TW510906B - Process for the polymerisation of ethylene or copolymerisation of ethylene and alpha-olefin and method for preparing complexes - Google Patents
Process for the polymerisation of ethylene or copolymerisation of ethylene and alpha-olefin and method for preparing complexes Download PDFInfo
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- TW510906B TW510906B TW89101189A TW89101189A TW510906B TW 510906 B TW510906 B TW 510906B TW 89101189 A TW89101189 A TW 89101189A TW 89101189 A TW89101189 A TW 89101189A TW 510906 B TW510906 B TW 510906B
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- Prior art keywords
- ethylene
- complex
- bis
- chemical formula
- complexes
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims description 19
- 239000005977 Ethylene Substances 0.000 title claims description 19
- 239000004711 α-olefin Substances 0.000 title 1
- -1 bis(cyclopentadienyl) zirconium complexes Chemical class 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- 239000003446 ligand Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 150000001336 alkenes Chemical class 0.000 claims abstract description 17
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000002841 Lewis acid Substances 0.000 claims abstract description 7
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 6
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 6
- 238000011049 filling Methods 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 15
- 150000002430 hydrocarbons Chemical group 0.000 claims description 13
- 230000002079 cooperative effect Effects 0.000 claims description 11
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- 125000005594 diketone group Chemical group 0.000 claims description 8
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 229910052726 zirconium Inorganic materials 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 7
- 229910052735 hafnium Inorganic materials 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical class OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 5
- 150000004678 hydrides Chemical class 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-M Methanesulfonate Chemical class CS([O-])(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-M 0.000 claims description 3
- 125000005228 aryl sulfonate group Chemical class 0.000 claims description 3
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002879 Lewis base Substances 0.000 claims description 2
- GTFKUGGPOZUWPY-UHFFFAOYSA-N NC(C1=C(C=C2S(OC(F)(F)F)(=O)=O)C3=CC=CC=C3C1)=C2S(OC(F)(F)F)(=O)=O Chemical class NC(C1=C(C=C2S(OC(F)(F)F)(=O)=O)C3=CC=CC=C3C1)=C2S(OC(F)(F)F)(=O)=O GTFKUGGPOZUWPY-UHFFFAOYSA-N 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical class [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 claims description 2
- 150000007527 lewis bases Chemical class 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 230000007704 transition Effects 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 abstract 1
- 239000012190 activator Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 32
- 229920000642 polymer Polymers 0.000 description 22
- 239000000243 solution Substances 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 239000010936 titanium Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000013543 active substance Substances 0.000 description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical group CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 8
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000002685 polymerization catalyst Substances 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 125000006178 methyl benzyl group Chemical group 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 239000000194 fatty acid Substances 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- VAUMWVVODNTNEA-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenyl)methoxyboronic acid Chemical compound FC1=C(C(=C(C(=C1COB(O)O)F)F)F)F VAUMWVVODNTNEA-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 2
- XFHFNPNYXNRRAR-UHFFFAOYSA-N CC1=CC(C)([Zr]C2(C)C=CC(C)=C2)C=C1 Chemical class CC1=CC(C)([Zr]C2(C)C=CC(C)=C2)C=C1 XFHFNPNYXNRRAR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 2
