US20030216590A1 - Novel dendrimer compounds, method for the production thereof, use thereof as catalysts - Google Patents
Novel dendrimer compounds, method for the production thereof, use thereof as catalysts Download PDFInfo
- Publication number
- US20030216590A1 US20030216590A1 US10/406,930 US40693003A US2003216590A1 US 20030216590 A1 US20030216590 A1 US 20030216590A1 US 40693003 A US40693003 A US 40693003A US 2003216590 A1 US2003216590 A1 US 2003216590A1
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- Prior art keywords
- compounds
- formula
- stated
- production
- dendrimeric
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 94
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000000412 dendrimer Substances 0.000 title description 4
- 229920000736 dendritic polymer Polymers 0.000 title description 4
- -1 allyl compound Chemical class 0.000 claims description 51
- 238000006243 chemical reaction Methods 0.000 claims description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 27
- 239000005977 Ethylene Substances 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 24
- 229910052723 transition metal Inorganic materials 0.000 claims description 15
- 150000003624 transition metals Chemical class 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- 150000002367 halogens Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000003747 Grignard reaction Methods 0.000 claims description 7
- 230000000737 periodic effect Effects 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 125000004104 aryloxy group Chemical group 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 5
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 4
- FEJUGLKDZJDVFY-UHFFFAOYSA-N 9-borabicyclo(3.3.1)nonane Chemical compound C1CCC2CCCC1B2 FEJUGLKDZJDVFY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- AKRQMTFHUVDMIL-UHFFFAOYSA-N tetrakis(prop-2-enyl)silane Chemical compound C=CC[Si](CC=C)(CC=C)CC=C AKRQMTFHUVDMIL-UHFFFAOYSA-N 0.000 claims description 4
- 125000000027 (C1-C10) alkoxy group Chemical group 0.000 claims description 3
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 239000005049 silicon tetrachloride Substances 0.000 claims description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004711 α-olefin Substances 0.000 claims description 3
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 2
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 2
- 125000004450 alkenylene group Chemical group 0.000 claims description 2
- 125000002947 alkylene group Chemical group 0.000 claims description 2
- 125000004419 alkynylene group Chemical group 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 238000006197 hydroboration reaction Methods 0.000 claims description 2
- 239000005052 trichlorosilane Substances 0.000 claims description 2
- 239000000806 elastomer Substances 0.000 claims 2
- 229920000642 polymer Polymers 0.000 abstract description 15
- 239000003426 co-catalyst Substances 0.000 abstract description 5
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 185
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 145
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 78
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 72
- 239000000243 solution Substances 0.000 description 71
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 34
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 32
- 239000000470 constituent Substances 0.000 description 31
- 239000011541 reaction mixture Substances 0.000 description 29
- 238000003756 stirring Methods 0.000 description 29
- 238000004821 distillation Methods 0.000 description 28
- 238000005481 NMR spectroscopy Methods 0.000 description 27
- 239000000203 mixture Substances 0.000 description 26
- 239000000047 product Substances 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 23
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 21
- YMWUJEATGCHHMB-DICFDUPASA-N dichloromethane-d2 Chemical compound [2H]C([2H])(Cl)Cl YMWUJEATGCHHMB-DICFDUPASA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 16
- 238000001914 filtration Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 9
- 239000012190 activator Substances 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 150000001993 dienes Chemical class 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- XEKTVXADUPBFOA-UHFFFAOYSA-N 1-bromo-2,3,4,5,6-pentafluorobenzene Chemical compound FC1=C(F)C(F)=C(Br)C(F)=C1F XEKTVXADUPBFOA-UHFFFAOYSA-N 0.000 description 6
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 5
- 239000005909 Kieselgur Substances 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 4
- WOAZEKPXTXCPFZ-UHFFFAOYSA-N dimethyl(phenyl)azanium;chloride Chemical compound Cl.CN(C)C1=CC=CC=C1 WOAZEKPXTXCPFZ-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 4
- JMRCCZJBDIJBGF-UHFFFAOYSA-N n,n-dimethylundecan-1-amine;hydrochloride Chemical compound Cl.CCCCCCCCCCCN(C)C JMRCCZJBDIJBGF-UHFFFAOYSA-N 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 125000002524 organometallic group Chemical group 0.000 description 4
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 4
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 description 4
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 3
- CSVCVIHEBDJTCJ-UHFFFAOYSA-N 1-bromo-3,5-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC(Br)=CC(C(F)(F)F)=C1 CSVCVIHEBDJTCJ-UHFFFAOYSA-N 0.000 description 3
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 3
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- 229910018540 Si C Inorganic materials 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 150000001642 boronic acid derivatives Chemical class 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- YWFWDNVOPHGWMX-UHFFFAOYSA-N n,n-dimethyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)C YWFWDNVOPHGWMX-UHFFFAOYSA-N 0.000 description 3
- MMWFTWUMBYZIRZ-UHFFFAOYSA-N n,n-dimethylundecan-1-amine Chemical compound CCCCCCCCCCCN(C)C MMWFTWUMBYZIRZ-UHFFFAOYSA-N 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 150000002899 organoaluminium compounds Chemical class 0.000 description 3
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 description 3
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910008455 Si—Ca Inorganic materials 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical group C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- GKWKOCYSCDZTAX-UHFFFAOYSA-N dichloroboron Chemical compound Cl[B]Cl GKWKOCYSCDZTAX-UHFFFAOYSA-N 0.000 description 2
- PGQAXGHQYGXVDC-UHFFFAOYSA-N dodecyl(dimethyl)azanium;chloride Chemical compound Cl.CCCCCCCCCCCCN(C)C PGQAXGHQYGXVDC-UHFFFAOYSA-N 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-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
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- UWLFCNHEPBTLHT-UHFFFAOYSA-N neopentyllithium Chemical compound [Li]CC(C)(C)C UWLFCNHEPBTLHT-UHFFFAOYSA-N 0.000 description 2
- 125000002868 norbornyl group Chemical group C12(CCC(CC1)C2)* 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
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- ZGXMNEKDFYUNDQ-GQCTYLIASA-N (5e)-hepta-1,5-diene Chemical compound C\C=C\CCC=C ZGXMNEKDFYUNDQ-GQCTYLIASA-N 0.000 description 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
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- JEKYMVBQWWZVHO-UHFFFAOYSA-N 1-chloro-2,2-dimethylpropane Chemical compound CC(C)(C)CCl JEKYMVBQWWZVHO-UHFFFAOYSA-N 0.000 description 1
- 238000004607 11B NMR spectroscopy Methods 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
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- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 1
- PXSCEAJMCLQOBY-UHFFFAOYSA-N 2,6,6-trimethyloxaluminane Chemical compound C[Al]1CCCC(C)(C)O1 PXSCEAJMCLQOBY-UHFFFAOYSA-N 0.000 description 1
- HANWWAAUFXCNBS-UHFFFAOYSA-N 2,6,6-tris(2-methylpropyl)oxaluminane Chemical compound CC(C)C[Al]1CCCC(CC(C)C)(CC(C)C)O1 HANWWAAUFXCNBS-UHFFFAOYSA-N 0.000 description 1
- MPNXSZJPSVBLHP-UHFFFAOYSA-N 2-chloro-n-phenylpyridine-3-carboxamide Chemical compound ClC1=NC=CC=C1C(=O)NC1=CC=CC=C1 MPNXSZJPSVBLHP-UHFFFAOYSA-N 0.000 description 1
- UQRONKZLYKUEMO-UHFFFAOYSA-N 4-methyl-1-(2,4,6-trimethylphenyl)pent-4-en-2-one Chemical group CC(=C)CC(=O)Cc1c(C)cc(C)cc1C UQRONKZLYKUEMO-UHFFFAOYSA-N 0.000 description 1
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- CIXLSKKRGPQNLF-UHFFFAOYSA-N C=CCC(CC=C)CCCO[Si](OCCCC(CC=C)CC=C)(OCCCC(CC=C)CC=C)OCCCC(CC=C)CC=C Chemical compound C=CCC(CC=C)CCCO[Si](OCCCC(CC=C)CC=C)(OCCCC(CC=C)CC=C)OCCCC(CC=C)CC=C CIXLSKKRGPQNLF-UHFFFAOYSA-N 0.000 description 1
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- 206010063601 Exposure to extreme temperature Diseases 0.000 description 1
- 229910004721 HSiCl3 Inorganic materials 0.000 description 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 1
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- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
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- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- NAPSCFZYZVSQHF-UHFFFAOYSA-N dimantine Chemical compound CCCCCCCCCCCCCCCCCCN(C)C NAPSCFZYZVSQHF-UHFFFAOYSA-N 0.000 description 1
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- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical group C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
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- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
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- VFLWKHBYVIUAMP-UHFFFAOYSA-N n-methyl-n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCCCCCC VFLWKHBYVIUAMP-UHFFFAOYSA-N 0.000 description 1
- SZEGKVHRCLBFKJ-UHFFFAOYSA-N n-methyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCNC SZEGKVHRCLBFKJ-UHFFFAOYSA-N 0.000 description 1
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- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 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 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 239000001294 propane Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- ASRAWSBMDXVNLX-UHFFFAOYSA-N pyrazolynate Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(=O)C=1C(C)=NN(C)C=1OS(=O)(=O)C1=CC=C(C)C=C1 ASRAWSBMDXVNLX-UHFFFAOYSA-N 0.000 description 1
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000007944 thiolates Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/003—Dendrimers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- 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
- 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
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- 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
Definitions
- the present invention relates to novel dendrimeric compounds, to a method for the production thereof and to the use thereof as catalysts for the production of polymers, in particular to the use thereof as co-catalysts for metallocenes for polymerising unsaturated compounds.
- metallocenes in combination with activating co-catalysts, preferably alumoxanes (MAOs), for polymerising olefins and diolefins (c.f. for example EP-A 129 368, 347 128, 347 129, 351 392, 485 821, 485 823).
- MAOs alumoxanes
- MAO metallocenes and alumoxanes
- MAO is a mixture of various species containing aluminiumalkyl which exist in equilibrium with each other, resulting in a loss of reproducibility during the polymerisation of olefinic compounds.
- MAO is not stable in storage and the composition thereof changes on exposure to extreme temperatures.
- Another serious disadvantage is the considerable excess of MAO which is necessary for the activation of metallocenes.
- this high MAO/metallocene ratio is an absolute prerequisite for achieving high catalyst activities. This results in a crucial processing disadvantage, however, since aluminium compounds must be separated from the polymers during work-up.
- MAO is a cost-determining factor in the use of catalyst systems containing MAO, meaning that excesses of MAO are uneconomic.
- Perfluorinated, tetraaromatic borate compounds in particular tetrakis(pentafluorophenyl)borate compounds, are used as ionising reagents (EP 468 537, EP 561 479).
- pentafluorophenyl substituents are complex and costly.
- tetrakis(pentafluorophenyl)borate compounds on an industrial scale is thus highly cost-intensive.
- Another disadvantage of tetrakis(pentafluorophenyl)borate compounds is the poor solubility thereof in hydrocarbons.
- WO 93/11172 describes polyanionic activators for metallocenes which consist, for example, of a polystyrene matrix onto which what are termed non-coordinating anions, preferably borate compounds comprising pentafluorophenyl substituents, are chemically bonded.
- the catalytic activity of the borate compounds described above decreases considerably, however, if the fluoroaromatic substituents on the boron are replaced by other substituents, for example by methyl or butyl substituents.
- the polyanionic activators described in WO 93/11172 exhibit lower polymerisation activity.
- Another disadvantage is the poor yield during the production of the polyanionic activators. Costly tris(pentafluorophenyl)borane is used as a starting compound which must be chemically bonded by a complicated method onto a matrix, for example crosslinked polystyrene.
- the polyanionic activators do not have a uniform surface, wherein accessibility of the molecular surface or the active end groups may be restricted.
- the precise composition, in particular the number of active end groups of the polyanionic activators is not known.
- the polyanionic activators have neither a defined molecular size nor dimensional stability.
- the poor meterability of polyanionic activators is industrially disadvantageous.
- the sparingly soluble polyanionic activators are used as solids for catalysing polymerisation, which is technically disadvantageous in a continuous polymerisation process.
- the object thus arose of identifying novel co-catalysts which avoid the above-stated disadvantages.
- the object consisted in creating a cost-effective catalyst system which is easy to produce, easy to handle industrially and is capable of polymerising unsaturated compounds, such as for example olefins and dienes, at a high level of catalytic activity.
- dendrimeric compounds which contain metals, preferably in combination with metallocenes, are particularly suitable for achieving the above-stated objects.
- the present invention accordingly provides novel dendrimeric compounds of the general formula
- X represents Me 2 R 2 R 3 (R y ) r ,
- R 1 , R 2 , R 3 , R y are identical or different, may optionally be mono- or polysubstituted and represent hydrogen, C 5 -C 20 cycloalkyl, C 1 -C 20 alkyl, C 7 -C 40 aralkyl, C 6 -C 40 aryl, C 1 -C 10 alkoxy, C 6 -C 40 aryloxy, silyloxy or halogen,
- R 4 represents an optionally mono- or polysubstituted alkylene, alkenylene or alkynylene residue, which is optionally interrupted by one or more heteroatoms,
- Me 1 represents an element of group IVa of the periodic system of the elements (IUPAC nomenclature),
- Me 2 represents an element of group IIIa of the periodic system of the elements (IUPAC nomenclature),
- i represents an integer from 2 to 4,
- n represents an integer from 1 to 20 and
- r represents 0 or 1
- X represents Me 1 R 5 a [(R 4 ) m Me 2 R 2 R 3- (R y ) r ] 3-a ,
- Me 1 , Me 2 , R 1 , R 2 , R 3 , R 4 , R y , i, n, r have the above-stated meanings
- R 5 has the meaning of the residues R 1 , R 2 , R 3 , R y ,
- n is identical to or different from n and represents integers from 1 to 20 and
- a 0, 1 or 2
- X represents Me 1 R 5 a [(R 4 ) m Me 1 R 6 b [(R 4 ) p Me 2 R 2 R 3 (R y ) r ] 3- b ] 3- a ,
- Me 1 , Me 2 , R 2 , R 3 , R 4 , R y , i, n, r, m, a have the above-stated meanings
- R 6 has the meaning of the residues R 1 , R 2 , R 3 , R y , R 5 ,
- p represents integers from 1 to 20,
- Suitable cations in the event that Me 2 bears a negative formal charge which may be considered are ions of atoms or molecules such as alkali metal ions, for example Li + , Na + or K + , alkaline earth metal ions such as Be 2+ , Mg 2+ , Ca 2+ , Ba 2+ , transition metal ions such as Zn 2+ , Cd 2+ , Mg 2+ , Cu + , Cu 2+ , or organic compounds such as ammonium or phosphonium ions of the NR 4 + or PR 4 + type, preferably Ph-N(CH 3 ) 2 H + , or carbocations of the CR 3 + type, preferably CPh 3 + .
