WO1996035751A1 - Dynamically vulcanizable polyolefin compositions - Google Patents
Dynamically vulcanizable polyolefin compositions Download PDFInfo
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- WO1996035751A1 WO1996035751A1 PCT/EP1996/001895 EP9601895W WO9635751A1 WO 1996035751 A1 WO1996035751 A1 WO 1996035751A1 EP 9601895 W EP9601895 W EP 9601895W WO 9635751 A1 WO9635751 A1 WO 9635751A1
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- ethylene
- compositions
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- 239000000203 mixture Substances 0.000 title claims abstract description 95
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 12
- 229920001155 polypropylene Polymers 0.000 claims abstract description 18
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 9
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 9
- 230000004927 fusion Effects 0.000 claims abstract description 6
- 229920001038 ethylene copolymer Polymers 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 33
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 26
- 239000005977 Ethylene Substances 0.000 claims description 26
- 229920001577 copolymer Polymers 0.000 claims description 24
- 239000004711 α-olefin Substances 0.000 claims description 23
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 18
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 150000004291 polyenes Chemical class 0.000 claims description 10
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000004606 Fillers/Extenders Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- OJOWICOBYCXEKR-APPZFPTMSA-N (1S,4R)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical group CC=C1C[C@@H]2C[C@@H]1C=C2 OJOWICOBYCXEKR-APPZFPTMSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 3
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 2
- 238000004898 kneading Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 abstract description 10
- -1 polypropylene Polymers 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 16
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 14
- 238000004132 cross linking Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- 239000007788 liquid Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 239000004743 Polypropylene Substances 0.000 description 7
- 238000012512 characterization method Methods 0.000 description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 229920001198 elastomeric copolymer Polymers 0.000 description 6
- 239000008096 xylene Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 150000003609 titanium compounds Chemical class 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 239000005662 Paraffin oil Substances 0.000 description 4
- 239000005062 Polybutadiene Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- JWCYDYZLEAQGJJ-UHFFFAOYSA-N dicyclopentyl(dimethoxy)silane Chemical compound C1CCCC1[Si](OC)(OC)C1CCCC1 JWCYDYZLEAQGJJ-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- ORECYURYFJYPKY-UHFFFAOYSA-N n,n'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine;2,4,6-trichloro-1,3,5-triazine;2,4,4-trimethylpentan-2-amine Chemical compound CC(C)(C)CC(C)(C)N.ClC1=NC(Cl)=NC(Cl)=N1.C1C(C)(C)NC(C)(C)CC1NCCCCCCNC1CC(C)(C)NC(C)(C)C1 ORECYURYFJYPKY-UHFFFAOYSA-N 0.000 description 4
- MMMNTDFSPSQXJP-UHFFFAOYSA-N orphenadrine citrate Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.C=1C=CC=C(C)C=1C(OCCN(C)C)C1=CC=CC=C1 MMMNTDFSPSQXJP-UHFFFAOYSA-N 0.000 description 4
- 229920002857 polybutadiene Polymers 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 4
- WBZVXZGPXBXMSC-UHFFFAOYSA-N 2,5,6,6-tetrakis(2-methylpropyl)oxaluminane Chemical compound CC(C)CC1CC[Al](CC(C)C)OC1(CC(C)C)CC(C)C WBZVXZGPXBXMSC-UHFFFAOYSA-N 0.000 description 3
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000113 differential scanning calorimetry Methods 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 2
- FUDNBFMOXDUIIE-UHFFFAOYSA-N 3,7-dimethylocta-1,6-diene Chemical compound C=CC(C)CCC=C(C)C FUDNBFMOXDUIIE-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- RLZZZVKAURTHCP-UHFFFAOYSA-N phenanthrene-3,4-diol Chemical compound C1=CC=C2C3=C(O)C(O)=CC=C3C=CC2=C1 RLZZZVKAURTHCP-UHFFFAOYSA-N 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- DMGCMUYMJFRQSK-AEJSXWLSSA-N (1s,4s,5r)-5-prop-1-en-2-ylbicyclo[2.2.1]hept-2-ene Chemical compound C1[C@@H]2[C@H](C(=C)C)C[C@H]1C=C2 DMGCMUYMJFRQSK-AEJSXWLSSA-N 0.000 description 1
