WO2002090399A1 - Polymerization process for producing copolymers - Google Patents
Polymerization process for producing copolymers Download PDFInfo
- Publication number
- WO2002090399A1 WO2002090399A1 PCT/GB2002/002057 GB0202057W WO02090399A1 WO 2002090399 A1 WO2002090399 A1 WO 2002090399A1 GB 0202057 W GB0202057 W GB 0202057W WO 02090399 A1 WO02090399 A1 WO 02090399A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- indenyl
- rac
- phenyl
- zrcl
- propylene
- Prior art date
Links
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 37
- 229920001577 copolymer Polymers 0.000 title claims description 16
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 21
- 229920001155 polypropylene Polymers 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 35
- 229910007928 ZrCl2 Inorganic materials 0.000 claims description 27
- 239000003446 ligand Substances 0.000 claims description 23
- 229920000642 polymer Polymers 0.000 claims description 20
- -1 3 -tertbutyl-indenyl Chemical group 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 12
- 229910007926 ZrCl Inorganic materials 0.000 claims description 10
- 230000004913 activation Effects 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 9
- 150000003624 transition metals Chemical class 0.000 claims description 9
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 150000001993 dienes Chemical class 0.000 claims description 5
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 4
- 229910052768 actinide Inorganic materials 0.000 claims description 3
- 150000001255 actinides Chemical class 0.000 claims description 3
- 239000000835 fiber Substances 0.000 claims description 3
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 3
- 150000002602 lanthanoids Chemical class 0.000 claims description 3
- 229910010068 TiCl2 Inorganic materials 0.000 claims description 2
- 238000009472 formulation Methods 0.000 claims description 2
- 125000003936 heterocyclopentadienyl group Chemical group 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- 239000012190 activator Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 238000010348 incorporation Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- 150000002736 metal compounds Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 4
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 4
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000013110 organic ligand Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- 125000003358 C2-C20 alkenyl group Chemical group 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 125000006649 (C2-C20) alkynyl group Chemical group 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical compound CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 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
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000003828 azulenyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940069096 dodecene Drugs 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002899 organoaluminium compounds Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- GDDAJHJRAKOILH-QFXXITGJSA-N (2e,5e)-octa-2,5-diene Chemical compound CC\C=C\C\C=C\C GDDAJHJRAKOILH-QFXXITGJSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- LQHZVCWJDRMVPT-UHFFFAOYSA-N amino pyridine-2-carboxylate Chemical compound NOC(=O)C1=CC=CC=N1 LQHZVCWJDRMVPT-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012986 chain transfer agent Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- KOMDZQSPRDYARS-UHFFFAOYSA-N cyclopenta-1,3-diene titanium Chemical compound [Ti].C1C=CC=C1.C1C=CC=C1 KOMDZQSPRDYARS-UHFFFAOYSA-N 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
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000012968 metallocene catalyst Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920005630 polypropylene random copolymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001384 propylene homopolymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000006478 transmetalation reaction Methods 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000010626 work up procedure 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
Definitions
- This invention relates to a process for the preparation of propylene polymers, in particular copolymers of propylene with higher molecular weight comonomers, and to the polymers thereby produced and their uses.
- the polymer product may contain significant residual levels of unreacted comonomer which can result in problems of odour and taste, especially with diene and hexene comonomers, and that the polymerization process is inefficient in its usage of the generally more expensive comonomer since it must be present in the polymerization reactor in a higher molar concentration relative to propylene than that would be the case if the incorporation rate was the same for both monomers.
- polypropylenes produced using single site, eg metallocene, catalysts tend to have a narrower molecular weight distribution than those produced using Ziegler-Natta catalysts resulting in corresponding poor melt strengths.
- melt strength is important for applications involving extrusion, blow molding, pipe, film or sheet formation, etc., this is a further disadvantage for single site catalyst based polypropylenes.
- the invention provides a process for the preparation of a propylene polymer in which propylene and a comonomer copolymerizable therewith and of greater molecular weight than propylene are polymerized in a single site catalyst (typically an organotransition metal catalyst (eg a metallocene catalyst) ) catalysed polymerization reaction, characterised in that said polymerization reaction is effected at least in part (e.g. for at least 5%, for example 10 to 100% of the polymerization time or of the average residence time in a continuous reactor) at a temperature of at least 70°C.
- the polymerization reaction is preferably effected at from 75 to 200°C, more preferably 80 to 125°C, still more preferably 85 to 120°C.
