WO2014015412A1 - Adjusting polymer composition - Google Patents
Adjusting polymer composition Download PDFInfo
- Publication number
- WO2014015412A1 WO2014015412A1 PCT/CA2013/000584 CA2013000584W WO2014015412A1 WO 2014015412 A1 WO2014015412 A1 WO 2014015412A1 CA 2013000584 W CA2013000584 W CA 2013000584W WO 2014015412 A1 WO2014015412 A1 WO 2014015412A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- group
- polymer component
- polymer
- scavenger
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 370
- 239000000203 mixture Substances 0.000 title claims abstract description 189
- 239000003054 catalyst Substances 0.000 claims abstract description 608
- 239000002516 radical scavenger Substances 0.000 claims abstract description 154
- 239000011651 chromium Substances 0.000 claims abstract description 135
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 125
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 125
- 239000002574 poison Substances 0.000 claims abstract description 76
- 231100000614 poison Toxicity 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims description 134
- 239000003446 ligand Substances 0.000 claims description 111
- 230000008569 process Effects 0.000 claims description 85
- 239000012190 activator Substances 0.000 claims description 63
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 53
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 50
- 238000009826 distribution Methods 0.000 claims description 33
- 230000009977 dual effect Effects 0.000 claims description 33
- 229910052751 metal Inorganic materials 0.000 claims description 31
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 28
- 239000005977 Ethylene Substances 0.000 claims description 28
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 28
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims description 26
- 230000007423 decrease Effects 0.000 claims description 26
- 239000002184 metal Substances 0.000 claims description 26
- 239000003426 co-catalyst Substances 0.000 claims description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 238000005227 gel permeation chromatography Methods 0.000 claims description 24
- QLNAVQRIWDRPHA-UHFFFAOYSA-N iminophosphane Chemical compound P=N QLNAVQRIWDRPHA-UHFFFAOYSA-N 0.000 claims description 23
- 230000003247 decreasing effect Effects 0.000 claims description 21
- 239000000178 monomer Substances 0.000 claims description 20
- CQBWEBXPMRPCSI-UHFFFAOYSA-M O[Cr](O[SiH3])(=O)=O Chemical group O[Cr](O[SiH3])(=O)=O CQBWEBXPMRPCSI-UHFFFAOYSA-M 0.000 claims description 19
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 18
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 15
- 230000002902 bimodal effect Effects 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 13
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical group CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 229910052735 hafnium Inorganic materials 0.000 claims description 7
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 6
- 150000004820 halides Chemical class 0.000 claims description 6
- 150000004678 hydrides Chemical class 0.000 claims description 6
- 230000037048 polymerization activity Effects 0.000 claims description 6
- 150000004703 alkoxides Chemical class 0.000 claims description 4
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims description 2
- -1 polyethylene Polymers 0.000 abstract description 121
- 230000000694 effects Effects 0.000 abstract description 55
- 229920000573 polyethylene Polymers 0.000 abstract description 32
- 239000004698 Polyethylene Substances 0.000 abstract description 31
- 239000012535 impurity Substances 0.000 abstract description 18
- 238000006116 polymerization reaction Methods 0.000 description 87
- 239000007789 gas Substances 0.000 description 34
- 229910052796 boron Inorganic materials 0.000 description 29
- 125000000217 alkyl group Chemical group 0.000 description 28
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 27
- 125000003118 aryl group Chemical group 0.000 description 25
- 150000001875 compounds Chemical class 0.000 description 23
- 125000001424 substituent group Chemical group 0.000 description 23
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- 239000000377 silicon dioxide Substances 0.000 description 22
- 239000001301 oxygen Substances 0.000 description 20
- 239000002002 slurry Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 229910052723 transition metal Inorganic materials 0.000 description 19
- 150000003624 transition metals Chemical class 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 17
- 150000001336 alkenes Chemical class 0.000 description 16
- 125000004429 atom Chemical group 0.000 description 15
- 239000004927 clay Substances 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 14
- 150000001845 chromium compounds Chemical class 0.000 description 14
- 239000003085 diluting agent Substances 0.000 description 14
- 238000011065 in-situ storage Methods 0.000 description 14
- 239000010936 titanium Substances 0.000 description 14
- 125000005842 heteroatom Chemical group 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- 239000012968 metallocene catalyst Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 13
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 12
- 125000003545 alkoxy group Chemical group 0.000 description 12
- 238000010924 continuous production Methods 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 150000003254 radicals Chemical class 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000000026 Pentaerythritol tetranitrate Substances 0.000 description 11
- 150000005840 aryl radicals Chemical class 0.000 description 11
- 239000002734 clay mineral Substances 0.000 description 11
- 125000004122 cyclic group Chemical group 0.000 description 11
- 239000000155 melt Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000004711 α-olefin Substances 0.000 description 11
- 229930195733 hydrocarbon Natural products 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 125000005843 halogen group Chemical group 0.000 description 9
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 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 8
- 229910052698 phosphorus Inorganic materials 0.000 description 8
- 239000002685 polymerization catalyst Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 230000004913 activation Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910000423 chromium oxide Inorganic materials 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 7
- 125000004433 nitrogen atom Chemical group N* 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 6
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
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- 229910052782 aluminium Inorganic materials 0.000 description 6
- 150000004658 ketimines Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000011593 sulfur Chemical group 0.000 description 6
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 description 6
- DJMUYABFXCIYSC-UHFFFAOYSA-N 1H-phosphole Chemical compound C=1C=CPC=1 DJMUYABFXCIYSC-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 125000004104 aryloxy group Chemical group 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
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- 239000011777 magnesium Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
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- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 125000003368 amide group Chemical group 0.000 description 4
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
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- 230000006870 function Effects 0.000 description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
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- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
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- 238000001694 spray drying Methods 0.000 description 4
- IMFACGCPASFAPR-UHFFFAOYSA-O tributylazanium Chemical compound CCCC[NH+](CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-O 0.000 description 4
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- 125000003710 aryl alkyl group Chemical group 0.000 description 3
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- 238000005516 engineering process Methods 0.000 description 3
- GCPCLEKQVMKXJM-UHFFFAOYSA-N ethoxy(diethyl)alumane Chemical compound CCO[Al](CC)CC GCPCLEKQVMKXJM-UHFFFAOYSA-N 0.000 description 3
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- KGPPDNUWZNWPSI-UHFFFAOYSA-N flurotyl Chemical group FC(F)(F)COCC(F)(F)F KGPPDNUWZNWPSI-UHFFFAOYSA-N 0.000 description 1
- 229950000929 flurotyl Drugs 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- VGRFVJMYCCLWPQ-UHFFFAOYSA-N germanium Chemical compound [Ge].[Ge] VGRFVJMYCCLWPQ-UHFFFAOYSA-N 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 239000007970 homogeneous dispersion Substances 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 229910001411 inorganic cation Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- CYPPCCJJKNISFK-UHFFFAOYSA-J kaolinite Chemical compound [OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[O-][Si](=O)O[Si]([O-])=O CYPPCCJJKNISFK-UHFFFAOYSA-J 0.000 description 1
- 229940094522 laponite Drugs 0.000 description 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 1
- MHERPFVRWOTBSF-UHFFFAOYSA-N methyl(phenyl)phosphane Chemical compound CPC1=CC=CC=C1 MHERPFVRWOTBSF-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- NOUWNNABOUGTDQ-UHFFFAOYSA-N octane Chemical compound CCCCCCC[CH2+] NOUWNNABOUGTDQ-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000000286 phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 150000004857 phospholes Chemical class 0.000 description 1
- 229910052615 phyllosilicate Inorganic materials 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000275 saponite Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- ZZIZZTHXZRDOFM-XFULWGLBSA-N tamsulosin hydrochloride Chemical compound [H+].[Cl-].CCOC1=CC=CC=C1OCCN[C@H](C)CC1=CC=C(OC)C(S(N)(=O)=O)=C1 ZZIZZTHXZRDOFM-XFULWGLBSA-N 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XBFJAVXCNXDMBH-UHFFFAOYSA-N tetracyclo[6.2.1.1(3,6).0(2,7)]dodec-4-ene Chemical compound C1C(C23)C=CC1C3C1CC2CC1 XBFJAVXCNXDMBH-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000004665 trialkylsilyl group Chemical group 0.000 description 1
- 125000005106 triarylsilyl group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 1
- 125000004360 trifluorophenyl group Chemical group 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 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
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- JQPMDTQDAXRDGS-UHFFFAOYSA-N triphenylalumane Chemical compound C1=CC=CC=C1[Al](C=1C=CC=CC=1)C1=CC=CC=C1 JQPMDTQDAXRDGS-UHFFFAOYSA-N 0.000 description 1
- RIOQSEWOXXDEQQ-UHFFFAOYSA-O triphenylphosphanium Chemical compound C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-O 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- GIIXTFIYICRGMZ-UHFFFAOYSA-N tris(2,3-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(P(C=2C(=C(C)C=CC=2)C)C=2C(=C(C)C=CC=2)C)=C1C GIIXTFIYICRGMZ-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- RKPWAHQNLQXPPH-UHFFFAOYSA-N tris(6-methylheptyl)alumane Chemical compound CC(C)CCCCC[Al](CCCCCC(C)C)CCCCCC(C)C RKPWAHQNLQXPPH-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- 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
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- 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
- C08F4/69—Chromium, molybdenum, tungsten or compounds thereof
-
- 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
-
- 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
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F4/65922—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring containing at least two cyclopentadienyl rings, fused or not
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
-
- 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
-
- 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
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
- Y10T428/139—Open-ended, self-supporting conduit, cylinder, or tube-type article
Definitions
- the present invention is a process to control a polymer composition produced by a combination catalyst comprising an inorganic chromium catalyst and a group 4 single site catalyst.
- polyethylene compositions comprising two (or more) polymer components, for example high and low molecular weight components, are well known in the art. These types of polymers can be useful for a huge range of applications which span from low density film, to high density pipe.
- One method to make such compositions involves taking two different ethylene polymers, for example polymers which differ in molecular weight and/or comonomer content, and blending them in a post-reactor extrusion or melt blending process.
- Another well-known process involves using a polymerization catalyst in two sequentially arranged polymerization zones, where each zone provides distinct conditions, such as high and low concentrations of hydrogen, to form in situ, a blend of low and high molecular weight polymers respectively.
- Multi-component blends can also be made in a single reactor by using at least two polymerization catalysts which provide divergent polymers under the same set of reactor conditions.
- Such multi component catalysts have taken many forms over the years and most typically involve mixed Ziegler-Natta catalysts, mixed Ziegler-Natta and single site catalysts (such as metallocene catalysts) or mixed single site catalysts.
- a chromium catalyst such as a silyl chromate catalyst
- a metallocene or a constrained geometry catalyst in a single reactor.
- the catalyst components were co-supported on a silica support or alternatively, a metallocene or constrained geometry catalyst was added to a supported chromium catalyst in situ.
- Catalysts comprising a silyl chromate catalyst and a group 4 single site catalyst which has at least one phosphinimine or ketimine ligand have been disclosed in U.S. Pat. Appl. Nos 20100190936A1 and 20100190937A1 .
- process control knobs such as hydrogen concentration to control melt index and other resin specifications can be a challenge and can lead to undesirable polymer compositions, since each catalyst component will typically have a different response to the parameter being changed.
- a bimodal or multimodal polymer may become unimodal at different hydrogen concentrations due to the different hydrogen response of each catalyst component present. Mitigation of unintended fluctuations in polymerization conditions, such as temperature excursions or impurity levels is also a challenge with multi component catalysts, as each parameter change may have a differential impact on the
- multi component catalysts are often co-supported, especially for use in gas phase or slurry phase polymerization in order to make well mixed or homogeneous polymer compositions.
- the amount of polymer produced by each catalyst species is generally fixed by the initial ratio of catalyst components present on a support. It is therefore desirable to have methods which can attenuate product drift or to control polymer compositions made with a multi component catalyst, without having to reformulate the catalyst.
- Another in-line method to control co-supported multi component catalysts is to change the relative activities of each active species by the introduction of a catalyst poison.
- catalysts composed of a Ziegler-Natta and metallocene species can be controlled through the introduction of carbon dioxide or water. The presence of carbon dioxide and/or water was found to decrease the amount of a high molecular weight component made by the multi component catalyst.
- U.S. Pat. No. 6,828,395 teaches the use of "control agents" such alcohols, ethers, amines, or oxygen to alter the properties of a bimodal polymer made by a "bimetallic catalyst".
- control agents such alcohols, ethers, amines, or oxygen
- a Ziegler-Natta catalyst was co-supported with a metallocene catalyst.
- Canadian Pat. Appl. No. 2,616,053AA demonstrates the effect of adding water or carbon dioxide to a "hybrid" catalyst comprising a late transition metal catalyst and a metallocene catalyst.
- Water had the effect of reducing the relative activity of the late transition metal catalyst which made a low molecular weight component, while carbon dioxide reduced the relative activity of the metallocene catalyst responsible for making a high molecular weight component.
- carbon dioxide reduced the relative activity of the metallocene catalyst responsible for making a high molecular weight component.
- water and carbon dioxide were used to increase and decrease the high to low molecular weight ratio respectively, of polymer components made in a single reactor.
