(4−クロロ−2−フルオロ−6−ヨードフェノキシ)プロパンの作製。
製法44:1,3−ビス(4−クロロ−2−ヨード−5−(1,1−ジメチルエチル)フェノキシ)プロパンの作製:
リガンド実施例:
1H NMR(CDCl3) δ 8.15(d, J = 1.51 Hz, 4H), 7.41-7.34(m, 8H), 7.04(d, J = 8.6 Hz, 4H), 6.92(m, 2H), 7.79(m, 2H), 5.63(s, 2H), 3.93(t, J = 5.7 Hz, 4H), 1.84(クインテット, J = 5.7 Hz, 2H), 1.71(s, 4H), 1.45(s, 36H), 1.35(s, 12H)および0.78(s,18H).
13C{1H} NMR(75 MHz, CDCl3) δ 157.71(dd, J = 244.5, 12.5 Hz), 155.39(dd, J = 249.7, 13.0 Hz), 149.87 - 147.30(m), 142.98(s), 142.86(s), 140.20(dd, J = 11.5, 3.6 Hz), 139.39(s), 134.27(d, J = 10.9 Hz), 128.75(s), 127.29(s), 124.78(s), 123.67(s), 123.48(s), 116.34(s), 113.36(d, J = 22.8 Hz), 109.22(s), 104.32(dd, J = 25.9, 24.7 Hz), 71.25(s), 57.09(s), 38.32(s), 34.82(s), 32.51(s), 32.13(s), 31.95(s), 31.66(s), 30.56(s), 30.45(s).
19F NMR(282 MHz) δ -114.73(m), -124.09(m).
ES-HRMS: m/e (M+Na, C83H98N2F4O4Na) 1285.736についての計算値,実測値1285.743.
1H NMR(CDCl3) δ 8.16(d, J = 1.8Hz, 4H), 7.43-7.33(m, 12H), 7.06(d, J = 8.5 Hz, 4H), 5.44(s, 2H), 3.85(t, J = 6.4 Hz, 4H), 1.90(クインテット, J = 6.4 Hz, 2H), 1.71(s, 4H), 1.46(s, 36 H), 1.34(s, 12H)および0.78(s,18H).
13C{1H} NMR(CDCl3) δ 151.12, 147.42, 143.29, 143.12, 139.42, 134.63, 130.53, 129.51, 129.45, 129.18, 128.81, 127.48, 124.75, 124.67, 123.86, 123.58, 116.45, 109.21, 71.23, 56.95, 38.26, 34.74, 32.39, 32.00, 31.86, 31.58, 30.56.
ES-HRMS: m/e (M+NH4, C83H102N3Cl4O4) 1344.662についての計算値,実測値1344.663.
1H NMR(CDCl3) δ 8.14(d, J = 1.78 Hz, 4H), 7.42(d, J = 2.3 Hz, 2H), 7.36(m, 6H), 7.23(d, J = 2.75 Hz, 2H), 7.13(d, J = 2.75 Hz, 2H), 7.02(d, J = 8.5 Hz, 4H), 6.14(s, 2H), 3.65(t, J = 6.3 Hz, 4H), 2.05(s, 6H), 1.72(クインテット, J = 6.3 Hz, 2H), 1.71(s, 4H), 1.43(s, 36H), 1.34(s, 12H)および0.76(s, 18H).
13C{1H} NMR(CDCl3) δ 152.71, 147.50, 143.20, 142.69, 139.62, 133.28, 132.99, 130.55, 129.59, 129.57, 128.66,127.39, 126.09, 125.32, 123.57, 123.37, 116.37, 109.18, 70.67, 57.01, 38.24, 34.70, 32.41, 32.02, 31.84, 31.63, 30.68, 16.25.
ES-HRMS: m/e (M+Na, C85H104N2Cl2O4Na) 1309.727についての計算値,実測値1309.719.
実施例Q1〜Q3の作製と同様の方法で、リガンド(Q4)〜(Q9)及び(Q14)〜(Q19)を作製することができ、リガンド(Q10)、(Q11)、(Q12)、(Q13)、及び(Q20)〜(Q22)を作製する。
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−オクチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q4);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−クロロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q5);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−フルオロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q6);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−フルオロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q6a);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−(1−メチルエチル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q6b);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q7);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−シアノ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q8);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−ジメチルアミノ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q9);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’,5’−ジメチル−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q10);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−エチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q11);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5’−tert−ブチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q12);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−フルオロ−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q13);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(9H−カルバゾール−9−イル)−5’−クロロ−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q14);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5’−トリフルオロメチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q15);
2’,2”−(2,2−ジメチル−2−シラプロパン−1,3−ジイルビス(オキシ))ビス(3’,5’−ジクロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q16);
2’,2”−(2,2−ジメチル−2−シラプロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q17);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’−ブロモ−5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q18);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))−(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−フルオロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)−(3”,5”−ジクロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q19);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))−(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)−(5”−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q19a);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−フルオロ−3’−トリフルオロメチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q20);
2’,2”−(ブタン−1,4−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q21);及び
2’,2”−(エタン−1,2−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q22)。
リガンド(Q1)〜(Q8)の構造を図5に示す。リガンド(Q9)〜(Q16)の構造を図6に示す。リガンド(Q17)〜(Q24)の構造を図7に示す。リガンド(Q25)〜(Q31)の構造を図14に示す。図5〜14及び本明細書において、「t−ブチル」は、tert−ブチル、第三ブチル、及び1,1−ジメチルエチルと同義である。「Me」とは、メチルを意味する。「Et」とは、エチルを意味する。「t−オクチル」は、tert−オクチル、第三オクチル、及び1,1−ジメチルヘキシルと同義である。「−CN」は、シアノである。「MeO」とは、メトキシを意味する。
2’,2”−(ペンタン−2,4−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q24);及び
2’,2”−(ヘキサン−1,6−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q25)。
リガンド(Q23)〜(Q25)は、製法15aの1,4−ジブロモブタンをそれぞれ1,5−ジブロモペンタン、2,4−ジブロモペンタン、及び1,6−ジブロモヘキサンで置き換えることを除いて、リガンド(Q21)の作製を反復することにより作製することができる。あるいは、対応するジオールから作製した対応するジトシラートを、上述のジブロミドの代わりに使用することができる。
一部の実施形態では、本発明のリガンドは、リガンド(Q26)〜(Q31)のいずれか1つである:
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−メトキシ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q26);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’,4’−ジメチル−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q27);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(4’−(tert−ブチル)−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q28);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−(tert−ブチル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q29);
2’,2”−(ブタン−1,4−ジイルビス(オキシ))ビス(4’−(tert−ブチル)−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q30);及び
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−4’−(tert−ブチル)−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q31)。
実施例1:(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’,5’−ジフルオロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(1)の作製。
1H NMR(500 MHz, C6D6) δ 8.54(d, J = 1.7 Hz, 2H), 8.35(d, J = 1.9 Hz, 2H), 7.84(d, J = 2.4 Hz, 2H), 7.83(dd, J = 8.1, 2.0 Hz, 2H), 7.73(dd, J = 8.6, 1.9 Hz, 2H), 7.56(dd, J = 8.7, 0.4 Hz, 2H), 7.40(dd, J = 8.8, 1.9 Hz, 2H), 7.19(d, J = 2.5 Hz, 2H), 6.65(ddd, J = 8.9, 2.9, 1.7 Hz, 2H), 6.02(ddd, J = 8.8, 8.1, 3.1 Hz, 2H), 3.84(dt, J = 10.7, 5.6 Hz, 2H), 3.16(dt, J = 10.6, 5.3 Hz, 2H), 1.64(d, J = 14.5 Hz, 2H), 1.58(s, 18H), 1.57(d, J = 14.5 Hz, 2H), 1.31(s, 18H), 1.25(s, 6H), 1.21(s, 6H), 1.19(p, J = 5.7 Hz, 2H), 0.83(s, 18H), -0.88(s, 6H).