- alkali metal ions for example Li + , Na + or K +
- alkaline earth metal ions such as Be 2+ , Mg 2+ , Ca 2+ , Ba 2+
- transition metal ions such as Zn 2+ , Cd 2+ , Mg 2+ ,
- the nature of the cation NR 4 + in particular also has an influence on the solubility of the salts, consisting of the dendrimeric compounds according to the invention of the formula (I) which have at least one negative formal charge (r 1) and cations which offset the formal charge.
- the solubility of the stated salts in non-polar solvents, such as for example toluene and xylene, may, for example, be improved by using ammonium salts NR′R 3 + which contain a relatively long-chain, branched or unbranched hydrocarbon residue R′.
- R′ is here preferably an unbranched C 6 -C 40 alkyl residue, particularly preferably a C 8 -C 12 alkyl residue.
- the remaining residues R in NR 3 R′ may, mutually independently, be hydrogen and optionally mono- or polysubstituted C 1 -C 5 alkyl and C 6 -C 12 aryl residues. At least one residue R in NR 3 R′ is preferably hydrogen. Specifically, cations such as undecyldimethylammonium and dodecyldimethylammonium may be mentioned.
- Cycloalkyl residues in the formula (I) which may in particular be considered are those having 5 to 10 carbon atoms.
- Example which may be mentioned are cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl residues, fused cycloaliphatic residues such as decalin or hydrindene residues or bicyclic residues such as norbornyl residues.
- Preferred alkyl residues are those having 1 to 10 carbon atoms, the following being mentioned by way of example: methyl, ethyl, propyl, n-butyl, pentyl, hexyl, heptyl, octyl, isopropyl, sec.-butyl, tert.-butyl or neopentyl, preferably methyl, ethyl, propyl, n-butyl, sec.-butyl, tert.-butyl.
- Aralkyl residues which may be mentioned are those having 7 to 20 carbon atoms, preferably the benzyl residue.
- Preferred aryl residues which may be considered are those having 6 to 20 carbon atoms, the following being mentioned by way of example: phenyl, toluyl, p-halo-phenyl, mesityl, pentafluorophenyl, bis(3,5-trifluoromethyl)phenyl, more preferably pentafluorophenyl, bis(3,5-trifluoromethyl)phenyl, most preferably pentafluorophenyl.
- Aryloxy residues which may in particular be considered are those having 6 to 10 carbon atoms, phenyloxy residues being mentioned by way of example.
- Silyloxy residues which may be considered are compounds of the type —O—SiR 3 , in which R denotes C 1 -C 10 alkyl residues or C 6 -C 10 aryl residues. Silyloxy residues, such as —O—SiMe 3 , —O—SiEt 3 and —O—SiPh 3 , are preferred.
- halogens which are used are fluorine, chlorine and bromine, in particular fluorine and chlorine.
- the residues R 1 , R 2 , R 3 , R 4 and R y of the formula (I) may be mono- or polysubstituted, preferably mono- to decasubstituted, particularly preferably mono- to pentasubstituted.
- Substituents which may be considered are, for example, the above-mentioned cycloalkyl, alkyl, aralkyl, aryl, alkoxy, aryloxy and silyloxy residues, as well as the stated halogens.
- Preferred substituents are halogens, in particular fluorine, alkyls, such as methyl and ethyl, perhalogenated alkyls, such as CF 3 , or perhalogenated aromatics, such as C 6 F 5 .
- Elements of main group 4 of the periodic system of elements which may be mentioned are Si, Ge, Sn and Pb, preferably Si, Ge, Sn, in particular Si.
- Elements of main group 3 of the periodic system of elements which may be considered are B, Al, In and Ga, preferably B, Al, very particularly preferably B.
- i preferably represents the numbers 3 or 4, particularly preferably 4, n is an integer from 1 to 10, in particular 2 to 5, and r represents 0.
- m furthermore preferably represents integers from 1 to 10, in particular from 2 to 5, a represents 0, b represents 0 and p represents integers from 1 to 10, in particular 2 to 5.
- Dendrimeric compounds which may be considered are preferably those of the formula (II)
- X represents Me 2 R 2 R 3 (R y ) r
- R 1 , R 2 , R 3 , R y are identical or different, preferably identical, may optionally be mono- or polysubstituted, and represent C 5 -C 6 cycloalkyl, C 6 -C 10 aryl, C 1 -C 10 alkyl and/or halogen,
- R 4 represents a methylene residue
- Me 2 represents boron or Al
- i represents an integer from 2 to 4,
- n represents an integer from 1 to 20
- r may be 0 or 1
- X represents SiR 5 a [(R 4 ) m Me 2 R 2 R 3 (R y ) r ] 3- a ,
- R 5 has the meaning of the residues R 1 , R 2 , R 3 , R y ,
- n is identical to or different from n and represents integers from 1 to 20,
- a 0, 1 or 2
- X represents SiR 5 a [(R 4 ) m SiR 6 b [(R 4 ) p Me 2 R 2 R 3 (R y ) r ] 3-b ] 3-a ,
- R 6 has the meaning of the residues R 1 , R 2 , R 3 , R 5 , R y ,
- p represents integers from 1 to 20.
- dendrimeric compounds are those of the general formula (III)
- X represents BR 2 R 3 (R y ) r
- R 1 , R 2 , R 3 , R y are identical or different, preferably identical, may optionally be mono- or polysubstituted and represent C 6 -C 10 aryl or C 1 -C 10 alkyl,
- n 1 to 20
- r represents 0 or 1
- X represents SiR 5 a [(CH 2 ) m BR 2 R 3 (R y ) r ] 3-a ,
- R 5 has the meaning of the residues R 1 , R 2 , R 3 , R y ,
- n is identical to or different from n and represents integers from 1 to 20,
- a 0, 1 or 2
- R 2 , R 3 , R 5 , R y , i, n, r have the above-stated meanings
- X represents SiR 5 a [(CH 2 ) m SiR 6 b [(CH 2 ) p BR 2 R 3 (R y ) r ] 3-b ] 3-a ,
- R 2 , R 3 , R 5 , R y , i, n, r, m, a have the above-stated meanings
- R 6 has the meaning of the residues R 1 , R 2 , R 3 , R y ,
- p represents integers from 1 to 20.
- K preferably represents alkali metal ions, such as for example Li + , Na + , K + or carbenium ions, such as for example the triphenylmethyl cation or di- or trisubstituted ammonium ions, such as for example N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri(n-butyl)ammonium, dimethylundecylammonium, dimethyldodecylammonium, dimethyloctadecylammonium, methyldioctadecylammonium, methyloctadecylammonium or dioctadecylammonium ions.
- alkali metal ions such as for example Li + , Na + , K + or carbenium ions, such as for example the triphenylmethyl cation or di- or trisubstituted ammonium ions, such as for example N,N-dimethyl
- the present invention also provides a method for the production of dendrimeric compounds of the general formula (I), which method is characterised in that compounds of the general formula (IV)
- Y represents CR 8 ⁇ CR 9 R 10 .
- R 8 , R 9 and R 10 are identical or different and represent hydrogen, alkyl, aryl or halogen,
- R 7 has the meaning of residue R 4 in the formula (I) and
- n represents an integer from 2 to 20
- Y represents Me 1 R 5 a [(R 7 ) m-2 (CR 8 ⁇ CR 9 R 10 )] 3-a ,
- R 5 has the definition stated in the formula (I),
- Y represents Me 1 R 5 a [(R 4 ) m Me 1 R 6 b [(R 7 ) p-2 (CR 8 ⁇ CR 9 R 10 )] 3-a ,
- R 6 has the definition stated in formula (I),
- m, p represent an integer from 2 to 20 and in which all the other residues stated in the formulae have the above-stated meanings for Y,
- R 11 represents hydrogen or C 1 -C 30 alkyl
- Me 3 represents an alkali metal and R y has the meaning stated in the formula (I),
- Me 4 represents an alkaline earth metal or transition metal of subgroups 1 or 2
- Hal represents halogen
- R y has the meaning as before.
- the preferred alkaline earth metal is Mg, with the preferred transition metals being Zn, Cd, Hg or Cu.
- Preferred alkali metals are Li, Na and K, particularly preferably Li.
- Y represents -CH ⁇ CH 2
- R 1 represents an optionally mono- or polysubstituted C 1 -C 6 alkyl or C 6 -C 12 aryl residue and
- n an integer from 1 to 10
- Y represents SiR 5 a [(CH 2 ) m (CH ⁇ CH 2 )] 3-a ,
- a 0, 1 or 2
- R 5 has the meaning of R 1 ,
- m represents an integer from 1 to 10
- Y represents SiR 5 a [(CH 2 ) m SiR 6 b [(CH 2 ) p CH ⁇ CH 2 ] 3-b ] 3-a ,
- R 6 has the meaning of R 1 and
- p and m represent an integer from 1 to 10;
- R 2 , R 3 have the meaning stated in the formula (I);
- Me 3 represents Li or Na
- R y has the meaning stated in the formula (I);
- Hal represents Cl or Br
- R y has the meaning as in formula (I) and
- Y represents -CH ⁇ CH 2
- n 1, 2, 3 or 4
- Y represents Si[(CH 2 ) m CH ⁇ CH 2 ] 3 and
- m represents 1, 2, 3 or 4,
- p represents 1, 2, 3 or 4 and
- the compounds of the general formula (IV) are reacted with compounds of the general formula (V) at temperatures of -100 to 150° C., preferably of -80 to 100° C., and at pressures from standard pressure to 10 bar, preferably at standard pressure.
- the molar ratio of compounds of the general formula (IV) to compounds of the general formula (V) during the reaction is generally such that at least one equivalent of the compound of the formula (V) is available for each residue CR 8 ⁇ CR 9 R 10 of the formula (IV).
- the reaction is optionally performed in the presence of solvents and/or diluents, such as for example alkanes. In many cases, however, it is also possible to dispense with the use of solvents and/or diluents. This is the case, for example, if an unsaturated compound of the formula (IV) is reacted with HBCl 2 .
- the necessary HBCl 2 may, for example, be produced during the reaction as an intermediate from trialkylsilanes, R 3 Si-H and BCl 3 . This method of preparation is described, for example, in J. Org. Chem. 1990, 55, 2274.
- reaction proceeds in this case at temperatures of -100 to +200° C. and standard pressure, preferably at -100 to 150° C.
- Solvents and/or diluents which may be considered are those stated above in the quantities which have likewise been stated above.
- an alkenylsilane such as for example tetravinyl- or tetrallylsilane
- a hydrochlorosilane such as HSiCl 3 , MSiMeCl 2 or MSiMe 2 Cl
- the resultant product is further reacted with an alkenylmagnesium compound (Grignard reaction).
- This reaction sequence hydrosilylation with a Grignard reaction
- novel dendrimeric compounds of the formula (I) may be used as catalysts or for the production of catalyst systems based on transition metal complexes.
- the stated use of the compounds of the formula (I) according to the invention is not restricted by the appended condition included in the formula (I).
- Catalyst systems based on transition metal complexes and the stated dendrimeric compounds of the unrestricted formula (I) consist, for example, of
- Me 5 represents a transtion metal of groups IIIb to VIIb or of group VIII of the periodic system of elements according to IUPAC nomenclature
- A represents an optionally singly- or multiply bridged anionic ligand
- R 12 has the same meaning as R 1 ,
- c, d represent an integer from 0 to 6 and
- component a) to component b) is conventionally in the range from 1:0.01-1:100, preferably from 1:0.1-1:1.
- Transition metal complexes of the formula (VIII) which may in particular be considered are those in which
- Me 5 is an metal from the group titanium, zirconium, hafnium, vanadium, niobium and tantalum,
- A is a pyrazolate of the formula N 2 C 3 R 13 3 a pyrazolylborate of the formula R 14 B(N 2 C 3 R 13 3 ) 3 , an alkoxide or phenolate of the formula OR 14 , a siloxane of the formula OSiR 14 3 , a thiolate of the formula SR 14 , an acetylacetonate of the formula (R 14 CO) 2 CR 14 , a diimine of the formula (R 15 N ⁇ CR 14 ) 2 , an amidinate of the formula R 14 C(NR 15 2 ) 2 , a cyclooctatetraenyl, an optionally mono- or polysubstituted cyclopentadienyl, an optionally mono- or polysubstituted indenyl and an optionally mono- or polysubstituted fluorenyl, wherein substituents which may be considered are a C 1 to C 20 alkyl group, a C 1 -
- R 12 represents hydrogen, fluorine, chlorine, bromine, methyl, benzyl, neopentyl and phenyl,
- R 13 in the formulae for A represents hydrogen or a C 1 -C 10 alkyl group
- R 14 , R 15 in the formulae for A have the same meaning as R 1 ,
- d 2 or 3.
- Preferred transition metal complexes of the formula (VIII) are those in which
- Me 5 represents titanium, zirconium and hafnium
- A represents bis(trimethylsilyl)amide, dimethylamide, diethylamide, diisopropylamide, 2,6-di-tert.-butyl-4-methylphenolate, cyclooctatetraenyl, cyclopentadienyl, methylcyclopentadienyl, benzylcyclopentadienyl, n-propylcyclopentadienyl, n-butylcyclopentadienyl, isobutylcyclopentadienyl, t-butylcyclopentadienyl, cyclopentylcyclopentadienyl, octadecylcyclopentadienyl, 1,2-dimethylcyclopentadienyl, 1,3-dimethylcyclopentadienyl, 1,3-diisopropylcyclopentadienyl, 1,3-di-t-butylcyclopentadien
- R 12 represents chlorine, methyl or benzyl
- d 2 or 3
- the anionic ligands A may be bridged by divalent groups such as Me 2 Si, Ph 2 Si, Ph(Me)Si, Me 2 C, Ph 2 C, Ph(Me)C or CH 2 CH 2 .
