WO2009139851A1 - Polyolefin compositions and methods of processing the same using metal salts - Google Patents

Abstract

A method for processing a polyolefin composition into a film is disclosed, the method including contacting a linear low density polyethylene (LLDPE) with a sufficient amount of a metal salt to reduce, for example, melt fracture, wherein the LLDPE has a molecular weight (Mw) from 50,000 g/mol to 180,000 g/mol, a molecular weight distribution from 1.5 to 3.0, and a melt index ratio from 15 to 25, and melt processing the LLDPE and the metal salt to form the film. Polyolefin compositions processed using metal salts are also disclosed.

Description

POLYOLEFIN COMPOSITIONS AND METHODS OF PROCESSING THE

SAME USING METAL SALTS

CROSS REFERENCE TO RELATED APPLICATIONS

[0001) This application claims the benefit of Serial No. 61/127,755, filed May 15, 2008, the disclosure of which is incorporated by reference in its entirety.

FIELD OF THE INVENTION

[0002] The present invention relates generally to polyolefin compositions and methods of processing the same using processing aids. More specifically, but without limitation, the present invention relates to polyolefin compositions and methods for processing the same using metal salts. Additionally, the invention relates to methods of producing films having an improvement in at least one of reduced melt fracture, head pressure, motor load, increased thermal stability, improved color, and combinations thereof.

BACKGROUND

[0003] Linear polyolefins, including linear polyethylenes such as linear low density polytethylene (LLDPE), may be difficult to melt process. Specifically, due to a low shear sensitivity when compared to highly branched polyethylenes, the linear polyethylenes can require more extruder power to pump an equivalent amount of polymer melt. As a result, higher extruder head pressures, higher torque, greater motor loads may be required.

[0004] Increases in parameters such as motor load, head pressure, and/or torque can place undesirable, unacceptable, or unattainable requirements on processing equipment. For example, a specific extruder having a specific motor power and gearing may reach a maximum of motor load or head pressure under certain melt temperature conditions for a given polymer being processed. Additionally, linear polyethylenes may exhibit other imperfections during blown film extrusion that may be undesirable, such as melt fracture. These imperfections are undesirable from a quality standpoint. For instance, melt fracture, also known as "shark skin," can lead to poorer optical properties such as high haze, low gloss, and/or diminished film physical properties that are generally unacceptable. [0005] The introduction of linear Ziegler-Natta catalyzed polyethylenes in the late 70s and early '80s provided the early manifestations of these problems. Attempts to use these polyethylenes in machines that had been previously used to extrude highly branched polyethylenes such as high-pressure low density polyethylenes (HP-LDPE) presented challenges due to increased extruder pressure, higher torque, and motor power requirements as well as an increase in melt temperature. The development of metallocene catalyzed linear polyethylenes such as metallocene linear low density polyethylene (mLLDPE) having a narrow molecular weight distribution, has continued the trend towards polymers that when fabricated into films, for example, offer better physical properties, and/or manufacturing economics, but have higher power requirements and/or greater tendency to exhibit melt fracture or thermal instability in the blown film process. [0006] Linear polyethylenes therefore have been the subject of a good deal of effort to eliminate or reduce such problems. Some of the attempts included regearing extruders, designing new and more efficient screws and dies, increasing the power train, and the like, which may add undesirable complexity to the extrusion process or may be costly.

[0007] Therefore, there is a need for processing aids and methods of production of blown films which when incorporated into a linear polyethylene, can reduce or eliminate processing problems such as, for example, melt fracture, thermal instability, increased motor load, increased head pressure, and combinations thereof.

SUMMARY

[00081 In a class of embodiments, the invention provides for a method for processing a linear polyethylene into a film, wherein the method includes contacting a linear low density polyethylene (LLDPE) with a sufficient amount of a carboxylate metal salt to reduce melt fracture and melt processing the LLDPE and the carboxylate metal salt to form the film. The LLDPE may have a molecular weight (Mw) from 50,000 g/mol to 180,000 g/mol, a molecular weight distribution from 1.5 to 3.0, and a melt index ratio from 15 to 25. |0009] In another class of embodiments, the invention provides a composition including a linear low density polyethylene (LLDPE) and a carboxylate metal salt, wherein the LLDPE may have a molecular weight (Mw) from 50,000 g/mol to 180,000 g/mol, a molecular weight distribution from 1.5 to 3.0, and a melt index ratio from 15 to 25.

10010) In yet another class of embodiments, the invention provides a method for processing a linear polyethylene into a film, wherein the method includes contacting a linear low density polyethylene (LLDPE) with a sufficient amount of a carboxylate metal salt to improve thermal stability of the polyethylene and melt processing the LLDPE and the carboxylate metal salt to form the film. The LLDPE may have a molecular weight (Mw) from 50,000 g/mol to 180,000 g/mol, a molecular weight distribution from between 1.5 to 5.0, and a melt index ratio from 15 to 100.

10011] In another exemplary class of embodiments, the invention provides a composition including a metallocene catalyzed linear low density polyethylene (mLLDPE) and a carboxylate metal salt, wherein the mLLDPE may have a molecular weight (Mw) of about 50,000 g/mol to about 180,000 g/mol, a molecular weight distribution of between 1.5 and 5.0, and a melt index ratio of between 20 and 100.

BRIEF DESCRIPTION OF THE DRAWINGS

[0012] FIG. 1 is a graph comparing the effects of processing aids on film heat seal properties during a first trial.

10013] FIG. 2 is a graph comparing the effects of processing aids on film heat seal properties during an alternative trial.

]0014] FIG. 3 is a graph comparing the effects of processing aids on film hot tack properties during a first trial.

|0015] FIG. 4 is a graph comparing the effects of processing aids on film hot tack properties during an alternative trial. [0016] FIG. 5 is a graph comparing the effects of metal stearates on melt indices of sample resins.

10017] FIG. 6 is a graph comparing of the effects of metal stearates on color of sample resins.

DETAILED DESCRIPTION

|0018] Before the present compounds, components, compositions, and/or methods are disclosed and described, it is to be understood that unless otherwise indicated this invention is not limited to specific compounds, components, compositions, reactants, reaction conditions, ligands, metallocene structures, or the like, as such may vary, unless otherwise specified. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

[0019] The invention is directed to polyolefin compositions, for example, a polyethylene composition and methods of processing the polyolefin composition. It is further directed to blown film processes having reduced melt fracture as a result of introducing a processing aid including, but not limited to, a metal stearate to a metallocene catalyzed linear polyethylene (for example, metallocene linear low density polyethylene (mLLDPE)). In several of the various embodiments, it has been surprisingly discovered that using metal stearates in combination with mLLDPE may result in improved properties in blown film such as, for example, at least one of reduced melt fracture, head pressure, and motor load.

Linear Low Density Polyethylene (LLDPE)

[0020] In one class of embodiments, the compositions and films are made from a linear low density polyethylene (LLDPE) polymer having a density from about 0.890 g/cm³ to 0.935 g/cm³, from 0.900 g/cm³ to 0.930 in another embodiment and from 0.910 g/cm³ to 0.927 in yet another embodiment. In another class of embodiments, the LLDPE may have a melt index (MI) or (I₂) as measured by ASTM-D-1238-E (190°C, 2.16 kg weight) in the range from 0.01 dg/min to 10 dg/min, from about 0.1 dg/min to 10 dg/min in another embodiment, and from 0.1 dg/min to 5 dg/min in yet another embodiment, and from 0.5 dg/min to 3.5 dg/min in yet another exemplary embodiment. In yet another class of embodiments, the LLDPE may have a melt flow ratio (MFR=I₂ i/I₂ where I₂] is measured by ASTM- D-1238-F, at 190°C, 21.6 kg weight) from 5 to 50, from 10 to less than 40 in another embodiment, from 15 to less than 20 in yet another embodiment. In another exemplary class of embodiments, the LLDPE may have a narrow weight average molecular weight to number average molecular weight (Mw/Mn) of greater than 1.5 to less than 5, greater than 2.0 to less than 3.5 in another embodiment and greater than 2.0 to less than 2.5 in yet another embodiment. [0021] In a class of embodiments, the polymer blends and films are made from a linear low density polyethylene (LLDPE) polymer having a density of from 0.890 g/cm³ to 0.940 g/cm³ and from 0.910 g/cm³ to 0.935 g/cm³ in another embodiment. In another class of embodiments, the LLDPE may have a melt index (MI) or (I₂) as measured by ASTM-D-1238-E (190°C, 2.16 kg weight) in the range from 0.01 dg/min to 10 dg/min, from 0.1 dg/min to 10 dg/min in another embodiment, and from 0.1 dg/min to 5 dg/min in yet another embodiment. In yet another class of embodiments, the LLDPE may have a melt flow ratio (MFR=I₂]/I₂ where I₂] is measured by ASTM-D-1238-F, at 190°C, 21.6 kg weight) of from 20 to 100. In another exemplary class of embodiments, the LLDPE may have a weight average molecular weight to number average molecular weight (Mw/Mn) of greater than 1.5 to 5.0.

