Polyethylene compositions and films prepared therefrom
A polyethylene composition comprising from about 0.5 to about 20 wt % of alpha-olefin derived units other than ethylene-derived units, with the balance including ethylene-derived units, total internal unsaturations (Vy1+Vy2+T1) of from about 0.10 to about 0.40 per 1000 carbon atoms, an MI of from about 0.1 to about 6 g/10 min, an HLMI of from about 5.0 to about 40 g/10 min, a density of from about 0.890 to about 0.940 g/ml, a Tw 1 -Tw 2 value of from about −25 to about −20° C., an Mw 1 /Mw 2 value of from about 1.2 to about 2.0, an Mw/Mn of from about 4.5 to about 12, an Mz/Mw of from about 2.0 to about 3.0, an Mz/Mn of from about 7.0 to about 20, and a g′ (vis) greater than 0.90.
1. A polyethylene composition comprising:
from about 80 wt % to about 99.5 wt % ethylene-derived units; and
from about 0.5 to about 20 wt % of alpha-olefin derived units other than ethylene-derived units;
wherein the composition has total internal unsaturations (Vy1+Vy2+T1) of from about 0.10 to about 0.40 per 1000 carbon atoms, an MI of from about 0.1 to about 6 g/10 min, an HLMI of from about 5.0 to about 40 g/10 min, a density of from about 0.890 to about 0.940 g/ml, a Tw 1 -Tw 2 value of from about −25 to about −20° C., an Mw 1 /Mw 2 value of from about 1.2 to about 2.0, an Mw/Mn of from about 4.5 to about 12, an Mz/Mw of from about 2.0 to about 3.0, an Mz/Mn of from about 7.0 to about 20, and a g′ (vis) greater than 0.90.
2. The polyethylene composition of claim 1 , where said polyethylene composition has a density of from about 0.912 to about 0.917 g/ml.
3. The polyethylene composition of claim 1 , wherein the polyethylene composition has an MIR, defined as the ratio of high load melt index (HLMI, determined per ASTM D1238, 190° C., 21.6 kg load)) to melt index (MI, determined per ASTM D1238, 190° C., 2.16 kg load), of from about 20 to about 40 and an HLMI of from about 7.0 to about 35 g/10 min.
4. The polyethylene composition of claim 1 , wherein the polyethylene composition has a Tw 1 -Tw 2 value of from about −24 to about −20.5° C., an Mw 1 /Mw 2 value of from about 1.35 to about 1.85, an Mw/Mn of from about 4.7 to about 12, an Mz/Mw of from about 2.2 to about 2.9, an Mz/Mn of from about 10 to about 18, and a g′ (vis) greater than 0.92.
5. The polyethylene composition of claim 1 , wherein the polyethylene composition has a Tw 1 -Tw 2 value of from about −23 to about −21° C., an Mw 1 /Mw 2 value of from about 1.5 to about 1.8, an Mw/Mn of from about 4.4 to about 9.5, an Mz/Mw of from about 2.3 to about 2.8, an Mz/Mn of from about 11 to about 17, and a g′ (vis) greater than 0.94.
6. The polyethylene composition of claim 1 any of claims 1 to 5 , wherein the polyethylene composition has tri-substituted olefins (T1) of from about 0.08 to about 0.35 per 1000 carbon atoms.
7. The polyethylene composition of claim 1 any of claims 1 to 6 , wherein the polyethylene composition has internal unsaturations without carbon substitutions (Vy1+Vy2) of from about 0.02 to about 0.1 per 1000 carbon atoms.
8. The polyethylene composition of claim 7 , where said polyethylene composition is characterized by internal unsaturations without carbon substitutions (Vy1+Vy2) of from about 0.04 to about 0.08 per 1000 carbon atoms.
9. A blown polyethylene film comprising:
a polyethylene composition comprising from about 0.5 to about 20 wt % of alpha-olefin derived units other than ethylene-derived units, with the balance including ethylene-derived units, total internal unsaturations (Vy1+Vy2+T1) of from about 0.10 to about 0.40 per 1000 carbon atoms, an MI of from about 0.1 to about 6 g/10 min, an HLMI of from about 5.0 to about 40 g/10 min, a density of from about 0.890 to about 0.940 g/ml, a Tw 1 -Tw 2 value of from about −25 to about −20° C., an Mw 1 /Mw 2 value of from about 1.2 to about 2.0, an Mw/Mn of from about 4.5 to about 12, an Mz/Mw of from about 2.0 to about 3.0, an Mz/Mn of from about 7.0 to about 20, and a g′ (vis) greater than 0.90;
wherein the blown film has a Dart Drop Impact (DI) that is greater than 300 g/mil, a haze of less than 30%, and a machine-direction tear resistance that is greater than 120 g/mil.