13C{1H} NMR(126 MHz, C6D6) δ 159.84(dd, J = 248.4, 11.6 Hz), 155.50(dd, J = 255.9, 13.6 Hz), 153.76(s), 142.72(s), 142.37(s), 141.10(s), 140.26(d, J = 2.6 Hz), 139.87(s), 138.94(dd, J = 12.9, 3.8 Hz), 136.86(d, J = 9.5 Hz), 128.62(s), 128.40(s), 128.29(s), 127.63(s), 127.33(s), 125.33(s), 124.29(s), 123.54(s), 122.73(s), 116.85(s), 116.07(s), 113.93(dd, J = 22.9, 3.2 Hz), 112.68(s), 109.93(d, J = 4.1 Hz), 103.82(dd, J = 26.5, 22.6 Hz), 76.32(d, J = 2.6 Hz), 57.38(s), 48.72(s), 38.21(s), 34.95(s), 34.70(s), 32.52(s), 32.42(s), 32.03(s), 31.98(s), 31.91(s), 31.28(s), 28.96(s).
19F NMR(470 MHz, C6D6) δ -111.15(m), -120.40(t, J = 6.8 Hz).
1H NMR(500 MHz, C6D6) δ 8.54(d, J = 1.8 Hz, 2H), 8.34(d, J = 1.8 Hz, 2H), 7.98(d, J = 8.5 Hz, 2H), 7.94(d, J = 2.4 Hz, 2H), 7.80(dd, J = 8.6, 1.9 Hz, 2H), 7.65(d, J = 8.8 Hz, 2H), 7.43(dd, J = 8.8, 1.9 Hz, 2H), 7.16(d, J = 2.4 Hz, 2H), 7.06(d, J = 2.6 Hz, 2H), 6.66(d, J = 2.6 Hz, 2H), 3.91(dt, J = 10.3, 5.1 Hz, 2H), 3.28(dt, J = 10.6, 5.5 Hz, 2H), 1.65(d, J = 14.5 Hz, 2H), 1.59(s, 18H), 1.56(d, J = 14.5 Hz, 2H), 1.35(s, 18H), 1.31(dt, J = 10.6, 5.1 Hz, 2H), 1.24(s, 6H), 1.21(s, 6H), 0.83(s, 18H), -0.73(s, 6H).
13C{1H} NMR(126 MHz, C6D6) δ 153.27(s), 149.70(s), 142.90(s), 142.82(s), 141.01(s), 139.97(s), 139.59(s), 132.18(s), 131.96(s), 130.46(s), 129.43(s), 128.90(s), 128.60(s), 127.24(s), 127.10(s), 125.78(s), 124.42(s), 123.64(s), 123.31(s), 117.40(s), 116.09(s), 113.48(s), 110.22(s), 76.49(s), 57.49(s), 50.04(s), 38.23(s), 35.00(s), 34.72(s), 32.53(s), 32.37(s), 32.03(s), 31.97(s), 31.75(s), 31.29(s), 29.67(s).
1H NMR(500 MHz, C6D6) δ 8.53(d, J = 1.9 Hz, 2H), 8.35(d, J = 1.9 Hz, 1H), 7.92(d, J = 8.6 Hz, 2H), 7.91(d, J = 2.5 Hz, 2H), 7.74(dd, J = 8.6, 2.0 Hz, 2H), 7.68(d, J = 8.8 Hz, 2H), 7.43(dd, J = 8.8, 1.9 Hz, 2H), 7.28(d, J = 2.5 Hz, 2H), 7.16(d, J = 2.6 Hz, 2H), 6.50(dd, J = 2.6, 0.6 Hz, 2H), 3.59(dt, J = 9.9, 4.9 Hz, 2H), 3.24(dt, J = 10.7, 5.5 Hz, 2H), 1.65(d, J = 14.5 Hz, 2H), 1.56(s, 18H), 1.56(d, J = 14.5 Hz, 2H), 1.33(s, 18H), 1.32(p, J = 5.0 Hz, 2H), 1.24(s, 6H), 1.21(s, 6H), 1.20(s, 6H), 0.83(s, 18H), -0.74(s, 6H).
13C{1H} NMR(126 MHz, C6D6) δ 153.28(s), 152.24(s), 143.17(s), 142.98(s), 140.85(s), 140.02(s), 139.47(s), 135.53(s), 134.60(s), 132.08(s), 131.46(s), 130.58(s), 130.09(s), 128.11(s), 127.76(s), 126.57(s), 125.75(s), 124.72(s), 123.36(s), 123.02(s), 117.17(s), 115.92(s), 113.82(s), 110.44(s), 76.10(s), 57.48(s), 49.70(s), 38.20(s), 34.95(s), 34.71(s), 32.51(d, J = 7.3 Hz), 32.35(s), 31.98(s), 31.96(s), 31.79(s), 31.26(s), 30.13(s), 16.23(s).