Metallocene Linear Low Density Polyethylene (mLLDPE) [0022] In several classes of embodiments, the compositions and films are made from a metallocene linear low density polyethylene (mLLDPE) polymer(s). As used herein, the terms "linear low density polyethylene" polymer or "mLLDPE" polymer refer to a polyethylene copolymer having a density of from 0.940 g/cm³ or less and from 0.890 to 0.940 g/cm³ in another embodiment. Polymers having more than two types of monomers, such as, for example, terpolymers, are also included within the term "copolymer" as used herein. The comonomers that are useful in general for making mLLDPE copolymers include alpha-olefins, such as C₃-C₂O alpha-olefins and C₃-Ci₂ alpha-olefins. The alpha-olefin comonomer can be linear or branched, and two or more comonomers can be used, if desired. Examples of suitable comonomers include linear C₃-C]₂ alpha-olefins and alpha- olefins having one or more Ci-C₃ alk yl branches, or an aryl group. Specific examples include propylene; 1-butene; 3-methyl-l-butene; 3,3-dimethyl-l-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 4- methyl-1-pentene; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; ethyl, methyl or dimethyl-substituted 1- decene; 1-dodecene; and styrene. It should be appreciated that the list of comonomers above is merely exemplary, and is not intended to be limiting. [0023] Other useful comonomers in producing mLLDPE may include polar vinyl, conjugated and non-conjugated dienes, acetylene and aldehyde monomers, which can be included in minor amounts in terpolymer compositions. Non-conjugated dienes useful as co-monomers are typically straight chain, hydrocarbon di-olefins or cycloalkenyl-substituted alkenes, having 6 to 15 carbon atoms. Suitable non- conjugated dienes include, for example: (a) straight chain acyclic dienes, such as 1 ,5-hexadiene and 1 ,7-octadiene; (b) branched chain acyclic dienes, such as 5- methyl-l,4-hexadiene; 3,7-dimethyl-l,6-octadiene; and 3,7-dimethyl-l,7- octadiene; (c) single ring alicyclic dienes, such as 1 ,4-cyclohexadiene; 1,5-cyclo- octadiene and 1,7-cyclododecadiene; (d) multi-ring alicyclic fused and bridged ring dienes, such as tetrahydroindene; norbornadiene; methyl-tetrahydroindene; dicyclopentadiene (DCPD); bicyclo-(2.2.1)-hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4- cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, and 5-vinyl-2- norbornene (VNB); and (e) cycloalkenyl-substituted alkenes, such as vinyl cyclohexene, allyl cyclohexene, vinyl cyclooctene, 4-vinyl cyclohexene, allyl cyclodecene, and vinyl cyclododecene. Of the non-conjugated dienes typically used, the preferred dienes are dicyclopentadiene, 1 ,5-hexadiene, 5-methylene-2- norbornene, 5-ethylidene-2-norbornene, and tetracyclo-(.DELTA.-l l,12)-5,8- dodecene. Particularly preferred diolefins are 5-ethylidene-2-norbornene (ENB), 1 ,5-hexadiene, dicyclopentadiene (DCPD), norbornadiene, and 5-vinyl-2- norbornene (VNB).

[0024] The amount of comonomer used will depend upon the desired density of the mLLDPE polymer and the specific comonomers selected. One skilled in the art can readily determine the appropriate comonomer content appropriate to produce an mLLDPE polymer having a desired density.

[0025] In a class of embodiments, the mLLDPE polymer is characterized by having a density of from 0.890 g/cm³ to 0.935 g/cm³, from 0.900 g/cm³ to 0.930 in another embodiment and from 0.910 g/cm³ to 0.927 in yet another embodiment. In another class of embodiments, the mLLDPE polymer is characterized by having a melt index (MI) or (I₂) as measured by ASTM-D-1238-E (190°C, 2.16 kg weight) in the range from 0.01 dg/min to 10 dg/min, from 0.1 dg/min to 10 dg/min in another embodiment, from 0.1 dg/min to 5 dg/min in yet another embodiment; and from 0.5 dg/min to 3.5 dg/min in another exemplary embodiment. In yet another class of embodiments, the mLLDPE polymer is characterized by having a melt flow ratio (MFR=I₂₁ZI₂ where I₂₁ is measured by ASTM-D-1238-F, at 190°C, 21.6 kg weight) of from 5 to 50, from about 10 to less than 40 in another embodiment and from 15 to less than 20 in yet another embodiment. In another exemplary class of embodiments, the mLLDPE polymer is characterized by having a narrow weight average molecular weight to number average molecular weight (Mw/Mn) of greater than 1.5 to less than 5, greater than about 2.0 to less than 3.5 in another embodiment and greater than 2.0 to less than 2.5 in yet another embodiment.

[0026] In a class of embodiments, the mLLDPE polymer is characterized by having a density of from 0.890 g/cm³ to 0.940 g/cm³ and from 0.910 g/cm³ to 0.935 g/cm³ in another embodiment. In another class of embodiments, the mLLDPE polymer is characterized by having a melt index (MI) or (I₂) as measured by ASTM-D-1238-E (190°C, 2.16 kg weight) in the range from 0.01 dg/min to 10 dg/min, from 0.1 dg/min to 10 dg/min in another embodiment and from about 0.1 dg/min to about 5 dg/min in yet another embodiment. In yet another class of embodiments, the mLLDPE polymer is characterized by having a melt flow ratio (MFR=I₂]/I₂ where I₂i is measured by ASTM-D-1238-F, at 190°C, 21.6 kg weight) of from 20 to 100. In another exemplary class of embodiments, the mLLDPE polymer is characterized by having a weight average molecular weight to number average molecular weight (Mw/Mn) of greater than 1.5 to about

5.

[0027] Although the LLDPE and mLLDPE polymers of the invention are at times discussed as single polymers, two or more LLDPE or mLLDPE polymers or combinations thereof, having the properties described herein are also contemplated. The mLLDPE polymers described herein may be commercially available under the trade names EXCEED™ and ENABLE™ from ExxonMobil Chemical Co., Houston, TX.

Metallocene Catalysts

[0028] Generally, metallocene catalyst compounds may contain one or more ligands including cyclopentadienyl (Cp) or cyclopentadienyl-type structures or other similar functioning structure such as pentadiene, cyclooctatetraendiyl and imides. It is understood by one of skill in the art that references made herein to metallocene catalyst compounds and/or systems may also refer to metallocene- type catalyst compounds and/or systems. As used herein, a catalyst system may be a combination of a catalyst compound and a cocatalyst or activator (described below). Typical metallocene compounds are generally described as containing one or more ligands capable of η-5 bonding to a transition metal atom, usually, cyclopentadienyl derived ligands or moieties, in combination with a transition metal selected from Group 3 to 8, preferably 4, 5 or 6 or from the lanthanide and actinide series of the Periodic Table of Elements. All reference to the Periodic Table of the Elements herein shall refer to the Periodic Table of the Elements, published and copyrighted by the International Union of Pure and Applied Chemistry, Inc., 2004. Also, any reference to a Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups. Exemplary of these metallocene catalyst compounds and catalyst systems are described in, for example, U.S. Pat. Nos. 4,530,914, 4,871,705, 4,937,299, 5,017,714, 5,055,438, 5,096, 867, 5,120,867, 5,124,418, 5,198,401, 5,210,352, 5,229,478, 5,264,405, 5,278,264, 5,278,1 19, 5,304,614, 5,324,800, 5,347,025, 5,350,723, 5,384,299, 5,391,790, 5,391,789, 5,399,636, 5,408,017, 5,491,207, 5,455,366, 5,534,473, 5,539,124, 5,554,775, 5,621,126, 5,684,098, 5,693,730, 5,698,634, 5,710,297, 5,712,354, 5,714,427, 5,714,555, 5,728,641, 5,728,839, 5,753,577, 5,767,209, 5,770,753 and 5,770,664. Also, the disclosures of European publications such as EP-A-O 591 756, EP-A-O 520 732, EP-A- 0 420 436, EP-Bl 0 485 822, EP-Bl 0 485 823, EP-A2-0 743 324 and EP-Bl 0 518 092 and PCT publications WO 91/04257, WO 92/00333, WO 93/08221, WO 93/08199, WO 94/01471, WO 96/20233, WO 97/15582, WO 97/19959, WO 97/46567, WO 98/01455, WO 98/06759 and WO 98/011144 describe typical metallocene catalyst compounds and catalyst systems. Furthermore, metallocene catalyst compounds may contain one or more leaving group(s) bonded to the transition metal atom. For the purposes of this patent specification and appended claims the term "leaving group" may refer to one or more chemical moieties, such as a ligand, bound to the center metal atom of a catalyst component that can be abstracted from the catalyst component by an activator or cocatalyst, thus producing a catalyst species active toward olefin polymerization or oligomerization. It must also be noted that, as used in the specification and the appended claims, the singular forms "a," "an" and "the" include plural referents unless otherwise specified. Thus, for example, reference to "a leaving group" as in a moiety "substituted with a leaving group" includes more than one leaving group, such that the moiety may be substituted with two or more such groups. Similarly, reference to "a halogen atom" as in a moiety "substituted with a halogen atom" includes more than one halogen atom, such that the moiety may be substituted with two or more halogen atoms, reference to "a substituent" includes one or more substituents, reference to "a ligand" includes one or more ligands, and the like.

[0029] The Cp ligands are generally represented by one or more bonding systems comprising n bonds that can be open systems or ring systems or fused system(s) or a combination thereof. These ring(s) or ring system(s) are typically composed of atoms selected from Groups 13 to 16 atoms, preferably the atoms are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, boron and aluminum or a combination thereof. Alternatively, the ring(s) or ring system(s) may be composed of carbon atoms such as, but not limited to, those cyclopentadienyl ligands or cyclopentadienyl-type ligand structures (structures isolobal to cyclopentadienyl). The metal atom may be selected from Groups 3 through 16 and the lanthanide or actinide series of the Periodic Table of Elements, and selected from Groups 4 through 12 in another embodiment, and selected from Groups 4, 5 and 6 in yet a more particular embodiment, and selected from Group 4 atoms in yet another embodiment. [0030] In one embodiment, metallocene catalyst compounds of the invention are represented by the formula:

L^AL^BMQ_n (I) wherein each L^Λ and L^B are bound to the metal atom (M), and each Q is bound to the metal center, n being 0 or an integer from 1 to 4, alternatively 1 or 2, and in another embodiment 2.

