GB2087907A - Olefin Polymerization Process and Catalyst - Google Patents
Olefin Polymerization Process and Catalyst Download PDFInfo
- Publication number
- GB2087907A GB2087907A GB8135365A GB8135365A GB2087907A GB 2087907 A GB2087907 A GB 2087907A GB 8135365 A GB8135365 A GB 8135365A GB 8135365 A GB8135365 A GB 8135365A GB 2087907 A GB2087907 A GB 2087907A
- Authority
- GB
- United Kingdom
- Prior art keywords
- reaction
- transition metal
- catalyst system
- process according
- aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 17
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 title claims description 48
- 238000006116 polymerization reaction Methods 0.000 title claims description 33
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 84
- -1 organo boron compounds Chemical class 0.000 claims abstract description 54
- 229910052751 metal Inorganic materials 0.000 claims abstract description 51
- 239000002184 metal Substances 0.000 claims abstract description 51
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 37
- 150000003624 transition metals Chemical class 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 150000004703 alkoxides Chemical class 0.000 claims abstract description 23
- 150000004820 halides Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 9
- 230000003647 oxidation Effects 0.000 claims abstract description 8
- 239000002685 polymerization catalyst Substances 0.000 claims abstract description 8
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 7
- 239000010936 titanium Substances 0.000 claims description 129
- 239000011777 magnesium Substances 0.000 claims description 86
- 229910052749 magnesium Inorganic materials 0.000 claims description 53
- 229910001868 water Inorganic materials 0.000 claims description 51
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 229910052719 titanium Inorganic materials 0.000 claims description 41
- 238000006460 hydrolysis reaction Methods 0.000 claims description 24
- 239000012190 activator Substances 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 230000007062 hydrolysis Effects 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052796 boron Inorganic materials 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical compound CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 239000000741 silica gel Substances 0.000 claims description 2
- 229910002027 silica gel Inorganic materials 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 2
- 238000007334 copolymerization reaction Methods 0.000 abstract description 3
- 125000002370 organoaluminium group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 132
- 239000007788 liquid Substances 0.000 description 68
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 57
- 239000002244 precipitate Substances 0.000 description 33
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 32
- 229940091250 magnesium supplement Drugs 0.000 description 32
- 239000007789 gas Substances 0.000 description 31
- 239000011347 resin Substances 0.000 description 27
- 229920005989 resin Polymers 0.000 description 27
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 26
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 24
- 239000002904 solvent Substances 0.000 description 24
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 23
- 239000005977 Ethylene Substances 0.000 description 23
- 238000010992 reflux Methods 0.000 description 22
- 229930195733 hydrocarbon Natural products 0.000 description 19
- 150000002430 hydrocarbons Chemical class 0.000 description 19
- 239000004215 Carbon black (E152) Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- 239000007787 solid Substances 0.000 description 17
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 description 16
- 229910001629 magnesium chloride Inorganic materials 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 15
- 239000000376 reactant Substances 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 13
- 239000004698 Polyethylene Substances 0.000 description 12
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 12
- 239000001282 iso-butane Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- NMVXHZSPDTXJSJ-UHFFFAOYSA-L 2-methylpropylaluminum(2+);dichloride Chemical compound CC(C)C[Al](Cl)Cl NMVXHZSPDTXJSJ-UHFFFAOYSA-L 0.000 description 9
- 235000010210 aluminium Nutrition 0.000 description 9
- 230000008859 change Effects 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 241000894007 species Species 0.000 description 9
- 238000005485 electric heating Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 5
- 239000012018 catalyst precursor Substances 0.000 description 5
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 5
- 239000012429 reaction media Substances 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 238000007514 turning Methods 0.000 description 5
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 239000011636 chromium(III) chloride Substances 0.000 description 4
- 235000007831 chromium(III) chloride Nutrition 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 150000001844 chromium Chemical class 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000008034 disappearance Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 3
- 159000000003 magnesium salts Chemical class 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 150000003609 titanium compounds Chemical class 0.000 description 3
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N 1-Heptene Chemical compound CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 240000007817 Olea europaea Species 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910001623 magnesium bromide Inorganic materials 0.000 description 2
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229920013716 polyethylene resin Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- 239000004711 α-olefin Substances 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical compound FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 description 1
- 238000006418 Brown reaction Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 108091060585 Mir-31 Proteins 0.000 description 1
- YLYYONKHQYTPJK-UHFFFAOYSA-N O.O.O.O.O.O.[Si](F)(F)(F)F.[Mg] Chemical compound O.O.O.O.O.O.[Si](F)(F)(F)F.[Mg] YLYYONKHQYTPJK-UHFFFAOYSA-N 0.000 description 1
- UQGKUQLKSCSZGY-UHFFFAOYSA-N Olmesartan medoxomil Chemical compound C=1C=C(C=2C(=CC=CC=2)C2=NNN=N2)C=CC=1CN1C(CCC)=NC(C(C)(C)O)=C1C(=O)OCC=1OC(=O)OC=1C UQGKUQLKSCSZGY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- FWCTZJNNLCYVMA-UHFFFAOYSA-L butan-1-ol;dichlorotitanium Chemical compound Cl[Ti]Cl.CCCCO.CCCCO FWCTZJNNLCYVMA-UHFFFAOYSA-L 0.000 description 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 239000012967 coordination catalyst Substances 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- AIGRXSNSLVJMEA-FQEVSTJZSA-N ethoxy-(4-nitrophenoxy)-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound O([P@@](=S)(OCC)C=1C=CC=CC=1)C1=CC=C([N+]([O-])=O)C=C1 AIGRXSNSLVJMEA-FQEVSTJZSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- LGLXXNHIGIJYQQ-UHFFFAOYSA-L magnesium;dibromide;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Br-].[Br-] LGLXXNHIGIJYQQ-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- YSTQWZZQKCCBAY-UHFFFAOYSA-L methylaluminum(2+);dichloride Chemical compound C[Al](Cl)Cl YSTQWZZQKCCBAY-UHFFFAOYSA-L 0.000 description 1
- 108091028606 miR-1 stem-loop Proteins 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 238000001175 rotational moulding Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- COEZWFYORILMOM-UHFFFAOYSA-M sodium 4-[(2,4-dihydroxyphenyl)diazenyl]benzenesulfonate Chemical compound [Na+].OC1=CC(O)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 COEZWFYORILMOM-UHFFFAOYSA-M 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 229940087562 sodium acetate trihydrate Drugs 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 1
- LFXVBWRMVZPLFK-UHFFFAOYSA-N trioctylalumane Chemical compound CCCCCCCC[Al](CCCCCCCC)CCCCCCCC LFXVBWRMVZPLFK-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 108091090261 virus miR-B1 stem-loop Proteins 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
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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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
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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
- 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
- C08F4/642—Component covered by group C08F4/64 with an organo-aluminium compound
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- E—FIXED CONSTRUCTIONS
- E03—WATER SUPPLY; SEWERAGE
- E03F—SEWERS; CESSPOOLS
- E03F5/00—Sewerage structures
- E03F5/04—Gullies inlets, road sinks, floor drains with or without odour seals or sediment traps
- E03F5/041—Accessories therefor
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- 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
- C08F2410/00—Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst
- C08F2410/04—Dual catalyst, i.e. use of two different catalysts, where none of the catalysts is a metallocene
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16H—GEARING
- F16H25/00—Gearings comprising primarily only cams, cam-followers and screw-and-nut mechanisms
- F16H25/18—Gearings comprising primarily only cams, cam-followers and screw-and-nut mechanisms for conveying or interconverting oscillating or reciprocating motions
- F16H25/20—Screw mechanisms
- F16H25/2015—Means specially adapted for stopping actuators in the end position; Position sensing means
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Abstract
A process for the copolymerization of 1-olefins, with an olefin polymerization catalyst system comprising a mixture of cocatalysts one of which is a halide activated intermetallic compound comprising the reaction product of a polymeric transition metal oxide alkoxide and reducing metal of higher oxidation potential than the transition metal. Suitable cocatalysts are organo aluminium and organo boron compounds. The polymeric transition metal oxide alkoxide is prepared by reacting a transition metal alkoxide with a hydrated metal salt e.g. MgCl26 . H2O.
Description
SPECIFICATION
Olefin Polymerization Process and Catalyst
This invention relates to the polymerisation of olefins and to catalysts therefor.
Polyethylene, produced by solution or slurry processes at lower pressures or in autoclave or tubular reactors at higher pressures, has been an object of commercial production for many years.
Recent interest has centered on linear low density polyethylene resins characterized by linearity and short chain branching afforded by alkene comonomers, and offering narrow molecular weight distribution, improved strength properties, higher melt viscosity, higher softening point, improved ESCR (Environmental Stress Crack Resistance) and improved low temperature brittleness. These and related properties provide advantages to the user in such applications as blown film, wire and cable coating, cast film, coextrusion, and injection and rotational molding.
The linear olefin polymers have typicaliy been produced using catalysts of the general type disclosed by Ziegler, thus comprising a transition metal compound, usually a titanium halide admixed with an organometallic compound such as alkyl aluminum. The transition metal component may be activated by reaction with a halide promoter such as an alkyl aluminum halide. Among the improved catalysts of this type are those incorporating a magnesium component, usually by interaction of magnesium or a compound thereof with the transition metal component or the organo-metallic component, as by milling or chemical reaction or association.
There is also interest in producing intermediate to high density resins of modified characteristics employing coordination catalysts of this type. In particular, resins of broader molecular weight distribution and higher melt index are sought.
The invention provides an olefin polymerization catalyst system comprising a mixture of cocatalysts one of which is a halide activated intermetallic compound comprising the reaction product of polymeric transition metal oxide alkoxide and at least one reducing metal, i.e. a metal of higher oxidation potential than the transition metal. Thus, a polymeric titanium alkoxide, or oxoalkoxide, is reacted with magnesium metal to provide a reaction product which may be activated to form an olefin polymerization catalyst element.
The invention also provides a process for the polymerization of 1 -olefins, alone or together with at least one copolymerizable monomer, under polymerization conditions of temperature and pressure, with such an olefin polymerization catalyst system.
The polymeric transition metal oxide alkoxide may be separately prepared by the controlled hydrolysis of the alkoxide; or the poiymeric oxoalkoxide may be provided by an in situ reaction, e.g., hydrolysis in a reaction medium including the reducing metal. For example, titanium or zirconium tetrabutoxide may be reacted with magnesium metal in a hydrocarbon solvent, and in the presence of a controlled source of water, preferably a hydrated metal salt such as magnesium halide hexahydrate.
Transition metal alkoxides, particularly titanium alkoxides, are known for their colligative properties in organic solvents, and their sensitivity to hydrolysis. It is reported that the hydrolysis reaction proceeding from the oligomeric, usually trimeric titanium alkoxides results in polymeric titanium oxide alkoxides, generally expressed as Ti(OR)4+nH20=TiOn(OR)4~2n+2n ROH
Condensation reactions may also occur especially at elevated temperatures to structures involving primary metal-oxygen-metal bridges such as:
which may in turn participate in or constitute precursors for hydrolysis reaction.
These polymeric titanium alkoxides or oxoalkoxides (sometimes also referred to as uoxoalkoxides) may be represented by the series [Ti3(X+a04X(OR)4(x+3)] where X=O, 1, 2, 3,. . ., the structure reflecting the tendency of the metal to expand its coordination beyond its primary valency coupled with the ability of the alkoxide to bridge two or more metal atoms.
Regardless of the particular form which the alkoxide is visualized to adopt, in practice it is sufficient to recognize that the alkoxide oligomers form upon controlled hydrolysis a series of polymeric oxide alkoxides ranging from the dimer through cyclic forms to linear chain polymer of up to infinite chain length. More complete hydrolysis, on the other hand, leads to precipitation of insoluble products eventuating, with complete hydrolysis, in orthotitanic acid.