- U.S. Pat. Appl. No. 2004/0242808A1 teaches a method to control the molecular weight distribution of bimodal polymers made with bimetallic catalyst comprising a Ziegler-Natta catalyst and a metallocene catalyst.
- the method comprises changing the ratio of a cocatalytic organometallic component to a cocatalytic modified
- U.S. Pat. No. 2010/0125124 describes a process employing a catalyst comprising a Ziegler-Natta catalyst and/or a metallocene catalyst component, as well as a cocatalyst. Adjusting the level of a catalyst component or the cocatalyst maintains a desired level of catalyst activity.
- U.S. Pat. No. 5,516,861 discloses a polymerization process in which a supported bulky ligand metallocene and a separately supported cocatalyst are individually fed to a gas phase reactor.
- One exemplified supported cocatalyst is triethylaluminum supported on silica.
- U.S. Pat. Appl. No. 20120041 47A1 describes the use of carbon dioxide to control the ratio of polymer components made with a combination catalyst comprising a chromium catalyst and a group 4 single site catalyst.
- organochromium catalyst preferably has a chromium carbon bond or a chromium heteroatom bond, where the heteroatom is O, N, S, or P, preferably N, and where at least one heteroatom is further substituted by a substituted or unsubstituted aryl group.
- inorganic chromium catalysts such as chromium oxide or silyl chromate is not taught.
- the molecular switch comprises oxygen and an alkylaluminum compound which are added to a reactor in sequence. The examples provided show that the molecular switch changes the polymer architecture in situ, from unimodal to bimodal with respect to molecular weight distribution profile. Since, the organochromium catalyst is relatively inactive before the in-situ addition of the molecular switch, only a single polymer component, that made by the group 4 or 5 transition metal catalyst, is initially present.
- the present invention utilizes controlled amounts of scavenger together with impurities inherently present in a polymerization reactor in order to control the polymer architecture made by a combination catalyst.
- the current invention allows for in-line polymer composition modification without the need to reformulate a combination catalyst recipe.
- a scavenger has a divergent effect on the activity of inorganic chromium catalysts and group 4 single site catalysts, particularly group 4 single site catalysts having at least one phosphinimine ligand.
- group 4 single site catalysts having at least one phosphinimine ligand.
- a scavenger compound increases the relative activity of a group 4 single site catalyst relative to an inorganic chromium catalyst when these catalysts are used simultaneously in an olefin
- a scavenger especially a supported scavenger, has little effect on the molecular weight of polymers made by an inorganic chromium catalyst and a group 4 single site catalyst.
- the process of the current invention allows one to control the relative amounts of for example, high and low molecular weight components and/or high and low comonomer content components, made by a combination catalyst, without significantly affecting the relative molecular weights of the polymer components.
- the present invention allows for control of a polymer composition, including the ability to maintain or reestablish on-spec resin properties in the presence of a
- scavenger can be used in the presence of a combination catalyst comprising an inorganic chromium catalyst and a single site catalyst by using the scavenger in supported form.
- said combination catalyst comprises:
- said inorganic chromium catalyst provides said first polymer component and said group 4 single site catalyst provides said second polymer component; wherein said catalyst poison reduces the polymerization activity of said group 4 single site catalyst relative to said inorganic chromium catalyst;
- lowering the level of scavenger in ppm (weight of the scavenger relative to the weight of polymer produced in parts per million) from a first higher level to a second lower level, increases said ratio of said first polymer component to said second polymer component, and raising the level of scavenger in ppm (weight the of scavenger relative to the weight of polymer produced in parts per million) from a first lower level to a second higher level, decreases said ratio of said first polymer component to said second polymer component.
- said combination catalyst comprises:
- said inorganic chromium catalyst provides said first polymer component and said group 4 single site catalyst provides said second polymer component; wherein said catalyst poison reduces the polymerization activity of said group 4 single site catalyst relative to said inorganic chromium catalyst;
- the present invention provides a continuous polymerization process in which increasing the level of scavenger in a polymerization zone, increases the relative amount of polymer made by a group 4 single site catalyst present in a combination catalyst also comprising an inorganic chromium catalyst, and one or more activators.
- the present invention provides a continuous polymerization process in which decreasing the level of scavenger in a polymerization zone or reactor system, decreases the relative amount of polymer made by a group 4 single site catalyst present in a combination catalyst also comprising an inorganic chromium catalyst and one or more activators.
- an inorganic chromium catalyst, a group 4 single site catalyst and at least one catalyst activator are co-supported on an inert support.
- the scavenger has the formula AI(R 1 )n(R 2 ) 3-n , where R 1 is a hydrocarbyl having from 1 to 20 carbon atoms; R 2 is independently selected from the group consisting of an alkoxide having from 1 to 20 carbon atoms, an aryloxide having from 6 to 20 carbon atoms, a halide, and a hydride; and n is a number from 1 to 3.
- the catalyst poison is oxygen
- the scavenger is supported.
- the scavenger is supported on an inorganic oxide.
- the scavenger is a trialkylaluminum
- the scavenger is triethylaluminum.
- the group 4 single site catalyst has at least one phosphinimine ligand.
- the group 4 single site catalyst has the formula: L(PI)MX 2 , where L is a cyclopentadienyl type ligand, PI is a phosphinimine ligand, M is Ti, Zr or Hf, and each X independently, is an activatable ligand.
- the inorganic chromium catalyst is a silyl chromate catalyst.
- the inorganic chromium catalyst is a chromium oxide catalyst.
- the combination catalyst is a dual catalyst in which each catalyst component is supported on the same batch of support particles.
- the dual catalyst is supported on an inorganic oxide.
- the comonomer is selected from the group consisting of 1 -butene, 1 -hexene and 1 -octene.
- the process is a gas phase process.
- a first polymer component has a lower comonomer content than a second polymer component.
- a first polymer component has a lower weight average molecular weight than a second polymer component.
- a polymer composition has a bimodal composition when analyzed by gel permeation chromatography.
- a first polymer component represents from 95 to 25 wt% of a polymer composition and a second polymer component represents from 5 to 75 wt% of a polymer composition.
- a first polymer component represents from 99 to 80 wt% of a polymer composition and a second polymer component represents from 1 to 20 wt% of a polymer composition.
- a polymer composition has a bimodal composition when analyzed by gel permeation chromatography and a first polymer component has a lower weight average molecular weight than a second polymer component.
- a polymer composition has a bimodal composition when analyzed by gel permeation chromatography; and a first polymer component has a lower weight average molecular weight than a second polymer component; and a first polymer component has a lower comonomer content than a second polymer component.
- a first polymer component is made by an inorganic chromium catalyst and a second polymer component is made by a group 4 single site catalyst.
- the process further comprises changing the level of carbon dioxide present in a reactor.
- the present invention also includes embodiments comprising one or more of the embodiments provided above in one or more suitable combination.
- Figure 1 shows how the polymer composition molecular weight distribution profile (from GPC) is affected by changes in the amount of scavenger present in a reactor for embodiments of the current invention.
- Figure 2 shows how the polymer composition molecular weight distribution profile (from GPC) is affected by changes in the amount of scavenger present in a reactor for embodiments of the current invention.
- Figure 3 shows how the polymer composition molecular weight distribution profile (from GPC) is affected by changes in the amount of scavenger present in a reactor for embodiments of the current invention.
- the present invention utilizes scavenger levels in the presence of impurities inherently present in a polymerization reactor in order to control the polymer architecture made by a combination catalyst.
- Polymer compositions are produced by co-polymerizing ethylene with one or more alpha-olefins using the combination catalyst.
- catalyst denotes a compound which is active for ethylene homopolymerization or copolymerization of ethylene with alpha-olefins.
- the term "combination catalyst” connotes a catalyst system which contains at least two different catalysts.
- the different catalysts can be independently un-supported or supported, but are preferably supported on one or more supports.
- Supported combination catalysts include dual catalysts and mixed catalysts.
- a combination catalyst preferably includes one or more catalyst activators and/or cocatalysts.
- the term “dual catalyst” refers to a combination catalyst in which a minimum of two different catalysts are supported on the same batch of support particles. Hence for a dual catalyst, each polymerization catalyst will be co- immobilized on a support particle of a particular composition.
- a dual catalyst comprising a chromium catalyst and single site group 4 catalyst comprising a phosphinimine ligand see U.S. Pat. Appl. No. 20100 ⁇ 90937 ⁇ 1 .
- the term "mixed catalyst” refers to a combination catalyst in which at least two different polymerization catalysts have been independently supported on different batches of support particles. Hence, for a mixed catalyst, each of at least two polymerization catalysts will be independently immobilized on a different support particle which may be of the same or different composition.
- a mixed catalyst comprising a chromium catalyst and single site group 4 catalyst comprising a phosphinimine ligand see U.S. Pat. Appl. No. 20 ⁇ 00190936 ⁇ 1 .
- group 4" means group 4 transition metal.
- Group 4 transition metals include Ti, Zr and Hf.
- the combination catalyst used in the current invention comprises an inorganic chromium catalyst, a group 4 single site catalyst, one or more activators and at least one support.
- an inorganic chromium and group 4 single site catalysts is contemplated by the current invention, provided that the relative activity (and productivity) of the inorganic chromium catalyst and the group 4 single site catalyst is sensitive to the presence of a scavenger. This will generally be the case where the polymerization reaction takes place in a reactor having some amount of impurity or catalyst poison present.
- the scavenger works indirectly by reacting with and changing the amount of one or more adventitious catalyst poison or impurity present in a polymerization reactor.
- the scavenger may react with oxygen, thereby reducing the amount of oxygen present to react with one or more components of the combination catalyst.
- the scavenger may react with other oxygen rich or polar molecules, such as for example C0 2 , alcohols, amines, water and the like, thereby reducing the impact of these catalyst poisons on the combination catalyst.
- Impurities or catalyst poisons can be added to the reactor deliberately but are more typically introduced through their inherent presence in one or more feed streams entering the reactor.
- a comonomer or monomer feedstream may include small amounts of catalyst poisons.
- methods to "scrub" or otherwise remove impurities and poisons from feed streams are well known in the art, these methods often fail to remove impurities and catalyst poisons to trace levels ( ⁇ ca. 5 ppm relative to the total moles of feedstream), and even when only trace levels remain, they can still negatively affect catalyst activity.
- a catalyst poison is added deliberately to a reactor. In an embodiment, a catalyst poison is added to a reactor before the
- Suitable catalyst poisons which may be added deliberately to the reactor include but are not limited to oxygen rich or polar molecules, such as for example C0 2 , H 2 0, alcohols, amines, 0 2 and the like.
- Catalyst poison is meant to be inclusive or one or more catalysts poisons.
- trace poisons When inherently present in a reactor or polymerization zone (e.g. because purifications systems fail to remove the levels of catalyst poison to zero), such trace poisons will generally be present in amounts of less than about 100 ppm, especially less than about 10 ppm, or about 5 ppm.
- polymerization zone then it can be added in an amount of up to about 500 molar ppm or less. For example, 250 ppm or less can be added, or 100 ppm or less can be added, or 50 ppm or less can be added, or 40 ppm or less, or 30 ppm or less may be added, or
- 20 ppm or less may be added, or 10 ppm or less may be added, or 5 ppm or less may be added.
- molar ppm refers to the parts per million in moles of a component such as a catalyst poison present in a reactor zone (or in the feed-stream entering the reactor zone), based on the total moles of gases present in a reactor zone (or in the feed- stream entering the reactor zone).
- volume ppm refers the parts per million in the volume of a catalyst poison present in a reactor zone, based on the total volume of gases present in a reactor zone.
- Molar ppm and volume ppm are equivalent under assumed ideal gas conditions.
- polymerization is carried out in the presence of from 0.001 to 500 molar ppm of catalyst poison, or from 0.001 to 250 molar ppm or from 0.001 to 100 molar ppm of catalyst poison, or from 0.01 to 100 molar ppm, or from 0.01 to 50 molar ppm, or from 0.1 to 100 molar ppm, or from 0.1 to 50 molar ppm.
- the catalyst poison has a larger negative impact, in terms of reduced polymerization activity, on the group 4 single site catalyst than on the inorganic chromium catalyst.
- a catalyst poison preferentially reduces the activity (or productivity defined as the grams or polymer produced per gram of catalyst used) for active sites associated with the group 4 single site catalyst, while having a negligible effect or a more modest effect on the activity (or productivity) of active sites associated with the inorganic chromium catalyst.
- a scavenger preferentially enhances the performance of active sites associated with the group 4 single site catalyst, while having a negligible effect or a more modest effect on the active sites associated with the inorganic chromium catalyst.
- a scavenger preferentially enhances the activity (or productivity defined as the grams or polymer produced per gram of catalyst used) for active sites associated with the group 4 single site catalyst, while having a negligible effect or a more modest effect on the activity (or productivity) of active sites associated with the inorganic chromium catalyst.
- the enhanced effect of scavenger presence on the group 4 single site catalyst relative to the inorganic chromium catalyst is due to the fact that the inorganic chromium catalyst may be less sensitive, in terms of reduced activity, than the group 4 single site catalyst to the presence of impurities or catalyst poisons.
- the process may be carried out in the presence of an inherently present catalyst poison, a scavenger and a direct activity modifier such as carbon dioxide to control the ratio of polymer components made by a combination catalyst.
