BRANT PATRICK (US)
HOLTCAMP MATTHEW (US)
SHI XIAO (CN)
BLANTON TAMARA (US)
WO2019027605A1 | 2019-02-07 | |||
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WO2017127808A1 | 2017-07-27 | |||
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WO2015138096A1 | 2015-09-17 | |||
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US20150258756A1 | 2015-09-17 | |||
US20090286024A1 | 2009-11-19 | |||
US20180237558A1 | 2018-08-23 | |||
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CLAIMS The invention claimed is: 1. An oriented polyethylene film comprising polyethylene having: (A) a melt flow index of 1.0 g/10 min or more, (B) a density of 0.90 g/cm3 to less than 0.940 g/cm3, (C) a g'LCB of greater than 0.8, (D) ratio of comonomer content at Mz to comonomer content at Mw greater than 1.0, (E) ratio of comonomer content at Mn to comonomer content at Mw greater than 1.0, and (F) a ratio of g'LCB to g'Zave greater than 1.0, where the film has a 1% secant in the transverse direction of 70,000 psi or more and Dart Drop of 350 g/mil or more. 2. The film of claim 1, wherein the polyethylene has: (A') a melt flow index of 1.5 g/10 min to 2.1 g/10 min, (B') a density of 0.91 g/cm3 to 0.93 g/cm3, (G) a z-average molecular weight of 300,000 g/mol or greater, and (H) a long chain branching (g’LCB) value of 0.8 to 0.9. 3. The film of claim 1 or 2, wherein the polyethylene also has one or more of the following: (I) a degree of shear thinning of 0.85 to 0.95, (J) a strain hardening ratio of 3 or greater, (K) a melting temperature of 122°C or greater, (L) a crystallization temperature of 110°C or greater, (M) a Mw of 100,000 g/mol to 150,000 g/mol, and (N) a Mw/Mn of 1 to 10. 4. The film of any preceding claim, wherein the polyethylene is present at 90 wt% to 100 wt% of the film. 5. The film of any of claims 1-3, wherein the machine direction oriented film further comprises an additive at 0.01 wt% to 1 wt% of film. 6. The film of any preceding claim, wherein the film has a thickness of 15 mils or less. 7. The film of any preceding claim, wherein the film has a thickness of 10 mils or less. 8. The film of any preceding claim, wherein the film has a thickness of 7 mils or less. 9. The film of any preceding claim, wherein the polyethylene has a ratio of the g'LCB to the g'Zave from 1.1 to 10. 10. The film of any preceding claim, wherein the film further has one or more of the following properties: (III) a 1% secant in the machine direction of 30,000 psi to 110,000 psi; (IV) a yield strength in the machine direction of 500 psi to 10,000 psi; (V) an elongation at yield in the machine direction of 5% to 15%; (VI) a tensile strength in the machine direction of 5,500 psi to 25,000 psi; (VII) a tensile strength per mil in the machine direction of 250 psi/mil to 4,000 psi/mil; (VIII) an elongation at break in the machine direction of 60% to 450%; (IX) an Elmendorf tear in the machine direction of 40 g to 1,500 g; (X) an Elmendorf tear per mil in the machine direction of 5 g/mil to 150 g/mil; and (XI) a shrink in the machine direction of 60% to 90%. 11. The film of claim 10, wherein the film further has one or more of the following properties: (XII) a yield strength in the transverse direction of 1,000 psi to 1,500 psi; (XIII) an elongation at yield in the transverse direction of 5% to 10%; (XIV) a tensile strength in the transverse direction of 200 psi to 3,000 psi; (XV) a tensile strength per mil in the transverse direction of 50 psi/mil to 500 psi/mil; (XVI) an elongation at break in the transverse direction of 300% to 1,200%; (XVII) an Elmendorf tear in the transverse direction 1,500 g to 6,000 g; (XVIII) an Elmendorf tear per mil in the transverse direction of 200 g to 700 g; and (XIX) a shrink in the transverse direction of 10% to 40%. 12. A method comprising: producing a polymer melt comprising a polyethylene having: (A) a melt flow index of 1.0 g/10 min or more, (B) a density of 0.90 g/cm3 to less than 0.940 g/cm3, (C) a g'LCB of greater than 0.8, (D) ratio of comonomer content at Mz to comonomer content at Mw greater than 1.0, (E) ratio of comonomer content at Mn to comonomer content at Mw greater than 1.0, and (F) a ratio of g'LCB to g'Zave greater than 1.0; extruding a film from the polymer melt; and stretching the film in a machine direction at a temperature below the melting temperature of the polyethylene, where the film has a 1% secant in the transverse direction of 70,000 psi or more and Dart Drop of 350 g/mil or more. 13. The method of claim 12, wherein the polyethylene has: (A) a melt flow index of 1.5 g/10 min to 2.1 g/10 min, (B) a density of 0.91 g/cm3 to 0.93 g/cm3, (G) a z-average molecular weight of 300,000 g/mol or greater, and (H) a long chain branching (g’LCB) value of 0.8 to 0.9. 14. The method of claim 13, wherein stretching is at a stretch ratio of 1 to 10. 15. The method of any of claims 12-14, wherein the polyethylene further has one or more of the following properties: (I) a degree of shear thinning of 0.85 to 0.95, (J) a strain hardening ratio of 3 or greater, (K) a melting temperature of 122°C or greater, (L) a crystallization temperature of 110°C or greater, (M) a Mw of 100,000 g/mol to 150,000 g/mol, and (N) a Mw/Mn of 1 to 10. 16. The method of any of claims 12-15, wherein the polyethylene is present at 90 wt% to 100 wt% of the polymer melt. 17. The method of any of claims 12-15, wherein polymer melt further comprises an additive at 0.01 wt% to 1 wt% of film. 18. The method of any of claims 12-17, wherein the film has a thickness of 15 mils or less. 19. The method of any of claims 12-18, wherein the film has a thickness of 10 mils or less. 20. The method of any of claims 12-19, wherein the film has a thickness of 7 mils or less. 21. The method of any of claims 12-20, wherein the film further has one or more of the following properties: (III) a 1% secant in the machine direction of 30,000 psi to 110,000 psi; (IV) a yield strength in the machine direction of 500 psi to 10,000 psi; (V) an elongation at yield in the machine direction of 5% to 15%; (VI) a tensile strength in the machine direction of 5,500 psi to 25,000 psi; (VII) a tensile strength per mil in the machine direction of 250 psi/mil to 4,000 psi/mil; (VIII) an elongation at break in the machine direction of 60% to 450%; (IX) an Elmendorf tear in the machine direction of 40 g to 1,500 g; (X) an Elmendorf tear per mil in the machine direction of 5 g/mil to 150 g/mil; and (XI) a shrink in the machine direction of 60% to 90%. 22. The method of claim 21, wherein the film further has one or more of the following properties: (XII) a yield strength in the transverse direction of 1,000 psi to 1,500 psi; (XIII) an elongation at yield in the transverse direction of 5% to 10%; (XIV) a tensile strength in the transverse direction of 200 psi to 3,000 psi; (XV) a tensile strength per mil in the transverse direction of 50 psi/mil to 500 psi/mil; (XVI) an elongation at break in the transverse direction of 300% to 1,200%; (XVII) an Elmendorf tear in the transverse direction 1,500 g to 6,000 g; (XVIII) an Elmendorf tear per mil in the transverse direction of 200 g to 700 g; and (XIX) a shrink in the transverse direction of 10% to 40%. |
wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R a , R b , X 1 , X 2 , T, and M are as defined above; and R 10 , R 11 , R 12 , R 13 , and R 14 are each independently H or a C 1 to C 40 substituted or unsubstituted hydrocarbyl. [0082] Particularly preferred metallocene compounds useful herein are represented by the formula: wherein R 1 , R 2 , R 3 , R 4 , R 5 , R a , R b , X 1 , X 2 , T, D, and M are as defined above. [0083] In particularly preferred embodiments, metallocene compounds useful herein may be represented by the following structure:
wherein R 1 , R 2 , R 3 , R 4 , R 5 , R a , R b , X 1 , X 2 , T, and M are as defined above. [0084] Examples of preferred metallocene compounds include: dimethylsilylene(3- phenyl-1-indenyl)(2,3,4,5-tetramethyl-1-cyclopentadienyl)zir conium dichloride; dimethylsilylene(3-phenyl-1-indenyl)(2,3,4,5-tetramethyl-1-c yclopentadienyl) zirconium methyl; bis(n-propyl ccyclopentadienyl)Hf dimethyl bis(n-propyl cyclopentadienyl)Hf dichloride; and the like. [0085] The polymerization process of the present invention may be carried out using any suitable process, such as, for example, solution, slurry, high pressure, and gas phase. A particularly desirable method for producing polyolefin polymers according to the present invention is a gas phase polymerization process preferably utilizing a fluidized bed reactor. Desirably, gas phase polymerization processes are such that the polymerization medium is either mechanically agitated or fluidized by the continuous flow of the gaseous monomer and diluent. Other gas phase processes contemplated by the process of the invention include series or multistage polymerization processes. [0086] The metallocene catalyst is used with an activator in the polymerization process to produce the inventive polyethylenes. The term "activator" is used herein to be any compound which can activate any one of the metallocene compounds described above by converting the neutral catalyst compound to a catalytically active metallocene compound cation. Preferably the catalyst system comprises an activator. Activators useful herein include alumoxanes or “non-coordinating anion” activators such as boron-based compounds (e.g., tris(perfluorophenyl)borane, or ammonium tetrakis(pentafluorophenyl)borate). [0087] The catalyst systems useful herein can include at least one non-coordinating anion (NCA) activator, such as NCA activators represented by the formula below: Z d + (A d- ) where: Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base; H is hydrogen; (L-H) is a Bronsted acid; A d- is a boron containing non-coordinating anion having the charge d-; d is 1, 2, or 3. [0088] The cation component, Z d + may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an alkyl or aryl, from the bulky ligand metallocene containing transition metal catalyst precursor, resulting in a cationic transition metal species. [0089] The activating cation Z d + may also be a moiety such as silver, tropylium, carboniums, ferroceniums and mixtures, preferably carboniums and ferroceniums. Most preferably Z d + is triphenyl carbonium. Preferred reducible Lewis acids can be any triaryl carbonium (where the aryl can be substituted or unsubstituted, such as those represented by the formula: (Ar 3 C + ), where Ar is aryl or aryl substituted with a heteroatom, a C 1 to C 40 hydrocarbyl, or a substituted C 1 to C 40 hydrocarbyl), preferably the reducible Lewis acids in formula (14) above as "Z" include those represented by the formula: (Ph 3 C), where Ph is a substituted or unsubstituted phenyl, preferably substituted with C 1 to C 40 hydrocarbyls or substituted a C 1 to C 40 hydrocarbyls, preferably C 1 to C 20 alkyls or aromatics or substituted C 1 to C 20 alkyls or aromatics, preferably Z is a triphenylcarbonium. [0090] When Z d + is the activating cation (L-H) d + , it is preferably a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethyl thioethers, tetrahydrothiophene, and mixtures thereof. [0091] The anion component A d- includes those having the formula [M k+ Q n ] d- wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4); n - k = d; M is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted- hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q a halide. Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group. Examples of suitable A d- also include diboron compounds as disclosed in US Patent No.5,447,895, which is fully incorporated herein by reference. [0092] Illustrative, but not limiting examples of boron compounds which may be used as an activating cocatalyst are the compounds described as (and particularly those specifically listed as) activators in US 8,658,556, which is incorporated by reference herein. [0093] Most preferably, the activator Z d + (A d- ) is one or more of N,N-dimethylanilinium tetra(perfluorophenyl)borate, N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N- dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N-dimethylanilinium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5- bis(trifluoromethyl)phenyl)borate, or triphenylcarbenium tetra(perfluorophenyl)borate. [0094] Alternately, preferred activators may include alumoxane compounds (or “alumoxanes”) and modified alumoxane compounds. Alumoxanes are generally oligomeric compounds containing -Al(R 1 )-O- sub-units, where R 1 is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, isobutylalumoxane, and mixtures thereof. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halide, alkoxide, or amide. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be preferable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution. Another useful alumoxane is a modified methylalumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, disclosed in US 5,041,584). Preferably of this invention, the activator is an alkylalumoxane, preferably methylalumoxane or isobutylalumoxane, most preferably methylalumoxane. [0095] Preferably, the activator is supported on a support material prior to contact with the metallocene compound. Also, the activator may be combined with the metallocene compound prior to being placed upon a support material. Preferably, the activator may be combined with the metallocene compound in the absence of a support material. [0096] In addition to activator compounds, cocatalysts may be used. Aluminum alkyl or organometallic compounds which may be utilized as cocatalysts (or scavengers) include, for example, triethylaluminum, tri-isobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, diethyl aluminum chloride, dibutyl zinc, diethyl zinc, and the like. [0097] Preferably, the catalyst system comprises an inert support material. Preferably, the supported material is a porous support material, for example, talc, and inorganic oxides. Other support materials include zeolites, clays, organoclays, or any other organic or inorganic support material, or mixtures thereof. [0098] Preferably, the support material is an inorganic oxide in a finely divided form. Suitable inorganic oxide materials for use in metallocene compounds herein include Groups 2, 4, 13, and 14 metal oxides such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be employed, either alone or in combination, with the silica or alumina are magnesia, titania, zirconia, and the like. Other suitable support materials, however, can be employed, for example, finely divided functionalized polyolefins such as finely divided polyethylene. Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, clays, and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania, and the like. Preferred support materials include Al 2 O 3 , ZrO 2 , SiO 2 , and combinations thereof, more preferably SiO 2 , Al 2 O 3 , or SiO 2 /Al 2 O 3 . [0099] The supported catalyst system may be suspended in a paraffinic agent, such as mineral oil, for easy addition to a reactor system, for example a gas phase polymerization system. [0100] Processes and catalyst compounds useful in making the polyethylene useful herein are further described in US 9,266,977, US 9,068,033, US 6,225,426, and US 2018/0237554, all of which are incorporated herein by reference. Polyethylene [0101] The polyethylene may be an ethylene homopolymer or an ethylene copolymer, such as ethylene-alphaolefin (preferably C 3 to C 20 ) copolymers (such as ethylene-butene copolymers, ethylene-hexene copolymers, and/or ethylene-octene copolymers) having an Mw/Mn of greater than 1 to 4 (preferably greater than 1 to 3). Unless otherwise specified, polyethylene encompasses both ethylene homopolymers and ethylene copolymers. [0102] The comonomer content (cumulatively if more than one comonomer is used) of the polyethylene can be 0 mol% (i.e., a homopolymer) to 25 mol% (or 0.5 mol% to 20 mol%, or 1 mol% to 15 mol %, or 3 mol% to 10 mol%, or 6 to 10 mol %) with the balance being ethylene. Accordingly, the ethylene content of the polyethylene can be 75 mol% or more ethylene (or 75 mol% to 100 mol%, or 80 mol% to 99.5 mol%, or 85 mol% to 99 mol%, or 90 mol% to 97 mol%, or 4 to 90 mol%). [0103] Alternately, the comonomer content (cumulatively if more than one comonomer is used) in the polyethylene can be 0 wt% (i.e., a homopolymer) to 25 wt% (or 0.5 wt% to 20 wt%, or 1 wt% to 15 wt%, or 3 wt% to 10 wt%, or 6 to 10 wt%) with the balance being ethylene. Accordingly, the ethylene content of the polyethylene can be 75 wt% or more ethylene (or 75 wt% to 100 wt%, or 80 wt% to 99.5 wt%, or 85 wt% to 99 wt%, or 90 wt% to 97 wt%, or 4 to 90 wt%). In a preferred embodiment, the comonomer is present at 6 to 10 wt%, and is preferably a C 3 to C 12 alpha-olefin (preferably one or more of propylene, butene, hexene, and octene). [0104] The comonomer can be one or more C 3 to C 20 olefin comonomer (preferably C 3 to C 12 alpha-olefin; more preferably propylene, butene, hexene, octene, decene, and/or dodecane; most preferably propylene, butene, hexene, and/or octene). Preferably, the monomer is ethylene and the comonomer is hexene, preferably from 1 mol% to 15 mol% hexene, or 1 mol% to 10 mol% hexene, or 5 mol% to 15 mol% hexene, or 7 mol% to 11 mol% hexene. [0105] The polyethylene used in films of the present disclosure can have: (A) a I2 of 1.0 g/10 min or greater (or 1.5 g/10 min to 2.1 g/10 min, or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to1.9 g/10 min); (B) a density of 0.90 g/cm 3 to 0.9 g/cm 3 (0.91 g/cm 3 to 0.93 g/cm 3 , or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g' LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, and (F) a ratio of the g'LCB to the g'Zave is greater than 1.0, or from 1.1 to 10. [0106] The polyethylene used in films of the present disclosure can have: (A) a I2 of 1.5 g/10 min to 2.1 g/10 min (or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to1.9 g/10 min); (B) a density of 0.91 g/cm 3 to 0.93 g/cm 3 (or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g'LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, and (F) a ratio of the g' LCB to the g' Zave is greater than 1.0, or from 1.1 to 10. [0107] The polyethylene used in films of the present disclosure can have: (A) a I2 of 1.0 g/10 min or greater (or 1.5 g/10 min to 2.1 g/10 min, or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to1.9 g/10 min); (B) a density of 0.90 g/cm 3 to 0.9 g/cm 3 (0.91 g/cm 3 to 0.93 g/cm 3 , or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g'LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (F) a ratio of the g'LCB to the g'Zave is greater than 1.0, or from 1.1 to 10, (G) a Mz-LS of 300,000 g/mol or greater (or 300,000 g/mol to 600,000 g/mol, or 375,000 g/mol to 525,000 g/mol), and (H) a g’LCB