US20010034411A1 - Propylene impact copolymers - Google Patents
Propylene impact copolymers Download PDFInfo
- Publication number
- US20010034411A1 US20010034411A1 US09/862,667 US86266701A US2001034411A1 US 20010034411 A1 US20010034411 A1 US 20010034411A1 US 86266701 A US86266701 A US 86266701A US 2001034411 A1 US2001034411 A1 US 2001034411A1
- Authority
- US
- United States
- Prior art keywords
- component
- weight
- propylene
- zirconium dichloride
- rac
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001577 copolymer Polymers 0.000 title claims abstract description 82
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 50
- VPGLGRNSAYHXPY-UHFFFAOYSA-L zirconium(2+);dichloride Chemical compound Cl[Zr]Cl VPGLGRNSAYHXPY-UHFFFAOYSA-L 0.000 claims description 48
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 41
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 33
- 239000005977 Ethylene Substances 0.000 claims description 33
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 23
- 239000004743 Polypropylene Substances 0.000 claims description 22
- 239000012968 metallocene catalyst Substances 0.000 claims description 21
- 238000009826 distribution Methods 0.000 claims description 17
- -1 polypropylene Polymers 0.000 claims description 14
- 238000002844 melting Methods 0.000 claims description 13
- 230000008018 melting Effects 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 13
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 11
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 claims description 11
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 11
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 9
- 229920001384 propylene homopolymer Polymers 0.000 claims description 9
- 229920001155 polypropylene Polymers 0.000 claims description 8
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 claims description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 7
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 3
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims 3
- 238000000034 method Methods 0.000 abstract description 31
- 230000008569 process Effects 0.000 abstract description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 77
- 239000000243 solution Substances 0.000 description 39
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 34
- 239000003054 catalyst Substances 0.000 description 34
- 239000007787 solid Substances 0.000 description 25
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 229920000642 polymer Polymers 0.000 description 19
- 150000001450 anions Chemical class 0.000 description 16
- 239000007788 liquid Substances 0.000 description 16
- 238000003756 stirring Methods 0.000 description 16
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 15
- 239000002002 slurry Substances 0.000 description 15
- 239000008096 xylene Substances 0.000 description 15
- 239000012190 activator Substances 0.000 description 13
- 150000001875 compounds Chemical class 0.000 description 13
- 239000002904 solvent Substances 0.000 description 13
- 239000000706 filtrate Substances 0.000 description 12
- 230000018044 dehydration Effects 0.000 description 11
- 238000006297 dehydration reaction Methods 0.000 description 11
- AQZWEFBJYQSQEH-UHFFFAOYSA-N 2-methyloxaluminane Chemical compound C[Al]1CCCCO1 AQZWEFBJYQSQEH-UHFFFAOYSA-N 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 10
- 239000011521 glass Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 229920001940 conductive polymer Polymers 0.000 description 9
- 229920001519 homopolymer Polymers 0.000 description 9
- 238000009616 inductively coupled plasma Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000011148 porous material Substances 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- HYBSMPZXNXDOCG-UHFFFAOYSA-N 4-(2-methylphenyl)-2-propan-2-yl-1h-indene Chemical compound C1C(C(C)C)=CC2=C1C=CC=C2C1=CC=CC=C1C HYBSMPZXNXDOCG-UHFFFAOYSA-N 0.000 description 4
- OCTIQWBTLNVDFV-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-2-propan-2-yl-1h-indene Chemical compound C1C(C(C)C)=CC2=C1C=CC=C2C1=CC(C)=CC(C)=C1 OCTIQWBTLNVDFV-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 description 4
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical class [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000002087 whitening effect Effects 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
- VDFIGYCUOGDOPV-UHFFFAOYSA-N 4-chloro-2-propan-2-yl-1h-indene Chemical compound C1=CC=C(Cl)C2=C1CC(C(C)C)=C2 VDFIGYCUOGDOPV-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 241000282326 Felis catus Species 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 229910007928 ZrCl2 Inorganic materials 0.000 description 3
- 229910007932 ZrCl4 Inorganic materials 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 3
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000007517 lewis acids Chemical class 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- XSXHWVKGUXMUQE-UHFFFAOYSA-N osmium dioxide Inorganic materials O=[Os]=O XSXHWVKGUXMUQE-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- DKQVJMREABFYNT-UHFFFAOYSA-N ethene Chemical group C=C.C=C DKQVJMREABFYNT-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012632 extractable Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- DWWZPYPYUFXZTL-UHFFFAOYSA-N lithium;2h-inden-2-ide Chemical compound [Li+].C1=CC=C2[CH-]C=CC2=C1 DWWZPYPYUFXZTL-UHFFFAOYSA-N 0.000 description 2
- JUCGGFUWKYLTMM-UHFFFAOYSA-N lithium;4-(2-methylphenyl)-2-propan-2-yl-1h-inden-1-ide Chemical compound [Li+].C1=CC=C2[CH-]C(C(C)C)=CC2=C1C1=CC=CC=C1C JUCGGFUWKYLTMM-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- ZBRJXVVKPBZPAN-UHFFFAOYSA-L nickel(2+);triphenylphosphane;dichloride Chemical compound [Cl-].[Cl-].[Ni+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 ZBRJXVVKPBZPAN-UHFFFAOYSA-L 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000002195 soluble material Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KWTSZCJMWHGPOS-UHFFFAOYSA-M chloro(trimethyl)stannane Chemical compound C[Sn](C)(C)Cl KWTSZCJMWHGPOS-UHFFFAOYSA-M 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000012718 coordination polymerization Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229920001038 ethylene copolymer Polymers 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000013213 extrapolation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 150000002367 halogens Chemical group 0.000 description 1
- 150000004678 hydrides Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910001504 inorganic chloride Inorganic materials 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- KNWDEBDWCAARDG-UHFFFAOYSA-N lithium;4-(3,5-dimethylphenyl)-2-propan-2-yl-1h-inden-1-ide Chemical compound [Li+].C1=CC=C2[CH-]C(C(C)C)=CC2=C1C1=CC(C)=CC(C)=C1 KNWDEBDWCAARDG-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- UWIBIDGHIMGNRC-UHFFFAOYSA-M magnesium;1,3-dimethylbenzene-5-ide;bromide Chemical compound [Mg+2].[Br-].CC1=C[C-]=CC(C)=C1 UWIBIDGHIMGNRC-UHFFFAOYSA-M 0.000 description 1
- YAMQOOCGNXAQGW-UHFFFAOYSA-M magnesium;methylbenzene;bromide Chemical compound [Mg+2].[Br-].CC1=CC=CC=[C-]1 YAMQOOCGNXAQGW-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011236 particulate material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- QMBQEXOLIRBNPN-UHFFFAOYSA-L zirconocene dichloride Chemical compound [Cl-].[Cl-].[Zr+4].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 QMBQEXOLIRBNPN-UHFFFAOYSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
- B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1608—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes the ligands containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/0827—Syntheses with formation of a Si-C bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/22—Tin compounds
- C07F7/2208—Compounds having tin linked only to carbon, hydrogen and/or halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/30—Germanium compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
-
- 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
- C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
- C08F297/06—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
- C08F297/08—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
- C08F297/083—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins the monomers being ethylene or propylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/48—Zirconium
-
- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/04—Monomers containing three or four carbon atoms
- C08F110/06—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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/04—Monomers containing three or four carbon atoms
- C08F210/06—Propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65916—Component covered by group C08F4/64 containing a transition metal-carbon bond supported on a carrier, e.g. silica, MgCl2, polymer
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2308/00—Chemical blending or stepwise polymerisation process with the same catalyst
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2314/00—Polymer mixtures characterised by way of preparation
- C08L2314/06—Metallocene or single site catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- This invention relates to propylene impact copolymer compositions.
- these unique and improved compositions can be produced using metallocene catalysts in commercial-scale processes.
- Propylene impact copolymers are commonly used in a variety of applications where strength and impact resistance are desired such as molded and extruded automobile parts, household appliances, luggage and furniture. Propylene homopolymers are often unsuitable for such applications because they are too brittle and have low impact resistance particularly at low temperature, whereas propylene impact copolymers are specifically engineered for applications such as these.
- a typical propylene impact copolymer contains two phases or components, a homopolymer component and a copolymer component. These two components are usually produced in a sequential polymerization process wherein the homopolymer produced in a first reactor is transferred to a second reactor where copolymer is produced and incorporated within the matrix of the homopolymer component.
- the copolymer component has rubbery characteristics and provides the desired impact resistance, whereas the homopolymer component provides overall stiffness.
- U.S. Pat. No. 5,258,464 describes propylene impact copolymers with improved resistance to “stress whitening.” Stress whitening refers to the appearance of white spots at points of impact or other stress.
- These otherwise conventional propylene impact copolymers have first and second components characterized by a numerical ratio of the second component intrinsic viscosity to the first component intrinsic viscosity which is near unity.
- nucleating agent is added to propylene impact copolymers having a numerical ratio of the intrinsic viscosity of the copolymer rubber phase (second component) to the intrinsic viscosity of the homopolymer phase (first component) which is near unity, and an ethylene content of the copolymer phase in the range of 38% to 60% by weight.
- second component the intrinsic viscosity of the copolymer rubber phase
- first component the intrinsic viscosity of the homopolymer phase
- ethylene content of the copolymer phase in the range of 38% to 60% by weight.
- U.S. Pat. No. 5,250,631 describes a propylene impact copolymer having a homopolypropylene first component and an ethylene/butene/propylene terpolymer second component. Again, the goal is to obtain high impact strength coupled with resistance to stress whitening.
- Propylene impact copolymers are also used to produce films as described in U.S. Pat. No. 5,948,839.
- the impact copolymer described in this patent contains a conventional first component and 25 to 45 weight percent ethylene/propylene second component having from 55 to 65 weight percent ethylene.
- This impact copolymer composition has a melt flow of from 7 to 60 dg/min. Such films are used in articles such as diapers.
- U.S. 5,990,242 approaches this problem by using an ethylene/butene (or higher ⁇ -olefin) copolymer second component, rather than a propylene copolymer, prepared using a hafnocene type metallocene.
- hafnocene type metallocene such hafnium metallocenes in general are known for producing relatively higher molecular weight polymers; however, their activities are much lower than the more commonly used zirconocenes.
- the second component molecular weights and intrinsic viscosities are lower than desired for good impact strength.
- the present inventors have discovered new propylene impact copolymer compositions having the benefits of metallocene catalyzed polymers in addition to properties needed for high impact strength. Importantly, these polymers can be economically produced using commercial-scale processes.
- the present invention provides reactor produced propylene impact copolymer compositions comprising:
- Component A comprising propylene homopolymer or copolymer wherein the copolymer comprises 10% or less by weight ethylene, butene, hexene or octene comonomer;
- Component B comprising propylene copolymer wherein the copolymer comprises from about 20% to about 70% by weight ethylene, butene, hexene and/or octene comonomer, and from about 80% to about 30% by weight propylene, wherein Component B:
- This invention also provides a process for producing propylene impact copolymer in a multiple stage process wherein Component A comprising propylene homopolymer or copolymer wherein the copolymer comprises 10% or less by weight ethylene, butene, hexene or octene comonomer is produced in a primary stage and Component B is produced in a subsequent stage, Component B comprising propylene copolymer wherein the copolymer comprises from about 20% to about 70% by weight ethylene, butene, hexene and/or octene comonomer, and from about 80% to about 30% by weight propylene, wherein at least one of Components A and/or B are polymerized using a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr,4-phenylindenyl) 2 zirconium dichloride; rac-dimethylsiladiyl(2-i
- the propylene impact copolymers (“ICPs”) of this invention comprise at least two major components, Component A and Component B.
- Component A is preferably an isotactic propylene homopolymer, though small amounts of a comonomer may be used to obtain particular properties.
- Such copolymers of Component A contain 10% by weight or less, preferably less than 6% by weight or less, comonomer such as ethylene, butene, hexene or octene. Most preferably less than 4% by weight ethylene is used.
- the end result is usually a product with lower stiffness but with some gain in impact strength compared to homopolymer Component A.
- Component A refers generally to the xylene insoluble portion of the ICP composition
- Component B refers generally to the xylene soluble portion.
- the xylene soluble portion clearly has both a high molecular weight component and a low molecular weight component, we have found that the low molecular weight component is attributable to amorphous, low molecular weight propylene homopolymer. Therefore, Component B in such circumstances refers only the high molecular weight portion.
- Component A preferably has a narrow molecular weight distribution Mw/Mn (“MWD”), i.e., lower than 4.0, preferably lower than 3.5, more preferably lower than 3.0, and most preferably 2.5 or lower. These molecular weight distributions are obtained in the absence of visbreaking using peroxide or other post reactor treatment designed to reduce molecular weight.
- Component A preferably has a weight average molecular weight (Mw as determined by GPC) of at least 100,000, preferably at least 200,000 and a melting point (Mp) of at least 145° C., preferably at least 150° C., more preferably at least 152° C., and most preferably at least 155° C.
- ICPs Another important feature of ICPs is the amount of amorphous polypropylene they contain.
- the ICPs of this invention are characterized as having low amorphous polypropylene, preferably less than 3% by weight, more preferably less than 2% by weight, even more preferably less than 1% by weight and most preferably there is no measurable amorphous polypropylene.
- Component B is most preferably a copolymer consisting essentially of propylene and ethylene although other propylene copolymers, ethylene copolymers or terpolymers may be suitable depending on the particular product properties desired.
- propylene/butene, hexene or octene copolymers, and ethylene/butene, hexene or octene copolymers may be used, and propylene/ethylene/hexene-1 terpolymers may be used.
- Component B is a copolymer comprising at least 40% by weight propylene, more preferably from about 80% by weight to about 30% by weight propylene, even more preferably from about 70% by weight to about 35% by weight propylene.
- the comonomer content of Component B is preferably in the range of from about 20% to about 70% by weight comonomer, more preferably from about 30% to about 65% by weight comonomer, even more preferably from about 35% to about 60% by weight comonomer.
- Most preferably Component B consists essentially of propylene and from about 20% to about 70% ethylene, more preferably from about 30% to about 65% ethylene, and most preferably from about 35% to about 60% ethylene.
- Component B For other Component B copolymers, the comonomer contents will need to be adjusted depending on the specific properties desired. For example, for ethylene/hexene copolymers, Component B should contain at least 17% by weight hexene and at least 83% by weight ethylene.
- Component B preferably has a narrow molecular weight distribution Mw/Mn (“MWD”), i.e., lower than 5.0, preferably lower than 4.0, more preferably lower than 3.5, even more preferably lower than 3.0 and most preferably 2.5 or lower. These molecular weight distributions should be obtained in the absence of visbreaking or peroxide or other post reactor treatment designed to reduce molecular weight.
- Component B preferably has a weight average molecular weight (Mw as determined by GPC) of at least 100,000, preferably at least 150,000, and most preferably at least 200,000.
- Component B preferably has an intrinsic viscosity greater than 1.00 dl/g, more preferably greater than 1.50 dl/g and most preferably greater than 2.00 dl/g.
- intrinsic viscosity or “IV” is used conventionally herein to mean the viscosity of a solution of polymer such as Component B in a given solvent at a given temperature, when the polymer composition is at infinite dilution.
- IV measurement involves a standard capillary viscosity measuring device, in which the viscosity of a series of concentrations of the polymer in the solvent at the given temperature are determined.
- decalin is a suitable solvent and a typical temperature is 135° C. From the values of the viscosity of solutions of varying concentrations, the “value” at infinite dilution can be determined by extrapolation.
- Component B preferably has a composition distribution (CD) of greater than 60%, more preferably greater than 65%, even more preferably greater than 70%, even more preferably greater than 75%, still more preferably greater than 80%, and most preferably greater than 85%.
- CD defines the compositional variation among polymer chains in terms of ethylene (or other comonomer) content of the copolymer as a whole. The measurement of CD is described in detail U.S. Pat. No. 5,191,042 which is hereby fully incorporated by reference. CD is defined herein as the weight percent of the copolymer molecules having a comonomer content within 50% of the median total molar comonomer content.
- CD is determined by first determining the mean ethylene (or other comonomer) content of the copolymer by a suitable test such as ASTM D-3900. Next, the copolymer sample is dissolved in solvent such as hexane and a number of fractions of differing composition are precipitated by the addition of incremental amounts of a liquid such as isopropanol in which the copolymer is insoluble. Generally from about 4 to 6 fractions are precipitated in this way and the weight and ethylene (or other comonomer) content of each fraction are determined after removing the solvent. From the weight of each fraction and its ethylene content, a plot is prepared of weight percent composition vs. cumulative weight percent of polymer, and a smooth curve is drawn through the points.
- Component B of the ICPs preferably has low crystallinity, preferably less than 10% by weight of a crystalline portion, more preferably less than 5% by weight of a crystalline portion. Where there is a crystalline portion of Component B, its composition is preferably the same as or at least similar to (within 15% by weight) the remainder of Component B in terms of overall comonomer weight percent.
- the ICPs of this invention are “reactor produced” meaning Components A and B are not physically or mechanically blended together. Rather, they are interpolymerized in at least one reactor. The final ICP as obtained from the reactor or reactors, however, can be blended with various other components including other polymers.
- the preferred melt flow rate (“MFR”) of these ICPs depends on the desired end use but is typically in the range of from about 0.2 dg/min to about 200 dg/min, more preferably from about 5 dg/min to about 100 dg/min. Significantly, high MFRs, i.e., higher than 50 dg/min are obtainable. MFR is determined by a conventional procedure such as ASTM-1238 Cond. L.