[0031] In formula (I), M is a metal from the Periodic Table of the Elements and may be a Group 3 to 12 atom or a metal from the lanthanide or actinide series Group atom in one embodiment; selected from the group consisting of Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, and Ni in another embodiment; and selected from the group consisting of Groups 4, 5 or 6 transition metal in yet another embodiment. In other illustrative embodiments, M is a transition metal from Group 4 such as Ti, Zr or Hf; selected from the group of Zr and Hf in another embodiment; and Zr in yet a more particular embodiment. The oxidation state of M may range from 0 to +7 in one embodiment; and in another embodiment, is +1, +2, +3, +4 or +5; and in yet another illustrative embodiment is +2, +3 or +4. The groups bound to M are such that the compounds described below in the formulas and structures are electrically neutral, unless otherwise indicated. The Cp ligand(s) form at least one chemical bond with the metal atom M to form a metallocene catalyst compound. The Cp ligands are distinct from the leaving groups bound to the catalyst compound in that they are not highly susceptible to substitution/abstraction reactions.

|0032] The L^A and L^B groups of formula (I) are Cp ligands, such as cycloalkadienyl ligands and hetrocylic analogues. The Cp ligands typically comprise atoms selected from the group consisting of Groups 13 to 16 atoms, and more particularly, the atoms that make up the Cp ligands are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum and combinations thereof, wherein carbon makes up at least 50% of the ring members. Also, L^Λ and L^B may be any other ligand structure capable of rj -5 bonding to M and alternatively, L^A and L^B may comprise one or more heteroatoms, for example, nitrogen, silicon, boron, germanium, and phosphorous, in combination with carbon atoms to form a cyclic structure, for example, a heterocyclopentadienyl ancillary ligand. Furthermore, each of L^Λ and L^B may also be other types of ligands including but not limited to amides, phosphides, alkoxides, aryloxides, imides, carbolides, borollides, porphyrins, phthalocyanines, corrins and other polyazomacrocycles. Each L^Λ and L^B may be the same or different type of ligand that is π-bonded to M. Even more particularly, the Cp ligand(s) are selected from the group consisting of substituted and unsubstituted cyclopentadienyl ligands and ligands isolobal to cyclopentadienyl, non-limiting examples of which include cyclopentadienyl, indenyl, fluorenyl and other structures. Further illustrative ligands may include cyclopentaphenanthreneyl, benzindenyl,, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthrindenyl, 3,4-benzofluorenyl, 9- phenylfluorenyl, 8-H-cyclopent[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[l,2-9]anthrene, thiophenoindenyl, thiophenofluorenyl, hydrogenated versions thereof (e.g., 4,5,6,7-tetrahydroindenyl, or "H4Ind"), substituted versions thereof (as described in more detail below), heterocyclic versions thereof and the like, including hydrogenated versions thereof.

|0033] Each L^A and L^B may be unsubstituted or substituted with a combination of substituent R groups. Non-limiting examples of substituent R groups include one or more from the group selected from hydrogen, or linear, branched, alkyl radicals or cyclic alkyl radicals, alkenyl, or aryl radicals or combination thereof, halogens and the like, including all their isomers, for example tertiary butyl, iso-propyl, etc. In illustrative embodiments, substituent R groups may comprise 1 to 30 carbon atoms or other substituents having up to 50 non-hydrogen atoms that can each be substituted with halogens or heteroatoms or the like. Alkyl or aryl substituent R groups may include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, including all their isomers, for example, tertiary butyl, isopropyl, and the like. Halogenated hydrocarbyl radicals may include fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substituted organometalloid radicals including tris(trifluoromethyl)-silyl, methyl-bis (difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstitiuted boron radicals including dimethylboron for example; and disubstituted pnictogen or Group 15- containing radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine; and chalcogen or Group 16-containing radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide, ethylsulfide and the like. Non-hydrogen substituent R groups may include the atoms carbon, silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, germanium and the like including olefins such as but not limited to olefinically unsaturated substituents including vinyl-terminated ligands, for example, but-3-enyl, prop-2-enyl, hex-5-enyl, 2- vinyl, or 1-hexene. Also, at least two R groups, preferably two adjacent R groups may be joined to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon, germanium, boron or a combination thereof. Also, an R group such as 1-butanyl may form a bond to the metal M.

[0034] The leaving groups Q of formula (I) are monoanionic labile ligands bound to M. Depending on the oxidation state of M, the value for n is 0, 1 or 2 such that formula (I) above represents a neutral metallocene catalyst compound, or a positively charged compound. In a class of embodiments, Q may comprise halogen ions or hydrides. In another class of embodiments, Q may comprise weak bases such as, but not limited to, alkyls, alkoxides, amines, alkylamines, phosphines, alkylphosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms, C₆ to Ci₂ aryls, C₇ to C₂₀ alkylaryls, C₇ to C₂₀ arylalkyls, hydrides or halogen atoms (e.g., Cl, Br or I) and the like, and combinations thereof. Other examples of Q radicals include those substituents for R as described above and including cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene and pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and the like.

(0035] In addition, metallocene catalyst compounds of the invention include those of formula (I) where L^A and L^B are bridged to each other by a bridging group, A. These bridged compounds are known as bridged, metallocene catalyst compounds represented by the formula (II):

L^A(A)L^BMQ_n (II) wherein each L^Λ and L^B are bound to the metal center M, and each Q is bound to the metal center, n being 0 or an integer from 1 to 4, alternatively 1 or 2, and in another embodiment 2; the groups L^A, L^B M and Q are as defined in formula (I); and the divalent bridging group A is bound to both L^A and L^B through at least one bond or divalent moiety, each.

[0036] Non-limiting examples of bridging group A from formula (II) include divalent bridging groups containing at least one Group 13 to 16 atom. In one possible embodiment, bridging group A may be referred to as a divalent moiety such as, but not limited to, carbon, oxygen, nitrogen, silicon, germanium and tin or a combination thereof. In other embodiment, bridging group A contains carbon, silicon or germanium atom and in yet another illustrative embodiment, A contains at least one silicon atom or at least one carbon atom. Other non-limiting examples of bridging groups A may be represented by R₂C==, R'₂Si==, ~ (RO₂Si(RO₂Si-, -(RO₂Si(RO₂C-, R'₂Ge==, -(RO₂Si(RO₂Ge-, -(RO₂Ge(RO₂C-, R¹N==, RT=, -(RO₂C(RON-, -(RO₂C(ROP-, -(RO₂Si(RON-, -(RO₂Si(ROP--, - -(RO₂Ge(RON-, -(RO₂Ge(ROP-, where R¹ is independently, a radical group which is hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted Group 15 atom, substituted Group 16 atom, or halogen; or two or more R¹ groups may be joined to form a ring or ring system; and independently, each Q can be a hydride, substituted or unsubstituted, linear, cyclic or branched, hydrocarbyl having from 1 to 30 carbon atoms, halogen, alkoxides, aryloxides, amides, phosphides, or any other univalent anionic ligand or combination thereof.

[0037] It is also contemplated that in one embodiment, the metallocene catalysts of the invention include their structural or optical or enantiomeric isomers (meso and racemic isomers) and mixtures thereof. In another embodiments, the metallocene compounds of the invention may be chiral and/or a bridged metallocene catalyst compound. Further, as used herein, a single, bridged, asymmetrically substituted metallocene catalyst component having a racemic and/or meso isomer does not, itself, constitute at least two different bridged, metallocene catalyst components.

Activators and Activation Methods for Catalyst Compounds [0038] An activator is defined as any combination of reagents that increases the rate at which a transition metal compound oligomerizes or polymerizes unsaturated monomers, such as olefins. An activator may also affect the molecular weight, degree of branching, comonomer content, or other properties of the oligomer or polymer. The transition metal compounds according to the invention may be activated for oligomerization and/or polymerization catalysis in any manner sufficient to allow coordination or cationic oligomerization and or polymerization.

[0039] Generally, catalysts may contain a formal anionic ligand, such as hydride or hydrocarbyl, with an adjacent (cis) coordination site accessible to an unsaturated monomer. Coordination of an unsaturated monomer to the cis coordination site allows a migratory insertion reaction to form a metal alkyl. Repetition of this process causes the chain growth associated with oligomerization and/or polymerization. An activator is thus any combination of reagents that facilitates formation of a transition metal compound containing cis coordinated olefin and hydride or hydrocarbyl.

[0040] When the transition metal compound contains at least one hydride or hydrocarbyl ligand, activation can be achieved by removal of formal anionic or neutral ligand(s), of higher binding affinity than the unsaturated monomer. This removal, also called abstraction, process may have a kinetic rate that is first-order or non-first order with respect to the activator. Activators that remove anionic ligands are termed ionizing activators. Alternatively, activators that remove neutral ligands are termed non-ionizing activators. Activators may be strong Lewis-acids which may play either the role of an ionizing or non-ionizing activator.

[0041] When the transition metal compound does not contain at least one hydride or hydrocarbyl ligands, then activation may be a one step or multi step process. One step in this process includes coordinating a hydride or hydrocarbyl group to the metal compound. A separate activation step is removal of anionic or neutral ligands of higher binding affinity than the unsaturated monomer. These activation steps may occur in the presence of an olefin and occur either in series or in parallel. More than one sequence of activation steps is possible to achieve activation.

[0042] The activator may also act to coordinate a hydride or hydrocarbyl group to the transition metal compound. When the transition metal compound does not contain at least one hydride or hydrocarbyl ligands but does contain at least one functional group ligand, activation may be effected by substitution of the functional group with a hydride, hydrocarbyl or substituted hydrocarbyl group. This substitution may be effected with appropriate hydride or alkyl reagents of group 1, 2, 12, 13 elements as are known in the art. To achieve activation, it may be necessary to also remove anionic or neutral ligands of higher binding affinity than the unsaturated monomer.

[0043] Alumoxane and aluminum alkyl activators are capable of alkylation and abstraction activation.

[0044] The activator may also act to coordinate a hydride or hydrocarbyl group to the transition metal compound. If the transition metal compound does not contain anionic ligands, then a hydride, hydrocarbyl or substituted hydrocarbyl may be coordinated to a metal using electrophilic proton or alkyl transfer reagents represented by H⁺(LB)_nA^", (R⁹)⁺(LB)_nA^". R⁹ may be a hydrocarbyl or a substituted hydrocarbyl; LB is a Lewis-base, and wherein n=0, 1 or 2. Non-limiting examples of preferred Lewis-bases are diethyl ether, dimethyl ether, ethanol, methanol, water, acetonitrile, N,N-dimethylaniline. A^' is an anion, preferably a substituted hydrocarbon, a functional group, or a non-coordinating anion. Non-limiting examples of A^" may include halides, carboxylates, phosphates, sulfates, sulfonates, borates, aluminates, alkoxides, thioalkoxides, anionic substituted hydrocarbons, anionic metal complexes and the like.

