CN105829326B - Bis- (indenyl) transition metal complexes of bridging, its preparation and application - Google Patents
Bis- (indenyl) transition metal complexes of bridging, its preparation and application Download PDFInfo
- Publication number
- CN105829326B CN105829326B CN201480068482.2A CN201480068482A CN105829326B CN 105829326 B CN105829326 B CN 105829326B CN 201480068482 A CN201480068482 A CN 201480068482A CN 105829326 B CN105829326 B CN 105829326B
- Authority
- CN
- China
- Prior art keywords
- alkyl
- aryl
- butyl
- group
- transition metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 87
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims description 9
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 title abstract description 45
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 title abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 132
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 86
- 229920000642 polymer Polymers 0.000 claims abstract description 82
- 150000001875 compounds Chemical class 0.000 claims abstract description 80
- 125000005843 halogen group Chemical group 0.000 claims abstract description 74
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 51
- -1 C1-C10Alkyl Chemical group 0.000 claims description 317
- 125000000217 alkyl group Chemical group 0.000 claims description 79
- 238000005658 halogenation reaction Methods 0.000 claims description 75
- 239000012190 activator Substances 0.000 claims description 71
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 60
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 49
- 239000000178 monomer Substances 0.000 claims description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims description 42
- 239000001257 hydrogen Substances 0.000 claims description 42
- 125000003342 alkenyl group Chemical group 0.000 claims description 36
- 229910052799 carbon Inorganic materials 0.000 claims description 34
- 125000003118 aryl group Chemical group 0.000 claims description 30
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 29
- 150000001450 anions Chemical class 0.000 claims description 27
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 26
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 25
- 125000004429 atom Chemical group 0.000 claims description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 21
- 239000005977 Ethylene Substances 0.000 claims description 18
- 229910052726 zirconium Inorganic materials 0.000 claims description 18
- 229910052735 hafnium Inorganic materials 0.000 claims description 15
- 229910052736 halogen Inorganic materials 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 14
- 150000002367 halogens Chemical class 0.000 claims description 14
- 229920001155 polypropylene Polymers 0.000 claims description 14
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 13
- 239000004411 aluminium Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 11
- 238000005259 measurement Methods 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 9
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- 239000002516 radical scavenger Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 229910052732 germanium Inorganic materials 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 4
- 125000001820 oxy group Chemical group [*:1]O[*:2] 0.000 claims description 3
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 51
- 125000005842 heteroatom Chemical group 0.000 abstract description 23
- 239000003446 ligand Substances 0.000 abstract description 19
- 125000001424 substituent group Chemical group 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 279
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 112
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 102
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 85
- 239000002585 base Substances 0.000 description 83
- 239000000243 solution Substances 0.000 description 83
- 229910007928 ZrCl2 Inorganic materials 0.000 description 68
- 239000002002 slurry Substances 0.000 description 64
- 238000006243 chemical reaction Methods 0.000 description 61
- 239000000203 mixture Substances 0.000 description 59
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 45
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 39
- 239000007787 solid Substances 0.000 description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 37
- 238000003756 stirring Methods 0.000 description 37
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 36
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 33
- 150000001336 alkenes Chemical class 0.000 description 29
- 239000003795 chemical substances by application Substances 0.000 description 29
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 28
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 28
- 239000002904 solvent Substances 0.000 description 27
- 239000000047 product Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 25
- 238000001816 cooling Methods 0.000 description 24
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 23
- 229910052744 lithium Inorganic materials 0.000 description 23
- 239000012876 carrier material Substances 0.000 description 22
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 21
- 229920001577 copolymer Polymers 0.000 description 21
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 19
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 18
- 239000012043 crude product Substances 0.000 description 18
- 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 18
- 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 18
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 17
- 150000001993 dienes Chemical class 0.000 description 17
- 239000010408 film Substances 0.000 description 17
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 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 17
- 229910000085 borane Inorganic materials 0.000 description 16
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 16
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 16
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 16
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 16
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 16
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 16
- 125000001400 nonyl 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])C([H])([H])[H] 0.000 description 15
- 150000001768 cations Chemical class 0.000 description 14
- 239000000460 chlorine Substances 0.000 description 14
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 14
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 150000002736 metal compounds Chemical class 0.000 description 14
- 239000000523 sample Substances 0.000 description 14
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 13
- 238000001914 filtration Methods 0.000 description 13
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 13
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 13
- 229910052796 boron Inorganic materials 0.000 description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 12
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 12
- 150000001642 boronic acid derivatives Chemical class 0.000 description 11
- 238000005227 gel permeation chromatography Methods 0.000 description 11
- 239000012044 organic layer Substances 0.000 description 11
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 11
- 239000000741 silica gel Substances 0.000 description 11
- 229910002027 silica gel Inorganic materials 0.000 description 11
- 230000004913 activation Effects 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- KKAXNAVSOBXHTE-UHFFFAOYSA-N boranamine Chemical group NB KKAXNAVSOBXHTE-UHFFFAOYSA-N 0.000 description 10
- 238000000113 differential scanning calorimetry Methods 0.000 description 10
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 10
- 239000000284 extract Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 9
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 239000004793 Polystyrene Substances 0.000 description 9
- 125000003545 alkoxy group Chemical group 0.000 description 9
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 235000011152 sodium sulphate Nutrition 0.000 description 9
- 238000006467 substitution reaction Methods 0.000 description 9
- 230000007704 transition Effects 0.000 description 9
- 239000004711 α-olefin Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 239000002841 Lewis acid Substances 0.000 description 8
- 239000004698 Polyethylene Substances 0.000 description 8
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical compound N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 235000019439 ethyl acetate Nutrition 0.000 description 8
- 230000026030 halogenation Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 8
- 150000002430 hydrocarbons Chemical class 0.000 description 8
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 8
- 150000007517 lewis acids Chemical class 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000012041 precatalyst Substances 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 7
- 238000010828 elution Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 125000001183 hydrocarbyl group Chemical group 0.000 description 7
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 7
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 229920002223 polystyrene Polymers 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 239000013049 sediment Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- KVPMZHAGRCBCAD-UHFFFAOYSA-N 4-bromo-1h-indene Chemical class BrC1=CC=CC2=C1C=CC2 KVPMZHAGRCBCAD-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 6
- 229910007932 ZrCl4 Inorganic materials 0.000 description 6
- 238000012662 bulk polymerization Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 6
- 239000003480 eluent Substances 0.000 description 6
- 150000002469 indenes Chemical class 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methylcycloheptane Chemical compound CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 6
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000011574 phosphorus Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 150000003459 sulfonic acid esters Chemical class 0.000 description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 6
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical group CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 5
- BUNVPENXPYPEPE-UHFFFAOYSA-N 4-(3,5-ditert-butylphenyl)-1H-indene Chemical class CC(C)(C)c1cc(cc(c1)C(C)(C)C)-c1cccc2CC=Cc12 BUNVPENXPYPEPE-UHFFFAOYSA-N 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 239000007848 Bronsted acid Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical class [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 5
- 239000000654 additive Substances 0.000 description 5
- 125000004104 aryloxy group Chemical group 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000004913 cyclooctene Substances 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 125000003709 fluoroalkyl group Chemical group 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 5
- 229910052809 inorganic oxide Inorganic materials 0.000 description 5
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 5
- 239000012968 metallocene catalyst Substances 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000376 reactant Substances 0.000 description 5
- WCGIGOVLOFXAMG-UHFFFAOYSA-N silver;trifluoromethanesulfonic acid Chemical compound [Ag].OS(=O)(=O)C(F)(F)F WCGIGOVLOFXAMG-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 4
- AWEIZPJLIGMMLJ-UHFFFAOYSA-N 2-(3,5-ditert-butylphenyl)-1h-indene Chemical class CC(C)(C)C1=CC(C(C)(C)C)=CC(C=2CC3=CC=CC=C3C=2)=C1 AWEIZPJLIGMMLJ-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002879 Lewis base Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 238000007710 freezing Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 238000003780 insertion Methods 0.000 description 4
- 230000037431 insertion Effects 0.000 description 4
- 150000007527 lewis bases Chemical class 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- GTRTWJNYYUOQMP-UHFFFAOYSA-N 2-bromo-4-(3,5-ditert-butyl-4-methoxyphenyl)-1H-indene Chemical class BrC=1CC2=CC=CC(=C2C1)C1=CC(=C(C(=C1)C(C)(C)C)OC)C(C)(C)C GTRTWJNYYUOQMP-UHFFFAOYSA-N 0.000 description 3
- UYCSCVNYHMENFG-UHFFFAOYSA-N 2-cyclopropyl-4-(3,5-ditert-butylphenyl)-1H-indene Chemical class CC(C)(C)c1cc(cc(c1)C(C)(C)C)-c1cccc2CC(=Cc12)C1CC1 UYCSCVNYHMENFG-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- HFKJQIJFRMRSKM-UHFFFAOYSA-N [3,5-bis(trifluoromethyl)phenoxy]boronic acid Chemical compound OB(O)OC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 HFKJQIJFRMRSKM-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000005018 aryl alkenyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000004927 clay Substances 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 3
- 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 3
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000001640 fractional crystallisation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000001282 iso-butane Substances 0.000 description 3
- 235000013847 iso-butane Nutrition 0.000 description 3
- 229910052752 metalloid Inorganic materials 0.000 description 3
- 150000002738 metalloids Chemical class 0.000 description 3
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 3
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 3
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000000565 sealant Substances 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 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 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical group CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 2
- RCJMVGJKROQDCB-UHFFFAOYSA-N 2-methylpenta-1,3-diene Chemical compound CC=CC(C)=C RCJMVGJKROQDCB-UHFFFAOYSA-N 0.000 description 2
- JDFRYHQEZDPCQH-UHFFFAOYSA-N 4-(3,5-ditert-butyl-4-methoxyphenyl)-1H-indene Chemical class C(C)(C)(C)C=1C=C(C=C(C1OC)C(C)(C)C)C1=C2C=CCC2=CC=C1 JDFRYHQEZDPCQH-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
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 2
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000005062 Polybutadiene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- MINODWQETVEGHY-UHFFFAOYSA-N chloro-[2-cyclopropyl-4-(3,5-ditert-butyl-4-methoxyphenyl)-1H-inden-1-yl]-dimethylsilane Chemical compound Cl[Si](C1C(=CC2=C(C=CC=C12)C1=CC(=C(C(=C1)C(C)(C)C)OC)C(C)(C)C)C1CC1)(C)C MINODWQETVEGHY-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000003851 corona treatment Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 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 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 238000003818 flash chromatography Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 2
- VJHGSLHHMIELQD-UHFFFAOYSA-N nona-1,8-diene Chemical compound C=CCCCCCC=C VJHGSLHHMIELQD-UHFFFAOYSA-N 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical class O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- SHWRGPMBBKBLKB-UHFFFAOYSA-N pentadeca-1,3-diene Chemical compound CCCCCCCCCCCC=CC=C SHWRGPMBBKBLKB-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003235 pyrrolidines Chemical class 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 2
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- 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 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
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- HRZMCADYEQRDQZ-FNORWQNLSA-N (3E)-tetracosa-1,3-diene Chemical compound CCCCCCCCCCCCCCCCCCCC\C=C\C=C HRZMCADYEQRDQZ-FNORWQNLSA-N 0.000 description 1
- OGQVROWWFUXRST-FNORWQNLSA-N (3e)-hepta-1,3-diene Chemical compound CCC\C=C\C=C OGQVROWWFUXRST-FNORWQNLSA-N 0.000 description 1
- CLNYHERYALISIR-FNORWQNLSA-N (3e)-nona-1,3-diene Chemical compound CCCCC\C=C\C=C CLNYHERYALISIR-FNORWQNLSA-N 0.000 description 1
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 1
- 125000006659 (C1-C20) hydrocarbyl group Chemical group 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- 125000006656 (C2-C4) alkenyl group Chemical group 0.000 description 1
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 1
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical class ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 description 1
- OTEKOJQFKOIXMU-UHFFFAOYSA-N 1,4-bis(trichloromethyl)benzene Chemical compound ClC(Cl)(Cl)C1=CC=C(C(Cl)(Cl)Cl)C=C1 OTEKOJQFKOIXMU-UHFFFAOYSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- UOEWIGRJKBJCLE-UHFFFAOYSA-N 1-(3,5-ditert-butyl-4-methoxyphenyl)-1H-indene Chemical class CC(C)(C)C1=CC(=CC(=C1OC)C(C)(C)C)C2C=CC3=CC=CC=C23 UOEWIGRJKBJCLE-UHFFFAOYSA-N 0.000 description 1
- AZJDMXYIFGDPIN-UHFFFAOYSA-N 1-(4-naphthalen-1-ylbuta-1,3-dienyl)naphthalene Chemical compound C1=CC=C2C(C=CC=CC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 AZJDMXYIFGDPIN-UHFFFAOYSA-N 0.000 description 1
- YTASJSCBLHWOQS-UHFFFAOYSA-N 1-butylperoxy-2-methyl-1-propan-2-yloxy-1-propoxypropane Chemical compound C(CC)OC(C(C)C)(OOCCCC)OC(C)C YTASJSCBLHWOQS-UHFFFAOYSA-N 0.000 description 1
- CWLKTJOTWITYSI-UHFFFAOYSA-N 1-fluoronaphthalene Chemical compound C1=CC=C2C(F)=CC=CC2=C1 CWLKTJOTWITYSI-UHFFFAOYSA-N 0.000 description 1
- ALLIZEAXNXSFGD-UHFFFAOYSA-N 1-methyl-2-phenylbenzene Chemical group CC1=CC=CC=C1C1=CC=CC=C1 ALLIZEAXNXSFGD-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- IQHSSYROJYPFDV-UHFFFAOYSA-N 2-bromo-1,3-dichloro-5-(trifluoromethyl)benzene Chemical group FC(F)(F)C1=CC(Cl)=C(Br)C(Cl)=C1 IQHSSYROJYPFDV-UHFFFAOYSA-N 0.000 description 1
- ONMSBNJJCUCYED-UHFFFAOYSA-N 2-bromo-n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1Br ONMSBNJJCUCYED-UHFFFAOYSA-N 0.000 description 1
- FCFDJAPULKUCSN-UHFFFAOYSA-N 2-cyclopropyl-4-(3,5-ditert-butyl-4-methoxyphenyl)-1H-indene Chemical class C(C)(C)(C)C=1C=C(C=C(C1OC)C(C)(C)C)C1=C2C=C(CC2=CC=C1)C1CC1 FCFDJAPULKUCSN-UHFFFAOYSA-N 0.000 description 1
- GKAIWFXCHDMHQQ-UHFFFAOYSA-N 2-cyclopropyl-7-(3,5-ditert-butyl-4-methoxyphenyl)-1H-indene Chemical class C(C)(C)(C)C=1C=C(C=C(C1OC)C(C)(C)C)C=1C=CC=C2C=C(CC12)C1CC1 GKAIWFXCHDMHQQ-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- RREAVEQOCKXSHQ-UHFFFAOYSA-N 2h-inden-2-ide Chemical compound C1=CC=C2[CH-]C=CC2=C1 RREAVEQOCKXSHQ-UHFFFAOYSA-N 0.000 description 1
- AOACQJFIGWNQBC-UHFFFAOYSA-N 3-(2-bromophenyl)propanoic acid Chemical compound OC(=O)CCC1=CC=CC=C1Br AOACQJFIGWNQBC-UHFFFAOYSA-N 0.000 description 1
- CXOZQHPXKPDQGT-UHFFFAOYSA-N 3-Methylcyclopentene Chemical compound CC1CCC=C1 CXOZQHPXKPDQGT-UHFFFAOYSA-N 0.000 description 1
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- HDFHMCUXEGKSRB-UHFFFAOYSA-N 4-(3,5-ditert-butyl-4-methoxyphenyl)-2-methyl-1H-indene Chemical class C(C)(C)(C)C=1C=C(C=C(C=1OC)C(C)(C)C)C1=C2C=C(CC2=CC=C1)C HDFHMCUXEGKSRB-UHFFFAOYSA-N 0.000 description 1
- JCQMGSFTMQWFPE-UHFFFAOYSA-N 4-bromo-2,3-dihydro-1h-indene Chemical class BrC1=CC=CC2=C1CCC2 JCQMGSFTMQWFPE-UHFFFAOYSA-N 0.000 description 1
- QWJRBTRSAZACSX-UHFFFAOYSA-N 4-chloro-2-methyl-1h-indene Chemical class C1=CC=C(Cl)C2=C1CC(C)=C2 QWJRBTRSAZACSX-UHFFFAOYSA-N 0.000 description 1
- IRAWLGHJHQBREM-UHFFFAOYSA-N 4-methyl-1h-indene Chemical class CC1=CC=CC2=C1C=CC2 IRAWLGHJHQBREM-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- YCNYCBYHUAGZIZ-UHFFFAOYSA-N 7-oxabicyclo[2.2.1]hept-2-ene Chemical compound O1C2CCC1C=C2 YCNYCBYHUAGZIZ-UHFFFAOYSA-N 0.000 description 1
- YKCNBNDWSATCJL-UHFFFAOYSA-N 7-oxabicyclo[2.2.1]hepta-2,5-diene Chemical compound C1=CC2C=CC1O2 YKCNBNDWSATCJL-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 1
- 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 1
- FDYAUVYPZOQMFE-UHFFFAOYSA-N C1(CC=C(C=C1)C)(C)C=CC=C Chemical compound C1(CC=C(C=C1)C)(C)C=CC=C FDYAUVYPZOQMFE-UHFFFAOYSA-N 0.000 description 1
- OBFROTIOIYUPQH-UHFFFAOYSA-N COC1=C(C=C(C=C1C2=CC=CC=C2)C3=CC=CC4=C3C=CC4)C5=CC=CC=C5 Chemical class COC1=C(C=C(C=C1C2=CC=CC=C2)C3=CC=CC4=C3C=CC4)C5=CC=CC=C5 OBFROTIOIYUPQH-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- LSRGXLRLWFDKNR-UHFFFAOYSA-N FC(F)(F)[S] Chemical compound FC(F)(F)[S] LSRGXLRLWFDKNR-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- YNHIGQDRGKUECZ-UHFFFAOYSA-L PdCl2(PPh3)2 Substances [Cl-].[Cl-].[Pd+2].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 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 229910003828 SiH3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 229910007926 ZrCl Inorganic materials 0.000 description 1
- AHOVSPJTUCSSLJ-UHFFFAOYSA-K [Cl-].C[SiH](C)[Zr+3].[Cl-].[Cl-] Chemical compound [Cl-].C[SiH](C)[Zr+3].[Cl-].[Cl-] AHOVSPJTUCSSLJ-UHFFFAOYSA-K 0.000 description 1
- BAOWVDHYZBLYMB-UHFFFAOYSA-N [F].C1=CC=NC=C1 Chemical compound [F].C1=CC=NC=C1 BAOWVDHYZBLYMB-UHFFFAOYSA-N 0.000 description 1
- NHYSHMZGBQMTLC-UHFFFAOYSA-N [amino(methyl)boranyl]methane Chemical compound CB(C)N NHYSHMZGBQMTLC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- QNXSIUBBGPHDDE-UHFFFAOYSA-N alpha-indanone Natural products C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 description 1
- 125000005013 aryl ether group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 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 1
- 230000002457 bidirectional effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- LKXYJYDRLBPHRS-UHFFFAOYSA-N bromocyclopropane Chemical compound BrC1CC1 LKXYJYDRLBPHRS-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 1
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- FPTFXFQGMZBIHA-UHFFFAOYSA-N chloro-[2-cyclopropyl-4-(3,5-ditert-butylphenyl)-1H-inden-1-yl]-dimethylsilane Chemical compound CC(C)(C)c1cc(cc(c1)C(C)(C)C)-c1cccc2C(C(=Cc12)C1CC1)[Si](C)(C)Cl FPTFXFQGMZBIHA-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229920003020 cross-linked polyethylene Polymers 0.000 description 1
- 239000004703 cross-linked polyethylene Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 1
- ZXIJMRYMVAMXQP-UHFFFAOYSA-N cycloheptene Chemical compound C1CCC=CCC1 ZXIJMRYMVAMXQP-UHFFFAOYSA-N 0.000 description 1
- WQPDQJCBHQPNCZ-UHFFFAOYSA-N cyclohexa-2,4-dien-1-one Chemical compound O=C1CC=CC=C1 WQPDQJCBHQPNCZ-UHFFFAOYSA-N 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- MJFCDPLEATUOPF-UHFFFAOYSA-L dichloronickel;triphenylphosphane Chemical compound Cl[Ni]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 MJFCDPLEATUOPF-UHFFFAOYSA-L 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 125000006202 diisopropylaminoethyl group Chemical group [H]C([H])([H])C([H])(N(C([H])([H])C([H])([H])*)C([H])(C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 description 1
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical class C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- HGVPOWOAHALJHA-UHFFFAOYSA-N ethene;methyl prop-2-enoate Chemical compound C=C.COC(=O)C=C HGVPOWOAHALJHA-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 229920006225 ethylene-methyl acrylate Polymers 0.000 description 1
- 239000005043 ethylene-methyl acrylate Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004407 fluoroaryl group Chemical group 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 1
- YLQFLHWATWECNM-UHFFFAOYSA-N heptacosa-1,3-diene Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC=CC=C YLQFLHWATWECNM-UHFFFAOYSA-N 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- AHAREKHAZNPPMI-UHFFFAOYSA-N hexa-1,3-diene Chemical compound CCC=CC=C AHAREKHAZNPPMI-UHFFFAOYSA-N 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- VFZXMEQGIIWBFJ-UHFFFAOYSA-M magnesium;cyclopropane;bromide Chemical compound [Mg+2].[Br-].C1C[CH-]1 VFZXMEQGIIWBFJ-UHFFFAOYSA-M 0.000 description 1
- UGVPKMAWLOMPRS-UHFFFAOYSA-M magnesium;propane;bromide Chemical compound [Mg+2].[Br-].CC[CH2-] UGVPKMAWLOMPRS-UHFFFAOYSA-M 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N methyl phenyl ether Natural products COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- CBZNDCXNWNCBHK-UHFFFAOYSA-N methylidenesilane Chemical compound [SiH2]=C CBZNDCXNWNCBHK-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 description 1
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000005026 oriented polypropylene Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920005638 polyethylene monopolymer Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 235000011056 potassium acetate Nutrition 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 229920006300 shrink film Polymers 0.000 description 1
- QRUBYZBWAOOHSV-UHFFFAOYSA-M silver trifluoromethanesulfonate Chemical compound [Ag+].[O-]S(=O)(=O)C(F)(F)F QRUBYZBWAOOHSV-UHFFFAOYSA-M 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920006132 styrene block copolymer Polymers 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- RAOIDOHSFRTOEL-UHFFFAOYSA-N tetrahydrothiophene Chemical compound C1CCSC1 RAOIDOHSFRTOEL-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N trifluoromethane acid Natural products FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- OHSJPLSEQNCRLW-UHFFFAOYSA-N triphenylmethyl radical Chemical compound C1=CC=CC=C1[C](C=1C=CC=CC=1)C1=CC=CC=C1 OHSJPLSEQNCRLW-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
The present invention relates to novel bridge metallocenes transition metal complexes, and wherein the complex compound includes an at least indenyl ligands, are replaced at 4 by phenyl, the 4- phenyl is preferably in 3', 4' and 5' by specific substituent group conjunction generation, especially wherein 4'- substituent group is formula (XR'n)‑Group, wherein X be atomic weight be 13-79 14-17 race hetero atom and R' be following one: hydrogen atom, halogen atom, C1‑C10Alkyl or C6‑C10Aryl and n are 0,1,2 or 3.Also disclose the catalyst system including the transition metal complex, the polymerization using the transition metal complex, and the polymer prepared using the transition metal complex.
Description
Inventor: Jian Yang, Matthew W.Holtcamp, Xiongdong Lian, and Gregory S.Day
Priority
The present invention claims on December 19th, 2013 submitting application No. is 61/918,328 U.S. Patent application and
Submit on April 8th, 2014 application No. is the priority of 14163818.9 European patent application and equity.
Technical field
The present invention relates to the novel catalyst compounds comprising bis- (indenyl) transition metal complexes of bridging and it is used for
The method for preparing above-mentioned complex compound.The transition metal complex may be used as the catalyst of olefine polymerizing process.
Background technique
Olefin polymerization catalysis has important application in the industry.Therefore concern finds new catalyst system, improves this and urges
Agent industrial usefulness and prepared polymer is had improve performance.
Olefin polymerization catalysis is often based on transition metal mixture, such as metallocene, as catalyst precarsor, or borrows
Help it is alumoxane activated, or with include non-coordinating anion activator activate.
WO 2002/002576 disclose metallocene composition and they in preparing olefin polymerization catalyst system
Using especially propylene polymerization.Bis- (the 2-R of bridging are disclosed wherein3- 4- pheny-indenylzirconium) metallocene includes those wherein phenyl
At least one ring 3' and 5' replace have butyl its can be it is same or different, such as, tert-butyl.
Other considered bibliography include: WO 98/403331；Organometallics 2012 or 31, the
4962-4970 pages；United States Patent (USP) US6,489,168；U.S. Patent application US 2011/0230622；International patent application WO
02/102575；With European patent application EP 2360163A1.
This field still needs new and improved olefin polymerization catalyst system, specific polymer to realize
Energy, such as high-melting-point, high molecular weight are introduced with improving conversion ratio or comonomer, or change comonomer distribution and do not have
There is the performance for making obtained polymer to deteriorate.Therefore target of the present invention is to provide novel catalyst compounds, comprising above-mentioned
The catalyst system of compound and the method for using above-mentioned compound and polymerization-filling alkene.
