CN1245806A - 基于金属富烯配合物的催化剂 - Google Patents
基于金属富烯配合物的催化剂 Download PDFInfo
- Publication number
- CN1245806A CN1245806A CN99117988.9A CN99117988A CN1245806A CN 1245806 A CN1245806 A CN 1245806A CN 99117988 A CN99117988 A CN 99117988A CN 1245806 A CN1245806 A CN 1245806A
- Authority
- CN
- China
- Prior art keywords
- fulvene
- metal
- alkyl
- compound
- structural formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- PGTKVMVZBBZCKQ-UHFFFAOYSA-N Fulvene Chemical compound C=C1C=CC=C1 PGTKVMVZBBZCKQ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 47
- 239000002184 metal Substances 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 22
- 238000013329 compounding Methods 0.000 title claims description 22
- 239000004615 ingredient Substances 0.000 title claims description 22
- 238000000034 method Methods 0.000 claims abstract description 15
- 150000001336 alkenes Chemical class 0.000 claims abstract description 10
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 4
- -1 Sauerstoffatom Chemical group 0.000 claims description 40
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- 150000001875 compounds Chemical class 0.000 claims description 26
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 claims description 10
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 125000003342 alkenyl group Chemical group 0.000 claims description 7
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 230000002829 reductive effect Effects 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- WXACXMWYHXOSIX-UHFFFAOYSA-N 5-propan-2-ylidenecyclopenta-1,3-diene Chemical compound CC(C)=C1C=CC=C1 WXACXMWYHXOSIX-UHFFFAOYSA-N 0.000 claims description 6
- 125000006374 C2-C10 alkenyl group Chemical group 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000004104 aryloxy group Chemical group 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- RYLMKTLFCIGRQD-UHFFFAOYSA-N 2,3,4,5-tetramethylfulvene Chemical compound CC1=C(C)C(=C)C(C)=C1C RYLMKTLFCIGRQD-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 3
- JWCQJEMOTHGHHH-UHFFFAOYSA-N (3-methylidene-2,4,5-triphenylcyclopenta-1,4-dien-1-yl)benzene Chemical compound C=C1C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 JWCQJEMOTHGHHH-UHFFFAOYSA-N 0.000 claims description 2
- VANVKDJJYBYKEA-UHFFFAOYSA-N 5-cyclopentylidenecyclopenta-1,3-diene Chemical compound C1CCCC1=C1C=CC=C1 VANVKDJJYBYKEA-UHFFFAOYSA-N 0.000 claims description 2
- 125000005865 C2-C10alkynyl group Chemical group 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 150000001408 amides Chemical class 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- MIODROMBEUMZIF-UHFFFAOYSA-N cyclopenta-2,4-dien-1-ylidenecyclohexane Chemical compound C1CCCCC1=C1C=CC=C1 MIODROMBEUMZIF-UHFFFAOYSA-N 0.000 claims description 2
- IGSGWPUSCLPKER-UHFFFAOYSA-N cyclopenta-2,4-dien-1-ylidenemethylbenzene Chemical group C=1C=CC=CC=1C=C1C=CC=C1 IGSGWPUSCLPKER-UHFFFAOYSA-N 0.000 claims description 2
- JZLAYHCMSHSZKE-UHFFFAOYSA-N cyclopenta-2,4-dien-1-ylidenemethylcyclohexane Chemical compound C1CCCCC1C=C1C=CC=C1 JZLAYHCMSHSZKE-UHFFFAOYSA-N 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 150000002736 metal compounds Chemical class 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims description 2
- 239000011295 pitch Substances 0.000 claims description 2
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 claims description 2
- 229910052767 actinium Inorganic materials 0.000 claims 1
- QQINRWTZWGJFDB-UHFFFAOYSA-N actinium atom Chemical compound [Ac] QQINRWTZWGJFDB-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 238000006884 silylation reaction Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 24
- 150000001993 dienes Chemical class 0.000 abstract description 3
- 238000003780 insertion Methods 0.000 abstract 3
- 230000037431 insertion Effects 0.000 abstract 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 63
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 22
- 239000000463 material Substances 0.000 description 19
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 17