- a direct activity modifier such as carbon dioxide
- between 0.001 and 500 molar ppm of carbon dioxide are deliberately added to a reactor or a polymerization zone.
- the process is carried out between 0 or 0.01 and 00 molar ppm of carbon dioxide.
- the level of catalyst poison and scavenger present in a reactor system will be such that both catalyst components present in the combination catalyst (i.e. the inorganic chromium catalyst and the group 4 single site catalyst) will be at least partially active toward olefin polymerization.
- a scavenger is any compound that will react with an impurity or catalyst poison present in a reactor to give as a product a relatively inert, or less reactive species in terms of reactions which negatively affect the activity of the combination catalyst components.
- a catalyst poison is any compound that will react with a combination catalyst species to give a catalyst species which is relatively inert or, less reactive, toward polymerizing olefins (and optionally present alpha olefins).
- the scavenger has the formula
- R 1 is a hydrocarbyl having from 1 to 20 carbon atoms
- R 2 is independently selected from the group consisting of an alkoxide having from 1 to 20 carbon atoms, an aryloxide having from 6 to 20 carbon atoms, a halide, and a hydride
- n is a number from 1 to 3.
- the scavenger is an alkylaluminum
- suitable alkylaluminum compounds include, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n- octylaluminum, tri-iso-octylaluminum, triphenylaluminum, tripropylaluminum, diethylaluminum ethoxide, tributylaluminum, diisobutylaluminum hydride,
- the scavenger is a methylaluminoxane compound or a more highly substituted analogue thereof.
- the scavenger is supported.
- use of a supported scavenger reduces direct interactions or reactions between the scavenger and the catalyst species within the combination catalyst, especially where the combination catalyst species are also supported. This is desirable, since it is known that metal alkyls can have an impact on the molecular weight performance of polymerization catalysts (see for example WO 2009/067201).
- use of a supported scavenger reduces the potential impact that the scavenger may have on the molecular weight of polymer components made by the inorganic chromium and group 4 single site catalysts present in the combination catalyst.
- Preferred supports for use with the scavenger are inorganic oxides.
- the inorganic oxide may be any oxide of the metals from groups 2, 3, 4, 11 , 12, 13 and 14 of the Period Table of Elements.
- Preferred inorganic oxides include silica, SiO 2 ; aluminophosphate, AIP0 4 ; magnesia, MgO; alumina, Al 2 0 3 ; titania, Ti0 2 ; zinc oxide, ZnO; and zirconia, Zr0 2 and the like or mixtures thereof, with Si0 2 being most preferred.
- the inorganic oxide is a silica support, it will contain not less than 80% by weight of pure Si0 2 , the balance being other oxides such as but not limited to oxides of Zr, Zn, Mg, Ti, Mg and P.
- the scavenger will be a trialkyl aluminum compound supported on silica. In a more particular embodiment of the invention, the scavenger will be triethylaluminum supported on silica.
- the chromium catalyst used in the current invention is an inorganic chromium catalyst or mixture of catalysts capable of polymerizing olefins.
- An "inorganic chromium catalyst” is a chromium based catalyst which lacks a ligand forming a chromium-carbon bond (although reactive chromium-carbon bonds may be formed after contact of an inorganic chromium catalyst with a co-catalyst and are necessarily formed during a polymerization mechanism).
- Preferred inorganic chromium catalysts are selected from chromium oxide catalysts, or chromate catalysts.
- the inorganic chromium catalyst is relatively less sensitive to the presence of catalyst poisons or impurities present in the reactor (i.e. the inorganic chromium catalyst used in a combination catalyst shows a relatively smaller or negligible drop in activity when in the presence of catalyst poisons when compared to the single site catalyst used in the combination catalyst).
- the inorganic chromium catalyst is preferably supported. Minor amounts of a secondary metal species such as titanium and or aluminum compounds may also be incorporated, together with the chromium.
- the inorganic chromium compound used to prepare the inorganic chromium catalyst can be any appropriate chromium salt or an inorganic chromium compound. For example, a silyl chromate or chromium trioxide (or a mixture thereof) may be used.
- Preferred inorganic chromium catalysts include chromium oxide catalysts and silyl chromate catalysts, with silyl chromate catalyst being especially preferred.
- the chromium oxide catalyst in the combination catalyst may be prepared from chromium trioxide Cr0 3 , as used directly in formulation of the combination catalyst, or the chromium oxide catalyst in the combination catalyst may be obtained after converting suitable chromium compounds to Cr0 3 under calcination and/or oxidizing conditions. Examples of compounds which are convertible to Cr0 3 under calcination and/or oxidizing conditions are disclosed in U.S. Pat.
- Nos 2,825,721 ; 3,023,203; 3,622,521 ; 4,011 ,382; 5,034,364 and 6,734,131 include but are not limited to chromic acetyl acetone, chromic chloride, chromic nitrate, chromic acetate, chromic sulfate, ammonium chromate, ammonium dichromate and other soluble salts of chromate.
- silyl chromate (or silyl chromium) catalysts will have at least one group of the formula:
- R' O wherein R' is a hydrocarbyl group having from 1 to 14 carbon atoms.
- the silyl chromate catalyst is a bis- trihydrocarbylsilylchromate having the formula:
- R' O R * wherein R' is a hydrocarbyl group having from 1 to 14 carbon atoms.
- R' can be any hydrocarbyl group having from 1 to 14 carbon atoms.
- hydrocarbyl group such as an alkyl, alkylaryl, arylalkyl or an aryl radical.
- Some non-limiting examples include methyl, ethyl, propyl, iso-propyl, n- butyl, iso-butyl, n-pentyl, iso-pentyl, t-pentyl, hexyl, 2-methyl-pentyl, heptyl, octyl, 2- ethylhexyl, nonyl, decyl, hendecyl, dodecyl, tridecyl, tetradecyl, benzyl, phenethyl, p- methyl-benzyl, phenyl, tolyl, xylyl, naphthyl, ethylphenyl, methylnaphthyl,
- silylchromates but by no means exhaustive or complete of those that can be employed in this process are such compounds as bis-trimethylsilylchromate,
- bis-triphenylsilylchromate bis-tritolylsilylchromate, bis-trixylylsilylchromate, bis- trinaphthylsilylchromate, bis-triethylphenylsilylchromate, bis-trimethylnaphthylsilylchromate, polydiphenylsilylchromate, polydiethylsilylchromate and the like.
- bis-trihydrocarbylsilylchromate catalysts are also disclosed in U.S. Pat. Nos 3,704,287 and 4, 100, 105.
- sufficient amounts of inorganic chromium catalyst are added to a support in order to obtain between 0.01 % and 10% by weight of chromium, calculated as metallic chromium, based on the weight of the support. In another embodiment of the invention, sufficient amounts of inorganic chromium catalyst are added to a support in order to obtain between 0.05% to 3%, by weight of chromium, calculated as metallic chromium, based on the weight of the support.
- the present invention is not limited to any particular procedure for supporting the inorganic chromium catalyst.
- Processes for depositing chromium compounds on supports are well known in the art (for some non-limiting examples of catalyst supporting methods, see "Supported Catalysts" by James H. Clark and Duncan J.
- a chromium compound may be added by co- precipitation with the support material or by spray-drying with the support material.
- a chromium compound may also be added by a wet incipient method (i.e. wet
- a supported chromium compound may be obtained by mechanically mixing a solid chromium compound with a support material, followed by heating the mixture.
- a chromium compound may be incorporated into the support during the manufacture thereof so as to obtain a homogeneous dispersion of the metal in the support.
- a chromium compound may be spray dried with the constituent parts of a clay-inorganic oxide agglomerate to provide a supported chromium catalyst, as taught in U.S. Pat. No. 6,734, 131 .
- a supported inorganic chromium catalyst may arise from activation of a suitable chromium precursor compound. Activation may involve calcination and oxygenation of a suitable chromium catalyst precursor (as is preferred in the case in the formation of a chromium oxide catalyst) or the addition of co-catalyst compounds (as is preferred in the case of silyl chromate catalyst). For example, activation may be accomplished by calcination in steam, dry air or another oxygen containing gas at temperatures up to the sintering temperature of the support. Activation temperatures are in the range of 350°C to 950°C, preferably from 500°C to 900°C and activation times are from about 10 mins. to about 72 hrs.
- the supported inorganic chromium catalyst may optionally be reduced after activation using for example, carbon monoxide or a mixture of carbon monoxide and nitrogen.
- the supported inorganic chromium catalysts may optionally comprise one or more than one co-catalyst and mixtures thereof.
- the term "inorganic chromium catalyst” includes polymerization active inorganic chromium compounds per se, as well as well as catalysts comprising a polymerization active combination of one or more inorganic chromium compounds and one or more co- catalysts.
- the co-catalyst can be added to the support using any well known method.
- the co-catalyst and inorganic chromium catalyst can be added to the support in any order or simultaneously.
- the co-catalyst can be added to the supported inorganic chromium catalyst in situ.
- the co-catalyst is added as a solution or slurry in hydrocarbon solvent to the supported inorganic chromium catalyst which is optionally also in hydrocarbon solvent.
- Co-catalysts include compounds represented by formula:
- M * represents an element of the Group , 2 or 13 of the Periodic Table, a tin atom or a zinc atom; and each R 3 independently represents a hydrogen atom, a halogen atom (e.g. , chlorine, fluorine, bromine, iodine and mixtures thereof), an alkyl group (e.g., methyl, ethyl, propyl, pentyl, hexyl, heptyl, octyl, decyl, isopropyl, isobutyl, s-butyl, t-butyl), an alkoxy group (e.g., methoxy, ethoxy, propoxy, butoxy, isopropoxy), an aryl group (e.g., phenyl, biphenyl, naphthyl), an aryloxy group (e.g., phenoxy), an arylalkyl group (e.g., benzyl, phenyle
- R 3 is selected from a hydrogen atom, an alkyl group having 1 to 24 carbon atoms or an aryl, arylalkyl or alkylaryl group having 6 to 24 carbon atoms; and n is the oxidation number of M * .
- Preferred co-catalysts are organoaluminum compounds having the formula:
- (X 1 ) is a hydrocarbyl having from 1 to about 20 carbon atoms
- (X 2 ) is selected from alkoxide having from 1 to about 20 carbon atoms; an aryloxide having from 6 to 20 carbon atoms; halide; or hydride
- n is a number from 1 to 3, inclusive.
- Specific examples of (X 1 ) moieties include, but are not limited to, ethyl, propyl, n-butyl, sec-butyl, isobutyl, hexyl, and the like.
- (X 2 ) may be independently selected from fluoro or chloro.
- n is not restricted to be an integer, therefore this formula includes sesquihalide compounds or other organoaluminum cluster
- aluminum co-catalyst compounds that can be used in this invention include, but are not limited to, trialkylaluminum compounds, dialkylaluminium halide compounds, dialkylaluminum alkoxide compounds,
- organoaluminum co-catalyst compounds that are useful in this invention include, but are not limited to: trimethylaluminum (TMA); triethylaluminum (TEA);
- the molar ratio of co-catalyst to inorganic chromium catalyst can be about from about 1 : 1 to about 30: 1 .
- the molar ratio of co-catalyst to inorganic chromium catalyst can be about from about 1 :1 to about 20: 1 .
- the molar ratio of co-catalyst to inorganic chromium catalyst can be about from about 5: 1 to about 20: 1.
- Preferred single site catalysts for use in the process of the current invention are group 4 single site catalysts (i.e. single site catalysts comprising a group 4 transition metal as the active center).
- Single site catalysts include metallocene catalysts, so called “constrained geometry catalysts" and catalysts comprising at least one
- the single site catalyst should be chosen so as to have different sensitivity to scavenger (in terms of activity) than the inorganic chromium catalyst chosen.
- the activity of the single site catalyst will be more positively impacted than the activity of the inorganic chromium catalyst n the presence of scavenger.
- the group 4 single site catalyst will have at least one phosphinimine ligand or at least one ketimine ligand. Especially preferred are group 4 single site catalysts having at least one phosphinimine ligand.
- a single site catalyst having at least one phosphinimine ligand or ketimine ligand can be represented by the following formula:
- M is a group 4 metal
- PI is independently a phosphinimine ligand or a ketimine ligand
- L is a monoanionic ligand selected from the group consisting of a
- M is selected from the group 4 transition metals with titanium being most preferred.
- the phosphinimine ligand is substituted with three hydrocarbyl radicals which can be the same or different. In another aspect of the invention, the phosphinimine ligand is substituted with three tert-butyl radicals.
- ketimine ligand refers to a ligand which: (a) is bonded to the transition metal via a metal-nitrogen atom bond; (b) has a single substituent on the nitrogen atom, (where this single substituent is a carbon atom which is doubly bonded to the N atom); and (c) has two substituents Sub 1 and Sub 2 (described below) which are bonded to the carbon atom. Conditions a, b and c are illustrated below:
- the substituents "Sub 1 " and “Sub 2" may be the same or different and can be bonded to each other by a bridging group to form a ring.
- the bridging group can be any saturated or unsaturated alkyl group or aryl group including fused ring aryl groups, where the alkyl or aryl groups can optionally contain heteroatoms or be further substituted by alkyl, aryl or heteroatom containing alkyl or aryl groups.