For ease of description herein, these materials will be referred to as polymeric oxide alkoxides of the respective transition metals, representing the partial hydrolysis products. The hydrolysis reaction can be carried out separately, and the products isolated and stored for further use, but this is inconvenient especially in view of the prospect of further hydrolysis, hence the preferred practice is to generate these materials in the reaction medium. Evidence indicates that the same hydrolysis reaction occurs in situ.
The hydrolysis reaction itself may be controlled directly by the quantity of water which is supplied to the transition metal alkoxide and the rate of addition. Water must be supplied incrementally or in a staged or sequenced manner: bulk addition does not lead to the desired reaction, effecting excessive hydrolysis, with precipitation of insolubles. Dropwise addition is suitable as is the use of water of reaction, but it is found more convenient to provide the water as water of crystallization, sometimes referred to as cation, anion, lattice or zeolitic water. Thus, common hydrated metal salts are usually employed, where the presence of the salts themselves are not deleterious to the system.It appears that the bonding provided by the coordinated sphere of water in a hydrated salt is adapted to control release and/or availability of water, or water related species to the system as required to effect, engage in cr control the reaction.
The overall amount of water employed, as aforesaid, has a direct bearing on the form of polymeric oxide alkoxide which is produced, and thus is selected relative to catalytic performance. (It is believed without limitation that the stereoconfiguration of the partially hydrolyzed transition metal alkoxide determines, or contributes in part to the nature, or result of the catalytic action of the activated catalyst component).
In general, it has been found sufficient to provide as little as 0.5 moles of water per mole of transition metal. Amounts of up to 1.5 moles are suitable with higher amounts up to 2.0 moles being operable whenever precipitation of hydrolysis products from the hydrocarbon solvent medium may be avoided. This may be achieved in principle by reducing the rate of addition and ceasing addition upon first evidence of precipitation. While it is believed that the reaction is essentially equimolar, a certain excess of water is appropriately employed in some cases, as is customary.
It will be understood that the stereoisomeric form, chain length, etc. of the hydrolysis product may be somewhat altered with the elevated temperature required by the ensuing reaction with the reducing metal, and in situ processes likewise will affect equilibria through the mass action effect.
Likewise, the cogeneration of alkanol may affect equilibria, reaction rates, etc.
The hydrolysis reaction proceeds under ambient conditions of pressure and temperature, and requires no special conditions. A hydrocarbon solvent may be used, but is not required. Mere contact of the materials for a period of time, usually 10-30 minutes to 2 hours is sufficient. The resultant material is stable under normal storage conditions, and can be made up to a suitable concentration level as desired, simply by dilution with hydrocarbon solvent.
The polymeric transition metal oxide alkoxides are reacted with a reducing metal having an oxidation potential higher than the transition metal. Preferably a polymeric titanium oxide alkoxide is used. The reducing metal preferably comprises at least one of magnesium, calcium, potassium, aluminum and zinc. Combinations of transition metal alkoxide, reducing metal and hydrated metal salt are usefully selected with reference to electropotentials to minimize side reactions, as known in the art; and in general to assure preferred levels of activity for olefin polymerization, magnesium values are supplied to the system by appropriate selection of reducing metal/hydrated metal salt.
In the preferred embodiment (to which illustrative reference is made in the following text, as a matter of convenience), titanium tetra-n-butoxide (TBT) is reacted with magnesium turnings and hydrated metal salt, most preferably magnesium chloride hexahydrate, at a temperature of 50 1 500C, in a reaction vessel under autogenous pressure. TBT may constitute the reaction medium, or a hydrocarbon solvent may be used. Ti/Mg molar ratios may vary from 1:0.1 to 1:1 although for the most homogeneous reaction system a stoichiometric relationship of TilV to MgO of 1:1 is preferred, with an amount of hydrated metal salt to supply during the reaction about 1 mole of water per mole of MgO.
The hydrocarbon soluble catalyst precursor comprises predominantly Ti values in association with Mg values, in one or more stereoconfiguration complexes believed to constitute principally oxygenated species. Some evidence of mixed oxidation states of the titanium values suggests an interrelated system of integral species of Ti'V, Ti"', and Ti" values perhaps in a quasi-equilibrium relation at least under dynamic reaction conditions. The preferred precursor is believed without limitation to incorporate (Ti-O-Mg) bridging structures.
The intermetallic compounds have special interest as catalyst precursors, in support or unsupported systems, for isomerization, dimerization, oligomerization or polymerization of alkenes, alkynes or substituted alkenes in the presence or absence of reducing agents or activators, e.g., organometallic compounds of Group IA, IIA, IIIA, or IIB metals.
In the preferred utilization of such precursors, they are reacted with a halide activator such as an alkyl aluminum halide and combined with an organometallic compound to form a catalyst system adapted particularly to the polymerization of ethylene and comonomers to polyethylene resins.
The transition metal component is an alkoxide, normally a titanium or zirconium alkoxide comprising essentiallyOR substituents where R may comprise up to 10 carbon atoms, preferably 2 to 5 carbon atoms, and most preferably n-alkyl such as n-butyl. The selected component is normally liquid under ambient conditions and the reaction temperatures for ease of handling, and to facilitate use is also hydrocarbon soluble.
It is generally preferred for facility in conducting the related hydrolysis reaction to employ transition metal compounds which comprise only alkoxide substituents, although other substituents may be contemplated where they do not interfere with the reaction in the sense of significantly modifying performance in use. In general, the halide-free n-alkoxides are employed.
The transition metal component is best used in the highest oxidation state for the transition metal, to provide the desired stereoconfigurationai structure, among other considerations. Most suitably, as aforesaid, the alkoxide is a titanium or zirconium alkoxide. Suitable titanium compounds include titanium tetraethoxide, as well as the related compounds incorporating one or more alkoxy radicals including n-propoxy, iso-propoxy, n-butoxy, isobutoxy, secbutoxy, tertbutoxy, n-pentoxy, tertpentoxy, tert-amyloxy, n-hexyloxy, n-heptyloxy, nonyloxy and so forth.
Some evidence suggests that the rate of hydrolysis of the normal derivatives decreases with increasing chain length, and the rate decreases with molecular complexity viz. tertiary, secondary, normal, hence these considerations may be taken into account in selecting a preferred derivative. In general, titanium tetrabutoxide has been found eminently suitable for the practice of the present invention, and related tetraalkoxides are likewise preferred. It will be understood that mixed alkoxides are perfectly suitable, and may be employed where conveniently available. Complex titanium alkoxides sometimes inclusive of other metallic components may also be employed.
The reducing metal is supplied at least in part in the zero oxidation state as a necessary element of the reaction system. A convenient source is the familiar turnings, or ribbon or powder. As supplied commercially, these materials may be in a passivated surface oxidized condition and milling or grinding to provide at least some fresh surface may be desirable, at least to control reaction rate. The reducing metal may be supplied as convenient, in the form of a slurry in the transition metal component and/or hydrocarbon diluent, or may be added directly to the reactor.
Whether in the case of the in situ preparation (or for independent preparation of the polymeric transition metal alkoxide), the source of water, or water related species is provided, whereby quantities of water are released or diffused or become accessible, as the case may be, in a delayed rate controlled manner during the reaction. As aforesaid, the coordination sphere afforded by a hydrated metal salt has been found suitable for the purpose; but other sources of water in the same proportions are also useable. Thus, calcined silica gel free of other active constituents but containing controlled amounts of bound water may be employed. In general, the preferred source of water is an aquo complex where water is coordinated with the base material in known manner.
Suitable materials include the hydrated metal salts especially the inorganic salts such as the halides, nitrates, sulphates, carbonates and carboxylates of sodium, potassium, calcium, aluminum, nickel, cobalt, chromium, iron, magnesium, and the like.
The interaction of these components is conveniently carried out in an enclosed reactor, preferably coupled with reflux capacity for volatile components at the elevated temperatures produced in the reaction vessel. Autogenous pressure is employed, as the reaction proceeds smoothly under ambient conditions, with heating to initiate and maintain the reaction. As in any such reaction stirring is preferred simply to avoid caking or coating of vessel surfaces, to provide intimate admixture of components, and to ensure a homogeneous reaction system.
Usually a hydrocarbon solvent such as hexane, heptane, octane, decalin, mineral spirits and the like is also used to facilitate intermixture of components, heat transfer and maintenance of a homogeneous reaction system.
Saturated hydrocarbons are preferred, having a boiling point in the range of 60 to 1 900 0. The liquid transition metal component also may serve at least in part as the reaction medium, especially where no added solvent is employed. The reaction involves a stage where additional volatile components form azeotropes with the solvent, or if the components are employed neat, constitute the source of reflux, but in either case it is preferred, at least to effectuate the reaction through intermediate stages with appropriate reaction times, to return volatiles to the reaction zone. Thus, butanol is generated when the titanium component is titanium tetra n-butoxide forming an azeotrope with the hydrocarbon solvent.Selection of solvent and/or alkoxide relative to possible suppression of reaction temperature is accordingly a consideration, as is known to one skilled in the art.
Reaction temperature will to some extent be a matter of choice within a broad range, depending upon the speed of reaction conveniently to be conducted. It has been found that the reaction system (constituted by the liquid transition metal component, dissolved hydrated metal salt, reducing metal particles and solvent, where desired) evidences visible gas generation at about 600--700C suggesting an initiation temperature or activation energy level at about 500C which therefore constitutes the minimum necessary temperature for reaction of the polymeric oxide alkoxide with the reducing metal.
The reaction is somewhat exothermic during consumption of the reducing metal hence may be readily driven to the ensuing stage, being the reflux temperature. As the alkanol generated is largely consumed in the course of the continuing reaction (as an independent species), the actual system temperature will change, and completion of the reaction is evidenced by consumption of visible metal and/or attainment of the reflux temperature for the pure solvent within a period of as little as 30 minutes to 4 hours or more. Such temperatures may reach 140 1 900C and of course higher temperatures might be imposed but without apparent benefit.It is most convenient to operate within the range of 50 1500 C, preferably 70--1400C. In the absence of solvent, the upper limit will simply be established by the reflux temperature for the alkanol generated in the course of the reaction.
Reaction of the components is most clearly apparent from the marked color change, with exotherm, that accompanies commencement of gas evolution. Where lack of opacity or turbidity of the solution admits observation, evolution of gas ranging from bubbling to vigorous effervescence is most evident at the surface of the metal, and the generally light colored solutions immediately turn greyish, then rapidly darker to blue, sometimes violet, usually blue black, sometimes with a greenish tint.
Analysis of the gas evidences no HCI; and is essentially H2. Following the rapid color change some deepening of color occurs during a gradual increase of temperature, with continuing gas evolution. In this stage, the alkanol corresponding to the alkoxide species is generated in amount sufficient to suppress the boiling point of the solvent, and appears to be gradually consumed in a rate related manner along with the remaining reducing metal.
The reaction product is hydrocarbon soluble at least in part, and is maintained in slurry form for convenience in further use. The viscous to semi-solid product when isolated evidences on X-ray diffraction analysis an essentially amorphous character.
Moiar ratios of the components may vary within certain ranges without significantly affecting the performance of the catalyst precursor in ultimate use. Thus, to avoid competing reactions rendering the reaction product inconveniently gelatinous or intractable, the transition metal component is ordinarily supplied in at least molar proportion relative to reducing metal, but the transition metai/reducing metal ratio may range from about 0.5:1 to about 3:1 or more, preferably 1:1 to 10:1.An insufficient level of reducing metal will result in suppression of the reaction temperature such that the reflux temperature of the pure solvent remains unattained; whereas an excess of reducing metal will be immediateiy apparent from the unconsumed portion thereof, hence the desired amount of this component is readily ascertained by one skilled in the art.