[0045] Other activators include those described in WO 98/07515 such as tris (2,2',2"- nonafluorobiphenyl) fluoroaluminate. Combinations of activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations, see for example, EP-Bl 0 573 120, WO 94/07928 and WO 95/14044 and U.S. Pat. Nos. 5,153,157 and 5,453,410. WO 98/09996 describes activating metallocene catalyst compounds with perchlorates, periodates and iodates including their hydrates. WO 98/30602 and WO 98/30603 describe the use of lithium (2,2'-bisphenyl-ditrimethylsilicate).4THF as an activator for a metallocene catalyst compound. WO 99/18135 describes the use of organo-boron- aluminum activators. EP-Bl-O 781 299 describes using a silylium salt in combination with a non-coordinating compatible anion. WO 2007/024773 suggests the use of activator-supports which may comprise a chemically-treated solid oxide, clay mineral, silicate mineral, or any combination thereof. Also, methods of activation such as using radiation (see EP-Bl-O 615 981), electrochemical oxidation, and the like are also contemplated as activating methods for the purposes of rendering the neutral metallocene catalyst compound or precursor to a metallocene cation capable of polymerizing olefins. Other activators or methods for activating a metallocene catalyst compound are described in, for example, U.S. Pat. Nos. 5,849,852, 5,859,653 and 5,869,723 and PCT WO 98/32775.

A. Aluminoxane and Aluminum Alkyl Activators

100461 1° one embodiment, alumoxanes activators may be utilized as an activator in the catalyst composition of the invention. Alumoxanes are generally oligomeric compounds containing -Al(R)-O-- subunits, where R is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is a halide. Mixtures of different alumoxanes and modified alumoxanes may also be used. For further descriptions, see U.S. Pat. Nos. 4,665,208, 4,952,540, 5,041,584, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031 and EP 0 561 476 Al, EP 0 279 586 Bl, EP 0 516 476 A, EP 0 594 218 Al and WO 94/10180.

I0047J When the activator is an alumoxane (modified or unmodified), some embodiments select the maximum amount of activator at a 5000-fold molar excess Al/M over the catalyst precursor (per metal catalytic site). The minimum activator-to-catalyst-precursor is a 1 : 1 molar ratio.

[0048] Alumoxanes may be produced by the hydrolysis of the respective trialkylaluminum compound. MMAO may be produced by the hydrolysis of trimethylaluminum and a higher trialkylaluminum such as triisobutylaluminum. MMAO's are generally more soluble in aliphatic solvents and more stable during storage. There are a variety of methods for preparing alumoxane and modified alumoxanes, non-limiting examples of which are described in, for example, U.S. Pat. Nos. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166, 5,856,256 and 5,939,346 and European publications EP-A-O 561 476, EP-Bl-O 279 586, EP-A-O 594-218 and EP-Bl-O 586 665, WO 94/10180 and WO 99/15534. 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 alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3 A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, disclosed in U.S. Pat. No. 5,041,584). [0049] Aluminum alkyl or organoaluminum compounds which may be utilized as activators (or scavengers) include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like. B. Ionizing Activators

|0050] It is within the scope of this invention to use an ionizing or stoichiometric activator, neutral or ionic, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (see, for example, WO 98/43983), boric acid (see, for example, U.S. Pat. No. 5,942,459) or a combination thereof. It is also within the scope of this invention to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.

[0051] Examples of neutral stoichiometric activators may include tri-substituted boron, tellurium, aluminum, gallium and indium or mixtures thereof. The three substituent groups may be each independently selected from the group of alkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy and halides. The three substituent groups may be independently selected from the group of halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures thereof; in a class of embodiments are alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms (including substituted aryls). Alternatively, the three groups are alkyls having 1 to 4 carbon groups, phenyl, napthyl or mixtures thereof. In other embodiments, the three groups are halogenated, fluorinated, aryl groups or mixtures thereof. In yet other illustrative embodiments, the neutral stoichiometric activator is trisperfluorophenyl boron or trisperfluoronapthyl boron.

[0052] Ionic stoichiometric activator compounds may contain an active proton, or some other cation associated with, but not coordinated to, or only loosely coordinated to, the remaining ion of the ionizing compound. Such compounds and the like are described in, for example, European publications EP-A-O 570 982, EP-A-O 520 732, EP-A-O 495 375, EP-Bl-O 500 944, EP-A-O 277 003 and EP-A- 0 277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. patent application Ser. No. 08/285,380, filed Aug. 3, 1994.

[0053] By way of example, activators may include a cation and an anion component, and may be represented by the following formula:

(W^f+)_g(NCA^h-)i (0054) W^f+ is a cation component having the charge f+; NCA^h' is a non- coordinating anion having the charge h-; f is an integer from 1 to 3; h is an integer from 1 to 3; g and h are constrained by the relationship: (g)x(f)=(h)x(i). The cation component, (W^f+) 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 an analogous metallocene or Group 15 -containing catalyst precursor, resulting in a cationic transition metal species.

[0055] In an illustrative embodiment, the activators include a cation and an anion component, and may be represented by the following formula: (LB-H^f+)_g(NCA^h')_ι wherein LB is a neutral Lewis base; H is hydrogen; NCA^h" is a non-coordinating anion having the charge h-; f is an integer from 1 to 3; h is an integer from 1 to 3; g and h are constrained by the relationship: (g)x(f)=(h)x(i).

[0056] The activating cation (W^f+) may be a Bronsted acid, (LB-H^f+), 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, 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, oxoniums from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethyl thioethers and tetrahydrothiophene and mixtures thereof.

[0057] The activating cation (W ⁺) may also be an abstracting moiety such as silver, carboniums, tropylium, carbeniums, ferroceniums and mixtures, carboniums and ferroceniums. In other embodiments, the activating cation (W^f+) is triphenyl carbonium or N, N-dimethylanilinium.

[0058] The anion component (NCA^h') includes those having the formula [T^j+Q_k]^h~ wherein j is an integer from 1 to 3; k is an integer from 2 to 6; k-j=h; T is an element selected from Group 13 or 15 of the Periodic Table of the Elements, 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, wherein Q may have up to 20 carbon atoms with the condition that in not more than 1 occurrence is Q a halide. Each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, alternatively each Q may be a fluorinated aryl group, and in another embodiment, each Q is a pentafluoryl aryl group. Examples of suitable (NCA^h~) also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895. [0059] Additional suitable anions are known in the art and will be suitable for use with the catalysts of the invention. See for example, U.S. Pat. No. 5,278,1 19 and the review articles by S. H. Strauss, "The Search for Larger and More Weakly Coordinating Anions", Chem. Rev., 93, 927 942 (1993) and C. A. Reed, "Carboranes: A New Class of Weakly Coordinating Anions for Strong Electrophiles, Oxidants and Superacids", Ace. Chem. Res., 31, 133 139 (1998). [0060) Illustrative, but not limiting examples of boron compounds which may be used as activating cocatalysts in the preparation of the improved catalysts of this invention are tri-substituted ammonium salts such as: trimethylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, tri(t-butyl)ammonium tetraphenylborate, N,N-dimethylanilinium tetraphenylborate, N,N- diethylanilinium tetraphenylborate, N,N-dimethyl-(2,4,6-trimethylanilinium) tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafiuorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethyl-(2,4,6-trimethylaniliniurn) tetrakis(pentafluorophenyl) borate, trimethylammonium tetrakis-(2,3,4,6- tetrafluorophenylborate, triethylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, tripropylammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, tri(n- butyl)ammonium tetrakis-(2,3,4,6-tetrafluoro-phenyl) borate, dimethyl(t- butyl)ammonium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N,N- dimethylanilinium tetrakis-(2,3,4,6-tetrafluorophenyl) borate, N ,N- diethylanilinium tetrakis-(2₅3,4,6-tetrafluoro-phenyl) borate, and N,N-dimethyl- (2,4,6-trimethylanilinium)tetrakis-(2,3,4,6-tetrafluoropheny- 1) borate; dialkyl ammonium salts such as: di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate, and dicyclohexylammonium tetrakis(pentafluorophenyl) borate; and tri- substituted phosphonium salts such as: triphenylphosphonium tetrakis(pentafluorophenyl) borate, tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl) borate, and tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate.

[0061] In one possible embodiment, the ionic stoichiometric activator is N₅N- dimethylanilinium tetra(perfluorophenyl)borate or triphenylcarbenium tetra(perfluorophenyl)borate.

[0062] An activation method using ionizing ionic compounds not containing an active proton but capable of producing a metallocene catalyst cation and its non- coordinating anion are also contemplated, and are described in, for example, EP- A-O 426 637, EP-A-O 573 403 and U.S. Pat. No. 5,387,568. [0063] The term "non-coordinating anion" (NCA) means an anion which either does not coordinate to said cation or which is only weakly coordinated to said cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base. "Compatible" non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Non-coordinating anions useful in accordance with this invention are those that are compatible, stabilize the metal cation in balancing its ionic charge, yet retain sufficient lability to permit displacement by an ethylenically or acetylenically unsaturated monomer during polymerization. These types of cocatalysts may use tri-isobutyl aluminum or tri-octyl aluminum as a scavenger.

