WO2001023445A1 - Preparation of curable polymers - Google Patents
Preparation of curable polymers Download PDFInfo
- Publication number
- WO2001023445A1 WO2001023445A1 PCT/US2000/026647 US0026647W WO0123445A1 WO 2001023445 A1 WO2001023445 A1 WO 2001023445A1 US 0026647 W US0026647 W US 0026647W WO 0123445 A1 WO0123445 A1 WO 0123445A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon group
- bound
- ring
- ring atom
- group
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title description 27
- 238000002360 preparation method Methods 0.000 title description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 72
- 239000005977 Ethylene Substances 0.000 claims abstract description 43
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000001993 dienes Chemical class 0.000 claims abstract description 32
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 7
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 97
- 125000006413 ring segment Chemical group 0.000 claims description 80
- 229910052739 hydrogen Inorganic materials 0.000 claims description 45
- 239000001257 hydrogen Substances 0.000 claims description 45
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 42
- 238000006384 oligomerization reaction Methods 0.000 claims description 37
- 125000000524 functional group Chemical group 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 125000003118 aryl group Chemical group 0.000 claims description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 19
- 229910052736 halogen Inorganic materials 0.000 claims description 18
- 150000002367 halogens Chemical group 0.000 claims description 18
- 150000002431 hydrogen Chemical group 0.000 claims description 18
- 239000003446 ligand Substances 0.000 claims description 16
- 125000003107 substituted aryl group Chemical group 0.000 claims description 15
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 12
- 239000002685 polymerization catalyst Substances 0.000 claims description 11
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 claims description 8
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims description 6
- NALBLJLOBICXRH-UHFFFAOYSA-N dinitrogen monohydride Chemical compound N=[N] NALBLJLOBICXRH-UHFFFAOYSA-N 0.000 claims description 6
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 3
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 17
- 239000004711 α-olefin Substances 0.000 abstract description 10
- 229920001971 elastomer Polymers 0.000 abstract description 7
- 239000000806 elastomer Substances 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 5
- 229920000098 polyolefin Polymers 0.000 abstract description 4
- 229920006126 semicrystalline polymer Polymers 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006116 polymerization reaction Methods 0.000 description 18
- 150000001336 alkenes Chemical class 0.000 description 17
- -1 ethylene, propylene Chemical group 0.000 description 16
- 150000001450 anions Chemical class 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 125000004429 atom Chemical group 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000002844 melting Methods 0.000 description 8
- 230000008018 melting Effects 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 150000004678 hydrides Chemical class 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- 239000012190 activator Substances 0.000 description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 5
- 229920002943 EPDM rubber Polymers 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 150000003623 transition metal compounds Chemical class 0.000 description 4
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 2
- 0 C=*[N+]1N=NN=N[N-]1 Chemical compound C=*[N+]1N=NN=N[N-]1 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000012685 gas phase polymerization Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000001072 heteroaryl group Chemical group 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 125000005538 phosphinite group Chemical group 0.000 description 2
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical compound OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229940095050 propylene Drugs 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 125000004953 trihalomethyl group Chemical group 0.000 description 2
- 238000013022 venting Methods 0.000 description 2
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 125000006519 CCH3 Chemical group 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 229930194542 Keto Natural products 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YSVZGWAJIHWNQK-UHFFFAOYSA-N [3-(hydroxymethyl)-2-bicyclo[2.2.1]heptanyl]methanol Chemical compound C1CC2C(CO)C(CO)C1C2 YSVZGWAJIHWNQK-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 229920005605 branched copolymer Polymers 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- QIUBLANJVAOHHY-UHFFFAOYSA-N hydrogen isocyanide Chemical group [NH+]#[C-] QIUBLANJVAOHHY-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 125000002346 iodo group Chemical group I* 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical group C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/602—Component covered by group C08F4/60 with an organo-aluminium compound
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/26—Catalytic processes with hydrides or organic compounds
- C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08F210/18—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers with non-conjugated dienes, e.g. EPT rubbers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- C07C2531/22—Organic complexes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61904—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with another component of C08F4/60
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
- C08F4/65927—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not two cyclopentadienyl rings being mutually bridged
Definitions
- Olefin containing branched polyolefms, especially elastomers are produced in processes using at least two active catalysts, one of which is a selected iron catalyst that oligomerizes ethylene, and another of which is a transition metal catalyst that copolyme ⁇ zes ethylene, ⁇ -olefms and non-conjugated dienes.