Within these ranges, a varying proportion of the reaction product may constitute a hydrocarbon insoluble component which however may and commonly is slurried with the soluble component for use, e.g., further reaction with a halide activator to form an olefin polymerization catalyst. The amount of such insoluble component may be controlled in part by the use of a solvent with an appropriate partition coefficient but where use of a common hydrocarbon solvent such as octane is preferred for practical reasons, equimolar ratios of, e.g., Ti/Mg/H2O components have been found most adapted to the formation of a homogeneous reaction product.
The water, or water-related species is also preferably supplied in molar ratio to the transition metal component, for similar reasons of homogeneity and ease of reaction. Thus, in the case of MgCI2. 6H2O, an amount of 0.17 moles supplies during the reaction about 1 mole of water and this proportion up to about 2 moles of water, provides the most facile reactions, with one or more moles of transition metal component. More generally, the H2O may range from about 0.66 to 3 moles per mole of transition metal. The amount of water present at any given stage of the reaction, of course, is likely to be considerably less, ranging to catalytic proportions relative to the remaining components, depending upon the manner and rate at which it participates in the reaction sequence, presently unknown.
It is nevertheless specifically contemplated without limitation, as an operative hypothesis that the water, or the rate of reaction controlling water-related species is activated, released, made accessible to or diffuses in a manner providing such species in a regular, sequenced, constant or variable raterelated manner. The same molar proportion of free water supplied at the commencement of the reaction is however wholly ineffective in initiating reaction at this or higher temperature, and results in undesirable complete hydrolysis reactions.
The measured amount of water is essentially in molar balance or molar excess relative to the reducing metal component and appears to be related to its consumption in the reaction, as a molar insufficiency of water will invariably result in excess reducing metal remaining. In general, a modest excess of water of 10 40% is suitable to ensure complete reaction. Higher proportions are suitable without limitation but should be kept in relative stoichiometric balance to the transition metal component.
The selection of aquo complexes or hydrated metal salts where employed is essentially a matter of the controlled availability of water it affords to the system. Thus, sodium acetate trihydrate is suitable, as is magnesium acetate tetrahydrate, magnesium sulphate heptahydrate and magnesium silicon fluoride hexahydrate. A salt of maximum degree of hydration consistently with the controlled release afforded by the coordinate bonding relationship is preferred. Most conveniently, a hydrated magnesium halide such as magnesium chloride hexahydrate or magnesium bromide hexahydrate is employed. These salts, like other hygroscopic materials, even when supplied in commercial anhydrous form contain some sorbed water, e.g., 17 mg/kg see U.K. Patent 1,401,708) although well below the molar quantities contemplated in accordance with this invention. Hence, anhydrous grade salts unless specially modified for the purpose are not suitable herein.
The reaction system, as defined in the above description does not require, although it will tolerate an electron donor or Lewis base, or a solvent performing in part those functions. As shown in the
Examples, the reaction is implemented in the preferred embodiment with water of crystallization, and an alcohol component in the system. It is not known with certainty, therefore, whether proton transfer or electron donor mechanisms participate or compete in the reaction system.
No separations are necessary as at least a portion of the reaction product is soluble in the saturated hydrocarbon where employed as a solvent or provides a solvation medium such that even where a precipitate also occurs, and even after storage, a workable reactive slurry may be readily formed.
For the purposes of the invention the reaction product (catalyst precursor) is further interreacted with a halide activator, such as an alkyl aluminum halide, a silicon halide, an alkyl silicon halide, a titanium halide, or an alkyl boron halide. It has been found that the catalyst precursor may be activated readily, by merely combining the product with the halide activator. The reaction is vigorously exothermic, hence the halide activator is typically added gradually to the reaction system. Normally, upon completion of addition, the reaction is also complete and may be terminated. The solid reaction product, or slurry may then be used immediately, or stored for future use. Usuaily, for best control over molecular weight characteristics, and particularly for production of low density resin, only the hydrocarbon washed solid reaction product is employed as the catalyst.
The halide activator is commonly supplied for interreaction at a molar ratio of 3:1 to 6:1 (aluminum, silicon or boron, relative to the transition metal) although ratios of 2:1 or more have been used successfully.
The resultant catalyst product may be used directly in the polymerization reaction although it is typically diluted, extended or reduced as required to provide in a convenient feed an amount of catalyst equivalent to 80-1 00 mg/transition metal, based upon a nominal productivity of greater than 200,000 gm polymer/gm transition metal in continuous polymerizations which the present catalyst ordinarily exceeds. Adjustments are made by the artisan to reflect reactivity and efficiency, ordinarily by mere dilution, and control of feed rates.
The transition metal containing-catalyst is combinable for use in polymerization with an organometallic co-catalyst such as triethyl aluminum or triisobutyl aluminum or a non-metallic compound such as triethyiborane. A typical polymerizer feed thus comprises 42 parts of isobutane solvent, 25 pts. of ethylene, 0.0002 pts. catalyst (calculated as Ti), and 0.009 pts. co-catalyst (TEA, calculated as Al), to a reactor maintained at 650 psig. and 1600 F. In general, the amount of cocatalyst, where employed, is calculated to range from between about 30 to 50 ppm calculated as Al or
B, based upon isobutane.
Examples of metallic cocatalysts include trialkyl aluminums, such as triethyl aluminum, triisobutyl aluminum, trinoctyl aluminum, alkyl aluminum halides, alkyl aluminum alkoxides, dialkyl zinc, dialkyl magnesium, and metal borohydrides including those of the alkali metals, especially sodium, lithium and potassium, and of magnesium, beryllium and aluminum. The non-metal cocatalysts include boron alkyls such as triethyl borane, triisobtuyl borane and trimethyl borane and hydrides or boron such as diborane, pentaborane, hexaborane and decaborane.
The polymerization reactor is preferably a loop reactor adapted for slurry operation, thus employing a solvent such as isobutane from which the polymer separates as a granular solid. The polymerization reaction is conducted at low pressure, e.g., 200 to 1 ,000 psi and a temperature in the range of 100 to 2000 F with applied hydrogen as desired to control molecular weight distribution.
Other n-alkenes may be fed to the reactor in minor proportion to ethylene, for copolymerization therewith. Typically, butene-1 or a mixture thereof with hexene-1 is employed, in an amount of 3 to 10 mol %, although other alpha olefin comonomers/proportions may be readily used. In utilizing such nalkene comonomers, one may secure resin densities over the range from .91 to .96.
Still other alpha olefincomonomers, such as 4-methyl-pentene-1, 3-methyl-butene-1, isobutylene, 1 -heptene, 1-decene, or 1 -dodecene may be used, from as little as 0.2% by weight, especially where monomer admixtures are employed.
The polymerization may nevertheiess be conducted at higher pressure, e.g., 20,000 to 40,000 psi, in autoclave or tubular reactors where desired.
In referring herein to an intermetallic "compound" or "complex" it is intended to denote any product of reaction, whether by coordination or association, or in the form of one or more inclusion or occlusion compounds, clusters, or other interengagement under the applicable conditions, the integrated reaction in general being evidenced by color change and gas evolution, probably reflective of reduction-oxidation, rearrangement and association among the unconsumed elements of the reaction system.
The following Examples taken in conjunction with the foregoing description serve to further illustrate the invention, and of the manner and making and using same. All parts are by weight except as otherwise noted. Melt indices are measured under conditions E 8 F, respectively, of ASTM D-123857T, for Ml and HLMI values, on powder or resin samples as specified. HLMI/MI or MIR is melt index ratio, a measure of shear sensitivity reflecting molecular weight distribution. Other tests are as indicated, or as conventionally conducted in the related arts.
Example I
A. 6.0 pts. of Ti(OBu)4 [TBT] and 4.2 pts. of CrCI36H20 were combined in a reaction vessel. The chromium salt was partially dissolved, and some heat was evolved upon stirring. Complete dissolution was accomplished with mild heating to 60--700C. An additional 3.3 pts. of chromium salt was dissolved with stirring over a period of 20 minutes. To the green solution there was added in portions a total of 0.3 pts. of magnesium shavings, which caused vigorous gas evolution. The cooled reaction product free of excess magnesium (which had completely disappeared), was a viscous green liquid, soluble in hexane.
B. In a similar run anhydrous chromium chloride was employed with the titanium alkoxide, but no reaction occurred, with heating at greater than 1000C for a half hour. Addition of zinc dust and further heating at greater than 1 500C still evidenced no reaction. Substitution of magnesium shavings also resulted in no reaction. It was concluded that the hydrated salt was a necessary component of the reaction system.
Example II A. TBT (0.121 m), CrCl3. 6H20 (0.015 m) and MgO (0.0075 m) were combined in a stirred reaction vessel equipped with an electric heating mantle. The chromium salt was wholly dissolved at about 600C, and reaction with the magnesium shavings was apparent from gas evolution at 850C, which was vigorous at 1000C, subsiding at 11 6 C with some Mg remaining. After dissolution of the remaining Mg, heating was continued, to a total reaction time of 1 hour and 45 minutes. The reaction product at room temperature was a dark green liquid which dissolved readily in hexane.
B. In the same manner, a reaction product was prepared in the proportions 0.116 m TBT, 0.029 m CrCl3. 6H20 and 0.029 m Mg. A muddy green reaction product at 1 180C took on a definite bluish color at 1200C with continued gas evolution. The reaction was terminated upon the disappearance of magnesium in one hour and fifteen minutes. The reaction product was soluble in hexane.
C. The aforedescribed runs were again replicated in the reactant amounts 0.1 16 m TBT, 0.058 m
CrCl3- 6H20, 0.0145 m Mg. The reaction was completed in 115 minutes, and a hexane soluble product resulted.
D. The ratio of the reactants was again modified in a further run, to 0.115 m TBT, 0.0287 m
CrCl3. 6H20, and 0.0144 m Mg. A muddy green material evident at 1 140C became blue at the Mg surface. The recovered reaction product was hexane soluble.
E. In a similar run, 0.176 m TBT, 0.30 m CrCl3. 6H20 and 0.176 m MgO were reacted in octane.
The clear green color of the reaction at 700C turned muddy with increasing gas evolution and darkened to almost black at 900 0. The color returned to green at 11 9 C and the reaction was terminated at
121 OC with complete disappearance of the magnesium. The reaction product (6.9 wgt.%, Ti, 3.5 wgt.% Mg, 1.3 wgt% Cr) was a dark olive green liquid and a solid of darker color (about 50:50/volume) which settled out.
F. In yet another run in octane, the reactants were provided in the proportions 0.150 m TBT, 0.051 m CrCI,. 6H20 and 0.1 50 m Mg. Again, the muddy green color changed to almost black with vigorous effervescence, forming at 1090 a dark blue black reaction product. (5.7 wgt.% Ti; 2.9% Mg, 2.1 wgt.%Cr).
Example Ill
A. The reaction product IIE was combined in a reaction vessel with isobutylaluminum chloride added dropwise in proportions to provide a 3:1 Al/Ti molar ratio. The green colored mixture changed initially to brown violet at 380C, which upon completion of reactant addition at 390C had changed to red brown in appearance. After 30 minute additional stirring, the reaction was terminated, the product being a dark red brown liquid and a dark brown precipitate.
B. Reaction product IIF was similarly reacted with isobutyl aluminum chloride (3.1 Al/Ti molar ratio). The peak temperature with complete addition was 480C, but no brown color change was evident. The reaction product was a clear liquid and a dark grey precipitate.
Example IV
The catalyst components prepared in Example Ill above were employed in the polymerization of ethylene (1 F, 10 mol % ethylene, 0.0002 pts. catalyst calculated as Ti, triethyl aluminum about 45 ppm, calculated as Al, H2 as indicated) with results set forth in Table I, as follows:
Table I
Prod. g Resin Properties
Catalyst H2 psig Pe/gTihr Ml HLMI HLMl/Ml IIIA 60 35160 10.1 265 26.3
120 29220 18.9 618 32.6 IlIB 60 30380 9.6 264 27
120 26880 32.8 855 26.1
In the following Example, the catalyst component of the invention was prepared from the
reactant admixture in the absence of added solvent.