- VYXHVRARDIDEHS-QGTKBVGQSA-N (1z,5z)-cycloocta-1,5-diene Chemical compound C\1C\C=C/CC\C=C/1 VYXHVRARDIDEHS-QGTKBVGQSA-N 0.000 description 1
- PRBHEGAFLDMLAL-XQRVVYSFSA-N (4z)-hexa-1,4-diene Chemical compound C\C=C/CC=C PRBHEGAFLDMLAL-XQRVVYSFSA-N 0.000 description 1
- MFEWNFVBWPABCX-UHFFFAOYSA-N 1,1,2,2-tetraphenylethane-1,2-diol Chemical compound C=1C=CC=CC=1C(C(O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(O)C1=CC=CC=C1 MFEWNFVBWPABCX-UHFFFAOYSA-N 0.000 description 1
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 description 1
- PRBHEGAFLDMLAL-UHFFFAOYSA-N 1,5-Hexadiene Natural products CC=CCC=C PRBHEGAFLDMLAL-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- RYPKRALMXUUNKS-UHFFFAOYSA-N 2-Hexene Natural products CCCC=CC RYPKRALMXUUNKS-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
- UGJBFMMPNVKBPX-UHFFFAOYSA-N 5-propan-2-ylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C(C)C)CC1C=C2 UGJBFMMPNVKBPX-UHFFFAOYSA-N 0.000 description 1
- FUFBWHAPKOALCJ-UHFFFAOYSA-L C1=CC(CCCC2)=C2[C@@H]1[Zr](Cl)(Cl)(=CC)[C@H]1C(CCCC2)=C2C=C1 Chemical compound C1=CC(CCCC2)=C2[C@@H]1[Zr](Cl)(Cl)(=CC)[C@H]1C(CCCC2)=C2C=C1 FUFBWHAPKOALCJ-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-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
- 241000786363 Rhampholeon spectrum Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910010062 TiCl3 Inorganic materials 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- 238000006653 Ziegler-Natta catalysis Methods 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- SJJCABYOVIHNPZ-UHFFFAOYSA-N cyclohexyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C1CCCCC1 SJJCABYOVIHNPZ-UHFFFAOYSA-N 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- GEAWFZNTIFJMHR-UHFFFAOYSA-N hepta-1,6-diene Chemical compound C=CCCCC=C GEAWFZNTIFJMHR-UHFFFAOYSA-N 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical compound C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- DPUXQWOMYBMHRN-UHFFFAOYSA-N hexa-2,3-diene Chemical compound CCC=C=CC DPUXQWOMYBMHRN-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- NETBVGNWMHLXRP-UHFFFAOYSA-N tert-butyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C(C)(C)C NETBVGNWMHLXRP-UHFFFAOYSA-N 0.000 description 1
- 238000003856 thermoforming Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3432—Six-membered rings
- C08K5/3435—Piperidines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
Definitions
- the present invention relates to polyolefin composi ⁇ tions which are capable of giving, after dynamic vulcanization, thermoplastic elastomeric products having optimum elastomeric properties and a good balance of elasto-mechanical properties.
- the present invention relates to polyolefin compositions comprising a crystalline polypropylene phase and a substantially amorphous phase having elastomeric properties.
- thermoplastic elastomers are materials which, unlike conventional elastomers, can be processed by means of apparatus usually associated with the use of thermoplastic resins. Such products are used in various sectors, in particular where articles are required which have a good combination of elastic properties and mechanical properties, such as, for example, in seal gaskets used in the automobile sector or in some types of electrical household appliances. In these applica ⁇ tions, they replace conventional elastomers which require long processing work in three stages (mixing with additives, moulding and crosslinking) . Moreover, the thermoplastic elastomeric pro ⁇ ducts, unlike the conventional elastomers used in thermoforming processes, can be totally or partially recycled.
- thermoplastic elastomeric products dynamically vulcanized compositions, comprising a crystalline or semicrystalline polypropylene phase and an amorphous phase constituted generally by an ethylene/ ⁇ -olefin/diene rubber, are those which are most suitable for the market demands, owing also to their favourable cost/performance balance.
