KR20000022454A - Method for producing high melting-point polyolefins - Google Patents
Method for producing high melting-point polyolefins Download PDFInfo
- Publication number
- KR20000022454A KR20000022454A KR1019980710890A KR19980710890A KR20000022454A KR 20000022454 A KR20000022454 A KR 20000022454A KR 1019980710890 A KR1019980710890 A KR 1019980710890A KR 19980710890 A KR19980710890 A KR 19980710890A KR 20000022454 A KR20000022454 A KR 20000022454A
- Authority
- KR
- South Korea
- Prior art keywords
- compound
- formula
- mol
- solution
- nmr
- Prior art date
Links
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 130
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 150000001450 anions Chemical group 0.000 claims abstract description 22
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 22
- 238000002844 melting Methods 0.000 claims abstract description 19
- 230000008018 melting Effects 0.000 claims abstract description 19
- 101000588928 Condylactis gigantea Delta-actitoxin-Cgg1a Proteins 0.000 claims abstract description 11
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 10
- 150000003624 transition metals Chemical class 0.000 claims abstract description 10
- 230000002441 reversible effect Effects 0.000 claims abstract description 9
- 230000000737 periodic effect Effects 0.000 claims abstract description 7
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 4
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 4
- 229910052768 actinide Inorganic materials 0.000 claims abstract description 3
- 150000001255 actinides Chemical class 0.000 claims abstract description 3
- 230000007935 neutral effect Effects 0.000 claims abstract description 3
- -1 polyethylene Polymers 0.000 claims description 129
- 125000004429 atom Chemical group 0.000 claims description 48
- 125000001424 substituent group Chemical group 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 26
- 239000000047 product Substances 0.000 claims description 24
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical class C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 23
- 239000004698 Polyethylene Substances 0.000 claims description 22
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 20
- 125000004122 cyclic group Chemical group 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 229910052796 boron Inorganic materials 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 15
- 125000002524 organometallic group Chemical group 0.000 claims description 15
- 239000003446 ligand Substances 0.000 claims description 14
- 229920006395 saturated elastomer Polymers 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 11
- 238000007334 copolymerization reaction Methods 0.000 claims description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims description 11
- 229920000573 polyethylene Polymers 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 10
- 150000001336 alkenes Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical class C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003574 free electron Substances 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000004711 α-olefin Substances 0.000 claims description 7
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 229910052716 thallium Inorganic materials 0.000 claims description 6
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 5
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052733 gallium Inorganic materials 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000002879 Lewis base Substances 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910000085 borane Inorganic materials 0.000 claims description 3
- 238000003776 cleavage reaction Methods 0.000 claims description 3
- 238000001938 differential scanning calorimetry curve Methods 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 150000007527 lewis bases Chemical class 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 230000007017 scission Effects 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052714 tellurium Inorganic materials 0.000 claims description 3
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052776 Thorium Inorganic materials 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000013522 chelant Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 150000002469 indenes Chemical class 0.000 claims description 2
- 238000003780 insertion Methods 0.000 claims description 2
- 230000037431 insertion Effects 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 229920001903 high density polyethylene Polymers 0.000 claims 1
- 239000004700 high-density polyethylene Substances 0.000 claims 1
- 239000000725 suspension Substances 0.000 abstract description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 231
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 231
- 239000000243 solution Substances 0.000 description 149
- 239000000460 chlorine Substances 0.000 description 87
- 238000005481 NMR spectroscopy Methods 0.000 description 62
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 61
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 58
- 238000005160 1H NMR spectroscopy Methods 0.000 description 51
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 50
- 238000001816 cooling Methods 0.000 description 48
- 238000006116 polymerization reaction Methods 0.000 description 38
- 239000007787 solid Substances 0.000 description 38
- 239000000203 mixture Substances 0.000 description 33
- 239000011541 reaction mixture Substances 0.000 description 29
- 239000003921 oil Substances 0.000 description 25
- 235000019198 oils Nutrition 0.000 description 25
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 25
- 229910052739 hydrogen Inorganic materials 0.000 description 24
- 239000002244 precipitate Substances 0.000 description 24
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 23
- 239000000843 powder Substances 0.000 description 21
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 19
- 239000005977 Ethylene Substances 0.000 description 19
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 239000000370 acceptor Substances 0.000 description 17
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 16
- 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 15
- 238000001914 filtration Methods 0.000 description 14
- 239000000706 filtrate Substances 0.000 description 12
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 229940125782 compound 2 Drugs 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 229910007926 ZrCl Inorganic materials 0.000 description 9
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 9
- 239000012043 crude product Substances 0.000 description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- RURFJXKOXIWFJX-UHFFFAOYSA-N (2,3,4,6-tetrafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C=C(F)C(F)=C1F RURFJXKOXIWFJX-UHFFFAOYSA-N 0.000 description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 7
- 238000004821 distillation Methods 0.000 description 7
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 125000006850 spacer group Chemical group 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- PYRKKGOKRMZEIT-UHFFFAOYSA-N 2-[6-(2-cyclopropylethoxy)-9-(2-hydroxy-2-methylpropyl)-1h-phenanthro[9,10-d]imidazol-2-yl]-5-fluorobenzene-1,3-dicarbonitrile Chemical compound C1=C2C3=CC(CC(C)(O)C)=CC=C3C=3NC(C=4C(=CC(F)=CC=4C#N)C#N)=NC=3C2=CC=C1OCCC1CC1 PYRKKGOKRMZEIT-UHFFFAOYSA-N 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- GCTFWCDSFPMHHS-UHFFFAOYSA-M Tributyltin chloride Chemical compound CCCC[Sn](Cl)(CCCC)CCCC GCTFWCDSFPMHHS-UHFFFAOYSA-M 0.000 description 5
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 5
- 239000000010 aprotic solvent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- XGRJZXREYAXTGV-UHFFFAOYSA-N chlorodiphenylphosphine Chemical compound C=1C=CC=CC=1P(Cl)C1=CC=CC=C1 XGRJZXREYAXTGV-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- ASGMFNBUXDJWJJ-JLCFBVMHSA-N (1R,3R)-3-[[3-bromo-1-[4-(5-methyl-1,3,4-thiadiazol-2-yl)phenyl]pyrazolo[3,4-d]pyrimidin-6-yl]amino]-N,1-dimethylcyclopentane-1-carboxamide Chemical compound BrC1=NN(C2=NC(=NC=C21)N[C@H]1C[C@@](CC1)(C(=O)NC)C)C1=CC=C(C=C1)C=1SC(=NN=1)C ASGMFNBUXDJWJJ-JLCFBVMHSA-N 0.000 description 4
- WZZBNLYBHUDSHF-DHLKQENFSA-N 1-[(3s,4s)-4-[8-(2-chloro-4-pyrimidin-2-yloxyphenyl)-7-fluoro-2-methylimidazo[4,5-c]quinolin-1-yl]-3-fluoropiperidin-1-yl]-2-hydroxyethanone Chemical compound CC1=NC2=CN=C3C=C(F)C(C=4C(=CC(OC=5N=CC=CN=5)=CC=4)Cl)=CC3=C2N1[C@H]1CCN(C(=O)CO)C[C@@H]1F WZZBNLYBHUDSHF-DHLKQENFSA-N 0.000 description 4
- YSUIQYOGTINQIN-UZFYAQMZSA-N 2-amino-9-[(1S,6R,8R,9S,10R,15R,17R,18R)-8-(6-aminopurin-9-yl)-9,18-difluoro-3,12-dihydroxy-3,12-bis(sulfanylidene)-2,4,7,11,13,16-hexaoxa-3lambda5,12lambda5-diphosphatricyclo[13.2.1.06,10]octadecan-17-yl]-1H-purin-6-one Chemical compound NC1=NC2=C(N=CN2[C@@H]2O[C@@H]3COP(S)(=O)O[C@@H]4[C@@H](COP(S)(=O)O[C@@H]2[C@@H]3F)O[C@H]([C@H]4F)N2C=NC3=C2N=CN=C3N)C(=O)N1 YSUIQYOGTINQIN-UZFYAQMZSA-N 0.000 description 4
- YSAXEHWHSLANOM-UHFFFAOYSA-N 2-methyl-1h-indene Chemical compound C1=CC=C2CC(C)=CC2=C1 YSAXEHWHSLANOM-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229940127007 Compound 39 Drugs 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 241001274216 Naso Species 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 235000011089 carbon dioxide Nutrition 0.000 description 4
- JZPDBTOWHLZQFC-UHFFFAOYSA-N chloro-di(propan-2-yl)phosphane Chemical compound CC(C)P(Cl)C(C)C JZPDBTOWHLZQFC-UHFFFAOYSA-N 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 4
- SSLYIXHGTXGSJZ-UHFFFAOYSA-L cyclopentane;dichlorozirconium;indene Chemical compound Cl[Zr]Cl.[CH]1[CH][CH][CH][CH]1.C1=CC=C[C]2[CH][CH][CH][C]21 SSLYIXHGTXGSJZ-UHFFFAOYSA-L 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229920000092 linear low density polyethylene Polymers 0.000 description 4
- 239000004707 linear low-density polyethylene Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 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 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 4
- 150000003606 tin compounds Chemical class 0.000 description 4
- 239000010936 titanium Substances 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
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 4
- YJLGPWIMQPBFSS-UHFFFAOYSA-N (1-dichloroboranyl-1h-inden-2-yl)-trimethylsilane Chemical compound C1=CC=C2C(B(Cl)Cl)C([Si](C)(C)C)=CC2=C1 YJLGPWIMQPBFSS-UHFFFAOYSA-N 0.000 description 3
- UAOUIVVJBYDFKD-XKCDOFEDSA-N (1R,9R,10S,11R,12R,15S,18S,21R)-10,11,21-trihydroxy-8,8-dimethyl-14-methylidene-4-(prop-2-enylamino)-20-oxa-5-thia-3-azahexacyclo[9.7.2.112,15.01,9.02,6.012,18]henicosa-2(6),3-dien-13-one Chemical compound C([C@@H]1[C@@H](O)[C@@]23C(C1=C)=O)C[C@H]2[C@]12C(N=C(NCC=C)S4)=C4CC(C)(C)[C@H]1[C@H](O)[C@]3(O)OC2 UAOUIVVJBYDFKD-XKCDOFEDSA-N 0.000 description 3
- AOSZTAHDEDLTLQ-AZKQZHLXSA-N (1S,2S,4R,8S,9S,11S,12R,13S,19S)-6-[(3-chlorophenyl)methyl]-12,19-difluoro-11-hydroxy-8-(2-hydroxyacetyl)-9,13-dimethyl-6-azapentacyclo[10.8.0.02,9.04,8.013,18]icosa-14,17-dien-16-one Chemical compound C([C@@H]1C[C@H]2[C@H]3[C@]([C@]4(C=CC(=O)C=C4[C@@H](F)C3)C)(F)[C@@H](O)C[C@@]2([C@@]1(C1)C(=O)CO)C)N1CC1=CC=CC(Cl)=C1 AOSZTAHDEDLTLQ-AZKQZHLXSA-N 0.000 description 3
- ABJSOROVZZKJGI-OCYUSGCXSA-N (1r,2r,4r)-2-(4-bromophenyl)-n-[(4-chlorophenyl)-(2-fluoropyridin-4-yl)methyl]-4-morpholin-4-ylcyclohexane-1-carboxamide Chemical compound C1=NC(F)=CC(C(NC(=O)[C@H]2[C@@H](C[C@@H](CC2)N2CCOCC2)C=2C=CC(Br)=CC=2)C=2C=CC(Cl)=CC=2)=C1 ABJSOROVZZKJGI-OCYUSGCXSA-N 0.000 description 3
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 3
- STBLNCCBQMHSRC-BATDWUPUSA-N (2s)-n-[(3s,4s)-5-acetyl-7-cyano-4-methyl-1-[(2-methylnaphthalen-1-yl)methyl]-2-oxo-3,4-dihydro-1,5-benzodiazepin-3-yl]-2-(methylamino)propanamide Chemical compound O=C1[C@@H](NC(=O)[C@H](C)NC)[C@H](C)N(C(C)=O)C2=CC(C#N)=CC=C2N1CC1=C(C)C=CC2=CC=CC=C12 STBLNCCBQMHSRC-BATDWUPUSA-N 0.000 description 3
- IWZSHWBGHQBIML-ZGGLMWTQSA-N (3S,8S,10R,13S,14S,17S)-17-isoquinolin-7-yl-N,N,10,13-tetramethyl-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-3-amine Chemical compound CN(C)[C@H]1CC[C@]2(C)C3CC[C@@]4(C)[C@@H](CC[C@@H]4c4ccc5ccncc5c4)[C@@H]3CC=C2C1 IWZSHWBGHQBIML-ZGGLMWTQSA-N 0.000 description 3
- UDQTXCHQKHIQMH-KYGLGHNPSA-N (3ar,5s,6s,7r,7ar)-5-(difluoromethyl)-2-(ethylamino)-5,6,7,7a-tetrahydro-3ah-pyrano[3,2-d][1,3]thiazole-6,7-diol Chemical compound S1C(NCC)=N[C@H]2[C@@H]1O[C@H](C(F)F)[C@@H](O)[C@@H]2O UDQTXCHQKHIQMH-KYGLGHNPSA-N 0.000 description 3
- KQZLRWGGWXJPOS-NLFPWZOASA-N 1-[(1R)-1-(2,4-dichlorophenyl)ethyl]-6-[(4S,5R)-4-[(2S)-2-(hydroxymethyl)pyrrolidin-1-yl]-5-methylcyclohexen-1-yl]pyrazolo[3,4-b]pyrazine-3-carbonitrile Chemical compound ClC1=C(C=CC(=C1)Cl)[C@@H](C)N1N=C(C=2C1=NC(=CN=2)C1=CC[C@@H]([C@@H](C1)C)N1[C@@H](CCC1)CO)C#N KQZLRWGGWXJPOS-NLFPWZOASA-N 0.000 description 3
- ONBQEOIKXPHGMB-VBSBHUPXSA-N 1-[2-[(2s,3r,4s,5r)-3,4-dihydroxy-5-(hydroxymethyl)oxolan-2-yl]oxy-4,6-dihydroxyphenyl]-3-(4-hydroxyphenyl)propan-1-one Chemical compound O[C@@H]1[C@H](O)[C@@H](CO)O[C@H]1OC1=CC(O)=CC(O)=C1C(=O)CCC1=CC=C(O)C=C1 ONBQEOIKXPHGMB-VBSBHUPXSA-N 0.000 description 3
- UNILWMWFPHPYOR-KXEYIPSPSA-M 1-[6-[2-[3-[3-[3-[2-[2-[3-[[2-[2-[[(2r)-1-[[2-[[(2r)-1-[3-[2-[2-[3-[[2-(2-amino-2-oxoethoxy)acetyl]amino]propoxy]ethoxy]ethoxy]propylamino]-3-hydroxy-1-oxopropan-2-yl]amino]-2-oxoethyl]amino]-3-[(2r)-2,3-di(hexadecanoyloxy)propyl]sulfanyl-1-oxopropan-2-yl Chemical compound O=C1C(SCCC(=O)NCCCOCCOCCOCCCNC(=O)COCC(=O)N[C@@H](CSC[C@@H](COC(=O)CCCCCCCCCCCCCCC)OC(=O)CCCCCCCCCCCCCCC)C(=O)NCC(=O)N[C@H](CO)C(=O)NCCCOCCOCCOCCCNC(=O)COCC(N)=O)CC(=O)N1CCNC(=O)CCCCCN\1C2=CC=C(S([O-])(=O)=O)C=C2CC/1=C/C=C/C=C/C1=[N+](CC)C2=CC=C(S([O-])(=O)=O)C=C2C1 UNILWMWFPHPYOR-KXEYIPSPSA-M 0.000 description 3
- FQMZXMVHHKXGTM-UHFFFAOYSA-N 2-(1-adamantyl)-n-[2-[2-(2-hydroxyethylamino)ethylamino]quinolin-5-yl]acetamide Chemical compound C1C(C2)CC(C3)CC2CC13CC(=O)NC1=CC=CC2=NC(NCCNCCO)=CC=C21 FQMZXMVHHKXGTM-UHFFFAOYSA-N 0.000 description 3
- FMKGJQHNYMWDFJ-CVEARBPZSA-N 2-[[4-(2,2-difluoropropoxy)pyrimidin-5-yl]methylamino]-4-[[(1R,4S)-4-hydroxy-3,3-dimethylcyclohexyl]amino]pyrimidine-5-carbonitrile Chemical compound FC(COC1=NC=NC=C1CNC1=NC=C(C(=N1)N[C@H]1CC([C@H](CC1)O)(C)C)C#N)(C)F FMKGJQHNYMWDFJ-CVEARBPZSA-N 0.000 description 3
- TVTJUIAKQFIXCE-HUKYDQBMSA-N 2-amino-9-[(2R,3S,4S,5R)-4-fluoro-3-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-7-prop-2-ynyl-1H-purine-6,8-dione Chemical compound NC=1NC(C=2N(C(N(C=2N=1)[C@@H]1O[C@@H]([C@H]([C@H]1O)F)CO)=O)CC#C)=O TVTJUIAKQFIXCE-HUKYDQBMSA-N 0.000 description 3
- LFOIDLOIBZFWDO-UHFFFAOYSA-N 2-methoxy-6-[6-methoxy-4-[(3-phenylmethoxyphenyl)methoxy]-1-benzofuran-2-yl]imidazo[2,1-b][1,3,4]thiadiazole Chemical compound N1=C2SC(OC)=NN2C=C1C(OC1=CC(OC)=C2)=CC1=C2OCC(C=1)=CC=CC=1OCC1=CC=CC=C1 LFOIDLOIBZFWDO-UHFFFAOYSA-N 0.000 description 3
- WYFCZWSWFGJODV-MIANJLSGSA-N 4-[[(1s)-2-[(e)-3-[3-chloro-2-fluoro-6-(tetrazol-1-yl)phenyl]prop-2-enoyl]-5-(4-methyl-2-oxopiperazin-1-yl)-3,4-dihydro-1h-isoquinoline-1-carbonyl]amino]benzoic acid Chemical compound O=C1CN(C)CCN1C1=CC=CC2=C1CCN(C(=O)\C=C\C=1C(=CC=C(Cl)C=1F)N1N=NN=C1)[C@@H]2C(=O)NC1=CC=C(C(O)=O)C=C1 WYFCZWSWFGJODV-MIANJLSGSA-N 0.000 description 3
- HCCNBKFJYUWLEX-UHFFFAOYSA-N 7-(6-methoxypyridin-3-yl)-1-(2-propoxyethyl)-3-(pyrazin-2-ylmethylamino)pyrido[3,4-b]pyrazin-2-one Chemical compound O=C1N(CCOCCC)C2=CC(C=3C=NC(OC)=CC=3)=NC=C2N=C1NCC1=CN=CC=N1 HCCNBKFJYUWLEX-UHFFFAOYSA-N 0.000 description 3
- OJRUSAPKCPIVBY-KQYNXXCUSA-N C1=NC2=C(N=C(N=C2N1[C@H]3[C@@H]([C@@H]([C@H](O3)COP(=O)(CP(=O)(O)O)O)O)O)I)N Chemical compound C1=NC2=C(N=C(N=C2N1[C@H]3[C@@H]([C@@H]([C@H](O3)COP(=O)(CP(=O)(O)O)O)O)O)I)N OJRUSAPKCPIVBY-KQYNXXCUSA-N 0.000 description 3
- 229940126657 Compound 17 Drugs 0.000 description 3
- 229940126639 Compound 33 Drugs 0.000 description 3
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- PNUZDKCDAWUEGK-CYZMBNFOSA-N Sitafloxacin Chemical compound C([C@H]1N)N(C=2C(=C3C(C(C(C(O)=O)=CN3[C@H]3[C@H](C3)F)=O)=CC=2F)Cl)CC11CC1 PNUZDKCDAWUEGK-CYZMBNFOSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- SPXSEZMVRJLHQG-XMMPIXPASA-N [(2R)-1-[[4-[(3-phenylmethoxyphenoxy)methyl]phenyl]methyl]pyrrolidin-2-yl]methanol Chemical compound C(C1=CC=CC=C1)OC=1C=C(OCC2=CC=C(CN3[C@H](CCC3)CO)C=C2)C=CC=1 SPXSEZMVRJLHQG-XMMPIXPASA-N 0.000 description 3
- MXZNUGFCDVAXLG-CHWSQXEVSA-N [(2S)-1-[(2R)-3-methyl-2-(pyridine-4-carbonylamino)butanoyl]pyrrolidin-2-yl]boronic acid Chemical compound CC(C)[C@@H](NC(=O)c1ccncc1)C(=O)N1CCC[C@@H]1B(O)O MXZNUGFCDVAXLG-CHWSQXEVSA-N 0.000 description 3
- PSLUFJFHTBIXMW-WYEYVKMPSA-N [(3r,4ar,5s,6s,6as,10s,10ar,10bs)-3-ethenyl-10,10b-dihydroxy-3,4a,7,7,10a-pentamethyl-1-oxo-6-(2-pyridin-2-ylethylcarbamoyloxy)-5,6,6a,8,9,10-hexahydro-2h-benzo[f]chromen-5-yl] acetate Chemical compound O([C@@H]1[C@@H]([C@]2(O[C@](C)(CC(=O)[C@]2(O)[C@@]2(C)[C@@H](O)CCC(C)(C)[C@@H]21)C=C)C)OC(=O)C)C(=O)NCCC1=CC=CC=N1 PSLUFJFHTBIXMW-WYEYVKMPSA-N 0.000 description 3
- MLABZTPUSJWJCV-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].[Zr+3](C1C=Cc2ccccc12)P(c1ccccc1)c1ccccc1 Chemical compound [Cl-].[Cl-].[Cl-].[Zr+3](C1C=Cc2ccccc12)P(c1ccccc1)c1ccccc1 MLABZTPUSJWJCV-UHFFFAOYSA-K 0.000 description 3
- SMNRFWMNPDABKZ-WVALLCKVSA-N [[(2R,3S,4R,5S)-5-(2,6-dioxo-3H-pyridin-3-yl)-3,4-dihydroxyoxolan-2-yl]methoxy-hydroxyphosphoryl] [[[(2R,3S,4S,5R,6R)-4-fluoro-3,5-dihydroxy-6-(hydroxymethyl)oxan-2-yl]oxy-hydroxyphosphoryl]oxy-hydroxyphosphoryl] hydrogen phosphate Chemical compound OC[C@H]1O[C@H](OP(O)(=O)OP(O)(=O)OP(O)(=O)OP(O)(=O)OC[C@H]2O[C@H]([C@H](O)[C@@H]2O)C2C=CC(=O)NC2=O)[C@H](O)[C@@H](F)[C@@H]1O SMNRFWMNPDABKZ-WVALLCKVSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- XRWSZZJLZRKHHD-WVWIJVSJSA-N asunaprevir Chemical compound O=C([C@@H]1C[C@H](CN1C(=O)[C@@H](NC(=O)OC(C)(C)C)C(C)(C)C)OC1=NC=C(C2=CC=C(Cl)C=C21)OC)N[C@]1(C(=O)NS(=O)(=O)C2CC2)C[C@H]1C=C XRWSZZJLZRKHHD-WVWIJVSJSA-N 0.000 description 3
- KGNDCEVUMONOKF-UGPLYTSKSA-N benzyl n-[(2r)-1-[(2s,4r)-2-[[(2s)-6-amino-1-(1,3-benzoxazol-2-yl)-1,1-dihydroxyhexan-2-yl]carbamoyl]-4-[(4-methylphenyl)methoxy]pyrrolidin-1-yl]-1-oxo-4-phenylbutan-2-yl]carbamate Chemical compound C1=CC(C)=CC=C1CO[C@H]1CN(C(=O)[C@@H](CCC=2C=CC=CC=2)NC(=O)OCC=2C=CC=CC=2)[C@H](C(=O)N[C@@H](CCCCN)C(O)(O)C=2OC3=CC=CC=C3N=2)C1 KGNDCEVUMONOKF-UGPLYTSKSA-N 0.000 description 3
- 229940125773 compound 10 Drugs 0.000 description 3
- 229940125797 compound 12 Drugs 0.000 description 3
- 229940125758 compound 15 Drugs 0.000 description 3
- 229940126142 compound 16 Drugs 0.000 description 3
- 229940125810 compound 20 Drugs 0.000 description 3
- 229940126208 compound 22 Drugs 0.000 description 3
- 229940125833 compound 23 Drugs 0.000 description 3
- 229940125961 compound 24 Drugs 0.000 description 3
- 229940125851 compound 27 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 229940125877 compound 31 Drugs 0.000 description 3
- 229940125878 compound 36 Drugs 0.000 description 3
- 229940126540 compound 41 Drugs 0.000 description 3
- 229940125936 compound 42 Drugs 0.000 description 3
- 229940127271 compound 49 Drugs 0.000 description 3
- 229940126545 compound 53 Drugs 0.000 description 3
- 229940127113 compound 57 Drugs 0.000 description 3
- YMNCCEXICREQQV-UHFFFAOYSA-L cyclopenta-1,3-diene;titanium(4+);dichloride Chemical compound [Cl-].[Cl-].[Ti+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 YMNCCEXICREQQV-UHFFFAOYSA-L 0.000 description 3
- 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 3
- IVTQDRJBWSBJQM-UHFFFAOYSA-L dichlorozirconium;indene Chemical compound C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)C1C2=CC=CC=C2C=C1 IVTQDRJBWSBJQM-UHFFFAOYSA-L 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 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 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- JAXFJECJQZDFJS-XHEPKHHKSA-N gtpl8555 Chemical compound OC(=O)C[C@H](N)C(=O)N[C@@H](CCC(O)=O)C(=O)N[C@@H](C(C)C)C(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@@H]1C(=O)N[C@H](B1O[C@@]2(C)[C@H]3C[C@H](C3(C)C)C[C@H]2O1)CCC1=CC=C(F)C=C1 JAXFJECJQZDFJS-XHEPKHHKSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- RENRQMCACQEWFC-UGKGYDQZSA-N lnp023 Chemical compound C1([C@H]2N(CC=3C=4C=CNC=4C(C)=CC=3OC)CC[C@@H](C2)OCC)=CC=C(C(O)=O)C=C1 RENRQMCACQEWFC-UGKGYDQZSA-N 0.000 description 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 125000003944 tolyl group Chemical group 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
- 239000005051 trimethylchlorosilane Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- WMKQKIWOJZZNNB-UHFFFAOYSA-N (1-dichloroboranylcyclopenta-2,4-dien-1-yl)-trimethylsilane Chemical compound C[Si](C)(C)C1(C=CC=C1)B(Cl)Cl WMKQKIWOJZZNNB-UHFFFAOYSA-N 0.000 description 2
- SZUVGFMDDVSKSI-WIFOCOSTSA-N (1s,2s,3s,5r)-1-(carboxymethyl)-3,5-bis[(4-phenoxyphenyl)methyl-propylcarbamoyl]cyclopentane-1,2-dicarboxylic acid Chemical compound O=C([C@@H]1[C@@H]([C@](CC(O)=O)([C@H](C(=O)N(CCC)CC=2C=CC(OC=3C=CC=CC=3)=CC=2)C1)C(O)=O)C(O)=O)N(CCC)CC(C=C1)=CC=C1OC1=CC=CC=C1 SZUVGFMDDVSKSI-WIFOCOSTSA-N 0.000 description 2
- IUSARDYWEPUTPN-OZBXUNDUSA-N (2r)-n-[(2s,3r)-4-[[(4s)-6-(2,2-dimethylpropyl)spiro[3,4-dihydropyrano[2,3-b]pyridine-2,1'-cyclobutane]-4-yl]amino]-3-hydroxy-1-[3-(1,3-thiazol-2-yl)phenyl]butan-2-yl]-2-methoxypropanamide Chemical compound C([C@H](NC(=O)[C@@H](C)OC)[C@H](O)CN[C@@H]1C2=CC(CC(C)(C)C)=CN=C2OC2(CCC2)C1)C(C=1)=CC=CC=1C1=NC=CS1 IUSARDYWEPUTPN-OZBXUNDUSA-N 0.000 description 2
- YJLIKUSWRSEPSM-WGQQHEPDSA-N (2r,3r,4s,5r)-2-[6-amino-8-[(4-phenylphenyl)methylamino]purin-9-yl]-5-(hydroxymethyl)oxolane-3,4-diol Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1CNC1=NC=2C(N)=NC=NC=2N1[C@@H]1O[C@H](CO)[C@@H](O)[C@H]1O YJLIKUSWRSEPSM-WGQQHEPDSA-N 0.000 description 2
- VIJSPAIQWVPKQZ-BLECARSGSA-N (2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-[[(2s)-2-acetamido-5-(diaminomethylideneamino)pentanoyl]amino]-4-methylpentanoyl]amino]-4,4-dimethylpentanoyl]amino]-4-methylpentanoyl]amino]propanoyl]amino]-5-(diaminomethylideneamino)pentanoic acid Chemical compound NC(=N)NCCC[C@@H](C(O)=O)NC(=O)[C@H](C)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CC(C)(C)C)NC(=O)[C@H](CC(C)C)NC(=O)[C@H](CCCNC(N)=N)NC(C)=O VIJSPAIQWVPKQZ-BLECARSGSA-N 0.000 description 2
- QFLWZFQWSBQYPS-AWRAUJHKSA-N (3S)-3-[[(2S)-2-[[(2S)-2-[5-[(3aS,6aR)-2-oxo-1,3,3a,4,6,6a-hexahydrothieno[3,4-d]imidazol-4-yl]pentanoylamino]-3-methylbutanoyl]amino]-3-(4-hydroxyphenyl)propanoyl]amino]-4-[1-bis(4-chlorophenoxy)phosphorylbutylamino]-4-oxobutanoic acid Chemical compound CCCC(NC(=O)[C@H](CC(O)=O)NC(=O)[C@H](Cc1ccc(O)cc1)NC(=O)[C@@H](NC(=O)CCCCC1SC[C@@H]2NC(=O)N[C@H]12)C(C)C)P(=O)(Oc1ccc(Cl)cc1)Oc1ccc(Cl)cc1 QFLWZFQWSBQYPS-AWRAUJHKSA-N 0.000 description 2
- HUWSZNZAROKDRZ-RRLWZMAJSA-N (3r,4r)-3-azaniumyl-5-[[(2s,3r)-1-[(2s)-2,3-dicarboxypyrrolidin-1-yl]-3-methyl-1-oxopentan-2-yl]amino]-5-oxo-4-sulfanylpentane-1-sulfonate Chemical compound OS(=O)(=O)CC[C@@H](N)[C@@H](S)C(=O)N[C@@H]([C@H](C)CC)C(=O)N1CCC(C(O)=O)[C@H]1C(O)=O HUWSZNZAROKDRZ-RRLWZMAJSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 2
- OJVAMHKKJGICOG-UHFFFAOYSA-N 2,5-hexanedione Chemical compound CC(=O)CCC(C)=O OJVAMHKKJGICOG-UHFFFAOYSA-N 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- QBWKPGNFQQJGFY-QLFBSQMISA-N 3-[(1r)-1-[(2r,6s)-2,6-dimethylmorpholin-4-yl]ethyl]-n-[6-methyl-3-(1h-pyrazol-4-yl)imidazo[1,2-a]pyrazin-8-yl]-1,2-thiazol-5-amine Chemical compound N1([C@H](C)C2=NSC(NC=3C4=NC=C(N4C=C(C)N=3)C3=CNN=C3)=C2)C[C@H](C)O[C@H](C)C1 QBWKPGNFQQJGFY-QLFBSQMISA-N 0.000 description 2
- DKLQZDIAQKGVTA-UHFFFAOYSA-N 4,7-dimethyl-1h-indene Chemical compound CC1=CC=C(C)C2=C1CC=C2 DKLQZDIAQKGVTA-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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- MXBBZANARLXZLS-UHFFFAOYSA-L CC1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)C1C=CC=C1 Chemical compound CC1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)C1C=CC=C1 MXBBZANARLXZLS-UHFFFAOYSA-L 0.000 description 2
- BQXUPNKLZNSUMC-YUQWMIPFSA-N CCN(CCCCCOCC(=O)N[C@H](C(=O)N1C[C@H](O)C[C@H]1C(=O)N[C@@H](C)c1ccc(cc1)-c1scnc1C)C(C)(C)C)CCOc1ccc(cc1)C(=O)c1c(sc2cc(O)ccc12)-c1ccc(O)cc1 Chemical compound CCN(CCCCCOCC(=O)N[C@H](C(=O)N1C[C@H](O)C[C@H]1C(=O)N[C@@H](C)c1ccc(cc1)-c1scnc1C)C(C)(C)C)CCOc1ccc(cc1)C(=O)c1c(sc2cc(O)ccc12)-c1ccc(O)cc1 BQXUPNKLZNSUMC-YUQWMIPFSA-N 0.000 description 2
- BZDUEIHRVRETDN-UHFFFAOYSA-L C[Si](C)(C)[Zr](Cl)(Cl)(C1C=CC=C1)C1C=CC=C1 Chemical compound C[Si](C)(C)[Zr](Cl)(Cl)(C1C=CC=C1)C1C=CC=C1 BZDUEIHRVRETDN-UHFFFAOYSA-L 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- BRVAZNMIVVUILY-UHFFFAOYSA-K ClB(Cl)[Ti](Cl)(Cl)(Cl)C1C=CC=C1 Chemical compound ClB(Cl)[Ti](Cl)(Cl)(Cl)C1C=CC=C1 BRVAZNMIVVUILY-UHFFFAOYSA-K 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OPFJDXRVMFKJJO-ZHHKINOHSA-N N-{[3-(2-benzamido-4-methyl-1,3-thiazol-5-yl)-pyrazol-5-yl]carbonyl}-G-dR-G-dD-dD-dD-NH2 Chemical compound S1C(C=2NN=C(C=2)C(=O)NCC(=O)N[C@H](CCCN=C(N)N)C(=O)NCC(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(=O)N[C@H](CC(O)=O)C(N)=O)=C(C)N=C1NC(=O)C1=CC=CC=C1 OPFJDXRVMFKJJO-ZHHKINOHSA-N 0.000 description 2
- 235000019502 Orange oil Nutrition 0.000 description 2
- YYMAMHZKCLJFGV-UHFFFAOYSA-N PBCl Chemical compound PBCl YYMAMHZKCLJFGV-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- LJOOWESTVASNOG-UFJKPHDISA-N [(1s,3r,4ar,7s,8s,8as)-3-hydroxy-8-[2-[(4r)-4-hydroxy-6-oxooxan-2-yl]ethyl]-7-methyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1-yl] (2s)-2-methylbutanoate Chemical compound C([C@H]1[C@@H](C)C=C[C@H]2C[C@@H](O)C[C@@H]([C@H]12)OC(=O)[C@@H](C)CC)CC1C[C@@H](O)CC(=O)O1 LJOOWESTVASNOG-UFJKPHDISA-N 0.000 description 2
- LNUFLCYMSVYYNW-ZPJMAFJPSA-N [(2r,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[(2r,3r,4s,5r,6r)-6-[[(3s,5s,8r,9s,10s,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,5,6,7,8,9,11,12,14,15,16,17-tetradecahydro-1h-cyclopenta[a]phenanthren-3-yl]oxy]-4,5-disulfo Chemical compound O([C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1[C@@H](COS(O)(=O)=O)O[C@H]([C@@H]([C@H]1OS(O)(=O)=O)OS(O)(=O)=O)O[C@@H]1C[C@@H]2CC[C@H]3[C@@H]4CC[C@@H]([C@]4(CC[C@@H]3[C@@]2(C)CC1)C)[C@H](C)CCCC(C)C)[C@H]1O[C@H](COS(O)(=O)=O)[C@@H](OS(O)(=O)=O)[C@H](OS(O)(=O)=O)[C@H]1OS(O)(=O)=O LNUFLCYMSVYYNW-ZPJMAFJPSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 125000001204 arachidyl 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])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 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- ZLVVDNKTHWEIOG-UHFFFAOYSA-N chloro(dimethyl)phosphane Chemical compound CP(C)Cl ZLVVDNKTHWEIOG-UHFFFAOYSA-N 0.000 description 2
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 2
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 2
- 229940126543 compound 14 Drugs 0.000 description 2
- 229940126086 compound 21 Drugs 0.000 description 2
- 229940125846 compound 25 Drugs 0.000 description 2
- 229940127204 compound 29 Drugs 0.000 description 2
- 229940125807 compound 37 Drugs 0.000 description 2
- 229940127573 compound 38 Drugs 0.000 description 2
- 229940125898 compound 5 Drugs 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- VHTUUTHYXRLKLY-UHFFFAOYSA-N cyclopenta-1,3-dien-1-yl(trimethyl)silane Chemical compound C[Si](C)(C)C1=CC=CC1 VHTUUTHYXRLKLY-UHFFFAOYSA-N 0.000 description 2
- CVEQRUADOXXBRI-UHFFFAOYSA-N cyclopentadienylthallium Chemical compound [Tl+].C=1C=C[CH-]C=1 CVEQRUADOXXBRI-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- GGSUCNLOZRCGPQ-UHFFFAOYSA-O diethyl(phenyl)azanium Chemical compound CC[NH+](CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-O 0.000 description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 2
- UIANJNAHYLTTOQ-UHFFFAOYSA-N dimethylamino methanesulfonate Chemical compound CN(C)OS(C)(=O)=O UIANJNAHYLTTOQ-UHFFFAOYSA-N 0.000 description 2
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000010348 incorporation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- DBKDYYFPDRPMPE-UHFFFAOYSA-N lithium;cyclopenta-1,3-diene Chemical compound [Li+].C=1C=C[CH-]C=1 DBKDYYFPDRPMPE-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- IOMMMLWIABWRKL-WUTDNEBXSA-N nazartinib Chemical compound C1N(C(=O)/C=C/CN(C)C)CCCC[C@H]1N1C2=C(Cl)C=CC=C2N=C1NC(=O)C1=CC=NC(C)=C1 IOMMMLWIABWRKL-WUTDNEBXSA-N 0.000 description 2
- PIDFDZJZLOTZTM-KHVQSSSXSA-N ombitasvir Chemical compound COC(=O)N[C@@H](C(C)C)C(=O)N1CCC[C@H]1C(=O)NC1=CC=C([C@H]2N([C@@H](CC2)C=2C=CC(NC(=O)[C@H]3N(CCC3)C(=O)[C@@H](NC(=O)OC)C(C)C)=CC=2)C=2C=CC(=CC=2)C(C)(C)C)C=C1 PIDFDZJZLOTZTM-KHVQSSSXSA-N 0.000 description 2
- 239000010502 orange oil Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002685 polymerization catalyst Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 125000004079 stearyl 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])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 2
- 238000006467 substitution reaction Methods 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 2
- HQLHTFLIBOBBPQ-UHFFFAOYSA-N trimethyl-(2-trimethylsilylcyclopenta-1,3-dien-1-yl)silane Chemical compound C[Si](C)(C)C1=C([Si](C)(C)C)C=CC1 HQLHTFLIBOBBPQ-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 2
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 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
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 125000005023 xylyl group Chemical group 0.000 description 2
- SNQCWGUCVXCALI-UHFFFAOYSA-N (2-methyl-3-tributylstannyl-1h-inden-1-yl)-di(propan-2-yl)phosphane Chemical compound C1=CC=C2C([Sn](CCCC)(CCCC)CCCC)=C(C)C(P(C(C)C)C(C)C)C2=C1 SNQCWGUCVXCALI-UHFFFAOYSA-N 0.000 description 1
- ZNEPTOHVCKLGAW-UHFFFAOYSA-N (3-dichloroboranyl-2-methyl-3h-inden-1-yl)-trimethylsilane Chemical compound C1=CC=C2C(B(Cl)Cl)C(C)=C([Si](C)(C)C)C2=C1 ZNEPTOHVCKLGAW-UHFFFAOYSA-N 0.000 description 1
- MPDDTAJMJCESGV-CTUHWIOQSA-M (3r,5r)-7-[2-(4-fluorophenyl)-5-[methyl-[(1r)-1-phenylethyl]carbamoyl]-4-propan-2-ylpyrazol-3-yl]-3,5-dihydroxyheptanoate Chemical compound C1([C@@H](C)N(C)C(=O)C2=NN(C(CC[C@@H](O)C[C@@H](O)CC([O-])=O)=C2C(C)C)C=2C=CC(F)=CC=2)=CC=CC=C1 MPDDTAJMJCESGV-CTUHWIOQSA-M 0.000 description 1
- CCQDDCADUDXRQU-UHFFFAOYSA-N (4,7-dimethyl-1-tributylstannyl-1h-inden-2-yl)-di(propan-2-yl)phosphane Chemical compound CC1=CC=C(C)C2=C1C([Sn](CCCC)(CCCC)CCCC)C(P(C(C)C)C(C)C)=C2 CCQDDCADUDXRQU-UHFFFAOYSA-N 0.000 description 1
- YQOLEILXOBUDMU-KRWDZBQOSA-N (4R)-5-[(6-bromo-3-methyl-2-pyrrolidin-1-ylquinoline-4-carbonyl)amino]-4-(2-chlorophenyl)pentanoic acid Chemical compound CC1=C(C2=C(C=CC(=C2)Br)N=C1N3CCCC3)C(=O)NC[C@H](CCC(=O)O)C4=CC=CC=C4Cl YQOLEILXOBUDMU-KRWDZBQOSA-N 0.000 description 1
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 1
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- 125000004916 (C1-C6) alkylcarbonyl group Chemical group 0.000 description 1
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- YWYRVWBEIODDTJ-UHFFFAOYSA-N 1-ethenyl-9h-fluorene Chemical compound C1C2=CC=CC=C2C2=C1C(C=C)=CC=C2 YWYRVWBEIODDTJ-UHFFFAOYSA-N 0.000 description 1
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 description 1
- RSNMEFYAFXJROM-UHFFFAOYSA-N 1-phenylphosphole Chemical compound C1=CC=CP1C1=CC=CC=C1 RSNMEFYAFXJROM-UHFFFAOYSA-N 0.000 description 1
- DAVVYCRMXOFZQG-UHFFFAOYSA-N 1h-inden-1-yl(trimethyl)silane Chemical compound C1=CC=C2C([Si](C)(C)C)C=CC2=C1 DAVVYCRMXOFZQG-UHFFFAOYSA-N 0.000 description 1
- JDYXFZDIBDTHHN-UHFFFAOYSA-N 2,3,4,5-tetramethyl-1-phenylphosphole Chemical compound CC1=C(C)C(C)=C(C)P1C1=CC=CC=C1 JDYXFZDIBDTHHN-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- CANPLUOLCLJNKT-UHFFFAOYSA-N 2-butoxy-1-[diethylamino(methoxymethyl)amino]-2-ethoxy-N,N-dimethyl-1-phenoxy-2-propoxyethanamine Chemical compound COCN(C(C(OCCCC)(OCCC)OCC)(N(C)C)OC1=CC=CC=C1)N(CC)CC CANPLUOLCLJNKT-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- JWVVFPXYZALZDT-UHFFFAOYSA-N 2-methyl-1,3-dihydroinden-2-ol Chemical compound C1=CC=C2CC(C)(O)CC2=C1 JWVVFPXYZALZDT-UHFFFAOYSA-N 0.000 description 1
- BGGKSZPSSRGVTP-UHFFFAOYSA-L 2-methyl-1h-inden-1-ide;zirconium(4+);dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C1=CC=C2[CH-]C(C)=CC2=C1.C1=CC=C2[CH-]C(C)=CC2=C1 BGGKSZPSSRGVTP-UHFFFAOYSA-L 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- SUWJESCICIOQHO-UHFFFAOYSA-N 4-methylhex-1-ene Chemical compound CCC(C)CC=C SUWJESCICIOQHO-UHFFFAOYSA-N 0.000 description 1
- XFJBGINZIMNZBW-CRAIPNDOSA-N 5-chloro-2-[4-[(1r,2s)-2-[2-(5-methylsulfonylpyridin-2-yl)oxyethyl]cyclopropyl]piperidin-1-yl]pyrimidine Chemical compound N1=CC(S(=O)(=O)C)=CC=C1OCC[C@H]1[C@@H](C2CCN(CC2)C=2N=CC(Cl)=CN=2)C1 XFJBGINZIMNZBW-CRAIPNDOSA-N 0.000 description 1
