WO1998042665A1 - Catalyst compositions and processes for olefin oligomerization and polymerization - Google Patents
Catalyst compositions and processes for olefin oligomerization and polymerization Download PDFInfo
- Publication number
- WO1998042665A1 WO1998042665A1 PCT/US1998/003175 US9803175W WO9842665A1 WO 1998042665 A1 WO1998042665 A1 WO 1998042665A1 US 9803175 W US9803175 W US 9803175W WO 9842665 A1 WO9842665 A1 WO 9842665A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- alkyl
- compound
- aryl
- substituted
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 94
- 230000008569 process Effects 0.000 title claims abstract description 89
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 48
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 title claims description 117
- 239000000203 mixture Substances 0.000 title claims description 76
- 238000006116 polymerization reaction Methods 0.000 title claims description 42
- 238000006384 oligomerization reaction Methods 0.000 title description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 107
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 39
- 150000003624 transition metals Chemical class 0.000 claims abstract description 39
- 239000003446 ligand Substances 0.000 claims abstract description 30
- 125000003118 aryl group Chemical group 0.000 claims description 87
- -1 2,6- di (isopropyl) phenyl Chemical group 0.000 claims description 86
- 125000000217 alkyl group Chemical group 0.000 claims description 69
- 239000002879 Lewis base Substances 0.000 claims description 53
- 150000007527 lewis bases Chemical class 0.000 claims description 53
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 53
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 52
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 52
- 125000003107 substituted aryl group Chemical group 0.000 claims description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims description 40
- 239000001257 hydrogen Substances 0.000 claims description 40
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 40
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 39
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 38
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 35
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 34
- 125000005843 halogen group Chemical group 0.000 claims description 33
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 33
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 26
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 25
- 239000005977 Ethylene Substances 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 23
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- 125000000743 hydrocarbylene group Chemical group 0.000 claims description 22
- 125000002947 alkylene group Chemical group 0.000 claims description 21
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 21
- 229910052763 palladium Inorganic materials 0.000 claims description 19
- 150000002148 esters Chemical class 0.000 claims description 18
- 150000001299 aldehydes Chemical class 0.000 claims description 17
- 125000000732 arylene group Chemical group 0.000 claims description 17
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 17
- 150000002170 ethers Chemical class 0.000 claims description 17
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 150000002576 ketones Chemical class 0.000 claims description 14
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 14
- 150000001408 amides Chemical class 0.000 claims description 13
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 claims description 13
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 150000001298 alcohols Chemical class 0.000 claims description 12
- 229920000098 polyolefin Polymers 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 11
- 239000004305 biphenyl Substances 0.000 claims description 11
- 235000010290 biphenyl Nutrition 0.000 claims description 11
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 10
- 238000006467 substitution reaction Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- 150000001983 dialkylethers Chemical class 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 7
- 229920000570 polyether Polymers 0.000 claims description 7
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims description 7
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 150000001925 cycloalkenes Chemical class 0.000 claims description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- 229930195733 hydrocarbon Natural products 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 6
- 239000012442 inert solvent Substances 0.000 claims description 6
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- IQZPDFORWZTSKT-UHFFFAOYSA-N nitrosulphonic acid Chemical compound OS(=O)(=O)[N+]([O-])=O IQZPDFORWZTSKT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052762 osmium Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 5
- 125000006267 biphenyl group Chemical group 0.000 claims description 5
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- 125000005270 trialkylamine group Chemical group 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 4
- 150000004292 cyclic ethers Chemical class 0.000 claims description 4
- 125000004971 nitroalkyl group Chemical group 0.000 claims description 4
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical group C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 claims description 3
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 150000008378 aryl ethers Chemical class 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 3
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 150000002895 organic esters Chemical class 0.000 claims description 3
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical class C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 claims description 3
- 150000005846 sugar alcohols Polymers 0.000 claims description 3
- 125000000229 (C1-C4)alkoxy group Chemical group 0.000 claims description 2
- NVJUHMXYKCUMQA-UHFFFAOYSA-N 1-ethoxypropane Chemical compound CCCOCC NVJUHMXYKCUMQA-UHFFFAOYSA-N 0.000 claims description 2
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000005702 oxyalkylene group Chemical group 0.000 claims 4
- 229910052707 ruthenium Inorganic materials 0.000 claims 4
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 claims 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims 2
- 125000003545 alkoxy group Chemical group 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 2
- 150000002815 nickel Chemical group 0.000 claims 2
- 150000003623 transition metal compounds Chemical class 0.000 claims 2
- OPIYWIOPMKFADN-UHFFFAOYSA-N C1(=CC=CC=C1)Cl.[Ni].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical group C1(=CC=CC=C1)Cl.[Ni].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 OPIYWIOPMKFADN-UHFFFAOYSA-N 0.000 claims 1
- 239000013522 chelant Substances 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 125000003518 norbornenyl group Chemical class C12(C=CC(CC1)C2)* 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 21
- 239000004711 α-olefin Substances 0.000 abstract description 9
- 230000000379 polymerizing effect Effects 0.000 abstract description 3
- 239000002685 polymerization catalyst Substances 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 description 43
- 238000006243 chemical reaction Methods 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- ZSKGQVFRTSEPJT-UHFFFAOYSA-N pyrrole-2-carboxaldehyde Chemical class O=CC1=CC=CN1 ZSKGQVFRTSEPJT-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 239000000654 additive Substances 0.000 description 13
- 230000000996 additive effect Effects 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 9
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229920001577 copolymer Polymers 0.000 description 7
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical group C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 125000002091 cationic group Chemical group 0.000 description 5
- 238000007334 copolymerization reaction Methods 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 125000002524 organometallic group Chemical group 0.000 description 5
- 229910052720 vanadium Inorganic materials 0.000 description 5
- FEJUGLKDZJDVFY-UHFFFAOYSA-N 9-borabicyclo(3.3.1)nonane Chemical compound C1CCC2CCCC1B2 FEJUGLKDZJDVFY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001624 naphthyl group Chemical group 0.000 description 4
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 3
- HCFAJYNVAYBARA-UHFFFAOYSA-N 4-heptanone Chemical compound CCCC(=O)CCC HCFAJYNVAYBARA-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000002837 carbocyclic group Chemical group 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002574 poison Substances 0.000 description 3
- 231100000614 poison Toxicity 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 2
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 2
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- 101100010897 Arabidopsis thaliana ECT4 gene Proteins 0.000 description 2
- 101100420683 Drosophila melanogaster Sarm gene Proteins 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- 239000004831 Hot glue Substances 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 229920005603 alternating copolymer Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- KQIADDMXRMTWHZ-UHFFFAOYSA-N chloro-tri(propan-2-yl)silane Chemical compound CC(C)[Si](Cl)(C(C)C)C(C)C KQIADDMXRMTWHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HOMQMIYUSVQSHM-UHFFFAOYSA-N cycloocta-1,3-diene;nickel Chemical compound [Ni].C1CCC=CC=CC1.C1CCC=CC=CC1 HOMQMIYUSVQSHM-UHFFFAOYSA-N 0.000 description 2
- KSMVZQYAVGTKIV-UHFFFAOYSA-N decanal Chemical compound CCCCCCCCCC=O KSMVZQYAVGTKIV-UHFFFAOYSA-N 0.000 description 2
- 230000005595 deprotonation Effects 0.000 description 2
- 238000010537 deprotonation reaction Methods 0.000 description 2
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 2
- 229910000071 diazene Inorganic materials 0.000 description 2
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- MMXKVMNBHPAILY-UHFFFAOYSA-N ethyl laurate Chemical compound CCCCCCCCCCCC(=O)OCC MMXKVMNBHPAILY-UHFFFAOYSA-N 0.000 description 2
- ZOCHHNOQQHDWHG-UHFFFAOYSA-N hexan-3-ol Chemical compound CCCC(O)CC ZOCHHNOQQHDWHG-UHFFFAOYSA-N 0.000 description 2
- AOGQPLXWSUTHQB-UHFFFAOYSA-N hexyl acetate Chemical compound CCCCCCOC(C)=O AOGQPLXWSUTHQB-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 150000002828 nitro derivatives Chemical class 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- WXHIJDCHNDBCNY-UHFFFAOYSA-N palladium dihydride Chemical compound [PdH2] WXHIJDCHNDBCNY-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 239000004416 thermosoftening plastic Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- WJTCHBVEUFDSIK-NWDGAFQWSA-N (2r,5s)-1-benzyl-2,5-dimethylpiperazine Chemical compound C[C@@H]1CN[C@@H](C)CN1CC1=CC=CC=C1 WJTCHBVEUFDSIK-NWDGAFQWSA-N 0.000 description 1
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1 -dodecene Natural products CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 1
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- FOZVXADQAHVUSV-UHFFFAOYSA-N 1-bromo-2-(2-bromoethoxy)ethane Chemical compound BrCCOCCBr FOZVXADQAHVUSV-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ARNKHYQYAZLEEP-UHFFFAOYSA-N 1-naphthalen-1-yloxynaphthalene Chemical compound C1=CC=C2C(OC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ARNKHYQYAZLEEP-UHFFFAOYSA-N 0.000 description 1
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- GKSPIKYEYHFEIS-UHFFFAOYSA-N 2-(1h-pyrrol-2-yl)phenol Chemical compound OC1=CC=CC=C1C1=CC=CN1 GKSPIKYEYHFEIS-UHFFFAOYSA-N 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 description 1