- the said compositions are character ⁇ ized by elastomeric properties which are still not satisfactory, because of both difficulties due to compatibility problems between the elastomeric phase and the crystalline phase and the presence of residual crystallinity in the elastomeric phase.
- One of the methods proposed for improving the compatibility of the two phases consists in producing the said compositions directly in the reactor by means of sequential polymerization in a multi-stage process.
- the propylene-based crystalline copolymer is generally produced, while the second stage comprises the polymerization of ethylene/propylene mixtures in the presence of the product obtained in the first stage, in order to obtain elastomeric copolymers.
- Both stages of these processes are carried out in the presence of the same catalytic system which generally con ⁇ sists of a conventional catalyst of the Ziegler/Natta type com ⁇ prising a titanium compound supported on a magnesium halide in active form.
- compositions obtained by means of this type of pro ⁇ cess are described in Patents US 4,521,566 and US 5,286,564.
- An analogous process is described in EP-A-433,989 and EP-A-433,990 in which an unsupported metallocene catalyst is used in both polymerization stages.
- the products obtained in these processes do not have a suitable balance of physico-mechanical properties.
- polyolefin compositions comprising a crystalline polypropylene phase and a substantially amorphous phase characterized by specific properties, are capable of giving, after dynamic vulcanization, thermoplastic elastomeric compositions having improved elastomeric properties and a better balance of elasto-mechanical properties.
- a subject of the present invention is therefore a polyolefin composition comprising:
- (B) 50 to 80 parts by weight of an elastomeric ethylene copolymer with olefins CH 2 CHR, in which R is alkyl having 1 to 10 carbon atoms, and, if appropriate, con ⁇ taining minor proportions of units derived from a polyene, the said copolymer containing 40 to 70% by weight of units derived from ethylene and 30 to 60% by weight of units derived from an ⁇ -olefin, and having the following characteristics: (a) a molecular weight distribution lower than 3.5 and (b) a crystallinity content, expressed as the enthalpy of fusion, lower than 20 J/g.
- component (B) has a content of 2-1 regioinvertions of the ⁇ -olefin units of lower than 5%.
- the molecular weight distribution, the crystallinity content and the content of regioinvertions are determined by the methods described later.
- compositions of the present invention comprise between 20 and 40 parts by weight of component (A) and between 60 and 80 parts by weight of component (B) , more prefer ⁇ ably between 30 and 40 parts of component (A) and between 60 and 70 parts of component (B) .
- the propylene polymer which constitutes component (A) preferably has an isotactic index, determined by measurement of the solubility in xylene, greater than 85 and more preferably greater than 90.
- propylene polymer which con ⁇ stitutes component (A) of the present invention prefferably has an MWD greater than 5 and generally between 5 and 50.
- the melt index (ASTM 1238 condition "L) of component (A) is generally between 0.1 and 50 g/10 minutes. The best results are obtained when the melt index of these polymers is between 0.1 and 30.
- component (A) of the invention consists of a propylene copolymer
- component (A) of the invention consists of a propylene copolymer
- particularly interesting results are obtained when copolymers containing from 2 to 10 mol% of an alpha-olefin other than propylene are used.
- the alpha-olefin is selected from the group comprising ethylene, 1-butene, 1-hexene, 1-octene and 4-methyl-l-pentene.
- ethylene and 1-butene are particularly preferred.
- Component (A) of the present invention can be prepared according to known technologies by polymerization of propylene, if appropriate in the presence of ethylene or other ⁇ -olefins, in the presence of conventional catalysts of the Ziegler/Natta type comprising the product of the reaction between an aluminium alkyl and a solid component comprising a transition metal sup ⁇ ported on MgCl 2 in an active form.
- catalysts comprising the product of the reaction between: (i) a solid component comprising a titanium compound without Ti- ⁇ bonds and an electron donor compound (internal donor) supported on a magnesium halide in an active form; (ii) an Al-alkyl compound and, if appropriate, an electron donor compound (external donor) .