- DFVOXRAAHOJJBN-UHFFFAOYSA-N 6-methylhept-1-ene Chemical compound CC(C)CCCC=C DFVOXRAAHOJJBN-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- NUISZNQWNAGOGN-UHFFFAOYSA-N C1(CCCCC1)C1=C(C(C=C1)([Li])B)C1CCCCC1 Chemical compound C1(CCCCC1)C1=C(C(C=C1)([Li])B)C1CCCCC1 NUISZNQWNAGOGN-UHFFFAOYSA-N 0.000 description 1
- NRIRQDNQYISBKS-UHFFFAOYSA-N C1C=CC2=CC=CC=C12.C(CCC)[Sn](CCCC)(CCCC)P(C(C)C)C(C)C Chemical compound C1C=CC2=CC=CC=C12.C(CCC)[Sn](CCCC)(CCCC)P(C(C)C)C(C)C NRIRQDNQYISBKS-UHFFFAOYSA-N 0.000 description 1
- XBKSWXYJLYXUJO-UHFFFAOYSA-N C1C=CC2=CC=CC=C12.C[SnH](C)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C1C=CC2=CC=CC=C12.C[SnH](C)P(C1=CC=CC=C1)C1=CC=CC=C1 XBKSWXYJLYXUJO-UHFFFAOYSA-N 0.000 description 1
- ULZKTLMBNKBBGQ-UHFFFAOYSA-K CB(C)[Ti](Cl)(Cl)(Cl)C1C=CC=C1 Chemical compound CB(C)[Ti](Cl)(Cl)(Cl)C1C=CC=C1 ULZKTLMBNKBBGQ-UHFFFAOYSA-K 0.000 description 1
- OHPFEOCVRAYCFH-UHFFFAOYSA-N CN(C)C1(C=CC=C1)[Li] Chemical compound CN(C)C1(C=CC=C1)[Li] OHPFEOCVRAYCFH-UHFFFAOYSA-N 0.000 description 1
- MAHPRWIILSLJGC-UHFFFAOYSA-K C[Si](C)(C)[Zr](Cl)(Cl)(Cl)(C1C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound C[Si](C)(C)[Zr](Cl)(Cl)(Cl)(C1C=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 MAHPRWIILSLJGC-UHFFFAOYSA-K 0.000 description 1
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 1
- HLWQRSMFJAVAPR-UHFFFAOYSA-M C[Sn](C)(C)C=1PC=CC1.C[Sn](Cl)(C)C Chemical compound C[Sn](C)(C)C=1PC=CC1.C[Sn](Cl)(C)C HLWQRSMFJAVAPR-UHFFFAOYSA-M 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JTMNOQKSQBSGPD-UHFFFAOYSA-L Cc1ccc(C)c2C(C=Cc12)[Zr](Cl)(Cl)C1C=CC=C1 Chemical compound Cc1ccc(C)c2C(C=Cc12)[Zr](Cl)(Cl)C1C=CC=C1 JTMNOQKSQBSGPD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101800004419 Cleaved form Proteins 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 229920003189 Nylon 4,6 Chemical group 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000004639 Schlenk technique Methods 0.000 description 1
- 238000000944 Soxhlet extraction Methods 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PEIZHQSRHFNIOK-UHFFFAOYSA-N [2,3-bis(trimethylsilyl)phenyl]-cyclopenta-1,3-dien-1-yl-phenylphosphane Chemical compound C[Si](C)(C)C=1C(=C(C=CC=1)P(C1=CC=CC=C1)C1=CC=CC1)[Si](C)(C)C PEIZHQSRHFNIOK-UHFFFAOYSA-N 0.000 description 1
- OCBFFGCSTGGPSQ-UHFFFAOYSA-N [CH2]CC Chemical compound [CH2]CC OCBFFGCSTGGPSQ-UHFFFAOYSA-N 0.000 description 1
- PQGAHNJECSVDEI-UHFFFAOYSA-N [CH2]CCCCC Chemical compound [CH2]CCCCC PQGAHNJECSVDEI-UHFFFAOYSA-N 0.000 description 1
- AQMHNCQZLQUNJI-UHFFFAOYSA-N [CH2]CCCCCC Chemical compound [CH2]CCCCCC AQMHNCQZLQUNJI-UHFFFAOYSA-N 0.000 description 1
- ZBRKUFYPLOQDAX-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].CC(C)P([Zr+3]C1C(C)=Cc2ccccc12)C(C)C Chemical compound [Cl-].[Cl-].[Cl-].CC(C)P([Zr+3]C1C(C)=Cc2ccccc12)C(C)C ZBRKUFYPLOQDAX-UHFFFAOYSA-K 0.000 description 1
- YCMBTBYKJHCLTR-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].CC(C)P([Zr+3]C1C=Cc2c1c(C)ccc2C)C(C)C Chemical compound [Cl-].[Cl-].[Cl-].CC(C)P([Zr+3]C1C=Cc2c1c(C)ccc2C)C(C)C YCMBTBYKJHCLTR-UHFFFAOYSA-K 0.000 description 1
- IFKHDSRMMPZTFQ-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].CC(C)P([Zr+3]C1C=Cc2ccccc12)C(C)C Chemical compound [Cl-].[Cl-].[Cl-].CC(C)P([Zr+3]C1C=Cc2ccccc12)C(C)C IFKHDSRMMPZTFQ-UHFFFAOYSA-K 0.000 description 1
- XKXAXTFYGSUUKU-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].CP(C)[Zr+3]C1C(C)=Cc2ccccc12 Chemical compound [Cl-].[Cl-].[Cl-].CP(C)[Zr+3]C1C(C)=Cc2ccccc12 XKXAXTFYGSUUKU-UHFFFAOYSA-K 0.000 description 1
- ACCFXINUGZJUBM-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].CP(C)[Zr+3]C1C=Cc2ccccc12 Chemical compound [Cl-].[Cl-].[Cl-].CP(C)[Zr+3]C1C=Cc2ccccc12 ACCFXINUGZJUBM-UHFFFAOYSA-K 0.000 description 1
- AVOXDQRYAFDRRB-UHFFFAOYSA-K [Cl-].[Cl-].[Cl-].[Ti+3]c1ccc[pH]1 Chemical compound [Cl-].[Cl-].[Cl-].[Ti+3]c1ccc[pH]1 AVOXDQRYAFDRRB-UHFFFAOYSA-K 0.000 description 1
- VQBCXFIFZNGRRW-UHFFFAOYSA-L [Cl-].[Cl-].[Ti+2].C1(C=CC=C1)C=1NC=CC1 Chemical compound [Cl-].[Cl-].[Ti+2].C1(C=CC=C1)C=1NC=CC1 VQBCXFIFZNGRRW-UHFFFAOYSA-L 0.000 description 1
- GMVORXVVTIQUKN-UHFFFAOYSA-L [Cl-].[Cl-].[Ti+2].CB(C)C(C=1PC(=C(C1C)C)C)C1C=CC=C1 Chemical compound [Cl-].[Cl-].[Ti+2].CB(C)C(C=1PC(=C(C1C)C)C)C1C=CC=C1 GMVORXVVTIQUKN-UHFFFAOYSA-L 0.000 description 1
- IDYUAVOOHBSBHD-UHFFFAOYSA-N [Li+].C=1C=[C-]PC=1 Chemical compound [Li+].C=1C=[C-]PC=1 IDYUAVOOHBSBHD-UHFFFAOYSA-N 0.000 description 1
- KOOADCGQJDGAGA-UHFFFAOYSA-N [amino(dimethyl)silyl]methane Chemical compound C[Si](C)(C)N KOOADCGQJDGAGA-UHFFFAOYSA-N 0.000 description 1
- 125000004018 acid anhydride group Chemical group 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000002168 alkylating agent Substances 0.000 description 1
- 229940100198 alkylating agent Drugs 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- HYGWNUKOUCZBND-UHFFFAOYSA-N azanide Chemical compound [NH2-] HYGWNUKOUCZBND-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 125000004799 bromophenyl group Chemical group 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- AAZXYDTXKRXEHM-UHFFFAOYSA-M butyltin(1+);chloride Chemical compound CCCC[Sn]Cl AAZXYDTXKRXEHM-UHFFFAOYSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 239000001913 cellulose Chemical class 0.000 description 1
- 229920002678 cellulose Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- PBBOKJIYEZCTEH-UHFFFAOYSA-N chloro(dicyclohexyl)borane Chemical compound C1CCCCC1B(Cl)C1CCCCC1 PBBOKJIYEZCTEH-UHFFFAOYSA-N 0.000 description 1
- ZZBNZZCHSNOXOH-UHFFFAOYSA-N chloro(trimethyl)germane Chemical compound C[Ge](C)(C)Cl ZZBNZZCHSNOXOH-UHFFFAOYSA-N 0.000 description 1
- MNKYQPOFRKPUAE-UHFFFAOYSA-N chloro(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 MNKYQPOFRKPUAE-UHFFFAOYSA-N 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 229940125844 compound 46 Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- RNPZZEPQLKZEQY-UHFFFAOYSA-N cyclopenta-1,3-dien-1-yl(diphenyl)phosphane Chemical compound C1C=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RNPZZEPQLKZEQY-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000005131 dialkylammonium group Chemical group 0.000 description 1
- ZPEBLEWLFFLZLD-UHFFFAOYSA-M dibutyl(chloro)tin Chemical compound CCCC[Sn](Cl)CCCC ZPEBLEWLFFLZLD-UHFFFAOYSA-M 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- XBPCUCUWBYBCDP-UHFFFAOYSA-O dicyclohexylazanium Chemical compound C1CCCCC1[NH2+]C1CCCCC1 XBPCUCUWBYBCDP-UHFFFAOYSA-O 0.000 description 1
- HJIMRHXQWRZAQN-UHFFFAOYSA-N diethyl-(2-methyl-3-tributylstannyl-1h-inden-1-yl)phosphane Chemical compound C1=CC=C2C([Sn](CCCC)(CCCC)CCCC)=C(C)C(P(CC)CC)C2=C1 HJIMRHXQWRZAQN-UHFFFAOYSA-N 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- UVURLDSBZQOHHK-UHFFFAOYSA-N dimethyl-(2-methyl-3-tributylstannyl-3h-inden-1-yl)phosphane Chemical compound C1=CC=C2C([Sn](CCCC)(CCCC)CCCC)(P(C)C)C(C)=CC2=C1 UVURLDSBZQOHHK-UHFFFAOYSA-N 0.000 description 1
- SLKIKWQXXAHUIK-UHFFFAOYSA-N dimethyl-(2-tributylstannyl-1h-inden-1-yl)phosphane Chemical compound C1=CC=C2C(P(C)C)C([Sn](CCCC)(CCCC)CCCC)=CC2=C1 SLKIKWQXXAHUIK-UHFFFAOYSA-N 0.000 description 1
- LRMLWYXJORUTBG-UHFFFAOYSA-N dimethylphosphorylmethane Chemical group CP(C)(C)=O LRMLWYXJORUTBG-UHFFFAOYSA-N 0.000 description 1
- JDKWCXXBMUKYGU-UHFFFAOYSA-N diphenyl-(2-tributylstannyl-1h-inden-1-yl)phosphane Chemical compound CCCC[Sn](CCCC)(CCCC)C1=CC2=CC=CC=C2C1P(C=1C=CC=CC=1)C1=CC=CC=C1 JDKWCXXBMUKYGU-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- HEAMQYHBJQWOSS-UHFFFAOYSA-N ethene;oct-1-ene Chemical compound C=C.CCCCCCC=C HEAMQYHBJQWOSS-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 150000002220 fluorenes Chemical class 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 229910021478 group 5 element Inorganic materials 0.000 description 1
- 229910021476 group 6 element Inorganic materials 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- UQEAIHBTYFGYIE-UHFFFAOYSA-N hexamethyldisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)C UQEAIHBTYFGYIE-UHFFFAOYSA-N 0.000 description 1
- 239000002044 hexane fraction Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000012966 insertion method Methods 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Inorganic materials [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 1
- GOYZJQHIHVWIRY-UHFFFAOYSA-N lithium;1,2-dihydropyrrol-2-ide Chemical compound [Li+].C=1C=[C-]NC=1 GOYZJQHIHVWIRY-UHFFFAOYSA-N 0.000 description 1
- UREYYHIKHPFJEA-UHFFFAOYSA-N lithium;1h-pyrrole Chemical compound [Li].C=1C=CNC=1 UREYYHIKHPFJEA-UHFFFAOYSA-N 0.000 description 1
- SNHFQMSMHWYXAX-UHFFFAOYSA-N lithium;2,3,4,5-tetramethyl-1h-phosphole Chemical compound [Li].CC=1PC(C)=C(C)C=1C SNHFQMSMHWYXAX-UHFFFAOYSA-N 0.000 description 1
- RVFBUMWHYQYOJO-UHFFFAOYSA-N lithium;cyclopenta-2,4-dien-1-yl-di(propan-2-yl)phosphane Chemical compound [Li+].CC(C)P(C(C)C)[C-]1C=CC=C1 RVFBUMWHYQYOJO-UHFFFAOYSA-N 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QARBMVPHQWIHKH-UHFFFAOYSA-N methanesulfonyl chloride Chemical compound CS(Cl)(=O)=O QARBMVPHQWIHKH-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- MHNNAWXXUZQSNM-UHFFFAOYSA-N methylethylethylene Natural products CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- HUYFFBCSEMCAGG-UHFFFAOYSA-N n,n,2,4,5-pentamethylaniline Chemical compound CN(C)C1=CC(C)=C(C)C=C1C HUYFFBCSEMCAGG-UHFFFAOYSA-N 0.000 description 1
- JZBZLRKFJWQZHU-UHFFFAOYSA-N n,n,2,4,6-pentamethylaniline Chemical compound CN(C)C1=C(C)C=C(C)C=C1C JZBZLRKFJWQZHU-UHFFFAOYSA-N 0.000 description 1
- OXQMIXBVXHWDPX-UHFFFAOYSA-N n,n,2-trimethylpropan-2-amine Chemical compound CN(C)C(C)(C)C OXQMIXBVXHWDPX-UHFFFAOYSA-N 0.000 description 1
- SRLHDBRENZFCIN-UHFFFAOYSA-N n,n-di(butan-2-yl)butan-2-amine Chemical compound CCC(C)N(C(C)CC)C(C)CC SRLHDBRENZFCIN-UHFFFAOYSA-N 0.000 description 1
- JNVBRCHEAVCGOA-UHFFFAOYSA-N n,n-dimethoxyhydroxylamine;hydrochloride Chemical compound Cl.CON(O)OC JNVBRCHEAVCGOA-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- CATWEXRJGNBIJD-UHFFFAOYSA-N n-tert-butyl-2-methylpropan-2-amine Chemical compound CC(C)(C)NC(C)(C)C CATWEXRJGNBIJD-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- DUUPDCPVCHSTFF-UHFFFAOYSA-N nonane Chemical compound [CH2]CCCCCCCC DUUPDCPVCHSTFF-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000000655 nuclear magnetic resonance spectrum Methods 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
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical group C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- XMGMFRIEKMMMSU-UHFFFAOYSA-N phenylmethylbenzene Chemical group C=1C=CC=CC=1[C]C1=CC=CC=C1 XMGMFRIEKMMMSU-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000004714 phosphonium salts Chemical class 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- OHUVHDUNQKJDKW-UHFFFAOYSA-N sodium;cyclopenta-1,3-diene Chemical compound [Na+].C=1C=C[CH-]C=1 OHUVHDUNQKJDKW-UHFFFAOYSA-N 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- VXKWYPOMXBVZSJ-UHFFFAOYSA-N tetramethyltin Chemical compound C[Sn](C)(C)C VXKWYPOMXBVZSJ-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- JSQJUDVTRRCSRU-UHFFFAOYSA-N tributyl(chloro)silane Chemical compound CCCC[Si](Cl)(CCCC)CCCC JSQJUDVTRRCSRU-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- BTFGBZUOMAPUOR-UHFFFAOYSA-N trimethyl(1h-phosphol-2-yl)stannane Chemical compound C[Sn](C)(C)C1=CC=CP1 BTFGBZUOMAPUOR-UHFFFAOYSA-N 0.000 description 1
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 1
- RCHVAAMUFAYMOD-UHFFFAOYSA-N trimethyl-(1-trimethylsilyl-1h-inden-2-yl)silane Chemical compound C1=CC=C2C([Si](C)(C)C)C([Si](C)(C)C)=CC2=C1 RCHVAAMUFAYMOD-UHFFFAOYSA-N 0.000 description 1
- QJGNREZQHSIKMQ-UHFFFAOYSA-N trimethyl-(2-methyl-3-trimethylsilyl-1h-inden-1-yl)silane Chemical compound C1=CC=C2C([Si](C)(C)C)C(C)=C([Si](C)(C)C)C2=C1 QJGNREZQHSIKMQ-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 description 1
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical group C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- RERMPCBBVZEPBS-UHFFFAOYSA-N tris(2,6-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(C)=C1P(C=1C(=CC=CC=1C)C)C1=C(C)C=CC=C1C RERMPCBBVZEPBS-UHFFFAOYSA-N 0.000 description 1
- RUHDHWYKQRTETI-UHFFFAOYSA-N tris(trifluoromethyl)borane Chemical compound FC(F)(F)B(C(F)(F)F)C(F)(F)F RUHDHWYKQRTETI-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 229960000834 vinyl ether Drugs 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic Table
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5018—Cycloaliphatic phosphines
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6568—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus atoms as the only ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61908—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/6192—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/61922—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/61927—Component covered by group C08F4/60 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
본 발명의 고융점 폴리올레핀은 화학식 I 또는 화학식 XIII의 메탈로센 화합물 또는 π 착화합물을 촉매로 사용하는 벌크상, 용액상, 현탁액상 또는 기체상에서 제조될 수 있다.The high melting point polyolefins of the present invention can be prepared in bulk, solution, suspension or gas phase using the metallocene compound of formula I or formula XIII or? Complex as a catalyst.
<화학식 I><Formula I>
<화학식 XIII><Formula XIII>
(상기 식 중,(In the above formula,
CpI 및 CpII는 시클로펜타디에닐 함유 구조를 갖는 카바니온이고,CpI and CpII are carbanions having a cyclopentadienyl containing structure,
πI 및 πII은 하전되거나 또는 전기적으로 중성인 π계이고,πI and πII are charged or electrically neutral π-based,
D는 공여체 원자이고,D is a donor atom,
A는 수용체 원자이고,A is a receptor atom,
여기서, D 및 A는 공여기가 (부분적) 양 전하를 띠고, 수용기가 (부분적) 음 전하를 띠도록 가역적 배위 결합에 의해 연결되어 있고,Where D and A are connected by reversible coordination bonds such that the donor has a (partially) positive charge and the receptor has a (partially) negative charge,
M은 란탄족 및 악티늄족을 비롯하여, 원소 주기율표(멘델리브)의 III, IV, V 또는 VI 아족의 전이 금속이고,M is a transition metal of the III, IV, V or VI subgroups of the Periodic Table of the Elements (Mendellib), including the Lanthanides and Actinides,
X는 음이온 등가기이고,X is an anion equivalent
n은 M의 전하에 따라 0, 1, 2, 3 또는 4이다).n is 0, 1, 2, 3 or 4 depending on the charge of M).
Description
본 발명은 2개 이상의 탄소 원자를 갖는 임의로 치환된 α-올레핀으로 구성되는 군으로부터 선택된 1종 이상의 단량체의 단독중합 또는 공중합에 의한 고융점 폴리올레핀의 제조 방법에서, 오르가노금속 촉매로서, 전이 금속과 2개의 π계, 특히 방향족 π계, 예를 들어 음이온성 시클로펜타디에닐 리간드 (카바니온)가 착물을 이루고, 이 2개의 계는 공여체 및 수용체의 1개 이상의 브릿지에 의해 서로 가역적으로 연결되어 있는, π계 또는 메탈로센 화합물의 이용에 관한 것이다. 공여체 원자와 수용체 원자 간에 형성된 배위 결합은 공여기 상에 (부분적) 양 전하와 수용기 상에 (부분적) 음 전하를 발생시킨다.The present invention relates to a process for producing a high melting point polyolefin by homopolymerization or copolymerization of one or more monomers selected from the group consisting of an optionally substituted α-olefin having two or more carbon atoms. Two π systems, in particular aromatic π systems, for example anionic cyclopentadienyl ligands (cabanions) are complexed, which are reversibly linked to one another by one or more bridges of donor and acceptor , π-based or metallocene compound. Coordination bonds formed between donor and acceptor atoms generate (partially) positive charges on the donor and (partially) negative charges on the acceptor.
Δ+Δ- Δ + Δ -
[공여기 → 수용기][Donor → receptor]
메탈로센 및 올레핀 중합에서 촉매로서의 그의 용도는 오랜동안 공지되어 있었다(유럽 특허 공개 제129 368호 및 그에 인용된 참고 문헌). 또한, 유럽 특허 공개 제129 368호에는 조촉매로서 알루미늄-알킬/물과 함께 메탈로센이 에틸렌의 중합에 유효한 계인 것으로 개시되어 있다 (예를 들어, 메틸알루미녹산(MAO)은 트리메틸알루미늄 1 몰과 물 1 몰로부터 형성된다. 또한, 다른 화학양론적 비율도 성공적으로 사용되어 왔다(WO 94/20506)). 시클로펜타디에닐 골격이 브릿지를 통하여 서로 공유 결합되어 있는 메탈로센은 이미 공지되어 있다. 이 분야에서의 수많은 특허 및 출원의 한 예로 유럽 특허 공개 제704 461호를 들 수 있고, 여기서 언급된 연결기는 (치환된) 메틸렌기 또는 에틸렌기, 실렌기, 치환된 실렌기, 치환된 게르밀렌기 또는 치환된 포스핀기이다. 또한, 유럽 특허 공개 제704 461호는 브릿징된 메탈로센이 올레핀에 대한 중합 촉매로서 나타내진다. 이 분야에서의 수많은 특허 및 출원에도 불구하고, 고활성이어서 중합체 내의 촉매 잔류량이 소량임을 특징으로 하며, 열가소성 및 엘라스토머성 생성물을 제공하는 올레핀의 중합 및 공중합, 그리고 올레핀과의 중합 및 공중합에 동등하게 적합한 개선된 촉매에 대한 요구가 아직도 계속되고 있다.Its use as catalyst in metallocene and olefin polymerizations has long been known (European Patent Publication 129 368 and references cited therein). European Patent Publication No. 129 368 also discloses that metallocenes together with aluminum-alkyl / water as promoters are effective systems for the polymerization of ethylene (for example, methylaluminoxane (MAO) is 1 mole of trimethylaluminum). And from 1 mole of water, and other stoichiometric ratios have also been used successfully (WO 94/20506). Metallocenes in which the cyclopentadienyl skeleton is covalently bonded to each other via a bridge are already known. An example of a number of patents and applications in this field is European Patent Publication No. 704 461, wherein the linking groups mentioned here are (substituted) methylene groups or ethylene groups, silane groups, substituted silane groups, substituted germanyls Group or substituted phosphine group. EP 704 461 also shows that bridged metallocenes as polymerization catalysts for olefins. Despite numerous patents and applications in this field, they are highly active and are characterized by a small amount of catalyst residual in the polymer, which is equivalent to the polymerization and copolymerization of olefins and the polymerization and copolymerization with olefins to give thermoplastic and elastomeric products. There is a continuing need for suitable and improved catalysts.
특히 유리한 촉매가, 2개의 π계의 브릿지가 1개, 2개 또는 3개의 가역적 공여체-수용체 결합에 의해 생성되고, 각 경우에 적어도 형식적으로는 이온 결합에 의해 중첩되는 배위 결합 또는 소위 부여(dative) 결합이 공여체 원자와 수용체 원자 간에 형성되고, 여기서 공여체 또는 수용체 원자 중 하나는 특정 π계의 일부가 될 수 있는 브릿징된 π 착화합물, 특히 메탈로센 화합물로부터 제조될 수 있다는 것이 발견되었다. 공여체-수용체 결합의 가역성은 D와 A간의 화살표에 의해 표시된 브릿징된 상태 외에도, 금속 착물의 일체성이 보존되면서 그들의 고유의 회전 에너지의 결과로서 2개의 π 시스템은 서로에 대해 예를 들어 360。로 회전할 수 있는 브릿지되지 않은 상태도 허용한다. 회전이 완료되면, 공여체-수용체 결합은 다시 "재빨리 결합된다". 여러개의 공여체 및(또는) 수용체가 존재하는 경우, 상기 "재빨리 결합하는 것"은 360°미만의 각으로 회전 한 후에 일어날 수 있다. 따라서, 본 발명에 따라 사용되는 π계, 예를 들어 메탈로센은 오직 이중 화살표로만 나타낼 수 있어서, 하위 화학식 Ia 및 Ib 또는 화학식 XIIIa 및 XIIIb 2가지 상태를 모두 포함하게 된다.Particularly advantageous catalysts are coordination bonds or so-called datives, in which two π-based bridges are produced by one, two or three reversible donor-receptor bonds, in each case at least formally overlapped by ionic bonds. It has been found that a bond is formed between a donor atom and a receptor atom, wherein one of the donor or acceptor atoms can be prepared from a bridged π complex, in particular a metallocene compound, which can be part of a particular π system. In addition to the bridged state indicated by the arrows between D and A, the reversibility of the donor-receptor bonds allows the two π systems, for example 360 °, to each other as a result of their inherent rotational energy while maintaining the integrity of the metal complex. It also allows an unbridged state to be rotated. When the rotation is complete, the donor-receptor binding is "quickly coupled". In the presence of multiple donors and / or receptors, the “quick binding” can occur after rotation at an angle of less than 360 °. Thus, the π-based, for example metallocenes used in accordance with the present invention can only be represented by double arrows, so as to encompass both states of sub-formulas Ia and Ib or formulas XIIIa and XIIIb.
따라서, 본 발명은 화학식 I의 메탈로센 화합물 또는 화학식 XIII의 π 착화합물, 특히 메탈로센 화합물을 오르가노금속 촉매로서 사용하는 것을 포함하는, 조촉매에 의해 활성화될 수 있는 오르가노금속 촉매의 존재 하에, 2개 이상의 탄소 원자를 갖는 임의로 치환된 α-올레핀으로 구성되는 군으로부터의 1종 이상의 단량체의 단독중합 또는 공중합에 의한 포화 또는 불포화 고융점 폴리올레핀의 제조 방법에관한 것이다.Accordingly, the present invention provides the presence of organometallic catalysts that can be activated by a promoter, including the use of a metallocene compound of formula (I) or a π complex of formula (XIII), in particular a metallocene compound, as organometallic catalyst The invention relates to a process for the production of saturated or unsaturated high melting point polyolefins by homopolymerization or copolymerization of at least one monomer from the group consisting of optionally substituted α-olefins having two or more carbon atoms.
(상기 식 중,(In the above formula,
CpI 및 CpII는 시클로펜타디에닐 함유 구조를 갖는 2개의 동일 또는 상이한 카바니온 (여기서, 1개 내지 모든 H 원자는 할로겐에 의해 1치환 내지 모두 치환되거나, 또는 페닐에 의해 1치환 내지 3치환되거나, 또는 비닐에 의해 1치환 내지 3치환될 수 있는 선형 또는 분지형 C1-C20-알킬; C6-C12-아릴; 탄소 원자수 6 내지 12의 할로게노아릴; 실릴, 트리메틸실릴 또는 페로세닐과 같은 오르가노금속 치환체로 구성된 군으로부터의 동일 또는 상이한 라디칼에 의해 치환될 수 있고, 1개 또는 2개가 D 및 A에 의해 치환될 수 있음이고,CpI and CpII are two identical or different carbanions having a cyclopentadienyl containing structure, wherein one to all H atoms are monosubstituted to all substituted by halogen, or monosubstituted to trisubstituted by phenyl, Or linear or branched C 1 -C 20 -alkyl which may be monosubstituted or trisubstituted by vinyl; C 6 -C 12 -aryl; halogenoaryl having 6 to 12 carbon atoms; silyl, trimethylsilyl or ferro May be substituted by the same or different radicals from the group consisting of organometallic substituents such as cenyl, one or two may be substituted by D and A,
D는, 추가의 치환체를 지닐 수 있고 특정의 결합 상태에서 1개 이상의 자유 전자쌍을 갖는 공여체 원자이고,D is a donor atom that may have additional substituents and has at least one free electron pair in a particular bond state,
A는, 추가의 치환체를 지닐 수 있고 특정의 결합 상태에서 1개 이상의 전자쌍이 부족한 수용체 원자이고,A is a receptor atom which may have additional substituents and lacks one or more electron pairs in certain binding states,
여기서, D 및 A는 공여기가 (부분적) 양 전하를 띠고, 수용기가 (부분적) 음 전하를 띠도록 가역적 배위 결합에 의해 연결되어 있고,Where D and A are connected by reversible coordination bonds such that the donor has a (partially) positive charge and the receptor has a (partially) negative charge,
M은 란탄족 및 악티늄족을 비롯하여, 원소 주기율표(멘델리브)의 III, IV, V 또는 VI 아족의 전이 금속이고,M is a transition metal of the III, IV, V or VI subgroups of the Periodic Table of the Elements (Mendellib), including the Lanthanides and Actinides,
X는 음이온 등가기이고,X is an anion equivalent
n은 M의 전하에 따라 0, 1, 2, 3 또는 4이다)n is 0, 1, 2, 3 or 4 depending on the charge of M)
(상기 식 중,(In the above formula,
πI 및 πII은 1 또는 2개의 불포화 또는 포화 5원 또는 6원 고리와 융합될 수 있는, 상이하게 하전되거나 또는 전기적으로 중성인 π계이고,πI and πII are differently charged or electrically neutral π systems, which can be fused with one or two unsaturated or saturated five or six membered rings,
D는, πI의 치환체 또는 πI의 π계의 일부이고 특정 결합 상태에서 1개 이상의 자유 전자쌍을 갖는 공여체 원자이고,D is a substituent of πI or a donor atom that is part of a π system of πI and has at least one free electron pair in a particular bonding state,
A는, πII의 치환체 또는 πII의 π계의 일부이고 특정 결합 상태에서 1개 이상의 전자쌍이 부족한 수용체 원자이고,A is a substituent of πII or a part of π system of πII and is a receptor atom lacking one or more electron pairs in a specific bonding state,
여기서, D 및 A는 공여기가 (부분적) 양 전하를 띠고, 수용기가 (부분적) 음 전하를 띠도록 가역적 배위 결합에 의해 연결되어 있고, D 및 A 중 1개 이상은 특정 결합된 π계의 일부이고, 또한 D 및 A는 치환체를 지닐 수 있고,Wherein D and A are linked by reversible coordination bonds such that the donor is (partially) positively charged and the receptor is (partially) negatively charged, and at least one of D and A is of Part and D and A may have substituents,
각 π계 및 각 융합된 고리계는 1개 이상의 D 또는 A, 또는 D 및 A를 함유할 수 있고,Each π system and each fused ring system may contain one or more D or A, or D and A,
비융합된 또는 융합된 형태의 πI 및 πII에서, π계의 1개 내지 모든 H 원자는 할로겐에 의해 1치환 내지 완전히 치환될 수 있거나, 또는 페닐에 의해 1치환 내지 3치환될 수 있거나, 또는 비닐에 의해 1치환 내지 3 치환될 수 있는 선형 또는 분지형 C1-C20-알킬; C6-C12-알릴; 탄소 원자수 6 내지 12의 할로게노아릴; 실릴, 트리메틸실릴 또는 페로세닐과 같은 오르가노금속 치환체로 구성된 군으로부터의 동일 또는 상이한 라디칼에 의해 서로 독립적으로 치환되거나, 또는 1개 또는 2개가 D 및 A에 의해 치환될 수 있으므로, 가역적 D→A 배위 결합 (i)이 D 및 A 모두 특정 π계 또는 융합된 고리계의 일부이거나, 또는 (ii) D 또는 A가 π계의 일부이거나, 또는 융합된 고리계의 일부이고, 각 경우에 다른 하나는 비융합된 π계 또는 융합된 고리계의 치환체인 D와 A 간에 형성될 수 있으며,In unfused or fused form of π I and π II, one to all H atoms of the π system may be monosubstituted to fully substituted by halogen, or monosubstituted to trisubstituted by phenyl, or vinyl Linear or branched C 1 -C 20 -alkyl which may be substituted with 1 to 3 substituents; C 6 -C 12 -allyl; Halogenoaryl having 6 to 12 carbon atoms; Reversible D → A, since one or two may be substituted independently by one another or by the same or different radicals from the group consisting of organometallic substituents such as silyl, trimethylsilyl or ferrocenyl, or by one or two The coordination bond (i) is both D and A part of a particular π or fused ring system, or (ii) D or A is part of the π system, or is part of a fused ring system, and in each case the other May be formed between D and A, which is a substituent of an unfused π or fused ring system,
M 및 X는 상기 정의된 바와 같고,M and X are as defined above,
n은 M의 전하, 및 π-I 및 π-II의 전하에 따라 0, 1, 2, 3 또는 4이다).n is 0, 1, 2, 3 or 4 depending on the charge of M and the charges of π-I and π-II).
본 발명에 따른 π계는 치환된 또는 비치환된 에틸렌, 알릴, 펜타디에닐, 벤질, 부타디엔, 벤젠, 시클로펜타디에닐 음이온 및 1개 이상의 C 원자를 헤테로원자에 의해 치환함으로써 생성된 종들이다.The π systems according to the invention are species produced by substituting substituted or unsubstituted ethylene, allyl, pentadienyl, benzyl, butadiene, benzene, cyclopentadienyl anions and one or more C atoms by heteroatoms.
상기 종들 중에서, 시클릭 종들이 바람직하다. 이러한 리간드(π계)의 금속에 대한 배위 결합 특성은 σ 유형 또는 π 유형일 수 있다.Among the species, cyclic species are preferred. The coordination binding property of the ligand (π-based) to the metal may be σ type or π type.
본 발명에 따라 사용되는 상기 화학식 I의 메탈로센 화합물은 비양성자성 용매의 존재 하에 M'X를 제거하면서 화학식 II와 화학식 III의 화합물, 또는 화학식 IV와 화학식 V의 화합물, 또는 화학식 VI과 화학식 VII의 화합물을 서로 반응시키거나, 또는 비양성자성 용매의 존재 또는 부재 하에 E(R1R2R3)X 및 F(R4R5R6)을 제거하면서 화학식 VIII과 화학식 III의 화합물, 또는 화학식 IV와 화학식 IX의 화합물, 또는 화학식 X과 화학식 VII의 화합물을 반응시킴으로써 제조가능하다.The metallocene compound of formula (I) used according to the invention is a compound of formula (II) and (III), or a compound of formula (IV) and (V), or formula (VI) Compounds of formula (VIII) and (III), with reaction of compounds of VII with each other or removal of E (R 1 R 2 R 3 ) X and F (R 4 R 5 R 6 ) in the presence or absence of an aprotic solvent, Or by reacting a compound of Formula IV with Formula IX, or a compound of Formula X with Formula VII.
상기 식 중,In the above formula,
CpI, CpII, D, A, M, X 및 n은 상기 정의된 바와 같고,CpI, CpII, D, A, M, X and n are as defined above,
CpIII, CpIV는 시클로펜타디엔 함유 구조를 갖는 2개의 동일 또는 상이한 비하전된 분자이거나, 또는 CpI 및 CpII와 동일하고,CpIII, CpIV are two identical or different uncharged molecules having a cyclopentadiene containing structure or are the same as CpI and CpII,
M'는 하나의 알칼리 또는 알칼리 토 금속 또는 Tl의 1가 양이온이고,M 'is a single alkali or alkaline earth metal or monovalent cation of Tl,
E 및 F는 서로 독립적으로 Si, Ge 또는 Sn 원소 중 하나이고,E and F are independently of each other one of the elements Si, Ge or Sn,
R1, R2, R3, R4, R5및 R6은 서로 독립적으로 선형 또는 분지형 C1-C20-알킬, C6-C12-아릴, C1-C6-알킬-C6-C12-아릴, C6-C12-아릴-C6-C12-알킬, 비닐, 알릴 또는 할로겐이고,R 1 , R 2 , R 3 , R 4 , R 5 and R 6 independently of one another are linear or branched C 1 -C 20 -alkyl, C 6 -C 12 -aryl, C 1 -C 6 -alkyl-C 6- C 12 -aryl, C 6 -C 12 -aryl-C 6 -C 12 -alkyl, vinyl, allyl or halogen,
여기서, 화학식 VIII, IX 및 X에서 수소가 E(R1R2R3) 및 F(R4R5R6)를 대신하여 존재할 수 있고, 이러한 경우에, X는 또한 R2N-유형의 아미드 음이온 또는 R3C-유형의 카바니온 또는 RO-유형의 알콜레이트 음이온을 나타낼 수 있고, 여기서 또한 화학식 V 또는 화학식 IX의 화합물의 존재 하에 화학식 II 또는 화학식 VIII의 화합물을 직접 화학식 VII의 전이 금속 화합물과 반응시킬 수 있다.Wherein in formulas VIII, IX and X, hydrogen may be present in place of E (R 1 R 2 R 3 ) and F (R 4 R 5 R 6 ), in which case X is also of R 2 N − type Amide anion or a carbanion of R 3 C - type or an alcoholate anion of RO - type, wherein the compound of Formula II or Formula VIII is also directly converted in the presence of the compound of Formula V or Formula IX React with the compound.
화학식 VIII과 화학식 III의 반응, 또는 화학식 IV와 화학식 IX의 반응, 또는 화학식 X과 화학식 VII의 반응에서, 마지막으로 언급된 변형 방법에서 화학식 I의 구조는 아민 R2NH 또는 R2NE(R1R2R3) 또는 R2NF(R4R5R6), 또는 화학식 R3CH 또는 R3CE(R1R2R3) 또는 R3CF(R4R5R6)의 탄화수소 화합물, 또는 에테르 ROE(R1R2R3) 또는 ROF(R4R5R6)를 제거하면서 형성되고, 여기서 유기 라디칼 R은 동일하거나 또는 상이하고, 독립적으로 C1-C20-알킬, C6-C12-아릴, 치환되거나 또는 비치환된 알릴, 벤질 또는 수소이다. 제거된 아민 또는 탄화수소, 에테르, 실란, 주석 또는 게르만의 예로는 디메틸아민, 디에틸아민, 디-(n-프로필)-아민, 디-(이소프로필)-아민, 디-(tert-부틸)-아민, 3급 부틸아민, 시클로헥실아민, 아닐린, 메틸-페닐-아민, 디-(알릴)-아민 또는 메탄, 톨루엔, 트리메틸실릴아민, 트리메틸실릴에테르, 테트라메틸실란 등을 들 수 있다.In the reaction of formula (VIII) and (III), or (IV) and (IX), or (X) and (VII), in the last mentioned variant method, the structure of formula (I) is represented by the amine R 2 NH or R 2 NE (R 1 R 2 R 3 ) or R 2 NF (R 4 R 5 R 6 ), or a hydrocarbon compound of the formula R 3 CH or R 3 CE (R 1 R 2 R 3 ) or R 3 CF (R 4 R 5 R 6 ) Or is formed while removing the ether ROE (R 1 R 2 R 3 ) or ROF (R 4 R 5 R 6 ), wherein the organic radicals R are the same or different and independently C 1 -C 20 -alkyl, C 6- C 12 -aryl, substituted or unsubstituted allyl, benzyl or hydrogen. Examples of amines or hydrocarbons, ethers, silanes, tins or germanes that have been removed are dimethylamine, diethylamine, di- (n-propyl) -amine, di- (isopropyl) -amine, di- (tert-butyl)- Amine, tertiary butylamine, cyclohexylamine, aniline, methyl-phenyl-amine, di- (allyl) -amine or methane, toluene, trimethylsilylamine, trimethylsilyl ether, tetramethylsilane and the like.
또한, 화학식 V 또는 IX의 화합물의 존재 하에, 화학식 II 또는 화학식 VIII의 화합물과 화학식 VII의 전이 금속 화합물을 직접 반응시킬 수 있다.It is also possible to directly react the compound of formula II or formula VIII with the transition metal compound of formula VII in the presence of a compound of formula V or IX.
π계가 시클릭 및 방향족(메탈로센)인 화학식 XIII의 π 착화합물은 유사한 방법으로 하기 화합물을 사용하여 제조할 수 있다.[pi] Complexes of the formula (XIII) in which the [pi] system is cyclic and aromatic (metallocene) can be prepared using the following compounds in a similar manner.
쇄가 개열된 π 착화합물은 전문가에게 공지된 공여기 및 수용기 삽입 방법에 의해 제조된다.Chain cleaved π complexes are prepared by donor and acceptor insertion methods known to the expert.
또한, 단량체로 1종 이상의 임의로 치환된 α-올레핀의 단독중합 또는 공중합에 대해 본 발명에 따라, 반응은 -60 내지 +250℃, 바람직하게는 0 내지 200℃에서, 0.5 내지 5000, 바람직하게는 1 내지 3000 bar에서, 기체, 용액, 고압 또는 슬러리 상으로, 포화된 또는 방향족 탄화수소, 또는 포화된 또는 방향족 할로게노-탄화수소의 존재 또는 부재 하에, 그리고 수소의 존재 또는 부재 하에, 메탈로센 화합물 또는 π 착화합물을 촉매로서 메탈로센 또는 π 착화합물의 몰 당 모든 단량체가 101내지 1012의 양이 되도록 사용하고, 또한 반응은 루이스산, 브뢴스테드산 또는 피어슨산 또는 추가로 루이스 염기의 존재 하에 수행할 수도 있다.Furthermore, according to the invention for the homopolymerization or copolymerization of at least one optionally substituted α-olefin with monomers, the reaction is from 0.5 to 5000, preferably from -60 to + 250 ° C, preferably from 0 to 200 ° C. Metallocene compound, at 1 to 3000 bar, in the presence of a gas, solution, high pressure or slurry, in the presence or absence of saturated or aromatic hydrocarbons, or saturated or aromatic halogeno-hydrocarbons, and in the presence or absence of hydrogen π complex is used as a catalyst so that all monomers per mole of metallocene or π complex are in an amount of 10 1 to 10 12 and the reaction is also in the presence of Lewis acid, Brønsted acid or Pearson acid or additionally Lewis base It can also be done.
상기 루이스산에는 예를 들어, 보란류 또는 알란류로서, 알루미늄-알킬, 알루미늄 할라이드, 알루미늄 알콜레이트, 오르가노보란 화합물, 보론 할라이드, 붕산 에스테르, 또는 할라이드 치환체와 알킬 또는 아릴 또는 알콜레이트 치환체를 모두 함유하는 붕소 또는 알루미늄 화합물, 및 상기의 혼합물 또는 트리페닐메틸 양이온이 있다. 특히 바람직하게는, 알루미녹산 또는 알루미늄 함유 루이스산과 물의 혼합물이 있다. 현재의 지식으로는, 모든 산은 메탈로센 양이온을 형성하는 이온화제로서 작용하고, 여기서 전하는 배위결합이 잘 되지 않는 벌키 음이온에 의해 보상된다.The Lewis acid includes, for example, boranes or alans, and includes both aluminum-alkyl, aluminum halides, aluminum alcoholates, organoborane compounds, boron halides, boric acid esters, or halide substituents and alkyl or aryl or alcoholate substituents. Containing boron or aluminum compounds, and mixtures or triphenylmethyl cations above. Especially preferably, there is a mixture of aluminoxane or aluminum containing Lewis acid and water. In the present knowledge, all acids act as ionizers to form metallocene cations, where charges are compensated by poorly coordinated bulky anions.
또한, 본 발명에 따라 상기 이온화제와 화학식 I의 메탈로센 화합물의 반응이 제공될 수 있다. 이들은 화학식 XIa 내지 화학식 XId에 의해 나타낼 수 있다.In addition, according to the present invention, a reaction between the ionizing agent and the metallocene compound of the formula (I) may be provided. These can be represented by the formulas (XIa) to (XId).
상기 식 중,In the above formula,
음이온은 쉽게 배위되지 않는 전체 벌키 음이온을 나타내고, 염기는 루이스 염기이다.Anions represent total bulky anions that are not easily coordinated, and the base is a Lewis base.
본 발명에 따라 사용될 수 있는 화학식 I 및 XIII의 촉매는 단량체, 및 이합체 또는 올리고머 형태로 존재할 수 있다.Catalysts of formulas (I) and (XIII) that can be used according to the invention may exist in the form of monomers and dimers or oligomers.
또한, 물질의 특정 특성 프로파일을 얻기 위해, 여러 D/A 촉매를 동시에 사용하는 것도 가능하다. 따라서, D/A 브릿지를 갖지 않는 다른 메탈로센과 조합하여 1종 이상의 D/A 촉매를 사용하는 것도 가능하다.It is also possible to use several D / A catalysts simultaneously in order to obtain a specific property profile of the material. Thus, it is also possible to use one or more D / A catalysts in combination with other metallocenes that do not have a D / A bridge.
