JPH09505848A - オレフィン重合用触媒およびその製造法 - Google Patents
オレフィン重合用触媒およびその製造法Info
- Publication number
- JPH09505848A JPH09505848A JP7515434A JP51543495A JPH09505848A JP H09505848 A JPH09505848 A JP H09505848A JP 7515434 A JP7515434 A JP 7515434A JP 51543495 A JP51543495 A JP 51543495A JP H09505848 A JPH09505848 A JP H09505848A
- Authority
- JP
- Japan
- Prior art keywords
- group
- metallocene compound
- solid inorganic
- catalyst
- metallocene
- 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.)
- Ceased
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 10
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 7
- 239000002685 polymerization catalyst Substances 0.000 title description 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 138
- 239000003054 catalyst Substances 0.000 claims abstract description 96
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 53
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000007787 solid Substances 0.000 claims abstract description 28
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 25
- 150000003624 transition metals Chemical class 0.000 claims abstract description 25
- 239000012190 activator Substances 0.000 claims abstract description 23
- 239000002638 heterogeneous catalyst Substances 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 5
- 238000009739 binding Methods 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 11
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052726 zirconium Inorganic materials 0.000 claims description 11
- -1 2-ethylhexyl group Chemical group 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 239000012968 metallocene catalyst Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 238000011282 treatment Methods 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 150000003623 transition metal compounds Chemical class 0.000 claims description 8
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 6
- 150000002738 metalloids Chemical class 0.000 claims description 6
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 6
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 6
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052752 metalloid Inorganic materials 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- IVTQDRJBWSBJQM-UHFFFAOYSA-L dichlorozirconium;indene Chemical compound C1=CC2=CC=CC=C2C1[Zr](Cl)(Cl)C1C2=CC=CC=C2C=C1 IVTQDRJBWSBJQM-UHFFFAOYSA-L 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 150000008040 ionic compounds Chemical class 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 230000000379 polymerizing effect Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000007848 Bronsted acid Substances 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- JXBKMHHGNJJERO-UHFFFAOYSA-L [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Ti+2]C1C2=CC=CC=C2C=C1 Chemical compound [Cl-].[Cl-].C1=CC2=CC=CC=C2C1[Ti+2]C1C2=CC=CC=C2C=C1 JXBKMHHGNJJERO-UHFFFAOYSA-L 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- QRUYYSPCOGSZGQ-UHFFFAOYSA-L cyclopentane;dichlorozirconium Chemical compound Cl[Zr]Cl.[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1 QRUYYSPCOGSZGQ-UHFFFAOYSA-L 0.000 claims description 2
- 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 claims description 2
- 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 claims 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 claims description 2
- 150000004678 hydrides Chemical group 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 150000007527 lewis bases Chemical class 0.000 claims 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 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- 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 claims description 2
- 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 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 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 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 125000003936 heterocyclopentadienyl group Chemical group 0.000 claims 9
- KSFCHHFBQJDGFF-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C1C=CC=C1.C1C=CC=C1 KSFCHHFBQJDGFF-UHFFFAOYSA-L 0.000 claims 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 1
- UNSDWONDAUAWPV-UHFFFAOYSA-N methylaluminum;oxane Chemical compound [Al]C.C1CCOCC1 UNSDWONDAUAWPV-UHFFFAOYSA-N 0.000 claims 1
- 239000012876 carrier material Substances 0.000 abstract description 24
- 230000000694 effects Effects 0.000 abstract description 15
