MXPA01000875A - Polymerization of olefins - Google Patents
Polymerization of olefinsInfo
- Publication number
- MXPA01000875A MXPA01000875A MXPA/A/2001/000875A MXPA01000875A MXPA01000875A MX PA01000875 A MXPA01000875 A MX PA01000875A MX PA01000875 A MXPA01000875 A MX PA01000875A MX PA01000875 A MXPA01000875 A MX PA01000875A
- Authority
- MX
- Mexico
- Prior art keywords
- independently
- hydrocarbyl
- compound
- recited
- substituted
- Prior art date
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 61
- 238000006116 polymerization reaction Methods 0.000 title claims description 43
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 37
- 230000027455 binding Effects 0.000 claims abstract description 35
- 239000003446 ligand Substances 0.000 claims abstract description 35
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 17
- 150000003624 transition metals Chemical class 0.000 claims abstract description 17
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 13
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 72
- 238000000034 method Methods 0.000 claims description 54
- 150000001875 compounds Chemical class 0.000 claims description 50
- 239000002685 polymerization catalyst Substances 0.000 claims description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 31
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 229910052757 nitrogen Inorganic materials 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- MYMOFIZGZYHOMD-UHFFFAOYSA-N oxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 25
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 22
- 229910052717 sulfur Inorganic materials 0.000 claims description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 21
- 239000011593 sulfur Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 19
- 150000001450 anions Chemical class 0.000 claims description 16
- 239000002841 Lewis acid Substances 0.000 claims description 12
- 229920000098 polyolefin Polymers 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 12
- 150000002910 rare earth metals Chemical class 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 11
- 239000011651 chromium Substances 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 229910052719 titanium Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- KLGZELKXQMTEMM-UHFFFAOYSA-N hydride Chemical compound [H-] KLGZELKXQMTEMM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052803 cobalt Inorganic materials 0.000 claims description 8
- 230000001264 neutralization Effects 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 125000003107 substituted aryl group Chemical group 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 150000007517 lewis acids Chemical class 0.000 claims description 7
- 150000002829 nitrogen Chemical group 0.000 claims description 7
- 125000005418 aryl aryl group Chemical group 0.000 claims description 6
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 claims description 6
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 6
- 239000007848 Bronsted acid Substances 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- ZWRMSOMIVOVMQX-UHFFFAOYSA-M 2-(2-aminoethyldisulfanyl)ethanamine;palladium(2+);chloride Chemical compound [Cl-].[Pd+2].NCCSSCCN ZWRMSOMIVOVMQX-UHFFFAOYSA-M 0.000 claims description 4
- 101700054578 DDM1 Proteins 0.000 claims description 4
- 101700071645 ROK1 Proteins 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004927 clay Substances 0.000 claims description 2
- 229910052570 clay Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium(0) Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 101700087158 nhr-10 Proteins 0.000 claims 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims 1
- 229910052706 scandium Inorganic materials 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 30
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 4
- 229920001971 elastomer Polymers 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract description 3
- 239000000806 elastomer Substances 0.000 abstract description 2
- 239000004202 carbamide Substances 0.000 abstract 1
- 229910000071 diazene Inorganic materials 0.000 abstract 1
- JOYRKODLDBILNP-UHFFFAOYSA-N ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 46
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 36
- XEKOWRVHYACXOJ-UHFFFAOYSA-N acetic acid ethyl ester Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 27
- 239000000460 chlorine Substances 0.000 description 27
- 239000005977 Ethylene Substances 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 24
- -1 ethylene Chemical class 0.000 description 24
- 239000000047 product Substances 0.000 description 24
- 239000008079 hexane Substances 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 23
- 230000002194 synthesizing Effects 0.000 description 22
- 239000011541 reaction mixture Substances 0.000 description 21
- 238000001035 drying Methods 0.000 description 19
- 239000002904 solvent Substances 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 125000000524 functional group Chemical group 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 13
- 239000002244 precipitate Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- JVVRCYWZTJLJSG-UHFFFAOYSA-N 4-Dimethylaminophenol Chemical compound CN(C)C1=CC=C(O)C=C1 JVVRCYWZTJLJSG-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000004698 Polyethylene (PE) Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 10
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 10
- 238000001914 filtration Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 101710026631 Os12g0623900 Proteins 0.000 description 8
- 238000000262 chemical ionisation mass spectrometry Methods 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000011065 in-situ storage Methods 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene dichloride Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 7
- 125000004429 atoms Chemical group 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 7
- 239000000178 monomer Substances 0.000 description 7
- 229920000573 polyethylene Polymers 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 239000007858 starting material Substances 0.000 description 6
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-dimethylaminopyridine Substances CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 230000004907 flux Effects 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (Z)-4-oxopent-2-en-2-olate Chemical group C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920001169 thermoplastic Polymers 0.000 description 3
- 239000004416 thermosoftening plastic Substances 0.000 description 3
- 150000003623 transition metal compounds Chemical class 0.000 description 3
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-Trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N AI2O3 Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 240000003598 Fraxinus ornus Species 0.000 description 2
- KVKFRMCSXWQSNT-UHFFFAOYSA-N N,N'-dimethylethane-1,2-diamine Chemical compound CNCCNC KVKFRMCSXWQSNT-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- 150000007942 carboxylates Chemical group 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 150000004696 coordination complex Chemical class 0.000 description 2
- 230000000875 corresponding Effects 0.000 description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 150000002816 nickel compounds Chemical class 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 150000002941 palladium compounds Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N precursor Substances N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHSVJTYBTJCDFL-UHFFFAOYSA-L 1,2-dimethoxyethane;nickel(2+);dibromide Chemical compound Br[Ni]Br.COCCOC VHSVJTYBTJCDFL-UHFFFAOYSA-L 0.000 description 1
- MXZROAOUCUVNHX-UHFFFAOYSA-N 1-aminopropan-1-ol Chemical compound CCC(N)O MXZROAOUCUVNHX-UHFFFAOYSA-N 0.000 description 1
- 238000004293 19F NMR spectroscopy Methods 0.000 description 1
- XBNGYFFABRKICK-UHFFFAOYSA-N 2,3,4,5,6-pentafluorophenol Chemical compound OC1=C(F)C(F)=C(F)C(F)=C1F XBNGYFFABRKICK-UHFFFAOYSA-N 0.000 description 1
- OXOBKZZXZVFOBB-UHFFFAOYSA-N 2-Diphenylmethylpyrrolidine Chemical compound C1CCNC1C(C=1C=CC=CC=1)C1=CC=CC=C1 OXOBKZZXZVFOBB-UHFFFAOYSA-N 0.000 description 1
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N 3-aminopropanol Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- 101700041090 ADH13 Proteins 0.000 description 1
- 101710035595 CDH4 Proteins 0.000 description 1
- 101710035598 CDH7 Proteins 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N Cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-SVYQBANQSA-N Deuterated THF Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 1
- NALBLJLOBICXRH-UHFFFAOYSA-N Dinitrogen monohydride Chemical group N=[N] NALBLJLOBICXRH-UHFFFAOYSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N Gadolinium Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- PEECTLLHENGOKU-UHFFFAOYSA-N N,N-dimethylpyridin-4-amine Chemical compound CN(C)C1=CC=NC=C1.CN(C)C1=CC=NC=C1 PEECTLLHENGOKU-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-Methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N Neodymium Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 102000014961 Protein Precursors Human genes 0.000 description 1
- 108010078762 Protein Precursors Proteins 0.000 description 1
- 101710045116 Redox1 Proteins 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N [N-]=C=O Chemical compound [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000003213 activating Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001414 amino alcohols Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- XDLDASNSMGOEMX-UHFFFAOYSA-N benzene benzene Chemical compound C1=CC=CC=C1.C1=CC=CC=C1 XDLDASNSMGOEMX-UHFFFAOYSA-N 0.000 description 1
- FXCLIEYDXXVEAI-UHFFFAOYSA-N benzene;dichloromethane Chemical compound ClCCl.C1=CC=CC=C1 FXCLIEYDXXVEAI-UHFFFAOYSA-N 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- 230000002902 bimodal Effects 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- KARVSHNNUWMXFO-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane;hydrate Chemical compound O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O KARVSHNNUWMXFO-UHFFFAOYSA-N 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 150000004820 halides Chemical group 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005842 heteroatoms Chemical group 0.000 description 1
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002440 hydroxy compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 150000002751 molybdenum Chemical class 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- IMNFDUFMRHMDMM-UHFFFAOYSA-N n-heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- MMIGMVBXZUIMCT-UHFFFAOYSA-M sodium;2,6-di(propan-2-yl)phenolate Chemical compound [Na+].CC(C)C1=CC=CC(C(C)C)=C1[O-] MMIGMVBXZUIMCT-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Abstract
Various olefins may be polymerized using a catalyst system containing selected&agr;-diimine, urethane or urea ligands, some of them novel, complexed to nickel, palladium or other selected transition metals. The polymers are useful as molding resins and elastomers.
Description
POLYMERIZATION OF OLEFINS
Field of Invention
Polymerization catalysts for olefins such as ethylene, various nickel and palladium complexes, for example of a-diimines substituted at carbon atoms by heteroatoms such as nitrogen or oxygen, and selected ureas and urethanes can be used. Palladium catalysts also polymerize polar comonomers.
Background of the Invention
Recently, it has been reported that polymerization catalysts contain less transition metals such as palladium and nickel. Among these compounds are the a-diimine complexes (see World Patent Application 96/23010) and various other types of liqandos (see U.S. Patent 5,714,556). These catalysts can, under various conditions, make unique polyolefins, such as those that contain "abnormal" branched patterns when
Ref: 126763
they are compared with polymers made by the well known metallocene and Ziegler-Natta type catalysts. In addition, some of these catalysts can polymerize olefins that are frequently not polymerizable with most catalysts based on transition metal compounds, for example polar olefins such as olefinic esters. Therefore, the new olefin polymerization catalysts containing less transition metals are of great interest.