value of 0.8 to 0.9 (or 0.81 to 0.85, or 0.82 to 0.84, or 0.830 to 0.839). [0108] The polyethylene used in films of the present disclosure can have: (A) a I 2 of 1.5 g/10 min to 2.1 g/10 min (or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to1.9 g/10 min); (B) a density of 0.91 g/cm 3 to 0.93 g/cm 3 (or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g' LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (F) a ratio of the g' LCB to the g' Zave is greater than 1.0, or from 1.1 to 10, (G) a Mz-LS of 300,000 g/mol or greater (or 300,000 g/mol to 600,000 g/mol, or 375,000 g/mol to 525,000 g/mol), and (H) a g’LCB value of 0.8 to 0.9 (or 0.81 to 0.85, or 0.82 to 0.84, or 0.830 to 0.839). [0109] The polyethylene used in films of the present disclosure can have: (A) a I2 of 1.0 g/10 min or greater (or 1.5 g/10 min to 2.1 g/10 min, or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to1.9 g/10 min); (B) density of 0.90 g/cm 3 to 0.9 g/cm 3 (0.91 g/cm 3 to 0.93 g/cm 3 , or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g' LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (F) a ratio of the g'LCB to the g'Zave is greater than 1.0, or from 1.1 to 10, (G) a Mz-LS of 300,000 g/mol or greater (or 300,000 g/mol to 600,000 g/mol, or 375,000 g/mol to 525,000 g/mol), (H) a g’ LCB value of 0.8 to 0.9 (or 0.81 to 0.85, or 0.82 to 0.84, or 0.830 to 0.839), and one or more of: (I) a DST of 0.85 to 0.95 (or 0.86 to 0.90, or 0.87), (J) a SHR of 3 or greater (or 3 to 8, or 3 to 5), (K) a melting temperature of 122°C or greater (or 122°C to 127°C, or 123°C to 125°C), (L) a crystallization temperature of 110°C or greater (or 110°C to 115°C, or 110°C to 113°C), (M) a Mw of 100,000 g/mol to 150,000 g/mol (or 105,000 g/mol to 140,000 g/mol, or 110,000 g/mol to 130,000 g/mol), and (N) a Mw/Mn of 1 to 10 (or 1 to 3, or 2 to 4, or 3 to 5, or 4 to 7, or 5 to 10). [0110] The polyethylene used in films of the present disclosure can have: (A) a I2 of 1.5 g/10 min to 2.1 g/10 min (or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to1.9 g/10 min); (B) a density of 0.91 g/cm 3 to 0.93 g/cm 3 (or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g' LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (F) a ratio of the g'LCB to the g'Zave is greater than 1.0, or from 1.1 to 10, (G) a Mz-LS of 300,000 g/mol or greater (or 300,000 g/mol to 600,000 g/mol, or 375,000 g/mol to 525,000 g/mol), (H) a g’LCB value of 0.8 to 0.9 (or 0.81 to 0.85, or 0.82 to 0.84, or 0.830 to 0.839), and one or more of: (I) a DST of 0.85 to 0.95 (or 0.86 to 0.90, or 0.87), (J) a SHR of 3 or greater (or 3 to 8, or 3 to 5), (K) a melting temperature of 122°C or greater (or 122°C to 127°C, or 123°C to 125°C), (L) a crystallization temperature of 110°C or greater (or 110°C to 115°C, or 110°C to 113°C), (M) a Mw of 100,000 g/mol to 150,000 g/mol (or 105,000 g/mol to 140,000 g/mol, or 110,000 g/mol to 130,000 g/mol), and (N) a Mw/Mn of 1 to 10 (or 1 to 3, or 2 to 4, or 3 to 5, or 4 to 7, or 5 to 10). [0111] Further, the polyethylene (including any of the foregoing) used in films of the present disclosure can have an Mz-LS/Mw-Ls of 2 or more, alternately 3 or more. [0112] Further, the polyethylene (including any of the foregoing) used in films of the present disclosure can have an Mz-LS/Mn-LS of 6 or more, alternately 8 or more, alternately 10 or more. Blends [0113] In another embodiment, the polyethylene composition produced herein is combined with one or more additional polymers in a blend prior to being formed into a film. As used herein, a “blend” may refer to a dry or extruder blend of two or more different polymers, and in-reactor blends, including blends arising from the use of multi or mixed catalyst systems in a single reactor zone, and blends that result from the use of one or more catalysts in one or more reactors under the same or different conditions (e.g., a blend resulting from in series reactors (the same or different) each running under different conditions and/or with different catalysts). [0114] Useful additional polymers include other polyethylenes, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, random copolymer of propylene and ethylene, and/or butene, and/or hexene, polybutene, ethylene vinyl acetate, LDPE, LLDPE, HDPE, ethylene vinyl acetate, ethylene methyl acrylate, copolymers of acrylic acid, polymethylmethacrylate or any other polymers polymerizable by a high-pressure free radical process, polyvinylchloride, polybutene-1, isotactic polybutene, ABS resins, ethylene- propylene rubber (EPR), vulcanized EPR, EPDM, block copolymer, styrenic block copolymers, polyamides, polycarbonates, PET resins, cross linked polyethylene, copolymers of ethylene and vinyl alcohol (EVOH), polymers of aromatic monomers such as polystyrene, poly-1 esters, polyacetal, polyvinylidine fluoride, polyethylene glycols, and/or polyisobutylene. Films and Methods [0115] The polyethylene prepared by the process described herein are preferably formed in to films, particularly oriented films, such as machine direction oriented films. [0116] The present disclosure relates to oriented polyethylene films comprising a LLDPE with properties that improve processability while providing a good balance between stiffness while providing high toughness (or impact resistance). [0117] For example, the invention relates to machine direction oriented films comprising polyethylene having: (A) a I2 of 1.0 g/10 min or greater (or 1.5 g/10 min to 2.1 g/10 min, or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to1.9 g/10 min); (B) a density of 0.90 g/cm 3 to 0.9 g/cm 3 (0.91 g/cm 3 to 0.93 g/cm 3 , or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g'LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, and (F) a ratio of the g' LCB to the g' Zave is greater than 1.0, or from 1.1 to 10, and wherein the film has a 1% secant in the transverse direction of 70,000 psi or more (alternately 75,000 psi to 150,000 psi, or 80,000 psi to 140,000 psi, or 90,000 psi to 130,000 psi) and Dart Drop of 350 g/mil or more (alternately 350 g/mil to 1300 g/mil, or 375 g/mil to 1250 g/mil, or 450 g/mil to 1225 g/mil). [0118] In another example, the invention relates to machine direction oriented films comprising polyethylene having: (A) a I 2 of 1.5 g/10 min to 2.1 g/10 min (or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to1.9 g/10 min); (B) a density of 0.91 g/cm 3 to 0.93 g/cm 3 (or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g' LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, and (F) a ratio of the g' LCB to the g' Zave is greater than 1.0, or from 1.1 to 10, and wherein the film has a 1% secant in the transverse direction of 70,000 psi or more (alternately 75,000 psi to 150,000 psi, or 80,000 psi to 140,000 psi, or 90,000 psi to 130,000 psi) and Dart Drop per mil of 350 g/mil or more (alternately 350 g/mil to 1300 g/mil, or 375 g/mil to 1250 g/mil, or 450 g/mil to 1225 g/mil). [0119] In embodiments the film has an Elmendorf Tear MD value of more than 400 g/mil, alternately more than 350 g/mil, alternately more than 400 g/mil, alternately from 300 to 600 g/mil. [0120] The films of the present disclosure are uniaxially stretched in the machine direction (MD) and comprise the polyethylene described herein. Preferably, the films of the present disclosure comprise polyethylene in an amount of at least 90 wt% (or 90 wt% to 100 wt%, or 90 wt% to 99.9 wt%, or 95 wt% to 99 wt%). Advantageously, the polyethylene described herein does not need to be mixed with another polymer to achieve good processability and film properties. [0121] In addition to the polyethylene, the films may comprise additives. Examples of additives include, but are not limited to, stabilization agents (e.g., antioxidants or other heat or light stabilizers), anti-static agents, crosslink agents or co-agents, crosslink promoters, release agents, adhesion promoters, plasticizers, anti-agglomeration agents (e.g., oleamide, stearamide, erucamide or other derivatives with the same activity), and fillers. [0122] Nonlimiting examples of antioxidants include, but are not limited to, IRGANOX® 1076 (a high molecular weight phenolic antioxidant, available from BASF), IRGAFOS® 168 (tris(2,4-di-tert-butylphenyl) phosphite, available from BASF), and tris(nonylphenyl)phosphite. A nonlimiting example of a processing aid is DYNAMAR® FX-5920 (a free-flowingfluropolymer based processing additive, available from 3M). [0123] When present, the amount of the additives cumulatively may range from 0.01 wt% to 1 wt% (or 0.01 wt% to 0.1 wt%, or 0.1 wt% to 1 wt%). [0124] Methods of producing machine direction oriented (MDO) polyethylene films can comprise: producing a polymer melt comprising a polyethylene described herein, extruding a film from the polymer melt; and stretching the film at a temperature below the melting temperature of the polyethylene. Stretching can be achieved by threading the film through a series of rollers where the temperature and speed of the individual rollers are controlled to achieve a desired film thickness and the stretch ratio. Typically, this series of rollers are called MDO rollers or part of the MDO stage of the film production. Examples of MDO may include, but are not limited to, pre-heat rollers, various stretching stages with or without annealing rollers between stages, one or more conditioning and annealing rollers, and one or more chill