10. The blown film of claim 9 , wherein the blown film has a Dart Drop Impact (DI) that is greater than 400 g/mil, a haze of less than 20%, and a machine-direction tear resistance that is greater than 130 g/mil.
11. The blown film of claim 9 , wherein the polyethylene composition has a density of from 0.914 to 0.917 g/ml, and where the film has a 1% secant modulus, in the transverse direction, of greater than 30,000 psi.
12. The blown film of claim 11 , wherein the polyethylene composition has a density of from 0.914 to 0.917 g/ml, and where the film has a 1% secant modulus, in the transverse direction, of greater than 32,000 psi.
13. The blown film of claim 9 , wherein the polyethylene composition has a density of from about 0.918 to about 0.921 g/ml, and where the film has a 1% secant modulus, in the transverse direction, of greater than 42,000 psi.
14. The blown film of claim 13 , wherein the polyethylene composition has a density of from about 0.918 to about 0.921 g/ml, and where the film has a 1% secant modulus, in the transverse direction, of greater than 45,000 psi.
15. The blown film of claim 9 , wherein the polyethylene composition has a density from about 0.912 to about 0.917 g/ml.
16. The blown film of claim 9 , wherein the polyethylene composition has an MIR, defined as the ratio of high load melt index (HLMI, determined per ASTM D1238, 190° C., 21.6 kg load) to melt index (MI, determined per ASTM D1238, 190° C., 2.16 kg load), of from about 20 to about 40 and an HLMI of from about 7.0 to about 35 g/10 min.
17. The blown film of claim 9 , wherein the polyethylene composition has a Tw 1 -Tw 2 value of from about −24 to about −20.5° C., an Mw 1 /Mw 2 value of from about 1.35 to about 1.85, an Mw/Mn of from about 4.7 to about 12, an Mz/Mw of from about 2.2 to about 2.9, an Mz/Mn of from about 10 to about 18, and a g′ (vis) greater than 0.92.
18. The blown film of claim 9 , wherein the polyethylene composition has a Tw 1 -Tw 2 value of from about −23 to about −21° C., an Mw 1 /Mw 2 value of from about 1.5 to about 1.8, an Mw/Mn of from about 4.9 to about 9.5, an Mz/Mw of from about 2.3 to about 2.8, an Mz/Mn of from about 11 to about 17, and a g′ (vis) greater than 0.94.
19. The blown film of claim 9 , wherein the polyethylene composition has tri-substituted olefins (T1) of from about 0.08 to about 0.35 per 1000 carbon atoms.
20. The blown film of claim 9 , wherein the polyethylene composition has internal unsaturations without carbon substitutions (Vy1+Vy2) of from about 0.02 to about 0.1 per 1000 carbon atoms.
21. The blown film of claim 20 , wherein the polyethylene composition has internal unsaturations without carbon substitutions (Vy1+Vy2) of from about 0.04 to about 0.08 per 1000 carbon atoms.
22. The blown film of claim 9 , where the polyethylene composition is prepared by combining a catalyst system with ethylene and an alpha-olefin comonomer other than ethylene, where the catalyst system includes (i) an unbridged hafnium metallocene compound; (ii) an unbridged zirconium metallocene compound; (iii) a support material; and (iv) activator.
23. The blown film of claim 22 , where the catalyst system includes an unbridged bis-cyclopentadienyl hafnium catalyst, an unbridged bis-cyclopentadienyl zirconium catalyst, and an activator, with ethylene and within the range from 0.1 to 5 wt % relative to the weight of all monomers of a C3 to C12 α-olefin at a temperature within the range from 60 to 100° C., wherein the unbridged zirconium metallocene is represented by the following formula (A):
where M* is hafnium; each of R 1 , R 2 , R 4 and R 5 is independently hydrogen, alkoxide, or C 1 to C 40 substituted or unsubstituted hydrocarbyl; R 3 is —R 11 —SiR′ 3 , where R 11 is a C 1 to C 4 hydrocarbyl, and each R′ is independently hydrogen or a C 1 to C 20 substituted or unsubstituted hydrocarbyl; each R 6 , R 7 , R 8 , R 9 , and R 10 is independently hydrogen, halide, alkoxide, C 1 to C 40 substituted or unsubstituted hydrocarbyl, or —R 11 —SiR′ 3 , where R 11 is a C 1 to C 4 hydrocarbyl, and each R′ is independently hydrogen or a C 1 to C 20 substituted or unsubstituted hydrocarbyl; and each X is independently a univalent anionic ligand, or two Xs are joined to form a metallocyclic ring, or two Xs are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.