- Polyolefms containing olefinic unsaturation, especially elastomers, are particularly useful, since they may be cured (crosslmked/vulcanized) by the use of sulfur cures or free radical cures.
- EPDM elastomers copolymers of ethylene, propylene and a nonconjugated diene such as ethylidene norbornene, dicyclo- pentadiene, or 1 , 4-hexad ⁇ ene .
- EPDMs have been made using metallocene catalysts, see for instance US5229478, WO88/04674, 099/18135 and O99/01460, and references described therein.
- Various reports of "simultaneous" oligomerization and polymerization of ethylene to form (in most cases) branched polyethylenes have appeared m the literature, see for instance O90/15085, O99/50318, US5753785, US5856610, US5686542, US5137994 and US5071927; C. Denger, et al, Makro- mol . Chem. Rapid Commun. , vol. 12, p. 697-701 (1991); and E. A. Benham, et al . , Polymer Engineering and Science, vol. 28, p. 1469-1472 (1988). None of these references specifically describes any of the processes or resulting branched polyolefms herein.
- step (2) (2) contacting an active transition metal copolymerization catalyst, with a second monomer component comprising ethylene, at least a portion of the ⁇ -olefins from step (1) and an active nonconjugated diene, under conditions to copolym- erize the second monomer component to a branched polyolefm containing olefinic bonds.
- This invention also concerns a polymerization catalyst system comprising the oligomerization and copolymenzation catalyst components described above.
- novel branched polyolefm in accordance with the present invention contains at least 2 ethyl branches, at least 2 hexyl or longer branches and at least one butyl branch per 1000 methylene groups, and olefinic bonds.
- Another such novel branched polyolefm in accordance with the present invention contains about 20 to about 150 branches of the formula -(CH 2 CH 2 ) n H, wherein n is an integer of 1 to 100, and olefinic bonds.
- hydrocarbyl is meant a umvalent radical containing only carbon and hydrogen.
- hydrocarbyls may be mentioned unsubstituted alkyls, cycloalkyls and aryls. If not otherwise stated, it is preferred that the hydrocarbyl groups herein contain 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms.
- substituted hydrocarbyl herein is meant a hydrocarbyl group that contains one or more "inert functional groups” that are inert under the process conditions to which the compound containing these groups is subjected .
- the inert functional groups also do not substantially interfere with the oligome ⁇ zation/polyme ⁇ zation process.
- inert functional groups are halo, ester, amino, imino, carboxyl, phosphite, phosphonite, phosphine, phosphinite, thioether, and amide.
- catalyst activator a compound that reacts with a transition metal compound to form an activated catalyst species.
- a preferred catalyst activator is an alkylaluminum compound, that is, a compound which has at least one alkyl group bound to an aluminum atom.
- anions those formed from aluminum compounds (such as those described in the i - mediately preceding paragraph) and X " (an anion as discussed in further detail below), including (R 19 ) 3 A1X ⁇ , (R 19 ) 2 A1C1X “ , R 19 A1C1 2 X ⁇ , and R 19 AlOX ⁇ , wherein R 19 is alkyl.
- an “active nonconjugated diene” is meant a diene that may be polymerized through one of the double bonds in the diene, while the other double bond is essentially inert under the polymerization conditions . This yields a repeat unit in the polymer that contains an olefin moiety in a branch which is part of that repeat unit.
- Suitable non- conjugated dienes have as the reactive olefinic bond a ter- minal olefin, as in 1 , 4-hexadiene, or a particularly strained olefin as the ring double bond in ethylidene nor- bornene .
- these olefinic bonds are in repeat units derived from nonconjugated diene monomers, as described herein. It is preferred that the branched polyolefms in accordance with the present invention contain at least some olefinic bonds not associated with end groups.
- the bond represented by the solid line is to a ring atom of an aryl or substituted aryl to which the secondary carbon group is attached, and both free bonds represented by the dashed lines are to an atom or atoms other than hydrogen.
- These atoms or groups may be the same or different .
- the free valences represented by the dashed lines may be hydrocarbyl, substituted hydrocarbyl or inert functional groups.