[0064] Processes of the current invention also can employ cocatalyst compounds or activator compounds that are initially neutral Lewis acids but form a cationic metal complex and a noncoordinating anion, or a zwitterionic complex upon reaction with the invention compounds. For example, tris(pentafluorophenyl) boron or aluminum act to abstract a hydrocarbyl or hydride ligand to yield an invention cationic metal complex and stabilizing noncoordinating anion, see EP- A-O 427 697 and EP-A-O 520 732 for illustrations of analogous Group-4 metallocene compounds. Also, see the methods and compounds of EP-A-O 495 375. For formation of zwitterionic complexes using analogous Group 4 compounds, see U.S. Pat. Nos. 5,624,878, 5,486,632, and 5,527,929. [0065] Additional neutral Lewis-acids are known in the art and are suitable for abstracting anionic ligands. See, for example, the review article by E. Y. -X. Chen and T. J. Marks, "Cocatalysts for Metal-Catalyzed Olefin Polymerization: Activators, Activation Processes, and Structure- Activity Relationships", Chem. Rev., 100, 1391 1434 (2000).

[0066] When the transition metal compound does not contain at least one hydride or hydrocarbyl ligand but does contain at least one functional group ligand, such as chloride, amido or alkoxy ligands, and the functional group ligand(s) are not capable of discrete ionizing abstraction with the ionizing, anion pre-cursor compounds, these functional group ligands can be converted via known alkylation reactions with organometallic compounds such as lithium or aluminum hydrides or alkyls, alkylalumoxanes, Grignard reagents, etc. See, for example, EP-A-O 500 944, EP-Al-O 570 982 and EP-Al-O 612 768 for analogous processes describing the reaction of alkyl aluminum compounds with analogous dihalide substituted metallocene compounds prior to or with the addition of activating noncoordinating anion precursor compounds. C. Non-ionizing Activators

[0067] Activators are typically strong Lewis-acids which may play either the role of ionizing or non-ionizing activator. Activators previously described as ionizing activators may also be used as non-ionizing activators.

[0068] Abstraction of formal neutral ligands may be achieved with Lewis acids that display an affinity for the formal neutral ligands. These Lewis acids are typically unsaturated or weakly coordinated. Examples of non-ionizing activators may include R^{1 O}(R")₃, where R¹⁰ is a group 13 element and R¹¹ is a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, or a functional group. Typically, R¹ ' is an arene or a perfluorinated arene. Non-ionizing activators may also include weakly coordinated transition metal compounds such as low valence olefin complexes. Non-limiting examples of non-ionizing activators include BMe₃, BEt₃, B(iBu)₃, BPh₃, B(C₆Fs)₃, AlMe₃, AlEt₃, Al(iBu)₃, AlPh₃, B(C₆F₅)₃, alumoxane, CuCl,

Ni(1 ,5-cyclooctadiene)₂.

[0069| Additional neutral Lewis-acids are known in the art and will be suitable for abstracting neutral ligands. See, for example, the review article by E. Y.-X. Chen and T. J. Marks, "Cocatalysts for Metal-Catalyzed Olefin Polymerization:

Activators, Activation Processes, and Structure-Activity Relationships", Chem.

Rev., 100, 1391 1434 (2000).

[0070] Illustrative non-ionizing activators include R¹⁰(R^π)₃, where R¹⁰ is a group

13 element and R¹¹ is a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, or a functional group. Typically, R¹¹ is an arene or a perfluorinated arene.

[0071] Alternative non-ionizing activators include B(R¹²)₃, where R¹² is an arene or a perfluorinated arene. Even more non-ionizing activators include B(C₆H₅)₃ and

B(C₆Fs)₃. A particularly preferred non-ionizing activator is B(C₆Fs)₃. More preferred activators are ionizing and non-ionizing activators based on perfluoroaryl borane and perfluoroaryl borates such as PhNMe₂H⁺B(C₆Fs)₄ ^",

(C₆Hs)₃C⁺B(C₆Fs)₄-, and B(C₆Fs)₃.

[0072] When the cations of noncoordinating anion precursors are Bronsted acids such as protons or protonated Lewis bases (excluding water), or reducible Lewis acids such as ferrocenium or silver cations, or alkali or alkaline earth metal cations such as those of sodium, magnesium or lithium, the catalyst-precursor-to-activator molar ratio may be any ratio. Combinations of the described activator compounds may also be used for activation. For example, tris(perfluorophenyl) boron can be used with methylalumoxane.

[0073] In general, the precursor compounds and the activator are combined in ratios of about 1000:1 to about 0.5:1. In an embodiment the precursor compounds and the activator are combined in a ratio of about 300: 1 to about 1 :1, alternatively about 150: 1 to about 1 :1, for boranes, borates, aluminates, etc. the ratio is about

1 :1 to about 10:1 and for alkyl aluminum compounds (such as diethylaluminum chloride combined with water) the ratio is about 0.5:1 to about 10: 1.

[0074] At times two or more catalyst precursor compounds may be present. In some embodiments, the ratio of the first catalyst precursor compound to the second or additional catalyst precursor compounds is 5:95 to 95:5, alternatively 25:75 to 75:25, in other embodiment 40:60 to 60:40.

[0075] The catalyst compositions of this invention may include a support material or carrier. For example, the one or more catalyst components and/or one or more activators may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, one or more supports or carriers.

[0076] The support material is any of the conventional support materials. The supported material may be a porous support material, for example, talc, inorganic oxides and inorganic chlorides. Other support materials may include resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.

[0077] Illustrative support materials such as inorganic oxides include Group 2, 3, 4, 5, 13 or 14 metal oxides. The preferred supports include silica, which may or may not be dehydrated, fumed silica, alumina (see, for example, WO 99/60033), silica-alumina and mixtures thereof. Other useful supports include magnesia, titania, zirconia, magnesium chloride (U.S. Pat. No. 5,965,477), montmorillonite (European Patent EP-Bl 0 511 665), phyllosilicate, zeolites, talc, clays (U.S. Pat. No. 6,034,187) and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica-titania and the like. Additional support materials may include those porous acrylic polymers described in EP 0 767 184 Bl, which is incorporated herein by reference. Other support materials include nanocomposites as disclosed in WO 99/47598, aerogels as disclosed in WO 99/48605, spherulites as disclosed in U.S. Pat. No. 5,972,510 and polymeric beads as disclosed in WO 99/50311.

[0078| The support material, such as an inorganic oxide, may have a surface area in the range of from about 10 to about 700 m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 5 to about 500 μm. The surface area of the support material may be in the range of from about 50 to about 500 m²/g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 μm. In another class of embodiments, the surface area of the support material may be in the range from about 100 to about 400 m²/g, pore volume from about 0.8 to about 3.0 cc/g and average particle size is from about 5 to about 100 μm. The average pore size of the carrier of the invention typically has pore size in the range of from 10 to 1000 A, alternatively 50 to about 500 A₅ and in some embodiment 75 to about 350 A.

Polymerization

10079] The polymerization processes of the invention may be carried out in solution, in bulk, in suspension, in gas-phase, in slurry-phase, as a high-pressure process, or any combinations thereof. Generally solution, gas-phase and slurry- phase processes are preferred. The processes may be carried out in any one or more stages and/or in any one or more reactors having any one or more reaction zones.

[0080] For example, certain polyethylenes can be made using a gas phase polymerization process, e.g., utilizing a fluidized bed reactor. This type reactor and means for operating the reactor are well known and completely described in, for example, U.S. Patent Nos. 3,709,853; 4,003,712; 4,011,382; 4,302,566; 4,543,399; 4,882,400; 5,352,749; 5,541,270; EP-A- 0 802 202 and Belgian Patent No. 839,380. These patents disclose gas phase polymerization processes wherein the polymerization medium is either mechanically agitated or fluidized by the continuous flow of the gaseous monomer and diluent.

[0081] A polymerization process may be effected as a continuous gas phase process such as a fluid bed process. A fluid bed reactor may comprise a reaction zone and a so-called velocity reduction zone. The reaction zone may comprise a bed of growing polymer particles, formed polymer particles and a minor amount of catalyst particles fluidized by the continuous flow of the gaseous monomer and diluent to remove heat of polymerization through the reaction zone. Optionally, some of the re-circulated gases may be cooled and compressed to form liquids that increase the heat removal capacity of the circulating gas stream when readmitted to the reaction zone. A suitable rate of gas flow may be readily determined by simple experiment. Make up of gaseous monomer to the circulating gas stream is at a rate equal to the rate at which particulate polymer product and monomer associated therewith is withdrawn from the reactor and the composition of the gas passing through the reactor is adjusted to maintain an essentially steady state gaseous composition within the reaction zone. The gas leaving the reaction zone is passed to the velocity reduction zone where entrained particles are removed. Finer entrained particles and dust may be removed in a cyclone and/or fine filter. The gas is passed through a heat exchanger wherein the heat of polymerization is removed, compressed in a compressor and then returned to the reaction zone. [0082] A slurry polymerization process can also be used. A slurry polymerization process generally uses pressures in the range of from 1 to 50 atmospheres and even greater and temperatures in the range of O⁰C to 12O⁰C, and more particularly from 3O⁰C to 100⁰C. In a slurry polymerization, a suspension of solid, particulate polymer is formed in a liquid polymerization diluent medium to which ethylene and comonomers and often hydrogen along with catalyst are added. The suspension including diluent is intermittently or continuously removed from the reactor where the volatile components are separated from the polymer and recycled, optionally after a distillation, to the reactor. The liquid diluent employed in the polymerization medium is typically an alkane having from 3 to 7 carbon atoms, a branched alkane in one embodiment. The medium employed should be liquid under the conditions of polymerization and relatively inert. When a propane medium is used the process must be operated above the reaction diluent critical temperature and pressure. In one embodiment, a hexane, isopentane or isobutane medium is employed.

[0083] Hydrogen gas is often used in olefin polymerization to control the final properties of the polyolefin, such as described in Polypropylene Handbook 76-78 (Hanser Publishers, 1996). Using certain catalyst systems, increasing concentrations (partial pressures) of hydrogen can increase the melt flow rate (MFR) (also referred to herein as melt index (MI)) of the polyolefin generated. The MFR or MI can thus be influenced by the hydrogen concentration. [0084] Further, it is common to use a staged reactor employing two or more reactors in series, wherein one reactor may produce, for example, a high molecular weight component and another reactor may produce a low molecular weight component. In one embodiment of the invention, the polyolefin is produced using a staged gas phase reactor. Such polymerization systems are described in, for example, 2 Metallocene-Based Polyolefins 366-378 (John Scheirs & W. Kaminsky, eds. John Wiley & Sons, Ltd. 2000); U.S. Patent Nos. 5,665,818, 5,677,375; 6,472,484; EP 0 517 868 and EP-A-O 794 200.