- 235000003140 Panax quinquefolius Nutrition 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 125000000304 alkynyl group Chemical group 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 150000001639 boron compounds Chemical class 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 235000008434 ginseng Nutrition 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 150000004820 halides Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000008040 ionic compounds Chemical class 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 125000005647 linker group Chemical group 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000003901 oxalic acid esters Chemical class 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003871 sulfonates Chemical class 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- IIFFFBSAXDNJHX-UHFFFAOYSA-N 2-methyl-n,n-bis(2-methylpropyl)propan-1-amine Chemical compound CC(C)CN(CC(C)C)CC(C)C IIFFFBSAXDNJHX-UHFFFAOYSA-N 0.000 description 1
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 1
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 1
- LZOUDFQJXQBMSZ-UHFFFAOYSA-N CC(C)C[Al](CC1=C(C(=C(C(=C1F)F)F)F)F)CC(C)C Chemical compound CC(C)C[Al](CC1=C(C(=C(C(=C1F)F)F)F)F)CC(C)C LZOUDFQJXQBMSZ-UHFFFAOYSA-N 0.000 description 1
- BDLXNUKTLKNYRE-UHFFFAOYSA-N CC1=C(C)C(C)=C(C)C1[Zr]C1C(C)=C(C)C(C)=C1C Chemical compound CC1=C(C)C(C)=C(C)C1[Zr]C1C(C)=C(C)C(C)=C1C BDLXNUKTLKNYRE-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- NYLHAXDZWHEQLZ-UHFFFAOYSA-N FC1=C(C(=C(C=2CC3=CC=CC=C3C12)CC(=O)O)F)F Chemical compound FC1=C(C(=C(C=2CC3=CC=CC=C3C12)CC(=O)O)F)F NYLHAXDZWHEQLZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZZUFZYCRBCATAB-UHFFFAOYSA-N NC(C1=C(C=C2S(C(F)(F)F)(=O)=O)C3=CC=CC=C3C1)=C2S(C(F)(F)F)(=O)=O Chemical class NC(C1=C(C=C2S(C(F)(F)F)(=O)=O)C3=CC=CC=C3C1)=C2S(C(F)(F)F)(=O)=O ZZUFZYCRBCATAB-UHFFFAOYSA-N 0.000 description 1
- 241001674048 Phthiraptera Species 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- GNVMUORYQLCPJZ-UHFFFAOYSA-M Thiocarbamate Chemical compound NC([S-])=O GNVMUORYQLCPJZ-UHFFFAOYSA-M 0.000 description 1
- VIORRMXBKMYJNZ-UHFFFAOYSA-L [Zr++].[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F Chemical compound [Zr++].[CH]1[CH][CH][CH][CH]1.[CH]1[CH][CH][CH][CH]1.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F VIORRMXBKMYJNZ-UHFFFAOYSA-L 0.000 description 1
- QUBWTXNVPULBEW-UHFFFAOYSA-N acetic acid;butanimidamide Chemical compound CC(O)=O.CCCC(N)=N QUBWTXNVPULBEW-UHFFFAOYSA-N 0.000 description 1
- WDJHALXBUFZDSR-UHFFFAOYSA-M acetoacetate Chemical compound CC(=O)CC([O-])=O WDJHALXBUFZDSR-UHFFFAOYSA-M 0.000 description 1
- 150000008062 acetophenones Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000001399 aluminium compounds Chemical class 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
- 229940077746 antacid containing aluminium compound Drugs 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 125000005588 carbonic acid salt group Chemical group 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- ZDQWVKDDJDIVAL-UHFFFAOYSA-N catecholborane Chemical compound C1=CC=C2O[B]OC2=C1 ZDQWVKDDJDIVAL-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- ZMMRKRFMSDTOLV-UHFFFAOYSA-N cyclopenta-1,3-diene zirconium Chemical compound [Zr].C1C=CC=C1.C1C=CC=C1 ZMMRKRFMSDTOLV-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- ORVACBDINATSAR-UHFFFAOYSA-N dimethylaluminum Chemical compound C[Al]C ORVACBDINATSAR-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001207 fluorophenyl group Chemical group 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical class OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000012685 gas phase polymerization Methods 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
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000003397 luteinic effect Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical class NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 1
- PWEBUXCTKOWPCW-UHFFFAOYSA-L squarate Chemical compound [O-]C1=C([O-])C(=O)C1=O PWEBUXCTKOWPCW-UHFFFAOYSA-L 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- XHGGEBRKUWZHEK-UHFFFAOYSA-L tellurate Chemical compound [O-][Te]([O-])(=O)=O XHGGEBRKUWZHEK-UHFFFAOYSA-L 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WCZKTXKOKMXREO-UHFFFAOYSA-N triethylsulfanium Chemical compound CC[S+](CC)CC WCZKTXKOKMXREO-UHFFFAOYSA-N 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical group [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- XDSSGQHOYWGIKC-UHFFFAOYSA-N tris(2-methylpropyl)borane Chemical compound CC(C)CB(CC(C)C)CC(C)C XDSSGQHOYWGIKC-UHFFFAOYSA-N 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 1
- 238000010792 warming Methods 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
- C07F17/00—Metallocenes
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9619081.4A GB9619081D0 (en) | 1996-09-12 | 1996-09-12 | Polymerization catalyst |
