CA2063375C - Catalyst component for making primarily isotactic elastomeric polypropylene or polybutene - Google Patents
Catalyst component for making primarily isotactic elastomeric polypropylene or polybutene Download PDFInfo
- Publication number
- CA2063375C CA2063375C CA002063375A CA2063375A CA2063375C CA 2063375 C CA2063375 C CA 2063375C CA 002063375 A CA002063375 A CA 002063375A CA 2063375 A CA2063375 A CA 2063375A CA 2063375 C CA2063375 C CA 2063375C
- Authority
- CA
- Canada
- Prior art keywords
- catalyst
- magnesium
- isotactic
- veratrole
- polypropylene
- 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.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- -1 polypropylene Polymers 0.000 title claims abstract description 52
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 38
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 38
- 229920001083 polybutene Polymers 0.000 title claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 40
- 239000011777 magnesium Substances 0.000 claims abstract description 28
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 25
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 23
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 150000004703 alkoxides Chemical class 0.000 claims description 8
- CRUILBNAQILVHZ-UHFFFAOYSA-N 1,2,3-trimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1OC CRUILBNAQILVHZ-UHFFFAOYSA-N 0.000 claims description 5
- WMXFNCKPYCAIQW-UHFFFAOYSA-N 1,2-dimethoxy-3-methylbenzene Chemical compound COC1=CC=CC(C)=C1OC WMXFNCKPYCAIQW-UHFFFAOYSA-N 0.000 claims description 5
- AGIQIOSHSMJYJP-UHFFFAOYSA-N 1,2,4-Trimethoxybenzene Chemical compound COC1=CC=C(OC)C(OC)=C1 AGIQIOSHSMJYJP-UHFFFAOYSA-N 0.000 claims description 4
- YFWBUVZWCBFSQN-UHFFFAOYSA-N 1,2-dimethoxy-4-nitrobenzene Chemical compound COC1=CC=C([N+]([O-])=O)C=C1OC YFWBUVZWCBFSQN-UHFFFAOYSA-N 0.000 claims description 3
- RVDLHGSZWAELAU-UHFFFAOYSA-N 5-tert-butylthiophene-2-carbonyl chloride Chemical group CC(C)(C)C1=CC=C(C(Cl)=O)S1 RVDLHGSZWAELAU-UHFFFAOYSA-N 0.000 claims 2
- 150000008282 halocarbons Chemical class 0.000 claims 2
- 229920000642 polymer Polymers 0.000 abstract description 43
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 abstract description 30
- 238000000034 method Methods 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 description 18
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 13
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 12
- 239000000178 monomer Substances 0.000 description 11
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 125000003118 aryl group Chemical group 0.000 description 8
- 229910052736 halogen Inorganic materials 0.000 description 8
- 150000002367 halogens Chemical class 0.000 description 8
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000008096 xylene Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 6
- 239000003085 diluting agent Substances 0.000 description 6
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 6
- 150000005826 halohydrocarbons Chemical class 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 5
- 239000001273 butane Substances 0.000 description 5
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 5
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 5
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinyl group Chemical group C1(O)=CC(O)=CC=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 4
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- JZBJIXRVUYHAQC-AOOOYVTPSA-N bis(2-methylpropyl) (2s,3r)-2,3-bis(sulfanyl)butanedioate Chemical compound CC(C)COC(=O)[C@@H](S)[C@@H](S)C(=O)OCC(C)C JZBJIXRVUYHAQC-AOOOYVTPSA-N 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- JFSCHMREAGZEOZ-UHFFFAOYSA-J chlorobenzene;tetrachlorotitanium Chemical compound Cl[Ti](Cl)(Cl)Cl.ClC1=CC=CC=C1 JFSCHMREAGZEOZ-UHFFFAOYSA-J 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- NHYFIJRXGOQNFS-UHFFFAOYSA-N dimethoxy-bis(2-methylpropyl)silane Chemical compound CC(C)C[Si](OC)(CC(C)C)OC NHYFIJRXGOQNFS-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 3
- 230000026030 halogenation Effects 0.000 description 3
- 238000005658 halogenation reaction Methods 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 150000002681 magnesium compounds Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 3
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229920001580 isotactic polymer Polymers 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- 235000010446 mineral oil Nutrition 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FNAIRYWIXALZFN-UHFFFAOYSA-N 1,1,1-trichloro-8-fluorooctane Chemical compound FCCCCCCCC(Cl)(Cl)Cl FNAIRYWIXALZFN-UHFFFAOYSA-N 0.000 description 1
- AVGQTJUPLKNPQP-UHFFFAOYSA-N 1,1,1-trichloropropane Chemical compound CCC(Cl)(Cl)Cl AVGQTJUPLKNPQP-UHFFFAOYSA-N 0.000 description 1
- DAIRXERGRJFMSC-UHFFFAOYSA-N 1,1,2-trichlorocyclohexane Chemical compound ClC1CCCCC1(Cl)Cl DAIRXERGRJFMSC-UHFFFAOYSA-N 0.000 description 1
- SEQRDAAUNCRFIT-UHFFFAOYSA-N 1,1-dichlorobutane Chemical compound CCCC(Cl)Cl SEQRDAAUNCRFIT-UHFFFAOYSA-N 0.000 description 1
- BRMUZICLDKLMTA-UHFFFAOYSA-N 1,2,3,6-tetramethyl-2h-pyrazine Chemical compound CC1N(C)C(C)=CN=C1C BRMUZICLDKLMTA-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- HEXGQYBAXAYZSP-UHFFFAOYSA-N 1,2-dibromo-1,1-difluorodecane Chemical compound CCCCCCCCC(Br)C(F)(F)Br HEXGQYBAXAYZSP-UHFFFAOYSA-N 0.000 description 1
- CSOWEPYJECMZOB-UHFFFAOYSA-N 1,2-dibromo-3,4-dichlorobenzene Chemical compound ClC1=CC=C(Br)C(Br)=C1Cl CSOWEPYJECMZOB-UHFFFAOYSA-N 0.000 description 1
- WARMPXOYOFFCPJ-UHFFFAOYSA-N 1,2-dimethoxy-3-methylbenzene Chemical compound COC1=C(C=CC=C1OC)C.CC1=C(C(=CC=C1)OC)OC WARMPXOYOFFCPJ-UHFFFAOYSA-N 0.000 description 1
- KPZGRMZPZLOPBS-UHFFFAOYSA-N 1,3-dichloro-2,2-bis(chloromethyl)propane Chemical compound ClCC(CCl)(CCl)CCl KPZGRMZPZLOPBS-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- RGPYMYQHGXCBPN-UHFFFAOYSA-N 1-methoxy-2-(methoxymethoxy)benzene Chemical compound COCOC1=CC=CC=C1OC RGPYMYQHGXCBPN-UHFFFAOYSA-N 0.000 description 1
- AKEUNCKRJATALU-UHFFFAOYSA-N 2,6-dihydroxybenzoic acid Chemical compound OC(=O)C1=C(O)C=CC=C1O AKEUNCKRJATALU-UHFFFAOYSA-N 0.000 description 1
- CNCNCAJAVNVOKY-UHFFFAOYSA-N 2-(2-methylbutan-2-yloxy)-2-oxoacetic acid Chemical compound CCC(C)(C)OC(=O)C(O)=O CNCNCAJAVNVOKY-UHFFFAOYSA-N 0.000 description 1
- UUGLJVMIFJNVFH-UHFFFAOYSA-N Benzoesaeure-n-hexylester Natural products CCCCCCOC(=O)C1=CC=CC=C1 UUGLJVMIFJNVFH-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- GAKBIFMUIMALON-UHFFFAOYSA-N CC(C)(C)CC(C)(Cl)C(Cl)(Cl)Cl Chemical compound CC(C)(C)CC(C)(Cl)C(Cl)(Cl)Cl GAKBIFMUIMALON-UHFFFAOYSA-N 0.000 description 1
- HEYWGIVDJPKIAQ-UHFFFAOYSA-N CCCCO[Mg]CC Chemical compound CCCCO[Mg]CC HEYWGIVDJPKIAQ-UHFFFAOYSA-N 0.000 description 1
- PRGODONYKGPBHC-UHFFFAOYSA-M CC[Mg+].[O-]C1=CC=CC=C1 Chemical compound CC[Mg+].[O-]C1=CC=CC=C1 PRGODONYKGPBHC-UHFFFAOYSA-M 0.000 description 1
- 101710180366 CDP-L-myo-inositol myo-inositolphosphotransferase Proteins 0.000 description 1
- MKRWRDGSPKNSAV-UHFFFAOYSA-N COC1=C(C(=CC=C1)OC)OC.COC1=C(C(=CC=C1)OC)OC Chemical compound COC1=C(C(=CC=C1)OC)OC.COC1=C(C(=CC=C1)OC)OC MKRWRDGSPKNSAV-UHFFFAOYSA-N 0.000 description 1
- XJMIQUFUMNHCTG-UHFFFAOYSA-N COC1=C(C=C(C=C1)OC)OC.COC=1C=C(C(=CC1)OC)OC Chemical compound COC1=C(C=C(C=C1)OC)OC.COC=1C=C(C(=CC1)OC)OC XJMIQUFUMNHCTG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- ZKVZQCMQYLOZNX-UHFFFAOYSA-N ClC1=CC=CC=C1.Cl.Cl.Cl.Cl Chemical compound ClC1=CC=CC=C1.Cl.Cl.Cl.Cl ZKVZQCMQYLOZNX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 1
- 241001331845 Equus asinus x caballus Species 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 241000212342 Sium Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- CJWANOYUFBSCHS-UHFFFAOYSA-L [Br-].[Br-].CCO[Ti+2]OCC Chemical compound [Br-].[Br-].CCO[Ti+2]OCC CJWANOYUFBSCHS-UHFFFAOYSA-L 0.000 description 1
- MJAANYBZHGEMLW-UHFFFAOYSA-K [I-].[I-].[I-].CC(C)O[Ti+3] Chemical compound [I-].[I-].[I-].CC(C)O[Ti+3] MJAANYBZHGEMLW-UHFFFAOYSA-K 0.000 description 1
- ADSXDBCZNVXTRD-UHFFFAOYSA-N [Mg]C1=CC=CC=C1 Chemical compound [Mg]C1=CC=CC=C1 ADSXDBCZNVXTRD-UHFFFAOYSA-N 0.000 description 1
- ABXDUVOCXLVBNG-UHFFFAOYSA-M [Ti]OC1=CC=CC=C1 Chemical compound [Ti]OC1=CC=CC=C1 ABXDUVOCXLVBNG-UHFFFAOYSA-M 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 229920001585 atactic polymer Polymers 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000013527 bean curd Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 description 1
- JBSLOWBPDRZSMB-FPLPWBNLSA-N dibutyl (z)-but-2-enedioate Chemical compound CCCCOC(=O)\C=C/C(=O)OCCCC JBSLOWBPDRZSMB-FPLPWBNLSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 1
- QMCVOSQFZZCSLN-VAWYXSNFSA-N dihexyl (e)-but-2-enedioate Chemical compound CCCCCCOC(=O)\C=C\C(=O)OCCCCCC QMCVOSQFZZCSLN-VAWYXSNFSA-N 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- ZVJXKUWNRVOUTI-UHFFFAOYSA-N ethoxy(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(OCC)C1=CC=CC=C1 ZVJXKUWNRVOUTI-UHFFFAOYSA-N 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- JJOYCHKVKWDMEA-UHFFFAOYSA-N ethyl cyclohexanecarboxylate Chemical compound CCOC(=O)C1CCCCC1 JJOYCHKVKWDMEA-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- IXUQHZKXQCGDFB-UHFFFAOYSA-M magnesium;2-methylpropan-1-olate;chloride Chemical compound [Mg+2].[Cl-].CC(C)C[O-] IXUQHZKXQCGDFB-UHFFFAOYSA-M 0.000 description 1
- CRGZYKWWYNQGEC-UHFFFAOYSA-N magnesium;methanolate Chemical compound [Mg+2].[O-]C.[O-]C CRGZYKWWYNQGEC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 150000008039 phosphoramides Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QMKUYPGVVVLYSR-UHFFFAOYSA-N propyl 2,2-dimethylpropanoate Chemical compound CCCOC(=O)C(C)(C)C QMKUYPGVVVLYSR-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- OUULRIDHGPHMNQ-UHFFFAOYSA-N stibane Chemical class [SbH3] OUULRIDHGPHMNQ-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920001576 syndiotactic polymer Polymers 0.000 description 1
- FINHMKGKINIASC-UHFFFAOYSA-N tetramethyl-pyrazine Natural products CC1=NC(C)=C(C)N=C1C FINHMKGKINIASC-UHFFFAOYSA-N 0.000 description 1
- ZLMGMVJGEULFPP-UHFFFAOYSA-J titanium(4+) trichloride phenoxide Chemical compound Cl[Ti](Cl)(Cl)OC1=CC=CC=C1 ZLMGMVJGEULFPP-UHFFFAOYSA-J 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- 229940030010 trimethoxybenzene Drugs 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/04—Monomers containing three or four carbon atoms
- C08F10/08—Butenes
Abstract
A catalyst component and catalyst composition useful in the production of elastomeric, primarily isotactic polypropylene and polybutene is disclosed and it comprises the reaction product of a magnesium alkoxide compound and a tetravalent titanium halide wherein the reaction takes place in the presence of an electron donor selected from the group consisting of veratrole and derivatives thereof. The invention also relates to a process for producing such polymers using the above catalyst.
Description
WO 91/00875 ' Z ~ .~ ~''~:,~ p~/tJS90/02037 h.
.. , 1 , Description CATALYST COMPONENT FOR MAKING
PRIMARILY ISOTACTIC ELASTOMERIC POLYPROPYLENE OR
POLYBUTENE
Technical 'Field ' This invention relates to a catalyst which is useful in the production of elastomeric, primarily isotactic polyolefins and a process for producing such polymers using said catalyst.
Background Art U.S. Patent 4,335,225,. issued 3une 15, 1982y discloses a fractionable elastic polypropylene which is said to have an isotactic content of 55% or less and also to contain some syndiotactic and atactic polypropylene. This : patent~.~and its companions on the catalyst system for making this elastic polypropylene, contain much information about elastic type polypropylene compositions, although the researchers. at Monteaatini, especially including Giul~io. Natta,., produced; same vpolypropylene -: .
.compositions,which exhibited the same ~~elastomerid::characteristics. : Specifically, U.S.
Patents,3,175,999; 3,257,370 and 3,258,455.
disclose-polypropylene compositions..which have elastic type properties..,.,:, .Simi~lar,ly.~ahe .;,;,.:researchers."at;Standard:,0il,,especially, ;;including .,Ronald-,Emrick;;;,had produced .~,,,;;;,;
polypropylene,oompasiti,ons"which exhibited the , 71;~«: same;,elastomeric characteristics : ~~ Specif ically ~:; , ~U:5. ;~I?atent;3.; 278,512discloses ;prima~ily_; .,_, ;~,r.; ~ ~,~.i,eotactie::pol.ypropylene-;compositions ,which have x;;elastic.~:~Ype ~propexties._:~~~:; t~e~~r,.,~~~c;E:~~~ .~~. c.:::f~ ; ~.
~:a Elastomeric .polypr.opylene is different:;from:Y:
" '.::i . . , , .. .:' : : ~ ,. ., wo 9~roos~s ~ fl ~'~ ~''~. ~ ~C'rrus9oro2o37 ~y:::
.. , 1 , Description CATALYST COMPONENT FOR MAKING
PRIMARILY ISOTACTIC ELASTOMERIC POLYPROPYLENE OR
POLYBUTENE
Technical 'Field ' This invention relates to a catalyst which is useful in the production of elastomeric, primarily isotactic polyolefins and a process for producing such polymers using said catalyst.
Background Art U.S. Patent 4,335,225,. issued 3une 15, 1982y discloses a fractionable elastic polypropylene which is said to have an isotactic content of 55% or less and also to contain some syndiotactic and atactic polypropylene. This : patent~.~and its companions on the catalyst system for making this elastic polypropylene, contain much information about elastic type polypropylene compositions, although the researchers. at Monteaatini, especially including Giul~io. Natta,., produced; same vpolypropylene -: .