- divalent groups such as Me 2 Si, Ph 2 Si, Ph(Me)Si, Me 2 C, Ph 2 C, Ph(Me)C or CH 2 CH 2 .
- Me 5 represents nickel and palladium
- A represents a diimine of the formula (R 15 N ⁇ CN 14 ) 2 ,
- R 12 , R 14 , R 15 have the above-stated meaning.
- Organoaluminium compounds may optionally additionally be added to the catalyst system comprising transition metal complexes and the dendrimers according to the invention.
- organoaluminium compounds are trialkylaluminium compounds, such as trimethylaluminium, triethylaluminium, triisobutylaluminium, triisooctylaluminium, as well as dialkylaluminium compounds, such as diisobutylaluminium hydride, or aluminoxanes, such as trimethylaluminoxane or triisobutylaluminoxane.
- the molar ratio of the organoaluminium compounds to transition metal complexes of the formula (VIII) is in the range from 10000:1-0.1:1, preferably from 1000:1-1:1, particularly preferably from 100:1-10:1.
- the present invention also provides the use of the novel catalysts or catalyst systems for the polymerisation of unsaturated organic compounds, in particular of olefins and dienes.
- Polymerisation is here taken to mean both homo- and copolymerisation of the stated unsaturated compounds.
- C 2 -C 10 alkenes such as ethylene, propylene, 1-butene, 1-pentene and 1-hexene, 1-octene, isobutylene and arylalkenes, such as styrene, are in particular used in said polymerisation.
- Dienes which are in particular used are: conjugated dienes, such as 1,3-butadiene, isoprene, 1,3-pentadiene, and unconjugated dienes, such as 1,4-hexadiene, 1,5-heptadiene, 5,7-dimethyl-1,6-octadiene, 4-vinyl-1-cylohexene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene and dicyclopentadiene.
- conjugated dienes such as 1,3-butadiene, isoprene, 1,3-pentadiene
- unconjugated dienes such as 1,4-hexadiene, 1,5-heptadiene, 5,7-dimethyl-1,6-octadiene, 4-vinyl-1-cylohexene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene and dicyclopen
- the novel dendrimeric compounds of the formula (I) may also be used on their own as catalysts, for example for polymerisation reactions.
- the dendrimeric compounds of the formula (I) are suitable not only for polymerising unsaturated compounds, but also for polymerising cyclic ethers, such as ethylene oxide, propylene oxide and tetrahydrofuran.
- the catalysts according to the invention are in particular suitable for the production of rubbers based on copolymers of ethylene with one or more of the stated ⁇ -olefins and the stated dienes.
- the catalyst system according to the invention is furthermore suitable for polymerising cycloolefins, such as norbornene, cyclopentene, cyclohexene or cyclooctane and for copolymerising cycloolefins with ethylene or ⁇ -olefins.
- Polymerisation may be performed in the liquid phase, in the presence or absence of an inert solvent, or in the gas phase.
- Suitable solvents are aromatic hydrocarbons, such as benzene and/or toluene, or aliphatic hydrocarbons, such as propane, hexane, heptane, octane, isobutane, cyclohexane, or mixtures of the various hydrocarbons.
- Suitable support materials which may be mentioned are, for example, inorganic or organic polymeric supports, such as silica gel, magnesium chloride, zeolites, carbon black, activated carbon, aluminium oxide, polystyrene and polypropylene.
- Polymerisation is generally performed at pressures of 1 to 1000, preferably of 1 to 100 bar, and temperatures of -100° C. to +250° C., preferably of 0° C. to +150° C. Polymerisation may be performed continuously or discontinuously in conventional reactors.
- novel dendrimeric compounds of the formula (I) are distinguished by elevated thermal stability and storage stability. They are produced from inexpensive educts which are industrially available in large quantities. The production method described above provides wide scope for various structural variants of the dendrimeric compound of the formula (I), which have a defined molecular structure. The optimum structure may accordingly be tailored to the intended application.
- the novel dendrimeric compounds In combination with transition metal complexes of the formula (VIII), the novel dendrimeric compounds have elevated catalytic activity for the polymerisation of unsaturated compounds. They moreover have improved catalyst service lives, i.e. consistently high catalytic activity over extended periods of polymerisation. Due to their elevated catalytic activity, only small quantities of the dendrimeric compounds are required. The residual catalyst content in the polymer is so low that no work-up is required to remove the catalyst. This gives rise to a processing advantage as a costly washing step to remove the catalyst is omitted.
- Another advantage is the favourable molar ratio of transition metal complexes of the formula (VIII) to dendrimeric compounds of the formula (I) in the production of catalyst system. Highly reproducible catalytic activities are obtained if the dendrimeric compounds are used in a molar deficit relative to the transition metal complex.
- olefins may be polymerised as follows: after the conventional cleaning operations, a steel autoclave is filled with a solvent and a scavenger, for example triisobutylaluminium. The scavenger renders harmless any possible contaminants and catalyst poisons, for example water or other compounds containing oxygen. A compound of the formula (VIII) is then added as a catalyst precursor. The reactor is then filled with monomers and polymerisation is started by adding a solution of the dendrimeric compounds described above. Separate feeding of the dendrimeric compound without preactivation is of particular advantage in a continuous polymerisation process.
- the organometallic compounds were produced and handled under a protective argon atmosphere and with the exclusion of air and moisture (Schlenk technique). All the necessary solvents were obtained in absolute form before use by boiling for several hours over a suitable desiccant and subsequent distillation under argon.
- the compounds were preferably characterised by 11 B NMR, optionally also by 1 H NMR and 13 C NMR. Other commercial educts were used without further purification. Tetraallylsilane was produced from silicon tetrachloride and allylmagnesium chloride.
- the autoclave was depressurised, the polymer filtered off, washed with methanol and dried for 20 h under a vacuum at 60° C. 36.6 g of polyethylene were obtained.
- the resultant polymer was isolated and dried for 20 h under a vacuum at 60° C. 70.1 g of copolymer were obtained having the following composition according to IR spectroscopy: 61.8% ethylene and 38.2% propylene. A Tg of -57° C. was determined by the DSC method.
- the reaction was terminated after 10 minutes' polymerisation by adding 10 ml of methanol, the polymer was filtered off, washed with methanol and dried in a vacuum drying cabinet. 1.9 g of polyethylene were obtained.
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Abstract
The present invention relates to a novel dendrimic compounds, to a method for the production thereof and to the use thereof as catalysts for the production of polymers, in particular to the use thereof as co-catalysts for metallocenes for polymerizing unsaturated compounds.
Description
- The present invention relates to novel dendrimeric compounds, to a method for the production thereof and to the use thereof as catalysts for the production of polymers, in particular to the use thereof as co-catalysts for metallocenes for polymerising unsaturated compounds.
- It has long been known to use metallocenes in combination with activating co-catalysts, preferably alumoxanes (MAOs), for polymerising olefins and diolefins (c.f. for example EP-A 129 368, 347 128, 347 129, 351 392, 485 821, 485 823).
- However, catalyst systems based on metallocenes and alumoxanes have considerable disadvantages. Thus alumoxanes, in particular MAOs, cannot be produced with a high degree of reproducibility either in situ or in a pre-forming process. MAO is a mixture of various species containing aluminiumalkyl which exist in equilibrium with each other, resulting in a loss of reproducibility during the polymerisation of olefinic compounds. Moreover, MAO is not stable in storage and the composition thereof changes on exposure to extreme temperatures. Another serious disadvantage is the considerable excess of MAO which is necessary for the activation of metallocenes. However, this high MAO/metallocene ratio is an absolute prerequisite for achieving high catalyst activities. This results in a crucial processing disadvantage, however, since aluminium compounds must be separated from the polymers during work-up. Furthermore, MAO is a cost-determining factor in the use of catalyst systems containing MAO, meaning that excesses of MAO are uneconomic.
- InJ. Am. Chem. Soc. 1991, 113, 3623, tris(pentafluorophenyl)borane is described as a co-catalyst for metallocene dialkyls. However, the polymerisation activity of catalysts based on tris(pentafluorophenyl)borane is unsatisfactory. EP-A 277 003 and 277 004 describe ionic catalyst systems which are produced by the reaction of metallocenes with ionising reagents. Perfluorinated, tetraaromatic borate compounds, in particular tetrakis(pentafluorophenyl)borate compounds, are used as ionising reagents (EP 468 537, EP 561 479). However, the production and introduction of pentafluorophenyl substituents is complex and costly. Using tetrakis(pentafluorophenyl)borate compounds on an industrial scale is thus highly cost-intensive. Another disadvantage of tetrakis(pentafluorophenyl)borate compounds is the poor solubility thereof in hydrocarbons.
- WO 93/11172 describes polyanionic activators for metallocenes which consist, for example, of a polystyrene matrix onto which what are termed non-coordinating anions, preferably borate compounds comprising pentafluorophenyl substituents, are chemically bonded. The catalytic activity of the borate compounds described above decreases considerably, however, if the fluoroaromatic substituents on the boron are replaced by other substituents, for example by methyl or butyl substituents.
- In comparison with the activators described in EP 468 537, for example N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, the polyanionic activators described in WO 93/11172 exhibit lower polymerisation activity. Another disadvantage is the poor yield during the production of the polyanionic activators. Costly tris(pentafluorophenyl)borane is used as a starting compound which must be chemically bonded by a complicated method onto a matrix, for example crosslinked polystyrene. The polyanionic activators do not have a uniform surface, wherein accessibility of the molecular surface or the active end groups may be restricted. The precise composition, in particular the number of active end groups of the polyanionic activators is not known. The polyanionic activators have neither a defined molecular size nor dimensional stability. The poor meterability of polyanionic activators is industrially disadvantageous. The sparingly soluble polyanionic activators are used as solids for catalysing polymerisation, which is technically disadvantageous in a continuous polymerisation process.
- The object thus arose of identifying novel co-catalysts which avoid the above-stated disadvantages. In particular, the object consisted in creating a cost-effective catalyst system which is easy to produce, easy to handle industrially and is capable of polymerising unsaturated compounds, such as for example olefins and dienes, at a high level of catalytic activity.
- It has surprisingly now been found that dendrimeric compounds which contain metals, preferably in combination with metallocenes, are particularly suitable for achieving the above-stated objects.
- The present invention accordingly provides novel dendrimeric compounds of the general formula
- R1 4- iMe1[(R4)nX]i (I),
- in which
- X represents Me2R2R3(Ry)r,
- R1, R2, R3, Ry are identical or different, may optionally be mono- or polysubstituted and represent hydrogen, C5-C20 cycloalkyl, C1-C20 alkyl, C7-C40 aralkyl, C6-C40 aryl, C1-C10 alkoxy, C6-C40 aryloxy, silyloxy or halogen,
- R4 represents an optionally mono- or polysubstituted alkylene, alkenylene or alkynylene residue, which is optionally interrupted by one or more heteroatoms,
- Me1 represents an element of group IVa of the periodic system of the elements (IUPAC nomenclature),
- Me2 represents an element of group IIIa of the periodic system of the elements (IUPAC nomenclature),
- i represents an integer from 2 to 4,
- n represents an integer from 1 to 20 and
- r represents 0 or 1
- wherein, when r=1, the Me2 residue bears a negative formal charge and in the event of a negative formal charge on Me2, this is offset by a cation,
- or in which
- X represents Me1R5 a[(R4)mMe2R2R3- (R y)r]3-a,
- Me1, Me2, R1, R2, R3, R4, Ry, i, n, r have the above-stated meanings,
- R5 has the meaning of the residues R1, R2, R3, Ry,
- m is identical to or different from n and represents integers from 1 to 20 and
- a represents 0, 1 or 2,
- or in which
- X represents Me1R5 a[(R4)mMe1R6 b[(R4)pMe2R2R3(Ry)r]3- b]3- a,
- Me1, Me2, R2, R3, R4, Ry, i, n, r, m, a have the above-stated meanings,
- R6 has the meaning of the residues R1, R2, R3, Ry, R5,
- b represents 0, 1 or 2 and
- p represents integers from 1 to 20,
- wherein the compounds described in DE 195 16 200 are excluded, said compounds being produced by the reaction of silicon tetrachloride in a Grignard reaction to form tetraallylsilane, which is subsequently reacted twice or more alternately
- a) with trichlorosilane in a quantitative reaction in the presence of a catalyst and then
- b) with an allyl compound in a Grignard reaction using a suitable solvent in each case until a dendrimeric skeleton comprising outwardly pointing allyl groups is obtained, the outer allyl groups of which
- c) are derivatised in a hydroboration reaction with 9-borabicyclo[3.3.1]nonane.
- Suitable cations in the event that Me2 bears a negative formal charge which may be considered are ions of atoms or molecules such as alkali metal ions, for example Li+, Na+ or K+, alkaline earth metal ions such as Be2+, Mg2+, Ca2+, Ba2+, transition metal ions such as Zn2+, Cd2+, Mg2+, Cu+, Cu2+, or organic compounds such as ammonium or phosphonium ions of the NR4 + or PR4 + type, preferably Ph-N(CH3)2H+, or carbocations of the CR3 + type, preferably CPh3 +.
- The nature of the cation NR4 + in particular also has an influence on the solubility of the salts, consisting of the dendrimeric compounds according to the invention of the formula (I) which have at least one negative formal charge (r=1) and cations which offset the formal charge. The solubility of the stated salts in non-polar solvents, such as for example toluene and xylene, may, for example, be improved by using ammonium salts NR′R3 + which contain a relatively long-chain, branched or unbranched hydrocarbon residue R′. R′ is here preferably an unbranched C6-C40 alkyl residue, particularly preferably a C8-C12 alkyl residue. The remaining residues R in NR3R′ may, mutually independently, be hydrogen and optionally mono- or polysubstituted C1-C5 alkyl and C6-C12 aryl residues. At least one residue R in NR3R′ is preferably hydrogen. Specifically, cations such as undecyldimethylammonium and dodecyldimethylammonium may be mentioned.
- Cycloalkyl residues in the formula (I) which may in particular be considered are those having 5 to 10 carbon atoms. Example which may be mentioned are cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl residues, fused cycloaliphatic residues such as decalin or hydrindene residues or bicyclic residues such as norbornyl residues.
- Cyclopentyl, cyclohexyl and norbornyl residues are preferred.