- an external electron donor compound is gen ⁇ erally necessary to obtain propylene polymers having an isotacticity index greater than 80. Nevertheless, if compounds of the type described in Patent EP-A-361,493 are used as internal electron donor compounds, the stereospecificity of the catalyst is by itself sufficiently high and it is not necessary to use an external electron donor compound.
- the magnesium halide ⁇ in an active form used as support for Ziegler-Natta catalysts are widely known from the patent literature.
- the magnesium halides used in the active form as support or co-support in catalyst components for the polymerization of olefins are characterized by X-ray spectra in which the most intense diffraction line appearing in the spectra of the inactive halide is reduced in intensity and replaced by a halo whose intensity maximum is displaced towards angles which are smaller with respect to that of the most intense line.
- the titanium compound is preferably selected from the halides and halogeno-alcoholates.
- Preferred titanium compounds are TiCl 4 , TiCl 3 and the halogeno-alcoholates of the formula Ti(OR 1 ) m X n in which R 1 is a hydrocarbon radical with 1-12 carbon atoms or a group COR 1 , X is halogen and (m+n) is the valency of the titanium.
- the catalytic component (i) is used in the form of spherical particles having an average diameter of between about 10 and 150 ⁇ m.
- Suitable internal electron donor compounds include the ethers, esters and in particular the esters of polycarboxylic acids, the amines, the ketones and the 1,3-diethers of the type described in the Patents EP-A-361,493, EP-A-361,494, EP-A-362,705 and EP-A-451,645.
- the Al-alkyl compound (ii) is preferably selected from the aluminium trialkyls, such as, for example, Al-triethyl, Al- triisobutyl, Al-tri-n-butyl, Al-tri-n-hexyl and Al-tri-n-octyl. Mixtures of Al-trialkyls with Al-alkyl halides, Al-alkyl hydrides or Al-alkyl sesquichlorides such as AlEt 2 Cl and Al 2 Et 3 Cl 3 may also be used.
- the external donor can be of the same type as or can differ from the internal donor. If the internal donor is the ester of a polycarboxylic acid, in particular a phthalate, the external donor is preferably selected from the silicon compounds of the formula R 1 R 2 Si(OR) 2 , where R and R 2 are alkyl, cycloalkyl or aryl radicals having 1-18 carbon atoms. Examples of such silanes are methyl-cyclohexyl-dimethoxy-silane, diphenyl- dimethoxy-silane, methyl-t-butyl-dimethoxy-silane and dicyclopenty1-dimethoxy-silane.
- the content by weight of units derived from ethylene is preferably between 50 and 70%, more preferably between 60 and 70%.
- the content by weight of units derived from ⁇ -olefins is preferably between 30 and 50%, more preferably between 30 and 40%.
- copolymers which contain 0.1 to 20% by weight, preferably 1 to 10%, of units derived from a polyene.
- a polyene can be selected from the group comprising trans-l,4-hexadiene, cis- 1, 4-hexadiene, 6-methyl-l,5-heptadiene, 3 ,7-dimethyl- 1,6-octadiene and 11-methyl-l,10-dodecadiene; monocyclic diolefins such as, for example, cis-1,5-cyclooctadiene and 5-methyl-l,5-cyclooctadiene; bicyclic diolefins such as, for example, 4,5,8,9-tetrahydroindene and 6- and/or 7-methyl- 4,5,8,9-tetrahydroindene; alkenyl- or alkylidene-norbornenes such as, for example, 5-ethylidene-2-nor
- the elastomeric copolymer used in the present invention is characterized by a low crystallinity.
- the crystallinity expressed as the enthalpy of fusion determined by DSC analysis, is lower than 10 J/g, more preferab ⁇ ly lower than 5.
- the elastomeric copolymer used in the pres ⁇ ent invention has an MWD of lower than 3, generally of between 2 and 3.
- the said elastomeric copolymer preferably has a content of 2-1 regioinvertions of the ⁇ -olefin units of lower than 3%, more preferably lower than 1%.
- the said copolymer can advantageously be prepared by polymerizing mixtures of ethylene, alpha-olefin and, if appro ⁇ priate, polyene in the presence of a catalytic system comprising a metallocene compound and an alumoxane.