- Exemplary substituents include hydrocarbyls having from 1 to 20 carbon atoms, silyl groups, amido groups and phosphido groups. For reasons of cost and convenience, these
- substituents may both be hydrocarbyl radicals, especially simple alkyl radicals (e.g. C-i. ⁇ ) such as but not limited to tertiary butyl radicals.
- the cyclopentadienyl type ligand L is a ligand comprising a 5-membered carbon ring having delocalized bonding within the ring and bound to the metal atom through ⁇ 5 bonds.
- a cyclopentadienyl type ligand may be a substituted or unsubstituted cyclopentadienyl ligand (Cp), but also includes, substituted or unsubstituted indenyl, and fluorenyl ligands and other fused ring systems which contain a 5-membered carbon ring having delocalized bonding within the ring and bound to the metal atom through ⁇ 5 bonds.
- the cyclopentadienyl type ligand L can be un-substituted, partially substituted, or fully substituted with one or more substituents selected from the group consisting of: halogens; Ci-io hydrocarbyl radicals in which the hydrocarbyl substituents are unsubstituted or further substituted with a halogen atom and/or d-s alkyl radical; a C -8 alkyl radical; a Ci-e alkoxy radical; a C 6- io aryl or aryloxy radical in which the aryl or aryloxy are un-substituted or further substituted by a halogen atom and/or a Ci -8 alkyl radical; an amido radical which is unsubstituted or substituted by alkyl or aryl radicals; a phosphido radical which is unsubstituted or substituted by alkyl or aryl radicals; a silyl radical which unsubstituted
- the cyclopentadienyl type ligand is a cyclopentandienyl ligand having at least a perfluoroaryl substituent or at least a partially fluorinated aryl substituent.
- the cyclopentadienyl type ligand is a cyclopentadienyl ligand Cp, which is substituted by a perfluoroaryl substituent such as for example a pentafluorophenyl group and a Ci -10 alkyl substituent in a ,2 or a 1 ,3 substitution pattern.
- a perfluoroaryl substituent such as for example a pentafluorophenyl group and a Ci -10 alkyl substituent in a ,2 or a 1 ,3 substitution pattern.
- heteroatom ligand refers to a ligand that contains at least one heteroatom selected from the group consisting of boron, nitrogen, oxygen, phosphorus or sulfur.
- the heteroligand may be sigma or pi-bonded to the metal.
- heteroligands include silicon-containing heteroligands, amido ligands, alkoxy ligands, boron heterocyclic ligands (e.g. borabenzene ligands) and phosphole ligands, as further described below.
- Silicon containing heteroligands are defined by the formula:
- the substituents on the Si atom namely R x , R y and R z are required in order to satisfy the bonding orbital of the Si atom.
- the use of any particular substituent R x , R y or R z is not specifically defined, but it is preferred that each of R x , R y and R z is a Ci -2 hydrocarbyl group (i.e. methyl or ethyl) simply because such materials are readily synthesized from commercially available materials.
- these ligands are characterized by (a) a metal-nitrogen bond; and (b) the presence of two substituents, which are typically alkyl, phenyl, trialkyl or triaryl silyl groups on the nitrogen atom.
- alkoxy and aryloxy are also intended to convey their conventional meaning.
- these ligands are characterized by (a) a metal oxygen bond; and (b) the presence of a hydrocarbyl group bonded to the oxygen atom.
- the hydrocarbyl group may be a CMO straight chained, branched or cyclic alkyl radical or a C 6- 13 aromatic radical which radicals are un-substituted or further substituted by one or more Ci -4 alkyl radicals (e.g. 2, 6 di-tertiary butyl phenoxy).
- Boron heterocyclic ligands are characterized by the presence of a boron atom in a closed ring ligand (e.g. borabenzene ligands which are un-substituted or may be substituted by one or more halogen atoms, Ci_i 0 alkyl groups, and/or CMO alkyl groups containing a hetero atom (e.g. O, or N atoms)).
- This definition includes heterocyclic ligands that may also contain a nitrogen atom in the ring.
- These ligands are well known to those skilled in the art of olefin polymerization and are fully described in the literature (see, for example, U.S. Pat. Nos. 5,637,659; 5,554,775; and references cited therein).
- Phospholes are cyclic dienyl structures having four carbon atoms and one
- the simplest phosphole is C 4 PH 4 (which is analogous to cyclopentadiene with one carbon in the ring being replaced by
- the phosphole ligands may be substituted with, for example, Ci-2o hydrocarbyl radicals (which may, optionally, contain halogen substituents); phosphido radicals; amido radicals; or silyl or alkoxy radicals.
- Ci-2o hydrocarbyl radicals which may, optionally, contain halogen substituents
- phosphido radicals amido radicals; or silyl or alkoxy radicals.
- Phosphole ligands are also well known to those skilled in the art of olefin polymerization and are described as such in
- the term "activatable”, means that the ligand X, may be cleaved from the metal center M, via a protonolysis reaction or abstracted from the metal center M, by suitable acidic or electrophilic activator compounds respectively, which are further described below.
- the activatable ligand X may also be transformed into another ligand which is cleaved or abstracted from the metal center M.
- the activatable ligand, X is independently selected from the group consisting of a hydrogen atom; a halogen atom, a d.- ⁇ hydrocarbyl radical, including a benzyl radical; a Ci-io alkoxy radical; a C 6- io aryl oxide radical, where each of the hydrocarbyl, alkoxy, and aryl oxide radicals may be un-substituted or further substituted by; an amido radical or a phosphido radical.
- Two X ligands may also be joined to one another and form for example, a substituted or unsubstituted diene ligand (i.e. 1 ,3-diene); or a delocalized heteroatom containing group such as an acetate or acetamidinate group.
- a substituted or unsubstituted diene ligand i.e. 1 ,3-diene
- a delocalized heteroatom containing group such as an acetate or acetamidinate group.
- each X is independently selected from the group consisting of a halide atom and a C 1-4 alkyl radical.
- the single site catalyst is represented by the formula L(PI)MX 2 where L is a cyclopentadienyl type ligand defined as above, PI is a phosphinimine ligand, M is Ti, Zr or Hf, and X is an activatable ligand.
- the metallocene catalysts contemplated for use with the current invention may have from one to three cyclopentadienyl type ligands defined as above, provided that the remaining ligands are activatable ligands.
- metallocene catalysts see for example U.S. Pat. Nos 4,808,561 ; 4,701 ,432; 4,937,301 ;
- metallocene catalysts are represented by the formula: L 2 n MX4-n
- M is a group 3 or 4 transition metal; each X is independently an activatable ligand defined as above, each L 2 group is independently a cyclopentadienyl type ligand further described below and n is from 1 to 3.
- M is a group 4 transition metal with a valency of 4.
- the cyclopentadienyl type ligand L 2 is a ligand comprising a 5-membered carbon ring having delocalized bonding within the ring and bound to the metal atom through ⁇ 5 bonds.
- the 5-membered ring can be un-substituted, partially substituted, or fully substituted with one or more substituents.
- the cyclopentadienyl type ligands L 2 in metallocene catalysts also include heterocyclic analogues of a 5-membered carbon ring.
- the L 2 ring may typically comprise atoms selected from the group consisting of Groups 13 to 16 atoms, and more particularly, the atoms that make up the L 2 ligands are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum and combinations thereof, wherein carbon makes up at least 50% of the ring members.
- L 2 may be the same or different cyclopentadienyl type ligands, either or both of which may contain heteroatoms and either or both of which may be substituted or unsubstituted.
- L 2 is independently selected from the group consisting of cyclopentadienyl, indenyl, tetrahydroindenyl, fluorenyl, and substituted derivatives of each.
- Non-limiting examples of substituents which may be present on L 2 include hydrogen radicals, halogens, alkyls, alkenyls, alkynyls, cycloalkyls, aryls, acyls, aroyls, alkoxys, aryloxys, alkylthiols, dialkylamines, alkylamidos, alkoxycarbonyls,
- alkyl substituents include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl, phenyl, methylphenyl, and tert-butylphenyl groups and the like, including all their isomers, for example tertiary-butyl, isopropyl, and the like.
- radicals include substituted alkyls and aryls such as, for example, fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)silyl, methylbis(difluoromethyl)silyl, bromomethyldimethylgermyi and the like; and disubstituted boron radicals including dimethylboron for example; and disubstituted Group 15 radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, Group 16 radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and
- substituents for L 2 include olefins such as but not limited to olefinically unsaturated substituents including vinyl- terminated ligands, for example 3-butenyl, 2-propenyl, 5-hexenyl and the like.
- at least two substituents on a L 2 are joined to form a ring structure having from 3 to 30 atoms selected from the group consisting of carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron and combinations thereof.
- a substituent such as 1-butanyl may form a bonding association to the element M.
- Two L 2 ligands may be bridged to each other by at least one bridging group, (A).
- A bridging group
- Non-limiting examples of bridging group (A) include divalent hydrocarbon groups containing at least one Group 13 to 16 atom, such as but not limited to at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom and combinations thereof; wherein the heteroatom may also be Ci to Ci 2 alkyl or aryl substituted to satisfy neutral valency.
- the bridging group (A) may also contain further substitution, such as alkyl, aryl, alkoxy, halide etc.
- the bridged metallocene catalyst has two bridging groups (A)
- the constrained geometry catalyst contemplated for use with the current invention has a cyclopentadienyl type ligand, L 3 forming a bringing moiety with a heteroatom ligand.
- a cyclopentadienyl type ligand L 3 forming a bringing moiety with a heteroatom ligand.
- Such compounds are well known in the art and are described in for example, U.S. Pat. Nos. 5,057,475; 5,096,867; 5,064,802; 5,132,380; 5,703,187; and 6,034,021 all of which are incorporated by reference herein in their entirety.
- Constrained geometry catalysts are conveniently represented by the formula:
- M is a group 3 or 4 transition metal, each X is independently an activatable ligand defined as above; L 3 is a cyclopentadienyl type ligand comprising a
- 5-membered carbon ring having delocalized bonding within the ring and bound to the metal atom through ⁇ 5 bonds and has at least one attachment point to Z; n is 1 or 2 depending on the valence of the metal; Q is a heteroatom-containing ligand bonded to the metal, and Z is a bridging group bonded to L 3 and Q.
- M is a group 4 transition metal.
- the cyclopentadienyl type ligand L 3 which is bonded to Z at one position can further be un-substituted, partially substituted, or fully substituted with one or more substituents selected from halogens; CMO hydrocarbyl radicals in which the hydrocarbyl substituents are unsubstituted or further substituted with a halogen atom and/or C-i-s alkyl radical; a C 1-8 alkyl radical; a Ci-s alkoxy radical; a C 6 -io aryl or aryloxy radical in which the aryl or aryloxy are un-substituted or further substituted by a halogen atom and/or a Ci -8 alkyl radical; an amido radical which is unsubstituted or substituted by alkyl or aryl radicals; a phosphido radical which is unsubstituted or substituted by alkyl or aryl radicals; a silyl radical which un
- the cyclopentadienyl type ligand L 3 also includes substituted or unsubstituted indenyl, fluorenyl or other fused ring systems which contain a 5-membered carbon ring having delocalized bonding within the ring and bound to the metal atom through ⁇ 5 bonds.
- the bridging group Z is a moiety comprising boron, or a member of group 14 of the periodic table of the elements, and optionally sulfur or oxygen, the moiety having up to 40 non-hydrogen atoms, and optionally L 3 and Z together form a fused ring system
- the group Q is an anionic or neutral ligand group bonded to Z and M, comprising nitrogen, phosphorus, oxygen or sulfur and having up to 40 non-hydrogen atoms, and optionally Q and Z together form a fused ring system.
- Q is— O— ,— S— ,— NR*— ,— PR*— , or a neutral two electron donor ligand selected from the group consisting of OR*, SR*, NR* 2 , PR* 2 where R* each occurrence is independently selected from the group consisting of hydrogen, alkyl, aryl, silyl, halogenated alkyl, halogenated aryl groups having up to 20 non-hydrogen atoms, and mixtures thereof, or two or more R* groups from Z, Q or both Z and Q form a fused ring system.
- Q is a substituted or un-substituted amido or phosphido group, preferably a substituted group with a C-M O alkyl, a C 6 -Ci 0 aryl, or a silyl group substituent.
- the single site catalyst used in the current invention will typically require activation with one or more suitable activators.
- suitable catalyst activators are selected from the group consisting of alkylaluminoxanes, ionic activators and electrophilic borane compounds, with alkylaluminoxanes and ionic activators being preferred.
- alkylaluminoxanes are complex aluminum compounds of the formula:
- each R 12 is independently selected from the group consisting of C 1 -20
- hydrocarbyl radicals and m is from 3 to 50.
- a hindered phenol can be added to the alkylaluminoxane to provide a molar ratio of Al 3 : hindered phenol of from 2: 1 to 5: 1 when the hindered phenol is present.
- R 12 of the alkylaluminoxane is a methyl radical and m is from 10 to 40.
- the molar ratio of Al 3 :hindered phenol, if it is present, is from 3.25: 1 to 4.50: 1 .
- the phenol is substituted in the 2, 4 and 6 position by a C 2- 6 alkyl radical.