- the higher molecular weight comonomer used in the process of the present invention is preferably an alkene or diene, in particular a C 4 _ 30 alkene or diene (e.g. a C 4 _ 20 ⁇ -olefin or diene, such as 7-methyl-l, 6-octadiene or 1, 7-octadiene) , still more preferably an ⁇ -olefin, e.g.
- a C 4 _ 18 ⁇ -olefin such as for example 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1- undecene, 1-dodecene, 1-tetradecene, 1-hexadecene and 4- methyl-1-pentene.
- the comonomer is especially preferably a C 4 _ 16 linear or singly, doubly or triply branched (more preferably linear or singly branched) 1- alkene or l,x-alkanediene (where x ⁇ 3) .
- the amount of comonomer used in the process of the invention is preferably up to 50 mole %, eg at least 0.1 mole %, more preferably 0.2 to 40 mole %, especially 0.4 to 30 mole %, more especially 0.5 to 25 mole %, still more especially 0.6 to 10 mole %, of the monomer mixture used in the copolymerization stage.
- the polymerization can of course be effected as a two or more stage process, e.g. to produce a block copolymer or bimodal polymer) .
- the organotransition metal catalyst system used in the process of the present invention may be any organotransition metal catalyst system capable of polymerizing propylene.
- Such catalyst systems are well known in the literature and consist of an organotransition metal compound and, optionally, one or more activator (s) and, optionally, one or more carrier (s) .
- the organotransition metal catalyst system typically comprises at least one type of organotransition metal compound, or one organotransition metal compound containing one or more transition metals.
- the organotransition metal compound can be a member of the group of compounds known as metallocenes .
- Metallocenes contain at least one organic ligand, generally 1, 2 or 3, e.g. 1 or 2, which is ⁇ -bonded to the metal, e.g. a ⁇ 2-6 -ligand, such as a ⁇ 5 -ligand.
- a metallocene contains a group 3 to 6 transition metal or a lanthanide metal or an actinide metal, and particularly preferably is a titanocene, zirconocene or hafnocene, and contains at least one ⁇ 5 -ligand, which is for example an optionally substituted cyclopentadienyl, an optionally substituted indenyl, an optionally substituted benzoindenyl , an optionally substituted azulenyl or an optionally substituted fluorenyl .
- the metallocene compound may thus for example be of formula I :
- each Cp independently is an unsubstituted or substituted and/or fused homo- or heterocyclopentadienyl ligand (e.g. substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl, substituted or unsubstituted benzoindenyl, substituted or unsubstituted azulenyl, substituted or unsubstituted fluorenyl ligand, substituted or unsubstituted indolyl, or substituted or unsubstituted 4-azaindenyl, the optional one or more substituent (s) being selected preferably from halogen, hydrocarbyl (e.g.
- R is a bridge of 1-7 atoms, e.g. a bridge of 1-4 C- atoms and 0-4 heteroatoms, wherein the heteroatom(s) can be e.g. Si, Ge, O, S, N, P and/or B atom(s) , whereby each of the bridge atoms may independently bear substituents, such as tri (C 1 _ 20 -alkyl) silyl, tri (C 1 _ 20 -alkyl) siloxy or C 6 _ 20 -aryl substituents), or a bridge of 1 to 3, e.g.
- heteroatoms such as silicon, germanium, oxygen, sulphur, nitrogen, phosphorus and/or boron atom(s) , e.g. -SiR 1 2 - (wherein each R 1 is independently a C 1 _ 20 -alkyl, C 6 _ 20 -aryl or tri (C ⁇ 20 -alkyl) silyl- group, such as a trimethylsilyl- group);
- M is a transition metal of group 3 to 6, a lanthanide or an actinide, preferably a group 4 metal, e.g.
- each X is independently a sigma-ligand, such as H, halogen, C 2 _ 20 -alkenyl, C 2 _ 20 - alkynyl, C 3 _ 12 -cycloalkyl, C 6 _ 20 -aryl, C 6 _ 20 -aryloxy, C 7 _ 20 - arylalkyl, C 7 _ 20 -arylalkenyl, -SR", -PR" 3 , -SiR" 3 , -0SiR” 3 or -NR" 2 (where R" is as defined hereinbefore) ; n is 0, 1 or 2; m is 1, 2 or 3 , e.g.
- Said metallocenes and their preparation are well known in the art, e.g. from EP-A-576970, EP-A-485823, EP-A-485821, EP-A-702030, EP-A-530647 and WO00/34341.