rollers. Stretching of the film in the MDO stage is accomplished by inducing a speed differential between two or more adjacent rollers. [0125] The stretch ratio can be used to describe the degree of stretching of the film. The stretch ratio is the speed of the fast roller divided by the speed of the slow roller. For example, stretching a film using an apparatus where the slow roller speed is 1 m/min and fast roller speed is 7 m/min means the stretch ratio was 7 (also referred to herein as 7 times or 7x). The physical amount of stretching of the film is close to but not exactly the stretch ratio because relaxation of the film can occur after stretching, although typically only to a marginal extent. [0126] Greater stretch ratios result in thinner films with greater orientation in the MD. The stretch ratio when stretching the polyethylene films described herein can be 1x to 10x (or 3x to 10x, or 5x to 10x, or 7x to 9x). One skilled in the art without undo experimentation can determine suitable temperatures and roller speeds for each roller in a given MDO stage of film production for producing the desired stretch ratios. [0127] The MDO polyethylene films described herein can have a thickness of 5 mils to 30 mils (or 15 mils or less, or 10 mils or less, or 8 mils or less, or 7 mils or less, or 5 mils to 10 mils, or 5 mils to 15 mils, or 10 mils to 30 mils). [0128] The MDO polyethylene films described herein have (I) a 1% secant in the transverse direction of 70,000 psi or more (alternately 75,000 psi to 150,000 psi, or 80,000 psi to 140,000 psi, or 90,000 psi to 130,000 psi) and (II) Dart Drop per mil of 350 g/mil or more (alternately 350 g/mil to 1300 g/mil, or 375 g/mil to 1250 g/mil, or 450 g/mil to 1225 g/mil). [0129] The MDO polyethylene films described herein can also have one or more of the following properties: (III) a 1% secant in the machine direction of 30,000 psi to 110,000 psi (or 40,000 psi to 1,000,000 psi, or 50,000 psi to 1,000,000 psi, or 60,000 psi to 1,000,000 psi, or 70,000 psi to 1,000,000 psi, or 80,000 psi to 1,000,000 psi); (IV) a yield strength in the machine direction of 500 psi to 10,000 psi (or 2,000 psi to 10,000 psi, or 4,000 psi to 10,000 psi); (V) an elongation at yield in the machine direction of 5% to 15% (or 7% to 14%, or 9% to 13%); (VI) a tensile strength in the machine direction of 5,500 psi to 25,000 psi (or 7,000 psi to 23,000 psi, or 10,000 psi to 22,000 psi); (VII) a tensile strength per mil in the machine direction of 250 psi/mil to 4,000 psi/mil (or 500 psi/mil to 3,500 psi/mil, or 1,500 psi/mil to 3,300 psi/mil, or 1,750 psi/mil to 3,200 psi/mil); (VIII) an elongation at break in the machine direction of 60% to 450% (or 100% to 400%, or 150% to 350%); (IX) an Elmendorf tear in the machine direction of 40 g to 1,500 g (or 200 g to 1,500 g, or 500 g to 1,500 g, or 1,000 g to 1,500 g); (X) an Elmendorf tear per mil in the machine direction of 5 g/mil to 150 g/mil (or 10 g/mil to 150 g/mil, or 50 g/mil to 150 g/mil, or 100 g/mil to 150 g/mil); and (XI) a shrink in the machine direction of 60% to 90% (or 70% to 90%, or 80% to 90%). [0130] Preferably, the MDO polyethylene films described herein has (I) and (II) and one or more of the following properties: (III), (IV), (V), (VI), (VII), (VIII), (IX), and (X). More preferably, the MDO polyethylene films described herein has one or more of the following properties: (IV), (V), (VI), and (VII). [0131] Because the films described herein are stretched only in the machine direction, the physical properties in the transverse direction may be comparable to other MDO polyethylene films produced with polyethylenes not described herein. The MDO polyethylene films described herein can also have one or more of the following properties: (XI) a yield strength in the transverse direction of 1,000 psi to 1,500 psi (or 1,100 psi to 1,400 psi); (XII) an elongation at yield in the transverse direction of 5% to 10% (or 7% to 10%); (XIII) a tensile strength in the transverse direction of 200 psi to 3,000 psi (or 2,250 psi to 2,800 psi); (XIV) a tensile strength per mil in the transverse direction of 50 psi/mil to 500 psi/mil (or 100 psi/mil to 400 psi/mil); (XV) an elongation at break in the transverse direction of 300% to 1,200% (or 500% to 1,200%, or 600% to 1,200%); (XVI) an Elmendorf tear in the transverse direction 1,500 g to 6,000 g (or 2,000 g to 5,000 g); (XVII) an Elmendorf tear per mil in the transverse direction of 200 g to 700 g (or 300 g to 600 g); and (XVIII) a shrink in the transverse direction of 10% to 40% (or 15% to 30%). [0132] Preferably, the MDO polyethylene films described herein has one or more of the following properties: (X), (XI), (XII), (XIII), (XIV), and (XV). More preferably, the MDO polyethylene films described herein has one or more of the following properties: (XIII) and (XIV). End Uses [0133] The MDO polyethylene films described herein may be used as monolayer films or as one or more layers of a multilayer film. Examples of other layers include, but are not limited to, unstretched polymer films, other MDO polymer films, and biaxially-oriented polymer films of polymers like polyethylene, polypropylene, polyethylene terephthalate, polystyrene, polyamide, and the like. [0134] Specific end use films include, for example, blown films, cast films, stretch films, stretch/cast films, stretch cling films, stretch handwrap films, machine stretch wrap, shrink films, shrink wrap films, green house films, laminates, and laminate films. Exemplary films are prepared by any conventional technique known to those skilled in the art, such as for example, techniques utilized to prepare blown, extruded, and/or cast stretch and/or shrink films (including shrink-on-shrink applications). [0135] The MDO polyethylene films described herein (alone or as part of a multilayer film) are useful end use applications that include, but are not limited to, film-based products, shrink film, cling film, stretch film, sealing films, snack packaging, heavy-duty bags, grocery sacks, baked and frozen food packaging, diaper backsheets, housewrap, medical packaging (e.g., medical films and intravenous (IV) bags), industrial liners, membranes, and the like. [0136] In one embodiment, multilayer films or multiple-layer films may be formed by methods well known in the art. The total thickness of multilayer films may vary based upon the application desired. A total film thickness of about 5-100 µm, more typically about 10-50 µm, is suitable for most applications. Those skilled in the art will appreciate that the thickness of individual layers for multilayer films may be adjusted based on desired end-use performance, resin or copolymer employed, equipment capability, and other factors. The materials forming each layer may be coextruded through a coextrusion feedblock and die assembly to yield a film with two or more layers adhered together but differing in composition. Coextrusion can be adapted for use in both cast film or blown film processes. Exemplary multilayer films have at least two, at least three, or at least four layers. In one embodiment, the multilayer films are composed of five to ten layers. [0137] To facilitate discussion of different film structures, the following notation is used herein. Each layer of a film is denoted "A" or "B". Where a film includes more than one A layer or more than one B layer, one or more prime symbols (', ", '", etc.) are appended to the A or B symbol to indicate layers of the same type that can be the same or can differ in one or more properties, such as chemical composition, density, melt index, thickness, etc. Finally, the symbols for adjacent layers are separated by a slash (/). Using this notation, a three-layer film having an inner layer disposed between two outer layers would be denoted A/B/A'. Similarly, a five-layer film of alternating layers would be denoted A/B/A'/B'/A". Unless otherwise indicated, the left-to-right or right-to-left order of layers does not matter, nor does the order of prime symbols; e.g., an A/B film is equivalent to a B/A film, and an A/A'/B/A" film is equivalent to an A/B/A'/A" film, for purposes described herein. The relative thickness of each film layer is similarly denoted, with the thickness of each layer relative to a total film thickness of 100 (dimensionless) indicated numerically and separated by slashes; e.g., the relative thickness of an A/B/A' film having A and A' layers of 10 µm each and a B layer of 30 µm is denoted as 20/60/20. [0138] The thickness of each layer of the film, and of the overall film, is not particularly limited, but is determined according to the desired properties of the film. Typical film layers have a thickness of from about 1 to about 1,000 µm, more typically from about 5 to about 100 µm, and typical films have an overall thickness of from about 10 to about 100 µm. [0139] In some embodiments, and using the nomenclature described above, the present invention provides for multilayer films with any of the following exemplary structures: (a) two-layer films, such as A/B and B/B'; (b) three-layer films, such as A/B/A', A/A'/B, B/A/B' and B/B'/B"; (c) four-layer films, such as A/A'/A"/B, A/A'/B/A", A/A'/B/B', A/B/A'/B', A/B/B'/A', B/A/A'/B', A/B/B'/B", B/A/B'/B" and B/B'/B"/B'"; (d) five-layer films, such as