Summary of the invention
Summary of the invention
The present invention relates to the novel bridging transition metal complexes that formula (I) is indicated:
Wherein M1Selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten；
R1And R2It can be same or different, and individually hydrogen atom, C1-C10Alkyl, C1-C10Alkoxy, C6-
C10Aryl, C6-C10Aryloxy group, C2-C10Alkenyl, C2-C40Alkenyl, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40(preferably
C8-C30) aryl alkenyl, OH group or halogen atom or optionally by one or more alkyl, three (alkyl) monosilanes
The conjugated diene that base or three (alkyl) silylhydrocarbyls replace, the diene have at most 30 atoms, are not included in hydrogen；
R3To R7Can be identical or different, and individually hydrogen atom, halogen atom can be by the C of halogenation1-C10Alkyl, can
By the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40Aryl alkenyl ,-NR'2,-
SR' ,-OR ,-OSiR'3Or-PR'2Group, wherein R' is following one: hydrogen atom, halogen atom, C1-C10Alkyl or C6-C10
Aryl or two or more adjacent group R5To R7The atom for the indenyl connecting with by them is formed together one or more
Ring；
R13It is-B (R15)-,-Al(R15)-,-Ge-,-Sn-,-O-,-S-,-SO-,-SO2-,-N(R15)-,-CO-,-P
(R15)-, or-P (O) (R15)-, amino borane base (amidoborane radical) meets following one:
Wherein: R15,R16,R17It is same or different, and is hydrogen atom, halogen atom, C1-C20Alkyl, C1-C20
Fluoro-alkyl or sila alkyl (silaalkyl), C6-C30Aryl, C6-C30Fluorinated aryl, C1-C20Alkoxy, C2-C20Alkene
Base, C7-C40Aryl alkyl, C8-C40Aryl alkenyl, C7-C40Alkylaryl, or a R15With a R16, together with R13Middle connection
Their atom is formed together one or more rings；M2It is carbon, silicon, one of germanium or tin or a variety of；
R8And R12It can be same or different, and individually hydrogen atom, halogen atom can be by the C of halogenation1-C10
Alkyl, can be by the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40(preferably C8-
C30) aryl alkenyl ,-NR'2,-SR',-OR,-OSiR'3Or-PR'2Group, wherein R' is as defined above；
Wherein R9And R11It is same or different, and selected from can be by the C of halogenation2-C20Alkyl, can be by the C of halogenation6-
C10Aryl, C2-C10Alkenyl, C7-C20Aryl alkyl, C7-C20Alkylaryl, C8-C20Aryl alkenyl；With
Wherein R10It is (XR'n)-, wherein X is the race's hetero atom of the 14th, 15,16 or 17 and R' with the atomic weight of 13-79
It is following one: hydrogen atom, halogen atom, C1-C10Alkyl, or C6-C10Aryl and n are 0,1,2 or 3；With
R14It is hydrogen atom, halogen atom can be by the C of halogenation3-C10Alkyl, can be by the C of halogenation6-C10Aryl, C2-C10Alkene
Base, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40Aryl alkenyl ,-NR'2,-SR',-OR,-OSiR'3Or-PR'2Base
Group, wherein R' is as defined above, the phenyl preferably replaced.
On the other hand, embodiment of the present invention provides bis- (4- phenyl indenyl) transition metal complexes of bridging, in which: at least
One 4- benzyl ring is replaced at 3' and 5' by following radicals: the group can be it is same or different, and selected from can quilt
The C of halogenation2-C20Alkyl, can be by the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C20Aryl alkyl, C7-C20Alkylaryl, C8-
C20Aryl alkenyl, wherein this at least one in 3' and 5' substituted benzyl ring also at 4' by formula (XR'n)-Group replaces,
Wherein X is the 14th, 15,16 or 17 race's hetero atom that atomic weight is 13-79 and R' is following one: hydrogen atom, halogen are former
Son, C1-C10Alkyl, or C6-C10Aryl and n are 0,1,2, or 3；It is preferred that at least one phenyl is at 4' by-NR'2,-
SR',-OR',-OSiR'3,-SiR'3, or-PR'2In one or more replace；Optionally, wherein in transition gold
Belong to one or more of rest position on the phenyl and/or indenyl rings (one or more) of complex compound, such as 2, is substituted.
More specifically, embodiment of the present invention provides formula (II) transition metal complex indicated:
Wherein M1It is Zr, Hf or Ti；R1And R2It is Cl；Each R3It is methyl；Each R4,R5,R6, and R7It is hydrogen atom；Each R8With
R12Individually hydrogen atom；R13It is-Si (CH3)2-；Each R9And R11It is tert-butyl；With each R10It is methoxyl group.
On the other hand, embodiment of the present invention provides catalyst system, and it includes activators and disclosed in the present application
Transition metal complex.
Another aspect, embodiment of the present invention provides polymerization, including a) makes one or more olefinic monomers and urge
The contact of agent system, which includes: i) activator and ii) transition metal complex disclosed in the present application.
The invention further relates to polymer compositions prepared by the method that is disclosed by this application.
Detailed description of the invention
The General reactions approach for being suitable for preparing transition metal complex disclosed in the present application has been illustrated in attached drawing 1.
2 graphic representation polypropylene molecule amount of attached drawing compares fusing point.
3 graphic representation of the attached drawing catalyst activity compares polypropylene fusing point.
Detailed description of the invention
This specification describes transition metal complex.The term complex compound is used to describe assistant ligand coordinating to central transition
The molecule of metallic atom.The ligand is large volume and stabilization is bonded to the transition metal so that during the application catalyst
(such as polymerization) keeps its influence.The ligand can be matched by covalent bond and/or the coordination of electronics donation or intermediate bond
Position is to the transition metal.The transition metal complex is activated the polymerization or oligomeric to implement them usually using activator
Function, it is believed that activator generates cation due to being usually referred to as the anionic group of leaving group from transition metal removing.
For the present invention and the attached claims, use Chemical and Engineering News public
The new numbering scheme of the periodic table race opened, 63 (5), page 27 (1985).Therefore, " group-4 metal " is the 4th race of periodic table member
Element, for example, Hf, Ti or Zr.
Following abbreviations use in this specification: DME is 1,2- dimethoxy-ethane, and Me is methyl, and Ph is phenyl, Et
It is ethyl, Pr is propyl, and iPr is isopropyl, and n-Pr is n-propyl, and Bu is butyl, and cPR is cyclopropyl, and iBu is isobutyl group, tBu
It is tert-butyl, p-tBu is to tert-butyl, and nBu is normal-butyl, and sBu is sec-butyl, and TMS is trimethyl silyl, and TIBAL is
Triisobutyl aluminium, TNOAL are three (n-octyl) aluminium, and MAO is methylaluminoxane, and p-Me is to methyl, and Ph is phenyl, and Bn is benzyl
(i.e. CH2Ph), THF (also referred to as THF) are tetrahydrofurans, and RT is room temperature (and being 23 DEG C, unless otherwise indicated), and tol is first
Benzene, EtOAc are ethyl acetate, and Cy is cyclohexyl.
For the purpose of the present invention and its claims, term " substituted " refers to that hydrogen-based has been replaced by miscellaneous original
Son has the hydrogen replaced by non-hydrogen atom containing heteroatomic group or in which cyclic hydrocarbon radical.For example, methoxy butylcyclopentadiene is
By methoxy-substituted cyclopentadiene, methylphenyl is by methyl substituted phenyl.
Term " hydrocarbyl group ", " alkyl ", " hydrocarbyl group ", " groups " and " alkyl " make entirely interchangeable everywhere herein
With.Similarly, term " group ", " base " and " substituent group " also may be used interchangeably in this document.For present disclosure
Speech, " alkyl " is defined as C1-C100Group can be straight chain, branch or cricoid, and then be aromatics if it is ring-type
Or it is non-aromatic.The example of this group includes, but are not limited to methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group,
Sec-butyl, tert-butyl, amyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclooctyl etc., including
Their substituted analog.Substituted alkyl be wherein alkyl at least one hydrogen atom by least one halogen group (such as
Br, Cl, F or I) or at least one functional group such as NR*2,OR*,SeR*,TeR*,PR*2,AsR*2,SbR*2,SR*,BR*2,SiR*3,
GeR*3,SnR*3,PbR*3 equal substitutions or in which at least one hetero atom are already inserted into alkyl ring.
Term " alkenyl " refers to the straight chain with one or more double bonds, branch or cyclic hydrocarbon group.These alkenyls can it is non-must
Strategic point is substituted.The example of suitable alkenyl includes, but are not limited to vinyl, acrylic, allyl, Isosorbide-5-Nitrae-butadienyl, ring
Acrylic, cyclobutane base, cyclopentenyl, cyclohexenyl group, cyclo-octene base etc., including their substitution analog.
Term " alkoxy " or " alcohol radical " refer to alkyl ether or aryl ether group, and wherein term alkyl is as defined above.It closes
The example of suitable alkylether radicals includes, but are not limited to methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutyl
Oxygroup, sec-butoxy, tert-butoxy, phenoxy group and analog.
Term " aryl " or " aryl group " refer to six carbon aromatic rings and its substituted variant, including but not limited to, phenyl,
2- methylphenyl, xylyl, the bromo- xylyl of 4-.Same heteroaryl refers to wherein ring carbon atom (or two or three rings
Carbon atom) it has been replaced by hetero atom, preferably N, the aryl of O or S.As used herein, term " aromatics " also refers to that quasi- aromatics is miscellaneous
Ring, they are following heterocyclic substituents: it has the property and structure (hither plane) similar with aromatic heterocycle ligand, but does not define
For aromatics；Similarly, term aromatic also refers to substituted aromatic substances.
If there is entitled alkyl, alkenyl, the isomers of alkoxy or aryl is (for example, normal-butyl, isobutyl group, Zhong Ding
Base and tert-butyl), then it is different will to specifically disclose remaining in the family for an object (for example, normal-butyl) in the mentioned group
Structure body (for example, isobutyl group, sec-butyl and tert-butyl).Similarly, it is referred to alkyl, alkenyl, alkoxy or aryl, without referring to
Fixed specific isomers (for example, butyl), then specifically disclose all isomers (for example, normal-butyl, isobutyl group, sec-butyl,
And tert-butyl).
Term " annular atom " refers to the atom of a part of cyclic annular ring structure.It is defined by this, there are six rings for benzyl tool
Atom and tetrahydrofuran have 5 annular atoms.
Heterocyclic ring be in ring structure have heteroatomic ring, rather than wherein the hydrogen on annular atom be replaced by it is heteroatomic
The ring that hetero atom replaces.Such as tetrahydrofuran is heterocyclic ring, and 4-N, N- dimethylaminophenyl are the rings that hetero atom replaces.
Term " catalyst system " definition refers to complex compound/activator pair.If " catalyst system " is for before activating
Description is such a pair of, then it mean non-activated catalyst complex (pre-catalyst) together with activator and, optionally
Conactivator.If it be used to describe activation after such a pair, it mean the complex compound and activator being activated or its
Its charge balance structure part.Transistion metal compound can be neutral as in pre-catalyst, or mean with resisting
The charge species of weighing apparatus ion, as in the catalyst system activated.
" complex compound " used herein, is also generally referred to as catalyst precarsor, pre-catalyst, catalyst, catalyst compounds
Object, transistion metal compound or transition metal complex.These words are used interchangeably.Activator and co-catalyst is also interchangeable makes
With.
Scavenger is general is added by removing impurity to promote the compound of polymerization.Some scavengers can also act as work
Agent and it can be described as conactivator.It is not the conactivator of scavenger, can also be used in combination with activator to form activity
Catalyst.In some embodiments, conactivator can be pre-mixed to form alkylated transition gold with transistion metal compound
Belong to compound.
Non-coordinating anion (NCA) is defined as referring to or be not coordinated that catalyst metals are cationic or only weak coordination
To the anion of metal cation.Term NCA be further defined as include the NCA containing multicomponent activator, such as N, N- dimethyl puratized agricultural spray
Four (pentafluorophenyl group) borates, contain acid cation group and non-coordinating anion.Term NCA is further defined as including neutral
Lewis acid, such as three (pentafluorophenyl group) boron can activate class object with catalyst reaction by extracting anionic group to be formed
Matter.The weak coordination of NCA is enough to make neutral Lewis base, as olefinic or acetylene series unsaturated monomer can replace it from catalyst center.
Any metal or metalloid that compatible weak co-ordination complex can be formed can be used or be included in non-coordinating anion it
In.Suitable metal includes, but are not limited to aluminium, gold and platinum.Suitable metalloid includes, but are not limited to boron, aluminium, phosphorus and silicon.
Activator containing non-coordinating anion can also be referred to as Stoichiometric activators.Stoichiometric activators can be neutrality or from
Son.The agent of term ion activation and stoichiometry ion activation agent are used interchangeably.Similarly, term neutral stoichiometric activator
It is used with can be interchanged with Lewis acid activation agent.Term non-coordinating anion activator includes neutral stoichiometric activator,
Ionic stoichiometric activator, ion activation agent and Lewis acid activation agent.
In the present specification, metallocene catalyst can be described as catalyst precarsor, pre-catalyst compound, and metallocene is urged
Agent compound or transistion metal compound, and these terms may be used interchangeably.Polymerisation catalyst system is can to make monomer
It is polymerized to the catalyst system of polymer." anion ligand " is negatively charged ligand, to metal ion provide it is a pair of or
Multipair electronics." neutral donor ligand " is the ligand of electroneutral, provides one or more pairs of electronics to metal ion.
Metallocene catalyst define be at least one pi bond close cyclopentadienyl moieties (or replace cyclopentadiene
Base portion point) and be more the cyclopentadienyl moieties of 2 pi bonds conjunctions or the organometallic of substituted cyclopentadienyl moieties
Close object.
For the metallocene catalyst compound of the present invention and the appended claims, " substitution " word refers to hydrogen-based
It is replaced by alkyl, hetero atom or containing heteroatomic group.For example, methyl cyclopentadiene (CP) is that have methyl substituted Cp
Base.
" catalyst productivity " is raw using the polymerization catalyst comprising W grams of catalyst (cat) within a period of time T hour
Produce the measurement of how many grams of polymer (P)；And it can be expressed from the next: P/ (T × W), and with unit gPgcat-1hr-1It indicates.
Conversion ratio is the amount that monomer is converted into polymer product, and is reported as a mole %, the yield based on the polymer and infeed reaction
The amount of monomer in device calculates.Catalyst activity is catalyst activity measurement how and is reported as using every mole catalyst
The quality (kgP/molcat) of resulting polymer (P) prepared by agent (cat).
It can be straight chain, branch or cyclic compound otherwise known as " alkene " for herein " alkene ", it includes carbon and hydrogen,
With at least one double bond.For this specification and the appended claims, when polymer or copolymer are related to comprising alkene
When, the alkene for being present in this polymer or copolymer is the alkene of polymerized form.For example, if copolymer has claimed 35 weights
%-55 weight % " propylene " content is measured, then it can be understood that monomeric unit in the copolymer is from the propylene in polymerization reaction
The derivative and derived units content is the 35 weight % of weight %~55, the weight based on copolymer.High alpha-olefin is defined as
Alpha-olefin with 4 or more carbon atoms.For present disclosure, ethylene is considered as a kind of alpha-olefin.
For purposes of the present application, " polymer " has two or more identical or different " monomer (mer) " units."
Polymers " is the polymer with same monomer unit." copolymer " refers to two or more monomeric units different from each other
Polymer." terpolymer " is the polymer with three kinds of monomeric units different from each other.About monomeric unit " difference "
Indicate that monomeric unit is different from each other because of at least one atom or belongs to different isomers.Therefore, copolymer as used herein
Definition include terpolymer etc..Oligomer is usually the polymer with low molecular weight, for example, Mn lower than 25,000 gram/rub
You, or the monomeric unit few less than 2500 grams/mol or quantity, such as 75 monomeric units or less or 50 monomeric units
Or it is less." ethene polymers " or " ethylene copolymer " is polymer or copolymer, and it includes the ethylene of at least 50 moles % to spread out
Raw unit, " acrylic polymers " or " propylene copolymer " are polymer or copolymer, and it includes the propylene of at least 50 moles %
Derivative unit, etc..
As used herein, Mn is number-average molecular weight, and Mw is weight average molecular weight, and Mz be z average molecular weight, wt% is weight
Percentage, and mol% is a mole %.Molecular weight distribution (MWD), also referred to as polydispersity (PDI), be defined as Mw divided by
Mn.Unless otherwise indicated, all molecular weight units (such as Mw, Mn, Mz) are gram/mol.
Term " continuous " means the system of no interrupting or stopping operation.Such as continuation method production polymer is it
Middle reactant is continually introduced into one or more reactors and polymer product is continuously withdrawn.
Polymerisation in solution refers to polymerization, and wherein polymer is dissolved in liquid polymerizaton medium, such as atent solvent or monomer
(one or more) or their blend.Polymerisation in solution is usually homogeneous.Homogeneous polymerization is wherein polymer product dissolution
In polymerisation medium.Such as in J.Vladimir Oliveira, C.Dariva and J.C.Pinto,
Ind.Eng.Chem.Res.29, disclosed in page 2000,4627, above-mentioned system is not preferably muddy.
Bulk polymerization refers to polymerization, wherein monomer to be polymerized and/or comonomer is used as solvent or diluent, it is several
Atent solvent is not with or without as solvent or diluent.Sub-fraction atent solvent may be used as catalyst and scavenger
Carrier.Bulk polymerization system contains atent solvent or diluent less than 25 weight %, preferably less than 10 weight %, preferably less than
1 weight %, preferably 0 weight %.
Transition metal complex
In specific embodiments, the present invention relates to the transition metal complexes of new bridge metallocenes, wherein the network
Closing object includes at least one indenyl ligands, is substituted by phenyl at 4, and the phenyl is specific 3', 4' and 5' substituted bases
Combination replaces.In preferred embodiments, the position 3' and 5' of benzyl ring is selected as steric hindrance (for example, branched hydrocarbyl)
(XR' is selected from 4'- substituent groupn)-, wherein X be the 14th, 15,16 or 17 race that atomic weight is 13-79 hetero atom (preferably N, O,
S, P or Si) and R' be following one: hydrogen atom, halogen atom, C1-C10Alkyl (such as methyl, ethyl, propyl, butyl, amyl,
Hexyl, octyl, nonyl, decyl or its isomers) or C6-C10Aryl and n are 0,1,2 or 3；It is preferred that (XR'n)-It is-NR'2,-
SR',-OR',-OSiR'3,-SiR'3, or-PR'2, preferably (XR'n)-It is-NR'2,-SR',-OR',-OSiR'3, or-PR
'2, preferably (XR'n)-It is-SR' ,-OR', or-OSiR'3, preferably (XR'n)-It is-NR'2Or-PR'2, or preferably (XR'n)-Be-
OR'。
In a preferred embodiment, the present invention relates to a kind of catalyst compounds and catalyst system, it includes
Above compound is indicated by formula (I):
Wherein, M1Selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten (preferably titanium, zirconium and hafnium)；
R1And R2Can be identical or different, and respectively hydrogen atom, C1-C10Alkyl (such as methyl, ethyl, propyl, butyl,
Amyl, hexyl, octyl and its isomers), C1-C10Alkoxy, C6-C10Aryl, C6-C10Aryloxy group, C2-C10Alkenyl, C2-C40Alkene
Base, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40Aryl alkenyl, OH base, halogen atom, optionally by one or more
The conjugated diene that a alkyl, three (alkyl) silicyls or three (alkyl) silylhydrocarbyls replace, the diene have at most
30 atoms (not being included in hydrogen), hydrogen-based (hydride), amino (amide), sulfenyl (sulfide), phosphorus base (phosphide),
Amine, phosphine, ether or their combination；
Each R3Can be identical or different, and individually hydrogen atom, halogen atom can be by the C of halogenation1-C10Alkyl is (preferably
C3-C10Alkyl, preferably C4-C8Alkyl), it can be by the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C40Aryl alkyl, C7-C40Alkyl
Aryl, C8-C40(preferably C8-C30) aryl alkenyl ,-NR'2,-SR',-OR,-OSiR'3Or-PR'2, wherein R' is following one:
Hydrogen atom, halogen atom, C1-C10Alkyl or C6-C10Aryl or two or more adjacent group R5-R7With connect theirs
The atom of indenyl is formed together one or more rings (preferably one or two R3It is not hydrogen, preferably one or two R3It is first
Base, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl is (in general, its isomery
Body, such as cyclopropyl) or the like)；
Wherein: R4,R5,R6, and R7Can be identical or different, and individually hydrogen atom, halogen atom can be by halogenation
C1-C10Alkyl (preferably methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, 12
Alkyl etc.), it can be by the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40Aryl alkene
Base ,-NR'2,-SR',-OR,-OSiR'3Or-PR'2Group, wherein R' is following one: hydrogen atom, halogen atom, C1-C10
Alkyl or C6-C10Aryl or two or more adjacent group R5-R7One is formed together with the atom for the indenyl for connecting them
A or multiple rings；
R13It is-B (R15)-,-Al(R15)-,-Ge-,-Sn-,-O-,-S-,-SO-,-SO2-,-N(R15)-,-CO-,-P
(R15)-, or-P (O) (R15)-, amino borane group is indicated by one of following formula:
Wherein: R15,R16,R17It is same or different, and is hydrogen atom, halogen atom, C1-C20Alkyl, C1-C20Fluorine
Substituted alkyl or sila alkyl, C6-C30Aryl, C6-C30Fluorinated aryl, C1-C20Alkoxy, C2-C20Alkenyl, C7-C40Aryl alkane
Base, C8-C40Aryl alkenyl, C7-C40Alkylaryl, or a R15With a R16, together with R13Middle their atom of connection, one
It rises and forms one or more rings；M2It is one of carbon, silicon, germanium or tin or a variety of；
R8And R12It is same or different, and individually hydrogen atom, halogen atom can be by the C of halogenation1-C10Alkyl is (excellent
Select C2-C10, preferably C3-C10, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, 11
Alkyl, dodecyl etc.), it can be by the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C40Aryl alkyl, C7-C40Alkylaryl,
C8-C40Aryl alkenyl ,-NR'2,-SR',-OR,-OSiR'3Or-PR'2Group, wherein R' is following one: hydrogen atom, halogen
Atom, C1-C10Alkyl, or C6-C10Aryl；
R9And R11It is same or different, and selected from can be by the C of halogenation2-C20Alkyl (preferably C3-C16, preferably C4-C12,
It is preferred that butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and its isomers), it can be by halogenation
C6-C10Aryl, C2-C10Alkenyl, C7-C20Aryl alkyl, C7-C20Alkylaryl, C8-C20Aryl alkenyl；With
R10Selected from (XR'n)-, wherein X be atomic weight be 13-79 the 14,15,16th or 17 race's hetero atoms and R' be with
It is one of lower: hydrogen atom, halogen atom, C1-C10Alkyl, or C6-C10Aryl and n are 0,1,2 or 3；Especially wherein R10Be-
NR'2,-SR',-OR',-OSiR'3,-SiR'3, or-PR'2, wherein R10Selected from-NR'2,-SR',-OR',-OSiR'3, or-
PR'2, wherein R10It is-SR' ,-OR' ,-OSiR'3, wherein R10It is-NR'2Or-PR'2Group, or wherein R10Be-
OR'；With
R14It is hydrogen atom, halogen atom can be by the C of halogenation3-C10Alkyl, can be by the C of halogenation6-C10Aryl, C2-C10Alkene
Base, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40Aryl alkenyl ,-NR'2,-SR',-OR,-OSiR'3Or-PR'2Base
Group, wherein R' is as defined above, the phenyl preferably replaced, preferably 3', the phenyl that 5' replaces, preferably 3', 4', the phenyl that 5' replaces.
In a preferred embodiment of the invention, the transition metal complex of the present invention being particularly useful can be expressed as formula
(II):
Wherein M1,M2,R1,R2,R3,R4,R5,R6,R7,R8,R9,R10,R11,R12,R13,R15,R16And R17As described above.
In the preferred embodiment of the invention in any embodiment that the application discloses any formula, M1It is Hf, Zr
Or Ti, preferably Hf or Zr, preferably Zr.
In the preferred embodiment of the invention in any embodiment that the application discloses any formula, M2Si, C or
Person Ge, preferably C or Si, preferably Si.
In the preferred embodiment of the invention in any embodiment that the application discloses any formula, R15,R16And R17
It is preferred that methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl.
In the preferred embodiment of the invention in any embodiment that the application discloses any formula, R13It is expressed as formula
R2 aJ, wherein J is C, Si, Ge, and each RaIt is independently hydrogen, halogen, C1-C20Alkyl (such as methyl, ethyl, propyl,
Butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl) or C1-C20Substituted alkyl,
And two RaCyclic structure, including aromatics, fractional saturation or saturated cyclic or fused ring system can be formed.It is preferred that R13
It is bridging group, includes carbon or silicon, such as dialkyl silyl, preferably R13Selected from CH2,CH2CH2,C(CH3)2,SiMe2,
SiPh2, SiMePh, silicyl cyclobutyl, (Si (CH2)3),(Ph)2C,(p-(Et)3SiPh)2C, and five methylene silane of ring
Base (Si (CH2)4)。
In alternate embodiment, disclosed in any formula in the application, each R1And R2It 1 is arrived independently selected from having
The alkyl of 20 carbon atoms, hydrogen-based, amino, alkoxy, sulfenyl, phosphorus base (phosphide), halogen, diene, amine, phosphine, ether, and
A combination thereof, (R1And R2A part of condensed ring or ring system can be formed), preferably each R1And R2Independently selected from halogen and
C1-C5 alkyl (preferably methyl).It is preferred that R1And R2Selected from chlorine, bromine, methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, pungent
Base, nonyl, decyl, undecyl and dodecyl.
It is alternatively R1And R2It can also connect together to form alkane diyl or conjugation C4-C40Diene ligand, with
Metal cyclopentene fashion is coordinating to M1；R1And R2It is also possible to same or different conjugated diene, optionally replacing has one
Or multiple alkyl, three (alkyl) silicyls or three (alkyl) silylhydrocarbyls, the diene have at most 30 atoms, not
It is included in hydrogen, and and M1Form π-complex compound.
Suitable for R1And/or R2Exemplary groups include 1,4- biphenyl, 1,3- butadiene, 1,3- pentadiene, 2- methyl-1,
3- pentadiene, 2,4- hexadiene, 1- phenyl, 1,3- pentadiene, 1,4- dibenzyl, 1,3- butadiene, 1,4- xylyl -1,3-
Butadiene, bis- (the trimethyl silyl) -1,3- butadiene of 1,4-, and 1,4- dinaphthyl -1,3- butadiene；It is preferred that R1And R2
It is identical and be C1-C3Alkyl or alkoxy, C6-CgAryl or aryloxy group, C2-C4Alkenyl, C7-C10Aryl alkyl, C7-C12
Alkylaryl, or halogen atom, especially chlorine.
In any embodiment of the present invention, including any formula (especially Formulas I or II), the one or more is disclosed herein
2 of indenyl, such as, the R in Formulas I or II3It can be selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, normal-butyl, different
Butyl, sec-butyl, tert-butyl, amyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, cyclooctyl,
Phenyl either replace or unsubstituted, especially methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec- fourth
More specifically base, tert-butyl are hydrogen or methyl.In any embodiment of the present invention, including any formula is disclosed herein (especially
Its Formulas I and II), 2 of the one or more indenyl, such as, the R in Formulas I or II3, it is not exchanged for heteroatoms, it is excellent
Each choosing is independently the hydrocarbyl group with 1 to 20 carbon atoms, is not exchanged for heteroatoms.
In any embodiment of the present invention, including any formula (especially Formulas I or II), R is disclosed herein4,R5,R6And R7
It is same or different, and individually hydrogen atom, halogen atom can be by the C of halogenation1-C10Alkyl (methyl, ethyl, propyl,
Butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl perhaps its isomers) or can be by halogen
The C of change6-C10Aryl.