쉽게 배위되지 않는 음이온의 예로는 B(C6H5)4 -, B(C6F5)4 -, B(CH3)(C6F5)3 -,, 또는 술포네이트, 예를 들어 토실레이트 또는 트리플레이트, 테트라플루오로보레이트, 헥사플루오로포스페이트 또는 헥사플루오로안티모네이트, 퍼클로레이트, 그리고 카보란 유형의 부피가 큰 집합 분자 음이온, 예를 들어 C2B9H12 -또는 CB11H12 -가 있다. 상기 음이온이 존재 하는 경우, 메탈로센 화합물은 알루미녹산의 부재 하에도 활성이 높은 중합 촉매로서 작용할 수 있다. 이는 무엇보다도 1개의 X 리간드가 알킬기 또는 벤질인 경우에 잘 나타난다. 그러나, 알루미늄-알킬, 예를 들어 (CH3)3Al, (C2H5)3Al, (n-/i-프로필)3Al, (n-/t-부틸)3Al, (i-부틸)3Al, 펜틸-, 헥실- 또는 옥틸알루미늄-알킬 이성질체, 또는 리튬알킬, 예를 들어 메틸리튬, 벤질리튬, 또는 부틸리튬, 또는 상응하는 오르가노마그네슘 화합물, 예를 들어 그리냐드 화합물 또는 오르가노아연 화합물과 혼합된 부피가 큰 음이온을 갖는 상기 메탈로센 착물을 사용하는 것이 유리할 수 있다. 상기 금속 알킬화물은 한편으로는 알킬기를 중심 금속으로 이동시키면서, 다른 한편으로는 중합 반응 내에서의 반응 매질 또는 단량체로부터 물 또는 촉매독을 제거한다. 상기 유형의 메틸-알킬은 유리하게는, 예를 들어, 요구되는 알루미녹산의 양을 감소시키기 위하여 알루미녹산 조촉매와 함께 사용될 수 있다. 사용될 때, 상기 음이온이 유도될 수 있는 붕소 화합물의 예로는 트리에틸암모늄 테트라페닐보레이트, 트리프로필암모늄 테트라페닐보레이트, 트리(n-부틸)암모늄 테트라페닐보레이트, 트리(t-부틸)암모늄 테트라페닐보레이트, N,N-디메틸아닐리늄 테트라페닐보레이트, N,N-디에틸아닐리늄 테트라페닐보레이트, N,N-디메틸(2,4,6-트리메틸아닐리늄) 테트라페닐보레이트, 트리메틸암모늄 테트라키스(펜타플루오로페닐)보레이트, 트리에틸암모늄 테트라키스(펜타플루오로페닐)보레이트, 트리프로필암모늄 테트라키스(펜타플루오로페닐)보레이트, 트리(n-부틸)암모늄 테트라키스(펜타플루오로페닐)보레이트, 트리(sec-부틸)암모늄 테트라키스(펜타플루오로페닐)보레이트, N,N-디메틸아닐리늄 테트라키스(펜타플루오로페닐)보레이트, N,N-디에틸아닐리늄 테트라키스(펜타플루오로페닐)보레이트, N,N-디메틸(2,4,5-트리메틸아닐리늄) 테트라키스(펜타플루오로페닐)보레이트, 트리메틸암모늄 테트라키스(2,3,4,6-테트라플루오로페닐)보레이트, 트리에틸암모늄 테트라키스(2,3,4,6-테트라플루오로페닐)보레이트, 트리프로필암모늄 테트라키스(2,3,4,6-테트라플루오로페닐)보레이트, 트리(n-부틸)암모늄 테트라키스(2,3,4,6-테트라플루오로페닐)보레이트, 디메틸(t-부틸)암모늄 테트라키스(2,3,4,6-테트라플루오로페닐)보레이트, N,N-디메틸아닐리늄 테트라키스(2,3,4,6-테트라플루오로페닐)보레이트, N,N-디에틸아닐리늄 테트라키스(2,3,4,6-테트라플루오로페닐)보레이트, 및 N,N-디메틸-(2,4,6-트리메틸아닐리늄) 테트라키스(2,3,4,6-테트라플루오로페닐)보레이트, 디알킬암모늄 염, 예를 들어 디(i-프로필)암모늄 테트라키스(펜타플루오로페닐)보레이트 및 디시클로헥실암모늄 테트라키스(펜타플루오로페닐)보레이트, 3치환된 포스포늄염, 예를 들어 트리페닐포스포늄 테트라키스(펜타프루오로페닐)보레이트, 트리(o-톨릴)포스포늄 테트라키스(펜타플루오로페닐)보레이트, 및 트리스(2,6-디메틸페닐)포스포늄 테트라키스(펜타플루오로페닐)보레이트, 트리올릴메틸 테트라키스(펜타플루오로페닐)보레이트, 트리페닐메틸 테트라페닐보레이트(트리틸 테트라페닐보레이트), 트리틸 테트라키스(펜타플루오로페닐)보레이트, 실버 테트라플루오로보레이트, 트리스(펜타플루오로페닐)보란, 및 트리스(트리플루오로메틸)보란이 있다.Examples of non-coordinating anion is easy B (C 6 H 5) 4 -, B (C 6 F 5) 4 -, B (CH 3) (C 6 F 5) 3 -, Or bulky aggregate molecular anions of type sulfonates, for example tosylate or triflate, tetrafluoroborate, hexafluorophosphate or hexafluoroantimonate, perchlorate, and carborane, for example C 2 a - B 9 H 12 -, or CB 11 H 12. When the anion is present, the metallocene compound can act as a high activity polymerization catalyst even in the absence of aluminoxane. This is especially apparent when one X ligand is an alkyl group or benzyl. However, aluminum-alkyl such as (CH 3 ) 3 Al, (C 2 H 5 ) 3 Al, (n- / i-propyl) 3 Al, (n- / t-butyl) 3 Al, (i- Butyl) 3 Al, pentyl-, hexyl- or octyl aluminum-alkyl isomers, or lithiumalkyl, for example methyllithium, benzylithium, or butyllithium, or the corresponding organomagnesium compound, for example Grignard compound or It may be advantageous to use such metallocene complexes having bulky anions mixed with the organoazin compound. The metal alkylate, on the one hand, moves the alkyl group to the central metal, while on the other hand removes water or catalyst poisons from the reaction medium or monomer in the polymerization reaction. Methyl-alkyl of this type can advantageously be used with, for example, aluminoxane cocatalysts to reduce the amount of aluminoxane required. When used, examples of the boron compound from which the anion can be derived include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, tri (t-butyl) ammonium tetraphenylborate , N, N-dimethylanilinium tetraphenylborate, N, N-diethylanilinium tetraphenylborate, N, N-dimethyl (2,4,6-trimethylanilinium) tetraphenylborate, trimethylammonium tetrakis (penta Fluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, tri (sec-butyl) ammonium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetra Kis (pentafluorophenyl) borate, N, N-dimethyl (2,4,5-trimethylanilinium) tetrakis (pentafluorophenyl) borate, trimethylammonium tetrakis (2,3,4,6-tetrafluoro Rophenyl) borate, triethylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, tri (n -Butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, dimethyl (t-butyl) ammonium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N -Dimethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, N, N-diethylanilinium tetrakis (2,3,4,6-tetrafluorophenyl) borate, and N , N-dimethyl- (2,4,6-trimethylanilinium) tetrakis (2,3,4,6-tetrafluorophenyl) borate, dialkylammonium salts such as di (i-propyl) ammonium tetra Keith (Pentafluoro) Phenyl) borate and dicyclohexylammonium tetrakis (pentafluorophenyl) borate, trisubstituted phosphonium salts such as triphenylphosphonium tetrakis (pentafluorophenyl) borate, tri (o-tolyl) force Phosphium tetrakis (pentafluorophenyl) borate, and tris (2,6-dimethylphenyl) phosphonium tetrakis (pentafluorophenyl) borate, triolylmethyl tetrakis (pentafluorophenyl) borate, triphenylmethyl tetra Phenylborate (trityl tetraphenylborate), trityl tetrakis (pentafluorophenyl) borate, silver tetrafluoroborate, tris (pentafluorophenyl) borane, and tris (trifluoromethyl) borane.
본 발명에 따라 사용되는 메탈로센 화합물 및 π 착화합물은 (공)중합에 사용하기 위하여 순수한 물질로 단리될 수 있다. 그러나, 또한 당업자에게 공지된 방법으로 중합 반응기 내에서 이들을 생성하고 "동일 반응계 내에서" 사용할 수도 있다.The metallocene compounds and π complexes used according to the invention can be isolated as pure materials for use in (co) polymerization. However, they can also be produced and used “in the same reaction system” in the polymerization reactor by methods known to those skilled in the art.
시클로펜타디에닐 골격을 함유하는 제1 및 제2 카바니온 CpI 및 CpII는 동일하거나 또는 상이할 수 있다. 시클로펜타디에닐 골격은 예를 들어 시클로펜타디엔, 치환된 시클로펜타디엔, 인덴, 치환된 인덴, 플루오렌 및 치환된 플루오렌으로 구성된 군으로부터 선택된 것일 수 있다. 시클로펜타디엔 또는 융합된 벤젠 고리 당 1 내지 4개의 치환체가 존재할 수 있다. 이 치환체들은 C1-C20-알킬, 예를 들어 메틸, 에틸, 프로필, 이소프로필, 부틸 또는 이소부틸, 헥실, 옥틸, 데실, 도데실, 헥사데실, 옥타데실 또는 에이코실, C1-C20-알콕시, 예를 들어 메톡시, 에톡시, 프로폭시, 이소프로폭시, 부톡시 또는 이소부톡시, 헥속시, 옥틸옥시, 데실옥시, 도데실옥시, 헥사데실옥시, 옥타데실옥시, 에이코실옥시, 할로겐, 예를 들어 불소, 염소 또는 브롬, C6-C12-아릴, 예를 들어 페닐, C1-C4-알킬페닐, 예를 들어 톨릴, 에틸페닐, (i-)프로필페닐, (i-, tert-)부틸페닐 또는 크실릴, 할로게노페닐, 예를 들어 플루오로페닐, 클로로페닐 또는 브로모페닐, 나프틸 또는 비페닐릴, 티오르가닐-실릴, 예를 들어 트리메틸실릴(TMS), 페로세닐, 및 상기 정의된 바와 같은 D 또는 A일 수 있다. 또한, 융합된 방향족 고리는 융합된 고리와 시클로펜타디엔 고리 모두에 의해 공유되는 이중 결합만이 존재할 수 있도록, (부분적)으로 또는 완전히 수소화될 수 있다. 인덴 또는 플루오렌과 같은 벤젠 고리를 추가로 1 또는 2개의 융합된 벤젠 고리를 함유할 수 있다. 또한, 시클로펜타디엔 또는 시클로펜타디에닐 고리 및 융합된 벤젠 고리는 함께 추가의 융합된 벤젠 고리를 함유할 수 있다.The first and second carbanion CpI and CpII containing the cyclopentadienyl backbone may be the same or different. The cyclopentadienyl backbone can be selected from the group consisting of, for example, cyclopentadiene, substituted cyclopentadiene, indene, substituted indene, fluorene and substituted fluorene. There may be 1 to 4 substituents per cyclopentadiene or fused benzene ring. These substituents may be C 1 -C 20 -alkyl, for example methyl, ethyl, propyl, isopropyl, butyl or isobutyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl or eicosyl, C 1 -C 20 -alkoxy, for example methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy, hexoxy, octyloxy, decyloxy, dodecyloxy, hexadecyloxy, octadecyloxy, Eicosyloxy, halogen, for example fluorine, chlorine or bromine, C 6 -C 12 -aryl, for example phenyl, C 1 -C 4 -alkylphenyl, for example tolyl, ethylphenyl, (i-) propyl Phenyl, (i-, tert-) butylphenyl or xylyl, halogenophenyl, for example fluorophenyl, chlorophenyl or bromophenyl, naphthyl or biphenylyl, thioorganyl-silyl, for example trimethyl Silyl (TMS), ferrocenyl, and D or A as defined above. In addition, the fused aromatic ring may be (partially) or fully hydrogenated such that only double bonds covalently exist by both the fused ring and the cyclopentadiene ring. Benzene rings such as indene or fluorene may further contain one or two fused benzene rings. In addition, the cyclopentadiene or cyclopentadienyl ring and the fused benzene ring may together contain further fused benzene rings.
상기 음이온 형태의 시클로펜타디엔 골격은 전이 금속의 우수한 리간드이고, 여기서 상기 임의로 치환된 형태의 시클로펜타디에닐 카바니온은 착물에서 중심 금속의 양 전하를 보상하는 것이다. 상기 카바니온의 개별적 예로는 시클로펜타디에닐, 메틸시클로펜타디에닐, 1,2,-디메틸시클로펜타디에닐, 1,3-디메틸시클로펜타디에닐, 인데닐, 페닐인데닐, 1,2-디에틸시클로펜타디에닐, 테트라메틸-시클로펜타디에닐, 에틸-시클로펜타디에닐, n-부틸-시클로펜타디에닐, n-옥틸-시클로펜타디에닐, β-페닐프로필-시클로펜타디에닐, 테트라히드로인데닐, 프로필-시클로펜타디에닐, t-부틸-시클로펜타디에닐, 벤질-시클로펜타디에닐, 디페닐메틸-시클로펜타디에닐, 트리메틸게르밀-시클로펜타디에닐, 트리플루오로메틸-시클로펜타디에닐, 트리메틸실릴-시클로펜타디에닐, 펜타메틸-시클로펜타디에닐, 플루오레닐, 테트라히드로플루오레닐 또는 옥타히드로플루오레닐, 6원 고리 상에 벤조 융합된 플루오레닐 및 인데닐, N,N-디메틸아미노-시클로펜타디에닐, 디메틸포스피노-시클로펜타디에닐, 메톡시-시클로펜타디에닐, 디메틸보라닐-시클로펜타디에닐, 및 (N,N-디메틸아미노메틸)-시클로펜타디에닐이 있다.The cyclopentadiene skeleton of the anionic form is an excellent ligand of the transition metal, wherein the optionally substituted form of cyclopentadienyl carbanion is to compensate for the positive charge of the central metal in the complex. Individual examples of the carbanion include cyclopentadienyl, methylcyclopentadienyl, 1,2, -dimethylcyclopentadienyl, 1,3-dimethylcyclopentadienyl, indenyl, phenylindenyl, 1,2- Diethylcyclopentadienyl, tetramethyl-cyclopentadienyl, ethyl-cyclopentadienyl, n-butyl-cyclopentadienyl, n-octyl-cyclopentadienyl, β-phenylpropyl-cyclopentadienyl, Tetrahydroindenyl, propyl-cyclopentadienyl, t-butyl-cyclopentadienyl, benzyl-cyclopentadienyl, diphenylmethyl-cyclopentadienyl, trimethylgeryl-cyclopentadienyl, trifluoromethyl -Cyclopentadienyl, trimethylsilyl-cyclopentadienyl, pentamethyl-cyclopentadienyl, fluorenyl, tetrahydrofluorenyl or octahydrofluorenyl, fluorenyl benzo fused on a six membered ring and Indenyl, N, N-dimethylamino-cyclopentadienyl, Dimethylphosphino-cyclopentadienyl, methoxy-cyclopentadienyl, dimethylboranyl-cyclopentadienyl, and (N, N-dimethylaminomethyl) -cyclopentadienyl.
반드시 존재하는 D와 A간의 제1 공여체-수용체 결합 외에, 추가의 공여체-수용체 결합은 추가의 D 및(또는) A가 특정 시클로펜타디엔계의 치환체 또는 π계의 치환체 또는 부분으로서 존재하는 경우에 형성될 수 있다. 모든 공여체-수용체 결합은 상기된 가역성을 지닌다. 다수의 D 및 A의 경우에 있어서, 상기된 것들 중에 다양한 위치에 자리할 수 있다. 따라서, 본 발명은 브릿징된 분자 상태(화학식 Ia 및 화학식 XIIIa) 및 브릿지되지 않은 상태(화학식 Ib 및 화학식 XIIIb) 모두를 포함한다. D기의 수는 A기의 수와 동일하거나 또는 상이할 수 있다. 바람직하게는 CpI 및 CpII는 오직 하나의 공여체-수용체 브릿지를 통해서만 연결된다.In addition to the first donor-receptor bond between D and A, which is necessarily present, additional donor-receptor bonds may occur when additional D and / or A is present as a substituent of a specific cyclopentadiene system or as a substituent or moiety of π system Can be formed. All donor-receptor bonds have the reversibility described above. In the case of many D and A, they may be located at various positions among those described above. Thus, the present invention encompasses both the bridged molecular state (Formula Ia and Formula XIIIa) and the unbridged state (Formula Ib and Formula XIIIb). The number of group D may be the same as or different from the number of group A. Preferably CpI and CpII are linked only through one donor-receptor bridge.
본 발명에 따른 D/A 브릿지 외에, 공유 브릿지도 존재할 수 있다. 이 경우에, D/A 브릿지는 촉매의 입체 고정성 및 열 안정성을 강화시킨다. 폐쇄된 D/A 결합과 개열된 D/A 결합을 바꿈으로써 상이한 화학적 조성의 공중합체 서열 중합체가 가능하다.In addition to the D / A bridge according to the present invention, there may also be a shared bridge. In this case, the D / A bridge enhances the steric fixation and thermal stability of the catalyst. By changing closed D / A bonds and cleaved D / A bonds, copolymer sequence polymers of different chemical compositions are possible.
이와 같이 π 착화합물은 공여체 원자 D와 수용체 원자 A간의 1개 이상의 배위 결합의 존재에 의해 특성화된다. D 및 A 모두가 특정 π계 πI 및 πII의 치환체, 또는 π계의 일부가 될 수도 있으나, D 및 A 중 적어도 1개는 항상 π계의 일부이다. 여기서, π계는 전체 π계를 의미하는 것으로 이해되며, 임의로는 1회 또는 2회 융합된다. 하기 실시양태는 D는 π계의 일부이고, A는 π계의 치환체이며; D는 π계의 치환체이고, A는 π계의 일부이며; D 및 A는 특정 π계의 일부라는 사실로부터 기인한다.As such, the π complex is characterized by the presence of one or more coordination bonds between donor atom D and acceptor atom A. While both D and A may be substituents of certain π-based πI and πII, or part of the π-based, at least one of D and A is always part of the π-based. Here, the π system is understood to mean the entire π system, optionally fused once or twice. In the following embodiments, D is a part of π-based, A is a substituent of π-based; D is a π-based substituent, and A is part of a π-based; D and A result from the fact that they are part of a particular π system.
D 또는 A가 고리계의 일부인 하기 헤테로시클릭 고리계는 다음과 같이 예시될 수 있다.The following heterocyclic ring systems in which D or A are part of the ring system can be illustrated as follows.
중요한 헤테로시클릭 고리계는 (a), (b), (c), (d), (g), (m), (n) 및 (o)로 표지되고, 표지된 (a), (b), (c) 및 (m)은 특히 중요하다.Important heterocyclic ring systems are labeled (a), (b), (c), (d), (g), (m), (n) and (o), labeled (a), (b) ), (c) and (m) are particularly important.
D 및 A 중 하나가 결합된 고리계의 치환체인 경우, 고리계는 전기 전하를 갖거나 또는 갖지않는 3원, 4원, 5원, 6원, 7원 또는 8원 고리계이고, 상기 기재된 방법으로 추가로 치환되고(되거나) 융합될 수 있다. 5원 및 6원 고리계가 바람직하다. 음성적으로 하전된 시클로펜타디에닐계가 특히 바람직하다.When one of D and A is a substituent of a bonded ring system, the ring system is a three-, four-, five-, six-, seven- or eight-membered ring system with or without an electric charge and the method described above May be further substituted and / or fused. 5- and 6-membered ring systems are preferred. Particular preference is given to negatively charged cyclopentadienyl systems.
제1 및 제2 π계 πI 및 πII는 각각, 고리계로서 형성된다면, D 및 A 중 하나가 고리계의 치환체인 경우의 CpI 및 CpII 각각에 상응할 수 있다.The first and second π systems πI and πII may each correspond to CpI and CpII when one of D and A is a substituent of the ring system, if formed as a ring system.
가능한 공여기에는 공여체 원자 D가 원소 주기율표(멘델리브)의 5, 6 또는 7족, 바람직하게는 5족 또는 6족의 원소이고, 1개 이상의 자유 전자쌍을 갖는 것이며, 5족 원소인 경우에 공여체 원자는 치환체를 지닌 결합 상태로 존재하고, 6족 원소인 경우에 공여체 원자는 상기와 같은 상태일 수 있고, 7족의 공여체 원자는 치환체를 갖지 않는다. 이는 예를 들어 인 P, 산소 O 및 염소 Cl를 공여체 원자의 예로서 설명할 수 있고, 여기서 "치환체"는 상기 언급된 치환체이고, "-Cp"는 시클로펜타디에닐 함유 카바니온에 대한 결합을 나타내고, 화학식 I에서 화살표는 배위 결합을 나타내며, 다른 선들은 존재하는 전자쌍을 의미한다.Possible donor groups include the donor atom D which is an element of group 5, 6 or 7, preferably of group 5 or 6 of the Periodic Table of the Elements (Mendelib), having one or more free electron pairs and a group 5 element The atoms are in a bonded state with substituents, and in the case of a Group 6 element, the donor atoms can be in this state, and the Group 7 donor atoms have no substituents. This may, for example, describe phosphorus P, oxygen O and chlorine Cl as examples of donor atoms, where "substituent" is the aforementioned substituent and "-Cp" is a bond to the cyclopentadienyl containing carbanion. In the formula (I), the arrow represents a coordination bond and the other lines represent electron pairs present.
적절한 수용체에는 특히 수용체 원자 A가 주기율표(멘델리브)의 3족의 원소, 예를 들어 붕소, 알루미늄, 갈륨, 인듐 및 탈륨이고, 치환체와 함께 결합 상태에 있고 전자가 부족한 것이다.Suitable receptors are, in particular, the acceptor atom A being an element of group 3 of the periodic table (mendelib), for example boron, aluminum, gallium, indium and thallium, in combination with substituents and lacking electrons.
D 및 A는 배위 결합에 의해 결합되고, 여기서 D는 (부분적)인 양전하를 띠고, A는 (부분적)인 음전하를 띤다.D and A are joined by coordination bonds, where D has a (partial) positive charge and A has a (partial) negative charge.
따라서, 공여체 원자 D와 공여기가 또는 수용체 원자 A와 수용기가 구별된다. 배위 결합 D → A는 공여체 원자 D와 수용체 원자 A간에 형성된다. 공여기는 공여체 원자 D가 일정한, 존재하는 임의의 치환체 및 존재하는 전자쌍으로 구성된 유닛이고, 이에 따라, 수용체는 수용체 원자 A, 임의의 치환체 및 전자쌍이 부족하게 구성된 유닛이다.Thus, donor atom D and donor group or acceptor atom A and receptor are distinguished. Coordination bonds D → A are formed between donor atom D and acceptor atom A. A donor is a unit consisting of any substituents present and electron pairs present, with a constant donor atom D, whereby the acceptor is a unit lacking receptor atom A, any substituents and electron pairs.
공여체 원자 또는 수용체 원자와 시클로펜타디에닐 함유 카바니온간의 결합은 D-스페이서-Cp 또는 A-스페이서-Cp에서의 스페이서기에 의해 방해될 수 있다. 상기 3번째 화학식의 예에서, =C(R)-은 O와 Cp 간의 스페이서이다. 스페이서기의 예로는 디메틸실릴, 디에틸실릴, 디-n-프로필실릴, 디이소프로필실릴, 디-n-부틸실릴, 디-t-부틸실릴, 디-n-헥실실릴, 메틸페닐실릴, 에틸메틸실릴, 디페닐실릴, 디(p-t-부틸페닐실릴), n-헥실메틸실릴, 시클로펜타메틸렌실릴, 시클로테트라메틸실릴, 시클로트리메틸렌실릴, 디메틸게르마닐, 디에틸게르마닐, 페닐아미노, t-부틸아미노, 메틸아미노, t-부틸포스피노, 에틸포스피노, 페닐포스피노, 메틸렌, 디메틸메틸렌(i-프로필리덴), 디에틸메틸렌, 에틸렌, 디메틸에틸렌, 디에틸에틸렌, 디프로필에틸렌, 프로필렌, 디메틸프로필렌, 디에틸프로필렌, 1,1-디메틸-3,3-디메틸프로필렌, 테트라메틸디실록산, 1,1,4,4-테트라메틸실릴에틸렌, 디페닐메틸렌이 있다.The bond between the donor atom or the acceptor atom and the cyclopentadienyl containing carbanion may be interrupted by a spacer group at D-Spacer-Cp or A-Spacer-Cp. In the example of the third formula, = C (R)-is a spacer between O and Cp. Examples of the spacer group include dimethylsilyl, diethylsilyl, di-n-propylsilyl, diisopropylsilyl, di-n-butylsilyl, di-t-butylsilyl, di-n-hexylsilyl, methylphenylsilyl, ethylmethyl Silyl, diphenylsilyl, di (pt-butylphenylsilyl), n-hexylmethylsilyl, cyclopentamethylenesilyl, cyclotetramethylsilyl, cyclotrimethylenesilyl, dimethylgermanyl, diethylgermanyl, phenylamino, t- Butylamino, methylamino, t-butylphosphino, ethylphosphino, phenylphosphino, methylene, dimethylmethylene (i-propylidene), diethylmethylene, ethylene, dimethylethylene, diethylethylene, dipropylethylene, propylene, Dimethylpropylene, diethylpropylene, 1,1-dimethyl-3,3-dimethylpropylene, tetramethyldisiloxane, 1,1,4,4-tetramethylsilylethylene, diphenylmethylene.
바람직하게는, D 및 A는 스페이서없이 시클로펜타디에닐 함유 카바니온에 결합된다.Preferably, D and A are bonded to the cyclopentadienyl containing carbanion without a spacer.
D 및 A는 서로 독립적으로 시클로펜타디엔(디에닐) 고리 또는 융합된 벤젠 고리 또는 CpI 및 CpII의 다른 치환체 상에, 또는 πI 및 πII의 다른 치환체 상에 각각 위치할 수 있다. D 또는 A가 다수인 경우에, 이들은 상기 언급된 것 중에서 다양한 위치를 차지할 수 있다.D and A, independently of one another, may be located on the cyclopentadiene (dienyl) ring or on the fused benzene ring or other substituents of CpI and CpII, or on other substituents of πI and πII, respectively. If D or A are plural, they may occupy various positions among those mentioned above.
공여체 원자 N, P, As, Sb, Bi, O, S, Se 및 Te 상의 치환체 또는 수용체 원자 B, Al, Ga, In 또는 Tl 상의 치환체는, 예를 들어 C1-C12-(시클로)알킬, 예를 들어 메틸, 에틸, 프로필, i-프로필, 시클로프로필, 부틸, i-부틸, tert-부틸, 시클로부틸, 페닐, 네오펜틸, 시클로펜틸, 헥실, 시클로헥실, 그리고 이성질체로서 헵틸, 옥틸, 노닐, 데실, 운데실, 및 도데실; 이에 상응하는 C1-C12-알콕시기; 비닐, 부테닐, 및 알릴; C6-C12-아릴, 예를 들어 페닐, 나프틸 또는 비페닐릴, 및 벤질 (이들은 각각 할로겐, 1 또는 2개의 C1-C4-알킬기, C1-C4-알콕시기, 니트로 또는 할로게노알킬기, C1-C6-알킬-카르복실, C1-C6-알킬-카르보닐 또는 시아노 (예: 퍼플루오로페닐, m,m'-비스(트리플루오로메틸)-페닐, 및 당업자에게 친숙한 동족 치환체)로 치환될 수 있음); 아릴옥시기 동족체; 인데닐; 할로겐, 예를 들어, F, Cl, Br 및 I, 1-티에닐, 2치환된 아미노, 예를 들어 (C1-C12-알킬)2아미노, 및 디페닐아미노, 트리스-(C1-C12-알킬)-실릴, NaSO3-아릴, 예를 들어 NaSO3-페닐 및 NaSO3-톨릴, 및 C6H5-C≡C; 지방족 및 방향족 C1-C20-실릴 (여기서, 알킬 치환체는 상기 언급된 것 외에, 옥틸, 데실, 도데실, 스테아릴 또는 에이코실일 수 있고, 아릴 치환체는 페닐, 톨릴, 크실릴, 나프틸 또는 비페닐일 수 있고, 치환된 실릴기는 -CH2-를 통해 공여체 원자 또는 수용체 원자에 결합됨), 예를 들어 (CH3)3SiCH2-, 및 상기의 아릴기를 갖는 (C1-C12-알킬)(페닐)-아미노, (C1-C12-알킬페닐)2아미노, C6-C12-아릴옥시, C1-C8-퍼플루오로알킬, 및 퍼플루오로페닐이 있다. 바람직한 치환체에는 C1-C6-알킬, C5-C6-시클로알킬, 페닐, 톨릴, C1-C6-알콕시, C6-C12-아릴옥시, 비닐, 알릴, 벤질, 퍼플루오로페닐, F, Cl, Br, 디-(C1-C6-알킬)-아미노, 디페닐아미노가 있다.Substituents on the donor atoms N, P, As, Sb, Bi, O, S, Se and Te or substituents on the acceptor atoms B, Al, Ga, In or Tl are for example C 1 -C 12- (cyclo) alkyl For example methyl, ethyl, propyl, i-propyl, cyclopropyl, butyl, i-butyl, tert-butyl, cyclobutyl, phenyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, and isomers as heptyl, octyl, Nonyl, decyl, undecyl, and dodecyl; Corresponding C 1 -C 12 -alkoxy groups; Vinyl, butenyl, and allyl; C 6 -C 12 -aryl, for example phenyl, naphthyl or biphenylyl, and benzyl (they are each halogen, 1 or 2 C 1 -C 4 -alkyl groups, C 1 -C 4 -alkoxy groups, nitro or Halogenoalkyl group, C 1 -C 6 -alkyl-carboxyl, C 1 -C 6 -alkyl-carbonyl or cyano (eg perfluorophenyl, m, m'-bis (trifluoromethyl) -phenyl , And cognate substituents familiar to those skilled in the art); Aryloxy group homologs; Indenyl; Halogen, for example F, Cl, Br and I, 1-thienyl, disubstituted amino, for example (C 1 -C 12 -alkyl) 2 amino, and diphenylamino, tris- (C 1- C 12 -alkyl) -silyl, NaSO 3 -aryl, such as NaSO 3 -phenyl and NaSO 3 -tolyl, and C 6 H 5 -C≡C; Aliphatic and aromatic C 1 -C 20 -silyl, wherein the alkyl substituents may be octyl, decyl, dodecyl, stearyl or eicosyl, in addition to those mentioned above, and the aryl substituents may be phenyl, tolyl, xylyl, naphthyl or And a substituted silyl group bonded to a donor atom or a receptor atom via -CH 2- , for example (CH 3 ) 3 SiCH 2- , and (C 1 -C 12 having an aryl group above -Alkyl) (phenyl) -amino, (C 1 -C 12 -alkylphenyl) 2 amino, C 6 -C 12 -aryloxy, C 1 -C 8 -perfluoroalkyl, and perfluorophenyl. Preferred substituents include C 1 -C 6 -alkyl, C 5 -C 6 -cycloalkyl, phenyl, tolyl, C 1 -C 6 -alkoxy, C 6 -C 12 -aryloxy, vinyl, allyl, benzyl, perfluoro Phenyl, F, Cl, Br, di- (C 1 -C 6 -alkyl) -amino, diphenylamino.
공여기는 자유 전자쌍이 N, P, As, Sb, Bi, O, S, Se, Te, F, Cl, Br, 및 I 상에 편재되어 있는 것이고, 이들 중 N, P, O, 및 S가 바람직하다. 거론될 수 있는 공여기의 예로는 (CH3)2N-, (C2H5)2N-, (C3H7)2N-, (C4H9)2N-, (C6H5)2N-, (CH3)2P, (C2H5)2P-, (C3H7)2P-, (i-C3H7)2P-, (C4H9)2P-, (t-C4H9)2P-, (시클로헥실)2P-, (C6H5)2P-, CH3O-, CH3S-, C6H5S-, C(C6H5)=O, -C(CH3)=O, -OSi(CH3)3및 -OSi(CH3)2-t-부틸을 들 수 있고, 여기서 N 및 P는 각각 1개의 자유 전자쌍을 지니고, O 및 S는 각각 2개의 자유 전자쌍을 지니고, 여기서 거론된 마지막 두 개의 예에서, 이중 결합된 산소는 스페이서기를 통해 결합되고, 고리원이 N이 아닌 피롤리돈 고리와 같은 계도 스페이서로 작용한다.The donor groups are free electron pairs which are localized on N, P, As, Sb, Bi, O, S, Se, Te, F, Cl, Br, and I, of which N, P, O, and S are preferred. Do. Examples of donor groups that may be mentioned include (CH 3 ) 2 N-, (C 2 H 5 ) 2 N-, (C 3 H 7 ) 2 N-, (C 4 H 9 ) 2 N-, (C 6 H 5 ) 2 N-, (CH 3 ) 2 P, (C 2 H 5 ) 2 P-, (C 3 H 7 ) 2 P-, (iC 3 H 7 ) 2 P-, (C 4 H 9 ) 2 P-, (tC 4 H 9 ) 2 P-, (cyclohexyl) 2 P-, (C 6 H 5 ) 2 P-, CH 3 O-, CH 3 S-, C 6 H 5 S-, C (C 6 H 5 ) = O, -C (CH 3 ) = O, -OSi (CH 3 ) 3 and -OSi (CH 3 ) 2 -t-butyl, where N and P are each one Having free electron pairs, O and S each having two free electron pairs, and in the last two examples discussed here, the double bonded oxygen is bound via a spacer group and the system is the same as a pyrrolidone ring whose ring member is not N It acts as a spacer.
수용기는 B, Al, Ga, In 또는 Tl 상에서 전자쌍이 부족한 것이고, 예를 들어 (CH3)2B-, (C2H5)2B-, H2B-, (C6H5)2B-, (CH3)(C6H5)2B-, (비닐)2B-, (벤질)2B-, Cl2B-, (CH3O)2B-, Cl2Al-, (CH3)2Al-, (i-C4H9)2Al-, (Cl)(C2H5)Al-, (CH3)2Ga-, (C3H7)2Ga-, ((CH3)3Si-CH2)2Ga-, (비닐)2Ga-, (C6H5)2Ga-, (CH3)2In-, ((CH3)3Si-CH2)2In, (시클로펜타디에닐)2In을 들 수 있다.Receptors are deficient in electron pairs on B, Al, Ga, In or Tl, for example (CH 3 ) 2 B-, (C 2 H 5 ) 2 B-, H 2 B-, (C 6 H 5 ) 2 B-, (CH 3 ) (C 6 H 5 ) 2 B-, (vinyl) 2 B-, (benzyl) 2 B-, Cl 2 B-, (CH 3 O) 2 B-, Cl 2 Al-, (CH 3 ) 2 Al-, (iC 4 H 9 ) 2 Al-, (Cl) (C 2 H 5 ) Al-, (CH 3 ) 2 Ga-, (C 3 H 7 ) 2 Ga-, (( CH 3 ) 3 Si-CH 2 ) 2 Ga-, (vinyl) 2 Ga-, (C 6 H 5 ) 2 Ga-, (CH 3 ) 2 In-, ((CH 3 ) 3 Si-CH 2 ) 2 In, (cyclopentadienyl) 2 In is mentioned.
키랄 중심을 함유하거나 또는 2개의 치환체가 D 또는 A원자와 함께 고리를 형성하는 공여기 및 수용기도 또한 가능하다. 이들의 예로는이 있다.Donor and acceptor groups which contain chiral centers or in which two substituents together with the D or A atoms form a ring are also possible. Examples of these are There is this.
CpI와 CpII간의 바람직한 공여체-수용체 브릿지는 예를 들어, 다음과 같다.Preferred donor-receptor bridges between CpI and CpII are as follows, for example.
1 또는 2개의 π계 πI 및(또는) πII는 상기 고리계 (a) 내지 (r)의 형태에서 헤테로시클릭 고리로 존재할 수 있다. 여기서, D는 바람직하게는 원소 주기율표(멘델리브)의 5족 또는 6족 원소이다. 여기서, 보론이 바람직하다. 상기 헤테로-π계, 특히 헤테로시클릭 화합물의 특정 예는 다음과 같다. One or two π-based πI and / or πII may be present as a heterocyclic ring in the form of the ring systems (a) to (r). Here, D is preferably a Group 5 or 6 element of the Periodic Table of the Elements (Mendelib). Here, boron is preferable. Specific examples of such hetero-π-based, in particular heterocyclic, compounds are as follows.
(여기서, R 및 R'는 H, 알킬, 아릴 또는 아랄킬, 예를 들어 메틸, 에틸, t-부틸, 페닐 또는 o,o'-디-(i-프로필)-페닐임)Wherein R and R 'are H, alkyl, aryl or aralkyl such as methyl, ethyl, t-butyl, phenyl or o, o'-di- (i-propyl) -phenyl
헤테로시클릭 라디칼의 예로는 피롤릴, 메틸피롤릴, 디메틸피롤릴, 트리메틸피롤릴, 테트라메틸피롤릴, t-부틸피롤릴, 디-t-부틸피롤릴, 인돌릴, 메틸인돌릴, 디메틸인돌릴, t-부틸인돌릴, 디-t-부틸인돌릴, 테트라메틸포스폴릴, 테트라페닐포스폴릴, 트리페닐포스폴릴, 트리메틸포스폴릴, 포스파인데닐, 디벤조포스폴릴(포스파플루오레닐) 및 디벤조피롤릴이 있다.Examples of heterocyclic radicals are pyrrolyl, methylpyrrolyl, dimethylpyrrolyl, trimethylpyrrolyl, tetramethylpyrrolyl, t-butylpyrrolyl, di-t-butylpyrrolyl, indolyl, methylindolyl, dimethyl Doryl, t-butylindolyl, di-t-butylindolyl, tetramethylphosphoryl, tetraphenylphosphoryl, triphenylphosphoryl, trimethylphosphoryl, phosphininyl, dibenzophosphoryl (phosphafluorenyl ) And dibenzopyrrolyl.
πI 및(또는) πII간의 바람직한 공여체-수용체 브릿지는 예를 들어, N→B, N→Al, P→B, P→Al, O→B, O→Al, Cl→B, Cl→Al, C=O→B 및 C=O→Al이 있고, 이 공여체-수용체 브릿지의 2 원자 모두는 헤테로-π계의 일부일 수 있거나, 또는 하나의 원자(공여체 또는 수용체)는 π계의 일부이고 다른 하나는 제2 π계의 치환체이거나, 또는 2원자 모두는 특정 고리의 치환체이고, 고리 중 하나는 추가로 헤테로 원자를 함유한다.Preferred donor-receptor bridges between π I and / or π II are, for example, N → B, N → Al, P → B, P → Al, O → B, O → Al, Cl → B, Cl → Al, C ═O → B and C═O → Al, both of the donor-receptor bridges may be part of the hetero-π system, or one atom (donor or acceptor) is part of the π system and the other Or a second atom is a substituent of a particular ring, and one of the rings further contains a hetero atom.
상기한 바에 따라, 2개의 리간드계 πI 및 πII는 1개, 2개 또는 3개의 공여체-수용체 브릿지에 의해 연결될 수 있다. 이는 본 발명에 따라 화학식 Ia가 상기된 D→A 브릿지를 함유하나, 리간드계 πI 및 πII는 치환체로서 추가의 D 및 A, 또는 헤테로-π 중심을 지닐 수 있기 때문에, 생성되는 추가의 D→A 브릿지의 수는 0, 1 또는 2개이다. πI 및 πII 상에서 D 및 A 치환체의 수는 각각 동일하거나 또는 상이할 수 있다. 2개의 리간드계 πI 및 πII는 추가로 공유적으로 브릿지될 수 있다 (공유적 브릿지의 예는 상기 스페이서기에서 기재되어 있다). 그러나, πI 및 πII가 오직 공여체-수용체 브릿지를 통해서만 결합되어 있는, 공유적 브릿지가 없는 화합물이 바람직하다.As noted above, the two ligand systems πI and πII can be linked by one, two or three donor-receptor bridges. It is according to the invention that the formula Ia contains a D → A bridge as described above, but the additional D → A that is produced since the ligand systems πI and πII may have additional D and A, or hetero-π centers as substituents. The number of bridges is zero, one or two. The number of D and A substituents on πI and πII may be the same or different, respectively. The two ligand systems pi and pi can be further covalently bridged (an example of a covalent bridge is described in the spacer group above). However, preference is given to compounds without a covalent bridge, in which [pi] I and [pi] II are bound only via a donor-receptor bridge.
M은 란탄족 및 악티늄족을 비롯하여, 원소 주기율표(멘델리브)의 3, 4, 5 또는 6 아족으로부터의 전이 금속이고, 그 예로서는 Sc, Y, La, Sm, Nd, Lu, Ti, Zr, Hf, Th, V, Nb, Ta, 및 Cr를 들 수 있다. Ti, Zr, 및 Hf가 바람직하다.M is a transition metal from the 3, 4, 5 or 6 subgroups of the Periodic Table of the Elements (Mendellib), including the Lanthanides and Actiniums, examples being Sc, Y, La, Sm, Nd, Lu, Ti, Zr, Hf , Th, V, Nb, Ta, and Cr. Ti, Zr, and Hf are preferred.
메탈로센 구조 또는 π 착물 구조를 형성하는데 있어서, 각 경우에 있어서 전이 금속 M의 양 전하는 각 경우에 시클로펜타디에닐 함유 카바니온에 의해 보상된다. 중심 원자 M에 아직 남아 있는 양 전하는 통상적으로 1가의 음이온 X, 서로 연결될 수 있는 2개의 동일하거나 또는 상이한 음이온 (디아니온), 예를 들어, 동일하거나 또는 상이한 선형 또는 분지형, 포화 또는 불포화 탄화수소, 아민, 포스핀, 티오알코올, 알코올 또는 페놀로부터의 1가 또는 2가의 음성 라디칼에 의해 상쇄된다. 단순 음이온, 예를 들어, CR3 -, NR2 -, PR2 -, OR-, SR-등은 포화 또는 불포화 탄화수소 또는 실란 브릿지에 의해 연결될 수 있고, 디아니온이 형성되며, 브릿지 원자의 수는 0, 1, 2, 3, 4, 5 또는 6이 될 수 있고, 0 내지 4개의 브릿지 원자가 바람직하고, 1개 또는 2개의 브릿지 원자가 특히 바람직하다. 또한, 브릿지 원자는 H 원자 외에 추가로 탄화수소 치환체 R을 지닐 수 있다. 단순 음이온 간의 브릿지의 예로는 예를 들어, -CH2-, -CH2-CH2-, -(CH2)3-, CH=CH, -(CH=CH)2-, -CH=CH-CH2-, CH2-CH=CH-CH2-, -Si(CH3)2- 및 C(CH3)2-가 있다. X의 예로는 히드로라이드, 클로라이드, 메틸, 에틸, 페닐, 플루오라이드, 브로마이드, 요오다이드, n-프로필 라디칼, i-프로필 라디칼, n-부틸 라디칼, 아밀 라디칼, i-아밀 라디칼, 헥실 라디칼, i-부틸 라디칼, 헵틸 라디칼, 옥틸 라디칼, 노닐 라디칼, 데실 라디칼, 세틸 라디칼, 메톡시, 에톡시, 프로폭시, 부톡시, 페녹시, 디메틸아미노, 디에틸아미노, 메틸에틸아민, 디-t-부틸아미노, 디페닐아미노, 디페닐포스피노, 디시클로헥실포스피노, 디메틸포스피노, 메틸리덴, 에틸리덴, 프로필리덴, 및 에틸렌 글리콜 디아니온이 있다. 디아니온의 예로는 1,4-디페닐-1,3-부타디엔디일, 3-메틸-1,3-펜타디엔디일, 1,4-디벤질-1,3-부타디엔디일, 2,4-헥사디엔디일, 1,3-펜타디엔디일, 1,4-디톨릴-1,3-부타디엔디일, 1,4-비스(트리메틸실릴)-1,3-부타디엔디일 및 1,3-부타디엔디일이 있다. 1,4-디페닐-1,3,-부타디엔디일, 1,3-펜타디엔디일, 1,4-디벤질-1,3-부타디엔디일, 2,4-헥사디엔디일, 3-메틸-1,3-펜타디엔디일, 1,4-디톨릴-1,3-부타디엔디일 및 1,4-비스(트리메틸실릴)-1,3-부타디엔디일이 특히 바람직하다. 디아니온의 추가의 예로는 헤테로 원자, 예를 들어가 있고, 여기서 브릿지는 상기 정의된 의미를 갖는다. 상기된 유형의 약하거나 비배위된 음이온은 전하 보상에 특히 바람직하다.In forming the metallocene structure or the π complex structure, in each case the positive charge of the transition metal M is compensated by the cyclopentadienyl containing carbanion in each case. The positive charge still remaining at the central atom M is typically a monovalent anion X, two identical or different anions that may be linked to each other (dianions). ), For example, offset by monovalent or divalent negative radicals from the same or different linear or branched, saturated or unsaturated hydrocarbons, amines, phosphines, thioalcohols, alcohols or phenols. Simple anions, e.g., CR 3 -, NR 2 - , PR 2 -, OR -, SR - , etc. can be connected by a saturated or unsaturated hydrocarbon or silane bridges, the dia trunnion is formed, the number of the bridge atoms are It may be 0, 1, 2, 3, 4, 5 or 6, with 0 to 4 bridge atoms being preferred, with 1 or 2 bridge atoms being particularly preferred. In addition, the bridge atom may further have a hydrocarbon substituent R in addition to the H atom. Examples of bridges between simple anions include, for example, -CH 2- , -CH 2 -CH 2 -,-(CH 2 ) 3- , CH = CH,-(CH = CH) 2- , -CH = CH- CH 2 —, CH 2 —CH═CH—CH 2 —, —Si (CH 3 ) 2 — and C (CH 3 ) 2 —. Examples of X include hydrolide, chloride, methyl, ethyl, phenyl, fluoride, bromide, iodide, n-propyl radical, i-propyl radical, n-butyl radical, amyl radical, i-amyl radical, hexyl radical, i-butyl radical, heptyl radical, octyl radical, nonyl radical, decyl radical, cetyl radical, methoxy, ethoxy, propoxy, butoxy, phenoxy, dimethylamino, diethylamino, methylethylamine, di-t- Butylamino, diphenylamino, diphenylphosphino, dicyclohexylphosphino, dimethylphosphino, methylidene, ethylidene, propylidene, and ethylene glycol dianione. Examples of dianions include 1,4-diphenyl-1,3-butadiendiyl, 3-methyl-1,3-pentadiendiyl, 1,4-dibenzyl-1,3-butadiendiyl, 2,4-hexa Dienediyl, 1,3-pentadienediyl, 1,4-ditolyl-1,3-butadienediyl, 1,4-bis (trimethylsilyl) -1,3-butadienediyl and 1,3-butadienediyl . 1,4-diphenyl-1,3, -butadienediyl, 1,3-pentadienediyl, 1,4-dibenzyl-1,3-butadienediyl, 2,4-hexadienediyl, 3-methyl-1 Particular preference is given to, 3-pentadiendiyl, 1,4-ditolyl-1,3-butadienediyl and 1,4-bis (trimethylsilyl) -1,3-butadienediyl. Further examples of dianions include heteroatoms, for example Where the bridge has the meaning defined above. Weak or uncoordinated anions of the type described above are particularly preferred for charge compensation.