| GBGB9714386.1A GB9714386D0 (en) | 1997-07-08 | 1997-07-08 | Polymerisation catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| TW510906B true TW510906B (en) | 2002-11-21 |
Family
ID=26310029
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW89101189A TW510906B (en) | 1996-09-12 | 1997-09-11 | Process for the polymerisation of ethylene or copolymerisation of ethylene and alpha-olefin and method for preparing complexes |
| TW86113216A TW424100B (en) | 1996-09-12 | 1997-09-11 | Polymerisation catalyst |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW86113216A TW424100B (en) | 1996-09-12 | 1997-09-11 | Polymerisation catalyst |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0925312A1 (id) |
| JP (1) | JP2001500550A (id) |
| AR (1) | AR009777A1 (id) |
| AU (1) | AU4128997A (id) |
| EG (1) | EG21243A (id) |
| ID (1) | ID22033A (id) |
| NO (1) | NO991190L (id) |
| TW (2) | TW510906B (id) |
| WO (1) | WO1998011144A1 (id) |
Families Citing this family (42)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19818219A1 (de) | 1998-04-24 | 1999-10-28 | Basf Ag | Katalysatorsystem mit Aluminiumfluoridaktivator |
| US6545108B1 (en) | 1999-02-22 | 2003-04-08 | Eastman Chemical Company | Catalysts containing N-pyrrolyl substituted nitrogen donors |
| WO2000050470A2 (en) | 1999-02-22 | 2000-08-31 | Eastman Chemical Company | Catalysts containing n-pyrrolyl substituted nitrogen donors |
| US6339134B1 (en) | 1999-05-06 | 2002-01-15 | Univation Technologies, Llc | Polymerization process for producing easier processing polymers |
| US6281306B1 (en) | 1999-12-16 | 2001-08-28 | Univation Technologies, Llc | Method of polymerization |
| US6605677B2 (en) | 2000-02-18 | 2003-08-12 | Eastman Chemical Company | Olefin polymerization processes using supported catalysts |
| US7056996B2 (en) | 2000-02-18 | 2006-06-06 | E. I. Du Pont De Nemours And Company | Productivity catalysts and microstructure control |
| US6579823B2 (en) | 2000-02-18 | 2003-06-17 | Eastman Chemical Company | Catalysts containing per-ortho aryl substituted aryl or heteroaryl substituted nitrogen donors |
| US6706891B2 (en) | 2000-11-06 | 2004-03-16 | Eastman Chemical Company | Process for the preparation of ligands for olefin polymerization catalysts |
| WO2004046214A2 (en) | 2002-10-15 | 2004-06-03 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
| US7223822B2 (en) | 2002-10-15 | 2007-05-29 | Exxonmobil Chemical Patents Inc. | Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom |
| WO2004094487A1 (en) | 2003-03-21 | 2004-11-04 | Dow Global Technologies, Inc. | Morphology controlled olefin polymerization process |
| BRPI0517210B1 (pt) | 2004-12-17 | 2017-01-24 | Dow Global Technologies Inc | composição adequada para tubos, composição adequada para películas sopradas, composição adequada para artigos moldados soprados, tubo, película, artigo moldado por sopro e método para melhorar o comportamento de fluxo de fluência de uma resina |
| EP1803747A1 (en) | 2005-12-30 | 2007-07-04 | Borealis Technology Oy | Surface-modified polymerization catalysts for the preparation of low-gel polyolefin films |
| KR20090014329A (ko) | 2006-05-02 | 2009-02-10 | 다우 글로벌 테크놀로지스 인크. | 고밀도 폴리에틸렌 조성물, 이의 제조 방법, 이로부터제조된 물품, 및 이러한 물품의 제조 방법 |
| US7456244B2 (en) | 2006-05-23 | 2008-11-25 | Dow Global Technologies | High-density polyethylene compositions and method of making the same |
| WO2008136849A1 (en) | 2007-05-02 | 2008-11-13 | Dow Global Technologies Inc. | High-density polyethylene compositions, method of making the same, injection molded articles made therefrom, and method of making such articles |
| US7981517B2 (en) | 2007-08-28 | 2011-07-19 | Dow Global Technologies Inc. | Bituminous compositions and methods of making and using same |
| TW200932762A (en) | 2007-10-22 | 2009-08-01 | Univation Tech Llc | Polyethylene compositions having improved properties |
| US8318872B2 (en) | 2007-12-18 | 2012-11-27 | Univation Technologies, Llc | Method for controlling bimodal catalyst activity during polymerization |
| EP2358767B1 (en) | 2008-12-18 | 2013-02-20 | Univation Technologies, LLC | Method for seed bed treatment for a polymerization reaction |
| MX2011008053A (es) | 2009-01-30 | 2012-01-12 | Dow Global Technologies Llc | Composiciones de polietileno de alta densidad, metodo para producir las mismas, dispositivos de cierre elaborados de las mismas, y metodo para elaborar dichos dispositivos de cierre. |
| IN2015DN03815A (id) | 2012-12-28 | 2015-10-02 | Univation Tech Llc | |