- tertiary carbon group a group of the formula
- aryl is meant a monovalent aromatic group in which the free valence is to the carbon atom of an aromatic ring.
- An aryl may have one or more aromatic rings which may be fused, connected by single bonds or other groups.
- substituted aryl is meant a monovalent aromatic group substituted as set forth in the above definition of “substituted hydrocarbyl”. Similar to an aryl, a substi- tuted aryl may have one or more aromatic rings which may be fused, connected by single bonds or other groups; however, when the substituted aryl has a heteroaromatic ring, the free valence in the substituted aryl group can be to a het- eroatom (such as nitrogen) of the heteroaromatic ring in- stead of a carbon.
- the preferrred oligomerization catalyst is an Fe complex (Fe [II] or Fe[III]) of a ligand of the general formula (I), wherein:
- R 6 and R 7 are each independently an aryl or substituted aryl having a first ring atom bound to the imino nitrogen, provided that : in R 6 , a second ring atom adjacent to said first ring atom is bound to a halogen, a primary carbon group, a secondary carbon group or a tertiary carbon group; and further provided that in R 6 , when said second ring atom is bound to a halogen or a primary carbon group, none, one or two of the other ring atoms in R 6 and R 7 adjacent to said first ring atom are bound to a halogen or a primary carbon group, with the re- mainder of the ring atoms adjacent to said first ring atom being bound to a hydrogen atom; or in R s , when said second ring atom is bound to a secondary carbon group, none, one or two of the other ring atoms in R 6 and R 7 adjacent to said first ring atom are bound to a halogen, a
- first ring atom in R 6 and R 7 bound to an imino nitrogen atom is meant the ring atom in these groups bound to an imino nitrogen shown in (I) , for example
- the atoms shown in the 1-position in the rings in (III) and (IV) are the first ring atoms bound to an imino carbon atom (other groups which may be substituted on the aryl groups are not shown) .
- Ring atoms adjacent to the first ring atoms are shown, for example, in (V) and (VI) , where the open valencies to these adjacent atoms are shown by dashed lines (the 2 , 6-positions in (V) and the 2 , 5-positions in (VI)).
- each of R 1 , R 2 , R 3 , R , R 5 , R 9 , R 10 , R 11 , R 14 , R 15 and R 16 is independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl and an inert functional group; and R 8 is halogen, a primary carbon group, a secondary carbon group or a tertiary carbon group; provided that : when R 8 is halogen or a primary carbon group none, one or two of R 12 , R 13 and R 17 are independently a primary carbon group, an inert functional group or a trihalo tertiary carbon group, and the remainder of R 12 , R 13 and R 17 are hydrogen; when R 8 is a secondary carbon group, none or one of R 12 , R 13 and R 17 is a primary carbon group, a secondary carbon group, a trihalo tertiary carbon group or an inert functional group, and the remainder of R 12 , R 13 and R 17 are hydrogen; when R 8 is
- R 4 and R 5 are methyl or hydrogen; and/or R 1 , R 2 , and R 3 are all hydrogen; and/or R 9 , R 10 , R 11 , R 14 , R 1S and R 1S are all hydrogen,- and/or R 17 is selected from the group consisting of methyl, ethyl, propyl isopropyl, halo and trihalomethyl; and/or R 12 is selected from the group consisting of hydrogen, methyl, ethyl, propyl, isopropyl, halo and trihalomethyl. In certain more preferred embodiments, both R 12 and R 17 are methyl or ethyl. In all such cases, R 8 is a primary carbon group, and R 13 is hydrogen.
- R 4 and R 5 are methyl; R 9 , R 10 , R 11 , R 13 , R 14 , R 15 and R 16 are all hydrogen; R 12 is hydrogen or ethyl; R 17 is ethyl; and R 8 is a primary carbon group; or
- R 4 and R 5 are methyl; R 9 , R 10 , R 11 , R 13 , R 14 , R 15 and R 16 are all hydrogen; R 12 is hydrogen or isopropyl; R 17 is isopropyl; and R 8 is a primary carbon group; or
- R 4 and R 5 are methyl; R 9 , R 10 , R 11 , R 13 , R 14 , R 15 and R 16 are all hydrogen; R 12 is hydrogen or chloro; R 17 is chloro; and R 8 is a primary carbon group; or R 4 and R 5 are methyl; R 9 , R 10 , R 11 , R 13 , R 14 , R 15 and R 16 are all hydrogen; R 12 is hydorgen or trifluoromethyl ; R 17 is trifluoromethyl ; and R 8 is a primary carbon group.