- metallocene compounds which can be used are rac-ethylidene-bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride and meso-ethylidene-bis(4,7-dimethylindenyl)zirconium dichloride.
- alumoxane compounds are methyl alumoxane (MAO) and tetraisobutyl alumoxane (TIBAO) .
- the polyolefin compositions according to the present invention can be obtained by using known methodologies such as mechanical mixing of the two components by means of internal mixers of the Banbury type, having a high homogenizing power.
- the said compositions can advantageously be obtained directly in the reactor by means of sequential polymerization.
- the compositions obtained according to this technique in fact show better elastomeric properties than those of the compositions obtained by simple mechanical mixing.
- the said compositions comprise between 20 and 40 parts by weight of component (A) and between 60 and 80 parts by weight of component (B) , more preferably between 30 and 40 parts of component (A) and between 60 and 70 parts of compo ⁇ nent (B) .
- the propylene polymer constituting component (A) pre ⁇ ferably has an isotactic index, determined by means of measuring the solubility in xylene, greater than 85, more preferably greater than 90, and an MWD greater than 5, generally between 5 and 50.
- the content by weight of units derived from ethylene is preferably between 50 and 70%, more preferably between 60 and 70%.
- the content by weight of units derived from the ⁇ -olefin is preferably between 30 and 50%, more preferably between 30 and 40%.
- the crystallinity of the said copolymer is preferably lower than 10 J/g, more preferably lower than 5.
- the elastomeric copolymer shows an MWD which is preferably lower than 3, generally between 2 and 3.
- compositions are preferably prepared by the process described in the Patent Application MI94A-002,028.
- the said process comprises a first stage in which, in the presence of a catalyst having a spherical morphol ⁇ ogy and containing a titanium compound supported on MgCl 2 in an active form, the olefin polymer constituting component (A) of the present invention is prepared by polymerization of propylene, if appropriate in a mixture with other alpha-olefins.
- the product obtained in the first stage is:
- a catalyst comprising a compound of a transition metal M selected from Ti, V, Zr and Hf, con ⁇ taining at least one M- ⁇ bond.
- compositions obtained by this process also have optimum morphol ⁇ ogical properties which evidently result from the spherical or spheroidal form of the polymer particles.
- compositions which are the subject of the present invention are subjected to vulcanization or crosslinking in order to produce thermoplastic elastomeric compositions for use in the application sectors cited above.
- vulcanization and crosslinking comprise both the actual crosslinking or vulcanization of the elastomer and the reaction by means of which the grafting of the more or less crosslinked elastomer on the crystalline polypropylene phase can take place as a result of the reaction promoted by the crosslinking system used.
- the preferred technique is dynamic vulcanization.
- the compositions of the invention are subjected to kneading or to other shear forces in the presence of crosslinking agents and, if appropriate, coadjuvants thereof, at temperatures between 140 and 240°C, pre ⁇ ferably at temperatures higher than the melting point of the crystalline phase.
- the compositions of the invention can be impregnated with an oil extender for regulating their hardness, either before the addition of the crosslinking agent or at the start or end of vulcanization.
- the oil extender used can be of various types, for example aromatic, naphthenic or preferably paraffinic.
- crosslinking agents which can be used are those commonly known in the art, such as organic peroxides, preferably having a half-life of the order of 10-200 seconds in the temperature range in which crosslinking normally takes place, and non-peroxidic agents such as the derivatives of 1,2-diphenylmethane, 1,2-diphenylethane and benzopinacol.
- a par ⁇ ticularly suitable group of non-peroxidic agents consists of the furan derivatives described in EP 361,205, among which difur- furalaldazine and l,5-difurfuryl-l,4-pentadien-3-one prove to be preferable.
- liquid 1,2-polybutadiene or compounds of the triallyl cyanurate type can be used as coadjuvant compounds for the crosslinking.
- compositions of the invention can be provided with various addi ⁇ tives, such as heat stabilizers, antioxidants, mineral fillers or any other type of agents customarily used in the art.
- a further subject of the invention is therefore vulcanized thermoplastic compositions obtained by the vulcaniz ⁇ ation processes described above, as manufactured, as well as moulded articles obtainable from the said compositions.