- metallocenes are disclosed for example in US-A-5770753, US-A-6057408 , WO 95/12622, EP-B-700406, and the documents cited above all of which are incorporated herein by reference .
- Particularly preferred metallocenes include-: rac- (CH 3 ) 2 Si (2-CH 3 -4-phenyl-indenyl) 2 ZrCl 2 rac- (CH 3 ) 2 Si (2-CH 3 -4-phenyl-indenyl) 2 TiCl 2 rac- (CH 3 ) 2 Si(2-CH 3 -4-phenyl-indenyl) 2 HfCl 2 rac- (CH 3 ) 3 Si(CH 3 ) Si (2 -CH 3 -4-phenyl-indenyl) 2 ZrCl 2 rac- (CH 3 ) 2 Si (2-CH 3 -4- (1-napthyl) -indenyl) 2 ZrCl 2 rac- (CH 3 ) 2 Si (2
- the metal bears a Cp group as defined above and additionally a ⁇ 1 or ⁇ 2 ligand, wherein said ligands may or may not be bridged to each other.
- This subgroup includes so called "scorpionate compounds" (with constrained geometry) in which the metal is complexed by a ⁇ 5 ligand bridged to a ⁇ 1 or ⁇ 2 ligand, preferably ⁇ 1 (for example a ⁇ -bonded) ligand, e.g. a metal complex of a Cp group as defined above, e.g.
- a cyclopentadienyl group which bears, via a bridge, member, an acyclic or cyclic group containing at least one heteroatom, e.g. -NR" 2 as defined above.
- a bridge, member an acyclic or cyclic group containing at least one heteroatom, e.g. -NR" 2 as defined above.
- heteroatom e.g. -NR" 2 as defined above.
- Any alkyl, alkenyl or alkynyl residue referred to above alone or as a part of a larger moiety may be linear or branched, and preferably contains up to 9, e.g. up to 6 , carbon atoms .
- Aryl is preferably phenyl or naphthyl .
- Halogen means F, Cl, Br or I , preferably Cl .
- the organotransition metal compounds usable in the present invention are the non- metallocenes wherein the transition metal (preferably a group 4 to 6 transition metal, suitably Ti, Zr or Hf) has a co-ordination ligand other than ⁇ 5 -ligand (i.e. other than cyclopentadienyl ligand) .
- the transition metal preferably a group 4 to 6 transition metal, suitably Ti, Zr or Hf
- a co-ordination ligand other than ⁇ 5 -ligand i.e. other than cyclopentadienyl ligand
- transition metal preferably a group 4 to 6 transition metal, suitably Ti, Zr or Hf
- a co-ordination ligand other than ⁇ 5 -ligand i.e. other than cyclopentadienyl ligand
- transition metal i.a. transition metal complexes with nitrogen-based, cyclic or acyclic aliphatic or aromatic ligands, e.
- oxygen-based ligands such as group 4 metal complexes bearing bidentate cyclic or acyclic aliphatic or aromatic alkoxide ligands, e.g. optionally substituted, bridged bisphenolic ligands (see i.a. the above review of Gibson et al . ) .
- oxygen-based ligands such as group 4 metal complexes bearing bidentate cyclic or acyclic aliphatic or aromatic alkoxide ligands, e.g. optionally substituted, bridged bisphenolic ligands (see i.a. the above review of Gibson et al . ) .
- non- ⁇ 5 ligands are amides, amide-diphosphane, amidinato, aminopyridinate, benzamidinate, triazacyclononane, allyl, hydrocarbyl, beta-diketimate and alkoxide. The disclosures of the above documents are incorporated herein by reference .
- bridged-bis- indenyl zirconocenes or hafnocenes especially where the C 6 ring of the indenyl groups are substituted, e.g. at the 6-position or 4-position, by pendant aryl groups, e.g. where the ligand is a bridged bis(2-(alkyl or alkylsiloxy) -4- (aryl) -indenyl) group.
- the preparation of metallocenes and the organic ligands thereof, usable in the invention is well documented in the prior art, and reference is made e.g. to the above cited documents . Some of said compounds are also commercially available.
- transition metal compounds can be prepared according to or analogously to the methods described in the literature, e.g. by first preparing the organic ligand moiety and then metalling said organic ligand ( ⁇ ligand) with a transition metal.
- a metal ion of an existing metallocene can be exchanged for another metal ion through transmetallation.
- the metallocene may be used together with a cocatalyst or catalyst activator.