- the hindered phenol is 2 , 6-d i-tertbutyl-4- ethyl-phenol.
- the alkylaluminoxanes are typically used in substantial molar excess compared to the amount of group single site catalyst.
- the Al 3 :single site catalyst transition metal molar ratios are from 10:1 to 10,000:1 , preferably about 30:1 to 500:1.
- the ionic activators include activators that activate the organometallic complex by protonolysis of a suitable activatable ligand or by the electrophilic abstraction of a suitable activatable ligand.
- the "ionic activator” may abstract or cleave one or more activatable ligand so as to ionize the catalyst center into a "cation", it does not covalently bond with the catalyst, providing instead, sufficient distance between the catalyst metal center and the ionizing activator to permit a polymerizable olefin to enter the resulting active site.
- the ionic activators used in the present invention are selected from compounds of the formula:
- R 13 is a cyclic C 5- 7 aromatic cation or a triphenyl methyl cation and each R 14 is independently selected from the group consisting of phenyl radicals which are un-substituted or substituted with 3 to 5 substituents selected from the group consisting of a fluorine atom, a C 1-4 alkyl or alkoxy radical which is un- substituted or substituted by a fluorine atom; and a silyl radical of the formula— Si— (R 5 ) 3 ; wherein each R 5 is independently selected from the group consisting of a hydrogen atom and a Ci -4 alkyl radical; and compounds of the formula:
- B is a boron atom
- H is a hydrogen atom
- Z * is a nitrogen atom or phosphorus atom
- t is 2 or 3
- R 8 is selected from the group consisting of Ci_8 alkyl radicals, a phenyl radical which is un-substituted or substituted by up to three Ci- alkyl radicals, or one R 8 taken together with the nitrogen atom may form an anilinium radical and R 4 is as defined above.
- ionic activators that may be used in the current invention include but are not limited to: triethylammonium tetra(phenyl)boron, tripropylammonium
- tetra(pentafluorophenyl)boron tripropylammonium tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p- trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tri(n- butyl)ammonium tetra(o-tolyl)boron, ⁇ , ⁇ -dimethylanilinium tetra(phenyl)boron, N,N- diethylanilinium tetra(phenyl)boron, ⁇ , ⁇ -diethylanilinium tetra(phenyl)n-butylboron, di- (isopropyl)ammonium tetra(pentafluorophenyl)boron, di
- phenyltrispentafluorophenyl borate tropillium tetrakis (2,3,5,6-tetrafluorophenyl) borate, triphenylmethylium tetrakis (2,3,5,6-tetrafluorophenyl) borate, tropillium tetrakis (3,4,5- 10 trifluorophenyl) borate, benzene (diazonium) tetrakis (3,4,5-trifluorophenyl) borate, tropillium tetrakis (1 ,2,2-trifluoroethenyl) borate, triphenylmethylium tetrakis (1 ,2,2- trifluoroethenyl) borate, tropillium tetrakis (2,3,4,5-tetrafluorophenyl) borate, and triphenylmethylium tetrakis (2,3,4,5-tetrafluorophenyl) borate.
- Some readily commercially available ionic activators include: N, Nil s dimethylaniliniumtetrakispentafluorophenyl borate; triphenylmethylium
- tetrakispentafluorophenyl borate tritylborate
- trispentafluorophenyl borane tritylborate
- the ionic activators may also have an anion containing at least one group comprising an active hydrogen or at least one of any substituent able to react with the support. As a result of these reactive substituents, the anionic portion of these ionic 0 activators may become bonded to the support under suitable conditions.
- One non- limiting example includes ionic activators with tris(pentafluorophenyl)(4-hydroxyphenyl) borate as the anion. These tethered ionic activators are more fully described in U.S. Pat. Nos 5,834,393; 5,783,512; and 6,087,293.
- electrophilic borane compounds that may be used in the present invention 5 include compounds of the formula:
- R 14 is as defined above.
- the ionic activators or electrophilic borane compounds may be used in amounts which provide a molar ratio of group 4 transition metal to boron that will be from 1 :1 to 0 :6, preferably from 1 :1 to :2.
- mixtures of alkylaluminoxanes, ionic activators, and electrophilic boranes may be used as activators in the second catalyst component of the current invention.
- the single site catalyst is supported.
- the present invention is not limited to any particular procedure for supporting the single site catalyst.
- Processes for depositing a single site catalyst complex as well as an activator on a support are well known in the art (for some non-limiting examples of catalyst supporting methods, see "Supported Catalysts" by James H. Clark and Duncan J. Macquarrie, published online November 15, 2002 in the Kirk-Othmer Encyclopedia of Chemical Technology Copyright ⁇ 2001 by John Wiley & Sons, Inc.; for some non- limiting methods to support a single site catalyst see U.S. Pat. No. 5,965,677).
- the single site catalyst may be added by co-precipitation with the support material.
- the activator can be added to the support before and/or after the single site catalyst or together with the single site catalyst.
- the activator can be added to a supported single site catalyst in situ or the single site catalyst may be added to the support in situ or the single site catalyst can be added to a supported activator in situ.
- the single site catalyst may be slurried or dissolved in a suitable diluent or solvent and then added to the support. Suitable solvents or diluents include but are not limited to hydrocarbons and mineral oil.
- the single site catalyst may be added to the solid support, in the form of a solid, solution or slurry, followed by the addition of the activator in solid form or as a solution or slurry.
- Single site catalyst, activator, and support can be mixed together in the presence or absence of a solvent.
- a solution or slurry containing a single site catalyst and activator in a hydrocarbon is added to a support.
- the amount of single site catalyst added to the support should be sufficient to obtain between 0.001 and 10% or between 0.01 % and 10%, by weight of group 4 transition metal, calculated as metallic Ti, Zr, Hf or combined total thereof, based on the weight of the support. In another embodiment, the single site catalyst added to the support should be sufficient to obtain between 0.01 % to 3%, by weight of group 4 transition metal, calculated as metallic Ti, Zr, Hf or combined total thereof, based on the weight of the support.
- the inorganic chromium and single site catalysts may be supported on one or more of any known support material.
- Catalyst supports are well known in the art and may be chosen from a wide range of well known materials or mixtures thereof.
- catalyst supports include inorganic oxides, such as but not limited to silica gel; magnesium halides; zeolites; layered clay minerals; agglomerated support materials; and polymer supports such as but not limited to polyethylene, polypropylene,
- a support material may also act as a polymerization catalyst activator or as a co-catalyst.
- supports that are Lewis acidic, contain aluminoxane functionalities, or where the support is capable of performing similar chemical functions as an aluminoxane are suitable for use as a "support-activator".
- Preferred supports for use in the current invention are inorganic oxides, and agglomerates of clays or clay minerals with inorganic oxides.
- the inorganic oxide may be any oxide of the metals from groups 2, 3, 4, 1 1 , 12, 13 and 14 of the Period Table of Elements.
- Preferred inorganic oxides include silica, Si0 2 ; aluminophosphate, AIPO 4 ; magnesia, MgO; alumina, AI 2 O 3 ; titania, Ti0 2 ; zinc oxide, ZnO; and zirconia, Zr0 2 and the like or mixtures thereof, with Si0 2 being most preferred.
- the inorganic oxide is a silica support, it will contain not less than 80% by weight of pure Si0 2 , the balance being other oxides such as but not limited to oxides of Zr, Zn, Mg, Ti, Mg and P.
- the inorganic oxide support will contain acidic surface hydroxyl groups that will react with a polymerization catalyst.
- the inorganic oxide may be dehydrated to remove water and to reduce the concentration of surface hydroxyl groups.
- the inorganic oxide may be heated at a temperature of at least 200°C for up to 24 hrs, typically at a temperature of from about 500°C to about 800°C for about 2 to 20 hrs, preferably 4 to 10 hrs.
- the resulting support will be free of adsorbed water and should have a surface hydroxyl content from about 0.1 to 5 mmol/g of support, preferably from 0.5 to 3 mmol/g.
- hydroxyl groups may also be removed by other removal means, such as chemical means.
- a desired proportion of OH groups may be reacted with a suitable chemical agent, such as a hydroxyl reactive aluminum compound (e.g. triethylaluminum) or a silane compound.
- a suitable chemical agent such as a hydroxyl reactive aluminum compound (e.g. triethylaluminum) or a silane compound.
- a silica support that is suitable for use in the present invention has a high surface area and is amorphous.
- useful silicas are commercially available under the trademark of Sylopol® 958, 955 and 2408 from Davison Catalysts, a Division of W. R. Grace and Company and ES-70WTM from Ineos Silica.
- the clay or clay mineral (i.e. "layered silicates”) contemplated for use in the current invention can be amorphous or crystalline and has a three dimensional structure which has its strongest chemical bonds in only two dimensions.
- clay minerals may be composed of layered silicates of nanometer scale thickness.
- a silicate layer is comprised of silicate sheets fused by alumina or magnesia. Stacking of the silicate layers provides a clay gallery, which is represented by a regular interlayer spacing between the silicate layers. The gallery typically contains hydrated inorganic cations, the nature of which is determined by the source of the clay mineral. Calcium, Ca 2+ , sodium, Na + and potassium, K + are common.
- the clay mineral is not specifically defined, but preferably includes any natural or synthetic layered silicate having a negative charge below zero and which is capable of forming an agglomerate with a inorganic oxide such as silica.
- Non-limiting examples of clay minerals which are useful in the current invention generally are smectites, vermiculites, and micas; including phyllosilicate,
- montmorillonite hectorite, betonite, laponite, saponite, beidellite, stevensite, kaolinite, hallosite, and magadite.
- MMT montmorillonite
- the interlaminar cations found in clay can be ion exchanged with other cations.
- the cation exchange capacity (CEC) of a clay is a measure of the exchangeable cations present in the clay or the total quantity of positive charge that can be absorbed onto the clay. It may be measured in SI units as the positive charge (coulombs) absorbed by the clay per unit of mass of the clay. It is also conveniently measured in milliequivalents per gram of clay (meq/g) or per 100 gram of clay (meq/1 OOg). 96.5 coulombs per gram of cation exchange capacity is equal to 1 milliequivalent per gram of cation exchange capacity.
- agglomerate in the current invention refers to a support in which particles of an inorganic oxide and a layered silicate or clay are held together by a variety of physical-chemical forces.
- An agglomerate is distinct from a simple "support blend” in which two types of support material have merely been stirred or mixed into one another.
- An "agglomerate” or “agglomerate support” is generally composed of inorganic oxide particles (i.e. primary particles) and clay or clay/inorganic oxide particles (i.e. smaller secondary particles), where inorganic oxide particles (i.e. primary particles) and clay particles or clay/inorganic oxide particles (i.e. secondary particles) are joined at some points of contact.
- Agglomerate supports comprising a clay mineral and an inorganic oxide may be prepared using a number techniques well known in the art including pelletizing, extrusion, drying or precipitation, spray-drying, shaping into beads in a rotating coating drum, and the like. A nodulization technique may also be used. Methods to make agglomerate supports comprising a clay mineral and an inorganic oxide include spray- drying a slurry of a clay mineral and an inorganic oxide. Methods to make agglomerate supports comprising a clay mineral and an inorganic oxide are disclosed in U.S. Pat. Nos. 6,686,306; 6,399,535; 6,734, 131 ; 6,559,090 and 6,958,375.
- the molar ratio of inorganic chromium catalyst to group 4 single site catalyst is not specifically defined, but the Crgroup 4 metal molar ratio can be in the range of 100: 1 to 1 : 100.
- the molar ratio of Crgroup 4 metal can be from 50: 1 to 1 :50 or from 25: 1 to 1 :25 or 10: 1 to 1 : 10 or from 5: 1 to 1 :5 or from 15: 1 to 1 :2 or from 15: 1 to 1 : 1 .
- the combination catalyst is a dual catalyst.
- the inorganic chromium catalyst and the group 4 single site catalyst as well as one or more activators and optional co-catalysts, may be co-immobilized on a support using any known method. Processes for depositing chromium compounds, single site catalysts, as well as activators and co-catalysts on a support are well known in the art (for some non-limiting examples of catalyst supporting methods, see "Supported Catalysts" by James H. Clark and Duncan J.
- catalysts, co-catalysts and activators may be added by co-precipitation or spray drying with the support material or alternatively by a wet incipient method (i.e. wet impregnation) or similar method using hydrocarbon solvents/diluents or other suitable solvents/diluents.
- the combination catalyst is a dual catalyst comprising:
- group 4 single site catalyst comprises:
- the molar ratio of Cr to group 4 metal is from 5:95 to 95:5.
- the inorganic chromium catalyst and the group 4 single site catalyst as well as activators and optional co-catalysts can be added to the support material in any order.
- the dual catalyst system can be prepared in a stepwise manner in which catalyst precursors or intermediates are isolated or not isolated.
- the inorganic chromium catalyst and the optional co-catalyst are added to a support prior to the addition of the group 4 single site catalyst and activator.
- the group 4 single site catalyst and activator can be added simultaneous or in pre-mixed form or they may be added separately and in any order.
- the group 4 single site catalyst and activator can also be added to the supported inorganic chromium catalyst in situ (i.e. in a polymerization reactor or on route to a reactor).