The use of palladium containing catalysts to polymerize olefins is described in S. Mecking, et al., J. Am. Chem. Soc., Vol. 120, pages 888-889 (1998). Nickel diimine complexes as olefin polymerization catalysts are described in L.K. Jonson, et al., J. Am. Chem. Soc., Vol. 117, pages 6414-6415 (1995), and L.K. Johnson, et al., J. Am. Chem. Soc., Vol. 118, pages 267-268 (1996). None of the catalysts described herein are described in these documents.
Certain iron, cobalt and molybdenum complexes of α-diimides having substituted nitrogen in the column are described in M. Doring, et al., Z. Anorg. Allg. Chem., Vol. 620, pages 551-560 (1994). None of these substituted a-diimines or these metal complexes are claimed herein.
The reactions of various bis (imidoyl chlorides) of oxalic acid with amines, diamines and aminoalcohols to form various a-diimines substituted with nitrogen and oxygen are described in D. Lauder, et al., J. Parkt. Chem., Vol. 337, pages 143-152 and, in the same, pages 508-515 (1995). None of the substituted α-diimines listed in these documents are claimed herein.
Brief description of the invention.
This invention concerns a first process for the polymerization of one or more olefins of the formula H2C = CHR1 and optionally one or more olefins of the formula H2C = CHR2, comprising, contacting said olefins with a complex which
contains a transition metal selected from the group consisting of palladium, nickel, titanium, zirconium, scadium, vanadium, chromium, iron, cobalt, and a rare earth metal and a ligand of the formula
(i)
(II (III)
which is an active polymerization catalyst, wherein: each R1 is independently hydrogen or alkyl;
each R 'is independently substituted alkyl or -C02R 50;
A and E are each independently oxygen, sulfur, phosphorus or nitrogen;
R3 and R8 are each independently hydrocarbyl or substituted hydrocarbyl, with the proviso that the carbon atom bonded to the nitrogen atom is bonded to at least two other carbon atoms
R, R5, R6 and R7 are each independently hydrocarbyl or substituted hydrocarbyl;
Ar1 and Ar2 are each independently aryl or substituted aryl
R and R, 10 are each independently hydrocarbyl or substituted hydrocarbyl;
R, 50 is hydrocarbyl or substituted hydrocarbyl; and on the condition that:
when said ligand is (II) or (III), said transition metal is nickel;
when H2C = CHR2 occurs, a palladium complex is present;
the members of any one or more of the pairs R4 and R5, R6 and R7, R4 and R6, and R5 and R7 taken together can form a ring;
when A is oxygen or sulfur, R5 is not present; Y
when E is oxygen or sulfur, R7 is not present.
This invention also concerns a second process for the polymerization of one or more olefins of the formula H2C = CHR1 and optionally one or more olefins of the formula H2C = CHR2, comprising, by contacting said olefins, a first compound of the formula
(IV)
MXn ((V) (VI)
(a) a second compound, which is a neutral Lewis acid capable of extracting X- from M to form WX-, and which is also capable of transferring an alkyl group or a hydride to M, with the proviso that WX- is a weak coordination anion; or
(b) a combination of a third compound that is capable of transferring an alkyl or hydride group to M and a fourth compound that is a neutral Lewis acid that is capable of extracting X-, a hydride or an alkyl group from M to form a weak coordination anion; or
(c) when at least one of X is an alkyl or hydride group, a fifth compound which is a
Lewis Cationic or Bronsted acid whose counter anion is a weak coordinating anion;
where :
M is Ni, Pd, Ti, Zr, Se, V, Cr, Fe, Co or a rare earth metal;
each X is independently a monoanion;
n is equal to the oxidation number of M
each R1 is independently hydrogen or alkyl;
each R 'is independently substituted alkyl or -C02R 50;
A and E are each independently oxygen, sulfur, phosphorus, or nitrogen;
R and R are each independently hydrocarbyl or substituted hydrocarbyl with the proviso that the carbon atom bonded to the
Nitrogen atom is linked to at least two other carbon atoms;
R4, R5, R6 and R7 are each independently hydrocarbyl or substituted hydrocarbyl;
Ar1 and Ar2 are each independently aryl or substituted aryl;
R9 and R10 are each independently hydrocarbyl or substituted hydrocarbyl;
R50 is hydrocarbyl or substituted hydrocarbyl; and with the condition that
when said first compound is (II) or (III), M is Ni;
the members of any one or more of the pairs R4 and R5, R6 and R7, R4 and R6, and R5 and R7 taken together can form a ring;
when H2C = CHR occurs, a palladium complex is present;
when A is oxygen or sulfur, R5 is not present; Y
when E is oxygen or sulfur, R7 is not present.
This invention also includes a compound of the formula
(IV) ÍAR HNC (0)
c [AraHNC (O) NHR '} MXn, • v (VI)
where
M is Ni, Pd, Ti, Zr, Se, V, Cr, Fe, Co or a rare earth metal;
each X is independently a monoanion;
n is equal to the oxidation number of M;
A and E are each independently oxygen, sulfur, phosphorus, or nitrogen;
R3 and R8 are each independently hydrocarbyl or substituted hydrocarbyl with the proviso that the carbon atom bonded to the nitrogen atom is linked to at least two other carbon atoms;
R4, R5, R6 and R7 are each independently hydrocarbyl or substituted hydrocarbyl;
Ar1 and Ar2 are each independently aryl or substituted aryl;
R9 and R10 are each independently hydrocarbyl or substituted hydrocarbyl;
and with the condition that
when said compound is (V] (VI) M is
Neither;
the members of any one or more of the pairs R4 and R5, R6 and R7, R4 and R6, and R5 and R7 taken together can form a ring;
when A is oxygen or sulfur, R5 is not present; Y
when E is oxygen or sulfur, R is not present.
Also described herein is a compound of the formula
. { VINE
where :
A and E are each independently oxygen, sulfur, phosphorus, or nitrogen;
R4, R5, R6 and R7 are each independently hydrocarbyl or substituted hydrocarbyl;
R11 is hydrocarbyl or substituted hydrocarbyl containing 2 or more carbon atoms, or a functional group;
R 12, R 13, R 14, R 15, R 16, R 17, R 18, R 19, and R 20 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group;
and with the condition that
the members of any one or more of the pairs R4 and R5, R6 and R7, R4 and R6, and R5 and R7 taken together can form a ring;
any two of R, R, R, R, R,
R 16 R17, R18, R19, and R20 which are neighbors of one another, taken together can form a ring with the additional proviso that if R11 and R12 are taken
together to form a ring, then R11 and R1"taken together contain at least 2 carbon atoms;
when A is oxygen or sulfur, R is not present; Y
when E is oxygen or sulfur, R7 is not present.
Detailed description of the invention.
In the present, certain terms are used Some of these are:
• A "hydrocarbyl group" is a univalent group that contains only carbon and hydrogen. Unless stated otherwise, it is preferred that the hydrocarbyl groups (and aluqyl groups) herein contain from 1 to about 30 carbon atoms.
Hereby, "substituted hydrocarbyl", means a hydrocarbyl group containing one or more substituent groups which are
inert under the process conditions to which the compound containing these groups is subjected. Substituent groups also do not substantially interfere with the process. Unless stated otherwise, it is preferred that the substituted hydrocarbyl groups herein contain from 1 to 30 carbon atoms. Included in the meaning of "substituted" are the heteroaromatic rings.
• By "functional groups (inert)", herein, means a group other than the hydrocarbyl or substituted hydrocarbyl which is inert under the process conditions, to which the compounds contained in the group are subjected. The functional groups also do not substantially interfere with any process described herein in which the compound in which it is present may take part. Examples of functional groups include halo (fluorine, chlorine, bromine and iodine), trialkylsilyl, ether such as -OR22 wherein R22 is hydrocarbyl or substituted hydrocarbyl. In cases where the functional group may be close to a nickel or palladium atom, the functional group does not
it coordinates the metal atom more strongly than the groups whose compounds are shown as coordinators of the metal atom, which therefore does not displace the desired coordinated group.
• "Alkyl aluminum compound" means a compound in which at least one alkyl group is bonded to an aluminum atom. Other groups such as alkoxide, hydride, and halogen can also be linked to the aluminum atoms in the compound.
• "Lewis neutral base" means a compound, which is not an ion, that acts as a Lewis base. Examples of such compounds include ethers, amines, sulfides, and organic nitriles.
• "Cationic Lewis acid" means a cation that acts as a Lewis acid. Examples of such cations are sodium and silver cations.
• For relatively uncoordinated anions
(or weak coordination) means those anions as are generally referred to in the art in
this way, and the coordinating ability of such anions is known and discussed in the literature, see for example W. Beck., et al., Chem. Rev., vol. 88 pages 1405-1421 (1998), and S. H. Strauss, Chem. Rev., vol. 93, pages 927-942 (1993), both of which are included herein for reference. Among such anions are those formed from the aforementioned aluminum compounds and X-, including R333A1X ", R332A1C12X", and "R33A10X", wherein R33 is alkyl. Other useful non-coordinating anions include BAF ~. { BAF = tetrakis [3,5-bis (trifluoromethyl) phenyl] borate} , SbF6 ~, PF6 ~, and BF4", trifluoromet anosulfonate, p-toluenesulfonate, (RfS02) N ~, and (C6 5) 4B".