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−オクチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(4);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−クロロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(5);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−フルオロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(6);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−フルオロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(6a);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−(1−メチルエチル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(6b);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(7);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−シアノ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(8);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−ジメチルアミノ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(9);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’,5’−ジメチル−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(10);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−エチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(11);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5’−tert−ブチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(12);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−フルオロ−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(13);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(9H−カルバゾール−9−イル)−5’−クロロ−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(14);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5’−トリフルオロメチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(15);
(2’,2”−(2,2−ジメチル−2−シラプロパン−1,3−ジイルビス(オキシ))ビス(3’,5’−ジクロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(16);
(2’,2”−(2,2−ジメチル−2−シラプロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(17);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’−ブロモ−5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(18);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))−(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−フルオロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)−(3”,5”−ジクロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(19);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))−(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)−(5”−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(19a);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−フルオロ−3’−トリフルオロメチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(20);
(2’,2”−(ブタン−1,4−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(21);
(2’,2”−(エタン−1,2−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(22);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ジルコニウム、(23);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’,5’−ジクロロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−チタン、(24);及び
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−チタン、(25)。
金属−リガンド錯体(26)〜(31)の名称は次の通りである:
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−メトキシ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(26);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’,4’−ジメチル−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(27);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(4’−(tert−ブチル)−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(28);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−(tert−ブチル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(29);
(2’,2”−(ブタン−1,4−ジイルビス(オキシ))ビス(4’−(tert−ブチル)−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(30);及び
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−4’−(tert−ブチル)−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(31)。
金属−リガンド錯体(32)〜(34)の名称は次の通りである:
(2’,2”−(ペンタン−1,5−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(32);
(2’,2”−(ペンタン−2,4−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(33);及び
(2’,2”−(ヘキサン−1,6−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(34)。
実施例A〜Nの結果を下の表1及び2に示す。
Claims (13)
- α−オレフィンの存在下でエチレンを選択的に重合させるための方法であって、前記方法が、触媒量の触媒、エチレン、及びα−オレフィンを一緒に接触させる段階を含み、前記触媒が、接触段階の前に作製される構成成分(a)及び(b)の混合物又は反応生成物を含み、構成成分(a)は、金属−リガンド錯体(本明細書においてプレ触媒とも称される)を含み、構成成分(b)は、活性化共触媒を含み;エチレンは、構成成分(c)を含み;かつ、α−オレフィンは、構成成分(d)を含み;
構成成分(a)の前記金属−リガンド錯体が、式(I)の1つ又はそれ以上の金属−リガンド錯体(本明細書においてプレ触媒とも称される)であり:
Mは、各々独立に、+2、+3、又は+4の形式酸化状態である、チタン、ジルコニウム、又はハフニウムであり;
nは、0〜3の整数であり(この際、nが0である場合、Xは存在しない);
各々のXは、独立に、中性、一価アニオン性、又は二価アニオン性である単座リガンドであるか;あるいは、2つのXは、一緒に、中性、一価アニオン性、又は二価アニオン性である二座リガンドを形成し;
X及びnは、式(I)の金属−リガンド錯体が、全体的に中性であるような方法で選ばれ;
各々のZは、独立に、O、S、Nヒドロカルビル、又はPヒドロカルビルであり;
Lは、ヒドロカルビレン又はヘテロヒドロカルビレンであり、前記ヒドロカルビレンは、式(I)中のZ原子を結合する1−炭素原子〜6−炭素原子のリンカー主鎖を含む部分を有し、前記ヘテロヒドロカルビレンは、式(I)中のZ原子を結合する1−原子〜6−原子のリンカー主鎖を含む部分を有し、前記ヘテロヒドロカルビレンの前記1−原子〜6−原子のリンカー主鎖の各々の原子は、独立に、炭素原子又はヘテロ原子であり、各々のヘテロ原子は、独立に、O、S、S(O)、S(O)2、Si(RC)2、Ge(RC)2、P(RP)、又はN(RN)であり、独立に、各々のRCは、非置換(C1−C18)ヒドロカルビルであるか、又は2つのRCは、一緒に(C2−C19))アルキレンを形成し、各々のRPは、非置換(C1−C18)ヒドロカルビルであり;かつ、各々のRNは、非置換(C1−C18)ヒドロカルビル、水素原子であるか又は存在せず;
R1a、R2a、R1b、及びR2bのうちの少なくとも1つは、独立に、ヒドロカルビル、ヘテロヒドロカルビル、又はハロゲン原子であり;かつ、R1a、R2a、R1b、及びR2bのうちのその他のものの各々は、独立に、水素原子、ヒドロカルビル、ヘテロヒドロカルビル、又はハロゲン原子であり;
R3a、R4a、R3b、R4b、R6c、R7c、R8c、R6d、R7d、及びR8dの各々は、独立に、水素原子;ヒドロカルビル;ヘテロヒドロカルビル;又はハロゲン原子であり;
R5c及びR5dの各々は、独立に、アリール又はヘテロアリールであり;
上述のアリール、ヘテロアリール、ヒドロカルビル、ヘテロヒドロカルビル、ヒドロカルビレン、及びヘテロヒドロカルビレン基の各々は、独立に、非置換であるか又は1つ若しくはそれ以上の置換基RSで置換され;かつ
各々のRSは、独立に、ハロゲン原子、ポリフルオロ置換、パーフルオロ置換、非置換(C1−C18)アルキル、F3C−、FCH2O−、F2HCO−、F3CO−、R3Si−、R3Ge−、RO−、RS−、RS(O)−、RS(O)2−、R2P−、R2N−、R2C=N−、NC−、RC(O)O−、ROC(O)−、RC(O)N(R)−、又はR2NC(O)−であるか、あるいは、RSの2つは、一緒に非置換(C1−C18)アルキレンを形成し、各々のRは、独立に、非置換(C1−C18)アルキルである);
前記構成成分(b)の前記活性化共触媒が、1つ若しくはそれ以上の活性化共触媒、又はその反応生成物を含み、前記式(I)の1つ又はそれ以上の金属−リガンド錯体のモルの総数の、前記1つ又はそれ以上の活性化共触媒のモルの総数に対する比は、1:10,000〜100:1であり;
接触段階が、オレフィン重合条件下で実施され、非重合α−オレフィンの存在下で高濃度のポリエチレンを作製し、前記高濃度ポリエチレンが、エチレン反復単位から実質的になる、高分子、又はそのセグメント;あるいは2つ又はそれ以上のかかる高分子の混合物又はブレンドであり;かつ
前記方法が、反応性の鎖を形成し、エチレン残留物を含む第1の反応性の鎖末端にエチレンを添加することに対する反応速度定数k11;エチレン残留物を含む第2の反応性の鎖末端にα−オレフィンを添加することに対する反応速度定数k12;及び、14よりも大きいk12で除算したk11に等しい反応性比r1、により特徴づけることができ;かつ
以下のリガンド(a)〜(f):
(b)各々のDは、1,2,3,4,5,6,7,8−オクタヒドロアントラセン−9−イルである;
(c)各々のDは、9H−カルボゾール(carbozol)−9−イルである;又は
(d)各々のDは、3,5−ビス(1,1−ジメチルエチル)フェニルである;
(f)各々のEは、メトキシである
のいずれか1つ又はそれ以上に基づくあらゆる式(I)の金属−リガンド錯体及び触媒が排除される、方法。 - R1a及びR1bの少なくとも1つが水素原子でないか、又はR2a及びR2bの少なくとも1つが、少なくとも4個の炭素原子を有するヒドロカルビル又は少なくとも3個の炭素原子を有するヘテロヒドロカルビルである、請求項1に記載の方法。
- 各々のZがOである、請求項1又は2に記載の方法。