- the ICP preferably has a melting point of at least 145° C., preferably at least 150° C., more preferably at least 152° C., and most preferably at least 155° C.
- the ICPs comprise from about 40% to about 95% by weight Component A and from about 5% to about 60% by weight Component B, preferably from about 50% to about 95% by weight Component A and from about 5% to about 50% Component B, even more preferably from about 60% to about 90% by weight Component A and from about 10% to about 40% by weight Component B.
- the ICP consists essentially of Components A and B.
- the overall comonomer (preferably ethylene) content of the total ICP is preferably in the range of from about 2% to about 30% by weight, preferably from about 5% to about 25% by weight, even more preferably from about 5% to about 20% by weight, still more preferably from about 5% to about 15% by weight comonomer.
- additives may be incorporated into the ICP for various purposes.
- Such additives include, for example, stabilizers, antioxidants, fillers, colorants, nucleating agents and mold release agents.
- the ICP compositions of this invention may be prepared by conventional polymerization processes such as a two-step process. It is conceivable, although currently impractical, to commercially produce ICPs in a single reactor. Each step may be independently carried out in either the gas or liquid slurry phase. For example the first step may be conducted in the gas phase and the second in liquid slurry or vice versa. Alternatively, each phase may be the same.
- the ICPs of this invention are produced in multiple reactors, preferably two or three, operated in series, Component B is preferably polymerized in a second, gas phase reactor. Component A is preferably polymerized first, in a liquid slurry or solution polymerization process.
- Component A is made in at least two reactors in order to obtain fractions with varying melt flow rate. This has been found to improve the processability of the ICP.
- stage is defined as that portion of a polymerization process during which one component of the ICP, Component A or Component B, is produced.
- One or multiple reactors may be used during each stage.
- Hydrogen may be added to one or both reactors to control molecular weight, IV and MFR.
- the use of hydrogen for such purposes is well known to those skilled in the art.
- a metallocene catalyst system is used to produce the ICP compositions of this invention.
- the most suitable metallocenes are those in the generic class of bridged, substituted bis(cyclopentadienyl) metallocenes, specifically bridged, substituted bis(indenyl) metallocenes known to produce high molecular weight, high melting, highly isotactic propylene polymers.
- those of the generic class disclosed in U.S. Pat. No. 5,770,753 should be suitable, however, it has been found that the exact polymer obtained is highly dependent on the metallocene's specific substitution pattern.
- racemic metallocenes are most suitable for preparing the ICP compositions of this invention: rac-dimethylsiladiyl(2-iPr,4-phenylindenyl) 2 zirconium dichloride; rac-dimethylsiladiyl(2-iPr,4-[1-naphthyl]indenyl) 2 zirconium dichloride; rac-dimethylsiladiyl(2-iPr, 4-[3,5-dimethylphenyl]indenyl) 2 zirconium dichloride; rac-dimethylsiladiyl(2-iPr, 4-[ortho-methyl-phenyl]indenyl) 2 zirconium dichloride; and rac-diphenylsiladiyl(2-methyl-4-[1-naphthyl]indenyl) 2 zirconium dichloride.
- Metallocenes are generally used in combination with some form of activator in order to create an active catalyst system.
- activator is defined herein to be any compound or component, or combination of compounds or components, capable of enhancing the ability of one or more metallocenes to polymerize olefins.
- Alkylalumoxanes such as methylalumoxane (MAO) are commonly used as metallocene activators. Generally alkylalumoxanes contain 5 to 40 of the repeating units:
- R is a C 1 -C 8 alkyl including mixed alkyls.
- Compounds in which R is methyl are particularly preferred.
- Alumoxane solutions, particularly methylalumoxane solutions, may be obtained from commercial vendors as solutions having various concentrations. There are a variety of methods for preparing alumoxane, non-limiting examples of which are described in U.S. Pat. Nos.
- Ionizing activators may also be used to activate metallocenes. These activators are neutral or ionic, or are compounds such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, which ionize the neutral metallocene compound. Such ionizing compounds may contain an active proton, or some other cation associated with, but not coordinated or only loosely coordinated to, the remaining ion of the ionizing compound. Combinations of activators may also be used, for example, alumoxane and ionizing activator combination, see for example, WO 94/07928.
- ionic catalysts for coordination polymerization comprised of metallocene cations activated by non-coordinating anions appear in the early work in EP-A-0 277 003, EP-A-0 277 004 and U.S. Pat. No. 5,198,401 and WO-A-92/00333 (incorporated herein by reference). These teach desirable methods of preparation wherein metallocenes (bisCp and monoCp) are protonated by an anion precursor such that an alkyl/hydride group is abstracted from a transition metal to make it both cationic and charge-balanced by the non-coordinating anion.
- Suitable ionic salts include tetrakis-substituted borate or aluminum salts having fluorided aryl-constituents such as phenyl, biphenyl and napthyl.
- noncoordinating anion means an anion which either does not coordinate to said cation or which is only weakly coordinated to said cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base.
- “Compatible” noncoordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral four coordinate metallocene compound and a neutral by-product from the anion.
- Particularly useful noncoordinating anions are those which are compatible, stabilize the metallocene cation in the sense of balancing its ionic charge in a +1 state, yet retain sufficient lability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization.
- ionizing ionic compounds not containing an active proton but capable of producing both the active metallocene cation and a noncoordinating anion. See, for example, EP-A-0 426 637 and EP-A-0 573 403 (incorporated herein by reference).
- An additional method of making the ionic catalysts uses ionizing anion precursors which are initially neutral Lewis acids but form the cation and anion upon ionizing reaction with the metallocene compounds, for example the use of tris(pentafluorophenyl) borane. See EP-A-0 520 732 (incorporated herein by reference).
- Ionic catalysts for addition polymerization can also be prepared by oxidation of the metal centers of transition metal compounds by anion precursors containing metallic oxidizing groups along with the anion groups, see EP-A-0 495 375 (incorporated herein by reference).
- the metal ligands include halogen moieties (for example, bis-cyclopentadienyl zirconium dichloride) which are not capable of ionizing abstraction under standard conditions, they can be converted via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc. See EP-A-0 500 944 and EP-A1-0 570 982 (incorporated herein by reference) for in situ processes describing the reaction of alkyl aluminum compounds with dihalo-substituted metallocene compounds prior to or with the addition of activating anionic compounds.
- organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc.
- the activator for the metallocene supported catalyst composition is a NCA
- the NCA is first added to the support composition followed by the addition of the metallocene catalyst.
- the activator is MAO
- the MAO and metallocene catalyst are dissolved together in solution.
- the support is then contacted with the MAO/metallocene catalyst solution.
- the catalyst systems used to prepare the compositions of this invention are preferably supported using a porous particulate material, such as for example, talc, inorganic oxides, inorganic chlorides and resinous materials such as polyolefin or polymeric compounds.
- a porous particulate material such as for example, talc, inorganic oxides, inorganic chlorides and resinous materials such as polyolefin or polymeric compounds.
- the support materials are porous inorganic oxide materials, which include those from the Periodic Table of Elements of Groups 2, 3, 4, 5, 13 or 14 metal oxides.
- Silica, alumina, silica-alumina, and mixtures thereof are particularly preferable.
- Other inorganic oxides that may be employed either alone or in combination with the silica, alumina or silica-alumina are magnesia, titania, zirconia, and the like.
- the support material is porous silica which has a surface area in the range of from 10 to 700 m 2 /g, a total pore volume in the range of from 0.1 to 4.0 cc/g and an average particle size in the range of from 10 to 500 ⁇ m. More preferably, the surface area is in the range of from 50 to 500 m 2 /g, the pore volume is in the range of from 0.5 to 3.5 cc/g and the average particle size is in the range of from 20 to 200 ⁇ m.
- the surface area is in the range of from 100 to 400 m 2 /g
- the pore volume is in the range of from 0.8 to 3.0 cc/g
- the average particle size is in the range of from 30 to 100 pm.
- the average pore size of typical porous support materials is in the range of from 10 to 1000 ⁇ .
- a support material is used that has an average pore diameter of from 50 to 500 ⁇ , and most desirably from 75 to 350 ⁇ . It may be particularly desirable to dehydrate the silica at a temperature of from 100° C. to 800° C. anywhere from 3 to 24 hours.
- the metallocenes, activator and support material may be combined in any number of ways. Suitable support techniques are described in U.S. Pat. Nos. 4,808,561 and 4,701,432 (each fully incorporated herein by reference). Preferably the metallocenes and activator are combined and their reaction product supported on the porous support material as described in U. S. Pat. No. 5,240,894 and WO 94/28034, WO 96/00243, and WO 96/00245 (each fully incorporated herein by reference). Alternatively, the metallocenes may be preactivated separately and then combined with the support material either separately or together. If the metallocenes are separately supported, then preferably, they are dried then combined as a powder before use in polymerization.
- the total volume of reaction solution applied to porous support is desirably less than 4 times the total pore volume of the porous support, more desirably less than 3 times the total pore volume of the porous support and even more desirably in the range of from more than 1 to less than 2.5 times the total pore volume of the porous support.
- Procedures for measuring the total pore volume of porous support are well known in the art. One such method is described in Volume 1, Experimental Methods in Catalyst Research, Academic Press, 1968, pages 67-96.
- Methods of supporting ionic catalysts comprising metallocene cations and noncoordinating anions are described in WO 91/09882, WO 94/03506, WO 96/04319 and in co-pending U.S. Ser. No. 08/248,284, filed Aug. 3, 1994 (incorporated herein by reference).
- the methods generally comprise either physical adsorption on traditional polymeric or inorganic supports that have been largely dehydrated and dehydroxylated, or using neutral anion precursors that are sufficiently strong Lewis acids to activate retained hydroxy groups in silica containing inorganic oxide supports such that the Lewis acid becomes covalently bound and the hydrogen of the hydroxy group is available to protonate the metallocene compounds.
- the supported catalyst system may be used directly in polymerization or the catalyst system may be prepolymerized using methods well known in the art.
- prepolymerization see U.S. Pat. Nos. 4,923,833 and 4,921,825, EP 0 279 863 and EP 0 354 893 each of which is fully incorporated herein by reference.
- Metallocene A racemic dimethylsiladiyl(2-isopropyl-4-phenylindenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
- Metallocene B racemic dimethylsiladiyl(2-isopropyl-4-[1-naphthyl]indenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
- Metallocene C racemic dimethylsiladiyl(2-isopropyl-4-[2-methyl-phenyl]indenyl) 2 zirconium dichloride was prepared as follows:
- Metallocene D racemic dimethylsiladiyl(2-isopropyl-4-[3,5-dimethylphenyl]indenyl) 2 zirconium dichloride was prepared as follows:
- Metallocene E racemic diphenylsiladiyl(2-methyl-4-[1-naphthyl]indenyl) 2 zirconium dichloride was prepared as follows.
- a slurry of Ph 2 Si(2-Methyl-4-[1-napthyl]indenyl lithium) 2 was prepared from addition of a 2.0 M solution of n-Butyl lithium and pentane (1.5 mL, 3.0 mmol) to a mixture of Ph 2 Si(2-Methyl, 4-napthyl indene) 2 (1.0 g, 1.44 mmol) and diethyl ether (20 mL). After stirring for two hours, trimethyl tin chloride (0.6 g, 3.0 mmol) was added. The color changed instantly from an intense to light yellow. The ether was removed and the product extracted with pentane (3 ⁇ 20 mL). Removal of solvent yielded product. Yield 0.88 g, 60%.
- Comparison Metallocene 1 racemic dimethylsiladiyl(2-methyl-4-phenylindenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
- Comparison Metallocene 2 racemic dimethylsiladiyl(2-methyl-4-[1-naphthyl]indenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
- Comparison Metallocene 3 racemic dimethylsiladiyl(2-methyl-4-phenylindenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
- Comparison Metallocene 4 racemic dimethylsiladiyl(2-ethyl-4-phenylindenyl) 2 zirconium dichloride was obtained from commercial sources and used as received.
- the polymerization procedure for producing ICP with the supported catalysts was as follows. In a clean, dry two liter autoclave which had been flushed with propylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added. Hydrogen gas was added at this point. The reactor was closed and filled with 800 mL liquid propylene. After heating the reactor to 70° C., the catalyst was added by washing in with propylene (200 mL). After the indicated time, typically one hour, the reactor was vented to about 170 psig pressure and then an ethylene/propylene gas mixture was passed through the reactor at the rates indicated while maintaining 200 psig. At the end of the gas phase stage, typically 90 to 150 minutes, the reactor was vented and cooled under N2. The granular ICP polymer was removed and dried. Results are shown in Tables 1A and 2A.
- Results are shown in Tables 1B, 2B and 3-8.
- DSC melting points were determined on commercial DSC instruments and are reported as the second melting point.
- the polymer sample was heated to 230.0° C. for ten minutes and then cooled from 230° C. to 50° C. at 10° C./minute. The sample is held at 50° C. for five minutes.
- the second melt is then recorded as the sample is heated from 50° C. to 200° C. at a rate of 10° C/minute.
- the peak temperature is recorded as the second melting point.
- the ICP polymer was dissolved in hot xylene and then allowed to cool overnight. After filtration the insolubes are dried. The xylene soluble portion was evaporated and the soluble material recovered. The IV of the recovered soluble material was measured in decalin at 135° C. by using know methods and instruments such as a Schott A VSPro Viscosity Automatic Sampler.
- the impact copolymers of this invention display improved impact properties as measured by the room temperature notched Izod values at similar Flexural Modulus. This can be seen by examining Table 8.
- the ICP from inventive run 43 with inventive metallocene F has a Flexural Modulus of 151.8K with a Notched Izod of 1.57 value
- the ICP from inventive run 50 with inventive metallocene G has a Flexural Modulus of 158.3K with a Notched Izod of 1.7 value.
- the comparative examples shown in runs 46, 47 and 48 where the second values for each are 158.6K, 155.8K and 155.7K with an inferior notched Izods of 1.25, 0.81 and 0.74 values.
- both inventive runs 43 and 50 have better impact strength as measured by notched Izod at similar Flexural modulus than the comparative runs.
- the known metallocenes comparison 1 and 2 are limited to low values for this molecular weight as measured by the IV of Component B.
- the maximum value of IV for the comparative metallocenes was a value of about 1.7 for run 9 (Table IB) with the ethylene/propylene at a 4.2/0.8 ratio.
- Inventive metallocene B at this ratio produced an IV that ranged from 1.99 in run 13 to 2.338 in run 18.
- the inventive metallocene D produced an ICP with an IV of 3.508 in run 40.
- the IV values were greater than 2.2 for all ICP products and ranged from 2.202 (run 39) to 3.667 (run 38). These high IV values will result in further improved impact properties.
- Homo PP Comp. 2 3.12 0.9 99.1 13 ICP B 129.0 12.4 86.9 21 Homo PP E 10.3 0.7 99.3 22 ICP E 3.66 24 75.6 10.95 50.37 21.7 2.185 23 ICP E 7.01 20.9 79.3 6.46 36.4 17.7 2.11 24 ICP E 131.01 22 78.1 9.37 47.34 19.8 2.06 25 Homo PP E 681.8 2.1 98
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
Abstract
This invention relates to propylene impact copolymer compositions. In particular, these unique and improved compositions can be produced using conventional, commercial-scale processes.
Description
- This is based on Provisional Application U.S. Ser. No. 60/181016 filed Feb. 8, 2000.
- This invention relates to propylene impact copolymer compositions. In particular, these unique and improved compositions can be produced using metallocene catalysts in commercial-scale processes.
- Propylene impact copolymers are commonly used in a variety of applications where strength and impact resistance are desired such as molded and extruded automobile parts, household appliances, luggage and furniture. Propylene homopolymers are often unsuitable for such applications because they are too brittle and have low impact resistance particularly at low temperature, whereas propylene impact copolymers are specifically engineered for applications such as these.
- A typical propylene impact copolymer contains two phases or components, a homopolymer component and a copolymer component. These two components are usually produced in a sequential polymerization process wherein the homopolymer produced in a first reactor is transferred to a second reactor where copolymer is produced and incorporated within the matrix of the homopolymer component. The copolymer component has rubbery characteristics and provides the desired impact resistance, whereas the homopolymer component provides overall stiffness.
- Many process variables influence the resulting impact copolymer and these have been extensively studied and manipulated to obtain various desired effects. For example U.S. Pat. No. 5,166,268 describes a “cold forming” process for producing propylene impact copolymers where finished articles are fabricated at temperatures below the melting point of the preform material, in this case, the propylene impact copolymer. The patented process uses a propylene impact copolymer comprised of either a homopolymer or crystalline copolymer matrix (first component) and at least ten percent by weight of an “interpolymer” of ethylene and a small amount of propylene (the second component). Adding comonomer to the first component lowers its stiffness. The ethylene/propylene copolymer second component enables the finished, cold-formed article to better maintain its shape.
- U.S. Pat. No. 5,258,464 describes propylene impact copolymers with improved resistance to “stress whitening.” Stress whitening refers to the appearance of white spots at points of impact or other stress. These otherwise conventional propylene impact copolymers have first and second components characterized by a numerical ratio of the second component intrinsic viscosity to the first component intrinsic viscosity which is near unity.
- In U.S. Pat. No. 5,362,782, nucleating agent is added to propylene impact copolymers having a numerical ratio of the intrinsic viscosity of the copolymer rubber phase (second component) to the intrinsic viscosity of the homopolymer phase (first component) which is near unity, and an ethylene content of the copolymer phase in the range of 38% to 60% by weight. These propylene impact copolymers are described as producing articles having good clarity as well as impact strength and resistance to stress whitening. The nucleating agents increase stiffness and impact strength.