- Preferred alkyl residues are those having 1 to 10 carbon atoms, the following being mentioned by way of example: methyl, ethyl, propyl, n-butyl, pentyl, hexyl, heptyl, octyl, isopropyl, sec.-butyl, tert.-butyl or neopentyl, preferably methyl, ethyl, propyl, n-butyl, sec.-butyl, tert.-butyl.
- Aralkyl residues which may be mentioned are those having 7 to 20 carbon atoms, preferably the benzyl residue.
- Preferred aryl residues which may be considered are those having 6 to 20 carbon atoms, the following being mentioned by way of example: phenyl, toluyl, p-halo-phenyl, mesityl, pentafluorophenyl, bis(3,5-trifluoromethyl)phenyl, more preferably pentafluorophenyl, bis(3,5-trifluoromethyl)phenyl, most preferably pentafluorophenyl.
- Aryloxy residues which may in particular be considered are those having 6 to 10 carbon atoms, phenyloxy residues being mentioned by way of example.
- Silyloxy residues which may be considered are compounds of the type —O—SiR3, in which R denotes C1-C10 alkyl residues or C6-C10 aryl residues. Silyloxy residues, such as —O—SiMe3, —O—SiEt3 and —O—SiPh3, are preferred.
- Examples of halogens which are used are fluorine, chlorine and bromine, in particular fluorine and chlorine.
- As mentioned above, depending upon the number of C atoms, the residues R1, R2, R3, R4 and Ry of the formula (I) may be mono- or polysubstituted, preferably mono- to decasubstituted, particularly preferably mono- to pentasubstituted. Substituents which may be considered are, for example, the above-mentioned cycloalkyl, alkyl, aralkyl, aryl, alkoxy, aryloxy and silyloxy residues, as well as the stated halogens. Preferred substituents are halogens, in particular fluorine, alkyls, such as methyl and ethyl, perhalogenated alkyls, such as CF3, or perhalogenated aromatics, such as C6F5.
- Elements of main group 4 of the periodic system of elements which may be mentioned are Si, Ge, Sn and Pb, preferably Si, Ge, Sn, in particular Si.
- Elements of main group 3 of the periodic system of elements which may be considered are B, Al, In and Ga, preferably B, Al, very particularly preferably B.
- In the formula (I), i preferably represents the numbers 3 or 4, particularly preferably 4, n is an integer from 1 to 10, in particular 2 to 5, and r represents 0.
- In the formula (I), m furthermore preferably represents integers from 1 to 10, in particular from 2 to 5, a represents 0, b represents 0 and p represents integers from 1 to 10, in particular 2 to 5.
- Dendrimeric compounds which may be considered are preferably those of the formula (II)
- R1 4- iSi[(R4)nX]i (II),
- in which
- X represents Me2R2R3(Ry)r, and R1, R2, R3, Ryare identical or different, preferably identical, may optionally be mono- or polysubstituted, and represent C5-C6 cycloalkyl, C6-C10 aryl, C1-C10 alkyl and/or halogen,
- R4 represents a methylene residue,
- Me2 represents boron or Al,
- i represents an integer from 2 to 4,
- n represents an integer from 1 to 20,
- r may be 0 or 1,
- or in which
- X represents SiR5 a[(R4)mMe2R2R3(Ry)r]3- a,
- R5 has the meaning of the residues R1, R2, R3, Ry,
- m is identical to or different from n and represents integers from 1 to 20,
- a represents 0, 1 or 2,
- and Me2, R2, R3, R4, i, n, r have the above-stated meanings,
- or in which
- X represents SiR5 a[(R4)mSiR6 b[(R4)pMe2R2R3(Ry)r]3-b]3-a,
- Me2, R2, R3, R4, R5, Ry, i, n, r, m, a have the above-stated meanings,
- and
- R6 has the meaning of the residues R1, R2, R3, R5, Ry,
- b represents 0, 1 or 2 and
- p represents integers from 1 to 20.
- Particularly preferred dendrimeric compounds are those of the general formula (III)
- R1 4-iSi[(CH2)nX]i (III),
- in which
- X represents BR2R3(Ry)r and
- R1, R2, R3, Ry are identical or different, preferably identical, may optionally be mono- or polysubstituted and represent C6-C10 aryl or C1-C10 alkyl,
- i represents 3 or 4,
- n represents 1 to 20 and
- r represents 0 or 1
- or in which
- X represents SiR5 a[(CH2)mBR2R3(Ry)r]3-a,
- R5 has the meaning of the residues R1, R2, R3, Ry,
- m is identical to or different from n and represents integers from 1 to 20,
- a represents 0, 1 or 2 and
- R2, R3, R5, Ry, i, n, r have the above-stated meanings,
- or in which
- X represents SiR5 a[(CH2)mSiR6 b[(CH2)pBR2R3(Ry)r]3-b]3-a,
- R2, R3, R5, Ry, i, n, r, m, a have the above-stated meanings,
- R6 has the meaning of the residues R1, R2, R3, Ry,
- b represents 0, 1 or 2 and
- p represents integers from 1 to 20.
- Emphasis should be placed upon the dendrimeric compounds of the following formulae:
- Si[(CH2)3BCl2]4
- Si[(CH2)3BMe2]4
- Si[(CH2)3B(C6F5)2]4
- Si[(CH2)3BMes2]4
- Si[(CH2)3B(C6H3(CF3)2)2]4
- Si[(CH2)3BMe3]4 4-4K+
- Si[(CH2)3B(n-Bu)3]4 4-4K+
- Si[(CH2)3B(n-Bu)2]4
- Si[(CH2)3B(C6F5)3]4 4-4K+
- Si[(CH2)3B(C6H3(CF3)2)3]4 4-4K+
- Si{(CH2)2Si[(CH2)3BCl2]3}4
- Si{(CH2)2Si[(CH2)3BMe2]3}4
- Si{(CH2)2Si[(CH2)3B(n-Bu)2]3}4
- Si{(CH2)2Si[(CH2)3B(C6F5)2]3}4
- Si{(CH2)2Si[(CH2)3BMe3]3}4 12-12K+
- Si{(CH2)2Si[(CH2)3B(n-Bu)3]3}4 12-12K+
- Si{(CH2)2Si[(CH2)3B(C6F5)3]3}4 12-12K+
- Si{(CH2)2Si[(CH2)3B(3,5-(CF3)2C6H3)3]3}4 12-12K+
- Si{(O—CH2)3Si(CH3)[(CH2)3BCl2]2}4
- Si{(O—CH2)3Si(CH3)[(CH2)3BMe2]2}4
- Si{(O—CH2)3Si(CH3)[(CH2)3B(n-Bu)2]2}4
- Si{(O—CH2)3Si(CH3)[(CH2)3B(C6H5)2]2}4
- Si{(O—CH2)3Si(CH3)[(CH2)3B(C6F5)2]2}4
- Si{(O—CH2)3Si(CH3)[(CH2)3BMe3]4 4-4K+
- Si{(O—CH2)3Si(CH3)[(CH2)3B(C6H5)3]4 4-4K+
- Si{(O—CH2)3Si(CH3)[(CH2)3B(C6F5)3]4 4-4K+
- wherein Mes represents 2,4,6-mesityl and K means a cation bearing one or more charges.
- K preferably represents alkali metal ions, such as for example Li+, Na+, K+ or carbenium ions, such as for example the triphenylmethyl cation or di- or trisubstituted ammonium ions, such as for example N,N-dimethylanilinium, trimethylammonium, triethylammonium, tri(n-butyl)ammonium, dimethylundecylammonium, dimethyldodecylammonium, dimethyloctadecylammonium, methyldioctadecylammonium, methyloctadecylammonium or dioctadecylammonium ions.
- The present invention also provides a method for the production of dendrimeric compounds of the general formula (I), which method is characterised in that compounds of the general formula (IV)
- R1 4-iMe1[(R7)n-2Y]i (IV)
- in which
- Y represents CR8═CR9R10,
- R8, R9 and R10 are identical or different and represent hydrogen, alkyl, aryl or halogen,
- R7 has the meaning of residue R4 in the formula (I) and
- n represents an integer from 2 to 20,
- R1, Me1 and i have the definition stated for the formula (I),
- or in which
- Y represents Me1R5 a[(R7)m-2(CR8═CR9R10)]3-a,
- R5 has the definition stated in the formula (I),
- or in which
- Y represents Me1R5 a[(R4)mMe1R6 b[(R7)p-2(CR8═CR9R10)]3-a,
- R6 has the definition stated in formula (I),
- m, p represent an integer from 2 to 20 and in which all the other residues stated in the formulae have the above-stated meanings for Y,
- are reacted with compounds of the general formula (V)
- R11Me2R2R3 (V),
- in which
- R11 represents hydrogen or C1-C30 alkyl and
- Me2, R2 and R3 have the meanings stated in the formula (I),
- and, in the event that r=1, the resultant product is further reacted with compounds of the general formula (VI)
- Me3-Ry (VI),
- in which
- Me3 represents an alkali metal and Ry has the meaning stated in the formula (I),
- or with compounds of the general formula (VII)
- Halq-Me4-Ry 2-q (VII),
- in which
- Me4 represents an alkaline earth metal or transition metal of subgroups 1 or 2,
- Hal represents halogen,
- q represents 0 or 1 and
- Ry has the meaning as before.
- The preferred alkaline earth metal is Mg, with the preferred transition metals being Zn, Cd, Hg or Cu. Preferred alkali metals are Li, Na and K, particularly preferably Li.
- Hydrogen and C1-C5 alkyl are preferred as residues R8, R9 and R10, with hydrogen being particularly preferred.
-
- as a result of which compounds of the formula (I) in which n, m or p=1 may be obtained.
- Compounds of the formulae (IV), (V), (VI) and (VII) which are preferably used are respectively those of the general formulae (IVa), (Va), (VIa) and (VIIa) shown below:
- R1 4-iSi[(CH2)nY]i (IVa)
- in which
- Y represents -CH═CH2,
- i represents 3 or 4,
- R1 represents an optionally mono- or polysubstituted C1-C6 alkyl or C6-C12 aryl residue and
- n represents an integer from 1 to 10,
- or in which
- Y represents SiR5 a[(CH2)m(CH═CH2)]3-a,
- a represents 0, 1 or 2 and
- R5 has the meaning of R1,
- m represents an integer from 1 to 10,
- or in which
- Y represents SiR5 a[(CH2)mSiR6 b[(CH2)pCH═CH2]3-b]3-a,
- R6 has the meaning of R1 and
- p and m represent an integer from 1 to 10;
- H-BR2R3 (Va),
- in which
- R2, R3 have the meaning stated in the formula (I);
- Me3-Ry (VIa),
- in which
- Me3 represents Li or Na and
- Ry has the meaning stated in the formula (I);
- Halq-Mg-Ry 2-q (VIIa),
- in which
- Hal represents Cl or Br and
- Ry has the meaning as in formula (I) and
- q represents 0 or 1.
- Compounds of the formula (IV) which are particularly preferably used are those of the general formula IVb):
- Si[(CH2)nY]4 (IVb)
- in which
- Y represents -CH═CH2 and
- n represents 1, 2, 3 or 4,
- or in which
- Y represents Si[(CH2)mCH═CH2]3 and
- m represents 1, 2, 3 or 4,
- or in which
- Y Si[(CH2)mSi[(CH2)pCH═CH2]3]3,
- p represents 1, 2, 3 or 4 and
- m has the above meaning.
- As mentioned above, in the method according to the invention, compounds of the general formula (IV) are reacted with compounds of the general formula (V) and in this manner nonionic dendrimeric compounds of the general formula (I) where r=0 are obtained.
- According to the invention, the compounds of the general formula (IV) are reacted with compounds of the general formula (V) at temperatures of -100 to 150° C., preferably of -80 to 100° C., and at pressures from standard pressure to 10 bar, preferably at standard pressure. The molar ratio of compounds of the general formula (IV) to compounds of the general formula (V) during the reaction is generally such that at least one equivalent of the compound of the formula (V) is available for each residue CR8═CR9R10 of the formula (IV).
- The reaction is optionally performed in the presence of solvents and/or diluents, such as for example alkanes. In many cases, however, it is also possible to dispense with the use of solvents and/or diluents. This is the case, for example, if an unsaturated compound of the formula (IV) is reacted with HBCl2. The necessary HBCl2 may, for example, be produced during the reaction as an intermediate from trialkylsilanes, R3Si-H and BCl3. This method of preparation is described, for example, in J. Org. Chem. 1990, 55, 2274.
- In order to produce dendrimeric compounds of an ionic structure of the general formula (I) (in the event that r=1), the reaction product obtained from compounds of the general formula (IV) and compounds of the general formula (V) is further reacted with organic alkali metal, alkaline earth metal or transition metal compounds of the formula (VI) or (VII).
- The reaction proceeds in this case at temperatures of -100 to +200° C. and standard pressure, preferably at -100 to 150° C. Solvents and/or diluents which may be considered are those stated above in the quantities which have likewise been stated above.
- The compounds of the formulae (VI) or (VII) are preferably used in an equimolar ratio or an excess relative to the residue Me2R2R3 of the dendrimeric compounds of the formula (I) where r=0 obtained from the reaction of compounds of the formula (IV) with compounds of the formula (V).
- Production of the starting compounds of the formula (IV) is known and may proceed in a similar manner to the production of carbosilane dendrimers. Instructions for the production of carbosilane dendrimers may be found, for example, inRubber Chem. Technol. 1992, 65, 303-314, Adv. Mater. 1993, 5, 466-468, Macromolecules 1993, 26, 963-968, J. Chem. Soc., Chem. Commun. 1994, 2575-2576, Organometallics 1994, 13, 2682-2690, Macromolecules 1995, 28, 6657-6661 and Organometallics 1995, 14, 5362-5366.
- During such production, an alkenylsilane, such as for example tetravinyl- or tetrallylsilane, is reacted with a hydrochlorosilane, such as HSiCl3, MSiMeCl2 or MSiMe2Cl, and the resultant product is further reacted with an alkenylmagnesium compound (Grignard reaction). This reaction sequence (hydrosilylation with a Grignard reaction) may be repeated twice or more.
-
-
- The novel dendrimeric compounds of the formula (I) may be used as catalysts or for the production of catalyst systems based on transition metal complexes. The stated use of the compounds of the formula (I) according to the invention is not restricted by the appended condition included in the formula (I).