- R 1 , R 2 , R 3 , R 4 , R 5 , R 9 , R 10 , R 11 , R 14 , R 15 and R 16 are as just defined, and if R 8 is a primary carbon group, R 12 and R 17 are hydrogen, and R 13 is a primary carbon group; or if R 8 is a secondary carbon group, R 12 and R 17 are hydrogen, and R 13 is a primary carbon group or a secondary carbon group . Also preferred is when R 8 is a primary carbon group, preferably selected from methyl, ethyl, propyls and butyls.
- each X is an anion
- n is 1, 2 or 3 so that the total number of negative charges on the X groups is equal to the oxidation state of the Fe in the pure Fe complex.
- each X is a monovalent anion, more preferably selected from the group consisting of a halide and a nitrile, and especially a halide such as chloride or bromide .
- These pure Fe complexes may in and of themselves be active oligomerization catalysts, or they may be activated (or made more active) preferably by preparation in situ by con- tact with a catalyst activator in a variety of methods.
- Ethylene may be oligomerized by contacting a first compound W, which is a neutral Lewis acid capable of abstracting X " to form WX " , with an iron halide complex of ligand (I) (or other X " complex of (I) ) , provided that the anion formed is a weakly coordinating anion; or a cationic Lewis or Bron- sted acid whose counterion is a weakly coordinating anion.
- W which is a neutral Lewis acid capable of abstracting X " to form WX "
- an iron halide complex of ligand (I) or other X " complex of (I) )
- the anion formed is a weakly coordinating anion
- a cationic Lewis or Bron- sted acid whose counterion is a weakly coordinating anion.
- a neutral Lewis acid or a cationic Lewis or Bronsted acid may also alkylate or add a hydride to the metal, i.e., causes an alkyl group or hydride to become bonded to the metal atom, or a separate compound is added to add the alkyl or hydride group .
- a preferred neutral Lewis acid which can alkylate the metal, is a selected alkyl aluminum compound, such as R 20 3 A1 , R 20 3 A1C1, R 20 A1C1 2 , and " R 20 AlO" (alkylaluminoxanes) , wherein R 20 is alkyl containing 1 to 25 carbon atoms, preferably 1 to 4 carbon atoms.
- Suitable alkyl aluminum compounds include methylaluminoxane (which is an oligomer with the general formula [MeAlO] n ) , (C 2 H 5 ) 2 A1C1, (C 2 H 5 )A1C1 2 and
- Metal hydrides such as NaBH 4 may be used to bond hydride groups to the metal M.
- the product of the oligomerization will be a mixture of oligomers of the above formula, preferably possessing a number average molecular weight of about 600 or less, more preferably about 400 or less.
- Other olefins, such as pro- pylene may optionally be added to the process at any point, so that they also copolymerize into the polyolefin ultimately formed.
- the only two monomers added to the system are ethylene the active nonconjugated diene (although, of course, other monomers are generated in situ from the oligomerization step) .
- the resulting polymer tends to be relatively high molecular weight and uniform.
- the synthesis of the branched copolymers in accordance with the present invention herein can produce unique polymers because of the nature of the two catalysts.
- the oligomerization and copolymerization are performed simultaneously, and/or the oligomerization and copolymerization oc- cur at comparable rates, to prepare various unique copolymers .
- the amount of these branches (as measured by total methyl groups) in the polymer preferably ranges from about 2 to about 200, espe- cially preferably about 5 to about 175, more preferably about 10 to about 150, and especially preferably about 20 to about 150 branches per 1000 methylene groups in the polymer (for the method of measurement and calculation, US5880241, incorporated by reference herein) .
- Another preferable range for these branches is about 50 to about 200 methyl groups per 1000 methylene carbon atoms.
- these branched polymers there is at least 2 branches each of ethyl and n-hexyl or longer and at least one n-butyl per 1000 methylene groups, more preferably at least 4 branches each of ethyl and n-hexyl or longer and at least 2 n-butyl branches per 1000 methylene groups, and especially preferably at least 10 branches each of ethyl and n-hexyl or longer and at least 5 n-butyl branches per 1000 methylene groups. It is also preferred that there are more ethyl branches than butyl branches.