.compositions,which exhibited the same ~~elastomerid::characteristics. : Specifically, U.S.
Patents,3,175,999; 3,257,370 and 3,258,455.
disclose-polypropylene compositions..which have elastic type properties..,.,:, .Simi~lar,ly.~ahe .;,;,.:researchers."at;Standard:,0il,,especially, ;;including .,Ronald-,Emrick;;;,had produced .~,,,;;;,;
polypropylene,oompasiti,ons"which exhibited the , 71;~«: same;,elastomeric characteristics : ~~ Specif ically ~:; , ~U:5. ;~I?atent;3.; 278,512discloses ;prima~ily_; .,_, ;~,r.; ~ ~,~.i,eotactie::pol.ypropylene-;compositions ,which have x;;elastic.~:~Ype ~propexties._:~~~:; t~e~~r,.,~~~c;E:~~~ .~~. c.:::f~ ; ~.
~:a Elastomeric .polypr.opylene is different:;from:Y:
" '.::i . . , , .. .:' : : ~ ,. ., wo 9~roos~s ~ fl ~'~ ~''~. ~ ~C'rrus9oro2o37 ~y:::
the "normal" or more well known polypropylenes.
These more well known types are crystalline and amorphous polypropylenes. It is normally accepted that crystalline,polypropylerie' generally has the isotactic or syndiotactic structure and that amorphous.polypropylene .
generally has considerable atactic (sometimes designated as heterotactic) structure. Giulio Natta's U.~. Patents 3,222,300 and 3,212,302 describe isotactic polypropylene and give structural formulae for isotactic and syndiotactic polypropylene. The former is a straight chain of propylene units wherein the methyl groups are all, aligned on one side of the 25 polymer chain. In the latter, the methyl groups alternate from one side of the chain to the other, In atactic (heterotactic) polypropylene, the methyl groups are arranged randomly on the two sides of the chain.
20 Almost all of the polypropylene which, is used commercially is highly crystalline..:.
polypropylene~.w,...These products are :wellv :known and have been. the subject of many patentsvand articles.Amorphous polypropylenes, which have 25 very'little strength, are used commeraialTy primarily in'adhesives and asphalt additives.
Disclosure''~of ~-the Invention : ' t :.. , ....,., :;s ..:;
The present invention 'relates ~to'~aa'catalyst admponent -rahicli 'is ~ useful '~in'-~tlie ~productiozi -of 30 '~'elastomeric, ~~low vcrystallinity, ''primarily ~~v''"
'.".".~~.isotaotic polymers=:of~=propylane='and~-butene~~~ xhe ~~
catalystv'component'~romp~ises ; a ~ magnesium halide ' >°%~;~which ~may~~be-~the~=?reactionaproduct'tofu"'magnesium alkoxide compound whichfmay~be'~of~?the~-formula 35n;a:> ~: ::Mg (R~y x~(R2yz-X;~ Where:L.R; ~ is' ~an alkoxide or aryl ewo 9iioos~s 2~(~ ~ ~ ~,'~ ~ ~.: PCT/US90/02037 oxide group and Rz is an alkoxide or aryl oxide group or halogen or other anion, and 0<x<2, and a tetravalent titanium halide wherein the reaction takes place in the presence of an.
5electron donor selected from the group consisting of veratrole and derivatives thereof which have essentially non-reactive substituents such as CZ-C1~ alkyl, C6-Coo aryl, halogen and methoxy. .
This invention also relates to a catalyst composition which comprises the reaction product described above and an organoaluminum compound.
Finally, the invention relates to a process for the production of such elastomeric, primarily isotactic polymers by polymerizing propylene. or butene in the presence of such a catalyst.
Best Mode for Carr~ing~ Out the Invention ' The "normal" well known polypropylenes discussed above are generally high molecular weight materials which consist of blocks of monomer units of relatively.or extremely long averagewisotacti:c blobk "1-ehgth "(<L~so>} , for~-example,' 50 to 200 monomer :units.":The prior art .::isotactic' polymers .(prepared via an MgClZ
supported catalyst) of short--average isotactic block '-Length '(about '6 t~o 15 monomer units) are characterized by having relatively.low tensile ~: 'strength : and being tacky ao the ~.touch~ and thus are presumed to contain'~na ~wide'~.'di'stributiari 'of ' polymer:' . .blocks',of~'.varying.lengths. -: . . , r.;~.~::u~r .
:'nf.L ., :1;11 J ' '9i=:-,°.L
' The ='elastome~ic .polypropylene' and .v~
.~ polybutane.v:compositinns:::of the present invention :~~: ~~ are .~.sp~cif icahly :=characterized as being =of =', '~~:?s~relatively high tensile'fstarength arid=':non~tacky 35v,.. :.to:r>.~he~:touchy.:a.characteristics::.which~Ymay .'be v- ...
WO 91100$75 ~ ~ ~ ~ . ~ . PCTlUS90/02037 ..:: ;
,.,:_ . , attributed to a narrow distribution of relatively short block lengths. By '°block length" it is meant the number of stereoregular , monomer (in this case propylene or butene) insertions which occur before there is:a defect in the polymer chain. By "defect" it is meant that the symmetry of the recurring units is ended and there may begin a different structure (e.g. a change from isotactic to syndiotactic or ZO to heterotactic) or units of another monomer may be placed therein. The average block length is determined by a numerical integration of the pentads which occur in the ~3C NMR spectrum (Polymer Seauence Determination: Carbon-13 NMR
Method, James C. Randall, Academic Press, NY, 1977). It is theorized that the average block length-has a great effect on the properties of the polymer. For instance, relatively short ' average block lengths, i.e. 7 to 12 monomer.
units, tend to occur in a flexible and rubbery polymer which exhibits. good elastic properties and_; is, relatively ,strong. ; On the-..other::hand, block lengths of .greater, than, about 50_are characteristic.of commercial, very stiff.., highly ~ crystalline isotactic polypropylene.- ~ : . . _....
. ~.U. S. Patent 4-,.335, 225,' discussed .above, v ,diSCIOSeS ~ how .to :make an ~.elastomeric.:-:: ::. :: ::v.::
polypropylene composition which oontains::,up .to X55%,' :and preferably :mu.ch ::,less; ..isotactic. . , .
polypropylene; ;,::This c.polypropylene ,;,as .--a,a ',r.~: ; ~: ~:
inherent~eviscosity~~.:of.;:l~.5 ,.to. 8, ;::a ;major melting .., ,. poilxt .between' 135 and :;155°C,v exhibits; no;.-.yield point,v~;has a ~:; tensile ,set not ;exceeding .15o% and d~:.v,co~tains y:10 to-.,80% ;°by,:,weight ,of..ua e~iethyl tether .
soluble;sfractionv.-.which~~has,;.anuinherent-~wiscosityrt::
W~ 91100875 ~ ~ ~ ~ ~ ~ ~ '-. PCT/iJS90t02037 exceeding 1.5 wherein said fraction has an isotactic crystalline content of about 0.5% to about 5% by weight. A special catalyst, which is the subject of several other related patents, 5 is said to be required to make this material. j These catalyst are homogeneous zirconium or hafnium catalysts supported upon partially hydrated alumina. Such catalyst systems are difficult to work with, have extremely low 20 productivities (on the order of Z-3o of the productivities of the catalysts of this invention) and are not used commercially to any appreciable extent.
The polypropylenes and polybutenes.of the present invention are made with a catalyst system for which there is a wealth of analogous commercial experience and..knowledge. In one embodiment the catalyst is comprised of the reaction productvof a magnesium alkoxide compound which may be of the formula Mg(R~)x(Rz)z-X, .where Ri is .anlkoxide or aryl oxide group and Rz r~is :van alkoxide ~~or,,aryl roxide .group or.°halogen or. other. anion;:andv0<x<_2, and a tetravalent:
titanium hahide.wherein the:reaationwaakes place in the presence of-an.electron donor and, ;~. : optionally, ..a halogena~ted hydrocarbon. . .Such r~:~w°~: catalysts':are welh.~ k.nownv.and have been ~used~~for several'~.'years ~cornmeroially:rr:~ The rpresent ~;::
catalys'~':.'uses~~'~an..'.el~ctron~:~donor .which; has. not been heretofore rdisclosed ~for::use~~in ..this : type ,:~ v ~
°of. 'catalyst:'. i : onew:electron:rdonor : ~ihiah :may gibe usad:~'~in-::order. ~tovmake ~ahe:~'polypropylene :; ~. :n s compositions of -ahe_:-present ::invention ..is. : ::.~
~°i.i~eratrole (:or ~avderivati~ie whereof o~~~xSuitable :<'derivatives-iinclude:3-methylveratrole<.-.(Z,3-.t ~-?_;
wo 9maos~~ ~ ~.~ ~ ~ '~ ~. . PCT/US90/02037 ;-'..
dimethoxytoluene), 3-methoxyveratrole (1,2,3°
trimethoxybenzene), 4-nitroveratrole and 4-methoxyveratrole (1,2,4-trimethoxybenzene). The catalyst is completed by the addition of an organoaluminum compound and, optionally, a selectivity control agent.
Veratrole has been mentioned previously as an electron donor (U.S. 4,107,414) and a selectivity control agent (U.S. 4,107,413) for specific catalyst systems to prepare highly stereoregular conventional..polypropylene.
Therefore, it is surprising to observe that compound and its derivatives may be used as an electron donor to produce extremely short average block length elastomeric polypropylene and polybutene.
Examples of halogen containing magnesium ' compounds that can be used as starting materials for the halagenating reaction are alkoxy and aryloxy magnesium halides, such as isobutoxy magnesium chloride,.ethoxy magnesium bromide, .;p::phenoxy magnesium::iodide, ~:cumyloxy.~magnesium~.
bromide and naphthenoxy magnesium chloride.., ..... :-~..Preferred.magnesium~compounds to.be::.~:~
halogenated are.selected.:from magnesium r:..
dialkoxides arid:: magnesium .diaryloxides. In: such _ ~:compounds::ahe alkoxide-~groupssuitably. have :from 1 to .8 ~~carbon.;atoms;:. and;~preferably,~from: 2w.to 8 carbon. atoms: :~. Examples~:.of :.these preferred : .
.~:gr.oups :of;.compounds ':'are :magnesium di-;. ,. ~s:: ~.i .:5isopropoxide; c~~magnesium. ~diethoxide; .magnesium dibutoxide;;;:magnesium::diphenoxide;v-magnesium dinaphtherioxide~and.::ethoxy~cmagnesium.~:r~::c:~:c~:a i~sobutoxide::a:-M~gnesiumv:.~alkoxides.~:disclosed yin U:~S. ' Patent'.~~4;:806; 648; ~~issued.v~~'ebruar.y:~l9;:1989 ...
WO 91/00875 ~~~'~;~"~'~-~' PCT/'US90%02037 ..:: ::
y:
to Robert C. Job, are also preferred for use herein. Especially preferred is Mg4 (OCH3) b (CH30H) ~oX2 where X is resorcinol or a substituted resorcinol monoanion.
Magnesium compounds comprising one alkyl group and one alkoxide or aryloxide group can be employed, as well as compounds comprising one aryl group and one alkoxide or aryloxide group.
Examples of such compoW ds are phenyl magnesium y l0 phenoxide, ethyl magnesium butoxide, ethyl magnesium phenoxide and naphthyl magnesium isoamyloxide.
'In the halogenation with a halide of tetravalent titanium, the magnesium compounds are preferably reacted to form a magnesium -halide in which the atomic ratio of halogen to magnesium is at least 1.2. Better results are obtained when the halogenation proceeds are completely, i.e. yielding magnesium halides in which the atomic ratio'of halogen to magnesium v is at least 1.'5.' Except in vaases where r resorcinols °(or ;otheW=plieiiolic nx rsubstituted phenolic compounds)vare used, the most' preferred reactionsv~xe 'those leading to'fully halogeriated reaction products: ~Such~~halogeriation reactions w "are suitably effectedrby"employing=a-molar ratio of ritariium coiripourid tov'magn~sium ~aompound 'of 05. 1 'tci 200: 1 "preferably 1: lw~o"~ 100:2': v v'These halogenation reactians~Y~are'~conduatedr5.n the' ".~aaditinzial''pxesenaeto'f an'~electron ~dorior and may:- , : , '::~ :. iziclude'ethe ~ adaxtionai vpre'sence of a~:a.~ _; r,:~~r« .~
lia~l.ohydroc~~bon.'- '~An ~' inert ~ hyarocaxb'on ' diluent or~'so~.ventLmayy°be used'as~ra"substitute'~fior'°the ;~l:i halohydrocarbon~~'~Alf(~~3nCtLl~, ."~ 'r~,.,r :i i :.':'~:l'!lf.:'... ' v~j''i'~~~~Suitabxe'~h'a~lides~''o~f ~tetraval.ent titanium ~'~
wo 9~ioas~~ ~~y~~ ~.r~ rcriu~9oroao3~
s include a~rjrloxy- or alkoxy di- and trihalides, such as dihexanoxytitanium dichloride, diethoxytitanium dibromide, isopropoxytitanium tri-iodide and phenoxytitanium trichloride.
Titanium tetrahalides are preferred. Most preferred ~is titanium tetrachloride.
Suitable halohydrocarbons are compounds such as butyl chloride, anyl chloride and the following more preferred.compounds. Preferred aliphatic halohydrocarbons are halogen substituted hydrocarbons with 1 to 12, particularly less than 9, carbon atoms per molecule, comprising at least two halogen atoms, such as dibromomethane, trichloromethane, 1,2-dichloroethane, dichlorobutane, 1,1,3-trichloroethane, trichlorocyclohexane, -dichlorcfluoroethane, trichloropropane, trichlorofluorooctane, dibromodifluorodecane, hexachloroethane and tetrachloroisooctane.
,.Carbon tetrachloride and 1,13-trichloroethane are preferred.aliphatic.halohydrocarbons. .
>Aromatic halohydrocarbons..may...also:be.employed, .;...e.,g.n chlorobenzene, bxomobenzene, ., .,.; -dichlorabenzene,, dichlorodibromobenzene, ,, ;. , ., _,inaphthyl ;chloride,,-Achlorotoluane,.- , ,.,.
-dichlorotoluenes,..and,the .like; chlorobenz~na -~and:dichlorobenzene.are preferred aromatic...
.... .. .,. . _, ...., ...__........,:. . . , . ...... , .. . .
r . ~ . .. ' ' C . , ~ ,.
._~;-~halohydrocarbons.,. Chlorobenzene,;is the;, most preferred,,halohydrocarbon:..:.,. :~:; .,a..;:arr. ,,o~:;~;-.
30,~~,~a ~,rr;A; ;Tk~e...~nalagenation normally; proceeds ;.under formation of a.rsolid.reaction.product,which;may "T: be:~ isolated, from. the liquid reaction ~ medium,.= by ' .
.,;l.~il~rat~on., ~decantationy, or a~other~ suitable) method . It may be subsequently ~.washed,,..with,j an f.~ i,nert:,hydrocarbon. diluent,,,, such as:.n-hexane, "' WO 91!00875 PCf/U~90102037 ~~~ ~ 3~3~'~y:
y .
isooctane or toluene, to remove any unreacted material, including physically adsorbed halohydrocarbon.
The product may also be contacted with a tetravalent titanium compound such as a ~ ,.
dialkoxy-titanium dihalide, alkoxy-titanium trihalide, phenoxy-titanium trihalide or titanium tetrahalide. The most preferred titanium compounds are. titanium tetrahalides and especially titanium tetrachloride. This treatment increases the content of titanium tetrachloride in the solid catalyst component.
This increase should preferably be sufficient to achieve a final atomic ratio of chloride~to magnesium in the solid catalyst component of from 1.5 to 2.0, particularly of.from 1:8 to 2.0: To this. purpose the contacting with.the tetravalent titanium compound is most suitably carried out at a temperature of from 60° to 136°
~ during 0.1 to 6 hours, optionally in the presence of an inert hydrocarbon diluent.