- U.S. Pat. No. 5,250,631 describes a propylene impact copolymer having a homopolypropylene first component and an ethylene/butene/propylene terpolymer second component. Again, the goal is to obtain high impact strength coupled with resistance to stress whitening.
- Propylene impact copolymers are also used to produce films as described in U.S. Pat. No. 5,948,839. The impact copolymer described in this patent contains a conventional first component and 25 to 45 weight percent ethylene/propylene second component having from 55 to 65 weight percent ethylene. This impact copolymer composition has a melt flow of from 7 to 60 dg/min. Such films are used in articles such as diapers.
- Recently, efforts have been made to prepare propylene impact copolymers using the newly developed metallocene catalysis technology in order to capitalize on the inherent benefits such catalysts provide. It is well known that homopolymers prepared with such “single-site” catalysts have narrow molecular weight distributions, and low extractables and a variety of other favorable properties associated therewith. Metallocene catalyzed copolymers have narrow composition distributions in addition to narrow molecular weight distribution and low extractables.
- Unfortunately, known metallocenes are not able to provide copolymer components with high enough molecular weight under commercially relevant process conditions. The resulting propylene impact copolymers have poor impact strength compared to their conventionally catalyzed counterparts.
- U.S. 5,990,242 approaches this problem by using an ethylene/butene (or higher α-olefin) copolymer second component, rather than a propylene copolymer, prepared using a hafnocene type metallocene. Such hafnium metallocenes in general are known for producing relatively higher molecular weight polymers; however, their activities are much lower than the more commonly used zirconocenes. In any event, the second component molecular weights and intrinsic viscosities are lower than desired for good impact strength.
- The present inventors have discovered new propylene impact copolymer compositions having the benefits of metallocene catalyzed polymers in addition to properties needed for high impact strength. Importantly, these polymers can be economically produced using commercial-scale processes.
- The present invention provides reactor produced propylene impact copolymer compositions comprising:
- (a) From about 40% to about 95% by weight Component A based on the total weight of the impact copolymer, Component A comprising propylene homopolymer or copolymer wherein the copolymer comprises 10% or less by weight ethylene, butene, hexene or octene comonomer;
- (b) From about 5% to about 60% by weight Component B based on the total weight of the impact copolymer, Component B comprising propylene copolymer wherein the copolymer comprises from about 20% to about 70% by weight ethylene, butene, hexene and/or octene comonomer, and from about 80% to about 30% by weight propylene, wherein Component B:
- (i) has a weight average molecular weight of at least 100,000;
- (ii) a composition distribution of greater than 60%; and
- (iii) an intrinsic viscosity of greater than 1.00 dl/g.
- This invention also provides a process for producing propylene impact copolymer in a multiple stage process wherein Component A comprising propylene homopolymer or copolymer wherein the copolymer comprises 10% or less by weight ethylene, butene, hexene or octene comonomer is produced in a primary stage and Component B is produced in a subsequent stage, Component B comprising propylene copolymer wherein the copolymer comprises from about 20% to about 70% by weight ethylene, butene, hexene and/or octene comonomer, and from about 80% to about 30% by weight propylene, wherein at least one of Components A and/or B are polymerized using a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr,4-phenylindenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr,4-[1-naphthyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr, 4-[3,5-dimethylphenyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr, 4-[ortho-methyl-phenyl]indenyl)2zirconium dichloride; and rac-diphenylsiladiyl(2-methyl-4-[1-naphthyl]indenyl)2zirconium dichloride.
- The propylene impact copolymers (“ICPs”) of this invention comprise at least two major components, Component A and Component B. Component A is preferably an isotactic propylene homopolymer, though small amounts of a comonomer may be used to obtain particular properties. Typically such copolymers of Component A contain 10% by weight or less, preferably less than 6% by weight or less, comonomer such as ethylene, butene, hexene or octene. Most preferably less than 4% by weight ethylene is used. The end result is usually a product with lower stiffness but with some gain in impact strength compared to homopolymer Component A.
- As used herein Component A refers generally to the xylene insoluble portion of the ICP composition, and Component B refers generally to the xylene soluble portion. Where the xylene soluble portion clearly has both a high molecular weight component and a low molecular weight component, we have found that the low molecular weight component is attributable to amorphous, low molecular weight propylene homopolymer. Therefore, Component B in such circumstances refers only the high molecular weight portion.
- Component A preferably has a narrow molecular weight distribution Mw/Mn (“MWD”), i.e., lower than 4.0, preferably lower than 3.5, more preferably lower than 3.0, and most preferably 2.5 or lower. These molecular weight distributions are obtained in the absence of visbreaking using peroxide or other post reactor treatment designed to reduce molecular weight. Component A preferably has a weight average molecular weight (Mw as determined by GPC) of at least 100,000, preferably at least 200,000 and a melting point (Mp) of at least 145° C., preferably at least 150° C., more preferably at least 152° C., and most preferably at least 155° C.
- Another important feature of ICPs is the amount of amorphous polypropylene they contain. The ICPs of this invention are characterized as having low amorphous polypropylene, preferably less than 3% by weight, more preferably less than 2% by weight, even more preferably less than 1% by weight and most preferably there is no measurable amorphous polypropylene.
- Component B is most preferably a copolymer consisting essentially of propylene and ethylene although other propylene copolymers, ethylene copolymers or terpolymers may be suitable depending on the particular product properties desired. For example, propylene/butene, hexene or octene copolymers, and ethylene/butene, hexene or octene copolymers may be used, and propylene/ethylene/hexene-1 terpolymers may be used. In a preferred embodiment though, Component B is a copolymer comprising at least 40% by weight propylene, more preferably from about 80% by weight to about 30% by weight propylene, even more preferably from about 70% by weight to about 35% by weight propylene. The comonomer content of Component B is preferably in the range of from about 20% to about 70% by weight comonomer, more preferably from about 30% to about 65% by weight comonomer, even more preferably from about 35% to about 60% by weight comonomer. Most preferably Component B consists essentially of propylene and from about 20% to about 70% ethylene, more preferably from about 30% to about 65% ethylene, and most preferably from about 35% to about 60% ethylene.
- For other Component B copolymers, the comonomer contents will need to be adjusted depending on the specific properties desired. For example, for ethylene/hexene copolymers, Component B should contain at least 17% by weight hexene and at least 83% by weight ethylene.
- Component B, preferably has a narrow molecular weight distribution Mw/Mn (“MWD”), i.e., lower than 5.0, preferably lower than 4.0, more preferably lower than 3.5, even more preferably lower than 3.0 and most preferably 2.5 or lower. These molecular weight distributions should be obtained in the absence of visbreaking or peroxide or other post reactor treatment designed to reduce molecular weight. Component B preferably has a weight average molecular weight (Mw as determined by GPC) of at least 100,000, preferably at least 150,000, and most preferably at least 200,000.
- Component B preferably has an intrinsic viscosity greater than 1.00 dl/g, more preferably greater than 1.50 dl/g and most preferably greater than 2.00 dl/g. The term “intrinsic viscosity” or “IV” is used conventionally herein to mean the viscosity of a solution of polymer such as Component B in a given solvent at a given temperature, when the polymer composition is at infinite dilution. According to the ASTM standard test method D 1601-78, IV measurement involves a standard capillary viscosity measuring device, in which the viscosity of a series of concentrations of the polymer in the solvent at the given temperature are determined. For Component B, decalin is a suitable solvent and a typical temperature is 135° C. From the values of the viscosity of solutions of varying concentrations, the “value” at infinite dilution can be determined by extrapolation.
- Component B preferably has a composition distribution (CD) of greater than 60%, more preferably greater than 65%, even more preferably greater than 70%, even more preferably greater than 75%, still more preferably greater than 80%, and most preferably greater than 85%. CD defines the compositional variation among polymer chains in terms of ethylene (or other comonomer) content of the copolymer as a whole. The measurement of CD is described in detail U.S. Pat. No. 5,191,042 which is hereby fully incorporated by reference. CD is defined herein as the weight percent of the copolymer molecules having a comonomer content within 50% of the median total molar comonomer content.
- As described in U.S. Pat. No. 5,191,042, CD is determined by first determining the mean ethylene (or other comonomer) content of the copolymer by a suitable test such as ASTM D-3900. Next, the copolymer sample is dissolved in solvent such as hexane and a number of fractions of differing composition are precipitated by the addition of incremental amounts of a liquid such as isopropanol in which the copolymer is insoluble. Generally from about 4 to 6 fractions are precipitated in this way and the weight and ethylene (or other comonomer) content of each fraction are determined after removing the solvent. From the weight of each fraction and its ethylene content, a plot is prepared of weight percent composition vs. cumulative weight percent of polymer, and a smooth curve is drawn through the points.
- Component B of the ICPs preferably has low crystallinity, preferably less than 10% by weight of a crystalline portion, more preferably less than 5% by weight of a crystalline portion. Where there is a crystalline portion of Component B, its composition is preferably the same as or at least similar to (within 15% by weight) the remainder of Component B in terms of overall comonomer weight percent.
- The ICPs of this invention are “reactor produced” meaning Components A and B are not physically or mechanically blended together. Rather, they are interpolymerized in at least one reactor. The final ICP as obtained from the reactor or reactors, however, can be blended with various other components including other polymers.
- The preferred melt flow rate (“MFR”) of these ICPs depends on the desired end use but is typically in the range of from about 0.2 dg/min to about 200 dg/min, more preferably from about 5 dg/min to about 100 dg/min. Significantly, high MFRs, i.e., higher than 50 dg/min are obtainable. MFR is determined by a conventional procedure such as ASTM-1238 Cond. L. The ICP preferably has a melting point of at least 145° C., preferably at least 150° C., more preferably at least 152° C., and most preferably at least 155° C.
- The ICPs comprise from about 40% to about 95% by weight Component A and from about 5% to about 60% by weight Component B, preferably from about 50% to about 95% by weight Component A and from about 5% to about 50% Component B, even more preferably from about 60% to about 90% by weight Component A and from about 10% to about 40% by weight Component B. In the most preferred embodiment, the ICP consists essentially of Components A and B. The overall comonomer (preferably ethylene) content of the total ICP is preferably in the range of from about 2% to about 30% by weight, preferably from about 5% to about 25% by weight, even more preferably from about 5% to about 20% by weight, still more preferably from about 5% to about 15% by weight comonomer.
- A variety of additives may be incorporated into the ICP for various purposes. Such additives include, for example, stabilizers, antioxidants, fillers, colorants, nucleating agents and mold release agents.
- The ICP compositions of this invention may be prepared by conventional polymerization processes such as a two-step process. It is conceivable, although currently impractical, to commercially produce ICPs in a single reactor. Each step may be independently carried out in either the gas or liquid slurry phase. For example the first step may be conducted in the gas phase and the second in liquid slurry or vice versa. Alternatively, each phase may be the same. Preferably the ICPs of this invention are produced in multiple reactors, preferably two or three, operated in series, Component B is preferably polymerized in a second, gas phase reactor. Component A is preferably polymerized first, in a liquid slurry or solution polymerization process.
- In an alternative embodiment, Component A is made in at least two reactors in order to obtain fractions with varying melt flow rate. This has been found to improve the processability of the ICP.
- As used herein “stage” is defined as that portion of a polymerization process during which one component of the ICP, Component A or Component B, is produced. One or multiple reactors may be used during each stage.
- Hydrogen may be added to one or both reactors to control molecular weight, IV and MFR. The use of hydrogen for such purposes is well known to those skilled in the art.
- Preferably a metallocene catalyst system is used to produce the ICP compositions of this invention. To date it appears that the most suitable metallocenes are those in the generic class of bridged, substituted bis(cyclopentadienyl) metallocenes, specifically bridged, substituted bis(indenyl) metallocenes known to produce high molecular weight, high melting, highly isotactic propylene polymers. Generally speaking, those of the generic class disclosed in U.S. Pat. No. 5,770,753 (fully incorporated herein by reference) should be suitable, however, it has been found that the exact polymer obtained is highly dependent on the metallocene's specific substitution pattern.
- We have found that the following racemic metallocenes are most suitable for preparing the ICP compositions of this invention: rac-dimethylsiladiyl(2-iPr,4-phenylindenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr,4-[1-naphthyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr, 4-[3,5-dimethylphenyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr, 4-[ortho-methyl-phenyl]indenyl)2zirconium dichloride; and rac-diphenylsiladiyl(2-methyl-4-[1-naphthyl]indenyl)2zirconium dichloride. It will be immediately apparent to those skilled in the art that certain modifications to these metallocene species are not likely to result in significantly modified ICP composition though activity or ease of synthesis may be impacted. While not wishing to be bound by theory, it is believed that the critical feature of these specific metallocenes is their substitution pattern on the base indenyl group. Thus, it is believed that changing the bridge, for example substituting carbon for silicon, or changing the metal to hafnium or titanium, or changing the metal dichloride to some other dihalide or dimethyl, will not significantly change the ICP compositions of this invention. On the other hand, substituting a group at any position on the indenyl for another or adding one or more groups or substitutents is likely to result in a significantly different composition which may or may not be an ICP of this invention.
- Metallocenes are generally used in combination with some form of activator in order to create an active catalyst system. The term “activator” is defined herein to be any compound or component, or combination of compounds or components, capable of enhancing the ability of one or more metallocenes to polymerize olefins. Alkylalumoxanes such as methylalumoxane (MAO) are commonly used as metallocene activators. Generally alkylalumoxanes contain 5 to 40 of the repeating units:
- R(AlRO )xAlR2 for linear species and
- (AlRO )x for cyclic species
- where R is a C1-C8 alkyl including mixed alkyls. Compounds in which R is methyl are particularly preferred. Alumoxane solutions, particularly methylalumoxane solutions, may be obtained from commercial vendors as solutions having various concentrations. There are a variety of methods for preparing alumoxane, non-limiting examples of which are described in U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,103,031 and EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and WO 94/10180, each fully incorporated herein by reference.
- Ionizing activators may also be used to activate metallocenes. These activators are neutral or ionic, or are compounds such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, which ionize the neutral metallocene compound. Such ionizing compounds may contain an active proton, or some other cation associated with, but not coordinated or only loosely coordinated to, the remaining ion of the ionizing compound. Combinations of activators may also be used, for example, alumoxane and ionizing activator combination, see for example, WO 94/07928.
- Descriptions of ionic catalysts for coordination polymerization comprised of metallocene cations activated by non-coordinating anions appear in the early work in EP-A-0 277 003, EP-A-0 277 004 and U.S. Pat. No. 5,198,401 and WO-A-92/00333 (incorporated herein by reference). These teach desirable methods of preparation wherein metallocenes (bisCp and monoCp) are protonated by an anion precursor such that an alkyl/hydride group is abstracted from a transition metal to make it both cationic and charge-balanced by the non-coordinating anion. Suitable ionic salts include tetrakis-substituted borate or aluminum salts having fluorided aryl-constituents such as phenyl, biphenyl and napthyl.
- The term “noncoordinating anion” (NCA) means an anion which either does not coordinate to said cation or which is only weakly coordinated to said cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base. “Compatible” noncoordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral four coordinate metallocene compound and a neutral by-product from the anion. Particularly useful noncoordinating anions are those which are compatible, stabilize the metallocene cation in the sense of balancing its ionic charge in a +1 state, yet retain sufficient lability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization.
- The use of ionizing ionic compounds not containing an active proton but capable of producing both the active metallocene cation and a noncoordinating anion is also known. See, for example, EP-A-0 426 637 and EP-A-0 573 403 (incorporated herein by reference). An additional method of making the ionic catalysts uses ionizing anion precursors which are initially neutral Lewis acids but form the cation and anion upon ionizing reaction with the metallocene compounds, for example the use of tris(pentafluorophenyl) borane. See EP-A-0 520 732 (incorporated herein by reference). Ionic catalysts for addition polymerization can also be prepared by oxidation of the metal centers of transition metal compounds by anion precursors containing metallic oxidizing groups along with the anion groups, see EP-A-0 495 375 (incorporated herein by reference).
- Where the metal ligands include halogen moieties (for example, bis-cyclopentadienyl zirconium dichloride) which are not capable of ionizing abstraction under standard conditions, they can be converted via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc. See EP-A-0 500 944 and EP-A1-0 570 982 (incorporated herein by reference) for in situ processes describing the reaction of alkyl aluminum compounds with dihalo-substituted metallocene compounds prior to or with the addition of activating anionic compounds.
- Methods for supporting ionic catalysts comprising metallocene cations and NCA are described in U.S. Pat. No. 5,643,847, U.S. patent application Ser. No. 09/84358, filed Nov. 2, 1998 and U.S. patent application Ser. No. 09/84389, filed Nov. 2, 1998 (all fully incorporated herein by reference).
- When the activator for the metallocene supported catalyst composition is a NCA, preferably the NCA is first added to the support composition followed by the addition of the metallocene catalyst. When the activator is MAO, preferably the MAO and metallocene catalyst are dissolved together in solution. The support is then contacted with the MAO/metallocene catalyst solution. Other methods and order of addition will be apparent to those skilled in the art.
- The catalyst systems used to prepare the compositions of this invention are preferably supported using a porous particulate material, such as for example, talc, inorganic oxides, inorganic chlorides and resinous materials such as polyolefin or polymeric compounds.
- Preferably, the support materials are porous inorganic oxide materials, which include those from the Periodic Table of Elements of Groups 2, 3, 4, 5, 13 or 14 metal oxides. Silica, alumina, silica-alumina, and mixtures thereof are particularly preferable. Other inorganic oxides that may be employed either alone or in combination with the silica, alumina or silica-alumina are magnesia, titania, zirconia, and the like.