- 229910052749 magnesium Inorganic materials 0.000 description 16
- 239000011777 magnesium Substances 0.000 description 16
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 14
- 239000010936 titanium Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 6
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 5
- 150000004645 aluminates Chemical class 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 5
- 239000012965 benzophenone Substances 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 125000002524 organometallic group Chemical group 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 238000013019 agitation Methods 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 125000003250 fulvenyl group Chemical group C1(=CC=CC1=C)* 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 4
- IPRROFRGPQGDOX-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopenta-1,3-diene;trichlorotitanium Chemical group Cl[Ti](Cl)Cl.CC=1C(C)=C(C)[C-](C)C=1C IPRROFRGPQGDOX-UHFFFAOYSA-K 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 239000004411 aluminium Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229940125904 compound 1 Drugs 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 150000004292 cyclic ethers Chemical class 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- HXVNBWAKAOHACI-UHFFFAOYSA-N 2,4-dimethyl-3-pentanone Chemical compound CC(C)C(=O)C(C)C HXVNBWAKAOHACI-UHFFFAOYSA-N 0.000 description 2
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 239000007818 Grignard reagent Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001399 aluminium compounds Chemical class 0.000 description 2
- 229910052728 basic metal Inorganic materials 0.000 description 2
- 150000003818 basic metals Chemical class 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 150000001983 dialkylethers Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004795 grignard reagents Chemical class 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 150000002527 isonitriles Chemical class 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- NUJGJRNETVAIRJ-UHFFFAOYSA-N octanal Chemical compound CCCCCCCC=O NUJGJRNETVAIRJ-UHFFFAOYSA-N 0.000 description 2
- 238000000643 oven drying Methods 0.000 description 2
- 230000011514 reflex Effects 0.000 description 2
- 229910001023 sodium amalgam Inorganic materials 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GDDAJHJRAKOILH-QFXXITGJSA-N (2e,5e)-octa-2,5-diene Chemical compound CC\C=C\C\C=C\C GDDAJHJRAKOILH-QFXXITGJSA-N 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
- 239000001211 (E)-4-phenylbut-3-en-2-one Substances 0.000 description 1
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- ZWKNLRXFUTWSOY-QPJJXVBHSA-N (e)-3-phenylprop-2-enenitrile Chemical compound N#C\C=C\C1=CC=CC=C1 ZWKNLRXFUTWSOY-QPJJXVBHSA-N 0.000 description 1
- QLXSKRXOTSWEEZ-UHFFFAOYSA-N 1,2,3,4,5-pentamethyl-5-[(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-ylidene)methyl]cyclopenta-1,3-diene Chemical compound CC1=C(C(=C(C1(C=C1C(=C(C(=C1C)C)C)C)C)C)C)C QLXSKRXOTSWEEZ-UHFFFAOYSA-N 0.000 description 1
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 1
- CTTYWXDVWGKHKJ-UHFFFAOYSA-N 1-(2,3,4,5,6-pentamethylphenyl)ethanone Chemical compound CC(=O)C1=C(C)C(C)=C(C)C(C)=C1C CTTYWXDVWGKHKJ-UHFFFAOYSA-N 0.000 description 1
- ZDPAWHACYDRYIW-UHFFFAOYSA-N 1-(4-fluorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(F)C=C1 ZDPAWHACYDRYIW-UHFFFAOYSA-N 0.000 description 1
- FYDUUODXZQITBF-UHFFFAOYSA-N 1-[2-(trifluoromethyl)phenyl]ethanone Chemical compound CC(=O)C1=CC=CC=C1C(F)(F)F FYDUUODXZQITBF-UHFFFAOYSA-N 0.000 description 1
- RIFKADJTWUGDOV-UHFFFAOYSA-N 1-cyclohexylethanone Chemical compound CC(=O)C1CCCCC1 RIFKADJTWUGDOV-UHFFFAOYSA-N 0.000 description 1
- DBLXXVQTWJFJFI-UHFFFAOYSA-N 1-phenyloctadecan-1-one Chemical compound CCCCCCCCCCCCCCCCCC(=O)C1=CC=CC=C1 DBLXXVQTWJFJFI-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- UIQGEWJEWJMQSL-UHFFFAOYSA-N 2,2,4,4-tetramethylpentan-3-one Chemical compound CC(C)(C)C(=O)C(C)(C)C UIQGEWJEWJMQSL-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- YSTPAHQEHQSRJD-UHFFFAOYSA-N 3-Carvomenthenone Chemical compound CC(C)C1CCC(C)=CC1=O YSTPAHQEHQSRJD-UHFFFAOYSA-N 0.000 description 1
