CN1297456A - 用于烯烃聚合的含三齿配体的金属催化剂配合物 - Google Patents
用于烯烃聚合的含三齿配体的金属催化剂配合物 Download PDFInfo
- Publication number
- CN1297456A CN1297456A CN99805212A CN99805212A CN1297456A CN 1297456 A CN1297456 A CN 1297456A CN 99805212 A CN99805212 A CN 99805212A CN 99805212 A CN99805212 A CN 99805212A CN 1297456 A CN1297456 A CN 1297456A
- Authority
- CN
- China
- Prior art keywords
- monomer
- catalyst
- family
- group
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 title claims description 26
- 239000002184 metal Substances 0.000 title claims description 22
- 150000001336 alkenes Chemical class 0.000 title abstract description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 34
- 150000003624 transition metals Chemical class 0.000 claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 239000003446 ligand Substances 0.000 claims abstract description 16
- 230000007935 neutral effect Effects 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 45
- -1 hydride ion Chemical class 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 33
- 239000000178 monomer Substances 0.000 claims description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 22
- 150000001450 anions Chemical class 0.000 claims description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 230000004913 activation Effects 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 239000012190 activator Substances 0.000 claims description 11
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 10
- 239000004711 α-olefin Substances 0.000 claims description 9
- 125000004429 atom Chemical group 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 7
- 150000008282 halocarbons Chemical group 0.000 claims description 7
- 125000002524 organometallic group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 150000001925 cycloalkenes Chemical class 0.000 claims description 5
- 239000002955 immunomodulating agent Substances 0.000 claims description 5
- 229940121354 immunomodulator Drugs 0.000 claims description 5
- 230000002584 immunomodulator Effects 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 150000001993 dienes Chemical class 0.000 claims 1
- 239000012685 metal catalyst precursor Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 30
- QUPDWYMUPZLYJZ-UHFFFAOYSA-N ethyl Chemical compound C[CH2] QUPDWYMUPZLYJZ-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 16
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 14
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 14
- 239000002585 base Substances 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 235000010210 aluminium Nutrition 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- 239000000126 substance Substances 0.000 description 12
- 239000012018 catalyst precursor Substances 0.000 description 11
- 239000005977 Ethylene Substances 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 230000000379 polymerizing effect Effects 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 239000010936 titanium Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000011651 chromium Substances 0.000 description 7
- 238000002329 infrared spectrum Methods 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000007334 copolymerization reaction Methods 0.000 description 6
- 150000007517 lewis acids Chemical group 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 5
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229910000765 intermetallic Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000005574 norbornylene group Chemical group 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 239000007848 Bronsted acid Substances 0.000 description 3
- 101150065749 Churc1 gene Proteins 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000002879 Lewis base Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 102100038239 Protein Churchill Human genes 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 229910052728 basic metal Inorganic materials 0.000 description 3
- 150000003818 basic metals Chemical class 0.000 description 3
- 229910052796 boron Inorganic materials 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 150000001457 metallic cations Chemical class 0.000 description 3
- 229910052752 metalloid Inorganic materials 0.000 description 3
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 description 2
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-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
- 239000004793 Polystyrene Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 238000004811 liquid chromatography Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229940006487 lithium cation Drugs 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229940096405 magnesium cation Drugs 0.000 description 2
- 150000002738 metalloids Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000012041 precatalyst Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000006884 silylation reaction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 229940083542 sodium Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- 238000012725 vapour phase polymerization Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CDULGHZNHURECF-UHFFFAOYSA-N 2,3-dimethylaniline 2,4-dimethylaniline 2,5-dimethylaniline 2,6-dimethylaniline 3,4-dimethylaniline 3,5-dimethylaniline Chemical group CC1=CC=C(N)C(C)=C1.CC1=CC=C(C)C(N)=C1.CC1=CC(C)=CC(N)=C1.CC1=CC=C(N)C=C1C.CC1=CC=CC(N)=C1C.CC1=CC=CC(C)=C1N CDULGHZNHURECF-UHFFFAOYSA-N 0.000 description 1
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical group CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- JNRLEMMIVRBKJE-UHFFFAOYSA-N 4,4'-Methylenebis(N,N-dimethylaniline) Chemical class C1=CC(N(C)C)=CC=C1CC1=CC=C(N(C)C)C=C1 JNRLEMMIVRBKJE-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- FXLIQHHYWFGJGQ-UHFFFAOYSA-N C(C)C([Si](O[Si](C)=C(C(C)C)C(C)C)(C=CCC)C)CC Chemical compound C(C)C([Si](O[Si](C)=C(C(C)C)C(C)C)(C=CCC)C)CC FXLIQHHYWFGJGQ-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 229920000181 Ethylene propylene rubber Polymers 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000002008 alkyl bromide group Chemical group 0.000 description 1
- 125000001118 alkylidene group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000005264 aryl amine group Chemical group 0.000 description 1
- DOMWDDGKVOOLGM-UHFFFAOYSA-N azane;1,1'-biphenyl Chemical compound N.C1=CC=CC=C1C1=CC=CC=C1 DOMWDDGKVOOLGM-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 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
- 238000004891 communication Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 125000004850 cyclobutylmethyl group Chemical group C1(CCC1)C* 0.000 description 1
- 150000001941 cyclopentenes Chemical class 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- JQZUMFHYRULBEN-UHFFFAOYSA-N diethyl(methyl)silicon Chemical compound CC[Si](C)CC JQZUMFHYRULBEN-UHFFFAOYSA-N 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- VZZJVOCVAZHETD-UHFFFAOYSA-N diethylphosphane Chemical compound CCPCC VZZJVOCVAZHETD-UHFFFAOYSA-N 0.000 description 1
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 1
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 1
- YOTZYFSGUCFUKA-UHFFFAOYSA-N dimethylphosphine Chemical compound CPC YOTZYFSGUCFUKA-UHFFFAOYSA-N 0.000 description 1
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- GPAYUJZHTULNBE-UHFFFAOYSA-N diphenylphosphine Chemical group C=1C=CC=CC=1PC1=CC=CC=C1 GPAYUJZHTULNBE-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- KUVXJBSVPBXHEK-UHFFFAOYSA-N octylaluminum Chemical compound CCCCCCCC[Al] KUVXJBSVPBXHEK-UHFFFAOYSA-N 0.000 description 1
- 150000002899 organoaluminium compounds Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 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
-
- 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
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic Table
- C07F11/005—Compounds containing elements of Groups 6 or 16 of the Periodic Table compounds without a metal-carbon linkage
-
- 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
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- 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
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- 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
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/005—Compounds of elements of Group 5 of the Periodic Table without metal-carbon linkages
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/02—Ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61908—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/619—Component covered by group C08F4/60 containing a transition metal-carbon bond
- C08F4/61912—Component covered by group C08F4/60 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
Abstract
公开一种烯烃聚合用活化的基于三齿一价阴离子配体的还原氧化态过渡金属催化剂。这些催化剂的过渡金属催化剂前体有式(A)、(B),其中M为还原氧化态的第4—9族过渡金属,X为一价阴离子配体,L为中性供电子基团,E为来自第15和16族的中性供电子基团,E’为来自第15族的一价阴离子供电子基团,T为桥连基,n根据平衡M上电荷的需要为1—3,p为0—3,q为1—2。举例为烯烃聚合。
Description
发明领域
本发明涉及用于烯烃聚合的过渡金属催化剂体系,更具体地涉及
不基于环戊二烯基配体的掺入三齿配体的还原氧化态过渡金属催化剂体系。
发明背景
离散的基于双环戊二烯基和基于单环戊二烯基的金属配合物用于烯烃聚合为本领域公知。少数情况下,已证明烯烃聚合始于有基于环戊二烯基的辅助配体体系和还原氧化态金属中心的离散催化剂前体配合物,例如在US5 374696和5494874(Rosen等);WO96/13529;和Theopold,Acc.Chem.Res.(美国化学研究报告),vol.23,pp.263-270(1990)中的那些。然而,这些催化剂前体配合物未表现出C2或假-C2对称(这是适用于许多金属茂催化剂的对称)。
近年来,在鉴别掺入非环戊二烯基辅助配体的催化体系方面的兴趣日增。例如,US5318935(Canich and Turner)公开了双氨基第4族过渡金属化合物,McConville,et.al.,大分子(Macromolecules),vol.29,p.5241(1996)公开了桥连的二价阴离子联氨配体。这些催化剂掺入最高氧化态的d0金属。WO96/23010和Gibson,et.al.,化学通讯(Chem.Comm.),pp.849-850(1998)都公开了用于第8-10族金属的二亚胺配体。这些二亚胺基辅助配体是中性的供电子配体。掺有非环戊二烯基辅助配体和还原氧化态金属的催化剂前体配合物的其它证明实例表明这些化合物有很低的活性,参见WO97/17379。
有非环戊二烯基阴离子配体(包括有还原氧化态金属中心的那些和结构特征在于有C2或假-C2对称的那些)在科学文献中是已知的。参见例如Fryzuk,加拿大化学杂志(Can.J.Chem.),vol.70,p.2839(1992);Edwards,et.al.,化学会志,(J.Chem.Soc.),道尔顿学报(Dalton Trans.),p.1253(1989);和van Koten,et.al.,美国化学会志(J.Am.Chem.Soc.),vol.104,p.5490(1982)。然而,这些文献的教导都未建议这些化合物作为聚合催化剂或催化剂前体化合物的潜在效用。
发明概述
本发明涉及基于还原氧化态的第4-9族第一或第二行过渡金属且有含第15和/或16族元素的一价阴离子非环戊二烯基三齿配体的催化剂配合物,所述配合物已被活化用于烯烃聚合。所述一价阴离子三齿辅助配体体系由两个通过配价键与所述过渡金属键合的第15或16族原子和一个与所述过渡金属共价键合的第15族原子或芳环碳原子构成。所述共价键合的原子通过含有一或多个第13-16族元素的桥连基与所述配价键合的第15或16族原子相连。
其中M为还原氧化态的第4-9族过渡金属;每个X独立地为卤素、醇根、芳氧根、氨根、膦根、氢负离子、烃基、取代的烃基、卤碳基、取代的卤碳基、烃基-或卤碳基-取代的有机准金属,或者两个X基相连并与所述过渡金属或L基键合形成环状结构,或者一或多个X可包含L基;L为稳定所述配合物的中性供电子基团;每个E独立地为选自第15和16族的中性供电子基团;E’为选自第15族的一价阴离子供电子基团;R有与X相同的定义,但可相同或不同;T为包含一个第13-16族元素或第13-16族元素的组合的桥连基团;n为1至3的数,通过平衡所述过渡金属上的电荷使所述过渡金属处于还原氧化态且所述配合物上总电荷为中性来决定;p为0至3的数,以满足稳定所述配合物的需要;q为1或2,以使E仍为中性供电子基团。E优选选自N、P、S和O,E’优选为N或P。M优选为Ti、V、Cr、Mn、Fe或Co。所述催化剂活化剂化合物可以是烷基铝氧烷、烷基铝助催化剂活化剂、或离子化非配位阴离子前体化合物。
另一方面,本发明涉及一种聚合方法,特征在于使一或多种可通过配位聚合而聚合的单体在适合的配位聚合条件下与上述催化剂体系接触。所述单体可选自乙烯、α-烯烃、环状烯烃、非共轭二烯烃、炔属不饱和单体、烯属不饱和芳族单体和C20-C200大分子单体。所述单体优选为至少一种选自乙烯和C3-C20α-烯烃的单体。所述催化剂体系可还包括一种固体颗粒状载体。
发明详述
其中所标记的取代基均如前面所定义。
所述过渡金属中心可以是处于还原氧化态的第4-9族的任何金属,优选钛、钒、铬、锰、铁或钴。本文所用术语“还原氧化态”意指低于所述金属可达到的最高氧化值的氧化值。例如,优选的还原氧化态金属包括Ti(Ⅱ)、Ti(Ⅲ)、V(Ⅱ)、V(Ⅲ)、V(Ⅳ)、Cr(Ⅱ)、Cr(Ⅲ)、Cr(Ⅳ)、Cr(Ⅴ)、Mn(Ⅱ)、Mn(Ⅲ)、Mn(Ⅳ)、Fe(Ⅱ)、Fe(Ⅲ)、Co(Ⅱ)、Co(Ⅲ)等。更优选的还原氧化态金属是处于+3氧化态的那些,例如V(Ⅲ)、Cr(Ⅲ)等。
用于所述中性供电子基团L的源化合物包括能为所述金属中心提供电子对的任何中性路易斯碱化合物。非限制性例子包括二乙醚、三甲胺、四氢呋喃、二甲基苯胺、苯胺、三甲基膦、正丁胺等。
所述桥连基团T包含任何来自第13-16族的元素或元素组,例如B、C、N、O、Al、Si、P、S、Ge、或Se等。T可以是饱和或不饱和的。优选的桥连基团包括二烷基、烷基芳基或二芳基硅基团;二烷基、烷基芳基或二芳基锗基团;烷基或芳基膦;烷基或芳基胺基团;氧或硫基;或有1或多个碳原子的二烃基如亚甲基和亚乙基等。适合的T基团的非限制性具体例子是二甲基甲硅烷基、二乙基甲硅烷基、二正丙基甲硅烷基、二异丙基甲硅烷基、二正丁基甲硅烷基、二叔丁基甲硅烷基、二正己基甲硅烷基、甲基苯基甲硅烷基、乙基甲基甲硅烷基、二苯基甲硅烷基、二(对叔丁基苯乙基甲硅烷基)、正己基甲基甲硅烷基、亚环戊基甲硅烷基、亚环丁基甲硅烷基、亚环丙基甲硅烷基、二甲基甲锗烷基、二乙基甲锗烷基、亚甲基、二甲基亚甲基、二乙基亚甲基、亚乙基、二甲基亚乙基、二乙基亚乙基、二丙基亚乙基、亚丙基、二甲基亚丙基、二乙基亚丙基、1,1-二甲基-3,3-二甲基亚丙基、四甲基二硅氧烷、1,1,4,4-四甲基-二甲硅烷基亚乙基、氧和硫。
用于X的烃基的例子是甲基、乙基、丙基、异丙基、丁基、戊基、异戊基、己基、异丁基、庚基、辛基、壬基、癸基、鲸蜡基、2-乙基己基、和苯基等,优选甲基。用于X的卤原子的例子包括氯、溴、氟和碘,优选氯。用于X的醇根和芳氧根的例子是甲醇根、乙醇根、丙醇根、丁醇根、酚根和取代的酚根如4-甲基酚根。X的氨根的例子是二甲氨根、二乙氨根、甲乙氨根、二叔丁氨根、二异丙氨根等。芳基氨根的例子是二苯基氨根和其它取代的苯基氨根。甲硅烷基氨根的例子是二-三甲基甲硅烷基氨根、二-三乙基甲硅烷基氨根和三乙基-三甲基甲硅烷基氨根,优选二-三甲基甲硅烷基氨根。X的膦根的例子是二苯基膦根、二环己基膦根、二乙基膦根、二甲基膦根等。两个X合一起的亚烷基的例子是亚甲基、亚乙基、亚丙基、或乙二醇的二价阴离子等。
适用于所述R基的烃基和取代的烃基含有1至约30个碳原子,包括单和多支化的烷基、环状烃基、烷基取代的环状烃基、芳基取代的环状烃基、芳基和烷基取代的芳基、氨基取代的烃基、膦基取代的烃基、烷氧基取代的烃基、和卤代烃基或被任何路易斯碱或酸官能团取代的烃基。适用于所述R基的有机金属基团包括三甲基甲硅烷基、三苯基甲硅烷基、三苯基甲锗烷基、和三甲基甲锗烷基等。其它适用于所述R基的基团包括氨基、膦基、烷氧基、烷基溴基团等。所述适用的有机金属R基中,优选硅的基团如三甲基甲硅烷基、三乙基甲硅烷基、乙基二甲基甲硅烷基和甲基二乙基甲硅烷基;最优选三甲基甲硅烷基。
本发明催化剂前体的说明性例子包括:
[(Me2PCH2SiMe2)2N]TiCl2 [(Et2PCH2CH2CH2)2N]FeEt2
[(Me2PCH2SiEt2)2N]VMe2 [(EtOCH2CH2)2N]CoI2
[(MeOCH2SiMe2)2N]CrBr2 [(EtN=CHCH2)2N]TiCl2
[(Et2PCH2SiMe2)2P]MnCl2 [(Ph2NCH2CH2)2N]VH2
[(Et2PCH2SiEt2)2P]FeMe2 [(Ph2PCH2CH2CH2)2N]CrMe2
[(MeN=CHSiMe2)2N]Co(CH2CHCH2)2 [(PhOCH2CH2)2N]MnEt2
[(Ph2PCH2SiMe2)2N]TiCl2 [(PhN=CHCH2)2N]FeCl2
[(Ph2PCH2SiEt2)=N]VBr2 [(Me2PSiMe2)2C6H3]TiCl2
[(PhN=CHSiMe2)2N]CrMe2 [(Me2NCH2)2C6H3]VBr2
[(Me2NCH2CH2)2N]MnEt2 [(MeSCH2)2C6H3]CrMe2
[((Me3Si)2NCH2CH2)2N]FeBr2 [(MeN=CH)2C6H3]MnEt2
[(Me2PCH2CH2CH2)2N]CoPh2 [(Et2NCH2)2C6H3]FeCl2
[(MeN=CHCH2)2N]Ti(OMe)2 [(Et2PSiMe2)2C6H3]Co(CH2Ph)2
[(Et2NCH2CH2)2N]VCl2 [(Ph2NCH2)2C6H3]Ti(NMe)2
[(EhNCH2CH2)2P]CrBr2 [(PhOCH2)2C6H3]VPh2
[(Et2NCH2CH2CH2)2N]MnMe2 [(Ph2PSiEt2)2C6H3]CrMe2
[(PhN=CH)2C6H3]FeCl2,和后面实施例中所列举的那些,其中Ph=苯基,Et=乙基,Me=甲基。本发明金属化合物可通过用于烯烃聚合用齐格勒-纳塔或金属茂过渡金属化合物之任一的已知方法活化而用于配位或插入聚合催化剂。通过包含至少一个有反应性金属-配体σ-键和至少一个与所述σ-键配体相邻(顺式)的空轨道实现此活化作用用于配位聚合,通过活化而又实现此要求。配位聚合领域的传统活化剂是适用的,典型地包括路易斯酸如齐格勒有机金属助催化剂和铝氧烷化合物、和夺取一个配体使所述金属中心电离成阳离子配合物并提供抗衡的弱配位或非配位阴离子的离子化阴离子前体化合物。
所述齐格勒助催化剂典型地为元素周期表第1、2、12、或13族金属的有机金属化合物。优选选自烷基铝和卤化烷基铝的有机铝化合物。这些可由下式表示:
Al(R2)sX’3-s
其中R2独立地为氢负离子或C1-C10烃基(包括脂族、脂环族或芳族烃基),X’为卤素,s为1至3的整数;和
Al2R2 3X’3
它们是倍半卤化烃基铝。例子包括三乙基铝、三异丁基铝、氯化二乙基铝、Al2Et3Cl3和Al2(i-Bu)3Cl3。
烷基铝氧烷和改性的烷基铝氧烷适用于作为催化剂活化剂,特别是用于包含卤离子配体的本发明金属化合物。适用作催化剂活化剂的铝氧烷组分典型地为以下通式所示低聚铝化合物:(R”-Al-O)n(为环状化合物)或R”(R”-Al-O)nAlR”2(为线型化合物)。式中R”独立地为C1-C10烷基,例如甲基、乙基、丙基、丁基或戊基,n为1至约50的整数。最优选地,R”为甲基,n为至少4。铝氧烷可通过本领域已知的各种方法制备。例如,可用溶解于惰性有机溶剂中的水处理烷基铝,或者使烷基铝与悬浮于惰性有机溶剂中的水合盐如水合硫酸铜接触产生铝氧烷。一般地,烷基铝与有限量的水反应产生线型和环状铝氧烷的混合物。优选甲基铝氧烷和改性的甲基铝氧烷。关于进一步的描述,参见US4665208、4952540、5041584、5091352、5206199、5204419、4874734、4924018、4908463、4968827、5329032、5248801、5235081、5157137、5103031和EP 0561476Al、EP 0279586B1、EP 0516476A、EP 0594218 Al和WO94/10180,这些文献引入本文供参考。
所述活化剂为铝氧烷时,所述优选的过渡金属化合物与活化剂之摩尔比为1∶2000至10∶1,更优选约1∶500至10∶1,甚至更优选约1∶250至1∶1。
术语“非配位阴离子”意指不与所述金属阳离子配位或仅与之弱配位从而仍保留足以被中性路易斯碱如烯属或炔属不饱和单体置换的易变性的阴离子。
适用于配位聚合的包含过渡金属阳离子配合物和非配位阴离子的离子型催化剂的描述见于US5 064802、5132380、5198401、5278119、5321106、5347024、5408017、5599671、和WO92/00333和WO93/14132中。这些文献中教导了一种优选的制备方法,其中非配位阴离子前体使金属茂质子化从而通过质子化作用从过渡金属上夺取烷基/氢负离子使之成为阳离子并与所述非配位阴离子电荷平衡。由于这种金属茂的夺取和插入配体也可以是本发明金属化合物的配体,所以可按类似的方法制备活性聚合催化剂组分。
也可使用不含活性质子但能产生活性金属阳离子配合物和非配位阴离子的电离离子化合物。参见EP-A-0426637、EP-A-0573403和US 5387568所教导的离子化合物。所述电离离子化合物(非布朗斯台德酸)的反应性阳离子包括二茂铁鎓、银、鎓、三苯基碳离子和三乙基硅锗,或碱金属或碱土金属阳离子如钠、镁或锂阳离子。另一类适用于本发明的非配位阴离子前体是包含碱金属或碱土金属阳离子和如上所述非配位阴离子的水合盐。所述水合盐可通过金属阳离子-非配位阴离子盐与水反应制备,例如可商购或易合成的LiB(pfp)4水解产生[LixH2O][B(pfp)4],其中(pfp)为五氟苯基或全氟苯基。
能形成耐水(或其它布朗斯台德或路易斯酸)降解的配位配合物的任何金属或准金属均可用于或包含在所述非配位阴离子中。适合的金属包括但不限于铝、金、和铂等。适合的准金属包括但不限于硼、磷、和硅等。前面几段的文献中关于非配位阴离子及其前体的描述引入本文供参考。
另一种制备本发明活性聚合催化剂的方法使用离子化阴离子前体,它们开始时为中性路易斯酸但与本发明化合物发生电离反应时形成金属阳离子配合物和非配位阴离子,例如三(五氟苯基)硼夺取烃基、氢负离子或甲硅烷基配体产生本发明金属阳离子配合物和稳定的非配位阴离子,参见EP-A-0427697和EP-A-0520732关于利用第4族金属茂化合物的说明。还参见EP-A-0495375的方法和化合物。这些文献中关于非配位阴离子及其前体的描述同样引入本文供参考。
当离子型非配位阴离子前体的阳离子部分为布朗斯台德酸如质子或质子化路易斯酸(不包括水)、或可还原的路易斯酸如二茂铁鎓或银阳离子、或碱金属或碱土金属阳离子如钠、镁或锂阳离子时,所述过渡金属与活化剂之摩尔比可以是任何比例,但优选为约10∶1至1∶10、更优选约5∶1至1∶5、甚至更优选约2∶1至1∶2、最优选约1.2∶1至1∶1.2,最优选约1∶1的比例。
本发明催化剂配合物适用于通常已知可在配位聚合条件下用金属茂聚合的不饱和单体的聚合。此条件是公知的,包括溶液聚合、淤浆聚合、气相聚合和高压聚合。本发明催化剂可被负载,同样特别适用于在单一、串联或并联反应器中进行的采用固定床、移动床、流化床、淤浆或溶液法的已知操作方式。
使用本发明催化剂时,特别是固定在载体上时,总的催化剂体系一般还包含一或多种清除化合物。本文所用术语“清除化合物”意指包括能有效地从反应环境中除去极性杂质的那些化合物。杂质可能不注意地随任何聚合反应组分特别是随溶剂、单体和催化剂进料一起引入,对催化剂活性和稳定性有不利影响。可能导致催化活性下降甚至消除,特别是离子化阴离子前体活化催化剂体系时。所述极性杂质或催化剂毒物包括水、氧气、金属杂质等。优选在其进入反应容器之前采取措施,例如在合成或制备各种组分之后或期间进行化学处理或仔细的分离技术,但在聚合过程中通常仍使用少量的清除化合物。
所述清除化合物典型地是有机金属化合物如US 5153157、5241025和WO-A-91/09882、WO-A-94/03506、WO-A-93/14132和WO95/07941的第13族有机金属化合物。例子包括三乙基铝、三乙基硼烷、三异丁基铝、甲基铝氧烷、异丁基铝氧烷、和正辛基铝。优选有与金属或准金属中心共价键合的庞大或C6-C20线型烃基取代基的那些清除化合物以使与活性催化剂的副作用最小。例子包括三乙基铝,但更优选庞大的化合物如三异丁基铝、三异戊烯基铝,和长链线型烷基取代的铝化合物如三正己基铝、三正辛基铝或三正十二烷基铝。用铝氧烷作活化剂时,存在的超过活化所述催化剂所需量的任何过量铝氧烷将起清除化合物的作用,可能不必加入其它的清除化合物。铝氧烷也可以清除量与其它活化方法一起使用,例如甲基铝氧烷和三异丁基铝氧烷。在聚合反应期间使与本发明第4-9族催化剂化合物一起使用的清除剂量小至提高活性的有效量,如果进料可能无外来杂质则完全避免。
本发明催化剂可被负载用于气相、本体、淤浆聚合法等。本领域已知许多负载方法用于烯烃的共聚,特别是用于铝氧烷活化的催化剂。在最宽的范围内任何方法均适用于本发明。参见例如US 5057475和5227440。负载型离子催化剂的例子见于WO94/03056。特别有效的方法是US 5643847和WO96/04319中所述的方法。可如US 5001205和5229478中关于乙烯-丙烯橡胶所述使用铝氧烷助催化剂活化的本体或淤浆法用负载型本发明第4-9族金属化合物,这些方法还适合于本申请的催化剂体系。根据该领域的知识可使用无机氧化物和聚合物颗粒载体。参见US 5422325、5427991、5498582和5466649,及WO93/11172和WO94/07928。上述文献均引入本文供参考。
在本发明方法的优选实施方案中,以液相(溶液、淤浆、悬浮液、本体相或其组合)、高压液体或超临界流体相、或气相使用所述催化剂体系。可在单一、并联或串联反应器中使用这些方法的任一种。所述液相法包括使烯烃单体与上述催化剂体系在适合的稀释剂或溶剂中接触,使所述单体反应足够长时间产生本发明共聚物。烃基溶剂是适用的,脂族和芳族均可,优选己烷和甲苯。卤代烃溶剂例如二氯甲烷也适用。典型地使催化剂与液态单体的浆液接触进行本体和淤浆法,催化剂体系被负载。气相法典型地使用负载型催化剂,以适用于通过配位聚合制备乙烯均聚物或共聚物的任何已知方式进行。说明性的例子可见US 4543399、4588790、5028670、5382638、5352749、5436304、5453471和5463999及WO95/07942。这些文献均引入本文供参考。
一般而言,聚合反应温度可从约-50℃至约250℃改变。优选反应温度条件为-20至220℃、更优选低于200℃。压力可为约1mmHg至2500bar、优选0.1至1600bar、最优选1.0至500bar。要生产较低分子量的共聚物(例如Mn<10000)时,适合在高于约0℃的温度和500bar的压力下进行反应。此外,US 5278119的多硼活化剂可用于促进本发明低分子量共聚物的制备。
将乙烯和可选地一或多种其它单体加入处于低压(典型地<50bar)、20-250℃的典型温度下的反应容器中,所述反应容器中有在溶剂如己烷或甲苯中形成淤浆的本发明催化剂,产生线型聚乙烯,包括高和超高分子量聚乙烯,包括均聚物和与其它α-烯烃单体、α-烯属和/或非共轭二烯烃例如C3-C20烯烃、二烯烃或环烯烃的共聚物。典型地通过冷却除去聚合热。例如,可使用氢气作为反应改性剂(100-200ppm)、C4-C8共聚单体进料流(0.5-1.2mol%)和C2进料流(25-35mol%),在2000-3000kPa和60-160℃下操作的连续流化床气相反应器中进行气相聚合。参见US 4543399、4588790、5028670、5405922和5462999,这些文献引入本文供参考。
用本发明催化剂在传统的溶液聚合工艺下或者通过将乙烯气体引入浆液中,用所述α-烯烃或环烯烃或其与其它单体(可聚合和不可聚合)的混合物作为聚合稀释剂,使本发明催化剂悬浮于其中,可制备高分子量和低结晶度的乙烯-α-烯烃(包括乙烯-环烯烃和乙烯-α-烯烃-二烯烃)弹性体。典型的乙烯压力在10和1000psig(69-6895kPa)之间,聚合稀释剂温度典型地在-10-160℃之间。所述方法可在搅拌罐式反应器或串联或并联操作的多个反应器中进行。参见US 5001205、WO96/33227和WO97/22639,这些文献中关于聚合方法、离子型活化剂和适用的清除化合物的描述引入本文供参考。
还可利用本发明负载型催化剂的预聚进一步控制按传统教导的典型淤浆或气相反应过程中聚合物颗粒的形态。例如,这可通过C2-C6α-烯烃预聚一段有限的时间实现,例如使乙烯与所述负载型催化剂在-15至30℃的温度和高达约250psig(1724kPa)的乙烯压力下接触75分钟获得在所述载体之上的分子量为30000-150000的聚合物涂层。然后将所述预聚的催化剂用于上面所指的聚合方法。此外还可利用聚合物树脂作为载体涂层,典型地将固态载体悬浮于诸如聚苯乙烯等材料的溶解树脂中,然后分离和干燥。
除前面已具体描述的那些单体之外,其它烯属不饱和单体也可用本发明催化剂聚合,例如苯乙烯、烷基取代的苯乙烯、亚乙基降冰片烯、降冰片二烯、二环戊二烯、和其它烯属不饱和单体,包括其它环烯烃,如环戊烯、降冰片烯和烷基取代的降冰片烯。此外,还可通过共聚掺入高达100或更多链节单元的α-烯属大分子单体。
本发明催化剂组合物可如上所述单独地用于配位聚合,或者可与其它已知的烯烃聚合催化剂化合物混合制备聚合物共混物。使用配位催化剂化合物的混合物,可在与使用单一催化剂组合物时相似的聚合条件下制备聚合物共混物。从而可获得分子量分布(“MWD”)增加的聚合物以改善加工性和用混合催化剂体系制备的聚合物所带来的其它传统的益处。
实施例
提供以下实施例进一步说明前面的论述。除非另有说明,所有份数、比例和百分率均基于重量。所有的反应和操作均用干燥无氧的溶剂在惰性氮气氛下进行。尽管这些实施例可能涉及本发明的一些实施方案,但不在任何方面限制本发明。在这些实施例中,使用一些缩写以便于描述。这些缩写包括对元素的标准化学缩写和一些普遍接受的缩写,如:Me=甲基、Et=乙基、Bu=丁基、ph=苯基、和thf=四氢呋喃。附表中所用缩写包括Cat=催化剂、T=温度、P=压力、t=时间、TM=过渡金属、Br=支链数/1000C原子。
除非另有说明,所有分子量均为重均分子量。除非另有说明,分子量(重均分子量(Mw)和数均分子量(Mn))用配有示差折光指数检测器并用聚苯乙烯标准校正的Waters 150 Gel PermeationChromatograph通过凝胶渗透色谱法测量。用三个串联的Shodex GPCAT-80 M/S柱根据试样的溶解度在THF(45℃)或1,2,4-三氯苯(145℃)中检测试样。该技术描述在“聚合物和相关材料的液相色谱Ⅲ(Liquid Chromatography of Polymers and Related Materials Ⅲ)”,J.Cazes Ed.,Marcel Decker,1981,p207中,该文献引入本文供参考。未采用柱分布校正,但按一般可接受的标准例如NationalBureau of Standards Polyethylene 1475,证明由洗脱时间计算的Mw/Mn精确为0.1单位。数字分析用来自Waters Corporation的Expert Ease软件进行。
实施例1
[(Ph2PCH2SiMe2)2N]TiCl2(1)的合成
向(Ph2PCH2SiMe2)2NH(0.500g,0.944mmol)的戊烷(15ml)溶液中加入1.6M BuLi的己烷溶液(0.59ml,0.94mmol)。添加时,生成白色沉淀,将混合物在室温下搅拌30分钟。使固体沉降,通过吸移管除去溶剂。固体用戊烷(10ml)洗涤,然后溶于thf(10ml)中。将所述thf溶液滴加至TiCl3·3thf(0.350g,0.944mmol)的thf(30ml)悬浮液中。添加时,颜色由浅蓝变成橄榄绿色。在室温下搅拌16小时后,在减压下除去挥发分,残余物用甲苯(30ml)萃取。深绿色溶液通过Celite过滤,浓缩至10ml,冷却至-30℃。离析出产品,为灰绿色晶体(0.291g,0.449mmol,48%)。元素分析、IR光谱、和磁矩与题目化合物一致。
实施例2
[(Ph2PCH2SiMe2)2N]VCl2(2)的合成
如实施例1中针对Ti衍生物所述由VCl3·3thf(0.353g,0.944mmol)和(Ph2PCH2SiMe2)2NH(0.500g,0.944mmol)合成该化合物。从甲苯/戊烷中离析出产品,为深红色晶体。产量为0.415g(0.638mmol,68%)。元素分析、IR光谱、磁矩、和X-射线晶体数据与题目化合物一致。
实施例3
[(Ph2PCH2SiMe2)2N]CrCl2(thf)(3)的合成
如实施例1中针对Ti衍生物所述由CrCl3·3thf(0.707g,1.89mmol)和(Ph2PCH2SiMe2)2NH(1.00g,1.89mmol)合成该化合物。从甲苯/戊烷中离析出产品,为品红微晶。一分子thf与所述金属配位。产量为0.644g(0.890mmol,47%)。元素分析、IR光谱、磁矩、和X-射线晶体数据与题目化合物一致。
实施例4
[(Ph2PCH2SiMe2)2N]FeCl2(4)的合成
如实施例1中针对Ti衍生物所述由FeCl3(0.153g,0.944mmol)和(Ph2PCH2SiMe2)2NH(0.500g,0.944mmol)合成该化合物。从甲苯/戊烷中离析出产品,为深绿-棕色晶体。产量为0.383g(0.584mmol,62%)。元素分析、IR光谱、和磁矩与题目化合物一致。
实施例5(对比)
[(Et2NCH2CH2)2N]ScCl2(5)的合成
将(Et2NCH2CH2)2NLi(0.731g,3.30mmol)的thf(7ml)溶液滴加至-78℃的ScCl3(0.500g,3.30mmol)的thf(30ml)悬浮液中。加完后,使混合物缓慢升至室温,搅拌18小时。在减压下除去挥发分,残余物用戊烷(80ml)萃取。溶液通过Celite过滤,冷却至-25℃。离析出产品,为白色块状晶体(0.244g,0.739mmol,22%)。元素分析和1H NMR波谱与题目化合物一致。
实施例6-7
[(Et2NCH2CH2)N]TiCl2(6)和[(Et2NCH2CH2)N]VCl2(7)的合成
题目化合物如Wills et al.,化学会志(J.Chem.Soc.),道尔顿学报(Dalton Trans.),p.1253(1989)中所述合成。
实施例8
[(Et2NCH2CH2)2N]CrCl2(8)的合成
如实施例5中针对Sc衍生物所述由CrCl3·3thf(1.69g,4.52mmol)和(Et2NCH2CH2)2NLi(1.00g,4.52mmol)合成该化合物,但反应在室温下搅拌3小时,产品从戊烷/甲苯中结晶。离析出产品,为深绿-棕色晶体(0.528g,1.57mmol,35%)。元素分析、IR光谱、和磁矩与题目化合物一致。
实施例9
[(Me2NCH2)2C6H3]VCl2(9)的合成
将(Me2NCH2)2C6H3Li(0.500g,2.52mmol)的苯(10ml)溶液滴加至VCl3·3thf(0.943g,2.52mmol)的苯(40ml)悬浮液中。添加时,固体溶解形成深红色溶液。在室温下搅拌18小时后,溶液通过Celite过滤,浓缩至20ml。溶液用戊烷(20ml)稀释,过滤。将溶液冷却至-30℃,形成大量红色针状物,所述苯部分结晶。使混合物升温直至所述苯刚熔化,收集所述晶体产品。产量为0.287g(0.916mmol,36%)。元素分析、IR光谱和磁矩与题目化合物一致。
实施例10
[(Me2NCH2)2C6H3]CrCl2(10)的合成
如实施例9中针对V衍生物所述由CrCl3·3thf(0.453g,1.21mmol)和(Me2NCH2)2C6H3Li(0.240g,1.21mmol)合成该化合物。离析出产品,为绿色微晶(0.152g,0.484mmol,40%)。元素分析、IR光谱、和磁矩与题目化合物一致。
实施例11
[(Me2NCH2)2C6H3]FeCl2(11)的合成
题目化合物如Kanters,et al.,Acta.Cryst.,vol.C4l,p.893(1985)中所述合成。
实施例12-13
[(Et2NCH2CH2)2N]TiMe2(12)和[(Et2NCH2CH2)2N]VMe2(13)的合成
题目化合物如Wills et al.,化学会志(J.Chem.Soc.),道尔顿学报(Dalton Trans.),p.1253(1989)中所述合成。
实施例14-54
乙烯均聚方法(MAO活化)
聚合在热氮气吹扫的500ml Zipperclave反应器(AutoclaveEngineers)中在作为聚合溶剂/稀释剂的无水己烷(250ml)中进行。除非另有说明,催化剂用甲基铝氧烷(MAO)在10%(重)甲苯溶液(Albemarle)中活化。通常,在注入所述装有己烷的反应器中之前,将2.5ml所述MAO溶液用新甲苯稀释。然后,在设计的压力和温度下用乙烯饱和反应器中的己烷。在所述干箱中使5-50mg催化剂前体与甲苯(50ml)混合制备催化剂溶液。将所述催化剂前体溶液泵入反应器中,与已预先加入的助催化剂溶液结合,直至聚合期间补充乙烯流量变得恒定。使蒸汽/水混合物流过反应器夹套控制反应器温度。聚合运行30分钟。运行结束时,排出乙烯,使反应器冷却。将反应器内容物倒入1L烧杯中,用异丙醇或丙酮处理。将聚合物溶剂混合物用氮气泄料或过滤以回收所述聚合物。最终的产品在60-90℃下真空干燥约12小时。聚合条件和结果示于表1中。
表1
实施例 | 催化剂 | T(℃) | P(psi) | t(min) | TM(μmol) | Al∶TM | 产量(g) | gPE/mmolTM·h | Mw(k) | MWD |
14 | 1 | 30 | 76 | 30 | 25.6 | 149 | 2.2 | 169 | 506 | 2.4 |
15 | 1 | 60 | 125 | 30 | 9.6 | 400 | 2.9 | 612 | 244 | 77 |
16 | 1 | 115 | 275 | 30 | 9.6 | 400 | 3.6 | 758 | 33 | 22 |
17 | 1 | 140 | 375 | 30 | 24.7 | 155 | 4.0 | 325 | 16 | 11 |
18 | 2 | 30 | 75 | 30 | 0.6 | 6079 | 0.6 | 1809 | 1437 | 2.6 |
19 | 2 | 60 | 125 | 30 | 1.1 | 3367 | 1.2 | 2145 | 1136 | 2.5 |
20 | 2 | 115 | 276 | 30 | 5.9 | 649 | 1.1 | 386 | 135 | 159 |
21 | 2 | 140 | 350 | 30 | 21.2 | 180 | 0.9 | 88 | 75 | 89 |
22 | 3 | 30 | 75 | 30 | 2.2 | 1733 | 2.8 | 2569 | 448 | 16 |
23 | 3 | 60 | 125 | 30 | 8.6 | 447 | 4.0 | 934 | 134 | 2.9 |
24 | 3 | 115 | 275 | 30 | 8.4 | 454 | 8.2 | 1936 | 53 | 2.2 |
25 | 3 | 140 | 351 | 30 | 12.1 | 318 | 0.4 | 66 | 42 | 7.2 |
26 | 4 | 30 | 75 | 30 | 44.9 | 171 | 0.5 | 22 | NM | NM |
27 | 4 | 60 | 125 | 30 | 43.9 | 174 | 0.6 | 27 | NM | NM |
28 | 4 | 115 | 275 | 30 | 44.9 | 171 | 0.7 | 29 | NM | NM |
29 | 5 | 30 | 75 | 30 | 30.2 | 127 | 0.4 | 23 | NM | NM |
30 | 5 | 60 | 125 | 30 | 60.5 | 63 | 0.5 | 15 | NM | NM |
31 | 5 | 115 | 275 | 30 | 95.2 | 40 | 0.3 | 6 | NM | NM |
32 | 5 | 140 | 350 | 30 | 82.0 | 47 | 1.2 | 29 | 182 | 54 |
33 | 6 | 30 | 75 | 30 | 87.3 | 44 | 0.3 | 6 | NM | NM |
34 | 6 | 60 | 125 | 30 | 88.2 | 43 | 1.3 | 29 | 504 | 6.4 |
35 | 6 | 115 | 275 | 30 | 11.3 | 338 | 7.6 | 1345 | 190 | 11 |
36 | 6 | 140 | 350 | 30 | 49.8 | 77 | 11.0 | 442 | 278 | 6.2 |
37 | 7 | 30 | 75 | 30 | 83.0 | 46 | 0.7 | 17 | NM | NM |
38 | 7 | 60 | 125 | 30 | 86.6 | 44 | 1.7 | 39 | 177 | 27 |
39 | 7 | 115 | 275 | 30 | 47.3 | 81 | 7.9 | 332 | 59 | 4.0 |
40 | 7 | 140 | 350 | 30 | 57.1 | 67 | 11.6 | 406 | 53 | 2.9 |
41 | 8 | 30 | 75 | 30 | 85.3 | 90 | 0.6 | 15 | NM | NM |
42 | 8 | 60 | 125 | 30 | 87.2 | 88 | 0.5 | 12 | NM | NM |
43 | 8 | 115 | 275 | 30 | 85.4 | 90 | 0.7 | 17 | NM | NM |
44 | 9 | 30 | 75 | 30 | 20.1 | 190 | 4.7 | 468 | NM | NM |
45 | 9 | 60 | 125 | 30 | 21.1 | 182 | 3.3 | 313 | NM | NM |
46 | 9 | 115 | 275 | 30 | 10.5 | 364 | 0.8 | 142 | NM | NM |
47 | 9 | 140 | 350 | 30 | 84.3 | 45 | 0.8 | 19 | NM | NM |
48 | 10 | 30 | 75 | 30 | 61.1 | 125 | 0.8 | 26 | NM | NM |
49 | 10 | 60 | 125 | 30 | 91.7 | 84 | 0.9 | 19 | NM | NM |
50 | 10 | 115 | 275 | 30 | 91.7 | 84 | 0.6 | 14 | NM | NM |
51 | 10 | 140 | 350 | 30 | 91.7 | 84 | 0.9 | 20 | NM | NM |
52 | 11 | 30 | 75 | 30 | 86.8 | 88 | 0.5 | 11 | NM | NM |
53 | 11 | 60 | 125 | 30 | 90.5 | 85 | 0.7 | 15 | NM | NM |
54 | 11 | 115 | 275 | 30 | 90.5 | 85 | 0.9 | 19 | NM | NM |
NM-未测量
实施例55-59
丙烯均聚方法(MAO活化)
聚合在热氮气吹扫的500ml Zipperclave反应器(AutoclaveEngineers)中进行。除非另有说明,催化剂用甲基铝氧烷(MAO)在10%(重)甲苯溶液(Albemarle)中活化。通常,在注入反应器中之前,将2.5ml所述MAO溶液用新甲苯稀释。然后,在室温下将液态丙烯(300ml)加入反应器中,将反应器内容物加热至要求的聚合温度。在所述干箱中使5-50mg催化剂前体与甲苯(50ml)混合制备催化剂溶液。将所述催化剂前体溶液泵入反应器中,与已预先加入的助催化剂溶液结合,直至聚合期间反应器温度和压力变得恒定。使蒸汽/水混合物流过反应器夹套控制反应器温度。聚合运行30分钟。运行结束时,排出丙烯,使反应器冷却。将反应器内容物倒入1L烧杯中用己烷或甲苯漂洗,用异丙醇或丙酮处理。将聚合物溶剂混合物用氮气泄料或过滤以回收所述聚合物。最终的产品在60-90℃下真空干燥约12小时。聚合条件和结果示于表2中。
表2
实施例 | 催化剂 | T(℃) | C3(mL) | t(min) | μmol TM | Al∶TM | 产量(g) | gPP/mmol TM·h |
55 | 3 | 60 | 300 | 30 | 1.1 | 3466 | 0.3 | 615 |
56 | 4 | 60 | 300 | 30 | 43.9 | 174 | 1.0 | 46 |
57 | 5 | 60 | 300 | 30 | 84.1 | 46 | 0.3 | 7 |
58 | 8 | 60 | 300 | 30 | 85.4 | 90 | 1.1 | 25 |
59 | 10 | 60 | 300 | 30 | 100.9 | 76 | 0.9 | 17 |
实施例60-72
乙烯/1-己烯共聚方法(MAO活化)
除在紧邻加入所述MAO之前将1-己烯加入反应器之外,如前面针对乙烯均聚所述进行乙烯/1-己烯的共聚。聚合条件和结果示于表3中,所选试样的聚合物特征示于表4中。
表3
实施例 | 催化剂 | T(℃) | PC2=(psi) | C6=(mL) | t(min) | TM(μmol) | Al∶TM | 产量(g) | gEH/mmol TM·h |
60 | 1 | 60 | 60 | 15 | 30 | 11.1 | 345 | 4.1 | 736 |
61 | 2 | 60 | 60 | 15 | 30 | 45.7 | 84 | 0.9 | 40 |
62 | 3 | 60 | 61 | 15 | 30 | 4.4 | 866 | 4.3 | 1922 |
63 | 4 | 60 | 60 | 15 | 30 | 43.9 | 174 | 0.6 | 25 |
64 | 5 | 60 | 60 | 15 | 30 | 91.7 | 42 | 0.2 | 5 |
65 | 6 | 60 | 60 | 15 | 30 | 85.5 | 45 | 0.5 | 11 |
66 | 6 | 115 | 115 | 15 | 30 | 14.4 | 532 | 8.9 | 1231 |
67 | 7 | 60 | 60 | 15 | 30 | 86.6 | 44 | 0.3 | 7 |
68 | 7 | 115 | 275 | 15 | 30 | 73.2 | 105 | 3.0 | 81 |
69 | 8 | 60 | 60 | 15 | 30 | 85.4 | 90 | 0.7 | 16 |
70 | 9 | 60 | 60 | 15 | 30 | 93.9 | 41 | 0.9 | 19 |
71 | 10 | 60 | 60 | 15 | 30 | 84.0 | 91 | 0.5 | 13 |
72 | 11 | 60 | 60 | 15 | 30 | 90.5 | 85 | 0.7 | 15 |
表4
实施例 | 催化剂 | Mw(k) | MWD | Br |
60 | 1 | 65 | 2.0 | 2 |
62 | 3 | 68 | 1.8 | 1 |
66 | 6 | 75 | 8.3 | 5 |
68 | 7 | 49 | 12.0 | 8 |
实施例73
使用[(Ph2PCH2SiMe2)2N]CrCl2(thf)(MAO活化)的乙烯/降冰片烯共聚
除在紧邻加入所述MAO之前将降冰片烯(22ml,80wt%己烷溶液)加入反应器之外,如前面针对乙烯均聚所述进行乙烯/降冰片烯的共聚。使用3.6mmol[(Ph2PCH2SiMe2)2N]CrCl2(thf)和1075的Al∶TM比,用61psi乙烯在60℃下进行聚合。共聚物的产量为2.6g,得到活性为1448g ENB/mmol TM·h。该共聚物的Mw=647k,MWD=2.9。
实施例74-81
乙烯均聚方法([Ph3C][B(C6F5)4]活化)
聚合在热氮气吹扫的500ml Zipperclave反应器(AutoclaveEngineers)中在作为聚合溶剂/稀释剂的无水己烷(250ml)中进行。向所述稀释剂中加入0.2ml 25%(重)三异丁基铝的庚烷溶液(AkzoNobel)。然后,在设计的压力和温度下用乙烯饱和反应器中的己烷。在所述干箱中使5-50mg催化剂前体与等摩尔量的[Ph3C][B(C6F5)4]在甲苯(50ml)中混合制备催化剂溶液。将所述催化剂溶液泵入反应器中,直至聚合期间补充乙烯流量变得恒定。使蒸汽/水混合物流过反应器夹套控制反应器温度。聚合运行30分钟。运行结束时,排出乙烯,使反应器冷却。将反应器内容物倒入1L烧杯中,用异丙醇或丙酮处理。将聚合物溶剂混合物用氮气泄料或过滤以回收所述聚合物。最终的产品在60-90℃下真空干燥约12小时。聚合条件和结果示于表5中。
表5
实施例 | 催化剂 | T(℃) | P(psi) | t(min) | TM(μmol) | 产量(g) | gPE/mmolTM·h | Mw(k) | MWD |
74 | 12 | 30 | 75 | 30 | 31.4 | 1.4 | 86 | 772 | 4.3 |
75 | 12 | 60 | 125 | 23 | 7.8 | 11.0 | 3679 | NM | NM |
76 | 12 | 115 | 275 | 30 | 7.2 | 7.4 | 2059 | NM | NM |
77 | 12 | 140 | 350 | 30 | 6.8 | 5.0 | 1463 | NM | NM |
78 | 13 | 32 | 75 | 30 | 29.2 | 0.1 | 4 | NM | NM |
79 | 13 | 60 | 125 | 30 | 28.4 | 0.3 | 18 | NM | NM |
80 | 13 | 115 | 275 | 30 | 65.7 | 3.3 | 100 | 241 | 3.5 |
81 | 13 | 140 | 350 | 30 | 38.3 | 0.8 | 41 | NM | NM |
实施例82-83
丙烯均聚方法([Ph3C][B(C6F5)4]活化)
聚合在热氮气吹扫的500ml Zipperclave反应器(AutoclaveEngineers)中进行。向所述反应器中加入0.2ml 25%(重)三异丁基铝的庚烷溶液(Akzo Nobel)。然后,在室温下将液态丙烯(300ml)加入所述反应器中,将内容物加热至要求的聚合温度。在所述干箱中使5-50mg催化剂前体与等摩尔量的[Ph3C][B(C6F5)4]在甲苯(50ml)中混合制备催化剂溶液。将所述催化剂前体溶液泵入反应器中,直至聚合期间反应器温度和压力变得恒定。使蒸汽/水混合物流过反应器夹套控制反应器温度。聚合运行30分钟。运行结束时,排出丙烯,使反应器冷却。将反应器内容物倒入1L烧杯中用己烷或甲苯漂洗,用异丙醇或丙酮处理。将聚合物溶剂混合物用氮气泄料或过滤以回收所述聚合物。最终的产品在60-90℃下真空干燥约12小时。聚合条件和结果示于表6中。
表6
实施例 | 催化剂 | T(℃) | C3(ml) | t(min) | TM(μmol) | 产量(g) | gPP/mmolTM·h | Mw(k) | MWD |
82 | 12 | 60 | 300 | 30 | 33.8 | 6.6 | 387 | 394 | 6.5 |
83 | 13 | 60 | 300 | 30 | 33.5 | 0.6 | 35 | NM | NM |
实施例84-87
乙烯/1-己烯共聚方法([Ph3C][B(C6F5)4]活化)除在紧邻加入所述三异丁基铝之前将1-己烯加入反应器之外,如前面针对用[Ph3C][B(C6F5)4]活化的乙烯均聚所述进行乙烯/1-己烯的共聚。聚合条件和结果示于表7中。
表7
实施例 | 催化剂 | T(℃) | PC2=(psi) | C6=(mL) | t(min) | TM(μmol) | 产量(g) | gEH/mmolTM·h | Mw(k) | MWD | Br |
84 | 12 | 60 | 60 | 15 | 30 | 12.2 | 5.1 | 829 | 549 | 2.6 | 34 |
85 | 12 | 115 | 150 | 15 | 30 | 11.6 | 4.6 | 785 | 157 | 4.0 | 12 |
86 | 13 | 60 | 60 | 15 | 30 | 59.9 | 0.1 | 3 | NM | NM | NM |
87 | 13 | 115 | 150 | 15 | 30 | 73.1 | 0.3 | 7 | NM | NM | NM |
Claims (14)
1.一种配位聚合用催化剂配合物,包括活化的还原氧化态的第4-9族第一或第二行过渡金属配合物,所述配合物有一价阴离子三齿辅助配体体系,所述一价阴离子三齿辅助配体体系由两个通过配价键与所述金属键合的第15或16族原子和一个与所述金属共价键合并通过含有第13-16族元素的桥连基与所述第15或16族原子相连的第15族原子或芳环碳原子构成。
其中M为还原氧化态的第4-9族过渡金属;
每个X独立地为卤素、醇根、芳氧根、氨根、膦根、氢负离子、烃基、取代的烃基、卤碳基、取代的卤碳基、烃基-或卤碳基-取代的有机准金属,或者两个X基相连并与所述过渡金属或L基键合形成环状结构,或者一或多个X可包含L基;
L为稳定所述配合物的中性供电子基团;
R有与X相同的定义;
E独立地为选自第15和16族的供电子基团;
E’为选自第15族的一价阴离子供电子基团;
T为包含第13-16族任一元素或元素组合的桥连基团;
n为1至3的数,通过平衡所述金属上的电荷使所述金属处于还原氧化态且所述配合物上总电荷为中性所决定;
p根据稳定所述配合物的需要为0至3的数;
q为1或2,以使E仍为中性供电子基团。
3.权利要求2的催化剂体系,其中E选自N、P、S和O,E’为N或P。
4.权利要求2的催化剂体系,其中M处于+3氧化态,n为2。
5.权利要求2的催化剂体系,其中M选自Ti、V、Cr、Mn、Fe和Co。
6.权利要求2的催化剂体系,其中所述催化剂活化剂化合物为烷基铝氧烷、烷基铝助催化剂活化剂、或离子化非配位阴离子前体化合物。
7.一种聚合方法,特征在于使一或多种可通过配位聚合而聚合的单体在适合的配位聚合条件下与权利要求1的催化剂配合物接触。
8.一种聚合方法,特征在于使一或多种可通过配位聚合而聚合的单体在适合的配位聚合条件下与权利要求2的催化剂配合物接触。
9.权利要求7的方法,其中所述单体选自乙烯、α-烯烃、环烯烃、非共轭二烯烃、炔属不饱和单体、烯属不饱和芳族单体和C20-C200大分子单体。
10.权利要求9的方法,其中所述单体包括至少一种选自乙烯和C3-C20α-烯烃的单体。
11.权利要求9的方法,其中所述催化剂体系包含一种固体颗粒状载体。
12.权利要求8的方法,其中所述单体选自乙烯、α-烯烃、环烯烃、非共轭二烯、炔属不饱和单体、烯属不饱和芳族单体和C20-C200大分子单体。
13.权利要求12的方法,其中所述单体包括至少一种选自乙烯和C3-C20α-烯烃的单体。
14.权利要求12的方法,其中所述催化剂体系包含一种固体颗粒状载体。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US8396698P | 1998-05-01 | 1998-05-01 | |
US60/083,966 | 1998-05-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1297456A true CN1297456A (zh) | 2001-05-30 |
CN1149229C CN1149229C (zh) | 2004-05-12 |
Family
ID=22181810
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB998052124A Expired - Fee Related CN1149229C (zh) | 1998-05-01 | 1999-04-29 | 用于烯烃聚合的含三齿配体的金属催化剂配合物 |
Country Status (10)
Country | Link |
---|---|
US (1) | US6294495B1 (zh) |
EP (1) | EP1084152B1 (zh) |
JP (1) | JP2002513823A (zh) |
KR (1) | KR100586118B1 (zh) |
CN (1) | CN1149229C (zh) |
BR (1) | BR9908887A (zh) |
CA (1) | CA2321712C (zh) |
DE (1) | DE69904469T2 (zh) |
ES (1) | ES2184448T3 (zh) |
WO (1) | WO1999057159A1 (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003010207A1 (fr) * | 2001-07-23 | 2003-02-06 | Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences | Catalyseurs de polymerisation ou de copolymerisation d'olefines, leur procede de preparation et leur utilisation |
CN104235795A (zh) * | 2013-06-17 | 2014-12-24 | 欧司朗有限公司 | 用于照明装置的散热装置和照明装置 |
Families Citing this family (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4195138B2 (ja) * | 1998-12-10 | 2008-12-10 | 出光興産株式会社 | アルミニウムオキシ化合物、オレフィン重合用触媒成分及びポリオレフィンの製造方法 |
GB9914200D0 (en) * | 1999-06-17 | 1999-08-18 | Borealis As | Catalysts |
US6274684B1 (en) * | 1999-10-22 | 2001-08-14 | Univation Technologies, Llc | Catalyst composition, method of polymerization, and polymer therefrom |
US6475946B1 (en) * | 1999-10-22 | 2002-11-05 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalysis with aryl substituted carbenium cationic complexes |
US6300439B1 (en) * | 1999-11-08 | 2001-10-09 | Univation Technologies, Llc | Group 15 containing transition metal catalyst compounds, catalyst systems and their use in a polymerization process |
CA2393327A1 (en) * | 1999-12-20 | 2001-06-28 | Exxon Chemical Patents Inc. | Processes for the preparation polyolefin resins using supported ionic catalysts |
KR100567100B1 (ko) * | 2000-03-24 | 2006-03-31 | 에스케이 주식회사 | 폴리에틸렌 제조용 균일활성종 촉매, 이의 제조방법 및이를 이용한 중합방법 |
JP2004530010A (ja) * | 2001-04-04 | 2004-09-30 | ダウ・グローバル・テクノロジーズ・インコーポレイテッド | 遷移金属ドナー錯体及びオレフィン重合方法 |
CA2447073A1 (en) * | 2001-05-10 | 2002-11-14 | Jessica A. Cook | Olefin polymerization catalysts containing a pyrrole bisimine ligand |