- Preferably the support material is porous silica which has a surface area in the range of from 10 to 700 m2/g, a total pore volume in the range of from 0.1 to 4.0 cc/g and an average particle size in the range of from 10 to 500 μm. More preferably, the surface area is in the range of from 50 to 500 m2/g, the pore volume is in the range of from 0.5 to 3.5 cc/g and the average particle size is in the range of from 20 to 200 μm. Most desirably the surface area is in the range of from 100 to 400 m2/g, the pore volume is in the range of from 0.8 to 3.0 cc/g and the average particle size is in the range of from 30 to 100 pm. The average pore size of typical porous support materials is in the range of from 10 to 1000 Å. Preferably, a support material is used that has an average pore diameter of from 50 to 500 Å, and most desirably from 75 to 350 Å. It may be particularly desirable to dehydrate the silica at a temperature of from 100° C. to 800° C. anywhere from 3 to 24 hours.
- The metallocenes, activator and support material may be combined in any number of ways. Suitable support techniques are described in U.S. Pat. Nos. 4,808,561 and 4,701,432 (each fully incorporated herein by reference). Preferably the metallocenes and activator are combined and their reaction product supported on the porous support material as described in U. S. Pat. No. 5,240,894 and WO 94/28034, WO 96/00243, and WO 96/00245 (each fully incorporated herein by reference). Alternatively, the metallocenes may be preactivated separately and then combined with the support material either separately or together. If the metallocenes are separately supported, then preferably, they are dried then combined as a powder before use in polymerization.
- Regardless of whether the metallocenes and their activator are separately precontacted or whether the metallocenes and activator are combined at once, the total volume of reaction solution applied to porous support is desirably less than 4 times the total pore volume of the porous support, more desirably less than 3 times the total pore volume of the porous support and even more desirably in the range of from more than 1 to less than 2.5 times the total pore volume of the porous support. Procedures for measuring the total pore volume of porous support are well known in the art. One such method is described in Volume 1, Experimental Methods in Catalyst Research, Academic Press, 1968, pages 67-96.
- Methods of supporting ionic catalysts comprising metallocene cations and noncoordinating anions are described in WO 91/09882, WO 94/03506, WO 96/04319 and in co-pending U.S. Ser. No. 08/248,284, filed Aug. 3, 1994 (incorporated herein by reference). The methods generally comprise either physical adsorption on traditional polymeric or inorganic supports that have been largely dehydrated and dehydroxylated, or using neutral anion precursors that are sufficiently strong Lewis acids to activate retained hydroxy groups in silica containing inorganic oxide supports such that the Lewis acid becomes covalently bound and the hydrogen of the hydroxy group is available to protonate the metallocene compounds.
- The supported catalyst system may be used directly in polymerization or the catalyst system may be prepolymerized using methods well known in the art. For details regarding prepolymerization, see U.S. Pat. Nos. 4,923,833 and 4,921,825, EP 0 279 863 and EP 0 354 893 each of which is fully incorporated herein by reference.
- While the present invention has been described and illustrated by reference to particular embodiments, it will be appreciated by those of ordinary skill in the art, that the invention lends itself to many different variations not illustrated herein. For these reasons, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.
- Although the appendant claims have single appendencies in accordance with U.S. patent practice, each of the features in any of the appendant claims can be combined with each of the features of other appendant claims or the main claim.
- All air sensitive experiments are carried out in nitrogen purged dry boxes. All solvents were purchased from commercial sources. 4-Chloro-2-isopropylindene was purchased from commercial sources. Aluminum alkyls were purchased as hydrocarbon solutions from commercial sources. The commercial methylalumoxane (“MAO”) was purchased from Albemarle as a 30 wt % solution in toluene.
- Metallocene A: racemic dimethylsiladiyl(2-isopropyl-4-phenylindenyl)2 zirconium dichloride was obtained from commercial sources and used as received.
- Metallocene B: racemic dimethylsiladiyl(2-isopropyl-4-[1-naphthyl]indenyl)2 zirconium dichloride was obtained from commercial sources and used as received.
- Metallocene C: racemic dimethylsiladiyl(2-isopropyl-4-[2-methyl-phenyl]indenyl)2 zirconium dichloride was prepared as follows:
- 4-Chloro-2-isopropylindene (9.8 g, 51 mmol) and NiCl2(PPh3)2 (1.8 g, 2.8 mmol) are dissolved in 150 mL of Et2O. 2-Methylphenylmagnesium bromide (51 mmol) as an Et2O solution was added to the solution and the reaction was stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl(aq) and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane. Yield was 6.6 g (52%).
- 4-(2-methylphenyl)-2-isopropylindene (6.6 g, 26.5 mmol) was dissolved in 80 mL of pentane. To this solution was added 10.6 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitates from solution and was collected by frit filtration and washed with additional pentane. Yield was 5.8 g (88%).
- Dimethylsiladiylbis[4-(2-methylphenyl)-2-isopropylindene]
- SiMe2Cl2 (0.88 g, 6.8 mmol) was dissolved in 60 mL of THF. While stirring, lithium 4-(2-methylphenyl)-2-isopropylindenide (3.5 g, 13.7 mmol) was added as a dry powder and the contents are allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky, white solid (3.0 g).
- Dimethylsiladiylbis[4-(2-methylphenyl)-2-isopropylindenyl]ZrCl2
- Dimethylsiladiylbis[4-(2-methylphenyl)-2-isopropylindene] (3.0 g, 5.4 mmol) was dissolved in 60 mL of Et2O. While stirring, 4.5 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 2 hours. After this time, the solution was cooled to −35° C. and ZrCl4 (1.25 g, 5.4 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in a mixture of methylene chloride and pentane and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to −35° C. to induce crystallization. 0.26 g (6.7%) of pure racemic compound was obtained.
- Metallocene D: racemic dimethylsiladiyl(2-isopropyl-4-[3,5-dimethylphenyl]indenyl)2 zirconium dichloride was prepared as follows:
- 4-Chloro-2-isopropylindene (10.4 g, 54 mmol) and NiCl2(PPh3)2 (1.8 g, 2.8 mmol) are dissolved in 150 mL of Et2O. 3,5-dimethylphenylmagnesium bromide (54 mmol) as an Et2O solution was added under vigorous stirring and the reaction was stirred overnight at room temperature. After overnight stirring, the reaction was slowly quenched with H2O to neutralize unreacted Grignard. The solution was subsequently treated with 100 mL of 10% HCl (aq) and neutralized with saturated sodium bicarbonate aqueous solution. The organic layer was dried with magnesium sulfate, and the solvent was removed by rotary evaporation. The remaining residue was loaded onto a silica gel column and eluted with hexane.
- Yield was 5.5 g (39%).
- 4-(3,5-Dimethylphenyl)-2-isopropylindene (5.5 g, 21 mmol) was dissolved in 80 mL of pentane. To this solution was added 8.3 mL of n-BuLi (2.5M in hexane) and the reaction was allowed to stir 4 hours at room temperature. A white solid precipitates from solution and was collected by frit filtration and washed with additional pentane. Yield was 3.28 g (60%).
- SiMe2Cl2 (0.69 g, 5.4 mmol) was dissolved in 80 mL of THF. While stirring, lithium 4-(3,5-methylphenyl)-2-isopropylindenide (2.9 g, 10.8 mmol) was added as a dry powder and the contents are allowed to stir overnight at room temperature. The solvent was removed in vacuo and the residue was taken up in pentane and filtered to remove LiCl salts. The pentane was removed in vacuo to yield a flaky, white solid (2.1 g, 67%)
- Dimethylsiladiylbis[4-(3,5-dimethylphenyl)-2-isopropylindene] (2.1g, 3.6 mmol) was dissolved in 60 mL of Et2O. While stirring, 2.9 mL of n-BuLi (2.5M in hexane) was added and allowed to stir at room temperature for 2 hours. After this time, the solution was cooled to −35° C. and ZrCl4 (0.83 g, 3.6 mmol) was added and allowed to stir at room temperature for 3 hours. The solvent was then removed in vacuo and the residue was taken up in toluene and filtered to remove LiCl salts. The filtrate was then concentrated and chilled to −35° C. to induce crystallization. 0.24 g (6.0%) of pure racemic compound was obtained.
- Metallocene E: racemic diphenylsiladiyl(2-methyl-4-[1-naphthyl]indenyl)2 zirconium dichloride was prepared as follows.
- 2-Methyl-4-[1-napthyl]indenyl lithiun (5.5 g, 21 mmol) was added to a solution of Ph2Si(OSO2CF3)2 (4.8 g, 10 mmol) and diethyl ether (50 mL). The mixture was stirred overnight then the product was isolated by filtration, washed with diethyl ether (4×50 mL) then dried in vacuo. Yield 4.71 g, 68%.
- The method described above reacting Ph2Si(OSO2CF3)2 with 2-Methyl-4-[1-napthyl]indenyl lithium to form the ligand system with a Ph2Si bridge is a general one. A wide variety of cyclopentadienyl or indenyl metal salts can be reacted with Ph2Si(OSO2CF3)2 when Ph2Si(Cl)2 is unreactive or slow with the cyclopentadienyl or indenyl metal salt reagent.
- A slurry of Ph2Si(2-Methyl-4-[1-napthyl]indenyl lithium)2 was prepared from addition of a 2.0 M solution of n-Butyl lithium and pentane (1.5 mL, 3.0 mmol) to a mixture of Ph2Si(2-Methyl, 4-napthyl indene)2 (1.0 g, 1.44 mmol) and diethyl ether (20 mL). After stirring for two hours, trimethyl tin chloride (0.6 g, 3.0 mmol) was added. The color changed instantly from an intense to light yellow. The ether was removed and the product extracted with pentane (3×20 mL). Removal of solvent yielded product. Yield 0.88 g, 60%.
- A 100 mL flask was charged with ZrCl4 (180 mg, 0.77 mmol), toluene (20 mL) then Ph2Si(2-Methyl-4-[1-napthyl]indenyl SnMe3)2 (815 mg, 0.8 mmol). The mixture was stirred overnight then heated in vacuo at 90° C. for 48 h. The orange powder was taken up in toluene (5 mL) then filtered through a 0.45 μm filter. Diethyl ether (2-3 mL) was added to the toluene solution and the solution cooled to −30° C. After prolonged cooling crystals were isolated then washed with cold toluene (3×1 mL) then pentane (3×5 mL). After further washing with toluene (3×1 mL) and hexane (3×5 mL) the sample was dried to obtain product. Yield 17 mg, 2.6%.
- Comparison Metallocene 1: racemic dimethylsiladiyl(2-methyl-4-phenylindenyl)2 zirconium dichloride was obtained from commercial sources and used as received.
- Comparison Metallocene 2: racemic dimethylsiladiyl(2-methyl-4-[1-naphthyl]indenyl)2 zirconium dichloride was obtained from commercial sources and used as received.
- Comparison Metallocene 3: racemic dimethylsiladiyl(2-methyl-4-phenylindenyl)2 zirconium dichloride was obtained from commercial sources and used as received.
- Comparison Metallocene 4: racemic dimethylsiladiyl(2-ethyl-4-phenylindenyl)2 zirconium dichloride was obtained from commercial sources and used as received.
- In a 100 mL round bottom flask dimethylsiladiyl(2-iPr-4-phenyl indenyl)2 zirconium dichloride (A, 0.060 g) was added to the MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600° C. dehydration). This slurry was stirred for twenty minutes, then dried at 40° C. for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and twenty minutes. The supported catalyst was recovered as a reddish purple, free flowing solid (5.71 g).
- In a 100 mL round bottom dimethylsiladiyl(2-isopropyl-4-[1-naphthyl]indenyl)2 zirconium dichloride (B, 0.069 g) was added to the MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600° C. dehydration). This slurry was stirred for thirty minutes, then dried at 40° C. for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was dried a total of about 2 hours and twenty minutes. The supported catalyst was recovered as a light purple, free flowing solid (5.4 g).
- In a 100 mL round bottom dimethylsiladiyl(2-isopropyl-4-[2-methyl-phenyl]indenyl)2 zirconium dichloride (C, 0.069 g) was added to the MAO- toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600° C. dehydration). This slurry was stirred for thirty minutes then dried at 40° C. for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and twenty minutes. The supported catalyst was recovered as a light purple, free flowing solid (5.4 g).
- In a 100 mL round bottom dimethylsiladiyl(2-isopropyl-4-[3,5-dimethylphenyl]indenyl)2 zirconium dichloride (D, 0066 g) was added to the MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600° C. dehydration). This slurry was stirred for twenty minutes then dried at 40° C. for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and twenty minutes. The supported catalyst was recovered as a purple, free flowing solid (5.11 g).
- In a 100 mL round bottom diphenylsiladiyl(2-methyl-4-[1-naphthyl]indenyl)2 zirconium dichloride (E, 0.017 g) was added to the MAO-toluene solution (1.52 g) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (3.2 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600° C. dehydration). This slurry was stirred for twenty minutes, then dried at 40° C. for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and twenty minutes. The supported catalyst was recovered as an orange, free flowing solid (1.06 g).
- In a 100 mL round bottom flask dimethylsiladiyl(2-iPr-4-phenylindenyl)2 zirconium dichloride (F, 0.065 g) was added to the MAO-toluene solution (5.1 g, 5.35 mL) and stirred fifteen minutes. This was filtered through a medium glass frit funnel and washed with toluene (11 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600° C. dehydration). Toluene (2 mL) was added to this slurry, stirred for twenty minutes, dried at 40° C. for ten minutes under vacuum on a rotary evaporator until the liquid evaporated, and then the solid was further dried a total of about two hours and twenty three minutes. The supported catalyst was recovered as a light purple, free flowing solid (5.58 g).
- In a 100 mL round bottom flask dimethylsiladiyl(2-iPr-4-phenylindenyl)2 zirconium dichloride (G, 0.065 g) was added to the MAO-toluene solution (5.1 g, 5.4 mL) and stirred fifty minutes. This was filtered through a medium glass frit funnel and washed with toluene (13 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600° C. dehydration). This slurry was stirred for twenty minutes, dried at 40° C. for ten minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 3 hours. The supported catalyst was recovered as a purple, free flowing solid (5.45 g).
- In a 100 mL round bottom racemic dimethylsiladiyl(2-methyl-4-phenylindenyl)2 zirconium dichloride (Comparison metallocene 1, 0.055 g) was added to the MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600° C. dehydration). This slurry was stirred for twenty minutes then dried at 40° C. for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours and twenty two minutes. The supported catalyst was recovered as a light orange, free flowing solid (5.63 g).
- In a 100 mL round bottom racemic dimethylsiladiyl(2-methyl-4-[1-naphthyl]indenyl)2 zirconium dichloride (Comparison metallocene 2, 0.064 g) was added to the MAO-toluene solution (6.74 g, 7.2 mL) and stirred twenty minutes. This was filtered through a medium glass frit funnel and washed with toluene (14 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600° C. dehydration). This slurry was stirred for twenty minutes then dried at 40° C. for two minutes under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of about 2 hours. The supported catalyst was recovered as an orange, free flowing solid (4.72 g).
- In a two gallon mixer racemic dimethylsiladiyl(2-methyl-4-phenylindenyl)2 zirconium dichloride (Comparison metallocene 3, 13.0 g) was dissolved in a MAO solution (300 mL). This was added to a MAO solution (800 mL diluted with 1600 mL toluene) and an additional 150 mL of toluene was added. This was mixed one hour. One half of this solution was added to dehydrated silica (802.2 g, Davison 948 Regular, 600° C. dehydration) and stirred five minutes. The remaining solution was then added and stirred twenty minutes. Additional toluene was added (450 mL). This slurry was stirred for twenty minutes then dried at 46° C. for 11.5 hours under nitrogen flow. The supported catalyst was recovered as an orange, free flowing solid (1092.2 g) which was passed through a 25 mesh screen.
- In a 100 mL round bottom racemic dimethylsiladiyl(2-ethyl-4-phenylindenyl)2 zirconium dichloride (Comparison metallocene 4, 0.065 g) was added to the MAO-toluene solution (5.1 g, 5.5 mL) and stirred fifteen minutes. This was filtered through a medium glass frit funnel and washed with toluene (11 mL). To the combined filtrates was added dehydrated silica (4.0 g, Davison 948 Regular, 600° C. dehydration). After one addition mL toluene was added this slurry was stirred for twenty minutes then dried at 40° C. under vacuum on a rotary evaporator until the liquid evaporated and then the solid was further dried a total of 2 hours and 23 minutes. The supported catalyst was recovered as a pink, free flowing solid (5.56 g).
- The polymerization procedure for producing homopolymers with the supported catalysts was as follows. In a clean, dry two liter autoclave which had been flushed with propylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added. Hydrogen gas was added at this point. The reactor was closed and filled with 800 mL liquid propylene. After heating the reactor to 70° C., the catalyst was added by washing in with propylene (200 mL). After the indicated time, typically one hour, the reactor was cooled, and the excess propylene vented. The polymer was removed and dried. Results are shown in Tables 1A and 2A.
- The polymerization procedure for producing ICP with the supported catalysts was as follows. In a clean, dry two liter autoclave which had been flushed with propylene vapor, TEAL scavenger (0.3 mL, 1.5M) was added. Hydrogen gas was added at this point. The reactor was closed and filled with 800 mL liquid propylene. After heating the reactor to 70° C., the catalyst was added by washing in with propylene (200 mL). After the indicated time, typically one hour, the reactor was vented to about 170 psig pressure and then an ethylene/propylene gas mixture was passed through the reactor at the rates indicated while maintaining 200 psig. At the end of the gas phase stage, typically 90 to 150 minutes, the reactor was vented and cooled under N2. The granular ICP polymer was removed and dried. Results are shown in Tables 1A and 2A.