상기와 같은 부피가 큰 음이온에 의한 활성화물은 예를 들어, D/A-π 착화합물, 특히 D/A 메탈로센을 트리스-(펜타플루오로페닐)-보란, 트리페닐보란, 트리페닐알루미늄, 트리틸 테트라키스-(펜타플루오로페닐)-보레이트 또는 N,N-디알킬페닐암모늄 테트라키스-(펜타플루오로페닐)-보레이트 또는 상응하는 보레이트의 포스포늄 또는 술포늄 염, 또는 보레이트, 카르보란, 토실레이트, 트리플레이트, 퍼플루오로카르복실레이트(예: 트리플루오로아세테이트)의 알칼리 금속 또는 알칼리 토 금속, 탈륨 또는 실버 염, 또는 상응하는 산과 반응시킴으로써 활성화된다. 등가의 음이온 X가 알킬, 알릴, 아릴 또는 벤질기를 나타내는 D/A 메탈로센이 바람직하게 사용된다. 또한, 상기 유도체는 D/A 메탈로센을, 알루미늄 알킬, 오르가노리튬 화합물 또는 그리냐드 화합물, 또는 아연-, 주석- 또는 납-알킬과 먼저 반응시키기 전에, 다른 등가의 음이온, 예를 들어 X=F, Cl, Br, OR 등과 반응시켜서 "동일 반응계" 내에서 제조될 수 있다. 상기로부터 얻은 반응 생성물은 단리하지 않고 상기된 보란 또는 보레이트에 의해 활성화될 수 있다.Such bulky anionic activators are for example D / A- [pi] complexes, especially D / A metallocenes, such as tris- (pentafluorophenyl) -borane, triphenylborane, triphenylaluminum, Phosphonium or sulfonium salts of trityl tetrakis- (pentafluorophenyl) -borate or N, N-dialkylphenylammonium tetrakis- (pentafluorophenyl) -borate or the corresponding borate, or borate, carborane Activated by reaction with an alkali metal or alkaline earth metal, thallium or silver salt of tosylate, triflate, perfluorocarboxylate (eg trifluoroacetate), or the corresponding acid. D / A metallocenes where the equivalent anion X represents an alkyl, allyl, aryl or benzyl group are preferably used. The derivative may also contain other equivalent anions such as X before reacting the D / A metallocene with an aluminum alkyl, organolithium compound or Grignard compound, or zinc-, tin- or lead-alkyl first. By reacting with = F, Cl, Br, OR, and the like, in the "same reaction system". The reaction product obtained from above can be activated by the borane or borate described above without isolation.
지수 n은 0, 1, 2, 3 또는 4를 의미하고, 바람직하게는 M의 전하에 따라 0, 1 또는 2이다. 상기된 아족 금속은 실제로 이들이 속해있는 아족에 따라 2 내지 6, 바람직하게는 2 내지 4의 원자가수/전하일 수 있고, 각 경우에 2의 원자가수/전하는 메탈로센 화합물의 카바니온에 의해 보상된다. La3+의 경우에, 지수 n은 따라서 1이고, Zr4+의 경우에 n값은 2이고, Sm2+의 경우에 n값은 0이 된다.The index n means 0, 1, 2, 3 or 4, preferably 0, 1 or 2 depending on the charge of M. The subgroup metals described above may in fact be from 2 to 6, preferably from 2 to 4 valences / charges, depending on the subgroup to which they belong, and in each case the valences / charges of 2 are compensated by the carbanion of the metallocene compound do. In the case of La 3+ , the index n is thus 1, in the case of Zr 4+ the value of n is 2 and in the case of Sm 2+ the value of n is zero.
화학식 I의 메탈로센 화합물을 제조하기 위하여, 비양성자성 용매 중에서 -78℃ 내지 +120℃, 바람직하게는 -40℃ 내지 +70℃의 온도에서, 화학식 II:화학식 III, 또는 화학식 IV:화학식 V, 또는 화학식 VI:화학식 VII, 또는 화학식 VIII:화학식 III, 또는 화학식 IV:화학식 IX, 또는 화학식 X:화학식 VII의 몰비가 1:0.5-2, 바람직하게는 1:0.8-1.2, 특히 바람직하게는 1:1이 되도록, 각 경우에 상기 화학식 II와 화학식 III의 화합물, 또는 각 경우에 화학식 IV와 화학식 V의 화합물, 또는 각 경우에 상기 화학식 VI와 화학식 VII의 화합물, 또는 각 경우에 화학식 VIII과 화학식 III의 화합물, 또는 각 경우에 화학식 IV와 화학식 IX의 화합물, 또는 각 경우에 화학식 X과 화학식 VII의 화합물을 반응시키고, 이때 알칼리 금속-X, 알칼리 토금속-X2, 실릴-X, 게르밀-X, 스탄닐-X 또는 HX 화합물은 제거되거나 또는 이탈된다. 화학식 VIII과 화학식 III, 또는 화학식 IV와 화학식 IX, 또는 화학식 X과 화학식 VII을 반응시키는 경우에, 반응 조건 하에서 화학식 VIII, IX 또는 X이 액체인 경우에 비양성자성 용매를 제거할 수 있다. 제거되거나 또는 이탈될 화합물의 예로는 TiCl, LiCl, LIiBr, LiF, LiI, NaCl, NaBr, KCl, KF, MgCl2, MgBr2, CaCl2, CaF2, 트리메틸클로로실란, 트리에틸클로로실란, 트리-(n-부틸)-클로로실란, 트리페닐클로로실란, 트리메틸클로로게르만, 트리메틸클로로스타난, 디메틸아민, 디에틸아민, 디부틸아민 및 상기 치환 유형으로부터 전문가에 의해 예견될 수 있는 다른 화합물이 있다.In order to prepare the metallocene compound of formula (I), at a temperature of -78 ° C to + 120 ° C, preferably -40 ° C to + 70 ° C in an aprotic solvent, Formula II: Formula III, or Formula IV: Formula The molar ratio of V, or Formula VI: Formula VII, or Formula VIII: Formula III, or Formula IV: Formula IX, or Formula X: Formula VII is 1: 0.5-2, preferably 1: 0.8-1.2, particularly preferably Is 1: 1, in each case a compound of Formula II and Formula III, or in each case a compound of Formula IV and Formula V, or in each case a compound of Formula VI and Formula VII, or in each case And a compound of formula III, or in each case a compound of formula IV and IX, or in each case a compound of formula X and VII, wherein alkali metal-X, alkaline earth metal-X 2 , silyl-X, ger Mill-X, Stanyl-X or HX compounds I or is leaving. In the case of reacting Formula (VIII) with Formula (III), or Formula (IV) with Formula (IX), or Formula (X) with Formula (VII), it is possible to remove the aprotic solvent when the reaction of the formula (VIII, IX or X) is liquid. Examples of compounds to be removed or eliminated include TiCl, LiCl, LIiBr, LiF, LiI, NaCl, NaBr, KCl, KF, MgCl 2 , MgBr 2 , CaCl 2 , CaF 2 , trimethylchlorosilane, triethylchlorosilane, tri- (n-butyl) -chlorosilane, triphenylchlorosilane, trimethylchlorogerman, trimethylchlorostannan, dimethylamine, diethylamine, dibutylamine and other compounds that can be predicted by experts from such substitution types.
따라서, 화학식 II 및 IV의 화합물은 시클로펜타디에닐 골격 또는 헤테로시클릭 골격을 갖는 카바니온으로서, 헤테로시클릭 고리원으로서 공유적으로 결합되거나 또는 혼입되고 D/A 브릿지 형성에 사용된 1 내지 3개의 공여기를 함유하고, 시클로펜타디에닐 골격의 음 전하에 대한 상대 이온으로서 양이온을 함유한다. 화학식 VIII의 화합물은 D/A 브릿지를 형성하는데 사용되는 1 내지 3개의 공여기를 갖는 비하전된 시클릭 골격이나, 이온기 대신에 쉽게 이탈될 수 있는 이탈기 E(R1R2R3), 예를 들어 실릴, 게르밀 또는 스탄닐기 또는 수소를 갖는다.Thus, compounds of formulas (II) and (IV) are carbanions having a cyclopentadienyl skeleton or a heterocyclic skeleton, covalently bonded or incorporated as heterocyclic ring members and used in forming D / A bridges. Donor groups and cations as relative ions to the negative charge of the cyclopentadienyl skeleton. Compounds of formula (VIII) are uncharged cyclic backbones having from 1 to 3 donor groups used to form D / A bridges, or leaving groups E (R 1 R 2 R 3 ) which can be easily released instead of ionic groups , For example, silyl, germanyl or stanyl groups or hydrogen.
본 발명에 따라 사용될 메탈로센 화합물을 형성하는 두 번째 성분 즉, 화학식 III 또는 V의 화합물은 화학식 II 또는 IV의 시클로펜타디에닐 골격과 동일하거나 또는 상이하나, 공여기 대신에 1 내지 3개의 수용기를 갖는 시클로펜타디에닐 골격을 갖는 카바니온이다. 상응하는 방법으로, 화학식 IX의 화합물은 1 내지 3개의 수용기 및 쉽게 이탈될 수 있는 이탈기 F(R1R2R3)를 갖는 비하전된 시클로펜타디엔 골격이다.The second component forming the metallocene compound to be used according to the invention, i.e. the compound of the formula III or V, is the same or different from the cyclopentadienyl skeleton of the formula II or IV but instead of 1 to 3 acceptors Carbanion having a cyclopentadienyl skeleton having In a corresponding manner, the compound of formula IX is an uncharged cyclopentadiene skeleton having 1 to 3 receptors and an easily leaving group F (R 1 R 2 R 3 ).
완전히 유사한 방법으로, 화학식 VI 또는 X의 화합물은 D→A 결합을 지닌 출발 물질로서, 가능한 총 1 내지 3개의 D→A 결합을 지닌 카바니온의 상대 양이온 화합물 또는 비하전된 시클로펜타디엔 구조이고, 화학식 VII의 화합물과의 반응에 의해 화학식 I의 메탈로센 화합물을 생성한다.In a very similar manner, the compound of formula VI or X is a starting material with a D → A bond, which is a counter cationic compound or uncharged cyclopentadiene structure of carbanion with a total of one to three D → A bonds, Reaction with a compound of formula VII produces a metallocene compound of formula I.
제조 방법에서 2개의 출발 물질 즉, 화학식 II와 화학식 III, 또는 화학식 IV와 화학식 V, 또는 화학식 VI와 화학식 VII, 또는 화학식 VIII과 화학식 III, 또는 화학식 IV와 IX, 또는 화학식 X과 VII은 함께 존재할 때, 동시에 공여기-수용기, -D→A-가 형성되거나 또는 금속 양이온 M과 착물을 형성하면서 자발적으로 반응하고, 이때 M'X 또는 E(R1R2R3)X 또는 F(R4R5R6)X 또는 HX가 제거된다. 공여기-수용기의 설명에서, D 및 A 상에서의 치환체는 간략함을 위해 생략하였다.In the preparation process two starting materials, i.e., formula II and formula III, or formula IV and formula V, or formula VI and formula VII, or formula VIII and formula III, or formula IV and IX, or formula X and VII, are present together At the same time, a donor-receptor, -D → A-, is formed or reacts spontaneously, forming a complex with the metal cation M, wherein M'X or E (R 1 R 2 R 3 ) X or F (R 4 R 5 R 6 ) X or HX are removed. In the description of the donor-acceptor, the substituents on D and A have been omitted for the sake of brevity.
M'는 알칼리 금속 또는 알칼리 토 금속, 예를 들어, Li, Na, K, 1/2Mg, 1/2Ca, 1/2Sr, 1/2Ba 또는 탈륨의 등가 양이온이다.M 'is an equivalent cation of an alkali or alkaline earth metal, for example Li, Na, K, 1 / 2Mg, 1 / 2Ca, 1 / 2Sr, 1 / 2Ba or thallium.
화학식 XIIIa+b의 화합물은 상기된 방법과 유사하게 제조된다.Compounds of formula (XIIIa + b) are prepared analogously to the process described above.
제조에 적합한 용매로는 비양성자성, 극성 또는 무극성 용매, 예를 들어 지방족 및 방향족 탄화수소 또는 지방족 및 방향족 할로겐화 탄화수소가 있다. 또한 당업자에게 공지된 다른 비양성자성 용매도 원리적으로는 가능하나, 작업의 용이성으로 인해 비점이 너무 높은 것은 바람직하지 못하다. 대표적인 예로는 n-헥산, 시클로헥산, 펜탄, 헵탄, 석유 에테르, 톨루엔, 벤젠, 클로로벤젠, 메틸렌클로라이드, 디에틸에테르, 테트라히드로푸란 및 에틸렌 글리콜 디메틸에테르가 있다.Suitable solvents for the preparation include aprotic, polar or nonpolar solvents such as aliphatic and aromatic hydrocarbons or aliphatic and aromatic halogenated hydrocarbons. Other aprotic solvents known to those skilled in the art are also possible in principle, but too high a boiling point is not preferred due to ease of operation. Representative examples are n-hexane, cyclohexane, pentane, heptane, petroleum ether, toluene, benzene, chlorobenzene, methylene chloride, diethyl ether, tetrahydrofuran and ethylene glycol dimethyl ether.
화학식 II, III, IV 및 V의 출발 물질은 문헌에 공지된 방법에 의해 또는 이와 유사하게 제조될 수 있다. 따라서, 예를 들어, 시판되고 있는 트리메틸실릴-시클로펜타디엔은 먼저 부틸-리튬과 반응한 후, 트리메틸실릴크롤라이드와 반응하여서 비스(트리메틸실릴)-시클로펜타디엔을 문헌[J. of Organometallic Chem. (1971), 29, 227]과 유사하게 생성한다. 이어서, 이 생성물은 삼염화붕소와 반응하여서 트리메틸실릴-시클로펜타디에닐-디클로로보란을 형성하고(J. of Organometallic Chem. (1971), 169, 327과 유사한 방법으로), 마지막으로 문헌[J. of Organometallic Chem. (1971), 169, 373]과 유사한 방법으로 티타늄테트라클로라이드와 반응하여서 디클로로보릴-시클로펜타디에닐-티타늄 트리클로라이드를 형성할 수 있다. 마지막으로 언급된 화합물은 이미 화학식 III의 화합물의 원형태(prototype)이고, 마지막으로 언급된 화합물은 추가로 트리메틸알루미늄과 선택적으로 반응할 수 있고, 붕소 원자와 결합된 2개의 염소 원자는 메틸기에 의해 대체되어서, 추가의 화학식 III의 화합물임이 입증된다. 시판되고 있는 시클로펜타디에닐탈륨은 문헌 [J. Am. Chem. Soc. (1983) 105, 3882 및 Organometallics(1982) 1, 591]의 방법과 유사하게 클로로디페닐포스핀과 반응하고 추가로 부틸-리튬과 반응할 수 있고, 화학식 II의 화합물의 원형태를 얻게된다. 상기된 바와 같이 인덴을 먼저 부틸-리튬과 반응시킨 후, 클로로디페닐포스핀과 반응시킴으로써 디메틸스탄닐-디페닐포스핀-인덴이 형성되는 것이 추가의 예시로서 언급될 수 있고, 추가의 반응으로 먼저 부틸-리튬과 반응한 후 클로로-부틸주석과 반응하여서 상기된 화합물을 형성한 후, 추가로 지르코늄 테트라클로라이드와 반응하여서 디페닐포스피노-인데닐-지르코늄 트리클로라이드를 대표적인 화학식 IV의 화합물로서 생성한다. 상기의 합성 방법 및 제조 방법은 오르가노금속 및 오르가노 원소 화학 분야에서의 전문가에게 친숙하고, 수많은 참고 문헌에 공개되어 있으나, 소수만이 상기 예시적 방법에 의해 제공되고 있다.Starting materials of the formulas (II), (III), (IV) and (V) can be prepared by methods analogous to or known in the literature. Thus, for example, commercially available trimethylsilyl-cyclopentadiene is first reacted with butyl-lithium followed by trimethylsilyl crolide to produce bis (trimethylsilyl) -cyclopentadiene as described in J. Chem. of Organometallic Chem. (1971), 29, 227]. This product then reacts with boron trichloride to form trimethylsilyl-cyclopentadienyl-dichloroborane (in a similar manner to J. of Organometallic Chem. (1971), 169, 327), and finally J. of Organometallic Chem. (1971), 169, 373 can be reacted with titanium tetrachloride to form dichloroboryl-cyclopentadienyl-titanium trichloride. The last mentioned compound is already a prototype of the compound of formula III, and the last mentioned compound can further react selectively with trimethylaluminum, and two chlorine atoms bonded with boron atoms are Substituted, it proves to be a further compound of formula III. Commercially available cyclopentadienyl thallium is described in J. Chem. Am. Chem. Soc. (1983) 105, 3882 and Organometallics (1982) 1, 591] can be reacted with chlorodiphenylphosphine and further with butyl-lithium to obtain the original form of the compound of formula II. As further described, dimethylstannyl-diphenylphosphine-indene is formed by first reacting indene with butyl-lithium and then with chlorodiphenylphosphine, which may be mentioned as further examples. First reaction with butyl-lithium followed by chloro-butyltin to form the compound described above, followed by further reaction with zirconium tetrachloride to produce diphenylphosphino-indenyl-zirconium trichloride as a representative compound of formula IV. do. Such synthesis and preparation methods are familiar to those skilled in the organometallic and organo elemental chemistry and are published in numerous references, but few are provided by these exemplary methods.
하기에 셜명된 예시들은 본 발명에 따른 상기 헤테로시클릭 전구체 및 촉매를 어떻게 사용하는 지를 보여준다. 피롤릴-리튬(화학식 II)은 예를 들어, 문헌 [J. Amer. Chem. Soc. (1982), 104, 2031]에 기재된 바와 같이 피롤을 부틸-리튬과 반응시킴으로써 제조될 수 있다. 트리메틸스탄닐-포스폴 (화학식 VIII)은 1-페닐포스폴이 리튬과 반응하고, 이어서 알루미늄 트리클로라이드와 반응하여서 포스폴릴-리튬 (화학식 II)를 형성하고, 추가로 트리메틸클로로스타난과 반응하여서 트리메틸스탄닐-포스폴을 형성한다. J. Chem. Soc. Chem. Comm. (1988), 770을 참조한다. 이 화합물은 티타늄 테트라클로라이드와 반응하여서 포스폴릴-티타늄 트리클로라이드(화학식 IV)를 형성할 수 있다.The examples listed below show how to use such heterocyclic precursors and catalysts according to the present invention. Pyrrolyl-lithium (Formula II) is described, for example, in J. Chem. Amer. Chem. Soc. (1982), 104, 2031, can be prepared by reacting pyrrole with butyl-lithium. Trimethylstannyl-phosphol (Formula VIII) is characterized in that 1-phenylphosphol reacts with lithium, followed by aluminum trichloride to form phospholyl-lithium (Formula II), and further with trimethylchlorostannan Trimethylstannyl-phosphole is formed. J. Chem. Soc. Chem. Comm. (1988), 770. This compound can react with titanium tetrachloride to form phospholyl-titanium trichloride (Formula IV).
-60 내지 +250 ℃, 바람직하게는 0 내지 200 ℃에서, 0.5 내지 5000 bar, 바람직하게는 1 내지 3000 bar의 압력하에서 1종 이상의 임의로 치환된 α-올레핀의 기체상, 용액상, 고압상 또는 슬러리상 단독중합 및 공중합 방법에서, 본 발명에 따라서 사용된 메탈로센 화합물이 촉매로서 특히 적당하고, 포화 또는 방향족 탄화수소, 또는 포화 또는 방향족 할로게노-탄화수소의 존재 또는 부재하에서 반응을 수행시키는 것이 가능하다. 이런 중합을 불연속적으로 또는, 바람직하게는 연속적으로 수행시킬 수 있다. 또한, 이들을 세미뱃치법으로 수행시킬 수 있다. 또한, 1종 이상의 반응기 또는 반응 영역에서 이런 방법을 수행시킬 수 있다. 반응 구역이 복수인 경우, 중합을 다른 중합 조건하에서 수행시킬 수 있다. 따라서, 추가의 반응기에서의 실제 (공)중합에 대한 불균일 촉매로 특히 적당한 예비 중합체를 하나의 반응기 내에서 형성할 수 있다. 무기 지지체에서 불균일 D/A 촉매가 이런 예비 중합체의 형성에 특히 적당하다. π 착화합물 또는 메탈로센 화합물의 몰 당 (공)단량체 101내지 1012몰을 반응시킨다. π 착화합물 또는 메탈로센 화합물은 조촉매와 함께 사용할 수 있다. π 착화합물 또는 메탈로센 화합물과 조촉매 간의 양적 비율은 π 착화합물 또는 메탈로센의 몰 당 조촉매 1 내지 100,000 몰이다. 예를 들어, 조촉매는 하기 화학식의 알루미녹산 화합물의 의미로 이해되어야 한다.Gas phase, solution phase, high pressure phase of at least one optionally substituted α-olefin at a pressure of from 0.5 to 5000 bar, preferably from 1 to 3000 bar, at -60 to +250 ° C, preferably 0 to 200 ° C, or In slurry phase homopolymerization and copolymerization processes, the metallocene compounds used according to the invention are particularly suitable as catalysts, and it is possible to carry out the reaction in the presence or absence of saturated or aromatic hydrocarbons, or saturated or aromatic halogeno-hydrocarbons. Do. This polymerization can be carried out discontinuously or preferably continuously. Furthermore, these can be performed by the semibatch method. It is also possible to carry out this method in one or more reactors or reaction zones. If there are a plurality of reaction zones, the polymerization can be carried out under different polymerization conditions. Thus, particularly suitable prepolymers can be formed in one reactor with heterogeneous catalysts for actual (co) polymerization in further reactors. Heterogeneous D / A catalysts on inorganic supports are particularly suitable for the formation of such prepolymers. 1 to 10 to 12 moles of (co) monomer per mole of? complex or metallocene compound are reacted. π complex compound or metallocene compound can be used together with a promoter. The quantitative ratio between the? complex or metallocene compound and the promoter is from 1 to 100,000 moles of promoter per mole of? complex or metallocene. For example, a promoter should be understood in the sense of an aluminoxane compound of the formula:
(상기 식 중,(In the above formula,
R은 C1-C20-알킬, C6-C12-아릴 및 벤질이고,R is C 1 -C 20 -alkyl, C 6 -C 12 -aryl and benzyl,
n은 2 내지 50의 수이고, 바람직하게는 10 내지 35이다)n is a number from 2 to 50, preferably 10 to 35)
다양한 알루미녹산의 혼합물 또는 물과 혼합된 그의 전구체(알루미늄 알킬)의 혼합물을 (기체, 액체, 고체 또는 결합 형태로, 예를 들어 결정수 형태로) 사용할 수 있다. 또한, 물은 단량체 또는 실리카겔과 같은 지지체의 중합 매질의 (잔류) 수분으로 공급될 수 있다.Mixtures of various aluminoxanes or mixtures of their precursors (aluminum alkyls) mixed with water can be used (in gas, liquid, solid or combined form, for example in the form of crystalline water). In addition, water may be supplied to the (residual) moisture of the polymerization medium of the support, such as monomer or silica gel.
화학식 XI의 사각괄호로부터 돌출된 결합은 R기 또는 AlR2기를 올리고머 알루미녹산의 말단기로 함유한다. 상기 알루미녹산은 대체로 쇄 길이가 상이한 것 중 여러개의 혼합물로서 존재한다. 또한 미세 분석은 시클릭 또는 우리 형태와 같은 구조의 알루미녹산을 나타내고 있다. 알루미녹산은 시판되고 있는 화합물이다. R=CH3인 경우에는, 메틸알루미녹산 (MAO)를 칭한다.The bond protruding from the square brackets of formula (XI) contains an R group or an AlR 2 group as an end group of the oligomeric aluminoxane. The aluminoxanes are generally present as a mixture of several of different chain lengths. Microanalysis also shows aluminoxanes of the same structure as cyclic or our form. Aluminoxane is a commercially available compound. In the case of R = CH 3 , methylaluminoxane (MAO) is referred to.
추가로 조촉매는 알루미늄-알킬, 리튬-알킬 또는 오르가노-Mg 화합물(예: 그리냐드 화합물) 또는 (부분적)으로 가수분해된 오르가노붕소 화합물이다. 바람직한 조촉매는 알루미녹산이다.Further promoters are organoboron compounds hydrolyzed to aluminum-alkyl, lithium-alkyl or organo-Mg compounds such as Grignard compounds or (partially). Preferred promoters are aluminoxanes.
조촉매를 사용한 활성화 또는 부피가 큰 비배위 또는 약하게 배위된 음이온의 제조는 오토클레이브 또는 분리된 반응 용기에서 수행될 수 있다. 활성화는 중합될 단량체의 존재 또는 부재 하에 수행될 수 있다. 활성화는 지방족 또는 방향족 또는 할로겐화 용매 또는 현탁화제의 존재 하에 수행될 수 있다.Activation using a promoter or preparation of bulky uncoordinated or weakly coordinated anions can be performed in an autoclave or in a separate reaction vessel. Activation can be carried out in the presence or absence of monomers to be polymerized. Activation can be carried out in the presence of an aliphatic or aromatic or halogenated solvent or suspending agent.
π 착화합물 또는 메탈로센 화합물 및 알루미녹산을 지지체 상에서 균일한 형태 그대로 그리고 불균일한 형태에서 각각 또는 함께 사용할 수 있다. 여기서, 지지체 물질은 특성상 무기물 또는 유기물일 수 있고, 예를 들어 실리카겔, Al2O3, MgCl2, NaCl, 셀룰로오즈 유도체, 녹말 및 폴리에틸렌 또는 폴리프로필렌과 같은 중합체일 수 있다. π 착화합물 또는 메탈로센 화합물을 먼저 가하거나, 또는 먼저 지지체에 알루미녹산을 가한 후, 다른 특정 성분을 가하는 것 모두 가능하다. 그러나, 알루미녹산을 사용하여 균일한 형태 또는 불균일한 형태에서 π 착화합물 또는 메탈로센 화합물을 활성화시키고, 활성화된 메탈로센 화합물을 임의로 알루미녹산이 충전된 지지체에 가하는 것도 동일하게 가능하다.The π complex or metallocene compound and aluminoxane can be used either individually or together in homogeneous form and in heterogeneous form on a support. Here, the support material may be inorganic or organic in nature and may be, for example, silica gel, Al 2 O 3 , MgCl 2 , NaCl, cellulose derivatives, starch and polymers such as polyethylene or polypropylene. It is possible to add the? complex compound or metallocene compound first, or first add aluminoxane to the support, and then add other specific components. However, it is equally possible to use aluminoxanes to activate π complexes or metallocene compounds in a homogeneous or non-uniform form, and to add the activated metallocene compound to the support optionally filled with aluminoxane.
지지체 물질은 수분 함량 또는 OH기 농도를 정의된 값으로 조절하거나 또는 낮은 값으로 유지하기 위하여, 가열 및(또는) 화합물질에 의해 처리하는 것이 바람직하다. 화학적 예비처리는 예를 들어, 지지체를 알루리늄-알킬과 반응시키는 것을 포함한다. 무기 지지체는 사용하기 전에 통상적으로 100℃ 내지 1000℃로 1 내지 100시간 동안 가열한다. 상기 무기 지지체, 특히 실리카(SiO2)의 표면적은 10 내지 1000 m2/g, 바람직하게는 100 내지 800 m2/g이다. 입도는 0.1 내지 500 마이크로미터, 바람직하게는 100 내지 200 마이크로미터이다.The support material is preferably treated by heating and / or compounding to control the moisture content or OH group concentration to a defined value or to keep it at a low value. Chemical pretreatment includes, for example, reacting the support with aluminium-alkyl. The inorganic support is typically heated to 100 ° C. to 1000 ° C. for 1 to 100 hours before use. The surface area of the inorganic support, in particular silica (SiO 2 ), is from 10 to 1000 m 2 / g, preferably from 100 to 800 m 2 / g. The particle size is 0.1 to 500 micrometers, preferably 100 to 200 micrometers.
단독중합 또는 공중합에 의해 반응될 올레핀은 예를 들어, 에틸렌, 프로필렌. 부트-1-엔, 펜트-1-엔, 헥스-1-엔, 옥트-1-엔, 3-메틸-부트-1-엔, 4-메틸-펜트-1-엔, 4-메틸-헥스-1-엔 및 이소옥텐이 있다.The olefins to be reacted by homopolymerization or copolymerization are for example ethylene, propylene. But-1-ene, pent-1-ene, hex-1-ene, oct-1-ene, 3-methyl-but-1-ene, 4-methyl-pent-1-ene, 4-methyl-hex- 1-en and isooctene.
올레핀은 추가로 예를 들어, 페닐, 치환된 페닐, 할로겐, 에스테르화 카르복실기 또는 산 무수물기에 의해 치환될 수 있고, 이러한 유형의 화합물로는 예를 들어, 스티렌, 메틸스티렌, 클로로스티렌, 플루오로스티렌, 인덴, 4-비닐-비페닐, 비닐-플루오렌, 비닐-안트라센, 메틸 메타크릴레이트, 에틸 아크릴레이트, 비닐실란, 트리메틸-알릴실란, 비닐클로라이드, 비닐리덴클로라이드, 테트라플루오로에틸렌, 비닐카르바졸, 비닐피롤리돈, 비닐에테르 및 비닐 에스테르가 있다. 또한, 본 발명에 따라서 고리-개방 중부가 반응, 예를 들어 락톤 (예를 들면, ε-카프로락톤 또는 δ-발레노락톤), 또는 락탐 (예를 들면, ε-카프로락탐)이 또한 가능하다. 바람직한 단량체에는 에틸렌, 프로필렌, 부텐, 헥센, 옥텐, 메틸메타크릴레이트 및 아세틸렌이 있다.The olefin may further be substituted by, for example, phenyl, substituted phenyl, halogen, esterified carboxyl groups or acid anhydride groups, and compounds of this type are, for example, styrene, methylstyrene, chlorostyrene, fluorostyrene , Indene, 4-vinyl-biphenyl, vinyl-fluorene, vinyl-anthracene, methyl methacrylate, ethyl acrylate, vinylsilane, trimethyl-allylsilane, vinyl chloride, vinylidene chloride, tetrafluoroethylene, vinylcar Basezol, vinylpyrrolidone, vinylether and vinyl esters. Also possible according to the invention are ring-opening polyaddition reactions, for example lactones (eg ε-caprolactone or δ-valenolactone), or lactams (eg ε-caprolactam) . Preferred monomers are ethylene, propylene, butene, hexene, octene, methylmethacrylate and acetylene.
본 발명에 따라서 π 착화합물 또는 메탈로센 화합물을 사용하는 단독중합 또는 공중합, 또는 중부가 반응이 단열 또는 등온으로 수행된다. 오토클레이브 또는 튜브 반응기에서의 고압법, 용액법 및 또한 벌크 중합, 교반 반응기 또는 루프 반응기에서의 슬러리상법, 및 기체상법이 있고, 슬러리, 용액 및 기체상의 압력은 65 bar를 넘지 않는다. 모든 이런 방법들이 오랫 동안 알려져 왔고, 전문가들에게는 익숙하다. 본 발명에 따른 π 착화합물 또는 메탈로센 화합물의 잇점으로는, 치환기의 선택에 의해 이들이 임의로 지지체에 사용된 용해성 π 착화합물 또는 메탈로센 화합물, 및 불용성 π 착화합물 또는 메탈로센 화합물로 모두 제조될 수 있다는 것이다. 용해성 π 착화합물 및 메탈로센 화합물은 고압법 및 용액법을 사용하고, 불균일 메탈로센 화합물은 슬러리상 및 기체상을 사용한다.According to the present invention, homopolymerization or copolymerization using a π complex or metallocene compound, or polyaddition reaction is carried out adiabatic or isothermal. High pressure method in autoclave or tube reactor, solution method and also bulk polymerization, slurry phase method in stirred reactor or loop reactor, and gas phase method, and the slurry, solution and gas phase pressures do not exceed 65 bar. All these methods have been known for a long time and are familiar to professionals. As an advantage of the π complex or metallocene compound according to the present invention, by the choice of substituents, both of them can be prepared from the soluble π complex or metallocene compound optionally used for the support, and the insoluble π complex or metallocene compound. Is there. The soluble π complex and the metallocene compound use the high pressure method and the solution method, and the heterogeneous metallocene compound uses the slurry phase and the gas phase.
본 발명에 따라서 제조될 수 있는 (공)중합체는 고결정도 및 최적 용융 범위를 갖는 특징을 갖는다. 폴리에틸렌의 경우에는 낮은 분지 정도에 의해, 3개 이상의 C 원자를 갖는 올레핀의 중합체의 경우에는 높은 입체규칙성 (이소택틱 (isotactic) 또는 신디오택틱 (syndiotactic))에 의해 이것이 달성된다. 공중합체는 공단량체의 혼입에서 고규칙성의 특징을 갖는다. 이런 중합체의 예로는 고밀도 선형 폴리에틸렌 (HDPE), 이소택틱 폴리프로필렌 (iPP), 신디오택틱 폴리프로필렌 (sPP), i- 또는 s-폴리부텐 또는 -폴리헥센, 폴리옥텐, 선형 저밀도 공중합체, 예를 들면, C3-C8-α-올레핀 (선형 저밀도 폴리에틸렌 LLDPE)를 갖는 에틸렌, 말하자면 에틸렌/프로필렌, 에틸렌/부틸렌, 에틸렌/헥센 및 에틸렌/옥텐, 및 또한 예를 들면, 프로필렌/부틸렌, 프로필렌/헥센 및 다른 것들이 있다. 공단량체로 부틸렌, 헥센 또는 옥텐을 갖는 HDPE, LLDPE, iPP 및 sPP가 바람직하다.The (co) polymers that can be prepared according to the invention have the characteristics of high crystallinity and optimum melting range. This is achieved by low degree of branching in the case of polyethylene and high stereoregularity (isotactic or syndiotactic) in the case of polymers of olefins having three or more C atoms. Copolymers are characterized by high regularity in the incorporation of comonomers. Examples of such polymers are high density linear polyethylene (HDPE), isotactic polypropylene (iPP), syndiotactic polypropylene (sPP), i- or s-polybutene or -polyhexene, polyoctene, linear low density copolymers, eg Ethylene with C 3 -C 8 -α-olefins (linear low density polyethylene LLDPE), ie ethylene / propylene, ethylene / butylene, ethylene / hexene and ethylene / octene, and also for example propylene / butylene , Propylene / hexene and others. Preferred are comonomers HDPE, LLDPE, iPP and sPP with butylene, hexene or octene.
본 발명에 따라서 사용될 수 있는 π 착화합물, 특히 메탈로센 화합물은 공여체-수용체 브릿지로 인한 부리 모양의 두 개의 시클로펜타디에닐 골격의 한정된 개열을 허용하여 고활성 이외에도 조절된 선택도, 조절된 분자량 분포 및 (공)단량체의 균일한 혼입을 보장한다. 한정된 부리 모양의 개열로 인해, 부피가 큰 (공)단량체에 대한 공간도 있다. 또한, 분자량 분포에서의 고균일성은 삽입 (1자리 촉매)에 의해 일어나는 중합의 균일하고, 한정된 자리를 만든다.Π complexes, in particular metallocene compounds, which can be used according to the invention, allow limited cleavage of two beta-shaped cyclopentadienyl backbones due to donor-receptor bridges, thereby allowing controlled selectivity, controlled molecular weight distribution in addition to high activity And uniform incorporation of the (co) monomer. Due to the limited beak-shaped cleavage, there is also room for bulky (co) monomers. In addition, the high uniformity in the molecular weight distribution creates a uniform, defined site of polymerization that is caused by intercalation (single catalyst).
물질의 특정 특성 프로파일을 얻기 위해 다수의 D/A 촉매를 동시에 사용하는 조절된 방법으로 분자량 분포를 개질 (확장)할 수 있다. 따라서, D/A 브릿지를 전혀 갖지 않는 다른 메탈로센과 조합하여 1종 이상의 D/A 촉매를 사용하는 것도 가능하다.The molecular weight distribution can be modified (expanded) in a controlled manner using multiple D / A catalysts simultaneously to obtain a specific property profile of the material. Therefore, it is also possible to use one or more D / A catalysts in combination with other metallocenes having no D / A bridge at all.
D/A 구조는 고온에 이르기까지 촉매의 과잉-안정화에 영향을 줄 수 있어서, 촉매를 고온 범위에서도 사용할 수 있다. 공여체-수용체 결합의 가능한 열 분해는 가역적이고, 이런 자가-조직법 및 자가-복구 메카니즘의 결과로 특히 고성능 촉매 성질을 준다. 본 발명에 따른 D/A 메탈로센 구조는, 예를 들어, 통상의 촉매로 달성할 수 없는 무결함 폴리에틸렌을 어느 정도 형성하게 한다. 따라서, 에텐 중합체는 예외적으로 고융점, 예를 들면 135 ℃ 초과 내지 160 ℃ (DSC 곡선의 최대값)를 가질 수 있다. 중합법에서 직접 얻어지는 선형 폴리에틸렌은 140 내지 160 ℃ (DSC 곡선의 최대값), 바람직하게는 142 내지 160 ℃, 특히 바람직하게는 144 내지 160 ℃, 특히 바람직하게는 146 내지 160 ℃의 융점을 갖는 화합물을 포함하는 것이 바람직하다. 이는 특히 청구된 메탈로센 화합물로 제조될 수 있는 화합물에 해당된다. 공지된 폴리에틸렌과 비교하여, 이런 신규한 고융점 폴리에틸렌은 예를 들어, 개선된 기계적 특성 및 열 뒤틀림 성능 (의료 용도의 살균능)을 나타내고, 결과적으로 지금까지는 폴리에틸렌에서는 가능하게 보이지 않았던, 예를 들어 지금까지 매우 규칙적인 폴리프로필렌에서만 충족될 수 있었던 용도의 가능성을 연다. 또 다른 특성으로는 고융해열 및 PE 고분자량이 있다.The D / A structure can affect over-stabilization of the catalyst up to high temperature, so that the catalyst can be used even in the high temperature range. Possible thermal decomposition of the donor-receptor bonds is reversible and gives particularly high performance catalytic properties as a result of this self-organization and self-recovery mechanism. The D / A metallocene structure according to the invention allows, for example, the formation of some degree of defect-free polyethylene that cannot be achieved with conventional catalysts. Thus, the ethene polymer may exceptionally have a high melting point, for example, greater than 135 ° C. to 160 ° C. (maximum value of the DSC curve). The linear polyethylene obtained directly by the polymerization method is a compound having a melting point of 140 to 160 ° C. (maximum value of the DSC curve), preferably 142 to 160 ° C., particularly preferably 144 to 160 ° C., particularly preferably 146 to 160 ° C. It is preferable to include. This particularly corresponds to compounds which can be prepared with the claimed metallocene compounds. Compared with known polyethylenes, these new high melting point polyethylenes exhibit, for example, improved mechanical properties and thermal warping performance (sterilizing ability in medical applications) and as a result have been shown to be, for example, not so far seen as possible in polyethylene. This opens up the possibility of applications that have so far been met only in very regular polypropylene. Another property is high heat of fusion and high molecular weight of PE.
넓은 온도 범위 내에서, 활성을 크게 감소시키지 않고, 산업상 이로운 PE 고분자량 및 PE 고융점의 총 범위를 이탈하지 않고도 중합 온도를 증가시킴으로써 PE 분자량을 감소시킨다.Within a wide temperature range, the PE molecular weight is reduced by increasing the polymerization temperature without significantly reducing activity and without leaving the total range of industrially beneficial PE high molecular weight and PE high melting point.
이소택틱 폴리올레핀의 제조를 위해, 예를 들어, 2 위치에 또는 4, 5, 6 또는 7 위치에, 예를 들어 알킬, 아릴 및(또는) 실릴 치환기 또는 벤조-융합 구조를 추가로 가져서 분자량 및 이소택티시티 (isotacticity) 및 융점을 증가시킬 수 있는 D/A 브릿지를 갖는 예를 들어, 유사-rac-비스(인데닐)메탈로센이 특히 적당하다. 그러나, 유사한 대칭의 (3,3') 치환 패턴을 갖는 D/A 비스(시클로펜타디에닐)-메탈로센도 가능하다.For the preparation of isotactic polyolefins, for example, at the 2 position or at the 4, 5, 6 or 7 position, for example, alkyl, aryl and / or silyl substituents or benzo-fusion structures can be further added to provide molecular weight and iso For example, quasi-rac-bis (indenyl) metallocenes with D / A bridges that can increase isotacticity and melting point are particularly suitable. However, D / A bis (cyclopentadienyl) -metallocenes with similar symmetrical (3,3 ') substitution patterns are also possible.
D/A-브릿지 (시클로펜타디에닐)(플루오레닐)-메탈로센 또는 (시클로펜타디에닐)(3,4-이치환 시클로펜타디에닐)-메탈로센이 예를 들어, 신디오택틱 폴리올레핀의 제조에 상당히 적당하다.D / A-Bridge (cyclopentadienyl) (fluorenyl) -metallocene or (cyclopentadienyl) (3,4-disubstituted cyclopentadienyl) -metallocene is for example syndiotactic It is quite suitable for the production of polyolefins.