- the vulcanized compositions of the present invention show improved elastic properties over those of the previously known composi ⁇ tions. This becomes evident from a comparison of the said compo ⁇ sitions with known compositions having either similar crystallinity values or similar values of ethylene content in component (B) . Both the compositions obtained directly in a reactor and those obtained by mechanical blending show tension- set and compression-set values better than those of the known art, while maintaining at the same time a good balance of elasto-mechanical properties.
- the dynamically vulcanized compositions show values of ultimate tensile stress greater than 5 MPa, tension-set values at 100°C which are always lower than 20%, and compression-set free values always lower than 45% and, in the best cases, lower than 35%.
- the behaviour of the compositions of the present invention when impregnated with the oil extender is particularly interesting. The tendency of compounds of low molecular weight to exude (blooming) is considerably lower than that of the compositions of the prior art.
- Comonomer content percent by weight of comonomer determined via the I.R. spectrum.
- Effective density ASTM-D 792
- Intrinsic viscosity ASTM 2857-70
- DSC differential scanning calorimetry
- Determination of the MWD determined by GPC on a Waters instrument 150 in orthodichlorobenzene at 150°C.
- Determination of the recrioinvertions determined by means of C 13 -NMR according to the methodology described by J.C. Randall in "Polymer sequence determination Carbon 13 NMR method", Academic Press 1977. The content of regioinvertions is calculated on the basis of the relative concentration of S ⁇ + S ⁇ methylene sequences. Compression set 100°C: ASTM D395, method B
- Compression set free the procedure is the same as for the compression set at 100°C, with the difference that, before the measurement, the sample is placed in an oven for 30 min ⁇ utes at 100°C.
- composition 1 Preparation of an elastomeric composition directly in the reactor (composition 1)
- 0.00307 g of a solid catalytic component prepared according to Example No. 3 of Patent EP-A-395,083, were pre-con- tacted in a 50 ml glass flask with 0.0856 g of triethylaluminium (TEAL) and 0.01713 g of dicyclopentyldimethoxysilane (DCPMS) in 8 ml of anhydrous hexane.
- TEAL triethylaluminium
- DCPMS dicyclopentyldimethoxysilane
- the mixture was fed to a 4.25 1 steel autoclave, previously purged by successive washings first with hexane for one hour at 80°C and then with gaseous propylene for one hour at 80°C.
- 1700 g of liquid propylene together with 4500 ml of hydrogen were then fed at 30°C.
- composition 2 Preparation of an elastomeric composition directly in the reactor (composition 2) Preparation of component A (Stage 1)
- 0.00916 g of a solid catalytic component prepared according to Example No. 3 of Patent EP-A-395,083, were pre-con- tacted in a 50 ml glass flask with 0.0856 g of triethylaluminium (TEAL) and 0.01713 g of dicyclopentyldimethoxysilane (DCPMS) in 8 ml of anhydrous hexane.
- TEAL triethylaluminium
- DCPMS dicyclopentyldimethoxysilane
- Example 3 The procedure described in Example 1 is repeated, but using 0.001 g of meso-EBDMIZrCl 2 , precontacted in cyclohexane for 10 minutes at 25°C with 0.4214 mmol of MMAO.
- Preparation of component B (Stage 3) In the same reactor at 40°C, 27.4 g of ethylene and 70.4 g of propylene were fed to the polymer treated in stage 2. The composition of the copolymer was kept constant by feeding a mixture of the two monomers with 70% by weight of ethylene. Copolymerization was carried out for 64 minutes at 40°C and 13 bar. This gave 161.5 g of a copolymer whose properties are shown in Table 1.
- This mixture (62 g) was introduced into an internal mixer of the Banbury type (volume 60 ml) at a temperature of 180°C, at 60 r.p.m. together with 1.235 g of a master batch of 80% by weight of ZnO, 0.988 g of Lithene PH (liquid polybutadiene), 0.136 g of di-furfuralaldazine and 0.124 g of Chimassorb 944, and mixed for 2 minutes. Then, 0.988 g of Trigonox 101/40 MD GR were introduced and the mixture was mixed for a further 6 minutes for the dynamic crosslinking of the product. The moulding and the characterization took place as in Example 3. The results of the characterization are given in Table 2.