24. The blown film of claim 23 , where R 3 and R 9 are both, independently, —R 11 —SiR′ 3 , where R 11 is a C 1 to C 4 hydrocarbyl, and each R′ is independently C 1 to C 20 substituted or unsubstituted hydrocarbyl.
25. The blown film of claim 22 , where the unbridged zirconium metallocene compound is one or more of: Cp(Ind)ZrCl 2 , Me 5 Cp(Ind)ZrCl 2 , Et 5 Cp(Ind)ZrCl 2 , n-Pr 5 Cp(Ind)ZrCl 2 , n-Bu 5 Cp(Ind)ZrCl 2 , Bz 5 Cp(Ind)ZrClz, Cp(1-Me Ind)ZrCl 2 , Cp(1-Et Ind)ZrCl 2 , Cp(1-n-Pr Ind)ZrCl 2 , Cp(1-n-Bu Ind)ZrCl 2 , Cp(1-n-Pn Ind)ZrCl 2 , Cp(1-n-hx Ind)ZrCl 2 , Cp(1-Bz Ind)ZrCl 2 , Cp(1-Me 3 SiCH 2 Ind)ZrCl 2 , Me 5 Cp(1-Me Ind)ZrCl 2 , Me 5 Cp(1-Et Ind)ZrCl 2 , Me 5 Cp(1-n-Pr Ind)ZrCl 2 , Me 5 Cp(1-n-Bu Ind)ZrCl 2 , Me 5 Cp(1-n-Pn Ind)ZrCl 2 , Me 5 Cp(1-n-hx Ind)ZrCl 2 , Me 5 Cp(1-Bz Ind)ZrCl 2 , Me 5 Cp(1-Me 3 SiCH 2 Ind)ZrCl 2 , Et 5 Cp(1-Me Ind)ZrCl 2 , Et 5 Cp(1-Et Ind)ZrCl 2 , Et 5 Cp(1-n-Pr Ind)ZrCl 2 , Et 5 Cp(1-n-Bu Ind)ZrCl 2 , Et 5 Cp(1-n-Pn Ind)ZrCl 2 , Et 5 Cp(1-n-hx Ind)ZrCl 2 , Et 5 Cp(1-Bz Ind)ZrCl 2 , Et 5 Cp(1-Me 3 SiCH 2 Ind)ZrCl 2 , n-Pr 5 Cp(1-Me Ind)ZrCl 2 , n-Pr 5 Cp(1-Et Ind)ZrCl 2 , n-Pr 5 Cp(1-n-Pr Ind)ZrCl 2 , n-Pr 5 Cp(1-n-Bu Ind)ZrCl 2 , n-Pr 5 Cp(1-n-Pn Ind)ZrCl 2 , n-Pr 5 Cp(1-n-hx Ind)ZrCl 2 , n-Pr 5 Cp(1-Bz Ind)ZrCl 2 , n-Pr 5 Cp(1-Me 3 SiCH 2 Ind)ZrCl 2 , n-Bu 5 CP(1-Me Ind)ZrCl 2 , n-Bu 5 Cp(1-Et Ind)ZrCl 2 , n-Bu 5 Cp(1-n-Pr Ind)ZrCl 2 , n-Bu 5 Cp(1-n-Bu Ind)ZrCl 2 , n-Bu 5 Cp(1-n-Pn Ind)ZrCl 2 , n-Bu 5 Cp(1-n-hx Ind)ZrCl 2 , n-Bu 5 Cp(1-Bz Ind)ZrCl 2 , n-Bu 5 Cp(1-Me 3 SiCH 2 Ind)ZrCl 2 , Bz 5 Cp(1-Me Ind)ZrCl 2 , Bz 5 Cp(1-Et Ind)ZrCl 2 , Bz 5 Cp(1-n-Pr Ind)ZrCl 2 , Bz 5 Cp(1-n-Bu Ind)ZrCl 2 , Bz 5 Cp(1-n-Pn Ind)ZrCl 2 , Bz 5 Cp(1-n-hx Ind)ZrCl 2 , Bz 5 Cp(1-Bz Ind)ZrCl 2 , Bz 5 Cp(1-Me 3 SiCH 2 Ind)ZrCl 2 , and the alkyl or halide versions thereof where the Cl 2 is substituted with Bz 2 , Et 2 , Me 2 , Br 2 , I 2 , or Ph 2 ; and wherein the unbridled hafnium metallocene compound generates hydrogen.