- Catalyst systems based on transition metal complexes and the stated dendrimeric compounds of the unrestricted formula (I) consist, for example, of
- a) a transition metal complex of the formula (VIII)
- AcMe5R12 d (VIII),
- in which
- Me5 represents a transtion metal of groups IIIb to VIIb or of group VIII of the periodic system of elements according to IUPAC nomenclature,
- A represents an optionally singly- or multiply bridged anionic ligand
- R12 has the same meaning as R1,
- and
- c, d represent an integer from 0 to 6 and
- b) a dendrimeric compound of the formula (I),
- wherein the molar ratio of component a) to component b) is conventionally in the range from 1:0.01-1:100, preferably from 1:0.1-1:1.
- Transition metal complexes of the formula (VIII) which may in particular be considered are those in which
- Me5 is an metal from the group titanium, zirconium, hafnium, vanadium, niobium and tantalum,
- A is a pyrazolate of the formula N2C3R13 3 a pyrazolylborate of the formula R14B(N2C3R13 3)3, an alkoxide or phenolate of the formula OR14, a siloxane of the formula OSiR14 3, a thiolate of the formula SR14, an acetylacetonate of the formula (R14CO)2CR14, a diimine of the formula (R15N═CR14)2, an amidinate of the formula R14C(NR15 2)2, a cyclooctatetraenyl, an optionally mono- or polysubstituted cyclopentadienyl, an optionally mono- or polysubstituted indenyl and an optionally mono- or polysubstituted fluorenyl, wherein substituents which may be considered are a C1 to C20 alkyl group, a C1-C10 alkoxy group, a C6 to C20 aryl group, a C6 to C10 aryloxy group, a C7 to C40 arylalkyl group, a C7-C40 alkylaryl group, a boranyl, silyl, amino or phosphinyl group optionally substituted by C1 to C10 hydrocarbon residues,
- R12 represents hydrogen, fluorine, chlorine, bromine, methyl, benzyl, neopentyl and phenyl,
- R13 in the formulae for A represents hydrogen or a C1-C10 alkyl group,
- R14, R15 in the formulae for A have the same meaning as R1,
- c represents 1 or 2 and
- d represents 2 or 3.
- Preferred transition metal complexes of the formula (VIII) are those in which
- Me5 represents titanium, zirconium and hafnium,
- A represents bis(trimethylsilyl)amide, dimethylamide, diethylamide, diisopropylamide, 2,6-di-tert.-butyl-4-methylphenolate, cyclooctatetraenyl, cyclopentadienyl, methylcyclopentadienyl, benzylcyclopentadienyl, n-propylcyclopentadienyl, n-butylcyclopentadienyl, isobutylcyclopentadienyl, t-butylcyclopentadienyl, cyclopentylcyclopentadienyl, octadecylcyclopentadienyl, 1,2-dimethylcyclopentadienyl, 1,3-dimethylcyclopentadienyl, 1,3-diisopropylcyclopentadienyl, 1,3-di-t-butylcyclopentadienyl, 1-ethyl-2-methylcyclopentadienyl, 1-isopropyl-3-methylcyclopentadienyl, 1-(n-butyl)-3-methylcyclopentadienyl, 1-(t-butyl)-3-methylcyclopentadienyl, pentamethylcyclopentadienyl, 1,2,3,4-tetra-methylcyclopentadienyl, 1,2,4-trimethylcyclopentadienyl, 1,2,4-triiso-propylcyclopentadienyl, 1,2,4-tri-(t-butyl)cyclopentadienyl, indenyl, tetrahydroindenyl, 2-methylindenyl, 4,7-dimethylindenyl, 2-methyl-4,5-benzo-indenyl, 2-methyl-4-phenylindenyl, fluorenyl or 9-methylfluorenyl,
- R12 represents chlorine, methyl or benzyl,
- c represents 1 or 2 and
- d represents 2 or 3,
- and the anionic ligands A may be bridged by divalent groups such as Me2Si, Ph2Si, Ph(Me)Si, Me2C, Ph2C, Ph(Me)C or CH2CH2. Examples of the stated transition metal compounds in which c=2 are described, inter alia, in EP 129 368, EP 351 392, EP 485 821, EP 485 823, EP 549 990, EP 659 758. Examples of the stated transition metal compounds in which c=1 are described, inter alia, in Macromol. Chem. Rapid Commun. (13) 1992, 265 and, in the case of bridged monocyclopentadienyl complexes, in EP 416 815, WO 91/04257 or WO 96/13529.
- Further transition metal complexes of the formula (VIII) which may be considered are those in which
- Me5 represents nickel and palladium,
- A represents a diimine of the formula (R15N═CN14)2,
- c represents 1 and d represents 2,
- and R12, R14, R15 have the above-stated meaning.
- Examples of the stated diimine complexes are described, inter alia, in WO 96/23010.
- Organoaluminium compounds may optionally additionally be added to the catalyst system comprising transition metal complexes and the dendrimers according to the invention. Examples of organoaluminium compounds are trialkylaluminium compounds, such as trimethylaluminium, triethylaluminium, triisobutylaluminium, triisooctylaluminium, as well as dialkylaluminium compounds, such as diisobutylaluminium hydride, or aluminoxanes, such as trimethylaluminoxane or triisobutylaluminoxane. The molar ratio of the organoaluminium compounds to transition metal complexes of the formula (VIII) is in the range from 10000:1-0.1:1, preferably from 1000:1-1:1, particularly preferably from 100:1-10:1.
- The present invention also provides the use of the novel catalysts or catalyst systems for the polymerisation of unsaturated organic compounds, in particular of olefins and dienes. Polymerisation is here taken to mean both homo- and copolymerisation of the stated unsaturated compounds. C2-C10 alkenes, such as ethylene, propylene, 1-butene, 1-pentene and 1-hexene, 1-octene, isobutylene and arylalkenes, such as styrene, are in particular used in said polymerisation. Dienes which are in particular used are: conjugated dienes, such as 1,3-butadiene, isoprene, 1,3-pentadiene, and unconjugated dienes, such as 1,4-hexadiene, 1,5-heptadiene, 5,7-dimethyl-1,6-octadiene, 4-vinyl-1-cylohexene, 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene and dicyclopentadiene.
- As mentioned above, however, the novel dendrimeric compounds of the formula (I) may also be used on their own as catalysts, for example for polymerisation reactions. The dendrimeric compounds of the formula (I) are suitable not only for polymerising unsaturated compounds, but also for polymerising cyclic ethers, such as ethylene oxide, propylene oxide and tetrahydrofuran.
- The catalysts according to the invention are in particular suitable for the production of rubbers based on copolymers of ethylene with one or more of the stated α-olefins and the stated dienes. The catalyst system according to the invention is furthermore suitable for polymerising cycloolefins, such as norbornene, cyclopentene, cyclohexene or cyclooctane and for copolymerising cycloolefins with ethylene or α-olefins.
- Polymerisation may be performed in the liquid phase, in the presence or absence of an inert solvent, or in the gas phase. Suitable solvents are aromatic hydrocarbons, such as benzene and/or toluene, or aliphatic hydrocarbons, such as propane, hexane, heptane, octane, isobutane, cyclohexane, or mixtures of the various hydrocarbons.
- It is possible to use the catalyst system according to the invention applied onto a support. Suitable support materials which may be mentioned are, for example, inorganic or organic polymeric supports, such as silica gel, magnesium chloride, zeolites, carbon black, activated carbon, aluminium oxide, polystyrene and polypropylene.
- Polymerisation is generally performed at pressures of 1 to 1000, preferably of 1 to 100 bar, and temperatures of -100° C. to +250° C., preferably of 0° C. to +150° C. Polymerisation may be performed continuously or discontinuously in conventional reactors.
- The novel dendrimeric compounds of the formula (I) are distinguished by elevated thermal stability and storage stability. They are produced from inexpensive educts which are industrially available in large quantities. The production method described above provides wide scope for various structural variants of the dendrimeric compound of the formula (I), which have a defined molecular structure. The optimum structure may accordingly be tailored to the intended application.
- In combination with transition metal complexes of the formula (VIII), the novel dendrimeric compounds have elevated catalytic activity for the polymerisation of unsaturated compounds. They moreover have improved catalyst service lives, i.e. consistently high catalytic activity over extended periods of polymerisation. Due to their elevated catalytic activity, only small quantities of the dendrimeric compounds are required. The residual catalyst content in the polymer is so low that no work-up is required to remove the catalyst. This gives rise to a processing advantage as a costly washing step to remove the catalyst is omitted.
- Another advantage is the favourable molar ratio of transition metal complexes of the formula (VIII) to dendrimeric compounds of the formula (I) in the production of catalyst system. Highly reproducible catalytic activities are obtained if the dendrimeric compounds are used in a molar deficit relative to the transition metal complex.
- No preactivation is required when the dendrimeric compounds of the formula (I) are used to produce catalyst systems. For example, olefins may be polymerised as follows: after the conventional cleaning operations, a steel autoclave is filled with a solvent and a scavenger, for example triisobutylaluminium. The scavenger renders harmless any possible contaminants and catalyst poisons, for example water or other compounds containing oxygen. A compound of the formula (VIII) is then added as a catalyst precursor. The reactor is then filled with monomers and polymerisation is started by adding a solution of the dendrimeric compounds described above. Separate feeding of the dendrimeric compound without preactivation is of particular advantage in a continuous polymerisation process.
- The invention is illustrated in greater detail by the following Examples.
- General Information:
- The organometallic compounds were produced and handled under a protective argon atmosphere and with the exclusion of air and moisture (Schlenk technique). All the necessary solvents were obtained in absolute form before use by boiling for several hours over a suitable desiccant and subsequent distillation under argon. The compounds were preferably characterised by11B NMR, optionally also by 1H NMR and 13C NMR. Other commercial educts were used without further purification. Tetraallylsilane was produced from silicon tetrachloride and allylmagnesium chloride.
- Production of Si[(CH2)3BCl2]4
- 23.5 g (0.2 mol) of boron trichloride were condensed at -65° C. into a flask equipped with a gas inlet, reflux condenser and internal thermometer. A mixture of 23.3 g (0.2 mol) of triethylsilane and 9.6 g (0.05 mol) of tetraallylsilane were then slowly added dropwise at this temperature. On completion of addition, the mixture was heated to room temperature. Volatile constituents (substantially triethylchlorosilane) were then removed under a 0.2 mbar vacuum, initially at room temperature, then at a bath temperature of 40° C. The product was obtained as a colourless, highly mobile oil.
- C12H24B4Cl8Si, M=523.271 g/mol
-
-
-
- Production of a Solution of Si[(CH2)3B(C6F5)3]4 4- 4 Li+
- 6.35 ml of n-butyllithium (1.6 M in hexane; 10.1 mmol) were added dropwise within 20 minutes at -70° C. to a solution of 2.5 g (10.1 mmol) of bromopentafluorobenzene in 60 ml of hexane. The resultant suspension was stirred for 2 hours at -70° C. A solution of 445 mg (0.85 mmol) of Si[(CH2)3BCl2]4 from Example 1 in 5 ml of hexane was then added dropwise within 5 minutes and the reaction solution was then slowly raised to room temperature within 3 hours and stirred overnight.
- Production of Si[(CH2)3B(C6F5)3]4 4- 4 C6H5-NH(CH3)2 +
- 536 mg (3.4 mmol) of dimethylanilinium hydrochloride in 20 ml of methylene chloride were added to a solution of Si[(CH2)3B(C6F5)3]4 4- 4 Li+, produced as in Example 2. The mixture was again stirred overnight and the volatile constituents removed under a vacuum. After addition of 40 ml of methylene chloride, the mixture was filtered through diatomaceous earth and volatile constituents were removed from the colourless filtrate under a vacuum. After washing twice with 20 ml portions of hexane, the product was obtained as a colourless wax.
- C116H72B4F60N4Si, M=2733.170 g/mol
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- Polymerisation of Ethylene
- 500 ml of toluene, 0.1 ml of TIBA and 1 ml of a solution of 12.4 mg of bis(cyclopentadienyl)zirconiumdimethyl in 24.7 ml of toluene (=1 μmol of bis(cyclopentadienyl)zirconiumdimethyl) were initially introduced into a 1.4 L steel autoclave. This solution was adjusted to a temperature of 60° C. Ethylene was then apportioned until the internal pressure in the reactor rose to 6 bar. Polymerisation was started by adding 1 ml of a solution of 57.4 mg of the compound from Example 3 in 42 ml of toluene (=0.5 μmol of Si[(CH2)3B(C6F5)3]4 4- 4 C6H5- NH(CH3)2 +. After 20 minutes' polymerisation at 60° C. and 6 bar, the autoclave was depressurised, the polymer filtered off, washed with methanol and dried for 20 h under a vacuum at 60° C. 36.6 g of polyethylene were obtained.
- Copolymerisation of Ethylene and 1-hexene
- 100 ml of toluene, 0.1 ml of TIBA and 5 ml of 1-hexene were initially introduced into a 250 ml glass reactor. 1 ml of a solution of 12.7 mg of ethylenebis(indenyl)zirconiumdimethyl in 16.8 ml of toluene (=1 μmol of ethylenebis(indenyl)zirconiumdimethyl) was then added. Ethylene was then continually introduced into the solution at 20° C. via a gas inlet tube at a pressure of 1.1 bar. Polymerisation was started by adding 1 ml of solution of 57.4 mg of the compound from Example 3 in 42 ml of toluene (=0.5 μmol of Si[(CH2)3B(C6F5)3]4 4- 4 C6H5-NH(CH3)2 +). At a temperature of 20° C. and a pressure of 1.1 bar, a highly viscous clear reaction solution was obtained after 30 minutes' polymerisation. Polymerisation was terminated by adding 100 ml of methanol. The precipitated polymer was filtered off, washed with methanol and dried in a vacuum drying cabinet. 5.44 g of ethylene/1-hexene copolymer were obtained which contained 14.4 mol % of 1-hexene (according to the 13C NMR spectrum).
- Polymerisation of Propylene
- Production of the catalyst solution: a solution of 5 μmol of dimethylsilylbis(indenyl)zirconium dichloride in 5 ml of toluene was combined with 10 μmol of triethylaluminium and stirred for 20 minutes at 20° C. 5 ml of a solution of 57.4 mg of the compound from Example 3 in 42 ml of toluene were then added (=2.5 μmol of Si[(CH2)3B(C6F5)3]4 4- 4 C6H5- NH(CH3)2 +) and the mixture stirred for 5 minutes.