Example V
A. 0.1212 m Ti (OBu)4 [TBT], 0.121 m magnesium turnings and 0.0012 m MgCI2. 6H20 (TBT/Mg/MgCl2. 6H20=1 :1:0.01 molar) were combined in a stirred reaction vessel equipped with an electric heating mantle. The magnesium salt dissolved entirely at room temperature, forming a homogeneous reaction mixture. The mixture was heated gradually and at 950C gas evolution commenced on the surface of the magnesium turnings. At 1400C with reflux the bubbling had become vigorous. The solution darkened in color and the bubbling ceased at 1 700 C, whereupon the reaction was terminated.The reaction product contained excess magnesium--only about 8.5 percent charged had reacted-and was soluble in hexane.
B. In another run, the molar ratio of MgCl2. 6H20 was increased (TBT/Mg/MgCI2. 6H20=1:1 :1:0.1 molar). The gold yellow liquid became greyish with gas evolution at 1 040 C, and darkened with further heating to 1680C. After 125 minutes of reaction time, the reaction product contained some excess magnesium-about 63 percent had reacted.
C. In a further run, the molar ratio employed was 1:1:0.17. The dark blue reaction product was very viscous and could not be readily diluted with hexane. All of the magnesium was consumed.
The following Example shows the preparation carried out in a hydrocarbon solvent.
Example VI
A. 50.2 pts. (0.148 m) of TBT was added to a stirred reaction vessel equipped with an electric heating mantle, and 58.6 pts. octane. The magnesium turnings (0.074 m) were added, stirring commenced and then 0.0125 m MgCI2 . 6H20 added with heating over one minute. At 750C (20 minutes) the magnesium salt had entirely dissolved, and at 950C (25 minutes) gas evolution at the surface of the magnesium turnings commenced, the evolution increasing as the solution turned greyish and then deep blue, with refluxing at 11700 (35 minutes). The magnesium metal had entirely reacted within 1 hour (128-129 C) and the reaction was terminated.The dark blue reaction product, solubilized in octane (a small amount of a greenish precipitate remained), was calculated to contain 6.8 wgt. % Ti and 2.0 wgt. % Mg values (Ti/Mg 3.4 to 1 by weight 1.7 to 1 molar).
B. The foregoing run was essentially repeated except that molar ratios of the reactants were modified with results as follows: Ti/Mg/MgCl2 6H2O Mol Ratio Ti/Mg (Molar) Notes 1.0/0.65/0.11 1.32 Dark blue black liquid and
green precipitate. 6.6 wgt. %
Ti, 2.6 wgt. % Mg values (calc) 1.0/0.75/0.1 28 1.14 Blue solution with greenish
tint. 6.5 wgt. % Ti, 2.8 wgt. %
Mg values (calc)
1.0/1.0/0.085 0.92 Blue black liquid with light
green precipitate (insoluble
in acetone, alkane and
methylene chloride).Some
unreacted MgO 1/1/0.17 0.85 Dark blue black liquid, 6.6
wgt. % Ti, 3.9 wgt. % Mg values
(calc)
1/1/0.34 0.75 Dark blue black liquid, 6.7
wgt. % Ti, 4.6 wgt. % Mg values
(calc)
1/1/0.51 0.66 Milky blue liquid. 3.7 wgt. %
Ti, 2.9 wgt. % Mg values (calc)
1/2/0.17 0.46 Dark blue black liquid and
viscous green gel. Some
unreacted MgO 1/2/0.34 0.43 Dark blue black liquid and
viscous gel. Some unreacted
Mg.
2/1/0.17 1.70 Example IIA
2/1/0.34 1.50 Blue black solution. 7.1 wgt. % Ti,
2.3 wgt. % Mg values (calc) 3/1/51 1.99 Blue black liquid with slight
green tint. 6.1 wgt. % Ti, 1.6
wgt. % Mg values (calc)
C. The preparation 1/1/0.34 obtained above was repeated except that 63.7 pts. TBT was employed with 67.5 hexane as the solvent reaction medium. A dark blue black liquid resulted, containing by calcination 8.2 wgt. % Ti and 1.6 wgt. % Mg values.
The following Example shows the stepwise preparation of the catalyst component.
Example VII
2.61 pts. MgCI2.6H20 and 34.2 pts. TBT were combined with stirring. Within 30 minutes, the yellow liquid-crystalline salt mixture was replaced with a milky yellow, opaque, viscous liquid.
Prolonged stirring resulted in a fading of the cloudiness to yield within 2 hours a clear yellow liquid (in a second run conducted in octane within 30 minutes the salt had totally dissolved to yield a yellow liquid with no intervening precipitate or opaqueness).
A TM Mg reaction product was prepared in the manner of foregoing Examples, utilizing the clear yellow liquid prepared above, and 1.83 pts. of MgO, for a 1/0.75/0.128 molar ratio of components in octane. The reaction proceeded smoothly to a dark blue black liquid and green precipitate in the same manner as other reported reactions.
The reaction product was activated with ethyl aluminum chloride at a 3/1 Al/Ti ratio to form a catalyst component for olefin polymerization.
The following Example evidences the significance of level of bound water.
Example VIII
A series of identical runs were performed at the molar ratio 1/0.75/0.128 (TBT/Mg/MgCl2. 6H2O) except that the degree of hydration of the magnesium salt was modified.
When MgCI2. 4H20 was employed (H20/Mg=.68/1 as compared to 1:1 for MgCl2. 6H20) only 89.1% of the magnesium metal reacted. Use of MgCI2.2H20 at the same overall molar ratio (H20/Mg 0.34/1) resulted in only 62.1% reaction of MgO.
In repeat runs, the amount of hydrated salt supplied was increased to provide a 1/1 H20/Mg ratio.
All of the magnesium metal reacted. It was also observed that the amount of insoluble reaction product increased with increasing salt levels.
The following Example illustrates the use of other titanium compounds.
Example IX A. 45.35 pts. (0.1595 m) Ti(OPri)4,0.1595 m MgO and 50.85 pts. octane added to a stirred reaction flask fitted with an electric heating mantle, and 0.027 m of MgCl2 . 6H20 were added. The milky yellow mixture became grey with reflux, at about 880 C, and turned blue at 900C with gas effervescence. Based upon magnesium remaining, it was concluded that the reaction was partially suppressed by the octane/isopropanol azeotrope present
B. The reaction described in A was repeated, at a reactant mol ratio of 1/0.75/0.128 using decalin (b.p. 1 85--1 890C) as the diluent. After six hours, the reflux temperature had attained 1400, and the reaction was terminated.A dark blue black liquid was obtained with a small amount of dark precipitate. Only 8.8% of the magnesium had reacted.
C. In a similar manner, reaction with tetraisobutyititanate was carried out, at a mole ratio of 1/0.75/0.128, providing a blue black liquid and dark precipitate. About 50% of the magnesium reacted.
D. Titanium tetranonylate was similarly employed, with magnesium and MgCI2. 6H20, at a mole ratio of 1/0.75/0.128. A blue liquid was formed, 45% of the magnesium having been consumed.
E. The reaction product of titanium tetrachloride and butanol, (believed to be dibutoxy titanium dichloride) was reacted with magnesium and magnesium chloride hexahydrate at a molar ratio of 1/0.75/0.128 under conditions similar to the above examples. About half the magnesium was consumed in about 3 hours, whereupon a dark blue black liquid and an olive green precipitate (50/50 v/v) was recovered.
The following Example employs a zirconium metal alkoxide.
Example X A. 12.83 parts of Zr(OBu)4. BuOH (0.028 m); 0.34 pts. MgO (0.14 m) in the form of commercially available turnings, and 8.8 pts. octane were placed in a reaction vessel and heated to reflux at 12500 with stirring for 1 5 minutes, without evidence of any reaction. 0.97 pts. of MgCl2. 6H20 (0.005 m) was added whereupon vigorous effervescence was noted, and the reaction mixture became milky in appearance.
B. In a second run 31.7 pts. of the zirconium compound (0.069 m) was combined with the magnesium metal turnings (0.069 m) and 57.6 pts. mineral spirits (bp 170--1950C) and 4.79 pts.
MgCl2. 6H20 (0.0235 m) was added with stirring. Heat was applied to the reaction vessel via an electric mantle. Within 5 minutes, the reaction mixture had become opaque in appearance, and gas evolution from the surface of the magnesium metal was evident when the temperature had attained 850C, at 8 minutes reaction time. Gas evolution continued with vigorous effervescence, the temperature rising to 1080C when a whitish solid appeared. With continued heating to 1330C (1 hour reaction time) all of the magnesium metal had disapperaed, the reactor containing a milky white liquid and a white solid. The reaction mixture was cooled and 92 pts. of a mixture collected, containing 6.8 wgt. % Zr and 2.4% Mg (2.8:1 Zr/Mg by weight; 0.75 Zr/Mg molar ratio) which was soluble in hydrocarbons.
The reaction product may be activated in known manner with, e.g., an alkyl aluminum halide by reaction therewith conveniently at a molar ratio of about 3/1 to 6/1 Al/Zr to provide, in combination with an organic or organometallic reducing agent, an olefin polymerization catalyst system adapted to the formation of polyethylene resin.
The following Example shows the substitution of calcium for magnesium as the reducing metal.
Example Xl A. 0.074 m Ti(OBu)4; 0.074 m CaO (thick turnings supplied commercially, mechanically cut into smaller pieces) and 0.0125 m MgCI2. 6H20 were combined in octane in a stirred reaction vessel equipped with an electric heating mantle. Upon attaining 1050C, the solution darkened in color, and at 1080C, with gas evolution, the solution took on a dark grey appearance. At 1 10.50C rapid gas evolution was evidenced, followed by formation of a dark blue liquid. At 90 minutes, the reaction was terminated and a reaction product comprising a dark blue black liquid with a greenish tint isolated.
The run was repeated at the same molar ratio. 50% of the calcium reacted to provide a dark blue liquid and grey solid containing 6.2 wgt. % Ti, 2.6 wgt. % Ca, and 1.1 wgt. % Mg (molar ratio 1/0.5/0.34) (XI Al).
In another run the same reactants were combined in the molar ratio 0.75/0.128. 63% of the calcium reacted, to provide a blue black liquid and a green solid. The reaction product (molar ratio 1/0.47/0.128) contained 6.6 wgt. % Ti, 2.6 wgt % Ca and 0.4 wgt. % Mg (Xl A2).
B. The reaction product Xl Al were further reacted with ethyl aluminum chloride at a 3/1 and 6/1 Al/ri molar ratio. The reaction products were diluted with hexane and the halide activator added slowly to control the highly exothermic reaction. In the 3/1 run the off white slurry initially formed resolved upon completion of the reaction to a pink liquid and a white precipitate. At 6/1 Al/Ti ratio, the slurry changed in color to grey, and then lime green.
Reaction product Xl A2 was likewise treated with EtAICI2 at a 3/1 and 6/1 Al/Ti molar ratio. The reactions were smooth, producing at 3/1 a deep brown slurry, and at 6/1 a red brown liquid with a brown precipitate.
C. Reaction products prepared in part B were employed in ethylene polymerization, with results as indicated in the following Table.