.:. Particularly preferred. aontacting.,:periods:. are between 0.5.to.~3~.5 hours: The treatment;may be carried out in successive contacts.of the-solid with separate portions of..vtitanium . _ :a ~:..~':w~. .
tetrachloride ~.. ... . , " . , After the :treatment'with-aetravalent~.~v,::.
v titaniuin~.compound',~=:the catalyst' component:;vis .suitably .°:isolated <from :.the liquid :reactiow,;
medium' and .'wa'shed ?..to. .:remove unreacted ; itanium ~ '°
compound:e:5 The titanium content of vthe rfinal, .. :.;:; :vwashed '.catalyst constituent is auitably:~between , about '1. 5 vto w3 : 5 ~-percent by .weight :or~up.:~to about'~4 Y5 :percent. v~~The:vpreferred halogeri;~atom;
-pos'sibly , contained :~iri'fthe v;magnesium ::compound to::~ ;.
WO 91/00875 PC,'T/US90/02037 2w~~33'~~
_ . . (~~=
be halogenat'ed, and contained in the titanium , compound which serves as halogenating agent and in the tetravalent titanium compound with which .
the halogenated product is contacted, is 5 chlorine..
The material used to wash to catalyst component is an inert, light hydrocarbon liquid.
Preferred light hydrocarbon liquids are aliphatic, alicyclic and aromatic hydrocarbons.
10 Examples of such liquids include isopentane, n-hexane, isooctane and toluene, with isopentane being most preferred. The.amount of light hydrocarbon liquid employed is 5 to 100 cc/gm of catalyst component. in each of 2 to 6 separate washes; preferably about:25 cc/gm. The resulting solid component is the procatalyst, which is-used with cocatalyst and optional selectivity control agent in the polymerization process.
Although the invention is operant without any added selectivity control agent, suitable ~:o-electron donors; :;.which are:. used ~in. combination with:or-reacted with. an.organoaluminum compound . ,..: as .selectivity.° control agents to .retard the.
production::of_ atactic polymer; are..ethers;_ esters, ketones, phenols, amines, amides,v~:.., imines;v;witri~les,: :phosphines; silanes, ;
vphosphites~;~ stibines, .arsines, ~ phosphoramides andalcoholates.: Examples of ;sua.table::donors ~c.~.'.are.;:those::referred:ao °in..:.'U:S.':Patent No:.':;:..:~~::
j .
~9~ f~~42;:~276c~ Preferred :.donors are esters :.and .;~cy:~;organ.ic~sili.con compounds:~:v Preferred;,.ester;s are esters-~of aromatic carboxylic _acids, auch.:as ,;ac~ethylc:and methyl::benzoate, ~p-methoxyrethyl 35~:~1 Fabenzoate; r.;p-.,.,ethoxy:methyl::.benzoate, ~,~p-ethoxy <: . i 'WO 91/00875 ~~ o,~ u'~4~,~ IPCT/US90/02037 ., -~ ':::. ..
.: ...:
ethyl benzoate, ethyl acrylate, methyl methacrylate, ethyl acetate, dimethyl carbanate, dimethyl adipate, dihexyl fumarate, dibutyl maleate, ethylisopropyl oxalate, p-chloroethyl benzoate,.p-amino hexyl benzoate, isopropyl naphthenate, n-amyl toluate, ethyl cyclohexanoate, propyl pivalate. Examples of the organic silicon compounds useful.herein include alkoxysilanes,and aryloxysilanes..of the general formula R~~Si(ORZ)4_n where n is between, zero and three, R1 is a hydrocarbon group or a halogen atom and RZ is a hydrocarbon group.
Specific examples include 'trimethylmethoxysilane,.triphenylethoxysilane, dimethyldimethoxysilane,.phenyltrimethoxysilane and the like. The donor used as selectivity control agent in the total catalyst.may.also be the same as the donor used fog preparing the titanium. containing (procatalyst) constituent., Preferred as selectivity control agent in the total catalyst are p-~ethoxy ethyl benzoate, .;r~phenyltr.imethoxysilane,.;..diphenyldimethoxysi,lane and;diisobutyldimethoxysil.ane. . ., . , The, organoaluminum._compound 'to be.,employed as ..cocatalyst,. _may be . chosen from ,any, ;o~ ,the known..activators in ohefin.polymerization catalyst, systems ,compri.sing ,a ;titanium halide ;abut :,is..most ;.suitably free _of, hal,oqens. ~",Whi,l.e .,,aluminum..trialkyl...compounds,, :dialkylaluminum , ;,;halides .and dialkylalumi,num,allcoxides..may...be , ,used, waluminumtrialkya;..,compounds .,ax;e.,pr,eferred, ~particularly;,those ..wherein,:each . of .ahe alkyl.
,.:.?,groups:.:has7l;to,~6 'carbon atoms; ~e~.,g;,,, :'. .
~,,.; f;rjtxiethxlalumW um t., trig?n~°,propyl~;luminum,~tri-35.; "fisobutylaluminuzn, ;~riisopxopylaluminum~.and.;.~ y .. ... , .; ". , . . . a , P~I"/US90/02037 wo 91 /oo~7s ~ ~ n. ~ ~ v ~ a ,, dibutyl-n-amylaluminum.
Suitable~electron donors for use in the production of the elastomeric, primarily isotactic polymers of the present invention include veratrole and derivatives thereof which have essentially non-reactive substituants suoh as Cz-C1o alkyl, C6-Coo aryl, halogen and methoxy.
Veratrole is otherwise known as l,2-dimethoxybenzene: Veratrol derivatives which may be used are 3-methylveratrole (2,3-dimethoxytoluene), 3-methoxyveratrole (1,2,3-trimethoxybenzene), 4-nitroveratrole-and 4-methoxyveratrole (1,2,4-trimethoxybenzene). The preferred electron donors are 4-methoxyveratrole and 3-methylveratrole because they yield catalysts which produce polymer with the highest . tensile strengths.
To prepare the final polymerization y .
catalyst composition, pracatalyst; cocatalyst and optional selectivity control agent may be simply combined, most suitably employing a~ molar vrati,of'to 'produce''~iri °~the'~finalcatalyst an 'atomic ratio of aluminum to'-titanium of from'lvto 150, and' suitably from' about l0~rto -about 150 .
Increasing' the Al:Ti ~~atio tends ~to sl'ightly ~ w increase catalyst activity at thevexpense~~of 'increased ~ catalyst. residue in the 'une~tx~aa~ed i 'product:w Thiese factors will ~e =considered in selecting the xAl : Vii: '~~xatio J~for ~ ariy "given '-p~ooess arid'vdesi'red 'product~'~ eIn 'general, -Al:Ti 'ratios >::,i~y.:th~:'rrarige of'~30:1'~~arid''100:1~'and yespecially of about 50:~1rto 80'i,~will' be~'foundtadvaritageous:
Polyme~izatiori nf-~propylene°o~''buterie~=inay kie~~~aonductec'!'-witNrth'e~'catalyats'of the-viriv~ntion inw''a~~'liquid''°sj~st~emvwith~° an inert~''diluent~-~r'"such as~ ~ . , W~ 91/00875 r. ~ ~ ~ y ~ r, ~ ':,. PC1C/LJS90/02037 (.,,, , ,., a paraffinic liquid of 3 to 15 carbon atoms per molecule, or in a liquid system containing propylene or butane as sole diluent or together with a small amount of propane or butane, or in vapor phase . -Propylene polymerization in liquid phase is conducted at a temperature of 50° to 80°C and at a pressure sufficient to maintain ' liquid conditions. In a continuous reaction system, the liquid in the reaction zone~is -maintained at reaction conditions, monomer is continuously charged to the reaction zone, catalyst components are also charged continuously-or at frequent intervals to the reaction zone, and reaction mixture containing polymer is withdrawn from the reaction zone continuously or at frequent intervals.
In propylene or butane polymerization, the ' reaction mixture is typically maintained at conditions at which~the polymer is produced as a slurry i,n the reaction mixture. The catalyst systems of this invention are extremely active -~v~and 'Wighly-v specif is in propylene -polymerization, sovthat no'removal of catalyst components or of atactic~polymervfrom~the-polymer product"is'=
~required~ . ... .. ~w ,.. . . ... _ While~thercatalysts of this invention ors:
particularlyxadapted fog=use~in~cont~.nuous polymerization systeins';''they~ inay", 'n~ ~~course;~~?
also"~be'vmployed ~' iiiv batcWpolymerization:-~'a'This ..: . . . , ~. ~ , ; ~, , y 3 0 may; be,, o.~, ,advantage' ~~in' mule.-stage: ~ ~ .:::;.; ~~, ~; a 'po~Tyinerizatxori~'-iri' whiahvpropylehe' polymers~'and propylene'~=ethy7:'ene"'polyitier's '-'are produced in;-' r r j~' separate W eaGtiori- zones ~~a~ranged -'~n~ ~~sequence~.
...., .L.'.i..3f, id ~la.:~'; c".':~
'xt' is ~wellr-ki~owri~ .than supported ~"coot'di.iiatioin'°procatalystsv-~amd cataljrst' syst'eims - -dV0 91/00875 PG'f/US90/02037 ~~!. i:
2063~~a ~ ,.:
of the type used' herein are highly sensitive, in -varying degrees, to catalyst poisons such as moisture, oxygen, carbon oxides, acetylenic .
compounds and sulfur;,compounds. It will be understood that. in the practice. of this invention,.as well as in the following examples, both the equipment_and the reagents and diluents are carefully,dried and free of.potential catalyst poisons. . ~.
20 The productivity.of the catalyst is.
determined as kg polymer/g procatalyst in a standard one hour batch reaction; it may also be expressed as kg polymer/g Ti. Catalyst activity is sometimes reported as kg polymer/g Z5 procatalyst or Ti/hr. If determined in a standard.one hour test, activity thus is numerically the same as productivity.
The specificity towards average isotacti.c ' block length may be determined by measuring the 20 amount of .xylene soluble polymer,(XS), in ,accordance_,with regulations of the U.S. Food.and :~,Drug,~Administration.-..,The XS ,test :is carried out _-as_.follows::.-_The.sample is completely dissolved in ,xylene~.in a:,stirred ,flask-.by, heating.-a~t ..
25 reflux. The flask is then immersed in,a water ,,,bath,at:25°C tr~ithout stirring "fox.,..one ,hour, during, which: a l precipitate,..is ., formed,. ; :,,The ; .;
-. . . , . , :. . , . , precipitate is;filtered..,off,and,~.the, so;lubles.
:~.::Presen~~.:in': the, :f i~,trate., are' determined.,by; ., .. :, . . , . , . ., ., . ..: , 30 evaporating,-a,;20.. mZ~ aliquot of.l Nthe, filtrate, ,. , ; , "dryinga~;~he: res,~due;.under,;:vacuum, 'and weighing the resi.due~, ,The~-xyleneY,.solubles.,may, also ~_-,include some ;amorpkzous and low~~,~molecular...;weight _ ; . . _~-..... _. ,...
crystalline: ,mate~,ia~,..t~ Ttie,;dcairable numerical ,.: ~ ..... .. .....~,. ....
35 _.~yalue of :XS f;or rthe .. ro lene ~homo of mers .of ~
.. _, :P . ._ PY . : P. . . Y _ = .: .. , i WO 91/00875 '~ ~ ~ ~ ~ ~ ~ PGT/US90102037 ..
this indention is typically between about 35%
and about 85%.
We have found that is highly advantageous to..make a polymer which is characterized by 5 average isotactic block lengths which are i relatively short (on the order of 7 to 20 monomer units) when compared to commonly known crystalline-and amorphous polypropylenes or ;
polybutenes. Average block-lengths are 10 determined by numerical. analysis, of the pentads observed in the ~~C NMR spectrum (see Polymer Sequence Determination, Carbon-13 NMR Method by James C. Randall, Academic Press, NY, 1977).
Such polymers generally have block lengths in 15 the range of 50 to 200 monomer units. It is also highly. advantageous to have a narrow distribution .of.block lengths.. This is not a characteristic of commonly known amorphous polypropylenes which, although they have ..
relatively low average,bl,ock lengths,,generally have a wide distribution of block lengths.. and contain much jr;atactic material ;,.as ~:.sug,gested ,,by their low tensile strength per unit, block length and high tackiness.:to,the..touch. .It is aheorized that it-,is ahe narrow distribution of . v low average block length that.imparts~to the polymers of this:.,inven~ion high:-tensile strength .. , . ~:, per unit ~block..le~gir,h. ;~:;:,n: ......;~:~.'1:' ' ", ,~;The~~short.;block;a~lengtrhs are:~important because,;; they allowa f gr~~ the;~,incorporatiop.: of :; ,, ,..
. . . , .. ... . , ,elastomeri~: properties.r in; essent~.ally~,.isptactic hpmppolymer:~ ~r~;;Achieying . a.,-~narrow~, distribution of. , ouch:: short:; block-;:;lengths .-is ;.importantw..because ::u-r~essentially,:no atactie.opolymer is~gresent,;and - :,'therefore"~tlae,; ten'sile:_st~ength of::-the.:~polymer isv _;
-' ~ ~ ~ dx ~'~ ~ PCT/US90/02037 1-f .., ~. 6 high and its tackiness to the touch is low.
the polyolefin's~of the present invention primarily comprise isotactic blocks, i.e. -greater than 50% isotactic material makes up the polymer and preferably greater than 60% ' isotactic material is present therein. It is important to'note that even though these polymers contain such high percentages of isotactic material, they do not exhibit the' properties characteristic of crystalline isotactic polypropylene but rather exhibit elastomeric-type properties. , EXAMPLES
~3C Magnetic Resonance spectra were obtained at 235°C on samples dissolved in 1,2,4-trichlorobenzene. The spectrum reference was the mmmm methyl group assigned at 21:68 ppm for polypropylene and 27.64 ppm for the CHz of the ethyl branch of polybutene. The pentad analyses were carried out utilizing-the following formulae: - . _ .r. ._ y:~I~::~:,~'%Isotactic _ -(mmmm''~~1 ~5~'=mmmr)°/ (total' .
-..~ ~wresanances ) X - 100 % . .. . . _. ,_- .
(II) L;so = 3 :+..:2~ :;(mmmin/minmr)-" .. .... ...
~ (III )~ ~-%Syndiotactic = ' (rrrr =+ 1:'5 -rrrm) / (total ._. rescinances) °:X 100% ~~' v _. . ,. ., .
'-~~' ' (IV)' ''L~y~' =-'3 ~'+'~:2 (rrrr/rrrm): _. a w .
(V) %Defects = 100% -~'%Iso'_:e.%ygyn ~ :.,., " ~ .
,::::.Iri:>n~dex °to"prepare'~'samplesvfor ~~tensile measuxements;~~'about ~ 60vg°' of~7the ~olymer~taas ~- ~ ~~'bl~ended'; in v a' Brabender a iniXer ~'at ~ 190°C~~with ' 0 .
3 g ~r~~ ~~'ofvAlgga''noit~~ 1010= antiokic~ant':'v'~Afte~ ~ cooling; a f.6m~:X:~:6u"X:;;2inin:iplate was.;fcoinpress~,oiic.mcilded;~at b~204°C''W rider~,'S tons ~ pres'si~~re: -~ Tensile a.barsv~:were 35;.~ .,, then~~cut'~,:from ~~hew plate~.u~sing" a?~!°.D~~.~ die;-~~,;The "i' WO~I/00875 ,~ ~, ~ PCT/US90/02037 . ._ .
1::._. ..
measurement conditions are as described in ASTM
D 412-83. Tensile set is the residual elongation imparted to a sample after stretching to 300% of its original length at a rate of 20 inches per minute and then allowing it to recover to~zero load at that same rate. Tensile at break is the stress required to break the sample at an elongation rate of 20 inches per minute. Elongation at break is the measured elongation at the break condition.
Melt flow index (M.F'.) was determined under ASTM condition ~. (2160 g, 230°C) on a Tinius 0lsen Plastometer. ..