- JBWTXXSIFIZLLF-UHFFFAOYSA-N 3-acetylheptane-2,4,5-trione Chemical compound CCC(=O)C(=O)C(C(C)=O)C(C)=O JBWTXXSIFIZLLF-UHFFFAOYSA-N 0.000 description 1
- PFCHFHIRKBAQGU-UHFFFAOYSA-N 3-hexanone Chemical compound CCCC(=O)CC PFCHFHIRKBAQGU-UHFFFAOYSA-N 0.000 description 1
- VXEUGLRMYAXWKM-UHFFFAOYSA-N 3-phenyl-1h-imidazole-2-thione Chemical compound S=C1NC=CN1C1=CC=CC=C1 VXEUGLRMYAXWKM-UHFFFAOYSA-N 0.000 description 1
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical group C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 description 1
- ZPQAKYPOZRXKFA-UHFFFAOYSA-N 6-Undecanone Chemical compound CCCCCC(=O)CCCCC ZPQAKYPOZRXKFA-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- JDSVRZVMPXFGPE-UHFFFAOYSA-N C1(=CC=CC=C1)C(=O)C1=CC=CC=C1.[F] Chemical compound C1(=CC=CC=C1)C(=O)C1=CC=CC=C1.[F] JDSVRZVMPXFGPE-UHFFFAOYSA-N 0.000 description 1
- 125000000041 C6-C10 aryl group Chemical group 0.000 description 1
- GDEWSCZCZPVTEG-UHFFFAOYSA-N C=C[Mg]C=C Chemical compound C=C[Mg]C=C GDEWSCZCZPVTEG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910000574 NaK Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- NSIKFNOYIGGILA-UHFFFAOYSA-N [Na].[Na].[K] Chemical compound [Na].[Na].[K] NSIKFNOYIGGILA-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 1
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910000573 alkali metal alloy Inorganic materials 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- GRJWDJVTZAUGDZ-UHFFFAOYSA-N anthracene;magnesium Chemical compound [Mg].C1=CC=CC2=CC3=CC=CC=C3C=C21 GRJWDJVTZAUGDZ-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229930008407 benzylideneacetone Natural products 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Chemical group 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- KMPWYEUPVWOPIM-UHFFFAOYSA-N cinchonidine Natural products C1=CC=C2C(C(C3N4CCC(C(C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 1
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- KQWGXHWJMSMDJJ-UHFFFAOYSA-N cyclohexyl isocyanate Chemical compound O=C=NC1CCCCC1 KQWGXHWJMSMDJJ-UHFFFAOYSA-N 0.000 description 1
- KDUIUFJBNGTBMD-VXMYFEMYSA-N cyclooctatetraene Chemical compound C1=C\C=C/C=C\C=C1 KDUIUFJBNGTBMD-VXMYFEMYSA-N 0.000 description 1
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 description 1
- 239000004913 cyclooctene Substances 0.000 description 1
- 150000001941 cyclopentenes Chemical class 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- TWXWPPKDQOWNSX-UHFFFAOYSA-N dicyclohexylmethanone Chemical compound C1CCCCC1C(=O)C1CCCCC1 TWXWPPKDQOWNSX-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000002223 garnet Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- 239000012943 hotmelt Substances 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 229910012375 magnesium hydride Inorganic materials 0.000 description 1
- YCCXQARVHOPWFJ-UHFFFAOYSA-M magnesium;ethane;chloride Chemical compound [Mg+2].[Cl-].[CH2-]C YCCXQARVHOPWFJ-UHFFFAOYSA-M 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- HAMGRBXTJNITHG-UHFFFAOYSA-N methyl isocyanate Chemical compound CN=C=O HAMGRBXTJNITHG-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 125000005574 norbornylene group Chemical group 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229930006968 piperitone Natural products 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- JAMNHZBIQDNHMM-UHFFFAOYSA-N pivalonitrile Chemical compound CC(C)(C)C#N JAMNHZBIQDNHMM-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 125000003226 pyrazolyl group Chemical group 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- VYNCPPVQAZGELS-UHFFFAOYSA-N toluene;trimethylalumane Chemical compound C[Al](C)C.CC1=CC=CC=C1 VYNCPPVQAZGELS-UHFFFAOYSA-N 0.000 description 1
- BWHOZHOGCMHOBV-BQYQJAHWSA-N trans-benzylideneacetone Chemical compound CC(=O)\C=C\C1=CC=CC=C1 BWHOZHOGCMHOBV-BQYQJAHWSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 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