Process Aids

[0085] As used herein, the terms process aid, processing aid and polymer processing aid are used interchangeably and is given the broadest definition including but not limited to any commercially available process aid or any additive that can aid the extrusion and processing of a polymer resin including, but not limited to, for example, carboxylate metal salts. Carboxylate Metal Salt

[0086] Carboxylate metal salts are well known in the art as additives for use with polyolefins. It has been surprisingly found that films of the present invention formed in the presence of metal stearates show improved quality as compared to films produced from commercial processing aids. Aspects of the improved quality include, but are not limited to, reduced melt fracture, reduced head pressure, reduced motor load, increased gloss and reduced haze, increased thermal stability and increased color stability.

[0087] For the purposes of this patent specification and appended claims the term "carboxylate metal salt" is any mono- or di- or tri-carboxylic acid salt with a metal portion from the Periodic Table of Elements. Non-limiting examples include saturated, unsaturated, aliphatic, aromatic or saturated cyclic carboxylic acid salts where the carboxylate ligand has from 2 to 24 carbon atoms, such as acetate, propionate, butyrate, valerate, pivalate, caproate, isobuytlacetate, t-butyl-acetate, caprylate, heptanate, pelargonate, undecanoate, oleate, octoate, palmitate, myristate, margarate, stearate, arachate and tercosanoate. Non-limiting examples of the metal portion includes a metal from the Periodic Table of Elements selected from the group of Al, Mg, Ca, Sr, Sn, Ti, V, Ba, Zn, Cd, Hg, Mn, Fe, Co, Ni, Pd, Li and Na.

[0088] In one embodiment, the carboxylate metal salt is represented by the following general formula: M(Q)x (OOCR)y where M is a metal from Groups 1 to 16 and the Lanthanide and Actinide series, preferably from Groups 1 to 7 and 13 to 16, more preferably from Groups 3 to 7 and 13 to 16, even more preferably Groups 2 and 13, and most preferably Group 13; Q is halogen, hydrogen, a hydroxy or hydroxide, alkyl, alkoxy, aryloxy, siloxy, silane or sulfonate group R is a hydrocarbyl radical having from 2 to 100 carbon atoms, preferably 4 to 50 carbon atoms; and x is an integer from 0 to 3 and y is an integer from 1 to 4 and the sum of x and y is equal to the valence of the metal. In a preferred embodiment of the above formula y is an integer from 1 to 3, preferably 1 to 2, especially where M is a Group 13 metal.

[0089] Non-limiting examples of R in the above formula include hydrocarbyl radicals having 2 to 100 carbon atoms that include alkyl, aryl, aromatic, aliphatic, cyclic, saturated or unsaturated hydrocarbyl radicals. In an embodiment of the invention, R is a hydrocarbyl radical having greater than or equal to 8 carbon atoms, preferably greater than or equal to 12 carbon atoms and more preferably greater than or equal to 17 carbon atoms. In another embodiment R is a hydrocarbyl radical having from 17 to 90 carbon atoms, preferably 17 to 72, and most preferably from 17 to 54 carbon atoms.

[0090] Non-limiting examples of Q in the above formula include one or more, same or different, hydrocarbon containing group such as alkyl, cycloalkyl, aryl, alkenyl, arylalkyl, arylalkenyl or alkylaryl, alkylsilane, arylsilane, alkylamine, arylamine, alkyl phosphide, alkoxy having from 1 to 30 carbon atoms. The hydrocarbon containing group may be linear, branched, or even substituted. Also, Q in one embodiment is an inorganic group such as a halide, sulfate or phosphate. [00911 In a class of embodiments, carboxylate metal salts may be aluminum carboxylates such as aluminum mono, di- and tri- stearates, aluminum octoates, oleates and cyclohexylbutyrates. In a more preferred embodiment, the carboxylate metal salt is (CH₃(CH₂)I₆COO)₃ Al, a aluminum tri-stearate, (CH₃ (CH₂)i₆COO)₂ — Al-OH, a aluminum di-stearate, and a CH₃(CH₂)i₆COO~Al(OH)₂, an aluminum mono-stearate.

[0092| In another class of embodiments, carboxylate metal salts may be zinc carboxylates such as zinc mono, and di-stearates, zinc octoates, oleates and cyclohexylbutyrates. In a more preferred embodiment, the carboxylate metal salt is (CH₃(CH₂)_I6COO)₂ Zn, a zinc di-stearate, and a CH₃(CH₂)i₆COO~Zn(OH), a zinc mono-stearate.

|0093] In another class of embodiments, carboxylate metal salts may be calcium carboxylates such as calcium mono, and di-stearates, calcium octoates, oleates and cyclohexylbutyrates. In a more preferred embodiment, the carboxylate metal salt is (CH₃(CH₂)I₆COO)₂ Ca, a calcium di-stearate, and a CH₃(CH₂) _I6COO-Ca(OH), a calcium mono-stearate.

[0094] In one embodiment the carboxylate metal salt has a melting point from about 30° C to about 250° C, more preferably from about 37° C to about 220° C, even more preferably from about 50° C to about 200° C, and most preferably from about 100° C to about 200° C.

[0095] Other examples of carboxylate metal salts include titanium stearates, tin stearates, magnesium stearates, sodium stearates boron stearate and strontium stearates.

Polymeric Compositions

[0096] In embodiments of the invention, the LLDPE or mLLDPE may be blended with any combination carboxylate metal salts in an amount sufficient to achieve the desired properties, such as reduction in melt fracture, reduction in motor load, extruder pressure, haze level, reblock gloss, thermal stability, and color stability. In some embodiments, one or more carboxylate metal salts may be present in the LLDPE from 0.01 to 10 weight percent in one embodiment, and from 0.01 to 5 weight percent in another embodiment, and from 0.05 to 5 weight percent in yet another embodiment, wherein a desirable range may include any combination of any upper weight percent limit with any lower weight percent limit. |0097] Antioxidants and stabilizers such as organic phosphites, hindered amines, and phenolic antioxidants may also be present in the LLDPE or mLLDPE composition of the present invention. Suitable levels range from 0.001 to 5 weight percent in one embodiment, from 0.01 to 0.8 weight percent in another embodiment, and from 0.02 to 0.5 weight percent in yet another embodiment. Other common additives in the polyolefin industry may be present in LLDPE or mLLDPE composition from 0.01 to 50 weight percent in one embodiment, and from 0.1 to 20 weight percent in another embodiment, and from 1 to 5 weight percent in yet another embodiment, wherein a desirable range may include any combination of any upper weight percent limit with any lower weight percent limit.

[0098] The LLDPE or mLLDPE composition may further contain additives such as slip, antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers, antistats, neutralizers, lubricants, surfactants, pigments, dyes and nucleating agents. Ono- limiting examples include silicon dioxide, synthetic silica, titanium dioxide, polydimethylsiloxane, calcium carbonate, talc, BaSO₄, diatomaceous earth, wax, carbon black, flame retarding additives, low molecular weight resins, hydrocarbon resins, glass beads and the like. The additives may be present in the typically effective amounts well known in the art, such as 0.001 weight % to 10 weight %. |0099] Fillers may be present from 0.1 to 50 weight percent in one embodiment, and from 0.1 to 25 weight percent of the composition in another embodiment, and from 0.2 to 10 weight percent in yet another embodiment. Desirable fillers include, but are not limited to, titanium dioxide, silicon carbide, silica (and other oxides of silica, precipitated or not), antimony oxide, lead carbonate, zinc white, lithopone, zircon, corundum, spinel, apatite, Barytes powder, barium sulfate, magnesiter, carbon black, dolomite, calcium carbonate, talc and hydrotalcite compounds of the ions Mg, Ca, or Zn with Al, Cr or Fe and CO₃ and/or HPO₄, hydrated or not; quartz powder, hydrochloric magnesium carbonate, glass fibers, clays, alumina, and other metal oxides and carbonates, metal hydroxides, chrome, phosphorous and brominated flame retardants, antimony trioxide, silica, silicone, and blends thereof. These fillers may particularly include any other fillers and porous fillers and supports known in the art.

Resin Properties and Film

(00100] Film and resin properties can be measured by techniques well known in the art, and specifically described in the Examples herein. It has been surprisingly found that resins show enhanced thermal stability and enhanced color stability in the presence of metal carboxylates. Furthermore, it has been surprisingly found that films of the present invention formed in the presence of metal carboxylates show improved quality as compared to films produced from commercial processing aids. Aspects of the improved film quality include, but are not limited to, reduced melt fracture, reduced head pressure, reduced motor load, increased gloss and reduced haze. Aspects of the improved film quality include, but are not limited to, thermal stability and enhanced color stability.