또한, 본 발명에 따라 사용될 수 있는 적당한 대칭의 메탈로센 화합물 및 π 착화합물이 3C 탄소로부터 α-올레핀에 입체 특이성 (이소택틱, 신디오택틱) 중합에 영향을 주지만, 언급된 온도의 상부에서 동일한 단량체에 단량체 단위의 상당히 비특이성 (어택틱 (atactic)) 결합을 유도한다는 것이 발견되었다. 이러한 현상은 아직 완전히 밝혀지지는 않았으나, 본 발명에 따른 메탈로센 화합물 중에서 공여체-수용체 결합과 같이, 이온 결합에 의해 중첩되는 배위 결합은 고온에서 가역성의 증가를 보인다는 관찰이 일치할 수 있다. 또한, 예를 들어, 에틸렌프로필렌 공중합의 경우에 있어서, 동일한 양의 2개의 공단량체가 사용되는 경우에 프로필렌을 많이 함유하는 공중합체는 낮은 공중합 온도에서 형성되는 반면에, 중합 온도가 증가되면서 마지막으로 에틸렌 함유 중합체 (LLDPE)가 고온에서 우세하게 형성될 때까지 프로필렌 함량은 감소된다. D/A 구조물의 가역적 해리 및 결합 및 결과적으로 가능해질 서로에 대한 π 골격의 회전은 하기와 같이 도시될 수 있다.In addition, suitable symmetrical metallocene compounds and π complexes which can be used according to the invention affect the stereospecific (isotactic, syndiotactic) polymerization from 3C carbon to α-olefins, but at the same temperature above mentioned It has been found that the monomers induce significantly nonspecific (atactic) bonds of the monomer units. Although this phenomenon is not yet fully understood, the observation that the coordination bonds overlapped by ionic bonds, such as donor-receptor bonds among the metallocene compounds according to the present invention, show an increase in reversibility at high temperature. In addition, for example, in the case of ethylene propylene copolymerization, when the same amount of two comonomers are used, a propylene-rich copolymer is formed at a low copolymerization temperature, while finally the polymerization temperature is increased. The propylene content is reduced until ethylene containing polymer (LLDPE) forms predominantly at high temperatures. The reversible dissociation and coupling of the D / A structures and the rotation of the π skeletons relative to each other, which will be possible as a result, can be shown as follows.
및And
본 발명에 따른 D/A-π 착화합물, 예를 들어, D/A 메탈로센 화합물의 다른 유용한 특성은 자가 활성화의 가능성으로서, 특히 디아니온유도체의 경우에, 고비용의 조촉매를 사용하지 않을 수 있다.Another useful property of the D / A- [pi] complexes according to the invention, for example D / A metallocene compounds, is the possibility of self activation, in particular dianion. In the case of derivatives, expensive promoters may not be used.
이러한 경우에, 개열된 형태의 D/A-π 착화합물, 예를 들어 D/A 메탈로센 화합물에서 수용체 원자 A가 X 리간드를 결합하고, 예를 들어, 디아니온의 한쪽과 결합하여서 양쪽성 메탈로센 구조를 형성하여서 전이 금속에서 양 전하를 생성하는 반면, 수용체 원자 A는 음 전하일 것으로 예측된다. 상기와 같은 자가 활성화는 분자내 또는 분자간에 이루어질 수 있다. 이는 2개의 리간드가 바람직하게 연결되어서 킬레이트 리간드 즉, 부타디엔디일 유도체를 형성하는 것에 의해 설명될 수 있다.In this case, in the cleaved form of the D / A- [pi] complex, for example the D / A metallocene compound, the receptor atom A binds the X ligand and, for example, binds to one side of the dianion to form an amphoteric metal. It is expected that the acceptor atom A will be a negative charge while forming a rosene structure to produce a positive charge on the transition metal. Such self activation can be intramolecular or intermolecular. This can be explained by the two ligands being preferably linked to form chelate ligands, ie butadienediyl derivatives.
및And
전이 금속 M과 H, 또는 치환된 또는 비치환된 C 간의 결합 부위, 예시된 화학식에서 도시된 부타디에닐 디아니온의 치환된 C는 이후에 중합을 위한 올레핀 삽입 부위이다.The binding site between the transition metal M and H, or substituted or unsubstituted C, the substituted C of the butadienyl dianion shown in the illustrated formula is then the olefin insertion site for polymerization.
모든 반응들은 쉬렌크 (Schlenk) 기술 또는 고진공 기술을 사용하여 엄격하게 혐기 조건하에서 수행되었다. 사용된 용매들은 수분이 없었고, 아르곤으로 포화시켰다. 화학 이동 δ는 특정 표준 물질1H (테트라메틸실란),13C (테트라메틸실란),31P (85 % H3PO4),11B (보론 트리플루오라이드-에테레이트-18.1 ppm)에 대해 ppm으로 나타내었다. 마이너스 부호는 더 상위 필드 (higher field)로의 이동을 나타낸다.All reactions were performed under strictly anaerobic conditions using Schlenk technique or high vacuum technique. The solvents used were free of moisture and saturated with argon. Chemical shift δ is determined for specific standards 1 H (tetramethylsilane), 13 C (tetramethylsilane), 31 P (85% H 3 PO 4 ), 11 B (boron trifluoride-etherate-18.1 ppm) It is expressed in ppm. Minus signs indicate a shift to a higher field.
<실시예 1><Example 1>
(비스-(트리메틸실릴)-시클로펜타디엔, 화합물 1)(Bis- (trimethylsilyl) -cyclopentadiene, compound 1)
트리메틸실릴-시클로펜타디엔 (플루카 (Fluka)사 제품) 14.7 g (0.106 몰) 및 테트라히드로푸란 (THF) 150 ml를 반응 플라스크에 도입하고, 0 ℃로 냉각시켰다. n-헥산 중의 부틸-리튬 용액 47.4 ml (2.3 몰; 총량 0.109 몰)를 20 분에 걸쳐 적가하였다. 첨가가 완료되었을 때, 황색 용액을 1 시간 동안 더 교반시키고, 그 후에 냉각조를 제거하였다. 이 용액을 실온에서 1 시간 동안 더 교반시키고, 이어서 -20 ℃로 냉각시켰다. 이어서 염화 트리메틸실릴 14.8 ml (0.117 몰)를 10 분에 걸쳐 적가하고, 반응 혼합물을 2 시간 동안 -10 ℃에서 교반시켰다. 그 후에, 냉각조를 제거하고, 반응 용액을 실온으로 가온하고, 이후에 1 시간 동안 더 교반시켰다. 반응 혼합물을 셀라이트로 여과하고, 이 여과제를 헥산으로 세척하고, 모아진 여과액으로부터 진공하에 헥산을 제거하였다. 0.4 mbar하에 26 ℃에서 증류하여, 조생성물로부터 화합물 1의 순수한 생성물 19 g (이론적인 수율의 85 %)을 수득했다. 융점 및 NMR 데이터는 문헌 데이터 [J. Organometallic Chem. 29 (1971), 227; ibid. 30 (1971), C 57; J. Am. Chem. Soc. 102, (1980), 4429; J. Gen. Chem. USSR, 영어 번역문 43 (1973), 1970; J. Chem. Soc., Dalton Trans. 1980, 1156]와 유사하다.14.7 g (0.106 mol) of trimethylsilyl-cyclopentadiene (manufactured by Fluka) and 150 ml of tetrahydrofuran (THF) were introduced into the reaction flask and cooled to 0 ° C. 47.4 ml (2.3 moles; total amount 0.109 moles) of butyl-lithium solution in n-hexane were added dropwise over 20 minutes. When the addition was complete, the yellow solution was further stirred for 1 hour, after which the cooling bath was removed. The solution was further stirred at rt for 1 h and then cooled to -20 ° C. Then 14.8 ml (0.117 mol) of trimethylsilyl chloride were added dropwise over 10 minutes, and the reaction mixture was stirred at -10 ° C for 2 hours. After that, the cooling bath was removed and the reaction solution was allowed to warm to room temperature and then further stirred for 1 hour. The reaction mixture was filtered through celite, and this filter was washed with hexane and hexane was removed from the collected filtrate under vacuum. Distillation at 26 ° C. under 0.4 mbar gave 19 g (85% of theoretical yield) of the pure product of compound 1 from the crude product. Melting point and NMR data are described in literature data [J. Organometallic Chem. 29 (1971), 227; ibid. 30 (1971), C 57; J. Am. Chem. Soc. 102, (1980), 4429; J. Gen. Chem. USSR, English Translation 43 (1973), 1970; J. Chem. Soc., Dalton Trans. 1980, 1156.
1H-NMR (400 MHz, C6D6); δ=67.4 (m, 2H), 6.43 (m, 2H), -0.04 (s, 18H). 1 H-NMR (400 MHz, C 6 D 6 ); delta = 67.4 (m, 2H), 6.43 (m, 2H), -0.04 (s, 18H).
<실시예 2><Example 2>
(트리메틸실릴-시클로펜타디에닐-디클로로보란, 화합물 2)(Trimethylsilyl-cyclopentadienyl-dichloroborane, compound 2)
화합물 1 16 g (0.076 몰)을 드라이 아이스 냉각조가 장착된 둥근 바닥 플라스크에 도입하였다. BCl38.9 g (0.076 몰)을 -78 ℃ 쉬렌크 튜브로 응축시키고, 이어서 5 분에 걸쳐 둥근 바닥 플라스크에 적가하였다. 반응 혼합물을 1 시간에 걸쳐 실온으로 천천히 가온하고, 이어서 2 시간 동안 55 내지 60 ℃에서 유지시켰다. 모든 휘발성 화합물을 진공 (3 mmHg=4 mbar)에서 제거하였다. 그 후에 0.012 mbar하에 39 ℃에서 증류하여 화합물 2 14.1 g (이론적인 수율의 85 %)을 수득했다.1H-NMR은 문헌 데이터와 일치하며, 많은 이성질체들이 제조되었음을 보여주었다 [J. Organometallic Chem. 169 (1979), 327 참조].11B-NMR (64.2 MHz, C6D6): δ = +31.5.16 g (0.076 mol) of compound 1 were introduced into a round bottom flask equipped with a dry ice cooling bath. 8.9 g (0.076 mol) of BCl 3 were condensed into a -78 ° C Schlenk tube and then added dropwise to a round bottom flask over 5 minutes. The reaction mixture was slowly warmed to room temperature over 1 hour and then held at 55-60 ° C. for 2 hours. All volatile compounds were removed in vacuo (3 mmHg = 4 mbar). Thereafter, distillation at 39 ° C. under 0.012 mbar gave 14.1 g (85% of theoretical yield) of compound 2. 1 H-NMR is consistent with literature data and showed that many isomers were prepared [J. Organometallic Chem. 169 (1979), 327]. 11 B-NMR (64.2 MHz, C 6 D 6 ): δ = +31.5.
<실시예 3><Example 3>
(디클로로보라닐-시클로펜타디에닐-티타늄 트리클로라이드, 화합물 3)(Dichloroboranyl-cyclopentadienyl-titanium trichloride, compound 3)
3 3
화합물 2 11.4 g (0.052 몰) 및 염화 메틸렌 (CH2Cl2) 100 ml를 250 ml의 쉬렌크 튜브에 도입하였다. 이 용액을 -78 ℃로 냉각하고, 사염화 티타늄 9.8 g (5.6 ml, 0.052 ml)을 10 분에 걸쳐 적가하였다. 결과의 적색 용액을 실온까지 천천히 가온하고, 3 시간 동안 더 교반시켰다. 이 용매를 진공하에 제거하고, 지저분한 황색 생성물을 수득했다. 헥산 200 ml를 이 조화합물 고체에 첨가하고, 결과의 황색 용액을 여과하고, 냉장고에서 하룻밤 동안 냉각시키고, 화합물 3의 황색 결정 12.3 g (이론적인 수율의 79 %)을 수득했다. 문헌 [J. Organometallic Chem. 169 (1979), 373]에서는, 석유 에테르 또는 메틸시클로헥산과 같은 탄화수소 용매 중에서 반응을 수행하여 이론적인 수율의 62 %가 얻어졌음에 주목해야 한다.11.4 g (0.052 mol) of compound 2 and 100 ml of methylene chloride (CH 2 Cl 2 ) were introduced into a 250 ml Schlenk tube. The solution was cooled to -78 ° C and 9.8 g (5.6 ml, 0.052 ml) of titanium tetrachloride were added dropwise over 10 minutes. The resulting red solution was slowly warmed up to room temperature and stirred for 3 more hours. This solvent was removed in vacuo to give a pale yellow product. 200 ml of hexane was added to this crude solid and the resulting yellow solution was filtered, cooled overnight in a refrigerator and 12.3 g (79% of theoretical yield) of yellow crystals of compound 3 were obtained. J. Organometallic Chem. 169 (1979), 373, it should be noted that 62% of the theoretical yield was obtained by carrying out the reaction in a hydrocarbon solvent such as petroleum ether or methylcyclohexane.
1H-NMR (400 MHz, CD2Cl2): δ=7.53 (t, J=2.6 Hz, 2H), 7.22 (t, J=2.6 Hz, 2H).11B-NMR (64.2 MHz, CD2Cl2): δ=+33. 1 H-NMR (400 MHz, CD 2 Cl 2 ): δ = 7.53 (t, J = 2.6 Hz, 2H), 7.22 (t, J = 2.6 Hz, 2H). 11 B-NMR (64.2 MHz, CD 2 Cl 2 ): δ = + 33.
<실시예 4><Example 4>
(디메틸보라닐-시클로펜타디에닐-티타늄 트리클로라이드, 화합물 4)(Dimethylboranyl-cyclopentadienyl-titanium trichloride, compound 4)
4 4
화합물 3 2.37 g (0.0079 몰)을 둥근 바닥 플라스크에서 헥산 100 ml 중에 용해시켰다. 이 용액을 0 ℃로 냉각하고, 톨루엔 (0.008 몰) 중의 알루미늄-트리메틸의 2 몰 용액 4 ml를 적가하였다. 첨가가 완료되었을 때, 냉각조를 제거하고, 모든 휘발성 화합물을 진공하에 제거하였다. 남아 있는 황색 고체를 펜탄 중에 용해시키고, 고체 내용물을 여과하고, 투명한 여과액을 -78 ℃로 냉각하고, 화합물 4 1.5 g (이론적인 수율의 74 %)을 수득했다. 문헌 [J. Organometallic Chem. 169 (1979), 373]에서는, 알킬화제로서 테트라메틸 주석을 사용하여 수율이 이론적인 수율의 87 %라고 언급하고 있지만, 화합물 4를 염화 트리메틸주석 형성이 없는 형태로 얻는 것은 불가능했다는 것을 주목해야 한다.2.37 g (0.0079 mol) of compound 3 were dissolved in 100 ml of hexane in a round bottom flask. The solution was cooled to 0 ° C. and 4 ml of a 2 molar solution of aluminum-trimethyl in toluene (0.008 mole) was added dropwise. When the addition was complete, the cooling bath was removed and all volatile compounds were removed under vacuum. The remaining yellow solid was dissolved in pentane, the solid contents were filtered off, the clear filtrate was cooled to -78 ° C and 1.5 g of compound 4 (74% of theoretical yield) were obtained. J. Organometallic Chem. 169 (1979), 373, mentioning that the yield is 87% of the theoretical yield using tetramethyl tin as the alkylating agent, it should be noted that it was not possible to obtain compound 4 in the form without trimethyltin chloride formation.
1H-NMR (400 MHz, CD2Cl2): δ=7.48 (t, J=2.5 Hz, 2H), 7.23 (t, J=2.5 Hz, 2H), 1.17 (s, 6H).11B-NMR (64.2 MHz, CD2Cl2): δ=+56. 1 H-NMR (400 MHz, CD 2 Cl 2 ): δ = 7.48 (t, J = 2.5 Hz, 2H), 7.23 (t, J = 2.5 Hz, 2H), 1.17 (s, 6H). 11 B-NMR (64.2 MHz, CD 2 Cl 2 ): δ = + 56.
<실시예 5>Example 5
((디페닐포스핀-시클로펜타디에틸)-리튬, 화합물 6)((Diphenylphosphine-cyclopentadiethyl) -lithium, compound 6)
5 65 6
시클로펜타디에닐-탈륨 (플루카사 제품) 50 g (0.186 몰)을 500 ml 플라스크에 디에틸 에테르 300 ml와 함께 도입하였다. 현탁액을 0 ℃로 냉각하였고, 디페닐클로로포스핀 34.2 ml (0.186 몰)를 10 분에 걸쳐 적가하였다. 현탁액을 실온으로 가온하고, 1 시간 동안 교반시키고, 프리트 (frit)로 최종 여과시켰다. 이어서, 용매를 진공하에 제거하여, 중간 생성물 디페닐포스피노시클로펜타디엔, 화합물 5의 39.5 g (이론적인 수율의 85 %)을 수득했다. 이어서, 화합물 5 18.6 g (0.074 몰)의 내용물을 톨루엔으로 희석하고, 0 ℃로 냉각시켰다. 헥산 (0.074 몰) 중의 부틸-리튬의 2.24 몰 용액 33.2 ml를 10 분에 걸쳐 이 용액에 첨가하였다. 실온까지 가온하고, 2 시간 동안 교반시킨 후, 황색 용액으로부터 침전물을 수득했고, 이를 여과하고, 톨루엔으로, 이어서 헥산으로 세척하였다. 진공하에 건조시킨 후, 화합물 6 (이론적인 수율의 70 %) 13.2 g을 갈색 분말로 수득했다 [J. Am. Chem. Soc. 105 (1983), 3882; Organometallics 1 (1982), 1591 참조].50 g (0.186 mole) of cyclopentadienyl- thallium (Fluka) were introduced into a 500 ml flask with 300 ml of diethyl ether. The suspension was cooled to 0 ° C and 34.2 ml (0.186 mol) of diphenylchlorophosphine were added dropwise over 10 minutes. The suspension was allowed to warm to rt, stirred for 1 h and finally filtered through frit. The solvent was then removed in vacuo to yield 39.5 g (85% of theoretical yield) of the intermediate product diphenylphosphinocyclopentadiene, compound 5. Then 18.6 g (0.074 mol) of compound 5 were diluted with toluene and cooled to 0 ° C. 33.2 ml of a 2.24 mol solution of butyl-lithium in hexane (0.074 mol) was added to this solution over 10 minutes. After warming to room temperature and stirring for 2 hours, a precipitate was obtained from a yellow solution which was filtered off, washed with toluene and then with hexane. After drying in vacuo, 13.2 g of compound 6 (70% of theoretical yield) were obtained as a brown powder [J. Am. Chem. Soc. 105 (1983), 3882; Organometallics 1 (1982), 1591].
1H-NMR (400 MHz, d8THF): δ=7.3 (m, 4H), 7.15 (m, 6H), 5.96 (m, 2H), 5.92 (m, 2H),31P-NMR (161.9 MHz, d8THF): δ=-20. 1 H-NMR (400 MHz, d 8 THF): δ = 7.3 (m, 4H), 7.15 (m, 6H), 5.96 (m, 2H), 5.92 (m, 2H), 31 P-NMR (161.9 MHz , d 8 THF): δ = -20.
<실시예 6)<Example 6)
((C6H5)2P → B(CH3)2-브릿지 비스-(시클로펜타디에닐)-티타늄 디클로라이드, 화합물 7)((C 6 H 5 ) 2 P → B (CH 3 ) 2 -bridged bis- (cyclopentadienyl) -titanium dichloride, compound 7)
7 7
화합물 6 0.36 g (0.00139 몰) 및 톨루엔 20 ml를 둥근 바닥 플라스크에 도입하였다. 형성된 용액을 -20 ℃로 냉각하고, 톨루엔 20 ml 중의 화합물 4 0.36 g (0.00139 몰)의 용액을 20 분에 걸쳐 적가하였다. 적가가 끝났을 때, 이 용액을 2 시간에 걸쳐 실온으로 가열하고, 이 온도에서 추가의 1 시간 동안 교반시켰다. 용해되지 않은 물질을 프리트로 제거하고, 용매는 진공하에 증류시켰다. 이어서, 적색의 오일상 고체를 헥산으로 세척해서, 이를 가만히 따라내고, 고체를 진공하에 다시 건조시켰다. 이런 방법으로 화합물 7 0.28 g (이론적인 수율의 42 %)을 적색 분말로 수득했다.0.36 g (0.00139 mol) of compound 6 and 20 ml of toluene were introduced into a round bottom flask. The resulting solution was cooled to −20 ° C. and a solution of 0.36 g (0.00139 mol) of compound 4 in 20 ml of toluene was added dropwise over 20 minutes. At the end of the dropping, the solution was heated to room temperature over 2 hours and stirred at this temperature for an additional hour. Undissolved material was removed with frit and the solvent was distilled under vacuum. The red oily solid was then washed with hexane, which was decanted and the solid was dried again under vacuum. In this way 0.28 g (42% of theoretical yield) of compound 7 were obtained as a red powder.
1H-NMR (300 MHz, CD2Cl2): δ=7.6-7.3 (br, m, 10H), 6.92 (m, 2H), 6.77 (m, 4H), 6.60 (m, 2H), 0.29 (d, JPH=19 Hz, 6H);31P-NMR (161.9 MHz, CD2Cl2): δ=17.1 (br);11B-NMR (64.2 MHz, CD2Cl2); δ=-29 (br). 1 H-NMR (300 MHz, CD 2 Cl 2 ): δ = 7.6-7.3 (br, m, 10H), 6.92 (m, 2H), 6.77 (m, 4H), 6.60 (m, 2H), 0.29 ( d, J PH = 19 Hz, 6H); 31 P-NMR (161.9 MHz, CD 2 Cl 2 ): δ = 17.1 (br); 11 B-NMR (64.2 MHz, CD 2 Cl 2 ); delta = -29 (br).
<실시예 7><Example 7>
(트리부틸스탄닐-디페닐포스피노-인덴, 화합물 8)(Tributylstannyl-diphenylphosphino-indene, compound 8)
인덴 10 g (0.086 몰)을 둥근 바닥 플라스크에 도입하고, 디에틸 에테르 200 ml로 희석하고, -20 ℃로 냉각시켰다. n-헥산 중의 부틸-리튬 (0.085 몰)의 2.36 몰 용액 36 ml를 이 용액에 첨가하였더니 이 용액은 즉시 황색을 띠었다. 냉각조를 제거하고, 반응 혼합물을 실온으로 가온하고, 1 시간 동안 더 교반시켰다. 그 후에, 반응 혼합물을 0 ℃로 다시 냉각시키고, 디페닐클로로포스핀 19 g (15.9 ml, 0.086 몰)을 첨가하여 침전물이 형성되었다. 냉각조를 다시 제거하고, 이후에 이 용액을 1 시간 더 교반시키면서 실온으로 가온시켰다. 이어서, 이 용액을 -20 ℃로 다시 냉각시키고, n-헥산 중의 부틸-리튬 36 ml (0.085 몰)를 적가하였다. 첨가가 끝났을 때, 냉각조를 다시 제거하고, 온도를 실온으로 올리고, 이후에 이 용액을 1.5 시간 동안 더 교반시켰다. 이어서, 현탁액을 0 ℃로 다시 냉각하고, 염화 트리부틸주석 28 g (0.086 몰)을 적가하였다. 결과의 현탁액을 실온으로 가온하고, 1.5 시간 동안 더 교반시키고, 이후에 프리트로 여과하고, 용매를 진공하에 제거하였다. 화합물 8 46.9 g (이론적인 수율의 92 %)을 진한 황색 오일로 수득했다.10 g (0.086 mol) of indene were introduced into a round bottom flask, diluted with 200 ml of diethyl ether and cooled to -20 ° C. 36 ml of a 2.36 molar solution of butyl-lithium (0.085 mole) in n-hexane was added to this solution, which immediately turned yellow. The cold bath was removed and the reaction mixture was allowed to warm to room temperature and stirred for 1 h more. Thereafter, the reaction mixture was cooled back to 0 ° C. and 19 g (15.9 ml, 0.086 mol) of diphenylchlorophosphine were added to form a precipitate. The cooling bath was removed again and the solution was then warmed to room temperature with stirring for an additional hour. The solution was then cooled back to -20 ° C and 36 ml (0.085 mol) of butyl-lithium in n-hexane were added dropwise. At the end of the addition, the cooling bath was removed again and the temperature was raised to room temperature, after which the solution was further stirred for 1.5 hours. The suspension was then cooled back to 0 ° C. and 28 g (0.086 mol) of tributyltin chloride were added dropwise. The resulting suspension was allowed to warm to rt, stirred for 1.5 h more, then filtered through frit and the solvent removed in vacuo. 46.9 g (92% of theoretical yield) of compound 8 were obtained as a dark yellow oil.
1H-NMR (400 MHz, CDCl3): δ=7.5-7.3 (m, 6H), 7.28 (br, s, 6H), 7.14 (유사-d t, 7.3 Hz/1.0 Hz, 1H), 7.08 (t, J=7.3 Hz, 1H), 6.5 (br m, 1H), 4.24 (br s, 1H), 1.4-1.25 (m, 6H), 1.25-1.15 (m, 6H), 0.82 (t, J=7.2 Hz, 9H), 0.53 (t, J=8 Hz, 6H),31P-NMR (161.9 MHz, CDCl3): δ=-20.6. 1 H-NMR (400 MHz, CDCl 3 ): δ = 7.5-7.3 (m, 6H), 7.28 (br, s, 6H), 7.14 (quasi-dt, 7.3 Hz / 1.0 Hz, 1H), 7.08 (t , J = 7.3 Hz, 1H), 6.5 (br m, 1H), 4.24 (br s, 1H), 1.4-1.25 (m, 6H), 1.25-1.15 (m, 6H), 0.82 (t, J = 7.2 Hz, 9H), 0.53 (t, J = 8 Hz, 6H), 31 P-NMR (161.9 MHz, CDCl 3 ): δ = -20.6.
<실시예 8><Example 8>
(디페닐포스피노-인데닐-지르코늄 트리클로라이드, 화합물 9)(Diphenylphosphino-indenyl-zirconium trichloride, compound 9)
9 9
톨루엔 300 ml 중의 화합물 8 37 g (0.0628 몰)의 용액을 실온에서 3 시간에 걸쳐 톨루엔 100 ml 중의 ZrCl4(99.9 % 순도, 0.0628 몰, 알드리치 (Aldrich)사 제품) 14.6 g의 현탁액에 첨가하였다. 이 용액은 즉시 적색이 되었고, 천천히 오렌지색으로 변해서 마지막에는 황색으로 변했다. 이후에 4 시간 동안 교반시킨 후, 황색 침전물을 여과하고, 톨루엔으로, 이어서 헥산으로 세척하였다. 고체를 진공하에 건조하고, 자유 유동성 황색 분말로서 화합물 9 15.3 g (이론적인 수율의 50 %)을 수득했다. 저온에서, 예를 들어 -30 ℃에서 30 분, 0 ℃에서 5 시간 동안 반응을 수행시킴으로써 70 % 이상으로 수율을 쉽게 증가시킬 수 있다. 속슬레 (Soxhlet) 추출기에서 펜탄을 사용하여 잔류 주석 화합물을 세척해서 (추출 시간: 8 시간) 생성물을 더 정제할 수 있다.A solution of 37 g (0.0628 mol) of compound 8 in 300 ml of toluene was added to a suspension of 14.6 g of ZrCl 4 (99.9% purity, 0.0628 mol, manufactured by Aldrich) in 100 ml of toluene over 3 hours at room temperature. The solution immediately turned red, slowly turning orange and eventually turning yellow. After stirring for 4 hours, the yellow precipitate was filtered off and washed with toluene and then with hexane. The solid was dried under vacuum and 15.3 g (50% of theoretical yield) of compound 9 were obtained as a free flowing yellow powder. The yield can easily be increased to at least 70% by running the reaction at low temperature, for example for 30 minutes at −30 ° C., for 5 hours at 0 ° C. The product can be further purified by washing the residual tin compound (extraction time: 8 hours) using pentane in a Soxhlet extractor.
<실시예 9>Example 9
((C6H5)2P-BCl2-브릿지 인데닐-시클로펜타디에닐-지르코늄 디클로라이드, 화합물 10)((C 6 H 5 ) 2 P-BCl 2 -bridged indenyl-cyclopentadienyl-zirconium dichloride, compound 10)
10 10
정제된 화합물 9 4.43 g (0.0089 몰) 및 톨루엔 100 ml를 쉬렌크 튜브에 도입하였다. 화합물 2 1.95 g (0.0089 몰)을 이 현탁액에 첨가하였다. 황색 현탁액을 6 시간 동안 실온에서 교반시키고, 이 시간 중에 엷은 백색 침전물이 형성되었다. 이 침전물 (4.1 g, 이론적인 수율의 75 %)을 여과로 분리하였고, 본질적으로 순수한 물질임이 밝혀졌다.4.43 g (0.0089 mol) of purified compound 9 and 100 ml of toluene were introduced into a Schlenk tube. 1.95 g (0.0089 mol) of compound 2 were added to this suspension. The yellow suspension was stirred for 6 hours at room temperature, during which time a pale white precipitate formed. This precipitate (4.1 g, 75% of theoretical yield) was isolated by filtration and found to be essentially pure material.
1H-NMR (500 MHz, CD2Cl2): δ=7.86 (유사 ddd, J=8.5/2.5/1 Hz, 1H), 7.75-7.55 (m, 10H), 7.35 (유사 ddd, J=8.5/6.9/0.9 Hz, 1H), 7.32 (br t, J=3.1 Hz, 1H), 7.22 (유사 ddd, J=8.8/6.8/1.1 Hz, 1H), 7.06 (유사 ddd, J=3.4/3.4/0.8 Hz, 1H), 6.92 (m, 1H), 6.72 (m, 1H), 6.70 (br m, 1H), 6.61 (유사 q, J=2.3 Hz, 1H), 6.53 (br d, 8.7 Hz, 1H);31P-NMR (161.9 MHz, CD2Cl2): δ=6.2 (br, m);11B (64.2 MHz, CD2Cl2): δ=-18 (br). 1 H-NMR (500 MHz, CD 2 Cl 2 ): δ = 7.86 (similar ddd, J = 8.5 / 2.5 / 1 Hz, 1H), 7.75-7.55 (m, 10H), 7.35 (similar ddd, J = 8.5 /6.9/0.9 Hz, 1H), 7.32 (br t, J = 3.1 Hz, 1H), 7.22 (similar ddd, J = 8.8 / 6.8 / 1.1 Hz, 1H), 7.06 (similar ddd, J = 3.4 / 3.4 / 0.8 Hz, 1H), 6.92 (m, 1H), 6.72 (m, 1H), 6.70 (br m, 1H), 6.61 (similar q, J = 2.3 Hz, 1H), 6.53 (br d, 8.7 Hz, 1H ); 31 P-NMR (161.9 MHz, CD 2 Cl 2 ): δ = 6.2 (br, m); 11 B (64.2 MHz, CD 2 Cl 2 ): δ = -18 (br).
<실시예 10><Example 10>
((C6H5)2P-B(CH3)2-브릿지 인데닐-시클로펜타디에닐-지르코늄 디클로라이드, 화합물 11)((C 6 H 5 ) 2 PB (CH 3 ) 2 -bridge indenyl-cyclopentadienyl-zirconium dichloride, compound 11)
11 11
톨루엔 50 ml를 실시예 9의 화합물 10 1.5 g (0.00247 몰)에 첨가하였다. 현탁액을 0 ℃로 냉각시키고, 헥산 (0.0024 몰) 중의 트리메틸알루미늄 2 몰 용액 1.2 ml를 5 분에 걸쳐 적가하였다. 첨가가 완료되었을 때, 냉각조를 제거하고, 이 용액을 실온으로 가온시키고, 2 시간 동안 더 교반시켰다. 잔류 침전물을 여과하고, 진공하에 여과액으로부터 용매를 제거하고, 화합물 11 0.37 g (이론적인 수율의 26 %)을 갈색 고체로 수득했다.50 ml of toluene was added to 1.5 g (0.00247 mol) of compound 10 of Example 9. The suspension was cooled to 0 ° C. and 1.2 ml of a 2 molar solution of trimethylaluminum in hexane (0.0024 mol) was added dropwise over 5 minutes. When the addition was complete, the cooling bath was removed and the solution was allowed to warm to room temperature and stirred for a further 2 hours. The residual precipitate was filtered off, the solvent was removed from the filtrate under vacuum and 0.37 g (26% of theoretical yield) of compound 11 were obtained as a brown solid.
31P-NMR (161.9 MHz, CD2Cl2): δ=14.6;11B-NMR (64.2 MHz, CD2Cl2): δ=-28 31 P-NMR (161.9 MHz, CD 2 Cl 2 ): δ = 14.6; 11 B-NMR (64.2 MHz, CD 2 Cl 2 ): δ = -28
<실시예 11><Example 11>
(트리메틸실릴-인덴, 화합물 12)(Trimethylsilyl-indene, compound 12)
12 12
인덴 25 ml (진공하에 CaH2에서 증류된 0.213 몰)를 THF 100 ml가 들어 있는 둥근 바닥 플라스크에 도입하고, 0 ℃로 냉각시켰다. 헥산 (0.216 몰) 중의 부틸-리튬 2.3 몰 용액의 94 ml를 20 분에 걸쳐 첨가하였다. 첨가가 완료되었을 때, 혼합물을 20 분 동안 교반시키고, 이어서 실온으로 가온하고, 30분 동안 더 교반시켰다. -20 ℃로 냉각시킨 후, 트리메틸클로로실란 27.5 ml (0.216 몰)를 적가해서 약간 흐린 오렌지색 용액이 형성되었다. 1 시간 동안 -10 ℃에서, 1.5 시간 동안 0 ℃에서 교반시킨 후, 용액을 실온으로 가온하고, 용매는 진공하에 제거하였다. 헥산 중에 다시 용해시킨 후, LiCl을 여과하고, 헥산을 진공하에 제거하였다. 생성물 (0.045 mbar, 58 내지 60 ℃)을 증류시켜서 화합물 12 26.6 g (이론적인 수율의 66 %)을 수득했다.25 ml of indene (0.213 moles distilled in CaH 2 under vacuum) were introduced into a round bottom flask containing 100 ml of THF and cooled to 0 ° C. 94 ml of a 2.3 mol solution of butyl-lithium in hexane (0.216 mol) was added over 20 minutes. When the addition was complete, the mixture was stirred for 20 minutes, then warmed to room temperature and further stirred for 30 minutes. After cooling to −20 ° C., 27.5 ml (0.216 mol) of trimethylchlorosilane were added dropwise to form a slightly cloudy orange solution. After stirring at −10 ° C. for 1 hour and at 0 ° C. for 1.5 hours, the solution is warmed to room temperature and the solvent is removed in vacuo. After dissolving again in hexane, LiCl was filtered off and hexane was removed in vacuo. The product (0.045 mbar, 58-60 ° C.) was distilled to give 26.6 g of compound 12 (66% of theoretical yield).
1H-NMR (400 MHz, CDCl3): δ=7.49 (t, J=7.6 Hz, 1H), 7.28 (ddd, J=7.3/7.2/1 Hz, 1H), 7.21 (ddd, J=7.3/7.3/1.1 Hz, 1H), 6.96 (dd, J=5.6/1.2 Hz, 1H), 6.69 (dd, J=5.3/1.8 Hz, 1H), 3.56 (s, 1H), 0.0 (s, 9H). 1 H-NMR (400 MHz, CDCl 3 ): δ = 7.49 (t, J = 7.6 Hz, 1H), 7.28 (ddd, J = 7.3 / 7.2 / 1 Hz, 1H), 7.21 (ddd, J = 7.3 / 7.3 / 1.1 Hz, 1H), 6.96 (dd, J = 5.6 / 1.2 Hz, 1H), 6.69 (dd, J = 5.3 / 1.8 Hz, 1H), 3.56 (s, 1H), 0.0 (s, 9H).
<실시예 12><Example 12>
(비스-(트리메틸실릴)-인덴, 화합물 13)(Bis- (trimethylsilyl) -indene, compound 13)
화합물 12 25.4 g (0.135 몰)을 THF 100 ml가 들어 있는 둥근 바닥 플라스크에 도입하고, 0 ℃로 냉각시켰다. 헥산 (0.136 몰) 중의 부틸-리튬 2.3 몰 용액 59 ml를 20 분에 걸쳐 첨가하였다. 첨가가 완료되었을 때, 혼합물을 20 분 동안 교반시키고, 이어서 실온으로 가온시켰다. 30 분 동안 교반시킨 후, -20 ℃로 냉각시키고, 트리메틸클로로실란 17.3 ml (0.136 몰)를 적가해서 약간 흐린 오렌지색 용액이 형성되었다. 이 용액을 1 시간 동안 0 ℃에서, 1 시간 동안 실온에서 교반시키고, 이어서 진공하에 용매를 제거하였다. 헥산 중에 재용해시킨 후, LiCl을 여과하고, 헥산을 진공하에 제거하였다. 화합물 13 32 g (이론적인 수율의 90 %)을 오일로 수득했다. 문헌 [J. Organometal. Chem. 23 (1970), 407; THF 대신 헥산]을 참조.25.4 g (0.135 mol) of compound 12 were introduced into a round bottom flask containing 100 ml of THF and cooled to 0 ° C. 59 ml of a 2.3 mol solution of butyl-lithium in hexane (0.136 mol) were added over 20 minutes. When the addition was complete, the mixture was stirred for 20 minutes and then warmed to room temperature. After stirring for 30 minutes, it was cooled to -20 ° C and 17.3 ml (0.136 mol) of trimethylchlorosilane was added dropwise to form a slightly cloudy orange solution. The solution was stirred at 0 ° C. for 1 hour and at room temperature for 1 hour and then the solvent was removed under vacuum. After redissolution in hexane, LiCl was filtered off and hexane was removed in vacuo. 32 g (90% of theoretical yield) of compound 13 were obtained as an oil. J. Organometal. Chem. 23 (1970), 407; Hexane instead of THF].
1H-NMR (400 MHz, CDCl3): δ=7.62 (d, J=7.6 Hz, 1H), 7.52 (d, J=7.5 Hz, 1H), 7.23 (ddd, J=7.35/7.3/0.9 Hz, 1H), 6.9 (d, J=1.7 Hz, 1H), 3.67 (d, J=1.6 Hz, 1H), 0.38 (s, 9H), 0.0 (s, 9H). 1 H-NMR (400 MHz, CDCl 3 ): δ = 7.62 (d, J = 7.6 Hz, 1H), 7.52 (d, J = 7.5 Hz, 1H), 7.23 (ddd, J = 7.35 / 7.3 / 0.9 Hz , 1H), 6.9 (d, J = 1.7 Hz, 1H), 3.67 (d, J = 1.6 Hz, 1H), 0.38 (s, 9H), 0.0 (s, 9H).
<실시예 13>Example 13
(트리메틸실릴-디클로로보라닐-인덴, 화합물 14)(Trimethylsilyl-dichloroboranyl-indene, compound 14)
화합물 2 제조와 비슷한 방법으로, 화합물 13 12.3 g (0.047 몰)을, -30 ℃로 냉각되고 드라이 아이스로 냉각된 환류 응축기를 갖는 둥근 바닥 플라스크에 도입하였다. BCl35.6 g (0.046 몰)을 이 플라스크에 첨가하였다. 첨가가 완결되었을 때, 냉각조를 제거하고, 반응 혼합물을 실온으로 가온하고, 3 시간 동안 교반시켰다. 이어서, 온도를 6 시간 동안 55 ℃로 올렸다. 냉각 및 진공하에 휘발성 성분의 제거 후에, 조생성물을 수득했다. 고진공하에서 증류하여 정제된 생성물인 다음과 같이 확인된 주요 이성질체를 수득했다.In a similar manner to the preparation of Compound 2, 12.3 g (0.047 mol) of Compound 13 were introduced into a round bottom flask having a reflux condenser cooled to −30 ° C. and cooled with dry ice. 5.6 g (0.046 mol) BCl 3 was added to this flask. When the addition was complete, the cooling bath was removed and the reaction mixture was allowed to warm to room temperature and stirred for 3 hours. The temperature was then raised to 55 ° C. for 6 hours. After cooling and removal of the volatile components under vacuum, the crude product is obtained. Distillation under high vacuum gave the major isomers identified as the purified product as follows.
1H-NMR (200 MHz, CDCl3): δ=8.3 (d, J=7 Hz, 1H), 8.1 (d, J=1.8 Hz, 1H), 7.5 (dd, J=7.0/1.2 Hz, 1H), 7.4 (m, 3H), 4.0 (d, J=1.8 Hz, 1H), 0.1 (s, 9H);11B-NMR (64.2 MHz, CD2Cl2): δ=38 (br). 1 H-NMR (200 MHz, CDCl 3 ): δ = 8.3 (d, J = 7 Hz, 1H), 8.1 (d, J = 1.8 Hz, 1H), 7.5 (dd, J = 7.0 / 1.2 Hz, 1H ), 7.4 (m, 3H), 4.0 (d, J = 1.8 Hz, 1H), 0.1 (s, 9H); 11 B-NMR (64.2 MHz, CD 2 Cl 2 ): δ = 38 (br).
<실시예 14><Example 14>
((C6H5)2P-BCl2-브릿지 비스-(인데닐)-지르코늄 디클로라이드, 화합물 15)((C 6 H 5 ) 2 P-BCl 2 -bridged bis- (indenyl) -zirconium dichloride, compound 15)
화합물 14 4.5 g (0.017 몰)을 톨루엔 200 ml 중의 화합물 9 8.3 g (0.017 몰)의 현탁액에 첨가하고, 혼합물을 50 ℃로 가열하고, 5 시간 동안 교반시켰다. 냉각 및 여과 후에, 헥산 200 ml를 첨가하고, 그 후에 침전물이 투명한 황색 용액으로부터 침전되고, 이 침전물을 여과하여 진공하에 건조시켰다. 생성물은 그의 X-선 분석에 따르면 화합물 15의 meso-이성질체인 것으로 확인되었다. 브릿지의 P-B 결합 길이가 2.01 Å로 측정되었다. 화합물 15의 라세미체 이성질체라고 판정된 두 번째 침전물을, 톨루엔/헥산 용액을 헥산 약 10 ml로 농축하고 200 ml를 더 첨가함으로써 수득하였다.4.5 g (0.017 mol) of compound 14 were added to a suspension of 8.3 g (0.017 mol) of compound 9 in 200 ml of toluene, and the mixture was heated to 50 ° C. and stirred for 5 hours. After cooling and filtration, 200 ml of hexanes were added, after which the precipitate precipitated out of a clear yellow solution, which was filtered and dried under vacuum. The product was identified by its X-ray analysis to be the meso-isomer of compound 15. The P-B bond length of the bridge was measured to be 2.01 mm 3. A second precipitate, determined to be the racemate isomer of compound 15, was obtained by concentrating the toluene / hexane solution to about 10 ml of hexane and adding 200 ml more.
<실시예 15><Example 15>
(N,N-디메틸-O-(메틸술포닐)-히드록실아민, 화합물 16)(N, N-dimethyl-O- (methylsulfonyl) -hydroxylamine, compound 16)
(CH3)2NOSO2CH316(CH 3 ) 2 NOSO 2 CH 3 16
N,N-디메틸-O-히드록실아민 히드로클로라이드 9.0 g (0.092 몰)을 트리에틸아민 20 g (0.2 몰)이 들어 있는 CH2Cl270 ml 중에 현탁시키고, 현탁액을 -10 ℃로 냉각시켰다. CH2Cl270 ml 중에 용해된 염화 메틸술포닐 9.5 g (0.083 몰)을 냉각된 현탁액에 천천히 적가하였다. 첨가가 완결되었을 때, 이후에 혼합물을 1 시간 동안 교반시켰다. 그 후에, 빙수를 반응 혼합물에 첨가하고, 유기층을 분리하였다. 남아있는 물은 에테르로 세척하였다. 세척액 에테르 및 CH2Cl2분획을 모아서 NaSO4에서 건조시키고, -10 ℃의 진공하에 용매를 제거하였다. 화합물 16 5.9 g (이론적인 수율의 46 %)을 오일로 수득했고, 이를 -20 ℃에서 저장하였다. 문헌 [Angew. Chem. Int. Ed. Engl. 17 (1978), 687]을 참조.9.0 g (0.092 mol) of N, N-dimethyl-O-hydroxylamine hydrochloride were suspended in 70 ml of CH 2 Cl 2 containing 20 g (0.2 mol) of triethylamine and the suspension was cooled to −10 ° C. . 9.5 g (0.083 mol) of methylsulfonyl chloride dissolved in 70 ml of CH 2 Cl 2 were slowly added dropwise to the cooled suspension. When the addition was complete, the mixture was then stirred for 1 hour. After that, ice water was added to the reaction mixture, and the organic layer was separated. The remaining water was washed with ether. The wash liquor ether and CH 2 Cl 2 fractions were combined and dried over NaSO 4 and the solvent removed under vacuum at −10 ° C. 5.9 g (46% of theoretical yield) of compound 16 were obtained as an oil, which was stored at -20 ° C. Angew. Chem. Int. Ed. Engl. 17 (1978), 687.