In any embodiment of the present invention, including any formula (especially Formulas I or II), R is disclosed herein8And R12It is identical
Or it is different, and individually hydrogen atom, halogen atom can be by the C of halogenation1-C10Alkyl (preferably C2-C10, preferably C3-C10, excellent
It selects methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or its is different
Structure body), it can be by the C of halogenation6-C10Aryl, preferably methyl, ethyl, propyl, butyl, amyl, hexyl, phenyl, octyl, nonyl, the last of the ten Heavenly stems
Base, undecyl, dodecyl, preferably methyl, ethyl or phenyl.
In any embodiment of the present invention, including any formula (especially Formulas I or II), R is disclosed herein9And R11It is identical
Or it is different, and selected from can be by the C of halogenation2-C20Alkyl (preferably C3-C16, preferably C4-C12, preferably butyl, amyl, hexyl,
Heptyl, octyl, nonyl, decyl, undecyl, dodecyl and its isomers), it can be by the C of halogenation6-C10Aryl.In some realities
It applies in scheme, R9And R11It can be same or different, and individually butyl, aryl, isopropyl or fluoro-alkyl, especially
Its wherein R9And R11Each is selected from propyl, isopropyl, n-propyl, normal-butyl, isobutyl group and tert-butyl.Of the invention
R in preferred embodiment9And R11It is same or different, and is C4-C20, preferably C4-C12Alkyl and each R3It is independently
Alkyl with 1 to 20 carbon atoms, is not exchanged for heteroatoms.
In any embodiment of the present invention, including any formula (especially Formulas I or II), R is disclosed herein10Selected from-NR
'2,-SR',-OR',-OSiR'3Or-PR'2Group, wherein R' is following one: hydrogen atom, halogen atom, C1-C10Alkyl,
Or C6-C10Aryl, especially wherein R10It is OR', wherein R' is C1-C10Alkyl, especially methoxyl group, ethyoxyl, n- third oxygen
Base, isopropoxy, n-butoxy, isobutoxy, sec- butoxy or t-butoxy, most especially methoxyl group.
In any embodiment of the present invention, including any formula (especially Formulas I or II), R is disclosed herein14Be replace or
The unsubstituted C of person6-C10Aryl (preferably phenyl, naphthalene, indenyl, preferably phenyl), can be substituted (such as halogenated), example
Such as, substituted or unsubstituted phenyl, naphthalene or indenyl.It is preferred that R14It can be phenyl, especially 3'- and/or 5'-
Substituted-phenyl, more specifically, wherein the 3' and/or 5' substituent group be selected from can be by the C of halogenation2-C20Alkyl, can be by halogenation
C6-C10Aryl, C2-C10Alkenyl, C7-C20Aryl alkyl, C7-C20Alkylaryl, C8-C20Aryl alkenyl.In the specific reality of the present invention
It applies in scheme, wherein R14Phenyl, 3' and 5' are same or different, and individually butyl, aryl, isopropyl or
Person's fluoro-alkyl each especially wherein is selected from normal-butyl, isobutyl group and tert-butyl, is most especially wherein individually tert-butyl.In
In specific embodiment of the present invention, wherein R14It is phenyl, 3' and 5' are same or different, and individually butyl, virtue
Base, isopropyl or fluoro-alkyl (each especially wherein be selected from normal-butyl, isobutyl group and tert-butyl, it is most especially wherein each
Tert-butyl naturally)；Also there is-NR' in 4' substitutions with the phenyl2,-SR',-OR',-OSiR'3Or-PR'2Group, wherein R'
It is following one: hydrogen atom, halogen atom, C1-C10Alkyl, or C6-C10Aryl, preferably alkoxy, preferably methoxyl group, ethoxy
Base, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec- butoxy or t-butoxy.
In some embodiments, R3Selected from hydrogen and methyl；R9And R11Each of selected from normal-butyl, isobutyl group,
And especially tert-butyl.In other embodiments, R3Selected from hydrogen and methyl；R9And R11In each be selected from normal-butyl, different
Butyl and especially tert-butyl；And R10It is methoxyl group, ethyoxyl, n-propoxy, isopropoxy, n-butoxy, isobutyl oxygen
Base, sec- butoxy or t-butoxy, especially methoxyl group.
In some embodiments, R3Selected from hydrogen and cyclopropyl；R9And R11In each be selected from normal-butyl, isobutyl group, with
And especially tert-butyl.In other embodiments, R3Selected from hydrogen and cyclopropyl；R9And R11In each be selected from normal-butyl, isobutyl
Base, and especially tert-butyl；And R10Be methoxyl group, ethyoxyl, n-propoxy, isopropoxy, n-butoxy, isobutoxy,
Sec- butoxy or t-butoxy, especially methoxyl group.
Some transition metal complexes for the application can be described as bis- (4- pheny-indenylzirconium) the transition metal networks of bridging
Close object, in which: at least one 4- benzyl ring is replaced at 3' and 5' by following radicals: the group can be same or different
, and selected from can be by the C of halogenation2-C20Alkyl, can be by the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C20Aryl alkyl, C7-
C20Alkylaryl, C8-C20Aryl alkenyl, wherein this at least one 3' and 5' substituted benzyl ring also 4' by-
NR'2,-SR',-OR',-OSiR'3Or-PR'2Group replaces, and wherein R' is following one: hydrogen atom, halogen atom, C1-C10
Alkyl, or C6-C10Aryl；Optionally, wherein the transition metal complex phenyl and/or indenyl rings (one or
It is multiple) on one or more of rest position be substituted.In certain embodiments, every 4- benzyl ring is in 3' and 5'
Position is replaced by following group: the group can be it is same or different, and selected from can be by the C of halogenation2-C20Alkyl, can be by halogen
The C of change6-C10Aryl, C2-C10Alkenyl, C7-C20Aryl alkyl, C7-C20Alkylaryl, C8-C20Aryl alkenyl.In some transition
In metal complex, at least one or two 4- pheny-indenylzirconium ligands all include R at 2 of the 4- pheny-indenylzirconium ligand3
Group, wherein R3It can be hydrogen atom, halogen atom can be by the C of halogenation1-C10Alkyl, can be by the C of halogenation6-C10Aryl, C2-
C10Alkenyl, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40Aryl alkenyl ,-NR'2,-SR',-OR',-OSiR'3Or-
PR'2Group, wherein R' is following one: halogen atom, C1-C10Alkyl, or C6-C10Aryl.In specific embodiment
In, if any R3It is hydrogen atom, methyl or ethyl, then two benzyl rings are all replaced at 3' and 5' by butyl, institute
State butyl can be it is same or different.In some transition metal complexes, at least one 4- phenyl is at 3' and 5'
Replaced and replaced by OR' group at 4' by tert-butyl, wherein R' is following one: hydrogen atom, halogen atom, C1-C10Alkane
Base, especially methoxyl group, or C6-C10Aryl.
The transition metal complex being particularly useful is the complex compound based on Zr- or Hf.In addition, some above-mentioned transition gold
Belong to complex compound and passes through dialkyl group sila diyl (siladiyl) or diisopropylaminoethyl borine (amidoborane) base bridging.
The especially preferred transition metal complex of the present invention is that the above formula (II) indicates: wherein M1Selected from titanium, zirconium and
Hafnium, especially zirconium or hafnium are more typically zirconium；R1And R2It is same or different, and is following one: hydrogen atom, C1-C10
Alkyl (preferably methyl, ethyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and its different
Structure body), or halogen atom (preferably Cl, Br, F or I).
In the specific embodiment according to formula (II) complex compound, R3Group is same or different, and individually hydrogen
Atom, halogen atom can be by the C of halogenation1-C10Alkyl (preferably C2-C10, preferably C3-C8, preferably methyl, ethyl, butyl, amyl,
Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl or its isomers), it can be by the C of halogenation6-C10Aryl.
In some embodiments, each R3It is same or different, and individually C1-C10Alkyl.In certain embodiments, R3
It is not hydrogen atom, such as, in certain embodiments, each R3It is identical and be fluorine, chlorine or bromine, it can be by the C of halogenation1-C4Alkane
Base, can be by the C of halogenation6-C8Aryl ,-NR'2,-SR',-OR,-OSiR'3Or-PR'2Group, wherein R' is following one: chlorine
Atom, C1-C4Alkyl, or C6-C8Aryl；It is preferred that R3It is identical, and individually C1-C3Alkyl, preferably each R3It is C1-C2(such as-
CH3Or-CH2CH3) group.
In preferred embodiments, in formula (II), R4-R7Group is same or different, and can be hydrogen, halogen
Atom, can be by the C of halogenation1-C10Alkyl (preferably methyl, ethyl, butyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, ten
One alkyl, dodecyl or its isomers), it can be by the C of halogenation6-C10Aryl.In certain embodiments, two or
More adjacent group R5-R7One or more rings, preferably 6 member rings, preferably 4-8 member are formed together with the atom for connecting them
Ring.
In preferred embodiments, the R in formula (II)13It is-SiR "2, wherein R " the group is same or different,
With each be selected from hydrogen or C1-C10Alkyl, preferably C1-C2Alkyl (such as methyl or ethyl) or wherein R13It is C1-C10Two
Alkyl amino borine.
In preferred embodiments, in formula (II), R8And R12It is individually same or different, and individually hydrogen is former
Son, halogen atom can be by the C of halogenation3-C10Alkyl, can be by the C of halogenation6-C10Aryl.
In preferred embodiments, in formula (II), R9And R11It is individually same or different, and being individually can be by halogen
The C of change1-C20Alkyl, can be by the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C20Aryl alkyl, C7-C20Alkylaryl, or
C8-C20Aryl alkenyl.In the specific embodiment according to formula (II), each R9With each R11Selected from primary, secondary or tert-butyl, virtue
Base, isopropyl, fluoro-alkyl, trialkylsilkl or Similar size other groups, preferred tert-butyl, especially just
Butyl, isobutyl group and tert-butyl.
In any embodiment of the present invention, including any formula (especially Formulas I or II, especially formula (II)) is disclosed herein,
Each R10Selected from (XR'n)-, wherein X be atomic weight be 13-79 14-17 race hetero atom and R' be following one: hydrogen atom, halogen
Plain atom, C1-C10Alkyl, or C6-C10Aryl and n are 0,1,2 or 3；It is preferred that R10It is-NR'2,-SR',-OR',-OSiR
'3,-SiR'3, or-PR'2, preferably R10It is-NR'2,-SR',-OR',-OSiR'3, or-PR'2, wherein R10It is-SR' ,-
OR', or-OSiR'3, preferably R10It is-NR'2Or-PR'2Group, preferably R10It is-OR'.It is preferred that each R10Selected from-NH2,-NH
(methyl) ,-NH (ethyl) ,-NH (n-propyl) ,-NH (isopropyl) ,-NH (phenyl) ,-N (methyl)2,-N (methyl) (ethyl) ,-
N (n-propyl) (phenyl),-N (isopropyl) (phenyl),-N (methyl) (phenyl), N (ethyl) (ethyl) ,-N (ethyl) (positive third
Base) ,-N (ethyl) (isopropyl) ,-N (n-propyl) (phenyl), the such as-N (phenyl) (phenyl)；- SH ,-S (methyl) ,-S (second
Base) ,-S (n-propyl) ,-S (isopropyl) ,-S (normal-butyl) ,-S (isobutyl group) ,-S (sec-butyl) ,-S (tert-butyl) ,-S (benzene
Base) etc.；- OH ,-O (methyl) ,-O (ethyl) ,-O (n-propyl) ,-O (isopropyl) ,-O (normal-butyl) ,-O (isobutyl group) ,-O is (secondary
Butyl) ,-O (tert-butyl) ,-O (phenyl) etc.；-OSiH3,-OSiH2(methyl) ,-OSiH (methyl)2,-OSi (methyl)3,-OSiH2
(ethyl) ,-OSiH (ethyl)2,-OSi (ethyl)3,-OSiH2(propyl) ,-OSiH (propyl)2,-OSi (propyl)3,-OSiH2(fourth
Base) ,-OSiH (butyl)2,-OSi (butyl)3,-OSiH (methyl) (ethyl) ,-OSi (methyl) (ethyl)2,-OSiH (methyl)
(propyl) ,-OSi (methyl) (propyl)2,-OSiH (methyl) (butyl) ,-OSi (methyl) (butyl)2,-OSiH (ethyl) (third
Base) ,-OSi (ethyl) (propyl)2,-OSiH (ethyl) (butyl) ,-OSi (ethyl) (butyl)2, etc.-PH2,-PH (methyl) ,-
PH (ethyl) ,-PH (n-propyl) ,-PH (isopropyl) ,-PH (phenyl) ,-P (methyl)2,-P (methyl) (ethyl) ,-P (positive third
Base) (phenyl),-P (isopropyl) (phenyl) ,-P (methyl) (phenyl), P (ethyl) (ethyl),-P (ethyl) (n-propyl) ,-P
(ethyl) (isopropyl) ,-P (n-propyl) (phenyl) ,-P (phenyl) (phenyl), etc.；-SiH3,-SiH2(methyl) ,-SiH (first
Base)2,-Si (methyl)3,-SiH2(ethyl) ,-SiH (ethyl)2,-OSi (ethyl)3,-SiH2(propyl) ,-SiH (propyl)2,-Si
(propyl)3,-SiH2(butyl) ,-SiH (butyl)2,-Si (butyl)3,-SiH (methyl) (ethyl) ,-Si (methyl) (ethyl)2,-
SiH (methyl) (propyl) ,-Si (methyl) (propyl)2,-SiH (methyl) (butyl) ,-Si (methyl) (butyl)2,-OSiH (ethyl)
(propyl) ,-OSi (ethyl) (propyl)2,-OSiH (ethyl) (butyl) ,-OSi (ethyl) (butyl)2Deng.
In any embodiment of the present invention, including any formula (especially Formulas I or II), each R is disclosed herein9With each R11
Selected from primary-, sec- or tert-butyl, aryl, isopropyl, preferably tert-butyl, especially tert-butyl；With at least one R10It is-OH ,-O
(methyl) ,-O (ethyl) ,-O (n-propyl) ,-O (isopropyl) ,-O (normal-butyl) ,-O (isobutyl group) ,-O (sec-butyl) ,-O (uncle
Butyl) ,-O (phenyl), especially-O (methyl).In particular, in the above-described embodiment, each R10Selected from-OH ,-O (methyl) ,-O
(ethyl) ,-O (n-propyl) ,-O (isopropyl) ,-O (normal-butyl) ,-O (isobutyl group) ,-O (sec-butyl) ,-O (tert-butyl) ,-O
(phenyl), especially wherein each R10It is-O (methyl).
In certain embodiments, more specifically, each R1And R2It is same or different, and individually halogen atom,
It is preferred that Cl；Each R3It is same or different, and individually C1-C10Alkyl, preferably methyl；Each R4,R5,R6And R7Be it is identical or
Different, and individually hydrogen atom or C1-C10Alkyl is preferably respectively hydrogen atom；Each R8And R12Individually hydrogen atom；R13Be-
SiR"2Wherein each R " is same or different, and individually hydrogen or C1-C10Alkyl, preferably methyl；Each R9And R11It is
C1-C10Alkyl, especially normal-butyl, isobutyl group and tert-butyl, more particularly tert-butyl；Wherein each R10It is-OH ,-O (first
Base) ,-O (ethyl) ,-O (n-propyl) ,-O (isopropyl) ,-O (normal-butyl) ,-O (isobutyl group) ,-O (sec-butyl) ,-O (tertiary fourth
Base) ,-O (phenyl), especially-O (methyl).
In certain embodiments, it include those according to the transition metal complex of formula (II): wherein each R1And R2It is
Chlorine；Each R3It is methyl；Each R4,R5,R6And R7,R8And R12It is hydrogen；R13It is-Si (CH3)2-；Wherein each R9And R11It is tert-butyl；With
Wherein each R10It is methoxyl group.
Following specific metallocene containing zirconium and their analog containing hafnium is clearly disclosed: racemic-dimethyl
Sila diyl (2- methyl, 4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl sila
Diyl (2- ethyl, 4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl sila diyl
(2- propyl, 4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl sila diyl (2- fourth
Base, 4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl sila diyl (2- methyl, 4-
[bis- (the trifluoromethyl) -4'- methoxyphenyls of 3', 5'-] indenyl)2ZrCl2；Racemic-dimethyl sila diyl (2- ethyl, 4-
[bis- (the trifluoromethyl) -4'- methoxyphenyls of 3', 5'-] indenyl)2ZrCl2；Racemic-dimethyl sila diyl (2- propyl, 4-
[bis- (the trifluoromethyl) -4'- methoxyphenyls of 3', 5'-] indenyl)2ZrCl2；Racemic-dimethyl sila diyl (2- butyl, 4-
[bis- (the trifluoromethyl) -4'- methoxyphenyls of 3', 5'-] indenyl)2ZrCl2；Racemic-dimethyl sila diyl (2- methyl, 4-
[3', 5'- diisopropyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl sila diyl (2- ethyl, 4- [3',
5'- diisopropyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl sila diyl (2- propyl, 4- [3', 5'- bis-
Isopropyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl sila diyl (2- butyl, 4- [3', 5'- diisopropyl
Base -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl sila diyl (2- methyl, 4- [3', 5'- diphenyl -4'-
Methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl sila diyl (2- ethyl, 4- [3', 5'- diphenyl -4'- methoxyl group
Phenyl] indenyl)2ZrCl2；Racemic-dimethyl sila diyl (2- propyl, 4- [3', 5'- diphenyl -4'- methoxyphenyl] indenes
Base)2ZrCl2；Racemic-dimethyl sila diyl (2- butyl, 4- [3', 5'- diphenyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl amino borane (2- methyl, 4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl amino borane (2- ethyl, 4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl amino borane (2- propyl, 4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl amino borane (2- butyl, 4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl amino borane (2- methyl, 4- [bis- (the trifluoromethyl) -4'- methoxyphenyls of 3', 5'-] indenyl)2ZrCl2；Racemic-dimethyl amino borane (2- ethyl, 4- [bis- (the trifluoromethyl) -4'- methoxyphenyls of 3', 5'-] indenyl)2ZrCl2；Racemic-dimethyl amino borane (2- propyl, 4- [bis- (the trifluoromethyl) -4'- methoxyphenyls of 3', 5'-] indenyl)2ZrCl2；Racemic-dimethyl amino borane (2- butyl, 4- [bis- (the trifluoromethyl) -4'- methoxyphenyls of 3', 5'-] indenyl)2ZrCl2；Racemic-dimethyl amino borane (2- methyl, 4- [3', 5'- diisopropyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl amino borane (2- ethyl, 4- [3', 5'- diisopropyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl amino borane (2- propyl, 4- [3', 5'- diisopropyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl amino borane (2- tert-butyl, 4- [3', 5'- diisopropyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl amino borane (2- methyl, 4- [3', 5'- diphenyl -4'- methoxyphenyl] indenyl)2ZrCl2；
Racemic-dimethyl amino borane (2- ethyl, 4- [3', 5'- diphenyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-
Dimethyl amino borane (2- propyl, 4- [3', 5'- diphenyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-dimethyl
Amino borane (2- butyl, 4- [3', 5'- diphenyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl
Borine (2- methyl, 4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl boron
Alkane (2- ethyl, 4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl borine
(2- propyl, 4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl borine (2-
Butyl, 4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl borine (2- first
Base, 4- [bis- (the trifluoromethyl) -4'- methoxyphenyls of 3', 5'-] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl borine (2-
Ethyl, 4- [bis- (the trifluoromethyl) -4'- methoxyphenyls of 3', 5'-] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl borine
(2- propyl, 4- [bis- (the trifluoromethyl) -4'- methoxyphenyls of 3', 5'-] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl boron
Alkane (2- butyl, 4- [bis- (the trifluoromethyl) -4'- methoxyphenyls of 3', 5'-] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl
Borine (2- methyl, 4- [3', 5'- diisopropyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl boron
Alkane (2- ethyl, 4- [3', 5'- diisopropyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl borine
(2- propyl, 4- [3', 5'- diisopropyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl borine (2-
Tert-butyl, 4- [3', 5'- diisopropyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl borine (2-
Methyl, 4- [3', 5'- diphenyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl borine (2- ethyl,
4- [3', 5'- diphenyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl borine (2- propyl, 4-
[3', 5'- diphenyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-diisopropylaminoethyl borine (2- butyl, 4- [3',
5'- diphenyl -4'- methoxyphenyl] indenyl)2ZrCl2；Bis- (trimethyl silyl) amino boranes of racemic-(2- methyl,
4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Bis- (trimethyl silyl) amino boranes of racemic-
(2- ethyl, 4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-is bis- (trimethyl silyl)
Amino borane (2- propyl, 4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Bis- (the trimethyl first of racemic-
Silylation) amino borane (2- butyl, 4- [3', 5'- di-t-butyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-is bis-
(trimethyl silyl) amino borane (2- methyl, 4- [bis- (the trifluoromethyl) -4'- methoxyphenyls of 3', 5'-] indenyl)2ZrCl2；Bis- (trimethyl silyl) amino boranes of racemic-(2- ethyl, 4- [bis- (the trifluoromethyl) -4'- methoxies of 3', 5'-
Base phenyl] indenyl)2ZrCl2；Bis- (trimethyl silyl) amino boranes of racemic-(2- propyl, the 4- [bis- (fluoroforms of 3', 5'-
Base) -4'- methoxyphenyl] indenyl)2ZrCl2；Bis- (trimethyl silyl) amino boranes of racemic-(2- butyl, 4- [3',
5'- is bis--trifluoromethyl -4'- methoxyphenyl] indenyl)2ZrCl2；Bis- (trimethyl silyl) amino borane (2- of racemic-
Methyl, 4- [3', 5'- diisopropyl -4'- methoxyphenyl] indenyl)2ZrCl2；Bis- (trimethyl silyl) amino of racemic-
Borine (2- ethyl, 4- [3', 5'- diisopropyl -4'- methoxyphenyl] indenyl)2ZrCl2；Bis- (the trimethyl silyls of racemic-
Base) amino borane (2- propyl, 4- [3', 5'- diisopropyl -4'- methoxyphenyl] indenyl)2ZrCl2；Bis- (the front threes of racemic-
Base silicyl) amino borane (2- butyl, 4- [3', 5'- diisopropyl -4'- methoxyphenyl] indenyl)2ZrCl2；Racemic-
Bis- (trimethyl silyl) amino boranes (2- methyl, 4- [3', 5'- diphenyl -4'- methoxyphenyl] indenyl)2ZrCl2；Outside
Bis- (trimethyl silyl) amino boranes of racemization-(2- ethyl, 4- [3', 5'- diphenyl -4'- methoxyphenyl] indenyl)2ZrCl2；Bis- (trimethyl silyl) amino boranes of racemic-(2- propyl, 4- [3', 5'- diphenyl -4'- methoxyphenyl]
Indenyl)2ZrCl2；Bis- (trimethyl silyl) amino boranes of racemic-(2- butyl, 4- [3', 5'- diphenyl -4'- methoxyl group
Phenyl] indenyl)2ZrCl2。
Although enumerating the above 4'- methoxyl group (that is, O (methyl)) isoreagent, following isoreagent :-O is disclosed with will also recognize that
(ethyl) ,-O (n-propyl) ,-O (isopropyl) ,-O (normal-butyl) ,-O (isobutyl group) ,-O (sec-butyl) ,-O (tert-butyl) ,-O
(phenyl), etc.；-OSiH3,-OSiH2(methyl) ,-OSiH (methyl)2,-OSi (methyl)3,-OSiH2(ethyl) ,-OSiH (second
Base)2,-OSi (ethyl)3,-OSiH2(propyl) ,-OSiH (propyl)2,-OSi (propyl)3,-OSiH2(butyl) ,-OSiH (fourth
Base)2,-OSi (butyl)3,-OSiH (methyl) (ethyl) ,-OSi (methyl) (ethyl)2,-OSiH (methyl) (propyl) ,-OSi (first
Base) (propyl)2,-OSiH (methyl) (butyl) ,-OSi (methyl) (butyl)2,-OSiH (ethyl) (propyl) ,-OSi (ethyl) (third
Base)2,-OSiH (ethyl) (butyl) ,-OSi (ethyl) (butyl)2.Equally, although dichloro substituted compound (- ZrCl2And-
HfCl2) listed above, but wherein each chlorine replaces with compound (such as-the Zr ((CH of methyl3)2And-Hf
(CH3)2)) will also recognize that it is open.Equally, although dichloro substituted compound (- ZrCl is enumerated above2And-HfCl2), still
Wherein each chlorine replaces with compound (such as-the Zr ((CH of methyl3)2And-Hf (CH3)2)) will also recognize that it is open.And to the greatest extent
It manages above-mentioned complex compound to be substituted at 2, indenes ring, but is wherein also expected in 1,3,4,5, the 6, and/or 7 generation substitution of indenes ring.
In another embodiment of the present invention, indenyl rings 2,4 and 6 are substituted, such as, in Formulas I, R3,R14And R6
It is not the H and R in formula (II)3And R6It is not H.
A kind of catalyst compounds are used in method preferred embodiment according to the present invention any one of disclosed in the present application,
Such as the catalyst compounds do not have difference.For purposes of the invention, if a kind of metallocene catalyst compound and other cyclopentadienyl
Metal catalyst compounds differ at least one atom, then it is assumed that they are different.Such as " double indenyl ZrCl2" it is different from (indenyl)
(2- methylindenyl) ZrCl2", it is different from " (indenyl) (2- methylindenyl) HfCl again2".Only because those of isomers difference is urged
Agent compound is considered the same for the purpose of the present invention, such as racemic-dimetylsilyl is bis- (2- methyl 4- phenyl)
Hf(Me)2It is considered being identical to bis- (the 2- methyl 4- phenyl) Hf (Me) of meso-dimetylsilyl2。
In some embodiments, two or more different catalyst compounds are present in catalysis used in this application
In agent system.In some embodiments, two or more different catalyst compounds are contained therein generation the application
The reaction zone of the method.One is used for instead as hybrid catalyst system based on the catalyst of transistion metal compound when two kinds
When answering device, preferably selecting two kinds of transistion metal compounds makes the two be compatible.Simple screening method is such as to pass through1H or13C NMR is that can be used for determining which transistion metal compound is compatible known to those of ordinary skill in the art.It is preferred that making
It is used for the transistion metal compound with identical activator, however, two different activators, such as non-coordinating anion activator
And aikyiaiurnirsoxan beta can be used in combination.If one or more transistion metal compounds include R1Or R2Ligand (its be not hydrogen-based,
Alkyl or substituted alkyl), then before adding the non-coordinating anion activator, which should be with transition gold
Belong to compound contact.