• For an empty coordination site, it means a potential coordination site that does not have a ligand linked to it. In this way, if an ethylene molecule is in the vicinity of the empty coordination site, the ethylene molecule can be coordinated to the metal atom.
• By a ligand that can be added to an olefin, it means a ligand coordinated to an
metal atom in which an olefin molecule as described above (or a coordinated olefin molecule) can be inserted to initiate or continue a polymerization. For example, this can take the form of the reaction (where L is a ligand and the olefin is ethylene):
CH2CH2I / / M >
• For rare earth metal, it means one of lanthanum, cerium, praeseodymium, neodymium, promised, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.
The compounds of the formulas (I) and (VII) can be made by the reaction of the corresponding bis (oxidic chlorides) of oxalic acid with compounds containing primary or secondary amines, alcohols, phenols, thiols, phosphines, or a combination of the same, see for example D. Lauder, and collaborators, J. Prakt. Chem., Vol.
337, pages 143-152 and, therein, pages 508-515 (1995), both of which are included herein for reference, and the examples herein.
The compounds of the formulas (II) and (III) can be made by the reaction of an organic isocyanate with the corresponding organic hydroxy compound, or primary or secondary amine, respectively.
Ni and Pd and other metal compounds described herein can be made by various methods (depending on other ligands present in the complex), and by methods described in World Patent Application 96/23010 and U.S. Pat. 5,714,556, both of which are included herein for reference. The Examples herein also illustrate such methods. These complexes can be made, that is, they can be added to the polymerization process in a form in which the ligand (I), (II) or
(III) is ready for the formation of the complex to the transition metal, or it can be formed in situ, that is, the transition metal (composite) and the
ligand are added separately to the polymerization process, but the desired complex is formed in situ. This includes all of the examples where the precursors for the desired transition of the metal complex are added. For example, the transition metal can be added in the form of an M [0] complex, such as bis (cyclooxytadiene) nickel, in which nickel can be oxidized to a Ni (II) by reaction with HY, where Y It is a relatively non-coordinating anion. Other methods of forming such in situ complexes are found in World Patent Application 96/23010 and U.S. Pat. 5, 714, 556.
In (I) and (VII), and all other compounds in which these substituents occur, it is preferred that:
A and E are each independently nitrogen or oxygen, more preferably both of A and E are nitrogen; I
A and E are both oxygen; I
A is nitrogen or phosphorus, more preferably nitrogen, and R4 and R5 taken together form a ring; I
R4 and R6 taken together form a ring, more preferably CH2) Z- where z is 2 and / or
RJ is
wherein R23, R24, R25, R26 and R27 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, with the proviso that any of R23, R24, R26 and R27 neighboring one another taken together, can form a ring; I
is
where 31
R, 2¿9 *, R, 3J0, R, J1 and R, 3J2¿ are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, with the proviso that any of R28, R29, R30, R31 and R32 neighbor one of the other taken together, can form a ring. In another preferred compound, (I) or (VII) A and E taken together are part of a ring, where it is applicable in combination with any of the foregoing.
In (II) or other compounds in the present in which cases these groups occur, it is preferred that:
Ar sea
wherein R34, R35, R36, R37 and R38 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, with the proviso that any of R34, R35, R36, R37 and R38 which are adjacent to each other taken together, may forming a ring, and more preferably one or both of R34 and R38 are alkyl containing 1 to 4 carbon atoms, and / or R35, R36 and R37 are hydrogen; I
R is alkyl, substituted alkyl, aryl or substituted aryl, especially alkyl or
wherein R39, R40, R41, R42 and R43 are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, with the proviso that any of R39, R40, R41, R42 and R43 which are adjacent to each other taken together, may forming a ring, and more preferably one or both of R39 and R43 are alkyl containing 1 to 4 carbon atoms, and / or R40, R41 and R42 are hydrogen.
In (III) or other compounds herein in which these groups occur, it is preferred that:
Ar sea
(XII)
where R, 4q
R, 4 * 53, R, 46, R, 47 'and R, 48O are each independently hydrogen, hydrocarbyl, substituted hydrocarbyl or a functional group, with the proviso that any of the neighboring R44, R45, R46, R47 and R48 one of the other taken together, they can form a ring, and more preferably one or both of R44 and R48 are alkyl containing 1 to 4 carbon atoms, and / or R45, R46 and R47 are hydrogen; I
R 10 is alkyl or substituted alkyl, especially alkyl substituted with hydroxyl.
It is preferred that X is halide, alkyl, carboxylate or acetylacetonate, more preferably chloride, bromide or iodide. When X is alkyl, it is more preferred that M is Pd and only one of X is alkyl,
It is preferred that R1 is hydrogen or n-alkyl containing from 1 to 18 carbon atoms, more preferably hydrogen or methyl, and especially preferably hydrogen, or any combination thereof. It is also preferred that R2 is - (CH2) qR48 where q is 0 or an integer from 1 to 18 and R48 is a functional group, more preferably q is 0 and / or R48 is C02R49, where R49 is hydrocarbyl or hydrocarbyl substituted, more preferably hydrocarbyl, and especially preferably alkyl.
In all complexes, one of the preferred metals is nickel. In other complexes, the preferred metals are Ti, Zr, Se, V, Cr or a rare earth metal, especially with (I) when R4 and R5 taken together form a ring, and R6 and R7 taken together do not form a ring.
In the first polymerization process described herein, a nickel, palladium or other metal complex is either added to the polymerization process or formed in situ in the process. In fact, more than one such complex can be formed during the course of the process, for example, the formation of an initial complex and then the reaction of such complex to form a final starting polymer containing such complex or.
Examples of such complexes that can be initially formed in situ include:
(XIII)
(XIV)
wherein R up to R8 and M are as defined above, TI is hydride or alkyl or any other anionic ligand in which ethylene can be inserted, and is a neutral ligand capable of being displaced by ethylene or a vacant coordination site, parallel lines "are an ethylene molecule coordinated to the metal, and Q is an anion
relatively uncoordinated. The complexes can be added directly to the process or formed in situ. For example, (XIII) can be formed by the reaction of (IV) with a neutral Lewis acid such as an aluminum alkyl compound. Another method for forming a complex in situ is to add an appropriate nickel or palladium compound such as nickel acetylacetonate [II], (I) and an aluminum alkyl compound. Other metal salts in which anions similar to acetylacetonate are present, and which can be removed by reaction with Lewis or Bronsted acid, can also be used. For example, metal halides and carboxylates (such as acetates) can be used, particularly if they are slightly soluble in the process medium. It is preferred that these precursor metal salts are at least slightly soluble in the process medium.
After the polymerization has started, the complex may be in a form such as
(XV)
where R up R, M, and Q are as defined above, P is a divalent polymeric group such as a (poly) ethylene group of the formula - (CH2CH2) X- where x is an integer of 1 or more, and T2 is a group final, for example the groups listed for T1 above. Those skilled in the art will note that (XV) is essentially a polymer that contains a fundamental starting end. It is preferred that M be in a +2 oxidation state in these compounds. The compounds such as (XIII), (XIV) and (XV) may or may not be stable throughout an environment similar to that of the polymerization process, but these can be detected by NMR spectroscopy,
particularly one or both of XH and 13C NMR, and particularly at low temperatures. Such techniques, especially for the polymerization of "intermediates" of these types are known, see for example World Patent Application 96/23010, especially Examples 197-203.
The (XIII), (XIV) and (XV) can be used, in the absence of any of the "co-catalysts" or "activators" to polymerize one or more appropriate olefins in a third polymerization process. Except for the ingredients in the process, the process conditions for the third process, such as pressure temperature, polymerization medium, etc., may be the same as for the first and second polymerization process, and the preferred conditions for those Processes are also preferred for the third polymerization process.
In the first, second and third polymerization processes herein, the temperature at which the polymerization is carried out is about -100 ° C to about + 200 ° C, preferably around -60 ° C to about
of 150 ° C, more preferably around -20 ° C to about 100 ° C. The pressure of the olefin (if this is a gas) at which the polymerization is carried out is not critical, the atmospheric pressure up to about 275 MPa is in an appropriate range.
The polymerization process herein can be carried in the presence of various liquids, particularly aprotic organic liquids. The catalyst system, olefin, and polyolefin may be soluble or insoluble in these liquids, but obviously these liquids should not prevent the polymerization from occurring. Suitable liquids include alkanes, cycloalkanes, selected halogenated hydrocarbons, and aromatic hydrocarbons. Specific useful solvents include hexane, toluene, benzene, methylene chloride, and 1,2,4-trichlorobenzene.
The olefin polymerizations, hereinafter, can also be carried out initially in the solid state by, for example, supporting the nickel or palladium compound on a substrate such as silica or alumina, activating them
with Lewis acid (such as W, for example an alkylaluminum compound) or Bronsted and exposing this to the olefin. Alternatively, the support can first be connected (reacted) with W such as an alkylaluminum compound, and then contacted with an appropriate transition metal compound such as (IV), (V) or (VI). The support may also be able to take the place of Lewis or Bronsted acid, for example an acid clay such as montmorillonite. Another method for making a catalyst support is to initiate the polymerization or at least make a transition metal complex from another olefin or oligomer of an olefin such as cyclopentene on a support such as silica or alumina. This "heterogeneous" catalyst can be used to catalyze the polymerization in the gas phase or in the liquid phase. Gas phase means that a gaseous olefin is transported to contact it with the catalyst particle.
In all the polymerization processes described herein, oligomers and polymers of various olefins are made. These can be
in a range in molecular weight from oligomeric olefins, to oils and waxes of low molecular weight, to high molecular weight polyolefins. A preferred product is a polymer with a degree of polymerization (DP) of about 10 or more, preferably about 40 or more. By "DP" it means the average number of repeating units (monomer) in a polymer molecule.