Example 1 2.2 grams of magnesium,ethoxide, 0.5 militers of veratrol.e (1,2-dimethoxybenzene) and 60 milliliters of a.50-50 mixture by volume of titanium tetrachloride-chlorobenzene were stirred for 1 hour at 100°C then filtered. The solid was treated twice with 60 milliliters of a similar., titanium tetrachloride-chlorobenzene ", 'mixture at 110°,C for. 30 .minutes a.nd ..filters,., The solid was washed six times. with 100 ml. portions of isopentane andl.dried;.for,two.hours using a flow of dry nitrogen at,40°C. Three additional catalysts; were prepared: according to this;"
,,;.,,procedure with ,the ,.exc,epti,on that..Ø.2: ml,; 0..3 ml ;,; .,:« ., and 1._0,_ml., respe,ctively,., of, ,..veratrole were employed :in the,."preparation .,..;Table,...1 ;showsi the ,_,:, characteristics ,af :ahe four. catalysts a.ncluding .. ., . .. , , . .. . ..,_ .. .. _. . . . . . , . . , .; , they titanium ~lcading ..which, ~it can,:e, .seen,...., , , . ., . , .. ,, . .., . ..._, . . . ... . ... . ~ , .,~:_L,", decreased, as ~~increasing .amounts, tof vveratro.le >.~ were;;;used thusdemonstratnng a .;str.ong.~:"~ r~~y :; "interaction ~o~ the electron ..donor ,mth ~the~ ;, catalytic site.~'Our experience dictates that WO 91/00875 , :, lower Ti loading is preferable.
Tabla 1 Catalyst Amount of. Veratrole (mll Ti (% wt) A , 0.2 ' ' 5.3 B 0.3 4.2 C 0.5 2.6 D 1.0 2.3 Example 2 Two catalysts were prepared in a manner identical to that given in Example 1 above with the exception that 2,3-dimethoxytoluene was , employed as electron donor instead of veratrole. ~, The titanium loading followed the same trend as in the case of veratrole.
Table 2 ~ w ' ' Catal st Amount of Electron Donor (ml) Ti (% wt) E 0.5 3.7 , .. F 1.0 2.7 Example 3 Approximately 2,200 ml of propylene was wt.ransferred into a 1 gallon stainless steel autoclave along~with 160 mmol of hydrogen and the 'contents were ~~heated ~to 60°C. 60 microliters ' of diphenyldimethoxysilane2.5~~m1 of a-5%
solution of~triethylaluminum in isooctane and ~0.32'ml of a mineral oil~slurry prepared'using 0.5' grams o~ vcatalyst C~lim ~10 ml'~of mineral' oil 'w r were'~injected~vinto the autaclave.v This'°l:~iquid phase palymer'ization~ was caxried out a -'67°C - for a ''~~ ' p'er3.od rod' j~ '.hour ~~.~;,' Th:~. r200': grains '~of s '' ;:~:~ i, .,~~;
~~"''~rpolypropylerie~.:obta'ined.~were~ arialyzed'~b~y.NriIR .
Spectroscopy and~it'wasrdetermined that the 'polypropylene.~compdsition'vias-°72% isotactic with an average~~isotac~ti.'a block4'length of "16'-'and 9%
syridio~tactic ~with~'anvaveracje sjindiotaatic~~block length ~'of f 5 . .. , -~.~ 3 .~:~; a _. ~~; .; z ,~ ~:;~ a:>.~~
WO 91/00875 ~ ~ ~ ~ ~ "~ ~ _. . . PCTI~1S90/02037 The following Examples utilize a magnesium alkoxide compound of the formula:
Mg4 ( OCH3 ) 6 ( CH30H ) to ( 1, 3 -0 ~ OH-C6H4 ) Z ( ' M' , a resorcinolate) which was prepared by the.
dropwise addition of a tetraethoxysilane stabilized'12% magnesium methoxide solution to a solution of resorcinol in methanol. Partial azeotropic desolvation was carried out by slurring 40 grams of M in 300 grams of cyclohexane containing 120 grams of tetraethoxysilane and boiling this mixture until a decrease of 20 'to 30% in solvent volume had occurred. ~.
Example 4 .
The procatalyst was prepared by stirring 7.8 grams of desolvated M with l2,mmoles of 4- .
methoxyveratrole in 200 -ml of a 50-50 .titanium tetrachloride-chlorobenzene solution for 1 hour at 115°C followed by two washes at 115°C with "fresh 200 ml portions. of that solvent mixture followed by a.:quick.rinse (less than l0~minutes) '%raith:100 ml of freshtitanium tetrachloride-:.
chlorobenzene solvent mixture. Excess titanium was removed by exhaustive isopentane rinses and 'the catalyst was dried under moving nitrogen at 40°C. Ti content was 3.55%. A portion of the dry procatalyst powder was. then made into a 5%
slurry in mineral ail.
Tn the following polymerizations, triethylaluminum was used as a 0.28 molar ..
solution in isooctane. Tiisobutyl aluminum was used as a 0.87 molar solution in heptane.
Diethylaluminum chloride was used as a 1.5 molar solution in heptane: In run numbers 6 through 12 selectivity control agents were utilized;
WO 91100875 ~ ~ ~ ~ ~ ~ ~; : ,_ : PCf/US90/02037 ~';
diisobutyldimethoxysilane as the neat liquid and 2,3,4,5-tetramethylpyrazine as a 12% solution in isooctane.
The polymerizations were carried~out by 5 mixing 0.015 to 0.03 mmol of procatalyst plus aluminum alkyl plus SCA and then,..after 20 -. ;
minutes, injecting the mixture into 2.7 liters of liquid propylene in a l.gallon stainless steel autoclave and carrying out the 20 polymerization for 90 minutes at:.67°C for 90' minutes. The polymer lumps were cut into small pieces and dried for several hours under aspirator vacuum at 80°C before physical and chemical characterizations were carried out.
The cocatalysts and relative amounts of each used in the various polymerizations are presented in Table 4 along with the amount of polymer produced, the xylene solubles and the melt flow index of each polymer. The xylene solubles levels were extremely high (as compared -to'known crystalline.isotactic-.polypropylenes) but'~in >no case.were any: of :the polymers: sticky.
_, r . .
r .. . . ' ~:;,-,~,;.-;.~~ . : ;-.~..v~~. ' ': w.::~.~ : ~: r ::a" :- . ..
,. , ,.. .. _ ~. , :,:. . .
:~; , ;;.~;'_; _ .._... :'v :.:;r , . , . .,. ~ :; -"
~, '..L)~:~~~:.,.., r.:'r ,.." .. , rV ~
)1..~Ys ~ : . ...r;,i ~1 '~'.i) ~ "~,.i ;:.... :~ :, .: '. .,. . n .7 ~. , , . :i 7.;, . a ':~ '.: r..l ::; :.u',~ ~'l..u i ~t .(.
, ~l s ~ ~. :'7 .i T ~ : .,~ -. .".
;:;G I ,'.'i:'s'i:,"'i:.'.. .,'.~..'.:. , W;i::'? .._ .'!:: . ....
..'3.~a::.~.~i! :,..;a.:..l.fu,-.":'.~. 7.', ~; ~...,.
~:'~ rv:, ,1 ~: ..., .., .... .i~~ ,., r....., .~.~t3,.... ..._... .
::.'l:.i..:..:ll..'':a.L~.':, ; _~ ;, ~'., v~~LIJ"L.i~ ;" :~' :.;rl~'ii7~::~'. i..~;:A"j. ~.L ', w:lrWr.,,:rs1 ~~.:: :~ n : :~ ii ','7~': . ~ .
,.7:;7'.;.~.~ C..':, i':'J"~i 'v~~l'i.:l''°~ _'~ ! ,"~J;:1 ''':F.L
/1..1:' )._...., v:,:: , WO 91!00875 ~ ~ PCT/~JS90/02037 f 'fable A
Autoclave runs to produce polymer with A-methoxyveratrol.e based catalyst (2.7 1 propylene, 0.015 -, 0.03 mmol Ti, 67°C, 90 min).
Run ~1 AlkYl (mo mol Ti SCt~_.(molLol Ti. Yield X.S. Pt.l'.
'fEA DEnC TIEInL L)IDDht/S P14PYR (Xalacat) (%wt) (.~Jc,LlOmin) 1 53 -- -- -- -- 23.8 55.1 O.A1 2 53 -- -- (GO mmol ltz, no SC11) 31.2 5A.1 A.79 3 20 70 -- ~- -- 17.5 50.5 0.52 A ~- -- 51 - -- 16.8 A7.5 0.39 l~ 5 1 -- -- -- -- 3.6 49.5 0.39 6 70 -- -- 15 -- ' 8.6 ' 39.2 0.13 7 70 -- -- -- 15 8.5 63.5 0.26 8 70 -- -- 15 15 7.2 39.A 0.10 9 23 7U -- 15 -- 13.2 4A.0 0.2A
1J 10 -- 93 -- 15 __ 6.8 50.6 0.8A
11 70 23 -- 15 10.5 36.9 0.22 TE11 - triethylaluminum DEAC - diethylaluminum chloride TzBAL - triisobutylaluminum 20 DIBDLdS = diisobutyldimethoxysilane M4PYR - tetramethylpyrazine r X.S. - xylene solubles~
M.r. - melt flora index (ASTM condition L) The NMR results for some of the bulk .. . , , , . . ,-.-25 homopolymers.produced,.~.rin the above~~~
palymerizations are summarized in Table 4n along ~wi~th ~'a .clarifying description of the- cocatalyst , '..combi.nation used'~:~to..produce each one. It can be seen that all of~-the polymers exhibit averag a 30 isotactic block'~Iengths between l3:and 17, the opfi,imum range =to ~exhib.it ~lastomeric properties.
In''>run ,#7 an sCA-was used vwhich i,s'°known , to induce the foxma'~io~n of ~syndiotactic polymer.
"~eThis ~vhas'':aaused ~'ttie ''syndiotactic -~leveT '~to rise 35 to~ 27 o='and -the'=isotactic ~level"ao 'd>=op below ::..~.:"::'55% Via:' ..... . . ;~.)<; ;;;.,.... ~ ~ v: .'. ~ : ; ,, ., ... : .
, . .
.. .,,. :i-.._'...~ J,. -._ ". ,:.iY.:, .., ~r .".'<,~FII~lf.)t.:';.7.i C. w~
.. ' , ..
.. 1.;.~.,.~~..~ , .. . .'.)s: ' n . ... . ...:. 'm~r )~.~1ry I ~;(.I , , .
~i fV~ 91/00875 . . PCT/US90l02037 ~0~~3'~a ' Table 4A
NMR results for some of the 4--methoxyveratrole Polymerizations Run Iso <Liso> Syn <Lsv~> X. S.
# cocatalyst ~%) units (~%L units % wt) 1 TEA ' 60 13 20 6.4 55.1 4 TIBAL 62 13.5 19.5 6.3 47.5 5 TEA (l per Ti) 60 13.5 21 6.3 49.5 6 TEA/DIBDMS 66.5 17 18 7.1 39.2 7 TEA/M4PYR 54 .13 27 7.1 63.5 8 TEA/(DIBDMS 65 17 20 6.9 39.4 + M4PYR) 10 DEAC/DIBDMS 60 14 21.5 6.5 50.6 The physical properties of some of the polymers prepared above are summarized in Table 4B, The Tset values represent the residual elongation imparted to a sample after. stretching to 400% of original length (at a rate of 20 inches per minute) then allowing to relax to zero stress (at the same rate).
Table 4B
Tensile~data for the polymers prepared in . ~ Example 4 ..,. ...... , . r . -. ;. ~ . _ ..
Elongation ' Run ' - -; Tbreak . Tset ~ .:.- 'fyiel~ _ . ., -at' break # (Psl) (%) (ps1).. - (%) 1.:: . 2920.;;. , -;,130 .::1381 ,, ._ : ~ 890 ~.2 : , 234Z" , .. . . X59 .. r;::;::1.392 . ~ .._ . . 873 ;
. :;. _...3 :~- 2755, ,,~;.:.:Z72 : ...: r1342 . ~;°~:,.,79~.-:
5 .. 2595, .. . ;.;a.;~.64 ;ri ;,~~.;11.?6 .. , ~; ; r.,,,7:6g.C
,10"rr :. : ~ 234,2 , ~ ,,;..::;~1.5~ ~ ::_a:1172;,r°; :rr;:.' ~>~.~83;;
,,.-; ~ ., ;.,;zf ,:tensil.e . s,et :is ;s,ignificantly ,less ythan 3,000.,,: the;_,polymer;~is.,..considered:~elastomeric:
Tensile at break of more than 2000 psi indicates toughness uncharacteristic of typical soft polypropylenes. Uniqueness is further . ... . _ : , ..:., .. _ WO 91/00$75 PCf/US90/02037 demonstrated because crystalline polypropylene exhibits an elongation at break of about 10% and a tensile at break lower than the tensile at yield.
Example 5 The magnesium compound 'M' from Example 4 was used to prepare procatalysts in this Example by stirring 7.8 grams of the desolvated M with 8.6 to 14 mmoles of the appropriate substituted veratrole compound (see Table 5) in 200 ml:of a 50-50 titanium tetrachloride-chlorobenzene solution for 1 hour at 115°C followed by two .
washes at 115°C with fresh.200 m1 portions of that solvent mixture followed by a quick rinse (less than 10 minutes) with 100 m1 of fresh solvent mixture: Excess titanium was removed by .exhaustive isopentane rinses, and .the~catalyst was dried under.moving nitrogen at 40°C. A
portion of the dry powder was then:made into a 5% slurry in mineral oil. The amounts of each electron. donor: used andvthe.analytical results for each'. catalyst= arewpresented ~i- Table 5~.5 ~ Use of higher=tlevelsrof electron donor ,in the digest -:: i ;: step normally :.leads to . lower titanium levels ~in the f.i.nal .procatalyst.~ In each _case;:~ the. goal was to use,.sufficient electron donor:to.keep the 'titanium'-level':belaw :4 % :but :with :.3- . . .
mettioxyveratro~le ' his 'wasw:not ::possible,.~::~ . ...
v.9'~;'~,l :Li.'r:)~:~.! 7t.i i;i!..:..W1::?:~i t."t~> t;"~': ',:.:,i o . ~ ..
':l ~.i:":'('4;j:: ~;G .., ;~,.~::~ .i ;,'j,".7a'C '~~y!~;'i"; . . , . ~.: ..:
:r.'~ii( ..~,i7 r~,: ~ ~.~..~
_.::i, . .i.:, . .. ,. '~ ~' .. F~ :. ... . . ... :_.~..
a ;.;~ 7,~ :.> :.~. ~:?-~"~Cj~t;:oa ~ , .~ . tJ ::a .x w:i~ ~:1 i. :~' ~ '..~~.o. S. L~t:'» :.:) 1. ,: . . n. ,i,Ji i~~ .. .J~.1 .."u. ,. .
~ b "'~ l ~:~fliFra:~ t't..C u:;~ ,:::1: 't~;l . zicz '~' .::'!: ',i.I. 3,..
."! _'. ~J' ::> '~.
. ~!:~:'; ~i v~.L_:n.~~-~.v,..~ :v .. .. . ° ~ ~.-, . ..;~t : : .. _.
:v: :. ~. ,o ~'~:~::
.:.-:: ...,: .. .: , ~ . : _ ..:-.. ,.; :...;. . _ ..,:, g WO 91/00875 . ~ ~ , PCT/US90/02037 Table 5 Catalysts with substituted veratroles as electron donors Catalyst Electron Donor Mg : Ti # (name) ymmol) (% wt) (%S wt) 1 ~ none 0 . ~ 16.5 6.55 2 VERA~ 8.6 20.2 3.01 3 3MV . 10 : - 19 . 5 . . 3 . 84 4. 30MV . 10 17.9 5.78 20 5 40MV 12 18.8 3.55 6 4P10V 14 13.8 2.93 .