Two kinds of transistion metal compounds (pre-catalyst) can be used by any ratio.It is preferred that (A) transistion metal compound
Opposite (B) transistion metal compound molar ratio belongs to (A:B) range 1:1000 to 1000:1, be alternatively 1:100 extremely
500:1 is alternatively 1:10 to 200:1, is alternatively 1:1 to 100:1, and can also be with 1:1 to 75:1, and can be replaced
It is 5:1 to 50:1 with changing.The selection of the specific ratios depends on the selection of exact pre-catalyst, activation method and required
Final products.In certain embodiments, when using two kinds of pre-catalysts, if the two is all living with identical activator
Change, useful mole percent, is based on the pre-catalyst molecular weight, is 10-99.9%A with respect to 0.1-90%B, is alternatively
25-99%A is alternatively 50-99%A with respect to 1-25%B with respect to 0.5-50%B, and can also be with 75-99%A with respect to 1-
10%B.
The method for preparing catalyst compounds
All air-sensitive synthesis carry out in nitrogen purging drying box.All solvents are obtained from commercial source.The bromo- 2- of 4-
Methyl indenes, 4- chloro-2-methyl-indenes and three (perfluorophenyl) borines in toluene are obtained from commercial source.Alkyl aluminum can be pressed
Hydrocarbon solution is obtained from commercial source.Methylaluminoxane (" MAO ") can be derived from by solution of the 30wt% in toluene
Albemarle.Racemic dimethyl sila diyl (2- methyl 4-phenyl indenyl)2ZrCl2Also it is obtained from commercial source.
In general, by schematically reaction process synthesizes such metallocene shown in attached drawing 1, wherein being (i) to pass through alkyl
Metal salt (such as n-BuLi) deprotonation of anion forms indenes salt (indenide)；It (ii) is before indenes salt and suitable bridging
Body (such as Me2SiCl2) reaction；It (iii) is that above-mentioned product is reacted with AgOTf；It (iv) is above-mentioned triflated conjunction object and another
The indenes reactant salt of monovalent；It (v) is that two anion are formed by alkyl anion (such as n-BuLi) deprotonation twice；(vi)
It is two anion and metal halide (such as ZrCl4) reaction.It is recrystallized by thick solid and obtains final products.
Activator
It, can be with any way known to document by by they and activator combination after the complex compound has synthesized
Catalyst system is formed, including is used for slurry or gas-phase polymerization by loading them.The catalyst system can also be added or
Person is in polymerisation in solution or bulk polymerization generates (in monomer).The catalyst system generally comprises transition metal as described above
Complex compound and activator such as aikyiaiurnirsoxan beta or non-coordinating anion activator.Aluminoxanes solution can be used in implementing in activation
Including methylaluminoxane, referred to as MAO, and it is modified MAO, in this application referred to as MMAO, it includes some senior alkyls to change
It is apt to the solubility.Particularly useful MAO can be bought from Albemarle, be usually 10wt% toluene solution.For the present invention
The activator that catalyst system is preferably applied is selected from aikyiaiurnirsoxan beta, such as methylaluminoxane, modified methylaluminoxane, ethyl alumina
Alkane, isobutyl aluminium alkoxide etc..
When using aikyiaiurnirsoxan beta or modified alumoxane, the complex compound-is opposite-and activator molar ratio is about 1:3000-
10:1；It is alternatively 1:2000-10:1；It is alternatively 1:1000-10:1；It is alternatively 1:500-1:1；Alternatively
It is 1:300-1:1；It is alternatively 1:200-1:1；It is alternatively 1:100-1:1；It is alternatively 1:50-1:1；Alternatively
Ground is 1:10-1:1.When the activator is aikyiaiurnirsoxan beta (modified or unmodified), some embodiments select the maximum amount
Activator, opposite catalyst precarsor (every metal catalytic site) the 5000- times of molar excess.It is preferred that activator-phase of minimum flow
P- complex compound ratio is 1:1 molar ratio.
Non-coordinating anion can also be used to be activated, referred to as NCA, the type is disclosed in EP 277 003A1 and EP
In 277 004A1.NCA can be added in the form that ion pair uses, such as, [DMAH]+[NCA]-, the wherein N, N- dimethyl
Puratized agricultural spray (DMAH) cation is reacted with leaving group alkaline on the transition metal complex to form transition metal complex
Cation and [NCA]-The cation can be in the precursor, be alternatively, trityl (trityl).It can replace
It is that the transition metal complex can be with neutral NCA precursors reaction, such as B (C with changing6F5)3, from the complex compound extract yin from
Subbase group is to form activated atom group.Useful activator includes N, N- dimethyl puratized agricultural spray four (pentafluorophenyl group) borate (i.e.,
[PhNMe2H]B(C6F5)4) and N, N- dimethyl puratized agricultural spray four (seven fluoronaphthalene bases) borate, wherein Ph is phenyl and Me is first
Base.
Other preferred activator for the application includes US 7,247,687 on column 169, row 50 to column 174, row 43,
Especially column 172, row 24 to column 173,53 those disclosed of row.
In embodiment of the present invention is disclosed herein, which is expressed as following formula (1):
(Z)d+(Ad-) (1)
Wherein Z is (L-H) or reducible lewis acid, and L is neutral lewis base, and H is hydrogen and (L-H)+It is
Bronsted acid；Ad-It is that non-coordination anion has charge d-；It is 1-3 integer with d.
When Z is that (L-H) makes the cationic components be (L-H)d+When, which may include Bronsted acid ratio
Such as protonated lewis base, proton can occur from the catalyst precarsor by the component part of such as alkyl or aryl etc
Change, generates the transition metal material or the activating cations (L-H) of cationicd+It is Bronsted acid, matter can be donated
Son to the catalyst precarsor generates transition-metal cation, including ammonium, oxygen, Phosphonium, silicyl, and its mixture, or
Methylamine, aniline, dimethylamine, diethylamine, methylphenylamine, diphenylamines, trimethylamine, triethylamine, N, N- dimethylaniline, methyl biphenyl
Amine, pyridine, to bromo N, N- dimethylaniline, to nitro-N, the ammonium of N- dimethylaniline, triethyl phosphine, triphenylphosphine and hexichol
Lin Phosphonium, the oxygen of ether, such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, thioether, such as diethyl sulfide
The sulfonium and its mixture of ether and thiophane.
When Z is reducible lewis acid, it is represented by formula: (Ar3C+), wherein Ar is that aryl or hetero atom replace
Aryl, or C1-C40Alkyl, reducible lewis acid can be expressed as formula: (Ph3C+), wherein Ph is phenyl or hetero atom
Substituted-phenyl, and/or C1-C40Alkyl.In embodiments, which is triphenyl carbon cation.
The anionic component Ad-Embodiment includes having formula [Mk+Qn]d-Those, wherein k is 1,2 or 3；N is 1,2,
3,4,5 or 6, either 3,4,5 or 6；N-k=d；M is selected from 13 race's element of the periodic table of elements, either boron or aluminium, and Q
It is independently hydrogen-based, bridging or non-bridging dialkyl amido, halogen, alkoxy, aryloxy group, hydrocarbyl group, the Q at most have
There are 20 carbon atoms on condition that at most in one case Q is halogen, and two Q can form cyclic structure.Each Q can be
With 1-20 carbon atom fluoro alkyl, or each Q fluorinated aryl, or five fluoro aryl of each Q.Suitable Ad- component example
It is included in two boron compounds disclosed in parent U.S.Patent No US5,447,895, is all hereby incorporated by reference.
In embodiments, it is indicated in any NCA in above-mentioned formula 1, the anionic component Ad- is expressed as formula [M*k*+Q*n*]
Wherein k* is 1,2, or 3 to d*-；N* is 1,2,3,4,5, either 6 (or 1,2,3, or 4)；N*-k*=d*；M* is boron；With
Q* is independently selected from hydrogen-based, bridging or non-bridging dialkyl amido, halogen, alkoxy, aryloxy group, hydrocarbyl group, the Q*
At most there are 20 carbon atoms, on condition that at most in one case Q* is halogen.
It include that alkene (such as propylene) contacts above-mentioned catalyst complex and NCA the invention further relates to olefin polymerization method
Activator is indicated by formula (2):
RnM**(ArNHal)4-n (2)
Wherein R is single anion ligand；M** is the 13rd race's metal or metalloid；ArNHal is the nitrogenous aromatic ring of halogenation,
Polycyclic aromatic ring, either aromatic ring assembly (assembly) two of them or more rings (or fused ring system) directly that
This is connected or connects together；It is 0,1,2, or 3 with n.General N CA include 2 anion of formula also include suitable cation its
The ionic catalyst complex compound for not interfering substantially the transistion metal compound to be formed, or the cation is Z as described aboved +。
In embodiments, in any NCA for indicating anion comprising above-mentioned formula 2, R is selected from C1-C30Hydrocarbyl group.In
In embodiment, C1-C30Hydrocarbyl group can be replaced with one or more following groups: C1-C20Hydrocarbyl group, halogen, alkyl
Substituted organic quasi-metal, dialkyl amide, alkoxy, aryloxy group, alkylthio group (alkysulfido), artyl sulfo
(arylsulfido), alkyl phosphorus base (alkylphosphido), aryl phosphorus base (arylphosphide), aryl phosphorus base
(phosphide), or other anion substituent；It is fluorine-based；Large volume hydrocarbon oxide, if large volume means C4-C20Hydrocarbon
Base；--SRa,--NRa2, and -- PRa2, wherein each Ra is independently the C of unit price4-C20It is greater than or equal to comprising molecular volume
The alkyl or C of isopropyl substituents molecular volume4-C20Molecular volume is greater than or equal to the hydrocarbon of isopropyl substituents molecular volume
The organic quasi-metal that base replaces.
In embodiments, in any NCA containing anion shown in above-mentioned formula 2, NCA also includes cation, is contained
Formula (Ar3C+) shown in reducible lewis acid, wherein Ar is aryl or by a hetero atom, and/or C1-C40Alkyl replaces
Aryl or reducible lewis acid be formula (Ph3C+) shown in, wherein Ph be phenyl or by a hetero atom, and/or
C1-C40The phenyl that alkyl replaces.
In embodiments, in any NCA for indicating anion comprising above-mentioned formula 2, NCA also includes formula (L-H)d+It is shown
Cation, wherein L is neutral Lewis base；H is hydrogen；It (L-H) is Bronsted acid；D is 1,2 or 3, preferably (L-H)d+It is
Selected from ammonium, Yang, Phosphonium, silicyl and its mixture Bronsted acid.
The other example of useful activator includes those disclosed in US 7,297,653 and US 7,799,879.
In embodiments, another activator used in this application include cation oxidant salt and noncoordinating phase
The anion of appearance, as shown in formula (3):
(OXe+)d(Ad-)e (3)
Wherein, OXe+It is the cation oxidant with e+ charge；E is 1,2 or 3；D is 1,2 or 3；And Ad-It is band d- electricity
The non-coordinating anion (as described above) of lotus.The example of cation oxidant include: ferrocene salt, alkyl replace ferrocene,
Ag+Or Pb+2.The preferred embodiment of Ad- includes four (pentafluorophenyl group) borates.
The activator useful to the application catalyst system includes: trimethyl ammonium four (perfluoronapthyl) borate, N, N- bis-
Methyl puratized agricultural spray four (perfluoronapthyl) borate, N, N- diethyl puratized agricultural spray four (perfluoronapthyl) borate, four (perfluor of triphenylcarbenium
Naphthalene) borate, trimethyl ammonium four (perfluorinated biphenyl) borate, N, N- dimethyl puratized agricultural spray four (perfluorinated biphenyl) borate,
Triphenylcarbenium four (perfluorinated biphenyl) borate, and the type are disclosed in United States Patent (USP) US7,297,653, and a full piece draws
Enter the application as reference.
Suitable activator further includes N, N- dimethyl puratized agricultural spray four (perfluoronapthyl) borate, N, N- dimethyl puratized agricultural spray four
(perfluorinated biphenyl) borate, N, N- dimethyl puratized agricultural spray four (3,5- bis- (trifluoromethyl) phenyl) borate, triphenylcarbenium four
(perfluorophenyl) borate, triphenylcarbenium four (perfluorinated biphenyl) borate, (3,5- bis- (trifluoromethyls) of triphenylcarbenium four
Phenyl) borate, triphenylcarbenium four (perfluorophenyl) borate, [Ph3C+][B(C6F5)4 -], [Me3NH+][B(C6F5)4 -]；
1- (4- (three (pentafluorophenyl group) borates) -2,3,5,6- tetrafluoro phenyl) pyrrolidines；With four (pentafluorophenyl group) borates；4-
(three (pentafluorophenyl group) borates) -2,3,5,6- ptfe pyridine.
In embodiments, which includes triaryl carbon salt (such as triphenylcarbenium tetraphenyl borate salts, triphen
Base carbon four (pentafluorophenyl group) borate, triphenylcarbenium four-(2,3,4,6- tetrafluoro phenyl) borate, triphenylcarbenium four
(perfluoronapthyl) borate, triphenylcarbenium four (perfluorinated biphenyl) borate, (3,5- bis- (trifluoromethyls) of triphenylcarbenium four
Phenyl) borate).
In embodiments, two kinds of NCA activators can be used in polymerization, the first NCA activator and the 2nd NCA activator
Molar ratio can be any ratio.In some embodiments, the molar ratio of the first NCA activator and the 2nd NCA activator
Rate is 0.01:1-10,000:1 perhaps 0.1:1-1000:1 or 1:1-100:1.
In the present embodiment, the NCA activator relative catalyst ratio 1:1 molar ratio or 0.1:1 to 100:
1 or 0.5:1 to 200:1 or 1:1 to 500:1 or 1:1 to 1000:1.In embodiments, the NCA activator relative catalytic
Agent ratio is 0.5:1 to 10:1, or 1:1 to 5:1.
In embodiments, catalyst compounds can in conjunction with combined aikyiaiurnirsoxan beta and NCA (see, e.g. US 5,153,
157,5 US, 453,410, EP 0 573 120B1, WO 94/07928 and WO 95/14044, all these documents introduce this Shen
It please be as reference).
In a preferred embodiment of the invention, if using NCA (such as ion or neutrality stoichiometry activation
Agent), then the complex compound relative activation agent molar ratio is usually 1:10 to 1:1；1:10 to 10:1；1:10 to 2:1；1:10 to 3:
1；1:10 to 5:1；1:2 to 1.2:1；1:2 to 10:1；1:2 to 2:1；1:2 to 3:1；1:2 to 5:1；1:3 to 1.2:1；1:3 is extremely
10:1；1:3 to 2:1；1:3 to 3:1；1:3 to 5:1；1:5 to 1:1；1:5 to 10:1；1:5 to 2:1；1:5 to 3:1；1:5 to 5:
1；1:1 to 1:1.2.
Or conactivator, such as the 1,2nd, or 13 race's organic metal substances (such as three n-octyl of alkyl aluminum compound
Aluminium), it can be used in the application catalyst system.The complex compound is 1:100 to 100:1 with respect to conactivator molar ratio；1:
75 to 75:1；1:50 to 50:1；1:25 to 25:1；1:15 to 15:1；1:10 to 10:1；1:5 to 5:1；1:2 to 2:1；1:100
To 1:1；1:75 to 1:1；1:50 to 1:1；1:25 to 1:1；1:15 to 1:1；1:10 to 1:1；1:5 to 1:1；1:2 to 1:1；1:
10 to 2:1.
Non-essential carrier material
In the application embodiment, catalyst system may include inert support material.It is preferred that the material loaded is porous
Carrier material, for example, talcum and inorganic oxide.Other carrier materials include zeolite, clay, organic clay or any other
Or mixtures thereof the carrier material etc. of organic or inorganic,.
It is preferred that carrier material is the inorganic oxide of form fine crushing.In this application for metallocene catalyst system
Suitable inorganic oxide material includes the 2nd, 4,13 and 14 family metal oxides, such as silica, aluminium oxide and its mixing
Object.Can be used alone or with silica or aluminium oxide associated with other inorganic oxides be magnesia, titanium dioxide, zirconium oxide
And analog.It is however possible to use other suitable carrier material, such as the functionalized polyolefin of subtle separation, such as carefully
Broken polyethylene.Particularly useful carrier material includes magnesia, titanium dioxide, zirconium oxide, montmorillonite, phyllosilicate, cunning
Stone, clay and or the like.Furthermore, it is possible to using the combination of these carrier materials, such as silica-chromium, silica-oxygen
Change aluminium, silica-titania etc..Preferred carrier material includes Al2O3,ZrO2,SiO2And their combination, it is more excellent
Select SiO2,Al2O3Or SiO2/Al2O3。
Preferred carrier materials, most preferably inorganic oxide have in about 10- about 700m2Surface area in/g range, about
Pore volume within the scope of 0.1- about 4.0cc/g, the average particle size in about 500 μ m of about 5-.More preferable carrier material has
About 50- about 500m2Pore volume within the scope of surface area in/g range, about 0.5- about 3.5cc/g, about 200 μ m of about 10-
Interior average particle size.Most preferably the major part of carrier material has about 100- about 400m2Surface area in/g range, about 0.8-
Average particle size in about 100 μ m of pore volume within the scope of about 3.0cc/g, about 5-.Useful carrier material in the present invention
Average pore size existIn range, preferably 50- is aboutMost preferably 75- is aboutOne
In a little embodiments, carrier material is a high surface area, amorphous silica (surface area=300m2/g；Pore volume
=1.65cm3/g).Preferred silica is with trade name DAVISON 952 or DAVISON 955 by Davison Chemical
Division, W.R.Grace and Company are sold.In other embodiments, using DAVISON 948.
Carrier material should be dry, that is, the water essentially free of absorption.The drying of carrier material can about 100 DEG C-about
1000 DEG C, the heating of preferably at least about 600 DEG C of temperature or calcine to carry out.When carrier material is silica, added
Heat is at least 200 DEG C, preferably from about 200 DEG C-about 850 DEG C, most preferably at least at about 600 DEG C；Heating time about 1 minute-about 100 is small
When, or about 12 hours-about 72 hours, or about 24 hours-about 60 hours.The carrier material of calcining must have at least some reactions
Hydroxyl (OH) group of property is to produce the catalyst system of load of the invention.The carrier material of calcining then at least in polymerize
Catalyst contact, polymerization catalyst include at least one metallocene compound and activator.
Carrier material has reactive surfaces group, generally hydroxyl, forms slurry in nonpolar solvent, obtains
Slurry is contacted with the solution of metallocene compound and activator.In some embodiments, the slurry of carrier material first with work
Agent contacts about 0.5 hour-about 24 hours or about 2 hours-about 16 hours or about 4 hours-about 8 hours.Then make metallocene
The solution of compound is contacted with isolated carrier/activator.In some embodiments, the catalyst system of load is given birth in situ
At.In an interchangeable embodiment, the slurry of carrier material contacted first with catalyst about 0.5 hour-about 24 hours,
Or about 2 hours-about 16 hours or about 4 hours-about 8 hours.The slurry of the metallocene compound of load is then and activator solution
Contact.
The mixture of metallocene, activator and carrier is heated to about 0 DEG C-about 70 DEG C, it is preferably from about 23 DEG C-about 60 DEG C, excellent
Select room temperature.Typical time of contact from about 0.5 hour to about 24 hour, or from about 2 hours to about 16 hour, or from about 4 hours
To about 8 hours.
Suitable nonpolar solvent is all reactants used in this application, that is, activator and metallocene compound, at least
Part is solvable wherein, and in the substance that reaction temperature is liquid.Preferred nonpolar solvent is alkane, for example, isopentane,
Hexane, normal heptane, octane, nonane and decane, although many other materials, including cycloalkane, such as hexamethylene can also be used
Alkane, aromatic hydrocarbons, such as benzene, toluene and ethylbenzene.
Polymerization
In the embodiment of the application, the present invention relates to polymerization, wherein monomer (such as propylene) and optionally
Comonomer contacted with the catalyst system as described above comprising activator and at least one metallocene compound.Catalyst
Closing object can be merged with activator with random order, and can be merged before contacting monomer.
Useful monomer includes substituted or unsubstituted C herein2-C40Alpha-olefin, preferably C2-C20Alpha-olefin, preferably C2-C12
Alpha-olefin, optimal ethylene, propylene, butylene, amylene, hexene, heptene, octene, nonene, decene, endecatylene, dodecylene and its
Isomers.In a preferred embodiment of the present invention, monomer includes propylene and optional comonomer, including it is below a kind of or
It is a variety of: ethylene or C4-C40Alkene, preferably C4-C20Alkene or preferred C6-C12Alkene.C4-C40Olefinic monomer can be straight chain,
Branch is cricoid.C4-C40Cycloolefin can be (strained) or non-by tension,
It and can optionally include hetero atom and/or one or more functional groups.In another preferred embodiment, monomer includes second
Alkene and comonomer optionally, comonomer includes one or more C3-C40Alkene, preferably C4-C20Alkene, or preferably
C6-C12Alkene.C3-C40Olefinic monomer can be straight chain, branch or cricoid.C3-C40Cycloolefin can be by tension or non-
It by tension, monocycle or polycyclic, and can optionally include hetero atom and/or one or more functional groups.
Exemplary C2-C40The example of olefinic monomer and optional comonomer include ethylene, propylene, butylene, amylene, oneself
Alkene, heptene, octene, nonene, decene, endecatylene, dodecylene, norbornene, norbornadiene, bicyclopentadiene, ring penta
Alkene, cycloheptene, cyclo-octene, cyclo-octadiene, cyclododecene, 7- oxanorbornene, 7- oxanorbornadiene, what is replaced spreads out
Biology, isomers, preferably hexene, heptene, octene, nonene, decene, dodecylene, cyclo-octene, 1,5- cyclo-octadiene, 1- hydroxyl
Base -4- cyclo-octene, 1- acetoxyl group -4- cyclo-octene, 5- methyl cyclopentene, cyclopentene, bicyclopentadiene, norbornene, drop ice
Piece diene and their own homologue and derivative, preferably norbornene, norbornadiene and bicyclopentadiene.
In preferred embodiments, in the polymer prepared herein, the total weight based on composition exists a kind of or more
Kind diene, is at most 10wt%, preferably 0.00001-1.0wt%, preferably 0.002-0.5wt%, even more preferably 0.003-
0.2wt%.In some embodiments, 500ppm perhaps less diene preferably 400ppm or less is added in polymerization,
Or preferably 300ppm or less.In other embodiments, at least diene of 50ppm is added into polymerization, or
100ppm or more or 150ppm or more.
Preferred diolefinic monomer useful in the present invention includes any hydrocarbon structure, preferably C4-C30, there are at least two
Unsaturated bond, wherein at least two unsaturated bonds easily pass through stereospecific or non-cubic special catalyst and introduce polymerization
In object.Further preferred diolefinic monomer is selected from α, ω-diene monomer (that is, two-vinyl monomers).It is further preferred that alkadienes
Monomer is linear di-vinyl monomers, most preferably containing those of 4-30 carbon atom.The example of preferred diene includes fourth two
Alkene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadinene, 11 carbon diene, 12 carbon diene, 13 carbon two
Alkene, 14 carbon diene, pentadecane diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon diene, 20 carbon two
Alkene, 21 carbon diene, 22 carbon diene, two oleatridecadienes, tetracosadiene, two pentadecane diene, 26 carbon
Diene, heptacosadiene, 28 carbon diene, 29 carbon diene, 30 carbon diene, particularly preferred diene include 1,6-
Heptadiene, 1,7- octadiene, 1,8- nonadiene, 1,9- decadinene, 11 carbon diene of 1,10-, 12 carbon diene of 1,11-, 1,12-
Oleatridecadiene, 14 carbon diene of 1,13- and low molecular weight polybutadiene (Mw is less than 1000g/mol).It is preferred that cyclic diene packet
Include cyclopentadiene, vinyl norbornene, norbornadiene, ethylidene norbornene, divinylbenzene, bicyclopentadiene or
Higher ring containing alkadienes is with or without substituent group on each ring site.
In some embodiments, when butylene is comonomer, butylene source can be the butene stream of mixing, include butylene
A variety of isomers.Think in polymerization it is preferable to use be 1- butene monomers.Using such mixed butene stream by band
Carry out economic benefit, because these mixed flows are often the waste stream of refining process, for example, C4Raffinate stream, and therefore than pure 1- fourth
Alkene is much cheap.
Polymerization of the invention can carry out in any manner known in the art.It can be used any known in the art outstanding
Floating polymerization, homogeneous polymerization, bulk polymerization, polymerisation in solution, slurry polymerization or gas phase polymerization process.The method can interval, half
Form intermittently or serially carries out.Homogeneous polymerization method and slurry phase polymerisation process are preferred.(homogeneous polymerization method be defined as to
The method that the product of few 90wt% dissolves in reaction medium.) ontology homogeneous polymerization method is particularly preferred.(bulk polymerization side
Method is defined as monomer concentration and accounts for all 70 volume % or higher for being added to reactor content.) alternatively, not deposited in reaction medium
Or be added without solvent or diluent and (in addition to the micro carrier as catalyst system or other additives, deposited in monomer
General quantity；For example, the propane in propylene).In another embodiment, polymerization is slurry process.It is as used herein
Term " slurry phase polymerisation process " refers in polymerization, and using the catalyst of load, monomer gathers on the catalyst granules of load
It closes.The polymer product at least 95wt% generated from the catalyst of load is the solid particle of granular form (insoluble in diluent
In).
Diluent/solvent suitable for polymerization includes noncoordinating, inert liquid.Example includes the hydrocarbon of straight chain and branch,
Such as iso-butane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane and its mixture；Cricoid and rouge
Ring race hydrocarbon, such as hexamethylene, cycloheptane, hexahydrotoluene, methylcycloheptane and its mixture, such as can find on the market
(IsoparTM)；Full halogenated hydrocarbon, such as perfluoro C4-10Alkane, chlorobenzene and aromatics and alkyl-substituted aromatic compounds, example
Such as benzene, toluene, mesitylene and dimethylbenzene.Suitable solvent further includes liquefied olefines, can be used as monomer or comonomer,
Including ethylene, propylene, 1- butylene, 1- hexene, 1- amylene, 3- Methyl-1-pentene, 4-methyl-1-pentene, 1- octene, 1- decene
And its mixture.In preferred embodiments, use aliphatic hydrocarbon solvent as solvent, for example, iso-butane, butane, pentane,
Or mixtures thereof isopentane, hexane, isohexane, heptane, octane, 12 carbon alkane；Cricoid and clicyclic hydrocarbon, such as hexamethylene,
Cycloheptane, hexahydrotoluene, methylcycloheptane and its mixture.In another embodiment, solvent is not aromatics, preferably
Based on the weight of solvent, existing arsol is less than 1wt%, preferably smaller than 0.5wt% in a solvent, preferably smaller than
0wt%.