Table II TBT-Ca-MgCI2 6H20 Reaction H2 Productivity Resin Powder Properties
(molar ratio) Ratio (psig) (gPE/gTi. hr) Ml HLMI MIR 1/0.5/0.34 3/1 60 40,950 3.84 131 34.1 1/0.5/0.34 6/1 60 43,810 1.03 47.7 46.3 1/0.47/0.128 3/1 60 20,930 1.73 73.7 42.6
120 11,260 7.0 320 45.7
6/1 60 27,420 0.35 21.0 60.1
120 33,050 1.75 116 66.0
Bench Scale Reactor Conditions Diluent-Isobutane Temperature-1 900F Hydrogenas indicated Co-catalyst-Triethylaluminum (TEAL) at about 45 ppm Al Ethylene-1 0 mole %
Run Time-60 minutes
The runs evidenced a somewhat broader molecular weight distribution in the resin as compared to the use of magnesium as the reducing metal.
The substitution of zinc as the reducing metal is shown in the following Example.
Example XII A. 0.204 m TBT, O. 1 53 m of ZnO granules, and 0.026 m of MgCl2. 6H20 were combined in octane in a stirred enclosed system equipped with reflux, and externally heated. Within 1 3 minutes (85"C) a rapid color change to blue black occurred, with increasing gas evolution to vigorous effervescence and foaming. The reaction product, a blue black liquid (no precipitate) comprising 7.7% Ti, 0.9% Zn, and 0.5% Mg by weight, fades to yellow on exposure to air.
B. The reaction product TiZnMg (molar ratio 1/0.86/0.128) was reacted with isobutyl aluminum chloride, at a 3/1 Al/Ti molar ratio, in hexane at 10--13"C. (XII B1).
C. Preparation of the TiZnMg reaction product (Xll A) was repeated, employing Zn dust, with similar results. A further run with mossy zinc utilized only 7% of the zinc, and evidenced formation of a green layer on the zinc surface.
D. The activated reaction product XII B1 prepared above was washed thoroughly in hexane and employed in the preparation of low density polyethylene resin. The reactor was preloaded with sufficient butene-1 to secure target density, and the reaction conducted (with incremental addition of butene-1 along with the ethylene) at 1 700F and 35 psig H2 in the presence of triethyl aluminum as cocatalyst. The resin recovered had the following properties: Density .9165, Ml 1.68, HLMI 52.1 and MIR 31.
The following Example involves the use of potassium as the reducing metal.
Example XIII
62.7 m mol of TBT, 47 m mol of fresh potassium metal (scraped clean of its oxide/hydroxide coating under octane), and 8.0 m mol of MgCl2. 6H20 were combined in octane in an enclosed system equipped with reflux, and externally heated. Within 2 minutes at 350C the color changed to blue black, and bubbles appeared. Vigorous gas evolution and effervescence followed. Upon disappearance of the potassium metal, the reaction was terminated (at 5 hours). A dark blue black liquid with a small amount of dark blue precipitate was recovered.
Examples XlV-XV describe the use of aluminum as the reducing metal.
Example XIV A. 112.31 pts. of Ti(OBu)4 (0.33 m), 8.91 pts. of Al (Alfa Inorganicspherical aluminum powder, -45 mesh) and 11.4 pts. of MgCl2. 6H20 (0.056 m) [molar ratio 1:1:0.17] were admixed in a reaction vessel with stirring, and heat applied, employing an electric mantle.
When 1000C was attained in about 10 minutes, the yellow color deepened, and at 1 180C vigorous effervescence commenced, with gas evolution. At 12200 the refluxing liquid took on a grey cast, and the temperature stabilized, as the reaction mixture changed in color from a deep grey with bluish tint to dark blue then blue black at 27 minutes reaction heating time. The temperature was maintained, rising to 1450C, within 1 hour and 20 minutes, whereupon gas evolution was essentially complete and the reaction was terminated.
The reaction product at room temperature was a viscous liquid, evidencing unreacted aluminum particles. The unreacted aluminum was separated, washed and weighed, indicating that 6.7 pts. Al reacted. The reaction product contained 7.9 wgt. % Ti, 3.4 wgt % Al and 0.7 wgt. % Mg (molar ratio 1:0.75:0.17).
B. 9.10 pts. of the reaction product prepared above (0.71 9 pts. Ti, or 0.01 5 m Ti) was added in hexane (13.0 pts.) to a reaction vessel in a cooling bath. 0.045 methyl aluminum dichloride was added gradually, the temperature being maintained at 15--200C. The admixture, stirred for 30 minutes provided a dark red brown slurry and an intractable solid. (B 1).
A second run was carried out (0.175 m Ti/0.0525 m Al) without cooling to a peak temperature of 38"C, and a red brown slurry again formed, with an intractable solid deposit. (82).
Example XV
The reaction products of Example XIV were employed as catalysts in the polymerization of ethylene under standard conditions (1900 F, 60 psig H2) employing triethyl aluminum as a co-catalyst, with results as follows:
Ml HLMI MIR B1 0.14 6.45 46.1
B2 0.38 17.4 45.7
Example XVI
A. In a similar manner to the foregoing, 0.133 m TBT, 0.100 m Al , and 0.017 m AICI3. 6H20 were combined in octane and reacted over 7 hours and 1 5 minutes to provide a dark blue black liquid and a small amount of a grey solid. About 40 per cent of the aluminum reacted to provide a reaction product comprised of 6.6 wgt. % Ti and 1.6% Al. (XVI Al).
In the same manner, the same reactants were combined in a 1/1/0.17 m ratio. About 58% of the
Al reacted, to provide a reaction product containing 6.5 wgt. % Ti and 2.7 wgt. % Al. (XVI A2).
B. The reaction products (XVI Al) and (XVI A2) were activated with ethyl aluminum chloride at 3/1 Al/Ti.
C. The solid portion of the activated reaction product (XVI A2) was isolated from the supernatant and employed with TEA as co-catalyst in the polymerization of ethylene, at 1700 F, 1 5 psig H2 to produce resin characterized by MI .02, HLMI 1.01, MIR 50.5 and in a second run MI .02, HLMI .45 and
MIR 22.5.
The following Examples are drawn to catalyst components prepared employing other aquo complexes.
Example XVII
A. 0.0335 mol TBT and 0.0335 mol MgO were stirred in octane in a heated reaction vessel, to which .0057 mol of MgBr2. 6H20 was added. (Reaction molar ratio 1/1/0.17). The salt dissolved in six minutes with heating to 650C. A grey color developed with gas effervescence, and the solution turned blue, then blue black with a greenish tint. The reaction was terminated at 1230C (about 10% unreacted
Mg) after a reaction period of 4 hours and 10 minutes. (XVII A).
In a similar manner, a reaction product was prepared at a mole ratio of (Ti/Mg/MgBr2.6H2O=1/0.65/0.11), which was a blue black liquid and dark green precipitate (6.5 wgt.
% Ti 2.5 wgt. % Mg (calc)).
B. The decanted reaction product (XVII A) was combined with isobutyl aluminum dichloride at
Al/Ti levels of 3/1 and 6/1 by gradually adding the alkyl aluminum halide. In the first run (3/1 Al/Ti) a peak temperature of 42 C was attained with addition at a rate of 1 drop/2-3 sec, whereupon the green liquid turned brown. The reaction product was a red brown liquid and brown precipitate. (IV B-1).
The 6/1 product (IV 8-2) was prepared in similar manner with the same results.
In a separate run, the reaction product (XVII A) was combined with SiCI4 in the same manner. The reaction product of a 30 minute reaction at a 3/1 Si/Ti ratio was a light yellow liquid and a brown precipitate. A similar run provided a 6/1 Si/Ti reaction product.
C. The activated reaction products XVII B-1 and XVII B-2 (1% Ti by weight) were employed in the polymerization of ethylene (10 mol % in isobutane) at 1 900F, with hydrogen modifier and triethyl aluminum cocatalyst (45 ppm Al) and compared to an identical run using magnesium chloride hydrate, with results set forth in Table III as follows::
Table III
Catalyst Al/Ti+ Productivity Powder Resin Properties TffOBu)4-Mg-A (molar) H2 (psig) (g PE/g Ti-hr) Ml HLMI HLMl/Ml A=MgCl2. 6H20 3/1 60 42,870 1.7 61 35.9
120 49,100 12.2 348 28.5 MgBr2 . 6H20 3/1 60 105,190 24 698 29
120 77,390 102 -
6/1 60 34,780 10.3 371 36
120 37,050 17.8 639 35.9
Example XVII I A. 42.23 pts. of TBT (0.124 m) were combined with 3.02 pts. Mg (0.124 m) in octane (42.8 pts.) in the presence of 5.7 pts. FeCI3. 6H20 (0.02 m) (TMgFe=1/1/0.1 7 molar) in an enclosed stirred reaction vessel equipped with reflux, and an electric heating mantle. Heating commenced, and within 6 minutes, at 65 C gas evolution began.The muddy yellow color turned dark brown at 80 C (7 minutes) and gas evolution increased. In about 30 minutes gas evolution had slowed and then ceased with consumption of Mg , and the reaction was terminated. The very dark liquid evidenced no residue.
(XVIII Al).
In a second run, the same reactants were combined in the molar ratio TMgFe=1/1/0.34 with similar results. Dilution with hexane caused no precipitate or deposition of residue. (XVIII A2).
B. Reaction product XVIII Al was activated by reaction with a 50 wgt. % solution of ethyl aluminum chloride in hexane at a 3/1 Al/Ti ratio. A brown liquid and solid was recovered, containing 16.5 Mg Ti/g. (XVIII B1).
In a similar manner, reaction product (XVIII A2) was activated. The dark brown liquid changed to a violet slurry and then to a dark grey slurry. The resulting clear liquid and grey precipitate contained 16
Mg Ti/g.
C. Activated reaction product XVIII B1 was employed in the polymerization of ethylene at 1900 F, 60 psi H2. 1 14,320 g PE/g Ti/hr were recovered, exhibiting the following properties: Ml 5.1, HLMI 155.3, MIR 30.3.
Example XIX
A. 1. 0.160 m Ti (OBu)4, 0.160 m magnesium turnings and 0.027 m CoCl2. 6H20 were combined in a stirred reaction vessel with 61.2 pts. of octane. The violet cobalt salt crystals provide upon dissolution a dark blue solution. The admixture is heated, employing an electric mantle, and gas evolution on the magnesium surfaces appears at 580 C, increasing to vigorous effervescence at 1070C within 12 minutes. The clear blue color becomes greyish on further heating and becomes almost black at 123-125 C when all the magnesium has disappeared and the reaction is terminated, at 90 minutes. The milky blue reaction product was hydrocarbon soluble, and resolved into a dark blue liquid and a dark precipitate upon standing.
The run was repeated, with essentially identical results.
B. The reaction product of the foregoing preparation was shaken, and 0.01 1 1 m (Ti) was combined with isobutyl aluminum chloride (0.0333 m Al) supplied dropwise to a reaction vessel. The temperature peaked at 400 C, with formation of a greyish precipitate, which upon further addition of
BuAICI2 turned brown. After stirring for an additional 30 minutes the reaction was terminated, providing a dark red brown liquid and a brown precipitate.
C. The catalyst component prepared in Example XIX above was employed in the polymerization of ethylene (1900 F, 10 mol % ethylene, 0.0002 pts. catalyst calculated as Ti, triethyl aluminum about 45 ppm calc as Ai, H2 as indicated) with the results set forth in Table IV, as follows:
Table IV
Prod Resin Properties
Catalyst H2 psig g PE/g Ti/hr Ml HLMI HLMl/Ml XIX B 60 105,180 6.2 206 33.6
120 75,290 33.9 950 28.1
Example XX
A. 0.169 m Ti(OBu)4 [TBT], 0.169 m magnesium turnings, and 0.029 m AICI3. 6H20 in octane as a diluent were combined in a stirred reaction vessel equipped with an electric heating mantle.The hydrated aluminum salt partly dissolved and at 111 C the solution rapidly darkened to a black liquid with vigorous effervescence originating with gas evolution at the surface of the magnesium. The solution took on a blue coloration and, with smooth refluxing to 1 22 0 C formed a dark blue-black liquid with some remaining magnesium. At 1250C, all the magnesium metal disappeared, the solution exhibiting a slight green tint. The reaction was terminated, and a dark blue black liquid and green precipitate recovered, in a votume ratio of about 95/5.