100101] The resin and film data were obtained according to the following testing protocols:

Density (g/cc): ASTM D- 1505;

Melt Indices and Melt Flow Ratios (dg/min): ASTM D-1238

Dart Drop Impact F50 (g/mil): ASTM D- 1709 A;

Elmendorf Tear (g/mil): ASTM D- 1922;

Secant Modulus (1%) (psi):ASTM D-882;

Tensile @ Yield (psi): ASTM D-882;

Ultimate Tensile (psi): ASTM D-882;

Ultimate Elongation (%): ASTM D-882

Haze (%): ASTM D- 1003

Gloss at 45° (%): ASTM D-2457

[00102] Heat seal and hot tack measurements were made according to the following procedure. The films were conditioned for heat seal and hot tack measurements by aging the samples for at least 40 hours at 23 °C and 50% humidity before testing. A Heatsealer (Model PC, available from Theller) was used to measure the heat seal characteristics of the films. The samples were cut into 20.3 cm by 15.2 cm (8 inch by 6 inch) sheets and sandwiched between Mylar sheets so that the inside surfaces of the blown films were in contact. The seal was created by placing the Mylar-covered films were between 12.7 cm (5 inch) long seal bars and a pressure of 0.5 MPa (73 psi) was applied for 1.0 seconds. Seals were created at temperatures ranging from 75°C to 150°C, and the seal length was approximately 25.4 mm (1 inch). The heat seals were then aged for a minimum of 24 hours at 23 C and 50% humidity and the seal strength was measured at a rate of 508 mm/min (20 inch/min). Hot tack curves were generated on a J&B Instruments hot tack tester using 15-mm wide film samples backed with 50 mm thick PET tape. The seal time and pressure was 0.5 s and 0.5 MPa, respectively. The seal strength was measured after 0.4 s delay time at a speed of 200 mm/min. [00103] The molecular weights and molecular weight distributions of the resins described in the present invention were characterized using a High Temperature Size Exclusion Chromatograph (PL 220, Polymer Laboratories), equipped with a differential refractive index detector (DRI). Three Polymer Laboratories PL gel 10mm Mixed-B columns were used. The nominal flow rate was 1.0 cm³ /min, and the nominal injection volume was 300 mL. The various transfer lines, columns and differential refractometer (the DRI detector) were contained in an oven maintained at 140 ⁰C.

[00104] Polymer solutions were prepared in filtered 1,2,4-Trichlorobenzene (TCB) containing 1000 ppm of butylated hydroxy toluene (BHT). The same solvent was used as the SEC eluent. Polymer solutions were prepared by dissolving the desired amount of dry polymer in the appropriate volume of SEC eluent to yield concentrations ranging from 0.5 to 1.5 mg/mL. The sample mixtures were heated at 140 ⁰C with continuous agitation for about 2 to 2.5 hours. Sample solution will be filtered off-line before injecting to GPC with 2μm filter using the Polymer Labs SP260 Sample Prep Station.

[00105] The separation efficiency of the column set was calibrated using a series of narrow MWD polystyrene standards, which reflects the expected MW range for samples and the exclusion limits of the column set. Eighteen individual polystyrene standards, ranging from Mp ~580 to 10,000,000, were used to generate the calibration curve. The polystyrene standards are obtained from Polymer Laboratories (Amherst, MA). To assure internal consistency, the flow rate is corrected for each calibrant run to give a common peak position for the flow rate marker (taken to be the positive inject peak) before determining the retention volume for each polystyrene standard. The flow marker peak position thus assigned was also used to correct the flow rate when analyzing samples therefore, it is an essential part of the calibration procedure. A calibration curve (log Mp vs. retention volume) is generated by recording the retention volume at the peak in the DRI signal for each PS standard, and fitting this data set to a 2nd- order polynomial. The equivalent polyethylene molecular weights are determined by using the following Mark-Houwink coefficients:

k (dL/g) A

PS 1 .75 x 10 -4 0. 67

PE 5 .79 x 10 -4 0. 695

Producing Films and Coatings

[00106] Films may be formed by any number of well known extrusion or coextrusion techniques. Any of the blown or chill roll techniques commonly used are suitable. For example, the composition can be extruded in a molten state through a flat die and then cooled to form a film. Alternatively, the composition can be extruded in a molten state through an annular die and then blown and cooled to form a tubular, blown film, which can then be axially slit and unfolded to form a flat film. Films of the invention may be unoriented, uniaxially oriented or biaxially oriented. Physical properties of the film may vary from those of the polymer blend, depending on the film forming techniques used.

EXAMPLES

EXAMPLE 1

[00107] The granular EXCEED 1018 SB feedstock was formulated with 0.05 % IRGANOX 1076, 0.2 % WESTON 399, and 0.5% OPTIBLOCK 10. Compounding and of the resins was carried out on a Werner & Pfleiderer ZSK 57rnm twin screw extruder under a nitrogen blanket. Output rate was 68.1 kg/h (150 Ib/h) and the melt temperature was about 210°C. A purge/ cleaning resin was formulated with 5% diatomaceous earth instead of the OPTIBLOCK 10. 100108] To produce the films for Examples 3 - 8, the resins were extruded into film using a 88.9 mm (3.5 inch) Sano blown film line (24:1 L:D) equipped with a 25.4 mm (10 inch) oscillating die and a Sano dual orifice non-rotating, non-adjustable air ring. Output rate and other extrusion conditions are listed in Tables 2 and 5. [00109] To produce the films for Example 9, the resins were extruded into film using a 63.5 mm (2.5 inch) Battenfield Gloucester blown film line (30:1 L:D) equipped with a 152.4 mm (6 inch) oscillating die and a Future Design air ring. Output rate was 3.36 kg/mm (188 lb/in) (or 7 g/mm/mm (10 lb/in/in) die circumference). The specific extrusion conditions are listed in Tables 7 and 8. [00110] For the film trials on the Sano line, the Zinc Stearate (St=Stearate), Calcium Stearate (St=Stearate), and the DYNAMAR FX5920A (available from 3M company, St. Paul, MN) were added via a masterbatch that contained 3% Zinc Stearate, or 3% Calcium Stearate, or 3% DYNAMAR FX5920A in EXCEED 1018 SB seedbed resin. The master batch was added by dry blending in a double cone mixer prior to film production.

100111] The Aluminum Stearate was from the same batch as used for the Gloucester film trials described below. Table 1 below lists the resin formulations for the purge/cleaning resin containing 5% diatomaceous earth.

EXAMPLE 2

[00112] Sample designations and process aid concentrations are indicated below in Table 1. All samples contained 0.05 wt% IRGANOX 1076, 0.2 wt% WESTON 399.

TABLE 1

Sample Purge Control Control 0027- 0027- 0027-

Resin #1 #2 132-040 132-040 132-040

IRGANOX 0.05% 0.05% 0.05% 0.05% 0.05% 0.05%

1076

WESTON 0.2% 0.2% 0.2% 0.2% 0.2% 0.2%

399

OPTIBLOCK 0.5% 0.5% 0.5% 0.5% 0.5%

10

Zinc 0.1%

Stearate

Calcium 0.1%

Stearate

Aluminum 0.1%

Distearate

DYNAMAR 0.08%

FX5920 A

Diatomaceous 5% earth

EXAMPLE 3 [00113] Film Blowing Sano Line - films were made on the Sano film line using two different settings: die gaps of 40 and 60 mil, output rates of 8 and 10 lb/hr/inch die, and melt temperature of 395 and 420 ⁰F, respectively. The target film gauge was 1 mil for all films. Details and run conditions for each film are listed in Table 2 below.

|00ll4l The films were made according to the following procedure: (1) The purge resin was run for at least 1 hour to remove residual process aid coating from the die surface; (2) Control resin #1 was introduced and run for at least 1 hour to ensure 100% melt fracture of the base resin; (3) The process aid containing resin was introduced; and (4) The time when melt fracture was 50% and when MF free film was obtained was recorded. Films were taken after all parameters stabilized (approximately 2 hrs). Steps 1-4 were repeated for all experimental formulations. 100115] First Sano run (40 mil die gap / 395 ⁰F / 8 lbs/in die) - All metal stearates and DYNAMAR FX5920 operated to remove melt fracture within a short period of time. The time to obtain completely melt fracture free film was about 40 minutes for calcium stearate CaSt and zinc stearate (ZnSt) containing resins and about 20 min for the samples with aluminum Stearate (AlSt) and DYNAMAR FX5920A.

[00116] In all instances, the films form the purge resin showed severe melt fracture and grey color 5 to 10 minutes after it was fed. Melt fracture remained 100% for at least 1 hour after the control #1 resin was introduced. [00117) Table 2 shows the process conditions for the experimental films as well as control resin #1. The data for the experimental samples reflect the process conditions of step 3 from the above procedure, i.e., after running the purge resin and the control resin #1 for 1 hour each. The only slight deviation from this procedure was the ZnSt containing resin, 00270-134-032, which was introduced after 2 hours of running control #1 resin. The data was recorded after one hour after all parameters stabilized.

[00118] Both the metal stearates and DYNAMAR FX5920 caused a decrease in extruder pressure compared to the control #1 resin. The decrease for the AlSt containing sample was more than 20% while CaSt, and DYNAMAR FX5920 showed a pressure drop of about 10%. It should be noted, however, that the output with DYNAMAR FX5920A was somewhat higher. There was no difference in melt temperature between these films.

100119] Film properties - The film properties of the AlSt films differ somewhat from the other samples. Dart impact strength of the AlSt film is about 20% lower than that of the film with DYNAMAR FX5920A. The AlSt film shows the best optical properties with haze of about 7% while other surface properties, such as friction coefficient or Reblock are similar.