In preferred embodiments, monomer and comonomer on the basis of feed stream total volume, for polymerization
Input concentration is that perhaps less preferably 40vol% is perhaps less or preferably 20vol% or less for 60vol% solvent.It is preferred that
Polymerization is carried out with bulk polymerization.
Preferred polymeric can be carried out in the case where being suitable for obtaining required polyvinyl any temperature and/or pressure.Typically
Temperature and/or pressure include temperature range from about 0 DEG C to about 300 DEG C, and preferably from about 20 DEG C to about 200 DEG C, preferably from about 35 DEG C to about
150 DEG C, preferably from about 40 DEG C to about 120 DEG C, preferably from about 45 DEG C to about 80 DEG C；Pressure limit is from about 0.35MPa to about
10MPa, preferably from about 0.45MPa are to about 6MPa, or preferably from about 0.5MPa to about 4MPa.
In typical polymerization, the progress time of reaction at most 300 minutes, preferably from about 5 minutes to about 250 minutes or excellent
Choosing is from about 10 minutes to 120 minutes.
In some embodiments, the hydrogen partial pressure being present in polymer reactor is (0.007 from 0.001 to 50psig
To 345kPa), preferably (0.07 to 172kPa) or 0.1 to 10psig (0.7 to 70kPa) from 0.01 to 25psig.
In this alternatively embodiment, the activity of catalyst is at least 50g/mmol/hr, preferably 500g/mmol/hr
Or higher, preferably 5000g/mmol/hr or higher, preferably 50000g/mmol/hr or higher.In a replaceable embodiment
In, the weight of the polymer based on generation and the monomer into reaction zone, the conversion ratio of olefinic monomer is at least 10%, preferably
20% or more, preferably 30% or more, preferably 50% or more, preferably 80% or more.In certain embodiments, should
Catalyst activity is 150,000 to about 320,000g/mmol/hour, and can especially generate following polypropylene: being had
Tm be 158 DEG C -162 DEG C, for example, 158.5 DEG C, 159.0 DEG C, 159.5 DEG C, 160.0 DEG C, 160.5 DEG C, 161.0 DEG C, 161.5
DEG C, or 162.0 DEG C).
In preferred embodiments, the polymer is generated for this method almost without aikyiaiurnirsoxan beta.It is preferred that aikyiaiurnirsoxan beta content
Zero mol%, or the aluminium of the aikyiaiurnirsoxan beta are less than 500:1, preferably smaller than 300:1 with respect to the molar ratio of transition metal, preferably small
In 100:1, preferably smaller than 1:1.
In preferred embodiments, scavenger is not used during producing ethene polymers or hardly uses.
It is preferred that scavenger (such as trialkylaluminium) exists with 0mol%, alternatively, scavenger is with scavenger metal phase to transition metal mole ratio
Amount less than 100:1, preferably smaller than 50:1, preferably smaller than 15:1, preferably smaller than 10:1 exists.
In preferred embodiments, polymerize: 1) 0-300 DEG C of temperature (preferably 25-150 DEG C, preferably 40-120 DEG C, it is excellent
Select 45-80 DEG C) it carries out；2) in pressure from atmospheric pressure to 10MPa (preferably 0.35-10MPa, preferably 0.45-6MPa, preferably
0.5-4MPa) carry out；3) (such as iso-butane, butane, pentane, isopentane, hexane, isohexane, heptane, pungent in aliphatic hydrocarbon solvent
Alkane, dodecane and its mixture；Cyclic hydrocarbon and clicyclic hydrocarbon, for example, hexamethylene, cycloheptane, hexahydrotoluene, methylcycloheptane and
Its mixture；It is preferred that solvent-based weight, existing amount is less than 1wt%, preferably smaller than 0.5wt% to aromatic hydrocarbons in a solvent, excellent
Be selected as 0wt%) in carry out；4) productivity of catalyst compounds at least 80,000g/mmol/hr (preferably at least 150,
000g/mmol/hr, preferably at least 200,000g/mmol/hr, preferably at least 250,000g/mmol/hr, preferably at least 300,
000g/mmol/hr).In preferred embodiments, the catalyst system of polymerization includes at most a kind of catalyst compounds."
Conversion zone " is also referred to as " polymeric area ", it is that polymerization place occurs in container, for example, batch reactor.When serial or parallel connection uses
When multiple reactors, each reactor is considered as independent polymeric area.For in batch reactor and flow reactor into
Capable multi-step polymerization, every polymer grade are considered as an individual polymeric area.In an embodiment according to the present invention, gather
It closes and occurs in a reaction zone.In preferred embodiments, it is aggregated in a reaction zone and carries out.Room temperature is 23 DEG C, unless
It is otherwise noted.
As needed, other additives can also use in polymerization, such as one or more scavengers, promotor, modification
Agent, chain-transferring agent (such as diethyl zinc), reducing agent, oxidant, hydrogen, alkyl aluminum or silane.
Useful chain-transferring agent is usually alkylaluminoxane, formula AlR3,ZnR2Indicate that (wherein each R is independently selected compound
From C1-C8Aliphatic group, preferably methyl, ethyl, propyl, butyl, phenyl, hexyl octyl or its isomers) or a combination thereof, than
Such as diethyl zinc, methylaluminoxane, trimethyl aluminium, triisobutyl aluminium, trioctylaluminum or a combination thereof.
Polyolefin products
The invention further relates to the composition of matter prepared by method described herein.
In a preferred embodiment, the method prepares Noblen or propylene copolymer, such as propylene-second
Alkene and/or propylene-alpha-olefin (preferably C3-C20) copolymer (for example, butene-hexene copolymer or propylene-octene Copolymer),
It has the Mw/Mn greater than 1 to 4 (preferably greater than 1-3).
Similarly, method of the invention prepares olefin polymer, preferably polyethylene and polypropylene homopolymer and copolymer.
In a preferred embodiment, the polymer prepared herein is the homopolymer of ethylene or propylene, is ethylene copolymer,
It is preferred that having the 0-25 moles of one or more C of % (or 0.5-20 moles of % or 1-15 moles of % or 3-10 moles of %)3-C20Alkene
Hydrocarbon comonomer (preferably C3-C12Alpha-olefin, preferably propylene, butylene, hexene, octene, decene, dodecylene, preferably propylene, fourth
Alkene, hexene, octene) or propylene copolymer, preferably having 0-25 moles of %, (or 0.5-20 moles of % or 1-15 rub
Your % or 3-10 moles of %) one or more C2Or C4-C20Olefin comonomer (optimal ethylene or C4-C12Alpha-olefin, preferably
Ethylene, butylene, hexene, octene, decene, dodecylene, optimal ethylene, butylene, hexene, octene).
In a preferred embodiment, monomer is propylene, and comonomer is hexene, preferably oneself from 1 to 15mol%
Alkene or 1 to 10mol%.
Typically, the polymer Mw prepared herein is 5,000-1,000,000g/mol (preferably 25000-750000g/
Mol, preferably 50000g/mol-500,000g/mol and/or Mw/Mn are greater than 1 to 40 perhaps 1.2 to 20 or 1.3 to 10,
Perhaps 1.4 to 5 perhaps 1.5 to 4 or 1.5 to 3.
In a preferred embodiment, it is measured using gel permeation chromatography (GPC), the polymer prepared herein has
The distribution of unimodal or multimodal molecular weight." unimodal " refers to that there are a peak value or inflection point in the track GPC." multimodal " refers to that the track GPC has
At least two peak values or inflection point.Inflection point is the point (such as from negative to positive, or vice versa) of second dervative reindexing.
In preferred embodiments, the application generate polymer composition Distribution Breadth Index (CDBI) be 50% with
On, preferably 60% or more, preferably 70% or more.CDBI is the scale that monomer composition is distributed within polymer chain, and measurement
Procedure publication in PCT Publication specification WO 93/03093, on 2 18th, 1993 announce, specifically the 7th and 8 columns and
Wild's et al., J.Poly.Sci., Poly.Phys.Ed., volume 20, page 441 (1982) and United States Patent (USP) US 5,
In 008,204, including when measuring CDBI 15,000 or less fraction of weight average molecular weight (Mw) is ignored.
In another embodiment, using following catalyst compounds, two of them R10Group is identical or not
Same group, and it is expressed as formula: (XR'n)-, wherein X is the race of the 14th, 15,16 or 17 hetero atom that atomic weight is 13-79
It is following one with R': hydrogen atom, halogen atom, C1-C10Alkyl or C6-C10Aryl and n are 0,1,2 or 3, prepared
Polymer, with by identical catalyst compounds (other than two R10 groups are hydrogen), in conjunction with identical activator and
With the polymer phase ratio of same monomer (such as ethylene and propylene) polymerization preparation under the same terms, the application polymer Mw high is at least
20% (or at least 30%, or at least 40%).In the useful embodiment, each R10It is independently-NR'2,-SR',-
OR',-OSiR'3,-SiR'3, or-PR'2, more specifically, R10Selected from-NR'2,-SR',-OR',-OSiR'3, or-PR
'2, preferably-OR'；Wherein R' is C1-C10Alkyl, especially each R10It is methoxyl group, ethyoxyl, n-propoxy, isopropoxy, n-
Butoxy, isobutoxy, sec- butoxy or t-butoxy, most especially methoxyl group.
In another embodiment, using two of them group R10It is same or different group and is expressed as
Formula: the catalyst compounds of OR', wherein R' is C1-C10Alkyl, the application prepare polymer containing ethylene and propylene, with by
Identical catalyst compounds (remove two R10Group is other than hydrogen), in conjunction with identical activator and under the same conditions with identical
The polymer phase ratio of monomer polymerization preparation, Mw high at least 20% (perhaps at least 30% or at least 40%).In useful implementation
In scheme, each R10It is independently methoxyl group, ethyoxyl, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec- fourth
Oxygroup or t-butoxy, effectively two R10It is methoxyl group.
In particularly useful embodiment, the application uses two of them R10Group is all the catalyst compounds of methoxyl group
The ethylene propylene copolymer of object preparation (removes two R with by identical catalyst compounds10Group is other than hydrogen), in conjunction with identical
Activator and the polymer phase ratio prepared under the same conditions with same monomer polymerization, Mw high at least 20% (or at least
30%, or at least 40%).
Blend
In another embodiment, the polymer (preferably polyethylene or polypropylene) for preparing herein and one or more another
Outer polymer combines, and film, mechanograph or other products is then made.Other useful polymer include polyethylene, Quan Tongli
Structure polypropylene, high isotactic polypropylene, syndiotactic polypropylene, propylene and ethylene, and/or butylene, and/or hexene it is random
Copolymer, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, third
Olefin(e) acid copolymer, polymethyl methacrylate or any other polymer polymerizable by high-pressure free radical method, polychlorostyrene
Ethylene, poly 1-butene, isotactic polybutene, ABS resin, ethylene-propylene rubber (EPR), EPR, EPDM of vulcanization, block are total
The copolymerization of polymers, styrene block copolymer, polyamide, polycarbonate, PET resin, crosslinked polyethylene, ethylene and vinyl alcohol
The polymer of object (EVOH), aromatic monomer, such as polystyrene, poly- 1 ester, polyacetals, polyvinylidene fluoride, polyethylene glycol or
Polyisobutene.
In a preferred embodiment, polymer present in blends described above (preferably polyethylene or polypropylene) is
10-99wt%, preferably 20-95wt%, even more desirably at least 30-90wt%, even more desirably at least 40 to 90wt%, very
To more preferably at least 50 to 90wt%, even more desirably at least 60 to 90wt%, even more preferably at east 70 to 90wt%, base
The weight of polymer in blend.
The preparation of above-mentioned blend can be by (as described above by polymer and one or more polymer of the invention
) mixing, reactor blend is prepared by tandem reactor, or by using more than one catalysis in same reactor
Agent prepares multiple polymers.Polymer can mix before being put into extruder, or can mix in an extruder.
Blend can be formed with conventional device and method, such as is then melted in mixing machine by dry-mixed each ingredient
Melt mixing, or by directly mixing each ingredient in mixing machine, such as, such as Banbury mixer, Haake mixing machine,
Brabender mixer or single or double screw extruder, may include continuous mixer (compounding extruder) and
It is directly used in the side arm extruder (side-arm extruder) in polymerization downstream, may include the storage in thin film extruding machine
The powder or particle of hybrid resin in glassware.In addition, additive can be included in blend, one or more blends as needed
In ingredient and/or the product being mixed to form, such as film.This kind of additive be it is known in the art that may include, such as: fill out
Material；Antioxidant is (for example, hindered phenol, such as IRGANOXTM1010 or IRGANOXTM1076, it can be obtained from Ciba-Geigy
)；Phosphite ester, such as IRGAFOSTM168, can be obtained from Ciba-Geigy)；Anti-attachment additive；Tackifier, such as poly- fourth
Alkene, terpene resin, aliphatic series and aromatic hydrocarbon resin, alkali metal and tristerin and hydrogenated rosin；UV stabilizer；It is hot steady
Determine agent；Antiblocking agent (anti-blocking)；Release agent；Antistatic agent；Pigment；Colorant；Dyestuff；Wax；Silica；It fills out
Material；Talcum etc..
Film
Particularly, any previous polymer, such as previous polypropylene or its blend, can be used for various final uses
Using.This kind of application includes, for example, single-layer or multi-layer blowing, extrusion and/or shrink film.These films pass through any well known crowded
Out or coextrusion technology is formed, and such as froth film processing technology, wherein a ring can be pressed through in molten condition for composition
Then shape die orifice is expanded into uniaxial or twin shaft an orientation molten mass, be then cooled into tubulose, and blown film can connect
Cut from axial and be unfolded to form planar film.Film then can omnidirectional, unidirectional orientation or bidirectional oriented to identical or different
Degree.One or more layers film transversal orientation and/or portrait orientation are to identical or different degree.Typical case can be used in uniaxial orientation
Cold stretch or hot-drawn stretching method complete.Tenter frame or double bubble processes can be used to complete for biaxial orientation, and can put together in each layer
Before or after carry out.For example, polyethylene layer can be extruded coating or the polypropylene layer by being laminated to orientation or polyethylene with
Polypropylene can be coextruded film forming together and then orient.Equally, oriented polypropylene (OPP) can be laminated to oriented polyethylene or the poly- second of orientation
Alkene can be coated on polypropylene and then optionally further be orientated compound.Generally, film is in machine direction (MD) at most
15, the ratio orientation preferably between 5-7, is oriented in transverse direction (TD) at most 15, preferably 7-9 ratio.But in a reality
It applies in scheme, in the identical degree oriented film in the direction MD and TD.
The thickness of film may change according to required purposes；But what film thickness was generally suitable at 1-50 μm.For wrapping
The film of dress is usually 10-50 μ m-thick.The thickness of sealant is usually 0.2 to 50 μm.There can be sealant in the surfaces externally and internally of film,
Or sealant can only exist on inner surface or outer surface.
In one embodiment, one or more layers can be by sided corona treatment, electron beam irradiation, gamma-irradiation, flame at
Reason, microwave improve.In a preferred embodiment, a surface layer or two surface layers are improved by sided corona treatment.
Specific embodiment
The invention further relates to:
Embodiment A: the transition metal complex that formula (I) indicates:
Wherein M1Selected from titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten；R1And R2Can be it is same or different,
Individually hydrogen atom, C1-C10Alkyl, C1-C10Alkoxy, C6-C10Aryl, C6-C10Aryloxy group, C2-C10Alkenyl, C2-C40Alkene
Base, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40Aryl alkenyl, OH group perhaps halogen atom or optionally
The conjugated diene replaced by one or more alkyl, three (alkyl) silicyls or three (alkyl) silylhydrocarbyls, it is described
Diene has at most 30 atoms, is not included in hydrogen；
R3To R7Can be identical or different, and individually hydrogen atom, halogen atom can be by the C of halogenation1-C10Alkyl, can
By the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40Aryl alkenyl ,-NR'2,-
SR' ,-OR ,-OSiR'3Or-PR'2Group, wherein R' is selected from following one: hydrogen atom, halogen atom, C1-C10Alkyl or C6-
C10Aryl or two or more adjacent group R5To R7The atom for the indenyl connecting with by them is formed together one or more
A ring；
R13It is-B (R15)-,-Al(R15)-,-Ge-,-Sn-,-O-,-S-,-SO-,-SO2-,-N(R15)-,-CO-,-P
(R15)-, or-P (O) (R15)-, amino borane base meets following one:
Wherein: R15,R16,R17It is same or different, and is hydrogen atom, halogen atom, C1-C20Alkyl, C1-C20
Fluoro-alkyl or sila alkyl, C6-C30Aryl, C6-C30Fluorinated aryl, C1-C20Alkoxy, C2-C20Alkenyl, C7-C40Aryl
Alkyl, C8-C40Aryl alkenyl, C7-C40Alkylaryl, or a R15With a R16, together with R13Middle their atom of connection,
It is formed together one or more rings；M2It is carbon, silicon, one of germanium or tin or a variety of；
Wherein R8、R12And R14It can be same or different, and individually hydrogen atom, halogen atom can be by halogenation
C3-C10Alkyl, can be by the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40,Virtue
Base alkenyl ,-NR'2,-SR',-OR,-OSiR'3Or-PR'2Group, wherein R' is hydrogen atom, halogen atom, C1-C10Alkyl,
Or C6-C10One of aryl；
Wherein R9And R11It is same or different, and selected from can be by the C of halogenation2-C20Alkyl, can be by the C of halogenation6-
C10Aryl, C2-C10Alkenyl, C7-C20Aryl alkyl, C7-C20Alkylaryl, C8-C20Aryl alkenyl；With
Wherein R10Selected from (XR'n)-, wherein X be atomic weight be 13-79 14-17 race hetero atom and R' be it is following it
One: hydrogen atom, halogen atom, C1-C10Alkyl, or C6-C10Aryl and n are the integers of 0-3；With
Especially wherein R10It is NR'2,-SR',-OR',-OSiR'3,-SiR'3, or PR'2, wherein R10Selected from-NR'2,-
SR',-OR',-OSiR'3Or PR'2, wherein R10It is-SR' ,-OR', or-OSiR'3, wherein R10It can be-NR'2Or-PR'2Base
Group, or wherein R10It is-OR'.
Embodiment B: the transition metal complex of embodiment A, wherein R14It is substitution or unsubstituted C6-C10
Aryl, can be by halogenation.
Embodiment C: the transition metal complex of embodiment A or B, wherein R14It is substitution or unsubstituted
Phenyl.
Embodiment D: any one of embodiment A to C transition metal complex, wherein R3It is C1-C10Alkyl or C6-
C10Aryl.
Embodiment E: any one of embodiment A to D transition metal complex, wherein R3It is methyl.
Embodiment F: any one of embodiment A to E transition metal complex, wherein R9And R11Can be it is identical or
Different, and individually butyl, aryl, isopropyl or fluoro-alkyl.
Embodiment G: any one of embodiment A to F transition metal complex, wherein R9And R11It each is selected from positive fourth
Base, isobutyl group, and tert-butyl and R10It is OR', wherein R' is C1-C10Alkyl.
Embodiment H: the transition metal complex of embodiment A is expressed as formula (II):
Wherein R8And R12It respectively can be same or different, and individually hydrogen atom, halogen atom can be by halogenation
C3-C10Alkyl, can be by the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40Aryl
Alkenyl ,-NR'2,-SR',-OR,-OSiR'3Or-PR'2Group, wherein R' is following one: hydrogen atom, halogen atom, C1-
C10Alkyl, or C6-C10Aryl；
Wherein each R9And R11It is same or different, and being individually can be by the C of halogenation2-C20Alkyl, can be by halogenation
C6-C10Aryl, C2-C10Alkenyl, C7-C20Aryl alkyl, C7-C20Alkylaryl, or C8-C20Aryl alkenyl；Wherein R10Choosing
From (XR'n)-, wherein X be atomic weight be 13-79 14-17 race hetero atom and R' be following one: hydrogen atom, halogen atom,
C1-C10Alkyl, or C6-C10Aryl and n are the integers of 0-3；Especially wherein R10It is-NR'2,-SR',-OR',-OSiR'3,-
SiR'3, or-PR'2, wherein R10Selected from-NR'2,-SR',-OR',-OSiR'3, or-PR'2, wherein R10It is-SR' ,-OR',
Or-OSiR'3, wherein R10It is-NR'2Or-PR'2Group, or wherein R10It is-OR'.
Embodiment I: the transition metal complex of embodiment H, wherein each R9With each R11Selected from normal-butyl, isobutyl
Base, and tert-butyl and each R10It is OR', wherein R' is C1-C10Alkyl.
Embodiment J: the transition metal complex of embodiment H or I, wherein each R9With each R11It is tert-butyl and extremely
A few R10It is methoxyl group.
Embodiment K: the transition metal complex of embodiment H to any one of J, wherein each R3It can be identical or not
Together, and individually C1-C10Alkyl.
Embodiment L: the transition metal complex of embodiment H to any one of K, wherein each R1And R2It can be identical
Or it is different, and individually halogen atom, preferably Cl；Wherein each R3It can be same or different, and individually C1-C10
Alkyl, preferably methyl；Wherein each R4,R5,R6, and R7It can be same or different, and individually hydrogen atom or C1-
C10Alkyl, and preferably each is hydrogen atom；Wherein each R8And R12Individually hydrogen atom；R13It is-SiR "2, wherein each R " is phase
With perhaps different and individually hydrogen or methyl, preferably methyl；Wherein each R9And R11It is tert-butyl；Wherein each R10It is
Methoxyl group.
Embodiment M: the transition metal complex of embodiment H to any one of K, wherein M1It is Zr or Hf.
Embodiment N: the transition metal complex that formula (II) indicates:
Wherein each R1And R2It is Cl；Each R3It is methyl；Each R4,R5,R6And R7It is hydrogen atom；
Each R8And R12Individually hydrogen atom；R13It is-Si (CH3)2-；Wherein each R9And R11It is tert-butyl；Wherein each R10It is
Methoxyl group.
Embodiment O: bis- (4- pheny-indenylzirconium) transition metal complexes of bridging, in which: at least one 4- benzyl ring is in 3'
Replaced with 5' by following group: the group can be it is same or different, and selected from can be by the C of halogenation2-C20Alkyl, can
By the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C20Aryl alkyl, C7-C20Alkylaryl, C8-C20Aryl alkenyl wherein should
At least one is in 3' and 5' substituted benzyl ring also at 4' by formula (XR'n)-Group replaces, and wherein X is that atomic weight is
The 14-17 race hetero atom and R' of 13-79 is following one: hydrogen atom, halogen atom, C1-C10Alkyl, or C6-C10Aryl
And n is the integer of 0-3；Especially wherein (XR'n)-It is-NR'2,-SR',-OR',-OSiR'3,-SiR'3, or-PR'2；Wherein
(XR'n)-It is selected from-NR'2,-SR' ,-OR', or-OSiR'3, or-PR'2, wherein (XR'n)-It is-SR' ,-OR' ,-
OSiR'3, wherein (XR'n)-It is-NR'2Or-PR'2Group, or wherein (XR'n)-It is-OR', wherein R' is following one:
Hydrogen atom, halogen atom, C1-C10Alkyl, or C6-C10Aryl；Also optionally, wherein the transition metal complex benzene
One or more of rest position is substituted on base and/or indenyl rings (one or more).
Embodiment P: the transistion metal compound of embodiment O, wherein every 4- benzyl ring 3' and 5' by with
Lower group replaces: the group can be it is same or different, and selected from can be by the C of halogenation2-C20Alkyl, can be by the C of halogenation6-
C10Aryl, C2-C10Alkenyl, C7-C20Aryl alkyl, C7-C20Alkylaryl, C8-C20Aryl alkenyl.
Embodiment Q: the transition metal complex of embodiment O or P, wherein: at least one 4- pheny-indenylzirconium ligand
2 in the 4- pheny-indenylzirconium ligand include R3Group, wherein R3It can be hydrogen atom, halogen atom can be by the C of halogenation1-C10
Alkyl, can be by the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40Aryl alkene
Base ,-NR'2,-SR',-OR',-OSiR'3Or-PR'2Group, wherein R' is following one: halogen atom, C1-C10Alkyl, or
Person C6-C10Aryl.
Embodiment R: any one of embodiment O to Q transition metal complex, wherein each 4- phenyl indenyl ligand exists
2 of 4- phenyl indenyl ligand include R3Substituent group, wherein R3It can be same or different, and individually hydrogen atom, halogen
Atom, can be by the C of halogenation1-C10Alkyl, can be by the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C40Aryl alkyl, C7-C40Alkane
Base aryl, C8-C40Aryl alkenyl ,-NR'2,-SR',-OR',-OSiR'3Or-PR'2Group, wherein R' is following one: halogen
Plain atom, C1-C10Alkyl, or C6-C10Aryl.
Embodiment S: any one of embodiment Q to R transition metal complex, condition are if any one R3It is hydrogen original
Son, methyl or ethyl, then two benzyl rings are all to have butyl in 3' and 5' substitution, and the butyl is same or different
's.
Embodiment T: any one of embodiment O to S transition metal complex, wherein at least one 4- phenyl 3' with
And 5' replaced by tert-butyl and in 4' substitutions have OR' group, wherein R' is following one: hydrogen atom, halogen atom,
C1-C10Alkyl, or C6-C10Aryl.
Embodiment U: the transition metal complex of embodiment T, wherein the OR' group is methoxyl group.
Embodiment V: any one of embodiment O to U transition metal complex, wherein the transition metal be Zr or
Hf。
Embodiment W: catalyst system, it includes activator and the transition metal networks of embodiment A to any one of V
Close object.
Embodiment X: the catalyst system of embodiment W, wherein the activator includes aikyiaiurnirsoxan beta.
Embodiment Y: the catalyst system of embodiment W or X, wherein the activator includes non-coordinating anion.
Embodiment Z: any one of embodiment W to Y catalyst system, wherein the activator includes below a kind of or more
Kind: trimethyl ammonium four (perfluoronapthyl) borate, N, N- dimethyl puratized agricultural spray four (perfluoronapthyl) borate, N, N- diethyl puratized agricultural spray
Four (perfluoronapthyl) borates, triphenylcarbenium four (perfluoronapthyl) borate, trimethyl ammonium four (perfluorinated biphenyl) borate,
N, N- dimethyl puratized agricultural spray four (perfluorinated biphenyl) borate, triphenylcarbenium four (perfluorinated biphenyl) borate；N, N- dimethyl
Puratized agricultural spray four (3,5- bis- (trifluoromethyl) phenyl) borate, triphenylcarbenium four (perfluoronapthyl) borate, triphenylcarbenium four
(perfluorinated biphenyl) borate, triphenylcarbenium four (3,5- bis- (trifluoromethyl) phenyl) borate, four (perfluor of triphenylcarbenium
Phenyl) borate, [Ph3C+][B(C6F5)4 -], [Me3NH+][B(C6F5)4 -]；1- (4- (three (pentafluorophenyl group) borates) -2,3,
5,6- tetrafluoro phenyl) pyrrolidines；With four (pentafluorophenyl group) borates；4- (three (pentafluorophenyl group) borates) -2,3,5,6- four
Fluorine pyridine；Triphenylcarbenium tetraphenyl borate salts, and triphenylcarbenium four-(2,3,4,6- tetrafluoro phenyl) borate.