VERA = veratrole ' 3MV = 3-methylveratrale 30MV = 3-methoxyveratrole 40MV = 4-methoxyveratrole 4NOV = 4-nitroveratrole For polymerization; procatalysts were .combined with triethyl aluminum (TEA)rwhich was used as a 0.28 molar solution in isooctane. The polymerizations were carried out by injecting a mixture of Ø01 to 0.03 mmoles of procatalyst and .TEA in the. ratio ..shown in Table 5A into: 2 . 7 v=liters of liquid-vpropylene in- a lw gallon autoclave::reactor .and . hen continuing: the .: _ ..
polymerization ..at .67..°C;:for one hour:..:The polymer lumps::were-::cut r: into .small pieces~:and :dried -for v. several .hours iunder .aspirator: vacuum at.80°C. .
bafore physicalrandr..chemical.characterizations were carried.;out::v.:vrThe;~:tensile .'set~,~,. tensile .sc yield, elongation and tensile at break were measured according to ASTM D 412-83 on tensile bars cut with a "D" die from 2mm thick compression molded plates.
The polymerization conditions and results 3g are shown in Table SA. Again, as in Example 4, the xylene soluble levels are extremely high:
WO 91/00875 ~ ~ ,~ ~.i ;' ;.' ",I P~/US9010Z037 ,, , .
The polymers made from the procatalysts containing the electron donors were not tacky to the touch, whereas 'the polymer made via the procatalyst without an electron donor was tacky, 5 indicating the presence of considerable atactic material. ' ..
Table 5A
Autoclave runs to produce homopolymer with veratrole based catalysts (2.7 liters- v 10 propylene, 0.01 - 0.03 mmol Ti, 67°C, 60 min.) Run Cat TEA/Ti Yield X.S.
# # (mol/mol) (Kq,Ja cat/hr) (o wt) 1 1 29 24.1 62.6 2 2 ~ 62 18.2, 64.3 ~
15 3 3 50 20.7 46.8 4 4 33 28.4 ~ 46.9 5 5 53 15.9 ~ 55.1 6 6 64 7,p - 54.3 7 6 200 11.7 47.1 20 TEA - triethylaluminum X.S. = xylene solubles .
The.. tensile ,data~for. the homopnlymers.~_T
produced in the above polymerizations are ,.
summarized in,Table 5B. . The tensile set values 25 reported in SB..differ from those in Table 4B in that~the samples were stretched to only 300%:of their originalvlength before relaxation.
:'. .:. s ."i /;i:,):)~.;~ri(l::i .. ~.'t~.~'l:a: ,.~,,r.','Y-t. '>i. .......t :!~:~~.
......
..., i..__.. ...,., ::. .... ..'7Y..:::., .;.'. ;:'i .... 't,i,:: .....
' . " , 1.,.': .... . ..., . . ,' .
...j~3.~ ~.~r-i :.."~ ':ir..t,~:.i ~.:....~ i ~.'',.7C.1 ~ ...:'S. . . .
'~:5 ~73~~'.:..:... ',:?,: ...?..:~~.,~ . : ~r., .:':i 3 _..,:1... ..
~.:y~~t ,;t.t.,'~~..~'.t .:..~:~ ~~. AJ ).: C(~Cl,i,~dt .::.s ~.. .
1,..r.4~:i.~~.:'~.;.... ~,r.~..X.::~ a . - .
~':f.':r7fr~ ;: -., a wi 'a~ ': .:.:7:.T':''i..r'i ef~'. ..'~"? .i.. ~n "T; S;7C !:
~'~ 91/0075 PCT/US90/02037 ~fl6~3"~5 2&
Table 5B
Tensile data for the polymers prepared in Example 5.
Ellongation T T T . at break break set p eld ED (psy i(%) fpszl t%) None 1690 85 788 963 VERA 2630 82 8?1 874 The NMR results for the homopolymers produced above are summarized in Table 5C. In all cases the polymer is at least 55% isotactic.
A11 of the polymers exhibited average isotactic block lengths between 12 and 15 monomer units.
Table 5C
NMR results for the polymers prepared in Example 5 , Iso <Lyso Syri ~ <LSY~>
ED ... ~ o ) :. :~ units ( o ~ ,:: ~ v v. units None ~ ~ 58 :12 lg . 5. 0 'VERA'~ 59 ' ' 12 20 6.2 ' g~ . .. . 6~ 14 ~- 17 5.6' 30MV : .: 64 . 13 16 . . . 5.6 40MV .. 60 .'. _ : 13 :. ...: . : 20 ;: . - 6.4 4NOV 62 15 20 6.1 i The conclusions drawn from the above data are the same as those drawn fromvthe data in i Tables 4A and 4B. ' Example 6 (po7.ymerizations in butane) . ' Butane polymerizations were carried out, in a nearly identical fashion to~the propylene polymerization, in a l gallon stainless steel WO 9l/00875 PC'f/US90/02037 ~p~6'33°~~
autoclave utilizing 1.8 liter of 1~butene: At the end of 90 minutes the reactions were terminated by injecting 600 ml of isopropyl alcohol to the cooled reactor prior to venting the unreacted monomer. The specific runs, utilizing procatalysts from example #5, are summarized in Table 6A. The pertinent properties of the elastomeric polybutenes are.
summarized in Table 6B. The NMR results l0 summarized in Table 6C reveal that these catalysts produce short block length polybutene.
Table 6A
Autoclave runs to produce polybutylene with veratrole based catalysts (1.8 liters 1-butene, lj 0.01 - 0.02 mmol Ti, 60°C, 90 min) Run Cat SCA/Ti TEA/Ti Yield # ~ SCA (mol/mol) (mol/mol) (Kd/acat) 1 ~'2 from Ex 5 CYANCL 4 105 8.0 2 f4 from Ex 5 DIDD1?S 5 107 A.2 3 ~'5 from Ex 5 none-- 70 7.0 TEA - triethylaluminum CYANCL = cyanuric chloride DIBUMS = diisobutyldimethoxysilane Table 6B
25 Tensile data fbr the polymers prepared in Example 6 Elongation Run T T T at break (psa.) (~~j ~LPsi) ( o) ' 30 1 2751 162 no 485 I
2 1932 166 yield 346 3 1609 110 point 557 1335 100 600 , These materials have a higher elongation at 35 break than normal crystalline polybutene (300--350%) and a lower tensile at break (4000-5000 psi expected for crystalline polybutene). j wo gxioos~s ~crius~oiozo37 psi expected for crystalline polybutene).
Elastomeric behavior is indicated by the low tensile set values.
Table 6C
NMR results for the polymers prepared in Example 6 .
Run ISO <L~so> Syn ~Lsyn~
# (%1 units (%) units I 68 17 ~ I3 5.7 .
2 64 16 ~ 14 6.0 3 60 ' 10 16 6.0
These more well known types are crystalline and amorphous polypropylenes. It is normally accepted that crystalline,polypropylerie' generally has the isotactic or syndiotactic structure and that amorphous.polypropylene .
generally has considerable atactic (sometimes designated as heterotactic) structure. Giulio Natta's U.~. Patents 3,222,300 and 3,212,302 describe isotactic polypropylene and give structural formulae for isotactic and syndiotactic polypropylene. The former is a straight chain of propylene units wherein the methyl groups are all, aligned on one side of the 25 polymer chain. In the latter, the methyl groups alternate from one side of the chain to the other, In atactic (heterotactic) polypropylene, the methyl groups are arranged randomly on the two sides of the chain.
20 Almost all of the polypropylene which, is used commercially is highly crystalline..:.
polypropylene~.w,...These products are :wellv :known and have been. the subject of many patentsvand articles.Amorphous polypropylenes, which have 25 very'little strength, are used commeraialTy primarily in'adhesives and asphalt additives.
Disclosure''~of ~-the Invention : ' t :.. , ....,., :;s ..:;
The present invention 'relates ~to'~aa'catalyst admponent -rahicli 'is ~ useful '~in'-~tlie ~productiozi -of 30 '~'elastomeric, ~~low vcrystallinity, ''primarily ~~v''"
'.".".~~.isotaotic polymers=:of~=propylane='and~-butene~~~ xhe ~~
catalystv'component'~romp~ises ; a ~ magnesium halide ' >°%~;~which ~may~~be-~the~=?reactionaproduct'tofu"'magnesium alkoxide compound whichfmay~be'~of~?the~-formula 35n;a:> ~: ::Mg (R~y x~(R2yz-X;~ Where:L.R; ~ is' ~an alkoxide or aryl ewo 9iioos~s 2~(~ ~ ~ ~,'~ ~ ~.: PCT/US90/02037 oxide group and Rz is an alkoxide or aryl oxide group or halogen or other anion, and 0<x<2, and a tetravalent titanium halide wherein the reaction takes place in the presence of an.
5electron donor selected from the group consisting of veratrole and derivatives thereof which have essentially non-reactive substituents such as CZ-C1~ alkyl, C6-Coo aryl, halogen and methoxy. .
This invention also relates to a catalyst composition which comprises the reaction product described above and an organoaluminum compound.
Finally, the invention relates to a process for the production of such elastomeric, primarily isotactic polymers by polymerizing propylene. or butene in the presence of such a catalyst.
Best Mode for Carr~ing~ Out the Invention ' The "normal" well known polypropylenes discussed above are generally high molecular weight materials which consist of blocks of monomer units of relatively.or extremely long averagewisotacti:c blobk "1-ehgth "(<L~so>} , for~-example,' 50 to 200 monomer :units.":The prior art .::isotactic' polymers .(prepared via an MgClZ
supported catalyst) of short--average isotactic block '-Length '(about '6 t~o 15 monomer units) are characterized by having relatively.low tensile ~: 'strength : and being tacky ao the ~.touch~ and thus are presumed to contain'~na ~wide'~.'di'stributiari 'of ' polymer:' . .blocks',of~'.varying.lengths. -: . . , r.;~.~::u~r .
:'nf.L ., :1;11 J ' '9i=:-,°.L
' The ='elastome~ic .polypropylene' and .v~
.~ polybutane.v:compositinns:::of the present invention :~~: ~~ are .~.sp~cif icahly :=characterized as being =of =', '~~:?s~relatively high tensile'fstarength arid=':non~tacky 35v,.. :.to:r>.~he~:touchy.:a.characteristics::.which~Ymay .'be v- ...
WO 91100$75 ~ ~ ~ ~ . ~ . PCTlUS90/02037 ..:: ;
,.,:_ . , attributed to a narrow distribution of relatively short block lengths. By '°block length" it is meant the number of stereoregular , monomer (in this case propylene or butene) insertions which occur before there is:a defect in the polymer chain. By "defect" it is meant that the symmetry of the recurring units is ended and there may begin a different structure (e.g. a change from isotactic to syndiotactic or ZO to heterotactic) or units of another monomer may be placed therein. The average block length is determined by a numerical integration of the pentads which occur in the ~3C NMR spectrum (Polymer Seauence Determination: Carbon-13 NMR
Method, James C. Randall, Academic Press, NY, 1977). It is theorized that the average block length-has a great effect on the properties of the polymer. For instance, relatively short ' average block lengths, i.e. 7 to 12 monomer.
units, tend to occur in a flexible and rubbery polymer which exhibits. good elastic properties and_; is, relatively ,strong. ; On the-..other::hand, block lengths of .greater, than, about 50_are characteristic.of commercial, very stiff.., highly ~ crystalline isotactic polypropylene.- ~ : . . _....
. ~.U. S. Patent 4-,.335, 225,' discussed .above, v ,diSCIOSeS ~ how .to :make an ~.elastomeric.:-:: ::. :: ::v.::
polypropylene composition which oontains::,up .to X55%,' :and preferably :mu.ch ::,less; ..isotactic. . , .
polypropylene; ;,::This c.polypropylene ,;,as .--a,a ',r.~: ; ~: ~:
inherent~eviscosity~~.:of.;:l~.5 ,.to. 8, ;::a ;major melting .., ,. poilxt .between' 135 and :;155°C,v exhibits; no;.-.yield point,v~;has a ~:; tensile ,set not ;exceeding .15o% and d~:.v,co~tains y:10 to-.,80% ;°by,:,weight ,of..ua e~iethyl tether .
soluble;sfractionv.-.which~~has,;.anuinherent-~wiscosityrt::
W~ 91100875 ~ ~ ~ ~ ~ ~ ~ '-. PCT/iJS90t02037 exceeding 1.5 wherein said fraction has an isotactic crystalline content of about 0.5% to about 5% by weight. A special catalyst, which is the subject of several other related patents, 5 is said to be required to make this material. j These catalyst are homogeneous zirconium or hafnium catalysts supported upon partially hydrated alumina. Such catalyst systems are difficult to work with, have extremely low 20 productivities (on the order of Z-3o of the productivities of the catalysts of this invention) and are not used commercially to any appreciable extent.
The polypropylenes and polybutenes.of the present invention are made with a catalyst system for which there is a wealth of analogous commercial experience and..knowledge. In one embodiment the catalyst is comprised of the reaction productvof a magnesium alkoxide compound which may be of the formula Mg(R~)x(Rz)z-X, .where Ri is .anlkoxide or aryl oxide group and Rz r~is :van alkoxide ~~or,,aryl roxide .group or.°halogen or. other. anion;:andv0<x<_2, and a tetravalent:
titanium hahide.wherein the:reaationwaakes place in the presence of-an.electron donor and, ;~. : optionally, ..a halogena~ted hydrocarbon. . .Such r~:~w°~: catalysts':are welh.~ k.nownv.and have been ~used~~for several'~.'years ~cornmeroially:rr:~ The rpresent ~;::
catalys'~':.'uses~~'~an..'.el~ctron~:~donor .which; has. not been heretofore rdisclosed ~for::use~~in ..this : type ,:~ v ~
°of. 'catalyst:'. i : onew:electron:rdonor : ~ihiah :may gibe usad:~'~in-::order. ~tovmake ~ahe:~'polypropylene :; ~. :n s compositions of -ahe_:-present ::invention ..is. : ::.~
~°i.i~eratrole (:or ~avderivati~ie whereof o~~~xSuitable :<'derivatives-iinclude:3-methylveratrole<.-.(Z,3-.t ~-?_;
wo 9maos~~ ~ ~.~ ~ ~ '~ ~. . PCT/US90/02037 ;-'..
dimethoxytoluene), 3-methoxyveratrole (1,2,3°
trimethoxybenzene), 4-nitroveratrole and 4-methoxyveratrole (1,2,4-trimethoxybenzene). The catalyst is completed by the addition of an organoaluminum compound and, optionally, a selectivity control agent.
Veratrole has been mentioned previously as an electron donor (U.S. 4,107,414) and a selectivity control agent (U.S. 4,107,413) for specific catalyst systems to prepare highly stereoregular conventional..polypropylene.
Therefore, it is surprising to observe that compound and its derivatives may be used as an electron donor to produce extremely short average block length elastomeric polypropylene and polybutene.
Examples of halogen containing magnesium ' compounds that can be used as starting materials for the halagenating reaction are alkoxy and aryloxy magnesium halides, such as isobutoxy magnesium chloride,.ethoxy magnesium bromide, .;p::phenoxy magnesium::iodide, ~:cumyloxy.~magnesium~.
bromide and naphthenoxy magnesium chloride.., ..... :-~..Preferred.magnesium~compounds to.be::.~:~
halogenated are.selected.:from magnesium r:..
dialkoxides arid:: magnesium .diaryloxides. In: such _ ~:compounds::ahe alkoxide-~groupssuitably. have :from 1 to .8 ~~carbon.;atoms;:. and;~preferably,~from: 2w.to 8 carbon. atoms: :~. Examples~:.of :.these preferred : .
.~:gr.oups :of;.compounds ':'are :magnesium di-;. ,. ~s:: ~.i .:5isopropoxide; c~~magnesium. ~diethoxide; .magnesium dibutoxide;;;:magnesium::diphenoxide;v-magnesium dinaphtherioxide~and.::ethoxy~cmagnesium.~:r~::c:~:c~:a i~sobutoxide::a:-M~gnesiumv:.~alkoxides.~:disclosed yin U:~S. ' Patent'.~~4;:806; 648; ~~issued.v~~'ebruar.y:~l9;:1989 ...