- 229920000642 polymer Polymers 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 7
- 238000007334 copolymerization reaction Methods 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 74
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 38
- 239000000377 silicon dioxide Substances 0.000 description 36
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 22
- 239000005977 Ethylene Substances 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- 239000000376 reactant Substances 0.000 description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 9
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229910052801 chlorine Inorganic materials 0.000 description 5
- IDASTKMEQGPVRR-UHFFFAOYSA-N cyclopenta-1,3-diene;zirconium(2+) Chemical compound [Zr+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 IDASTKMEQGPVRR-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000010926 purge Methods 0.000 description 5
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000012685 gas phase polymerization Methods 0.000 description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 4
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product 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
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000037048 polymerization activity Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical compound [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 2
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004846 x-ray emission Methods 0.000 description 2
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 description 2
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 241000233855 Orchidaceae Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 238000012662 bulk polymerization Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- MKNXBRLZBFVUPV-UHFFFAOYSA-L cyclopenta-1,3-diene;dichlorotitanium Chemical compound Cl[Ti]Cl.C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 MKNXBRLZBFVUPV-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- DKQVJMREABFYNT-UHFFFAOYSA-N ethene Chemical group C=C.C=C DKQVJMREABFYNT-UHFFFAOYSA-N 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052735 hafnium Chemical group 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 235000011147 magnesium chloride Nutrition 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- CWEHKOAQFGHCFQ-UHFFFAOYSA-N methylalumane Chemical compound [AlH2]C CWEHKOAQFGHCFQ-UHFFFAOYSA-N 0.000 description 1
- NRQNMMBQPIGPTB-UHFFFAOYSA-N methylaluminum Chemical compound [CH3].[Al] NRQNMMBQPIGPTB-UHFFFAOYSA-N 0.000 description 1
- 230000036651 mood Effects 0.000 description 1
- 238000003947 neutron activation analysis Methods 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
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Classifications
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- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI935417A FI95276C (fi) | 1993-12-03 | 1993-12-03 | Olefiinien polymerointikatalyytti ja menetelmä sen valmistamiseksi |
FI935417 | 1993-12-03 | ||
PCT/FI1994/000547 WO1995015216A1 (en) | 1993-12-03 | 1994-12-02 | Catalyst for olefin polymerization and a method for the manufacture thereof |
Publications (1)
Publication Number | Publication Date |
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JPH09505848A true JPH09505848A (ja) | 1997-06-10 |
Family
ID=8539078
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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JP7515434A Ceased JPH09505848A (ja) | 1993-12-03 | 1994-12-02 | オレフィン重合用触媒およびその製造法 |
Country Status (10)
Country | Link |
---|---|
US (2) | US5767032A (en:Method) |
EP (1) | EP0731729B1 (en:Method) |
JP (1) | JPH09505848A (en:Method) |
CN (1) | CN1079400C (en:Method) |
AU (1) | AU693831B2 (en:Method) |
DE (1) | DE69423237T2 (en:Method) |
FI (1) | FI95276C (en:Method) |
IL (1) | IL111854A (en:Method) |
TW (1) | TW287174B (en:Method) |
WO (1) | WO1995015216A1 (en:Method) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002528573A (ja) * | 1998-10-26 | 2002-09-03 | ビーピー ケミカルズ リミテッド | 重合触媒 |
JP2003501523A (ja) * | 1999-06-03 | 2003-01-14 | ユニベーション・テクノロジーズ・エルエルシー | 担持された触媒系の製造方法及び重合方法におけるその使用 |
JP2004520476A (ja) * | 2001-05-25 | 2004-07-08 | エルジー ケミカル エルティーディー. | 表面改質担体と作用基を有する触媒前駆体を使用した重合担持触媒及びこれを利用したオレフィン重合の方法 |
JP2017531081A (ja) * | 2014-10-17 | 2017-10-19 | シェブロン フィリップス ケミカル カンパニー エルピー | 固体メタロセン系触媒系を調製するプロセス |