- Results are shown in Tables 1B, 2B and 3-8. Molecular weight determinations were made by gel permeation chromatography (GPC) according to the following technique. Molecular weights and molecular weight distributions were measured using a Waters 150° C. gel permeation chromatography equipped with Shodex (Showa Denko) AT-80 M/S columns and a differential refractive index (DRI) detector operating at 145° C. with 1,2,4-trichlorobenzene as the mobile phase at a 1.0 mL/min. flow rate. The sample injection volume was 300 microliters. The columns were calibrated using narrow polystyrene standards to generate a universal calibration curve. The polypropylene calibration curve was established using k=8.33×10−5 and a=0.800 as the Mark-Houwink coefficients. The numerical analyses were performed using Waters “Millennium” software.
- DSC melting points were determined on commercial DSC instruments and are reported as the second melting point. The polymer sample was heated to 230.0° C. for ten minutes and then cooled from 230° C. to 50° C. at 10° C./minute. The sample is held at 50° C. for five minutes. The second melt is then recorded as the sample is heated from 50° C. to 200° C. at a rate of 10° C/minute. The peak temperature is recorded as the second melting point.
- The ICP polymer was dissolved in hot xylene and then allowed to cool overnight. After filtration the insolubes are dried. The xylene soluble portion was evaporated and the soluble material recovered. The IV of the recovered soluble material was measured in decalin at 135° C. by using know methods and instruments such as a Schott A VSPro Viscosity Automatic Sampler.
- At very high ICP MFR this method can extract some low molecular weight isotactic PP and thus lower the observed IV.
- The ICP samples were sent to Polyhedron Laboratories, Inc. to be fractionated and analyzed by GPC. A general description of the procedure is found in the reference J. C. Randall, J. Poly. Sci.: Part A Polymer Chemistry, Vol. 36, 1527-1542 (1998).
- The impact copolymers of this invention display improved impact properties as measured by the room temperature notched Izod values at similar Flexural Modulus. This can be seen by examining Table 8. For example, the ICP from inventive run 43 with inventive metallocene F has a Flexural Modulus of 151.8K with a Notched Izod of 1.57 value, and the ICP from inventive run 50 with inventive metallocene G has a Flexural Modulus of 158.3K with a Notched Izod of 1.7 value. The comparative examples shown in runs 46, 47 and 48 where the second values for each are 158.6K, 155.8K and 155.7K with an inferior notched Izods of 1.25, 0.81 and 0.74 values. Thus both inventive runs 43 and 50 have better impact strength as measured by notched Izod at similar Flexural modulus than the comparative runs.
- This is further illustrated for all the data by plotting the notched Izod versus the Flexural Modulus for each the comparative examples relative to the inventive examples. As the plot below illustrates the inventive examples have a higher impact property (notched Izod) at equivalent Flexural Modulus.
- The improved impact strength at comparable modulus results from a higher molecular weight, as measured by IV, of Component B. The higher the molecular weight of component B, the better the impact test values.
- The known metallocenes comparison 1 and 2 are limited to low values for this molecular weight as measured by the IV of Component B. The maximum value of IV for the comparative metallocenes was a value of about 1.7 for run 9 (Table IB) with the ethylene/propylene at a 4.2/0.8 ratio. Inventive metallocene B at this ratio produced an IV that ranged from 1.99 in run 13 to 2.338 in run 18. The inventive metallocene D produced an ICP with an IV of 3.508 in run 40. In fact, for all runs with inventive metallocene D the IV values were greater than 2.2 for all ICP products and ranged from 2.202 (run 39) to 3.667 (run 38). These high IV values will result in further improved impact properties.
TABLE 1A Supported Cat Time RUN Metallocene Amount Yield Efficiency H2 split C2 =/C3 = flow # Catalyst System (mg) (g) (Kg/g cat) (mmol) (min.) rates (1/min.) 1 E 31 243.9 7.87 78 60/150 4.1/0.9 2 E 30 155.1 5.17 78 60 3 COMP 1 31 198.9 6.42 78 60 4 COMP 1 30 224.8 7.49 78 60/90 4.1/0.9 5 A 59 226.1 3.83 47 60/120 4.2/0.8 6 A 59 212.8 3.61 47 60/120 4.4/0.6 7 A 59 191.1 3.24 47 60 8 A 60 215.6 3.59 47 60/120 4.7/0.3 9 COMP 2 60 272.6 4.54 54 60/120 4.2/0.8 10 COMP 2 61 196.9 3.23 54 60 11 A 61 141.8 2.32 47 60/120 4.4/0.6 12 A 60 192.4 3.21 47 60/120 4.7/0.3 13 B 63 80.0 1.27 23 60/120 4.2/0.8 14 B 63 97.8 1.55 23 60/120 4.4/0.6 15 B 60 72.2 1.20 23 60 16 B 61 82.2 1.35 23 60/120 4.0/1.0 17 B 60 89.0 1.48 23 60/120 4.1/0.9 18 B 150 180.2 1.20 23 30/120 4.2/0.8 19 B 152 153.8 1.01 23 30/120 4.0/1.0 20 B 151 87.4 0.58 23 30 21 E 43 139.0 3.23 62 60 22 E 44 154.0 3.50 62 60/150 4.1/0.9 23 E 43 102.2 2.38 62 60/150 3.6/1.4 24 E 43 81.1 1.89 78 60/150 4.0/1.0 25 E 41 53.3 1.30 78 60 -
TABLE 1B Total Ethylene Ethylene in Comp. B Total Comp. B Final MFR Melting Point Comp. B RUN # (wt %) (wt %) (wt %) (dg/10 min.) (° C.) MW MWD IV 1 10.24 50.80 20.16 114.0 151.1 103.5 2.88 0.9786 2 459.2 150.2 75.4 3.15 3 58.95 150.9 135.7 3.15 4 7.82 50.04 15.63 127.16 150.0 100.4 3.11 0.708 5 3.87 47.36 8.17 490 149.6 116.5 4.18 1.637 6 5.93 51.70 11.5 118 149.8 148.7 4.74 2.36 2.46 7 123 148.6 73.5 2.78 8 8.13 58.96 13.8 74.2 150.3 160.0 4.98 2.221 2.199 9 9.74 51.52 18.91 4.98 151.0 210.4 2.96 1.7127 10 3.12 151.0 278.0 2.49 11 5.23 55.72 9.39 129.0 150.4 147.4 4.25 2.18 12 12.08 63.62 18.99 10.02 150.3 1,139.0 456 1.55 13 6.19 47.44 13.05 21.1 154.97 168.6 2.84 1.99 14 8.81 54.69 16.11 19.9 155.3 169.7 3.00 2.37 15 72.84 156.57 158.2 2.77 16 4.12 40.33 10.22 53.03 154.7 148.1 2.74 1.585 17 3.59 45.88 7.82 51.27 154.2 145.2 2.79 1.351 18 11.10 49.56 22.40 15.47 155.5 192.8 3.09 2.338 19 8.80 43.02 20.46 16.95 155.3 194.1 3.47 1.742 20 30.26 154.63 106.6 2.27 21 10.3 151.83, minor 225.6 1.93 138.33 22 10.95 50.37 21.74 3.66 151.97 302.3 2.78 2.185 23 6.46 36.4 17.75 7.01 152.77 240.3 2.44 2.11 24 9.37 47.34 19.79 131.01 150.83 122.6 4.26 2.063 25 681.8 151.23 76.9 3.5 -
TABLE 2A Supported Cat Time RUN Metallocene Amount Yield Efficiency H2 split C2 =/C3 = flow # Catalyst System (mg) (g) (Kg/g cat) (mmol) (min.) rates (1/min.) 26 C 61 158.2 2.59 47 60/120 4.0/1.0 27 C 60 139.9 2.33 47 60 28 C 61 168.9 2.77 47 60/120 4.4/0.6 29 C 60 42.3 0.71 16 60 30 C 61 94.7 1.55 31 60 31 C 300 159.8 0.53 7.8 60 32 C 300 51.4 0.17 7.8 21 33 C 300 276.2 0.92 7.8 64/180 4.0/1.0 34 D 121 63.0 0.52 7.8 60 35 D 120 79.4 0.66 7.8 60/90 4.0/1.0 36 D 122 99.1 0.81 7.8 60/90 4.1/0.9 37 D 123 71.2 0.58 7.8 60/90 3.6/1.4 38 D 120 95.2 0.79 7.8 60/120 4.0/1.0 39 D 121 143.7 1.19 16 60/90 4.0/1.0 40 D 124 167.6 1.35 16 60/90 4.2/0.8 41 D 120 101.5 0.85 16 60 42 D 121 121.2 1.00 16 60/90 4.4/0.6 -
TABLE 2B Total Ethylene Ethylene in Comp. B Total Comp. B Final MFR Melting Point IV of RUN # (wt %) (wt %) (wt %) (dg/10 min.) (° C.) MW MWD Comp. B 26 3.584 43.25 971.02 152.17 75.6 2.50 1.121 27 1013.8 152.1 70.9 2.27 (157.17 minor) 28 4.62 57.52 954.7 151.57 69.2 2.39 2.083 29 142.5 152.91 120.1 2.38 30 420.7 152.1 91.7 2.19 31 129.85 153.23 127.3 3.62 32 268.69 152.97 108.1 4.41 33 15.07, 48.96, 11.94 154.1 238.1 14.49 1.993 14.24 47.85 34 76.55 151.83 138.5 2.20 35 8.199 39.92 14.16 153.43 213.6 3.05 2.833 36 7.068 42.81 15.43 152.03 196.3 3.01 2.505 37 8.294 26.52 4.92 152.77 248.0 3.28 2.662 38 15.85 39.17 0.479 153.23 306.7 4.14 3.667 39 7.521 37.72 27.72 153.03 204.7 3.61 2.202 40 10.02 44.73 5.8 152.63 235.8 3.58 3.508 41 75.86 151.03 135.8 2.30 42 21.21 56.17 0.53 152.10 280.9 3.84 -
TABLE 3 Supported FTIR data Metallocene % Xylene C2 in Comp. Total Comp. Catalyst MFR Sol % Xylene Insol Total C2 B B APPL. RUN # Description System (dg/10 min) (wt %) (wt %) (wt %) (wt %) (wt %) 5 ICP A 490 6.6 93.8 3.87 47.36 8.2 6 ICP A 118 6.8 93.2 5.93 51.7 11.5 7 Homo PP A 123 1 98.8 8 ICP A 74.2 5.4 94.5 8.13 58.96 13.8 11 ICP A 129.0 6.7 93.5 5.23 55.72 9.5 12 ICP A 10.02 4.3 95.9 12.08 63.62 19 13 ICP B 21.1 13.3 86.7 6.19 47.44 13 14 ICP B 19.9 14.3 85.7 8.81 54.69 16.1 15 Homo PP B 72.84 1.1 99 16 ICP B 53.03 11.7 88.5 4.12 40.33 10.2 17 ICP B 51.27 8.4 91.6 3.59 45.88 7.8 18 ICP B 15.47 19.2 80.4 11.1 49.56 22.4 19 ICP B 16.95 20.9 79.2 8.8 43.02 20.5 20 Homo PP B 30.26 1.1 98.9 -
TABLE 4 Supported FTIR data Metallocene % Xylene C2 in Comp. Total Comp. Catalyst MFR Sol % Xylene Insol Total C2 B B APPL. RUN # Description System (dg/10 min) (wt %) (wt %) (wt %) (wt %) (wt %) IV Of Comp. B 1 ICP E 114.0 25.6 74.5 10.24 50.8 20.2 0.979 2 Homo PP E 459.2 1.2 98.8 3 Homo PP Comp. 1 58.95 0.6 99.4 4 ICP Comp. 1 127.16 20.4 79.7 7.82 50.04 15.6 0.708 9 ICP Comp. 2 4.98 23.5 76.2 9.74 51.52 18.9 1.713 10 Homo PP Comp. 2 3.12 0.9 99.1 13 ICP B 129.0 12.4 86.9 21 Homo PP E 10.3 0.7 99.3 22 ICP E 3.66 24 75.6 10.95 50.37 21.7 2.185 23 ICP E 7.01 20.9 79.3 6.46 36.4 17.7 2.11 24 ICP E 131.01 22 78.1 9.37 47.34 19.8 2.06 25 Homo PP E 681.8 2.1 98 -
TABLE 5 De- Supported MFR Xylene Solubles APPL scrip- Metallocene (dg/ (‘low’ MW peak) Xylene Solubles (‘high’ MW peak) Xylene Insolubles RUN # tion Cat Syst. 10 min) Mn Mw Mz Mw/Mn Mn Mw Mz Mw/Mn Mn Mw Mz Mw/Mn 1 ICP E 114.0 1251 1554 1874 1.24 38015 74567 115589 1.96 12314 32426 54966 2.63 2 Homo E 459.2 1513 2013 2599 1.33 18384 30191 45639 1.64 17552 41149 67038 2.34 PP 3 Homo Comp. 1 58.95 1441 1952 2630 1.35 14448 22536 35314 1.56 30510 63658 97817 2.09 pp 4 ICP Comp. 1 127.16 981 1062 1140 1.08 15647 33205 51601 2.12 16342 42791 71409 2.62 9 ICP Comp. 2 4.98 987 1180 1433 1.2 48475 118629 214628 2.45 41276 106195 179010 2.57 10 Homo Comp. 2 3.12 1071 1376 1834 1.29 15113 30638 56220 2.03 61668 142260 249807 2.31 PP 13 ICP B 21.1 941 1099 1308 1.17 44501 187149 515199 4.21 69282 167811 342963 2.42 21 Homo E 10.3 1114 1383 1715 1.24 12228 23656 42278 1.93 82347 184675 309914 2.24 PP 22 ICP E 3.66 929 1153 1502 1.24 77378 211251 413832 2.73 97431 248553 471070 2.55 23 ICP E 7.01 982 1165 1403 1.19 57316 166144 312133 2.9 85158 206876 354334 2.43 24 ICP E 131.01 1515 2556 4282 1.69 74803 161031 319874 2.15 27750 76477 129002 2.76 25 Homo E 681.8 1430 1868 2472 1.31 10530 13500 17834 1.28 24398 76119 137103 3.12 PP -
TABLE 6 De- Supported MFR Xylene Solubles APPL scrip- Metallocene dg/ (‘low’ MW peak) Xylene Solubles (‘high’ MW peak) Xylene Insolubles RUN # tion Cat Syst. 10 min Mn Mw Mz Mw/Mn Mn Mw Mz Mw/Mn Mn Mw Mz Mw/Mn 5 ICP A 490 713 740 772 1.04 46485 196796 608279 4.23 36452 117941 384107 3.24 6 ICP A 118 721 751 786 1.04 32808 173994 652286 5.3 38405 150533 577951 3.92 7 Homo A 123 746 775 805 1.04 2224 3418 6092 1.54 31525 77176 139014 2.45 PP 8 ICP A 74.2 714 743 776 1.04 36731 157042 553553 4.28 37994 133529 493184 3.51 11 ICP A 129.0 712 741 774 1.04 39823 188272 544445 4.73 39618 147046 523576 3.71 12 ICP A 10.02 739 774 814 1.05 22407 91802 367841 4.1 49352 214835 834003 4.35 13 ICP B 21.1 741 775 814 1.05 32783 13448 347619 4.1 73240 168231 330135 2.3 14 ICP B 19.9 774 822 884 1.06 76080 247012 646524 3.25 48027 140429 300877 2.92 15 Homo B 72.84 720 756 800 1.05 11124 16144 23634 1.45 65242 150447 276068 2.31 PP 16 ICP B 53.03 735 765 803 1.04 26643 128696 380989 4.83 67746 158765 317323 2.34 17 ICP B 51.27 733 759 790 1.04 40054 99847 204429 2.49 37641 130382 468779 3.46 18 ICP B 15.47 721 741 764 1.03 61128 250368 694151 4.1 50670 134806 284392 2.66 19 ICP B 16.95 710 726 744 1.02 71050 246743 632260 3.47 53550 131611 251500 2.46 20 Homo B 30.26 857 1043 1371 1.22 9567 16302 25965 1.7 75064 161464 317578 2.15 PP -
TABLE 7A Supported TEAL Cat H2 Time Run Metallocene Amount Amount Yield Efficiency (delta split C2 =/C3 = flow # Cat. System (mls) (mg) (g) (Kg/g cat) psi) (min.) rates (l/min.) 43 F 0.3 123 261.1 2.12 697.5 60/90 4.0/1.0 44 F 0.3 120 289.8 2.42 542.5 60/90 4.0/1.0 45 Comp 3 0.3 60 219.6 3.66 930.0 60/75 4.8/1.2 46 Comp 3 0.3 64 220.0 3.44 930.0 60/75 2.0/0.5 47 Comp 4 0.3 61 275.9 4.52 1007.5 35/45 4.8/1.2 48 Comp 4 0.3 61 278.4 4.56 1007.5 35/45 2.0/0.5 49 G 0.3 124 246.3 1.99 542.5 60/90 4.0/1.0 50 G 0.3 122 269.5 2.21 542.5 60/90 4.0/1.0 -
TABLE 7B Ethylene Total In Total Melting Ethylene Rubber Rubber Final MFR Point RUN # (wt %) (wt %) (wt %) (g/10 min.) (° C.) IV of Copolymer 43 6.34 43.23 14.7 206 147.98 1.678 44 2.07 40.89 5.1 671 148.05 45 12.66 50.85 24.9 27.0 149.69 0.789 46 8.60 47.40 18.1 33.2 149.04 0.651 47 11.48 53.03 21.6 18.2 151.61 0.637 48 7.61 49.49 15.4 44.6 151.69 0.786 49 7.09 44.46 15.9 69.2 147.55 1.618 50 5.15 43.51 11.8 132 147.34 1.619 -
TABLE 8 Supported Application Metallocene MFR FLEX Notched IZOD Run Catalyst (dg/ HDT MOD (23° C.) Number System min) (° C.) (psi) (ft.lb./in.) 43 F 206 95.8 151846 1.57 44 F 671 114.9 211749 0.42 46* Comp. 3 33.2 81 97490 1.86 98 158627 1.25 47* Comp. 4 18.2 87 124709 1.4 107 155790 0.81 48* Comp. 4 44.6 76 91609 1.51 102 155702 0.74 49 G 69.2 95 136745 2.37 50 G 132 97.5 158309 1.7
Claims (20)
1. A reactor produced propylene impact copolymer composition comprising:
(a) From about 40% to about 95% by weight Component A based on the total weight of the impact copolymer, Component A comprising propylene homopolymer or copolymer wherein the copolymer comprises 10% or less by weight ethylene, butene, hexene or octene comonomer;
(b) From about 5% to about 60% by weight Component B based on the total weight of the impact copolymer, Component B comprising propylene copolymer wherein the copolymer comprises from about 20% to about 70% by weight ethylene, butene, hexene and/or octene comonomer, and from about 80% to about 30% by weight propylene, wherein Component B:
(i) has a weight average molecular weight of at least 100,000;
(ii) a composition distribution of greater than 60%; and
(iii) an intrinsic viscosity of greater than 1.00 dl/g.