- R5a及びR5bの各々が、独立に、9H−カルバゾール−9−イル、2,7−二置換9H−カルバゾール−9−イル又は3,6−二置換9H−カルバゾール−9−イルであり、各々の置換基がRSである、請求項1、2、又は3に記載の方法。
- 式(I)の金属−リガンド錯体が、式(Ia)、(If)、又は(Ip):
の金属−リガンド錯体である、請求項4に記載の方法。 - R5c及びR5dの各々が、独立に、各々の置換基がRSである2,4−二置換フェニルである(C6−C40)アリール;各々の置換基がRSである2,5−二置換フェニル;各々の置換基がRSである2,6−二置換フェニル;各々の置換基がRSである3,5−二置換フェニル;各々の置換基がRSである2,4,6−三置換フェニル;各々の置換基がRSであるナフチル又は置換ナフチル;1,2,3,4−テトラヒドロナフチル;アントラセニル;1,2,3,4−テトラヒドロアントラセニル;1,2,3,4,5,6,7,8−オクタヒドロアントラセニル;フェナントレニル;あるいは1,2,3,4,5,6,7,8−オクタヒドロフェナントレニルである、請求項1、2、又は3に記載の方法。
- 前記反応性比r1が、20以上である、請求項1から6のいずれか一項に記載の方法。
- R1a、R1b、R3a、及びR3bの少なくとも1つが、R7c及びR7dが各々メチルである場合にメチルでない、請求項1から7のいずれか一項に記載の方法。
- 1つ又は2つ以上の式(I)の金属−リガンド錯体の少なくとも1つが、金属−リガンド錯体(1)、(2)、(10)、(11)、(20)〜(22)、及び(23):
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’,5’−ジフルオロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(1);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’,5’−ジクロロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(2);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’,5’−ジメチル−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(10);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−エチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(11);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−フルオロ−3’−トリフルオロメチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(20);
(2’,2”−(ブタン−1,4−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(21);
(2’,2”−(エタン−1,2−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(22);及び
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ジルコニウム、(23)のいずれか1つであるか;あるいは
1つ又は2つ以上の式(I)の金属−リガンド錯体の少なくとも1つが、金属−リガンド錯体(3):
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(3)であるか;あるいは
1つ又は2つ以上の式(I)の金属−リガンド錯体の少なくとも1つが、金属−リガンド錯体(13):
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−フルオロ−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(13)であるか;あるいは
1つ又は2つ以上の式(I)の金属−リガンド錯体の少なくとも1つが、金属−リガンド錯体(3a)、(6a)、(6b)、(19a)、(4)〜(9)、(12)、(14)〜(19)、(24)、及び(25):
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(3a);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−オクチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(4);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−クロロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(5);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−フルオロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(6);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−フルオロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(6a);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−(l−メチルエチル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(6b);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(7);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−シアノ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(8);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−ジメチルアミノ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(9);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5’−tert−ブチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(12);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(9H−カルバゾール−9−イル)−5’−クロロ−3’−メチル−5−(2,4、4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(14);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5’−トリフルオロメチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(15);
(2’,2”−(2,2−ジメチル−2−シラプロパン−1,3−ジイルビス(オキシ))ビス(3’,5’−ジクロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(16);
(2’,2”−(2,2−ジメチル−2−シラプロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(17);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’−ブロモ−5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(18);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))−(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−フルオロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)−(3”,5”−ジクロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(19);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))−(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)−(5”−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(19a);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’,5’−ジクロロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−チタン、(24);及び
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−チタン、(25)のいずれか1つであるか;あるいは
1つ又は2つ以上の式(I)の金属−リガンド錯体の少なくとも1つが、金属−リガンド錯体(26)〜(31):
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−メトキシ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(26);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’,4’−ジメチル−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(27);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(4’−(tert−ブチル)−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(28);
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−(tert−ブチル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(29);
(2’,2”−(ブタン−1,4−ジイルビス(オキシ))ビス(4’−(tert−ブチル)−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(30);及び
(2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−4’−(tert−ブチル)−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(31)のいずれか1つであるか;あるいは
1つ又は2つ以上の式(I)の金属−リガンド錯体の少なくとも1つが、金属−リガンド錯体(32)〜(34):
(2’,2”−(ペンタン−1,5−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(32);
(2’,2”−(ペンタン−2,4−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(33);及び
(2’,2”−(ヘキサン−1,6−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール))ジメチル−ハフニウム、(34)のいずれか1つである、請求項1に記載の方法。 - 請求項1から9のいずれか一項に記載される式(I)の金属−リガンド錯体。
- 請求項10に記載される1つ又はそれ以上の式(I)の金属−リガンド錯体及び1つ若しくはそれ以上の活性化共触媒、又はその反応生成物を含むか又はそれらから作製される触媒であって、前記1つ又はそれ以上の式(I)の金属リガンド錯体のモルの総数の、前記1つ又はそれ以上の活性化共触媒のモルの総数に対する比が、1:10,000〜100:1である、触媒。
- 式(Q)のリガンド:
- 前記リガンドが、リガンド(Q1)、(Q2)、(Q10)、(Q11)、及び(Q20)〜(Q22):
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’,5’−ジフルオロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q1);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’,5’−ジクロロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q2);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’,5’−ジメチル−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q10);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−エチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q11);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−フルオロ−3’−トリフルオロメチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q20);
2’,2”−(ブタン−1,4−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q21);及び