- cocatalysts for metallocenes are the alumoxanes, in particular the C_ 10 alkylalumoxanes, most particularly methylalumoxane (MAO) .
- Such alumoxanes can be used as the sole cocatalyst or together with other cocatalyst (s) .
- other cation complex forming activators can be used.
- Said activators are commercially available or can be prepared according to the prior art literature.
- alumoxane cocatalysts are described i.a. in WO-A-94/28034 which is incorporated herein by reference. These are linear or cyclic oligomers having up to 40, preferably 3 to 20, - (Al (R" ' ) O) - repeat units (wherein R" ' is hydrogen, alkyl (preferably methyl) or C 6 _ 18 aryl or mixtures thereof) .
- the quantity of cocatalyst to be employed in the catalyst of the invention is thus variable, and depends on the conditions and the particular transition metal compounds chosen in a manner well known to a person skilled in the art .
- the metallocene used in the process of the invention may be used as a homogeneous or, more preferably a heterogeneous catalyst.
- a porous particulate catalyst support which may be organic or more preferably inorganic, e.g. silica, silica-alumina, etc.
- a cocatalyst or catalyst activator generally an aluminium or boron containing compound, e.g. an organoaluminium compound (such as an alumoxane) or a non-coordinating ionic cocatalyst such as a boron activator
- the catalyst and cocatalyst may be brought together in the polymerization reactor or beforehand.
- the metallocene is pre-reacted with an alumoxane (e.g. MAO, HIBAO or TIBAO, especially MAO) and the reaction product is impregnated into a porous particulate support, preferably in a dry mix procedure as described for example in WO 95/12622.
- an alumoxane e.g. MAO, HIBAO or TIBAO, especially MAO
- the aluminium:metallocene metal molar ratio is conveniently 3000:1 to 10:1, preferably 500:1 to 10:1, especially 400:1 to 20:1, particularly 300:1 to 50:1 in the catalyst system.
- a 5:1 to 1:5 preferably 2:1 to 1:2, such as 1:1
- the transition metal to boron activator may be used.
- metallocene is impregnated into a porous inorganic support, this is preferably calcined beforehand, e.g. as described in WO 95/12622.
- the process of the invention may be carried out in any known polymerisation process, such as in solution, suspension, slurry (in liquid or in bulk) or gas phase polymerisation process.
- it may be effected in propylene, either in liquid or supercritical fluid depending on the reaction conditions used.
- the critical temperature of propylene is 91.4°C and the critical pressure is 45.5 bar.
- it may be effected in slurry which contains monomer and an inert liquid, preferably an aliphatic hydrocarbon, e.g. heptane or octane, rather than an aromatic diluent such as toluene.
- the critical temperature and pressure may be suppressed by using other chemicals such as hydrocarbons in accordance with known methods.
- the process of the invention occurs in liquid or supercritical propylene. For subcritical temperatures, supercritical pressures may also be used.
- the polymerisation may also be effected in continuous or batch mode.
- Conventional polymerisation reactors e.g. loop or stirred tank or gas phase reactors, may be used and if desired polymerisation may be effected in more than one stage and/or in more than one reactor.
- hydrogen may be used as a chain transfer agent in the polymerization reaction.
- a scavenger may be included in the reaction mixture, for example an organoaluminium compound, eg a trialkylaluminium such as triethylaluminium (TEAL) or triisobutylaluminium (TIBAL) or an alumoxane (such as MAO, TIBAO, HIBAO, etc) .
- organoaluminium compound eg a trialkylaluminium such as triethylaluminium (TEAL) or triisobutylaluminium (TIBAL) or an alumoxane (such as MAO, TIBAO, HIBAO, etc) .
- the flow activation energy (E a ) which represents the temperature dependence of the viscosity of the polymer melt, is sensitive to the presence of long chain branches in the polymer backbone. A higher flow activation energy can be related to the growing number of long branches.
- Flow activation energy values. of up to about 40 kj/mol have been reported in the literature for linear polypropylene homopolymers or random copolymers (see Mavridis et al . in Polym. Eng. Sci . 32.: 1778-1791 (1992)). Descriptions of flow activation energies and their determination may also be found for example in Mavridis et al . (supra), Eckstein et al . Macromolecules 31:1335-1340 (1998), and Saini et al . J. Macromol. Sci., Phys . B22:432-449 (1983).
- the long chain branching can also be evaluated by comparing the shear thinning behaviour of polymers .