Embodiment AA: polymerization, including a) contact one or more olefinic monomers with catalyst system, the catalysis
Agent system includes: i) activator and ii) any one of embodiment A to V transition metal complex.
Embodiment AB: the method for embodiment AA, wherein the activator includes aikyiaiurnirsoxan beta.
Embodiment AC: the method for embodiment AA, wherein the activator includes non-coordinating anion.
Embodiment AD: the method for embodiment AA to any one of AC, wherein one or more olefinic monomers include third
Alkene.
Embodiment AE: the method for embodiment AA to any one of AD, wherein the catalyst compounds are loads.
Embodiment AF: the method for embodiment AA to any one of AE, wherein this method the following conditions carry out: temperature from
About 0 DEG C to about 300 DEG C, pressure was in about 0.35MPa to about 10MPa, and the duration at most 300 minutes.
Embodiment AG: the method for embodiment AA to any one of AF further includes obtaining polymer.
Embodiment AH: the method for embodiment AG, wherein the polymer includes following polypropylene: fusing point > 152.0 DEG C,
Especially > 155.0 DEG C, > 158.0 DEG C, > 160.0 DEG C, > 162.0 DEG C or > 165.0 DEG C (for example, 152.0 DEG C to about 162.0 DEG C；
155.0 DEG C to about 162.0 DEG C；158.0 DEG C to about 162.0 DEG C；Or 160.0 DEG C to about 162.0 DEG C)；MwIt is 60,000 to 1,
400,000g/mol, especially 60,000 to 1,200,000g/mol, especially, 200,000 to 700,000g/mol, or 400,
000 to 600,000g/mol；And MWD > 1.0 to 5, especially 1.2 to 4.5, especially 1.5 to 4.0, especially 1.5 to 3.5, especially 1.8
To 3.0, especially 2.0 to 2.5.In some embodiments of the invention, such as when two kinds of catalyst use, MWD can be >
1.0 to 25, especially 1.2 to 20, especially 1.5 to 10, especially 1.5 to 5, especially 1.8 to 3.0, especially 2.0 to 2.5.
Experiment
1H NMR is characterized for metallocene: racemic and mesoisomer quantity pass through proton NMR measurement1H NMR
Data are collected with 5mm probe at 23 DEG C and use 400MHz Bruker spectrometer, using deuterated dichloromethane or deuterate benzene.Note
Data are recorded, maximum pulse 45 is usedo, the 8 second time between pulse, 16 transients of signal averaging.The wave spectrum is normalized to
Protonation benzene in the deuterate benzene, it is contemplated that it is in 7.16ppm peak value display.
Catalyst 1 is bis- (2- methyl -4- (3', 5'- the di-t-butyl 4'- methoxybenzenes of racemic-dimetylsilyl
Base)-indenyl) zirconium dichloride.
Catalyst 2 is bis- (the 2- methyl 4-phenyl indenyl) zirconium dichlorides of racemic-dimetylsilyl.
Catalyst 3 is that racemic-dimetylsilyl is bis- (4- (3', 5'- di-tert-butyl-phenyl) -2- cyclopropyl indenyl)
Zirconium dichloride.
Catalyst 4 is bis- (4- (3', 5'- di-t-butyl -4'- the methoxyphenyl) -2- of racemic-dimetylsilyl
Cyclopropyl indenyl) zirconium dichloride.
Catalyst 5 is racemic-dimetylsilyl (the o- xenyl -2- cyclopropyl indenyl of 4-) (2- methyl -4-
(3', 5'- di-t-butyl -4'- methoxyphenyl)-indenyl) zirconium dichloride.
Catalyst 6 is racemic-dimetylsilyl (the o- xenyl -2- cyclopropyl indenyl of 4-) (4- (3', 5'- bis-
Tert-butyl-phenyl) -2- methyl-indenyl) zirconium dichloride.
Catalyst 7 is that racemic-dimetylsilyl is bis- (2- methyl -4- (3', 5'- di-tert-butyl-phenyl)-indenyl)
Zirconium dichloride.
MAO is methylaluminoxane (30wt% is in toluene), is obtained from Albemarle.
Embodiment
Synthesize the bis- (2- methyl -4- (3', 5'- di-t-butyl -4'- methoxyphenyl)-of racemic-dimetylsilyl
Indenyl) zirconium dichloride (catalyst 1).
Lithium { 1- [2- methyl -4- (3', 5'- di-t-butyl -4'- methoxyphenyl)-indenes salt] }.
By 2- methyl -7- (3,5- di-t-butyl -4'- methoxyl groups-phenyl)-indenes (7.15g, 20.515mmol) in diethyl
Solution in ether (50ml) is in -35 DEG C of pre-cooling 20min.N-BuLi (2.5M, 8.5ml, 21.25mmol) solution is added.This is molten
Liquid is stirred at room temperature 4 hours.Evaporate all volatile matters.Residue is washed with pentane (20ml × 3) and is done under vacuum
It is dry, crude product is obtained, 0.06 equivalent Et is contained2O(8.05g)。
Chloro-(2- methyl -4- (3', 5'- di-t-butyl -4'- methoxyl group-phenyl)-indenyl) dimethyl silane
By Me2SiCl2(23g) is added to lithium { 1- [2- methyl -4- (3', the 5'- di-t-butyl -4'- methoxybenzene of pre-cooling
Base)-indenes salt] (Et2O)0.06(4.1g) is in the solution in diethyl ether (50mL).The slurry is stirred at room temperature 17 hours.
All volatile matters are removed in a vacuum.Residue is extracted with pentane (40mL × 2).The pentane filtrate is evaporated under vacuum to produce
Raw chloro-(2- methyl -4- (3', 5'- di-t-butyl -4'- methoxyl group-phenyl)-indenyl) dimethyl silane is sent out in canescence
Cementation body (3.765g).
(2- methyl -4- (3', 5'- di-t-butyl -4'- methoxyl group-phenyl)-indenyl) dimetylsilyl fluoroform
Sulphonic acid ester
Toluene (25mL) is added to trifluoro-methane sulfonic acid silver (1.21g) and chloro (2- methyl -4- (bis- uncle of 3', 5'-
Butyl -4'- methoxyphenyl)-indenyl) dimethyl silane (2g) solid mixture in.The slurry is stirred at room temperature 4
Hour.Toluene is removed under vacuum.The residue is extracted with pentane (40mL).Generation is concentrated under vacuum in the pentane filter liquor
Crude product (including about 0.26 equivalent toluene and about 10% unknown compound) (2.56g).Using this crude product, without further
Purification.
Double-(2- methyl -4- (3', 5'- di-t-butyl -4'- methoxyl group-phenyl)-indenyl) dimethyl silane
By above-mentioned lithium { 1- [2- methyl -4- (3', 5'- di-t-butyl -4'- methoxyl group-phenyl) indenes salt] } (Et2O)0.06
The cooled solution of (1.575 grams) in diethyl ether (20mL) is added to above-mentioned (2- methyl -4- (3,5- di-t-butyl -4- methoxyl group
Phenyl)-indenyl) dimetylsilyl trifluoromethane sulfonic acid ester (2.54g) in diethyl ether (15mL) cooled solution (- 35
DEG C, 15min) in.The reaction carries out 2 days under stirring at room temperature.Whole volatile matters are removed under vacuum.Residue hexane
(20mL × 2) are extracted.The hexane filter liquor is concentrated and dried so that white solid is precipitated.The solid is dissolved in hexane (10mL).This is molten
Liquid is concentrated into about 5mL and puts -35 DEG C of refrigerators into.(3.2g) is washed and is dried in vacuo in sediment separation with cold hexane.Make
With this crude product, purified without further.
Double bis- { 1- [2- methyl -4- (3', 5'- di-t-butyl -4'- methoxyl group-phenyl) indenes of lithium dimetylsilyl
Salt] }
Above-mentioned crude product (3.12g) is added in diethyl ether (30mL) in n-BuLi (2.5M, 3.5mL, 8.75mmol)
Pre-cooling slurry in.The solution is stirred at room temperature 22 hours.Then the slurry is cooled to -35 DEG C and continues 0.5 hour.The slurry
Filtering.The solid is collected, is washed with cold diethyl ether (10mL × 2), and vacuum drying is to generate as Et2O (0.9 equivalent) adduction
Object (2.15g) two-lithium compound
Racemic-dimetylsilyl-is bis--(2- methyl -4- (3', 5'- di-t-butyl -4'- methoxyl group-phenyl)-indenes
Base) zirconium dichloride
By ZrCl4(0.6g, 2.575mmol) is added to the bis- { 1- [2- methyl -4- of above-mentioned double lithium dimetylsilyls
(3', 5'- di-t-butyl -4'- methoxyl group-phenyl) indenes salt] } [Et2O]0.9(2.14g, 2.573mmol) is in toluene (30mL)
Pre-cooling (- 35 DEG C, continue 15min) slurry in.Other toluene (10mL) (in -35 DEG C of pre-cooling 15min) is also added.The orange
The slurry of color is stirred at room temperature 16 hours.Then the reaction mixture is filtered and the insoluble solid is further used into first
Benzene (10mL × 2) is washed.The filter liquor and washings merging and evaporated in vacuo.Hexane (45mL) and toluene (6mL) are added.It should
Slurry mixing is abundant and allows to retain at room temperature overnight.The sediment is separated and is washed with hexane (6mL × 4) and very
Sky is dry to generate 1.85g metallocene, and having racemic/meso ratio is about 1.08:1.Further fractional crystallization provides 0.31g
(12%) (this fraction is following for synthesizing for racemic metallocene (racemic/meso > 50/1, the toluene comprising about 1.2 equivalents)
Supported catalyst).Other racemic metallocene fraction (racemic/meso > 25/1) also obtains (0.438g, comprising 1.2-
The toluene of 1.3 equivalents).
1H NMR(400MHz,C6D6,23℃):rac:7.93(s,4H),7.47(d,2H),7.43(d,2H),7.13(s,
2H),6.91(m,2H),3.44(s,6H,-OCH3),2.01(s,6H,ind-CH3),1.60(s,36H,4×tBu),0.79(s,
6H,SiMe2).
Synthesize racemic-dimetylsilyl-it is bis--(2- cyclopropyl -4- (3', 5'- di-tert-butyl-phenyl)-indenyl) two
Zirconium chloride (catalyst 3, comparative example)
Indenes synthesis
4- bromo -2,3- dihydro 1H- 1-Indanone (b): 3- (2- bromophenyl) propionic acid (a) (550g, 2.4mol, 1 equivalent) is molten
In 1,2- dichloroethanes (5.5L).Solution and mixture reflux 24 is added in thionyl chloride (437.8mL, 6mol, 2.5 equivalent)
Hour.The reaction, which is cooled to room temperature, to be concentrated under reduced pressure.The residue is dissolved in methylene chloride (1L) and is added dropwise to mechanical stirring
Suspension (526.9g, 3.96mol, 1.65 equivalent) of the anhydrous aluminum chloride in methylene chloride (1L), while keeping the reaction temperature
27 DEG C of degree or less.Before entering the five gallon bottle bucket quenching of half barrel of ice, which is stirred at room temperature three hours.Generated mixture
It is extracted with methylene chloride (3x 3L).Merged organic layer sequence saturated brine (2L) and wash saturated sodium bicarbonate (2L)
It washs.The organic layer is dry via sodium sulphate, and is concentrated under reduced pressure.Produced solid is dried overnight generationization at 30 DEG C of vacuum drying oven
Closing object b (435g, 86% yield) is in pale solid.
4- bromo -2,3- dihydro -1H- indenes -1- alcohol (c): compound b (435g, 2.06mol, 1 equivalent) is in ethanol (5L)
Solution handled and (101.6g, 2.68mol, 1.3 equivalent) and be stirred at room temperature overnight with sodium borohydride.Reaction decompression is dense
Contracting and the residue distribute between 10% aqueous hydrochloric acid of 4L methylene chloride and 4L.Separating layer and the water-bearing layer dichloro
Methane (3 × 1L) extracts.Merged organic layer sequence is washed with saturated brine (2L), dry via sodium sulphate, and is depressurized dense
Contracting.It is solid in canescence that produced solid is dried overnight generation compound c (422g, 96% yield) in vacuum drying oven at 30 DEG C
Body.
4- bromo -1H- indenes (d): compound c (150g, 704mmol, 1 equivalent) is suspended in the concentrated sulfuric acid (250mL) and water
In the mixture of (1.25L).The mixture is refluxed overnight.The cooling and methylene chloride with 1.5L of the reaction extracts.Organic layer
Sequence is washed with saturated sodium bicarbonate (1.5L), dry via sodium sulphate, and is concentrated under reduced pressure.The residue is via silica gel
(800g) purification, being eluted with heptane and generating compound d (95g, 69% yield) is in light yellow oil.
4- (3', 5'- di-tert-butyl-phenyl) -1H- indenes (e): compound d (60g, 308mmol, 1 equivalent), 2- (3,5- bis-
Tert-butyl-phenyl) -4,4,5,5- tetramethyl -1,3,2- dioxaborinate (borolane) (126g, 400mmol, 1.3 equivalent) is mixed
Conjunction object, powder potassium carbonate (128g, 924mmol, 3 equivalent) and bis- (triphenylphosphine) palladium (II) dichloride (25.3g,
31mmol, 0.1 equivalent), 1,4- dioxane (300mL) and water (150mL) are heated overnight at 80 DEG C.The reaction implanbation
700mL water and with ethyl acetate (3x 500mL) extract.Merged organic layer is washed with saturated brine (1L), via sodium sulphate
It is dry, and be concentrated under reduced pressure.The generation residue via silica gel (1Kg) purify, with heptane elute generate compound e (59g,
63% yield) it is in light yellow oil.
The bromo- 4- of 2- (3', 5'- di-tert-butyl-phenyl) -1H- indenes (f): cold soln (5 DEG C) compound e (49g, 161mmol, 1
Equivalent), dimethyl sulfoxide (500mL) and water (5mL) are handled with N-bromosuccinimide (43g, 241mmol, 1.5 equivalent)
It is integrally formed.It removes the bath and the reaction is allowed to be stirred at room temperature overnight.Among the reaction implanbation water (1L) and this is mixed
It closes object and is extracted with ethyl acetate (2 × 500mL).Merged organic layer washs (1L) with saturated brine, dry via sodium sulphate, and
And it is concentrated under reduced pressure.Produced residue is dissolved in toluene (500mL) and p- toluenesulfonic acid is added (6.2g, 32.6mmol, 0.2 work as
Amount).The mixture flows back 20 hours and removes water with Dean-Rodney Stark moisture trap simultaneously.The reaction, which is cooled to room temperature, to be subtracted
Pressure concentration.It is white with heptane elution generation compound f (41g, 66% yield) via silica gel (1Kg) purification to generate residue
Solid.
2- cyclopropyl -4- (3', 5'- di-tert-butyl-phenyl) -1H- indenes (g): compound f solution (16.1g,
42.0mmol, 1 equivalent) and anhydrous toluene (200mL) processing [bis- (diphenylphosphino) ferrocene of 1,1'-] palladium chloride
(II) DCM adduct (3.43g, 4.2mmol, 0.1 equivalent).After stirring 10 minutes, the 0.5M ring in tetrahydrofuran is added dropwise
Propyl magnesium bromide (420mL, 210mmol, 5 equivalent).The reaction is heated overnight at 60 DEG C.The reaction is cooled with an ice bath, uses 1N
HCl is acidified to pH 3 and is extracted with ethyl acetate (3 × 500mL).Merged organic layer washs (800mL) with saturated brine,
It is dry via sodium sulphate, and be concentrated under reduced pressure.The residue fills AnaLogix (65-200g) column purification through dry, uses heptane
Elution generates compound g (7.0g, 48% yield) white solid.
Lithium { 1- [2- cyclopropyl -4- (3', 5'- di-tert-butyl-phenyl) indenes salt] }: by 2- cyclopropyl -7- (bis--uncle of 3', 5'-
Butyl phenyl) the solution of-indenes (9) (5.93g, 17.21mmol) in diethyl ether (40ml) is in -35 DEG C of pre-cooling 30min.It is added just
Butyl lithium (2.5M, 7mL, 17.5mmol).16h is stirred at room temperature in the solution.Evaporate all volatile matters.With pentane (10mL ×
4,40mL × 1) residue and vacuum drying are washed to generate crude product (4.68g)
Chloro (2- cyclopropyl -4- (3', 5'- di-tert-butyl-phenyl)-indenyl) dimethyl silane:
Lithium { 1- [2- cyclopropyl -4- (3,5- di-tert-butyl-phenyl) indenes salt] } (2.38g, 6.791mmol) is in diethyl ether
The solution of (30 milliliters) is in -35 DEG C of pre-cooling 10min.Me2SiCl2(12.9g, 99.95mmol) is added and the white slurry is in room
Temperature is lower to stir 28h.Evaporate all volatile matters.The residue is extracted with pentane (40mL).By the pentane filter liquor evaporated in vacuo with
Generate chloro (2- cyclopropyl -4- (3', 5'- di-tert-butyl-phenyl)-indenyl) dimethyl silane, white tacky solid
(1.68g)。
(2- cyclopropyl -4- (3', 5'- di-tert-butyl-phenyl)-indenyl) dimetylsilyl trifluoromethane sulfonic acid ester: add
Enter chloro (2- cyclopropyl -4- (3,5- di-tert-butyl-phenyl)-indenyl) dimethyl silane (1.64g, 3.752mmol) in toluene
In (10mL) solution to stir trifluoro-methane sulfonic acid silver (1g, 3.892mmol) (10mL) mixture in toluene.By the slurry
3h is stirred at room temperature.Toluene is removed under vacuum and extracts the residue with pentane (40mL).The pentane filter liquor is true
Sky concentration is to generate thick (2- cyclopropyl -4- (3', 5'- di-tert-butyl-phenyl)-indenyl) dimetylsilyl trifluoromethyl sulphur
Acid esters (1.93g).
Bis- (2- cyclopropyl -4- (3', 5'- di-tert-butyl-phenyl)-indenyl) dimethylsilanes: lithium { 1- [2- cyclopropyl -4-
(3,5- di-tert-butyl-phenyl) indenyl] } (1.26g, 3.595mmol) cooled solution of (20 milliliters) in diethyl ether be added to
(2- cyclopropyl -4- (3,5- di-tert-butyl-phenyl)-indenyl) dimetylsilyl trifluoromethayl sulfonic acid ester (1.93g,
3.504mmol) cooled solution (- 35 DEG C, 30min is pre-chilled) in diethyl ether (10mL).23hr is stirred at room temperature in the mixture.In
Whole volatile matters are removed under vacuum.The residue is extracted with pentane (40mL).The pentane filter liquor is evaporated to generate the thick production
Object (2.6g).
Double lithium dimetylsilyls are bis- { 1- [2- cyclopropyl -4- (3', 5'- di-t-butyl-phenyl) indenes salt] }: on and then
It states crude product (2.54g, 3.408mmol) and is dissolved in diethyl ether (25mL) and -20 DEG C of pre-cooling 1h.-butyl lithium (2.5M,
2.8mL, 7mmol) it is added.22h is stirred at room temperature in the solution.Whole volatile matters are removed under vacuum.With pentane (5mL × 3)
The residue and vacuum drying are washed to generate two-lithium compound as Et2O (0.88eq) adduct (2.66g).
Bis- (2- cyclopropyl -4- (3', the 5'- di-tert-butyl-phenyl)-indenyl) zirconium dichlorides of dimetylsilyl: double lithiums two
Bis- { 1- [2- cyclopropyl -4- (3,5- di-t-butyl-phenyl) indenes salt] } [Et of methyl silicane base2O]0.88(2.64g,
3.211mmol) in Et2The solution being pre-chilled in O (15mL) is added in Et2Be pre-chilled in O (20mL) ZrCl4 (0.75g,
3.218mmol) in.20h is stirred at room temperature in the slurry.The mixture is evaporated.It is mentioned with pentane (15mL is primary, and 5mL is primary)
Take the residue (fraction 1).Then residue (fraction 2) is extracted with toluene (15mL)
Fraction 1: the pentane filter liquor is concentrated and generates thick metallocene to be dried in vacuo.In -15 DEG C of pentane (20mL)
It is 7:1 (0.79g, 27%) that crystallization crude product, which provides the metallocene with racemic/meso-ratio,.Further fractional crystallization
Separation generate racemic-dimetylsilyl-it is bis--(2- cyclopropyl -4- (3,5- di-tert-butyl-phenyl)-indenyl) be in dichloride
It is greater than 20:1 that zirconium yellow solid (0.15g, 5.2%), which has racemic/meso ratio,.
Fraction 2: toluene filter liquor is concentrated and dried to generate 0.74 gram of (25%) metallocene, there is racemic/meso
Ratio is 1:28.This raw material of 0.5g further being washed with pentane, 0.4g metallocene being provided, having racemic/meso ratio is 1:
56。
1H NMR(400MHz,C6D6,23℃):rac:7.95(m,4H),7.62(m,2H),7.49(m,4H),6.98(s,
2H),6.90(m,2H),1.84(m,2H),1.42(s,36H),0.99(s,6H,SiMe2),0.86(m,2H),0.66(m,2H),
0.50(m,2H),0.13(m,2H).meso:7.92(m,4H),7.61(m,2H),7.59-7.27(m,4H),6.86-6.82(m,
4H),1.91(m,2H),1.44(s,36H),1.27(m,2H),1.09(s,3H,SiMe),0.91(s,3H,SiMe),0.68(m,
2H),0.61(m,2H),0.13(m,2H).
Synthesize racemic-dimetylsilyl-it is bis--(4- (3', 5'- di-t-butyl -4'- methoxyl group-phenyl) -2- ring
Propyl indenyl) zirconium dichloride (catalyst 4)
2- (1H- indenes -4- base) -4,4,5,5- tetramethyl -1,3,2- dioxaborolanes: mixture: 4- bromo -1H-
Indenes (21.0g, 107.7mmol), bis- (pinacolato) two boron (30.0g, 118.1mmol), powdered anhydrous potassium acetate (21.0g,
214.3mmol), bis- (triphenylphosphine) palladium chlorides (II) (2.4g, 3.4mmol), and lower 110 DEG C of DMF (100mL) nitrogen plus
Heat 5 hours.The mixture injects 500mL water and is extracted with hexane (2 × 100mL).The merging organic phase is washed with water (50mL)
And it is concentrated under reduced pressure.Produced residue is purified via silica gel (eluant, eluent: hexane) to generate 2- (1H- indenes -4- base) -4,4,5,
5- tetramethyl -1,3,2- dioxaborolanes (21.63g, 83%) are in colorless oil.
4- (3,5- di-t-butyl -4- methoxyphenyl) -1H- indenes: mixture: 5- bromo -1,3- di-t-butyl -2- methoxy
Base benzene (11.0g, 36.9mmol), 2- (1H- indenes -4- base) -4,4,5,5- tetramethyl -1,3,2- dioxaborinate (8.9g,
36.9mmol), potassium carbonate (10.2g, 73.8mmol), tetrabutylammonium bromide (2.37g, 7.38mmol) are bis- (triphenylphosphine)
Palladium chloride (II) (0.52g, 0.74mmol), water (100mL) and ethyl alcohol (10mL) flow back 3 hours.The reaction cools
And with hexane (2 × 100mL) extract the merging organic layer be concentrated under reduced pressure, then generate residue via silica gel (eluant, eluent:
Hexane) it purifies to obtain 4- (3,5- di-t-butyl -4- methoxyphenyl) -1H- indenes (10.8g, 88%) in colorless oil.
2- bromo -4- (3,5- di-t-butyl -4- methoxyphenyl) -1H- indenes: pre-cooling (5 DEG C) 4- (3,5- di-t-butyl -
4- methoxyphenyl -1H- indenes (10.5g, 31.4mmol) (100mL) solution and water (1mL) and N- bromine in dimethyl sulfoxide
One is treated as succinimide (8.3g, 47.2mmol) and the reaction is stirred at room temperature overnight.Mixture note
Enter among water (500mL) and is extracted with toluene (2 × 200mL).The merging organic phase is washed with water (100mL).Then molten to this
P- toluenesulfonic acid monohydrate (1.2g, 6.3mmol) is added in liquid, and the mixture is flowed back 6 hours and uses Dean-Si Da simultaneously
Gram gas-liquid separator removes water.The mixture is cooled and is concentrated under reduced pressure.The residue is via silica gel purification (elution
Agent: hexane) to obtain 2- bromo -4- (3,5- di-t-butyl -4- methoxyphenyl) -1H- indenes (7.21g, 56%) in yellowish solid
Body.
4- (3,5- di-t-butyl -4- methoxyphenyl) -2- cyclopropyl indenes: by 2- bromo -4- (3,5- di-t-butyl -4-
Methoxyphenyl) -1H- indenes (2.80g, 6.8mmol) and [1,3- bis- (2,6- diisopropyl phenyl) imidazoles -2- fork bases] triphenyl
Phosphine dichloride nickel (II) (95mg, 0.14mmol) solution by cyclopropyl bromide solution (0.5M in THF, 16.0mL,
It 8.2mmol) handles, and generated mixture is flowed back 5 hours.Then by the aqueous 0.5N HCl of reaction implanbation 50ml with
And extracted with toluene (50mL × 2), merged organic phase is washed with water (50mL), via MgSO4It is dry, and be concentrated under reduced pressure.Institute
Obtained sediment generates product as off-white solid (1.40g, 55%) via silica gel purification (eluant, eluent: hexane).
Lithium { 1- [4- (3,5- di-t-butyl -4- methoxyphenyl) -2- cyclopropyl indenes salt] }: by 7- (3,5- di-t-butyl -
4- methoxyphenyl) -2- cyclopropyl indenes (1.35g, 3.61mmol) in diethyl ether (20mL) solution by n-BuLi
(2.5M, 1.5mL, 3.79mmol) processing, and 3h is stirred into the reaction at room temperature.Then all volatile matter volatilizations.Residue
White solid product (1.28g, 93%) is washed and is dried under vacuum to hexane (5mL × 2).
Chloro dimethyl [4- (3,5- di-t-butyl -4- methoxyphenyl) -2- cyclopropyl indenyl] silane: lithium 1- [4- (3,
5- di-t-butyl -4- methoxyphenyl) -2- cyclopropyl indenes salt] solution of (0.65g, 1.71mmol) in diethyl ether (30mL)
By Me2SiCl2(1.30g, 10.3mmol) processing, and produced slurry stir 5h at room temperature.All volatile matters volatilize and should
Residue is extracted with hexane (30mL × 3).Merge solution to be concentrated into anhydrous and produce via vacuum drying to generate white foam
Object (0.77g, 96%).