- Polymerisation: 100 ml of hexane, 0.1 ml of TIBA and the catalyst solution were initially introduced into a 250 ml glass reactor. Propylene was then continuously introduced into the solution at 40° C. via a gas inlet tube at a pressure of 1.1 bar. After 30 minutes' polymerisation, the reaction was terminated by adding 100 ml of methanol. The precipitated polymer was filtered off, washed with methanol and dried in a vacuum drying cabinet. 4.4 g of polypropylene powder were obtained.
- Terpolymerisation of Ethylene, Propylene and 5-ethylidene-2-norbornene
- 500 ml of hexane, 1 ml of triisobutylaluminium and 0.5 ml of a solution of 41.8 mg of a ethylenebis(tetrahydroindenyl)zirconium dichloride in 9 ml of triisobutylaluminium and 40 ml of hexane (=1 μmol of ethylenebis(tetrahydroindenyl)zirconium dichloride) were initially introduced into a 1.4 L steel autoclave equipped with a mechanical stirrer, manometer, temperature sensor, temperature controller, catalyst lock and monomer feed devices for ethylene and propylene. 51 g of propylene and 5 ml of 5-ethylidene-2-norbornene were then apportioned. The internal temperature was adjusted to 40° C. with a thermostat. Ethylene was then apportioned until the internal pressure in the reactor rose to 4 bar. Polymerisation was started by adding 2 ml of a solution of 57.4 mg of the compound from Example 3 in 42 ml of toluene (=1 μmol of Si[(CH2)3B(C6F5)3]4 4- 4 C6H5—NH(CH3)2 +) and ethylene was continuously apportioned such that the internal pressure at 40° C. remained constant at 4 bar. After 50 minutes' polymerisation, the autoclave was depressurised and the polymer solution combined with a 0.1 wt. % solution of Vulkanox BKF in hexane, the mixture stirred for 10 min and the polymer then precipitated with methanol. The resultant polymer was isolated and dried for 20 h under a vacuum at 60° C. 80.1 g of terpolymer were obtained having the following composition according to IR spectroscopy: 58.9% ethylene, 35.5% propylene and 5.6% ENB. A Tg of -49° C. was determined by the DSC method.
- Reaction of Si[(CH2)3B(C6F5)3]4 4- 4 Li+ with Trityl Chloride
- A solution of 948 mg (3.4 mmol) of trityl chloride in 20 ml of methylene chloride were added dropwise within 15 min to a solution of Si[(CH2)3B(C6F5)3]4 4- 4 Li+, produced according to Example 2, and the reaction batch stirred for 14 h at 25° C. The solvent was then removed to dryness by distillation under a vacuum and the residue combined with 40 ml of methylene chloride. A dark red coloured solution containing finely divided solid was obtained, said solid being separated by decanting and subsequent filtration. The clear solution was again evaporated to dryness under a vacuum, the red oily residue was washed twice with 40 ml portions of n-hexane, the hexane decanted and the solid again dried under at vacuum at 25° C. A reddish coloured, slightly tacky product was obtained.
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- Polymerisation of Ethylene
- 100 ml of toluene, 0.1 ml of triisobutylaluminium and 1 ml of solution of 27.2 mg of bis(indenyl)zirconium dimethyl in 15.5 ml of toluene (=5 μmol of bisindenylzirconiumdimethyl) were initially introduced into a 250 ml glass reactor. Ethylene was then continually introduced into the solution at via a gas inlet tube at a pressure of 1.1 bar. Polymerisation was started by adding a solution of 15.9 mg of the product from Example 8 in 1 ml of toluene. At a temperature of 40° C. and an ethylene pressure of 1.1 bar, the reaction was terminated after 15 minutes' polymerisation by adding 10 ml of methanol, the polymer was filtered off, washed with methanol and dried in a vacuum drying cabinet. 1.72 g of highly crystalline polyethylene were obtained having a melting point of +136.5° C. and a heat of fusion of 306 J/g (on first heating) as measured by DSC.
- Copolymerisation of Ethylene and Propylene
- 100 ml of toluene, 0.1 ml of TIBA and 1 ml of a solution of 20.1 mg of ethylenebis(indenyl)zirconiumdimethyl in 10.6 ml of toluene (=5 μmol of ethylenebis(indenyl)zirconiumdimethyl) were initially introduced into a 250 ml glass reactor. An ethylene/propylene mixture (1:1 molar ratio) was then continually introduced at 20° C. into the solution via a gas inlet tube at a pressure of 1.1 bar. Polymerisation was started by adding a solution of 16.9 mg of the product from Example 8 in 1 ml of toluene. At a temperature of 20° C. and a pressure of 1.1 bar, a highly viscous clear reaction solution was obtained after 1 hour's polymerisation. Polymerisation was terminated by adding 100 ml of methanol. The precipitated, elastic polymer was filtered off, washed with methanol and dried in a vacuum drying cabinet. 22.5 g of amorphous ethylene/propylene copolymer were obtained.
- Production of Si[(CH2)3B(3,5-(CF3)2C6H3)3]4 4- 4 Li+
- The solvent was removed from 15.6 ml of n-butyllithium (1.6 M in hexane, 25 mmol) under a vacuum at 0° C. After cooling to -75° C., 50 ml of diethyl ether, which had been precooled to -50° C., were added and stirred until the n-butyllithium had completely redissolved. After addition of 4.3 ml (7.3 g; 25 mmol) of bromo-3,5-bis(trifluoromethyl)benzene, the reaction mixture was stirred for a further 15 minutes at -75° C. and then 1.1 g (2.1 mmol) of Si[(CH2)3BCl2]4 from Example 1 were added. After 1 hour's stirring, the mixture was heated to room temperature and stirred overnight. The reaction mixture was then poured into approx. 100 ml of iced water, the aqueous phase was extracted twice with 50 ml portions of ether and the extract washed once with saturated NaCl solution and once with water. After drying over sodium sulfate and removal of the solvent under a vacuum, the product was obtained as a colourless oil.
- C108H60B4F72Si, M=2824.751 g/mol
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- Production of Si[(CH2)3B(3,5-(CF3)2C6H3)3]4 4- 4 C6H5-NH(CH3)2 +
- The solvent was removed from 15.6 ml of n-butyllithium (1.6 M in hexane, 25 mmol) under a vacuum at 0° C. After cooling to -75° C., 50 ml of diethyl ether, which had been precooled to -50° C., were added and stirred until the n-butyllithium had completely redissolved. After addition of 4.3 ml (7.3 g; 25 mmol) of bromo-3,5-bis(trifluoromethyl)benzene, the reaction mixture was stirred for a further 15 minutes at -75° C. and then 1.1 g (2.1 mmol) of Si[(CH2)3BCl2]4 from Example 1 were added. After 1 hour's stirring, the reaction mixture was heated to room temperature and, after addition of 1.3 g (8.33 mmol) of dimethylanilinium hydrochloride, stirred overnight. The volatile constituents were then removed under a vacuum and the residue extracted with 40 ml of methylene chloride. After filtration and removal of the solvent by distillation, the product was obtained as a colourless oil.
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- Production of Si[(CH2)3B(3,5-(CF3)2C6H3)3]4 4- 4 (C6H5)3C+
- The solvent was removed from 15.6 ml of n-butyllithium (1.6 M in hexane, 25 mmol) under a vacuum at 0° C. After cooling to -75° C., 50 ml of diethyl ether, which had been precooled to -50° C., were added and stirred until the n-butyllithium had completely redissolved. After addition of 4.3 ml (7.3 g; 25 mmol) of bromo-3,5-bis(trifluoromethyl)benzene, the reaction mixture was stirred for a further 15 minutes at -75° C. and then 1.1 g (2.1 mmol) of Si[(CH2)3BCl2]4 from Example 1 were added. After 1 hour's stirring, the reaction mixture was heated to room temperature and stirred for a further 60 hours. After removal of the volatile constituents by distillation under a vacuum, 40 ml of hexane and 2.3 g (8.3 mmol) of trityl chloride were added and the reaction mixture refluxed overnight. After cooling to room temperature, the volatile constituents were removed under a vacuum and the residue extracted with 40 ml of methylene chloride. After filtration and removal of the solvent by distillation, the product was obtained as a yellow oil.
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- Production of Si[(CH2)2Si(C3H5)3]4
- (Si[(CH2)2SiCl3]4 was produced as described in Organometallics 1994, 13, 2682-2690.)
- 77.2 g (3.2 mol) of magnesium chips were suspended in 1900 ml of absolute THF and cooled to 0° C. At 0 to 5° C., 131.4 g (1.7 mol) of freshly distilled allyl chloride were added dropwise (the reaction began as soon as a few ml of allyl chloride had been added). Once addition was complete, the reaction mixture was heated to room temperature and then refluxed for 2 hours. After cooling, 143.6 g (0.21 mol) of Si[(CH2)2SiCl3]4 in 100 ml of THF were added dropwise, wherein the temperature rose to 35° C. After addition, the reaction mixture was stirred overnight and then diluted with 1200 ml of hexane. After hydrolysis with 1200 ml of water, the separated organic phase was washed three times with 1000 ml portions of water and once with a saturated sodium chloride solution. After drying over MgSO4 and removal of the volatile constituents by distillation under a vacuum, the product was obtained as a pale yellow oil.
- Production of Si[(CH2)2Si[(CH2)3BCl2]3]4
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- C44H88B12Cl24Si5, M=1738.199 g/mol
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- Production of Si[(CH2)2Si[(CH2)3B(C4H9)2]3]4
- A solution of 487 mg (0.28 mmol) of Si[(CH2)2Si[(CH2)3BCl2]3]4 in 5 ml of hexane was rapidly added at -70° C. to a mixture of 4.2 ml of n-butyllithium (1.6 M in hexane, 6.7 mmol) in 60 ml of hexane. After 30 minutes' stirring, the mixture was first heated to room temperature and finally refluxed for a further 2 hours. Once the volatile constituents had been removed by distillation under a vacuum, 40 ml of methylene chloride were added and the mixture filtered through diatomaceous earth. After removal of the volatile constituents by distillation, the product was obtained as a light yellow oil.
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- Production of Si[(CH2)2Si(CH2)3B(C6F5)3]3]4 12- 12 C6H5-NH(CH3)2 +
- 6.35 ml of n-butyllithium (1.6 M in hexane; 10.1 mmol) were added dropwise within 20 minutes at -70° C. to a solution of 2.5 g (10.1 mmol) of bromopentafluorobenzene in 60 ml of hexane. The resultant suspension was stirred for 2 hours at -70° C. A solution of 487 mg (0.28 mmol) of Si[(CH2)2Si[(CH2)3BCl2]3]4 from Example 15 in 5 ml of hexane was then added dropwise within 5 minutes and the reaction solution then slowly heated to room temperature within 3 hours and stirred overnight. After addition of 536 mg (3.4 mmol) of dimethylanilinium hydrochloride in 20 ml of methylene chloride, the mixture was again stirred overnight and finally the volatile constituents removed by distillation under a vacuum. After addition of 40 ml of methylene chloride, the mixture was filtered through diatomaceous earth and the volatile constituents removed from the colourless filtrate under a vacuum. After washing twice with 20 ml portions of hexane, the product was obtained as a colourless wax.
- C356H232B12F180N12Si5, M=8367.896 g/mol.
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- Polymerisation of Ethylene
- The polymerisation from Example 9 was repeated, with the difference that 1 ml of a solution of 132 mg of the compound from Example 17 in 31.6 ml of methylene chloride (=0.5 μmol of Si[(CH2)2Si[(CH2)3B(C6F5)3]3]4 12- 12 C6H5-NH(CH3)2 +) was used instead of the solution of the compound from Example 8. 2.1 g of polyethylene were obtained.
- Copolymerisation of Ethylene and Propylene
- 500 ml of hexane and 0.1 ml of triisobutylaluminium were initially introduced into a 1.4 L steel autoclave equipped with a mechanical stirrer, manometer, temperature sensor, temperature controller, catalyst lock and monomer feed devices for ethylene and propylene. 0.5 ml of a solution of 41.8 mg of ethylenebis(tetrahydroindenyl)zirconium dichloride in 9 ml of triisobutylaluminium and 40 ml of hexane (=1 μmol of ethylenebis(tetrahydroindenyl)zirconium dichloride) were added thereto. 51 g of propylene were then apportioned. The internal temperature was adjusted to 40° C. with a thermostat. Ethylene was then apportioned until the internal pressure in the reactor rose to 4 bar. Polymerisation was started by adding 0.5 ml of a solution of 132 mg of the compound from Example 17 in 31.6 ml of methylene chloride (=0.25 μmol of Si[(CH2)2Si[(CH2)3B(C6F5)3]3]4 12- 12 C6H5-NH(CH3)2 +) and ethylene was continuously apportioned such that the internal pressure at 40° C. remained constant at 4 bar. After 40 minutes' polymerisation, the autoclave was depressurised and the polymer then precipitated with methanol. The resultant polymer was isolated and dried for 20 h under a vacuum at 60° C. 70.1 g of copolymer were obtained having the following composition according to IR spectroscopy: 61.8% ethylene and 38.2% propylene. A Tg of -57° C. was determined by the DSC method.
- Production of Si[(CH2)3B(C6F5)3]4 4- 4 H3C-(CH2)10-N(CH3)2H+
- a) 26.8 ml (42.6 mmol) of a 1.6 molar solution of n-butyllithium in hexane were added dropwise with stirring at -70° C. to 10.5 g (42.6 mmol) of bromopentafluorobenzene in 250 ml of hexane in such a manner that there was no observable rise in temperature. After a further 2 hours' stirring at this temperature, 1.9 g (3.6 mmol) of Si[(CH2)3BCl2]4 in 15 ml of hexane were finally added dropwise, then the reaction mixture was heated to room temperature within 3 hours and stirred for a further 60 hours. A colourless suspension was obtained.
- b) 20 g (0.1 mol) of N,N-dimethylundecylamine were added in portions with stirring to 14.8 g (0.15 mol) of concentrated hydrochloric acid (37 wt. %). After the exothermic reaction (up to approx. 35° C.), the highly viscous mixture was diluted with 5 ml of concentrated hydrochloric acid and 5 ml of water, stirred for a further 2 hours and finally left to stand overnight. The aqueous phase was then extracted with 80 ml of methylene chloride, the organic phase dried with sodium sulfate and the solvent removed under a vacuum. In order to remove any traces of water, the residue was resuspended in 80 ml of toluene and concentrated under a vacuum and the operation was then repeated in 100 ml of hexane. Once the solvent had again been removed by distillation under a vacuum, N,N-dimethylundecylammonium hydrochloride was obtained as a colourless solid.