- the presence of long chain branching increases the elasticity of the polymer and results in higher shear thinning compared to a linear polymer.
- the higher shear thinning can be seen as the deeper decrease of the complex viscosity (Eta*) when moving from low to high values of complex modulus (G*) .
- Eta* complex viscosity
- G* complex modulus
- the invention provides a propylene copolymer having on polymerization a flow activation energy of at least 43 kJ/mol, more preferably at least 45 kJ/mol, e.g. up to 90 kJ/mol.
- the propylene polymers produced by the processes of the invention are themselves novel and form a further aspect of the invention. Viewed from this aspect the invention provides a propylene polymer produced or producible by a process according to the invention.
- the invention provides a propylene polymer article, e.g. a pipe, fibre, film, sheet, foamed or molded article formed from a polymer according to the invention, optionally after formulation (e.g. by addition of antioxidants, further polymers, light absorbers, colorants, fillers, etc.
- a propylene polymer article e.g. a pipe, fibre, film, sheet, foamed or molded article formed from a polymer according to the invention, optionally after formulation (e.g. by addition of antioxidants, further polymers, light absorbers, colorants, fillers, etc.
- the invention provides the use of the copolymers of the invention for the manufacture of pipe, film, sheet, fibre, molded articles and foamed articles.
- silica-supported catalysts used in the Examples were prepared as described in WO 95/12622.
- Weight average (M w ) and number average (M n ) molecular weights were measured with a Waters Alliance GPCV 2000 high temperature gel permeation chromatograph (GPC) operating at 140°C using 1, 2 , 4-trichlorobenzene as an eluant .
- the calibration of columns was done with polystyrene standards and polypropylene equivalent molecular weights were calculated using a universal calibration method.
- the rheological properties were measured by Rheometrics Scientific SR-500 stress controlled rotational rheometer (cone and plate geometry) .
- the flow activation energies (Ea) were calculated from the frequency sweeps
- compositions of the produced copolymers are near to identical to the corresponding monomer compositions in the polymerization medium, even in the case of the higher molecular weight comonomers like 1-dodecene and 1-hexadecene .
- compositions of the produced propylene/1-octene copolymers are near to identical to the corresponding monomer compositions in the polymerization medium, irrespective of the type of the catalyst used.
Abstract
Description
Claims
Priority Applications (5)
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BR0209401-0A BR0209401A (en) | 2001-05-04 | 2002-05-03 | Process for the preparation of a propylene polymer, propylene polymer and copolymer, propylene polymer article, and use of a copolymer |
ES02720305T ES2428318T3 (en) | 2001-05-04 | 2002-05-03 | Polymerization process to produce propylene copolymers |
EP02720305.8A EP1401896B1 (en) | 2001-05-04 | 2002-05-03 | Polymerization process for producing propylene copolymers |
US10/476,646 US7157534B2 (en) | 2001-05-04 | 2002-05-03 | Polymerization process for producing copolymers |
US11/543,117 US7449534B2 (en) | 2001-05-04 | 2006-10-05 | Polymerization process for producing propylene copolymers |
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GBGB0111020.4A GB0111020D0 (en) | 2001-05-04 | 2001-05-04 | Process |
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PCT/GB2002/002064 WO2002090400A1 (en) | 2001-05-04 | 2002-05-03 | Process for preparing propylene copolymers |
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EP (2) | EP1401896B1 (en) |
CN (2) | CN1289554C (en) |
BR (2) | BR0209401A (en) |
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Publication number | Publication date |
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CN1537123A (en) | 2004-10-13 |
CN1289554C (en) | 2006-12-13 |
GB0111020D0 (en) | 2001-06-27 |
BR0209401A (en) | 2004-07-06 |
US20040158010A1 (en) | 2004-08-12 |
US7038000B2 (en) | 2006-05-02 |
EP1401896B1 (en) | 2013-08-28 |
US20070129513A1 (en) | 2007-06-07 |
US20040176551A1 (en) | 2004-09-09 |
CN100351277C (en) | 2007-11-28 |
EP1401896A1 (en) | 2004-03-31 |
BR0209402A (en) | 2004-07-06 |
ES2428318T3 (en) | 2013-11-07 |
US7449534B2 (en) | 2008-11-11 |
EP1395621A1 (en) | 2004-03-10 |
US7157534B2 (en) | 2007-01-02 |
CN1636025A (en) | 2005-07-06 |
WO2002090400A1 (en) | 2002-11-14 |
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