WO 91/00875 ~~~'~;~"~'~-~' PCT/'US90%02037 ..:: ::
y:
to Robert C. Job, are also preferred for use herein. Especially preferred is Mg4 (OCH3) b (CH30H) ~oX2 where X is resorcinol or a substituted resorcinol monoanion.
Magnesium compounds comprising one alkyl group and one alkoxide or aryloxide group can be employed, as well as compounds comprising one aryl group and one alkoxide or aryloxide group.
Examples of such compoW ds are phenyl magnesium y l0 phenoxide, ethyl magnesium butoxide, ethyl magnesium phenoxide and naphthyl magnesium isoamyloxide.
'In the halogenation with a halide of tetravalent titanium, the magnesium compounds are preferably reacted to form a magnesium -halide in which the atomic ratio of halogen to magnesium is at least 1.2. Better results are obtained when the halogenation proceeds are completely, i.e. yielding magnesium halides in which the atomic ratio'of halogen to magnesium v is at least 1.'5.' Except in vaases where r resorcinols °(or ;otheW=plieiiolic nx rsubstituted phenolic compounds)vare used, the most' preferred reactionsv~xe 'those leading to'fully halogeriated reaction products: ~Such~~halogeriation reactions w "are suitably effectedrby"employing=a-molar ratio of ritariium coiripourid tov'magn~sium ~aompound 'of 05. 1 'tci 200: 1 "preferably 1: lw~o"~ 100:2': v v'These halogenation reactians~Y~are'~conduatedr5.n the' ".~aaditinzial''pxesenaeto'f an'~electron ~dorior and may:- , : , '::~ :. iziclude'ethe ~ adaxtionai vpre'sence of a~:a.~ _; r,:~~r« .~
lia~l.ohydroc~~bon.'- '~An ~' inert ~ hyarocaxb'on ' diluent or~'so~.ventLmayy°be used'as~ra"substitute'~fior'°the ;~l:i halohydrocarbon~~'~Alf(~~3nCtLl~, ."~ 'r~,.,r :i i :.':'~:l'!lf.:'... ' v~j''i'~~~~Suitabxe'~h'a~lides~''o~f ~tetraval.ent titanium ~'~
wo 9~ioas~~ ~~y~~ ~.r~ rcriu~9oroao3~
s include a~rjrloxy- or alkoxy di- and trihalides, such as dihexanoxytitanium dichloride, diethoxytitanium dibromide, isopropoxytitanium tri-iodide and phenoxytitanium trichloride.
Titanium tetrahalides are preferred. Most preferred ~is titanium tetrachloride.
Suitable halohydrocarbons are compounds such as butyl chloride, anyl chloride and the following more preferred.compounds. Preferred aliphatic halohydrocarbons are halogen substituted hydrocarbons with 1 to 12, particularly less than 9, carbon atoms per molecule, comprising at least two halogen atoms, such as dibromomethane, trichloromethane, 1,2-dichloroethane, dichlorobutane, 1,1,3-trichloroethane, trichlorocyclohexane, -dichlorcfluoroethane, trichloropropane, trichlorofluorooctane, dibromodifluorodecane, hexachloroethane and tetrachloroisooctane.
,.Carbon tetrachloride and 1,13-trichloroethane are preferred.aliphatic.halohydrocarbons. .
>Aromatic halohydrocarbons..may...also:be.employed, .;...e.,g.n chlorobenzene, bxomobenzene, ., .,.; -dichlorabenzene,, dichlorodibromobenzene, ,, ;. , ., _,inaphthyl ;chloride,,-Achlorotoluane,.- , ,.,.
-dichlorotoluenes,..and,the .like; chlorobenz~na -~and:dichlorobenzene.are preferred aromatic...
.... .. .,. . _, ...., ...__........,:. . . , . ...... , .. . .
r . ~ . .. ' ' C . , ~ ,.
._~;-~halohydrocarbons.,. Chlorobenzene,;is the;, most preferred,,halohydrocarbon:..:.,. :~:; .,a..;:arr. ,,o~:;~;-.
30,~~,~a ~,rr;A; ;Tk~e...~nalagenation normally; proceeds ;.under formation of a.rsolid.reaction.product,which;may "T: be:~ isolated, from. the liquid reaction ~ medium,.= by ' .
.,;l.~il~rat~on., ~decantationy, or a~other~ suitable) method . It may be subsequently ~.washed,,..with,j an f.~ i,nert:,hydrocarbon. diluent,,,, such as:.n-hexane, "' WO 91!00875 PCf/U~90102037 ~~~ ~ 3~3~'~y:
y .
isooctane or toluene, to remove any unreacted material, including physically adsorbed halohydrocarbon.
The product may also be contacted with a tetravalent titanium compound such as a ~ ,.
dialkoxy-titanium dihalide, alkoxy-titanium trihalide, phenoxy-titanium trihalide or titanium tetrahalide. The most preferred titanium compounds are. titanium tetrahalides and especially titanium tetrachloride. This treatment increases the content of titanium tetrachloride in the solid catalyst component.
This increase should preferably be sufficient to achieve a final atomic ratio of chloride~to magnesium in the solid catalyst component of from 1.5 to 2.0, particularly of.from 1:8 to 2.0: To this. purpose the contacting with.the tetravalent titanium compound is most suitably carried out at a temperature of from 60° to 136°
~ during 0.1 to 6 hours, optionally in the presence of an inert hydrocarbon diluent.
.:. Particularly preferred. aontacting.,:periods:. are between 0.5.to.~3~.5 hours: The treatment;may be carried out in successive contacts.of the-solid with separate portions of..vtitanium . _ :a ~:..~':w~. .
tetrachloride ~.. ... . , " . , After the :treatment'with-aetravalent~.~v,::.
v titaniuin~.compound',~=:the catalyst' component:;vis .suitably .°:isolated <from :.the liquid :reactiow,;
medium' and .'wa'shed ?..to. .:remove unreacted ; itanium ~ '°
compound:e:5 The titanium content of vthe rfinal, .. :.;:; :vwashed '.catalyst constituent is auitably:~between , about '1. 5 vto w3 : 5 ~-percent by .weight :or~up.:~to about'~4 Y5 :percent. v~~The:vpreferred halogeri;~atom;
-pos'sibly , contained :~iri'fthe v;magnesium ::compound to::~ ;.
WO 91/00875 PC,'T/US90/02037 2w~~33'~~
_ . . (~~=
be halogenat'ed, and contained in the titanium , compound which serves as halogenating agent and in the tetravalent titanium compound with which .
the halogenated product is contacted, is 5 chlorine..
The material used to wash to catalyst component is an inert, light hydrocarbon liquid.
Preferred light hydrocarbon liquids are aliphatic, alicyclic and aromatic hydrocarbons.
10 Examples of such liquids include isopentane, n-hexane, isooctane and toluene, with isopentane being most preferred. The.amount of light hydrocarbon liquid employed is 5 to 100 cc/gm of catalyst component. in each of 2 to 6 separate washes; preferably about:25 cc/gm. The resulting solid component is the procatalyst, which is-used with cocatalyst and optional selectivity control agent in the polymerization process.
Although the invention is operant without any added selectivity control agent, suitable ~:o-electron donors; :;.which are:. used ~in. combination with:or-reacted with. an.organoaluminum compound . ,..: as .selectivity.° control agents to .retard the.
production::of_ atactic polymer; are..ethers;_ esters, ketones, phenols, amines, amides,v~:.., imines;v;witri~les,: :phosphines; silanes, ;
vphosphites~;~ stibines, .arsines, ~ phosphoramides andalcoholates.: Examples of ;sua.table::donors ~c.~.'.are.;:those::referred:ao °in..:.'U:S.':Patent No:.':;:..:~~::
j .
~9~ f~~42;:~276c~ Preferred :.donors are esters :.and .;~cy:~;organ.ic~sili.con compounds:~:v Preferred;,.ester;s are esters-~of aromatic carboxylic _acids, auch.:as ,;ac~ethylc:and methyl::benzoate, ~p-methoxyrethyl 35~:~1 Fabenzoate; r.;p-.,.,ethoxy:methyl::.benzoate, ~,~p-ethoxy <: . i 'WO 91/00875 ~~ o,~ u'~4~,~ IPCT/US90/02037 ., -~ ':::. ..
.: ...:
ethyl benzoate, ethyl acrylate, methyl methacrylate, ethyl acetate, dimethyl carbanate, dimethyl adipate, dihexyl fumarate, dibutyl maleate, ethylisopropyl oxalate, p-chloroethyl benzoate,.p-amino hexyl benzoate, isopropyl naphthenate, n-amyl toluate, ethyl cyclohexanoate, propyl pivalate. Examples of the organic silicon compounds useful.herein include alkoxysilanes,and aryloxysilanes..of the general formula R~~Si(ORZ)4_n where n is between, zero and three, R1 is a hydrocarbon group or a halogen atom and RZ is a hydrocarbon group.
Specific examples include 'trimethylmethoxysilane,.triphenylethoxysilane, dimethyldimethoxysilane,.phenyltrimethoxysilane and the like. The donor used as selectivity control agent in the total catalyst.may.also be the same as the donor used fog preparing the titanium. containing (procatalyst) constituent., Preferred as selectivity control agent in the total catalyst are p-~ethoxy ethyl benzoate, .;r~phenyltr.imethoxysilane,.;..diphenyldimethoxysi,lane and;diisobutyldimethoxysil.ane. . ., . , The, organoaluminum._compound 'to be.,employed as ..cocatalyst,. _may be . chosen from ,any, ;o~ ,the known..activators in ohefin.polymerization catalyst, systems ,compri.sing ,a ;titanium halide ;abut :,is..most ;.suitably free _of, hal,oqens. ~",Whi,l.e .,,aluminum..trialkyl...compounds,, :dialkylaluminum , ;,;halides .and dialkylalumi,num,allcoxides..may...be , ,used, waluminumtrialkya;..,compounds .,ax;e.,pr,eferred, ~particularly;,those ..wherein,:each . of .ahe alkyl.
,.:.?,groups:.:has7l;to,~6 'carbon atoms; ~e~.,g;,,, :'. .
~,,.; f;rjtxiethxlalumW um t., trig?n~°,propyl~;luminum,~tri-35.; "fisobutylaluminuzn, ;~riisopxopylaluminum~.and.;.~ y .. ... , .; ". , . . . a , P~I"/US90/02037 wo 91 /oo~7s ~ ~ n. ~ ~ v ~ a ,, dibutyl-n-amylaluminum.
Suitable~electron donors for use in the production of the elastomeric, primarily isotactic polymers of the present invention include veratrole and derivatives thereof which have essentially non-reactive substituants suoh as Cz-C1o alkyl, C6-Coo aryl, halogen and methoxy.
Veratrole is otherwise known as l,2-dimethoxybenzene: Veratrol derivatives which may be used are 3-methylveratrole (2,3-dimethoxytoluene), 3-methoxyveratrole (1,2,3-trimethoxybenzene), 4-nitroveratrole-and 4-methoxyveratrole (1,2,4-trimethoxybenzene). The preferred electron donors are 4-methoxyveratrole and 3-methylveratrole because they yield catalysts which produce polymer with the highest . tensile strengths.
To prepare the final polymerization y .
catalyst composition, pracatalyst; cocatalyst and optional selectivity control agent may be simply combined, most suitably employing a~ molar vrati,of'to 'produce''~iri °~the'~finalcatalyst an 'atomic ratio of aluminum to'-titanium of from'lvto 150, and' suitably from' about l0~rto -about 150 .
Increasing' the Al:Ti ~~atio tends ~to sl'ightly ~ w increase catalyst activity at thevexpense~~of 'increased ~ catalyst. residue in the 'une~tx~aa~ed i 'product:w Thiese factors will ~e =considered in selecting the xAl : Vii: '~~xatio J~for ~ ariy "given '-p~ooess arid'vdesi'red 'product~'~ eIn 'general, -Al:Ti 'ratios >::,i~y.:th~:'rrarige of'~30:1'~~arid''100:1~'and yespecially of about 50:~1rto 80'i,~will' be~'foundtadvaritageous:
Polyme~izatiori nf-~propylene°o~''buterie~=inay kie~~~aonductec'!'-witNrth'e~'catalyats'of the-viriv~ntion inw''a~~'liquid''°sj~st~emvwith~° an inert~''diluent~-~r'"such as~ ~ . , W~ 91/00875 r. ~ ~ ~ y ~ r, ~ ':,. PC1C/LJS90/02037 (.,,, , ,., a paraffinic liquid of 3 to 15 carbon atoms per molecule, or in a liquid system containing propylene or butane as sole diluent or together with a small amount of propane or butane, or in vapor phase . -Propylene polymerization in liquid phase is conducted at a temperature of 50° to 80°C and at a pressure sufficient to maintain ' liquid conditions. In a continuous reaction system, the liquid in the reaction zone~is -maintained at reaction conditions, monomer is continuously charged to the reaction zone, catalyst components are also charged continuously-or at frequent intervals to the reaction zone, and reaction mixture containing polymer is withdrawn from the reaction zone continuously or at frequent intervals.
In propylene or butane polymerization, the ' reaction mixture is typically maintained at conditions at which~the polymer is produced as a slurry i,n the reaction mixture. The catalyst systems of this invention are extremely active -~v~and 'Wighly-v specif is in propylene -polymerization, sovthat no'removal of catalyst components or of atactic~polymervfrom~the-polymer product"is'=
~required~ . ... .. ~w ,.. . . ... _ While~thercatalysts of this invention ors:
particularlyxadapted fog=use~in~cont~.nuous polymerization systeins';''they~ inay", 'n~ ~~course;~~?
also"~be'vmployed ~' iiiv batcWpolymerization:-~'a'This ..: . . . , ~. ~ , ; ~, , y 3 0 may; be,, o.~, ,advantage' ~~in' mule.-stage: ~ ~ .:::;.; ~~, ~; a 'po~Tyinerizatxori~'-iri' whiahvpropylehe' polymers~'and propylene'~=ethy7:'ene"'polyitier's '-'are produced in;-' r r j~' separate W eaGtiori- zones ~~a~ranged -'~n~ ~~sequence~.
...., .L.'.i..3f, id ~la.:~'; c".':~
'xt' is ~wellr-ki~owri~ .than supported ~"coot'di.iiatioin'°procatalystsv-~amd cataljrst' syst'eims - -dV0 91/00875 PG'f/US90/02037 ~~!. i:
2063~~a ~ ,.:
of the type used' herein are highly sensitive, in -varying degrees, to catalyst poisons such as moisture, oxygen, carbon oxides, acetylenic .
compounds and sulfur;,compounds. It will be understood that. in the practice. of this invention,.as well as in the following examples, both the equipment_and the reagents and diluents are carefully,dried and free of.potential catalyst poisons. . ~.
20 The productivity.of the catalyst is.
determined as kg polymer/g procatalyst in a standard one hour batch reaction; it may also be expressed as kg polymer/g Ti. Catalyst activity is sometimes reported as kg polymer/g Z5 procatalyst or Ti/hr. If determined in a standard.one hour test, activity thus is numerically the same as productivity.
The specificity towards average isotacti.c ' block length may be determined by measuring the 20 amount of .xylene soluble polymer,(XS), in ,accordance_,with regulations of the U.S. Food.and :~,Drug,~Administration.-..,The XS ,test :is carried out _-as_.follows::.-_The.sample is completely dissolved in ,xylene~.in a:,stirred ,flask-.by, heating.-a~t ..
25 reflux. The flask is then immersed in,a water ,,,bath,at:25°C tr~ithout stirring "fox.,..one ,hour, during, which: a l precipitate,..is ., formed,. ; :,,The ; .;
-. . . , . , :. . , . , precipitate is;filtered..,off,and,~.the, so;lubles.