2’,2”−(エタン−1,2−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q22)のいずれか1つであるか;あるいは
前記リガンドが、リガンド(Q3)又は(Q13):
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q3);又は
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−フルオロ−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q13)であるか;あるいは、
前記リガンドが、リガンド(Q3a)、(Q6a)、(Q6b)、(Q19a)、(Q4)〜(Q9)、(Q12)、及び(Q14)〜(Q19):
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q3a);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−オクチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q4);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−クロロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q5);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−フルオロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q6);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−フルオロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q6a);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−(1−メチルエチル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q6b);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q7);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−シアノ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q8);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−ジメチルアミノ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q9);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5’−tert−ブチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q12);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(9H−カルバゾール−9−イル)−5’−クロロ−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q14);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5’−トリフルオロメチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q15);
2’,2”−(2,2−ジメチル−2−シラプロパン−1,3−ジイルビス(オキシ))ビス(3’,5’−ジクロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q16);
2’,2”−(2,2−ジメチル−2−シラプロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q17);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’−ブロモ−5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q18);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))−(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−フルオロ−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)−(3”,5”−ジクロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q19);及び
2’,2”−(プロパン−1,3−ジイルビス(オキシ))−(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)−(5”−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q19a)のいずれか1つであるか;あるいは
前記リガンドが、リガンド(Q23)〜(Q25):
2’,2”−(ペンタン−1,5−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q23);
2’,2”−(ペンタン−2,4−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q24);及び
2’,2”−(ヘキサン−1,6−ジイルビス(オキシ))ビス(5’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q25)のいずれか1つであるか;あるいは
前記リガンドが、リガンド(Q26)〜(Q31):
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−メトキシ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−3’−メチル−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q26);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’,4’−ジメチル−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q27);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(4’−(tert−ブチル)−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q28);
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(3’−クロロ−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5’−(tert−ブチル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q29);
2’,2”−(ブタン−1,4−ジイルビス(オキシ))ビス(4’−(tert−ブチル)−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q30);及び
2’,2”−(プロパン−1,3−ジイルビス(オキシ))ビス(5’−クロロ−4’−(tert−ブチル)−3−(3,6−ジ−tert−ブチル−9H−カルバゾール−9−イル)−5−(2,4,4−トリメチルペンタン−2−イル)ビフェニル−2−オール)、(Q31)
のいずれか1つである、請求項12に記載のリガンド。
Applications Claiming Priority (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US2010/035096 WO2011146044A1 (en) | 2010-05-17 | 2010-05-17 | Process for selectively polymerizing ethylene and catalyst therefor |
USPCT/US2010/035096 | 2010-05-17 | ||
US201161467627P | 2011-03-25 | 2011-03-25 | |
US61/467,627 | 2011-03-25 | ||
PCT/US2011/036004 WO2011146291A1 (en) | 2010-05-17 | 2011-05-11 | Process for selectively polymerizing ethylene and catalyst therefor |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2013534934A true JP2013534934A (ja) | 2013-09-09 |
JP5767318B2 JP5767318B2 (ja) | 2015-08-19 |
Family
ID=44462019
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2013511220A Active JP5767318B2 (ja) | 2010-05-17 | 2011-05-11 | エチレンを選択的に重合させるための方法及びそのための触媒 |
Country Status (8)
Country | Link |
---|---|
US (2) | US8609794B2 (ja) |
EP (1) | EP2491062B1 (ja) |
JP (1) | JP5767318B2 (ja) |
KR (1) | KR101788892B1 (ja) |
CN (1) | CN102906129B (ja) |
BR (1) | BR112012022591B1 (ja) |
MX (1) | MX350592B (ja) |
WO (1) | WO2011146291A1 (ja) |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013060396A (ja) * | 2011-09-13 | 2013-04-04 | Konica Minolta Holdings Inc | 縮合複素環化合物の製造方法 |
JP2016506446A (ja) * | 2012-12-27 | 2016-03-03 | ダウ グローバル テクノロジーズ エルエルシー | エチレン系ポリマーを製造するための重合法 |
JP2016506445A (ja) * | 2012-12-27 | 2016-03-03 | ダウ グローバル テクノロジーズ エルエルシー | エチレン系ポリマーを製造するための重合法 |
JP2016524024A (ja) * | 2013-06-28 | 2016-08-12 | ダウ グローバル テクノロジーズ エルエルシー | ハロゲン化ビス−フェニルフェノキシ触媒を使用するポリオレフィンの分子量制御 |
JP2017519874A (ja) * | 2014-06-30 | 2017-07-20 | ダウ グローバル テクノロジーズ エルエルシー | オレフィン重合のためのプロセス |
JP2017522425A (ja) * | 2014-07-24 | 2017-08-10 | ダウ グローバル テクノロジーズ エルエルシー | 低分子量エチレン系ポリマー重合用のビス−ビフェニルフェノキシ触媒 |
JP2018504371A (ja) * | 2014-12-04 | 2018-02-15 | ダウ グローバル テクノロジーズ エルエルシー | エチレン系ポリマーの調製物のための五配位ビス−フェニルフェノキシ触媒 |
JP2018510244A (ja) * | 2015-03-31 | 2018-04-12 | ダウ グローバル テクノロジーズ エルエルシー | 低レベルの長鎖分岐を有する高分子量エチレン/α−オレフィン/非共役インターポリマーの生成方法 |
US10214622B2 (en) | 2012-12-27 | 2019-02-26 | Dow Global Technologies Llc | Catalyst systems for olefin polymerization |
KR20190129999A (ko) * | 2017-03-31 | 2019-11-20 | 다우 글로벌 테크놀로지스 엘엘씨 | 올레핀 중합을 위한 비스-바이페닐-페녹시 촉매 |
US10597473B2 (en) | 2015-06-30 | 2020-03-24 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
US10647797B2 (en) | 2015-09-30 | 2020-05-12 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
JP2020158771A (ja) * | 2014-06-30 | 2020-10-01 | ダウ グローバル テクノロジーズ エルエルシー | オレフィン重合用の触媒系 |
US10870713B2 (en) | 2015-09-30 | 2020-12-22 | Dow Global Technologies Llc | Procatalyst and polymerization process using the same |
US11041027B2 (en) | 2015-06-30 | 2021-06-22 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