- methyl branches there is less than 20 methyl branches, more preferably less than 2 methyl branches, and especially pref- erably less than 2 methyl branches (all after correction for end groups) per 1000 methylene groups.
- the transition metal compounds may also be coated onto a support such as a polyolefm (polyethylene, polypropylene, etc.) support, optionally along with other needed catalyst components such as one or more alkylaluminum compounds .
- a support such as a polyolefm (polyethylene, polypropylene, etc.) support, optionally along with other needed catalyst components such as one or more alkylaluminum compounds .
- the oligomers made by the oligomerization catalyst and the polymer made by the polymerization catalyst may be made in sequence, i.e., the oligomerization followed by the polymerization, as by using two vessels in series.
- Another preferred process is to add all components to the vessel at the same time - ethylene, nonconjugated diene, oligomerization catalyst and copolymerization catalyst - and conduct the oligomerization/copolymerization simultaneously.
- essen- tially only ethylene and the active nonconjugated diene as monomers added into the process.
- other monomers/oligomers will be generated in situ and incorporated into the final copolymer, but the only monomers required to operate the process and generate the products are ethylene and the nonconjugated diene.
- the amount of branching in the polyolefms formed by the process of the present invention is sufficient so that an elastomer is formed.
- a particularly preferred aspect of the process utilizes ethylene and the nonconjugated diene as the sole added mono- mers, with ⁇ -olefins being incorporated into the final copolymer solely as a result of the in situ oligomerization of ethylene.
- the reactor was pressured with nitrogen, and the nitrogen was then released. Reactor was heated to 65°C, then, pressurized 2X to 690 kPa ethylene, venting each time and finally pressurized to 830 kPa with stirring.
- the MAO solution was added from the Hoke cylinder at slightly higher pressure.
- the ethylene pressure of the reactor was then ad- justed to 1.24 MPa.
- the reaction mixture was allowed to stir at around 90°C for 40 min.
- the heat source was removed. Ethylene was vented to about 210 kPa.
- the reactor was back filled with 1.38 MPa nitrogen and was then vented to 210 kPa . This was repeated once.
- the reaction mixture was then cooled to RT.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Graft Or Block Polymers (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020027004029A KR20020037365A (en) | 1999-09-29 | 2000-09-28 | Preparation Of Curable Polymer |
AT00967007T ATE257491T1 (en) | 1999-09-29 | 2000-09-28 | PRODUCTION OF CURABLE POLYMERS |
BR0014636-6A BR0014636A (en) | 1999-09-29 | 2000-09-28 | Process of preparing a polyolefin, polymerization catalyst and polyolefin system |
DE60007660T DE60007660T3 (en) | 1999-09-29 | 2000-09-28 | PREPARATION OF HARDENABLE POLYMERS |
JP2001526593A JP2003510428A (en) | 1999-09-29 | 2000-09-28 | Production of curable polymers |
EP00967007A EP1237948B2 (en) | 1999-09-29 | 2000-09-28 | Preparation of curable polymers |
AU77269/00A AU7726900A (en) | 1999-09-29 | 2000-09-28 | Preparation of curable polymers |
CA002381288A CA2381288A1 (en) | 1999-09-29 | 2000-09-28 | Preparation of curable polymers |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15655099P | 1999-09-29 | 1999-09-29 | |
US60/156,550 | 1999-09-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2001023445A1 true WO2001023445A1 (en) | 2001-04-05 |
Family
ID=22560038
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2000/026647 WO2001023445A1 (en) | 1999-09-29 | 2000-09-28 | Preparation of curable polymers |
Country Status (11)
Country | Link |
---|---|
US (2) | US20030045658A1 (en) |
EP (1) | EP1237948B2 (en) |