- Example 7 (comparison)
- Example 3 The procedure of Example 3 is repeated using, in place of composition 1, 37.5 g of composition 4 which was obtained directly in the reactor and in which the component B is charac ⁇ terized by an ethylene content of 26% and an MWD of 10 and a crystallinity of 10 J/g (Table 1) .
- the composition is processed as in Example 3, using 24.5 g of oil, 0.994 g of Lithene PH, 0.137 g of di-furfuralaldazina, 0.124 g of Chimassorb and 0.944 g of Trigonox. The results of the characterization are given in Table 2.
- Example 8 (comparison)
- Example 3 The procedure of Example 3 is repeated using, in place of composition 1, 38.75 g of composition 5 which was obtained directly in the reactor and in which the component B is charac ⁇ terized by an ethylene content of 65%, an MWD of 8 and a crystallinity of 35 J/g (Table 1) .
- the composition is processed as in Example 3, using 23.25 g of oil, 1.163 g of ZnO, 0.93 g of Lithene PH, 0.128 g of di-furfuralaldazina, 0.116 g of Chimassorb and 0.93 g of Trigonox.
- the results of the character ⁇ ization are given in Table 2.
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Abstract
Description
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Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
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BR9606960A BR9606960A (en) | 1995-05-11 | 1996-05-07 | Dynamically vulcanizable polyolefinic compositions and process for the preparation of vulcanized thermoplastic elastomeric compositions |
CA002194856A CA2194856C (en) | 1995-05-11 | 1996-05-07 | Dynamically vulcanizable polyolefin compositions |
EP96915023A EP0770106B2 (en) | 1995-05-11 | 1996-05-07 | Dynamically vulcanizable polyolefin compositions |
JP53373496A JP3746297B2 (en) | 1995-05-11 | 1996-05-07 | Dynamic vulcanizable polyolefin composition |
DE69603241T DE69603241T3 (en) | 1995-05-11 | 1996-05-07 | DYNAMICALLY VULCANIZED POLYOLEFIN COMPOSITIONS |
AU56938/96A AU698706B2 (en) | 1995-05-11 | 1996-05-07 | Dynamically vulcanizable polyolefin compositions |
NO970117A NO970117L (en) | 1995-05-11 | 1997-01-10 | Dynamically vulcanizable polyolefin materials and process for making them |
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ITMI950945A IT1274469B (en) | 1995-05-11 | 1995-05-11 | DYNAMICALLY VULCANIZABLE POLYOLEFINIC COMPOSITIONS |
ITMI95A0000945 | 1995-05-11 |
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WO1996035751A1 true WO1996035751A1 (en) | 1996-11-14 |
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PCT/EP1996/001895 WO1996035751A1 (en) | 1995-05-11 | 1996-05-07 | Dynamically vulcanizable polyolefin compositions |
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US (2) | US6100333A (en) |
EP (1) | EP0770106B2 (en) |
JP (1) | JP3746297B2 (en) |
KR (1) | KR100439465B1 (en) |
CN (1) | CN1092687C (en) |
AT (1) | ATE182167T1 (en) |
AU (1) | AU698706B2 (en) |
BR (1) | BR9606960A (en) |
CA (1) | CA2194856C (en) |
DE (1) | DE69603241T3 (en) |
ES (1) | ES2134618T3 (en) |
IT (1) | IT1274469B (en) |
NO (1) | NO970117L (en) |
WO (1) | WO1996035751A1 (en) |
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-
1995
- 1995-05-11 IT ITMI950945A patent/IT1274469B/en active IP Right Grant
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1996
- 1996-05-07 AU AU56938/96A patent/AU698706B2/en not_active Ceased
- 1996-05-07 DE DE69603241T patent/DE69603241T3/en not_active Expired - Fee Related
- 1996-05-07 WO PCT/EP1996/001895 patent/WO1996035751A1/en not_active Application Discontinuation