Depending on its properties, the polymer made by the process described herein is used in many ways. For example, if they are thermoplastic, they can be used as molding resins, extrusion, films, etc. If these are elastomeric, they can be used as elastomers. If these contain functionalized monomers such as acrylate esters, these are useful for other purposes, see, for example, World Patent Application 96/23010.
Polyolefins are more frequently prepared by polymerization processes in which a transition metal containing the catalyst system is used. Depending on
the process conditions used and the chosen catalyst system, the polymers, even those made from the same monomer (s), can have varying properties. Some of the properties that can change are molecular weight and molecular weight distribution, crystallinity, boiling point, and glass transition temperature. Except for the molecular weight and the molecular weight distribution, the branching can affect all the other properties mentioned.
It is known that certain transition metals containing polymerization catalysts, including those described herein, are especially useful for varying the branching in the polyolefins made therewith, see, for example, International Patent Applications 96/23010 and 97. / 02298, and US Patent Applications 09 / 006,628, filed January 13, 1998, and 09 / 006,536, filed January 13, 1998. It is also known that mixtures of different polymers, which vary for example in the properties listed above, may have advantageous properties compared to the
"simple" polymers. For example, it is known that polymers with broad or bimodal molecular weight distributions can be processed by fusion (to be formed) more easily than polymers with narrow molecular weight distributions. Similarly, thermoplastics such as crystalline polymers can often be cured by mixing them with elastomeric polymers.
Therefore, methods for producing polymers that inherently produce polymer blends are useful, especially if a step of mixing the separated polymer to the latter (and expanded) can be avoided. However, in such polymerizations, one must be aware that two different catalysts can interfere with one another, or interact in such a way that they give a simple polymer.
In such processes, the catalysts described herein may terminate the first active polymerization catalyst. The monomers useful with these catalysts are
those described (and also preferred above.
A second active polymerization catalyst (and optionally one or more of others) is used in conjunction with the first active polymerization catalyst. The second active polymerization catalyst can be another ultimate transition metal catalyst, for example as described in the World Patent Applications 96/23010 and 97/02298, and U.S. Patent Applications. 09 / 006,628, filed January 13, 1998, 09 / 006,536, filed January 13, 1998, and 08 / 991,372, filed December 16, 1997. Other useful types of catalysts can also be used for the second catalyst of active polymerization. For example, catalysts also called Ziegler-Natta and / or metallocene type, can also be used. These types of catalysts are well known in the field of polyolefins, see, for example, Angew. Chem., Int. Ed. Engl., Vol. 34, pages 1143-1170 (1995), European Patent Application 416,815 and U.S. Pat. 5,198,401 for information about metallocene type catalysts, and J.
Boor Jr., Ziegler-Natta Catalysts and Polymerizations, Academic Press, New York, 1979, for information about Ziegler-Natta type catalysts, all of which are included herein for reference. Many of the polymerization conditions useful for all these types of catalysts and the first active polymerization catalyst coincide, such conditions for the polymerizations with the first and second polymerization catalysts are easily accessible. Frequently, the "co-catalyst" or the "activator" is required for the metallocene or Ziegler-Natta polymerizations. In many cases, the same compound, such as an alkylaluminum compound, can be used as an "activator" for some or all of these various polymerization catalysts.
In a preferred process described herein, the first olefin (s) [the monomer (s) polymerized by the first active polymerization catalyst] and the second olefin [the (s) monomer (s) polymerized by the second active polymerization catalyst] are
identical, and the preferred olefins in such processes are the same as described immediately above. The first and / or second olefins can also be a single olefin or a mixture of olefins to make a copolymer. Again it is preferred that these be identical, particularly in a process in which the polymerization by the first and second polymerization catalysts makes a polymer simultaneously.
In some processes herein, the first active polymerization catalyst can polymerize a monomer in such a way that it can not be polymerized by said second active polymerization catalyst, and / or vice versa. In one example, two chemically distinct polymers can be produced. In another scenario, two monomers are presented, with one polymerization catalyst producing a copolymer, and the other polymerization catalyst producing a homopolymer, or two copolymers can be produced which vary in molar ratio or repeating units of the various monomers. Other analogous combinations will be evident to the craftsman.
In another variation of this process, one of the polymerization catalysts produces an oligomer of an olefin, preferably ethylene, whose oligomer has the formula R70CH = CH2, wherein R70 is n-alkyl, preferably with a constant number of carbon atoms. The other polymerization catalyst in the process (co) then polymerizes this olefin, either by itself or preferably with at least one other olefin, preferably ethylene, to form a branched polyolefin. The preparation of the oligomer (which is sometimes called an α-olefin) by a second catalyst of active polymerization type, can be found in World Patent Application 96/23010, and U.S. Patent Application. 09 / 005,965, filed on January 12, 1998.
Likewise, the conditions for such polymerizations using catalysts of the second type of active polymerization, is also found in the appropriate references mentioned above.
Two chemically different active polymerization catalysts are used in this polymerization process. The first active polymerization catalyst is described in detail below. The second active polymerization catalyst may also meet the limitations of the first active polymerization catalyst, but it must be chemically distinct. For example, this may have a different transition metal present, and / or use a different type of ligand and / or the same type of ligand with different structure between the first and second active polymerization catalysts. In a preferred process, the type of ligand and the metal are the same, but the ligands differ in their substituents.
Included within the definition of two active polymerization catalysts are systems in which a simple polymerization catalyst is added together with another ligand, preferably the same type of ligand, which can displace the original ligand coordinated to the metal of the polymerization catalyst. active
original, to produce in situ two different polymerization catalysts.
The molar ratio of the first active polymerization catalyst to the second active polymerization catalyst used will depend on the ratio of the polymer for each of the desired catalysts, and the relative polymerization ratio of each catalyst under the process conditions. For example, if one wants to prepare a "hardened" thermoplastic polyethylene containing 80% crystalline polyethylene and 20% polyethylene, and the polymerization ratios of the two catalysts are equal, then one should use a molar ratio of 4. : 1 of the catalyst that gives the crystalline polyethylene to the catalyst that gives the rubberized polyethylene. More than two active polymerization catalysts can be used if the desired product contains more than two different types of polymer.
The polymers made by the first active polymerization catalyst and the second active polymerization catalyst can be made in
sequence, that is, polymerization with one (either the first or second) of the catalysts, followed by polymerization with the other catalyst, using two series polymerization vessels. However, it is preferred to carry out the polymerization using the first and second polymerization catalysts active in the same vessel (s), that is, simultaneously. This is possible because in most cases the first and second polymerization catalysts are compatible with one another, and these produce their distinctive polymers in the presence of the other catalyst. Any of the processes applicable to the individual catalyst can be used in this polymerization process with 2 or more catalysts, that is, gas phase, liquid phase, continuous, etc.
The polymers produced by this process can vary in their molecular weight and / or molecular weight distribution and / or melting point and / or level of crystallinity, and / or glass transition temperature and / or other factors. For copolymers, polymers may differ in co-monomer ratios if different
Polymerization catalysts polymerize the monomers present at different relative ratios. The polymers produced are useful as molding and extrusion resins and in films as for packaging. These have advantages such as improved processing point, hardness and improved low temperature properties.
Hydrogen can be used for the low molecular weight polyolefin produced in the first or second process. It is preferred that the amount of hydrogen present is from about 0.01 to about 50 mole percent of the olefin present, preferably about 1 to 20 mole percent. When liquid monomers
(olefins) are present, it may be necessary to experiment briefly to find the relative amounts of liquid monomers and hydrogen (like a gas). If both hydrogen and monomer (s) are gaseous, their relative concentrations can be regulated by their partial pressures.
In the examples, certain abbreviations are used:
? H5 - heat of fusion BAF - tetrakis [bis (3, 5-trifluoromethyl) phenyl] borate DMAP-4-dimethylaminopyridine DSC - Differential Calorimetry Random (at a heating portion of 15 ° C / minute, first heating at -150 ° C up to + 160 ° C, second heating -150 ° C up to + 250 ° C) EOC - end of chain Et - ethyl GPC - gel permeation chromatography MAO and PMAO - methylaminohexane Me meti lo Mn number average molecular weight Mw weighted average molecular weight PDI - polydispersity, Mw / Mn TLC - thin layer chromatography Tg - glass transition temperature Pf melting point TO productivity, moles of polymerized olefin per mole of transition metal compound.
All pressures in the 'Examples are pressure measurements. The metal complexes are designated by the number of the ligand, the metal, and other ligands (neutral or charged) in the complex. For example, the complex of ligand 4 with NiBr2 is written as 4'NiBr2.
In the examples, certain compounds are made and / or used. Its structures are shown below.
11 12 13
Examples 1-13
The compounds 1-13 were synthesized in accordance with equations 1-3 shown below. These syntheses are based on
Literature methods: see (a) Lindauer, D .; Beckert, R .; Doring, M.; Fehling, P.; Gorls, H. J. Prakt. Chem. 1995, 337, 143-152 and references in these and (b) Lindauer, D .; Beckert, R .; Billert, T .; Doring, M .; Gorls, H. J. Prakt. Chem. 1995, 337, 508-515 and their references therein. Compounds 8, 9b, 10, 11, 12 and 13 are hydrolysis products of the product ArN = C (X) -C (X) = NAr shown in equation 3.
Cl Cl? A (3)
ArN XX NAr (a) 2 (XH + NEfe) or ArN) Í NAr (b) 2 (XH + DMAP) or (c) 2 NaX
Example 1. Synthesis of 1.