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 101100010896 Arabidopsis thaliana ECT3 gene Proteins 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- YWIZAKRBNSCDEQ-UHFFFAOYSA-M Cl[Ni]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 Chemical compound Cl[Ni]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 YWIZAKRBNSCDEQ-UHFFFAOYSA-M 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004820 Pressure-sensitive adhesive Substances 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 150000004705 aldimines Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229920005601 base polymer Polymers 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
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QXJJQWWVWRCVQT-UHFFFAOYSA-K calcium;sodium;phosphate Chemical compound [Na+].[Ca+2].[O-]P([O-])([O-])=O QXJJQWWVWRCVQT-UHFFFAOYSA-K 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000022261 cerebral cortex tangential migration using cell-cell interactions Effects 0.000 description 1
- 238000010516 chain-walking reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- MNKYQPOFRKPUAE-UHFFFAOYSA-N chloro(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 MNKYQPOFRKPUAE-UHFFFAOYSA-N 0.000 description 1
- LLYBHTUGIHXUKO-UHFFFAOYSA-N chlorobenzene nickel Chemical compound [Ni].ClC1=CC=CC=C1 LLYBHTUGIHXUKO-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 150000003997 cyclic ketones Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- DCZFGQYXRKMVFG-UHFFFAOYSA-N cyclohexane-1,4-dione Chemical compound O=C1CCC(=O)CC1 DCZFGQYXRKMVFG-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000022244 formylation Effects 0.000 description 1
- 238000006170 formylation reaction Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002641 lithium Chemical class 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- CPRRHERYRRXBRZ-SRVKXCTJSA-N methyl n-[(2s)-1-[[(2s)-1-hydroxy-3-[(3s)-2-oxopyrrolidin-3-yl]propan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]carbamate Chemical compound COC(=O)N[C@@H](CC(C)C)C(=O)N[C@H](CO)C[C@@H]1CCNC1=O CPRRHERYRRXBRZ-SRVKXCTJSA-N 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- AFFLGGQVNFXPEV-UHFFFAOYSA-N n-decene Natural products CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002848 norbornenes Chemical class 0.000 description 1
- YYZUSRORWSJGET-UHFFFAOYSA-N octanoic acid ethyl ester Natural products CCCCCCCC(=O)OCC YYZUSRORWSJGET-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- DMDPGPKXQDIQQG-UHFFFAOYSA-N pentaglyme Chemical compound COCCOCCOCCOCCOCCOC DMDPGPKXQDIQQG-UHFFFAOYSA-N 0.000 description 1
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 1
- HPUOAJPGWQQRNT-UHFFFAOYSA-N pentoxybenzene Chemical compound CCCCCOC1=CC=CC=C1 HPUOAJPGWQQRNT-UHFFFAOYSA-N 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- BOTNYLSAWDQNEX-UHFFFAOYSA-N phenoxymethylbenzene Chemical group C=1C=CC=CC=1COC1=CC=CC=C1 BOTNYLSAWDQNEX-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000001321 pyrrole-3,4-diyl group Chemical group N1C=C(C(=C1)*)* 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000012748 slip agent Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 125000005425 toluyl group Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 150000003738 xylenes Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 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
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
-
- 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
- C07C2/36—Catalytic processes with hydrides or organic compounds as phosphines, arsines, stilbines or bismuthines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/335—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/12—Olefin polymerisation or copolymerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/12—Olefin polymerisation or copolymerisation
- B01J2231/122—Cationic (co)polymerisation, e.g. single-site or Ziegler-Natta type
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/20—Olefin oligomerisation or telomerisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
-
- 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
- C07C2531/24—Phosphines
-
- 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
Definitions
- the present invention is directed to organometallic catalysts and catalyst compositions useful in the oligomerization or polymerization of alpha-olefins alone or in combination with functionalized olefins, certain bidentate ligand compounds useful in providing the subject catalysts, processes of forming the bidentate ligand compounds and catalysts therefrom, processes of forming olefin oligomers and polymers utilizing the subject catalysts, and catalyst compositions and the oligomers and polymers formed therefrom.
- the polyolefin industry has relied on various catalyst and initiator systems.
- the polymerization of ethylene and other non-polar 1-olefins has been commonly accomplished using organometallic Ziegler-Natta coordination-type catalysts, chromium catalysts, other early transition metal catalysts as well as free-radical type initiators.
- organometallic Ziegler-Natta coordination-type catalysts chromium catalysts, other early transition metal catalysts as well as free-radical type initiators.
- the array of catalysts available provides different approaches to the manufacture of polyolefins with differing physical and mechanical properties, these catalysts are highly susceptible to a range of substances which poison or deactivate the catalyst's activity. It is well known that even trace amounts of oxygen, carbon monoxide, acetylene or water causes deactivation.
- catalyst deactivation is caused by organic compounds having oxygen donor groups such as ethers, esters, alcohols, or ketones .
- organic compounds having oxygen donor groups such as ethers, esters, alcohols, or ketones .
- Industrial application of these organometallic catalysts requires careful and elaborate measures to assure the absence of such poisons . Because these catalysts are easily poisoned, they tend to form low molecular weight materials, can not be used to provide copolymerization of ethylene with an oxygenated functional monomer, such as an ester, acid or ether functionalized olefin, and generally may produce highly branched polymer products.
- U.S. Patents 4,310,716; 4,382,153; 4,293,727; 4,301,318; and 4,293,502 each disclose late transition metal (e.g. Ni) complexes which provide low molecular weight oligomers of ethylene.
- late transition metal e.g. Ni
- polymerization of ethylene has been successfully shown using complexes based on phosphorus ylide ligands in Patent U.S. 4,537,982 as well as in U.S. Patents
- EP 94/304642 and EP 94/630910 disclose that Lewis base, such as dialkyl ether, substantially terminates olefin polymerization by a single-site catalyst composition composed of a metallocene compound and partially hydrolyzed aluminum alkyl compound (aluminoxane) .
- Lewis base such as dialkyl ether
- a metallocene compound substantially terminates olefin polymerization by a single-site catalyst composition composed of a metallocene compound and partially hydrolyzed aluminum alkyl compound (aluminoxane) .
- an unsaturated Lewis base e.g., vinyl ether, either reacts with the cationic late transition metal catalysts to destroy their activity or causes reduction of the resultant polymer molecular weight.
- a catalyst for the oligomerization and polymerization of olefins, in particular ethylene which provides a substantially linear (low degree of branching) product. It is also highly desired to provide a nonionic catalyst which can provide the linear polymer product. It is still further desired to provide a nonionic catalyst which is capable of providing a product of high molecular weight which is substantially linear and, optionally, which is capable of promoting copolymerization of olefin and functionalized olefin monomer units.
- a catalyst composition composed of a non-ionic catalyst in combination with an adjunct agent and/or a Lewis base which is capable of providing a product of high molecular weight which is substantially linear and, optionally, which is capable of promoting copolymerization of olefin and functionalized olefin monomer units.
- the present invention is directed to certain late transition metal pyrrolaldimine chelates as olefin oligomerization or polymerization catalysts, to the bidentate ligand compounds of substituted pyrrolaldimine which are precursors for said catalysts, to catalyst compositions composed of said pyrrolaldimine chelates in combination with an adjunct agent and/or a Lewis base, the methods of forming said precursor compounds and said catalysts, and the method of polymerizing olefin monomers, especially ethylene, as well as copolymerization of olefin and functionalized olefin monomers .
- the present invention provides a process for polymerizing olefin monomers, in particular ethylene, in the presence of catalysts taken from the selected family of pyrrolaldimine late transition metal chelates and to catalyst compositions composed of said pyrrolaldimine chelates in combination with an adjunct agent and/or a Lewis base, to produce olefin oligomers or polyolefins which can be either substantially linear and have a weight average molecular weight of at least 150.
- pyrrolaldimine late transition metal chelates can provide catalyst systems for the oligomerization or homopolymerization of ethylene and copolymerization of ethylene and functionalized olefins to provide substantially linear polymer products.
- the catalyst of the present invention can be represented by the following general formula:
- R 1 represents a hydrogen atom, C--C.. alkyl (preferably C j -C j and most preferably tert-butyl) ; aryl, such as phenyl , biphenyl , terphenyl , naphthyl , anthracyl , phenanthracyl and the like; substituted aryl wherein the substitution group is selected from C x -C 6 alkyl, perfluoroalkyl , nitro, sulfonate, or halo group; arylalkyl, such as toluyl and the like; halo, such as chloro, bromo, and the like; nitro group; sulfonate group or siloxyl (-OSiA 3 where A is selected from phenyl or C x -C 4 alkyl such as isopropyl or butyl and the like) ; or a hydrocarbyl terminated oxyhydrocarbylene group,
- R 1 represents a C j -C ⁇ (preferably a C ⁇ C j ) hydrocarbyl group such as an alkyl or an unsubstituted or substituted aryl group, such as phenyl, biphenyl , naphthyl and the like, alone or substituted with one or more C j -C,.
- R 1 is preferably a steric bulky group selected from aryl, substituted aryl or a branched C 3 -C 6 alkyl group and most preferably, phenyl, anthracyl , phenanthracyl, terphenyl or t-butyl :
- R 2 represents hydrogen atom, aryl, substituted aryl, C 1 -C 11 alkyl, halogen atom or R 1 and R 2 can, together provide a hydrocarbylene or substituted hydrocarbylene which forms a carbocyclic ring which may be non-aromatic or aromatic;
- R 2 is preferably hydrogen or, taken with R 1 as a carbocyclic ring group:
- R 3 represents hydrogen:
- R 4 represents hydrogen atom, a C 1 -C 11 alkyl, an aryl group such as a phenyl or a substituted aryl group such as 2 , 6-dimethylphenyl or the like, and is preferably selected from hydrogen,
- R 5 represents a C ⁇ C ⁇ alkyl group (preferably a C 4 -C 8 alkyl group) such as methyl, ethyl, propyl , t-butyl, and the like, a cycloalkyl group such as cyclohexyl and the like, an aryl group, such as phenyl, biphenyl, naphthyl or the like or a substituted aryl having one or both ortho positions of the aromatic group (especially the phenyl group) substituted with a C 1 -C 4 alkyl and/or the para position (with respect to the N-R 5 bond) substituted with a hydrogen atom, nitro, trifluoromethyl , halogen atom, methoxy, or C 1 -C 4 alkyl or fused or unfused aryl, sulfonate, or a hydrocarbyl terminated oxyhydrocarbylene group, -(BO) z R 7 as defined in R 1 above.