- the combination catalyst is a dual catalyst which is made by a method comprising the following sequence of steps:
- M is a group 4 metal
- PI is a phosphinimine ligand
- L is a
- cyclopentadienyl type ligand X is an activatable ligand
- m is 1
- n is 1
- p is an integer and the sum of m+n+p equals the valence state of M
- the activator is selected from the group consisting of alkylaluminoxanes, ionic activators and mixtures thereof.
- an activator to the inorganic oxide, wherein the activator is selected from the group consisting of alkylaluminoxanes, ionic activators and mixtures thereof;
- the combination catalyst will provide a polymer composition comprising a first polymer component produced by an inorganic chromium catalyst and a second polymer component produced by a group 4 single site catalyst.
- the first and second polymer components may be of similar or different weight average molecular weights and have similar or different comonomer contents.
- the inorganic chromium catalyst and the group 4 single site catalyst will produce polymer components having different concentrations of comonomer (i.e. the first and second polymer components will have different comonomer content).
- Comonomer concentration or "comonomer content” is typically reported as mol% or as weight%. Either mol% or weight% can be used in the present invention to represent comonomer content.
- the comonomer content in an ethylene/alpha-olefin copolymer or copolymer component can be obtained using FTIR methods or GPC-FTIR methods (for multicomponent polymers) as is well known to persons skilled in the art.
- an FTIR measurement as per the ASTM D6645-01 can be used to obtain the short chain branch (SCB) frequency of an ethylene/alpha-olefin copolymer in branches per 1000 carbons, which can then be converted into a mol% or weight% number.
- SCB short chain branch
- Comonomer content can also be measured using 13 C NMR techniques as discussed in Randall, Rev. Macromol. Chem. Phys., C29 (2&3), p 285; U.S. Pat. No. 5,292,845 and WO 2005/121239.
- the inorganic chromium catalyst will produce a polymer component which has a lower comonomer content than a polymer component produced by the group 4 single site catalyst.
- Such polymer compositions can be made using a dual or mixed catalyst comprising an inorganic chromium catalyst and a group 4 single site catalyst having at least one phosphinimine ligand as is described in U.S. Pat. Appl. Nos 20100190936A1 and 20100190937A1 which are incorporated herein by reference.
- a component may be designated a high molecular weight (HMW) component or a low molecular weight (LMW) component.
- the inorganic chromium catalyst and the group 4 single site catalyst will produce polymer components with a different weight average molecular weight (M w ) (i.e. the first and second polymer components will have different weight average molecular weights).
- M w weight average molecular weight
- Polymer compositions in which the inorganic chromium catalyst and the group 4 single site catalyst produce polymer components with similar weight average molecular weights are also part of the current invention (i.e. the first and second polymer components have similar weight average molecular weights).
- the inorganic chromium catalyst produces a relatively lower molecular weight (LMW) or relatively higher molecular weight (HMW) component of a polyethylene composition
- the group 4 single site catalyst produces a corresponding higher molecular weight (HMW) or lower molecular weight (LMW) component of a polyethylene composition.
- the inorganic chromium catalyst or the group 4 single site catalyst produces a polymer component of relatively higher or lower molecular weight may generally depend on the hydrogen concentration. If the single site catalyst is more sensitive to hydrogen than the inorganic chromium catalysts, which is generally (but need not always be) the case, then for certain catalyst combinations, sufficient levels of hydrogen may shift the molecular weight of the polymer component made by the single site catalyst to a value that is lower than the molecular weight of the polymer
- the inorganic chromium catalyst produces the low molecular weight (LMW) component of a polymer composition, while the single site catalyst produces the high molecular weight of a polymer composition.
- the first polymer component if made by the inorganic chromium catalyst will preferably have a lower weight average molecular weight, than the weight average molecular weight of the second polymer component if made by a single site catalyst.
- the inorganic chromium catalyst produces the high molecular weight (HMW) component of a polymer composition, while the single site catalyst produces the low molecular weight component of a polymer composition.
- the first polymer component if made by the inorganic chromium catalyst will preferably have a higher weight average molecular weight, than the weight average molecular weight of the second polymer component if made by a single site catalyst.
- the LMW component of the polymer made with the current invention may have a weight average molecular weight (M w ), as measured by Gel Permeation
- the LMW component may have a Mw of from 25,000 to 400,000, or from 25,000 to 350,000, or from 50,000 to 300,000, or from 100,000 to 250,000.
- the HMW component of the polymer made with the current invention may have a weight average molecular weight (M w ), as measured by Gel Permeation Chromatography (GPC), of from 50,000 to 750,000.
- M w weight average molecular weight
- the HMW component may have a Mw of from 100,000 to 750,000, or from 125,000 to 500,000, or from 125,000 to 425,000, or from 150,000 to 400,000, or from 175,000 to 350,000.
- the component of the polymer composition arising from the inorganic chromium catalyst may have a molecular weight distribution (Mw/Mn) of from about 8 to about 30.
- the component of the polymer composition arising from the single site catalyst may have a molecular weight distribution (Mw/Mn) of from about 1 .5 to about 6.0
- the weight average molecular weight of the high molecular weight component (M W -HMW) has an average molecular weight which is less than 200% higher than the weight average molecular weight of the low molecular weight component (M W -LMW).
- the M W -HMW may be less than 150% higher, or less than 100% higher, or less than 75% higher, or less than 50% higher than the M W -LMW.
- the first polymer component which is made with an inorganic chromium catalyst, will have both a lower weight average molecular weight and a lower comonomer content than the second polymer component made with a single site catalyst.
- a polymer composition can be made using a dual or mixed catalyst comprising an inorganic chromium catalyst and a single site catalyst as is described in U.S. Pat. Appl. Nos 20 00190936A1 and 20100190937A1 which are incorporated herein by reference. It is well known in the art that comonomer content can be determined using 13 C NMR techniques, FTIR branching analysis, combined GPC-FTIR methods or by determination of the resin density.
- the polyethylene composition of the present invention may be a copolymer of ethylene with an alpha olefin.
- Suitable alpha olefins are well known in the art and may be selected from 1 -butene, 4-methyl-1 -pentene, 1 -hexene, 1 -octene and the like with 1 - hexene being preferred.
- the molecular weight distribution of the overall polymer composition may be unimodal, broad and unimodal, bimodal or multimodal, and may or may not include peaks and shoulders and may or may not show peaks which are or are not fully resolved when the molecular weight distribution of the polymer composition is examined by gel permeation chromatography (GPC).
- GPC gel permeation chromatography
- the molecular weight distribution of the polymer composition made during use of the present invention may or may not have resolved high and low molecular weight peaks in a GPC chromatograph.
- the individual polymer components may themselves be unimodal, broad and unimodal, bimodal, or multimodal, and may or may not include peaks and shoulders and may or may not show peaks which are or are not fully resolved when the molecular weight distribution of the polymer composition is examined by gel permeation chromatography.
- the polymer composition molecular weight distribution is bimodal at all times and the relative amounts of the high and low molecular weight modes (or components) change, when the level of scavenger is adjusted or changed.
- the combination catalyst and process of the current invention produces a polymer composition having reversed or partially reversed comonomer distributions.
- the phrase "reversed comonomer distribution” or “partially reversed comonomer distribution” means that on deconvolution of GPC-FTIR (or temperature raising elution fractionation, TREF) data (profiles) (typically using molecular weight distribution segments of not less than 10,000) there is one or more higher molecular weight components having a higher comonomer incorporation than in one or more lower molecular weight segments. If the comonomer incorporation rises with molecular weight, the distribution is described as "reversed”. Where the phrase “reversed comonomer distribution” or “partially reversed comonomer distribution” means that on deconvolution of GPC-FTIR (or temperature raising elution fractionation, TREF) data (profiles) (typically using molecular weight distribution segments of not less than 10,000) there is one or more higher molecular weight
- the polymer composition will have a low, medium or high density (d in g/cc) and which generally falls in the range of from 0.890 to 0.960 g/cc.
- the polymer composition will have a high density in the range of from 0.940 to 0.960 g/cc, preferably from 0.947 to 0.955 g/cc, making it suitable for use in high density pipe applications.
- the polyethylene composition is a high density resin with a density of from 0.941 to 0.953g/cc.
- polyethylene composition will be in the range of less than 2.5 weight percent (wt%), or less than 1 wt %.
- the weight average molecular weight (Mw) of the polyethylene composition will be from 150,000 to 500,000, preferably from 200,000 to 350,000.
- the molecular weight distribution, M w /M n of the polyethylene composition will be from about 8 to about 45, or from about 12 to 35, or from 12 to 30, or from 12 to 25.
- the polymer composition will have a high load melt index, i in the range of from 1 to 100 g/10min. In further embodiments of the invention the polymer composition will have an l 2 i in the range of from 1 to 50 or from 1 to 20 or from 1 to 15 or from 1 to 10 or from 3 to 10 g/1 Omin.
- the high load index, l 2 i of the polyethylene composition can range from about 1 to about 20 g/1 Omin.
- the l 2 i will be in the range of about 2 to about 15 g/1 Omin.
- composition is less than about 1 g/1 Omin, or less than about 0.2 g/1 Omin.
- the melt index, I5 for the polyethylene composition is less than about 1 g/1 Omin.
- composition is from 0.025 to 1 g/1 Omin, or from 0.05 to 0.75 g/1 Omin, or from 0.05 to 0.5 g/10min.
- the melt flow ratio (MFR) which is defined as the high load melt index, l 2 i divided by the melt index, l 5 will be at least 15 for the polymer composition. In further embodiments of the invention, the melt flow ratio (MFR) which is defined as the high load melt index, l 2 i divided by the melt index, l 5 will be from 15 to 50, or from 15 to 45 for the polymer composition.
- the polymer composition will have a reversed comonomer incorporation.
- the polyethylene composition is suitable for application in the manufacture of pipe.
- the polyethylene composition will have a PENT value at 2.4 Mpa of greater than 700hrs.
- the polyethylene composition will have a PENT value at 3.0 MPa of greater than 700hrs.
- the polyethylene composition will have a PENT value at 3.0 MPa of greater than 700hrs.
- polyethylene composition will have a PENT value at 3.0 Mpa of greater than 1000hrs. In yet another aspect of the invention, the polyethylene composition will have a PENT value at 3.0 Mpa of greater than 2000hrs. In yet another aspect of the invention, the polyethylene composition will have a PENT value at 3.0 Mpa of greater than 5000hrs. In yet another aspect of the invention, the polyethylene composition will have a PENT value at 3.0 Mpa of greater than 10,000hrs. In yet another aspect of the invention, the polyethylene composition will have a PENT value at 3.0 Mpa of greater from 15,000hrs.
- the polymer composition is more than about 20 cN, preferably more than about 25 cN.
- the polymer composition will have a melt strength of from 20 to 40 cN, or from 20 to 35 cN, or from 25 to 40 cN.
- the polymerization process is carried out in a reactor system in the presence of a combination catalyst, a catalyst poison and a scavenger.
- impurity is from 0.01 : 1 to 10,000:1 , including narrower ranges within this range.
- the total amount of catalyst poison or impurity present in a reactor need not be known, but it should be sufficient to negatively affect the activity of at least one catalyst component of the combination catalyst toward olefin polymerization.
- the total amount of catalyst poison or impurity present in or added to a reactor is not specified, but by way of a non-limiting example, it should be sufficient to negatively affect the activity of at least one catalyst component of the combination catalyst toward olefin polymerization.
- the total amount of catalyst poison will be in the range of from about 0.001 ppm to about 500 molar ppm (the term "molar ppm" refers the parts per million in moles of catalyst poison, such as for example oxygen, present in a reactor zone, based on the total moles of gases present in a reactor zone; alternatively, the term “volume ppm” refers the parts per million in the volume of catalyst poison, such as for example oxygen, present in a reactor zone, based on the total volume of gases present in a reactor zone. Molar ppm and volume ppm are equivalent under assumed ideal gas conditions.).
- the polymer composition is made in a reactor system in the presence of a combination catalyst and from 0.001 to 500 molar ppm of a catalyst poison.
- the process is carried out in the presence of from 0.01 to 500 molar ppm of catalyst poison.
- the process is carried out in the presence of from 0.01 to 250 molar ppm of catalyst poison.
- the process is carried out in the presence of from 0.01 to 100 molar ppm of catalyst poison.
- the process is carried out in the presence of from 0.01 to 50 molar ppm of catalyst poison.
- the process is carried out in the presence of from 0.01 to 25 molar ppm of catalyst poison. In another aspect of the invention the process is carried out in the presence of from 0.01 to 10 molar ppm of catalyst poison. In another aspect of the invention the process is carried out in the presence of from 0.01 to 5 molar ppm of catalyst poison.
- the amount of catalyst poison or impurity present in a reactor is deliberately changed by an amount of from 0.1 ppm to 100 molar ppm including all numbers within this range (where ppm refers the parts per million in moles of catalyst poison, such as for example oxygen, present in a reactor zone, based on the total moles of gases present in a reactor zone).
- the total amount of scavenger present in a reactor is not specified, but by way of a non-limiting example, it should be sufficient so that an increase in the level of scavenger positively affects the activity of at least one catalyst component of the combination catalyst toward olefin polymerization and where a decrease in the amount of scavenger negatively affects the activity of at least one catalyst component of the combination catalyst toward olefin polymerization.