JP (1) | JP2003510428A (en) |
KR (1) | KR20020037365A (en) |
CN (1) | CN1217963C (en) |
AT (1) | ATE257491T1 (en) |
AU (1) | AU7726900A (en) |
BR (1) | BR0014636A (en) |
CA (1) | CA2381288A1 (en) |
DE (1) | DE60007660T3 (en) |
WO (1) | WO2001023445A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1322576A2 (en) * | 2000-10-03 | 2003-07-02 | Shell Internationale Researchmaatschappij B.V. | Process for the co-oligomerisation of ethylene and alpha olefins |
US9637567B2 (en) | 2011-05-13 | 2017-05-02 | Univation Technologies, Llc | Spray-dried catalyst compositions and polymerization processes employing the same |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1237948B2 (en) † | 1999-09-29 | 2007-03-07 | E.I. Du Pont De Nemours And Company | Preparation of curable polymers |
US20050014983A1 (en) * | 2003-07-07 | 2005-01-20 | De Boer Eric Johannes Maria | Process for producing linear alpha olefins |
ES2299015T3 (en) * | 2004-03-24 | 2008-05-16 | Shell Internationale Research Maatschappij B.V. | COMPLEX TRANSITION METALS. |
JP5749718B2 (en) * | 2009-08-17 | 2015-07-15 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニーE.I.Du Pont De Nemours And Company | Improvement of olefin polymerization method |
JP7050544B2 (en) * | 2018-03-27 | 2022-04-08 | Eneos株式会社 | Wax isomerized oil manufacturing method |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997048735A1 (en) * | 1996-06-17 | 1997-12-24 | Exxon Chemical Patents Inc. | Mixed transition metal catalyst systems for olefin polymerization |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3621763A1 (en) * | 1986-06-28 | 1988-01-21 | Bayer Ag | METHOD FOR PRODUCING BRANCHED LOW-PRESSURE POLYETHENS, NEW LOW-PRESSURE POLYETHENS AND PRE-FORMED BIFUNCTIONAL CATALYSTS |
US5071927A (en) * | 1990-10-09 | 1991-12-10 | Phillips Petroleum Company | High-temperature slurry polymerization of ethylene |
US5137994A (en) * | 1991-05-23 | 1992-08-11 | Union Carbide Chemicals & Plastics Technology Corporation | Process for the simultaneous trimerization and copolymerization of ethylene |
JPH09143228A (en) * | 1995-11-22 | 1997-06-03 | Sumitomo Chem Co Ltd | Production of ethylene/alpha-olefin copolymer |
HUP9603449A3 (en) * | 1995-12-15 | 2000-03-28 | Union Carbide Chem Plastic | Process for production of long-chain branched polyolefins, polyethylene composition and product |
US5753785A (en) * | 1996-12-16 | 1998-05-19 | Fina Technology, Inc. | Production of E-B copolymers with a single metallocene catalyst and a single monomer |
CN1216079C (en) † | 1998-03-12 | 2005-08-24 | 英国石油化学品有限公司 | Polymersation catalysts |
WO1999050318A1 (en) † | 1998-03-30 | 1999-10-07 | E.I. Du Pont De Nemours And Company | Polymerization of olefins |
JP2000191719A (en) * | 1998-12-28 | 2000-07-11 | Mitsui Chemicals Inc | Olefin polymerization catalyst and polymerization of olefin |
JP2000191712A (en) * | 1998-12-28 | 2000-07-11 | Mitsui Chemicals Inc | Olefin polymerization catalyst and olefin polymerization |
GB9906296D0 (en) † | 1999-03-18 | 1999-05-12 | Bp Chem Int Ltd | Polymerisation catalysts |
EP1237948B2 (en) † | 1999-09-29 | 2007-03-07 | E.I. Du Pont De Nemours And Company | Preparation of curable polymers |
-
2000
- 2000-09-28 EP EP00967007A patent/EP1237948B2/en not_active Expired - Lifetime
- 2000-09-28 CN CN008134693A patent/CN1217963C/en not_active Expired - Fee Related
- 2000-09-28 CA CA002381288A patent/CA2381288A1/en not_active Abandoned
- 2000-09-28 DE DE60007660T patent/DE60007660T3/en not_active Expired - Lifetime
- 2000-09-28 BR BR0014636-6A patent/BR0014636A/en not_active IP Right Cessation
- 2000-09-28 JP JP2001526593A patent/JP2003510428A/en active Pending
- 2000-09-28 AT AT00967007T patent/ATE257491T1/en not_active IP Right Cessation
- 2000-09-28 AU AU77269/00A patent/AU7726900A/en not_active Abandoned
- 2000-09-28 KR KR1020027004029A patent/KR20020037365A/en not_active Application Discontinuation