US11066428B2 (en) | 2017-09-29 | 2021-07-20 | Dow Global Technologies Llc | Bis-phenyl-phenoxy polyolefin catalysts having a methylenetrialkylsilicon ligand on the metal for improved solubility |
US11066489B2 (en) | 2017-09-29 | 2021-07-20 | Dow Global Technologies Llc | Bis-phenyl-phenoxy polyolefin catalysts having two methylenetrialkylsilicon ligands on the metal for improved solubility |
US11242415B2 (en) | 2017-09-29 | 2022-02-08 | Dow Global Technologies Llc | Bis-phenyl-phenoxy polyolefin catalysts having an alkoxy- or amido-ligand on the metal for improved solubility |
Families Citing this family (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012027448A1 (en) * | 2010-08-25 | 2012-03-01 | Dow Global Technologies Llc | Process for polymerizing a polymerizable olefin and catalyst therefor |
US9643900B2 (en) | 2011-03-25 | 2017-05-09 | Dow Global Technologies Llc | Hyperbranched ethylene-based oils and greases |
US9522855B2 (en) * | 2011-12-29 | 2016-12-20 | Dow Global Technologies Llc | Process for producing low molecular weight ethylene- and alpha-olefin-based materials |
MX368963B (es) | 2011-12-29 | 2019-10-23 | Dow Global Technologies Llc | Fluido dielectrico basado en aceite de olefina hiper-ramificado. |
JP6174682B2 (ja) * | 2012-05-09 | 2017-08-02 | ダウ グローバル テクノロジーズ エルエルシー | ポリオレフィン重合方法、それによって製造した半結晶性エチレン系ポリマー、およびそのポリマーから製造した物品 |
KR101391693B1 (ko) | 2012-11-14 | 2014-05-07 | 주식회사 엘지화학 | 3원계 탄성 공중합체 및 이의 제조 방법 |
WO2014105412A1 (en) | 2012-12-27 | 2014-07-03 | Dow Global Technologies Llc | An ethylene based polymer |
EP2938644B1 (en) * | 2012-12-27 | 2019-08-28 | Dow Global Technologies LLC | Process for the polymerization of ethylene and octene |
CN104884483B (zh) * | 2013-01-18 | 2018-10-09 | 陶氏环球技术有限责任公司 | 高分子量聚合物的聚合方法 |
WO2014209256A1 (en) | 2013-06-24 | 2014-12-31 | Dow Global Technologies Llc | Reinforced polypropylene composition |
CN105339327B (zh) * | 2013-06-28 | 2020-01-21 | 陶氏环球技术有限责任公司 | 基于乙烯的超支化寡聚物 |
ES2660464T3 (es) | 2013-06-28 | 2018-03-22 | Dow Global Technologies Llc | Proceso para la preparación de poliolefinas ramificadas para aplicaciones lubricantes |
US10196336B2 (en) | 2013-06-28 | 2019-02-05 | Dow Global Technologies Llc | Process for the preparation of lightly-branched hydrophobes and the corresponding surfactants and applications thereof |
BR112016029671A2 (pt) * | 2014-06-30 | 2017-08-22 | Dow Global Technologies Llc | polímeros à base de olefinas |
JP6479167B2 (ja) | 2014-09-22 | 2019-03-06 | ダウ グローバル テクノロジーズ エルエルシー | 超分岐状オレフィン流体を基とする放熱グリス |
MY184826A (en) | 2014-12-04 | 2021-04-24 | Dow Technology Investments Llc | Hydroformylation process |
EP3453452A3 (en) * | 2015-03-13 | 2019-06-05 | Dow Global Technologies Llc | Phosphacycle-containing ligand for chromium complex and olefin oligomerisation catalyst therefrom |
BR112017020598A2 (pt) * | 2015-03-31 | 2018-07-03 | Dow Global Technologies Llc | compostos de enchimento para cabos de telecomunicações |
US20190143635A1 (en) | 2016-07-21 | 2019-05-16 | Dow Global Technologies Llc | Composite cushioning structures, and methods of manufacturing thereof |
US10221260B2 (en) | 2016-07-29 | 2019-03-05 | Exxonmobil Chemical Patents Inc. | Phenolate transition metal complexes, production and use thereof |
WO2018022279A1 (en) | 2016-07-29 | 2018-02-01 | Exxonmobil Chemical Patents Inc. | Phenolate transition metal complexes, production and use thereof |
BR112019001249B1 (pt) | 2016-07-29 | 2022-10-18 | Dow Global Technologies Llc | Elastômero multimodal, olefina termoplástica e método para produzir um elastômero multimodal |
SG10202101020PA (en) | 2016-07-29 | 2021-03-30 | Dow Global Technologies Llc | Silyl-bridged bis-biphenyl-phenoxy catalysts for olefin polymerization |
US11208503B2 (en) | 2017-03-31 | 2021-12-28 | Dow Global Technologies Llc | Germanium-bridged bis-biphenyl-phenoxy catalysts for olefin polymerization |
EP3642249B1 (en) * | 2017-06-20 | 2021-08-11 | Dow Global Technologies LLC | Biaryl phenoxy group iv transition metal catalysts for olefin polymerization |
KR102100142B1 (ko) * | 2017-12-21 | 2020-04-14 | 사빅 에스케이 넥슬렌 컴퍼니 피티이 엘티디 | 금속-리간드 착체, 이를 포함하는 에틸렌계 중합용 촉매 조성물 및 이를 이용한 에틸렌계 중합체의 제조방법 |
CN108686706B (zh) | 2018-06-22 | 2020-12-01 | 中国石油天然气股份有限公司 | 一种乙烯选择性齐聚的方法及催化剂 |
SG11202105946XA (en) * | 2018-12-20 | 2021-07-29 | Dow Global Technologies Llc | Biaryl hydroxythiophene group iv transition metal polymerization catalysts with chain transfer capability |
KR20200097870A (ko) | 2019-02-08 | 2020-08-20 | 삼성디스플레이 주식회사 | 축합환 화합물 및 이를 포함한 유기 발광 소자 |
WO2021091983A1 (en) | 2019-11-04 | 2021-05-14 | Dow Global Technologies Llc | Biphenylphenol polymerization catalysts |
KR20220118487A (ko) | 2019-12-19 | 2022-08-25 | 다우 글로벌 테크놀로지스 엘엘씨 | 기체상 비페닐페놀 중합 촉매 |
KR20220123415A (ko) * | 2019-12-26 | 2022-09-06 | 다우 글로벌 테크놀로지스 엘엘씨 | 탁월한 가공성을 갖는 중합체 조성물의 제조 공정 |
KR20230018410A (ko) | 2020-05-29 | 2023-02-07 | 다우 글로벌 테크놀로지스 엘엘씨 | 감쇠된 하이브리드 촉매 |
BR112022023873A2 (pt) * | 2020-05-29 | 2022-12-20 | Dow Global Technologies Llc | Pró-catalisador, sistema catalisador, método para produzir um sistema catalisador, e, processo para produzir polietileno |
BR112022023744A2 (pt) | 2020-05-29 | 2022-12-20 | Dow Global Technologies Llc | Métodos para produzir um catalisador pós-metalocênico atenuado, de alimentar um catalisador pós-metalocênico a um reator de polimerização em fase de lama ou em fase gasosa e para produzir um polímero poliolefínico, catalisador pós-metalocênico atenuado, e, sistema de catalisador multimodal |
WO2022173905A1 (en) | 2021-02-15 | 2022-08-18 | Dow Global Technologies Llc | Biphenylphenol polymerization catalysts |
EP4291584A1 (en) | 2021-02-15 | 2023-12-20 | Dow Global Technologies LLC | Method for making a poly(ethylene-co-1-alkene) copolymer with reverse comonomer distribution |
TW202330558A (zh) * | 2021-12-29 | 2023-08-01 | 新加坡商沙特基礎工業愛思開奈克斯林恩私人有限公司 | 金屬—配位基錯合物、含有該金屬—配位基錯合物之用於生產乙烯系聚合物之觸媒組成物、以及使用該觸媒組成物來生產乙烯系聚合物之方法 |
WO2024097488A1 (en) * | 2022-11-03 | 2024-05-10 | University Of Virginia Patent Foundation | Bis(phosphino)boryl supported ni complexes and method of use thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060025548A1 (en) * | 2002-04-24 | 2006-02-02 | Symyx Technologies, Inc. | Bridged bi-aromatic catalysts, complexes, and methods of using the same |