- the amount of scavenger present in the reactor may be in the range of from about 0 ppm to about 10,000 ppm (where ppm is parts per million relative to the weight of polymer produced). In an embodiment of the invention the amount of scavenger present in a reactor is deliberately changed by an amount of from 0.1 ppm to 0,000 ppm (where ppm is parts per million relative to the weight of polymer produced), including all numbers within this range.
- the amount of scavenger present in a reactor is increased by an amount of from 0.1 ppm to 10,000 ppm (where ppm is parts per million relative to the weight of polymer produced), including all numbers within this range.
- the amount of scavenger present in a reactor is decreased by an amount of from 0.1 ppm to 10,000 ppm (where ppm is parts per million relative to the weight of polymer produced), including all numbers within this range.
- the actual amount of scavenger required to control the ratio of high to low molecular weight components may depend mainly on the sensitivity of the single site catalyst to catalyst poisons. If the single site catalyst has a low sensitivity to catalyst poisons, then lower amounts of scavenger may be required to change the activity of the single site catalyst. Conversely, a single site catalyst which has high sensitivity to catalyst poison may require higher amounts of scavenger to increase its polymerization activity.
- the ratio of the first polymer component to the second polymer component may be represented as weight percent (wt%) ratio, which is based on the weight of each component over the sum of the weights of the first and second polymer components or the entire weight of the polymer composition.
- the weight ratios for first and second polymer components may be estimated by deconvolution of a GPC curve obtained for the polymer composition. Methods of polymer deconvolution are well known to persons skilled in the art; see for example Computer Applications in Applied Polymer Science, ACS Symposium Series, 1982, v197, Broyer, E. and Abbott, R. , p 45-64. Flory's most probable distribution is often the method of choice to represent the molecular weight distribution (MWD) of polymers or polymer components.
- MWD molecular weight distribution
- Polymers or polymer components with broad MWD can be represented by the sum of multiple Flory distributions.
- a deconvolution procedure may require the optimization of the Flory distribution parameter using a least-square objective function minimization, where the least-square function is the difference between the sample molecular weight distribution obtained by GPC analysis and the sum of the Flory distributions.
- the deconvolution process can be further improved using experimental knowledge about the catalyst system, which can be used to further constrain the solution of the objective function minimization.
- the weight fraction of polymer produced by each catalyst in a combination catalyst may be estimated by integrating the molecular weight distributions representing those polymer components made by each catalyst in the combination catalyst.
- the first polymer component represents from 99 to 1 weight per cent of the polymer composition and the second polymer component represents from 1 to 99 weight percent of the polymer composition based on the total weight of polymer composition.
- the first polymer component represents from 95 to 25 weight per cent of the polymer composition and the second polymer component represents from 5 to 75 weight percent of the polymer composition.
- the first polymer component represent from 90 to 50 weight per cent of the polymer composition and the second polymer component represents from 10 to 50 weight percent of polymer composition.
- the first polymer component represents from 90 to 65 weight per cent of the polymer composition and the second polymer component represents from 10 to 35 weight percent of the polymer composition.
- the first polymer component represents from 95 to 75 weight per cent of the polymer composition and the second polymer component represents from 5 to 25 weight percent of the polymer composition. In still another embodiment of the invention, the first polymer component represents from 95 to 80 weight per cent of the polymer composition and the second polymer component represents from 5 to 20 weight percent of the polymer composition. In still another embodiment of the invention, the first polymer component represents from 99 to 80 weight per cent of the polymer composition and the second polymer component represents from 1 to 20 weight percent of the polymer composition. In still another embodiment of the invention, the first polymer component represents from 95 to 85 weight per cent of the polymer composition and the second polymer component represents from 5 to 15 weight percent of the polymer composition.
- changing the level of scavenger in a polymerization zone in the presence of a catalyst poison will change the weight percent of the first or second polymer components in the polymer composition by at least 0.5%.
- changing the level of a scavenger in a polymerization zone in the presence of a catalyst poison will change the weight percent of the first and second polymer components in the polymer composition by at least 1 %, or at least 5% or at least 10% or at least 20% or at least 25%.
- An embodiment of the invention is a continuous process to copolymerize ethylene and a co-monomer using a dual catalyst to provide a polymer composition comprising a first polymer component and a second polymer component
- the continuous process comprises: controlling the ratio of the first polymer component to the second polymer component by conducting the process in the presence of between 0.01 and 500 molar ppm of catalyst poison; wherein lowering the level of scavenger in ppm (where here, with respect to the scavenger, "ppm” refers to the weight of the scavenger relative to the weight of the polymer produced) from a first higher level to a second lower level, increases the ratio of a first polymer component to a second polymer component, and raising the level of scavenger in ppm from a first lower level to a second higher level, decreases the ratio of the first polymer component to the second polymer component;
- the dual catalyst comprises: an inorganic chromium catalyst, a group 4 single site catalyst,
- An embodiment of the invention is a continuous process to copolymerize ethylene and a co-monomer using a dual catalyst to provide a polymer composition comprising a first polymer component and a second polymer component
- the continuous process comprises: controlling the ratio of the first polymer component to the second polymer component by conducting the process in the presence of between 0.01 and 500 molar ppm of catalyst poison; wherein lowering the level of scavenger in ppm by at least 5 ppm (where here, with respect to the scavenger, "ppm” refers to the weight of the scavenger relative to the weight of the polymer produced), increases the ratio of a first polymer component to a second polymer component, and raising the level of scavenger in ppm by at least 5 ppm, decreases the ratio of the first polymer component to the second polymer component;
- the dual catalyst comprises: an inorganic chromium catalyst, a group 4 single site catalyst, one or more catalyst activators, and a support
- An embodiment of the invention is a continuous process to copolymerize ethylene and a co-monomer using a dual catalyst to provide a polymer composition comprising a first polymer component and a second polymer component
- the continuous process comprises: controlling the ratio of the first polymer component to the second polymer component by conducting the process in the presence of between 0.01 and 500 molar ppm of catalyst poison; wherein lowering the level of scavenger in ppm by at least 10 ppm (where here, with respect to the scavenger, "ppm” refers to the weight of the scavenger relative to the weight of the polymer produced), increases the ratio of a first polymer component to a second polymer component, and raising the level of scavenger in ppm by at least 10 ppm, decreases the ratio of the first polymer component to the second polymer component;
- the dual catalyst comprises: an inorganic chromium catalyst, a group 4 single site catalyst, one or more catalyst activators, and a support
- An embodiment of the invention is a continuous process to copolymerize ethylene and a co-monomer using a dual catalyst to provide a polymer composition comprising a first polymer component and a second polymer component
- the continuous process comprises: controlling the ratio of the first polymer component to the second polymer component by conducting the process in the presence of between 0.01 and 500 molar ppm of catalyst poison; wherein lowering the level of scavenger in ppm by at least 25 ppm (where here, with respect to the scavenger, "ppm" refers to the weight of the scavenger relative to the weight of the polymer produced), increases the ratio of a first polymer component to a second polymer component, and raising the level of scavenger in ppm by at least 25 ppm, decreases the ratio of the first polymer component to the second polymer component; provided that the dual catalyst
- an inorganic chromium catalyst comprises: an inorganic chromium catalyst, a group 4 single site catalyst, one or more catalyst activators, and a support; and where the inorganic chromium catalyst provides the first polymer component and the group 4 single site catalyst provides the second polymer component.
- An embodiment of the invention is a continuous process to copolymerize ethylene and a co-monomer using a dual catalyst to provide a polymer composition comprising a first polymer component and a second polymer component
- the continuous process comprises: controlling the ratio of the first polymer component to the second polymer component by conducting the process in the presence of between 0.01 and 500 molar ppm of catalyst poison; wherein lowering the level of scavenger in ppm by at least 100 ppm (where here, with respect to the scavenger, "ppm” refers to the weight of the scavenger relative to the weight of the polymer produced), increases the ratio of a first polymer component to a second polymer component, and raising the level of scavenger in ppm by at least 00 ppm, decreases the ratio of the first polymer component to the second polymer component;
- the dual catalyst comprises: an inorganic chromium catalyst, a group 4 single site catalyst, one or more catalyst activators, and a
- the process of the current invention can be a batch polymerization process or a continuous polymerization process both of which are well understood by persons skilled in the art.
- a batch polymerization process will involve adding a combination catalyst, monomer and comonomer as well as any diluents or other reagents such as scavengers, once to a polymerization reactor.
- the polymerization reaction is typically initiated by injecting the combination catalyst into the reactor in the presence of polymerizable monomers.
- polymer is usually isolated after the reaction has been quenched with a suitable quenching agent.
- scavenger may be added once, before or after the polymerization reaction starts. Scavenger may also be added several times to obtain a desired concentration in the reactor.
- the process is a continuous polymerization process.
- a continuous polymerization process will involve continuous feeding of catalyst, monomer, diluents, scavengers, and the like to continuously produce polymer.
- scavenger is continuously fed to a continuous polymerization reactor or reaction zone in addition to monomer, optional comonomers and a combination catalyst.
- the ratio of scavenger to combination catalyst being fed to the reactor can be increased or decreased.
- the flow of combination catalyst to the reactor may be kept approximately constant while the ratio of scavenger to some other process parameter (such as for example the polymer production rate) is increased or decreased. Either way, the ratio of scavenger to combination catalyst present in the reactor is changed. Polymer is removed from the reactor in a continuous or periodic manner.
- Continuous reactor processes are well known by persons skilled in the art and include, solution, slurry and gas phase processes.
- the present invention employs a slurry phase process or a gas phase process, especially a continuous gas phase process.
- the present invention employs a gas phase process, especially a continuous gas phase process carried out in a single gas phase reactor.
- the amount of scavenger present can be predetermined, or changed in situ.
- the scavenger can be continuously added in constant or varying amounts, or intermittently added in constant or varying amounts.
- the level of scavenger is changed during the polymerization process (i.e. is altered in situ) to alter the polymer composition.
- the level of scavenger used in the presence of the combination catalyst is determined before or after a polymerization run is started or finished respectively.
- the scavenger is present during catalyst kills or catalyst transitions.
- the amount of scavenger will be increased to increase the activity of the single site catalyst, which correspondingly decreases the relative amount of low molecular weight component in the polymer composition. In another embodiment of the invention, the amount of scavenger is decreased to decrease the activity of the single site catalyst, which correspondingly decreases the relative amount of high molecular weight component in the polymer composition.
- the amount of scavenger will be increased to increase the activity of the single site catalyst, which correspondingly increases the relative amount of low molecular weight component in the polymer composition. In another embodiment of the invention, the amount of scavenger will be decreased to decrease the activity of the single site catalyst, which correspondingly increases the relative amount of high molecular weight component in the polymer composition.
- the amount of scavenger will be increased to increase the activity of the single site catalyst, which correspondingly increases the relative amount of a polymer component which has a relatively higher comonomer content in the polymer composition. In another embodiment of the invention, the amount of scavenger will be decreased to decrease the activity of the single site catalyst, which correspondingly decreases the relative amount of a polymer component having a relatively higher comonomer content in the polymer composition.
- the amount of scavenger will be increased to increase the activity of the single site catalyst, which correspondingly increases the relative amount of a polymer component which has a relatively higher molecular weight and comonomer content in the polymer composition. In another embodiment of the invention, the amount of scavenger will be decreased to decrease the activity of the single site catalyst, which correspondingly decreases the relative amount of a polymer component having a relatively higher molecular weight and comonomer content in the polymer composition.
- the process is a continuous polymerization process, and the amount of scavenger present relative to the amount of combination catalyst present can be increased or decreased over time.
- the level of scavenger present relative to the amount of combination catalyst present is adjusted by controlling the feed rate of scavenger and the feed rate of the combination catalyst to a continuous reactor or polymerization zone. More specifically, the feed ratio of scavenger to combination catalyst or to some other process parameter is adjusted.
- the combination catalyst and scavenger are fed to a reactor zone in a continuous manner. Preferably they are fed separately.
- the feed rates of the combination catalyst and the scavenger can be monitored and adjusted.
- the feed rate of the combination catalyst may be kept approximately constant while the feed rate of scavenger is increased or decreased.
- the polymerization zone of the present invention may represent a single reactor, or the reaction zone may represent a reactor which is part of a larger reactor system comprising further polymerization zones and reactors.
- scavenger as described in the present invention, can be used to maintain a consistent polymer product or it may be used to obtain a desired polymer composition by "fine-tuning" a dual catalyst having a fixed ratio of inorganic chromium and single site catalysts so that the desired amounts of high and low molecular weight components are formed. It will be recognized by persons skilled in the art, that changing the ratio of high to low molecular weight components in the polymer composition, by the use of scavenger provides a means to control or adjust the high load melt index l 2 i of the polymer composition. If the l 2 i of the polymer being produced is not on target, then the amounts of scavenger present may be increased or decreased to change the l 2 i accordingly.
- the group 4 single site catalyst produces a polymer component with higher molecular weight than the inorganic chromium catalyst and when l 2 i is lower than desired, a decrease in the amount of scavenger present will increase the l 2 i (i.e. by decreasing the weight % of the HMW component); alternatively, if the l 2 i of the polymer composition is higher than desired, an increase in the amount of scavenger present will decrease the l 2 i (i.e. by increasing the weight % of the HMW component). If the inorganic chromium catalyst makes a polymer component having a higher molecular weight than the single site catalyst, then the above conditions will be reversed.