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/28—Titanium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
生产金属富烯***式配合物的方法,以及新型富烯金属***式配合物和其他为烯烃和/或二烯烃的聚合反应的催化剂和作为氢化催化剂的用途。
Description
本发明涉及基于金属富烯配合物的催化剂,涉及生产该催化剂的方法和涉及其在烯烃和/或二烯烃的聚合和共聚合反应中的用途。
由于茂铁的发现,人们已考察了带有环戊二烯基配体的金属配合物。双环戊二烯基-金属配合物(金属茂)与活化用助催化剂(优选铝氧烷)混合用于烯烃和二烯烃的聚合反应的用途长时间以来是已知的(例如EP-A 69 951,129 368,351 392,485 821,485,823)。金属茂已被证明是烯烃聚合反应的高效的、特定的催化剂。与助催化剂结合,仅具有一个环戊二烯基配体(半-夹心配合物)的金属配合物也适合作为特定的聚合催化剂(US5 132 380,EP416 815,WO91/04257,WO96/13529)。所以有多种近年来开发的新型金属茂催化剂或半-夹心催化剂可用于烯烃化合物的聚合反应,为的是提高催化剂活性和选择性和控制其微观结构、分子量和分子量分布。有环戊二烯基配体的金属配合物(尤其手性柄型金属茂)也被描述为例如烯烃或亚胺的氢化催化剂(J.Am.Chem.Soc.1993年,115,12569。J.Am.Chem.Soc.1994年,116,8952-8965)。手性金属茂也可用作不对称合成,例如不对称Diels-Alder反应的催化剂(J.Chem.Soc.Chem.Commun,1995年,1181)。
相对来说对具有富烯配体的金属配合物知道较少。
根据Bercaw等人,JACS(1972),94,1219,由二甲基·双(η5-五甲基环戊二烯基)合钛的热解形成富烯配合物甲基·(η6-2,3,4,5-四甲基环戊二烯基-1-亚甲基)(η5-五甲基环戊二烯基)合钛。T.J.Marks等人,JACS(1988),110,7701描述了锆和铪的五甲基环戊二烯基配合物的热解。富烯配合物苯基·(η6-2,3,4,5-四甲基环戊二烯基-1-亚甲基)(η5-五甲基环戊二烯基)合锆是由二苯基·双(η5-五甲基环戊二烯基)合锆的热解形成的。富烯配合物由热方法的制备被限制在几个结构变体上。热方法并不总是产生同样的产物。
金属富烯配合物和生产它们的方法描述在前面的申请(德国专利申请19 756 742.8)中。不能由热方法获得的金属富烯配合物能够由富烯化合物与合适的过渡金属配合物在还原剂存在下的反应以高产率获得。富烯配体的直接引入为获得多种富烯金属配合物提供了便捷之道。与助催化剂结合,能够生产出特定的聚合催化剂,其催化活性与基于金属茂的催化剂的活性具有可比性。
金属富烯配合物的热途径生产方法和它们与助催化剂混合用作聚合催化剂的用途被描述在现有的申请DE 19 732 804.0中。
一个缺点是金属富烯配合物对空气和水汽极其敏感。金属富烯配合物因此必须在惰性气体条件下生产和贮存。
对于金属富烯配合物的反应行为知之甚少。醛和酮与配合物化合物(η6-环戊二烯基-1-亚甲基)(η5-甲基环戊二烯基)苯基合钛的反应在Z.Naturforsch.44b,1989年,1593-1598有描述。异腈与钛和锆的五甲基环戊二烯基-四甲基富烯配合物的反应被描述在有机金属,1991,10,2665-2671中。氯·(η6-2,3,4,5-四甲基环戊二烯基-1-亚甲基)·(η5-五甲基环戊二烯基)合钛与乙酰苯的反应被描述在有机金属,1991,10,1637-1639中。其中所形成的反应没有清楚地表征。上述的反应限于另外还包括环戊二烯基配体并由热方法生产出来的金属富烯配合物。
对于由富烯配体直接引入到金属配合物中所生产出来的金属富烯配合物的反应行为人们毫无所知。
本发明的目的是确认新型的催化剂,它至少部分地避免上述缺点。
现已惊奇地发现,非常适合作为催化剂的新型金属富烯***式配合物能够由金属富烯配合物与含有一个或多个杂原子的不饱和化合物的反应生产。
锕系元素, A 是除环戊二烯基配体以外的阴离子配体,任意性地单或多桥接,X 表示氢原子,C1-C10烷基,C1-C10烷氧基,C6-C10芳基,C6-C10
芳氧基,C2-C10链烯基,C7-C40芳烷基,C7-C40烷芳基,C8-C40
芳基链烯基,由C1-C10烃基取代的甲硅烷基,卤素原子或通式
NR7 2的酰胺,L 表示中性配位体,R1,R2,R3,R4,R5,R6可以相同或不同,且表示氢,卤素,氰基,
C1-C20烷基,C1-C10氟烷基,C6-C10氟芳基,C1-C10烷氧基,C6-
C20芳基,C6-C10芳氧基,C2-C10链烯基,C7-C40芳烷基,C7-C40
烷芳基,C8-C40芳基链烯基,C2-C10炔基,由C1-C10烃基取代的
甲硅烷基,由C1-C10烃基取代的硫基,或任意性地由C1-C20烃
基取代的氨基,或R1,R2,R3,R4,R5,R6可以与连接它们的原子一起形成一种或
多种脂族或芳族环体系,每个环体系可以包含1个或多个杂原
子(O,N,S)和包括5-10个碳原子,R7 表示氢,C1-C20烷基,C6-C20芳基,C7-C40芳烷基,C7-C40烷芳
基,可由C1-C10烃基取代的甲硅烷基,或任意性地由C1-C20烃
基取代的氨基,m,p表示从M的价态和键接状态得到的数字0,1,2,3或4,k 表示1,2或3,k+m+p的总和是1-5中的数,取决于M的氧化
态,和n 是0-10中的数,与b)通式(II)的不饱和化合物
R8 aR9 bCY (II)
其中R8和R9可以相同或不同,表示氢原子,卤素原子,羟基,C1-C10烷
基,C1-C10烷氧基,任意性地由卤素原子取代的C6-C10芳基,C6-C10
芳氧基,C2-C10链烯基,C7-C40芳烷基,C7-C40烷芳基,C8-C40
芳基链烯基,任意性地由C1-C20烃基取代的氨基,或任意性地
由C1-C20烃基取代的亚氨基,Y 表示氮原子,氧原子,硫原子或通式NR10的基团,其中R10与R8
和R9相同,和
a和b表示整数0或1,进行反应。
本发明也涉及能够由该方法制得的金属富烯***式配合物。
根据本发明的金属富烯***式配合物的生产能够由以下反应历程来说明:
碳原子形成环体系,它可含有一个或多个杂原子(O,N,S),或结构式(IIb)的化合物,
R11-C≡N (IIb)或结构式(IIc)的化合物
C≡N-R11 (IIc)或结构式(IId)的化合物
R11-N=C=Y (IId)其中Y表示氧原子或硫原子,和R11 表示氢原子,C1-C10烷基,C6-C10芳基,该芳基可任意性地被卤素原子取代,C7-C40芳烷基或C7-C40烷芳基。
其中Y表示氧原子以及R8和R9具有以上给出的意义的结构式(IIa)的化合物是特别优选的。这些化合物例如包括醛类如甲醛、乙醛、丙醛、正丁醛、异丁醛、新戊醛、辛醛、十八醛、丙烯醛、巴豆醛、苯甲醛或糠醛,二醛类如乙二醛,和酮类,如丙酮、丁酮、二乙基酮、己酮-(2)、己酮-(3)、甲基叔丁基酮、二正丙基酮、二异丙基酮、二异丁基酮、二叔丁基酮、二环己基酮、甲基环己基酮、二戊基酮、十七烷基苯基酮、异丙叉丙酮、佛尔酮、异佛尔酮、乙酰苯、4-氟乙酰苯、3,5-二(三氟甲基)乙酰苯、五甲基乙酰苯、二苯甲酮、4,4’-二氟二苯甲酮、十氟二苯甲酮、亚苄基丙酮、脱氧苯偶茵、环己酮、薄荷酮、樟脑和芴酮,和二酮类如二乙酰基乙酰丙酮,羧酸酯类如乙酸乙酯或苯甲酸苄基酯。
结构式(IIb)的优选化合物包括腈类,如乙腈,正丁腈,4-氯苯基腈,新戊腈和肉桂腈。结构式(IIc)的优选化合物包括异腈,如2,6-二-甲基苯基异腈。结构式(IId)的优选化合物包括异氰酸酯和硫代异氰酸酯,如环己基异氰酸酯和甲基异氰酸酯。
结构式(II)的其它优选化合物包括结构式(IIa)的不饱和化合物,其中Y表示式NR10的基团以及R8和R9具有以上给出的意义。这些化合物包括亚胺类,如乙酰苯苄基亚胺,和腙,如乙酰苯腙。
本发明的金属富烯***式配合物的生产方法是在合适的反应介质中在-100~+250℃,优选-78~+130℃,最优选-10~+60℃之间的温度下进行。
合适的反应介质的实例包括脂族或芳族烃,卤代烃,醚类和环醚类。其特别合适的实例包括未支化脂族烃,如丁烷,戊烷,己烷,庚烷或辛烷,支化脂族烃如异丁烷,异戊烷或异己烷,环状脂族烃如环己烷或甲基环己烷,芳族烃如苯,甲苯和二甲苯。醚类如二烷基醚或二甲氧基乙烷是优选的;四氢呋喃是特别优选的。不同溶剂的混合物也是合适的。
本发明金属富烯***式配合物的生产是在惰性条件(保护气体技术)下在排除了空气和水的情况下进行的。惰性气体的实例包括氮气和氩气。对于有机金属物质一般常用的Schlenk技术适合作为保护气体技术。
例如,结构式(I)的富烯金属配合物可由结构式(III)的过渡金属化合物
AmXsLnM (III)
其中A,X,L,M,m和n具有以上给出的意义,和
s 表示2,3,4,5或6和s>p,
其中
R1,R2,R3,R4,R5和R6具有以上给出的意义,在还原剂存在下进行反应。
结构式(I)的富烯配合物能够在单个反应步骤中进行,即在单釜反应中,其中各反应组分的添加顺序不是固定的。结构式(I)的富烯金属配合物能够被分离出来,然后在单独的步骤中与结构式(II)的不饱和化合物反应。结构式(I)的金属富烯配合物的预先分离也能够省略掉。(I)与(II)的摩尔比是在100∶1-0.1∶1,优选10∶1-0.5∶1范围内。