B. The reaction product described above was combined with isobutyl aluminum chloride in a molar ratio of 3:1 and 6:1 Al/Ti by dropwise addition of the chloride to a reaction vessel containing the titanium material. In the first reaction (3:1), the alkyl chloride was added at a rate of 1 drop/2-3 seconds until a peak temperature of 420C was attained, with a color change from blue-green to brown.
After stirring for an additional 30 minutes, the reaction product, a red-brown liquid and a brown precipitate, was isolated. (XX B).
C. In a similar manner, a 6:1 Al/Ti product was secured, with the same results. (XX C).
D. Reaction products XX B and XX C were employed with triethylaluminum co-catalyst (45 ppm
Al) in the polymerization of ethylene (10 mol %) with isobutane diluent at 1 900F and hydrogen as indicated. The runs were terminated after 60 minutes, with results indicated in Table V, as follows:
Table V
Prod Resin Properties
Catalyst H2 psig PE mole gPE/gTi/hr Ml HLMI HLMl/Ml XXB 60 406 84,580 17.2 517 30.1
120 542 75,280 54.9 1413 25.7 XXC 60 245 54,440 4.11 129 31.4
120 183 34,860 26.2 801 30.5
Example XXI
A. 0.153 m Ti(OBu)4 [TBT], 0.153 m MgO turnings and 0.026 m NiCI2 . 6H20 were combined with 61.75 pts. of octane in a stirred reaction vessel equipped with an electric heating mantle.With heating to 440C the yellow solution deepened in color, and gas evolution on the magnesium metal surface became observable at about 570C. With continued heating, the gas evolution increased until at 1020C (15 minutes reaction) the reaction system turned a light muddy brown color. Vigorous effervescence continued with darkening of the brown color until at 1260C (75 minutes) all the magnesium had disappeared, and the reaction was terminated. The reaction product (XXIA-1) was a hydrocarbon soluble dark brown liquid and a small amount of a fine precipitate.
In a second run 0.149 m TBT, 0.149 m Mg, and 0.051 m Nick,. 6H20 were combined in octane in the same manner. Mg metal disappeared at 1150C, 120 minutes, and the reaction resulted in a dark brown black hydrocarbon soluble liquid, which resolved on standing to a very fine dark precipitate and a yellow liquid, about 50/50 by volume (XXIA-2).
B. Reaction product IA-1 was shaken, and a portion (0.0137 m Ti) was placed in a reaction vessel with hexane diluent, to which iBuAlCI2 (0.0411 m Al) was added dropwise, at a rate of 1 drop/2-3 sec. to 280C, and a 1 drop/sec. to a peak temperature of 390 C. After completion of addition the vessel contents were stirred for 30 minutes, and the reaction product, a dark red brown liquid and a dark grey precipitate, isolated. (XXIB-1).
The same reaction product (XXIA-1) was combined with ethyl aluminum chloride in the same manner, at a 3/1 Al/Ti molar ratio. The reaction product was a dark red brown liquid and a dark grey solid. (XXIB-2).
In an essentially identical manner, reaction product XXIA-2 (Ti/Mg/Ni molar ratio 1/1/0.34) was combined with iBuAlCI2 at a 3:1 Al/Ti ratio, with the same results, except that the supernatant liquid was a pale red brown color. (XXIB-3).
In a further run, reaction product XXIA-2 was reacted in the same manner with iBuAlCI2 at a 6:1
Al:Ti molar ratio, to form, similarly, a dark liquid and dark precipitate. (XXIB-4).
The same reaction product XXIA-2 was combined with ethyl aluminum chloride in the same manner, producing a dark red brown liquid and a dark grey solid. (XXIB-5).
Example XXII
A. Example XXIA was repeated, with the reactants supplied in the molar ratio Ti:Mg:Ni of 1:0.65:0.11. The color change was from deep brown yellow to dark brown with gas evolution, and thence through a grey brown to dark blue black upon consumption of magnesium, in a reaction occurring over a period of 6 hours. (XXI IA).
B. Reaction product XXI IA was combined with ethyl aluminum chloride in the manner of Example
XXIB at a 3:1 Al/Ti molar ratio. A red brown liquid and red brown precipitate was recovered. (XXIIB).
Example XXIII
Example XXIIA was repeated, with the reactants supplied in the molar ratio 1/0.75/0.128. The dark brown reaction product contained 5.9% Ti, 2.2% Mg and 0.97% Ni.
The reaction product was then treated with isobutyl aluminum chloride at an Al/Ti molar ratio of 3/1.
Example XXIV
A series of TMgNi catalysts, prepared as set forth in Examples XXIB and XXIIB, were employed as catalyst components in the polymerization of ethylene (1900 F, 10 mol % ethylene, triethyl aluminum about 45 ppm calc as Al, H2 as indicated) with the results set forth in Table VI, as follows::
Table VI
Productivity Resin Properties
Catalyst H2 psig g PE/g TiHr Ml HLMI HLMl/ML XXIB-3 60 90,750 9.55 270 28
120 104,980 24.6 683 27.8
60 111,940 0.29 10.7 36.8
120 112,260 3.1 119 38.9
XXIB-4 60 59,790 0.25 10.9 43.6
120 62,720 1.0 43.6 43.6
XXIIB 60 57,890 1.66 54.9 33.1
120 64,740 6.13 183 29.8
XXIB-2 60 238,670 0.65 19.5 30.2
120 271,560 6.7 188 28.1
XXIB-5 301 175,000 Low - - 'Runs at higher levels of hydrogen were extremely rapid, resulting in polymer buildup requiring termination of runs.
Example XXV
A. TBT, MgO and MgSiF6. 6H20 were combined in octane in a heated reaction vessel equipped with reflux in the manner of the foregoing Examples, to provide reaction products at molar ratios of 1/1/0.34 and 1/0.75/0.128, respectively.
B. The latter reaction product was activated by reaction with ethyl aluminum chloride at a ratio of 3/1 Al/Ti.
C. The resulting brown precipitate was separated from the supernatant red brown liquid, and employed with TEA to provide about 45 ppm Al under standard conditions for polyethylene polymerization (1900 F, 60 psig H2) producing resin at 107,500 g PE/gTi/hr characterized by Ml 2.85,
HLMI 84.5 and MIR 29.6.
D. The 1/1/0.34 reaction product prepared above was likewise activated with isobutyl aluminum chloride at 3/1 Al/Ti. The solid reaction product was washed several times with hexane and employed with TEA in a polyethylene polymerization reactor preloaded with butene-1 to provide resin of targeted density at 1 700 F, 30 psi H2 from the ethylene/butene-1 feed. The resulting resin had a density of .9193, Ml 1.91, HLMI 60.8 and MIR 31.8.
In the following Example, catalyst components were activated by reaction with a halide component.
Example XXVI
A. In the following runs, TMMg reaction products were reacted with the halide component added gradually thereto, usually dropwise to control the exothermic reaction. The reaction was conducted
under ambient conditions for a period of time sufficient to complete addition with stirring of reactant,
for 10 to 30 minutes after occurrence of peak temperature (where applicable, TMMg solid and liquid
components were intermixed into a slurry and employed in that form).Reactants and reactant
proportions are set forth as follows:
Catalyst Component, mol ratio
Ti/Mg/MgCl2. 6H2O (H20) Halide Activator Mol Ratio
1/0.65/0.11(0.66) Bu1AlCl2 2/1 Al/Ti
1/0.65/0.11(0.66) Bu1AlCI2 3/1 1/0.65/0.11(0.66) BU'AICI2 4/1
1/0.65/0.11(0.66) Bu1AICl2 6/1 1/0.65/0.11(0.66) EtAICI2 3/1
1/0.65/0.11(0.66) EtBCI2 1.25/1 (B/Ti)
1/0.65/0.11(0.66) EtBCI2 3/1 (B/Ti)
1/0.65/0.11(0.66) SiCI4 3/1 (Si/Ti)
1/0.65/0.11(0.66) SiCI4 6/1 (Si/Ti)
1/0.75/0.128(.768) EtAiCI2 3/1
1/0.75/0.128(.768) Et3Al2Cl3 3/1
1/0.75/0.1 28(.768) BU1AlCI2 3/1
1/0.75/0.128(.768) BuAlCl2 6/1
1/0.75/0.128(.768) EtBCI2 3/1 (B/Ti)
1/0.75/0.128(.768) (CH3)2SiCl2 6/1 (Si/Ti)
1/0.75/0.1 28(.768) (CH3)3SiCI 6/1 (Si/Ti)
1/0.75/0.128(.768) (CH3)2SiHCI 6/1 (Si/Ti)
1/0.75/0.128(.768) SiCI4 3/1 (Si/Ti)
1/0.75/0.128(.768) SiCI4 6/1 (Si/Ti)
1/0.75/0.128(.768) TiCl4 1.5/1 (Ti/Ti)
1/0.75/0.128(.768) TiCI4 3/1 (Ti/Ti)
1/1/.17(1.02) BuAlCl2 3/1
1/1/.17(1.02) EtAlCl2 3/1
1/1/.34/(2.04) BuAlCl2 3/1
1/1/.34(2.04) BU1AlCI2 6/1
1/1/0.51(3.06) BuAlCl2 3/1
1/1/0.51(3.06) BuAlCl2 6/1
2/1/0.17(1.02) BU1AlCI2 3/1
2/1/0.17(1.02) Bu1AlCl2 6/1
2/1/0.34(2.04) Bu1AlCI2 3/1
2/1/0.34(2.04) Bu1AICl2 6/1
3/1/0.51(3.06) BuAlCl2 3/1
3/1/0.51(3.06) BU1AlCI2 6/1
Example XXVII
A. Catalyst samples activated with BuiAICI2 (3:1 Al/Ti) were employed in a series of polymerization runs, with results set forth in Table VII as follows:
Table VII Ti/MgCl2 6H2O Productivity Resin Powder Properties (molar ratio) (molar ratio) H2 (psig) (g PE/g Ti-hr.) Ml HLMI HLMI/MI 1/1/0.17 5.9 60 42,870 1.7 61 35.9
120 49,102 12.2 348 28.5 1/1/0.34 2.9 60 63,385 3.8 135 35.5
120 43,655 15.7 519 33.0 2/1/0.34 5.9 60 57,510 2.5 81 32.3
120 54,200 12.5 452 36.2 3/1/0.51 5.9 60 53,975 2.4 89 37.1
120 56,560 13.2 430 32.6 1/0.75/0.128 7.8 60 124,930 5.3 179 33.8
120 116,990 22.8 630 27.6 1/0.65/0.11 9.1 60 76,785 8.1 245 30.2
120 61,550 44.5 1300 2/1/0.17 11.8 60 138,820 2.25 67.3 29.9
120 89,900 17.4 491 28.2
Reactor Conditions Diluent-Isobutane Temperature-190 F Hydrogen-as indicated
Co-catalyst-triethylaluminium (45 ppm Al)
Catalyst-Ti(OBu)4-Mg-MgCl2.6H2O reaction product activated with BuAlCl2 (3:1 Al/Ti) Ethylene-1 0 mol %
Run Time-60 minutes
As may be seen from a comparison of Ti/MgCl2.6H2O molar ratio, peak melt index is observed at a 9:1 ratio (1.5:1 Ti/H2O).