1H-NMR (400 MHz, CDCl3): δ=3.03 (s, 3H), 2.84 (s, 6H). 1 H-NMR (400 MHz, CDCl 3 ): δ = 3.03 (s, 3H), 2.84 (s, 6H).
<실시예 16><Example 16>
(N,N-디메틸아미노-시클로펜타디에닐-리튬, 화합물 17)(N, N-dimethylamino-cyclopentadienyl-lithium, compound 17)
17 17
THF 30 ml 중의 시클로펜타디에닐-리튬 3 g (0.042 몰) 용액을 -30 ℃에서 THF 20 ml 중의 화합물 16 5.9 g (0.042 몰) 용액에 천천히 첨가하였다. 이어서, 혼합물을 -20 ℃로 가온하고, 30 분 동안 교반시켰다. 이어서, 헥산을 첨가하고, 용액을 여과하였다. 그 후에, 헥산 중의 부틸-리튬 (0.042 몰) 2.3 몰 용액 1.8 ml를 -20 ℃에서 첨가하고, 그 후에 침전물이 형성되었다. 침전물을 여과하고, 매번 헥산 20 ml로 두 번 세척하였다. 진공하에 건조시킨 후, 화합물 17 2.0 g (이론적인 수율의 40 %)을 백색 분말로 수득했다. 문헌 [Angew. Chem. Int. Ed. Engl. 19 (1980), 1010]을 참조.A solution of 3 g (0.042 mol) of cyclopentadienyl-lithium in 30 ml of THF was slowly added to a solution of 5.9 g (0.042 mol) of compound 16 in 20 ml of THF at −30 ° C. The mixture was then warmed to -20 ° C and stirred for 30 minutes. Hexane was then added and the solution was filtered. Thereafter, 1.8 ml of a 2.3 mol solution of butyl-lithium (0.042 mol) in hexane was added at -20 ° C, after which a precipitate formed. The precipitate was filtered off and washed twice with 20 ml of hexane each time. After drying in vacuo, 2.0 g of compound 17 (40% of theoretical yield) were obtained as a white powder. Angew. Chem. Int. Ed. Engl. 19 (1980), 1010.
1H-NMR (400 MHz, THF): δ=5.34 (br d, J=2.2 Hz, 2H), 5.15 (br d, J=2.2 Hz, 2H), 2.56 (s, 6H). 1 H-NMR (400 MHz, THF): δ = 5.34 (br d, J = 2.2 Hz, 2H), 5.15 (br d, J = 2.2 Hz, 2H), 2.56 (s, 6H).
<실시예 17><Example 17>
((CH3)2N B(CH3)2-브릿지 비스-(시클로펜타디에닐)-티타늄 디클로라이드, 화합물 18)((CH 3 ) 2 NB (CH 3 ) 2 -bridged bis- (cyclopentadienyl) -titanium dichloride, compound 18)
18 18
톨루엔 10 ml 중의 화합물 4 0.18 g (0.7 mmol)의 용액을 -20 ℃에서 10 분에 걸쳐 톨루엔 10 ml 중의 화합물 17 0.081 g (0.7 mmol)의 현탁액에 첨가해서 진한 적색 용액이 형성되었다. 2 시간 동안 실온에서 가온시킨 후, 이 용액을 여과하고, 용매는 진공하에 제거하였다. 형성된 적색 분말을 따뜻한 톨루엔 10 ml 중에 재용해시키고, 불용성 물질은 여과하고, 이 용액을 냉장고에 하룻밤 동안 저장하여 적색 바늘모양의 생성물 0.1 g (이론적인 수율의 43 %)이 형성되었다.A solution of 0.18 g (0.7 mmol) of compound 4 in 10 ml of toluene was added to a suspension of 0.081 g (0.7 mmol) of compound 17 in 10 ml of toluene over 10 minutes at −20 ° C. to form a dark red solution. After warming at room temperature for 2 hours, the solution is filtered and the solvent is removed in vacuo. The red powder formed was redissolved in 10 ml of warm toluene, the insoluble material was filtered off, and the solution was stored overnight in the refrigerator to form 0.1 g (43% of theoretical yield) of the red needle-shaped product.
1H-NMR (400 MHz, CD2Cl2): δ=6.85 (t, J=2.3 Hz, 2H), 6.15 (t, J=2.3 Hz, 2H), 6.1 (t, J=2.8 Hz, 2H), 5.57 (t, J=2.8 Hz, 2H), 1.98 (s, 6H), 0.35 (s, 6H);11B-NMR (64.2 MHz, CD2Cl2): δ=2.8 (br). 1 H-NMR (400 MHz, CD 2 Cl 2 ): δ = 6.85 (t, J = 2.3 Hz, 2H), 6.15 (t, J = 2.3 Hz, 2H), 6.1 (t, J = 2.8 Hz, 2H ), 5.57 (t, J = 2.8 Hz, 2H), 1.98 (s, 6H), 0.35 (s, 6H); 11 B-NMR (64.2 MHz, CD 2 Cl 2 ): δ = 2.8 (br).
<실시예 18>Example 18
(트리부틸스탄닐-디이소프로필포스핀-인덴, 화합물 19)(Tributylstannyl-diisopropylphosphine-indene, compound 19)
19 19
에테르 100 ml를 인덴 3.8 g (0.033 ml)이 들어 있는 둥근 바닥 플라스크에 도입하고, 혼합물을 -20 ℃로 냉각하였다. 헥산 (0.033 몰) 중의 부틸-리튬 2.3 몰 용액 14.4 ml를 5 분에 걸쳐 이 용액에 첨가해서 황색 용액이 형성되었다. 냉각조를 제거한 후, 이 용액을 실온으로 가온하고, 이후에 1.5 시간 동안 교반시켰다. 그 후에, 반응 혼합물을 0 ℃로 냉각하고, 클로로디이소프로필포스핀 5.0 g (0.033 몰)을 첨가하고, 그 후에 침전물이 형성되었다. 냉각조를 제거한 후, 용액을 실온으로 가온하고, 1 시간 동안 교반시켰다. 그 후에, 용액을 -20 ℃로 냉각시키고, 헥산 (0.033 몰) 중의 부틸-리튬 2.3 몰 용액 14.4 ml를 적가하였다. 첨가가 완료되었을 때, 냉각조를 제거하고, 용액을 실온으로 천천히 가온하고, 이후에 1.5 시간 동안 교반시켰다. 현탁액을 0 ℃로 냉각시킨 후, 클로로트리부틸주석 10.1 g (0.031 몰)을 적가하였다. 형성된 현탁액을 실온으로 가온하고 1.5 시간 동안 교반시켰다. 에테르를 진공하에 제거하고, 조생성물을 헥산 중에 다시 용해하고, 용액을 여과하고, 여과액을 진공하에 건조해서 화합물 19 16.6 g (수율: 97 %)을 진한 황색 오일로 수득했다. 두 개의 이성질체를 1.5:1의 비율로 수득했다. 주요 이성질체가 다음과 같이 구별되었다:1H-NMR (400 MHz, CD2Cl2): δ 7.71 (d, J=7.2 Hz, 1H), 7.41 (d, J=7.3 Hz, 1H), 7.13 (m, 2H), 6.96 (m, 1H), 4.28 (Sn 인접 s, 1H), 2.21 (m, 1H), 1.54 (m, 1H), 1.45-0.65 (m, 39H).31P-NMR (161.9 MHz, CD2Cl2): δ-11.3 ppm. 제2의 이성질체는 다음과 같이 확인되었다:1H-NMR (400 MHz, CD2Cl2) δ 7.6 (d, J=7.4 Hz, 1H), 7.46 (d, J=7.2 Hz, 1H), 7.26 (t, J=7.5 Hz, 1H), 7.1 (m, 1H), 6.71 (m, 1H), 3.48 (m, 1H), 2.21 (m, 1H), 1.54 (m, 1H), 1.45-0.65 (m, 39H).31P-NMR (161.9 MHz, CD2Cl2): d-11.5 ppm.100 ml of ether was introduced into a round bottom flask containing 3.8 g (0.033 ml) of indene and the mixture was cooled to -20 ° C. 14.4 ml of a 2.3 mol solution of butyl-lithium in hexane (0.033 mol) was added to this solution over 5 minutes to form a yellow solution. After the cooling bath was removed, the solution was warmed to room temperature and then stirred for 1.5 hours. Thereafter, the reaction mixture was cooled to 0 ° C., and 5.0 g (0.033 mol) of chlorodiisopropylphosphine were added, after which a precipitate formed. After removing the cooling bath, the solution was warmed to room temperature and stirred for 1 hour. Thereafter, the solution was cooled to −20 ° C. and 14.4 ml of a 2.3 mol solution of butyl-lithium in hexane (0.033 mol) was added dropwise. When the addition was complete, the cooling bath was removed and the solution was slowly warmed to room temperature and then stirred for 1.5 hours. After the suspension was cooled to 0 ° C., 10.1 g (0.031 mol) of chlorotributyltin were added dropwise. The resulting suspension was warmed to room temperature and stirred for 1.5 hours. The ether was removed in vacuo, the crude product was dissolved again in hexane, the solution was filtered and the filtrate was dried under vacuum to give 16.6 g (yield: 97%) of compound 19 as a dark yellow oil. Two isomers were obtained in a ratio of 1.5: 1. The main isomers were distinguished as follows: 1 H-NMR (400 MHz, CD 2 Cl 2 ): δ 7.71 (d, J = 7.2 Hz, 1H), 7.41 (d, J = 7.3 Hz, 1H), 7.13 ( m, 2H), 6.96 (m, 1H), 4.28 (Sn adjacent s, 1H), 2.21 (m, 1H), 1.54 (m, 1H), 1.45-0.65 (m, 39H). 31 P-NMR (161.9 MHz, CD 2 Cl 2 ): δ-11.3 ppm. The second isomer was identified as follows: 1 H-NMR (400 MHz, CD 2 Cl 2 ) δ 7.6 (d, J = 7.4 Hz, 1H), 7.46 (d, J = 7.2 Hz, 1H), 7.26 (t, J = 7.5 Hz, 1H), 7.1 (m, 1H), 6.71 (m, 1H), 3.48 (m, 1H), 2.21 (m, 1H), 1.54 (m, 1H), 1.45-0.65 ( m, 39H). 31 P-NMR (161.9 MHz, CD 2 Cl 2 ): d-11.5 ppm.
<실시예 19>Example 19
(디이소프로필포스피노-인데닐-지르코늄 트리클로라이드, 화합물 20)(Diisopropylphosphino-indenyl-zirconium trichloride, compound 20)
20 20
톨루엔 50 ml 중의 화합물 19 15.0 g (0.029 몰)의 용액을 -78 ℃에서 톨루엔 300 ml 중의 99.9 % 순도 ZrCl46.7 g (0.029 몰)의 현탁액에 적가하였다. 첨가가 완료되었을 때, 반응 혼합물을 0.5 시간 동안 -30 ℃에서, 이어서 4 시간 동안 0 ℃에서 교반시켰다. 형성된 황색 침전물을 여과하고, 톨루엔 및 헥산으로 세척하였다. 고체를 진공하에 건조하고, 화합물 20 (수율: 71 %) 8.8 g을 자유 유동성 황색 분말로 수득했다. 30 mmHg하에서 3 시간에 걸쳐 환류하면서 공급된 톨루엔으로, 이어서 속슬레 추출기에서 2 시간에 걸쳐 펜탄으로 추출하여 남아 있는 주석 화합물의 제거에 의해 분말을 더 정제하였다. 형성된 화합물의 불용성 때문에,1H-NMR은 전혀 얻어지지 않았다.A solution of 15.0 g (0.029 mol) of compound 19 in 50 ml of toluene was added dropwise to a suspension of 6.7 g (0.029 mol) of 99.9% purity ZrCl 4 in 300 ml of toluene at −78 ° C. When the addition was complete, the reaction mixture was stirred at −30 ° C. for 0.5 h and then at 0 ° C. for 4 h. The yellow precipitate formed was filtered off and washed with toluene and hexane. The solid was dried under vacuum and 8.8 g of compound 20 (yield: 71%) was obtained as a free flowing yellow powder. The powder was further purified by toluene fed with reflux at 30 mmHg over 3 hours, followed by extraction with pentane over 2 hours in a Soxhlet extractor to remove the remaining tin compound. Because of the insolubility of the formed compound, no 1 H-NMR was obtained.
<실시예 20>Example 20
(디이소프로필포스피노-디클로로보라닐-브릿지 인데닐-시클로펜타디에닐-지르코늄 디클로라이드, 화합물 21)(Diisopropylphosphino-dichloroboranyl-bridge indenyl-cyclopentadienyl-zirconium dichloride, compound 21)
21 21
화합물 20 0.52 g (0.0012 몰) 및 톨루엔 30 ml를 쉬렌크 튜브에 도입하였다. 화합물 2 0.27 g (0.0012 몰)을 5 분에 걸쳐 이 현탁액에 첨가하였다. 황색 현탁액을 3 시간 동안 실온에서 교반시켜 약간 흐린 용액을 수득했다. 침전물을 여과에 의해 제거하여 엷은 황색 톨루엔 용액을 수득했다. 진공하에 톨루엔을 제거한 후에, 생성물이 0.47 g (수율: 87 %)의 양으로 백색 고체로 수득했다.1H-NMR (400 MHz, CD2Cl2) δ 7.84 (유사 dd, J=8.5, 0.8 Hz, 1H), 7.73 (d, J=8.8 Hz, 1H), 7.5 (유사 dt, J=7.8, 0.8 Hz, 1H), 7.38 (m, 2H), 6.98 (m, 1H), 6.67 (m, 1H), 6.64 (m, 1H), 6.54 (m, 1H), 6.29 (m, 1H), 3.39 (septet, J=7.1 Hz, 1H), 2.94 (m, 1H), 1.68 (dd, JH-P=18.1 Hz, J=7.2 Hz, 3H), 1.64 (dd, JH-P=17.4, J=7.2 Hz, 3H), 1.45 (dd, JH-P=15 Hz, J=7.2 Hz, 3H), 1.33 (dd, JH-P=14.6 Hz, J=7.3 Hz, 3H).31P-NMR (161.9 MHz, CD2Cl2): δ 23.1 (br, m);11B-NMR (80 MHz, CD2Cl2): δ-14.8 (br d, J=110 Hz).0.52 g (0.0012 mol) of compound 20 and 30 ml of toluene were introduced into a Schlenk tube. 0.27 g (0.0012 mol) of compound 2 were added to this suspension over 5 minutes. The yellow suspension was stirred for 3 hours at room temperature to give a slightly cloudy solution. The precipitate was removed by filtration to give a pale yellow toluene solution. After toluene was removed under vacuum, the product was obtained as a white solid in an amount of 0.47 g (yield: 87%). 1 H-NMR (400 MHz, CD 2 Cl 2 ) δ 7.84 (similar dd, J = 8.5, 0.8 Hz, 1H), 7.73 (d, J = 8.8 Hz, 1H), 7.5 (similar dt, J = 7.8, 0.8 Hz, 1H), 7.38 (m, 2H), 6.98 (m, 1H), 6.67 (m, 1H), 6.64 (m, 1H), 6.54 (m, 1H), 6.29 (m, 1H), 3.39 ( septet, J = 7.1 Hz, 1H), 2.94 (m, 1H), 1.68 (dd, J HP = 18.1 Hz, J = 7.2 Hz, 3H), 1.64 (dd, J HP = 17.4, J = 7.2 Hz, 3H ), 1.45 (dd, J HP = 15 Hz, J = 7.2 Hz, 3H), 1.33 (dd, J HP = 14.6 Hz, J = 7.3 Hz, 3H). 31 P-NMR (161.9 MHz, CD 2 Cl 2 ): δ 23.1 (br, m); 11 B-NMR (80 MHz, CD 2 Cl 2 ): δ-14.8 (br d, J = 110 Hz).
<실시예 21>Example 21
(트리부틸스탄닐-디메틸포스피노-인덴, 화합물 22)(Tributylstannyl-dimethylphosphino-indene, compound 22)
22 22
에테르 150 ml를 인덴 5.5 g (0.047 몰)이 들어 있는 둥근 바닥 플라스크에 도입하고, 혼합물을 -20 ℃로 냉각하였다. 헥산 (0.048 몰) 중의 부틸-리튬 2.3 몰 용액 20.8 ml를 5 분에 걸쳐 이 용액에 첨가해서 황색 용액이 형성되었다. 냉각조를 제거한 후, 용액을 실온으로 가온하고, 이후에 1 시간 동안 교반시켰다. 반응 혼합물을 -30 ℃로 냉각시킨 후, 에테르 30 ml 중의 클로로디메틸포스핀 4.6 g (0.048 몰)을 20 분에 걸쳐 첨가하고, 침전물이 형성되었다. 2 시간 동안 -20 ℃에서 교반시킨 후, 헥산 (0.048 몰) 중의 부틸-리튬 2.3 몰 용액의 20.8 ml를 적가하였다. 첨가가 완료되었을 때, 냉각조를 제거하고, 용액을 실온으로 천천히 가온하고, 이후에 1.5 시간 동안 교반시켰다. 현탁액을 0 ℃로 냉각시킨 후, 클로로트리부틸주석 15.6 g (0.048 몰)을 적가하였다. 형성된 현탁액을 실온으로 가온하고, 1.5 시간 동안 교반시켰다. 에테르를 진공하에 제거하고, 조생성물을 헥산 중에 다시 용해하고, 용액을 여과하고, 여과액을 진공하에 건조시키고, 화합물 22 17.4 g (수율: 78 %)을 진한 황색 오일로 수득했다.1H-NMR (400 MHz, CD2Cl2) δ 7.67 (d, J=7.5 Hz, 1H), 7.47 (d, J=7.4 Hz, 1H), 7.18 (m, 2H), 6.83 (m, 1H), 4.28 (Sn 인접 s, 1H), 1.43-0.78 (m, 33H).31P-NMR (161.9 MHz, CD2Cl2): δ-61.6 ppm.150 ml of ether was introduced into a round bottom flask containing 5.5 g (0.047 mol) of indene and the mixture was cooled to -20 ° C. 20.8 ml of a 2.3 mol solution of butyl-lithium in hexane (0.048 mol) was added to this solution over 5 minutes to form a yellow solution. After removing the cooling bath, the solution was allowed to warm to room temperature and then stirred for 1 hour. After cooling the reaction mixture to −30 ° C., 4.6 g (0.048 mol) of chlorodimethylphosphine in 30 ml of ether were added over 20 minutes, and a precipitate formed. After stirring at −20 ° C. for 2 hours, 20.8 ml of a 2.3 mol solution of butyl-lithium in hexane (0.048 mol) was added dropwise. When the addition was complete, the cooling bath was removed and the solution was slowly warmed to room temperature and then stirred for 1.5 hours. After the suspension was cooled to 0 ° C., 15.6 g (0.048 mol) of chlorotributyltin were added dropwise. The resulting suspension was warmed to room temperature and stirred for 1.5 hours. The ether was removed in vacuo, the crude product was dissolved again in hexane, the solution was filtered, the filtrate was dried under vacuum and compound 22 17.4 g (yield: 78%) was obtained as a dark yellow oil. 1 H-NMR (400 MHz, CD 2 Cl 2 ) δ 7.67 (d, J = 7.5 Hz, 1H), 7.47 (d, J = 7.4 Hz, 1H), 7.18 (m, 2H), 6.83 (m, 1H ), 4.28 (Sn adjacent s, 1 H), 1.43-0.78 (m, 33 H). 31 P-NMR (161.9 MHz, CD 2 Cl 2 ): δ-61.6 ppm.
<실시예 22><Example 22>
(디메틸포스피노-인데닐-지르코늄 트리클로라이드, 화합물 23)(Dimethylphosphino-indenyl-zirconium trichloride, compound 23)
23 23
톨루엔 50 ml 중의 화합물 22 17.0 g (0.037 몰)의 용액을 -78 ℃에서 톨루엔 200 ml 중의 순도 99.9 %의 ZrCl48.5 g (0.036 몰)의 현탁액에 첨가하였다. 첨가가 완료되었을 때, 반응 혼합물을 0.5 시간 동안 -30 ℃에서, 이어서 4 시간 동안 0 ℃에서 교반시켰다. 형성된 황색 침전물을 여과하고, 톨루엔 및 헥산으로 세척하였다. 고체를 진공하에 건조시키고, 화합물 23 8.3 g (수율: 61 %)을 자유 유동성 황색 분말로 수득했다. 30 mmHg하에서 3 시간에 걸쳐 환류하에서 공급된 톨루엔으로, 속슬레 추출기에서 2 시간에 걸쳐 펜탄으로 추출에 의해 남아 있는 주석 화합물의 제거에 의해 분말을 더 정제하고, 생성물 7.2 g (수율: 53 %)을 수득했다. 이 화합물의 불용성 때문에,1H-NMR이 전혀 얻어지지 않았다.A solution of 17.0 g (0.037 mol) of compound 22 in 50 ml of toluene was added to a suspension of 8.5 g (0.036 mol) of 99.9% purity ZrCl 4 in 200 ml of toluene at −78 ° C. When the addition was complete, the reaction mixture was stirred at −30 ° C. for 0.5 h and then at 0 ° C. for 4 h. The yellow precipitate formed was filtered off and washed with toluene and hexane. The solid was dried under vacuum and 8.3 g (yield: 61%) of compound 23 were obtained as a free flowing yellow powder. Toluene supplied under reflux over 3 hours at 30 mmHg, further purified by removal of the remaining tin compound by extraction with pentane over 2 hours in a Soxhlet extractor, product 7.2 g (yield: 53%) Obtained. Because of the insolubility of this compound, no 1 H-NMR was obtained.
<실시예 23><Example 23>
(디메틸포스피노-디클로로보라닐-브릿지 인데닐-시클로펜타디에닐-지르코늄 디클로라이드, 화합물 24)(Dimethylphosphino-dichloroboranyl-bridge indenyl-cyclopentadienyl-zirconium dichloride, compound 24)
24 24
톨루엔 30 ml 및 화합물 23 0.55 g (0.0015 몰)을 쉬렌크 튜브에 도입하였다. 화합물 2 0.31 g (0.0014 몰)을 5 분에 걸쳐 이 현탁액에 첨가하였다. 황색 현탁액을 6.5 시간 동안 실온에서 교반시키고, 약간 흐린 용액을 수득했다. 침전물을 여과에 의해 제거하고, 엷은 황색 톨루엔 용액을 수득했다. 진공하에 톨루엔의 제거 후에, 생성물을 백색 고체로 수득했다. 생성물을 헥산으로 세척하고, 진공하에 건조한 후, 화합물 24를 엷은 백색 고체 (0.54 g; 수율: 76 %)로 수득했다.1H-NMR (400 MHz, CD2Cl2) δ 7.84 (유사 dd, J=7.4 Hz, 1.0 Hz, 1H), 7.60 (m, 2H), 7.51 (m, 1H), 7.38 (m, 1H), 6.93 (m, 1H), 6.71 (m, 1H), 6.66 (m, 1H), 6.49 (m, 1H), 6.30 (br s, 1H), 2.11 (d JH-P=11.9 Hz, 3H), 1.94 (d, JH-P=11.9 Hz, 3H).31P-NMR (161.9 MHz, CD2Cl2)-5.9 (br, m);11B-NMR (80 MHz, CD2Cl2) δ-14.6 (br d, JB-P=126 Hz).30 ml of toluene and 0.55 g (0.0015 mol) of compound 23 were introduced into a Schlenk tube. 0.31 g (0.0014 mol) of compound 2 were added to this suspension over 5 minutes. The yellow suspension was stirred for 6.5 hours at room temperature and a slightly cloudy solution was obtained. The precipitate was removed by filtration to give a pale yellow toluene solution. After removal of toluene under vacuum, the product was obtained as a white solid. The product was washed with hexanes and dried in vacuo to give compound 24 as a pale white solid (0.54 g; yield: 76%). 1 H-NMR (400 MHz, CD 2 Cl 2 ) δ 7.84 (similar dd, J = 7.4 Hz, 1.0 Hz, 1H), 7.60 (m, 2H), 7.51 (m, 1H), 7.38 (m, 1H) , 6.93 (m, 1H), 6.71 (m, 1H), 6.66 (m, 1H), 6.49 (m, 1H), 6.30 (br s, 1H), 2.11 (d J HP = 11.9 Hz, 3H), 1.94 (d, J HP = 11.9 Hz, 3H). 31 P-NMR (161.9 MHz, CD 2 Cl 2 ) -5.9 (br, m); 11 B-NMR (80 MHz, CD 2 Cl 2 ) δ-14.6 (br d, J BP = 126 Hz).
<실시예 24><Example 24>
(2-메틸인덴, 화합물 26)(2-methylindene, compound 26)
25 2625 26
2-인다논 38.7 g (0.29 몰) 및 에테르 300 ml를 둥근 바닥 플라스크에 도입하였다. 에테르 150 ml로 희석한, 에테르 (0.29 몰) 중의 CH3MgI 3.0 몰 용액 96.7 ml를 두 번째 플라스크에 도입하였다. 그 후에, 2-인다논 용액을 환류가 유지되는 양으로 캐뉼러 (cannula)를 통해 CH3MgI 용액에 첨가하고, 침전물이 형성되었다. 첨가가 완료되었을 때, 추가의 4 시간 동안 환류하에서 현탁액을 유지하고, 0 ℃로 냉각하고, 그 후에 NH4Cl의 포화 용액 100 ml를 천천히 첨가하였다. 생성물을 에테르로 추출하고, MgSO4로 건조하였다. 진공하에 용매를 제거한 후, 2-메틸-2-인다놀 (화합물 25) 30.1 g (수율: 70 %)을 오일상 고체로 수득했다.1H-NMR (400 MHz, CDCl3) δ 7.15 (br m, 4H), 3.01 (s, 2H), 2.99 (s, 2H), 1.5 (s, 3H); OH 변화성.38.7 g (0.29 mol) of 2-indanonone and 300 ml of ether were introduced into a round bottom flask. Diluted with 150 ml of ether, 96.7 ml of a 3.0 molar solution of CH 3 MgI in ether (0.29 mol) was introduced into a second flask. Thereafter, the 2-indanonone solution was added to the CH 3 MgI solution via a cannula in an amount such that reflux was maintained, and a precipitate formed. When the addition was complete, the suspension was kept under reflux for an additional 4 hours, cooled to 0 ° C., after which slowly 100 ml of saturated solution of NH 4 Cl were added. The product was extracted with ether and dried over MgSO 4 . After removal of solvent in vacuo, 30.1 g (yield: 70%) of 2-methyl-2-indanol (Compound 25) were obtained as an oily solid. 1 H-NMR (400 MHz, CDCl 3 ) δ 7.15 (br m, 4H), 3.01 (s, 2H), 2.99 (s, 2H), 1.5 (s, 3H); OH variability.
화합물 25 25.5 g (0.17 몰), p-톨루엔술폰산 3.2 g (0.017 몰) 및 헥산 500 ml를 딘-스타르크 (Dean-Stark) 수집기가 있는 둥근 바닥 플라스크에 도입하였다. 이 현탁액을 3 시간 동안 환류하에서 유지하였다. 냉각시킨 후, 헥산 분획을 불용성 생성물로부터 제거하고, 용매는 진공하에 제거하여 오일이 남았고, 이어서 0.03 mbar하에서 45 ℃에서 짧은 증류 칼럼에서 증류시키고, 그 후에 화합물 26 15 g (수율: 68 %)을 수득했다.1H-NMR (400 MHz, CDCl3) δ 7.33 (d, J=7.6 Hz, 1H), 7.21 (m, 2H), 7.06 (유사 d t, J=7.2, 1.4 Hz, 1H), 6.45 (br s, 1H), 3.25 (s, 2H), 2.12 (s, 3H).25.5 g (0.17 mole) of compound 25, 3.2 g (0.017 mole) of p-toluenesulfonic acid and 500 ml of hexane were introduced into a round bottom flask with Dean-Stark collector. This suspension was kept under reflux for 3 hours. After cooling, the hexane fraction was removed from the insoluble product, the solvent was removed under vacuum to leave an oil, followed by distillation in a short distillation column at 45 ° C. under 0.03 mbar, after which compound 26 15 g (yield: 68%) were obtained. Obtained. 1 H-NMR (400 MHz, CDCl 3 ) δ 7.33 (d, J = 7.6 Hz, 1H), 7.21 (m, 2H), 7.06 (similar dt, J = 7.2, 1.4 Hz, 1H), 6.45 (br s , 1H), 3.25 (s, 2H), 2.12 (s, 3H).
1. Morrison, H; Giacherio, D., J. Org. Chem. 1982, 47, 1058.1. Morrison, H; Giacherio, D., J. Org. Chem. 1982, 47, 1058.
2. Ready, T. E.; Chien, J. C. W.; Rausch, M. D., J. Organom. Chem. 591, 1996, 21.2. Ready, T. E .; Chien, J. C. W .; Rausch, M. D., J. Organom. Chem. 591, 1996, 21.
3. Wilt, Pawlikowki, Wieczorek, J. Org. Chem. 37, 1972, 824.3. Wilt, Pawlikowki, Wieczorek, J. Org. Chem. 37, 1972, 824.
을 참고로 한다.See also.
<실시예 25><Example 25>
(트리부틸스탄닐-디이소프로필포스피노-2-메틸인덴, 화합물 27)(Tributylstannyl-diisopropylphosphino-2-methylindene, compound 27)
27 27
에테르 150 ml를 2-메틸인덴 화합물 26 5.08 g (0.039 몰)이 들어 있는 둥근 바닥 플라스크에 도입하고, 혼합물을 -20 ℃로 냉각하고, 헥산 (0.039 몰) 중의 부틸-리튬 2.3 몰 용액의 17.0 ml를 5 분에 걸쳐 이 용액에 첨가하고, 황색 용액이 형성되었다. 냉각조를 제거한 후, 용액을 실온으로 가온하고, 이후에 1 시간 동안 교반시켰다. 그 후에, 반응 혼합물을 -20 ℃로 냉각하고, 클로로디이소프로필포스핀 5.8 g (0.039 몰)을 5 분에 걸쳐 첨가하고, 침전물이 형성되었다. 그 후에, 냉각조를 제거하고, 반응 혼합물을 1 시간 동안 실온에서 교반시켰다. -20 ℃로 냉각시킨 후, 헥산 (0.039 몰) 중의 부틸-리튬 2.3 몰 용액의 17.0 ml를 적가하였다. 첨가가 완료되었을 때, 냉각조를 제거하고, 용액을 실온으로 천천히 가온하고, 이후에 1.5 시간 동안 교반시켰다. 현탁액을 0 ℃로 냉각한 후, 클로로디부틸주석 12.4 g (0.038 몰)을 적가하였다. 형성된 현탁액을 실온으로 가열하고, 1.5 시간 동안 교반시켰다. 에테르를 진공하에 제거하고, 헥산 중에 조생성물을 다시 용해시키고, 용액을 여과하고, 여과액은 진공하에 건조시키고, 화합물 27 20.4 g (수율: 98 %)을 진한 황색 오일로 수득했다.31P-NMR에 의해 두 개의 이성질체가 확인되었다.31P-NMR (161.9 MHz, CD2Cl2) δ-5.9 및 -6.6 (2:1의 비율).150 ml of ether was introduced into a round bottom flask containing 5.08 g (0.039 mol) of 2-methylindene compound 26, the mixture was cooled to -20 ° C and 17.0 of a 2.3 mol solution of butyl-lithium in hexane (0.039 mol) ml was added to this solution over 5 minutes and a yellow solution formed. After removing the cooling bath, the solution was allowed to warm to room temperature and then stirred for 1 hour. Thereafter, the reaction mixture was cooled to -20 ° C, 5.8 g (0.039 mol) of chlorodiisopropylphosphine was added over 5 minutes, and a precipitate formed. After that, the cooling bath was removed and the reaction mixture was stirred for 1 hour at room temperature. After cooling to -20 ° C, 17.0 ml of a 2.3 mol solution of butyl-lithium in hexane (0.039 mol) was added dropwise. When the addition was complete, the cooling bath was removed and the solution was slowly warmed to room temperature and then stirred for 1.5 hours. After the suspension was cooled to 0 ° C., 12.4 g (0.038 mol) of chlorodibutyltin were added dropwise. The suspension formed was heated to room temperature and stirred for 1.5 hours. The ether was removed in vacuo, the crude product was dissolved again in hexane, the solution was filtered, the filtrate was dried under vacuum and 20.4 g (yield: 98%) of compound 27 were obtained as a dark yellow oil. Two isomers were identified by 31 P-NMR. 31 P-NMR (161.9 MHz, CD 2 Cl 2 ) δ-5.9 and −6.6 (ratio of 2: 1).
<실시예 26>Example 26
(디이소프로필포스피노-2-메틸인데닐-지르코늄 트리클로라이드, 화합물 28)(Diisopropylphosphino-2-methylindenyl-zirconium trichloride, compound 28)
28 28
염화 메틸렌 100 ml 중의 화합물 27 17.7 g (0.033 몰)의 용액을 -25 ℃에서 10 분에 걸쳐 염화 메틸렌 200 ml로 99.9 % 순도 ZrCl47.7 g (0.033 몰)의 현탁액에 첨가하였다. 첨가가 완료되었을 때, 반응 혼합물을 3 시간에 걸쳐 10 ℃로 천천히 가온하고, 그 후에 투명한 오렌지색 용액이 형성되었다. 실온에서 1 시간 후에, 용매를 진공하에 제거하였고, 형성된 오일을 헥산 50 ml로 2회 세척하고, 그 후에 오일상 조생성물 (화합물 28)을 수득했고, 이를 화합물 29의 제조에 직접 사용하였다. 화합물의 불용성 때문에,1H-NMR이 전혀 얻어지지 않았다.A solution of 17.7 g (0.033 mol) of compound 27 in 100 ml of methylene chloride was added to a suspension of 7.7 g (0.033 mol) of 99.9% purity ZrCl 4 in 200 ml of methylene chloride over 10 minutes at −25 ° C. When the addition was complete, the reaction mixture was slowly warmed to 10 ° C. over 3 hours, after which a clear orange solution formed. After 1 hour at room temperature, the solvent was removed in vacuo and the oil formed was washed twice with 50 ml of hexane, after which an oily crude product (compound 28) was obtained, which was used directly for the preparation of compound 29. Because of the insolubility of the compound, no 1 H-NMR was obtained.
<실시예 27>Example 27
(디이소프로필포스피노-디클로로보라닐-브릿지 2-메틸인데닐-시클로펜타디에닐-지르코늄 디클로라이드, 화합물 29)(Diisopropylphosphino-dichloroboranyl-bridge 2-methylindenyl-cyclopentadienyl-zirconium dichloride, compound 29)
29 29
화합물 2 5.5 g (0.025 몰)을 톨루엔 200 ml 중의 불순한 화합물 28 0.025 몰이 들어 있는 둥근 바닥 플라스크에 0 ℃에서 5 분에 걸쳐 도입하였다. 0 ℃에서 1 시간 후에, 교반이 종결되었고, 용해성 툴루엔 분획물을 형성된 오일로부터 제거하였다. 진공하에 톨루엔을 제거한 후에, 헥산 100 ml를 오일상 고체에 첨가하고, 황색 분말 7.4 g (수율: 54 %)이 약 90 %의 순도로 형성되었다. 환류하에 공급된 펜탄으로 속슬레 추출기에서 생성물을 더 정제하였다. 최종 생성물은 엷은 황색 분말을 포함하였다.1H-NMR (400 MHz, CD2Cl2) δ 8.67 (br d, J=7.6 Hz, 1H), 7.71 (m, 1H), 7.35 (m, 2H), 6.62 (br s, 1H), 6.54 (br s, 1H), 6.47 (m, 1H), 6.33 (m, 1H), 6.06 (br s, 1H), 3.3 (br m, 1H), 3.2 (br m, 1H), 2.6 (s, 3H), 1.78 (dd, J=7.1 Hz, JH-P=15.3 Hz, 3H), 1.70 (dd, J=7.2 Hz, JH-P=15.7 Hz, 3H). 1.57 (dd, J=7.1 Hz, HH-P=15.3 Hz, 3H), 1.12 (dd, J=7.1 Hz, JH-P=14.0 Hz, 3H).31P-NMR (161.9 MHz, CD2Cl2) 28.4 (br m);11B (80 MHz, CD2Cl2) δ-14.3 (br d, JP-B=106 Hz).5.5 g (0.025 mol) of compound 2 were introduced into a round bottom flask containing 0.025 mol of impure compound 28 in 200 ml of toluene at 0 ° C. over 5 minutes. After 1 hour at 0 ° C., stirring was terminated and the soluble toluene fraction was removed from the oil formed. After toluene was removed in vacuo, 100 ml of hexane was added to the oily solid and 7.4 g (yield: 54%) of yellow powder was formed with a purity of about 90%. The product was further purified in a Soxhlet extractor with pentane fed under reflux. The final product contained a pale yellow powder. 1 H-NMR (400 MHz, CD 2 Cl 2 ) δ 8.67 (br d, J = 7.6 Hz, 1H), 7.71 (m, 1H), 7.35 (m, 2H), 6.62 (br s, 1H), 6.54 (br s, 1H), 6.47 (m, 1H), 6.33 (m, 1H), 6.06 (br s, 1H), 3.3 (br m, 1H), 3.2 (br m, 1H), 2.6 (s, 3H ), 1.78 (dd, J = 7.1 Hz, J HP = 15.3 Hz, 3H), 1.70 (dd, J = 7.2 Hz, J HP = 15.7 Hz, 3H). 1.57 (dd, J = 7.1 Hz, H HP = 15.3 Hz, 3H), 1.12 (dd, J = 7.1 Hz, J HP = 14.0 Hz, 3H). 31 P-NMR (161.9 MHz, CD 2 Cl 2 ) 28.4 (br m); 11 B (80 MHz, CD 2 Cl 2 ) δ-14.3 (br d, J PB = 106 Hz).
<실시예 28><Example 28>
(비스(트리메틸실릴)-디페닐포스피노)-시클로펜타디엔, 화합물 30)(Bis (trimethylsilyl) -diphenylphosphino) -cyclopentadiene, compound 30)
30 30
헥산 (0.19 몰) 중의 부틸-리튬 2.5 몰 용액 76.6 ml를 0 ℃에서 10 분에 걸쳐 에테르 500 ml 중의 화합물 1 (40.2 g; 0.19 몰) 용액에 첨가하였다. 첨가가 완료되었을 때, 배쓰를 제거하고, 용액을 1 시간 동안 실온에서 교반시켰다. 0 ℃로 냉각시킨 후, 클로로디페닐포스핀 42.2 g (0.19 몰)을 10 분에 걸쳐 첨가하고, 그 후에 배쓰를 제거하고, 현탁액을 실온으로 가온하였다. 1 시간 동안 실온에서 교반시킨 후, 에테르를 진공하에 제거하고, 생성물을 헥산 중에 다시 용해시켰다. 염을 여과한 후, 헥산을 진공하에 제거하고, 화합물 30 69.1 g (수율: 91 %)을 오일로 수득했다.1H-NMR (400 MHz, CDCl3) δ 7.45 (m, 4H), 7.35 (m, 6H), 6.8 (m, 1H), 6.65 (m, 1H), 6.6 (m, 1H), 0 (s, 18H).31P-NMR (161.9 MHz, CDCl3): δ-19.5 ppm.76.6 ml of a 2.5 mol solution of butyl-lithium in hexane (0.19 mol) was added to a solution of Compound 1 (40.2 g; 0.19 mol) in 500 ml of ether at 0 ° C. over 10 minutes. When the addition was complete, the bath was removed and the solution was stirred for 1 hour at room temperature. After cooling to 0 ° C., 42.2 g (0.19 mol) of chlorodiphenylphosphine were added over 10 minutes, after which the bath was removed and the suspension was allowed to warm to room temperature. After stirring for 1 hour at room temperature, the ether was removed in vacuo and the product dissolved again in hexane. After the salts were filtered off, the hexanes were removed in vacuo and 69.1 g (yield: 91%) of compound 30 were obtained as an oil. 1 H-NMR (400 MHz, CDCl 3 ) δ 7.45 (m, 4H), 7.35 (m, 6H), 6.8 (m, 1H), 6.65 (m, 1H), 6.6 (m, 1H), 0 (s , 18H). 31 P-NMR (161.9 MHz, CDCl 3 ): δ-19.5 ppm.
<실시예 29><Example 29>
(트리메틸실릴-디페닐포스피노-시클로펜타디에닐-지르코늄 트리클로라이드, 화합물 31)(Trimethylsilyl-diphenylphosphino-cyclopentadienyl-zirconium trichloride, compound 31)
31 31
염화 메틸렌 200 ml 중의 화합물 30 (69.1 g, 0.175 몰) 용액을 캐뉼러를 통해 염화 메틸렌 200 ml 중의 99.9 % 순도 ZrCl441.5 g (0.178 몰)의 현탁액에 첨가하고, 이 혼합물을 8 시간 동안 실온에서 교반시켰다. 이 시간 중에, 용액은 뿌옇게 되었다. 고체를 여과하고, 톨루엔 20 ml로 2회, 이어서 헥산 20 ml로 2회 세척하고, 진공하에 건조시켰다. 생성물은 엷은 황색 분말 35 g (수율: 39 %)을 포함하였다. 생성물의 불용성 때문에,1H-NMR이 전혀 얻어지지 않았다.A solution of Compound 30 (69.1 g, 0.175 mol) in 200 ml of methylene chloride was added via cannula to a suspension of 41.5 g (0.178 mol) of 99.9% purity ZrCl 4 in 200 ml of methylene chloride and the mixture was allowed to stand at room temperature for 8 hours. Stirred. During this time, the solution became cloudy. The solid was filtered off, washed twice with 20 ml of toluene and then twice with 20 ml of hexanes and dried under vacuum. The product contained 35 g pale yellow powder (yield: 39%). Because of the insolubility of the product, no 1 H-NMR was obtained.
<실시예 30><Example 30>
(디페닐포스피노-디클로로보라닐-브릿지 트리메틸실릴시클로펜타디에닐-시클로펜타디에닐-지르코늄 디클로라이드, 화합물 32)(Diphenylphosphino-dichloroboranyl-bridge trimethylsilylcyclopentadienyl-cyclopentadienyl-zirconium dichloride, compound 32)
32 32
화합물 2 (2.6 g, 0.012 몰)의 용액을 0 ℃에서 톨루엔 100 ml 중의 화합물 31 (5.6 g, 0.011 몰)의 현탁액에 첨가하였다. 혼합물을 5 시간 동안 0 ℃에서 교반시킨 후, 황갈색 고체를 여과에 의해 제거하고, 백색 용액을 수득했다. 진공하에 톨루엔을 제거하고, 펜탄과 함께 남아 있는 고체를 세척한 후, 화합물 32를 공기-고민감성 백색 분말 (5.5 g; 수율: 81 %)로 수득했다.1H-NMR (400 MHz, CD2Cl2) δ: 7.8-7.5 (m, 10H), 7.06 (m, 1H), 6.92 (m, 1H), 6.83 (m, 1H), 6.75 (m, 2H), 6.68 (m, 1H), 6.63 (m, 1H), 0.26 (s, 9H).31P-NMR (161.9 MHz, CD2Cl2) δ 0 (br, m);11B-NMR (80 MHz, CD2Cl2) δ-16.3 (br d, JB-P=82 Hz).A solution of compound 2 (2.6 g, 0.012 mole) was added to a suspension of compound 31 (5.6 g, 0.011 mole) in 100 ml of toluene at 0 ° C. After the mixture was stirred for 5 hours at 0 ° C., the tan solid was removed by filtration and a white solution was obtained. After toluene was removed in vacuo and the remaining solid with pentane was washed, compound 32 was obtained as an air-sensitive white powder (5.5 g; yield: 81%). 1 H-NMR (400 MHz, CD 2 Cl 2 ) δ: 7.8-7.5 (m, 10H), 7.06 (m, 1H), 6.92 (m, 1H), 6.83 (m, 1H), 6.75 (m, 2H ), 6.68 (m, 1 H), 6.63 (m, 1 H), 0.26 (s, 9 H). 31 P-NMR (161.9 MHz, CD 2 Cl 2 ) δ 0 (br, m); 11 B-NMR (80 MHz, CD 2 Cl 2 ) δ-16.3 (br d, J BP = 82 Hz).