- R 5 is preferably a t-butyl or a cycloalkyl such as adamantyl , or a 2,6-di(C 1 - C 4 alkyl)phenyl group and most preferably 2 , 6-diisopropyl phenyl or 2 , 6-diisopropyl-4-nitrophenyl :
- R 1 and R 5 can, together, form an oxyhydrocarbylene chain, e.g., -(B0) m B- wherein each B independently represents a C 1 -C 3 alkylene group or an arylene group and m is an integer of from 2 to 5 preferably 3-5; n is an integer of 0 or 1 ; R 6 represents, when n is 1, an unsubstituted or substituted aromatic group, such as phenyl which is preferably unsubstituted, a C j -C ⁇ alkyl (preferably a C 1 -C 5 alkyl and most preferably methyl) , a hydrogen atom or halogen atom (preferably chloro or bromo) , or when n is 0, R 6 repesents an allyl or substituted allyl group wherein the substitution can be selected from a halogen atom, a nitro group or a sulfonate group:
- L represents a coordination ligand such as triphenylphosphine, tri (C ⁇ C g alkyl) phosphine, tricycloalkyl phosphine, diphenyl alkyl phosphine, dialkyl phenylphosphine, trialkylamine, arylamine such as pyridine, C 2 -C 20 alkene such as octene, decene, dodecene, alkyl and the like, a substituted alkene wherein the substitution group may be selected from a halogen atom (preferably chloro) , an ester group, a C 1 -C 4 alkoxy group, an amine group (-NR 2 wherein each R is hydrogen, or a C ⁇ C..
- a coordination ligand such as triphenylphosphine, tri (C ⁇ C g alkyl) phosphine, tricycloalkyl phosphine, diphenyl alkyl phosphine
- M represents one of the transition metals, that is a Group VIII or Group IV transition metal selected from Fe, Co, Ni , Ru, Rh, Pd, Os, Ir, Pt in the +2 oxidation state or Ti, Zr, Hf in the +4 oxidation state and preferably a late transition metal selected from iron, cobalt, nickel or palladium and most preferably either nickel or palladium.
- the present invention provides a catalyst which contains sterically bulky groups both above and below as well as within the plane of orientation with respect to the transition metal of the complex. It is believed, though not meant to be a limitation of the invention, that the steric and electronic configuration of the presently achieved complex provides the following desired characteristics:
- the steric bulk which is within the plane of the transition metal (II) square planar complex may inhibit chain migration processes and thereby cause substantially linear polymerization.
- the steric bulk which is within the plane of the transition metal (II) square planar complex may promote dissociation of the ancillary ligand, L, and thereby result in an increase in the number of active polymerization sites.
- the catalysts (I) are most preferably those having bulky substituents , such as aryl as, for example, anthracenyl, phenanthracenyl, or terphenyl and the like, and substituted aryl groups such as 2 , 6-diisopropylphenyl and the like, in the R 1 and/or R 5 positions.
- the substitution group may be a C 1 -C 4 alkyl and/or an electron withdrawing group such as N0 2 , halogen, sulfonate (S0 3 ⁇ ), sulfonyl ester (S0 2 R) , carboxyl (COO " ) , or perfluoroalkyl group .
- the catalyst (I) of the present invention may further contain an ether or polyether group as part of structure of the subject pyrrolaldimine.
- the incorporation of such group (s) can be made at R 1 and/or at R 5 or as an oxyhydrocarbylene chain between R 1 and R 5 such that a hydrocarbon moiety of said oxyhydrocarbylene is directly bonded to the nitrogen atom at R 5 and to the ring at R 1' .
- Such catalysts provide enhanced catalytic activity over catalyst (I) absent said group (s) and do not require the use of adjunct agent or Lewis base additive, as described herein below.
- Synthesis of the precursor ligands can be achieved by reacting the appropriate pyrrole-2-carboxaldehyde (having desired substituent groups on the pyrrole ring) with a primary amine (R 5 NH 2 ) , such as 2,6- diisopropylaniline and the like.
- a primary amine R 5 NH 2
- the reaction can be carried out in solution with an inert solvent, such as a C 1 -C 5 alcohol (e.g. methanol, ethanol or the like) or aromatic compound (e.g., benzene, toluene or the like) .
- the reaction is preferably carried out at temperatures of from about 15°C to 80°C (most preferably at from 15 to 25°C) for a period of from one to twenty hours (most preferably from 10 to 12 hours) .
- the reaction is carried out at atmospheric pressure and in the presence of a catalytic amount of an organic acid, such as toluenesulfonic acid to provide the pyrrole-2- carboxaldehyde ligand (IV) according to the equation below:
- the bidentate ligand (IV) can be deprotonated using a strong alkali metal alkyl, such as a lithium alkyl (e.g., n-butyl Li) to form the alkali metal (e.g., lithium) salt (V) .
- a strong alkali metal alkyl such as a lithium alkyl (e.g., n-butyl Li) to form the alkali metal (e.g., lithium) salt (V) .
- the deprotonation is carried out at low temperatures such as about 0° to 30°C (preferably 0° to 10°C) at normal atmospheric pressure and in the presence of an inert solvent, such as tetrahydrofuran, dialkyl ether, C 5 -C 10 hydrocarbon, dioxane and the like.
- the reaction normally is completed in a short period, such as from about 5 to 30 minutes.
- the lithium salt (V) can then be reacted with a late transition metal coordination compound of the type R ⁇ (L) 2 MY, wherein each R 6 and L are as defined above, and Y represents a halogen atom, as for example bis ( triphenylphosphine) phenyl nickel chloride, and the like.
- This reaction may be conducted in an inert solvent, such as tetrahydrofuran, dialkyl ether, C 5 -C 10 hydrocarbon, and the like at temperatures of from about 10 to 90°C (preferably 10° to 30°C) for periods of from one to fifteen hours (normally 10-15 hours) to provide catalyst (I) as follows:
- the R 1 may be hydrogen but preferably is a bulky group which provides a steric shield of the transition metal's equatorial face by being well- positioned in the plane of the transition metal complex as well as some bulk in the axial face.
- R 1 is preferably an aryl, such as phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, or phenanthracenyl , a nitro-substituted aryl, or a bulky alkyl, such as a tert- butyl group.
- Such substituted pyrrole carboxaldehydes (II) are readily formed by formylation of an appropriately substituted pyrrole. This is conventionally accomplished by reacting the substituted pyrrole with an aldehyde source, such as formaldehyde
- R 1 may be selected from sterically bulky groups other than hydrocarbyl groups as, for example, siloxane groups. Such substitution can be readily accomplished by using a 5-hydroxy-2- carboxaldehyde pyrrole as the starting material II to form the Schiff base aldimine compound IV.
- the hydroxyl group can then be converted to a siloxy group by reaction with the appropriate aryl, alkyl or mixed substituted silyl halide as, for example triisopropyl silyl chloride, diphenyl-t-butyl silyl chloride, triphenyl silyl chloride and the like.
- Deprotonation and reaction with transition metal coordination compound of the type R 6 (L) 2 MY provides the desired catalyst compound I in the manner described above .
- R 1 and R 5 may each independently be selected from a hydrocarbyl terminated oxyhydrocarbylene containing group.
- Such groups may be represented as -(BO) z R 7 wherein each B is independently selected from a C 1 -C 4 (preferably a C 2 -C 3 ) alkylene group or an arylene group and R 7 represents a C j -C ⁇ (preferably C 1 -C 3 ) hydrocarbyl group such as alkyl, an aryl, an alkaryl , or an aralkyl group and z represents an integer of 1 to 4.
- Such oxyhydrocarbylene group may be made part of compound I by by mono-alkylation of 2- (2-hydroxyphenyl) -pyrrole or the N-protected 2-hydrophenylpyrrole with bromoethyl ether, followed by formayltion of the pyrrole ring adjacent to the nitrogen, followed by imine formation and finally metallation with R 6 (L) 2 MY in the manner described previously.
- substituted pyrrolaldimine complexes (I) of late transition metals described above provide a catalytic composition having catalytic activity for olefin (e.g., ethylene) oligomerization or polymerization and provide substantially linear product having a low degree of branching.
- olefin e.g., ethylene
- These complexes are neutral compounds and, as such do not require the presence of organo aluminum or hydrolyzed organo aluminum compounds or other reducing agent to cause activation of the complex towards olefin insertion reaction and polymerization.
- organo aluminum and hydrolyzed organo aluminum compounds such as methyl alumoxane or trialkyl aluminum compounds and the like, may be present
- the subject catalysts (I) may be used as the sole catalyst component of the catalyst composition (this is especially acceptable when the bulky group R 1 is large such as phenyl, biphenyl, terphenyl, anthracenyl, phenanthracenyl , nitro-substituted aryl or the like) or may be used in combination with an adjunct agent and/or a Lewis base.
- the adjunct agent comprises known phosphine sponge material capable of facilitating phosphine (ligand L) dissociation and trapping of free phosphine.
- Such catalyst composition adjunct agents are, for example, bis (cyclooctadiene) -nickel, tris (pentafluorophenyl) boron, 9-borabicyclo [3.3.1] nonane (9-BBN) , methyl iodide and the like.
- the subject catalyst provides an enhanced catalyst composition when combined with a Lewis base as, for example ethers, esters, aldehydes, ketones, alcohols, amides, organo carbonates, organonitro compounds, or mixtures thereof and even water. It is commonly believed that organometallic catalysts should be combined with Lewis acid compounds to provide effective catalyst systems and that water acts as a poison to such catalysts. In contrast to the present unexpected finding, it has been previously deemed important to use conventional single site catalysts, such as metallocene catalysts, in the absence of moisture or other oxygenated compounds in order to provide an effective catalyst system.
- a Lewis base as, for example ethers, esters, aldehydes, ketones, alcohols, amides, organo carbonates, organonitro compounds, or mixtures thereof and even water. It is commonly believed that organometallic catalysts should be combined with Lewis acid compounds to provide effective catalyst systems and that water acts as a poison to such catalysts.
- conventional single site catalysts such as metallocene catalysts
- the Lewis base additives found useful in forming a catalyst composition with the catalyst of compound I or V comprise ether compounds, such as dialkyl ethers where each alkyl group is independently selected from a C x -C 18 alkyl, preferably a C 1 -C 5 alkyl group as, for example,
- diethyl ether methyl ethyl ether, diisopropyl ether, ethyl propyl ether, dibutyl ether and the like; vinyl ethers such as ethyl vinyl ether and the like; aryl ethers as, for example, dibenzyl ether, diphenyl ether, dinaphthyl ether and the like, mixed ethers as, for example, amyl phenyl ether, methyl benzohydryl ether, benzyl phenyl ether, anisole, phenetole and the like.