合适的还原剂的实例包括碱金属,碱土金属,铝,锌,碱金属的合金,如钠-钾合金或钠汞齐,碱土金属的合金,以及金属氢化物。金属氢化物的实例包括氢化锂,氢化钠,氢化镁,氢化铝,氢化锂铝和硼氢化钠。还原剂的特殊实例包括萘基钠,石墨钾,烷基锂,丁二烯镁,蒽镁,三烷基铝化合物和Grignard试剂。优选的还原剂是碱金属或碱土金属,C1-C6烷基锂,三-C1-C6烷基铝化合物和Grignard试剂,如乙基氯化镁。特别优选的还原剂是锂,钠汞齐,镁和正丁基锂,以及三乙基铝和三异丁基铝。代替使用上述还原剂,也能够进行电化学还原。
生产金属富烯配合物(I)的方法是在合适的反应介质中在-100-+250℃,优选-78~+130℃,最优选-10~+60℃的温度下进行的。
合适的反应介质的实例包括脂族或芳族烃,卤代烃,醚类和环醚类。其实例包括未支化脂族烃,如丁烷,戊烷,己烷,庚烷或辛烷,支化脂族烃如异丁烷,异戊烷或异己烷,环状脂族烃如环己烷或甲基环己烷,芳族烃如苯,甲苯和二甲苯。醚类如二烷基醚或二甲氧基乙烷是优选的;四氢呋喃是特别优选的。不同溶剂的混合物也是合适的。
根据本发明的催化剂的生产是在惰性气体条件下(保护气体技术)排除空气和水的情况下进行的。惰性气体的实例包括氮和氩气。对于有机金属物质一般常用的Schlenk技术适合作为保护气体技术。
特别合适的结构式(III)的过渡金属配合物是满足以下情况的那些:
M 是选自钛、锆、铪、钒、铌、钽和铬的金属,
A 是具有结构式N2C3R103的吡唑基,其中R10表示氢,C1-C10
烷基或C6-C10芳基,
具有结构式R7B(N2C3R10 3)3的硼酸吡唑酯,
具有结构式OR7的醇根或酚根,
具有结构式OSiR7 3的硅氧烷,
具有结构式SR7的硫醇根,
具有结构式(R7CO)2CR7的乙酰基丙酮,
具有结构式(R7N=CR7)2的二亚胺,
具有结构式R7C(NR7 2)2的胺基,
具有结构式C8HqR7 8-q的环辛四烯基,其中q表示0,1,2,3,
4,5,6或7,
其中
R7 具有以上给出的意义,
L 表示醚,硫醚,环醚,环硫醚,胺或膦,和
X,R7,m,n和s具有以上给出的意义。
结构式(III)的过渡金属配合物满足以下条件时是特别优选的:
M 表示钛,锆或铪,
X 表示氟,氯或溴,
L表示***或四氢呋喃,
m 表示数0,
s 表示数值2,3或4,和
n 是0-4中的数字。
特别合适的富烯化合物是具有结构式(IV)的满足以下条件的那些:R1-R6表示C1-C30烷基,C6-C10芳基,C7-C40烷芳基,和尤其表示氢,
甲基,三氟甲基,乙基,正丙基,异丙基,正丁基,异丁基,叔
丁基,苯基,五氟苯基,甲基苯基,环己基,苄基或二甲基胺基。
特别优选的结构式(IV)化合物包括6-环己基富烯,6-异丙基富烯,6-叔丁基富烯,6-苯基富烯,6-(二甲基胺基)富烯,6,6-双(二甲基胺基)富烯,6,6-二甲基富烯,6,6-双(三氟甲基)富烯,6,6-二苯基富烯,6,6-双(五氟苯基)富烯,6,6-五亚甲基富烯,6,6-四亚甲基富烯,6,6-三亚甲基富烯,2-(2,4-环戊二烯-1-叉基)-1,3-二硫杂环戊烷,5-亚苄基-1,2,3-三苯基-1,3-环戊二烯,1,2,3,4-四甲基富烯,1,2,3,4-四苯基富烯,2,3-二甲基富烯,2,3-二异丙基富烯,2,3-二苯基富烯,1,4-二甲基-2,3-二苯基富烯和1,4-二乙基-2,3-二苯基富烯。
结构式(IV)、(V)和(VI)的富烯化合物的合成能够例如按J.Org.Chem.,49卷,No.11(1984),1849中所述进行。
对于金属富烯配合物给出的结构式(I)应该被认为是键接关系的形式代表,并构成了结构变体的一个实例。在这些金属配合物中的键接关系将(在众多因素中)取决于中心原子,取决于氧化态,和取决于富烯配体上的取代基。
本发明进一步涉及这些富烯金属***式配合物在烯烃和/或二烯烃的聚合反应中的用途。根据本发明的催化剂也能够用作氢化催化剂。
聚合方法的合适助催化剂包括金属茂催化技术领域中已知的助催化剂,如聚合或低聚铝氧烷,路易斯酸以及铝酸盐和硼酸盐。在这一方面可参见Macromol.Symp.97卷,1995年7月,1-246页(关于铝氧烷)和参见EP277 003,EP277 004,有机金属1997,16,842-857(对于硼酸盐)和参见EP 573 403(对于铝酸盐)。
特别合适的助催化剂包括甲基铝氧烷,被三异丁基铝改性的甲基铝氧烷,二异丁基铝氧烷,三烷基铝化合物类如三甲基铝、三乙基铝、三异丁基铝或三异辛基铝,以及二烷基铝化合物类如二异丁基氢化铝,二异丁基氟化铝和二乙基氯化铝,被取代的三芳基铝化合物类如三-(五氟苯基)铝,含有四(五氟苯基)铝酸根作为阴离子的离子化合物类如三苯基甲基-四(五氟苯基)铝酸盐以及N,N-二甲基苯铵-四(五氟苯基)铝酸盐,取代的三芳基硼化合物类如三(五氟苯基)硼,和含有四(五氟苯基)硼酸根作为阴离子的离子化合物类如三苯基甲基-四(五氟苯基)硼酸盐和N,N-二甲基苯铵四(五氟苯基)硼酸盐。不同助催化剂的混合物也适合用于活化本发明的催化剂。
术语“聚合反应”被理解为指烯烃和/或二烯烃的均聚合和共聚合反应。下面的烯烃尤其可用于聚合:C2-C10链烯烃类,如乙烯,丙烯,丁烯-1,戊烯-1和己烯-1,辛烯-1,异丁烯和芳基链烯基如苯乙烯。下面这些化合物尤其可用作二烯烃类:共轭二烯烃类如1,3-丁二烯,异戊二烯或1,3-戊二烯,和非共轭二烯烃如1,4-己二烯,1,5-庚二烯,5,7-二甲基-1,6-辛二烯,4-乙烯基-1-环己烯,5-乙叉基-2-降冰片烯,5-乙烯基-2-降冰片烯和二环戊二烯。
根据本发明的催化剂适合生产聚乙烯,特别适合生产以乙烯与上述烯烃和上述二烯烃中一种或多种的共聚物为基础的橡胶。本发明的催化剂也适合于环烯烃如降冰片烯、环戊烯、环己烯和环辛烯的聚合反应,并适合环烯烃与乙烯或α-烯烃的共聚合反应。
聚合反应能够在液相中,在存在或不存在惰性溶剂的情况下,或在气相中进行。合适的溶剂包括芳族烃如苯和/或甲苯,或脂族烃类如丙烷,己烷,庚烷,辛烷,异丁烷,环己烷或不同烃类的混合物。
还有可能使用沉积在载体上的本发明催化剂体系。合适的载体材料的例子包括无机或有机聚合物载体,如硅石,沸石,炭黑,活性炭,氧化铝,聚苯乙烯或聚丙烯。
本发明的催化剂能够以常规方式沉积在载体材料上。承载催化剂体系的方法例如描述在US4 808 561,4 912 075,5 008 228和4 914 253中。
聚合反应一般是在常压至1000巴,优选1-100巴的压力下和在-100~+250℃、优选0~+150℃之间的温度下进行。聚合反应能够在普通反应器中以连续或间歇方式进行。
例如,乙烯与或不与前述共聚单体的(共)聚合反应能够按以下进行:在常规的制备操作之后,钢制压力釜中装入溶剂和装入清除剂如三异丁基铝或甲基铝氧烷。可能的杂质和催化剂毒物,例如水或其它含氧化合物将被清除剂改变为无害。反应器内填充单体至所确定的压力,在所选择的温度下保持恒温,通过添加预先活化的催化剂来引发聚合反应。预活化例如可通过将催化剂与助催化剂(例如甲基铝氧烷)按预定的用量比在溶剂中的混合物进行搅拌来进行。聚合反应能够由连续或间歇方法进行。
本发明将参考下面的实施例更详细地叙述。
一般信息:有机金属化合物的制备和处理是在保护氩气氛围中在排除空气和水汽的情况下进行(Schlenk技术)。所有必须的溶剂在使用之前通过在合适干燥剂上沸腾几小时和然后在氩气下蒸馏而最终赋予绝对无水性质。化合物由1H NMR,13C NMR和质谱法表征。
聚合物表征:DSC测量是在Perkin-Elmer提供的并被称作DSC-2差示扫描量热仪的仪器中,按以下操作程序进行:两个加热阶段,从-90℃加热至+180℃,加热速率20K/min,以320K/min的速度快速冷却至-90℃,用氮气吹扫;称取12.3g样品加入到标准胶囊中。根据ASTM D3900,由IR光谱测定聚合物组成。
缩写:THF:四氢呋喃RT:室温HV:高真空MS:质谱MAO:甲基铝氧烷dH:热熔 焓(DSC测量)Tg:玻璃化转变温度(DSC测量)
实施例1
由6,6-二甲基富烯与TiCl4·2THF在镁存在下反应和然后与二苯甲酮反应来合成化合物1
将TiCl4·2THF(710mg,2.13mmol)和当量的镁(52mg,2.13mmol)加入到容器内的25mlTHF中。在RT下滴加1.01当量6,6-二甲基富烯(230mg,2.16mmol)。该批料在RT和搅拌下保持一夜,因此使所有的镁消耗完。在缓慢滴加二苯甲酮(0.387g,2.13mmol)在5mlTHF中的溶液之后,该批料在RT下搅拌2小时,在HV下除去溶剂,产物被调和在甲苯中。过滤出固体物,溶液被浓缩至10ml。通过添加20ml己烷沉淀出红色固体。该批料被冷却至-20℃进行结晶。分离出固体物并在HV下干燥。获得了230mg(27%)的暗红色固体形式的化合物1,由NMR和质谱表征。
1H-NMR:(C6D6,300MHz):δ=0.92(s,6H,C(CH3)2),5.79(dd,2H,2J(H,H)=2.69
Hz,C5H4),6.81(dd,2H,2J(H,H)=2.69Hz,C5H4),7.03-7.26(m,6H,C6H5),7.70-
7.75(m,4H,C6H5)ppm.
13C NMR:(C6D6,75MHz):δ=27.89(C(CH3)2),45.23(C(CH3)2),115.09/116.39/
119.83/120.49(C4H4),112.74/128.53/130.33/132.31(o,m,p-C6H5),138.33(ipso-
C5H4),144.45(i-C6H5)ppm.