In a drying box, a 50 mL round bottom flask was charged, with PhN = C (Cl) -C (Cl) = NPh
(0.693 g, 2.5 mmol), pentafluorophenol (0.965 g, 5 mmol), DMAP (0.615 g, 5 mmol) and anhydrous toluene
(15 mL) and capped. The flask moved to the
cover and reflux under N2 for about 3 hours, while the reaction was monitored by TLC (5% ethyl acetate / hexane). The precipitate (DMAP'HCl) was removed by filtration and rinsed thoroughly with toluene. The extracted solvent yielded an oily solid, which was purified by column chromatography (silica gel, 5% ethyl acetate / hexane). A white solid was obtained (0.822 g, 57%):: H NMR (CDC13) 5 7.15 (m, 6, Hph). 6.52 (m, 4, Hph); 13C NMR (CDC13) 6 146.5 and 143.25 (N = CC = N and Ph: Cipso), 142.1 (d of d, J = 248, C6F5: C0), 140.5 (d of t, J = 258, C6F5: Cp) , 138.8 (d of t J = 253, C6F5: Cm), 128.8, 125.7 and 120.6 (Ph: CQ, Cm, and Cp); 19F NMR (CDC13) d -151.6 (d, F0), -158.02 (t, Fp), -162.6 (t, Fm). [There are no apparent peaks in the 1 H NMR spectrum that may be indicative of the NH proton of the potential hydrolysis product PhNHC (O) (OC6F5). ]
Example 2. Synthesis of 2
A covered 100 mL round bottom flask was charged with PhN = C (Cl) -C (Cl) = NPh (1.111
g, 4 mmol), tetrabutylammonium chloride (0.078 g, 0.2 mmol), phenol (0.760 g, 8 mmol), and methylene chloride (20 mL). Sodium hydroxide (400 μL, 25 M) and water (500 μL) were added via syringe. The reaction was refluxed gently until the starting material disappeared by TLC (5. hexahexyl acetate). The aqueous layer was extracted with methylene chloride (3 x 10 mL) and the organic layers were combined and dried over MgSO4. The solvent was removed in vacuo and the product was recrystallized from hot hexane. After drying the product under vacuum, 1,006 g (64%) of white powder was obtained: XH NMR (CDC13) d 7.29 (t, 2, Hm) 7.17 (t, 2, H'm), 7.12 (t, 1 , Hp), 7.03 (t, 1,
H '6.95 (d, 2, H0), 6.69 (d, 2, H'D) 13 C NMR
(CDC13) d 151.9, 151.3, and 145.0 (C pso.spo.N = CC = N), 129.4, 128.5, 125.8, 124.5, 121.8, and 121.1 (Ph: C0, Cm, Cp, pH ': C0, Cm, Cp). [There are no apparent peaks in the 1 H NMR spectrum that can be indicative of the NH proton of the potential hydrolysis product PhNHC (O) (Oph). ]
Example 3. Synthesis of 3
In a drying box, a small vial was charged with 0.277 g (1 mmol) of PhN = C (Cl) -C (Cl) = NPh, the sodium salt of 2, 5-dimet ilpirrolo
(0.239 g, 2 mmol) and anhydrous tetrahydrofuran (10 mL), and capped. The bottle was transferred to the cover and the reaction was allowed to stir at room temperature and was observed by TLC
(5% ethyl acetate / hexane) until no starting material was present (about 24 hours). The reaction was filtered to remove the precipitate, which was then rinsed with THF. The solvent was removed under vacuum and the product was purified by column chromatography (silica gel, 5% ethyl acetate / hexane). A solid (0.145 g, 37%) was obtained: 1 NMR (THF-d8) d 7.3 -7.0 (m, 6, Ph: Hm and Hp), 6.62 (d, 4, Ph: H0), 5.75 (s, 4, Hr? Rroio). 2.05 (s, 12, Me); 13C / APT NMR (CDC13) d 147.9 and 145.3 (Ph: C? Pso and N = C-C = N), 127.2 (pyrrolo: C-Me), 128.4, 127.6, and 123.6 (C0, Cm, Cp); 107.6 (pyrrolo: CH), 13.1 (Me). [There are no apparent peaks in the XH NMR spectrum that may be indicative of the NH proton of the product of
potential hydrolysis PhNH (0) (2,5-dimethylpyrrolo).
Example . Synthesis of 4.
In a drying box, a small bottle was charged with 2080 g (7.5 mmol) of PhN = C (Cl) -C (Cl) = NPh and anhydrous toluene (10 mL). Triethylamine (2.10 μL, 15 mmol) was added via syringe and capped. The bottle was transferred to the cover and N '-dimethylethylenediamine (800 μL, 7.5 mmol) was added via syringe. The reaction became very warm and a precipitate formed quickly. The reaction mixture was allowed to stir for about 24 hours and then filtered to remove NEt3'HCl, which was completely rinsed with toluene. The solvent was removed under vacuum to give an oil. Diethyl ether was added to precipitate a solid, which was collected in an alkaline flux. A pale yellow orange powder (1.336 g, 47%) was isolated: 1 H NMR (CDC13) d 6.85 (t, 4, Hm), 6.74 (t, 2, Hp), 6.10 (t, 4, Hp), 3.82 and 3.02 (br s of 2H and the superposition of br and the form of
singlets of 8H, CH2 and Me); 13C NMR (CDC13) d 148.6 and 148.2 (Ph: Cipso and N = C-C = N), 128.0, 121.7 and 121.3 (Ph: Co, Cm, and Cp), 49.8 (CH2), 36.4 (NCH3); NW calculated for C? 8H20N4 292.39 g / mol; MS (CIMS) 293. Om / z (M + l).
Example 5. Synthesis of 5.
In a drying box, a 50 mL round bottom flask was charged, with 1666 g (5 mmol) of ArN = C (Cl) -C (Cl) = NAr (Ar = 2.6-C6H3-Me2) and anhydrous toluene (10 mL). Triethylamine (1.4 mL, 10 mmol) was added via syringe and capped. The flask was transferred to the cover where N, N '-dimethylethylenediamine (540 μL, 5 mmol) was added via syringe. The reaction was allowed to stir at room temperature for about 48 hours; at this point, TLC (5% ethyl acetate / hexane) indicated that the starting material was still present. However, the reaction was slowly heated for about 24 hours and was observed again by TLC. The precipitate (Net3"HCl) was removed by filtration and rinsed thoroughly with toluene.
removed under vacuum. Diethyl ether was added to precipitate the product, which was collected. The filtrate was reduced in volume and hexane was added to precipitate more of the product. All fractions were combined and rinsed with hexane, harvested and dried under vacuum. The product (0.782 g, 45%) was isolated as a pale yellow powder. The resonances of 1H and 13C NMR are extensive at room temperature, and therefore are reported at 60 ° C, where they are formed: 1H NMR (CDC13, 60 ° C) d 6.84 (d, 4, Hm), 6.68 (t , 2, Hp), 3.41 (s, 4, CH2), 2.78 (s, 6, NMe), 1.86 (s, 12, Ar: Me); 13C / APT NMR (CDC13, 60 ° C) d 148.4 and 145.5 (Ar: Cipso and N = CC = N), 127.2 (Ar: Co), 120.7 (Ar: Cp), 49.3 (CH2), 37.2 (NMe) , 18.2 (Ar: Me); NW caled by C22H28N4 348.5 g / mol; MS (CIMS) 349.1m / z (M + l).
Example 6. Synthesis of 6
In a drying box, a small vial was charged with 2232 g (5 mmol) of ArN = C (Cl) = NAr (Ar = 2.6-C6H3- (i-Pr) 2), DMAP (1222 g, 10 mmol) and anhydrous toluene (10 mL) and capped. The bottle is
transferred to the cover and N, N'-dimethylethylenediamine (532 μL, 5 mmol) was added via syringe. The reaction mixture became clear and then after about 5 minutes, a precipitate formed. The reaction mixture was allowed to stir at room temperature for about 2 days and was followed by TLC (5% ethyl acetate / hexane). CH2C12 was added to the reaction mixture to dissolve the precipitate and the resulting solution was extracted with HCl (aq) (3 x 25 mL), and the organic layer was dried over MgSO4. The solvent was removed under vacuum and the resulting solid was recrystallized from hot hexane to give 0.843 g (37%) of a pale yellow powder: XH NMR (CDC13) d 7.5-7.0 (m, 6, Hr). 3.56 (s, 4, CH2), 3.14 (s, 6, NMe), 3.08 (septet, 4, CHMe2), 1.17 (d, 24, CHMe2).
Example 7. Synthesis of 7
In a drying box, a 50 mL round bottom flask was charged with 1666 g (5 mmol) of ArN = C (Cl) -C (Cl) = NAr (Ar = 2.6-C6H3-Me2) and toluene
anhydrous (10 mL). Triethylamine (1.4 mL, 10 mmol) was added via syringe, and the flask was capped and transferred to the cap. On the cover, N, N '-dimet-1, 3-propanediamine (630 μL, 5mmol) was added via syringe. The reaction mixture was allowed to stir at room temperature for about 48 hours; at this point, TLC (5% ethyl acetate / hexane) showed that the starting material was still present. Consequently, the reaction was slowly heated for about 24 hours, and checked again by TLC. The precipitate (Net3'HCl) was removed by filtration and rinsed thoroughly with toluene. The solvent was removed under vacuum. Diethyl ether was added to precipitate the product, which was collected. The filtrate was reduced in volume and hexane was added to further precipitate the product. All fractions were combined and rinsed with hexane, collected and dried under vacuum to give 0.844 g (47%) of an off white powder: 1H NMR (CDC13, 500 MHz, at room temperature) d 6.71 (br s, 4, Hm), 6.61
(t, 2, Hp), 1.79 (penteth, 2, CH2CH2CH2); the following resonances correspond to the
resonances NMe, Ar: Me, and -CH2CH2CH2-: 3.63 (br s), 3.07 (br s), 2.75 (br s), 2.01 (br s), 1.30 (br s); 13C NMR / APT (CD2CL2) d 151, 146.7, and 130.4 (Ar: Cipso, C0 and N = CC = N), 127.1 (Ar: Cm), 121.3 (Ar: Cp), 47.9 (NCH2CH2CH2N), 36.0 (NMe ), 24.5 (NCH2CH2CH2N), 17.6 (Ar: Me); M calculated for C23H30N4 362.5 g / mol; MS (CIMS) 363.0m / z (M + l).