- the ether additive may also be selected from cyclic ethers as, for example, tetrahydrofuran, dioxane-1,4, dioxane-1,3, crown ethers such as 18-crown-6, 14-crown-5, 12-crown-4 and the like as well as polyethers such as dimethyoxyethane, diglyme, triglyme, pentaglyme or polyoxyalkylenes as, for example, polyoxyethylene (preferably lower molecular weight polymers which are miscible in the polymerization solvent used) .
- cyclic ethers as, for example, tetrahydrofuran, dioxane-1,4, dioxane-1,3, crown ethers such as 18-crown-6, 14-crown-5, 12-crown-4 and the like as well as polyethers such as dimethyoxyethane, diglyme, triglyme, pentaglyme or polyoxyalkylenes as, for example, polyoxy
- ethers especially the alkyl and/or aryl group containing ethers and cyclic ethers described above, and most preferably dialkyl ether (e.g., diethyl ether) and low molecular weight polyethers (e.g., dimethyoxyethane) have been found to be effective solvents or co-solvents for use in the polymerization process when the subject catalyst of compound I or compound V is used, as described herein below.
- dialkyl ether e.g., diethyl ether
- low molecular weight polyethers e.g., dimethyoxyethane
- the Lewis base may be selected from an organic ester represented by the formula
- each R 9 is independently selected from a C 1 -C 11 alkyl group, preferably a C ⁇ C j alkyl group as, for example, ethyl acetate, propyl acetate, hexyl acetate, ethyl butyrate, propyl butyrate, ethyl caproate, ethyl caprylate, ethyl laurate and the like.
- aldehydes and ketones have been found useful as a Lewis base additive in forming the subject catalyst composition. They may be represented by the formula
- R represents a C.-C 12 hydrocarbyl selected from unsubstituted or substituted (e.g., carbonyl) alkyl, aryl, alkaryl or aralkyl groups and R 11 represents a hydrogen atom or an R 10 group, which is independently selected.
- the aldehyde or ketone may be selected from acetone, propanone, butyrone, 4-heptanone, 2 , 4-pentanedione and the like, as well as cyclic ketones such as cyclohexanone, 1, 4-cyclohexanedione and the like, or an aldehyde such as acetaldehyde, capraldehyde, valeraldehyde and the like.
- an alcohol can be used as the Lewis base additive in forming the subject catalyst composition.
- They may be selected from monohydric or polyhydric alcohols including, for example, alcohols having hydrocarbyl moiety composed of a C--C 12 (preferably C 1 -C 3 ) alkyl, aryl (e.g., phenyl or benzyl), alkaryl and aralkyl groups .
- alcohols include methanol, ethanol, propanol, isopropanol, butanol, t- butanol, 2-pentanol, 3-hexanol, glycol, 1,2,3- propanetriol, phenol, phenethyl alcohol, para-methyl phenol and the like.
- Amides can be used as the Lewis base additive in forming the subject catalyst composition.
- the amides may be represented by the formula
- R 12 and R each independently represent a C j -C ⁇ hydrocarbyl
- R 14 represents hydrogen or a C 1 -C 11 hydrocarbyl
- R 13 and R 14 are, preferably, independently selected from a C x -C 3 alkyl group.
- Nitroalkanes and nitroaromatics have also been found to be useful as a Lewis base additive in forming the subject catalyst composition.
- the nitroalkanes may be a mono (preferred) or poly nitro compound formed with a C j - C 1X (preferably a C ⁇ C.,) alkyl group.
- the aromatic nitro should be a mono nitro compound such as nitrobenzene and the like.
- the subject catalyst composition may contain small amounts of water and that the presence of water does not destroy the activity of the catalyst of the subject invention.
- the presently described catalyst can be used in the presence of small amounts of moisture to provide a catalyst composition which can remain active in the polymerization or oligomerization of olefins or mixtures of olefins and a functional olefin monomer (s) .
- the amount of the Lewis base (except water) additive can be substantially any amount desired with from 10° to 10 4 times the amount of compound I or V on a molar base being preferred and, most preferred, from 10 1 to 10 3 times the molar amount of catalyst when ether is the Lewis base used and from 10° to 10 2 times the molar amount of catalyst with respect to other Lewis bases.
- the molar ratio of water to catalyst can range from 0 to about 10 2 , preferably, from 0 to 10 1 .
- This invention concerns processes for making polymers, comprising, contacting the subject catalyst composition with one or more selected olefins or
- the subject catalyst composition is composed of the subject transition metal containing compound (I) described above or a combination of compound (V) and transition metal complex, as described herein below.
- the "polymerization process” described herein (and the polymers made therein) is defined as a process which produces a polymer or oligomer with a weight average molecular weight (Mw) of at least about 150, preferably at about 1000.
- the subject catalysts may generally be written as
- M is Ni(II) or Pd(II) .
- the catalytic polymerization of the present invention can be carried by contacting one or more selected olefins or cycloolefins alone or optionally with a functional olefin monomer, as described above with a catalyst composition composed of one or more bidentate ligand (V) described above in combination with a transition metal (M) organic complex.
- a catalyst composition composed of one or more bidentate ligand (V) described above in combination with a transition metal (M) organic complex.
- the ligand (V) and complex should be used in about a 1:1 molar ratio.
- the bidentate ligand V is combined with a transition metal organic complex of the formula R 6 (L) 2 MY in about a 1:1 molar ratio in the presence of olefin and/or cycloolefin alone or optionally with a functional olefin monomer.
- the catalyst composition composed of ligand (V) and transition metal organic complex may further contain a phosphine sponge and/or Lewis base additive, such as those described above, or an organo aluminum or hydrolyzed organo aluminum compound or mixtures thereof as described above with respect to catalyst compositions composed of compound (I) which have a halogen as R 6 .
- R 1 and R 5 are each independently a sterically bulky hydrocarbyl. In one form it is especially preferred that R 1 and R 5 are each independently aryl or substituted aryl groups. In another form, it is preferred that R 1 and/or R 5 be independently selected from a hydrocarbyl terminated oxyhydrocarbylene containing group, as described above. It is preferred that when R 5 is a substituted aryl the 4 position of the aryl (with respect to the N-bond) be either hydrogen or nitro.
- R 2 , R 3 and R 4 are hydrogen or methyl, unless R 2 is, when taken together with R 1 , a C 4 -C 10 carbocyclic group which may or may not be aromatic.
- R and R 5 are biphenyl, terphenyl , anthracenyl, phenanthracenyl, 2 , 6-diisopropylphenyl , 2,6- dimethylphenyl , 2 , 6-diethylphenyl , 4-methylphenyl , 2- isopropyl-6-methylphenyl, phenyl, 2 , 4 , 6-trimethylphenyl, 2-t-butylphenyl , 2-t-butyl-6-methylphenyl , 2,6- diisopropyl-4-nitrophenyl , and 10-nitroanthracenyl .
- the structure of the ligand associated with compound I or compound V may influence the polymer microstructure and polymer molecular weight.
- R 1 be a bulky aryl or substituted aryl group. Complexes with R 1 of this type generally produce higher molecular weight and more linear polymer product for any given set of conditions.
- the liquid phase may include a compound added just as a solvent and/or may include the monomer (s) itself and/or may comprise the Lewis base (especially an ether compound) in the liquid phase at reaction conditions.
- the molar ratio of adjunct to compound I or V is from about 0.001:1 to 15:1, preferably about 0.01:1 to about 8 : 1 and most preferably from 0.1:1 to 3:1.
- the temperature at which the polymerization is carried out is from about -100°C to about +200°C, preferably about -20°C
- the pressure at which the polymerization is carried out is not critical, atmospheric pressure to about 100 MPa, or more, being a suitable range.
- the pressure may affect the yield, molecular weight and linearity of the polyolefin produced, with increased pressure providing higher molecular weight, more linear oligomer or polymer product.
- Preferred alpha-olefins and cyclic olefins in the polymerization are one or more of ethylene, propylene, 1- butene, 2-butene, 1-hexene, 1-octene, 1-pentene, 1- tetradecene, norbornene, and cyclopentene, with ethylene, propylene, cyclopentene and norbornene being more preferred.
- Ethylene (alone as a monomer) is especially preferred.
- the polymerization may be run in the presence of various liquids.
- the solvent in which the polymerization may be conducted can be selected from (i) the monomer (s), per se or (ii) any organic compound which is liquid under the reaction conditions and is substantially inert to the reactants and product, or (iii) a Lewis base additive (except water which, when used, should be present in limited amounts) which is liquid under the reaction conditions, or mixtures thereof. Particularly preferred are aprotic organic liquids or organic ethers or mixtures thereof.
- the catalyst system, monomer (s), and polymer may be soluble or insoluble in these liquids, but obviously these liquids should not prevent the polymerization from occurring. Suitable liquids include alkanes, cycloalkanes , halogenated hydrocarbons, ethers, halogenated aromatic hydrocarbons and aromatic hydrocarbons. Specific useful solvents include hexane,
- the catalyst compositions of the present invention cause polymerization of one or more alpha-olefin, with functional olefins such as those described herein above.
- carbon monoxide When carbon monoxide is used as a comonomer, it forms alternating copolymers with the various alpha-olefins .
- the polymerization to form the alternating copolymers is carried out with both CO and the olefin simultaneously present in the process mixture, and in the presence of the present catalyst composition.
- the catalyst of the present invention may also be supported on a solid material (as opposed to just being added as a suspended solid or in solution) , for instance on silica gel, zeolites, crosslinked organic polymers, such as styrene-divinylbenzene copolymer and the likes thereof.
- a solid material as opposed to just being added as a suspended solid or in solution
- silica gel silica gel
- zeolites zeolites
- crosslinked organic polymers such as styrene-divinylbenzene copolymer and the likes thereof.
- the period of time during which the catalyst of compound I or the catalyst composition formed from compound V, remains active is influenced by the particular ligand structure, polymerization temperature, or type of Lewis base present.
- Catalyst lifetime is long when Lewis base such as ether is present, co-catalyst adjunct is absent, and R 1 is a bulky aryl or substituted aryl group .
- the polymer product of the present invention is a copolymer of functionalized group containing monomer, the functional group may be further used to cross-link the polymer.
- copolymers of an olefinic carboxylic acid or olefinic ester and an alpha-olefin may be crosslinked by various methods known in the art, depending on the specific monomers used to make the polymer.
- carboxyl or ester containing polymers may be crosslinked by reaction with diamines or with diisocyanates to form bisamides .