Families Citing this family (78)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1996000243A1 (en) * | 1994-06-24 | 1996-01-04 | Exxon Chemical Patents Inc. | Polymerization catalyst systems, their production and use |
US5625015A (en) * | 1994-11-23 | 1997-04-29 | Exxon Chemical Patents Inc. | Method for making supported catalyst systems and catalyst systems therefrom |
US6451725B1 (en) | 1995-04-12 | 2002-09-17 | Borealis Technology Oy | Method for preparing catalyst components |
FI104975B (fi) * | 1995-04-12 | 2000-05-15 | Borealis As | Menetelmä katalyyttikomponenttien valmistamiseksi |
ATE153675T1 (de) * | 1995-09-13 | 1997-06-15 | Witco Gmbh | Verfahren zur herstellung von metallocen- katalysatorsystemen auf inerten trägermaterialien unter verwendung von gasphasenreaktoren |
ES2104454T3 (es) * | 1995-09-13 | 1997-10-01 | Witco Gmbh | Procedimiento para la preparacion de sistemas de catalizadores del tipo de metalocenos sobre materiales de soporte inertes. |
US7507483B2 (en) * | 1997-02-04 | 2009-03-24 | Jeffrey Schwartz | Enhanced bonding layers on native oxide surfaces |
US6645644B1 (en) | 1996-10-17 | 2003-11-11 | The Trustees Of Princeton University | Enhanced bonding of phosphoric and phosphoric acids to oxidized substrates |
US7396594B2 (en) * | 2002-06-24 | 2008-07-08 | The Trustees Of Princeton University | Carrier applied coating layers |
US7815963B2 (en) | 1996-10-17 | 2010-10-19 | The Trustees Of Princeton University | Enhanced bonding layers on titanium materials |
US7569285B2 (en) * | 1996-10-17 | 2009-08-04 | The Trustees Of Princeton University | Enhanced bonding layers on titanium materials |
US6146767A (en) * | 1996-10-17 | 2000-11-14 | The Trustees Of Princeton University | Self-assembled organic monolayers |
GB9822123D0 (en) | 1998-10-09 | 1998-12-02 | Borealis As | Catalyst |
DE19940151A1 (de) * | 1999-08-24 | 2001-03-01 | Targor Gmbh | Geträgerte Katalysatorsysteme, Verfahren zu ihrer Herstellung und Verfahren zur Herstellung von Poly-1-alkenen mit bimodaler oder multimodaler Molekularmassenverteilung |
US20040265571A1 (en) * | 2003-02-11 | 2004-12-30 | Princeton University | Surface-bonded, organic acid-based mono-layers |
US20060194008A1 (en) | 1999-09-22 | 2006-08-31 | Princeton University | Devices with multiple surface functionality |
US6548442B1 (en) * | 1999-12-03 | 2003-04-15 | Phillips Petroleum Company | Organometal compound catalyst |
US6576583B1 (en) | 2000-02-11 | 2003-06-10 | Phillips Petroleum Company | Organometal catalyst composition |
US6388017B1 (en) | 2000-05-24 | 2002-05-14 | Phillips Petroleum Company | Process for producing a polymer composition |
US6630199B1 (en) * | 2000-11-08 | 2003-10-07 | General Electric Company | Ceramic layer produced by reacting a ceramic precursor with a reactive gas |
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1994
- 1994-12-02 AU AU11111/95A patent/AU693831B2/en not_active Ceased
- 1994-12-02 IL IL11185494A patent/IL111854A/en not_active IP Right Cessation
- 1994-12-02 CN CN94194919A patent/CN1079400C/zh not_active Expired - Fee Related
- 1994-12-02 EP EP95902149A patent/EP0731729B1/en not_active Expired - Lifetime
- 1994-12-02 DE DE69423237T patent/DE69423237T2/de not_active Expired - Lifetime
- 1994-12-02 JP JP7515434A patent/JPH09505848A/ja not_active Ceased
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1995
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1998
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2002528573A (ja) * | 1998-10-26 | 2002-09-03 | ビーピー ケミカルズ リミテッド | 重合触媒 |
JP2003501523A (ja) * | 1999-06-03 | 2003-01-14 | ユニベーション・テクノロジーズ・エルエルシー | 担持された触媒系の製造方法及び重合方法におけるその使用 |
JP2004520476A (ja) * | 2001-05-25 | 2004-07-08 | エルジー ケミカル エルティーディー. | 表面改質担体と作用基を有する触媒前駆体を使用した重合担持触媒及びこれを利用したオレフィン重合の方法 |
JP2017531081A (ja) * | 2014-10-17 | 2017-10-19 | シェブロン フィリップス ケミカル カンパニー エルピー | 固体メタロセン系触媒系を調製するプロセス |
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US5767032A (en) | 1998-06-16 |
FI935417A7 (fi) | 1995-06-04 |
TW287174B (en:Method) | 1996-10-01 |
US6143844A (en) | 2000-11-07 |
CN1079400C (zh) | 2002-02-20 |
EP0731729A1 (en) | 1996-09-18 |
DE69423237T2 (de) | 2000-08-24 |
AU1111195A (en) | 1995-06-19 |
AU693831B2 (en) | 1998-07-09 |
EP0731729B1 (en) | 2000-03-01 |
WO1995015216A1 (en) | 1995-06-08 |
DE69423237D1 (de) | 2000-04-06 |
CN1142788A (zh) | 1997-02-12 |
FI95276B (fi) | 1995-09-29 |
FI935417A0 (fi) | 1993-12-03 |
IL111854A (en) | 2001-01-28 |
IL111854A0 (en) | 1995-03-15 |
FI95276C (fi) | 1996-01-10 |
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