MS:(70eV)m/e:406(2)[M+],372(5)[M+-HCl],330(30)[M+-Ph],224(25)
[M+-OCPh2],182(65)[OCPh2],105(100)[6,6-dimethylfulvene],77(70)[Ph].
实施例2
乙烯的聚合反应
500ml甲苯和1ml的10%MAO甲苯溶液加入到1.4升钢制压力釜中并在25℃的控制温度下保持。加入乙烯直至反应器内压升至6巴为止。催化剂的预活化:将2.0mg实施例1的化合物1在2.5ml甲苯中的溶液在RT下与2ml的10%MAO甲苯溶液一起搅拌10分钟。通过添加预活化的催化剂溶液(5μmol钛)来引发聚合反应。在25℃和7巴下聚合30分钟的时间之后,压力釜减压,通过添加1%的HCl在甲醇中的溶液来停止聚合反应,该批料被搅拌1小时。所获得的聚合物被过滤出来,用甲醇洗涤,分离和在真空和60℃下干燥20小时。获得了26.5g高度结晶的聚乙烯。在第一加热阶段中DSC熔点是147.1℃(dH=251.8J/g),和在第二加热阶段中熔点是135.9℃(dH=144J/g)。
实施例3
乙烯和1-己烯的共聚合
500ml甲苯,20ml已烯-1和1ml的10%MAO甲苯溶液加入到1.4升钢制压力釜中。该溶液在40℃的控制温度下保持。加入乙烯直至反应器内压升至6巴为止。催化剂的预活化:将4.0mg实施例1的产物在5ml甲苯中的溶液在RT下与5ml的10%MAO甲苯溶液一起搅拌10分钟。通过添加预活化的催化剂溶液(10μmol钛)来引发聚合反应。在40℃和6巴下聚合60分钟的时间之后,压力釜减压,通过添加1%的HCl在甲醇中的溶液来停止聚合反应,该批料被搅拌1小时。所获得的聚合物被过滤出来,用甲醇洗涤,分离和在真空和60℃下干燥20小时。获得了22.2g乙烯/1-己烯共聚物。在第二加热阶段中DSC熔点是118℃(dH=112.5J/g)。DSC测量得到Tg为-20.5℃。
实施例4
TiCl4·2THF(510mg,1.53mmol)和镁(37mg,1.53mmol)加入到容器内的10mlTHF中。将1.05当量的2,3,4,5-四甲基富烯(215mg,1.60mmol)滴加到该溶液中。该批料在搅拌下保持一夜以使镁完全消耗。在RT下添加二苯甲酮(0.280g,1.53mmol)在5mlTHF中的溶液。2小时后批料在HV下蒸发至干,产物被调和在30ml己烷中,过滤除掉氯化镁。批料浓缩到其一半体积,随后在-20℃下结晶得到280mg(42%)棕红色固体形式的化合物2,由NMR和质谱表征。
1H NMR:(C6D6,300MHz):δ=1.69(s,6H,C5(CH3)4),1.95(s,6H,C5(CH3)4),3.94
(s,2H,-CH2-)6.91(m,4H C6H5),7.13(m,4H,C6H5),7.56(m,2H C6H5)ppm.
13C NMR:(C6D6,75MHz):δ=13.05,14.18(C5(CH3)4),44.04(-CH2-),124.67,
127.38,128.97(o,m,p-C6H5),118.04,128.88,130.42(C5(CH3)4),149.27(i-C6H5)
ppm.
MS:(70eV)m/e:434(10)[M+],356(5)[M+-Ph],332(100)[M+-2HCl-2CH3],316
(10)[M+-TiCl2],252(30)[M+-OCPh2],182(35)[OCPh2],135(25)[C5(CH3)4=CH2],
77(65)[Ph].
实施例5
在镁存在下6,6-二甲基富烯与TiCl4·2THF反应和随后与4-氟苯基甲基酮反应
710mg(2.13mmol)的TiCl4·2THF和51.4mg(2.13mmol)的镁加入到容器内的25mlTHF中。将0.26ml(2.16mmol)的6,6-二甲基富烯在RT下滴加到该溶液中。该批料在搅拌下保持一夜以使镁完全消耗。在缓慢滴加294mg(2.13mmol)4-氟苯基甲基酮在5mlTHF中的溶液并搅拌2小时之后,批料在HV下蒸发至干,产物被调和在25ml己烷中,过滤除掉氯化镁。批料浓缩到其一半体积,随后在-20℃下结晶得到242mg深棕色结晶固体。
实施例6
乙烯的聚合
将100ml甲苯和5ml 10%甲基铝氧烷(MAO)溶液加入到250ml玻璃反应器中。由气体导入管连续将处于1.1巴下的乙烯导入溶液中。通过添加4.4mg的实施例5的产物在5ml甲苯中的溶液来引发聚合。反应(该反应在40℃的温度和1.1巴的乙烯压力下进行)是在10分钟的聚合时间之后通过添加10ml甲醇来停止,过滤出所得到的聚合物,用甲醇洗涤,并在真空干燥箱中干燥。获得0.96g聚乙烯。
实施例7
在镁存在下6,6-二甲基富烯与TiCl4·2THF反应和随后与3,3-二甲基-2-丁酮反应
384.8mg(1.15mmol)的TiCl4·2THF和28mg(1.15mmol)的镁加入到容器内的15mlTHF中。将0.14ml(1.16mmol)的6,6-二甲基富烯在RT下滴加到该溶液中。该批料在搅拌下保持一夜以使镁完全消耗。在缓慢滴加15mg(1.15mmol)3,3-二甲基-2-丁酮在2.5mlTHF中的溶液之后和在搅拌2小时之后,批料在HV下蒸发至干,残余物被调和在28.8ml甲苯中。获得了悬浮液,它含有40μmol钛/ml。
实施例8
乙烯的聚合
重复实施例6的聚合程序,只是实施例7的悬浮液用作催化剂,代替实施例5的产物。通过添加0.25ml的实施例7的悬浮液(10μmol钛)来引发聚合反应。获得1.71g的聚乙烯。
实施例9
在镁存在下6,6-二苯基富烯与TiCl4·2THF反应和随后与3,3-二甲基-2-丁酮反应
710mg(2.13mmol)的TiCl4·2THF和51.4mg(2.13mmol)的镁加入到容器内的20mlTHF中。将490.6mg(2.13mmol)的6,6-二苯基富烯在RT下滴加到该溶液中。该批料在搅拌下保持一夜以使镁完全消耗。在缓慢滴加213mg(2.13mmol)3,3-二甲基-2-丁酮在5mlTHF中的溶液之后和在搅拌2小时之后,批料在HV下蒸发至干,残余物被调和在25ml甲苯中。获得了悬浮液,它含有42.6μmol钛/ml。
实施例10
乙烯的聚合
将90ml正己烷,0.5ml的2M三甲基铝甲苯溶液和18.4ml(20μmol)CPh3[B(C6F5)4]在10ml甲苯中的溶液加入到玻璃反应器中。由气体导入管连续将处于1.1巴下的乙烯导入溶液中。通过添加0.23ml的实施例9的悬浮液(10μmol钛)来引发聚合。反应(该反应在40℃的温度和1.1巴的乙烯压力下进行)是在15分钟的聚合时间之后通过添加甲醇来停止,过滤出所得到的聚合物,用丙酮洗涤,并在真空干燥箱中干燥。获得2.14g聚乙烯。
实施例11
乙烯的聚合
500ml正己烷和5ml的10%MAO甲苯溶液加入到1.4升钢制压力釜中并在40℃的控制温度下保持。加入乙烯直至反应器内压升至6巴为止。催化剂的预活化:将0.23ml实施例9的悬浮液在RT下与5ml的10%MAO甲苯溶液一起搅拌10分钟。通过添加预活化的催化剂溶液(10μmol钛)来引发聚合反应。在40℃和6巴下聚合10分钟的时间之后,压力釜减压。通过添加1%的HCl在甲醇中的溶液来停止聚合反应,该批料被搅拌1小时。所获得的聚合物被过滤出来,用甲醇洗涤,分离和在真空和60℃下干燥20小时。获得了13.6g高度结晶聚乙烯。在第一加热阶段中DSC熔点是145.4℃(dH=215J/g),和在第二加热阶段中的DSC熔点是135.9℃(dH=138J/g)。
实施例12
乙烯和丙烯的共聚合
500ml己烷和5ml的10%MAO甲苯溶液加入到1.4升钢制压力釜中,该压力釜中装有机械搅拌器,压力计,温度传感器,温度控制器,催化剂开关以及乙烯和丙烯的单体计量装置。内部温度由恒温器设定在40℃。随后将14g乙烯和28.3g丙烯计量加入。催化剂的预活化:将0.23ml实施例9的悬浮液在RT下与5ml的10%MAO甲苯溶液一起搅拌10分钟。通过添加预活化的催化剂溶液(10μmol钛)来引发聚合反应。使用半间歇方法,乙烯和丙烯以3∶7重量比连续计量加入,以使在40℃下保持恒定的情况下内部压力为5巴。在聚合40分钟的时间之后,通过添加1%的HCl在甲醇中的溶液来停止聚合反应,该批料被搅拌1小时。所获得的聚合物被过滤出来,用甲醇洗涤,分离和在真空和60℃下干燥20小时,获得了49.8g共聚物。DSC测量方法测定Tg为-54℃(第二阶段)。