- 1996-05-07 EP EP96915023A patent/EP0770106B2/en not_active Expired - Lifetime
- 1996-05-07 KR KR1019970700129A patent/KR100439465B1/en not_active IP Right Cessation
- 1996-05-07 ES ES96915023T patent/ES2134618T3/en not_active Expired - Lifetime
- 1996-05-07 AT AT96915023T patent/ATE182167T1/en not_active IP Right Cessation
- 1996-05-07 CN CN96190704A patent/CN1092687C/en not_active Expired - Fee Related
- 1996-05-07 BR BR9606960A patent/BR9606960A/en not_active IP Right Cessation
- 1996-05-07 JP JP53373496A patent/JP3746297B2/en not_active Expired - Fee Related
- 1996-05-07 CA CA002194856A patent/CA2194856C/en not_active Expired - Fee Related
- 1996-05-08 US US08/647,020 patent/US6100333A/en not_active Expired - Fee Related
-
1997
- 1997-01-10 NO NO970117A patent/NO970117L/en not_active Application Discontinuation
-
2000
- 2000-05-16 US US09/571,997 patent/US7019078B1/en not_active Expired - Fee Related
Patent Citations (6)
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EP0574040A1 (en) * | 1987-07-08 | 1993-12-15 | Sumitomo Chemical Company Limited | Olefinic thermoplastic elastomer composition |
EP0424145A2 (en) * | 1989-10-19 | 1991-04-24 | Mitsubishi Chemical Corporation | Process for producing propylene block copolymer |
EP0433990A2 (en) * | 1989-12-21 | 1991-06-26 | Hoechst Aktiengesellschaft | Process for preparing polypropylene molding compositions |
EP0603724A2 (en) * | 1992-12-15 | 1994-06-29 | Montell North America Inc. | Thermoplastic olefin elastomers and process for their preparation |
EP0614938A1 (en) * | 1993-03-02 | 1994-09-14 | Mitsubishi Chemical Corporation | Resin composition for injection molding |
EP0643078A2 (en) * | 1993-09-13 | 1995-03-15 | Montell Technology Company bv | Process for the preparation of ethylene polymers and products obtained therefrom |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6245856B1 (en) | 1996-12-17 | 2001-06-12 | Exxon Chemical Patents, Inc. | Thermoplastic olefin compositions |
EP1129135A1 (en) * | 1998-06-08 | 2001-09-05 | Advanced Elastomer Systems, L.P. | Polypropylene thermoplastic elastomer compositions having improved processing properties and physical property balance |
EP1129135A4 (en) * | 1998-06-08 | 2001-12-19 | Advanced Elastomer Systems | Polypropylene thermoplastic elastomer compositions having improved processing properties and physical property balance |
US8487033B2 (en) | 2007-05-16 | 2013-07-16 | Exxonmobil Chemical Patents Inc. | Thermoplastic elastomer compositions, methods for making the same, and articles made therefrom |
Also Published As
Publication number | Publication date |
---|---|
AU698706B2 (en) | 1998-11-05 |
CN1092687C (en) | 2002-10-16 |
EP0770106B2 (en) | 2005-10-19 |
EP0770106B1 (en) | 1999-07-14 |
BR9606960A (en) | 1997-11-04 |
IT1274469B (en) | 1997-07-17 |
ES2134618T3 (en) | 1999-10-01 |
ITMI950945A1 (en) | 1996-11-11 |
JPH10502968A (en) | 1998-03-17 |
EP0770106A1 (en) | 1997-05-02 |
US6100333A (en) | 2000-08-08 |
CA2194856C (en) | 2008-09-02 |
ATE182167T1 (en) | 1999-07-15 |
DE69603241T3 (en) | 2006-11-23 |
CN1158140A (en) | 1997-08-27 |
NO970117D0 (en) | 1997-01-10 |
DE69603241D1 (en) | 1999-08-19 |
CA2194856A1 (en) | 1996-11-14 |
ITMI950945A0 (en) | 1995-05-11 |
DE69603241T2 (en) | 1999-12-30 |
US7019078B1 (en) | 2006-03-28 |
KR100439465B1 (en) | 2004-10-14 |
NO970117L (en) | 1997-02-17 |
JP3746297B2 (en) | 2006-02-15 |
AU5693896A (en) | 1996-11-29 |
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