- the carboxyl groups may also be neutralized with a monovalent or divalent metal containing base (e.g., NaOH, CaO) to form ionomeric or pseudo-crosslinked polyolefin copolymer.
- the resultant polymers formed according to the present invention may have varying degrees of branching in the polymer.
- Branching may be determined by NMR spectroscopy (see the Examples for details), and this analysis can determine the total number of branches, the branching distribution and to some extent the length of the branches.
- the amount of branching is expressed as the number of branches per 1000 of the total methylene (- CH 2 -) groups in the polymers, with one exception. Methylene groups that are in an ester grouping, i.e., - C0 2 R; a ketone group, i.e., -C(0)R are not counted as part of the 1000 methylenes .
- the polymers formed with the aid of the present catalyst have low branching of from about 10 to 150 branches per 1000, and normally from about 20 to 120 branches per 1000, for example, ethylene homopolymers have a branch content of about 0 to about
- Zl 150 branches per 1000 methylene groups, preferably about
- the polymers formed by the present invention may be mixed with various additives normally added to elastomers and thermoplastics [see EPSE (below), vol. 14, p. 327- 410] which teaching is incorporated herein by reference.
- additives normally added to elastomers and thermoplastics such as carbon black, glass fiber, minerals such as silica, clay, mica and talc, glass spheres, barium sulfate, zinc oxide, carbon fiber, and aramid fiber or fibrids, may be used.
- Antioxidants , antiozonants , pigments, dyes, slip agents, antifog agents, antiblock agents, delusterants , or compounds to promote crosslinking may be added.
- Plasticizers such as various hydrocarbon oils may also be used.
- the polymers formed by the present invention may be used for one or more of the applications listed below. In some cases a reference is given which discusses such uses for polymers in general. All of these references are hereby included by reference.
- U refers to W. Gerhartz, et al . , Ed., Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed. VCH Verlagsgesellschaft mBH, Weinheim, for which the volume and page number are given
- ECT3 refers to the H. F. Mark, et al . , Ed., Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., John Wiley & Sons, New York
- ECT4 refers to the J. I. Kroschwitz, et al . , Ed., Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed. , John Wiley
- EMT refers to H. F. Mark, et al . , Ed., Encyclopedia of Polymer Science and Technology, 1st Ed. , John Wiley & Sons, New York, for which the volume and
- polyolefins herein are especially useful in blown film applications because of their particular rheological properties (EPSE, vol. 7, p. 88-106). It is preferred that these polymers have some crystallinity .
- the polymers are useful for blown or cast films or as sheet (see EPSE, vol. 7 p. 88-106; ECT4 , vol. 11, p 843-856; PM, p. 252 and p. 432ff).
- the films may be single layer or multilayer, the multilayer films may include other polymers, adhesives, etc.
- the films may be stretch-wrap, shrink-wrap or cling wrap and may be heat sealable.
- the films are useful for many applications such as packaging foods or liquids, geomembranes and pond liners. It is preferred that these polymers have some crystallinity.
- Extruded films or coextruded films may be formed from these polymers, and these films may be treated, for example by uniaxial or biaxial orientation after crosslinking by actinic radiation, especially electron beam irradiation. Such extruded films are useful for packaging of various sorts.
- the extruded films may also be laminated to other films using procedures known to those skilled in the art.
- the laminated films are also useful for packaging of various sorts .
- the polymers particularly the elastomers, may be used as tougheners for other polyolefins such as polypropylene and polyethylene.
- Tackifiers for low strength adhesives (U, vol. Al , p 235-236) are a use for these polymers. Elastomers and/or relatively low molecular weight polymers are preferred.
- the polymers are useful as base resins for hot melt adhesives (U, vol. Al, p 233-234), pressure sensitive adhesives (U, vol. Al, p 235-236) or solvent applied adhesives.
- Thermoplastics are preferred for hot melt adhesives.
- Base polymer for caulking of various kinds is another use.
- An elastomer is preferred.
- Lower molecular weight polymers are often used.
- Wire insulation and jacketing may be made from any of the polyolefins (see EPSE, vol. 17, p. 828-842).
- elastomers it may be preferable to crosslink the polymer after the insulation or jacketing is formed, for example by free radicals.
- the Li salt of the product from Example I (0.24 g, 0.72 mmol) and bis ( triphenylphosp ine) nickel (phenyl) chloride (0.50 g, 0.73 mmol) in Et 2 0 (20 mL) .
- the reaction was stirred at room temperature for 1 hour. After this time, the reaction was filtered by cannula filtration, and the filtrate was concentrated in vacuo to ⁇ 5 mL .
- Example III 1.8 mM of the catalyst product formed in Example II above was weighed out and introduced into a pressure container under an atmosphere of nitrogen. The container was evacuated and backfilled with ethylene. 80 mL of dry toluene was then cannula transferred into the pressure container. 5 L of toluene solution containing 2 meq. of a phosphine sponge adjunct, bis (cyclooctadiene) -nickel was syringed into the container. Additional ethylene was introduced to raise the pressure to 80 psi at 25°C. The reaction was allowed to proceed with stirring for 40 minutes. After completion of the polymerization, methanol (500 mL) was introduced to terminate the reaction. No precipitate was recovered. The reaction solution was analyzed by gas chromatography using standard analytical techniques . The reaction mixture was found to contain a mixture of C -C hydrocarbons .
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyethers (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9804790A BR9804790A (en) | 1997-03-24 | 1998-02-18 | Catalyst compositions and processes for oligomerization and polymerization of olefins |
EP98908596A EP0917529A4 (en) | 1997-03-24 | 1998-02-18 | Catalyst compositions and processes for olefin oligomerization and polymerization |
JP54569698A JP2002510286A (en) | 1997-03-24 | 1998-02-18 | Catalyst compositions and methods for oligomerizing and polymerizing olefins |
AU66594/98A AU725160B2 (en) | 1997-03-24 | 1998-02-18 | Catalyst compositions and processes for olefin oligomerization and polymerization |
NZ332843A NZ332843A (en) | 1997-03-24 | 1998-02-18 | Pyrrolaldimine transition metal catalyst, compositions and processes for olefin oligomerization and polymerization thereof |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US82253697A | 1997-03-24 | 1997-03-24 | |
US08/822,536 | 1997-03-24 | ||
US09/007,442 US6573345B1 (en) | 1997-03-24 | 1998-01-15 | Catalyst compositions and processes for olefin oligomerization and polymerization |
US09/007,442 | 1998-01-15 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1998042665A1 true WO1998042665A1 (en) | 1998-10-01 |
Family
ID=26676992
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/003175 WO1998042665A1 (en) | 1997-03-24 | 1998-02-18 | Catalyst compositions and processes for olefin oligomerization and polymerization |
Country Status (8)
Country | Link |
---|---|
US (1) | US6573345B1 (en) |
EP (1) | EP0917529A4 (en) |
JP (1) | JP2002510286A (en) |
AU (1) | AU725160B2 (en) |
BR (1) | BR9804790A (en) |
CA (1) | CA2257792A1 (en) |
NZ (1) | NZ332843A (en) |
WO (1) | WO1998042665A1 (en) |
Cited By (51)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999050313A1 (en) * | 1998-03-27 | 1999-10-07 | E.I. Du Pont De Nemours And Company | Polymerization of olefins |
US6103658A (en) * | 1997-03-10 | 2000-08-15 | Eastman Chemical Company | Olefin polymerization catalysts containing group 8-10 transition metals, processes employing such catalysts and polymers obtained therefrom |
US6117959A (en) * | 1998-09-02 | 2000-09-12 | Eastman Chemical Company | Polyolefin catalysts |
WO2000056787A1 (en) * | 1999-03-23 | 2000-09-28 | Cryovac, Inc. | Supported catalysts and olefin polymerization processes utilizing same |
WO2000056781A2 (en) * | 1999-03-23 | 2000-09-28 | Cryovac, Inc. | Linear functionalized copolymer and articles formed thereof |
WO2000056786A1 (en) * | 1999-03-23 | 2000-09-28 | Cryovac, Inc. | Supported catalysts and olefin polymerization processes utilizing same |
US6136743A (en) * | 1996-04-09 | 2000-10-24 | Mitsui Chemicals, Inc. | Olefin polymerization catalyst, olefins polymerization methods, and olefin polymer compositions, and heat molded products |
US6174976B1 (en) | 1998-02-24 | 2001-01-16 | Eastman Chemical Company | Neutral nickel complexes for olefin polymerization |
WO2001018097A1 (en) * | 1999-09-07 | 2001-03-15 | E.I. Du Pont De Nemours And Company | Heat-sealable polyolefins and articles made therefrom |
US6245871B1 (en) | 1997-04-18 | 2001-06-12 | Eastman Chemical Company | Group 8-10 transition metal olefin polymerization catalysts |
JP2001261638A (en) * | 2000-03-14 | 2001-09-26 | Mitsubishi Chemicals Corp | New metal complex compound having ligand having 2, 5- diiminomethylpyrrole skeleton and catalyst which contain the complex compound and is used for polymerizing alpha-olefin |