:~.::Presen~~.:in': the, :f i~,trate., are' determined.,by; ., .. :, . . , . , . ., ., . ..: , 30 evaporating,-a,;20.. mZ~ aliquot of.l Nthe, filtrate, ,. , ; , "dryinga~;~he: res,~due;.under,;:vacuum, 'and weighing the resi.due~, ,The~-xyleneY,.solubles.,may, also ~_-,include some ;amorpkzous and low~~,~molecular...;weight _ ; . . _~-..... _. ,...
crystalline: ,mate~,ia~,..t~ Ttie,;dcairable numerical ,.: ~ ..... .. .....~,. ....
35 _.~yalue of :XS f;or rthe .. ro lene ~homo of mers .of ~
.. _, :P . ._ PY . : P. . . Y _ = .: .. , i WO 91/00875 '~ ~ ~ ~ ~ ~ ~ PGT/US90102037 ..
this indention is typically between about 35%
and about 85%.
We have found that is highly advantageous to..make a polymer which is characterized by 5 average isotactic block lengths which are i relatively short (on the order of 7 to 20 monomer units) when compared to commonly known crystalline-and amorphous polypropylenes or ;
polybutenes. Average block-lengths are 10 determined by numerical. analysis, of the pentads observed in the ~~C NMR spectrum (see Polymer Sequence Determination, Carbon-13 NMR Method by James C. Randall, Academic Press, NY, 1977).
Such polymers generally have block lengths in 15 the range of 50 to 200 monomer units. It is also highly. advantageous to have a narrow distribution .of.block lengths.. This is not a characteristic of commonly known amorphous polypropylenes which, although they have ..
relatively low average,bl,ock lengths,,generally have a wide distribution of block lengths.. and contain much jr;atactic material ;,.as ~:.sug,gested ,,by their low tensile strength per unit, block length and high tackiness.:to,the..touch. .It is aheorized that it-,is ahe narrow distribution of . v low average block length that.imparts~to the polymers of this:.,inven~ion high:-tensile strength .. , . ~:, per unit ~block..le~gir,h. ;~:;:,n: ......;~:~.'1:' ' ", ,~;The~~short.;block;a~lengtrhs are:~important because,;; they allowa f gr~~ the;~,incorporatiop.: of :; ,, ,..
. . . , .. ... . , ,elastomeri~: properties.r in; essent~.ally~,.isptactic hpmppolymer:~ ~r~;;Achieying . a.,-~narrow~, distribution of. , ouch:: short:; block-;:;lengths .-is ;.importantw..because ::u-r~essentially,:no atactie.opolymer is~gresent,;and - :,'therefore"~tlae,; ten'sile:_st~ength of::-the.:~polymer isv _;
-' ~ ~ ~ dx ~'~ ~ PCT/US90/02037 1-f .., ~. 6 high and its tackiness to the touch is low.
the polyolefin's~of the present invention primarily comprise isotactic blocks, i.e. -greater than 50% isotactic material makes up the polymer and preferably greater than 60% ' isotactic material is present therein. It is important to'note that even though these polymers contain such high percentages of isotactic material, they do not exhibit the' properties characteristic of crystalline isotactic polypropylene but rather exhibit elastomeric-type properties. , EXAMPLES
~3C Magnetic Resonance spectra were obtained at 235°C on samples dissolved in 1,2,4-trichlorobenzene. The spectrum reference was the mmmm methyl group assigned at 21:68 ppm for polypropylene and 27.64 ppm for the CHz of the ethyl branch of polybutene. The pentad analyses were carried out utilizing-the following formulae: - . _ .r. ._ y:~I~::~:,~'%Isotactic _ -(mmmm''~~1 ~5~'=mmmr)°/ (total' .
-..~ ~wresanances ) X - 100 % . .. . . _. ,_- .
(II) L;so = 3 :+..:2~ :;(mmmin/minmr)-" .. .... ...
~ (III )~ ~-%Syndiotactic = ' (rrrr =+ 1:'5 -rrrm) / (total ._. rescinances) °:X 100% ~~' v _. . ,. ., .
'-~~' ' (IV)' ''L~y~' =-'3 ~'+'~:2 (rrrr/rrrm): _. a w .
(V) %Defects = 100% -~'%Iso'_:e.%ygyn ~ :.,., " ~ .
,::::.Iri:>n~dex °to"prepare'~'samplesvfor ~~tensile measuxements;~~'about ~ 60vg°' of~7the ~olymer~taas ~- ~ ~~'bl~ended'; in v a' Brabender a iniXer ~'at ~ 190°C~~with ' 0 .
3 g ~r~~ ~~'ofvAlgga''noit~~ 1010= antiokic~ant':'v'~Afte~ ~ cooling; a f.6m~:X:~:6u"X:;;2inin:iplate was.;fcoinpress~,oiic.mcilded;~at b~204°C''W rider~,'S tons ~ pres'si~~re: -~ Tensile a.barsv~:were 35;.~ .,, then~~cut'~,:from ~~hew plate~.u~sing" a?~!°.D~~.~ die;-~~,;The "i' WO~I/00875 ,~ ~, ~ PCT/US90/02037 . ._ .
1::._. ..
measurement conditions are as described in ASTM
D 412-83. Tensile set is the residual elongation imparted to a sample after stretching to 300% of its original length at a rate of 20 inches per minute and then allowing it to recover to~zero load at that same rate. Tensile at break is the stress required to break the sample at an elongation rate of 20 inches per minute. Elongation at break is the measured elongation at the break condition.
Melt flow index (M.F'.) was determined under ASTM condition ~. (2160 g, 230°C) on a Tinius 0lsen Plastometer. ..
Example 1 2.2 grams of magnesium,ethoxide, 0.5 militers of veratrol.e (1,2-dimethoxybenzene) and 60 milliliters of a.50-50 mixture by volume of titanium tetrachloride-chlorobenzene were stirred for 1 hour at 100°C then filtered. The solid was treated twice with 60 milliliters of a similar., titanium tetrachloride-chlorobenzene ", 'mixture at 110°,C for. 30 .minutes a.nd ..filters,., The solid was washed six times. with 100 ml. portions of isopentane andl.dried;.for,two.hours using a flow of dry nitrogen at,40°C. Three additional catalysts; were prepared: according to this;"
,,;.,,procedure with ,the ,.exc,epti,on that..Ø.2: ml,; 0..3 ml ;,; .,:« ., and 1._0,_ml., respe,ctively,., of, ,..veratrole were employed :in the,."preparation .,..;Table,...1 ;showsi the ,_,:, characteristics ,af :ahe four. catalysts a.ncluding .. ., . .. , , . .. . ..,_ .. .. _. . . . . . , . . , .; , they titanium ~lcading ..which, ~it can,:e, .seen,...., , , . ., . , .. ,, . .., . ..._, . . . ... . ... . ~ , .,~:_L,", decreased, as ~~increasing .amounts, tof vveratro.le >.~ were;;;used thusdemonstratnng a .;str.ong.~:"~ r~~y :; "interaction ~o~ the electron ..donor ,mth ~the~ ;, catalytic site.~'Our experience dictates that WO 91/00875 , :, lower Ti loading is preferable.
Tabla 1 Catalyst Amount of. Veratrole (mll Ti (% wt) A , 0.2 ' ' 5.3 B 0.3 4.2 C 0.5 2.6 D 1.0 2.3 Example 2 Two catalysts were prepared in a manner identical to that given in Example 1 above with the exception that 2,3-dimethoxytoluene was , employed as electron donor instead of veratrole. ~, The titanium loading followed the same trend as in the case of veratrole.
Table 2 ~ w ' ' Catal st Amount of Electron Donor (ml) Ti (% wt) E 0.5 3.7 , .. F 1.0 2.7 Example 3 Approximately 2,200 ml of propylene was wt.ransferred into a 1 gallon stainless steel autoclave along~with 160 mmol of hydrogen and the 'contents were ~~heated ~to 60°C. 60 microliters ' of diphenyldimethoxysilane2.5~~m1 of a-5%
solution of~triethylaluminum in isooctane and ~0.32'ml of a mineral oil~slurry prepared'using 0.5' grams o~ vcatalyst C~lim ~10 ml'~of mineral' oil 'w r were'~injected~vinto the autaclave.v This'°l:~iquid phase palymer'ization~ was caxried out a -'67°C - for a ''~~ ' p'er3.od rod' j~ '.hour ~~.~;,' Th:~. r200': grains '~of s '' ;:~:~ i, .,~~;
~~"''~rpolypropylerie~.:obta'ined.~were~ arialyzed'~b~y.NriIR .
Spectroscopy and~it'wasrdetermined that the 'polypropylene.~compdsition'vias-°72% isotactic with an average~~isotac~ti.'a block4'length of "16'-'and 9%
syridio~tactic ~with~'anvaveracje sjindiotaatic~~block length ~'of f 5 . .. , -~.~ 3 .~:~; a _. ~~; .; z ,~ ~:;~ a:>.~~
WO 91/00875 ~ ~ ~ ~ ~ "~ ~ _. . . PCTI~1S90/02037 The following Examples utilize a magnesium alkoxide compound of the formula:
Mg4 ( OCH3 ) 6 ( CH30H ) to ( 1, 3 -0 ~ OH-C6H4 ) Z ( ' M' , a resorcinolate) which was prepared by the.
dropwise addition of a tetraethoxysilane stabilized'12% magnesium methoxide solution to a solution of resorcinol in methanol. Partial azeotropic desolvation was carried out by slurring 40 grams of M in 300 grams of cyclohexane containing 120 grams of tetraethoxysilane and boiling this mixture until a decrease of 20 'to 30% in solvent volume had occurred. ~.
Example 4 .
The procatalyst was prepared by stirring 7.8 grams of desolvated M with l2,mmoles of 4- .
methoxyveratrole in 200 -ml of a 50-50 .titanium tetrachloride-chlorobenzene solution for 1 hour at 115°C followed by two washes at 115°C with "fresh 200 ml portions. of that solvent mixture followed by a.:quick.rinse (less than l0~minutes) '%raith:100 ml of freshtitanium tetrachloride-:.
chlorobenzene solvent mixture. Excess titanium was removed by exhaustive isopentane rinses and 'the catalyst was dried under moving nitrogen at 40°C. Ti content was 3.55%. A portion of the dry procatalyst powder was. then made into a 5%
slurry in mineral ail.
Tn the following polymerizations, triethylaluminum was used as a 0.28 molar ..
solution in isooctane. Tiisobutyl aluminum was used as a 0.87 molar solution in heptane.
Diethylaluminum chloride was used as a 1.5 molar solution in heptane: In run numbers 6 through 12 selectivity control agents were utilized;
WO 91100875 ~ ~ ~ ~ ~ ~ ~; : ,_ : PCf/US90/02037 ~';
diisobutyldimethoxysilane as the neat liquid and 2,3,4,5-tetramethylpyrazine as a 12% solution in isooctane.
The polymerizations were carried~out by 5 mixing 0.015 to 0.03 mmol of procatalyst plus aluminum alkyl plus SCA and then,..after 20 -. ;
minutes, injecting the mixture into 2.7 liters of liquid propylene in a l.gallon stainless steel autoclave and carrying out the 20 polymerization for 90 minutes at:.67°C for 90' minutes. The polymer lumps were cut into small pieces and dried for several hours under aspirator vacuum at 80°C before physical and chemical characterizations were carried out.
The cocatalysts and relative amounts of each used in the various polymerizations are presented in Table 4 along with the amount of polymer produced, the xylene solubles and the melt flow index of each polymer. The xylene solubles levels were extremely high (as compared -to'known crystalline.isotactic-.polypropylenes) but'~in >no case.were any: of :the polymers: sticky.
_, r . .
r .. . . ' ~:;,-,~,;.-;.~~ . : ;-.~..v~~. ' ': w.::~.~ : ~: r ::a" :- . ..
,. , ,.. .. _ ~. , :,:. . .
:~; , ;;.~;'_; _ .._... :'v :.:;r , . , . .,. ~ :; -"
~, '..L)~:~~~:.,.., r.:'r ,.." .. , rV ~
)1..~Ys ~ : . ...r;,i ~1 '~'.i) ~ "~,.i ;:.... :~ :, .: '. .,. . n .7 ~. , , . :i 7.;, . a ':~ '.: r..l ::; :.u',~ ~'l..u i ~t .(.
, ~l s ~ ~. :'7 .i T ~ : .,~ -. .".
;:;G I ,'.'i:'s'i:,"'i:.'.. .,'.~..'.:. , W;i::'? .._ .'!:: . ....
..'3.~a::.~.~i! :,..;a.:..l.fu,-.":'.~. 7.', ~; ~...,.
~:'~ rv:, ,1 ~: ..., .., .... .i~~ ,., r....., .~.~t3,.... ..._... .
::.'l:.i..:..:ll..'':a.L~.':, ; _~ ;, ~'., v~~LIJ"L.i~ ;" :~' :.;rl~'ii7~::~'. i..~;:A"j. ~.L ', w:lrWr.,,:rs1 ~~.:: :~ n : :~ ii ','7~': . ~ .
,.7:;7'.;.~.~ C..':, i':'J"~i 'v~~l'i.:l''°~ _'~ ! ,"~J;:1 ''':F.L
/1..1:' )._...., v:,:: , WO 91!00875 ~ ~ PCT/~JS90/02037 f 'fable A
Autoclave runs to produce polymer with A-methoxyveratrol.e based catalyst (2.7 1 propylene, 0.015 -, 0.03 mmol Ti, 67°C, 90 min).
Run ~1 AlkYl (mo mol Ti SCt~_.(molLol Ti. Yield X.S. Pt.l'.
'fEA DEnC TIEInL L)IDDht/S P14PYR (Xalacat) (%wt) (.~Jc,LlOmin) 1 53 -- -- -- -- 23.8 55.1 O.A1 2 53 -- -- (GO mmol ltz, no SC11) 31.2 5A.1 A.79 3 20 70 -- ~- -- 17.5 50.5 0.52 A ~- -- 51 - -- 16.8 A7.5 0.39 l~ 5 1 -- -- -- -- 3.6 49.5 0.39 6 70 -- -- 15 -- ' 8.6 ' 39.2 0.13 7 70 -- -- -- 15 8.5 63.5 0.26 8 70 -- -- 15 15 7.2 39.A 0.10 9 23 7U -- 15 -- 13.2 4A.0 0.2A
1J 10 -- 93 -- 15 __ 6.8 50.6 0.8A
11 70 23 -- 15 10.5 36.9 0.22 TE11 - triethylaluminum DEAC - diethylaluminum chloride TzBAL - triisobutylaluminum 20 DIBDLdS = diisobutyldimethoxysilane M4PYR - tetramethylpyrazine r X.S. - xylene solubles~
M.r. - melt flora index (ASTM condition L) The NMR results for some of the bulk .. . , , , . . ,-.-25 homopolymers.produced,.~.rin the above~~~
palymerizations are summarized in Table 4n along ~wi~th ~'a .clarifying description of the- cocatalyst , '..combi.nation used'~:~to..produce each one. It can be seen that all of~-the polymers exhibit averag a 30 isotactic block'~Iengths between l3:and 17, the opfi,imum range =to ~exhib.it ~lastomeric properties.
In''>run ,#7 an sCA-was used vwhich i,s'°known , to induce the foxma'~io~n of ~syndiotactic polymer.
"~eThis ~vhas'':aaused ~'ttie ''syndiotactic -~leveT '~to rise 35 to~ 27 o='and -the'=isotactic ~level"ao 'd>=op below ::..~.:"::'55% Via:' ..... . . ;~.)<; ;;;.,.... ~ ~ v: .'. ~ : ; ,, ., ... : .
, . .
.. .,,. :i-.._'...~ J,. -._ ". ,:.iY.:, .., ~r .".'<,~FII~lf.)t.:';.7.i C. w~
.. ' , ..
.. 1.;.~.,.~~..~ , .. . .'.)s: ' n . ... . ...:. 'm~r )~.~1ry I ~;(.I , , .
~i fV~ 91/00875 . . PCT/US90l02037 ~0~~3'~a ' Table 4A
NMR results for some of the 4--methoxyveratrole Polymerizations Run Iso <Liso> Syn <Lsv~> X. S.