JP2007529616A (ja) * | 2004-03-17 | 2007-10-25 | ダウ グローバル テクノロジーズ インコーポレイティド | エチレンコポリマーを形成するためのシャトリング剤を含む触媒組成物 |
JP2009509003A (ja) * | 2005-09-15 | 2009-03-05 | ダウ グローバル テクノロジーズ インコーポレイティド | 多中心シャトリング剤(multi−centeredshuttlingagent)によるポリマー構造および分子量分布の制御 |
JP2009537656A (ja) * | 2006-05-17 | 2009-10-29 | ダウ グローバル テクノロジーズ インコーポレイティド | 高温ポリエチレン溶液重合方法 |
Family Cites Families (41)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3914342A (en) | 1971-07-13 | 1975-10-21 | Dow Chemical Co | Ethylene polymer blend and polymerization process for preparation thereof |
US3953413A (en) | 1974-06-13 | 1976-04-27 | Chemplex Company | Supported chromium-containing catalyst and process of polymerizing 1-olefins |
US4173548A (en) | 1977-02-02 | 1979-11-06 | Chemplex Company | Ethylene polymerization catalyst and method |
US4330646A (en) | 1979-08-13 | 1982-05-18 | Asahi Kasei Kogyo Kabushiki Kaisha | Polymerization of an α-olefin |
US4564660A (en) | 1983-06-30 | 1986-01-14 | Union Carbide Corporation | Use of alkylaluminum compounds and hydroxyl-containing compounds to initiate polymerization of ethylene with chromium oxide catalysts |
US4612300A (en) | 1985-06-06 | 1986-09-16 | The Dow Chemical Company | Novel catalyst for producing relatively narrow molecular weight distribution olefin polymers |
JPS63154753A (ja) | 1986-12-18 | 1988-06-28 | Nippon Oil Co Ltd | ポリエチレン系組成物 |
US5153157A (en) | 1987-01-30 | 1992-10-06 | Exxon Chemical Patents Inc. | Catalyst system of enhanced productivity |
US7163907B1 (en) | 1987-01-30 | 2007-01-16 | Exxonmobil Chemical Patents Inc. | Aluminum-free monocyclopentadienyl metallocene catalysts for olefin polymerization |
US4981927A (en) | 1987-05-20 | 1991-01-01 | National Distillers And Chemical Corporation | Chromium catalyst compositions and polymerization utilizing same |
US5064802A (en) | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
JP2545006B2 (ja) | 1990-07-03 | 1996-10-16 | ザ ダウ ケミカル カンパニー | 付加重合触媒 |
US5721185A (en) | 1991-06-24 | 1998-02-24 | The Dow Chemical Company | Homogeneous olefin polymerization catalyst by abstraction with lewis acids |
US5296433A (en) | 1992-04-14 | 1994-03-22 | Minnesota Mining And Manufacturing Company | Tris(pentafluorophenyl)borane complexes and catalysts derived therefrom |
US5350723A (en) | 1992-05-15 | 1994-09-27 | The Dow Chemical Company | Process for preparation of monocyclopentadienyl metal complex compounds and method of use |
US5372682A (en) | 1993-06-24 | 1994-12-13 | The Dow Chemical Company | Electrochemical preparation of addition polymerization catalysts |
US5625087A (en) | 1994-09-12 | 1997-04-29 | The Dow Chemical Company | Silylium cationic polymerization activators for metallocene complexes |
US5869575A (en) | 1995-08-02 | 1999-02-09 | The Dow Chemical Company | Ethylene interpolymerizations |
KR20000005027A (ko) | 1996-03-27 | 2000-01-25 | 그레이스 스티븐 에스. | 분산된 촉매 활성화제를 사용하는 용액 중합 방법 |
ES2147985T3 (es) | 1996-03-27 | 2000-10-01 | Dow Chemical Co | Activador de catalizador de la polimerizacion de olefinas altamente soluble. |
US5783512A (en) | 1996-12-18 | 1998-07-21 | The Dow Chemical Company | Catalyst component dispersion comprising an ionic compound and solid addition polymerization catalysts containing the same |
US6103657A (en) | 1997-07-02 | 2000-08-15 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst for the production of olefin polymers |
US6696379B1 (en) | 1997-09-19 | 2004-02-24 | The Dow Chemical Company | Supported modified alumoxane catalyst activator |
MY131000A (en) | 2001-03-16 | 2007-07-31 | Dow Global Technologies Inc | High melt strength polymers and method of making same |
US7060848B2 (en) | 2002-04-24 | 2006-06-13 | Symyx Technologies, Inc. | Bridged bi-aromatic catalysts, complexes, and methods of using the same |
DE60335459D1 (de) | 2002-04-24 | 2011-02-03 | Symyx Solutions Inc | Verbrückte bi-aromatische liganden, komplexe, katalysatoren, verfahren zur polymerisierung und entstehende polymere |
US6953764B2 (en) | 2003-05-02 | 2005-10-11 | Dow Global Technologies Inc. | High activity olefin polymerization catalyst and process |
JP2007518870A (ja) | 2004-01-22 | 2007-07-12 | ダウ グローバル テクノロジーズ インコーポレイティド | 官能基化されたエラストマー組成物 |
US7608668B2 (en) | 2004-03-17 | 2009-10-27 | Dow Global Technologies Inc. | Ethylene/α-olefins block interpolymers |
CN1976965B (zh) | 2004-03-17 | 2012-10-10 | 陶氏环球技术有限责任公司 | 用于形成乙烯多嵌段共聚物的包含梭移剂的催化剂组合物 |
US7355089B2 (en) | 2004-03-17 | 2008-04-08 | Dow Global Technologies Inc. | Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates |
ES2397701T3 (es) | 2004-03-17 | 2013-03-08 | Dow Global Technologies Llc | Composición de catalizador que comprende un agente de transporte para la formación de un copolímero de multi-bloques de olefina superior |
AU2006227976A1 (en) | 2005-03-17 | 2006-09-28 | Dow Global Technologies Inc. | Catalyst composition comprising shuttling agent for regio-irregular multi-block copolymer formation |
JP5193600B2 (ja) | 2005-07-05 | 2013-05-08 | 株式会社カネカ | メタクリル系樹脂組成物 |
KR101519805B1 (ko) | 2005-09-15 | 2015-05-12 | 다우 글로벌 테크놀로지스 엘엘씨 | 제어된 블록 서열 분포를 갖는 촉매적 올레핀 블록 공중합체 |
AR058449A1 (es) | 2005-09-15 | 2008-02-06 | Dow Global Technologies Inc | Copolimeros de bloque de olefina cataliticos via un agente de transferencia polimerizable |
CA2669533A1 (en) | 2006-11-30 | 2008-06-05 | Dow Global Technologies Inc. | Stretch fabrics with wrinkle resistance and garment |
EP2170604B1 (en) | 2007-07-13 | 2019-05-15 | Dow Global Technologies LLC | Ethylene/alpha-olefin interpolymers having low crystallinity hard blocks |
US8124709B2 (en) | 2008-01-30 | 2012-02-28 | Dow Global Technologies Llc | Ethylene/α-olefin block interpolymers |
CN101983214A (zh) | 2008-01-30 | 2011-03-02 | 陶氏环球技术公司 | 乙烯/α-烯烃嵌段互聚物 |
WO2010151433A1 (en) | 2009-06-26 | 2010-12-29 | Dow Global Technologies Inc. | Process selectively polymerizing ethylene and catalyst therefor |
-
2011
- 2011-05-11 US US13/105,018 patent/US8609794B2/en active Active
- 2011-05-11 JP JP2013511220A patent/JP5767318B2/ja active Active
- 2011-05-11 WO PCT/US2011/036004 patent/WO2011146291A1/en active Application Filing
- 2011-05-11 CN CN201180024264.5A patent/CN102906129B/zh active Active
- 2011-05-11 MX MX2012007036A patent/MX350592B/es active IP Right Grant