| WO2014109832A1 (en) | 2013-01-14 | 2014-07-17 | Univation Technologies, Llc | Methods for preparing catalyst systems with increased productivity |
| BR112017010747B1 (pt) | 2014-11-25 | 2021-11-16 | Univation Technologies, Llc | Métodos de controle de índice de fusão de poliolefina |
| US10377841B2 (en) | 2015-05-08 | 2019-08-13 | Exxonmobil Chemical Patents Inc. | Polymerization process |
| WO2018063765A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
| WO2018063767A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
| WO2018063764A1 (en) | 2016-09-27 | 2018-04-05 | Exxonmobil Chemical Patents Inc. | Polymerization process |
| WO2018118155A1 (en) | 2016-12-20 | 2018-06-28 | Exxonmobil Chemical Patents Inc. | Polymerization process |
| US11591417B2 (en) | 2017-12-13 | 2023-02-28 | Exxonmobil Chemical Patents Inc. | Deactivation methods for active components from gas phase polyolefin polymerization processes |
| WO2019173030A1 (en) | 2018-03-08 | 2019-09-12 | Exxonmobil Chemical Patents Inc. | Methods of preparing and monitoring a seed bed for polymerization reactor startup |
| EP3788081B1 (en) | 2018-05-02 | 2025-07-02 | ExxonMobil Chemical Patents Inc. | Methods for scale-up from a pilot plant to a larger production facility |
| CN112055720B (zh) | 2018-05-02 | 2022-11-22 | 埃克森美孚化学专利公司 | 从中试装置放大到较大生产设施的方法 |
| WO2020014138A1 (en) | 2018-07-09 | 2020-01-16 | Exxonmobil Chemical Patents Inc. | Polyethylene cast films and methods for making the same |
| WO2020023207A1 (en) | 2018-07-26 | 2020-01-30 | Exxonmobil Chemical Patents Inc. | Multilayer foam films and methods for making the same |
| US11649331B2 (en) | 2018-11-13 | 2023-05-16 | Exxonmobil Chemical Patents Inc. | Polyethylene blends and films |
| US20220025135A1 (en) | 2018-11-13 | 2022-01-27 | Exxonmobil Chemical Patents Inc. | Polyethylene Films |
| WO2020163079A1 (en) | 2019-02-06 | 2020-08-13 | Exxonmobil Chemical Patents Inc. | Films and backsheets for hygiene articles |
| US20230018505A1 (en) | 2019-12-17 | 2023-01-19 | Exxonmobil Chemical Patents Inc. | Films Made of Polyethylene Blends for Improved Sealing Performance and Mechanical Properties |
| WO2021183337A1 (en) | 2020-03-12 | 2021-09-16 | Exxonmobil Chemical Patents Inc. | Films made of polyethylene blends for improved bending stiffness and high md tear resistance |
| CN117098785A (zh) | 2021-04-30 | 2023-11-21 | 埃克森美孚化学专利公司 | 用于聚合反应器中不同聚合催化剂之间的转变的方法 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2071706C (en) * | 1991-06-20 | 1996-09-17 | Junichi Imuta | Catalyst for olefin polymerization, process for the polymerization of olefin, and transition metal compound employable for the catalyst |
| EP0591756B1 (en) * | 1992-09-22 | 1998-11-25 | Idemitsu Kosan Company Limited | Polymerization catalysts and process for producing polymers |
| JP3332051B2 (ja) * | 1992-12-18 | 2002-10-07 | 出光興産株式会社 | 重合用触媒及び該触媒系を用いる重合体の製造方法 |
| US5543480A (en) * | 1994-06-28 | 1996-08-06 | The Dow Chemical Company | Polymerization process using diene containing catalysts |
| JPH08134122A (ja) * | 1994-11-11 | 1996-05-28 | Idemitsu Kosan Co Ltd | 重合用触媒及びそれを用いたスチレン系重合体の製造方法 |
| US5527752A (en) * | 1995-03-29 | 1996-06-18 | Union Carbide Chemicals & Plastics Technology Corporation | Catalysts for the production of polyolefins |
-
1997
- 1997-09-05 EP EP97939065A patent/EP0925312A1/en not_active Withdrawn
- 1997-09-05 WO PCT/GB1997/002419 patent/WO1998011144A1/en not_active Ceased
- 1997-09-05 JP JP10513353A patent/JP2001500550A/ja not_active Withdrawn
- 1997-09-05 ID IDW990080A patent/ID22033A/id unknown
- 1997-09-05 AU AU41289/97A patent/AU4128997A/en not_active Abandoned
- 1997-09-10 EG EG92197A patent/EG21243A/xx active
- 1997-09-11 TW TW89101189A patent/TW510906B/zh not_active IP Right Cessation
- 1997-09-11 TW TW86113216A patent/TW424100B/zh not_active IP Right Cessation
- 1997-09-12 AR ARP970104196 patent/AR009777A1/es not_active Application Discontinuation
-
1999
- 1999-03-11 NO NO991190A patent/NO991190L/no not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| EG21243A (en) | 2001-04-30 |
| NO991190D0 (no) | 1999-03-11 |
| ID22033A (id) | 1999-08-26 |
| WO1998011144A1 (en) | 1998-03-19 |
| JP2001500550A (ja) | 2001-01-16 |
| EP0925312A1 (en) | 1999-06-30 |
| TW424100B (en) | 2001-03-01 |
| NO991190L (no) | 1999-05-12 |
| AR009777A1 (es) | 2000-05-03 |
| AU4128997A (en) | 1998-04-02 |
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| GD4A | Issue of patent certificate for granted invention patent | ||
| MM4A | Annulment or lapse of patent due to non-payment of fees |