2. The composition of wherein Component A is a propylene homopolymer.
claim 1
3. The composition of wherein Component B consists essentially of propylene and from about 20% to about 70% by weight ethylene.
claim 1
4. The composition of wherein Component B consists essentially of propylene and from about 30% to about 65% by weight ethylene.
claim 1
5. The composition of wherein Component B has a molecular weight distribution of less than 3.5.
claim 1
6. The composition of wherein Component B has a weight average molecular weight of at least 200,000.
claim 1
7. The composition of wherein Component B has a composition distribution of greater than 70%.
claim 1
8. The composition of wherein Component B has an intrinsic viscosity of greater than 2.00 dl/g.
claim 1
9. The composition of wherein Component B has less than 10% by weight of a crystalline portion.
claim 1
10. The composition of wherein Component B has less than 10% by weight of a crystalline portion and the crystalline portion, if detectable, has the same comonomer content as the remainder of Component B.
claim 1
11. The composition of wherein Component A consists essentially of polypropylene homopolymer and has less than 2% by weight amorphous polypropylene.
claim 1
12. The composition of wherein Component A has a melting point of at least 155° C.
claim 1
13. A reactor produced propylene impact copolymer composition comprising:
(a) From about 40% to about 95% by weight Component A based on the total weight of the impact copolymer, Component A comprising propylene homopolymer having a melting point of at least 155° C. and less than 2% by weight amorphous polypropylene;
(b) From about 5% to about 60% by weight Component B based on the total weight of the impact copolymer, Component B comprising propylene copolymer wherein the copolymer comprises from about 30% to about 65% by weight ethylene and from about 70% to about 35% by weight propylene, wherein Component B:
(i) has a weight average molecular weight of at least 150,000;
(ii) a molecular weight distribution of less than 3.5;
(iii) a composition distribution of greater than 65%; and
(iv) an intrinsic viscosity of greater than 2.00 dl/g.
(v) less than 10% by weight of a crystalline portion.
14. The composition of consisting essentially of from about 60% to about 90% by weight Component A and from about 10% to about 40% by weight Component B.
claim 13
15. The composition of wherein Component B consists essentially of propylene and from about 35% to about 60% ethylene.
claim 13
16. A propylene impact copolymer prepared in a two-stage polymerization process using a metallocene catalyst system comprising a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr-4-phenylindenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[1-naphthyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[3,5-dimethylphenyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[2-methyl-phenyl]indenyl)2zirconium dichloride; and rac-diphenylsiladiyl(2-methyl-4-[1-naphthyl]indenyl)2zirconium dichloride.
17. A propylene impact copolymer prepared in a two-stage polymerization process using a metallocene catalyst system comprising a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr-4-phenylindenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[1-naphthyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[3,5-dimethylphenyl]indenyl)2zirconium dichloride; and rac-dimethylsiladiyl(2-iPr-4-[2-methyl-phenyl]indenyl)2zirconium dichloride.
18. A propylene impact copolymer prepared in a two-stage polymerization process using a metallocene catalyst system comprising a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr-4-phenylindenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr,4-[1-naphthyl]indenyl)2zirconium dichloride; and rac-dimethylsiladiyl(2-iPr-4-[3,5-dimethylphenyl]indenyl)2zirconium dichloride.
19. A propylene impact copolymer prepared in a two-stage polymerization -process using a metallocene catalyst system comprising a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr-4-phenylindenyl)2zirconium dichloride; and rac-dimethylsiladiyl(2-iPr-4-[1-naphthyl]indenyl)2zirconium dichloride.
20. A reactor produced propylene impact copolymer composition comprising:
(a) From about 40% to about 95% by weight Component A based on the total weight of the impact copolymer, Component A comprising propylene homopolymer having a melting point of at least 155° C. and less than 2% by weight amorphous polypropylene;
(b) From about 5% to about 60% by weight Component B based on the total weight of the impact copolymer, Component B comprising propylene copolymer wherein the copolymer comprises from about 30% to about 65% by weight ethylene and from about 70% to about 35% by weight propylene, wherein Component B:
(i) has a weight average molecular weight of at least 150,000;
(ii) a molecular weight distribution of less than 3.5;
(iii) a composition distribution of greater than 65%; and
(iv) an intrinsic viscosity of greater than 2.00 dl/g.
(v) less than 10% by weight of a crystalline portion.
wherein the impact copolymer is prepared using a metallocene catalyst system comprising a metallocene selected from the group consisting of: rac-dimethylsiladiyl(2-iPr-4-phenylindenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[1-naphthyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[3,5-dimethylphenyl]indenyl)2zirconium dichloride; rac-dimethylsiladiyl(2-iPr-4-[2-methyl-phenyl]indenyl)2zirconium dichloride; and rac-diphenylsiladiyl(2-methyl-4-[1 -naphthyl]indenyl)2zirconium dichloride.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/862,667 US6342566B2 (en) | 2000-02-08 | 2001-05-21 | Propylene impact copolymers |
US09/996,245 US6472474B2 (en) | 2000-02-08 | 2001-11-27 | Propylene impact copolymers |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US18101600P | 2000-02-08 | 2000-02-08 | |
US09/535,357 US6384142B1 (en) | 2000-02-08 | 2000-03-24 | Propylene impact copolymers |
US09/862,667 US6342566B2 (en) | 2000-02-08 | 2001-05-21 | Propylene impact copolymers |
Related Parent Applications (3)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/535,357 Division US6384142B1 (en) | 2000-02-08 | 2000-03-24 | Propylene impact copolymers |
US09/535,357 Continuation US6384142B1 (en) | 2000-02-08 | 2000-03-24 | Propylene impact copolymers |
US09/535,537 Division US6363590B1 (en) | 1999-12-16 | 2000-03-27 | Safety buckle with buffer means |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/535,357 Division US6384142B1 (en) | 2000-02-08 | 2000-03-24 | Propylene impact copolymers |
US09/996,245 Division US6472474B2 (en) | 2000-02-08 | 2001-11-27 | Propylene impact copolymers |
Publications (2)
Publication Number | Publication Date |
---|---|
US20010034411A1 true US20010034411A1 (en) | 2001-10-25 |
US6342566B2 US6342566B2 (en) | 2002-01-29 |
Family
ID=22662533
Family Applications (4)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/535,357 Expired - Fee Related US6384142B1 (en) | 2000-02-08 | 2000-03-24 | Propylene impact copolymers |
US09/534,556 Expired - Fee Related US6492465B1 (en) | 2000-02-08 | 2000-03-24 | Propylene impact copolymers |
US09/862,667 Expired - Lifetime US6342566B2 (en) | 2000-02-08 | 2001-05-21 | Propylene impact copolymers |
US09/996,245 Expired - Fee Related US6472474B2 (en) | 2000-02-08 | 2001-11-27 | Propylene impact copolymers |
Family Applications Before (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/535,357 Expired - Fee Related US6384142B1 (en) | 2000-02-08 | 2000-03-24 | Propylene impact copolymers |
US09/534,556 Expired - Fee Related US6492465B1 (en) | 2000-02-08 | 2000-03-24 | Propylene impact copolymers |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/996,245 Expired - Fee Related US6472474B2 (en) | 2000-02-08 | 2001-11-27 | Propylene impact copolymers |
Country Status (10)
Country | Link |
---|---|
US (4) | US6384142B1 (en) |
EP (2) | EP1254186B1 (en) |
JP (1) | JP2003522259A (en) |
KR (2) | KR20020074509A (en) |
CN (1) | CN1398272A (en) |
AT (1) | ATE286082T1 (en) |
BR (1) | BR0108150A (en) |
CA (1) | CA2398509A1 (en) |
DE (1) | DE60108075T2 (en) |
WO (1) | WO2001058970A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080281046A1 (en) * | 2005-08-22 | 2008-11-13 | Ryoji Mori | Propylene Based Resin Composition |
US7855258B2 (en) | 1998-07-01 | 2010-12-21 | Exxonmobil Chemical Patents Inc. | Propylene olefin copolymers |
US8026323B2 (en) | 2001-04-12 | 2011-09-27 | Exxonmobil Chemical Patents Inc. | Propylene ethylene polymers and production process |
WO2015108634A1 (en) | 2014-01-15 | 2015-07-23 | Exxonmobil Chemical Patents Inc. | Propylene-based impact copolymers |
US10465025B2 (en) | 2014-01-15 | 2019-11-05 | Exxonmobil Chemical Patents Inc. | Low comonomer propylene-based impact copolymers |
Families Citing this family (203)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6583227B2 (en) | 1996-09-04 | 2003-06-24 | Exxonmobil Chemical Patents Inc. | Propylene polymers for films |
US7919561B2 (en) * | 1996-09-04 | 2011-04-05 | Exxonmobil Chemical Patents Inc. | Process of producing thermoplastic polymer blends |
WO1998010016A1 (en) | 1996-09-04 | 1998-03-12 | Exxon Chemical Patents Inc. | Improved propylene polymers for oriented films |
US6921794B2 (en) * | 1997-08-12 | 2005-07-26 | Exxonmobil Chemical Patents Inc. | Blends made from propylene ethylene polymers |
US7232871B2 (en) * | 1997-08-12 | 2007-06-19 | Exxonmobil Chemical Patents Inc. | Propylene ethylene polymers and production process |
US6635715B1 (en) * | 1997-08-12 | 2003-10-21 | Sudhin Datta | Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers |
JP2000072933A (en) * | 1998-08-31 | 2000-03-07 | Asahi Chem Ind Co Ltd | Olefin elastomer composition |
JP2003522194A (en) * | 2000-02-08 | 2003-07-22 | エクソンモービル・ケミカル・パテンツ・インク | Method for preparing group 14 bridged biscyclopentadienyl ligands |
US6384142B1 (en) * | 2000-02-08 | 2002-05-07 | Exxonmobil Chemical Patents Inc. | Propylene impact copolymers |
GB0008690D0 (en) * | 2000-04-07 | 2000-05-31 | Borealis Polymers Oy | Process |
US6870016B1 (en) * | 2000-06-30 | 2005-03-22 | Exxonmobil Chemical Patents Inc. | Polymerization process and polymer composition |
US7122498B2 (en) | 2000-06-30 | 2006-10-17 | Exxonmobil Chemical Patents Inc. | Metallocenes and catalyst compositions derived therefrom |
JP2005522406A (en) | 2001-06-29 | 2005-07-28 | エクソンモービル・ケミカル・パテンツ・インク | Metallocene and catalyst composition derived from the metallocene |
DE10158656A1 (en) | 2001-11-30 | 2003-06-26 | Basell Polyolefine Gmbh | Organo transition metal compound, biscyclopentadienyl ligand system, catalyst system and process for making polyolefins |
CN101565708B (en) | 2002-03-29 | 2011-09-21 | 组合化学工业株式会社 | Genes encoding acetolactate synthase |
CA2483326C (en) * | 2002-04-23 | 2011-01-04 | Dow Global Technologies Inc. | Alkaryl-substituted group 4 metal complexes, catalysts and olefin polymerization process |
KR101186268B1 (en) | 2002-06-26 | 2012-09-27 | 애버리 데니슨 코포레이션 | Oriented films comprising polypropylene/olefin elastomer blends |
US7531594B2 (en) * | 2002-08-12 | 2009-05-12 | Exxonmobil Chemical Patents Inc. | Articles from plasticized polyolefin compositions |
BR0313398A (en) * | 2002-08-12 | 2005-06-28 | Exxonmobil Chem Patents Inc | Plasticized Polyolefin Compositions |
US8003725B2 (en) * | 2002-08-12 | 2011-08-23 | Exxonmobil Chemical Patents Inc. | Plasticized hetero-phase polyolefin blends |
US7271209B2 (en) * | 2002-08-12 | 2007-09-18 | Exxonmobil Chemical Patents Inc. | Fibers and nonwovens from plasticized polyolefin compositions |
US7998579B2 (en) * | 2002-08-12 | 2011-08-16 | Exxonmobil Chemical Patents Inc. | Polypropylene based fibers and nonwovens |
WO2004022613A1 (en) * | 2002-09-06 | 2004-03-18 | Basell Polyolefine Gmbh | Process for the copolymerization of ethylene |
WO2004046214A2 (en) | 2002-10-15 | 2004-06-03 | Exxonmobil Chemical Patents Inc. | Multiple catalyst system for olefin polymerization and polymers produced therefrom |
US7700707B2 (en) | 2002-10-15 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
WO2004037872A2 (en) | 2002-10-24 | 2004-05-06 | Exxonmobil Chemical Patents Inc. | Branched crystalline polypropylene |
US7459500B2 (en) * | 2002-11-05 | 2008-12-02 | Dow Global Technologies Inc. | Thermoplastic elastomer compositions |
US20040147169A1 (en) | 2003-01-28 | 2004-07-29 | Allison Jeffrey W. | Power connector with safety feature |
DE602004031607D1 (en) * | 2003-05-28 | 2011-04-14 | Mitsui Chemicals Inc | PROPYLENE POLYMERIC COMPOSITION AND USE THEREOF |
US8192813B2 (en) | 2003-08-12 | 2012-06-05 | Exxonmobil Chemical Patents, Inc. | Crosslinked polyethylene articles and processes to produce same |
US20070299208A1 (en) * | 2003-09-11 | 2007-12-27 | Baseball Polyolefine Gmbh | Multistep Process For Preparing Heterophasic Propylene Copolymers |
JP2007505176A (en) * | 2003-09-11 | 2007-03-08 | バセル ポリオレフィン ジーエムビーエイチ | Multi-stage process for producing heterophasic propylene copolymers |
US6995213B2 (en) * | 2003-09-29 | 2006-02-07 | Fina Technology, Inc. | Oriented films prepared using impact copolymer polypropylene |
JP4590037B2 (en) * | 2003-09-30 | 2010-12-01 | 日本ポリプロ株式会社 | Olefin polymerization catalyst component, α-olefin polymerization catalyst and method for producing α-olefin polymer |
US7458839B2 (en) | 2006-02-21 | 2008-12-02 | Fci Americas Technology, Inc. | Electrical connectors having power contacts with alignment and/or restraining features |
WO2005065254A2 (en) | 2003-12-31 | 2005-07-21 | Fci Americas Technology, Inc. | Electrical power contacts and connectors comprising same |
WO2005080495A1 (en) | 2004-02-12 | 2005-09-01 | Exxonmobil Chemical Patents Inc. | Plasticized polyolefin compositions |
US20050234172A1 (en) * | 2004-04-19 | 2005-10-20 | Fina Technology, Inc. | Random copolymer-impact copolymer blend |
US20050234198A1 (en) * | 2004-04-20 | 2005-10-20 | Fina Technology, Inc. | Heterophasic copolymer and metallocene catalyst system and method of producing the heterophasic copolymer using the metallocene catalyst system |
SI1781737T1 (en) * | 2004-07-30 | 2009-04-30 | Saudi Basic Ind Corp | Propylene copolymer compositions with high transparency |
EP1793997A1 (en) * | 2004-09-10 | 2007-06-13 | ExxonMobil Oil Corporation | Cavitated opaque polymer film and methods related thereto |
CA2583225A1 (en) † | 2004-10-04 | 2006-04-13 | Basell Poliolefine Italia S.R.L. | Elastomeric polyolefin compositions |
US8389615B2 (en) | 2004-12-17 | 2013-03-05 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin |
US7384289B2 (en) | 2005-01-31 | 2008-06-10 | Fci Americas Technology, Inc. | Surface-mount connector |
CN101142272B (en) * | 2005-03-18 | 2012-09-05 | 三井化学株式会社 | Propylene-based polymer composition, use thereof, and method for producing thermpolastic polymer composition |