US6350837B1 (en) | 2000-06-09 | 2002-02-26 | Eastman Chemical Company | Copolymerization of norbornene and functional norbornene monomers |
US6355735B1 (en) | 1999-08-17 | 2002-03-12 | 3M Innovative Properties Company | Semi-interpenetrating polymer network from epoxy monomer and olefin |
US6372682B2 (en) | 1997-03-13 | 2002-04-16 | Eastman Chemical Company | Catalyst compositions for the polymerization of olefins |
US6395668B1 (en) | 1998-12-15 | 2002-05-28 | Basell Technology Company Bv | Catalyst system for olefin polymerization |
US6399724B1 (en) | 1998-04-16 | 2002-06-04 | Mitsui Chemicals, Inc. | Catalyst for olefin polymerization and method of polymerizing olefin |
WO2002064645A2 (en) * | 2001-02-13 | 2002-08-22 | Basf Aktiengesellschaft | Complex compounds and their use in olefin polymerization |
US6451728B1 (en) | 1998-12-11 | 2002-09-17 | Mitsui Chemicals, Inc. | Olefin polymerization catalyst and process for olefin polymerization |
US6506861B2 (en) | 2000-05-31 | 2003-01-14 | E. I. Du Pont De Nmeours And Company | Polymerization of olefins |
US6521724B2 (en) | 2000-03-10 | 2003-02-18 | E. I. Du Pont De Nemours And Company | Polymerization process |
US6521793B1 (en) | 1998-10-08 | 2003-02-18 | Symyx Technologies, Inc. | Catalyst ligands, catalytic metal complexes and processes using same |
US6531424B2 (en) | 1999-12-17 | 2003-03-11 | E. I. Du Pont De Nemours And Company | Polymerization of olefins |
WO2003027130A2 (en) * | 2001-09-25 | 2003-04-03 | Exxonmobil Research And Engineering Company | Transition metal complexes for preparing olefin oligomers |
US6545108B1 (en) | 1999-02-22 | 2003-04-08 | Eastman Chemical Company | Catalysts containing N-pyrrolyl substituted nitrogen donors |
US6559091B1 (en) | 1999-02-22 | 2003-05-06 | Eastman Chemical Company | Catalysts containing N-pyrrolyl substituted nitrogen donors |
US6562751B2 (en) | 2000-03-10 | 2003-05-13 | E. I. Du Pont De Nemours And Company | Polymerization of olefins |
US6562922B1 (en) * | 1999-03-23 | 2003-05-13 | Cryovac, Inc | Vicinal hydroxyl group containing copolymer and articles formed therefrom |
US6579823B2 (en) | 2000-02-18 | 2003-06-17 | Eastman Chemical Company | Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors |
US6593266B1 (en) | 1998-04-16 | 2003-07-15 | Mitsui Chemicals, Inc. | Olefin polymerization catalyst and polymerization process |
US6605677B2 (en) | 2000-02-18 | 2003-08-12 | Eastman Chemical Company | Olefin polymerization processes using supported catalysts |
US6620896B1 (en) | 1999-02-23 | 2003-09-16 | Eastman Chemical Company | Mixed olefin polymerization catalysts, processes employing such catalysts, and polymers obtained therefrom |
US6660677B1 (en) | 1997-03-10 | 2003-12-09 | Eastman Chemical Company | Supported group 8-10 transition metal olefin polymerization catalysts |
US6706891B2 (en) | 2000-11-06 | 2004-03-16 | Eastman Chemical Company | Process for the preparation of ligands for olefin polymerization catalysts |
US6733851B2 (en) | 2001-11-06 | 2004-05-11 | Cryovac, Inc. | Packaging article having heat seal layer containing blend of hyperbranched and semicrystalline olefin polymers |
US6737130B2 (en) | 2001-11-06 | 2004-05-18 | Cryovac, Inc. | Hermetically heat-sealable, pressure-reclosable packaging article containing substantially spherical homogeneous polyolefin |
US6761965B2 (en) | 2001-11-06 | 2004-07-13 | Cryovac, Inc. | Irradiated multilayer film having seal layer containing hyperbranched polymer |
US6800699B2 (en) | 2001-12-17 | 2004-10-05 | Basf Aktiengesellschaft | Process for the production of aqueous polymer dispersions |
US6822062B2 (en) | 1997-03-10 | 2004-11-23 | Eastman Chemical Company | Supported group 8-10 transition metal olefin polymerization catalysts |
US6900278B2 (en) | 2000-07-20 | 2005-05-31 | Basf Aktiengesellschaft | Ligands, complex compounds and their use for polymerising olefins |
US6992153B1 (en) | 1999-03-09 | 2006-01-31 | Basell Polyolefine Gmbh | Multi-stage process for the (CO) polymerization of olefins |
US7056996B2 (en) | 2000-02-18 | 2006-06-06 | E. I. Du Pont De Nemours And Company | Productivity catalysts and microstructure control |
US7094848B2 (en) | 2003-05-13 | 2006-08-22 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalyst system |
US7129292B1 (en) | 1999-12-17 | 2006-10-31 | Basf Aktiengesellschaft | Method for the emulsion polymerization of olefins |
US7253133B2 (en) | 2001-07-23 | 2007-08-07 | Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences | Catalyst for polymerization or copolymerization of olefins, preparation and use of the same |
US7259214B2 (en) | 2003-02-28 | 2007-08-21 | The Regents Of The University Of California | Metal catalyst for olefin polymerization and co-polymerization with functional monomers |
EP1925623A1 (en) * | 2006-11-24 | 2008-05-28 | Total Petrochemicals Research Feluy | Polymerisation of ethylene and alpha-olefins with pyrrol-iminophenol complexes. |
WO2008085236A1 (en) * | 2007-01-05 | 2008-07-17 | The Regents Of The University Of California | Single component, phosphine-free, initiators for ethylene homopolymerization and copolymerization with functionalized co-monomers |
US7566760B2 (en) | 2002-08-29 | 2009-07-28 | Basf Aktiengesellschaft | Preparation of aqueous polymer dispersions |
US7754839B2 (en) | 2003-03-03 | 2010-07-13 | The Regents Of The University Of California | Quasi-living metal catalyst for ethylene homo-polymerization and co-polymerization with 5-norbornen -2-yl acetate |
CN105218711A (en) * | 2015-09-17 | 2016-01-06 | 淄博新塑化工有限公司 | A kind of double activated component olefin polymerization catalysis and preparation method |
WO2018236237A1 (en) | 2017-06-21 | 2018-12-27 | Instituto Superior Técnico | Tridentate iminopyrrolyl nickel complexes and their use as catalysts for the reaction of polymerisation of ethylene to hyperbranched polyethylene |
Families Citing this family (22)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10304158A1 (en) * | 2003-02-03 | 2004-08-05 | Bayer Ag | New transition metal complexes with azo ligands, useful as catalysts, particularly for polymerization of olefins, especially in presence of polar additives |
DE10310289A1 (en) * | 2003-03-10 | 2004-09-23 | Bayer Ag | Process for the preparation of an azo catalyst for the polymerization of olefins |
TWI251587B (en) * | 2003-12-23 | 2006-03-21 | Univ Nat Sun Yat Sen | Ligand, metallic complex, and catalytic reaction with saturated or unsaturated C-C bonds formation |
US20090163740A1 (en) * | 2004-06-23 | 2009-06-25 | National Sun Yat-Sen University | Ligands for metals as catalysts for carbon-carbon bond formation |
US7271276B2 (en) * | 2004-06-23 | 2007-09-18 | National Sun Yat-Sen University | Metal complexes for catalytic carbon-carbon bond formation |
JP2009072665A (en) * | 2007-09-19 | 2009-04-09 | Mitsui Chemicals Inc | Catalyst for olefin polymerization, and manufacturing method of ethylene polymer |
WO2009046144A1 (en) * | 2007-10-01 | 2009-04-09 | California Institute Of Technology | Solvent, additive and co-catalyst effects for ethylene oligomerization catalysis |
JP5800727B2 (en) * | 2012-02-16 | 2015-10-28 | 三井化学株式会社 | Olefin polymerization catalyst and process for producing olefin polymer |
WO2014055868A1 (en) | 2012-10-04 | 2014-04-10 | Bridgestone Corporation | Organometallic complex catalyst and polymerization method employing same |
MX2015013672A (en) | 2013-03-28 | 2016-02-16 | Procter & Gamble | Cleaning compositions containing a polyetheramine, a soil release polymer, and a carboxymethylcellulose. |
US9719052B2 (en) | 2014-03-27 | 2017-08-01 | The Procter & Gamble Company | Cleaning compositions containing a polyetheramine |
WO2015148361A1 (en) | 2014-03-27 | 2015-10-01 | The Procter & Gamble Company | Cleaning compositions containing a polyetheramine |
FR3020287B1 (en) * | 2014-04-28 | 2017-12-08 | Ifp Energies Now | NOVEL CYCLIC COMPLEXES BASED ON NICKEL AND THEIR USE IN PROCESS FOR PROCESSING OLEFINS |
FR3020286B1 (en) * | 2014-04-28 | 2017-12-08 | Ifp Energies Now | NOVEL NICKEL COMPLEXES AND THEIR USE IN A PROCESS OF OLEFIN PROCESSING |
WO2015187757A1 (en) | 2014-06-06 | 2015-12-10 | The Procter & Gamble Company | Detergent composition comprising polyalkyleneimine polymers |
US9617501B2 (en) | 2014-08-27 | 2017-04-11 | The Procter & Gamble Company | Method of treating a fabric by washing with a detergent comprising an acrylamide/DADMAC cationic polymer |
EP3186345A1 (en) | 2014-08-27 | 2017-07-05 | The Procter and Gamble Company | Detergent composition comprising a cationic polymer |
WO2016032991A1 (en) | 2014-08-27 | 2016-03-03 | The Procter & Gamble Company | Detergent composition comprising a cationic polymer |
WO2016032992A1 (en) | 2014-08-27 | 2016-03-03 | The Procter & Gamble Company | Detergent composition comprising a cationic polymer |
JP6430632B2 (en) | 2014-09-25 | 2018-11-28 | ザ プロクター アンド ギャンブル カンパニー | Fabric care composition containing polyetheramine |
MY191782A (en) * | 2016-09-29 | 2022-07-15 | Sulzer Management Ag | A process to prepare a polyester polymer and a polyester polymer obtainable thereby |
CA3228918A1 (en) | 2021-08-10 | 2023-02-16 | Nippon Shokubai Co., Ltd. | Polyalkylene-oxide-containing compound |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3686159A (en) * | 1969-12-19 | 1972-08-22 | Shell Oil Co | Ethylene polymerization |
US4382153A (en) * | 1982-04-05 | 1983-05-03 | Gulf Research & Development Company | Process for the oligomerization of ethylene in methanol |