A/A'/A"/A'"/B, A/A'/A"/B/A'", A/A'/B/A"/A'", A/A'/A"/B/B', A/A'/B/A"/B', A/A'/B/B'/A", A/B/A'/B'/A", A/B/A'/A"/B, B/A/A'/A"/B', A/A'/B/B'/B", A/B/A'/B'/B", A/B/B'/B"/A', B/A/A'/B'/B", B/A/B'/A'/B", B/A/B'/B"/A', A/B/B'/B"/B'", B/A/B'/B"/B'", B/B'/A/B"/B'", and B/B'/B"/B'"/B""; and similar structures for films having six, seven, eight, nine, twenty-four, forty-eight, sixty-four, one hundred, or any other number of layers. It should be appreciated that films having still more layers. [0140] In any of the embodiments above, one or more A layers can be replaced with a substrate layer, such as glass, plastic, paper, metal, etc., or the entire film can be coated or laminated onto a substrate. Thus, although the discussion herein has focused on multilayer films, the films may also be used as coatings for substrates such as paper, metal, glass, plastic, and other materials capable of accepting a coating. [0141] The films can further be embossed, or produced or processed according to other known film processes. The films can be tailored to specific applications by adjusting the thickness, materials and order of the various layers, as well as the additives in or modifiers applied to each layer. Example Embodiments [0142] A first non-limiting example embodiment is a composition comprising: a machine direction oriented film comprising a polyethylene having: (A) a I 2 of 1.0 g/10 min or greater (or 1.5 g/10 min to 2.1 g/10 min, or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to1.9 g/10 min); (B) a density of 0.90 g/cm 3 to 0.9 g/cm 3 (0.91 g/cm 3 to 0.93 g/cm 3 , or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g'LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, and (F) a ratio of the g' LCB to the g' Zave is greater than 1.0, or from 1.1 to 10, and wherein the film has (I) a 1% secant in the transverse direction of 70,000 psi or more (alternately 75,000 psi to 150,000 psi, or 80,000 psi to 140,000 psi, or 90,000 psi to 130,000 psi) and (II) Dart Drop per mil of 350 g/mil or more (alternately 350 g/mil to 1,300 g/mil, or 375 g/mil to 1,250 g/mil, or 450 g/mil to 1,225 g/mil). [0143] The first non-limiting example embodiment can further include one or more of the following: Element 1: wherein the polyethylene also has one or more of the following: (G) a Mz-LS of 300,000 g/mol or greater (or 300,000 g/mol to 600,000 g/mol, or 375,000 g/mol to 525,000 g/mol), (H) a g’LCB value of 0.8 to 0.9 (or 0.81 to 0.85, or 0.82 to 0.84, or 0.830 to 0.839), (I) a DST of 0.85 to 0.95 (or 0.86 to 0.90, or 0.87), (J) a SHR of 3 or greater (or 3 to 8, or 3 to 5), (K) a melting temperature of 122°C or greater (or 122°C to 127°C, or 123°C to 125°C), (L) a crystallization temperature of 110°C or greater (or 110°C to 115°C, or 110°C to 113°C), (M) a Mw of 100,000 g/mol to 150,000 g/mol (or 105,000 g/mol to 140,000 g/mol, or 110,000 g/mol to 130,000 g/mol), and (N) a Mw/Mn of 1 to 10 (or 1 to 3, or 2 to 4, or 3 to 5, or 4 to 7, or 5 to 10); Element 2: wherein the polyethylene is present at 90 wt% to 100 wt% of the film; Element 3: wherein the machine direction oriented film further comprises an additive at 0.01 wt% to 1 wt% of film; Element 4: wherein the film has a thickness of 5 mils to 30 mils (or 15 mils or less, or 10 mils or less, or 8 mils or less, or 7 mils or less, or 5 mils to 10 mils, or 5 mils to 15 mils, or 10 mils to 30 mils); Element 5: wherein the film has one or more of the following properties: (III) a 1% secant in the machine direction of 30,000 psi to 110,000 psi (or 40,000 psi to 1,000,000 psi, or 50,000 psi to 1,000,000 psi, or 60,000 psi to 1,000,000 psi, or 70,000 psi to 1,000,000 psi, or 80,000 psi to 1,000,000 psi); (IV) a yield strength in the machine direction of 500 psi to 10,000 psi (or 2,000 psi to 10,000 psi, or 4,000 psi to 10,000 psi); (V) an elongation at yield in the machine direction of 5% to 15% (or 7% to 14%, or 9% to 13%); (VI) a tensile strength in the machine direction of 5,500 psi to 25,000 psi (or 7,000 psi to 23,000 psi, or 10,000 psi to 22,000 psi); (VII) a tensile strength per mil in the machine direction of 250 psi/mil to 4,000 psi/mil (or 500 psi/mil to 3,500 psi/mil, or 1,500 psi/mil to 3,300 psi/mil, or 1,750 psi/mil to 3,200 psi/mil); (VIII) an elongation at break in the machine direction of 60% to 450% (or 100% to 400%, or 150% to 350%); (IX) an Elmendorf tear in the machine direction of 40 g to 1,500 g (or 200 g to 1,500 g, or 500 g to 1,500 g, or 1,000 g to 1,500 g); (X) an Elmendorf tear per mil in the machine direction of 5 g/mil to 150 g/mil (or 10 g/mil to 150 g/mil, or 50 g/mil to 150 g/mil, or 100 g/mil to 150 g/mil); and (XI) a shrink in the machine direction of 60% to 90% (or 70% to 90%, or 80% to 90%); and Element 6: Element 5 and wherein the film also has one or more of the following properties: (XII) a yield strength in the transverse direction of 1,000 psi to 1,500 psi (or 1,100 psi to 1,400 psi); (XIII) an elongation at yield in the transverse direction of 5% to 10% (or 7% to 10%); (XIV) a tensile strength in the transverse direction of 200 psi to 3,000 psi (or 2,250 psi to 2,800 psi); (XV) a tensile strength per mil in the transverse direction of 50 psi/mil to 500 psi/mil (or 100 psi/mil to 400 psi/mil); (XVI) an elongation at break in the transverse direction of 300% to 1,200% (or 500% to 1,200%, or 600% to 1,200%); (XVII) an Elmendorf tear in the transverse direction 1500 g to 6,000 g (or 2,000 g to 5,000 g); (XVIII) an Elmendorf tear per mil in the transverse direction of 200 g to 700 g (or 300 g to 600 g); and (XIX) a shrink in the transverse direction of 10% to 40% (or 15% to 30%). Examples of combinations include, but are not limited to, two or more of Elements 1-3 in combination (where when Elements 2 and 3 are in combination the polyethylene is present at 90 wt% to 99.9 wt% of the film); Elements 4 and 5 in combination and optionally in further combination with Element 6; and one or more of Elements 1-3 in combination with one or more of Elements 4-6. [0144] A second non-limiting example embodiment is a method comprising: producing a polymer melt comprising a polyethylene having: (A) a I2 of 1.0 g/10 min or greater (or 1.5 g/10 min to 2.1 g/10 min, or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to1.9 g/10 min); (B) a density of 0.90 g/cm 3 to 0.9 g/cm 3 (0.91 g/cm 3 to 0.93 g/cm 3 , or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g'LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, and (F) a ratio of the g'LCB to the g'Zave is greater than 1.0, or from 1.1 to 10; extruding a film from the polymer melt; and stretching the film in a machine direction at a temperature below the melting temperature of the polyethylene. The second non-limiting example embodiment can further include one or more of the following: Element 1; Element 2; Element 3; Element 4; Element 5; Element 6; and Element 7: wherein stretching is at a stretch ratio of 1 to 10. Examples of combinations include, but are not limited to, two or more of Elements 1-3 in combination (where when Elements 2 and 3 are in combination the polyethylene is present at 90 wt% to 99.9 wt% of the film); Elements 4 and 5 in combination and optionally in further combination with Element 6; one or more of Elements 1-3 in combination with one or more of Elements 4-6; and Element 7 in combination with one or more of Elements 1-6. [0145] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the present specification and associated claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the embodiments of the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claim, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. [0146] One or more illustrative embodiments incorporating the invention embodiments disclosed herein are presented herein. Not all features of a physical implementation are described or shown in this application for the sake of clarity. It is understood that in the development of a physical embodiment incorporating the embodiments of the present invention, numerous implementation-specific decisions must be made to achieve the developer's goals, such as compliance with system-related, business-related, government- related and other constraints, which vary by implementation and from time to time. While a developer's efforts might be time-consuming, such efforts would be, nevertheless, a routine undertaking for those of ordinary skill in the art and having benefit of this disclosure. [0147] While compositions and methods are described herein in terms of “comprising” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components and steps. [0148] The invention relates to machine direction oriented films comprising polyethylene having: (A) a I2 of 1.0 g/10 min or greater (or 1.5 g/10 min to 2.1 g/10 min, or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to1.9 g/10 min); (B) a density of 0.90 g/cm 3 to 0.9 g/cm 3 (0.91 g/cm 3 to 0.93 g/cm 3 , or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g'LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, and (F) a ratio of the g'LCB to the g'Zave is greater than 1.0, or from 1.1 to 10, and wherein the film has a 1% secant in the transverse direction of 70,000 psi or more (alternately 75,000 psi to 150,000 psi, or 80,000 psi to 140,000 psi, or 90,000 psi to 130,000 psi) and Dart Drop of 350 g/mil or more (alternately 350 g/mil to 1,300 g/mil, or 375 g/mil to 1,250 g/mil, or 450 g/mil to 1,225 g/mil). [0149] The invention also relates to machine direction oriented films comprising polyethylene having: (A) a