DE602006005645D1 (en) | 2005-05-12 | 2009-04-23 | Dow Global Technologies Inc | Thermoformed and extruded film with reduced gloss |
WO2007011541A1 (en) | 2005-07-15 | 2007-01-25 | Exxonmobil Chemical Patents Inc. | Elastomeric compositions |
CN101291986B (en) * | 2005-10-21 | 2011-12-14 | 巴塞尔聚烯烃股份有限公司 | Polypropylene for injection molding |
US7709577B2 (en) | 2005-12-07 | 2010-05-04 | Exxonmobil Chemical Patents Inc. | Process of making polymer blends |
CN101415737B (en) * | 2006-02-02 | 2013-06-12 | 巴塞尔聚烯烃股份有限公司 | Propylene melt blown resins, propylene melt blown resin fibers and non-woven fabric made from the same, and methods of making the same |
CN101466543B (en) | 2006-06-14 | 2014-03-19 | 艾利丹尼森公司 | Conformable and die-cuttable machine direction oriented labelstocks and labels, and process for preparing |
US7726982B2 (en) | 2006-06-15 | 2010-06-01 | Fci Americas Technology, Inc. | Electrical connectors with air-circulation features |
WO2007149900A2 (en) | 2006-06-20 | 2007-12-27 | Avery Dennison Corporation | Multilayered polymeric film for hot melt adhesive labeling and label stock and label thereof |
ATE406393T1 (en) * | 2006-07-10 | 2008-09-15 | Borealis Tech Oy | SHORT CHAIN BRANCHED POLYPROPYLENE |
CA2662177A1 (en) * | 2006-08-29 | 2008-04-24 | Martin B. Rawls-Meehan | A foam spring mattress configured with variable firmness |
US8198373B2 (en) * | 2006-10-02 | 2012-06-12 | Exxonmobil Chemical Patents Inc. | Plastic toughened plastics |
US7256240B1 (en) * | 2006-12-22 | 2007-08-14 | Exxonmobil Chemical Patents Inc. | Process of making polymer blends |
US7905731B2 (en) | 2007-05-21 | 2011-03-15 | Fci Americas Technology, Inc. | Electrical connector with stress-distribution features |
US8283399B2 (en) * | 2007-09-07 | 2012-10-09 | Dow Global Technologies Llc | Filled TPO compositions with good low temperature ductility |
US7762857B2 (en) * | 2007-10-01 | 2010-07-27 | Fci Americas Technology, Inc. | Power connectors with contact-retention features |
EP2235071A2 (en) | 2007-10-25 | 2010-10-06 | Novolen Technology Holdings, C.V. | Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo and copolymers |
US8299287B2 (en) | 2007-10-25 | 2012-10-30 | Lammus Novolen Technology GmbH | Metallocene compounds, catalysts comprising them, process for producing an olefin polymer by use of the catalysts, and olefin homo- and copolymers |
EP2062937A1 (en) * | 2007-11-26 | 2009-05-27 | Total Petrochemicals Research Feluy | Heterophasic propylene copolymer for corrugated sheet and cast film applications |
EP2363433B1 (en) * | 2007-12-17 | 2018-02-07 | Borealis Technology OY | Heterophasic polypropylene with high flowability and excellent low temperature impact properties |
US20090171030A1 (en) * | 2007-12-26 | 2009-07-02 | Sumitomo Chemical Company, Limited | Polypropylene-based copolymer and film comprising the polypropylene-based copolymer |
JP5156415B2 (en) * | 2008-02-01 | 2013-03-06 | トピー工業株式会社 | High rigidity and high impact resistance resin composition |
US8404773B2 (en) | 2008-03-17 | 2013-03-26 | Dow Global Technologies Llc | Coating composition, method of producing the same, articles made therefrom, and method of making such articles |
EP3266909A1 (en) * | 2008-06-12 | 2018-01-10 | 3M Innovative Properties Co. | Melt blown fine fibers and methods of manufacture |
MX2010013656A (en) | 2008-06-12 | 2011-01-14 | 3M Innovative Properties Co | Biocompatible hydrophilic compositions. |
US8062051B2 (en) | 2008-07-29 | 2011-11-22 | Fci Americas Technology Llc | Electrical communication system having latching and strain relief features |
US8246918B2 (en) * | 2008-10-21 | 2012-08-21 | Fina Technology, Inc. | Propylene polymers for lab/medical devices |
US7851554B2 (en) * | 2008-10-27 | 2010-12-14 | Exxonmobil Chemical Patents Inc. | Propylene impact copolymers with balanced impact strength and stiffness |
US8323049B2 (en) | 2009-01-30 | 2012-12-04 | Fci Americas Technology Llc | Electrical connector having power contacts |
USD619099S1 (en) | 2009-01-30 | 2010-07-06 | Fci Americas Technology, Inc. | Electrical connector |
US8366485B2 (en) | 2009-03-19 | 2013-02-05 | Fci Americas Technology Llc | Electrical connector having ribbed ground plate |
EP2414574B1 (en) | 2009-03-31 | 2018-12-12 | 3M Innovative Properties Company | Dimensionally stable nonwoven fibrous webs and methods of making and using the same |
USD618180S1 (en) | 2009-04-03 | 2010-06-22 | Fci Americas Technology, Inc. | Asymmetrical electrical connector |
USD618181S1 (en) | 2009-04-03 | 2010-06-22 | Fci Americas Technology, Inc. | Asymmetrical electrical connector |
RU2554352C2 (en) * | 2009-06-26 | 2015-06-27 | Базелль Полиолефин Италия С.Р.Л. | Polyolefin compositions |
WO2011008582A1 (en) | 2009-07-14 | 2011-01-20 | Dow Global Technologies Inc. | Vacuum thermoformed, extruded sheeting with improved reduced gloss |
BR112012000907A2 (en) * | 2009-07-14 | 2017-08-08 | Dow Global Technologies Inc | impact copolymer to prepare an impact copolymer |
US9828699B2 (en) * | 2009-09-21 | 2017-11-28 | Basell Poliolefine Italia S.R.L. | Polymer filament |
BR112012008527B1 (en) * | 2009-10-13 | 2020-01-14 | Basell Poliolefine Italia Srl | propylene composition and thermoformed article comprising the same |
US8721943B2 (en) * | 2009-12-17 | 2014-05-13 | 3M Innovative Properties Company | Process of making dimensionally stable nonwoven fibrous webs |
WO2011084670A1 (en) * | 2009-12-17 | 2011-07-14 | 3M Innovative Properties Company | Dimensionally stable nonwoven fibrous webs and methods of making and using the same |
WO2011106205A2 (en) | 2010-02-23 | 2011-09-01 | 3M Innovative Properties Company | Dimensionally stable nonwoven fibrous webs and methods of making and using the same |
EP2426171A1 (en) | 2010-08-30 | 2012-03-07 | Borealis AG | Heterophasic polypropylene with high flowability and enhanced mechanical properties |
TW201221714A (en) | 2010-10-14 | 2012-06-01 | 3M Innovative Properties Co | Dimensionally stable nonwoven fibrous webs and methods of making and using the same |
US8980415B2 (en) | 2010-12-03 | 2015-03-17 | Benoit Ambroise | Antistatic films and methods to manufacture the same |
PL2655505T3 (en) * | 2010-12-20 | 2019-03-29 | Braskem America, Inc. | Propylene-based compositions of enhanced appearance and excellent mold flowability |
US20120272468A1 (en) | 2011-04-26 | 2012-11-01 | The Procter & Gamble Company | Oral Care Device Comprising A Synthetic Polymer Derived From A Renewable Resource And Methods Of Producing Said Device |
US8809461B2 (en) * | 2011-04-28 | 2014-08-19 | Braskem America, Inc. | Multimodal heterophasic copolymer and thermoformed articles from same |
US8530581B2 (en) | 2011-12-12 | 2013-09-10 | Exxonmobil Chemical Patents Inc. | Powder, compositions thereof, processes for making the same, and articles made therefrom |
EP2624034A1 (en) | 2012-01-31 | 2013-08-07 | Fci | Dismountable optical coupling device |
MX352811B (en) | 2012-04-05 | 2017-12-08 | Borealis Ag | High flow thermoplastic polyolefin with balanced mechanical performance and low shrinkage and clte. |
US8944831B2 (en) | 2012-04-13 | 2015-02-03 | Fci Americas Technology Llc | Electrical connector having ribbed ground plate with engagement members |
USD718253S1 (en) | 2012-04-13 | 2014-11-25 | Fci Americas Technology Llc | Electrical cable connector |
USD727268S1 (en) | 2012-04-13 | 2015-04-21 | Fci Americas Technology Llc | Vertical electrical connector |
US9257778B2 (en) | 2012-04-13 | 2016-02-09 | Fci Americas Technology | High speed electrical connector |
USD727852S1 (en) | 2012-04-13 | 2015-04-28 | Fci Americas Technology Llc | Ground shield for a right angle electrical connector |
US9543703B2 (en) | 2012-07-11 | 2017-01-10 | Fci Americas Technology Llc | Electrical connector with reduced stack height |
USD751507S1 (en) | 2012-07-11 | 2016-03-15 | Fci Americas Technology Llc | Electrical connector |
US9676532B2 (en) | 2012-08-15 | 2017-06-13 | Avery Dennison Corporation | Packaging reclosure label for high alcohol content products |
US10179852B2 (en) | 2012-09-11 | 2019-01-15 | Sika Technology Ag | Thermoplastic mixture with high flexibility and high melting point |
CN104755511B (en) | 2012-10-31 | 2016-12-28 | 埃克森美孚化学专利公司 | Propylene copolymer compositions and preparation method thereof |
US9322114B2 (en) | 2012-12-03 | 2016-04-26 | Exxonmobil Chemical Patents Inc. | Polypropylene fibers and fabrics |
EP2928958B1 (en) | 2012-12-05 | 2019-08-21 | ExxonMobil Chemical Patents Inc. | Hdpe modified polyethylene blown film compositions having excellent bubble stability |
CN104903100B (en) | 2012-12-18 | 2017-11-14 | 埃克森美孚化学专利公司 | Polyethylene film and its manufacture method |
USD745852S1 (en) | 2013-01-25 | 2015-12-22 | Fci Americas Technology Llc | Electrical connector |
USD720698S1 (en) | 2013-03-15 | 2015-01-06 | Fci Americas Technology Llc | Electrical cable connector |
BR112015026427B1 (en) | 2013-05-14 | 2020-07-21 | Exxonmobil Chemical Patents Inc. | ethylene-based polymers and articles made of the same |
WO2014193985A1 (en) | 2013-05-28 | 2014-12-04 | Tredegar Film Products Corporation | Polyolefin volumetric diffuser |
WO2014204780A1 (en) * | 2013-06-18 | 2014-12-24 | Exxonmobil Chemical Patents Inc. | Fibers and nonwoven materials prepared therefrom |
US9938364B2 (en) | 2013-07-17 | 2018-04-10 | Exxonmobil Chemical Patents Inc. | Substituted metallocene catalysts |
WO2015009480A1 (en) | 2013-07-17 | 2015-01-22 | Exxonmobil Chemical Patents Inc. | Process using substituted metallocene catalysts and products therefrom |
CN105377904B (en) | 2013-07-17 | 2018-07-10 | 埃克森美孚化学专利公司 | Metallocene and by its derivative carbon monoxide-olefin polymeric |
EP3539993A1 (en) | 2013-07-17 | 2019-09-18 | ExxonMobil Chemical Patents Inc. | Cyclopropyl substituted metallocene catalysts |
JP2016531978A (en) | 2013-07-17 | 2016-10-13 | エクソンモービル ケミカル パテンツ インコーポレイテッド | Substituted metallocene catalyst |
US9644047B2 (en) | 2013-07-17 | 2017-05-09 | Exxonmobil Chemical Patents Inc. | Metallocenes and catalyst compositions derived therefrom |
WO2015022127A1 (en) * | 2013-08-14 | 2015-02-19 | Borealis Ag | Propylene composition with improved impact resistance at low temperature |
CN105452365B (en) | 2013-08-21 | 2018-04-17 | 博里利斯股份公司 | High flowing polyolefin composition with high rigidity and toughness |
JP2016528368A (en) | 2013-08-21 | 2016-09-15 | ボレアリス・アクチェンゲゼルシャフトBorealis Ag | High flow polyolefin composition having high rigidity and toughness |
PT2853563T (en) | 2013-09-27 | 2016-07-14 | Borealis Ag | Films suitable for bopp processing from polymers with high xs and high tm |
JP2016535112A (en) | 2013-09-30 | 2016-11-10 | スリーエム イノベイティブ プロパティズ カンパニー | Compositions, wipes, and methods |
WO2015047890A1 (en) | 2013-09-30 | 2015-04-02 | 3M Innovative Properties Company | Fibers and wipes with epoxidized fatty ester disposed thereon, and methods |
US9982128B2 (en) | 2013-09-30 | 2018-05-29 | 3M Innovative Properties Company | Fibers, wipes, and methods |
ES2568615T3 (en) | 2013-10-11 | 2016-05-03 | Borealis Ag | Label film oriented in the machine direction |
EP2865713B1 (en) | 2013-10-24 | 2016-04-20 | Borealis AG | Blow molded article based on bimodal random copolymer |
WO2015059229A1 (en) | 2013-10-24 | 2015-04-30 | Borealis Ag | Low melting pp homopolymer with high content of regioerrors and high molecular weight |
US9266910B2 (en) | 2013-10-29 | 2016-02-23 | Exxonmobil Chemical Patents Inc. | Asymmetric polypropylene catalysts |
WO2015062936A1 (en) | 2013-10-29 | 2015-05-07 | Borealis Ag | Solid single site catalysts with high polymerisation activity |
ES2644829T3 (en) | 2013-11-22 | 2017-11-30 | Borealis Ag | Low emission propylene homopolymer with high melt flow |
US9376559B2 (en) | 2013-11-22 | 2016-06-28 | Exxonmobil Chemical Patents Inc. | Reverse staged impact copolymers |
CN105793298B (en) | 2013-12-04 | 2019-06-28 | 博里利斯股份公司 | The PP homopolymer without phthalic acid ester for meltblown fibers |
WO2015085446A1 (en) | 2013-12-10 | 2015-06-18 | Exxonmobil Chemical Patents Inc. | Methods for making multilayer films and films made thereby |
CN105980457B (en) | 2013-12-18 | 2019-03-22 | 博里利斯股份公司 | With improved rigidity/tough sexual balance BOPP film |
CN105849178B (en) | 2013-12-20 | 2018-05-15 | 沙特基础工业公司 | Polyolefin composition |
MX2016008028A (en) | 2013-12-20 | 2017-05-12 | Saudi Basic Ind Corp | Heterophasic propylene copolymer. |
CN105829364B (en) | 2014-01-17 | 2017-11-10 | 博里利斯股份公司 | Method for preparing the butylene copolymer of propylene/1 |
CN112225997B (en) | 2014-02-06 | 2023-09-22 | 北欧化工公司 | High impact strength flexible copolymers |
PL3102634T3 (en) | 2014-02-06 | 2020-11-16 | Borealis Ag | Soft and transparent impact copolymers |
EP2907841A1 (en) | 2014-02-14 | 2015-08-19 | Borealis AG | Polypropylene composite |
BR112016018641B1 (en) | 2014-02-24 | 2021-06-22 | Dow Global Technologies Llc | THERMOPLASTIC POLYOLEFIN WITH REDUCED BRIGHTNESS FOR FLOOR WITHOUT CARPET |
ES2659731T3 (en) | 2014-05-20 | 2018-03-19 | Borealis Ag | Polypropylene composition for automotive interior applications |
AU2015270854B2 (en) | 2014-06-02 | 2018-08-02 | Avery Dennison Corporation | Films with enhanced scuff resistance, clarity, and conformability |
EP3191529A1 (en) | 2014-09-12 | 2017-07-19 | Borealis AG | Process for the preparation of copolymers of propylene |
CN106795237B (en) | 2014-10-03 | 2019-07-26 | 埃克森美孚化学专利公司 | Polyethylene polymer, the film being made from it and its manufacturing method |
CN105906929B (en) * | 2015-02-19 | 2020-07-17 | 住友化学株式会社 | Thermoplastic elastomer composition |
WO2016145549A1 (en) | 2015-03-17 | 2016-09-22 | Exxonmobil Chemical Patents Inc. | Multilayer films and methods thereof |
WO2016172099A1 (en) | 2015-04-20 | 2016-10-27 | Exxonmobil Chemical Patents Inc. | Polyethylene composition |
CN107922537B (en) | 2015-06-05 | 2021-07-27 | 埃克森美孚化学专利公司 | Preparation of multiphase polymers in gas or slurry phase |
WO2016196331A1 (en) | 2015-06-05 | 2016-12-08 | Exxonmobil Chemical Patents Inc. | Supported metallocene catalyst systems for polymerization |
US9809664B2 (en) | 2015-06-05 | 2017-11-07 | Exxonmobil Chemical Patents Inc. | Bimodal propylene polymers and sequential polymerization |
US10329360B2 (en) | 2015-06-05 | 2019-06-25 | Exxonmobil Chemical Patents Inc. | Catalyst system comprising supported alumoxane and unsupported alumoxane particles |
US10294316B2 (en) | 2015-06-05 | 2019-05-21 | Exxonmobil Chemical Patents Inc. | Silica supports with high aluminoxane loading capability |
US10280235B2 (en) | 2015-06-05 | 2019-05-07 | Exxonmobil Chemical Patents Inc. | Catalyst system containing high surface area supports and sequential polymerization to produce heterophasic polymers |
US10280233B2 (en) | 2015-06-05 | 2019-05-07 | Exxonmobil Chemical Patents Inc. | Catalyst systems and methods of making and using the same |