- the process of the current invention can be used to compensate for fluctuations in the polymerization conditions (e.g. hydrogen concentration, temperature, pressure, comonomer concentration, impurities level, etc.) which may themselves change the l 2 i of the polymer composition, in order to produce polymer compositions with constant performance characteristics.
- the presence of scavenger will affect the ratio of first to second polymer components without affecting the molecular weight performance of each catalyst species of a dual catalyst.
- the present invention may be carried out in the following manner: the polymer composition is sampled and analyzed using rheological methods (e.g. melt index measurements, etc. ) which are well known in the art; if the polymer composition does not have the desired rheological properties the feed ratio of the combination catalyst to scavenger is adjusted to change the ratio of first and second polymer components (such as for example, high to low molecular weight components); the polymer composition is again sampled and analyzed using rheological methods to determine whether the polymer composition has the targeted properties, and where not, the sequence of adjustment and testing is repeated until the desired properties are achieved.
- rheological methods e.g. melt index measurements, etc.
- controlling the relative amounts of first and second polymer components in accordance with the current invention may also be part of a more complex polymer composition regulation protocol.
- controlling the ratio of high molecular weight to low molecular weight components by conducting the polymerization in the presence of a dual catalyst, a catalyst poison and a scavenger may additionally comprise the following: i) measuring the ratio of first to second polymer components in the polymer composition or measuring the high load melt index l 2 i of the polymer composition, ii) calculating the amount of scavenger necessary to achieve a prescribed ratio of first to second polymer components or polymer composition high load melt index l 2 i , and iii) increasing or decreasing the amount of scavenger present to produce a polymer composition with the desired high load melt index l 2 i.
- the level of scavenger is increased by an amount sufficient to decrease the high load melt index l 2 i of the polymer composition by at least 0.1 %. In an embodiment of the invention, the level of scavenger is decreased by an amount sufficient to increase the high load melt index l 2 i of the polymer composition by at least 0.1 %.
- Suitable monomers which can be polymerized using the process of the current invention are ethylene for ethylene homopolymerization or ethylene and one or more alpha-olefins (also called “comonomers”) for ethylene copolymerization. Ethylene copolymerization is preferred.
- Alpha-olefins include propylene, -butene, 1-pentene, 1 - hexene, l-heptene, -octene, -decene or other branched C 2 -Cio alpha olefins such as 4-methyl-1 -pentene, conjugated and nonconjugated dienes such as 1 ,3-butadiene, 1 ,4- hexadiene or 1 ,7- octadiene or vinylaromatic compounds such as styrene or substituted styrene.
- Other alpha olefins include ones in which the double bond is part of a cyclic structure which can comprise one or more ring systems.
- cyclopentene examples are cyclopentene, norbornene, tetracyclododecene or methylnorbornene or dienes such as 5-ethylidene- 2-norbornene, norbornadiene or ethylnorbornadiene.
- ethylene is copolymerized with propene, 1 -butene, 1-hexene and/or 1- octene.
- the inventive method of polymerizing olefins can be carried out at temperatures in the range from 0 to 250°C, preferably from 25 to 150°C and particularly preferably from 40 to 130°C, and under pressures of from 0.05 to 10 MPa, particularly preferably from 0.3 to 4 MPa, using all industrially known polymerization processes such as solution, slurry or gas phase processes.
- the invention is carried out in the gas phase or the slurry phase.
- a combination catalyst e.g. a dual catalyst
- the prepolymerization can be carried out in the gas phase, in suspension or in the monomer (bulk), and can be carried out continuously in a prepolymerization unit installed upstream of the polymerization reactor or in a discontinuous prepolymerization unit independent of the reactor operation.
- Slurry polymerization is well known in the art.
- the polymerization is conducted in an inert diluent in which the resulting polymer is not soluble.
- the monomers may be soluble in the diluent.
- the diluent is typically a hydrocarbyl compound such as a C 5- i 2 hydrocarbon that may be un-substituted or substituted by a d -4 alkyl radical.
- Some potential diluents include pentane, hexane, heptane, octane, isobutene cyclohexane and methylcyclohexane.
- the diluent may be hydrogenated naphtha.
- the diluent may also be a C 8- 12 aromatic hydrocarbon such as that sold by Exxon Chemical Company under the trademark ISOPAR® E. Typically, monomers are dispersed or dissolved in the diluent.
- the polymerization reaction takes place at temperatures from about 20° C to about 120° C, preferably from about 40° C to 100° C.
- the pressure in the reactor may be from about 15 psi to about 4,500 psi, preferably from about 100 to 1 ,500 psi.
- the reactors may be stirred tank or "loop" reactors with a settling leg to remove product polymer.
- the solids content of the suspension is generally in the range from 10 to 80%.
- the polymerization can be carried out either batch wise, e. g. in stirring autoclaves, or continuously, e.g. in tube reactors, preferably in loop reactors.
- pressures can be in the range of 25 to 1000 psi, preferably 50 to 500 psi, most preferably 100 to 450 psi, and temperatures will be in the range of from 30 to 130° C, preferably 65 to 1 15° C.
- Stirred or preferably fluidized bed gas phase reactors can be used.
- the polymerization is conducted in a fluidized bed reactor wherein a bed of polymer particles are maintained in a fluidized state by means of an ascending gas stream comprising the gaseous reaction monomer.
- the polymerization of olefins in a stirred bed reactor differs from polymerization in a gas fluidized bed reactor by the action of a mechanical stirrer within the reaction zone that contributes to fluidization of the bed.
- the gas phase polymerization may be conducted in dry mode, condensed mode or super condensed mode, all of which are well known in the art. Polymerization takes place in the presence of a non polymerizable gas that may be inert or may be an alkane, or a mixture thereof and typically hydrogen.
- a non polymerizable gas that may be inert or may be an alkane, or a mixture thereof and typically hydrogen.
- Such a multizone or multi reactor systems include multiple slurry reactors, the mixture of slurry and gas phase reactors or multiple gas phase in series or in parallel reactors.
- Such reactors see WO 97/04015 and WO 00/02929.
- the polymerization process is carried out in a single reactor.
- the product is removed from the reactor by conventional means and separated from the diluent and/or residual monomers before further treatment.
- the combination catalyst system may be fed to a polymerization reactor in a number of ways.
- combination catalyst components may be fed to the reactor using one or more catalyst feeders.
- the combination catalyst or supported combination catalyst components may be fed to a reactor via a dry catalyst feeder or as a slurry in a hydrocarbon or other suitable viscous inert liquid such as but not limited to mineral oil.
- the catalyst slurry can be fed into the reactor using any suitable liquid delivery system, such as but not limited to a high pressure syringe pump or other displacement device.
- scavenger or supported scavenger can be fed to a polymerization reactor in a number of ways.
- a scavenger can be fed directly to the reactor as a separate feed or combined with another feed stream.
- a supported scavenger may be fed to a reactor via a dry catalyst feeder or as a slurry in a hydrocarbon or other suitable viscous inert liquid such as but not limited to mineral oil.
- a supported scavenger can be fed into the reactor using any suitable liquid delivery system, such as but not limited to a high pressure syringe pump or other displacement device.
- the branch frequency of copolymer samples i.e. the short chain branching, SCB per 1000 carbons
- C 6 comonomer content in wt% or mol%
- FTIR Fourier Transform Infrared Spectroscopy
- PENT is an abbreviation of the Pennsylvania Notch Test.
- the test measures the failure times of asymmetrically sharp-notched samples in a constant tensile load in a controlled condition as per ASTM 1473 "Standard Test Method for the Notched Tensile Test to Measure Slow Crack Growth Resistance of Polyethylene - PE Notch Test".
- the PENT values in hours are in general a measure of the slow crack growth of polyethylene (PE) resins or extruded solid wall pipe.
- the test is usually performed at 2.4 MPa and 80°C per ASTM 1473 F1473-1 1 .
- the PENT test can be performed at an elevated stress level where failure is still brittle in nature. As an example, the test can be run at 3.0 MPa and 80°C, resulting in shorter failure times that could be approximately half as long as those measured at 2.4 MPa and the same temperature if the same brittle failure dominates the PENT test.
- the melt strength of a polymer is measured on Rosand RH-7 capillary rheometer
- Combination Catalyst 2 Al/Cr molar ratio of 8/1 ; Cr/Ti molar ratio 8.9/1
- Combination Catalyst 3 Al/Cr molar ratio of 8/1 ; Cr/Ti molar ratio 7.5/1 .
- Proportional-Integral-Derivative controllers Hydrogen was metered into the reactor in a molar feed ratio relative to ethylene feed during polymerization. Nitrogen constituted the remainder of the gas phase mixture.
- the polymerization run reaction times were from about 2.25 to about 2.75 hrs.
- the 1 -hexene/ethylene (C6/C2) molar ratio for each polymerization run was maintained at 0.005: 1 .
- the hydrogen/ethylene (H2/C2) molar ratio for each polymerization run was maintained at 0.003: 1 .
- Relevant process data, including the level of scavenger used in each run, and details about the combination catalyst composition are provided in Table 1 . Relevant polymer data is also included in Table 1 and in Figures 1 , 2 and 3.
- Polymerization run Nos 1 and 2 employing combination catalyst No. 1 , were run back to back under analogous conditions except that the level of scavenger was changed.
- Polymerization run Nos 3, 4 and 5, employing combination catalyst No. 2 were run back to back under analogous conditions except that the level of scavenger was changed.
- Polymerization run Nos. 6, 7 and 8, employing combination catalyst No. 3, were run back to back under analogous conditions except that the level of scavenger was changed.
- Multicomponent catalysts have found application in the polyethylene
- the present invention is directed to a polymerization process to control a polyethylene composition made with a combination catalyst comprising an inorganic chromium catalyst and a group 4 single site catalyst.
- a scavenger is used to indirectly control the ratio of polymer components in a polyethylene composition made using the combination catalyst.
Abstract
Description
Claims
Priority Applications (7)
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JP2015523353A JP6329946B2 (en) | 2012-07-23 | 2013-06-20 | Adjustment of polymer composition |
MX2015000974A MX2015000974A (en) | 2012-07-23 | 2013-06-20 | Adjusting polymer composition. |
EP13822494.4A EP2875053B1 (en) | 2012-07-23 | 2013-06-20 | Adjusting polymer composition |
KR1020157004514A KR102043410B1 (en) | 2012-07-23 | 2013-06-20 | Adjusting polymer composition |
CN201380039056.1A CN104684939B (en) | 2012-07-23 | 2013-06-20 | Regulation polymer composition |
BR112015001148-9A BR112015001148B1 (en) | 2012-07-23 | 2013-06-20 | processes for copolymerizing ethylene and at least one comonomer in the presence of at least one catalyst poison |
ES13822494T ES2927874T3 (en) | 2012-07-23 | 2013-06-20 | Adjustment of a polymeric composition |
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CA2783494A CA2783494C (en) | 2012-07-23 | 2012-07-23 | Adjusting polymer composition |
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CN110167975A (en) | 2017-01-11 | 2019-08-23 | Sabic环球技术有限责任公司 | Chromium oxide catalyst for vinyl polymerization |
WO2018130539A1 (en) * | 2017-01-11 | 2018-07-19 | Sabic Global Technologies B.V. | Chromium oxide catalyst for ethylene polymerization |
JP7046554B2 (en) * | 2017-10-11 | 2022-04-04 | 三井化学株式会社 | Method for Producing Catalyst for Olefin Polymerization and Ethylene Polymer |
EP3700948B1 (en) * | 2017-10-27 | 2023-09-20 | Univation Technologies, LLC | Polyethylene copolymer resins and films |
US11225568B2 (en) * | 2017-12-20 | 2022-01-18 | Lg Chem, Ltd. | Polyethylene copolymer and method for preparing same |
WO2021039675A1 (en) * | 2019-08-30 | 2021-03-04 | 日本ゼオン株式会社 | Binder composition for non-aqueous secondary battery, production method for same, slurry composition for non-aqueous secondary battery electrode, non-aqueous secondary battery electrode, and non-aqueous secondary battery |
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EP2875053A4 (en) | 2016-04-27 |
ES2927874T3 (en) | 2022-11-11 |
CN104684939A (en) | 2015-06-03 |
EP2875053B1 (en) | 2022-09-14 |
BR112015001148B1 (en) | 2021-03-09 |
MX2015000974A (en) | 2015-04-10 |
KR20150038219A (en) | 2015-04-08 |
CN104684939B (en) | 2016-08-17 |
CA2783494A1 (en) | 2014-01-23 |
KR102043410B1 (en) | 2019-11-11 |
BR112015001148A2 (en) | 2017-06-27 |
JP2015526552A (en) | 2015-09-10 |
US20140363599A1 (en) | 2014-12-11 |
EP2875053A1 (en) | 2015-05-27 |
US8846835B2 (en) | 2014-09-30 |
US20140024789A1 (en) | 2014-01-23 |
CA2783494C (en) | 2019-07-30 |
JP6329946B2 (en) | 2018-05-23 |
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