US4537982A (en) * | 1982-08-03 | 1985-08-27 | Bayer Aktiengesellschaft | Production of organic nickel compounds |
US5557023A (en) * | 1995-05-23 | 1996-09-17 | The Governors Of The University Of Alberta | Olefin oligomerization in the presence of novel complexes |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3678022A (en) * | 1969-03-10 | 1972-07-18 | Ameripol Inc | Polymerizing unsaturated monomers with a catalyst of an iron complex, a dialkyl aluminum compound and a bidentate ligand |
US3647915A (en) | 1969-11-04 | 1972-03-07 | Shell Oil Co | Ethylene oligomerization |
US3635937A (en) | 1969-11-05 | 1972-01-18 | Shell Oil Co | Ethylene polymerization |
US3644563A (en) * | 1969-11-05 | 1972-02-22 | Shell Oil Co | Ethylene oligomerization |
US4301318A (en) * | 1980-08-18 | 1981-11-17 | Gulf Research & Development Company | Process for recovering oligomerization product |
US4293727A (en) * | 1980-08-18 | 1981-10-06 | Gulf Research & Development Company | Process for the oligomerization of ethylene |
US4310716A (en) * | 1980-08-18 | 1982-01-12 | Gulf Research & Development Company | Process for the oligomerization of ethylene in methanol |
US4293502A (en) * | 1980-08-18 | 1981-10-06 | Gulf Research & Development Company | Nickel ylides |
JPS59500166A (en) | 1982-02-17 | 1984-02-02 | コモンウェルス・サイエンティフィック・アンド・インダストリアル・リサ−チ・オ−ガニゼイション | Catalysts for olefin oligomerization and isomerization |
US4680354A (en) * | 1986-05-21 | 1987-07-14 | The Glidden Company | Low molecular weight polymers and copolymers |
US5210360A (en) | 1992-09-01 | 1993-05-11 | Phillips Petroleum Company | Ethylene oligomerization |
US5282696A (en) | 1992-10-30 | 1994-02-01 | Jim Solomon | Pneumatic ram pipe replacement |
US5539124A (en) | 1994-12-19 | 1996-07-23 | Occidental Chemical Corporation | Polymerization catalysts based on transition metal complexes with ligands containing pyrrolyl ring |
KR100418168B1 (en) | 1995-01-24 | 2004-02-14 | 이.아이,듀우판드네모아앤드캄파니 | Polymerization Process |
KR100517852B1 (en) * | 1997-01-14 | 2005-09-30 | 이 아이 듀폰 디 네모아 앤드 캄파니 | Polymerization of Olefins |
US6174975B1 (en) * | 1998-01-13 | 2001-01-16 | E.I. Du Pont De Nemours And Company | Polymerization of olefins |
-
1998
- 1998-01-15 US US09/007,442 patent/US6573345B1/en not_active Expired - Fee Related
- 1998-02-18 EP EP98908596A patent/EP0917529A4/en not_active Withdrawn
- 1998-02-18 CA CA002257792A patent/CA2257792A1/en not_active Abandoned
- 1998-02-18 BR BR9804790A patent/BR9804790A/en not_active IP Right Cessation
- 1998-02-18 NZ NZ332843A patent/NZ332843A/en unknown
- 1998-02-18 WO PCT/US1998/003175 patent/WO1998042665A1/en not_active Application Discontinuation
- 1998-02-18 JP JP54569698A patent/JP2002510286A/en active Pending
- 1998-02-18 AU AU66594/98A patent/AU725160B2/en not_active Ceased
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3686159A (en) * | 1969-12-19 | 1972-08-22 | Shell Oil Co | Ethylene polymerization |
US4382153A (en) * | 1982-04-05 | 1983-05-03 | Gulf Research & Development Company | Process for the oligomerization of ethylene in methanol |
US4537982A (en) * | 1982-08-03 | 1985-08-27 | Bayer Aktiengesellschaft | Production of organic nickel compounds |
US5557023A (en) * | 1995-05-23 | 1996-09-17 | The Governors Of The University Of Alberta | Olefin oligomerization in the presence of novel complexes |
Non-Patent Citations (1)
Title |
---|
See also references of EP0917529A4 * |
Cited By (88)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6136743A (en) * | 1996-04-09 | 2000-10-24 | Mitsui Chemicals, Inc. | Olefin polymerization catalyst, olefins polymerization methods, and olefin polymer compositions, and heat molded products |
US6303720B1 (en) | 1997-03-10 | 2001-10-16 | Eastman Chemical Company | Olefin polymerization catalysts containing group 8-10 transition metals, processes employing such catalysts and polymers obtained therefrom |
US6103658A (en) * | 1997-03-10 | 2000-08-15 | Eastman Chemical Company | Olefin polymerization catalysts containing group 8-10 transition metals, processes employing such catalysts and polymers obtained therefrom |
US6822062B2 (en) | 1997-03-10 | 2004-11-23 | Eastman Chemical Company | Supported group 8-10 transition metal olefin polymerization catalysts |
US6660677B1 (en) | 1997-03-10 | 2003-12-09 | Eastman Chemical Company | Supported group 8-10 transition metal olefin polymerization catalysts |
US6372682B2 (en) | 1997-03-13 | 2002-04-16 | Eastman Chemical Company | Catalyst compositions for the polymerization of olefins |
US6844404B2 (en) | 1997-03-13 | 2005-01-18 | Eastman Chemical Company | Catalyst compositions for the polymerization of olefins |
US6245871B1 (en) | 1997-04-18 | 2001-06-12 | Eastman Chemical Company | Group 8-10 transition metal olefin polymerization catalysts |
US6656869B2 (en) | 1997-04-18 | 2003-12-02 | Eastman Chemical Company | Group 8-10 transition metal olefin polymerization catalysts |
US6174976B1 (en) | 1998-02-24 | 2001-01-16 | Eastman Chemical Company | Neutral nickel complexes for olefin polymerization |
WO1999050313A1 (en) * | 1998-03-27 | 1999-10-07 | E.I. Du Pont De Nemours And Company | Polymerization of olefins |
US6410660B1 (en) | 1998-03-27 | 2002-06-25 | E. I. Du Pont De Nemours And Company | Polymerization of olefins |
US6593266B1 (en) | 1998-04-16 | 2003-07-15 | Mitsui Chemicals, Inc. | Olefin polymerization catalyst and polymerization process |
US6399724B1 (en) | 1998-04-16 | 2002-06-04 | Mitsui Chemicals, Inc. | Catalyst for olefin polymerization and method of polymerizing olefin |
US6365539B1 (en) | 1998-09-02 | 2002-04-02 | Eastman Chemical Company | Polyolefin catalysts |
US6117959A (en) * | 1998-09-02 | 2000-09-12 | Eastman Chemical Company | Polyolefin catalysts |
US6610805B1 (en) | 1998-10-08 | 2003-08-26 | Symyx Technologies, Inc. | Catalyst ligands, catalytic metal complexes and processes using same |
US6534664B1 (en) | 1998-10-08 | 2003-03-18 | Symyx Technologies, Inc. | Catalyst ligands, catalytic metal complexes and processes using same |
US6521793B1 (en) | 1998-10-08 | 2003-02-18 | Symyx Technologies, Inc. | Catalyst ligands, catalytic metal complexes and processes using same |
US6451728B1 (en) | 1998-12-11 | 2002-09-17 | Mitsui Chemicals, Inc. | Olefin polymerization catalyst and process for olefin polymerization |
CN100381474C (en) * | 1998-12-11 | 2008-04-16 | 三井化学株式会社 | Olefine polymerizing catalyst and method thereof |
US6395668B1 (en) | 1998-12-15 | 2002-05-28 | Basell Technology Company Bv | Catalyst system for olefin polymerization |
US6545108B1 (en) | 1999-02-22 | 2003-04-08 | Eastman Chemical Company | Catalysts containing N-pyrrolyl substituted nitrogen donors |
US6825356B2 (en) | 1999-02-22 | 2004-11-30 | Eastman Chemical Company | Catalysts containing N-pyrrolyl substituted nitrogen donors |
US6559091B1 (en) | 1999-02-22 | 2003-05-06 | Eastman Chemical Company | Catalysts containing N-pyrrolyl substituted nitrogen donors |
US6620896B1 (en) | 1999-02-23 | 2003-09-16 | Eastman Chemical Company | Mixed olefin polymerization catalysts, processes employing such catalysts, and polymers obtained therefrom |
US6992153B1 (en) | 1999-03-09 | 2006-01-31 | Basell Polyolefine Gmbh | Multi-stage process for the (CO) polymerization of olefins |
WO2000056781A2 (en) * | 1999-03-23 | 2000-09-28 | Cryovac, Inc. | Linear functionalized copolymer and articles formed thereof |
US6562922B1 (en) * | 1999-03-23 | 2003-05-13 | Cryovac, Inc | Vicinal hydroxyl group containing copolymer and articles formed therefrom |
AU754761B2 (en) * | 1999-03-23 | 2002-11-21 | Cryovac, Inc. | Supported catalysts and olefin polymerization processes utilizing same |
WO2000056786A1 (en) * | 1999-03-23 | 2000-09-28 | Cryovac, Inc. | Supported catalysts and olefin polymerization processes utilizing same |
WO2000056781A3 (en) * | 1999-03-23 | 2000-12-28 | Cryovac Inc | Linear functionalized copolymer and articles formed thereof |
US6197715B1 (en) | 1999-03-23 | 2001-03-06 | Cryovac, Inc. | Supported catalysts and olefin polymerization processes utilizing same |
US6197714B1 (en) | 1999-03-23 | 2001-03-06 | Cryovac, Inc. | Supported catalysts and olefin polymerization processes utilizing same |
WO2000056787A1 (en) * | 1999-03-23 | 2000-09-28 | Cryovac, Inc. | Supported catalysts and olefin polymerization processes utilizing same |
US6355735B1 (en) | 1999-08-17 | 2002-03-12 | 3M Innovative Properties Company | Semi-interpenetrating polymer network from epoxy monomer and olefin |
US6620897B1 (en) | 1999-09-07 | 2003-09-16 | E. I. Du Pont De Nemours And Company | Heat-sealable polyolefins and articles made therefrom |
US7005488B2 (en) | 1999-09-07 | 2006-02-28 | E. I. Du Pont De Nemours And Company | Heat-sealable polyolefins and articles made therefrom |
US6765075B2 (en) | 1999-09-07 | 2004-07-20 | E. I. Du Pont De Nemours And Company | Heat-sealable polyolefins and articles made therefrom |
WO2001018097A1 (en) * | 1999-09-07 | 2001-03-15 | E.I. Du Pont De Nemours And Company | Heat-sealable polyolefins and articles made therefrom |
US6531424B2 (en) | 1999-12-17 | 2003-03-11 | E. I. Du Pont De Nemours And Company | Polymerization of olefins |
US7129292B1 (en) | 1999-12-17 | 2006-10-31 | Basf Aktiengesellschaft | Method for the emulsion polymerization of olefins |
US6579823B2 (en) | 2000-02-18 | 2003-06-17 | Eastman Chemical Company | Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors |
US6946532B2 (en) | 2000-02-18 | 2005-09-20 | Eastman Chemical Company | Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors |
US6605677B2 (en) | 2000-02-18 | 2003-08-12 | Eastman Chemical Company | Olefin polymerization processes using supported catalysts |
US6844446B2 (en) | 2000-02-18 | 2005-01-18 | Eastman Chemical Company | Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors |
US7056996B2 (en) | 2000-02-18 | 2006-06-06 | E. I. Du Pont De Nemours And Company | Productivity catalysts and microstructure control |
US6562751B2 (en) | 2000-03-10 | 2003-05-13 | E. I. Du Pont De Nemours And Company | Polymerization of olefins |
US6905999B2 (en) | 2000-03-10 | 2005-06-14 | E. I. Du Pont De Nemours And Company | Polymerization of olefins |
US6747106B2 (en) | 2000-03-10 | 2004-06-08 | E. I. Du Pont De Nemours And Company | Polymerization of olefins |
US6521724B2 (en) | 2000-03-10 | 2003-02-18 | E. I. Du Pont De Nemours And Company | Polymerization process |
JP2001261638A (en) * | 2000-03-14 | 2001-09-26 | Mitsubishi Chemicals Corp | New metal complex compound having ligand having 2, 5- diiminomethylpyrrole skeleton and catalyst which contain the complex compound and is used for polymerizing alpha-olefin |
US6689928B2 (en) | 2000-04-04 | 2004-02-10 | Exxonmobil Research And Engineering Company | Transition metal complexes and oligomers therefrom |
US7115763B2 (en) | 2000-05-31 | 2006-10-03 | E. I. Du Pont De Nemours And Company | Polymerization of olefins |
US6506861B2 (en) | 2000-05-31 | 2003-01-14 | E. I. Du Pont De Nmeours And Company | Polymerization of olefins |
US6350837B1 (en) | 2000-06-09 | 2002-02-26 | Eastman Chemical Company | Copolymerization of norbornene and functional norbornene monomers |
US6538085B2 (en) | 2000-06-09 | 2003-03-25 | Eastman Kodak Company | Copolymerization of norbornene and functional norbornene monomers |
US7022786B2 (en) | 2000-07-20 | 2006-04-04 | Basf Aktiengesellschaft | Ligands, complexes and their use for the polymerization of olefins |
US6900278B2 (en) | 2000-07-20 | 2005-05-31 | Basf Aktiengesellschaft | Ligands, complex compounds and their use for polymerising olefins |
US6706891B2 (en) | 2000-11-06 | 2004-03-16 | Eastman Chemical Company | Process for the preparation of ligands for olefin polymerization catalysts |
WO2002064645A3 (en) * | 2001-02-13 | 2002-12-27 | Basf Ag | Complex compounds and their use in olefin polymerization |
US6933400B2 (en) | 2001-02-13 | 2005-08-23 | Basf Aktiengesellschaft | Complex compounds and their use in olefin polymerization |
WO2002064645A2 (en) * | 2001-02-13 | 2002-08-22 | Basf Aktiengesellschaft | Complex compounds and their use in olefin polymerization |
US7253133B2 (en) | 2001-07-23 | 2007-08-07 | Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences | Catalyst for polymerization or copolymerization of olefins, preparation and use of the same |
WO2003027130A3 (en) * | 2001-09-25 | 2003-12-04 | Exxonmobil Res & Eng Co | Transition metal complexes for preparing olefin oligomers |
WO2003027130A2 (en) * | 2001-09-25 | 2003-04-03 | Exxonmobil Research And Engineering Company | Transition metal complexes for preparing olefin oligomers |
US6737130B2 (en) | 2001-11-06 | 2004-05-18 | Cryovac, Inc. | Hermetically heat-sealable, pressure-reclosable packaging article containing substantially spherical homogeneous polyolefin |
US6733851B2 (en) | 2001-11-06 | 2004-05-11 | Cryovac, Inc. | Packaging article having heat seal layer containing blend of hyperbranched and semicrystalline olefin polymers |
US6761965B2 (en) | 2001-11-06 | 2004-07-13 | Cryovac, Inc. | Irradiated multilayer film having seal layer containing hyperbranched polymer |
US6800699B2 (en) | 2001-12-17 | 2004-10-05 | Basf Aktiengesellschaft | Process for the production of aqueous polymer dispersions |
US7566760B2 (en) | 2002-08-29 | 2009-07-28 | Basf Aktiengesellschaft | Preparation of aqueous polymer dispersions |
US7259214B2 (en) | 2003-02-28 | 2007-08-21 | The Regents Of The University Of California | Metal catalyst for olefin polymerization and co-polymerization with functional monomers |
US7968487B2 (en) * | 2003-02-28 | 2011-06-28 | The Regents Of The University Of California | Single component, phosphine-free, initiators for ethylene homopolymerization and copolymerization with functionalized co-monomers |
EP2305721A2 (en) | 2003-02-28 | 2011-04-06 | The Regents Of the University of California | A metal catalyst for olefin polymerization and co-polymerization with functional monomers |
US7754839B2 (en) | 2003-03-03 | 2010-07-13 | The Regents Of The University Of California | Quasi-living metal catalyst for ethylene homo-polymerization and co-polymerization with 5-norbornen -2-yl acetate |
US7285609B2 (en) | 2003-05-13 | 2007-10-23 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalyst system useful for polar monomers |
US7094848B2 (en) | 2003-05-13 | 2006-08-22 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalyst system |
US7479531B2 (en) | 2003-05-13 | 2009-01-20 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalyst system useful for polar monomers |
EP1925623A1 (en) * | 2006-11-24 | 2008-05-28 | Total Petrochemicals Research Feluy | Polymerisation of ethylene and alpha-olefins with pyrrol-iminophenol complexes. |
WO2008061901A1 (en) * | 2006-11-24 | 2008-05-29 | Total Petrochemicals Research Feluy | Polymerisation of ethylene and alpha-olefins with pyrroliminophenol complexes. |
US8497331B2 (en) | 2006-11-24 | 2013-07-30 | Total Petrochemicals Research Feluy | Polymerisation of ethylene and alpha-olefins with pyrrol-iminophenol complexes |
EP2104687A4 (en) * | 2007-01-05 | 2010-01-27 | Univ California | Single component, phosphine-free, initiators for ethylene homopolymerization and copolymerization with functionalized co-monomers |
EP2104687A1 (en) * | 2007-01-05 | 2009-09-30 | The Regents of the University of California | Single component, phosphine-free, initiators for ethylene homopolymerization and copolymerization with functionalized co-monomers |
WO2008085236A1 (en) * | 2007-01-05 | 2008-07-17 | The Regents Of The University Of California | Single component, phosphine-free, initiators for ethylene homopolymerization and copolymerization with functionalized co-monomers |
CN105218711A (en) * | 2015-09-17 | 2016-01-06 | 淄博新塑化工有限公司 | A kind of double activated component olefin polymerization catalysis and preparation method |
WO2018236237A1 (en) | 2017-06-21 | 2018-12-27 | Instituto Superior Técnico | Tridentate iminopyrrolyl nickel complexes and their use as catalysts for the reaction of polymerisation of ethylene to hyperbranched polyethylene |
CN110914283A (en) * | 2017-06-21 | 2020-03-24 | 超级技术研究所 | Tridentate imino pyrrolyl nickel complexes and use thereof as catalysts for reactions in which ethylene is polymerized to hyperbranched polyethylene |
US11117913B2 (en) | 2017-06-21 | 2021-09-14 | Instituto Superior Técnico | Tridentate iminopyrrolyl nickel complexes and their use as catalysts for the reaction of polymerisation of ethylene to hyperbranched polyethylene |
Also Published As
Publication number | Publication date |
---|---|
EP0917529A4 (en) | 2002-10-02 |
JP2002510286A (en) | 2002-04-02 |
EP0917529A1 (en) | 1999-05-26 |
NZ332843A (en) | 2000-09-29 |
AU725160B2 (en) | 2000-10-05 |
AU6659498A (en) | 1998-10-20 |
CA2257792A1 (en) | 1998-10-01 |
BR9804790A (en) | 1999-08-17 |
US6573345B1 (en) | 2003-06-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6573345B1 (en) | Catalyst compositions and processes for olefin oligomerization and polymerization | |
US6576779B1 (en) | Catalyst compositions and processes for olefin polymers and copolymers | |
US6197715B1 (en) | Supported catalysts and olefin polymerization processes utilizing same | |
US20030114610A1 (en) | Copolymerization of olefins | |
US6255414B1 (en) | Polymerization of olefins | |
US6197714B1 (en) | Supported catalysts and olefin polymerization processes utilizing same | |
US6506704B1 (en) | Olefin polymerization catalysts and processes for making and using same | |
US7034093B2 (en) | Catalysts for olefin polymerization | |
MXPA98009758A (en) | Catalyst compositions and processes for olefin oligomerization and polymerization | |
Rahman | Zwitterionic late transition metal alkene polymerisation catalysts containing aminofulvene-aldiminate (AFA) ligands | |
MXPA01000875A (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 GE GH GM GW HU ID IL 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 UZ VN YU ZW |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG |
|
WWE | Wipo information: entry into national phase |
Ref document number: 332843 Country of ref document: NZ Ref document number: 66594/98 Country of ref document: AU |
|
ENP | Entry into the national phase |
Ref document number: 2257792 Country of ref document: CA Kind code of ref document: A Ref document number: 2257792 Country of ref document: CA |
|
WWE | Wipo information: entry into national phase |
Ref document number: PA/a/1998/009758 Country of ref document: MX |
|
WWE | Wipo information: entry into national phase |
Ref document number: 1998908596 Country of ref document: EP |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
WWP | Wipo information: published in national office |
Ref document number: 1998908596 Country of ref document: EP |
|
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
WWG | Wipo information: grant in national office |
Ref document number: 66594/98 Country of ref document: AU |
|
WWW | Wipo information: withdrawn in national office |
Ref document number: 1998908596 Country of ref document: EP |