B. In the following additional runs the effect of Al/Ti ratio in the activated TMMg (molar ratio 1/0.65/0.11) catalysts was explored in the polymerization of ethylene. Results are set forth in Table VIII as follows:
Table VIII
Activating
Activating Compound/Ti Productivity Resin Powder Properties
Compound (molar) H2(psig) (g PE/g Ti-hr) MI HLMI HLMI/MI
BuAlCl2 2/1 60 54,285 16.8 489 29.1
120 45,670 51 1436 28.2 BUiAICI2 3/1 60 76,785 8.1 245 30.2
120 61,550 44.5 -
BuAlCl2 4.5/1 60 66,410 7.7 257 33.4
120 67,255 35.5 1119 31.5
BuAlCl2 6/1 60 43,830 2.7 105 39
120 44,370 15.0 495 33
EtAICI2 3/1 60 60,790 7.0 214 30.6
120 97,310 39 -
EtBI2 3/1 60 94,755 3.7 128 34.6
120 56,290 21.5 616 28.6
EtBCI2 1.25/1 60 34,300 3.5 105 30
120 27,290 18 560 31
Reactor Conditions Diluent-Isobutane Temperature-190 F
Hydrogen-as indicated
Co-catalyst-triethylaluminum, (45 ppm Al)
Catalyst-Ti(OBu)2-Mg-MgCl2.6H2O reaction product, activated as above Ethylene-1 0 mole %
Run Time-60 minutes
C. In a further series of experiments, employing a TMMg catalyst at 1/0.75/0.128 molar ratio, the
effect of activating agent was analyzed, with results set forth in Table VIX as follows::
Table VIX
Activation Mole Ratio Productivity Resin Powder Properties
Agent Cl/Ti H2 (psig) (g PE/g Ti-hr) Ml HLMI HLMl/Ml BuAlCl2 6 60 124,930 5.3 179 33.8
120 116,990 22,8 630 27.6
EtBCI2 6 60 94,850 3.2 103 32.2
120 80,060 29.0 -
Me2SiCl2 12 60 24,860 2.44 58.5 24.0
120 21,120 10.4 259 24.9
Me3SiCI 4 60 32,225 7.25 214 29.5
120 28,770 16.3 460 28.2
Me2SiHCI 6 60 33,010 1.94 51.7 26.6
120 18,140 7.29 198 27.2 SiCI4 12 60 61,210 8.86 210 23.7
120 55,435 25.2 611 24.2
SiCI4 24 60 145,830 0.99 29.0 29.3
120 71,670 7.96 229 28.7
TiCI4 6 60 31,950 1.8 61.7 34.2
120 24.555 8.8 297 33.7
Reactor Conditions
Diluent-isobutane
Temperature-190 F Hydrogen-as indicated Co-catalyst-triethylaluminum, (45 ppm Al)
Ethylene-10 0 mole %
Run Time-60 minutes
D. Larger scale polymerization runs were conducted at 160 F with the TMMg 1/0.75/0.128 catalyst (slurry, separated from supernatant liquid, and washed with hexane) and TEA co-catalyst employing ethylene and butene-1 as a comonomer, utilizing varying butene-1 feed, activators and activator ratios.Results are set forth in Table X as follows:
Table X
Ethylene Butene-1
Feed(Wgt.% Feed (Wgt. %
monomer in Total H2/Ethylene Pellet Density
Run No. reactor) monomer) (mol ratio) Ml HLMI/MI Annealed Activator
A 4.41 7.55 .12 12.7 1300 0.948 6/1 Al/Ti iBuAlCI2 B 2.39 7.14 .06 1.9 40 0.939 6/1 Al/TiiBuAICl2 C 3.02 11.56 .05 1.0 41.2 0.934 6/1 Al/Ti (BuAlCl2
D 2.43 11.59 .07 3.2 28.5 0.939 3/1 Al/Ti EADC
E - - - 3.9 28.6 0.934 3/1 Al/Ti EADC
F - - - 0.6 33.4 0.931 3/1 Al/Ti EADC
G 2.32 14.66 .03 0.7 30.2 0.929 3/1 Al/Ti EADC
H 2.34 15.77 .03 0.6 31.3 0.928 3/1 Al/Ti EADC I - - - 5.8 29.7 0.935 3/1 Al/Ti EADC J 1.75 17.82 .06 1.1 43.9 0.924 6/1 Al/Ti EADC
The resin batches collected as noted above were stabilized with 100 ppm calcium stearate and 1000 ppm Irganox 1076; characterized by conventional tests; and converted into blown film in a 1 1/2" Hartig extruder (60 rpm screw; 3" die at 0.082" die gap; cooling air 37-40 F) and further tested, all as set forth below in Tables Xl and XII: Table XI
Linear Low Density Resins
Resin Properties
A B C D E F G H I J
ETA 1000x10-3 1.56 3.67 4.36MF 3.56 3.35 3.95MF 4.00MF 3.90MF 2.89 4.15
Die Swell @Eta 1000 146 164 - 152 150
Tensile Strength, psi @ 20"/min 3690 1790 1850 1810 1700 2250 3420 3310 1660 1910
Yield Strength, psi @ 20"/min - 3210 2770 3220 2830 2670 2480 2400 2910 2050
Elongation, % @ 20"/min 100 130 680 160 290 740 750 740 100 810
Tensile Modulus, psix10 66.3 52.0 42.2 49.1 39.0 39.5 33.8 34.8 44.3 27.7
Tensile Impact, ft-lb/ln 47.7 94.6 130 88.3 79.2 213.7 267.4 299.0 96.6 181.9
Vicat, C 115 115 114 115 114 112 112 110 109 100
LTB, C -76 -76 -76 -76 -76 -76 -76 -76 -76 -76
Shore Hardness, "D" 61 58 57 59 58 57 57 56 58 58 52 MF=at least some melt fracture, indicating need for optimization of conditions for actual extrusion.
Table XII
Linear Low Density Resins
Blown Film Properties
B C F
Film Thickness, mils 2.0 1.0 2.0 1.0 2.0 Haze, % 45.5 30.0 28.4 32.2 18.3 Gloss, 600, % 3.3 3.3 4.4 4.9 3.9 7.1 Tensile Strength, psi MD 3740 4130 5620 6060 5500
TD 2940 2070 3320 4410 4900
Yield Strength, psi MD 2610 2550 2390 2250 2180
TD 2840 2400 2620 2330 2410
Elongation, % MD 750 560 670 670 700
TD 830 320 780 880 550
ElmendorfTear,g/mil MD 16 6 21 21 35
TD 17 346 177 492 256
TearASTM D1004, Ib/mil MD 1.07 1.12 0.94 0.74 0.99
TD 0.97 0.97 0.94 0.82 0.96
Tensile Modulus, psi MD 72350 68440 60130 55250 49830
TD 92930 87910 74340 67800 68520
Dart Drop, gms (mils) 72(2.2) 10.5(1.0) 92(2.2) 45(1.3) 81(2.0)
Dynamic Ball Burst 2.44 1.40(1.0) 3.94(2.2) 2.48(1.2) 4.26(2.0)
cm-kg (mils)
Draw down mils - 0.25 - 0.2 MeltTemp., F 331 330 359 359 405
Head Pressure, psig 3400 3400 3850 3850 4450
Cooling Air Temp., OF 38 38 39 39 38
Table XII (Cont'd)
Linear Low Density Resins
Blown Film Properties
G H J
Film Thickness, mils 2.0 1.0 2.0 1.0 2.0 1.0
Haze, % 24.4 22.6 24.4 18.9 24.5 20.0 Gloss, 600, % 5.6 5.6 5.6 6.1 6.0 6.0
Tensile Strength, psi 5710 6930 5710 7700 4340 6180
5250 5290 5250 5010 3290 3610
Yield Strength, psi 1960 1960 1960 2010 2070 1930
2210 2090 2210 2020 1840 1640 Elongation, % 680 590 680 520 670 610
850 830 850 810 830 860
Elmendorf Tear, q/mil 80 53 80 32 80 99
277 429 277 559 366 503
Tear ASTM D1004, Ib/mil 1.03 0.98 1.03 1.25 0.83 0.86
0.95 1.21 0.95 1.14 0.80 0.80
Tensile Modulus, psi 46200 46585 46200 42940 37450 35360
56590 54880 56590 50343 44770 48370 DartDrop,gms(mils) 109(2.1) 38(1.0) 109(2.1) 36(1.0) 85(2.5) 43(1.2)
Dynamic Ball Burst 6.50(2.3) 3.11(1.0) 6.50(2.3) 3.14(1.0) 6.62(2.4) 3.62(1.2)
cm-kg (mils)
Drawdown, mils - 0.3 - - - 0.3
Melt Temp., F 405 405 406 405 360 360
Head Pressure 4500 4500 4800 4800 3900 3900 CoolingAirTemp. OF 38 38 37 37. 40 40
E. In further large scale polymerizations conducted in a similar manner employing TMMg catalyst (slurry, separated from supernatant liquid and hexane washed) at molar ratio 1/0.75/0.128 (3/1 Al/Ti, EADC), hexene-1 was fed to the reactor as a comonomer with ethylene, and then butene-1 was substituted providing, as followed by off-gas analysis, ethylene/butene-1/hexene-1 copolymers and terpolymers in the course of the operation.Results are set forth in Table XI II, as follows:
Table XIII
Comonomer Density Ml HLMI HLMl/Ml Hexene 0.9339 0.83 26.9 32
Hexene 0.9293 0.73 23.9 33
Hexene/Butene 0.9157 0.94 31.4 33
Butene 0.9148 0.70 25.2 36
Butene 0.9148 0.70 25.2 36
Butene 0.9135 0.94 29.9 32
Example XXVIII
TMMg catalyst prepared in accordance with the Examples and activated with isobutyl aluminum chloride (3/1 Al/Ti) was also employed to produce other copolymers at varying comonomer preload, isobutane diluent, 1700F reactor temperature, 30--40 psig H2 and TEA to provide 60 ppm Al, with results as follows::
Ml MIR Density
Ethylene/3-Methylbutene-1 1.25 27.4 0.9488
1.25 28.9 0.9483
1.36 27.9 0.9507
1.55 27.7 0.9497
1.56 27.5 0.9495
1.87 29.9 0.9496
1.63 28.5 0.9455
2.25 28.8 0.9437
1.46 30.0 0.9428
5.01 30.3 0.9411
1.59 31.9 0.9400
Isobutylene 0.37 32.4 0.9518
1.35 29.6 0.9564
1.79 31.1 0.9542
1.17 31.7 0.9567
4.20 30.1 0.9582
3.30 32.9 0.9557
Polymerization or copolymerization of other alpha olefin monomers such as propylene, 4-methyl pentene-1, the alkyl acrylates and methacrylates and alkyl esters may be accomplished in similar manner.
The following comparative experiments were also conducted:
Comparative Examples
A. In the same reaction vessel used in other preparations TBT, MgO and anhydrous MgCI2 were combined in octane at a molar ratio of 2/1/0.34 and heated to reflux for 1 5 minutes without evidence of reaction. The anhydrous MgCI2 remained undissolved. See also Example IB above.
B. To the same system, an amount of free water equivalent to an Mg0/MgCI2. 6H20 ratio of
1/0.34 was added in bulk, but no change was evident.
C. TBT and MgO were combined in a 2/1 molar ratio in octane and heated to reflux. While the yellow color became somewhat more intense, no evidence of reaction occurred.
D. To the system C above, an amount of free water equivalent to an Mg/MgCl2. 6H20 ratio of
1/0.34 was added. A small amount of light yellow precipitate was formed evidencing hydrolysis of the titanium compound, but the magnesium remained unreacted.
E. TBT and MgCl2 . 6H20 were combined in octane at a molar ratio of 1/0.34 and heated to reflux.
After the salt had entirely dissolved, the solution became cloudy and somewhat viscous with continued refluxing for three hours but cleared and settled to a cloudy yellow liquid and whitish precipitate overnight. A further run at molar ratio 1/0.128 developed a clear golden yellow liquid with heating to reflux over only 16 minutes. At a molar ratio of 1/1.1 7 foaming and formation of a thick cream colored gel terminated reaction after 45 minutes. Compare Example VII, above.