Example 8. Synthesis of
In a drying box, a small vial was charged with 2232 g (5 mmol) of ArN = C (Cl) = NAr (Ar = 2.6-C6H3- (i-Pr) 2), DMAP (1229 g, 10 mmol) and anhydrous toluene (10 mL) and capped. On the cover, 2- (methylamino) ethanol (420 μL, 5 mmol) was added via syringe. The reaction mixture was allowed to stir at room temperature for about 48 hours and was observed by TLC (5% ethyl acetate / hexane). Then, the reaction mixture was diluted in CH2C12 and the resulting solution was extracted with 5% HCl (aq)
(3 x 25 mL), and the organic layer was dried over
MgS0. After the solvent was removed, the product was washed with hexane and then dried in
vacuum to give 0.986 g of a pale yellow solid: H NMR (CDC13) d 7.40-6.56 (m, 3, Harium). 6.31 (s, 1, NH or OH), 3.65 (t, 2, CH2), 3.41 (t, 2, CH2), 2.99 (septet, 2, CHMe2), 2.92 (s, 3, Me), 1.08 (m , 12, CHMe2). [The product contains some impurities that mark some NMR assignments, particularly integrations, uncertain. The structure of the compound is proposed to be the hydrolysis product shown above based on the appearance of the 6.31 ppm resonance -NH or -OH. ]
Example 9. Synthesis of 9a and 9b.
In a drying box, a small flask was charged with 0.831 g (3 mmol) of PhN = C (Cl) -C (Cl) = NPh, 2,6-diisopropylphenoxide sodium (1,201 g, 6 mmol) and tetrahydrofuran of anhydrous (10 mL), and capped. The bottle was transferred to the cover, and the reaction mixture was allowed to stir at room temperature for about 2 days, until TLC (5% ethyl acetate / hexane) showed no starting material. Sodium chloride was removed by filtration and rinsed
completely with THF. The solvent was removed under vacuum and the remaining solid was re-crystallized from hot hexane. The product was isolated and dried in vacuo to yield 1326 g (79%) of a yellow-orange solid as a mixture of 9a and 9b in a ratio 6.7 to 1. 9a: XH NMR (CDC13) d 7.2-6.5 (m , 16, Harlo), 2.99 (septet, 4, CHMe2), 1.13 (d, 12, CHMeMe '). 1.06 (d, 12, CHMeMe '); 13C / APT NMR (CDC13) d 151.0, 146.7, 145.2, and 140.9
(Ph: Cipso; Ar: Cip30; C0; N-C-C = N), 128.2, 125.6, 124.1 and 120.6 (Ph: C0.Cm, Cp; Ar: Cra, Cp), 26.9
(CHMe2), 24.1 and 23.3 (CHMeMe '); NW calculated for C38H44N202 560.79 g / mol; MS (CIMS) 561.4m / z (M + l). 9b: 1 H NMR (CDCl 3, only non-aromatic resonances) d 4.69 (NH), 3.08 (septet, 2, CHMe2), 1.20 (d, 12, CHMe2); NW calculated for d9H2302N 297.4 g / mol; MS (CIMS) 297.9m / z (M + 1).
Example 10. Synthesis of 10.
In a drying box, a small vial was charged with 3341 g (7.5 mmol) of ArN = C (Cl) -C (Cl) = NAr (Ar = 2.6-C6H3- (i-Pr) 2), methoxide of anhydrous sodium (0.854 g, 15.75 mmol), and anhydrous methanol
(10 mL) and covered. The bottle was transferred to the cover, and the reaction mixture was allowed to stir at room temperature for about 3 days until the TLC showed some starting material present. The white solid was completely filtered and rinsed with methanol. Then, the solvent was removed and then the product was dried under vacuum. The solid was then washed with hexane and dried in vacuo. A white crystalline solid was obtained (1446 g, 44%). The restricted rotation around the amide junction resulted in the observation of two rotamers at room temperature in approximately a ratio of 1.16 to 1. Only one set of rotamers was observed at 60 ° C: 1R NMR (CDC13, room temperature, 500 MHz ) d 7.33 (t, 1, Ar: Hp), 7.21 (d, 2, Ar: Hm), 6.49 and 6.10 (s, NH and NH '), 3.82 and 3.69 (Orne and Orne'), 3.22 (br s) , 2, CHMe2), 1.25 (d, 12, CHMe2); aH NMR (CDC13, 60 ° C, 500 MHz) d 7.32 (t, 1, Ar: Hp), 7.20 (d, 2, Ar:
Hm), 6.08 (br s, 1, NH), 3.76 (br s, 3, OMe), 3.23
(septet, 2, CHMe2), 1.26 (d, 12, CHMe2); 13C NMR
(CDC13, room temperature 125 MHz) d 156.3,
146. 9 and 131.1 (Ar: C? Sso C0; C = 0), 127.9 and 123.5 (Ar: C__, Cp), 52.4 (OCH3), 28.6 (CHMe2); NW
Called for pa C_4H2? 02N 235. 33 g / mol; MS (C IMS) 2 3 6. Om / z (M + 1).
Example 11. Summary of 11.
In a drying box, a small vial was charged with 2229 g (5 mmol) of ArN = C (Cl) -C (Cl) = NAr (Ar = 2.6-C6H3- (i-Pr) 2), triethylamine (1.4 mL, 10 mmol), 1-aminopropanol (400 μL, 5 mmol), and anhydrous toluene (10 mL) and capped. The reaction mixture was allowed to stir at room temperature for about 7 days. During this time, a precipitate formed (Net3"HCl), which was removed by filtration and rinsed thoroughly with toluene.The solvent was removed under vacuum, and the product was washed with hexane and dried by pumping to give 0.444 g (20%) of a pale yellow powder:? Ti NMR (CDC13) d 7.26 (t, 1, Hp), 7.14 (d, 2, Hm), 6.15 and 4.52 (s, 1 each, NH NH ' or OH), 3.75 (m, 1, CHMeO), 3.23 (m, 3, CHH'NH and CHMe2), 3.00 (m, 2, CHH'NH), 1.14 (m, 12, CHMe2), 1.03 (d, 3, CHMeO); 13C / APT NMR (CDC13) 159.1, 147.9 and 130.8 (C ==, Ar: Cipso, C0), 129.0 (Ar: Cp), 124.1 (Ar: Cm), 68.2 (OCHMe), 47.9 ( CH2), 28.3 (CHMe2), 24.3 and
23. 1 (CHMeMe '), 20.6 (OCHMe); MW calculated for C16H2602N2 278.40 g / mol; MS (CIMS) 279.0m / z (M + 1).
Example 12. Synthesis of 12
In a drying box, a small vial was charged with 2.234 g (5 mmol) of ArN = C (Cl) -C (Cl) = NAr (Ar = 2.6-C6H3- (i-Pr) 2), triethylamine (1.4 L, 10 mol), dl-alaninol (400 μL, 5 mmol), and anhydrous toluene (10 L) and capped. The reaction mixture was allowed to stir at room temperature for about 48 hours, during which time a thick precipitate formed. Then, the precipitate (Net3"HCl) was removed by filtration and thoroughly rinsed with toluene.The solvent was removed under vacuum and the product was washed with hexane and dried in vacuo to give 0.592 g (26%) of a pale yellow powder: 1 H NMR (CDC13) d 7.27 (t, 1, Hp), 7.15 (d, 2, Hm), 6.03 and 4.18 (s, 1 each, NH, NH ', or OH), 3.86 ( m, 1, CHMeN), 3.50 (m, 1, CHH'O), 3.36 (, 1, CHH '=), 3.20 (m, 2, CHMe2), 1.12 (m, 12, CHMe2), 0.98 (d, 3, CHMeNH); 13C / APT NMR (CDC13) d 157.1, 147.7, 130.7 (C = 0, Ar: C? Pso, CD), 128.8 (Ar: Cp), 67.6 (CH2),
48. 3 (CHMeN), 24.6 and 24.3 (CHMeMe '), 17.2 (CHMeN); MW calculated for C? 6H2602N2 278.40 g / mol; MS (CIMS) 279.0 m / z (M + 1).
E j usu 13. Summary of 13
In a drying box, a small vial was charged with 2229 g (5 mmol) of ArN = C (Cl) -C (Cl) = NAr (Ar = 2.6-C6H3- (i-Pr) 2), triethylamine (1.40 mL, 10 mol), 3-amino-1-propanol (400 μL, 5 mmol), and anhydrous toluene (10 mL) and capped. The reaction mixture was allowed to stir at room temperature for about 3-4 days during which time a thick precipitate formed. The reaction mixture was diluted with CH2C12 and the resulting solution was extracted with 5% HCl (aq) (3 x 25 mL) and dried over MgSO4, the solvent was removed and the product was washed with hexane and dried in vacuo. to yield 0.592 g (26%) of a white powder LH
NMR (CDC13) 7.37 (t, 1, Hp), 7.34 (d, 2, Hm), 6.40, 4.45 and 4.04 (br s, 1 each, NH, NH ', and OH), 3.64 (t, 2, CH2 ), 3.37 (t, 2, CH2), 3.30 (septet, 2, CHMe2), 1.59 (penteto, 2, CH2), 1.22 (br, 12, CHMe2); 13C / APT NMR (CDC13) d 158.8 145.6 and 128.8
: C = 0; d pso. ^ o. . 125.7 (Ar: Cp), 123.3 (Ar Cm)
58. 2, 33.7 and 32.9 (CH2CH2CH2), 28.2 (CHMe2), 24.1 and 22.8 (CHMeMe '); MW calculated for C? 6H2602N2 278.40 g / mol; MS (CIMS) 279.0m / z (M + 1).