Claims (8)
1、生产金属富烯***式配合物的方法,其特征在于a)具有结构式(I)的金属富烯配合物其中M 是IUPAC元素周期表的IIIb、IVb、Vb、VIb族金属或镧系或锕
系元素,A 是除环戊二烯基配体以外的阴离子配体,任意性地单或多桥接,X 表示氢原子,C1-C10烷基,C1-C10烷氧基,C6-C10芳基,C6-C10
芳氧基,C2-C10链烯基,C7-C40芳烷基,C7-C40烷芳基,C8-C40
芳基链烯基,由C1-C10烃基取代的甲硅烷基,卤素原子或通式NR7 2
的酰胺,L 表示中性配位体,R1,R2,R3,R4,R5,R6可以相同或不同,且表示氢,卤素,氰基,
C1-C20烷基,C1-C10氟烷基,C6-C10氟芳基,C1-C10烷氧基,C6-C20
芳基,C6-C10芳氧基,C2-C10链烯基,C7-C40芳烷基,C7-C40烷
芳基,C8-C40芳基链烯基,C2-C10炔基,由C1-C10烃基取代的甲
硅烷基,由C1-C10烃基取代的硫基,或任意性地由C1-C20烃基
取代的氨基,或R1,R2,R3,R4,R5,R6可以与连接它们的原子一起形成一种或多种脂族或芳族环体系,每个环体系可以包含1个或多个杂原子(O,N,S)和包括5-10个碳原子,R7 表示氢,C1-C20烷基,C6-C20芳基,C7-C40芳烷基,C7-C40烷芳基,可由C1-C10烃基取代的甲硅烷基,或任意性地由C1-C20烃基取代的氨基,m,p表示从M的价态和键接状态得到的数字0,1,2,3或4, k 表示1,2或3,k+m+p的总和是1-5中的数,取决于M的氧化
态,和n 是0-10中的数,与b)通式(II)的不饱和化合物
R8 aR9 bCY (II)其中R8和R9可以相同或不同,表示氢原子,卤素原子,羟基,C1-C10烷
基,C1-C10烷氧基,任意性地由卤素原子取代的C6-C10芳基,C6-C10
芳氧基,C2-C10链烯基,C7-C40芳烷基,C7-C40烷芳基,C8-C40
芳基链烯基,任意性地由C1-C20烃基取代的氨基,或任意性地
由C1-C20烃基取代的亚氨基,Y 表示氮原子,氧原子,硫原子或通式NR10的基团,其中R10与R8
和R9相同,和
a和b表示整数0或1,进行反应。
2、根据权利要求1的方法,其特征在于:
M 表示Ti,Zr或Hf,
X 表示卤素,
L 表示***或四氢呋喃,
p 表示数值2,
k 表示数值1,
m 是0,和
n 是0-4范围内的整数。
3、根据权利要求1的方法,其特征在于
Y 表示氧或氮,
R8和R9 表示氢和/或C1-C10烷基。
4、由权利要求1的方法生产的金属富烯***式配合物。
5、根据权利要求1的方法,其特征在于结构式(I)的富烯金属配合物可由结构式(III)的过渡金属化合物
AmXsLnM (III)其中A,X,L,M,m和n具有权利要求1的a中同样的意义,和s 表示2,3,4,5或6和s>p,与结构式(IV)的富烯化合物
其中
R1,R2,R3,R4,R5和R6具有权利要求1中同样的意义,在还原剂存在下进行反应。
6、根据权利要求5的方法,其特征在于
M 表示Ti,Zr或Hf,
X 表示卤素,
L 表示***或四氢呋喃,
m 表示数0,
s 表示数值2,3或4,和
n 是0-4中的数字。
7、根据权利要求1的方法,其特征在于6-环己基富烯,6-异丙基富烯,6-叔丁基富烯,6-苯基富烯,6-(二甲基胺基)富烯,6,6-双(二甲基胺基)富烯,6,6-二甲基富烯,6,6-双(三氟甲基)富烯,6,6-二苯基富烯,6,6-双(五氟苯基)富烯,6,6-五亚甲基富烯,6,6-四亚甲基富烯,6,6-三亚甲基富烯,2-(2,4-环戊二烯-1-叉基)-1,3-二硫杂环戊烷,5-亚苄基-1,2,3-三苯基-1,3-环戊二烯,1,2,3,4-四甲基富烯,1,2,3,4-四苯基富烯,2,3-二甲基富烯,2,3-二异丙基富烯,2,3-二苯基富烯,1,4-二甲基-2,3-二苯基富烯或1,4-二乙基-2,3-二苯基富烯可用作富烯化合物。
8、权利要求4的金属富烯***式配合物任意性地与助催化剂一起作为催化剂用于烯烃和/或二烯烃的聚合反应的催化剂或作为氢化催化剂的用途。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19837734A DE19837734C1 (de) | 1998-08-20 | 1998-08-20 | Verfahren zur Herstellung von Katalysatoren auf Basis von Fulven-Metallkomplexen |
DE19837734.7 | 1998-08-20 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN1245806A true CN1245806A (zh) | 2000-03-01 |
Family
ID=7878103
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN99117988.9A Pending CN1245806A (zh) | 1998-08-20 | 1999-08-20 | 基于金属富烯配合物的催化剂 |
Country Status (7)
Country | Link |
---|---|
US (1) | US6214762B1 (zh) |
EP (1) | EP0980872A2 (zh) |
JP (1) | JP2000128894A (zh) |
CN (1) | CN1245806A (zh) |
CA (1) | CA2280433A1 (zh) |
DE (1) | DE19837734C1 (zh) |
RU (1) | RU99118218A (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107312045A (zh) * | 2017-07-20 | 2017-11-03 | 上海化工研究院有限公司 | 一种取代环戊二烯基茂金属化合物的制备方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19732804A1 (de) * | 1997-07-30 | 1999-02-04 | Bayer Ag | Katalysatoren auf Basis von Fulven-Metallkomplexen |
DE19837739A1 (de) * | 1998-08-20 | 2000-02-24 | Bayer Ag | Katalysatorsystem auf Basis von Fulven-Cyclopentadienyl-Metallkomplexen |
KR100515585B1 (ko) * | 2002-08-29 | 2005-09-16 | 주식회사 엘지화학 | 풀벤계 화합물 및 이의 제조방법 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3127133A1 (de) | 1981-07-09 | 1983-01-27 | Hoechst Ag, 6000 Frankfurt | Verfahren zur herstellung von polyolefinen und deren copolymerisaten |
ZA844157B (en) | 1983-06-06 | 1986-01-29 | Exxon Research Engineering Co | Process and catalyst for polyolefin density and molecular weight control |
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 |
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 |