Dimetylsilyl [4- (3,5- di-t-butyl -4- methoxyphenyl) -2- cyclopropyl indenyl] fluoroform sulphur
Acid esters: by chloro dimethyl [4- (3,5- di-t-butyl -4- methoxyphenyl) -2- cyclopropyl indenyl] silane (0.76g,
While 1.64mmol) solution in toluene (30mL) stirs, handled by trifluoro-methane sulfonic acid silver (0.48g, 1.80mmol),
And produced white slurry stirs 5h at room temperature.Toluene and the residue is removed in vacuum to be extracted by hexane (30mL × 3).It closes
And solution be concentrated into it is anhydrous and via vacuum drying to generate white foam product (0.93g, 98%).
Bis- (4- (3,5- di-t-butyl -4- methoxyphenyl) -2- cyclopropyl indenyl]) dimethyl silane: by dimethyl
Silicyl [4- (3,5- di-t-butyl -4- methoxyphenyl) -2- cyclopropyl indenyl] trifluoromethayl sulfonic acid ester (0.90g,
1.55mmol) solution in diethyl ether (30mL) is by lithium 1- [4- (3,5- di-t-butyl -4- methoxyphenyl) -2- cyclopropyl
Indenes salt] (0.59g, 1.55mmol) is handled, and the reaction is stirred 6 hours at room temperature.Solvent volatilization and produced remnants
Object carry out flash chromatography (flash chromatography) (silica gel, eluant, eluent: hexane) with generate white solid (0.96g,
77%).
Double lithium dimetylsilyls are bis- (4- (3,5- di-t-butyl -4- methoxyphenyl) -2- cyclopropyl indenes salt]): will
Bis- (4- (3,5- di-t-butyl -4- methoxyphenyl) -2- cyclopropyl indenyl]) dimethylsilanes (0.95g, 1.18mmol) are two
Solution in ether (20mL) is handled by n-BuLi (2.5M, 0.97mL, 2.42mmol), and the reaction is stirred at room temperature
3h.All volatile matter volatilizations.Residue with cooling hexane (10mL × 2) wash and be dried under vacuum to white solid (0.89g,
92%).
Bis- (4- (3', 5'- di-t-butyl -4'- the methoxyphenyl) -2- cyclopropyl indenyl) dichlorides of dimetylsilyl
Zirconium: by double lithium dimetylsilyls bis- (4- (3,5- di-t-butyl -4- methoxyphenyl) -2- cyclopropyl indenes salt]) (0.86g,
1.05mmol) solution in diethyl ether (30mL) is handled by ZrCl4 (0.24g, 1.05mmol).The mixture stirs at room temperature
It mixes overnight.All volatile matters are evaporated.Residue is extracted with toluene (40mL).Extraction solution concentration and residue 10ml
Hexane wash to obtain crude product (0.72g), racemic/meso ratio be 2.0:1.The crude product from the hexane of 20ml and
1.5ml toluene is recrystallized to generate the metallocene of 433mg, racemic/meso ratio 4.8:1.Then the product is from 20ml's
Hexane and 1.0ml toluene recrystallization are to provide the metallocene of 261mg, racemic/meso ratio 8.5:1.The product is into one
Step is recrystallized from the hexane and 0.5ml toluene of 15ml to provide dimetylsilyl bis- (4- (3,5- di-t-butyl -4- first
Phenyl) -2- cyclopropyl indenyl) zirconium dichloride is (remaining comprising about 0.44 equivalent hexane and about 0.07 equivalent toluene
Object) there is racemic/meso ratio 15:1 (0.121g, 11.4%)1H NMR(400MHz,C6D6,23℃,rac:7.96
(m,4H),7.48(m,4H),6.97(s,2H),6.89(m,2H),3.37(s,6H),1.83(m,2H),1.59(s,tBu×4,
36H),0.96(s,SiMe2,6H),0.90-0.81(m,2H),0.65(m,2H),0.50(m,2H),0.10(m,2H)。
Synthesize racemic-dimetylsilyl (the o- xenyl -2- cyclopropyl indenyl of 4-) (2- methyl -4- (3', 5'-
Di-t-butyl -4'- methoxyphenyl)-indenyl) zirconium dichloride (catalyst 5).Indenes synthesis:
4- ([1,1'- biphenyl] -2- base) -1H- indenes (h): mixture: compound d (40g, 205mmol, 1 equivalent), (connection
Benzene -2- base) boric acid (81.2g, 410mmol, 2 equivalent), powder potassium carbonate (85g, 615mmol, 3 equivalent), and bis- (triphenyls
Phosphine)-palladium chloride (II) (7.2g, 10.3mmol, 0.05 equivalent), 1,4- dioxane (300mL) and water (150mL)
It is heated overnight at 80 DEG C.It is extracted among reaction implanbation 500mL water and with ethyl acetate (3x 400mL).Merged organic layer
It is washed with saturated brine (300mL), it is dry via sodium sulphate, and be concentrated under reduced pressure.Obtained sediment is via silica gel (400g)
The elution of purification heptane is stood with generating compound (h) (50g, 91% yield) in faint yellow oil, and it is solid to slowly become canescence
Body.
4- ([1,1'- biphenyl] -2- base) -2- bromo -1H- indenes (i): cryogenic fluid (5 DEG C of compound h (40g, 149mmol,
1 equivalent), dimethyl sulfoxide (400mL) and water (5mL) integrate with N-bromosuccinimide (39.8g, 224mmol,
1.5 equivalents) processing.It removes the bath and the reaction is stirred at room temperature overnight.The reaction implanbation water (1L) and use second
Acetoacetic ester (2x 500mL) extracts.Merged organic layer is washed with saturated brine (1L), dry via sodium sulphate, and decompression is dense
Contracting.Obtained residue is dissolved in 500ml toluene and p- toluenesulfonic acid (5.6g, 29.4mmol, 0.2 equivalent) is added.This
Mixture flows back 20 hours and removes water with Dean-Rodney Stark moisture trap simultaneously.The reaction is cooled to room temperature and depressurizes dense
Contracting.Obtained sediment is purified via silica gel (1Kg), is eluted with heptane to generate compound i (39g, 75% yield) in light
Yellow solid.
4- ([1,1'- biphenyl] -2- base) -2- cyclopropyl -1H- indenes (j): compound i (10g, 28.8mmol, 1 equivalent) with
And dry toluene (100mL) solution is handled by bis- (triphenylphosphine)-palladium chlorides (II) (2.35g, 2.9mmol, 0.1 equivalent).
After stirring 10 minutes, the 0.5M cyclopropyl magnesium bromide in tetrahydrofuran (300mL, 149.7mmol, 5.2 equivalent) is added dropwise.It should
Reaction is heated overnight at 60 DEG C.Additional bis- (triphenylphosphine)-palladium chlorides (II) (2.35g, 2.9mmol, 0.1 equivalent) are added
And the reaction is additionally heated 24 hours at 60 DEG C.The reaction is concentrated under reduced pressure and the residue is in water (1L) and ethyl acetate
It is distributed between (1L).Layer separation and the aqueous layer with ethyl acetate (1L) are washed.Merged organic layer is washed with saturated brine (1L),
It is dry via sodium sulphate, and be concentrated under reduced pressure.Obtained sediment is purified via silica gel (200g), is eluted with heptane to generate
Compound j (3.3g, 37% yield) is in light yellow oil.
Lithium [1- (the o- biphenyl -2- cyclopropyl indenes salt of 4-)]: the o- biphenyl -2- cyclopropyl-indenes (j) of 7- (2.538g,
8.229mmol) lasting 0.5h is pre-chilled at -35 DEG C for solution in diethyl ether (40mL).-butyl lithium (2.5M, 3.3mL,
8.25mmol) be added.The solution stirs 18h at room temperature.All volatile matter volatilizations.The yellow solid with pentane 5mL twice, (
10mL is primary) it washes and is dried in vacuo to generate lithium compound (2.11g)
Lithium { 1- [2- methyl -4- (3', 5'- di-t-butyl -4'- methoxyphenyl)-indenes salt] }.2- methyl -7- (3', 5'-
Di-t-butyl -4'- methoxyphenyl) the solution of-indenes (7.15g, 20.515mmol) in diethyl ether (50mL) -35 DEG C be pre-chilled
20min.-butyl lithium (2.5M, 8.5mL, 21.25mmol) is added.The solution stirs 4 hours at room temperature.All volatile matters are waved
Hair.Residue is washed and is dried in vacuo to be generated semifinished product with pentane (20mL × 3), includes 0.06 equivalent Et2O(8.05g)。
Chlorodimethyl [the o- xenyl -2- cyclopropyl indenyl of 4-] silane: the lithium [1- (o- xenyl -2- cyclopropyl indenes of 4-
Salt)] solution of (0.87g, 2.768mmol) in diethyl ether (30mL) and THF (10mL) is in -35 DEG C of pre-cooling 30min.
Me2SiCl2(5.8g, 44.94mmol) is added and the slurry stirs 21h at room temperature.All volatile matter volatilizations.Residue is with penta
Alkane (50mL) extracts and the filtrate is concentrated and generates the product (1.037g) to be dried in vacuo.
Dimetylsilyl [the o- xenyl -2- cyclopropyl indenyl of 4-] trifluoromethayl sulfonic acid ester: trifluoro-methane sulfonic acid silver
The above product (1.02g, 2.544mmol) of agitation is added in first in the solution of (0.67g, 2.618mmol) in toluene (15mL)
Solution in benzene (10mL).The slurry stirs 3h at room temperature.Toluene and the residue is removed in vacuum to be extracted by hexane (50mL).It should
Pentane filter vacuum is concentrated to generate the product (1.13g).
(the o- xenyl -2- cyclopropyl indenyl of 4-) (2- methyl -4- (3', 5'- di-t-butyl -4'- methoxyphenyl)-indenes
Base) dimethylsilane: by the lithium { 1- [2- methyl -4- (3', 5'- di-t-butyl -4'- methoxyphenyl)-indenes salt] } of pre-cooling
(Et2O)0.06The solution of (0.71g, 1.978mmol) in diethyl ether (20mL) adds to dimetylsilyl [the o- biphenyl-of 4-
2- cyclopropyl indenyl] cooled solution of the trifluoromethayl sulfonic acid ester (1.01g, 1.963mmol) in diethyl ether (15mL).The reaction
21h is stirred at room temperature.Diethyl ether volatilization.Hexane (40ml) adds to the residue.The hexane slurry is through Celite on the fritTM
Filtering.The frit is washed with other hexane (20mL is primary, and 10mL is primary).All filtrates merge and are concentrated in vacuo to generate
Crude product (1.515g).
Double lithium dimetylsilyl (the o- biphenyl -2- cyclopropyl indenes salt of 4-) (2- methyl -4- (3', 5'- di-t-butyls -
4'- methoxyphenyl) indenes salt): above-mentioned crude product (1.5g) is added in diethyl ether in -butyl lithium (2.5M, 1.8mL, 4.5mmol)
Cooled solution in (30mL).The solution stirs 23h at room temperature.All volatile matters are removed in vacuum.Residue hexane (30mL mono-
Secondary, 20mL is twice) it washes and is dried in vacuo to generate crude product (1.25g).
Dimetylsilyl (the o- biphenyl -2- cyclopropyl indenyl of 4-) (2- methyl -4- (3', 5'- di-t-butyl -4'- first
Phenyl)-indenyl) zirconium dichloride: above-mentioned crude product (1.2g) cooled solution in toluene (30mL) is added to ZrCl4
(0.386g,1.656mmol).Other low temperature toluene (20mL) is added.16h is stirred at room temperature in the mixture.The mixture
It is concentrated into about 35ml and through in frit CeliteTMUpper filtering.The CeliteTMIt is washed with other toluene (5mL).All
Filtrate merges and is concentrated into anhydrous.Et2O (20mL) is added and puts mixture into -35 DEG C of refrigerators.This is mixed after 2h
Conjunction object is again concentrated to anhydrous.Residue extracts (20mL tetra- times) with pentane.Pentane filtrate merges and is evaporated.Et2O(10mL)
It is added and the solution is evaporated again.Pentane (20mL) is added to the residue.The slurry stirs 3d at room temperature.The sediment point
From, with pentane wash (10ml is twice) and vacuum drying (0.185g, racemic/meso=4/1).Further from hexane/first
Benzene fractional crystallization provides the product (0.055g, racemic/meso=79/1).1H NMR(400MHz,CD2Cl2,23℃:
rac:7.67(m,1H),7.58(m,2H),7.48(s,2H),7.43(m,3H),7.28(m,1H),7.15(m,1H),7.08(m,
5H),7.0(m,1H),6.96(m,1H),6.84(s,1H),5.99(s,1H),3.71(s,3H),2.22(s,3H),1.90(m,
1H),1.43(tBu×2,18H),1.33(s,3H),1.32(s,3H),0.94(m,1H),0.70-0.60(m,2H),0.15(m,
1H).
Synthesize racemic-dimetylsilyl (the o- biphenyl -2- cyclopropyl indenyl of 4-) (4- (3', 5'- di-tert-butyl
Base) -2- methyl-indenyl) zirconium dichloride (catalyst 6, comparative example).
Lithium { 1- [4- (3', 5'- di-tert-butyl-phenyl) -2- methyl indenes salt] }: 7- (3,5- di-tert-butyl-phenyl) -2- methyl
Solution of the indenes (5.46g, 17.14mmol) in diethyl ether (50mL) is in -35 DEG C of pre-cooling 0.5h.-butyl lithium (2.5M, 7mL,
17.5mmol) be added.The solution stirs 17h at room temperature.All volatile matter volatilizations.Residue washed with hexane (10mL × 4) and
Vacuum drying is to generate crude product (5.7g).
Chloro dimethyl [4- (3', 5'- di-tert-butyl-phenyl) -2- methylindenyl] silane: above-mentioned crude product (1.4g,
4.315mmol) solution in diethyl ether (20mL) is in -35 DEG C of pre-cooling 30min.Me2SiCl2(8g, 61.99mmol) be added with
And the white slurry stirs 17h at room temperature.All volatile matter volatilizations.Residue is extracted with pentane (20mL) and the filtrate is concentrated
The product (1.74g, 98%) is generated to be dried in vacuo.
Dimetylsilyl [4- (3', 5'- di-tert-butyl-phenyl) -2- methylindenyl] trifluoromethayl sulfonic acid ester: chloro
Dimethyl [4- (3', 5'- di-tert-butyl-phenyl) -2- methyl-indenyl] silane (1.71g, 4.16mmol) is in toluene (10mL)
Solution with stirring be added to trifluoro-methane sulfonic acid silver solution (1.1g, 4.28mmol) in toluene (5mL).The white slurry
3h is stirred at room temperature.Toluene and the residue is removed in vacuum to be extracted by pentane (25mL).The pentane filter vacuum is concentrated to produce
Raw product (1.88g)
(the o- biphenyl -2- cyclopropyl indenyl of 4-) (4- (3', 5'- di-tert-butyl-phenyl) -2- methyl-indenyl) dimethyl-silicon
Alkane: dimetylsilyl [4- (3', 5'- di-tert-butyl-phenyl) -2- methyl-1 H- indenes -1- base] trifluoromethayl sulfonic acid ester
The cooled solution of (0.71g, 1.353mmol) in diethyl ether (10mL) is added to the lithium [1- (o- biphenyl -2- cyclopropyl indenes of 4-
Salt)] pre-cooled mixture of (0.435g, 1.384mmol) in diethyl ether (20mL).The solution stirs 17h at room temperature.Diethyl ether
Volatilization.Residue pentane (30mL) extracts and pentane filter vacuum concentration is to generate the white solid of crude product
(0.9g)。
Double lithium dimetylsilyl (the o- biphenyl -2- cyclopropyl indenes salt of 4-) (4- (3', 5'- di-tert-butyl-phenyl) -2-
Methyl indenes salt): -butyl lithium (2.5M, 1mL, 2.5mmol) is added to above-mentioned crude product (0.86g, 1.259mmol) in diethyl
Cooled solution in ether (25mL).The solution stirs 22h at room temperature.All volatile matters are removed in vacuum.Residue with pentane (10mL ×
2) it washes and is dried in vacuo to generate two-lithium compound as Et2O adduct (0.915g).
Dimetylsilyl (the o- biphenyl -2- cyclopropyl indenyl of 4-) (4- (3', 5'- di-tert-butyl-phenyl) -2- methyl -
Indenyl) zirconium dichloride: by above-mentioned [double lithium dimetylsilyl (the o- biphenyl -2- cyclopropyl indenes salt of 4-) (4- (bis- uncles of 3', 5'-
Butyl phenyl) -2- methyl indenes salt)] [Et2O] (0.9g, 1.17mmol) in Et2Cooled solution in O (15mL) is added to ZrCl4
(0.275g, 1.18mmol) is in Et2Pre-cooling slurry in O (15mL).20h is stirred at room temperature in the mixture.The solution is evaporated.
Residue is washed (15mL is primary and 5mL is primary) with pentane and is then extracted with toluene (20mL).The toluenic filtrate is evaporated and uses
Diethyl ether is washed and then is washed with pentane to provide 0.11g (11%) racemic/meso ratio 5:1 metallocene.The product is further
Washed with diethyl ether with generate the dimetylsilyl of 0.04g (4.1%) (the o- biphenyl -2- cyclopropyl indenyl of 4-) (4- (3',
5'- di-tert-butyl-phenyl) -2- methyl-indenyl) zirconium dichloride, racemic/meso ratio 33:1.1H NMR(400MHz,
CD2Cl2,23℃:rac:7.67(m,1H),7.59(m,2H),7.4(m,6H),7.33(m,1H),7.15(m,1H),7.08(m,
5H),7.01(m,1H),6.96(m,1H),6.85(s,1H),6.00(s,1H),2.22(s,3H),1.89(m,1H),1.34-
1.32(tBu×2overlapped with SiMe2, 24H), 0.94 (m, 1H), 0.73-0.60 (m, 2H), 0.15, pairs of (m, 1H)
It is displaced in the feature 1H nmr chemical of meso: s, 1H), 2.38 (s, 3H), 1.90 (m, 1H), 1.46 (s, 3H, SiMe), 1.33
(s,18H,tBu×2),1.23(s,3H,SiMe).
Supported catalyst
Load the bis- (2- methyl -4- (3', 5'- di-t-butyl -4'- methoxyphenyl)-of racemic-dimetylsilyl
Indenyl) zirconium dichloride (catalyst A).43.0mg, 0.0420mmol catalyst 1 (wherein have 1.2 equivalent toluene) and
0.3854g 30wt%MAO stirs 1.5h in 2mL toluene together in toluene.In celstir bottles small, MAO will be used
(SMAO) (1.0499g) pretreated 130 DEG C of calcined silicas are slurried in 20ml toluene and freeze.By the transition
Metallic catalyst is added to the silica and stirs 1 hour.By the way that the slurry is placed on refrigerator during this hour
Middle holding cooling.Then the slurry stirs 1 hour at 40 DEG C.Thereafter it is filtered, it is reslurried at 60 DEG C in 20ml toluene
Change 30min and refilters.The slurry in 20ml toluene 60 DEG C still further slurried 30min and in addition filtering twice.It should
Solid is washed with the pentane of 25ml toluene and 10ml.The solid is dried in vacuum overnight.0.9177g obtains pink solid.
SMAO is generally prepared as follows: by 130 DEG C of calcining DavisonTM(20.8606g is forged 948 silica at 130 DEG C
Burn) it is slurried in 121ml toluene, and the cooling in refrigerator (- 35 DEG C).By MAO, (50.5542g, 30wt% are in toluene
Middle solution) it is slowly added into together by 3 parts and SiO 2 slurry, refrigerator is returned it to, is continued between charging rather
Clock (about 2min).The slurry is stirred at room temperature 2 hours, is filtered with Fine glass sintering feed filter, in 80mL toluene
In be reslurried 15min at room temperature, then filter again.It is right that the solid is reslurried 30min at 80 DEG C in 80ml toluene
After filter.The solid is reslurried 30min in 80ml toluene at 80 DEG C, and then last time filters.The celstir bottles and solid
Body 40ml toluene rinse.Then the solid is washed and is dried in vacuo with pentane 24 hours.Collect the runny of 28.9406g
White powder.
Load bis- (2- methyl -4- (3', the 5'- di-t-butyl-phenyl)-indenyl) dichloros of racemic-dimetylsilyl
Change zirconium (catalyst B).Bis- (2- methyl -4- (3', 5'- di-t-butyl-phenyl)-indenyls) two of racemic-dimetylsilyl
Zirconium chloride (catalyst 7) (36mg, 0.042mmol) and MAO (0.3480g 30 weight % in toluene solution) and 2ml toluene
Mixing, and start that 1hr 10min is stirred at room temperature.SMAO (1.0598g) is slurried in 20ml toluene and is freezing
Freezing in device (- 35 DEG C).The catalyst solution is added to the slurry and stirring 1h.The slurry be placed into refrigerator frequently with
It is kept to be slightly less than room temperature.Then the slurry is filtered in 40 DEG C of stirring 2h, be reslurried 30min at 60 DEG C in 20ml toluene
With refilter.Before filtering again, the slurry in 20ml toluene in 60 DEG C of still further slurried 30min, then at 60 DEG C
Last time is reslurried 30min.Slurry filtering is for the last time and the celstir bottles is used 20ml toluene rinse.The solid
It is washed and is dried with pentane to generate the pink solid of 0.9494g.
Load bis- (4- (3', 5'- di-t-butyl -4'- the methoxyphenyl) -2- cyclopropyl indenyls) two of dimetylsilyl
Zirconium chloride (catalyst C).Bis- (4- (3', 5'- di-t-butyl -4'- the methoxyphenyl) -2- cyclopropyl indenes of dimetylsilyl
Base) zirconium dichloride (catalyst 4) (25.5mg, 0.0252mmol) and MAO (0.2141g, 30 weight % are in toluene solution)
It is mixed with 2ml toluene and starts that 1h is stirred at room temperature.SMAO (0.6308g) is slurried in 20ml toluene and is freezing
5min is freezed in device (- 35 DEG C).The catalyst solution is added to the slurry and stirring 1h.The slurry be placed into refrigerator with
It is kept to be slightly less than room temperature.Then the slurry is filtered in 40 DEG C of stirring 2h, be reslurried 30min at 60 DEG C in 20ml toluene
With refilter.Before filtering again, the slurry in 20ml toluene in 60 DEG C of still further slurried 30min, then at 60 DEG C
Last time is reslurried 30min.Slurry filtering is for the last time and the celstir bottles is used 20ml toluene rinse.The solid
It is washed and is dried in vacuo with pentane.Collect the pink solid of 0.5682g.
Load bis- (4- (3', 5'- di-t-butyl-phenyl) -2- cyclopropyl indenyl) zirconium dichlorides of dimetylsilyl (are urged
Agent D).Bis- (4- (3', 5'- di-t-butyl-phenyl) -2- cyclopropyl indenyl) zirconium dichloride (catalyst of dimetylsilyl
3).(31.0mg, 0.0342mmol) and MAO (30 weight % of 0.2869g is in toluene solution) mixed with 2ml toluene and
Start that 1h is stirred at room temperature.SMAO (0.8565g) is slurried in 20ml toluene and freezes in refrigerator (- 35 DEG C)
5min.The catalyst solution is added to the slurry and stirring 1h.The slurry is placed into refrigerator frequently to keep it slightly
Lower than room temperature.Then the slurry is filtered in 40 DEG C of stirring 2h, be reslurried 30min at 60 DEG C in 20ml toluene and refilter.
Before filtering again, the slurry in 20ml toluene in 60 DEG C of still further slurried 30min, then 60 DEG C of last times again
Slurried 30min.Slurry filtering is for the last time and the celstir bottles is used 20ml toluene rinse.The solid with pentane wash with
And vacuum drying.Collect the pink solid of 0.8066g.
Load dimetylsilyl (the o- biphenyl -2- cyclopropyl indenyl of 4-) (2- methyl -4- (3', 5'- di-t-butyl -
4'- methoxyphenyl)-indenyl) zirconium dichloride (catalyst E).Dimetylsilyl (the o- biphenyl -2- cyclopropyl indenyl of 4-)
(2- methyl -4- (3', 5'- di-t-butyl -4'- methoxyphenyl)-indenyl) zirconium dichloride (catalyst 5).(22.4mg,
0.0257mmol) and MAO (30 weight % of 0.22g is in toluene solution) is mixed with 2ml toluene and is started to stir at room temperature
Mix 1h.SMAO (0.6439g) it is slurried in 20ml toluene and in refrigerator (- 35 DEG C) freezing 5min.The catalyst is molten
Liquid is added to the slurry and stirring 1h.The slurry is placed into refrigerator to keep it to be slightly less than room temperature.The slurry is 40
Then DEG C stirring 2h is filtered, 30min is reslurried at 60 DEG C in 20ml toluene and is refiltered.Before filtering again, the silt
Slurry, in 60 DEG C of still further slurried 30min, is then reslurried 30min in 60 DEG C of last times in 20ml toluene.The slurry
Filtering is for the last time and the celstir bottles is used 20ml toluene rinse.The solid is washed and is dried in vacuum overnight with pentane.It collects
The pink solid of 0.5910g.
Load dimetylsilyl (the o- biphenyl -2- cyclopropyl indenyl of 4-) (2- methyl -4- (3', 5'- di-t-butyl -
Phenyl)-indenyl) zirconium dichloride (catalyst F).In 20ml bottle, the metallocene dimetylsilyl (o- biphenyl -2- of 4-
Cyclopropyl indenyl) (2- methyl -4- (3', 5'- di-t-butyl-phenyl)-indenyl) zirconium dichloride (catalyst 6) (19.4mg,
0.0230mmol) 1h is stirred together with other 2ml toluene with MAO (30 weight % in toluene, 0.2125g solution).Small
In the celstir bottle of type, SMAO (0.5747g) is slurried in 20ml toluene.The catalyst solution be added to the slurry it
Before, the celstir bottles freezes 1min in refrigerator.Every 10min stops 1min to slurry stirring 1h in refrigerator simultaneously.So
The slurry is heated to 40 DEG C and stirring 2h afterwards.Then the slurry filters, and is reslurried in 20ml toluene and at 60 DEG C
It is further stirred for 30min.Then the slurry filters, and is reslurried in 20ml toluene and is further stirred for 30min at 60 DEG C.Then
Slurry filtering is reslurried in 20ml toluene and is further stirred at 60 DEG C 30min and then filters last time.It should
Celstir bottles are dried in vacuo with 20ml toluene rinse and the solid.Collect the pink solid of 0.5044g.