<실시예 31><Example 31>
(디이소프로필포스피노-시클로펜타디에닐-리튬, 화합물 33)(Diisopropylphosphino-cyclopentadienyl-lithium, compound 33)
33 33
에테르 50 ml를 시클로펜타디에닐-리튬 1.68 g (0.023 몰)이 들어 있는 둥근 바닥 플라스크에 도입하였다. 반응 플라스크를 -20 ℃로 냉각시킨 후, 클로로디이소프로필포스핀 3.6 g (0.023 몰)을 적가하였다. 첨가가 완료되었을 때, 냉각조를 0 ℃로 가온하고, 반응 혼합물을 1 시간 동안 교반시켰다. 그 후에, 에테르를 진공하에 제거하고, 생성물을 톨루엔에 용해시키고, 용액을 여과하였다. 프리트를 톨루엔 10 ml로 2회 세척한 후, 반응 혼합물을 -20 ℃로 냉각하고, 헥산 (0.023 몰) 중의 부틸리튬 2.5 몰 용액의 9.3 ml를 첨가하고, 오렌지색 용액이 형성되었다. 적은 분획물은 NMR 분석을 하고, 진공하에 톨루엔의 제거 및 헥산과 함께 형성된 오일의 세척 후에 엷은 황색 고체 (화합물 33)를 수득했다.1H-NMR (400 MHz, THF) δ: 5.89 (m, 2H), 5.83 (br s, 2H), 1.86 (m, 2H), 1.0-0.8 (m, 12H). 대부분의 양은 화합물 34의 제조에 직접 사용되었다.50 ml of ether was introduced into a round bottom flask containing 1.68 g (0.023 mol) of cyclopentadienyl-lithium. After cooling the reaction flask to -20 ° C, 3.6 g (0.023 mol) of chlorodiisopropylphosphine was added dropwise. When the addition was complete, the cooling bath was warmed to 0 ° C. and the reaction mixture was stirred for 1 hour. Thereafter, the ether was removed in vacuo, the product was dissolved in toluene and the solution was filtered. After washing the frit twice with 10 ml of toluene, the reaction mixture was cooled to -20 ° C, 9.3 ml of a 2.5 mol solution of butyllithium in hexane (0.023 mol) was added and an orange solution formed. The small fractions were subjected to NMR analysis to give a pale yellow solid (Compound 33) after removal of toluene under vacuum and washing of the oil formed with hexane. 1 H-NMR (400 MHz, THF) δ: 5.89 (m, 2H), 5.83 (br s, 2H), 1.86 (m, 2H), 1.0-0.8 (m, 12H). Most of the amount was used directly in the preparation of compound 34.
<실시예 32><Example 32>
(디이소프로필포스피노-디메틸보라닐-브릿지 비스-시클로펜타디에닐-티타늄 디클로라이드, 화합물 34)(Diisopropylphosphino-dimethylboranyl-bridge bis-cyclopentadienyl-titanium dichloride, compound 34)
34 34
톨루엔 50 ml 중의 화합물 4 6.1 g (0.023 몰)의 용액을 -78 ℃에서 전술한 반응으로부터 화합물 33 (0.023 몰)의 톨루엔 용액에 첨가하였다. 혼합물을 30 분 동안 - 78 ℃에서 교반시킨 후, 냉각조를 제거하고, 이후에 용액을 2 시간 동안 실온에서 교반시켰다. 그 후에, 고체를 여과로 제거하고, 톨루엔을 진공하에 제거하였다. 이어서, 헥산을 적색 오일상 생성물에 첨가하고, 적색 분말이 형성되었고, 이를 여과하고, 헥산 20 ml로 2회 세척하고, 진공하에 건조하고, 그 후에 화합물 34가 적색 분말 (5.95 g, 수율: CpLi를 기준으로 61 %)로 형성되었다.1H-NMR (400 MHz, CD2Cl2) δ: 6.96 (m, 2H), 6.94 (유사 t, J=2.4 Hz, 2H), 6.59 (m, 2H), 6.42 (m, 2H), 2.58 (m, 2H), 1.44 (dd, J=7.3 Hz, JH-P=14.7 Hz, 6H), 1.27 (dd, J=7.2 Hz, JH-P=13.1 Hz, 6H), 0.31 (d, JH-P=16.4 Hz, 6H).31P-NMR (161.9 MHz, CD2Cl2) δ 28.7 (br m);11B-NMR (80 MHz, CD2Cl2) δ-29.7 (br m).A solution of 6.1 g (0.023 mol) of compound 4 in 50 ml of toluene was added to the toluene solution of compound 33 (0.023 mol) from the reaction described above at -78 ° C. The mixture was stirred for 30 minutes at -78 ° C, then the cooling bath was removed, after which the solution was stirred for 2 hours at room temperature. Thereafter, the solids were removed by filtration and toluene was removed under vacuum. Hexane was then added to the red oily product, which formed a red powder, which was filtered off, washed twice with 20 ml of hexane, dried under vacuum, and then compound 34 was red powder (5.95 g, yield: CpLi). 61%). 1 H-NMR (400 MHz, CD 2 Cl 2 ) δ: 6.96 (m, 2H), 6.94 (similar t, J = 2.4 Hz, 2H), 6.59 (m, 2H), 6.42 (m, 2H), 2.58 (m, 2H), 1.44 (dd, J = 7.3 Hz, J HP = 14.7 Hz, 6H), 1.27 (dd, J = 7.2 Hz, J HP = 13.1 Hz, 6H), 0.31 (d, J HP = 16.4 Hz, 6H). 31 P-NMR (161.9 MHz, CD 2 Cl 2 ) δ 28.7 (br m); 11 B-NMR (80 MHz, CD 2 Cl 2 ) δ-29.7 (br m).
<실시예 33><Example 33>
(디메틸포스피노-트리부틸스탄닐-2-메틸인덴, 화합물 35)(Dimethylphosphino-tributylstannyl-2-methylindene, compound 35)
35 35
에테르 100 ml를 2-메틸인덴 (화합물 26) 6.76 g (0.052 몰)이 들어 있는 둥근 바닥 플라스크에 도입하고, 혼합물을 -20 ℃로 냉각시켰다. 헥산 (0.052 몰) 중의 부틸-리튬 2.5 몰 용액 21 ml를 5 분에 걸쳐 이 용액에 첨가하고, 황색 용액이 형성되었다. 냉각조를 제거한 후, 용액을 실온으로 가온하고, 이후에 1 시간 동안 교반시켰다. 반응 혼합물을 -20 ℃로 냉각시킨 후, 클로로디메틸포스핀 5.0 g (0.052 몰)을 5 분에 걸쳐 첨가하고, 침전물이 형성되었다. 이어서, 냉각조를 제거하고, 반응 혼합물을 1 시간 동안 실온에서 교반시켰다. -20 ℃로 냉각시킨 후, 헥산 (0.052 몰) 중의 부틸-리튬 2.5 몰 용액의 21.0 ml를 적가하였다. 첨가가 완료되었을 때, 냉각조를 제거하고, 그 후에 용액을 실온으로 천천히 가온하고, 1.5 시간 동안 교반시켰다. 현탁액을 0 ℃로 냉각시킨 후, 클로로트리부틸주석 16.9 g (0.052 몰)을 적가하였다. 형성된 현탁액을 실온으로 가온하고, 1.5 시간 동안 교반시켰다. 진공하에 에테르를 제거한 후, 조생성물을 헥산 중에 다시 용해시키고, 용액을 여과하고, 여과액을 진공하에 건조하고, 화합물 35 24.3 g (수율: 98 %)을 진한 황색 오일로 수득했다.31P-NMR (161.9 MHz, CD2Cl2) δ-68.5 (s).100 ml of ether was introduced into a round bottom flask containing 6.76 g (0.052 mol) of 2-methylindene (Compound 26) and the mixture was cooled to -20 ° C. 21 ml of a 2.5 molar solution of butyl-lithium in hexane (0.052 mole) was added to this solution over 5 minutes and a yellow solution formed. After removing the cooling bath, the solution was allowed to warm to room temperature and then stirred for 1 hour. After cooling the reaction mixture to −20 ° C., 5.0 g (0.052 mol) of chlorodimethylphosphine were added over 5 minutes and a precipitate formed. The cooling bath was then removed and the reaction mixture was stirred for 1 hour at room temperature. After cooling to −20 ° C., 21.0 ml of a 2.5 mol solution of butyl-lithium in hexane (0.052 mol) was added dropwise. When the addition was complete, the cooling bath was removed, after which the solution was slowly warmed to room temperature and stirred for 1.5 hours. After the suspension was cooled to 0 ° C., 16.9 g (0.052 mol) of chlorotributyltin were added dropwise. The resulting suspension was warmed to room temperature and stirred for 1.5 hours. After the ether was removed in vacuo, the crude product was dissolved again in hexane, the solution was filtered, the filtrate was dried under vacuum and 24.3 g (yield: 98%) of compound 35 was obtained as a dark yellow oil. 31 P-NMR (161.9 MHz, CD 2 Cl 2 ) δ-68.5 (s).
<실시예 34><Example 34>
(디메틸포스피노-2-메틸인데닐-지르코늄 트리클로라이드, 화합물 36)(Dimethylphosphino-2-methylindenyl-zirconium trichloride, compound 36)
36 36
톨루엔 100 ml 중의 화합물 35 17.4 g (0.035 몰) 용액을 0 ℃에서 10 분에 걸쳐 톨루엔 100 ml 중의 순도 99.9 % ZrCl48.5 g (0.036 몰)의 현탁액에 첨가하였다. 첨가가 완료되었을 때, 반응 혼합물을 1 시간에 걸쳐 10 ℃로 천천히 가온하고, 이어서 6 시간 동안 실온에서 교반시켰다. 이후에 황색 침전물을 여과하고, 톨루엔 20 ml로 2회, 헥산 20 ml로 2회 세척하고, 진공하에 건조시켰다. 30 mmHg하에서 3 시간에 걸쳐 환류하에서 공급된 톨루엔으로, 이어서 속슬레 추출기에서 2 시간에 걸쳐 펜탄으로 추출에 의해 남아 있는 주석 화합물의 제거에 의해 분말을 더 정제하고, 화합물 36 5.8 g (수율: 41 %)을 발광 황색 분말로 수득했다. 이 화합물의 불용성 때문에,1H-NMR이 전혀 얻어지지 않았다.A solution of 17.4 g (0.035 mol) of compound 35 in 100 ml of toluene was added to a suspension of 8.5 g (0.036 mol) of purity 99.9% ZrCl 4 in 100 ml of toluene over 10 minutes at 0 ° C. When the addition was complete, the reaction mixture was slowly warmed to 10 ° C. over 1 hour and then stirred at room temperature for 6 hours. The yellow precipitate was then filtered off, washed twice with 20 ml of toluene, twice with 20 ml of hexanes and dried under vacuum. The powder was further purified by toluene fed under reflux over 30 hours at 30 mmHg, followed by removal of the remaining tin compound by extraction with pentane over 2 hours in a Soxhlet extractor, 5.8 g of compound 36 (yield: 41 %) Was obtained as a luminescent yellow powder. Because of the insolubility of this compound, no 1 H-NMR was obtained.
<실시예 35><Example 35>
(디메틸포스피노-디클로로보라닐-브릿지 2-메틸인데닐-시클로펜타디에닐-지르코늄 디클로라이드, 화합물 37)(Dimethylphosphino-dichloroboranyl-bridge 2-methylindenyl-cyclopentadienyl-zirconium dichloride, compound 37)
37 37
화합물 2 2.7 g (0.012 몰)을 실온에서 5 분에 걸쳐 톨루엔 125 ml 중의 화합물 36 4.8 g (0.012 몰)이 들어 있는 둥근 바닥 플라스크에 도입하였다. 혼합물을 7 시간 동안 교반시킨 후, 어두운 황색 고체를 여과하고, 헥산 20 ml로 2회 세척하고, 진공하에 건조하고, 화합물 37 5.5 g (수율: 89 %)을 엷은 황색 고체로 수득했다.1H-NMR (400 MHz, CD2Cl2) δ 8.39 (d, J=8.5 Hz, 1H), 7.71 (m, 1H), 7.4 (m, 2H), 6.64 (m, 2H), 6.46 (유사 q, J=5.3, 2.9 Hz, 1H), 6.37 (m, 1H), 6.08 (m, 1H), 2.51 (s, 3H), 2.1 (d, JH-P=12 Hz, 3H), 2.0 (d, JH-P=12 Hz, 3H);31P-NMR (161.9 MHz, CD2Cl2) 5.3 (br, m);11B (80 MHz, CD2Cl2) δ-16.5 (br d, JB-P=116 Hz).2.7 g (0.012 mol) of compound 2 were introduced into a round bottom flask containing 4.8 g (0.012 mol) of compound 36 in 125 ml of toluene over 5 minutes at room temperature. After the mixture was stirred for 7 hours, the dark yellow solid was filtered, washed twice with 20 ml of hexane, dried under vacuum and 5.5 g (yield: 89%) of compound 37 were obtained as a pale yellow solid. 1 H-NMR (400 MHz, CD 2 Cl 2 ) δ 8.39 (d, J = 8.5 Hz, 1H), 7.71 (m, 1H), 7.4 (m, 2H), 6.64 (m, 2H), 6.46 (similar to q, J = 5.3, 2.9 Hz, 1H), 6.37 (m, 1H), 6.08 (m, 1H), 2.51 (s, 3H), 2.1 (d, J HP = 12 Hz, 3H), 2.0 (d, J HP = 12 Hz, 3H); 31 P-NMR (161.9 MHz, CD 2 Cl 2 ) 5.3 (br, m); 11 B (80 MHz, CD 2 Cl 2 ) δ-16.5 (br d, J BP = 116 Hz).
<실시예 36><Example 36>
(디시클로헥실보라닐시클로펜타디에닐-리튬, 화합물 39)(Dicyclohexyl boranylcyclopentadienyl-lithium, compound 39)
38 3938 39
문헌 [Herberich, G. E; Fischer, A. Organometallics 1996, 15, 58]을 참조한다.See Herberich, G. E; Fischer, A. Organometallics 1996, 15, 58.
헥산 (0.04 몰) 중의 클로로디시클로헥실보란 1 몰 용액의 40 ml를 -78 ℃에서 헥산 100 ml 중의 시클로펜타디에닐-나트륨 (THF 중의 2M; 0.04 몰) 20 ml에 첨가하였다. 냉각조를 제거한 후, 반응 혼합물을 실온으로 가온하고, 1 시간 동안 교반시켰다. 여과 및 진공하에 용매 제거 후에, 화합물 38 9.1 g (수율: 94 %)이 황색 오일로 남았고, 이를 화합물 39의 합성에 직접 사용하였다.40 ml of a 1 molar solution of chlorodicyclohexylborane in hexane (0.04 mole) were added to 20 ml of cyclopentadienyl-sodium (2M in THF; 0.04 mole) in 100 ml of hexane at -78 ° C. After removal of the cooling bath, the reaction mixture was warmed to room temperature and stirred for 1 hour. After filtration and solvent removal under vacuum, 9.1 g (yield: 94%) of compound 38 remained as a yellow oil, which was used directly for the synthesis of compound 39.
2,2,6,6-테트라메틸피페리딘 5.3 g (0.038 몰)을 THF 40 ml가 들어 있는 둥근 바닥 플라스크에 도입하였다. -20 ℃로 냉각하고, 헥산 (0.038 몰) 중의 부틸-리튬 2.5 몰 용액의 15 ml를 첨가한 후, 혼합물을 1 시간 동안 -20 ℃에서 교반시키고, -78 ℃에서 냉각시켰다. 헥산 20 ml 중의 화합물 38 9.1 g (0.038 몰)을 10 분에 걸쳐 이 용액에 첨가하였다. 냉각조를 제거하고, 용액을 1 시간 동안 실온에서 교반시켰다. 진공하에 용매를 제거하고, 헥산을 첨가한 후, 이후에 혼합물을 2 시간 동안 교반시키고, 백색 현탁액이 형성되고, 이를 여과하고, 생성물을 진공하에 건조시켰다. 화합물 39 4.6 g (수율: 50 %)이 백색 분말로 형성되었다.11B-NMR (80 MHz, THF) δ 43.9.5.3 g (0.038 mol) of 2,2,6,6-tetramethylpiperidine were introduced into a round bottom flask containing 40 ml of THF. After cooling to -20 ° C and 15 ml of a 2.5 molar solution of butyl-lithium in hexane (0.038 mol) was added, the mixture was stirred at -20 ° C for 1 hour and cooled at -78 ° C. 9.1 g (0.038 mol) of compound 38 in 20 ml of hexanes were added to this solution over 10 minutes. The cooling bath was removed and the solution was stirred for 1 hour at room temperature. The solvent was removed in vacuo and hexane was added, after which the mixture was stirred for 2 h, a white suspension formed, which was filtered off and the product was dried in vacuo. 4.6 g (yield 50%) of compound 39 were formed as a white powder. 11 B-NMR (80 MHz, THF) δ 43.9.
<실시예 37><Example 37>
(디페닐포스피노-디시클로헥실보라닐-브릿지 트리메틸실릴-시클로펜타디에닐-시클로펜타디에닐-지르코늄 디클로라이드, 화합물 40)(Diphenylphosphino-dicyclohexylboranyl-bridge trimethylsilyl-cyclopentadienyl-cyclopentadienyl-zirconium dichloride, compound 40)
40 40
화합물 39 1.4 g (0.0056 몰) 및 화합물 31 2.9 g (0.0056 몰)이 들어 있는 쉬렌크 플라스크를 -20 ℃로 냉각시킨 후, 톨루엔 100 ml를 첨가하였다. 배쓰를 제거한 후, 현탁액을 6 시간 동안 실온에서 첨가하고, 이어서 여과하였다. 용매를 진공하에 제거하고, 남아 있는 오일상 고체는 헥산으로 세척해서 여과하였다. 고체를 진공하에 건조시킨 후, 화합물 40 1.9 g (수율: 48 %)을 핑크색 고체로 수득했다.1H-NMR (400 MHz, CD2Cl2) δ 7.6-7.2 (br m, 10H), 7.04 (br s, 1H), 6.95 (m, 1H), 6.82 (m, 1H), 6.76 (br s, 1H), 6.66 (m, 1H), 6.63 (m, 1H), 6.52 (m, 1H), 1.6-1.1 (br m, 22H), 0.26 (s, 9H);31P-NMR (161.9 MHz, CD2Cl2) δ 16.3;11B-NMR (80 MHz, CD2Cl2) δ-13.8.The Schlenk flask containing 1.4 g (0.0056 mol) of compound 39 and 2.9 g (0.0056 mol) of compound 31 was cooled to −20 ° C., and then 100 ml of toluene was added. After the bath was removed, the suspension was added for 6 hours at room temperature and then filtered. The solvent was removed in vacuo and the remaining oily solid was washed with hexane and filtered. After drying the solid under vacuum, 1.9 g of compound 40 (yield: 48%) were obtained as a pink solid. 1 H-NMR (400 MHz, CD 2 Cl 2 ) δ 7.6-7.2 (br m, 10H), 7.04 (br s, 1H), 6.95 (m, 1H), 6.82 (m, 1H), 6.76 (br s , 1H), 6.66 (m, 1H), 6.63 (m, 1H), 6.52 (m, 1H), 1.6-1.1 (br m, 22H), 0.26 (s, 9H); 31 P-NMR (161.9 MHz, CD 2 Cl 2 ) δ 16.3; 11 B-NMR (80 MHz, CD 2 Cl 2 ) δ-13.8.
<실시예 38><Example 38>
(4,7-디메틸인덴, 화합물 41)(4,7-dimethylindene, compound 41)
41 41
문헌 [Erker G.외, Tetrahedron 1995, 51, 4347]을 참고한다.See Erker G. et al., Tetrahedron 1995, 51, 4347.
메탄올 중의 나트륨 메톡사이드 153 g (2.8 몰)의 30 % 용액을 메탄올 60 ml로 희석하고, 0 ℃로 냉각하였다. 시클로펜타디엔 34 g (0.52 몰)을 이 용액에 첨가하였다. 15 분 후에, 2,5-헥산디온 39 g (0.34 몰)을 적가하고, 그 후에 냉각조를 제거하고, 반응 혼합물을 2 시간 동안 실온에서 교반시켰다. 이어서, 물 200 ml 및 에테르 200 ml를 첨가하였다. 에테르층을 제거하고, 물 및 염화 나트륨 용액으로 세척하고, 이어서 Na2SO4에서 건조시켰다. 진공하에 용매를 제거하고, 0.1 mbar, 65 ℃에서 증류한 후, 화합물 41을 오렌지색 오일 (40 g, 수율: 81 %)로 수득했다.1H-NMR (400 MHz, CDCl3) δ 7.35-7.27 (m, 2H), 7.23 (d, J=7.6 Hz, 1H), 6.82 (m, 1H), 3.51 (s, 2H), 2.75 (s, 3H), 2.63 (s, 3H).A 30% solution of 153 g (2.8 mol) of sodium methoxide in methanol was diluted with 60 ml of methanol and cooled to 0 ° C. 34 g (0.52 mol) of cyclopentadiene were added to this solution. After 15 minutes, 39 g (0.34 mol) of 2,5-hexanedione were added dropwise, after which the cooling bath was removed and the reaction mixture was stirred for 2 hours at room temperature. Then 200 ml of water and 200 ml of ether were added. The ether layer was removed, washed with water and sodium chloride solution and then dried over Na 2 SO 4 . After removal of solvent in vacuo and distillation at 0.1 mbar, 65 ° C., compound 41 was obtained as an orange oil (40 g, yield: 81%). 1 H-NMR (400 MHz, CDCl 3 ) δ 7.35-7.27 (m, 2H), 7.23 (d, J = 7.6 Hz, 1H), 6.82 (m, 1H), 3.51 (s, 2H), 2.75 (s , 3H), 2.63 (s, 3H).
<실시예 39><Example 39>
(디이소프로필포스피노-트리부틸스탄닐-4,7-디메틸인덴, 화합물 42)(Diisopropylphosphino-tributylstannyl-4,7-dimethylindene, compound 42)
42 42
에테르 100 ml를 4,7-디메틸인덴 (화합물 41) 5.0 g (0.035 ml)이 들어 있는 둥근 바닥 플라스크에 도입하고, 이 혼합물을 -20 ℃로 냉각시켰다. 헥산 (0.035 몰) 중의 부틸-리튬 2.5 몰 용액의 14 ml를 5분에 걸쳐 이 용액에 첨가하고, 황색 용액이 형성되었다. 냉각조를 제거한 후, 용액을 실온으로 가온하고, 이후에 1 시간 동안 교반시켰다. 반응 혼합물을 -20 ℃까지 냉각시키고, 클로로디이소프로필포스핀 5.3 g (0.035 몰)을 5 분에 걸쳐 첨가하고, 침전물이 형성되었다. 그 후에, 냉각조를 제거하고, 반응 혼합물을 실온에서 1 시간 동안 교반시켰다. -20 ℃로 냉각시킨 후, 헥산 (0.035 몰) 중의 부틸-리튬 2.5 몰 용액의 14.0 ml를 적가하였다. 첨가가 완료되었을 때, 냉각조를 제거하고, 용액을 실온으로 천천히 가온하고, 1.5 시간 동안 교반시켰다. 현탁액을 0 ℃로 냉각시킨 후, 클로로트리부틸주석 (0.035 몰) 11.4 g을 적가하였다. 형성된 현탁액을 실온으로 가온하고, 1.5 시간 동안 교반시켰다. 에테르를 진공하에 제거하고, 조생성물을 헥산 중에 다시 용해시키고, 용액을 여과하고, 여과액을 진공하에 농축시키고, 화합물 42 16 g (수율:83 %)을 진한 황색 오일로 수득했다.31P-NMR (161.9 MHz, CD2Cl2) δ-9 ppm.100 ml of ether was introduced into a round bottom flask containing 5.0 g (0.035 ml) of 4,7-dimethylindene (compound 41) and the mixture was cooled to -20 ° C. 14 ml of a 2.5 mol solution of butyl-lithium in hexane (0.035 mol) was added to this solution over 5 minutes and a yellow solution formed. After removing the cooling bath, the solution was allowed to warm to room temperature and then stirred for 1 hour. The reaction mixture was cooled to -20 ° C, 5.3 g (0.035 mol) of chlorodiisopropylphosphine was added over 5 minutes, and a precipitate formed. After that, the cooling bath was removed and the reaction mixture was stirred at room temperature for 1 hour. After cooling to −20 ° C., 14.0 ml of a 2.5 molar solution of butyl-lithium in hexane (0.035 mole) was added dropwise. When the addition was complete, the cooling bath was removed and the solution was slowly warmed to room temperature and stirred for 1.5 hours. After the suspension was cooled to 0 ° C., 11.4 g of chlorotributyltin (0.035 mol) was added dropwise. The resulting suspension was warmed to room temperature and stirred for 1.5 hours. The ether was removed in vacuo, the crude product was again dissolved in hexanes, the solution was filtered, the filtrate was concentrated in vacuo and 16 g (yield: 83%) of compound 42 were obtained as a dark yellow oil. 31 P-NMR (161.9 MHz, CD 2 Cl 2 ) δ-9 ppm.
<실시예 40><Example 40>
(디이소프로필포스피노-4,7-디메틸인데닐-지르코늄 트리클로라이드, 화합물 43)(Diisopropylphosphino-4,7-dimethylindenyl-zirconium trichloride, compound 43)
43 43
CH2Cl2(100 ml) 중의 화합물 42 16.0 g (0.029 몰) 용액을 -20 ℃에서 10 분에 걸쳐 CH2Cl2100 ml 중의 순도 99.9 % ZrCl46.4 g (0.029몰)의 현탁액에 첨가하였다. 첨가가 완료되었을 때, 반응 혼합물을 2 시간에 걸쳐 실온으로 천천히 가온하고, 이어서 2 시간 동안 더 실온에서 교반시켰다. 그 후에, 고체를 여과에 의해 제거하고, 용매를 진공하에 제거하고, 오일로 남아 있는 조화합물 43은 화합물 44의 제조에 직접 사용하였다.A solution of 16.0 g (0.029 mol) of Compound 42 in CH 2 Cl 2 (100 ml) was added to a suspension of 6.4 g (0.029 mol) of purity 99.9% ZrCl 4 in 100 ml of CH 2 Cl 2 over 10 minutes at −20 ° C. . When the addition was complete, the reaction mixture was slowly warmed to room temperature over 2 hours and then stirred for a further 2 hours at room temperature. Thereafter, the solid was removed by filtration, the solvent was removed in vacuo, and crude compound 43 remaining as an oil was used directly for the preparation of compound 44.
<실시예 41><Example 41>
(디이소프로필포스피노-디클로로보라닐-브릿지 4,7-디메틸인데닐 시클로펜타디에닐-지르코늄 디클로라이드, 화합물 44)(Diisopropylphosphino-dichloroboranyl-bridge 4,7-dimethylindenyl cyclopentadienyl-zirconium dichloride, compound 44)
44 44
화합물 2 5.0 g (0.023 몰)을 톨루엔 125 ml 중의 화합물 43 10.6 g (0.023 몰)이 들어 있는 둥근 바닥 플라스크에 0 ℃에서 5 분에 걸쳐 도입하였다. 혼합물을 1.5 시간 동안 0 ℃에서 교반시킨 후, 냉각조를 제거하고, 현탁액을 3 시간 더 실온에서 교반시켰다. 그 후에, 반응 중에 형성된 다량의 오일로부터 톨루엔-용해성 분획물을 제거하고, 진공하에 건조하여 농축시키고, 진한 오일을 수득했다. 이 오일에 헥산 100 ml를 첨가한 후, 이후에 혼합물을 교반시키고, 진한 황색 분말을 여과하고, 진공하에 건조시켰다. 이 처리 후에, 화합물 44 6.3 g (수율: 48 %)을 진한 황색 분말로 수득했다. 생성물은 탄화수소 용매 중에서 화합물 44의 CH2Cl2용액의 침전에 의해 더 정제될 수 있다.1H-NMR (400 MHz, CD2Cl2) δ 8.03 (유사, t, J=8.5 Hz, 1H), 7.22 (d, J=7 Hz, 1H), 7.08 (d, J=7.1 Hz, 1H), 7.02 (m, 1H), 6.77 (m, 1H), 6.70 (m, 1H), 6.58 (m, 1H), 6.44 (br s, 1H), 3.51 (m, 1H), 2.82 (m, 1H), 2.64 (s, 3H), 2.50 (s, 3H), 1.77 (dd, J=7.2 Hz, JH-P=16.3 Hz, 3H), 1.69 (dd, J=7.1 Hz, JH-P=15.2 Hz, 3H), 1.58 (dd, J=7.1 Hz, JH-P=15.5 Hz, 3H), 1.28 (dd, J=7.2 Hz, JH-P=14.5 Hz, 3H);31P-NMR (161.9 MHz, CD2Cl2) δ 28.4 (br m);11B-NMR (80 MHz, CD2Cl2) δ-15.3 (d, JP-B=107 Hz).5.0 g (0.023 mol) of compound 2 were introduced into a round bottom flask containing 10.6 g (0.023 mol) of compound 43 in 125 ml of toluene at 0 ° C. over 5 minutes. The mixture was stirred for 1.5 h at 0 ° C., then the cooling bath was removed and the suspension was stirred for another 3 h at room temperature. Thereafter, the toluene-soluble fractions were removed from the large amount of oil formed during the reaction, dried in vacuo to give a thick oil. 100 ml of hexane was added to this oil, after which the mixture was stirred and the dark yellow powder was filtered off and dried under vacuum. After this treatment, 6.3 g (yield 48%) of compound 44 were obtained as a dark yellow powder. The product can be further purified by precipitation of a CH 2 Cl 2 solution of compound 44 in a hydrocarbon solvent. 1 H-NMR (400 MHz, CD 2 Cl 2 ) δ 8.03 (similar, t, J = 8.5 Hz, 1H), 7.22 (d, J = 7 Hz, 1H), 7.08 (d, J = 7.1 Hz, 1H ), 7.02 (m, 1H), 6.77 (m, 1H), 6.70 (m, 1H), 6.58 (m, 1H), 6.44 (br s, 1H), 3.51 (m, 1H), 2.82 (m, 1H ), 2.64 (s, 3H), 2.50 (s, 3H), 1.77 (dd, J = 7.2 Hz, J HP = 16.3 Hz, 3H), 1.69 (dd, J = 7.1 Hz, J HP = 15.2 Hz, 3H ), 1.58 (dd, J = 7.1 Hz, J HP = 15.5 Hz, 3H), 1.28 (dd, J = 7.2 Hz, J HP = 14.5 Hz, 3H); 31 P-NMR (161.9 MHz, CD 2 Cl 2 ) δ 28.4 (br m); 11 B-NMR (80 MHz, CD 2 Cl 2 ) δ-15.3 (d, J PB = 107 Hz).
<실시예 42><Example 42>
(피롤-리튬, 화합물 45)(Pyrrole-lithium, compound 45)
45 45
부틸-리튬 (헥산 중의 2.5 몰, 0.148 몰) 용액 59 ml를 -20 ℃에서 헥산 200 ml 중의 피롤 9.9 g (0.148 몰)의 용액에 천천히 첨가하고, 백색 고체가 형성되었다. 이후에 혼합물을 실온에서 2 시간 동안 교반시키고, 고체를 여과에 의해 분리하고, 매번 헥산 20 ml로 두 번 세척하고, 진공하에 건조시켰다. 이 방법으로 화합물 45 6 g (이론적인 수율의 56 %)을 수득했다.59 ml of a butyl-lithium (2.5 mol in hexane, 0.148 mol) solution was slowly added to a solution of 9.9 g (0.148 mol) of pyrrole in 200 ml of hexane at −20 ° C., and a white solid formed. The mixture was then stirred at rt for 2 h, the solids were separated by filtration, washed twice with 20 ml of hexane each time and dried under vacuum. This method yielded 6 g of compound 45 (56% of theoretical yield).
1H-NMR (400 MHz, THF): δ=6.71 (s, 2H), 5.95 (s, 2H). 1 H-NMR (400 MHz, THF): δ = 6.71 (s, 2H), 5.95 (s, 2H).
<실시예 43><Example 43>
(디메틸보라닐-브릿지 시클로펜타디에닐-피롤-티타늄 디클로라이드, 화합물 46)(Dimethylboranyl-bridge cyclopentadienyl-pyrrole-titanium dichloride, compound 46)
46 46
톨루엔 20 ml 중의 화합물 4 1.34 g (0.005 몰)의 용액을 -78 ℃에서 5 분에 걸쳐 화합물 45 0.38 g (0.005 몰)에 첨가하였다. 이어서, 냉각조를 제거하고, 2 시간 동안 실온에서 교반시켰다. 그 후에, 형성된 적색 고체를 여과하고, 황색 여과액은 버렸다. 적색 고체를 톨루엔으로 세척하고, 진공하에 건조시켰다. 적은 함량의 LiCl을 갖는 1.14 g을 수득했다.A solution of 1.34 g (0.005 mol) of compound 4 in 20 ml of toluene was added to 0.38 g (0.005 mol) of compound 45 over 5 minutes at −78 ° C. The cooling bath was then removed and stirred for 2 hours at room temperature. Thereafter, the formed red solid was filtered off and the yellow filtrate was discarded. The red solid was washed with toluene and dried under vacuum. 1.14 g were obtained with a small amount of LiCl.
1H-NMR (400 MHz, THF): δ=6.89 (유사-t, J=2.3 Hz, 2H), 6.64 (m, 2H), 6.59 (유사-t, J=2.35 Hz, 2H), 5.73 (유사-t, J=1.7 Hz, 2H), 0.06 (s, 6H).11B-NMR (80 MHz, THF) δ=-26 ppm. 1 H-NMR (400 MHz, THF): δ = 6.89 (Like-t, J = 2.3 Hz, 2H), 6.64 (m, 2H), 6.59 (Like-t, J = 2.35 Hz, 2H), 5.73 ( Pseudo-t, J = 1.7 Hz, 2H), 0.06 (s, 6H). 11 B-NMR (80 MHz, THF) δ = -26 ppm.
<실시예 44><Example 44>
(1-페닐-2,3,4,5-테트라메틸-포스폴, 화합물 47)(1-phenyl-2,3,4,5-tetramethyl-phosphol, compound 47)
47 47
문헌 [Organometallics 7 (1988), 921]에 따라서, CH2Cl2150 ml 중의 2-부틴 11.7 g (0.216 몰) 용액을 CH2Cl2중의 AlCl315.3 g (0.115 몰)에 천천히 첨가하였다 (0 ℃; 30 분). 이후에 혼합물을 0 ℃에서 45 분 동안 교반시키고, 이어서 냉각조를 제거하고, 이후에 혼합물을 1 시간 더 교반시켰다. 그 후에, 용액을 -50 ℃로 냉각시키고, CH2Cl2중의 페닐-디클로로포스핀 21.4 g (0.12 몰) 용액을 20 분에 걸쳐 첨가하였다. 이어서, 냉각조를 제거하고, 이후에 진한 적색 용액을 1 시간 동안 교반시키고, 이어서 -30 ℃에서 CH2Cl2100 ml 중의 트리부틸포스핀 27 g (0.13 몰) 용액에 첨가하였다. 곧바로 적색이 사라지고, 황색 용액을 수득했다. 첨가가 끝났을 때, 용매를 진공하에 제거하고, 진한 황색 오일을 수득했다. 오일을 헥산 중에 취하고, NaHCO3포화 수용액 및 H2O로 Ar 대기 하에서 세척하였다. MgSO4로 건조시킨 후, 헥산을 진공하에 제거하였다. 18.2 g을 투명한 오일 (수율: 78 %)로 수득했다.Document [Organometallics 7 (1988), 921 ], CH 2 Cl 2 150 ml solution of 2-butyne 11.7 g (0.216 mol) was slowly added to the AlCl 3 15.3 g (0.115 mol) in CH 2 Cl 2 (0 according to C; 30 minutes). The mixture was then stirred at 0 ° C. for 45 minutes, then the cooling bath was removed, after which the mixture was further stirred for 1 hour. Thereafter, the solution was cooled to −50 ° C., and a solution of 21.4 g (0.12 mol) of phenyl-dichlorophosphine in CH 2 Cl 2 was added over 20 minutes. The cooling bath was then removed and the dark red solution was then stirred for 1 hour and then added to a solution of 27 g (0.13 mol) of tributylphosphine in 100 ml of CH 2 Cl 2 at −30 ° C. Immediately the red disappeared and a yellow solution was obtained. At the end of the addition, the solvent was removed in vacuo to give a dark yellow oil. The oil was taken up in hexanes and washed with saturated aqueous NaHCO 3 and H 2 O under Ar atmosphere. After drying with MgSO 4 , hexanes were removed in vacuo. 18.2 g was obtained as a clear oil (yield: 78%).
1H-NMR (400 MHz, CDCl3) δ:7.3 (m, 5H), 2.0 (m, 12H),31P-NMR (161.9 MHz, CDCl3) δ:16.8 ppm. 1 H-NMR (400 MHz, CDCl 3 ) δ: 7.3 (m, 5H), 2.0 (m, 12H), 31 P-NMR (161.9 MHz, CDCl 3 ) δ: 16.8 ppm.
<실시예 45><Example 45>
(리튬-2,3,4,5-테트라메틸-포스폴, 화합물 48)(Lithium-2,3,4,5-tetramethyl-phosphol, compound 48)
48 48
문헌 [Organometallics 7 (1988), 921]에 따라서, 리튬 0.52 g (0.074 몰)을 테트라히드로푸란 (THF) 150 ml 중의 화합물 47 7 g (0.032 몰) 용액에 첨가하고, 이 혼합물을 하룻밤 동안 교반시켰다. 결과의 적색 용액을 프리트로 여과하여 잔류 고체를 제거하고, 여과액은 0 ℃로 냉각시켰다. 그 후에, THF 20 ml 중의 AlCl31.45 g (0.01 몰) 용액을 적가하고, 이 용액을 실온으로 만들었다. 분취량을 분석을 위해 분리해 놓고, 남아 있는 용액은 화합물 49의 제조에 직접 사용하였다.31P-NMR (161.9 MHz, THF) δ: 63.7 ppm.According to Organicmetallics 7 (1988), 921, 0.52 g (0.074 mol) of lithium was added to a solution of 7 g (0.032 mol) of compound 47 in 150 ml of tetrahydrofuran (THF) and the mixture was stirred overnight. . The resulting red solution was filtered through frit to remove residual solids and the filtrate was cooled to 0 ° C. Thereafter, a solution of 1.45 g (0.01 mol) of AlCl 3 in 20 ml of THF was added dropwise, and the solution was brought to room temperature. Aliquots were separated for analysis and the remaining solution was used directly for the preparation of compound 49. 31 P-NMR (161.9 MHz, THF) δ: 63.7 ppm.
<실시예 46>Example 46
(디메틸보라닐-시클로펜타디에닐-테트라메틸포스폴-티타늄 디클로라이드, 화합물 49)(Dimethylboranyl-cyclopentadienyl-tetramethylphosphol-titanium dichloride, compound 49)
49 49
화합물 48 1.46 g (0.01 몰)을 갖는 실시예 45의 THF 용액을 둥근 바닥 플라스크에 도입하고, 진공하에 THF를 제거하였다. 톨루엔을 첨가하고, -78 ℃로 냉각시킨 후, 톨루엔 20 ml 중의 화합물 44 2.6 g (0.01 몰) 용액을 교반시키면서 천천히 첨가하고, 적색 현탁액이 형성되었다. 첨가가 끝났을 때, 현탁액을 실온으로 만들고, 이후에 1 시간 동안 교반시켰다. 용해되지 않고 남아 있는 고체를 여과한 후, 톨루엔을 진공하에 제거하고, 헥산을 남아 있는 오일상 고체에 첨가하였다. 또한, 용해되지 않고 남아 있는 고체를 헥산 용액으로부터 여과하고, 용액을 -20 ℃에서 하룻밤 동안 저장하였다. 헥산을 제거한 후, 화합물 49로 확인된 녹색 고체 0.5 g (수율 14 %)을 수득했다.1H-NMR (200 MHz, CD2Cl2) δ:6.64 (m, 2H), 6.57 (m, 2H), 2.11 (d, JH-P=10 Hz, 6H), 2.09 (s, 6H), 0.87 (d, JH-P=5.3 Hz, 6H).31P-NMR (161.9 MHz, THF) δ: 95.6 ppm,11B-NMR (80 MHz, CD2Cl2) δ: 39 (br, m) ppm.The THF solution of Example 45 with 1.46 g (0.01 mol) of Compound 48 was introduced into a round bottom flask and the THF was removed under vacuum. Toluene was added and cooled to −78 ° C., then a solution of 2.6 g (0.01 mol) of compound 44 in 20 ml of toluene was added slowly with stirring to form a red suspension. At the end of the addition, the suspension was brought to room temperature and then stirred for 1 hour. After filtration of the solid remaining insoluble, toluene was removed under vacuum and hexane was added to the remaining oily solid. In addition, the solid that remained undissolved was filtered from the hexane solution and the solution was stored overnight at -20 ° C. After removal of the hexanes, 0.5 g (14% yield) of green solid identified as compound 49 was obtained. 1 H-NMR (200 MHz, CD 2 Cl 2 ) δ: 6.64 (m, 2H), 6.57 (m, 2H), 2.11 (d, J HP = 10 Hz, 6H), 2.09 (s, 6H), 0.87 (d, J HP = 5.3 Hz, 6H). 31 P-NMR (161.9 MHz, THF) δ: 95.6 ppm, 11 B-NMR (80 MHz, CD 2 Cl 2 ) δ: 39 (br, m) ppm.
<실시예 47><Example 47>
(에틸렌 중합)(Ethylene polymerization)
건조의, 산소-무함유 톨루엔 50 ml를 진공에서 엄격하게 가열했던 건조의, 산소-무함유의, 자기적으로 교반되는 V4A 강철 오토클레이브로 빨아들였다. D/A 메탈로센 촉매 (화합물 10)을 MAO (메틸알루미녹산, 톨루엔 중의 10 %, 분자량 900 g/몰)와 함께 실온에서 톨루엔 중에서, 15 분에 걸쳐 Al/Zr=66,666:1의 원자 (몰)비로 수행시켰다. 6.8 ml 중에 Zr 1.5×10-7몰 및 Al 1.0×10-2몰을 포함하는 분취량을 공기가 전혀 없는 오토클레이브로 주입하고, 이후에 오토클레이브를 추가의 톨루엔 50 ml로 채웠다. 이어서, 실온에서 1 시간 동안 10 bar의 일정한 에틸렌 압력하에서 중합을 수행하고, 내부 온도는 42 ℃로 상승시켰다. 오토클레이브를 낮춘 후에, 반응 혼합물을 에탄올 500 ml 및 진한 염산 수용액 50 ml에 도입하고, 하룻밤 동안 교반시키고, 중합체를 여과하고, 에탄올로 철저히 세척하고, 100 ℃의 회전 공기 건조 캐비넷에서 일정한 중량으로 건조시켰다. PE 수율은 2.9 g이었고, 이는 Zr의 몰 당 및 시간 당 공중합체 19.3 톤의 촉매 활성에 해당한다. 140 ℃에서 o-디클로로벤젠 중에서 측정한 한계 점도는 4.36 dl/g이었다. DSC 측정에 의해 139 ℃의 융점 및 164 J/g의 융해열이 얻어졌다.50 ml of dry, oxygen-free toluene was sucked into a dry, oxygen-free, magnetically stirred V4A steel autoclave which was heated strictly in vacuo. The D / A metallocene catalyst (Compound 10) was combined with MAO (methylaluminoxane, 10% in toluene, molecular weight 900 g / mol) in atoms of Al / Zr = 66,666: 1 over 15 minutes in toluene at room temperature ( Molar) ratio. An aliquot containing 1.5 × 10 −7 moles of Zr and 1.0 × 10 −2 moles of Al in 6.8 ml was injected into an airless autoclave, after which the autoclave was charged with additional 50 ml of toluene. Subsequently, the polymerization was carried out under constant ethylene pressure of 10 bar at room temperature for 1 hour, and the internal temperature was raised to 42 ° C. After lowering the autoclave, the reaction mixture is introduced into 500 ml of ethanol and 50 ml of concentrated hydrochloric acid solution, stirred overnight, the polymer is filtered off, washed thoroughly with ethanol and dried to constant weight in a rotary air drying cabinet at 100 ° C. I was. The PE yield was 2.9 g, which corresponds to 19.3 tonnes of catalytic activity per mole of Zr and per hour. The limit viscosity measured in o-dichlorobenzene at 140 ° C. was 4.36 dl / g. DSC measurements yielded a melting point of 139 ° C. and a heat of fusion of 164 J / g.