Claims (26)
1. A process for the polymerization of a 1 -olefin, alone or together with at least one copolymerizable monomer, under polymerization conditions of temperature and pressure, which uses an olefin polymerization catalyst system comprising a mixture of cocatalysts one of which is a halide activated intermetallic compound comprising the reaction product of polymeric transition metal oxide alkoxide and reducing metal of higher oxidation potential than the transition metal.
2. A process according to claim 1 wherein the reducing metal comprises at least one of magnesium, calcium, zinc, aluminum and potassium.
3. A process according to claim 1 or 2 wherein the transition metal comprises titanium or zirconium.
4. A process according to any preceding claim wherein the transition metal and reducing metal are present in a molar ratio of from about 0.5:1 to about 3:1.
5. A process according to any of claims 1 to 3 wherein the transition metal and reducing metal are in a molar ratio of from about 1:1 to about 10:1.
6. A process according to any preceding claim wherein the halide activator comprises at least one activator selected from alkyl aluminum halides, silicon halides, alkyl silicon halides, titanium halides and alkyl boron halides.
7. A process according to any preceding claim wherein the catalyst system includes a cocatalyst which comprises an organo aluminum or organo boron compound.
8. A process according to claim 7 wherein the catalyst system includes a cocatalyst which comprises triethyl aluminum or triethyl borane.
9. A process according to any preceding claim wherein the polymeric transition metal oxide alkoxide is one produced by partial hydrolysis of the transition metal alkoxide.
10. A process according to claim 9 wherein the hydrolysis is effected with an aquo complex as a water source.
1 A process according to claim 10 wherein water is provided in the form of a hydrated salt.
12. A process according to claim 11 wherein water is provided in the form of a hydrate of a salt of aluminum, cobalt, iron, magnesium or nickel.
1 3. A process according to claim 10 wherein water is provided in the form of a hydrated oxide.
14. A process according to claim 13 wherein water is provided in the form of silica gel.
1 5. A process according to any of claims 9 to 14 wherein the molar ratio of transition metal to water is from about 1 :0.5 to about 1:1.5.
1 6. An olefin polymerization catalyst system comprising a mixture of cocatalysts one of which is a halide activated intermetallic compound comprising the reaction product of polymeric transition metal oxide alkoxide and reducing metal of higher oxidation potential than the transition metal.
1 7. A catalyst system according to claim 1 6 wherein the halide activator comprises at least one of activator selected from alkyl aluminum halides, silicon halides, alkyl silicon halides, titanium halides and alkyl boron halides.
18. A catalyst system according to claim 1 6 or 1 7 wherein the transition metal comprises titanium or zirconium.
1 9. A catalyst system according to any of claims 1 6 to 1 8 wherein the reducing metal comprises at least one of magnesium, calcium, zinc, aluminum and potassium.
20. A catalyst system according to any of claims 16 to 19 wherein the transition metal and reducing metal are present in a molar ratio of at least 0.5:1.
21. A catalyst system according to claim 20 wherein the said ratio is from about 1:1 to about 10:1.
22. A catalyst system according to any of claims 1 6 to 21 including a cocatalyst which comprises an organo aluminum or organo boron compound.
23. A catalyst system according to claim 22 including a cocatalyst which comprises triethyl aluminum or triethylborane.
24. A catalyst system according to any of claims 16 to 23 wherein the polymeric transition metal oxide alkoxide is the product of the controlled partial hydrolysis of a titanium alkoxide.
25. A catalyst system including a halide-activated intermetallic compound and substantially as hereinbefore described in any Example.
26. An olefin polymerization substantially as hereinbefore described in any of Examples I to XXVIII.
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
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US20922380A | 1980-11-24 | 1980-11-24 | |
US20922980A | 1980-11-24 | 1980-11-24 | |
US20922680A | 1980-11-24 | 1980-11-24 | |
US20922880A | 1980-11-24 | 1980-11-24 | |
US20922580A | 1980-11-24 | 1980-11-24 | |
US20922480A | 1980-11-24 | 1980-11-24 | |
US20922780A | 1980-11-24 | 1980-11-24 | |
US22883181A | 1981-01-27 | 1981-01-27 |
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GB2087907A true GB2087907A (en) | 1982-06-03 |
GB2087907B GB2087907B (en) | 1985-05-09 |
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---|---|---|---|
GB8135364A Expired GB2088862B (en) | 1980-11-24 | 1981-11-24 | Intermetallic compounds and their production |
GB8135365A Expired GB2087907B (en) | 1980-11-24 | 1981-11-24 | Olefin polymerisation process and catalyst |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
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GB8135364A Expired GB2088862B (en) | 1980-11-24 | 1981-11-24 | Intermetallic compounds and their production |
Country Status (17)
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AT (2) | AT386212B (en) |
AU (2) | AU550723B2 (en) |
BR (2) | BR8107639A (en) |
DE (2) | DE3146524C2 (en) |
DK (2) | DK520381A (en) |
FI (2) | FI71569C (en) |
FR (2) | FR2494694B1 (en) |
GB (2) | GB2088862B (en) |
IN (2) | IN156133B (en) |
IT (1) | IT1139827B (en) |
MX (1) | MX6918E (en) |
NL (2) | NL189411C (en) |
NO (2) | NO160583C (en) |
NZ (2) | NZ199047A (en) |
SE (2) | SE461100B (en) |
TR (2) | TR21347A (en) |
YU (2) | YU275581A (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2589157A1 (en) * | 1985-10-25 | 1987-04-30 | Nat Distillers Chem Corp | INTERMETALLIC COMPOUNDS AND THEIR USE AS COMPONENT OF A CATALYST SYSTEM FOR POLYMERIZING ALPHA-OLEFINS |
US5688887A (en) * | 1992-05-26 | 1997-11-18 | Amoco Corporation | Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture |
EP0894098A1 (en) * | 1996-04-15 | 1999-02-03 | Mobil Oil Corporation | High impact lldpe films |
US6043401A (en) * | 1992-05-26 | 2000-03-28 | Bp Amoco Corporation | Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture |
WO2001000685A2 (en) * | 1999-06-30 | 2001-01-04 | Union Carbide Chemicals & Plastics Technology Corporation | Mixed metal alkoxide complexes and polymerization catalysts made therefrom |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102006031960A1 (en) | 2006-07-11 | 2008-01-17 | Oxeno Olefinchemie Gmbh | Process for the preparation of polymers of 3-methylbut-1-ene |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IT1020055B (en) * | 1973-09-08 | 1977-12-20 | Solvay | LOW PRESSURE POLYMERIZATION OF OLEFINS |
DE2906639C2 (en) * | 1979-02-21 | 1982-03-25 | Chemische Werke Hüls AG, 4370 Marl | Process for the production of largely amorphous homo- and / or copolymers of α-olefins having 3-3 2 carbon atoms |
IT1113421B (en) * | 1979-03-07 | 1986-01-20 | Anic Spa | METHOD FOR THE REDUCTION OF METALLIC ALCOXIDS AND USE OF THE COMPOUNDS SO OBTAINED |
-
1981
- 1981-11-23 IT IT25230/81A patent/IT1139827B/en active
- 1981-11-24 AU AU77815/81A patent/AU550723B2/en not_active Ceased
- 1981-11-24 SE SE8106988A patent/SE461100B/en not_active IP Right Cessation
- 1981-11-24 GB GB8135364A patent/GB2088862B/en not_active Expired
- 1981-11-24 AT AT0505981A patent/AT386212B/en not_active IP Right Cessation
- 1981-11-24 SE SE8106989A patent/SE451587B/en not_active IP Right Cessation
- 1981-11-24 TR TR21347A patent/TR21347A/xx unknown
- 1981-11-24 FR FR8121999A patent/FR2494694B1/en not_active Expired
- 1981-11-24 TR TR22074A patent/TR22074A/en unknown
- 1981-11-24 IN IN1317/CAL/81A patent/IN156133B/en unknown
- 1981-11-24 GB GB8135365A patent/GB2087907B/en not_active Expired
- 1981-11-24 YU YU02755/81A patent/YU275581A/en unknown
- 1981-11-24 NO NO813992A patent/NO160583C/en unknown
- 1981-11-24 DK DK520381A patent/DK520381A/en not_active Application Discontinuation
- 1981-11-24 FR FR8122000A patent/FR2494700B1/en not_active Expired
- 1981-11-24 BR BR8107639A patent/BR8107639A/en not_active IP Right Cessation
- 1981-11-24 NL NLAANVRAGE8105319,A patent/NL189411C/en not_active IP Right Cessation
- 1981-11-24 DE DE3146524A patent/DE3146524C2/en not_active Expired - Fee Related
- 1981-11-24 YU YU02754/81A patent/YU275481A/en unknown
- 1981-11-24 FI FI813745A patent/FI71569C/en not_active IP Right Cessation
- 1981-11-24 FI FI813744A patent/FI71568C/en not_active IP Right Cessation
- 1981-11-24 NL NLAANVRAGE8105318,A patent/NL188652C/en not_active IP Right Cessation
- 1981-11-24 DE DE3146568A patent/DE3146568C2/en not_active Expired - Fee Related
- 1981-11-24 AU AU77816/81A patent/AU551320B2/en not_active Ceased
- 1981-11-24 AT AT0506081A patent/AT386214B/en not_active IP Right Cessation
- 1981-11-24 NO NO813991A patent/NO160584C/en unknown
- 1981-11-24 BR BR8107638A patent/BR8107638A/en not_active IP Right Cessation
- 1981-11-24 DK DK520481A patent/DK520481A/en not_active Application Discontinuation
- 1981-11-24 NZ NZ199047A patent/NZ199047A/en unknown
- 1981-11-24 NZ NZ199048A patent/NZ199048A/en unknown
- 1981-11-24 IN IN1316/CAL/81A patent/IN156404B/en unknown
- 1981-11-24 MX MX819778U patent/MX6918E/en unknown
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2589157A1 (en) * | 1985-10-25 | 1987-04-30 | Nat Distillers Chem Corp | INTERMETALLIC COMPOUNDS AND THEIR USE AS COMPONENT OF A CATALYST SYSTEM FOR POLYMERIZING ALPHA-OLEFINS |
GB2182047A (en) * | 1985-10-25 | 1987-05-07 | Nat Distillers Chem Corp | Intermetallic compounds and catalysts containing them |
GB2182047B (en) * | 1985-10-25 | 1990-01-17 | Nat Distillers Chem Corp | Intermetallic compounds and olefin polymerization catalysts containing them. |
US5688887A (en) * | 1992-05-26 | 1997-11-18 | Amoco Corporation | Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture |
US6043401A (en) * | 1992-05-26 | 2000-03-28 | Bp Amoco Corporation | Reactive, low molecular weight, viscous poly(1-olefins) and copoly(1-olefins) and their method of manufacture |
EP0894098A1 (en) * | 1996-04-15 | 1999-02-03 | Mobil Oil Corporation | High impact lldpe films |
EP0894098A4 (en) * | 1996-04-15 | 2001-01-24 | Mobil Oil Corp | High impact lldpe films |
WO2001000685A2 (en) * | 1999-06-30 | 2001-01-04 | Union Carbide Chemicals & Plastics Technology Corporation | Mixed metal alkoxide complexes and polymerization catalysts made therefrom |
WO2001000685A3 (en) * | 1999-06-30 | 2002-06-20 | Union Carbide Chem Plastic | Mixed metal alkoxide complexes and polymerization catalysts made therefrom |
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Legal Events
Date | Code | Title | Description |
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PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19951124 |