US5064802A (en) | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
EP0485823B1 (de) | 1990-11-12 | 1995-03-08 | Hoechst Aktiengesellschaft | 2-Substituierte Bisindenylmetallocene, Verfahren zu ihrer Herstellung und ihre Verwendung als Katalysatoren bei der Olefinpolymerisation |
ES2090209T3 (es) | 1990-11-12 | 1996-10-16 | Hoechst Ag | Metalocenos con ligandos basados en derivados de indenilo sustituidos en posicion 2, procedimiento para su preparacion y su empleo como catalizadores. |
EP0789718B1 (en) | 1994-10-31 | 1998-04-08 | Dsm N.V. | Catalyst composition and process for the polymerization of an olefin |
DE19732804A1 (de) * | 1997-07-30 | 1999-02-04 | Bayer Ag | Katalysatoren auf Basis von Fulven-Metallkomplexen |
-
1998
- 1998-08-20 DE DE19837734A patent/DE19837734C1/de not_active Expired - Fee Related
-
1999
- 1999-08-09 EP EP99115111A patent/EP0980872A2/de not_active Withdrawn
- 1999-08-13 US US09/374,551 patent/US6214762B1/en not_active Expired - Fee Related
- 1999-08-16 JP JP11229798A patent/JP2000128894A/ja active Pending
- 1999-08-17 CA CA002280433A patent/CA2280433A1/en not_active Abandoned
- 1999-08-19 RU RU99118218/04A patent/RU99118218A/ru not_active Application Discontinuation
- 1999-08-20 CN CN99117988.9A patent/CN1245806A/zh active Pending
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107312045A (zh) * | 2017-07-20 | 2017-11-03 | 上海化工研究院有限公司 | 一种取代环戊二烯基茂金属化合物的制备方法 |
CN107312045B (zh) * | 2017-07-20 | 2019-12-13 | 上海化工研究院有限公司 | 一种取代环戊二烯基茂金属化合物的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
CA2280433A1 (en) | 2000-02-20 |
DE19837734C1 (de) | 1999-12-23 |
JP2000128894A (ja) | 2000-05-09 |
EP0980872A2 (de) | 2000-02-23 |
US6214762B1 (en) | 2001-04-10 |
RU99118218A (ru) | 2001-06-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1058015C (zh) | 双环戊二烯基二烯配合物 | |
CN1049899C (zh) | 烯烃的聚合方法 | |
Bochmann et al. | Insertion reactions of nitriles in cationic alkylbis (cyclopentadienyl) titanium complexes: the facile synthesis of azaalkenylidene titanium complexes and the crystal and molecular structure of [(indenyl) 2Ti (NCMePh)(NCPh)] BPh4 | |
JP5393456B2 (ja) | 3−メチルブテ−1−エンからポリマーを製造する方法 | |
JP5589087B2 (ja) | グアニジナト配位子を有するオレフィンの重合用の触媒成分 | |
CN1270596A (zh) | 双金属配合物和从其获得的聚合催化剂 | |
CN101054388B (zh) | 聚合催化剂活化剂化合物、其制备方法及其应用 | |
KR20170106110A (ko) | 혼성 담지 메탈로센 촉매의 제조방법, 상기 제조방법으로 제조된 혼성 담지 메탈로센 촉매, 및 이를 이용하는 폴리올레핀의 제조방법 | |
CN1364818A (zh) | 新型烯烃聚合催化剂 | |
EP3218385A1 (en) | Metallocenes and their use as polymerization catalysts | |
CN107531822A (zh) | 合成锆和铪的单环戊二烯基络合物的方法 | |
JPH10510262A (ja) | チタン(ii)又はジルコニウム(ii)錯体の改良製法 | |
CN1575295A (zh) | 连接金属茂配合物,催化剂体系和使用该催化剂体系的烯烃聚合方法 | |
CN1291986A (zh) | 双(四氢茚基)金属茂作为烯烃聚合催化剂 | |
CA2294608A1 (en) | Metallocenes, ligands and olefin polymerization | |
CN1278265A (zh) | 制备富烯金属配合物的方法 | |
EP2623522B1 (en) | Preparation method of hybrid supported metallocene catalyst | |
CN1245806A (zh) | 基于金属富烯配合物的催化剂 | |
JPH10101607A (ja) | ヘテロ原子含有基により置換されているシクロペンタジエン化合物 | |
EP1248806A1 (en) | Metallocene catalysts comprising monocyclic siloxy substituted cyclopentadienyl group(s) for the polymerisation of olefins | |
JP2001026598A (ja) | インデニル化合物、その配位子前駆物質、配位子前駆物質の製造法およびオレフィンの重合法 | |
US6258744B1 (en) | Catalyst system based on fulvene cyclopentadienyl metal complexes | |
JP4133734B2 (ja) | 新規な遷移金属化合物、オレフィン重合用触媒およびポリオレフィンの製造方法 | |
CN1348458A (zh) | 齐聚催化剂 | |
KR20190023926A (ko) | 에틸렌 올리고머화용 전이금속 화합물을 포함하는 촉매 시스템 및 이를 이용한 선형 알파 올레핀의 제조방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1025972 Country of ref document: HK |