I 2 of 1.5 g/10 min to 2.1 g/10 min (or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to1.9 g/10 min); (B) a density of 0.91 g/cm 3 to 0.93 g/cm 3 (or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g' LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, and (F) a ratio of the g'LCB to the g'Zave is greater than 1.0, or from 1.1 to 10, and wherein the film has a 1% secant in the transverse direction of 70,000 psi or more (alternately 75,000 psi to 150,000 psi, or 80,000 psi to 140,000 psi, or 90,000 psi to 130,000 psi) and Dart Drop per mil of 350 g/mil or more (alternately 350 g/mil to 1,300 g/mil, or 375 g/mil to 1,250 g/mil, or 450 g/mil to 1,225 g/mil). [0150] This invention relates to compositions comprising: 1) a machine direction oriented film comprising a polyethylene present at 90 wt% to 100 wt% (or 90 wt% to 100 wt%, or 90 wt% to 99.9 wt%, or 95 wt% to 99 wt%) of the film and an additive at 0 wt% to 1 wt% (or 0.01 wt% to 0.1 wt%, or 0.1 wt% to 1 wt%) of the film; 2) wherein the polyethylene has: (A) a I2 of 1.5 g/10 min to 2.1 g/10 min (or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to1.9 g/10 min); (B) a density of 0.91 g/cm 3 to 0.93 g/cm 3 (or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g'LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (F) a ratio of the g'LCB to the g'Zave is greater than 1.0, or from 1.1 to 10, (G) a Mz-LS of 300,000 g/mol or greater (or 300,000 g/mol to 600,000 g/mol, or 375,000 g/mol to 525,000 g/mol), (H) a g’ LCB value of 0.8 to 0.9 (or 0.81 to 0.85, or 0.82 to 0.84, or 0.830 to 0.839), and one or more of: (I) a DST of 0.85 to 0.95 (or 0.86 to 0.90, or 0.87), (J) a SHR of 3 or greater (or 3 to 8, or 3 to 5), (K) a melting temperature of 122°C or greater (or 122°C to 127°C, or 123°C to 125°C), (L) a crystallization temperature of 110°C or greater (or 110°C to 115°C, or 110°C to 113°C), (M) a Mw of 100,000 g/mol to 150,000 g/mol (or 105,000 g/mol to 140,000 g/mol, or 110,000 g/mol to 130,000 g/mol), and (N) a Mw/Mn of 1 to 10 (or 1 to 3, or 2 to 4, or 3 to 5, or 4 to 7, or 5 to 10); and 3) wherein the film has a thickness of 5 mils to 30 mils (or 15 mils or less, or 10 mils or less, or 8 mils or less, or 7 mils or less, or 5 mils to 10 mils, or 5 mils to 15 mils, or 10 mils to 30 mils); and 4) wherein the machine direction oriented film has (I) and (II) properties and optionally one or more of (III)-(XIX) properties: (I) a 1% secant in the transverse direction of 70,000 psi or more (alternately 75,000 psi to 150,000 psi, or 80,000 psi to 140,000 psi, or 90,000 psi to 130,000 psi), (II) Dart Drop per mil of 350 g/mil or more (alternately 350 g/mil to 1,300 g/mil, or 375 g/mil to 1,250 g/mil, or 450 g/mil to 1,225 g/mil), (III) a 1% secant in the machine direction of 30,000 psi to 110,000 psi (or 40,000 psi to 1,000,000 psi, or 50,000 psi to 1,000,000 psi, or 60,000 psi to 1,000,000 psi, or 70,000 psi to 1,000,000 psi, or 80,000 psi to 1,000,000 psi); (IV) a yield strength in the machine direction of 500 psi to 10,000 psi (or 2,000 psi to 10,000 psi, or 4,000 psi to 10,000 psi); (V) an elongation at yield in the machine direction of 5% to 15% (or 7% to 14%, or 9% to 13%); (VI) a tensile strength in the machine direction of 5,500 psi to 25,000 psi (or 7,000 psi to 23,000 psi, or 10,000 psi to 22,000 psi); (VII) a tensile strength per mil in the machine direction of 250 psi/mil to 4,000 psi/mil (or 500 psi/mil to 3,500 psi/mil, or 1,500 psi/mil to 3,300 psi/mil, or 1,750 psi/mil to 3,200 psi/mil); (VIII) an elongation at break in the machine direction of 60% to 450% (or 100% to 400%, or 150% to 350%); (IX) an Elmendorf tear in the machine direction of 40 g to 1,500 g (or 200 g to 1,500 g, or 500 g to 1,500 g, or 1,000 g to 1,500 g); (X) an Elmendorf tear per mil in the machine direction of 5 g/mil to 150 g/mil (or 10 g/mil to 150 g/mil, or 50 g/mil to 150 g/mil, or 100 g/mil to 150 g/mil); (XI) a shrink in the machine direction of 60% to 90% (or 70% to 90%, or 80% to 90%), (XII) a yield strength in the transverse direction of 1,000 psi to 1,500 psi (or 1,100 psi to 1,400 psi); (XIII) an elongation at yield in the transverse direction of 5% to 10% (or 7% to 10%); (XIV) a tensile strength in the transverse direction of 200 psi to 3,000 psi (or 2,250 psi to 2,800 psi); (XV) a tensile strength per mil in the transverse direction of 50 psi/mil to 500 psi/mil (or 100 psi/mil to 400 psi/mil); (XVI) an elongation at break in the transverse direction of 300% to 1,200% (or 500% to 1,200%, or 600% to 1,200%); (XVII) an Elmendorf tear in the transverse direction 1,500 g to 6,000 g (or 2,000 g to 5,000 g); (XVIII) an Elmendorf tear per mil in the transverse direction of 200 g to 700 g (or 300 g to 600 g); and (XIX) a shrink in the transverse direction of 10% to 40% (or 15% to 30%). [0151] This invention also relates to methods of making said compositions, the methods comprising: 1) producing a polymer melt comprising a polyethylene having (A)-(E) properties and optionally one or more of (F)-(K) properties: (A) a I 2 of 1.5 g/10 min to 2.1 g/10 min (or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to1.9 g/10 min); (B) a density of 0.91 g/cm 3 to 0.93 g/cm 3 (or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g' LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (F) a ratio of the g' LCB to the g' Zave is greater than 1.0, or from 1.1 to 10, (G) a Mz-LS of 300,000 g/mol or greater (or 300,000 g/mol to 600,000 g/mol, or 375,000 g/mol to 525,000 g/mol), (H) a g’LCB value of 0.8 to 0.9 (or 0.81 to 0.85, or 0.82 to 0.84, or 0.830 to 0.839), and one or more of: (I) a DST of 0.85 to 0.95 (or 0.86 to 0.90, or 0.87), (J) a SHR of 3 or greater (or 3 to 8, or 3 to 5), (K) a melting temperature of 122°C or greater (or 122°C to 127°C, or 123°C to 125°C), (L) a crystallization temperature of 110°C or greater (or 110°C to 115°C, or 110°C to 113°C), (M) a Mw of 100,000 g/mol to 150,000 g/mol (or 105,000 g/mol to 140,000 g/mol, or 110,000 g/mol to 130,000 g/mol), and (N) a Mw/Mn of 1 to 10 (or 1 to 3, or 2 to 4, or 3 to 5, or 4 to 7, or 5 to 10); and 2) extruding a film from the polymer melt; and 3) stretching the film in a machine direction (e.g., at a stretch ratio of 1 to 10) at a temperature below the melting temperature of the polyethylene to form a machine direction oriented film (e.g., having a thickness of 5 mils to 30 mils (or 15 mils or less, or 10 mils or less, or 8 mils or less, or 7 mils or less, or 5 mils to 10 mils, or 5 mils to 15 mils, or 10 mils to 30 mils)), wherein the film has (I) and (II) properties and optionally one or more of (III)-(XIX) properties: (I) a 1% secant in the transverse direction of 70,000 psi or more (alternately 75,000 psi to 150,000 psi, or 80,000 psi to 140,000 psi, or 90,000 psi to 130,000 psi), (II) Dart Drop per mil of 350 g/mil or more (alternately 350 g/mil to 1,300 g/mil, or 375 g/mil to 1,250 g/mil, or 450 g/mil to 1,225 g/mil), (III) a 1% secant in the machine direction of 30,000 psi to 110,000 psi (or 40,000 psi to 1,000,000 psi, or 50,000 psi to 1,000,000 psi, or 60,000 psi to 1,000,000 psi, or 70,000 psi to 1,000,000 psi, or 80,000 psi to 1,000,000 psi); (IV) a yield strength in the machine direction of 500 psi to 10,000 psi (or 2,000 psi to 10,000 psi, or 4,000 psi to 10,000 psi); (V) an elongation at yield in the machine direction of 5% to 15% (or 7% to 14%, or 9% to 13%); (VI) a tensile strength in the machine direction of 5,500 psi to 25,000 psi (or 7,000 psi to 23,000 psi, or 10,000 psi to 22,000 psi); (VII) a tensile strength per mil in the machine direction of 250 psi/mil to 4,000 psi/mil (or 500 psi/mil to 3,500 psi/mil, or 1,500 psi/mil to 3,300 psi/mil, or 1,750 psi/mil to 3,200 psi/mil); (VIII) an elongation at break in the machine direction of 60% to 450% (or 100% to 400%, or 150% to 350%); (IX) an Elmendorf tear in the machine direction of 40 g to 1,500 g (or 200 g to 1,500 g, or 500 g to 1,500 g, or 1,000 g to 1,500 g); (X) an Elmendorf tear per mil in the machine direction of 5 g/mil to 150 g/mil (or 10 g/mil to 150 g/mil, or 50 g/mil to 150 g/mil, or 100 g/mil to 150 g/mil); (XI) a shrink in the machine direction of 60% to 90% (or 70% to 90%, or 80% to 90%), (XII) a yield strength in the transverse direction of 1,000 psi to 1,500 psi (or 1,100 psi to 1,400 psi); (XIII) an elongation at yield in the transverse direction of 5% to 10% (or 7% to 10%); (XIV) a tensile strength in the transverse direction of 200 psi to 3,000 psi (or 2,250 psi to 2,800 psi); (XV) a tensile strength per mil in the transverse direction of 50 psi/mil to 500 psi/mil (or 100 psi/mil to 400 psi/mil); (XVI) an elongation at break in the transverse direction of 300% to 1,200% (or 500% to 1,200%, or 600% to 1,200%); (XVII) an Elmendorf tear in the transverse direction 1,500 g to 6,000 g (or 2,000 g to 5,000 g); (XVIII) an Elmendorf tear per mil in the transverse direction of 200 g to 700 g (or 300 g to 600 g); and (XIX) a shrink in the transverse direction of 10% to 40% (or 15% to 30%). [0152] The invention also relates to Embodiment A1, which is a composition comprising: a machine direction oriented film comprising a polyethylene having: (A) a I2 of 1.0 g/10 min or greater (or 1.5 g/10 min to 2.1 g/10 min, or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to1.9 g/10 min); (B) a density of 0.90 g/cm 3 to 0.9 g/cm 3 (0.91 g/cm 3 to 0.93 g/cm 3 , or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g' LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, and (F) a ratio of the g' LCB to the g' Zave is greater than 1.0, or from 1.1 to 10. [0153] The invention also relates to Embodiment A2, which is the composition of Embodiment A1, wherein the polyethylene also has one or more of the following: (G) a Mz-LS of 300,000 g/mol or greater (or 300,000 g/mol to 600,000 g/mol, or 375,000 g/mol to 525,000 g/mol), (H) a g’ LCB value of 0.8 to 0.9 (or 0.81 to 0.85, or 0.82 to 0.84, or 0.830 to 0.839), (I) a DST of 0.85 to 0.95 (or 0.86 to 0.90, or 0.87), (J) a SHR of 3 or greater (or 3 to 8, or 3 to 5), (K) a melting temperature of 122°C or greater (or 122°C to 127°C, or 123°C to 125°C), (L) a crystallization temperature of 110°C or greater (or 110°C to 115°C, or 110°C to 113°C), (M) a Mw of 100,000 g/mol to 150,000 g/mol (or 105,000 g/mol to 140,000 g/mol, or 110,000 g/mol to 130,000 g/mol), and (N) a Mw/Mn of 1 to 10 (or 1 to 3, or 2 to 4, or 3 to 5, or 4 to 7, or 5 to 10). [0154] The invention also relates to Embodiment A3, which is the composition of Embodiment A1 or A2, wherein the polyethylene is present at 90 wt% to 100 wt% of the film. [0155] The invention also relates to Embodiment A4, which is the composition of Embodiment A1 or A2 or A3, wherein the machine direction oriented film further comprises an additive at 0.01 wt% to 1 wt% of film (where when Embodiments A3 and A4 are in combination the polyethylene is present at 90 wt% to 99.9 wt% of the film). [0156] The invention also relates to Embodiment A5, which is the composition of Embodiment A1 or A2 or A3 or A4, wherein the film has a thickness of 15 mils or less. [0157] The invention also relates to Embodiment A6, which is the composition of Embodiment A1 or A2 or A3 or A4 or A5, wherein the film has a thickness of 10 mils or less. [0158] The invention also relates to Embodiment A7, which is the composition of Embodiment A1 or A2 or A3 or A4 or A5 or A6, wherein the film has a thickness of 7 mils or less. [0159] The invention also relates to Embodiment A7, which is the composition of Embodiment A1 or A2 or A3 or A4 or A5 or A6 or A7, wherein the film has one or more of the following properties: (III) a 1% secant in the machine direction of 30,000 psi to 110,000 psi (or 40,000 psi to 1,000,000 psi, or 50,000 psi to 1,000,000 psi, or 60,000 psi to 1,000,000 psi, or 70,000 psi to 1,000,000 psi, or 80,000 psi to 1,000,000 psi); (IV) a yield strength in the machine direction of 500 psi to 10,000 psi (or 2,000 psi to 10,000 psi, or 4,000 psi to 10,000 psi); (V) an elongation at yield in the machine direction of 5% to 15% (or 7% to 14%, or 9% to 13%); (VI) a tensile strength in the machine direction of 5,500 psi to 25,000 psi (or 7,000 psi to 23,000 psi, or 10,000 psi to 22,000 psi); (VII) a tensile strength per mil in the machine direction of 250 psi/mil to 4,000 psi/mil (or 500 psi/mil to 3,500 psi/mil, or 1,500 psi/mil to 3,300 psi/mil, or 1,750 psi/mil to 3,200 psi/mil); (VIII) an elongation at break in the machine direction of 60% to 450% (or 100% to 400%, or 150% to 350%); (IX) an Elmendorf tear in the machine direction of 40 g to 1,500 g (or 200 g to 1,500 g, or 500 g to 1,500 g, or 1,000 g to 1,500 g); (X) an Elmendorf tear per mil in the machine direction of 5 g/mil to 150 g/mil (or 10 g/mil to 150 g/mil, or 50 g/mil to 150 g/mil, or 100 g/mil to 150 g/mil); and (XI) a shrink in the machine direction of 60% to 90% (or 70% to 90%, or 80% to 90%). [0160] The invention also relates to Embodiment A7, which is the composition of Embodiment A8, wherein the film also has one or more of the following properties: (XII) a yield strength in the transverse direction of 1,000 psi to 1,500 psi (or 1,100 psi to 1,400 psi); (XIII) an elongation at yield in the transverse direction of 5% to 10% (or 7% to 10%); (XIV) a tensile strength in the transverse direction of 200 psi to 3,000 psi (or 2,250 psi to 2,800 psi); (XV) a tensile strength per mil in the transverse direction of 50 psi/mil to 500 psi/mil (or 100 psi/mil to 400 psi/mil); (XVI) an elongation at break in the transverse direction of 300% to 1,200% (or 500% to 1,200%, or 600% to 1,200%); (XVII) an Elmendorf tear in the transverse direction 1,500 g to 6,000 g (or 2,000 g to 5,000 g); (XVIII) an Elmendorf tear per mil in the transverse direction of 200 g to 700 g (or 300 g to 600 g); and (XIX) a shrink in the transverse direction of 10% to 40% (or 15% to 30%). [0161] The invention also relates to Embodiment B1, which is a method comprising: producing a polymer melt comprising a polyethylene having: (A) a I2 of 1.0 g/10 min or greater (or 1.5 g/10 min to 2.1 g/10 min, or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to 1.9 g/10 min); (B) a density of 0.90 g/cm 3 to 0.9 g/cm 3 (0.91 g/cm 3 to 0.93 g/cm 3 , or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g' LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, and (F) a ratio of the g' LCB to the g' Zave is greater than 1.0, or from 1.1 to 10; extruding a film from the polymer melt; and stretching the film in a machine direction at a temperature below the melting temperature of the polyethylene. [0162] The invention also relates to Embodiment B2, which is the method of Embodiment B1, wherein stretching is at a stretch ratio of 1 to 10. [0163] The invention also relates to Embodiment B3, which is the composition of Embodiment B1 or B2, wherein the polyethylene also has one or more of the following: (G) a Mz-LS of 300,000 g/mol or greater (or 300,000 g/mol to 600,000 g/mol, or 375,000 g/mol to 525,000 g/mol), (H) a g’ LCB value of 0.8 to 0.9 (or 0.81 to 0.85, or 0.82 to 0.84, or 0.830 to 0.839), (I) a DST of 0.85 to 0.95 (or 0.86 to 0.90, or 0.87), (J) a SHR of 3 or greater (or 3 to 8, or 3 to 5), (K) a melting temperature of 122°C or greater (or 122°C to 127°C, or 123°C to 125°C), (L) a crystallization temperature of 110°C or greater (or 110°C to 115°C, or 110°C to 113°C), (M) a Mw of 100,000 g/mol to 150,000 g/mol (or 105,000 g/mol to 140,000 g/mol, or 110,000 g/mol to 130,000 g/mol), and (N) a Mw/Mn of 1 to 10 (or 1 to 3, or 2 to 4, or 3 to 5, or 4 to 7, or 5 to 10). [0164] The invention also relates to Embodiment B4, which is the composition of Embodiment B1 or B2 or B3, wherein the polyethylene is present at 90 wt% to 100 wt% of the film. [0165] The invention also relates to Embodiment B5, which is the composition of Embodiment B1 or B2 or B3 or B4, wherein the machine direction oriented film further comprises an additive at 0.01 wt% to 1 wt% of film (where when Embodiments B4 and B5 are in combination the polyethylene is present at 90 wt% to 99.9 wt% of the film). [0166] The invention also relates to Embodiment B6, which is the composition of Embodiment B1 or B2 or B3 or B4 or B5, wherein the film has a thickness of 15 mils or less. [0167] The invention also relates to Embodiment B7, which is the composition of Embodiment B1 or B2 or B3 or B4 or B5 or B6, wherein the film has a thickness of 10 mils or less. [0168] The invention also relates to Embodiment B8, which is the composition of Embodiment B1 or B2 or B3 or B4 or B5 or B6 or B7, wherein the film has a thickness of 7 mils or less. [0169] The invention also relates to Embodiment B9, which is the composition of Embodiment B1 or B2 or B3 or B4 or B5 or B6 or B7 or B8, wherein the film has one or more of the following properties: (III) a 1% secant in the machine direction of 30,000 psi to 110,000 psi (or 40,000 psi to 1,000,000 psi, or 50,000 psi to 1,000,000 psi, or 60,000 psi to 1,000,000 psi, or 70,000 psi to 1,000,000 psi, or 80,000 psi to 1,000,000 psi); (IV) a yield strength in the machine direction of 500 psi to 10,000 psi (or 2,000 psi to 10,000 psi, or 4,000 psi to 10,000 psi); (V) an elongation at yield in the machine direction of 5% to 15% (or 7% to 14%, or 9% to 13%); (VI) a tensile strength in the machine direction of 5,500 psi to 25,000 psi (or 7,000 psi to 23,000 psi, or 10,000 psi to 22,000 psi); (VII) a tensile strength per mil in the machine direction of 250 psi/mil to 4,000 psi/mil (or 500 psi/mil to 3,500 psi/mil, or 1,500 psi/mil to 3,300 psi/mil, or 1,750 psi/mil to 3,200 psi/mil); (VIII) an elongation at break in the machine direction of 60% to 450% (or 100% to 400%, or 150% to 350%); (IX) an Elmendorf tear in the machine direction of 40 g to 1,500 g (or 200 g to 1,500 g, or 500 g to 1,500 g, or 1,000 g to 1,500 g); (X) an Elmendorf tear per mil in the machine direction of 5 g/mil to 150 g/mil (or 10 g/mil to 150 g/mil, or 50 g/mil to 150 g/mil, or 100 g/mil to 150 g/mil); and (XI) a shrink in the machine direction of 60% to 90% (or 70% to 90%, or 80% to 90%). [0170] The invention also relates to Embodiment B10, which is the composition of Embodiment B9, wherein the film also has one or more of the following properties: (XII) a yield strength in the transverse direction of 1,000 psi to 1,500 psi (or 1,100 psi to 1,400 psi); (XIII) an elongation at yield in the transverse direction of 5% to 10% (or 7% to 10%); (XIV) a tensile strength in the transverse direction of 200 psi to 3,000 psi (or 2,250 psi to 2,800 psi); (XV) a tensile strength per mil in the transverse direction of 50 psi/mil to 500 psi/mil (or 100 psi/mil to 400 psi/mil); (XVI) an elongation at break in the transverse direction of 300% to 1,200% (or 500% to 1,200%, or 600% to 1,200%); (XVII) an Elmendorf tear in the transverse direction 