# cocatalyst ~%) units (~%L units % wt) 1 TEA ' 60 13 20 6.4 55.1 4 TIBAL 62 13.5 19.5 6.3 47.5 5 TEA (l per Ti) 60 13.5 21 6.3 49.5 6 TEA/DIBDMS 66.5 17 18 7.1 39.2 7 TEA/M4PYR 54 .13 27 7.1 63.5 8 TEA/(DIBDMS 65 17 20 6.9 39.4 + M4PYR) 10 DEAC/DIBDMS 60 14 21.5 6.5 50.6 The physical properties of some of the polymers prepared above are summarized in Table 4B, The Tset values represent the residual elongation imparted to a sample after. stretching to 400% of original length (at a rate of 20 inches per minute) then allowing to relax to zero stress (at the same rate).
Table 4B
Tensile~data for the polymers prepared in . ~ Example 4 ..,. ...... , . r . -. ;. ~ . _ ..
Elongation ' Run ' - -; Tbreak . Tset ~ .:.- 'fyiel~ _ . ., -at' break # (Psl) (%) (ps1).. - (%) 1.:: . 2920.;;. , -;,130 .::1381 ,, ._ : ~ 890 ~.2 : , 234Z" , .. . . X59 .. r;::;::1.392 . ~ .._ . . 873 ;
. :;. _...3 :~- 2755, ,,~;.:.:Z72 : ...: r1342 . ~;°~:,.,79~.-:
5 .. 2595, .. . ;.;a.;~.64 ;ri ;,~~.;11.?6 .. , ~; ; r.,,,7:6g.C
,10"rr :. : ~ 234,2 , ~ ,,;..::;~1.5~ ~ ::_a:1172;,r°; :rr;:.' ~>~.~83;;
,,.-; ~ ., ;.,;zf ,:tensil.e . s,et :is ;s,ignificantly ,less ythan 3,000.,,: the;_,polymer;~is.,..considered:~elastomeric:
Tensile at break of more than 2000 psi indicates toughness uncharacteristic of typical soft polypropylenes. Uniqueness is further . ... . _ : , ..:., .. _ WO 91/00$75 PCf/US90/02037 demonstrated because crystalline polypropylene exhibits an elongation at break of about 10% and a tensile at break lower than the tensile at yield.
Example 5 The magnesium compound 'M' from Example 4 was used to prepare procatalysts in this Example by stirring 7.8 grams of the desolvated M with 8.6 to 14 mmoles of the appropriate substituted veratrole compound (see Table 5) in 200 ml:of a 50-50 titanium tetrachloride-chlorobenzene solution for 1 hour at 115°C followed by two .
washes at 115°C with fresh.200 m1 portions of that solvent mixture followed by a quick rinse (less than 10 minutes) with 100 m1 of fresh solvent mixture: Excess titanium was removed by .exhaustive isopentane rinses, and .the~catalyst was dried under.moving nitrogen at 40°C. A
portion of the dry powder was then:made into a 5% slurry in mineral oil. The amounts of each electron. donor: used andvthe.analytical results for each'. catalyst= arewpresented ~i- Table 5~.5 ~ Use of higher=tlevelsrof electron donor ,in the digest -:: i ;: step normally :.leads to . lower titanium levels ~in the f.i.nal .procatalyst.~ In each _case;:~ the. goal was to use,.sufficient electron donor:to.keep the 'titanium'-level':belaw :4 % :but :with :.3- . . .
mettioxyveratro~le ' his 'wasw:not ::possible,.~::~ . ...
v.9'~;'~,l :Li.'r:)~:~.! 7t.i i;i!..:..W1::?:~i t."t~> t;"~': ',:.:,i o . ~ ..
':l ~.i:":'('4;j:: ~;G .., ;~,.~::~ .i ;,'j,".7a'C '~~y!~;'i"; . . , . ~.: ..:
:r.'~ii( ..~,i7 r~,: ~ ~.~..~
_.::i, . .i.:, . .. ,. '~ ~' .. F~ :. ... . . ... :_.~..
a ;.;~ 7,~ :.> :.~. ~:?-~"~Cj~t;:oa ~ , .~ . tJ ::a .x w:i~ ~:1 i. :~' ~ '..~~.o. S. L~t:'» :.:) 1. ,: . . n. ,i,Ji i~~ .. .J~.1 .."u. ,. .
~ b "'~ l ~:~fliFra:~ t't..C u:;~ ,:::1: 't~;l . zicz '~' .::'!: ',i.I. 3,..
."! _'. ~J' ::> '~.
. ~!:~:'; ~i v~.L_:n.~~-~.v,..~ :v .. .. . ° ~ ~.-, . ..;~t : : .. _.
:v: :. ~. ,o ~'~:~::
.:.-:: ...,: .. .: , ~ . : _ ..:-.. ,.; :...;. . _ ..,:, g WO 91/00875 . ~ ~ , PCT/US90/02037 Table 5 Catalysts with substituted veratroles as electron donors Catalyst Electron Donor Mg : Ti # (name) ymmol) (% wt) (%S wt) 1 ~ none 0 . ~ 16.5 6.55 2 VERA~ 8.6 20.2 3.01 3 3MV . 10 : - 19 . 5 . . 3 . 84 4. 30MV . 10 17.9 5.78 20 5 40MV 12 18.8 3.55 6 4P10V 14 13.8 2.93 .
VERA = veratrole ' 3MV = 3-methylveratrale 30MV = 3-methoxyveratrole 40MV = 4-methoxyveratrole 4NOV = 4-nitroveratrole For polymerization; procatalysts were .combined with triethyl aluminum (TEA)rwhich was used as a 0.28 molar solution in isooctane. The polymerizations were carried out by injecting a mixture of Ø01 to 0.03 mmoles of procatalyst and .TEA in the. ratio ..shown in Table 5A into: 2 . 7 v=liters of liquid-vpropylene in- a lw gallon autoclave::reactor .and . hen continuing: the .: _ ..
polymerization ..at .67..°C;:for one hour:..:The polymer lumps::were-::cut r: into .small pieces~:and :dried -for v. several .hours iunder .aspirator: vacuum at.80°C. .
bafore physicalrandr..chemical.characterizations were carried.;out::v.:vrThe;~:tensile .'set~,~,. tensile .sc yield, elongation and tensile at break were measured according to ASTM D 412-83 on tensile bars cut with a "D" die from 2mm thick compression molded plates.
The polymerization conditions and results 3g are shown in Table SA. Again, as in Example 4, the xylene soluble levels are extremely high:
WO 91/00875 ~ ~ ,~ ~.i ;' ;.' ",I P~/US9010Z037 ,, , .
The polymers made from the procatalysts containing the electron donors were not tacky to the touch, whereas 'the polymer made via the procatalyst without an electron donor was tacky, 5 indicating the presence of considerable atactic material. ' ..
Table 5A
Autoclave runs to produce homopolymer with veratrole based catalysts (2.7 liters- v 10 propylene, 0.01 - 0.03 mmol Ti, 67°C, 60 min.) Run Cat TEA/Ti Yield X.S.
# # (mol/mol) (Kq,Ja cat/hr) (o wt) 1 1 29 24.1 62.6 2 2 ~ 62 18.2, 64.3 ~
15 3 3 50 20.7 46.8 4 4 33 28.4 ~ 46.9 5 5 53 15.9 ~ 55.1 6 6 64 7,p - 54.3 7 6 200 11.7 47.1 20 TEA - triethylaluminum X.S. = xylene solubles .
The.. tensile ,data~for. the homopnlymers.~_T
produced in the above polymerizations are ,.
summarized in,Table 5B. . The tensile set values 25 reported in SB..differ from those in Table 4B in that~the samples were stretched to only 300%:of their originalvlength before relaxation.
:'. .:. s ."i /;i:,):)~.;~ri(l::i .. ~.'t~.~'l:a: ,.~,,r.','Y-t. '>i. .......t :!~:~~.
......
..., i..__.. ...,., ::. .... ..'7Y..:::., .;.'. ;:'i .... 't,i,:: .....
' . " , 1.,.': .... . ..., . . ,' .
...j~3.~ ~.~r-i :.."~ ':ir..t,~:.i ~.:....~ i ~.'',.7C.1 ~ ...:'S. . . .
'~:5 ~73~~'.:..:... ',:?,: ...?..:~~.,~ . : ~r., .:':i 3 _..,:1... ..
~.:y~~t ,;t.t.,'~~..~'.t .:..~:~ ~~. AJ ).: C(~Cl,i,~dt .::.s ~.. .
1,..r.4~:i.~~.:'~.;.... ~,r.~..X.::~ a . - .
~':f.':r7fr~ ;: -., a wi 'a~ ': .:.:7:.T':''i..r'i ef~'. ..'~"? .i.. ~n "T; S;7C !:
~'~ 91/0075 PCT/US90/02037 ~fl6~3"~5 2&
Table 5B
Tensile data for the polymers prepared in Example 5.
Ellongation T T T . at break break set p eld ED (psy i(%) fpszl t%) None 1690 85 788 963 VERA 2630 82 8?1 874 The NMR results for the homopolymers produced above are summarized in Table 5C. In all cases the polymer is at least 55% isotactic.
A11 of the polymers exhibited average isotactic block lengths between 12 and 15 monomer units.
Table 5C
NMR results for the polymers prepared in Example 5 , Iso <Lyso Syri ~ <LSY~>
ED ... ~ o ) :. :~ units ( o ~ ,:: ~ v v. units None ~ ~ 58 :12 lg . 5. 0 'VERA'~ 59 ' ' 12 20 6.2 ' g~ . .. . 6~ 14 ~- 17 5.6' 30MV : .: 64 . 13 16 . . . 5.6 40MV .. 60 .'. _ : 13 :. ...: . : 20 ;: . - 6.4 4NOV 62 15 20 6.1 i The conclusions drawn from the above data are the same as those drawn fromvthe data in i Tables 4A and 4B. ' Example 6 (po7.ymerizations in butane) . ' Butane polymerizations were carried out, in a nearly identical fashion to~the propylene polymerization, in a l gallon stainless steel WO 9l/00875 PC'f/US90/02037 ~p~6'33°~~
autoclave utilizing 1.8 liter of 1~butene: At the end of 90 minutes the reactions were terminated by injecting 600 ml of isopropyl alcohol to the cooled reactor prior to venting the unreacted monomer. The specific runs, utilizing procatalysts from example #5, are summarized in Table 6A. The pertinent properties of the elastomeric polybutenes are.
summarized in Table 6B. The NMR results l0 summarized in Table 6C reveal that these catalysts produce short block length polybutene.
Table 6A
Autoclave runs to produce polybutylene with veratrole based catalysts (1.8 liters 1-butene, lj 0.01 - 0.02 mmol Ti, 60°C, 90 min) Run Cat SCA/Ti TEA/Ti Yield # ~ SCA (mol/mol) (mol/mol) (Kd/acat) 1 ~'2 from Ex 5 CYANCL 4 105 8.0 2 f4 from Ex 5 DIDD1?S 5 107 A.2 3 ~'5 from Ex 5 none-- 70 7.0 TEA - triethylaluminum CYANCL = cyanuric chloride DIBUMS = diisobutyldimethoxysilane Table 6B
25 Tensile data fbr the polymers prepared in Example 6 Elongation Run T T T at break (psa.) (~~j ~LPsi) ( o) ' 30 1 2751 162 no 485 I
2 1932 166 yield 346 3 1609 110 point 557 1335 100 600 , These materials have a higher elongation at 35 break than normal crystalline polybutene (300--350%) and a lower tensile at break (4000-5000 psi expected for crystalline polybutene). j wo gxioos~s ~crius~oiozo37 psi expected for crystalline polybutene).
Elastomeric behavior is indicated by the low tensile set values.
Table 6C
NMR results for the polymers prepared in Example 6 .
Run ISO <L~so> Syn ~Lsyn~
# (%1 units (%) units I 68 17 ~ I3 5.7 .
2 64 16 ~ 14 6.0 3 60 ' 10 16 6.0
Claims (7)
1. A catalyst component useful in the production of elastomeric, primarily isotactic polypropylene and polybutene which comprises the reaction product of a magnesium alkoxide and a tetravalent titanium halide wherein the reaction takes place in the presence of an electron donor which is selected from the group consisting of a 3-methyl-veratrole, 3-methoxy-veratrole, 4-nitro-veratrole and 4-methoxy-veratrole.
2. The component of claim 1 wherein the reaction also takes place in the presence of a halogenated hydrocarbon.
3. The catalyst component of claim 1 wherein the alkoxide is magnesium ethoxide.
4. A catalyst composition useful in the production of elastomeric, primarily isotactic polypropylene which comprises the catalyst component of claim 1 and an organoaluminum compound.
5. The catalyst composition of claim 4 wherein the reaction also takes place in the presence of a halogenated hydrocarbon.
6. The catalyst composition of claim 4 wherein the catalyst composition also includes a selectivity control agent.
7. The catalyst composition of claim 4 wherein the alkoxide is magnesium ethoxide.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US377,654 | 1989-07-10 | ||
US07/377,654 US4971936A (en) | 1989-07-10 | 1989-07-10 | Catalyst component for making primarily isotactic elastomeric polypropylene or polybutene |
PCT/US1990/002037 WO1991000875A1 (en) | 1989-07-10 | 1990-04-19 | Catalyst component for making primarily isotactic elastomeric polypropylene or polybutene |
Publications (2)
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CA2063375A1 CA2063375A1 (en) | 1991-01-11 |
CA2063375C true CA2063375C (en) | 2000-04-11 |
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CA002063375A Expired - Fee Related CA2063375C (en) | 1989-07-10 | 1990-04-19 | Catalyst component for making primarily isotactic elastomeric polypropylene or polybutene |
Country Status (10)
Country | Link |
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US (1) | US4971936A (en) |
EP (1) | EP0500530B1 (en) |
JP (1) | JPH05501120A (en) |
KR (1) | KR0165560B1 (en) |
AT (1) | ATE142650T1 (en) |
AU (1) | AU630726B2 (en) |
CA (1) | CA2063375C (en) |
DE (1) | DE69028546T2 (en) |
ES (1) | ES2095877T3 (en) |
WO (1) | WO1991000875A1 (en) |
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-
1989
- 1989-07-10 US US07/377,654 patent/US4971936A/en not_active Expired - Lifetime
-
1990
- 1990-04-19 KR KR1019920700045A patent/KR0165560B1/en not_active IP Right Cessation
- 1990-04-19 CA CA002063375A patent/CA2063375C/en not_active Expired - Fee Related
- 1990-04-19 JP JP2510077A patent/JPH05501120A/en active Pending
- 1990-04-19 EP EP90911180A patent/EP0500530B1/en not_active Expired - Lifetime
- 1990-04-19 DE DE69028546T patent/DE69028546T2/en not_active Expired - Fee Related
- 1990-04-19 AU AU59618/90A patent/AU630726B2/en not_active Ceased
- 1990-04-19 AT AT90911180T patent/ATE142650T1/en not_active IP Right Cessation
- 1990-04-19 WO PCT/US1990/002037 patent/WO1991000875A1/en active IP Right Grant
- 1990-04-19 ES ES90911180T patent/ES2095877T3/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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JPH05501120A (en) | 1993-03-04 |
EP0500530A4 (en) | 1992-05-14 |
DE69028546D1 (en) | 1996-10-17 |
ATE142650T1 (en) | 1996-09-15 |
KR927003651A (en) | 1992-12-18 |
AU630726B2 (en) | 1992-11-05 |
ES2095877T3 (en) | 1997-03-01 |
WO1991000875A1 (en) | 1991-01-24 |
AU5961890A (en) | 1991-02-06 |
KR0165560B1 (en) | 1999-03-20 |
EP0500530B1 (en) | 1996-09-11 |
EP0500530A1 (en) | 1992-09-02 |
US4971936A (en) | 1990-11-20 |
CA2063375A1 (en) | 1991-01-11 |
DE69028546T2 (en) | 1997-02-27 |
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