- 2000-09-28 WO PCT/US2000/026647 patent/WO2001023445A1/en active IP Right Grant
-
2002
- 2002-09-20 US US10/251,444 patent/US20030045658A1/en not_active Abandoned
-
2007
- 2007-10-31 US US11/981,047 patent/US20080058485A1/en not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1997048735A1 (en) * | 1996-06-17 | 1997-12-24 | Exxon Chemical Patents Inc. | Mixed transition metal catalyst systems for olefin polymerization |
Non-Patent Citations (1)
Title |
---|
MECKING S: "REACTOR BLENDING WITH EARLY/LATE TRANSITION METAL CATALYST COMBINATIONS IN ETHYLENE POLYMERIZATION", MACROMOLECULAR: RAPID COMMUNICATIONS,DE,WILEY VCH, WEINHEIM, vol. 20, no. 3, March 1999 (1999-03-01), pages 139 - 143, XP000834998, ISSN: 1022-1336 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1322576A2 (en) * | 2000-10-03 | 2003-07-02 | Shell Internationale Researchmaatschappij B.V. | Process for the co-oligomerisation of ethylene and alpha olefins |
JP2004510727A (en) * | 2000-10-03 | 2004-04-08 | シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー | Method for co-oligomerization of ethylene and α-olefin |
US9637567B2 (en) | 2011-05-13 | 2017-05-02 | Univation Technologies, Llc | Spray-dried catalyst compositions and polymerization processes employing the same |
Also Published As
Publication number | Publication date |
---|---|
AU7726900A (en) | 2001-04-30 |
CA2381288A1 (en) | 2001-04-05 |
JP2003510428A (en) | 2003-03-18 |
DE60007660T3 (en) | 2007-08-09 |
BR0014636A (en) | 2002-06-11 |
EP1237948B1 (en) | 2004-01-07 |
DE60007660D1 (en) | 2004-02-12 |
ATE257491T1 (en) | 2004-01-15 |
EP1237948A1 (en) | 2002-09-11 |
EP1237948B2 (en) | 2007-03-07 |
CN1376169A (en) | 2002-10-23 |
KR20020037365A (en) | 2002-05-18 |
DE60007660T2 (en) | 2004-11-11 |
US20080058485A1 (en) | 2008-03-06 |
US20030045658A1 (en) | 2003-03-06 |
CN1217963C (en) | 2005-09-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP1068245B2 (en) | Polymerization of olefins | |
US6214761B1 (en) | Iron catalyst for the polymerization of olefins | |
US6417305B2 (en) | Oligomerization of ethylene | |
US6423848B2 (en) | Tridentate ligand | |
US7977268B2 (en) | Polymerization of olefins | |
US6432862B1 (en) | Cobalt catalysts for the polymerization of olefins | |
US6555631B1 (en) | Manufacture of polyethylenes | |
US6297338B1 (en) | Polymerization of olefins | |
US6407188B1 (en) | Polymerization of olefins | |
KR20010043881A (en) | Copolymerization of Olefins | |
US20080058485A1 (en) | Preparation of curable polymers | |
EP1237964A1 (en) | Copolymerization of ethylene and dienes | |
EP1237949B1 (en) | Polymerization of olefins with bimetallic polymerisation catalyst system | |
US6933359B2 (en) | Copolymerization of ethylene and dienes | |
MXPA00008831A (en) | Polymerization of olefins |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
WWE | Wipo information: entry into national phase |
Ref document number: 2381288 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: 77269/00 Country of ref document: AU |
|
ENP | Entry into the national phase |
Ref country code: JP Ref document number: 2001 526593 Kind code of ref document: A Format of ref document f/p: F |
|
WWE | Wipo information: entry into national phase |
Ref document number: 008134693 Country of ref document: CN |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1020027004029 Country of ref document: KR |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2000967007 Country of ref document: EP |
|
WWP | Wipo information: published in national office |
Ref document number: 1020027004029 Country of ref document: KR |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWP | Wipo information: published in national office |
Ref document number: 2000967007 Country of ref document: EP |
|
WWG | Wipo information: grant in national office |
Ref document number: 2000967007 Country of ref document: EP |