Example 1 . Synthesis of 5'PdMeCl.
In the drying box, compound 5 (255 mg, 0.731 mmol) and COCPdMeCl (194 mg, 0.731 mmol), were dissolved in ~ 15 mL of CH2C12. After stirring overnight, the reaction mixture was filtered and the solvent was removed in vacuo. The resulting yellow powder was washed with Et20 and dried (272 mg, 73.5%): XH NMR (CD2C12) d 7.4 -7.0 (m, 6, Harium). 3.57 (s, 4, NCH2CH2N '), 2.68 and 2.67 (s, 3 each, NMe, N'Me), 2.62 and 2.59 (s, 6 each, Ar, Ar': Me), 0.00) s, 3 , PdMe).
Example 15. Synthesis of 5'PdMeCl.
In the drying box, compound 7 (113 mg, 0.312 mmol) and CODPdMeCl (82.6 mg, 0.312 mmol) were suspended in ~ 15 mL of Et20. After being
stirred overnight, the reaction mixture was allowed to settle and the solvent decanted. The resulting yellow powder was washed twice more with Et20 and then dried in vacuo (92.6 mg,
57. 1%); 1 H NMR (CD2C12) d 7.2-7.0 (m, 6, Ha). 3.35 (t, 4, NCH2CH2CH2N), 2.51 and 2.46 (s, 6, each, Ar, Ar ': Ne), 2.40 and 2.38 (s, 3 each, NMe, N'Me), 2.08 (penteto, 2 , NCH2CH2CH2 '), 0.00 (s, 3, PdMe).
Example 16. Synthesis of [5 • Pd (Me) (NCMe)] BAF,
In the drying cabinet at room temperature, 1 mL of CH3CN and 14 mL of Et20 were added to a mixture of 5'PdMeCl (272 mg, 0.538 mmol) and NaBAF
(476 mg, 0.538 mmol). The reaction mixture was stirred overnight, the sodium chloride was removed by filtration, and the solvent was removed in vacuo to give 595 mg (80.5%) of a pale orange powder: XH NMR (CD2C12) d 7.83 ( s, 8, BAF: H0), 7.67 (s, 4, BAF: Hp), 7.3 - 6.9 (m, 6, Harium). 3.49 (s, 4, NCH2CH2N '), 2.65 and 2.56 (s, 3 each, NMe, N'Me), 2.45 and 2.37 (s, 6 each, Ar, Ar': Me), 1.76 (NCMe), 0.00 (PdMe).
Example 17. Synthesis of [7'Pd (Me) (NCMe) BAF.
In the drying cabinet at room temperature, 1 mL of CH3CN and 14 mL of Et20 were added to a mixture of 7'PdMeCl (92.6 mg, 0.178 mmol) and NaBAF
(158 mg, 0.178 mmol). The reaction mixture was stirred overnight, the sodium chloride was removed by filtration, and the solvent was removed in vacuo to give 201 mg (81.4%) of a yellow powder: XH NMR (CD2C12) d 7.69 (s) , 8, BAF:
H0), 7.51 (s, 4, BAF: Hp), 7.2 - 6.9 (m, 6, Hari? 0),
3. 29 and 3.27 (t, 2 each, NCH2CH2CH2N '), 2.37 and
2. 29 (s, 3 each, NMe, N'Me), 2.35 and 2.28 (s, 6 each, Ar Ar ': Me), 1.98 (penteto, 2,
NCH2CH2CH2N '), 1. 64 (s, 3, NCMe), 0. 0 1 (s, 3,
PdMe).
Example 18. Polymerization of ethylene by [[5"Pd (Me) (NCMe)] BAF.
A solution of 40 mL of CH2C12 of
[5-Pd (Me) (NCMe)] BAF (137 mg, 0.1 mmol) was stirred and placed under 0 kPa (1 atom) of ethylene per 72
hours. After precipitation of the reaction mixture in methanol, filtering, and drying under vacuum, polyethylene (6.35 g, 2.264 TO) was isolated: total 143 Me / 1000 CH2; Mw = 50.087; Mn = 28,027; PDI = 1.54.
Examples 19 and 20. Copolymerization of ethylene / methyl acrylate by [5'Pd (Me) (NCMe)] BAF or [7 • Pd (Me) (NCMe)] BAF.
The copolymerizations of the ethylene and methyl acrylate catalyzed by [(ArN = C (X) -C (X) = NAr) Pd (Me) (NCMe)] BAF (0.1 mmol) were carried out at room temperature under 0 kPa ( 1 atom) of ethylene in a 40 L solution of CH2C12 which was 1.2 M in methyl acrylate. The results of the copolymerization for the palladium catalyst derived from ligands 5 and 7 are reported in Table 1.
Table 1. Copolymerizations of ethylene (E) / methyl acrylate (MA) catalyzed by. [(ArN = C (X) - (X) = NAr) Pd (Me) (NCMe) BAF.
Ej Ligando TON MA Incorp. M / pn. Total Me E / MA (mol%) nvrui per 100OCH2
e-N N-Me 19 97/27 22% 7700 / 1.5 157
Me-N G? N-Me 20 36/13 26% 6700 / 1.8 233
Examples 21-26. General procedure for the synthesis of complexes (ligand) NiBr2.
Under an inert atmosphere, a small flask was charged with nickel dibromide of 1,2-dimethoxyethane (0.20 mmol to 0.30 mmol), the ligand (1 equivalent) and anhydrous CH2C12 (10 mL) and
It was covered. The reaction mixture was allowed to stir for about 48 hours and then filtered through an alkaline flux with celite, rinsing thoroughly with anhydrous CH2C12. After removing the solvent under vacuum, the product was washed with anhydrous hexane, collected in an alkaline flux, transferred to a flask, and dried under vacuum.
Example 21. Synthesis of 5"NiBr2.
The general procedure above was followed on a scale of 0.20 mmol; yield: 56 mg (49%) of pale brown powder. This compound was recrystallized from methylene chloride and an X-ray crystal structure obtained using a CAD4 Enraf-Nonius diffractometer and Mokalpha radiation. The compound had the following characteristics: monoclinic, C2 / c (No. 15), a = ll.648 (2) A, b = l 4.302 (2) A, c = 13.995 (4) A, beta = 104.71 (2) °, T = -75 ° C, Vol = 2255. OA3, Z = 4, formula by weight 565.01, Density 1.664g / cc, μ (Mo) = 3.90cm-1. The crystal structure indicated that this ligand is a bidentate ligand for the
coordinate atom of nickel with the imino nitrogen atoms.
Example 22. Synthesis of 6"NiBr2.
The general procedure above was followed on a scale of 0.20 mmol; yield 76 mg (56%) of a green powder boil.
Example 23. Synthesis of 8"NiBr2.
The general procedure above was followed on a scale of 0.25 mmol); yield 120 mg (72%) of a yellow solid.
Example 24. Synthesis of ll'NiBr2.
The above general procedure was followed on a scale of 0.25 mmol; yield: 173 mg of a green solid boil.
Example 25. Synthesis of 12'NiBr2
The above general procedure was followed on a scale of 0.25 mmol; yield: 179 mg of a green solid boil.
Example 26. Synthesis of 13"NiBr2
The general procedure above was followed on a scale of 0.20 mmol; yield: 126 mg of a pale green solid.
Examples 27-32. Polymerizations of Ethylene with Ligand Complexes "NiBr2.
In a drying box, a Schlenk thick-walled flask was charged with the ligand'NiBr2 complex, 20 mL of toluene and a stir bar. The vessel was sealed and transferred to a Schlenk line on the deck and first purged with nitrogen and then with ethylene. It was then added quickly
polymethylaluminoxane / toluene (PMAO) (9.5% Al, 1.4 mmol Al) and the reaction mixture was stirred under 28-35 kPa of ethylene for 19.5 hours. The reaction mixture was quenched with 15 mL of 90/10 methanol / HCl. The polymer was collected in an alkaline flux, rinsed with methanol and acetone and then dried overnight. The polymer was exposed to the following analyzes: 1R NMR, GPC and DSC.
Table 2. Polymerization of ethylene by purifying with MAO activation of the ligand -NiBr2
Ex. Ligand Performance DSC / XH NMR GPC PE 27 0.523 g Tm-86.3 C Mw = 806, 122 311 TO? Hf = 21.71 j / g Mn = 192, 786 NMR: not soluble 28 2,630 g Tg = -65 45 ° C Mw = 73.519 1560TO NMR: 181.1 Mn = 39.317 Me / 1000 CH2 29 0.819 g Tg = -94 05 ° C Mw = 637, 232 487TO Tm = 104.84 ° C Mn = 222, 280? Hf = 46.65 j / g
Ex Ligand Performance DSC / 1H NMR GPC PE 30 11 0.678 g = -75, -30 ° C Mw = 931.625 403TO Tm = 105.120 ° C Mn = 491.427? Hf = 4.6.0.94 j / g 31 12 0551 g Tg = 101.05 ° C Mw = 627,620 327TO Tm = 102.58 ° CM "= lll, 466? Hf = 90.56 j / g 32 13 0.431 g Tm = 104.80 ° C Mw = 878.578 260TO? Hf = 18.79 j / gn = 243,875 NMR: not soluble
Example 33
A mixture of 0.075 g (0.21 mmol) of 7 and 0.060 g (0.19 mmol) of nickel-dimethoxyethane dibromide complex in 3 mL of methylene chloride was stirred at room temperature under nitrogen for 20 hours and then evaporated by rotating until dry, yield 0.115 g (98%) of the NiBr2 complex of 7 as a brown powder.