1,500 g to 6,000 g (or 2,000 g to 5,000 g); (XVIII) an Elmendorf tear per mil in the transverse direction of 200 g to 700 g (or 300 g to 600 g); and (XIX) a shrink in the transverse direction of 10% to 40% (or 15% to 30%). [0171] The invention also relates to Embodiment B1, which is a method comprising: producing a polymer melt comprising a polyethylene having: (A) a I2 of 1.0 g/10 min or greater (or 1.5 g/10 min to 2.1 g/10 min, or 1.6 g/10 min to 2.0 g/10 min, or 1.7 g/10 min to 1.9 g/10 min); (B) a density of 0.90 g/cm 3 to 0.9 g/cm 3 (0.91 g/cm 3 to 0.93 g/cm 3 , or 0.912 g/cm 3 to 0.927 g/cm 3 , or 0.915 g/cm 3 to 0.925 g/cm 3 ); (C) a g'LCB of greater than 0.8 (or from 0.81 to 0.95), (D) a ratio of comonomer content at Mz-LS to comonomer content at Mw-LS (CCMz/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, (E) a ratio of comonomer content at Mn-LS to comonomer content at Mw-LS (CCMn/CCMw) of greater than 1.0, or from 1.1 to 3.5, or from 1.3 to 3.0, and (F) a ratio of the g'LCB to the g'Zave is greater than 1.0, or from 1.1 to 10; extruding a film from the polymer melt; and stretching the film in a machine direction at a temperature below the melting temperature of the polyethylene. [0172] To facilitate a better understanding of the embodiments of the present invention, the following examples of preferred or representative embodiments are given. In no way should the following examples be read to limit, or to define, the scope of the invention. EXAMPLES [0173] Me2Si[Me4Cp][3-Ph-Ind]ZrCl2, dimethylsilyl (tetramethylcyclopentadienyl)(3- phenylindenyl)zirconium dichloride was prepared as generally described in US 9,266,977 (see Metallocene 1). Preparation of Me 2 Si[Me 4 Cp][3-Ph-Ind]ZrCl 2 Supported Catalyst [0174] Activation and supportation of Me 2 Si[Me 4 Cp][3-Ph-Ind]ZrCl 2 was prepared as follows. In a 4L stirred vessel in the drybox a 687 g amount of methylaluminoxane (MAO) (30 wt % in toluene) was added along with a 1504 g amount of toluene. A 15.7 g amount of the metallocene dissolved in 200 mL of toluene was added. This solution was then stirred at 60 rpm for 5 minutes. Another 165 g amount of toluene was added. The solution was stirred for 30 minutes at 120 rpm. The stir rate was reduced to 8 rpm. ES-70™ silica (PQ Corporation, Conshohocken, Pennsylvania) that had been calcined at 875°C was added to the vessel. This slurry with another 154 grams of toluene for rinse was stirred for 30 minutes before drying under vacuum at room temperature for twenty-two hours. After emptying the vessel and sieving the supported catalyst, a 763 gram amount was collected. Gas Phase Polymerization [0175] The polymerizations were run employing the Me2Si[Me4Cp][3-Ph-Ind]ZrCl2 supported catalyst (Polymerizations 1 and 2 see Table A). Each polymerization was performed in an 18.5 ft tall gas-phase fluidized bed reactor with a 10 ft body and an 8.5 ft expanded section. Cycle and feed gases were fed into the reactor body through a perforated distributor plate, and the reactor was controlled at 300 psi and 70 mol% ethylene. The reactor temperature was maintained at 185°F (85°C) throughout each of the polymerizations by controlling the temperature of the cycle gas loop. Each catalyst was delivered in a mineral oil slurry containing 20 wt% supported catalyst. Specific information relevant to each polymerization is provided in Table 1. Table 1 [0176] Example 1. Ethylene 1-hexene copolymer samples with properties reported in Table 2 were used in preparing polyethylene films. The C-1 is a comparative sample, and I-1 and I-2 are inventive samples. C-1 is a metallocene ethylene 1-hexene copolymer LLDPE. C-1, I-1 and I-2 granules were pelletized using a 57mm Werner-Pfleiderer compounder with 300 ppm IRGANOX™ 1076, 1500 ppm IRGAFOS™ 168, and 400 ppm DYNAMAR™ FX-5929 (a free-flowing fluropolymer based processing additive, available from 3M). Table 2
[0177] FIGURE 1 (FIG. 1) is a GPC-4D print out of example I-1 with a table of various characteristics of said printout. [0178] FIGURE 2 (FIG.2) is a graph of the weight fraction versus molecular weight (LS), comonomer content (wt%) versus molecular weight and branching index versus molecular weight for Example C-1. [0179] FIGURE 3 (FIG.3) is a graph of the weight fraction versus molecular weight (LS), comonomer content (wt%) versus molecular weight and branching index versus molecular weight for Example I-1. [0180] FIGURE 4 (FIG.4) is a graph of the weight fraction versus molecular weight (LS), comonomer content (wt%) versus molecular weight and branching index versus molecular weight for Example I-2. [0181] The polyethylene films were fabricated by using a Cincinnati Milacron S-PAK 150. The equipment is designed to support the reducer, barrel, and control cabinet. The extrusion section was mounted on the floor and stabilized with a set of mobile and fixed casters. The motor has the capability to 10 HP and the gear reducer is rated for 24 HP at 100 rpm. A single layer extrusion cast line with a 12-inch die was used to obtain monolayer films. FIGURE 5 (FIG.5) is a diagram of the extruder and rollers used to make the MDO polyethylene films of the present examples. This illustrates the five temperature zones of the extruder including the temperature at the die (Zone 5). The extruder temperature profile was set according to Table 4 and monitored. The single screw pressure and rate were controlled to ensure optimal processing conditions. The processing conditions of the extrusion section are reported in Table 5. Table 4 Table 5 [0182] The pelletized samples were fed in the extruder where it was applied an accurate temperature, pressure, and rate control. The molten material was spread on two rolls (mid roll: T=90°C, rotation rate=1 m/min and bot roll T=90°C, rotation rate=1m/min) and then guided to the MDO rollers, see FIG.5. The extruder and roll stack section were needed in order to have a homogeneous gauge and width before reaching the MDO section. The temperature profile was well-controlled at the roll/film interface due to an internal oil circulation but not at the air/film interface where the film was exposed at the environment (room temperature). This temperature gradient may generate some shear orientation on the pre-oriented film. [0183] The stretch ratio were controlled by rotation speed and temperature of the rollers, see Table 6. The bulk of the stretching in the MD occurs between rollers 3 and 4. Table 6 [0184] Three stretch ratio (3x, 5x and 7x) were aimed for the 4 samples. Unfortunately, C-1 could not be stretched at ratio higher than 5x. Above 5x, periodic transversal streaks were observed on the films due to stickiness and slippage issues on the slow and fast roll, respectively. Although some adjustments could be done for example with the roll speed and temperature, in general, the two materials were not performing equally well as I-1 and I-2. Sometimes the transversal streaks or inhomogeneities in the cast films can be solved by increasing the stretch ratio. [0185] On the other hand, I-1 and I-2 were easily stretched at higher deformations (7x and 8x, respectively) and also processed at higher temperatures. [0186] The MDO polyethylene films after production were conditioned for 40 hours at 23°C±2°C and 50%±10% relative humidity per ASTM D618-08. [0187] Table 7 provides the properties of the MDO polyethylene films. Relative to strain hardening, for all samples, the tensile stress growth exhibit deviations from LVE for extension rate between 0.1 s -1 and 10 s -1 at 150°C. In the nonlinear regime, branching and high molecular weight polymers present strain-hardening profiles in extensional viscosity testing. Table 7
[0188] As illustrated in Table 7, the polyethylenes described herein can be stretched and down-gauged to smaller thicknesses with properties superior (e.g., 7x I-1 8.0 mil with 19,000 psi tensile strength and 8x I-2 at 6.6 mil with 20,000 psi tensile strength as compared to thicker films produced with polyethylenes (e.g., 5x C-1 with 17,000 psi tensile strength). [0189] FIGURES 6 and 7 further illustrate the superior properties of films produced with the polyethylenes described herein. FIGURE 6 (FIG.6) is a plot of the 1% secant modulus in the machine direction as a function of the stretch ratio. FIGURE 7 (FIG. 7) is a blot of the tensile strength per mil in the machine direction as a function of the stretch ratio. [0190] Both the modulus and tensile strength per mil along MD for 8x I-1, which has the largest deformation, is greater than said properties for less stretched samples. [0191] Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered, combined, or modified and all such variations are considered within the scope and spirit of the present invention. The invention illustratively disclosed herein suitably may be practiced in the absence of any element that is not specifically disclosed herein and/or any optional element disclosed herein. While compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components and steps. All numbers and ranges disclosed above may vary by some amount. Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee. Moreover, the indefinite articles “a” or “an,” as used in the claims, are defined herein to mean one or more than one of the element that it introduces. [0192] All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure.
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