- Yield: 17.8 g, corresponding to 75% of theoretical.
- c) 3.4 g (14.3 mmol) of N,N-dimethylundecylammonium hydrochloride in 80 ml of methylene chloride were stirred into the solution obtained in a) and stirred for 20 hours at room temperature. The volatile constituents were then removed under a vacuum and the residue extracted with 80 ml of methylene chloride. After filtration and removal of the solvent by distillation under a vacuum, the product was obtained as a light yellow wax.
- Yield: 7.0 g, corresponding to 64% of theoretical.
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- Polymerisation of Ethylene
- 100 ml of toluene, 0.1 ml of triisobutylaluminium and 2 ml of a solution of 60.0 mg of bis(indenyl)zirconiumdimethyl in 34.2 ml of toluene (=10 μmol of bisindenylzirconiumdimethyl) were initially introduced into a 250 ml glass reactor. Ethylene was then continually introduced into the solution via a gas inlet tube at a pressure of 1.1 bar. Polymerisation was started by adding 0.5 ml of solution of 19.0 mg of the product from Example 20 in 1.25 ml of toluene (=2.5 μmol of Si[(CH2)3B(C6F5)3]4 4- 4 CH2(CH2)10(CH3)2 +). At a temperature of 40° C. and an ethylene pressure of 1.1 bar, the reaction was terminated after 10 minutes' polymerisation by adding 10 ml of methanol, the polymer was filtered off, washed with methanol and dried in a vacuum drying cabinet. 1.9 g of polyethylene were obtained.
- Production of Si[(CH2)3B(C6F5)3]4 4- 4 H3C-(CH2)11- N(CH3)2H+
- a) 20.3 ml (32.2 mmol) of a 1.6 molar solution of n-butyllithium in hexane were added dropwise with stirring at-70° C. to 8.0 g (32.2 mmol) of bromopentafluorobenzene in 190 ml of hexane in such a manner that there was no observable rise in temperature. After a further 2 hours' stirring at this temperature, 1.4 g (2.7 mmol) of Si[(CH2)3BCl2]4 in 15 ml of hexane were finally added dropwise, then the reaction mixture was heated to room temperature within 3 hours and stirred for a further 60 hours. A colourless suspension was obtained.
- b) 43.3 g (0.2 mol) of N,N-dimethyldodecylamine were added in portions with stirring to 30.0 g (0.3 mol) of concentrated hydrochloric acid (37 wt. %). After the exothermic reaction (up to approx. 35° C.), the highly viscous mixture was diluted with 25 ml of concentrated hydrochloric acid and 25 ml of water and stirred overnight. The aqueous phase was then extracted with 100 ml of methylene chloride, the organic phase was washed once with 50 ml of water, dried with sodium sulfate and the solvent was removed under a vacuum. In order to remove any traces of water, the residue was resuspended in 50 ml of toluene and concentrated under a vacuum and the operation was then repeated in 80 ml of hexane. Once the solvent had again been removed by distillation under a vacuum, N,N-dimethyldodecylammonium hydrochloride was obtained as a colourless solid.
- Yield: 27.6 g, corresponding to 55% of theoretical.
- c) 2.3 g (10.8 mmol) of N,N-dimethyldodecylammonium hydrochloride in 60 ml of methylene chloride were stirred into the solution obtained in a) and stirred for 20 hours at room temperature. The volatile constituents were then removed under a vacuum and the residue extracted with 80 ml of methylene chloride. After filtration and removal of the solvent by distillation under a vacuum, the product was obtained as a light yellow wax.
- Yield: 7.0 g, corresponding to 64% of theoretical.
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- Production of Si{(CH2)2Si[(CH2)3B(C6F5)3]3}4 12 - 12 H3C-(CH2)10-N(CH3)2H+
- a) 12.7 ml (20.2 mmol) of a 1.6 molar solution of n-butyllithium in hexane were added dropwise with stirring at -70° C. to 5.0 g (20.2 mmol) of bromopentafluorobenzene in 120 ml of hexane in such a manner that there was no observable rise in temperature. After a further 2 hours' stirring at this temperature, 974 mg (0.6 mmol) of Si{(CH2)2Si[(CH2)3BCl2]3}4 in 10 ml of toluene were finally added dropwise, then the reaction mixture was heated to room temperature within 3 hours and stirred for a further 60 hours. A colourless suspension was obtained.
- b) 1.6 g (6.7 mmol) of N,N-dimethylundecylammonium hydrochloride (produced as described in b) in Example 20) in 40 ml of methylene chloride were stirred into the solution obtained in a) and stirred for 20 hours at room temperature. The volatile constituents were then removed under a vacuum and the residue extracted with 60 ml of methylene chloride. After filtration and removal of the solvent by distillation under a vacuum, the product was obtained as a light yellow wax.
- Yield: 3.1 g, corresponding to 60% of theoretical.
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- Polymerisation of Ethylene
- The polymerisation from Example 21 was repeated, with the difference that 0.5 ml of a solution of 70 mg of the compound from Example 23 in 2.3 ml of toluene (=1.7 μmol of Si[(CH2)2Si[(CH2)3B(C6F5)3]3]4 12- 12 CH3(CH2)10NH(CH3)2 +) was used instead of the solution of the compound from Example 21. 1.7 g of polyethylene were obtained.
- Production of Si{(CH2)2Si[(CH2)2Si(C3H5)3]3}4
- (Si{(CH2)2Si[(CH2)2SiCl3]3}4 was produced as described in Organometallics 1994, 13, 2682—2690).
- At an initial temperature of 0° C., 23 ml (21.6 g; 282 mmol) of allyl chloride were added dropwise with vigorous stirring to 22.3 g (919 mmol) of magnesium chips in 400 ml of THF in such a manner that the reaction temperature never exceeded 5° C. (the Grignard reaction was started with a little 1,2—dibromoethane). Once addition was complete, the reaction mixture was heated first to room temperature and was finally refluxed for a further 2 hours.
- After cooling to room temperature, 15 g (6.8 mmol) of Si{(CH2)2Si[(CH2)2SiCl3]3}4 in 35 ml of THF were added dropwise with occasional cooling with ice in such a manner that the reaction temperature was 20 to 30° C. Stirring was then continued for a further 6 hours at room temperature; after dilution with 250 ml of hexane, the mixture was finally hydrolysed with 250 ml of saturated ammonium chloride solution, the organic phase was separated and washed three times with 200 ml portions of saturated sodium chloride solution and once with 200 ml of water. After drying over magnesium sulfate and removal of the volatile constituents by distillation, the product was obtained as a light yellow oil.
- Yield: 13.2 g, corresponding to 81% of theoretical.
- Si{(CH2)2Si[(CH2)2Si[(CH2)3BCl2]3]3}4
- A mixture of 16 ml (11.6 g; 100.2 mmol) of triethylsilane and 6.12 g (2.54 mmol) of Si{(CH2)2Si[(CH2)2Si(C3H5)3]3} were added dropwise to 8.5 ml (11.5 g; 97.7 mmol) of boron trichloride at -70° C. in such a manner that the temperature during the exothermic reaction did not rise above -60° C. (internal thermometer). After the dropwise addition (approx. 90 min), the reaction mixture was stirred for a further 30 minutes at -70° C., then heated to room temperature and stirred for a further 15 hours. In order to remove small quantities of pyrophoric, highly volatile constituents, argon was then passed through the solution for 2 hours (passage through dilute sodium hydroxide solution). Finally, any remaining volatile constituents were removed by distillation under a vacuum, the reaction mixture slowly being heated to up to 40° C. during this operation. The product was obtained as a colourless wax.
- Yield: 11.8 g, corresponding to 86% of theoretical.
-
- Production of Si{(CH2)2Si[(CH2)2Si[(CH2)3B(C6F5)3]3]3}4 36- 36 H3C—(CH2)10—N(CH3)2H+
- a) 12.7 ml (20.2 mmol) of a 1.6 molar solution of n—butyllithium in hexane were added dropwise with stirring at -70° C. to 5.0 g (20.2 mmol) of bromopentafluorobenzene in 120 ml of hexane in such a manner that there was no observable rise in temperature. After a further 2 hours' stirring at this temperature, 1.0 g (0.2 mmol) of Si{(CH2)2Si[(CH2)2Si[(CH2)3BCl2]3]3}4 in 10 ml of toluene were finally added dropwise, then the reaction mixture was heated to room temperature within 3 hours and stirred for a further 60 hours. A colourless suspension was obtained.
- b) 1.6 g (6.7 mmol) of N,N—dimethylundecylammonium hydrochloride (produced as described in b) in Example 20) in 40 ml of methylene chloride were stirred into the solution obtained in a) and stirred for 20 hours at room temperature. The volatile constituents were then removed under a vacuum and the residue extracted with 60 ml of methylene chloride. After filtration and removal of the solvent by distillation under a vacuum, the product was obtained as a light yellow wax.
- Yield: 3.7 g, corresponding to 70% of theoretical.
-
- Polymerisation of Ethylene
- The polymerislation from Example 21 was repeated, with the difference that 0.5 ml of a solution of 132.6 mg of the compound from Example 27 in 4.25 ml of toluene (=0.6 μmol of Si{(CH2)2Si[(CH2)2Si[(CH2)3B(C6F5)3]3]3} 4 36- 36[CH3(CH2)10NH(CH3)2]+ was used instead of the solution of the compound from Example 21. 1.6 g of polyethylene were obtained.
- Production of Si[(CH2)3B(C4H9)3]4 4- 4 Li+
- 14.3 ml (22.9 mmol) of a 1.6 molar solution of n—butyllithium in hexane were diluted with 30 ml of hexane and cooled to -70° C. 5.5 g (22.9 mmol) of MPEDA were then stirred in and 1.0 g (1.9 mmol) of Si[(CH2)3BCl2]4 in 5 ml of hexane was finally added dropwise. After the exothermic reaction (up to approx. -60° C.), the reaction mixture was stirred for a further 30 minutes at -70° C. and then heated to room temperature. After 15 hours' stirring, the volatile constituents were removed by distillation under a vacuum; a white solid was obtained which was completely soluble in DMSO.
-
- Production of Si[(CH2)3B(C4H9)3]4 4- 4 N(CH3)4 +
- a) 14.3 ml (22.9 mmol) of a 1.6 molar solution of n—butyllithium in hexane were diluted with 30 ml of hexane and cooled to -70° C. 1.0 g (1.9 mmol) of Si[(CH2)3BCl2]4 in 5 ml of hexane was then added dropwise. After the exothermic reaction (up to approx. -60° C.), the reaction mixture was stirred for a further 30 minutes at -70° C. and finally heated to room temperature. After 60 hours' stirring, the reaction mixture was filtered and the resultant colourless solid dried under a vacuum.
- Yield: 1.8 g.
-
- b) 0.84 g (7.6 mmol) of tetramethylammonium chloride and 40 ml of methylene chloride were added to the solid obtained according to a) and the reaction mixture was stirred for 60 hours at room temperature. After filtration and removal of the volatile constituents by distillation, the product was obtained from the mother liquor as a colourless solid.
- Yield: 1.4 g, corresponding to 59% of theoretical.
-
- Production of Si[(CH2 3B(CH2)—Si(CH3)3)3]4 4- 4 Li+
- 22.9 ml (22.9 mmol) of a 1.0 molar solution of trimethylsilylmethyllithium in hexane were diluted with 60 ml of hexane and cooled to -70° C. 5.5 g (22.9 mmol) of MPEDA were then stirred in and 1.0 g (1.9 mmol) of Si[(CH2)3BCl2]4 in 5 ml of hexane was finally added dropwise. The reaction mixture was then stirred for 30 minutes at -70° C. and then heated to room temperature. After 15 hours' stirring, the volatile constituents were removed by distillation under a vacuum; a white solid was obtained, which was completely soluble in DMSO.
-
- Production of Si{(CH2)2Si[(CH2)3B(n—C4H9)3]3}4 12- 12 Li+
- 12.9 ml (20.7 mmol) of a 1.6 molar solution of n—butyllithium in hexane were diluted with 30 ml of hexane and cooled to -70° C. 4.9 g (20.7 mmol) of MPEDA were then stirred in and 1.0 g (0.57 mmol) of Si{(CH2)2Si[(CH2)3BCl2]3}4 in 5 ml of hexane was finally added dropwise. The reaction mixture was then stirred for 30 minutes at -70° C. and then heated to room temperature. After 15 hours' stirring, the volatile constituents were removed by distillation under a vacuum; a white solid was obtained, which was completely soluble in DMSO.
-
- Production of Si{(CH2)2Si[(CH2)3B(sec.—C4H9)3]3}4 12- 12 Li+
- 15.9 ml (20.7 mmol) of a 1.3 molar solution of sec.—butyllithium in cyclohexane were diluted with 30 ml of hexane and cooled to -70° C. 4.9 g (20.7 mmol) of MPEDA were then stirred in and 1.0 g (0.57 mmol) of Si{(CH2)2Si[(CH2)3BCl2]3}4 in 5 ml of hexane was finally added dropwise. After the exothermic reaction (up to -60° C.), the reaction mixture was then stirred for 30 minutes at -70° C. and then heated to room temperature. After 15 hours' stirring, the volatile constituents were removed by distillation under a vacuum; a white solid was obtained, which was completely soluble in DMSO.
-
- Production of Si{(CH2)2Si[(CH2)3B(CH2—C(CH3)3)3]3}4 12- 12 Li+
- (Neopentyllithium was produced according toJ. Am. Chem. Soc. 1959, 81, 1617 from neopentyl chloride and lithium powder; content was determined by double titration according to J. Am. Chem. Soc. 1944, 66, 1515).
- 23.0 ml (23.0 mmol) of a 1.0 molar solution of neopentyllithium in diethyl ether were diluted with 30 ml of hexane and cooled to -70° C. 1.0 g (0.57 mmol) of Si{(CH2)2Si[(CH2)3BCl2]3}4 in 5 ml of hexane was then added dropwise with stirring and the reaction mixture was then stirred for 30 minutes at -70° C. and then heated to room temperature. After 15 hours' stirring, the volatile constituents were removed by distillation under a vacuum; a white solid was obtained, which was completely soluble in DMSO.