The universal method polymerizeing on a small scale
Unless otherwise indicated, propylene homo and ethylene-propylene copolymer (if any) in parallel, pressurized reactor into
Row, such as in US 6,306,658；US 6,455,316；WO00/09255 and Murphy et al., J.Am.Chem.Soc., 2003,
125, disclosed in the 4306-4317 pages, every is all incorporated herein as reference.Although being aggregated to down from one
One polymerization, specific amount, temperature, solvent, reactant, reactant ratio, pressure and its dependent variable may need to adjust, still
Following discloses the typical polymerizations carried out in parallel, pressurized reactor.
Use the propylene polymerization embodiment 1-18 of metallocene.By pre-weighed vial insertion body (glass vial
Insert it) is assembled in each reaction vessel of reactor with disposable agitating paddle, reactor includes 48 individually reaction appearances
Device.Then, reactor is closed, propylene (usually 1ml) is introduced into each container as gas, then, solvent is added (usually
For isohexane) so that total reaction volume (including what is be then added) is reached 5ml, heating response device container to its set temperature is (usually
Between 50 DEG C and 110 DEG C).
The content of the container stirs at 800 rpm.Then by the aluminium methyl of the 100-1000 molar equivalent in toluene
Oxygen alkane (MAO) activator solution is injected into the reaction vessel of 500 microlitres of toluene, is subsequently added into the toluene solution of catalyst
(0.50mM, usual 20-40 nanomole catalyst typically in toluene) and another equal portions toluene (500 microlitres).Equivalent is
It is determined based on the molar equivalent relative to the amount of the substance of transition metal in transition metal complex.Then carry out reaction until
Reach predetermined pressure drop by reaction.It is alternatively that can carry out reaction to reach scheduled time quantum.Thereafter, compressed air is used
To container pressurization, reaction was completed.After polymerization, by the vial insertion body containing polymer product and solvent from pressure
Room and inert-atmosphere glove box remove, and are evaporated in vacuo with Genevac HT-12 centrifugal separator and Genevac VC3000D
Device removes volatile component at raised temperature and decompression.Then bottle is weighed, measures the yield of polymer product.Gained
Polymer is analyzed with quick GPC, to determine molecular weight, determines fusing point with DSC.
Pre-weighed vial insertion body and disposable agitating paddle are filled using the ethylene propylene copolymer of supported catalyst
It is fitted in each reaction vessel of reactor, reactor includes 48 individual reaction vessels.Then, reactor is closed, it will
Propylene is introduced into each container and removes nitrogen from system.If any unit receives hydrogen, i.e. by it during reset procedure
It introduces.Then solvent (usually isohexane) is added according to the reaction volume of setting makes total reaction volume (including what is be then added)
Generally reach 5ml.Scavenger and/or co-catalyst and/or chain-transferring agent, the three-n-octyls such as in toluene are added at this moment
Aluminium (usually 100-1000 nanomole).Now in the content of 800rpm stirring container.Addition propylene gas, which reaches, now sets
Fixed pressure.Now, reactor vessel is heated to the running temperature of its setting (usually between 50 DEG C and 110 DEG C).Now
Ethylene is added as comonomer, it is added to scheduled pressure (usually 10-100psi) as gas, which is higher than third
The pressure of alkene, simultaneous reactions container are heated to scheduled running temperature.Vortex stirring slurry catalyst is so as to by catalyst particle
It suspends in the solution.Now, buffer toluene (usually 100 microlitres) are injected in the reactor, the toluene solution of catalyst (leads to
Often it is 3mg/ml concentration) and another equal portions toluene (500 microlitres).Then reaction is carried out until reaching predetermined pressure by reaction.
It is alternatively that can carry out reaction to reach scheduled time quantum.At this point, to container pressurization, reaction was completed with compressed air.Poly-
After closing reaction, the vial insertion body containing polymer product and solvent is removed from pressure chamber and inert-atmosphere glove box,
And with Genevac HT-12 centrifugal separator and Genevac VC3000D cold boiler at raised temperature and decompression
Remove volatile component.Then bottle is weighed, measures the yield of polymer product.Resulting polymers are divided with quick GPC
Analysis, to determine molecular weight, determines fusing point with DSC.
In order to measure various molecular weight relative values with GPC, Temperature Size Exclusion is carried out using automation " quick GPC " system
Chromatography, in US 6,491,816；US 6,491,823；US 6,475,391；US 6,461,515；US 6,436,292；US
6,406,632；US 6,175,409；US 6,454,947；US 6,260,407；With in US 6,294,388 generally
Description, for US, an each of these piece, which is cited in full text, to be described herein by reference.The device has concatenated three 30 cm x 7.5
The linear columns of millimeter, each column contain root PLgel 10um, Mix B.GPC system 580-3,390,000g/mol range
Polystyrene standard calibration.The system is in the elution flow rate of 2.0ml/min and the operation of 165 DEG C of oven temperature.1,2,4-
Trichloro-benzenes is used as eluant, eluent.Polymer samples are dissolved in 1,2,4- trichloro-benzenes with the concentration of 0.1-0.9mg/ml.By 250uL's
Polymer solution is injected into system.Use the concentration of polymer in Polymer Char IR4 detector monitors eluant, eluent.Institute
The molecular weight shown is not corrected relative to linear polystyrene standard, and.
Differential scanning calorimetry (DSC) (DSC program -1) measurement carries out on TA-Q200 instrument, to determine polymer
Fusing point.Then sample allows to cool to ambient temperature overnight in 220 DEG C of progress, 15 minutes preannealings.Then, by sample with 100 DEG C/
The rate of min is heated to 220 DEG C, then cooling with the rate of 50 DEG C/min.Fusing point is collected during heating.
The amount (wt%) of the ethylene combined in polymer is by quick FT-IR spectrum in Bruker Vertex 70IR with anti-
Emission mode measures.The sample of form of film is prepared by vapor deposition techniques.From 729.8 and 1157.9cm-1Locate the ratio between peak height
Obtain the weight percent of ethylene.This method is calibrated using the ethylene/propene copolymer of wt% ethylene contents known to one group.
The general process of supported catalyst polypropylene is used in 2L reactor
The catalyst of load is in HYDROBRITETMCatalyst slurried in oil, that obtained slurry is loaded containing 5wt%.2L
Propylene (600ml), H are housed in reactor2(being provided from the container of 183ml, under the pressure shown in table 3) and three n-octyls
Aluminium, the hexane solution of the 4.76vol% of 1.0ml.Thereafter, temperature of reactor is increased to 70 DEG C.Then, together with 200ml propylene
It is injected into required amount of in 2 raising pressure autoclave reactors containing catalyst slurry.Polymerization reaction is set to carry out the time of predetermined period,
Usually 60 minutes.Then, reactor is cooling and be vented.
Melt flow rate (MFR) (MFR)
MFR is with melt index apparatus according to ASTM D1238, condition L, in 230 DEG C and 2.16kg load measurement.
The determination of Mw, Mn and Mw/Mn use high-temperature gel permeation chromatography method (Polymer Laboratories), equipped with poor
Show refractive index detector (DRI).Use three Polymer LaboratoriesPLgel, 10 μm of Mixed-B columns.Nominal flow rate
For 1.0ml/min, nominal injection volume is 300 μ L.Various transfer lines, column and differential refractometer (DRI detector) are placed in guarantor
It holds in 160 DEG C of baking oven.4 liters of Aldrich preparation grade 1,2,4- tri- are dissolved in using 6g butylated hydroxytoluene as antioxidant
Solvent of the preparation for experiment in chlorobenzene (TCB).Then, TCB mixture is filtered through 0.1 μm of teflon filter.Into
Before entering GPC instrument, TCB deaerates through on-line degassing device.By the way that the polymer dried is placed in vial, it is added the desired amount of
Then mixture is heated at 160 DEG C and continuously shakes about 2 hours and prepare polymer solution by TCB.All amounts are surveyed by weight
Amount.Injection concentration is 0.5 to 2.0mg/ml, and the sample of higher molecular weight uses lower concentration.Before each sample sample introduction, clean
DRI detector.Then flow velocity in a device increases to 1.0ml/min, and DRI stablizes 8 hours before injecting first sample.
The column carried out using a series of monodisperse polystyrenes (PS) standard sample calibration is combined to measure molecule by universal calibration relationship
Amount.MW is calculated in each elution volume with equation.
Wherein, subscript variable " X " represents test sample, and the representative polystyrene of those subscriptings " PS ".In this method
In, aPS=0.67 and KPS=0.000175, wherein aXAnd KXIt is obtained from disclosed document.Specifically, for vinyl polymerization
Object, a and K=0.695 and 0.000579 are 0.705 and 0.0002288 for acrylic polymers.
Concentration c, each point in chromatogram are the DRI signal subtracted from baseline, IDRI, it is calculated using following equation:
C=KDRIIDRI/(dn/dc)
Wherein KDRIIt is the constant determined by calibration DRI, and (dn/dc) is system refractive index increment.Specifically,
For acrylic polymers and ethene polymers, dn/dc=0.109.
Mass recovery is obtained to the integral area of elution volume and the ratio calculation of plastic injection quality from concentration chromatogram, etc.
In the predetermined concentration multiplied by injection loop volumes.
All molecular weight are recorded with g/mol, unless otherwise indicated.If in GPC-DRI program and " Rapid GPC ",
There is conflict between GPC-DR, it should use above-mentioned GPC-DRI method immediately.The further details of related measurement Mw, Mn, MWD
The 24-25 pages of US 2006/0173123 is disclosed in, in paragraph [0334]-[0341].
Differential scanning calorimetry (DSC)-program -2
Melting temperature (Tm) is measured by using DSCQ200 unit via differential scanning calorimetry (" DSC ").Sample is first
It is balanced at 25 DEG C, is then heated to 220 DEG C (heating for the first time) using the rate of heat addition of 10 DEG C/min.Sample is maintained at 220
DEG C 3 minutes.Sample is then cooled to -100 DEG C (cooling for the first time) with the constant cooling rate of 10 DEG C/min.Sample is at -100 DEG C
Then balance is heated to 220 DEG C (second of heating) with the constant heating rate of 10 DEG C/min.Use TA Gneral analysis software point
It analyses crystalline exotherm peak (cooling down for the first time) and determines and the corresponding temperature peaks of 10 DEG C/min cooling rate.Use TA Gneral analysis
Software analysis fusing endothermic peak (second of heating) simultaneously determines the melting temperature peak (Tm) for corresponding to the 10 DEG C/min rate of heat addition.In
When clashing between DSC process -1 and DSC process -2, DSC process -2 should be used.
1% Secant flexural modulus
The measurement of 1% Secant flexural modulus uses Instron machine according to ASTM D 790 (A, 1.0mm/min), uses
3 stick of ISO 37- type, using the crosshead speed of 1.0mm/min and the support span of 30.0mm.
Aggregated data is disclosed in table 1-5.
Table 1: small-scale Solution Propylene polymerization uses the catalyst of 0.025 μm of ol and the MAO condition of 500 molar equivalents:
Isohexane solvent, total volume=5ml.
As Fig. 2 is illustrated, there is high-melting-point and high molecular weight using the polymer that catalyst 1 produces.Fig. 3 citing
Illustrate that catalyst 1 balances catalyst activity and more high-melting-point.In other words, the polymer can not reduce catalyst activity and
Improve fusing point.
All documents disclosed herein, including any priority document and/or test program, with not with conflict herein
Degree introducing is described herein by reference, as shown in from foregoing general description and specific embodiment, although having been described above and retouching
Form of the invention has been stated, but various improvement can also be made without departing from the spirit and scope of the present invention.Cause
This, is not intended that the invention be limited to this.It is also contemplated that term " including (comprising) " is in Australian law
The synonym of term " including (including) ".Similarly, transition phrase is had before component, element or one group of element "
Comprising ", it should be understood that we also contemplate the group of same composition or element, have transition phrase " substantially by ... group
At ", " by ... form ", before " be selected from by ... the group formed " or " being " is located at the component, element or element set,
Vice versa.
Claims (31)
1. the transition metal complex that formula (I) indicates:
Wherein M1Selected from titanium, zirconium and hafnium；
R1And R2It can be same or different, and individually hydrogen atom, C1-C10Alkyl, C1-C10Alkoxy, C6-C10Virtue
Base, C6-C10Aryloxy group, C2-C40Alkenyl, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40Aryl alkenyl, OH group or
Halogen atom；
R3To R7Can be identical or different, and individually hydrogen atom, cyclopropyl, halogen atom can be by the C of halogenation1-C10Alkyl,
It can be by the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40Aryl alkenyl ,-NR
'2,-SR' ,-OR' ,-OSiR'3Or-PR'2Group, wherein R' is following one: hydrogen atom, halogen atom, C1-C10Alkyl；
R13Meet following one:
Wherein: R15,R16,R17It is same or different, and is hydrogen atom, halogen atom, C1-C20Alkyl, C1-C20Fluoro
Alkyl or sila alkyl, C6-C30Aryl, C7-C40Aryl alkyl, or a R15With a R16, together with R13It is middle to connect them
Atom, be formed together one or more rings；M2It is one of carbon, silicon, germanium or tin or a variety of；
R8And R12It can be same or different, and individually hydrogen atom, halogen atom can be by the C of halogenation3-C10Alkyl, can
By the C of halogenation6-C10Aryl, C7-C40Aryl alkyl ,-NR'2,-SR',-OR',-OSiR'3Or-PR'2Group, wherein R' be
Hydrogen atom, halogen atom, C1-C10Alkyl or C6-C10One of aryl；
R9And R11It is same or different, and selected from can be by the C of halogenation2-C20Alkyl, can be by the C of halogenation6-C10Aryl, C2-
C10Alkenyl, C7-C20Aryl alkyl, C7-C20Alkylaryl, C8-C20Aryl alkenyl；With
R10It is-OR ' ,-OSiR '3, wherein R' is following one: hydrogen atom, halogen atom, C1-C10Alkyl, or C6-C10Virtue
Base；With
R14It is hydrogen atom, halogen atom can be by the C of halogenation3-C10Alkyl, can be by the C of halogenation6-C10Aryl, C7-C40Aryl alkane
Base ,-NR'2,-SR',-OR',-OSiR'3Or-PR'2Group, wherein R' is as defined above.
2. the transition metal complex of claim 1, wherein R10It is-OR' or-OSiR'3, wherein R' is following one: hydrogen is former
Son, halogen atom, C1-C10Alkyl.
3. the transition metal complex of claim 1, wherein R10It is-OR' group, wherein R' is following one: hydrogen atom, halogen
Atom, C1-C10Alkyl, or C6-C10Aryl.
4. the transition metal complex of claim 1, wherein R3It is C1-C10Alkyl or C6-C10Aryl.
5. the transition metal complex of claim 1, wherein R9And R11Each be selected from normal-butyl, isobutyl group, and tert-butyl and
R10It is OR', wherein R' is C1-C10Alkyl.
6. a kind of transition metal complex is indicated by formula (II):
M1Selected from titanium, zirconium and hafnium；
R1And R2It can be same or different, and individually hydrogen atom, C1-C10Alkyl, C1-C10Alkoxy, C6-C10Virtue
Base, C6-C10Aryloxy group, C2-C40Alkenyl, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40Aryl alkenyl, OH group or
Halogen atom；
R3To R7Can be identical or different, and individually hydrogen atom, cyclopropyl, halogen atom can be by the C of halogenation1-C10Alkyl,
It can be by the C of halogenation6-C10Aryl, C2-C10Alkenyl, C7-C40Aryl alkyl, C7-C40Alkylaryl, C8-C40Aryl alkenyl ,-NR
'2,-SR' ,-OR' ,-OSiR'3Or-PR'2Group, wherein R' is following one: hydrogen atom, halogen atom, C1-C10Alkyl；
R13Meet following one:
Wherein R15,R16,R17It is same or different, and is hydrogen atom, halogen atom, C1-C20Alkyl, C1-C20Fluoroalkane
Base or sila alkyl；M2It is one of carbon, silicon, germanium or tin or a variety of；
Wherein R8And R12It respectively can be same or different, and individually hydrogen atom, halogen atom can be by the C of halogenation3-
C10Alkyl, can be by the C of halogenation6-C10Aryl, C7-C40Aryl alkyl ,-NR'2,-SR',-OR',-OSiR'3Or-PR'2Group,
Wherein R' is following one: hydrogen atom, halogen atom, C1-C10Alkyl, or C6-C10Aryl；
Wherein each R9And R11It is same or different, and being individually can be by the C of halogenation2-C20Alkyl, can be by the C of halogenation6-C10
Aryl, C2-C10Alkenyl, C7-C20Aryl alkyl, C7-C20Alkylaryl, or C8-C20Aryl alkenyl；With
Wherein each R10It is respectively selected from-OR ' ,-OSiR '3, wherein R' is following one: hydrogen atom, halogen atom, C1-C10Alkyl,
Or C6-C10Aryl.
7. the transition metal complex of claim 6, wherein each R10It is-OR' ,-OSiR' respectively3, wherein R' be it is following it
One: hydrogen atom, halogen atom, C1-C10Alkyl.
8. the transition metal complex of claim 6, wherein each R10It is-OR' or-OSiR' respectively3, wherein R' be it is following it
One: hydrogen atom, halogen atom, C1-C10Alkyl, or C6-C10Aryl.
9. the transition metal complex of claim 6, wherein each R10It is-OR' respectively, wherein R' is following one: hydrogen atom,
Halogen atom, C1-C10Alkyl.
10. the transition metal complex of claim 7, wherein each R10It is methoxyl group, ethyoxyl, positive propoxy, isopropyl respectively
Oxygroup, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy.
11. the transition metal complex of claim 6, wherein each R9With each R11Selected from normal-butyl, isobutyl group, and tertiary fourth
Base and each R10It is OR', wherein R' is C1-C10Alkyl.
12. the transition metal complex of claim 6, wherein each R1And R2It can be same or different, and individually halogen
Atom；
Wherein each R3It can be same or different, and individually C1-C10Alkyl；
Wherein each R4,R5,R6And R7It can be same or different, and individually hydrogen atom or C1-C10Alkyl；With
Wherein each R8And R12Individually hydrogen atom；R13It is-SiR "2, wherein each R " can be it is same or different, and respectively
It is hydrogen or methyl；Wherein each R9And R11It is tert-butyl；Wherein each R10It is methoxyl group.
13. the transition metal complex of claim 6, wherein each R1And R2It is Cl atom；Wherein each R3It is methyl；Wherein each R4,
R5,R6And R7It is hydrogen atom；And R13It is-SiR "2, wherein each R " is methyl.
14. catalyst system, it includes the transition metal complexes of activator and claim 1 or 6.
15. the catalyst system of claim 14, wherein the activator includes aikyiaiurnirsoxan beta.
16. the catalyst system of claim 14, wherein the activator includes non-coordinating anion.
17. polymerization, including a) contact one or more olefinic monomers with catalyst system, which includes:
I) activator and ii) claim 1 or 6 transition metal complex.
18. the method for claim 17, wherein the activator includes aikyiaiurnirsoxan beta.
19. the method for claim 17, wherein the activator includes non-coordinating anion.
20. the method for claim 17, wherein one or more olefinic monomers include propylene.
21. the method for claim 17, wherein the catalyst compounds are loads.
22. the method for claim 17 further includes obtaining polymer.
23. the method for claim 22, wherein the polymer includes and is led to by 152.0 DEG C to 162.0 DEG C of fusing point of dsc measurement
Cross the M of gpc measurementwFor 60,000-1,400,000g/mol；The polypropylene for being 1.5-3.5 with the Mw/Mn by gpc measurement.
24. the transition metal complex of claim 1, wherein R3Selected from hydrogen and cyclopropyl；R9And R11Each of be selected from positive fourth
Base, isobutyl group；And R10Be methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or
Person's tert-butoxy.
25. the method for claim 17, wherein one or more olefinic monomers include ethylene and propylene.
26. the method for claim 22, wherein preparing polymer, two of them R using following transition metal complexes10Group is
Same or different group, and it is expressed as formula :-OR ' ,-OSiR '3, wherein R' is following one: hydrogen atom, and halogen is former
Son, C1-C10Alkyl or C6-C10Aryl, prepared polymer with by similar transition metal complex, in addition to two R10Base
Group is all other than hydrogen, in conjunction with identical activator and under the same conditions with the polymer phase ratio of same monomer polymerization preparation, Mw
Height at least 20%.
27. the method for claim 26, wherein one or more olefinic monomers include ethylene and propylene.
28. the method for claim 17, wherein there are alkyl aluminum scavengers, and the aluminium in alkyl aluminum scavenger is with respect to the mistake
The molar ratio for crossing the transition metal of metal complex is 100:1 or lower.
29. the transition metal complex of claim 1 or 6, wherein each R3It is cyclopropyl；With each R10It is ethyoxyl.
30. the method for claim 26, wherein one or more olefinic monomers are made of ethylene and propylene.
31. the transition metal complex of claim 6, wherein R3Selected from hydrogen and cyclopropyl；R9And R11Each of be selected from positive fourth
Base, isobutyl group；And R10Be methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or
Person's tert-butoxy.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361918328P | 2013-12-19 | 2013-12-19 | |
| US61/918,328 | 2013-12-19 | ||
| EP14163818.9 | 2014-04-08 | ||
| EP14163818 | 2014-04-08 | ||
| PCT/US2014/070591 WO2015095188A1 (en) | 2013-12-19 | 2014-12-16 | Bridged bis(indenyl) transitional metal complexes, production, and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105829326A CN105829326A (en) | 2016-08-03 |
| CN105829326B true CN105829326B (en) | 2019-11-08 |
Family
ID=50439281
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480068482.2A Expired - Fee Related CN105829326B (en) | 2013-12-19 | 2014-12-16 | Bis- (indenyl) transition metal complexes of bridging, its preparation and application |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP3083649A1 (en) |
| CN (1) | CN105829326B (en) |
| WO (1) | WO2015095188A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6840464B2 (en) * | 2016-02-16 | 2021-03-10 | 三井化学株式会社 | Method for producing transition metal compound, catalyst for olefin polymerization and olefin polymer |
| KR102064411B1 (en) * | 2016-11-22 | 2020-01-09 | 주식회사 엘지화학 | Metallocene supported catalyst and method for preparing polypropylene using the same |
| KR102431269B1 (en) * | 2018-11-02 | 2022-08-10 | 주식회사 엘지화학 | Novel transition metal compound and method for preparing polypropylene with the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1274701C (en) * | 2000-06-30 | 2006-09-13 | 埃克森美孚化学专利公司 | Metallocenes with bridged 4-phenyl-indenyl-ligand for olefin polymerization |
| CN102245620A (en) * | 2008-12-17 | 2011-11-16 | 日本聚丙烯株式会社 | Metallocene complex and method for polymerizing olefin |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE60102156T8 (en) * | 2000-06-30 | 2005-06-23 | Exxonmobil Chemical Patents Inc., Baytown | Bridged Bisindenyl Substituted Metallocene Compounds |
| KR20060028603A (en) * | 2004-09-25 | 2006-03-30 | 주식회사 엘지화학 | Ansa-metallocene compound, method for preparing the same and method for preparing polyolefin using the same |
| WO2013168928A1 (en) * | 2012-05-08 | 2013-11-14 | 주식회사 엘지화학 | Ansa-metallocene compound and method for preparing supported catalyst using same |
-
2014
- 2014-12-16 EP EP14871995.8A patent/EP3083649A1/en not_active Withdrawn
- 2014-12-16 WO PCT/US2014/070591 patent/WO2015095188A1/en active Application Filing
- 2014-12-16 CN CN201480068482.2A patent/CN105829326B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1274701C (en) * | 2000-06-30 | 2006-09-13 | 埃克森美孚化学专利公司 | Metallocenes with bridged 4-phenyl-indenyl-ligand for olefin polymerization |
| CN1332966C (en) * | 2000-06-30 | 2007-08-22 | 埃克森美孚化学专利公司 | Bridged bis (indenyl) metallocene compounds |
| CN102245620A (en) * | 2008-12-17 | 2011-11-16 | 日本聚丙烯株式会社 | Metallocene complex and method for polymerizing olefin |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2015095188A1 (en) | 2015-06-25 |
| EP3083649A4 (en) | 2016-10-26 |
| EP3083649A1 (en) | 2016-10-26 |
| CN105829326A (en) | 2016-08-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7196197B2 (en) | Non-coordinating anionic activators containing cations with long-chain alkyl groups | |
| JP2994746B2 (en) | Monocyclopentadienyl transition metal olefin polymerization catalyst | |
| RU2232766C2 (en) | Bridge-bound metallocenes, method for polymerization | |
| KR101685664B1 (en) | Supported hybrid catalyst and method for preparing of olefin based polymer using the same | |
| JP3382311B2 (en) | Catalyst composition and method for producing polyolefins | |
| JP2000511156A (en) | Open pentadienyl metallocenes, their precursors and polymerization catalysts therefrom | |
| CA2646567A1 (en) | Substituted group 4 metal complexes, catalysts and olefin polymerization process | |
| CN109996820A (en) | Metallocene catalyst, catalyst system and the method using it | |
| KR20100024433A (en) | 1-butene ethylene copolymers | |
| JP2002544282A (en) | Di- and tri-heteroatom-substituted indenyl metal complexes | |
| JP6681462B2 (en) | Hybrid supported catalyst system for ethylene slurry polymerization and method for producing ethylene polymer using the same | |
| CN110062777A (en) | Hybrid catalyst system and its application method | |
| KR101139108B1 (en) | Method for producing syndiotactic propylene polymer | |
| JP7238135B2 (en) | Olefin polymerization catalyst and olefin polymer prepared using the same | |
| JP2014513735A (en) | NOVEL CATALYST FOR PRODUCING VINYL-TERMINATE POLYMER AND METHOD OF USING THE SAME | |
| CN105829326B (en) | Bis- (indenyl) transition metal complexes of bridging, its preparation and application | |
| JP2022528411A (en) | Propylene-ethylene random copolymer | |
| US6319874B1 (en) | Method for producing metallocenes | |
| US11472828B2 (en) | Indacene based metallocene catalysts useful in the production of propylene polymers | |
| KR20220023004A (en) | Catalyst Comprising Mixed Transition Metal Compounds, Polyolefin Prepared Using the Same, and Processes for Preparing the Same | |
| JP2005504853A (en) | Branched polymers based on alpha-olefins | |
| JP2023116696A (en) | Polar olefin polymer and method for producing copolymer | |
| KR20220009900A (en) | Transition metal compound and catalyst composition comprising the same | |
| KR20210061954A (en) | Hybride supported metallocene catalyst and method for preparing polyethylene copolymer using the same | |
| JP2016164264A (en) | Olefin polymer production method and olefin polymerization catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20191108 |