- 2011-05-11 EP EP11724080.4A patent/EP2491062B1/en active Active
- 2011-05-11 KR KR1020127018508A patent/KR101788892B1/ko active IP Right Grant
- 2011-05-11 BR BR112012022591-0A patent/BR112012022591B1/pt active IP Right Grant
-
2013
- 2013-11-11 US US14/076,322 patent/US9000108B2/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060025548A1 (en) * | 2002-04-24 | 2006-02-02 | Symyx Technologies, Inc. | Bridged bi-aromatic catalysts, complexes, and methods of using the same |
JP2007529616A (ja) * | 2004-03-17 | 2007-10-25 | ダウ グローバル テクノロジーズ インコーポレイティド | エチレンコポリマーを形成するためのシャトリング剤を含む触媒組成物 |
JP2009509003A (ja) * | 2005-09-15 | 2009-03-05 | ダウ グローバル テクノロジーズ インコーポレイティド | 多中心シャトリング剤(multi−centeredshuttlingagent)によるポリマー構造および分子量分布の制御 |
JP2009537656A (ja) * | 2006-05-17 | 2009-10-29 | ダウ グローバル テクノロジーズ インコーポレイティド | 高温ポリエチレン溶液重合方法 |
JP2009537655A (ja) * | 2006-05-17 | 2009-10-29 | ダウ グローバル テクノロジーズ インコーポレイティド | 高効率溶液重合プロセス |
Cited By (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013060396A (ja) * | 2011-09-13 | 2013-04-04 | Konica Minolta Holdings Inc | 縮合複素環化合物の製造方法 |
US10059787B2 (en) | 2012-12-27 | 2018-08-28 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
JP2016506446A (ja) * | 2012-12-27 | 2016-03-03 | ダウ グローバル テクノロジーズ エルエルシー | エチレン系ポリマーを製造するための重合法 |
JP2016506445A (ja) * | 2012-12-27 | 2016-03-03 | ダウ グローバル テクノロジーズ エルエルシー | エチレン系ポリマーを製造するための重合法 |
US10214602B2 (en) | 2012-12-27 | 2019-02-26 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
US10214622B2 (en) | 2012-12-27 | 2019-02-26 | Dow Global Technologies Llc | Catalyst systems for olefin polymerization |
US10144791B2 (en) | 2013-06-28 | 2018-12-04 | Dow Global Technologies Llc | Molecular weight control of polyolefins using halogenated bis-phenylphenoxy catalysts |
JP2016524024A (ja) * | 2013-06-28 | 2016-08-12 | ダウ グローバル テクノロジーズ エルエルシー | ハロゲン化ビス−フェニルフェノキシ触媒を使用するポリオレフィンの分子量制御 |
JP2020158771A (ja) * | 2014-06-30 | 2020-10-01 | ダウ グローバル テクノロジーズ エルエルシー | オレフィン重合用の触媒系 |
JP2017519874A (ja) * | 2014-06-30 | 2017-07-20 | ダウ グローバル テクノロジーズ エルエルシー | オレフィン重合のためのプロセス |
JP6999742B2 (ja) | 2014-06-30 | 2022-01-19 | ダウ グローバル テクノロジーズ エルエルシー | オレフィン重合用の触媒系 |
JP2017522425A (ja) * | 2014-07-24 | 2017-08-10 | ダウ グローバル テクノロジーズ エルエルシー | 低分子量エチレン系ポリマー重合用のビス−ビフェニルフェノキシ触媒 |
JP2018504371A (ja) * | 2014-12-04 | 2018-02-15 | ダウ グローバル テクノロジーズ エルエルシー | エチレン系ポリマーの調製物のための五配位ビス−フェニルフェノキシ触媒 |
JP2018510244A (ja) * | 2015-03-31 | 2018-04-12 | ダウ グローバル テクノロジーズ エルエルシー | 低レベルの長鎖分岐を有する高分子量エチレン/α−オレフィン/非共役インターポリマーの生成方法 |
US11041027B2 (en) | 2015-06-30 | 2021-06-22 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
US10597473B2 (en) | 2015-06-30 | 2020-03-24 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
US10647797B2 (en) | 2015-09-30 | 2020-05-12 | Dow Global Technologies Llc | Polymerization process for producing ethylene based polymers |
US10870713B2 (en) | 2015-09-30 | 2020-12-22 | Dow Global Technologies Llc | Procatalyst and polymerization process using the same |
JP2020512462A (ja) * | 2017-03-31 | 2020-04-23 | ダウ グローバル テクノロジーズ エルエルシー | オレフィン重合のためのビス−ビフェニル−フェノキシ触媒 |
KR20190129999A (ko) * | 2017-03-31 | 2019-11-20 | 다우 글로벌 테크놀로지스 엘엘씨 | 올레핀 중합을 위한 비스-바이페닐-페녹시 촉매 |
JP7173983B2 (ja) | 2017-03-31 | 2022-11-17 | ダウ グローバル テクノロジーズ エルエルシー | オレフィン重合のためのビス-ビフェニル-フェノキシ触媒 |
KR102567217B1 (ko) | 2017-03-31 | 2023-08-16 | 다우 글로벌 테크놀로지스 엘엘씨 | 올레핀 중합을 위한 비스-바이페닐-페녹시 촉매 |
US11066428B2 (en) | 2017-09-29 | 2021-07-20 | Dow Global Technologies Llc | Bis-phenyl-phenoxy polyolefin catalysts having a methylenetrialkylsilicon ligand on the metal for improved solubility |
US11066489B2 (en) | 2017-09-29 | 2021-07-20 | Dow Global Technologies Llc | Bis-phenyl-phenoxy polyolefin catalysts having two methylenetrialkylsilicon ligands on the metal for improved solubility |
US11242415B2 (en) | 2017-09-29 | 2022-02-08 | Dow Global Technologies Llc | Bis-phenyl-phenoxy polyolefin catalysts having an alkoxy- or amido-ligand on the metal for improved solubility |
Also Published As
Publication number | Publication date |
---|---|
US20140163186A1 (en) | 2014-06-12 |
KR20130079313A (ko) | 2013-07-10 |
MX2012007036A (es) | 2012-07-04 |
US20110282018A1 (en) | 2011-11-17 |
JP5767318B2 (ja) | 2015-08-19 |
CN102906129B (zh) | 2015-02-25 |
WO2011146291A1 (en) | 2011-11-24 |
BR112012022591B1 (pt) | 2022-11-08 |
BR112012022591A2 (pt) | 2021-03-16 |
EP2491062B1 (en) | 2013-12-11 |
US8609794B2 (en) | 2013-12-17 |
US9000108B2 (en) | 2015-04-07 |
MX350592B (es) | 2017-09-11 |
EP2491062A1 (en) | 2012-08-29 |
KR101788892B1 (ko) | 2017-11-15 |
CN102906129A (zh) | 2013-01-30 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5767318B2 (ja) | エチレンを選択的に重合させるための方法及びそのための触媒 | |
KR101865645B1 (ko) | 중합성 올레핀의 중합 방법 및 그를 위한 촉매 | |
WO2011146044A1 (en) | Process for selectively polymerizing ethylene and catalyst therefor | |
KR101827023B1 (ko) | 금속-리간드 착체 및 촉매 | |
US9522855B2 (en) | Process for producing low molecular weight ethylene- and alpha-olefin-based materials | |
CN111620976A (zh) | 烯烃聚合方法 | |
CN112585172A (zh) | 具有两个蒽基配体的双苯基苯氧基聚烯烃主催化剂 | |
CN115298227B (zh) | Iii族和镧系元素双-苯基-苯氧基金属-配体络合物 | |
US8318874B2 (en) | Process of selectively polymerizing ethylene and catalyst therefor | |
KR20210105949A (ko) | 올레핀 중합용 비아릴 페녹시 iv족 전이금속 촉매 | |
CN115038725B (zh) | 包括iii族和镧系元素双-苯基-苯氧基金属-配体络合物以及链转移剂的聚合方法 | |
KR20210107735A (ko) | 올레핀 중합을 위한 헤테로고리-헤테로고리계 제iv족 전이 금속 촉매 | |
CN114096569B (zh) | 作为用于烯烃聚合的催化剂的双齿二嗪基氨基络合物 | |
CN112533964B (zh) | 双齿唑基氨基金属-配体络合物和烯烃聚合催化剂 | |
JP2024509386A (ja) | Iv族ポリオレフィン触媒のためのビス-フェノキシ-エーテル配位子 | |
KR20230109261A (ko) | 올레핀계 중합체 및 그 제조방법 | |
JP2022525889A (ja) | 超高分子量許容性および超低コモノマー取り込み性を有する単座二座アミノピリジン第4族遷移金属オレフィン共重合触媒 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20140310 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20140623 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140708 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20141008 |
|
A602 | Written permission of extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A602 Effective date: 20141016 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20141110 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20150526 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20150618 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5767318 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |