JP2000513398A - 最近の遷移金属触媒系での高圧重合方法 - Google Patents
最近の遷移金属触媒系での高圧重合方法Info
- Publication number
- JP2000513398A JP2000513398A JP10503219A JP50321998A JP2000513398A JP 2000513398 A JP2000513398 A JP 2000513398A JP 10503219 A JP10503219 A JP 10503219A JP 50321998 A JP50321998 A JP 50321998A JP 2000513398 A JP2000513398 A JP 2000513398A
- Authority
- JP
- Japan
- Prior art keywords
- transition metal
- compound
- catalyst
- coordinating anion
- anion precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 41
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 39
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims description 54
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000005977 Ethylene Substances 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims description 46
- 150000001450 anions Chemical class 0.000 claims description 42
- -1 metalloid halide salt Chemical class 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 28
- 239000012190 activator Substances 0.000 claims description 20
- 239000003446 ligand Substances 0.000 claims description 19
- 150000003623 transition metal compounds Chemical class 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000178 monomer Substances 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 229910052752 metalloid Inorganic materials 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 230000007704 transition Effects 0.000 claims description 6
- 150000004696 coordination complex Chemical class 0.000 claims description 3
- ZOICEQJZAWJHSI-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)boron Chemical compound [B]C1=C(F)C(F)=C(F)C(F)=C1F ZOICEQJZAWJHSI-UHFFFAOYSA-N 0.000 claims 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims 2
- 239000003426 co-catalyst Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 25
- 239000000725 suspension Substances 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 229910052782 aluminium Inorganic materials 0.000 description 13
- 229930195733 hydrocarbon Natural products 0.000 description 13
- 150000002430 hydrocarbons Chemical class 0.000 description 13
- 239000004215 Carbon black (E152) Substances 0.000 description 12
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical group C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 11
- 150000002738 metalloids Chemical group 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 150000001768 cations Chemical class 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 150000001721 carbon Chemical class 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910001868 water Inorganic materials 0.000 description 6
- 239000002841 Lewis acid Substances 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 150000007517 lewis acids Chemical class 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- GOYDNIKZWGIXJT-UHFFFAOYSA-N 1,2-difluorobenzene Chemical compound FC1=CC=CC=C1F GOYDNIKZWGIXJT-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000012718 coordination polymerization Methods 0.000 description 4
- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 239000012018 catalyst precursor Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 description 3
- 150000002825 nitriles Chemical class 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000002685 polymerization catalyst Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 239000007848 Bronsted acid Substances 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
- 239000002879 Lewis base Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 description 2
- 230000003213 activating effect Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 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 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 150000007527 lewis bases Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012685 metal catalyst precursor Substances 0.000 description 2
- 239000012968 metallocene catalyst Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000010557 suspension polymerization reaction Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 241001143500 Aceraceae Species 0.000 description 1
- 229910017048 AsF6 Inorganic materials 0.000 description 1
- 229940126062 Compound A Drugs 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 1
- 241001676573 Minium Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000034 Plastomer Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 239000012683 anionic precursor Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052795 boron group element Inorganic materials 0.000 description 1
- 229910052800 carbon group element Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000000498 cooling water Substances 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
- 238000012937 correction Methods 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- OJOSABWCUVCSTQ-UHFFFAOYSA-N cyclohepta-2,4,6-trienylium Chemical compound C1=CC=C[CH+]=C[CH]1 OJOSABWCUVCSTQ-UHFFFAOYSA-N 0.000 description 1
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical compound [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 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
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction 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
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- SOEVKJXMZBAALG-UHFFFAOYSA-N octylalumane Chemical compound CCCCCCCC[AlH2] SOEVKJXMZBAALG-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000005062 perfluorophenyl group Chemical group FC1=C(C(=C(C(=C1F)F)F)F)* 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052696 pnictogen Inorganic materials 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 229920005638 polyethylene monopolymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 150000003254 radicals Chemical group 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940054334 silver cation Drugs 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 1
- CXKQHHJKHZXXPZ-UHFFFAOYSA-N triethylsilanylium Chemical compound CC[Si+](CC)CC CXKQHHJKHZXXPZ-UHFFFAOYSA-N 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-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
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- C08F10/02—Ethene
-
- 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
- B01J31/02—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
- B01J31/146—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 boron
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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Abstract
Description
Claims (1)
- 【特許請求の範囲】 1 少なくとも60psia(413.7kPa)のエチレン圧力及び90℃ 以上の反応温度において、エチレン及び任意に1以上のエチレン性不飽和モノマ ーを、2座配位子によって安定化された活性化された8、9、又は10族遷移金 属化合物を含む、担持されていない最近の遷移金属触媒系と接触させることを含 むオレフィン重合方法。 2 該接触が溶媒又は希釈剤中で行われる、請求項1の方法。 3 該接触が連続溶液方法で行われる、請求項2の方法。 4 反応温度が120乃至160℃でエチレン圧力が20乃至200バール( 2000乃至20016kPa)である、請求項3の方法。 5 反応温度が120乃至160℃でエチレン圧力が60乃至365psia (414乃至2517kPa)である、請求項3の方法。 6 該遷移金属系がアルモキサン又はチグラー助触媒活性化剤によって活性化 された最近の遷移金属化合物を含む、請求項1の方法。 7 遷移化合物の活性化剤に対する比率が1:1000乃至1:1である、請 求項6の方法。 8 該遷移金属系が非配位陰イオン前駆体化合物によって活性化された最近の 遷移金属化合物から得られる、請求項1の方法。 9 該非配位陰イオン前駆体化合物が非配位陰イオンであるテトラキス(ペル フルオロフェニル)ホウ素を含む、請求項8の触媒系。 10 該非配位陰イオン前駆体化合物が13〜16族金属又はメタロイドのハロ ゲン化物塩である、請求項8の触媒系。 11 該金属錯体が、遷移金属化合物を非配位陰イオン前駆体化合物と、該遷移 金属化合物の該イオン化陰イオン前駆体に対するモル比が約10:1乃至1:1 0であるように組合せて調製される、請求項8の触媒。 12 該遷移金属系が捕捉化合物をさらにに含む、請求項8の方法。 13 少なくとも200バール(2.03×104kPa)のエチレン圧力及び 120℃以上の反応温度において、エチレン及び任意に1以上のエチレン性不飽 和モノマーを、2座配位子によって安定化された活性化された8、9、又は10 族遷移金属化合物を含む、担持されていない最近の遷移金属触媒系とを接触させ ることを含むオレフィン重合方法。 14 該接触が溶媒又は希釈剤中で行われる、請求項13の方法。 15 該接触が連続単一相方法で行われる、請求項14の方法。 16 反応温度が120乃至160℃でエチレン圧力が500乃至2500バー ル(5.06×104乃至2.53×105kPa)である、請求項15の方法。 17 該遷移金属系がアルモキサン又はチグラー助触媒活性化剤によって活性化 された最近の遷移金属化合物を含む、請求項13の方法。 18 遷移化合物の活性化剤に対する比率が1:1000乃至1:1である、請 求項17の方法。 19 該遷移金属系が非配位陰イオン前駆体化合物によって活性化された最近の 遷移金属化合物を含む、請求項13の方法。 20 該非配位陰イオン前駆体化合物が非配位陰イオンであるテトラキス(ペル フルオロフェニル)ホウ素を含む、請求項19の触媒系。 21 該非配位陰イオン前駆体化合物が13〜16族金属又はメタロイドのハロ ゲン化物塩である、請求項19の触媒系。 22 該金属錯体が、遷移金属化合物をイオン化陰イオン前駆体化合物と、該遷 移金属化合物の該イオン化陰イオン前駆体に対するのモル比が約10:1乃至1 :10であるように組合せて調製される、請求項19の触媒。 23 該遷移金属系が捕捉化合物をさらに含む、請求項19の方法。
Applications Claiming Priority (5)
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US2009596P | 1996-06-17 | 1996-06-17 | |
US60/020,095 | 1996-06-17 | ||
US2019996P | 1996-06-21 | 1996-06-21 | |
US60/020,199 | 1996-06-21 | ||
PCT/US1997/010419 WO1997048737A1 (en) | 1996-06-17 | 1997-06-17 | Elevated pressure polymerization processes with late transition metal catalyst systems |
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JP2000513398A true JP2000513398A (ja) | 2000-10-10 |
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JP10503219A Pending JP2000513398A (ja) | 1996-06-17 | 1997-06-17 | 最近の遷移金属触媒系での高圧重合方法 |
Country Status (10)
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US (1) | US6127497A (ja) |
EP (1) | EP0906344B2 (ja) |
JP (1) | JP2000513398A (ja) |
CN (1) | CN1125829C (ja) |
AU (1) | AU736911B2 (ja) |
CA (1) | CA2257818C (ja) |
DE (1) | DE69702978T3 (ja) |
ES (1) | ES2151279T3 (ja) |
HU (1) | HUP0003447A3 (ja) |
WO (1) | WO1997048737A1 (ja) |
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JP2004511437A (ja) * | 2000-08-03 | 2004-04-15 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | α−オレフィンの連続製造方法 |
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- 1997-06-17 CA CA002257818A patent/CA2257818C/en not_active Expired - Fee Related
- 1997-06-17 EP EP97928038A patent/EP0906344B2/en not_active Expired - Lifetime
- 1997-06-17 US US08/877,213 patent/US6127497A/en not_active Expired - Lifetime
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- 1997-06-17 DE DE69702978T patent/DE69702978T3/de not_active Expired - Lifetime
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- 1997-06-17 HU HU0003447A patent/HUP0003447A3/hu unknown
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Cited By (3)
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JP2002526609A (ja) * | 1998-10-05 | 2002-08-20 | ダブリュー・アール・グレース・アンド・カンパニー−コーン | 担持二座配位および三座配位触媒組成物および同触媒組成物を使用するオレフィンの重合 |
JP4798847B2 (ja) * | 1998-10-05 | 2011-10-19 | ダブリュー・アール・グレース・アンド・カンパニー−コーン | 担持二座配位および三座配位触媒組成物および同触媒組成物を使用するオレフィンの重合 |
JP2004511437A (ja) * | 2000-08-03 | 2004-04-15 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | α−オレフィンの連続製造方法 |
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AU3235097A (en) | 1998-01-07 |
HUP0003447A3 (en) | 2004-03-01 |
CN1125829C (zh) | 2003-10-29 |
CN1222164A (zh) | 1999-07-07 |
DE69702978D1 (de) | 2000-10-05 |
EP0906344A1 (en) | 1999-04-07 |
WO1997048737A1 (en) | 1997-12-24 |
ES2151279T3 (es) | 2000-12-16 |
EP0906344B1 (en) | 2000-08-30 |
DE69702978T2 (de) | 2001-03-15 |
AU736911B2 (en) | 2001-08-02 |
HUP0003447A2 (hu) | 2001-02-28 |
CA2257818C (en) | 2005-08-09 |
US6127497A (en) | 2000-10-03 |
CA2257818A1 (en) | 1997-12-24 |
EP0906344B2 (en) | 2009-02-18 |
DE69702978T3 (de) | 2009-08-13 |
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