WO2016196334A1 (en) | 2015-06-05 | 2016-12-08 | Exxonmobil Chemical Patents Inc. | Single reactor production of polymers in gas or slurry phase |
WO2016200600A1 (en) | 2015-06-11 | 2016-12-15 | Dow Global Technologies Llc | Cable insulation comprising a blend of ldpe and polypropylene |
US10696027B2 (en) | 2016-03-11 | 2020-06-30 | Exxonmobil Chemical Patents, Inc. | Multilayer films and methods of making the same |
US11299607B2 (en) | 2016-04-22 | 2022-04-12 | Exxon Mobil Chemical Patents Inc. | Polyethylene sheets |
EP3464390A1 (en) | 2016-05-27 | 2019-04-10 | ExxonMobil Chemical Patents Inc. | Metallocene catalyst compositions and polymerization process therewith |
WO2018102091A1 (en) | 2016-12-02 | 2018-06-07 | Exxonmobil Chemical Patents Inc. | Polyethylene films |
WO2018106480A1 (en) | 2016-12-06 | 2018-06-14 | Exxonmobil Chemical Patents Inc. | Multilayer films and methods of making the same |
WO2018151903A1 (en) | 2017-02-20 | 2018-08-23 | Exxonmobil Chemical Patents Inc. | Supported catalyst systems and processes for use thereof |
WO2018187047A1 (en) | 2017-04-06 | 2018-10-11 | Exxonmobil Chemical Patents Inc. | Cast films and processes for making the same |
WO2018194740A1 (en) | 2017-04-19 | 2018-10-25 | Exxonmobil Chemical Patents Inc. | Multilayer films and methods of making the same |
WO2018226311A1 (en) | 2017-06-08 | 2018-12-13 | Exxonmobil Chemical Patents Inc. | Polyethylene blends and extrudates and methods of making the same |
WO2019027524A1 (en) | 2017-08-02 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | Multilayer films and methods of making the same |
WO2019027587A1 (en) | 2017-08-04 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | Polyethylene compositions and films prepared therefrom |
WO2019027586A1 (en) | 2017-08-04 | 2019-02-07 | Exxonmobil Chemical Patents Inc. | Mixed catalysts with 2, 6-bis(imino)pyridy| iron complexes and bridged hafnocenes |
US10913808B2 (en) | 2017-08-04 | 2021-02-09 | Exxonmobil Chemical Patents Inc. | Mixed catalysts with unbridged hafnocenes with -CH2-SiMe3 moieties |
CN111491959B (en) | 2017-08-04 | 2023-08-25 | 埃克森美孚化学专利公司 | Film made of polyethylene composition and method for producing same |
US10920053B2 (en) | 2017-10-16 | 2021-02-16 | Exxonmobil Chemical Patents Inc. | Propylene impact copolymer blends with improved gloss |
EP3717241B1 (en) | 2017-11-28 | 2021-08-04 | ExxonMobil Chemical Patents Inc. | Multilayer films and methods of making the same |
WO2019108327A1 (en) | 2017-12-01 | 2019-06-06 | Exxonmobil Chemical Patents Inc. | Films comprising polyethylene composition |
CN115850552A (en) | 2017-12-01 | 2023-03-28 | 埃克森美孚化学专利公司 | Catalyst system and polymerization process using the same |
US11952480B2 (en) | 2018-02-05 | 2024-04-09 | Exxonmobil Chemical Patents Inc. | Enhanced processability of LLDPE by addition of ultra-high molecular weight density polyethylene |
ES2970673T3 (en) | 2018-06-13 | 2024-05-30 | Exxonmobil Chemical Patents Inc | Compositions of polyolefin blends |
CN112313254B (en) | 2018-06-19 | 2023-04-18 | 埃克森美孚化学专利公司 | Polyethylene compositions and films made therefrom |
WO2020068497A1 (en) | 2018-09-25 | 2020-04-02 | Exxonmobil Chemical Patents Inc. | Multilayer films and methods of making the same |
EP3873949A1 (en) | 2018-11-01 | 2021-09-08 | ExxonMobil Chemical Patents Inc. | Slurry trim catalyst feeder modifications |
EP3873947A1 (en) | 2018-11-01 | 2021-09-08 | ExxonMobil Chemical Patents Inc. | On-line adjustment of mixed catalyst ratio by trim and olefin polymerization with the same |
WO2020092584A2 (en) | 2018-11-01 | 2020-05-07 | Exxonmobil Chemical Patents Inc. | In-line trimming of dry catalyst feed |
CN113039211B (en) | 2018-11-01 | 2023-04-14 | 埃克森美孚化学专利公司 | In-line conditioning and olefin polymerization by trimmed catalyst |
WO2020092606A1 (en) | 2018-11-01 | 2020-05-07 | Exxonmobil Chemical Patents Inc. | On-line adjustment of mixed catalyst ratio and olefin polymerization |
WO2020139499A1 (en) | 2018-12-26 | 2020-07-02 | Exxonmobil Chemical Patents Inc. | Multilayer metallized cast polypropylene films doped with hydrocarbon resin |
WO2020167929A1 (en) | 2019-02-13 | 2020-08-20 | Exxonmobil Chemical Patents Inc. | Methods for making films and films made thereby |
CN113518715B (en) | 2019-02-13 | 2024-03-22 | 埃克森美孚化学专利公司 | Oriented multilayer polyethylene film and laminate thereof |
EP3927771A1 (en) | 2019-02-19 | 2021-12-29 | Braskem, S.A. | No break polypropylene impact copolymers with melt flow rate higher than 90 g/10 min |
WO2020190507A1 (en) | 2019-03-19 | 2020-09-24 | Exxonmobil Chemical Patents Inc. | Multilayer oriented films |
EP3722363A1 (en) * | 2019-04-12 | 2020-10-14 | Thai Polyethylene Co., Ltd. | Impact copolymer polypropylene for thin-wall injection packaging |
WO2021034400A1 (en) | 2019-08-20 | 2021-02-25 | Exxonmobil Chemical Patents Inc. | Films and methods of making the same |
US11472828B2 (en) | 2019-10-11 | 2022-10-18 | Exxonmobil Chemical Patents Inc. | Indacene based metallocene catalysts useful in the production of propylene polymers |
US11518154B2 (en) | 2020-01-27 | 2022-12-06 | Exxonmobil Chemical Patents Inc. | Barrier films for packaging |
EP4106994A1 (en) | 2020-02-18 | 2022-12-28 | ExxonMobil Chemical Patents Inc. | High tenacity handwrap stretch film for improved pallet stability |
WO2021195070A1 (en) | 2020-03-26 | 2021-09-30 | Exxonmobil Chemical Patents Inc. | Processes for making 3-d objects from blends of polypropylene and semi-amorphous polymers |
WO2022187814A2 (en) | 2021-03-05 | 2022-09-09 | Exxonmobil Chemical Patents Inc. | Processes for making and using slurry catalyst mixtures |
WO2022203463A1 (en) * | 2021-03-26 | 2022-09-29 | 주식회사 엘지화학 | Polypropylene resin composition and non-woven fabric prepared using same |
WO2022203461A1 (en) * | 2021-03-26 | 2022-09-29 | 주식회사 엘지화학 | Polypropylene resin composition and method for preparing same |
CN116648535A (en) * | 2021-03-26 | 2023-08-25 | 株式会社Lg化学 | Polypropylene resin composition and nonwoven fabric prepared by using same |
CN116670189A (en) * | 2021-03-26 | 2023-08-29 | 株式会社Lg化学 | Polypropylene resin composition and preparation method thereof |
WO2023150480A1 (en) | 2022-02-07 | 2023-08-10 | Exxonmobil Chemical Patents Inc. | C1 symmetric 5-ome-6-alkyl substituted metallocenes |
Family Cites Families (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5382631A (en) | 1988-09-30 | 1995-01-17 | Exxon Chemical Patents Inc. | Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distributions |
US5258464A (en) | 1990-01-29 | 1993-11-02 | Shell Oil Company | Impact copolymer compositions |
US5118757A (en) | 1990-03-26 | 1992-06-02 | Shell Oil Company | Polymer production |
US5166268A (en) | 1990-04-12 | 1992-11-24 | Union Carbide Chemicals & Plastics Technology Corporation | Process for cold forming propylene copolymers |
US5362782A (en) | 1990-05-14 | 1994-11-08 | Shell Oil Company | Polymer compositions |
US5250631A (en) | 1990-06-13 | 1993-10-05 | Shell Oil Company | Polymer compositions |
DE4130429A1 (en) | 1991-09-13 | 1993-03-18 | Basf Ag | METHOD FOR PRODUCING MULTI-PHASE BLOCK COPOLYMERISATS BASED ON ALK-1-ENEN |
US5830821A (en) | 1991-11-30 | 1998-11-03 | Targor Gmbh | Process for olefin preparation using metallocenes having benzo-fused indenyl derivatives as ligands |
TW294669B (en) | 1992-06-27 | 1997-01-01 | Hoechst Ag | |
ES2128371T3 (en) | 1992-08-15 | 1999-05-16 | Targor Gmbh | PROCEDURE FOR OBTAINING POLYOLEFINS. |
EP0812854B2 (en) | 1993-06-07 | 2011-04-20 | Mitsui Chemicals, Inc. | Novel transition metal compound, olefin polymerization catalyst comprising said compound, process for olefin polymerization using said catalyst and propylene homo- and copolymer |
DE69413651T2 (en) * | 1993-06-30 | 1999-04-08 | Mitsui Chemicals, Inc., Tokio/Tokyo | POLYPROPYLENE COMPOSITION |
TW354792B (en) * | 1993-08-13 | 1999-03-21 | Mitsui Petrochemical Ind | Olefin polymerization catalyst and process for preparing polypropylene and propylene block copolymer |
KR100353463B1 (en) * | 1994-04-11 | 2003-01-24 | 미쓰이 가가쿠 가부시키가이샤 | Process for producing propylene polymer composition and propylene polymer composition |
JP4024295B2 (en) | 1994-04-11 | 2007-12-19 | 三井化学株式会社 | Propylene polymer composition production method and propylene polymer composition |
JP3357186B2 (en) | 1994-07-14 | 2002-12-16 | 三菱化学株式会社 | Method for producing propylene block copolymer |
CA2187204C (en) | 1995-02-07 | 2002-09-10 | Kenji Sugimura | Process for preparing olefin polymer |
US5674630A (en) | 1995-05-08 | 1997-10-07 | Union Carbide Chemicals & Plastics Technology Corporation | Polymer compositions and cast films |
JPH09151294A (en) | 1995-09-29 | 1997-06-10 | Mitsubishi Chem Corp | Talc-containing propylene resin composition |
US5712344A (en) | 1996-01-04 | 1998-01-27 | Union Carbide Chemicals & Plastics Technology Corporation | Modified polypropylene impact copolymer compositions |
JPH09208881A (en) | 1996-02-07 | 1997-08-12 | Mitsubishi Chem Corp | Propylene resin composition for coating |
SG67392A1 (en) | 1996-05-27 | 1999-09-21 | Sumitomo Chemical Co | Propylene/ethylene-alpha-olefin block copolymer and process for producing the same |
EP0890590B1 (en) | 1997-01-10 | 2002-09-04 | Chisso Corporation | Propylene/ethylene copolymer, process for the production thereof, and molded articles thereof |
WO1998040331A1 (en) | 1997-03-07 | 1998-09-17 | Targor Gmbh | Preparation of preparing substituted indanones |
US6303696B1 (en) | 1997-04-11 | 2001-10-16 | Chisso Corporation | Propylene (co)polymer composition using metallocene catalyst |
US6635715B1 (en) * | 1997-08-12 | 2003-10-21 | Sudhin Datta | Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers |
AU8886898A (en) * | 1997-08-29 | 1999-03-22 | Chisso Corporation | Polypropylene/propylene-ethylene copolymer composition and process for the preparation thereof |
DE19739946A1 (en) | 1997-09-11 | 1999-03-18 | Targor Gmbh | Process for the production of metallocenes |
US5942587A (en) | 1997-11-21 | 1999-08-24 | Exxon Chemical Patents Inc. | Ethylene polymers with a norbornene comonomer for LLDPE like resins of improved toughness and processibility for film production |
US5986009A (en) * | 1997-12-03 | 1999-11-16 | The Dow Chemical Company | Blends of polypropylenes |
DE69916170T2 (en) | 1998-06-04 | 2005-03-17 | Japan Polychem Corp. | Propylene block copolymer and resin composition |
US6384142B1 (en) * | 2000-02-08 | 2002-05-07 | Exxonmobil Chemical Patents Inc. | Propylene impact copolymers |
-
2000
- 2000-03-24 US US09/535,357 patent/US6384142B1/en not_active Expired - Fee Related
- 2000-03-24 US US09/534,556 patent/US6492465B1/en not_active Expired - Fee Related
-
2001
- 2001-02-08 KR KR1020027010213A patent/KR20020074509A/en not_active Application Discontinuation
- 2001-02-08 JP JP2001558115A patent/JP2003522259A/en active Pending
- 2001-02-08 EP EP01910477A patent/EP1254186B1/en not_active Expired - Lifetime
- 2001-02-08 CN CN01804671A patent/CN1398272A/en active Pending
- 2001-02-08 CA CA002398509A patent/CA2398509A1/en not_active Abandoned
- 2001-02-08 DE DE60108075T patent/DE60108075T2/en not_active Expired - Lifetime
- 2001-02-08 WO PCT/US2001/004126 patent/WO2001058970A1/en active IP Right Grant
- 2001-02-08 BR BR0108150-0A patent/BR0108150A/en not_active IP Right Cessation
- 2001-02-08 EP EP04021067A patent/EP1481997B1/en not_active Expired - Lifetime
- 2001-02-08 AT AT01910477T patent/ATE286082T1/en not_active IP Right Cessation
- 2001-02-08 KR KR1020027010245A patent/KR20020073209A/en not_active Application Discontinuation
- 2001-05-21 US US09/862,667 patent/US6342566B2/en not_active Expired - Lifetime
- 2001-11-27 US US09/996,245 patent/US6472474B2/en not_active Expired - Fee Related
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7855258B2 (en) | 1998-07-01 | 2010-12-21 | Exxonmobil Chemical Patents Inc. | Propylene olefin copolymers |
US8026323B2 (en) | 2001-04-12 | 2011-09-27 | Exxonmobil Chemical Patents Inc. | Propylene ethylene polymers and production process |
US8501892B2 (en) | 2001-04-12 | 2013-08-06 | Exxonmobil Chemical Patents Inc. | Propylene ethylene polymers and production process |
US20080281046A1 (en) * | 2005-08-22 | 2008-11-13 | Ryoji Mori | Propylene Based Resin Composition |
WO2015108634A1 (en) | 2014-01-15 | 2015-07-23 | Exxonmobil Chemical Patents Inc. | Propylene-based impact copolymers |
US9309334B2 (en) | 2014-01-15 | 2016-04-12 | Exxonmobil Chemical Patents Inc. | Propylene-based impact copolymers |
US9745395B2 (en) | 2014-01-15 | 2017-08-29 | Exxonmobil Chemical Patents Inc. | Propylene-based impact copolymers |
US10465025B2 (en) | 2014-01-15 | 2019-11-05 | Exxonmobil Chemical Patents Inc. | Low comonomer propylene-based impact copolymers |
Also Published As
Publication number | Publication date |
---|---|
EP1481997A1 (en) | 2004-12-01 |
US6492465B1 (en) | 2002-12-10 |
BR0108150A (en) | 2003-01-21 |
CA2398509A1 (en) | 2001-08-16 |
CN1398272A (en) | 2003-02-19 |
US20020086947A1 (en) | 2002-07-04 |
DE60108075D1 (en) | 2005-02-03 |
KR20020074509A (en) | 2002-09-30 |
US6384142B1 (en) | 2002-05-07 |
US6342566B2 (en) | 2002-01-29 |
DE60108075T2 (en) | 2005-12-08 |
JP2003522259A (en) | 2003-07-22 |
KR20020073209A (en) | 2002-09-19 |
EP1254186A1 (en) | 2002-11-06 |
EP1481997B1 (en) | 2006-08-16 |
ATE286082T1 (en) | 2005-01-15 |
EP1254186B1 (en) | 2004-12-29 |
US6472474B2 (en) | 2002-10-29 |
WO2001058970A1 (en) | 2001-08-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US6384142B1 (en) | Propylene impact copolymers | |
US6380122B1 (en) | Metallocene compositions | |
EP1411058B1 (en) | Bridged bisindenyl metallocene compositions | |
CN101124252B (en) | Metallocene catalysts, their synthesis and their use for the polymerization of olefins | |
US6380331B1 (en) | Metallocene compositions | |
US7081543B2 (en) | Bridged biscyclopentadienyl ligands and method of preparation | |
US6376413B1 (en) | Metallocene compositions | |
US6380121B1 (en) | Metallocene compositions | |
US6380334B1 (en) | Metallocene compositions | |
US6380123B1 (en) | Metallocene compositions | |
EP1421090A2 (en) | Metallocenes and catalyst compositions derived therefrom | |
EP0705283A1 (en) | PROCESS FOR PRODUCING AMORPHOUS POLY-$g(a)-OLEFINS WITH A MONOCYCLOPENTADIENYL TRANSITION METAL CATALYST SYSTEM | |
JP3704205B2 (en) | Transition metal compound and catalyst component for olefin polymerization comprising the transition metal compound |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: EXXONMOBIL CHEMICAL PATENTS INC., TEXAS Free format text: CHANGE OF NAME;ASSIGNOR:EXXON CHEMICAL PATENTS INC.;REEL/FRAME:012356/0925 Effective date: 20010125 |
|
STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
FPAY | Fee payment |
Year of fee payment: 4 |
|
FPAY | Fee payment |
Year of fee payment: 8 |
|
FPAY | Fee payment |
Year of fee payment: 12 |