DE10163884A1 (de) | 2001-12-22 | 2003-07-10 | Henkel Kgaa | Neue Alkalische Protease aus Bacillus sp. (DSM 14392) und Wasch- und Reinigungsmittel enthaltend diese neue Alkalische Protease |
EP1325925A1 (en) * | 2002-01-03 | 2003-07-09 | Repsol Quimica S.A. | Chromium catalysts active in olefin polymerization |
EP1325924B1 (en) * | 2002-01-03 | 2005-03-16 | Repsol Quimica S.A. | Chromium catalysts active in olefin polymerisation |
US7943700B2 (en) * | 2002-10-01 | 2011-05-17 | Exxonmobil Chemical Patents Inc. | Enhanced ESCR of HDPE resins |
WO2004046214A2 (en) | 2002-10-15 | 2004-06-03 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
US6982305B2 (en) * | 2004-01-26 | 2006-01-03 | Equistar Chemicals, Lp | Olefin polymerization in the presence of a dehydrogenation catalyst |
EP1840130B1 (en) | 2005-01-21 | 2012-12-26 | Riken | Metal complex containing tridentate ligand, and polymerization catalyst comprising the same |
US20070117713A1 (en) * | 2005-11-21 | 2007-05-24 | Abbas Razavi | Tridentate metal catalyst for olefin polymerization |
US8092720B2 (en) * | 2006-07-25 | 2012-01-10 | National University Corporation Hokkaido University | Polymer-supported metal complex catalyst |
US8198373B2 (en) * | 2006-10-02 | 2012-06-12 | Exxonmobil Chemical Patents Inc. | Plastic toughened plastics |
CN101274968B (zh) * | 2007-03-28 | 2012-11-21 | 中国石油化工股份有限公司 | 一种用于生产宽分子量分布的聚乙烯的复合催化剂 |
CN107922441A (zh) * | 2015-06-30 | 2018-04-17 | 埃克森美孚化学专利公司 | 三齿双阴离子cnn配体的过渡金属络合物及其生产和用途 |
US9598444B2 (en) | 2015-06-30 | 2017-03-21 | Exxonmobil Chemical Patents Inc. | Transition metal complexes of tridentate dianionic CNN ligands, production and use thereof |
WO2018022263A1 (en) | 2016-07-29 | 2018-02-01 | Exxonmobil Chemical Patents Inc. | Polymerization processes using high molecular weight polyhydric quenching agents |
KR102587780B1 (ko) * | 2017-06-20 | 2023-10-13 | 다우 글로벌 테크놀로지스 엘엘씨 | 올레핀 중합을 위한 비아릴 페녹시기 iv 전이 금속 촉매 |
TW202120432A (zh) | 2019-10-08 | 2021-06-01 | 法商液態空氣喬治斯克勞帝方法研究開發股份有限公司 | 用於沉積含鋰層、島或簇的鋰前驅體 |
Family Cites Families (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0569388B1 (en) | 1990-12-27 | 1996-03-13 | Exxon Chemical Patents Inc. | An amido transition metal compound and a catalyst system for the production of isotactic polypropylene |
US5374696A (en) | 1992-03-26 | 1994-12-20 | The Dow Chemical Company | Addition polymerization process using stabilized reduced metal catalysts |
EP0789718B1 (en) | 1994-10-31 | 1998-04-08 | Dsm N.V. | Catalyst composition and process for the polymerization of an olefin |
US5880241A (en) * | 1995-01-24 | 1999-03-09 | E. I. Du Pont De Nemours And Company | Olefin polymers |
TR199700681T1 (xx) | 1995-01-24 | 1998-02-21 | E.I. Du Pont De Nemours And Company | alfa-olefinler ve olefin polimerleri ve bunlarla ilgili i�lemler. |
GB9522859D0 (en) | 1995-11-08 | 1996-01-10 | Borealis As | Compounds |
DE19548146C1 (de) * | 1995-12-21 | 1997-11-20 | Basf Ag | Tris(pyrazolyl)boratmetallkomplex-Katalysatoren und deren Verwendung |
EP0896589A1 (en) | 1996-05-03 | 1999-02-17 | Dsm N.V. | Supported catalyst composition and process for the polymerization of olefin monomers |
NL1003017C2 (nl) | 1996-05-03 | 1997-11-06 | Dsm Nv | Met een heteroatoom-bevattende groep gesubstitueerd fluoreen. |
AU2412597A (en) | 1996-05-03 | 1997-11-26 | Dsm N.V. | Inverted polyolefin copolymers |
NL1003018C2 (nl) | 1996-05-03 | 1997-11-06 | Dsm Nv | Met een heteroatoom-bevattende groep gesubstitueerde indeen. |
AU2411897A (en) | 1996-05-03 | 1997-11-26 | Dsm N.V. | Process for the polymerization of vinyl aromatic monomers |
NL1003007C2 (nl) | 1996-05-03 | 1997-11-06 | Dsm Nv | Met vertakte alkylgroepen gesubstitueerde cyclopentadieenverbinding. |
NL1003015C2 (nl) | 1996-05-03 | 1997-11-06 | Dsm Nv | Met chirale groepen gesubstitueerde cyclopentadieenverbinding. |
NL1003005C2 (nl) | 1996-05-03 | 1997-11-06 | Dsm Nv | Met lineaire groepen gesubstitueerde cyclopentadieenverbinding. |
BR9709144A (pt) | 1996-05-03 | 1999-08-03 | Dsm Nv | Processo para co-polimerização de uma olefina e um monômero aromático vinílico |
NL1003019C2 (nl) | 1996-05-03 | 1997-11-06 | Dsm Nv | Meervoudig gesubstitueerd cyclopentadieen. |
BR9708971A (pt) | 1996-05-03 | 1999-08-03 | Dsm Nv | Processo para a polimerização de alfa-olefinas |
NL1003012C2 (nl) | 1996-05-03 | 1997-11-06 | Dsm Nv | Met aralkylgroepen gesubstitueerde cyclopentadieenverbinding. |
WO1997042235A1 (en) | 1996-05-03 | 1997-11-13 | Dsm N.V. | Process for the production of polymers containing cyclic olefins |
AU2411797A (en) | 1996-05-03 | 1997-11-26 | Dsm N.V. | A process for making polyolefins having broad molecular weight distributions |
NL1003021C2 (nl) | 1996-05-03 | 1997-11-06 | Dsm Nv | Meervoudig gesubstitueerd cyclopentadieen. |
NL1003008C2 (nl) | 1996-05-03 | 1997-11-06 | Dsm Nv | Met een heteroatoom-bevattende groep gesubstitueerde cyclopentadieen- verbinding. |
NL1003016C2 (nl) | 1996-05-03 | 1997-11-06 | Dsm Nv | Gesubstitueerde pentadieenverbinding. |
JP2000510175A (ja) | 1996-05-03 | 2000-08-08 | ディーエスエム エヌ.ブイ. | エチレン、α―オレフィン及びジエンのターポリマーを調製する方法 |
EP0896596A1 (en) | 1996-05-03 | 1999-02-17 | Dsm N.V. | Process for the production of functional polyolefins |
NL1003014C2 (nl) | 1996-05-03 | 1997-11-06 | Dsm Nv | Met tertiaire groepen gesubstitueerde cyclopentadieenverbinding. |
AU3304997A (en) | 1996-05-31 | 1998-01-05 | Southern Illinois University | Methods of modulating aspects of brain neural plasticity by vagus nerve stimulation |
JP3893674B2 (ja) * | 1996-07-05 | 2007-03-14 | Jsr株式会社 | 重合用触媒 |
IL129929A0 (en) * | 1996-12-17 | 2000-02-29 | Du Pont | Polymerization of ethylene with specific iron or cobalt complexes novel pyridinebis (imines) and novel complexes of pyridinebis(imines) with iron and cobalt |
US6214761B1 (en) * | 1996-12-17 | 2001-04-10 | E. I. Du Pont De Nemours And Company | Iron catalyst for the polymerization of olefins |
EP0952998B1 (en) * | 1997-01-14 | 2002-06-19 | E.I. Du Pont De Nemours And Company | Polymerization of ethylene |
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 |
US5981783A (en) * | 1997-04-11 | 1999-11-09 | Polt Hill Institute | Chiral ligand system for main group and transition metal catalysts |
DE19719397A1 (de) * | 1997-05-07 | 1998-11-12 | Clariant Gmbh | Bleichaktive Metall-Komplexe |
DE19728021A1 (de) * | 1997-07-01 | 1999-01-07 | Clariant Gmbh | Metall-Komplexe als Bleichaktivatoren |
DE19728126A1 (de) * | 1997-07-02 | 1999-01-07 | Bayer Ag | Katalysatorsystem auf Basis von Monoazadien-Metallkomplexen |
US6096676A (en) * | 1997-07-02 | 2000-08-01 | Union Carbide Chemicals & Plastics Technology Corporation | Catalyst for the production of olefin polymers |
US5977393A (en) * | 1997-11-21 | 1999-11-02 | California Institute Of Technology | Schiff base derivatives of ruthenium and osmium olefin metathesis catalysts |
JP4062756B2 (ja) * | 1997-12-18 | 2008-03-19 | 東ソー株式会社 | オレフィン重合用触媒およびそれを用いたポリオレフィンの製造方法 |
JP4103161B2 (ja) * | 1997-12-18 | 2008-06-18 | 東ソー株式会社 | オレフィン重合用触媒およびそれを用いたポリオレフィンの製造方法 |
US6060568A (en) * | 1998-12-18 | 2000-05-09 | The Governors Of The University Of Alberta | Carbene transition metal catalysts |
-
1999
- 1999-04-29 KR KR1020007011335A patent/KR100586118B1/ko not_active IP Right Cessation
- 1999-04-29 US US09/302,243 patent/US6294495B1/en not_active Expired - Lifetime
- 1999-04-29 BR BR9908887-8A patent/BR9908887A/pt active Search and Examination
- 1999-04-29 WO PCT/US1999/009306 patent/WO1999057159A1/en active IP Right Grant
- 1999-04-29 CA CA002321712A patent/CA2321712C/en not_active Expired - Fee Related
- 1999-04-29 ES ES99920143T patent/ES2184448T3/es not_active Expired - Lifetime
- 1999-04-29 JP JP2000547127A patent/JP2002513823A/ja active Pending
- 1999-04-29 EP EP99920143A patent/EP1084152B1/en not_active Expired - Lifetime
- 1999-04-29 CN CNB998052124A patent/CN1149229C/zh not_active Expired - Fee Related
- 1999-04-29 DE DE69904469T patent/DE69904469T2/de not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003010207A1 (fr) * | 2001-07-23 | 2003-02-06 | Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences | Catalyseurs de polymerisation ou de copolymerisation d'olefines, leur procede de preparation et leur utilisation |
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 |
CN104235795A (zh) * | 2013-06-17 | 2014-12-24 | 欧司朗有限公司 | 用于照明装置的散热装置和照明装置 |
Also Published As
Publication number | Publication date |
---|---|
CA2321712C (en) | 2008-03-18 |
CN1149229C (zh) | 2004-05-12 |
BR9908887A (pt) | 2000-11-21 |
DE69904469D1 (de) | 2003-01-23 |
JP2002513823A (ja) | 2002-05-14 |
KR20010071147A (ko) | 2001-07-28 |
KR100586118B1 (ko) | 2006-06-02 |
ES2184448T3 (es) | 2003-04-01 |
DE69904469T2 (de) | 2003-04-17 |
EP1084152A1 (en) | 2001-03-21 |
EP1084152B1 (en) | 2002-12-11 |
CA2321712A1 (en) | 1999-11-11 |
WO1999057159A1 (en) | 1999-11-11 |
US6294495B1 (en) | 2001-09-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN1149229C (zh) | 用于烯烃聚合的含三齿配体的金属催化剂配合物 | |
CN1113900C (zh) | 用于烯烃聚合的混合过渡金属催化剂体系及用其聚合烯属不饱和单体的方法 | |
CN1095848C (zh) | 催化剂组合物、聚合方法及催化剂活化剂组合物 | |
CN1048255C (zh) | 烯烃聚合的固体催化剂与烯烃的聚合方法 | |
CN1106413C (zh) | 高温溶液聚合法 | |
KR100564506B1 (ko) | 에틸렌 공중합 방법 | |
CN1080268C (zh) | 催化剂组合物及其制备方法 | |
KR101414338B1 (ko) | 구아니디네이트 리간드를 갖는 올레핀 중합용 촉매 요소 | |
CN1292004A (zh) | 提高epdm型聚合中二烯单体转化率的方法 | |
CN1319103A (zh) | 具有唯一可活化配体的环戊二烯基/膦亚胺催化剂 | |
CN1321161A (zh) | 双-膦亚胺催化剂 | |
CN1631910A (zh) | 使用负载的离子催化剂制备聚烯烃树脂的方法,及该树脂的应用 | |
CN1328576A (zh) | 载体上的二齿和三齿催化剂组合物及使用该组合物的烯烃聚合 | |
CN1086707C (zh) | 金属茂,其制备方法及在α-烯烃聚合上的应用 | |
CN1199404A (zh) | 在高压下制备乙烯共聚物的方法 | |
CN1069646C (zh) | 过渡金属化合物 | |
CN1487956A (zh) | 催化剂组合物及其制备方法和在聚合方法中的用途 | |
CN1213076C (zh) | 催化剂体系及其在烯烃聚合中的应用 | |
CN1178949C (zh) | 作为聚合催化剂的环戊二烯基过渡金属配合物 | |
CN1235919C (zh) | 聚合方法 | |
CN1128821C (zh) | 适用作烯烃聚合催化剂的还原氧化态过渡金属化合物 | |
CN1178964C (zh) | 活性、非均相的二齿或三齿配体/过渡金属催化剂 | |
CN1243774C (zh) | 催化剂组合物的制备方法及其在聚合过程中的应用 | |
CN1850872A (zh) | 一种用于制备宽/双峰分布高密度聚乙烯的复合催化体系 | |
CN1535178A (zh) | 阳离子催化剂体系 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C53 | Correction of patent of invention or patent application | ||
CB02 | Change of applicant information |
Applicant after: Exxon Chemical Patents Inc. Applicant before: Exxon Chemical Patents Inc. |
|
COR | Change of bibliographic data |
Free format text: CORRECT: APPLICANT; FROM: EXXON CHEMICAL PATENTS INC. TO: EXXON.MOBIL CHEMICAL PATENTS CORP. |
|
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20040512 Termination date: 20130429 |