<실시예 48 내지 51><Examples 48 to 51>
(에틸렌 중합)(Ethylene polymerization)
또 다른 에틸렌 중합 실험에서, D/A-메탈로센 7을 촉매로 사용하고, 다른 양의 MAO를 사용하는 것을 제외하고는 상기 실시예 47의 방법과 동일하였다. Ti의 양은 1×10-6몰이고, 오토클레이브는 약 100 ℃로 가열하였다. Al/Zr 비는 1250, 2500, 5000 및 10,000 중에서 변하였다. 4가지 모든 실험에서, 촉매 활성은 Ti의 몰당 및 시간 당 PE 약 3 내지 4 톤이었다.In another ethylene polymerization experiment, the procedure of Example 47 was identical except that D / A-metallocene 7 was used as catalyst and another amount of MAO was used. The amount of Ti was 1 × 10 −6 mol and the autoclave was heated to about 100 ° C. Al / Zr ratios varied among 1250, 2500, 5000 and 10,000. In all four experiments, the catalytic activity was about 3-4 tons of PE per mole of Ti and per hour.
<실시예 52><Example 52>
(에틸렌 중합)(Ethylene polymerization)
톨루엔 100 ml를 초기에 직접 오토클레이브에 도입하는 것을 제외하고는 실시예 47의 방법을 따랐다. 오토클레이브를 80 ℃로 가열하고, 촉매를 주입하고, 에틸렌 압력을 10 bar로 조정하였다. 톨루엔 3.3 몰 중의 MAO 5×10-3몰로 수행시킨 톨루엔 2.4 ml 중의 화합물 18 1×10-6몰을 촉매로 사용하였다. 내부 온도를 80 ℃에서 94 ℃로 올렸다. 30 분 후에, 중합을 중단하였다. PE 수율은 3.5 g이었고, 이는 촉매의 몰 당 및 시간 당 중합체 약 7 톤의 촉매 활성에 해당한다. 한계 점도 η는 140 ℃에서 오르토-디클로로벤젠 중에서 측정하였고, 2.95 dl/g이었다. DSC 측정은 융점 139 ℃ 및 융해열 165 J/g의 결과를 주었다.The method of Example 47 was followed except that 100 ml of toluene was initially introduced directly into the autoclave. The autoclave was heated to 80 ° C., the catalyst was injected and the ethylene pressure was adjusted to 10 bar. 1 x 10 -6 moles of compound 18 in 2.4 ml of toluene, carried out with 5 x 10 -3 moles of MAO in 3.3 moles of toluene, was used as catalyst. The internal temperature was raised from 80 ° C to 94 ° C. After 30 minutes, the polymerization was stopped. The PE yield was 3.5 g, which corresponds to about 7 tons of catalyst activity per mole of catalyst and per hour. The limit viscosity η was measured in ortho-dichlorobenzene at 140 ° C. and was 2.95 dl / g. DSC measurements gave a melting point of 139 ° C. and a heat of fusion of 165 J / g.
<실시예 53 내지 56><Examples 53 to 56>
(에틸렌 중합)(Ethylene polymerization)
방법은 실시예 51과 동일하였다. Ti (화합물 7)의 양은 1×10-6몰이고, Al/Zr 비는 10,000이었다. 오토클레이브를 다른 온도로 가열하고, 한계 점도 및 융점 Tm의 중합체 특성을 측정하였다.The method was the same as in Example 51. The amount of Ti (Compound 7) was 1 × 10 −6 mol and the Al / Zr ratio was 10,000. The autoclave was heated to different temperatures and the polymer properties of the limit viscosity and melting point T m were measured.
T: RT에서 60 ℃=7.2 dl/g, Tm=143 ℃T at 60 ° C. = 7.2 dl / g at RT, T m = 143 ° C.
T: RT에서 80 ℃=4.6 dl/g, Tm=142 ℃T: 80 ° C = 4.6 dl / g at RT, T m = 142 ° C
T: RT에서 100 ℃=3.2 dl/g, Tm=144 ℃T: 100 ° C. = 3.2 dl / g at RT, T m = 144 ° C.
T: RT에서 120 ℃=2.2 dl/g, Tm=140 ℃T: 120 ° C. = 2.2 dl / g at RT, T m = 140 ° C.
(RT - 실온)(RT-room temperature)
<실시예 57><Example 57>
(에틸렌 중합)(Ethylene polymerization)
내부압을 100 ℃로 조정하는 것을 제외하고는 실시예 52의 방법을 따랐다. 톨루엔 3.3 몰 중의 5×10-3몰로 수행된 클로로벤젠 0.4 몰 중의 화합물 24 5×10-7몰을 촉매로 사용하였다. 내부 온도를 100 ℃에서 120 ℃로 올렸다. 30 분 동안 중합시킨 후, PE 6.2 g이 형성되었고, 이는 촉매 몰 당 및 시간 당 중합체 약 2.5 톤의 촉매 활성에 해당한다. 140 ℃에서 오르토-디클로로벤젠에서 측정된 한계 점도 η는 1.85 dl/g이었다.The method of Example 52 was followed except that the internal pressure was adjusted to 100 ° C. 5 x 10 -7 moles of compound 24 in 0.4 moles of chlorobenzene performed with 5 x 10 -3 moles in 3.3 moles of toluene were used as catalyst. The internal temperature was raised from 100 ° C to 120 ° C. After polymerization for 30 minutes, 6.2 g of PE were formed, which corresponds to about 2.5 tons of catalytic activity per mole of catalyst and per hour. The limit viscosity η measured in ortho-dichlorobenzene at 140 ° C. was 1.85 dl / g.
<실시예 58><Example 58>
(에틸렌 중합)(Ethylene polymerization)
화합물 21을 촉매로 사용하는 것을 제외하고는 실시예 57의 방법을 따랐다. 이 경우, 내부 온도를 100 ℃에서 128 ℃로 올렸다. 30 분 후에 PE 수율은 7.9 g이었고, 이것은 촉매 몰 당 시간 당 약 31.6 톤의 촉매 활성에 해당한다. 140 ℃에서 오르토-디클로로벤젠에서의 한계 점도 η는 1.01 dl/g이었다.The method of Example 57 was followed except that Compound 21 was used as a catalyst. In this case, internal temperature was raised from 100 degreeC to 128 degreeC. After 30 minutes the PE yield was 7.9 g, which corresponds to about 31.6 tonnes of catalytic activity per hour per mole of catalyst. The limit viscosity η in ortho-dichlorobenzene at 140 ° C. was 1.01 dl / g.
<실시예 59><Example 59>
(에틸렌 중합)(Ethylene polymerization)
중합을 20 ℃에서 시작하는 것을 제외하고는 실시예 52의 방법을 따랐다. 이 방법에서는 촉매로 메탈로센 32를 사용하였다. 이를 위해, 촉매 2.5×10-7몰을 툴루엔 중의 MAO 2.5×10-3몰과 수행시켰다. 내부 온도를 20 ℃ 내지 34 ℃로 올렸다. 30 분 동안 중합시킨 후, PE 1.3 g이 형성되었고, 이는 촉매 몰 당 및 시간 당 중합체 10.4 톤의 촉매 활성에 해당한다. 한계 점도 η (오르토-디클로로벤젠, 140 ℃)는 5.3 dl/g이었다.The method of Example 52 was followed except that the polymerization was started at 20 ° C. In this method, metallocene 32 was used as a catalyst. To this end, 2.5 × 10 −7 moles of catalyst were carried out with 2.5 × 10 −3 moles of MAO in toluene. The internal temperature was raised to 20 ° C to 34 ° C. After polymerization for 30 minutes, 1.3 g of PE were formed, corresponding to 10.4 tonnes of catalyst activity per mole of catalyst and per hour. The limit viscosity η (ortho-dichlorobenzene, 140 ° C.) was 5.3 dl / g.
DSC 측정으로 20 K/분의 속도로 첫 번째 가열에서 융점 153 ℃가 얻어졌다. 320 K/분에서 샘플을 종료한 후, 두 번째 가열에서 최대 융점은 146 ℃로 측정되었다.DSC measurements showed a melting point of 153 ° C. on the first heating at a rate of 20 K / min. After the sample was terminated at 320 K / min, the maximum melting point at the second heating was measured at 146 ° C.
<실시예 60><Example 60>
(에틸렌 중합)(Ethylene polymerization)
촉매로 사용된 D/A 메탈로센이 화합물 메조-15라는 것을 제외하고는 실시예 47의 실험을 따라서 수행하였다. Zr의 양은 5×10-7몰이고, Al의 양은 1×10-2몰이었다. 촉매 및 에틸렌을 첨가한 후, 오토클레이브를 약 120 ℃까지 빠르게 가열하였다. 30 분 동안 중합시킨 후에, 폴리에틸렌 4.3 g이 분리되었고, 이는 Zr의 몰 당 및 시간 당 PE 약 17 t의 활성에 해당된다. 140 ℃에서, o-디클로로벤젠 중에서 측정된 한계 점도 η는 1.9 dl/g이었다.The experiment of Example 47 was carried out except that D / A metallocene used as catalyst was compound meso-15. The amount of Zr was 5 x 10 -7 mol, and the amount of Al was 1 x 10 -2 mol. After the catalyst and ethylene were added, the autoclave was quickly heated to about 120 ° C. After polymerization for 30 minutes, 4.3 g of polyethylene was isolated, corresponding to an activity of about 17 t of PE per mole of Zr and per hour. At 140 ° C., the limit viscosity η measured in o-dichlorobenzene was 1.9 dl / g.
<실시예 61><Example 61>
(디페닐포스피노-디클로로보라닐-가교 비스(인데닐)-지르코늄 디클로라이드, 화합물 50)(Diphenylphosphino-dichloroboranyl-crosslinked bis (indenyl) -zirconium dichloride, compound 50)
트리메틸실릴-디클로로보라닐-인덴 0.011 몰을 실온에서 톨루엔 150 ml 중의 디페닐포스피노-인데닐-지르코늄 트리클로라이드 0.012 몰의 현탁액에 첨가하였다. 이어서, 반응 혼합물을 1 시간 동안 75 ℃에서 교반시켰다. 냉각 및 여과 후에, 헥산 150 ml를 투명한 오렌지색 용액에 첨가하고, 그 후 진한 적색 오일 및 엷은 황색 침전물이 형성되었다. 침전물을 여과하고, 헥산으로 세척하고, 진공에서 건조시켰다. 엷은 황색 고체가1H-NMR 분광학에 의해 순수한 meso 화합물로 확인되었다. 적색 오일과 여과액을 30 ml로 농축시키고, 헥산 200 ml를 적가하고, 그 후에 두 번째 엷은 황색 침전물이 형성되었고, 이 침전물을 여과하여 진공에서 건조시켰다. 이 생성물은 X-선 구조 분석의 도움으로 순수한 rac 이성질체로 확인되었다. 본 목적에 적당한 결정을 상온에서 CH2Cl2포화 용액으로 헥산을 느리게 확산시켜 배양시켰다. 공여체-수용체 결합 P→B는 2.02 Å의 길이를 갖는다. 수율은 40 %이고, meso/rac 비율은 1:1이었다. 반응 혼합물을 75 ℃에서 (1 시간 대신) 5 시간 동안 교반시켰더니, 원하는 rac 이성질체의 양이 증가되었고, meso/rac 비율은 1:4였다. 동시에, 총수율은 40 %에서 45 %로 약간 증가되었다.0.011 mol of trimethylsilyl-dichloroboranyl-indene was added to a suspension of 0.012 mol of diphenylphosphino-indenyl-zirconium trichloride in 150 ml of toluene at room temperature. The reaction mixture was then stirred at 75 ° C. for 1 hour. After cooling and filtration, 150 ml of hexane was added to a clear orange solution, which then formed a dark red oil and a pale yellow precipitate. The precipitate was filtered off, washed with hexanes and dried in vacuo. Pale yellow solid was identified as pure meso compound by 1 H-NMR spectroscopy. The red oil and the filtrate were concentrated to 30 ml, 200 ml of hexane was added dropwise, after which a second pale yellow precipitate formed, which was filtered and dried in vacuo. This product was identified as pure rac isomer with the aid of X-ray structural analysis. Crystals suitable for this purpose were incubated with slow diffusion of hexane with saturated CH 2 Cl 2 solution at room temperature. Donor-receptor bonds P → B have a length of 2.02 mm 3. Yield 40% and meso / rac ratio 1: 1. The reaction mixture was stirred at 75 ° C. (instead of 1 hour) for 5 hours when the amount of desired rac isomer was increased and the meso / rac ratio was 1: 4. At the same time, the total yield increased slightly from 40% to 45%.
원소 분석: 56.05 % C (이론적인 수율의 55.90 %), 4.35 % H (4.38 %)Elemental analysis: 56.05% C (55.90% of theoretical yield), 4.35% H (4.38%)
스펙트럼 meso 이성질체:1H-NMR (400 MHz, CD2Cl2, 실온 RT): 8.01 ppm (1H, d, 8.8 Hz); 7.8-7.0 ppm (몇개의 겹친 다중 피크, 28H); 6.94 ppm (1H, t, 3.3 Hz); 6.77 ppm (1H, d, 3.44 Hz); 6.31 ppm (1H, d, 8.7 Hz),31P-NMR (161.9 MHz, CD2Cl2): 5.6 ppm.11B-NMR (80.2 MHz, CD2Cl2): -17.0 ppm (72 Hz).Spectral meso isomer: 1 H-NMR (400 MHz, CD 2 Cl 2 , room temperature RT): 8.01 ppm (1H, d, 8.8 Hz); 7.8-7.0 ppm (some overlapping multiple peaks, 28H); 6.94 ppm (1H, t, 3.3 Hz); 6.77 ppm (1 H, d, 3.44 Hz); 6.31 ppm (1H, d, 8.7 Hz), 31 P-NMR (161.9 MHz, CD 2 Cl 2 ): 5.6 ppm. 11 B-NMR (80.2 MHz, CD 2 Cl 2 ): -17.0 ppm (72 Hz).
스펙트럼 rac 이성질체:1H-NMR (400 MHz, CD2Cl2, RT): 8.39 ppm (1H, d, 8.5 Hz); 7.68-7.05 ppm (27H, 여러개의 겹친 다중 피크); 6.65 ppm (1H, d, 2.9 Hz), 6.59 ppm (1H, t, 3.5 Hz); 6.51 ppm (1H, t, 2.8 Hz); 6.40 ppm (1H, d, 3.5 Hz).Spectral rac isomer: 1 H-NMR (400 MHz, CD 2 Cl 2 , RT): 8.39 ppm (1H, d, 8.5 Hz); 7.68-7.05 ppm (27H, multiple overlapping multiple peaks); 6.65 ppm (1H, d, 2.9 Hz), 6.59 ppm (1H, t, 3.5 Hz); 6.51 ppm (1H, t, 2.8 Hz); 6.40 ppm (1H, d, 3.5 Hz).
31P-NMR (161.9 MHz, CD2Cl2): 8.1 ppm.11B-NMR (80.2 MHz, CD2Cl2)=-14.0 ppm (JP-B=74 Hz). 31 P-NMR (161.9 MHz, CD 2 Cl 2 ): 8.1 ppm. 11 B-NMR (80.2 MHz, CD 2 Cl 2 ) =-14.0 ppm (J PB = 74 Hz).
<실시예 62-64><Example 62-64>
(디알킬포스피노-디클로로보라닐-가교 비스(인데닐)-지르코늄 디클로라이드; 알킬=i-프로필=화합물 51; 에틸=화합물 52; 메틸=화합물 53)(Dialkylphosphino-dichloroboranyl-crosslinked bis (indenyl) -zirconium dichloride; alkyl = i-propyl = compound 51; ethyl = compound 52; methyl = compound 53)
톨루엔 50 ml 중의 트리메틸실릴-디클로로보라닐-인덴 0.016 몰을 실온에서 톨루엔 250 ml 중의 디알킬포스피노인데닐-지르코늄 트리클로라이드 0.0157 몰의 현탁액에 첨가하였다. 이어서, 반응 혼합물을 교반시키면서 몇 시간 동안 가열하였다. 냉각 및 여과 후에, 헥산 300 ml를 투명한 오렌지색 용액에 첨가하고, 그 후 진한 적색 오일 및 투명한 황색 용액이 형성되었다. 톨루엔/헥산 용액으로부터 분별 증류에 의해 meso 및 rac 이성질체를 분리하였다.0.016 mol of trimethylsilyl-dichloroboranyl-indene in 50 ml of toluene was added to a suspension of 0.0157 mol of dialkylphosphinoinyl-zirconium trichloride in 250 ml of toluene at room temperature. The reaction mixture was then heated for several hours with stirring. After cooling and filtration, 300 ml of hexane was added to a clear orange solution, which then formed a dark red oil and a clear yellow solution. The meso and rac isomers were separated from the toluene / hexane solution by fractional distillation.
화합물의 특성 (실온에서 CD2Cl2중의 NMR 스펙트라;1H-NMR: 400 MHz,31P-NMR: 161.9 MHz,11B-NMR: 80.2 MHz):Characterization of the compound (NMR spectra in CD 2 Cl 2 at room temperature; 1 H-NMR: 400 MHz, 31 P-NMR: 161.9 MHz, 11 B-NMR: 80.2 MHz):
rac 화합물 51 (i-Pr):rac compound 51 (i-Pr):
1H-NMR: 8.41 ppm (1H, d, 9.0 Hz); 8.31 ppm (1H, d, 8.4 Hz); 7.84 ppm (1H, d, 8.5 Hz); 7.64-7.24 ppm (6H, 여러개의 겹친 다중 피크); 6.70 ppm (2H, m); 6.60 ppm (1H, m): 3.78 ppm (1H, m, P(CH(CH3)2)2; 3.21 ppm (1H, m, P(CH(CH3)2)2; 1.81 ppm (6H, m, P(CH(CH3)2)2; 1.72 ppm (3H, dd, P(CH(CH3)2)2, 14.9 Hz, 7.3 Hz); 1.32 ppm (3H, dd, P(CH(CH3)2)2, 14.1Hz, 7.4 Hz).31P-NMR: 22.7 ppm.11B-NMR: -14.1 ppm (100 Hz). 1 H-NMR: 8.41 ppm (1H, d, 9.0 Hz); 8.31 ppm (1H, d, 8.4 Hz); 7.84 ppm (1 H, d, 8.5 Hz); 7.64-7.24 ppm (6H, several overlapping multiple peaks); 6.70 ppm (2H, m); 6.60 ppm (1H, m): 3.78 ppm (1H, m, P (CH (CH 3 ) 2 ) 2 ; 3.21 ppm (1H, m, P (CH (CH 3 ) 2 ) 2 ; 1.81 ppm (6H, m , P (CH (CH 3 ) 2 ) 2 ; 1.72 ppm (3H, dd, P (CH (CH 3 ) 2 ) 2 , 14.9 Hz, 7.3 Hz); 1.32 ppm (3H, dd, P (CH (CH 3) .) 2) 2, 14.1Hz, 7.4 Hz) 31 P-NMR:. 22.7 ppm 11 B-NMR: -14.1 ppm (100 Hz).
원소 분석: 49.4 % C (이론적인 수율의 48.9 %), 4.6 % H (4.4 %).Elemental analysis: 49.4% C (48.9% of theoretical yield), 4.6% H (4.4%).
meso 화합물 52 (Et):meso compound 52 (Et):
1H-NMR: 7.83 ppm (1H, d, 9.0 Hz); 7.76 ppm (1H, m); 7.63 ppm (1H, d, 7.2 Hz); 7.47 ppm (1H, d, 8.5 Hz); 7.33 ppm (2H, m); 7.20-7.03 ppm (4H, 여러개의 겹친 다중 피크); 6.76 ppm (2H, m); 2.68 ppm (2H, m, P(CH2(CH3)2); 2.44 ppm (2H, m, P(CH2CH3)2); 1.62 ppm (3H, m, P(CH2(CH3)2; 1.27 ppm (3H, m, P(CH2(CH3)2).31P-NMR: 7.1 ppm.11B-NMR: -15.8 ppm (100 Hz). 1 H-NMR: 7.83 ppm (1 H, d, 9.0 Hz); 7.76 ppm (1 H, m); 7.63 ppm (1 H, d, 7.2 Hz); 7.47 ppm (1H, d, 8.5 Hz); 7.33 ppm (2H, m); 7.20-7.03 ppm (4H, multiple overlapping multiple peaks); 6.76 ppm (2H, m); 2.68 ppm (2H, m, P (CH 2 (CH 3 ) 2 ); 2.44 ppm (2H, m, P (CH 2 CH 3 ) 2 ); 1.62 ppm (3H, m, P (CH 2 (CH 3 ) .. 2; 1.27 ppm (3H , m, P (CH 2 (CH 3) 2) 31 P-NMR: 7.1 ppm 11 B-NMR: -15.8 ppm (100 Hz).
rac 화합물 52 (Et):rac compound 52 (Et):
1H-NMR: 8.28 ppm (1H, d, 8.6 Hz); 8.10 ppm (1H, d, 8.6 Hz); 7.62 ppm (1H, d, 8.4 Hz); 7.46 ppm (1H, d, 8.5 Hz); 7.41-7.10 ppm (4H, 여러개의 겹친 다중 피크); 6.81 ppm (1H, m); 6.47 ppm (2H, m): 6.38 ppm (1H, d, 3.4 Hz), 2.68 ppm (2H, m, P(CH2(CH3)2); 2.35 ppm (2H, m, P(CH2(CH3)2); 1.30 ppm (6H, m, P(CH2(CH3)2).31P-NMR: 12.3 ppm.11B-NMR: -15.7 ppm. 1 H-NMR: 8.28 ppm (1 H, d, 8.6 Hz); 8.10 ppm (1 H, d, 8.6 Hz); 7.62 ppm (1 H, d, 8.4 Hz); 7.46 ppm (1 H, d, 8.5 Hz); 7.41-7.10 ppm (4H, several overlapping multiple peaks); 6.81 ppm (1 H, m); 6.47 ppm (2H, m): 6.38 ppm (1H, d, 3.4 Hz), 2.68 ppm (2H, m, P (CH 2 (CH 3 ) 2 ); 2.35 ppm (2H, m, P (CH 2 (CH) 3 ) 2 ); 1.30 ppm (6H, m, P (CH 2 (CH 3 ) 2 ). 31 P-NMR: 12.3 ppm. 11 B-NMR: -15.7 ppm.
원소 분석: 47.6 % C (이론적인 수율의 47.1 %), 4.3 % H (4.0 %).Elemental analysis: 47.6% C (47.1% of theoretical yield), 4.3% H (4.0%).
meso 화합물 53 (Me):meso compound 53 (Me):
1H-NMR: 7.84 ppm (1H, d); 7.75 ppm (1H, d, 8.2 Hz); 7.68 ppm (1H, d, 7.7 Hz); 7.51 ppm (1H, d, 8.5 Hz); 7.40-7.10 ppm (4H, 여러개의 겹친 다중 피크); 6.77 ppm (2H, br); 2.13 ppm (3H, P(CH3)2, d, 11.8 Hz); 1.92 ppm (3H, P(CH3)2, d, 11.8 Hz).31P-NMR: -8.4 ppm.11B-NMR: -16.1 ppm (103 Hz). 1 H-NMR: 7.84 ppm (1 H, d); 7.75 ppm (1 H, d, 8.2 Hz); 7.68 ppm (1 H, d, 7.7 Hz); 7.51 ppm (1H, d, 8.5 Hz); 7.40-7.10 ppm (4H, several overlapping multiple peaks); 6.77 ppm (2H, br); 2.13 ppm (3H, P (CH 3 ) 2 , d, 11.8 Hz); 1.92 ppm (3H, P (CH 3 ) 2 , d, 11.8 Hz). 31 P-NMR: -8.4 ppm. 11 B-NMR: −16.1 ppm (103 Hz).
rac 화합물 53 (Me):rac compound 53 (Me):
1H-NMR: 8.21 ppm (1H, d, 8.7 Hz); 8.15 ppm (1H, d, 8.6 Hz); 7.63 ppm (1H, d, 8.5 Hz); 7.44-7.07 ppm (6H, 여러개의 겹친 다중 피크); 6.40 ppm (3H, br); 2.03 ppm (3H, d, P(CH3)2, 11.9 Hz); 1.98 ppm (3H, d, P(CH3)2, 11.6 Hz).31P-NMR: -1.5 ppm.11B-NMR: -16.0 ppm (119 Hz). 1 H-NMR: 8.21 ppm (1H, d, 8.7 Hz); 8.15 ppm (1H, d, 8.6 Hz); 7.63 ppm (1 H, d, 8.5 Hz); 7.44-7.07 ppm (6H, several overlapping multiple peaks); 6.40 ppm (3H, br); 2.03 ppm (3H, d, P (CH 3 ) 2 , 11.9 Hz); 1.98 ppm (3H, d, P (CH 3 ) 2 , 11.6 Hz). 31 P-NMR: -1.5 ppm. 11 B-NMR: −16.0 ppm (119 Hz).
<실시예 65><Example 65>
(1,3-비스(트리메틸실릴)-2-메틸인덴, 화합물 54)(1,3-bis (trimethylsilyl) -2-methylindene, compound 54)
헥산 500 ml 및 부틸리튬 (헥산 중의 2.5 몰 용액) 70 ml를 1000 ml 플라스크에 도입하였다. 2-메틸인덴 0.175 몰을 외부 온도에서 적가하고, 이 혼합물을 10 시간 동안 더 교반시켰다. 이어서, 염화 트리메틸실릴 0.18 몰을 실온에서 적가하고, 이 혼합물을 10 시간 동안 더 교반시켰다. LiCl을 여과하고, 부틸리튬 (헥산 중의 2.5 몰 용액) 70 ml를 투명한 여과액에 첨가하였다. 10 시간 동안 더 교반시킨 후, 염화 트리메틸실릴 0.18 몰을 다시 첨가하고, 혼합물을 10 시간 동안 더 교반시켰다. LiCl을 여과하고, 용매를 진공에서 제거하였다. 화합물 54를 무색 오일로 수득했다. 수율: 이론적인 수율의 85 %.500 ml of hexane and 70 ml of butyllithium (2.5 molar solution in hexane) were introduced into a 1000 ml flask. 0.175 mol of 2-methylindene was added dropwise at external temperature, and the mixture was further stirred for 10 hours. Subsequently, 0.18 mol of trimethylsilyl chloride was added dropwise at room temperature, and the mixture was further stirred for 10 hours. LiCl was filtered off and 70 ml of butyllithium (2.5 molar solution in hexane) was added to the clear filtrate. After further stirring for 10 hours, 0.18 mole of trimethylsilyl chloride was added again and the mixture was further stirred for 10 hours. LiCl was filtered off and the solvent was removed in vacuo. Compound 54 was obtained as a colorless oil. Yield: 85% of theoretical yield.
1H-NMR (CD2Cl2): 7.51 ppm (1H, d, 7.7 Hz); 7.38 ppm (1H, d, 7.5 Hz); 7.19 ppm (1H, t, 7.4 Hz); 7.08 ppm (1H, t, 7.3 Hz); 3.54 ppm (1H, s); 2.32 ppm (3H, s); 0.41 ppm (9H, s, Si(CH3)3); 0.0 ppm (9H, s, Si(CH3)3). 1 H-NMR (CD 2 Cl 2 ): 7.51 ppm (1H, d, 7.7 Hz); 7.38 ppm (1 H, d, 7.5 Hz); 7.19 ppm (1H, t, 7.4 Hz); 7.08 ppm (1H, t, 7.3 Hz); 3.54 ppm (1 H, s); 2.32 ppm (3H, s); 0.41 ppm (9H, s, Si (CH 3 ) 3 ); 0.0 ppm (9H, s, Si (CH 3 ) 3 ).
<실시예 66>Example 66
(트리메틸실릴-디클로로보라닐-2-메틸인덴, 화합물 55)(Trimethylsilyl-dichloroboranyl-2-methylindene, compound 55)
화합물 54 0.096 몰을 드라이 아이스 응축기 (-30 ℃)가 장착된 250 ml 플라스크에 도입하였다. 이어서, BCl30.096 몰을 첨가하고, 혼합물을 3 시간 동안 외부 온도에서, 6 시간 동안 55 ℃에서 교반시켰다. 부생성물 (CH3)3SiCl을 제거하고, 갈색 오일을 조생성물로 수득했다. 콜드 트랩 (cold trap)에서 콜드 트랩으로 증류를 하여 점착성 고체로 75 % 수율의 화합물 55를 수득했다.0.096 moles of compound 54 were introduced into a 250 ml flask equipped with a dry ice condenser (-30 ° C.). Then 0.096 moles of BCl 3 were added and the mixture was stirred at external temperature for 3 hours and 55 ° C. for 6 hours. Byproduct (CH 3 ) 3 SiCl was removed and a brown oil was obtained as crude product. Distillation from the cold trap to the cold trap gave 75% yield of compound 55 as a tacky solid.
1H-NMR (CD2Cl2): 8.09 ppm (1H, d, 7.9 Hz); 7.37 ppm (1H, d, 7.6 Hz); 7.26 ppm (1H, t, 7.5 Hz); 7.16 ppm (1H, t, 7.5 Hz); 3.89 ppm (1H, s); 2.61 ppm (3H, s); 0.0 ppm (9H, s, Si(CH3)3).11B-NMR (CD2Cl2): 31.9 ppm. 1 H-NMR (CD 2 Cl 2 ): 8.09 ppm (1H, d, 7.9 Hz); 7.37 ppm (1H, d, 7.6 Hz); 7.26 ppm (1H, t, 7.5 Hz); 7.16 ppm (1H, t, 7.5 Hz); 3.89 ppm (1 H, s); 2.61 ppm (3H, s); 0.0 ppm (9H, s, Si (CH 3 ) 3 ). 11 B-NMR (CD 2 Cl 2 ): 31.9 ppm.
<실시예 67><Example 67>
(트리부틸스탄닐-디에틸포스피노-2-메틸인덴; 화합물 56)(Tributylstannyl-diethylphosphino-2-methylindene; compound 56)
방법은 실시예 7과 동일하였다.The method was the same as in Example 7.
<실시예 68><Example 68>
(디에닐포스피노-2-메틸인데닐-지르코늄 트리클로라이드, 화합물 57)(Dienylphosphino-2-methylindenyl-zirconium trichloride, compound 57)
용매로 톨루엔 대신 CH2Cl2를 사용하는 것을 제외하고는 실시예 8의 방법과 동일하였다. 반응 온도는 25 ℃였다. CH2Cl2로 속슬레 추출에 의해 정제를 수행하였다. 화합물 57을 이론적인 수율의 78 %의 불용성 황색 고체로 수득했다.The procedure of Example 8 was identical except that CH 2 Cl 2 was used instead of toluene as the solvent. The reaction temperature was 25 ° C. Purification was performed by Soxhlet extraction with CH 2 Cl 2 . Compound 57 was obtained in 78% of an insoluble yellow solid in theoretical yield.
<실시예 69><Example 69>
((C2H5)2P-BCl2-가교 비스(2-메틸인데닐)-지르코늄 디클로라이드, 화합물 58)((C 2 H 5 ) 2 P-BCl 2 -crosslinked bis (2-methylindenyl) -zirconium dichloride, compound 58)
톨루엔 50 ml 중의 화합물 55 0.019 몰을 실온에서 톨루엔 350 ml 중의 화합물 57 0.019 몰의 현탁액에 첨가하였다.0.019 moles of compound 55 in 50 ml of toluene were added to a suspension of 0.019 moles of compound 57 in 350 ml of toluene at room temperature.
이어서, 반응 혼합물을 80 ℃로 가열하고, 24 시간 동안 교반시켰다. 냉각 및 여과 후에, 헥산 300 ml를 투명한, 오렌지색 용액에 첨가하고, 그 후 진한 오렌지색 오일과 투명한 황색 용액이 형성되었다. 응축시키고, -25 ℃로 냉각시켜서 엷은 황색 분말로 화합물 rac-58을 수득했다.The reaction mixture was then heated to 80 ° C. and stirred for 24 hours. After cooling and filtration, 300 ml of hexane was added to a clear, orange solution, which then formed a dark orange oil and a clear yellow solution. Condensation and cooling to −25 ° C. gave compound rac-58 as a pale yellow powder.
1H-NMR: 8.14 ppm (1H, d, 8.6 Hz); 7.96 ppm (1H, d, 8.9 Hz); 7.47-7.05 ppm (6H, 여러개의 겹친 다중 피크) 6.53 ppm (1H, d, 1.9 Hz); 6.47 ppm (1H, s); 3.0-2.55 ppm (4H, 여러개의 겹친 다중 피크), P(CH2(CH3)2); 2.21 ppm (3H, s, CH3); 2.08 ppm (3H, s, CH3); 1.44 ppm (3H, m, P(CH2(CH3)2), 1.07 ppm (3H, m, P(CH2(CH3)2).31P-NMR: 21.4 ppm.11B-NMR: -14.7 ppm. 1 H-NMR: 8.14 ppm (1H, d, 8.6 Hz); 7.96 ppm (1H, d, 8.9 Hz); 7.47-7.05 ppm (6H, several overlapping multiple peaks) 6.53 ppm (1H, d, 1.9 Hz); 6.47 ppm (1 H, s); 3.0-2.55 ppm (4H, several overlapping multiple peaks), P (CH 2 (CH 3 ) 2 ); 2.21 ppm (3H, s, CH 3 ); 2.08 ppm (3H, s, CH 3 ); 1.44 ppm (3H, m, P (CH 2 (CH 3 ) 2 ), 1.07 ppm (3H, m, P (CH 2 (CH 3 ) 2 ). 31 P-NMR: 21.4 ppm. 11 B-NMR:- 14.7 ppm.
<실시예 70><Example 70>
(프로펜 중합)(Propene polymerization)
철저하게 가열된 300 ml V4A 강철 오토클레이브를 건조, 산소-무함유 톨루엔 100 ml 및 1 몰 트리이소부틸알루미늄/톨루엔 용액 0.5 ml에 충전시켰다. 이어서, 프로펜 약 1 몰을 오토클레이브로 이동시켰다. 디메틸아닐리늄 테트라키스(펜타플루오로페닐)보레이트 4×10-6몰을 포함하는 클로로벤젠 용액 1 ml를 30 분 동안 실온에서 수행시키고 rac[(2-Me-ind)Et2PBCl2(2-Me-ind)ZrCl2] 1×10-6몰 및 트리이소부틸알루미늄 (TiBA) 0.1 mmol을 포함하는 톨루엔 중의 촉매 용액 3.1 ml로 압력 통로로 첨가하고, 혼합물을 톨루엔으로 5 ml까지 채웠다. 촉매 용액을 압력하에 오토클레이브로 이동시킨 후, 드라이 아이스/아세톤으로 외부 냉각에도 불구하고, 내부 온도를 20 ℃에서 48 ℃로 올렸다.A thoroughly heated 300 ml V4A steel autoclave was charged to 100 ml of dry, oxygen-free toluene and 0.5 ml of 1 mol triisobutylaluminum / toluene solution. Then about 1 mole of propene was transferred to the autoclave. 1 ml of a chlorobenzene solution containing 4 × 10 −6 moles of dimethylanilinium tetrakis (pentafluorophenyl) borate was carried out for 30 minutes at room temperature and rac [(2-Me-ind) Et 2 PBCl 2 (2- Me-ind) ZrCl 2 ] 3.1 ml of a catalyst solution in toluene containing 1 × 10 −6 mol and 0.1 mmol of triisobutylaluminum (TiBA) was added via pressure passage and the mixture was charged with toluene to 5 ml. After moving the catalyst solution to the autoclave under pressure, the internal temperature was raised from 20 ° C. to 48 ° C., despite external cooling with dry ice / acetone.
촉매를 첨가한지 20 분 후에, 중합을 중단하고, 오토클레이브의 내용물을 에탄올 500 ml 및 진한 염산 수용액 50 ml 중에서 2 시간 동안 교반시키면서 추출하였다. 이어서, 폴리프로필렌 백색 분말을 여과에 의해 분리하고, 에탄올로 세척하고, 115 ℃에서 건조하였다.20 minutes after the addition of the catalyst, the polymerization was stopped and the contents of the autoclave were extracted with stirring for 2 hours in 500 ml of ethanol and 50 ml of concentrated aqueous hydrochloric acid solution. The polypropylene white powder was then separated by filtration, washed with ethanol and dried at 115 ° C.
중합체 수율: 11.6 gPolymer yield: 11.6 g
촉매 활성: 촉매 몰 당 및 시간 당 i-PP 34.8 톤Catalyst activity: 34.8 tons of i-PP per mole of catalyst and per hour
두 번째 가열에서 DSC 측정으로 융점 Tm=155 ℃이 얻어졌다.DSC measurements at the second heating gave a melting point of T m = 155 ° C.
NMR 측정으로 이소택틸리티 (isotactility) 지수 I.I.=88 %가 얻어졌다.NMR measurements yielded isotactility index I.I. = 88%.
140 ℃에서 오르토-디클로로벤젠 (ODCB) 중에서 측정된 한계 점도 [η]는 분자량 Mvisc.=798 kg/몰에 상응하는 3.60 dl/g이었다 (문헌 [Atkinson 외, Makromol. Chem. (1976), 177, 213]의 방법에 의해 계산됨).The limit viscosity [η] measured in ortho-dichlorobenzene (ODCB) at 140 ° C. was determined by molecular weight M visc. = 3.60 dl / g, corresponding to 798 kg / mol (calculated by the method of Atkinson et al., Makromol. Chem. (1976), 177, 213).
10 ℃ 내지 20 ℃의 중합 온도에서 비교할 만한 실험상 조건하에서 rac-52로, I.I.=92 % 및 [η]=1.20 dl/g를 갖는 i-PP가 얻어졌고, 이는 이론상 평균 분자량 Mvisc.=169 kg/몰에 해당한다.Under comparable experimental conditions at polymerization temperatures of 10 ° C. to 20 ° C., rac-52 gave i-PP with II = 92% and [η] = 1.20 dl / g, which in theory average molecular weight M visc. Equivalent to = 169 kg / mol.
<실시예 71><Example 71>
(에틸렌 중합)(Ethylene polymerization)
건조의, 산소-무함유 톨루엔 100 ml를 철저하게 가열된 300 ml V4A 강철 오토클레이브에 채우고, 100 ℃로 가열하였다. 에틸렌으로 압력을 10 bar로 일정하게 하고, 압력 통로로 촉매를 첨가하였다.100 ml of dry, oxygen-free toluene was charged to a thoroughly heated 300 ml V4A steel autoclave and heated to 100 ° C. The pressure was kept constant at 10 bar with ethylene and the catalyst was added to the pressure passage.
톨루엔 5 ml 중의 MAO 5×10-3몰로 실온에서 15 분 동안 수행된 meso-[(ind)Et2PBCl2(ind)ZrCl2] 5×10-7몰을 촉매로 사용하였다.5 × 10 −7 moles of meso-[(ind) Et 2 PBCl 2 (ind) ZrCl 2 ] carried out for 15 minutes at room temperature with 5 × 10 −3 moles of MAO in 5 ml of toluene were used as catalyst.
중합 중에 내부 온도를 111 ℃로 올렸다.The internal temperature was raised to 111 ° C during the polymerization.
30 분 후 폴리에틸렌 수율: 12.1 gPolyethylene yield after 30 minutes: 12.1 g
촉매 활성: 촉매 몰 당 및 시간 당 중합체 48.4 톤Catalytic activity: 48.4 tons of polymer per mole of catalyst and per hour
140 ℃에서 오르토-디클로로벤젠 중의 한계 점도: [η]=0.91 dl/gLimit viscosity in ortho-dichlorobenzene at 140 ° C .: [η] = 0.91 dl / g
DSC 분석: Tm=136 ℃DSC analysis: T m = 136 ° C
<실시예 72><Example 72>
단지 2 bar의 프로펜 압력 하에서 수행시켰다는 차이점을 제외하고는 실시예 70의 방법과 동일하였다. 내부 온도는 20 ℃에서 23 ℃로 올렸다. 이 경우 형성된 폴리프로필렌의 융점 Tm=158 ℃였다.Same as the method of Example 70 except for the difference that it was performed under propene pressure of only 2 bar. The internal temperature was raised from 20 ° C to 23 ° C. In this case, the melting point T m of the formed polypropylene was 158 占 폚.
Claims (14)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR10-1998-0710890A KR100472591B1 (en) | 1996-07-05 | 1997-07-02 | Method for Producing High Melting-Point Polyolefins |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19627064.2 | 1996-07-05 | ||
DE19714058.0 | 1997-04-05 | ||
KR10-1998-0710890A KR100472591B1 (en) | 1996-07-05 | 1997-07-02 | Method for Producing High Melting-Point Polyolefins |
Publications (2)
Publication Number | Publication Date |
---|---|
KR20000022454A true KR20000022454A (en) | 2000-04-25 |
KR100472591B1 KR100472591B1 (en) | 2005-05-16 |
Family
ID=43666284
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
KR10-1998-0710890A KR100472591B1 (en) | 1996-07-05 | 1997-07-02 | Method for Producing High Melting-Point Polyolefins |
Country Status (1)
Country | Link |
---|---|
KR (1) | KR100472591B1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100722171B1 (en) * | 1999-10-12 | 2007-05-29 | 소시에떼 드 테크놀로지 미쉐린 | Catalytic system, its method for preparation, and method for preparation of a copolymer of ethylene and a conjugated diene |
CN115109189A (en) * | 2022-06-15 | 2022-09-27 | 宁夏清研高分子新材料有限公司 | Preparation method of cycloolefin copolymer material, catalyst system and application thereof |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0709393A3 (en) * | 1994-10-25 | 2003-04-16 | Tosoh Corporation | Olefin polymerization catalyst and process for producing olefin polymer |
-
1997
- 1997-07-02 KR KR10-1998-0710890A patent/KR100472591B1/en not_active IP Right Cessation
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100722171B1 (en) * | 1999-10-12 | 2007-05-29 | 소시에떼 드 테크놀로지 미쉐린 | Catalytic system, its method for preparation, and method for preparation of a copolymer of ethylene and a conjugated diene |
CN115109189A (en) * | 2022-06-15 | 2022-09-27 | 宁夏清研高分子新材料有限公司 | Preparation method of cycloolefin copolymer material, catalyst system and application thereof |
CN115109189B (en) * | 2022-06-15 | 2024-01-30 | 宁夏清研高分子新材料有限公司 | Preparation method of cycloolefin copolymer material, catalyst system and application thereof |
Also Published As
Publication number | Publication date |
---|---|
KR100472591B1 (en) | 2005-05-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6191241B1 (en) | Method for producing high melting-point polyolefins | |
US6184320B1 (en) | Method for producing metallocene compounds formed by two carbanions | |
US6353064B1 (en) | Supported catalysts with a donor-acceptor interaction | |
US20040063877A1 (en) | Process for preparing homopolymers, copolymers and/or block copolymers by living polymerization with metallocenes having a donor-acceptor interaction | |
US6657027B2 (en) | Catalysts with a donor-acceptor interaction | |
KR100472591B1 (en) | Method for Producing High Melting-Point Polyolefins | |
US6433112B1 (en) | π-complex compounds | |
KR20010033431A (en) | Method for Producing Elastomers | |
KR100472592B1 (en) | Method for Producing Elastomers | |
KR100523497B1 (en) | Metallocene Compounds | |
KR100480849B1 (en) | Method for Producing Cycloolefin (Co)Polymers for Technical Applications | |
KR100483866B1 (en) | Method for Producing Thermoplastic Elastomers | |
US6423659B1 (en) | π-complex compounds | |
CA2246061C (en) | Heteroatom substituted metallocene compounds for olefin polymerization catalyst systems and methods for preparing them |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PA0105 | International application |
Patent event date: 19981230 Patent event code: PA01051R01D Comment text: International Patent Application |
|
PG1501 | Laying open of application | ||
A201 | Request for examination | ||
PA0201 | Request for examination |
Patent event code: PA02012R01D Patent event date: 20020426 Comment text: Request for Examination of Application |
|
E902 | Notification of reason for refusal | ||
PE0902 | Notice of grounds for rejection |
Comment text: Notification of reason for refusal Patent event date: 20040727 Patent event code: PE09021S01D |
|
E701 | Decision to grant or registration of patent right | ||
PE0701 | Decision of registration |
Patent event code: PE07011S01D Comment text: Decision to Grant Registration Patent event date: 20041229 |
|
GRNT | Written decision to grant | ||
PR0701 | Registration of establishment |
Comment text: Registration of Establishment Patent event date: 20050207 Patent event code: PR07011E01D |
|
PR1002 | Payment of registration fee |
Payment date: 20050211 End annual number: 3 Start annual number: 1 |
|
PG1601 | Publication of registration | ||
LAPS | Lapse due to unpaid annual fee | ||
PC1903 | Unpaid annual fee |