-
- Production of Si{(CH2) 2Si[(CH2)3B(C6H5)3]3}4 12- 12 Li+
- 12.7 ml (23.0 mmol) of a 1.8 molar solution of phenyllithium in cyclohexane/diethyl ether (70:30) were diluted with 30 ml of hexane and cooled to -70° C. 1.0 g (0.57 mmol) of Si{(CH2)2Si[(CH2)3BCl2]3}4 in 5 ml of hexane was then added dropwise with stirring and the reaction mixture was then stirred for 30 minutes at -70° C. and then heated to room temperature. After 15 hours' stirring, the volatile constituents were removed by distillation under a vacuum; a white solid was obtained, which was completely soluble in DMSO.
-
- Production of Si{(CH2)2Si[(CH2)3B(C6H5)3]3}4 12- 12 N(CH3)4 +
- a) 12.7 ml (23.0 mmol) of a 1.8 molar solution of phenyllithium in cyclohexane/diethyl ether (70:30) were diluted with 30 ml of hexane and cooled to -70° C. 1.0 g (0.57 mmol) of Si{(CH2)2Si[(CH2)3BCl2]3}4 in 5 ml of hexane was then added dropwise with stirring and the reaction mixture was then stirred for 30 minutes at -70° C. and then heated to room temperature. After 15 hours' stirring, the volatile constituents were removed by distillation under a vacuum; a white solid was obtained, which was completely soluble in DMSO.
-
- b) The solid obtained according to a) was suspended in 50 ml of methylene chloride and cooled to -70° C. 0.66 g (6.9 mmol) of trimethylammonium chloride were then stirred in, the reaction mixture was heated to room temperature and stirred for a further 15 hours. After filtration through diatomaceous earth, volatile constituents were removed from the resultant clear mother liquor under a vacuum; the product was obtained as a light yellow wax.
-
- Production of Si{(CH2)2Si[(CH2)3B(C6H5)3]3}4 12- 12 C6H5—N(CH3)2H+
- a) 12.7 ml (23.0 mmol) of a 1.8 molar solution of phenyllithium in cyclohexane/diethyl ether (70:30) were diluted with 30 ml of hexane and cooled to -70° C. 1.0 g (0.57 mmol) of Si{(CH2)2Si[(CH2)3BCl2]3}4 in 5 ml of hexane was then added dropwise with stirring and the reaction mixture was then stirred for 30 minutes at -70° C. and then heated to room temperature. After 15 hours' stirring, the volatile constituents were removed by distillation under a vacuum.
- b) The solid obtained according to a) was suspended in 100 ml of methylene chloride and cooled to -70° C. 1.1 g (6.0 mmol) of dimethylanilinium chloride were then stirred in and stirred for 30 minutes at -70° C. The reaction mixture was then heated to room temperature and stirred for a further 15 hours. After filtration through diatomaceous earth, volatile constituents were removed from the resultant clear mother liquor under a vacuum; the product was obtained as a light yellow wax.
-
- Production of Si[(CH2)3BF2]4
- At 0° C., 6.53 g (28.7 mmol) of antimony trifluoride were stirred into 5 g (9.6 mmol) of Si[(CH2)3BCl2]4 in 70 ml of hexane. After 1 hour at 0° C., the white suspension was heated to room temperature and stirred overnight. The precipitate was then filtered off and the volatile constituents removed by distillation under a vacuum. During the vacuum distillation, a small quantity of a colourless precipitate again precipitated; in order to separate this precipitate, 30 ml of hexane were added to the resultant residue and the mixture kept overnight at 4° C. Filtration was then repeated and, once the solvent had been removed by distillation under a vacuum, the product was obtained as a colourless oil.
- C12H24B4F8Si, M=391.647 g/mol
-
Claims (8)
1. Dendrimeric compounds of the general formula
R1 4-iMe1[(R4)nX]i (I),
in which
X represents Me2R2R3(Ry)r,
R1, R2, R3, Ry are identical or different, may optionally be mono—or polysubstituted and represent hydrogen, C5—C20 cycloalkyl, C1—C20 alkyl, C7—C40 aralkyl, C6—C40 aryl, C1—C10 alkoxy, C6—C40 aryloxy, silyloxy or halogen,
R4 represents an optionally mono—or polysubstituted alkylene, alkenylene or alkynylene residue, which is optionally interrupted by one or more heteroatoms,
Me1 represents an element of group IVa of the periodic system of the elements (IUPAC nomenclature),
Me2 represents an element of group IIIa of the periodic system of the elements (IUPAC nomenclature),
i represents an integer from 2 to 4,
n represents an integer from 1 to 20 and
r represents 0 or 1,
wherein, when r=1, the Me2 residue bears a negative formal charge and in the event of a negative formal charge on Me2, this is offset by a cation,
or in which
X represents Me1R5 a[(R4)mMe2R2R3(Ry)r]3-a,
Me1, Me2, R1, R2, R3, R4, Ry, i, n, r have the above—stated meanings,
R5 has the meaning of the residues R1, R2, R3, Ry,
m is identical to or different from n and represents integers from 1 to 20 and
a represents 0, 1 or 2,
or in which
X represents Me1R5 a[(R4)mMe1R6 b[(R4)pMe2R2R3(Ry)r]3-b]3-a,
Me1, Me2, R1, R2, R3, R4, Ry, i, n, r, m, a have the above—stated meanings,
R6 has the meaning of the residues R1, R2, R3, Ry, R5,
b represents 0, 1 or 2 and
p represents integers from 1 to 20,
wherein the compounds described in DE 195 16 200 are excluded, said compounds being produced by the reaction of silicon tetrachloride in a Grignard reaction to form tetraallylsilane, which is subsequently reacted twice or more alternately
a) with trichlorosilane in a quantitative reaction in the presence of a catalyst and then
b) with an allyl compound in a Grignard reaction using a suitable solvent in each case until a dendrimeric skeleton comprising outwardly pointing allyl groups is obtained, the outer allyl groups of which
c) are derivatised in a hydroboration reaction with 9—borabicyclo—[3.3.1]nonane.
2. Method for the production of the novel dendrimeric compounds of claim 1 , characterised in that compounds of the general formula (IV)
R1 4-iMe1[(R7)n-2Y]i (IV)
in which
Y represents CR8═CR9R10,
R8, R9 and R10 are identical or different and represent hydrogen, alkyl, aryl or halogen,
R7 has the meaning of residue R4 in the formula (I),
n represents an integer from 2 to 20,
R1, Me1 and i have the definition stated for the formula (I),
or in which
Y represents Me1R5 a[(R7)m-2(CR8═CR9R10)]3-a,
R5 has the definition stated in the formula (I),
or in which
Y represents Me1R5 a[(R4)mMe1R6 b[(R7)p-2(CR8═CR9R10)]3-b]3-a,
R6 has the definition stated in formula (I),
m, p represent integers from 2 to 20 and in which all the other residues stated in the formulae have the above—stated meanings for Y,
are reacted with compounds of the general formula (V)
R11Me2R2R3 (V),
in which
R11 represents hydrogen or C1—C30 alkyl and
Me2, R2 and R3 have the meanings stated in the formula (I),
and, in the event that r=1, the resultant product is further reacted with compounds of the general formula (VI)
Me3—Ry (VI),
in which
Me3 represents an alkali metal and Ry has the above—stated meaning,
or with compounds of the general formula (VII)
Halq—Me4—Ry 2-q (VII),
in which
Me4 represents an alkaline earth metal or transition metal of subgroups 1 or 2,
Hal represents halogen,
q represents 0 or 1 and
Ry has the meaning as before.
3. Use of the dendrimeric compounds of the formula (I), including the dendrimeric compounds excluded from the formula (I), as catalysts.
4. Use of the dendrimeric compounds according to claim 3 for the production of catalyst systems based on transition metal complexes.
5. Use of the dendrimeric compounds according to claim 3 for the polymerisation of unsaturated organic compounds.
6. Use of the dendrimeric compounds according to claim 3 for the production of elastomers.
7. Use of the dendrimeric compounds according to claim 3 for the production of elastomers based on copolymers of ethylene and α—olefins.
8. Use of the dendrimeric compounds according to claim 3 for the production of EP(D)M.
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US09/646,839 US6570031B1 (en) | 1998-03-24 | 1999-03-11 | Dendrimer compounds, method for the production thereof, use thereof as catalysts |
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CA2276282A1 (en) * | 1999-06-23 | 2000-12-23 | Bayer Inc. | Olefin polymerization process and catalyst system therefor |
JP4424996B2 (en) | 2002-03-18 | 2010-03-03 | イシス イノベイション リミテッド | Phosphorescent dendrimer |
GB0220092D0 (en) | 2002-08-29 | 2002-10-09 | Isis Innovation | Reactive dendrimers |
WO2004019993A1 (en) * | 2002-08-30 | 2004-03-11 | Ramot At Tel Aviv University Ltd. | Self-immolative dendrimers releasing many active moieties upon a single activating event |
WO2004022231A1 (en) * | 2002-09-04 | 2004-03-18 | Johnson Matthey Plc | Catalysts |
US20070249744A1 (en) * | 2003-11-19 | 2007-10-25 | Landskron Kai Manfred M | Template-Directed Synthesis of Porous Materials Using Dendrimer Precursors |
US20060269480A1 (en) * | 2005-05-31 | 2006-11-30 | Ramot At Tel Aviv University Ltd. | Multi-triggered self-immolative dendritic compounds |
WO2008153615A2 (en) * | 2007-03-07 | 2008-12-18 | Ada Technologies, Inc. | Preparing carbohydrate microarrays and conjugated nanoparticles |
CN102858851A (en) * | 2010-02-18 | 2013-01-02 | 阿尔卡拉德埃纳雷斯大学 | Carbosilane dendrimers and the use thereof as antiviral agents |
CN106398574B (en) * | 2016-09-06 | 2020-06-23 | 哈尔滨工业大学无锡新材料研究院 | Polyacrylate pressure-sensitive adhesive and preparation method thereof |
Family Cites Families (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2045681A1 (en) * | 1970-09-16 | 1972-03-23 | Schering Ag | Aluminium-diene polymers, for prepn of - catalysts for (co) polymerisation |
DE1956353A1 (en) * | 1969-11-08 | 1971-05-19 | Schering Ag | Aluminium-diene polymers, for prepn of - catalysts for (co) polymerisation |
ZA844157B (en) | 1983-06-06 | 1986-01-29 | Exxon Research Engineering Co | Process and catalyst for polyolefin density and molecular weight control |
IL85097A (en) | 1987-01-30 | 1992-02-16 | Exxon Chemical Patents Inc | Catalysts based on derivatives of a bis(cyclopentadienyl)group ivb metal compound,their preparation and their use in polymerization processes |
PL276385A1 (en) | 1987-01-30 | 1989-07-24 | Exxon Chemical Patents Inc | Method for polymerization of olefines,diolefins and acetylene unsaturated compounds |
US4871705A (en) | 1988-06-16 | 1989-10-03 | Exxon Chemical Patents Inc. | Process for production of a high molecular weight ethylene a-olefin elastomer with a metallocene alumoxane catalyst |
US5229478A (en) | 1988-06-16 | 1993-07-20 | Exxon Chemical Patents Inc. | Process for production of high molecular weight EPDM elastomers using a metallocene-alumoxane catalyst system |
US4892851A (en) | 1988-07-15 | 1990-01-09 | Fina Technology, Inc. | Process and catalyst for producing syndiotactic polyolefins |
NZ235032A (en) | 1989-08-31 | 1993-04-28 | Dow Chemical Co | Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component |
US6075077A (en) | 1989-08-31 | 2000-06-13 | The Dow Chemical Company | Asphalt, bitumen, and adhesive compositions |
US5026798A (en) | 1989-09-13 | 1991-06-25 | Exxon Chemical Patents Inc. | Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system |
ES2090209T3 (en) | 1990-11-12 | 1996-10-16 | Hoechst Ag | METALLOCENES WITH LIGANDS BASED ON SUBSTITUTED INDENYL DERIVATIVES IN POSITION 2, PROCEDURE FOR THEIR PREPARATION AND USE AS CATALYSTS. |
EP0485823B1 (en) | 1990-11-12 | 1995-03-08 | Hoechst Aktiengesellschaft | 2-Substituted bisindenyl-metallocenes, process for their preparation and their use as catalysts for the polymerization of olefins |
DE69222317T2 (en) | 1991-11-25 | 1998-02-12 | Exxon Chemical Patents Inc | POLYIONIC TRANSITION METAL CONTAINER COMPOSITION |
FI945959A (en) | 1993-12-21 | 1995-06-22 | Hoechst Ag | Metallocenes and their use as catalysts |
FI945958A (en) | 1993-12-21 | 1995-06-22 | Hoechst Ag | Process for the preparation of polyolefins |
CN1171794A (en) | 1994-10-31 | 1998-01-28 | Dsm有限公司 | Catalyst composition and process for polymerization of olefin |
DE19516200A1 (en) * | 1995-05-08 | 1996-11-14 | Merck Patent Gmbh | Dendrimeric cpds. with liq. crystal properties |
US5677410A (en) * | 1995-05-16 | 1997-10-14 | Bayer Ag | Carbosilane-dendrimers, carbosilane-hybrid materials, methods for manufacturing them and a method for manufacturing coatings from the carbosilane-dendrimers |
US5798430A (en) * | 1995-06-28 | 1998-08-25 | E. I. Du Pont De Nemours And Compnay | Molecular and oligomeric silane precursors to network materials |
US6313239B1 (en) * | 1996-03-05 | 2001-11-06 | Bayer Corporation | Olefin polymerization with group 4 metal-containing organosilicon dendrimers |
WO1997032918A2 (en) * | 1996-03-05 | 1997-09-12 | Massachusetts Institute Of Technology | Group 4 metal-containing organosilicon dendrimers and method for synthesizing organosilicon dendrimers |
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US20100034789A1 (en) * | 2005-07-22 | 2010-02-11 | Francisco De La Mata De La Mata | Novel carbosilane dendrimers, preparation method thereof and use of same |
US8603493B2 (en) * | 2005-07-22 | 2013-12-10 | Dendrico, S.L. | Carbosilane dendrimers, preparation method thereof and use of same |
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