A 600-mL Parr® autoclave (connected to a 1 L ethylene tank) was charged with 200 mL of dry hexane (dried over MAO, supported by silica). The solvent was stirred and saturated with ethylene at 60 ° C and 200 kPag. The autoclave was discharged and a red solution of 2.0 mg (0.0034 mmol) of the above complex and 1 mL of modified methylaluminoxane (Akzo MMAO-3A, nominal 1.7 M in heptane, containing about 30% of isobutyl groups) in 3 mL of toluene (the complex and MMAO were mixed for about 1 minute before the injection) were taken in a 5 mL syringe and injected rapidly into the autoclave through an overhead port. The autoclave was immediately pressurized to 1.03 Mpag with ethylene and stirred in a water bath at 60 ° C for 1 hour as the ethylene fed and the drop pressure of the 1 L ethylene tank was observed with time ( see data below). The ethylene was then discharged and the clear solution was diluted with acetone until the sticky polymer precipitated; oven dried (70 ° C / nitrogen) yielding 2.37 g (24,600 TO / Hr; 11.8 Kg PE / g Ni) of polyethylene in rubber, clear. H NMR (CDC12CDC12; 120 ° C): 173 CH3 / 1000 CH2. GPC
(TCB: 135 ° C; PE standard): Mn = 46,000; Mw = 103,000; Mz = 164,000; Mw / Mn = 2.23; Mp = 92,100. 13C NMR: total Me (179.0); Me (125.1); Et (18.0); Pr (5.4); Bu
(9.4); Am (3.3); Hex + and EOC (17.4).
Drop pressure of the ethylene tank against polymerization time (tank ÍL)
Time, E tank, E tank minute MPa MPa 0.00 '3.67 4.74 1.00 3.63 4.67 4.00 3.61 4.64 10.0 3.60 4.62 15.00 3.58 4.60 30.00 3.56 4.56 60.00 3.53 4.51
It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.
Claims (19)
1. A process for the polymerization of one or more olefins of the formula H2C = CHR1 and optionally one or more olefins of the formula H2C = CHR2, characterized in that it comprises contacting the olefins with a complex containing a transition metal selected from the group consisting of palladium, nickel, titanium, zirconium, scandium, vanadium, chromium, iron, cobalt, and a rare earth metal and a ligand of the formula (I) (II (III) which is an active polymerization catalyst, where: each R1 is independently hydrogen or alkyl; each is independently substituted alkyl or -C02R 5-0 A and E are each independently oxygen, sulfur, phosphorus or nitrogen; R- and R are each independently hydrocarbyl or substituted hydrocarbyl, with the proviso that the carbon atom bonded to the nitrogen atom is bonded to at least two other carbon atoms R4, R5, R6 and R7 are each independently hydrocarbyl or substituted hydrocarbyl; Ar1 and Ar2 are each independently aryl or substituted aryl R: R, 1J0 are each independently hydrocarbyl or substituted hydrocarbyl; R, 5-0 is hydrocarbyl substituted hydrocarbyl; and with the condition that when the ligand is (II) or (III), the transition metal is nickel; when H2C = CHR2 occurs, a palladium complex is present; the members of any one or more of the pairs R4 and R5, R6 and R7, R4 and R6, and R5 and R7 taken together can form a ring; when A is oxygen or sulfur, R5 is not present; Y when E is oxygen or sulfur, R is not present.
2. A process for the polymerization of one more olefins of the formula H2C = CHR1 and optionally one or more olefins of the formula H2C = CHR2, characterized in that it comprises, contacting the olefins, a first compound of the formula (IV) or [Ar'HNC (O) HR1 C] MXn, (V) (VI) and: (a) a second compound W, which is a neutral Lewis acid capable of extracting X- from M to form WX-, and which is also capable of transferring an alkyl group or a hydride to M, with the proviso that WX- is a weak coordination anion; or (b) a combination of a third compound that is capable of transferring an alkyl or hydride group to M and a fourth compound which is an acid Neutral Lewis which is capable of extracting X-, a hydride or an alkyl group from M to form a weak coordination anion; or (c) when at least one of X is an alkyl or hydride group, a fifth compound which is a cationic or Bronsted Lewis acid whose anion counter is a weak coordination anion; where M is Ni, Pd, Ti, Zr, Se, V, Cr, Fe, Co or a rare earth metal each X is independently a monoanion; n is equal to the oxidation number of M; each R is independently hydrogen or alkyl; each R 'is independently substituted alkyl or -C02R 50; A and E are each independently oxygen, sulfur, phosphorus, or nitrogen; R3 and R8 are each independently hydrocarbyl or substituted hydrocarbyl with the proviso that the carbon atom bonded to the nitrogen atom is linked to at least two other carbon atoms; R4, R5, R6 and R7 are each independently hydrocarbyl or substituted hydrocarbyl; Ar1 and Ar2 are each independently aryl or substituted aryl; R9 and R10 are each independently hydrocarbyl or substituted hydrocarbyl; R50 is hydrocarbyl or substituted hydrocarbyl; and with the condition that when the first compound is (II) or (III), M is Ni; the members of any one or more of the pairs R4 and R5, R6 and R7, R4 and R6, and R5 and R7 taken together can form a ring; when H2C = CHR2 occurs, a palladium complex is present; when A is oxygen or sulfur, R is not present; Y when E is oxygen or sulfur, R7 is not present.
3. The process as recited in claim 1, characterized in that when the ligand is (I) the transition metal is Ti, Zr, Se, V, Cr or a rare earth metal.
4. The process as recited in claim 2, characterized in that when the first compound is (IV) the transition metal is Ti, Zr, Se, V, Cr or a rare earth metal.
5. The process as recited in claim 1, characterized in that the complex is supported on a solid support.
6. The process as recited in claim 5, characterized in that the support is an acid clay.
7. The process as recited in claim 2, characterized in that the first compound is supported on a solid support.
8. The process as recited in claim 7, characterized in that the support can take the place of Lewis or Bronsted acid.
9. The process as recited in any of claims 1-8, characterized in that a second active polymerization catalyst is also present.
10. The process as recited in claim 9, characterized in that the second active polymerization catalyst is a Ziegler-Natta or metallocene catalyst.
11. The process as recited in any of claims 1-8, characterized in that R1 is hydrogen.
12. The process as recited in claim 11, characterized in that only one olefin is present.
13. The process as recited in any of claims 1-8, characterized in that a polyolefin is produced and hydrogen is formed to reduce the molecular weight of the polyolefin.
14. The process as recited in claim 9, characterized in that a polyolefin is produced and hydrogen is used to reduce the molecular weight of the polyolefin.
15. A compound of the formula (IV) [Ar1H? \ TC (0) OR9] MXn, or [Ar1HNC (O) NHR10] MXnf (v; (vi) characterized because: M is Ni, Pd, Ti, Zr, Se, V, Cr, Fe, Co or a rare earth metal each X is independently a monoanion, n is equal to the oxidation number of M; A and E are each independently oxygen, sulfur, phosphorus, or nitrogen; R and R are each independently hydrocarbyl or substituted hydrocarbyl with the proviso that the carbon atom linked to the Nitrogen atom is linked to at least two other carbon atoms; R4, R5, R6 and R7 are each independently hydrocarbyl or substituted hydrocarbyl; Ar1 and Ar2 are each independently aryl or substituted aryl; R9 and R10 are each independently hydrocarbyl or substituted hydrocarbyl; and with the condition that when the first compound is (V) or (VI), M is Ni; the members of any one or more of the pairs R4 and R5, R6 and R7, R4 and R6, and R5 and R7 taken together can form a ring; when A is oxygen or sulfur, R is not present; Y when E is oxygen or sulfur, R7 is not present.
16. The compound as recited in claim 15, characterized in that M is Ni, Ti, Zr, Se, V, Cr or a rare earth metal.
17. The compound as recited in claim 16, characterized in that M is Ti, Zr, Se, V, Cr or a rare earth metal.
18. The compound as recited in any of claims 15-17, characterized in that it is supported on a solid support.
19. The compound as recited in claim 18, characterized in that the support can take the place of Lewis or Bronsted acid.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US60/094,502 | 1998-07-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
MXPA01000875A true MXPA01000875A (en) | 2001-12-13 |
Family
ID=
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1115758B1 (en) | Polymerization of olefins | |
US6531424B2 (en) | Polymerization of olefins | |
US7683147B2 (en) | Polymerization of olefins | |
US20020061987A1 (en) | Polymerization of ethylene | |
AU5711098A (en) | Polymerization of ethylene | |
US6562751B2 (en) | Polymerization of olefins | |
US6451940B1 (en) | Catalysts for olefin polymerizations | |
MXPA01000875A (en) | Polymerization of olefins | |
EP1127897A2 (en) | Catalyst composition comprising specific iron or cobalt complexes and process for the oligomerization or polymerization of ethylene therewith | |
US20010044511A1 (en) | Polymerization of olefins | |
CZ2001300A3 (en) | Polymerization process of olefins |