TABLE 2

Film ID 00270-134 - -021 -042 032 132-031 051

ZnSt CaSt

1000 1000 AlSt FX5920 process aid none ppm ppm 1000 ppm 800 ppm

Film Line SANO SANO SANO SANO SANO

Die Gap (mil) 40 40 40 40 40

Target Output

(lb/h/in) 8 8 8 8 8

BUR 2.5 2.5 2.5 2.5 2.5

Target Gauge (mil) 1 1 1 1 1

Comments

100 %

Time for 100% MF MF after free film 2 h 45 min 45 min 20 min 20 min

Shear rate at die (s^"1) 251.5 249.3 256.9 257.96 279

Film collected after no Film after 2 h after 2 h after 1 h after 1 h

Temperature Profile

(⁰F)

BZl 310 309 310 309 310

BZ2 420 420 420 420 420

BZ3 390 390 390 390 390

BZ4 375 375 375 375 375

BZ5 376 374 374 376 373

Screen Body 390 389 390 391 391

Adapter 390 390 390 390 390 Die Body Out Mid 392 391 392 392 392

Inside Stem 446 445 447 443 444

Inside Die Mid 443 446 444 441 447

Torque (%) 33.5 33.4 33.2 33.6 34.2

Head Pressure (psi) 6540 6040 5740 5180 6000

Melt Temperature

(⁰F) 393 396 395 394 396

HP 16 20 19 20 19

HP/RPM 0.48 0.48 0.46 0.46 0.46 lb/h/RPM 6.84 5.48 5.67 5.49 6.52 lb/HP-h 14.55 11.52 12.51 11.95 13.60 lbs/hr/inch die. 7.41 7.34 7.57 7.61 8.23

Screw Speed (rpm) 34.0 42.0 41.9 43.5 39.5

Line Speed (fpm) 131 126 126 131 131

Output Rate (lb/h) 233 231 238 239 259

Gauge (mils) 0.93 1.00 1.00 1.02 1.06

Air Temp (F) 50 50 50 50 50

Air (% speed) 32.8 32.8 32.8 32.8 32.8

FLH (in) 35 35 35 35 35

EXAMPLE 4

[00120] Table 3 lists the mechanical properties from the first Sano trial. The mechanical properties of the CaSt, ZnSt and DYNAMAR FX5920A films are similar

TABLE 3

00270-134- 00270-134- 00270-132- 00270-134- Sample ID

042 032 031 051 process aid 1000 ppm lOOO ppm 1000 ppm 800 ppm ZnSt CaSt AlSt FX5920

1% Secant

Modulus (psi) 24,356 24,240 23,900 24,232

MD

1% Secant Modulus (psi) 24,441 24,772 23,751 25,132

TD Yield Strength

1,222 1,239 1,256 1,237

(psi) MD Yield Strength

1,221 1,223 1,250 1,258

(psi) TD Elongation @

5.7 5.9 6.0 6.0 Yield (%) MD

Elongation @

5.8 5.6 5.8 5.8

Yield (%) TD

Tensile Strength

6,956 6,978 7,248 7,501

(psi) MD

Tensile Strength

6,208 5,981 6,975 6,491

(psi) TD

Elongation @ Break (%) MD

Elongation @

540 547 542 555

Break (%) TD

Elmendorf Tear

303 295 299 277

(g/mil) MD

Elmendorf Tear

354 363 363 344

(g/mil) TD

Dart Drop

424 476 351 461

(g/mil)

Puncture - Method B Peak Load (lbs) 9.5 9.9 10.0 9.4

Peak/mil

9.4 9.4 10.0 8.7 (lbs/mil)

Break Energy

20.4 22.3 21.9 19.: (in-lb)

Break

Energy/mil (in- 20.2 21.2 21.9 17.1 lb/mil)

Shrink (%) MD 39 41 40 42

Shrink (%) TD 10 8 11 8

Gauge Mic

1.01 1.05 1 1.0! (mils)

EXAMPLE 5

[00121] Films with stearates show lower haze and higher gloss compared to the DYNAMAR FX5920A films. Table 4 lists optical and surface properties including reblock and coefficient of friction while. The heat seal and hot tack properties of the CaSt, ZnSt and DYNAMAR FX5920A films are similar (see FIGs. 1 and 2) but one data point in the AlSt film indicates a 5 ⁰C higher heat seal initiation temperature.

TABLE 4

00270-134- 00270-134- 00270-132- 00270-134-

Sample ID 042 032 031 051 lOOO ppm 1000 ppm 1000 ppm 800 ppm process aid ZnSt CaSt AlSt FX5920

Gloss (GU) MD 67 58 72 51 Gloss (GU) TD 68 59 72 51

Haze(%) 9.2 10.8 7.2 13.8 Clarity 93.6 92.2 94.2 91.2

Transmittance 92.6 92.6 92.7 92.5

Internal Haze 1.1 1.2 0.9 1.5

Reblock (g) 18.4 15.3 15.1 15.4

COF(I/O) Static 0.81 0.79 0.86 0.76

COF(I/O)

0.75 0.73 0.79 0.71 Kinetic

Gauge Mic

1.01 1.05 1 1.08 (mils)

EXAMPLE 6

[00122] Now referring to Second Sano run (60 mil die gap / 420 ⁰F / 10 lbs/in die) - This second trial was conducted to determine if higher metal stearate concentrations (0.2%) and higher extrusion temperatures lead to die lip build-up or significant changes in the film's properties. For this trial, two stearate resins with 0.2% ZnSt, and 0.2% CaSt, respectively were prepared using the masterbatch and dry blending in a double cone mixer prior to film production. [00123] After running the purge and control resins, the CaSt and ZnSt containing resins were run for 4 hours each. After 8 hours of operation with 0.2% of a metal stearate, there was no visible build-up on the die exit.

[00124] Table 5 shows the process conditions for the second Sano trial and Table 6 comparing mechanical data. The only notable difference is a lower reblock value of the films with higher ZnSt concentration. All other properties are very similar. Heat seal properties of the film with 0.2% ZnSt are included in FIGs. 3 and 4. There is practically no difference to the films with 0.1% ZnSt concentration. High melt temperature and longer run duration did not result in die lip build-up. TABLE 5

Film ID 00270-134 - 081 -061 -071

FX5920 ZnSt CaSt process aid 800 ppm 2000 ppm 2000 ppm

Film Line SANO SANO SANO

Die Gap (mil) 60 60 60

Target Output (lb/h/in) 10 10 10

BUR 2.5 2.5 2.5

Target Gauge (mil) 1 1 1

Comments

Shear rate at die (s^~ ) 146 140.5 144.3

Film collected after after 1 h after 4 h after 4 h

Temperature Profile

(°F)

BZl 310 309 309

BZ2 460 460 460

BZ3 450 451 449

BZ4 450 450 450

BZ5 450 452 449

Screen Body 410 410 410

Adapter 409 409 410

Die Body Out Mid 413 413 414

Inside Stem 471 481 474

Inside Die Mid 461 481 478

Torque (%) 31.1 30.6 30.3

Head Pressure (psi) 3820 4520 4270

Melt Temperature (⁰F) 417 421 420

HP 19 21 20 HP/RPM 0.44 0.43 0.42 lb/h/RPM 7.03 5.97 6.27 lb/HP-h 16.03 13.94 15.02 lb/h/in die cir. 9.70 9.32 9.56

Screw Speed (rpm) 43.3 48.9 47.9

Line Speed (fpm) 155 154 154

Output Rate (lb/h) 305 293 301

Gauge (mils) 1.08 1.06 1.06

Air Temp (F) 50 50 50

Air (% speed) 32.8 32.8 32.8

FLH (in) 34 35 34

EXAMPLE 7

100125] Shown in Table 6 below is a comparison of the mechanical properties the films produced from ZnSt during first and second Sano trials.

TABLE 6

270-134-042

270-134-061

Sample ID First Second Sano trial Sano trial

1000 ppm ZnSt 2000 ppm ZnSt

1 % Secant Modulus

24,356 23,647 (psi) MD

1% Secant Modulus

24,441 24,066 (psi) TD

Yield Strength (psi)

1,222 1,198 MD

Yield Strength (psi) 1,221 1,213 TD

Elongation @ Yield

J S.7 / 5.8

(%) MD

Elongation @ Yield

J « . C O 5.8

(%) TD

Tensile Strength

6,956 6,628 (psi) MD

Tensile Strength

6,208 6,349 (psi) TD

Elongation @ Break

(%) MD

Elongation @ Break

CΛ ft 541

(%) TD

Elmendorf Tear

303 288 (g/mil) MD

Elmendorf Tear

354 359 (g/mil) TD

Dart Drop (g/mil) 424 447

Puncture - Method B

Peak Load (lbs) 9.5 9.7

Peak/mil (lbs/mil) 9.4 9.3

Break Energy (in-lb) 20.4 21.7

Break Energy /mil

9 Δ0KJ.9Δ 20.7

(in-lb/mil)

Shrink (%) MD 39 41

Shrink (%) TD 10 7

Gauge Mic (mils) 1.01 1.05

EXAMPLE 8

100126] Shown in Table 7 below is a comparison of the optical and surface properties of the films produced from ZnSt during first and second Sano trials. TABLE 7

270-134-042

270-134-061

Sample ID First Second Sano trial Sano trial

1000 ppm ZnSt 2000 ppm ZnSt

Gloss (GU) MD 67 60

Gloss (GU) TD 68 60

Haze(%) 9.2 10.6

Clarity 93.6 91.9

Transmittance 92.6 92.6

Internal Haze 1.1 1.3

Reblock (g) 18.4 5.9

COF(I/O) Static 0.81 0.78

COF(I/O) Kinetic 0.75 0.73

Gauge Mic (mils) 1.01 1.05

EXAMPLE 9

[00127] Film Blowing: Gloucester Line - Two film blowing runs were conducted on the Gloucester line using different die gaps, 45 and 30 mils, resulting in shear rates at the die exit of about 260 and 600 s^"1, respectively. The output rate was about 10 lbs/hr/inch die in both cases. Details and run conditions for each film are listed in Tables 8 and 9. Shown in Table 8 are process conditions for a first Gloucester line trial in which AlSt did not remove melt fracture. Also shown below is Table 9 indicating process conditions for a second Gloucester line trial showing higher shear rate and higher melt temperature). The stearates and the DYNAMAR FX5920 were equally effective for melt fracture removal. [00128) For the Gloucester trial, the metal stearate and DYNAMAR FX5920 was added to the respective resin during the compounding step along with the IRGANOX 1076 (0.05%), WESTON 399 (0.2 %), and OPTIBLOCK 10 (0.5 %). The base resin was granular EXCEED 1018 SB. Compounding and pelleting was done on a ZSK 57 mm twin-screw extruder under a nitrogen blanket. The purge/cleaning resin contained 5% diatomaceous earth rather than OPTIBLOCK 10.

[00129] Films were made according to the procedure described above. Similar to the trial on the Sano line, the films from the purge resin showed severe melt fracture and the melt fracture remained 100% for 1 hour after the control #1 resin was introduced.

100130] In the first Gloucester trial, the ZnSt sample removed melt fracture while the AlSt sample still showed 100% melt fracture after two hours of operation. In the second trial, however, both the ZnSt and the AlSt were very effective and the time for removing melt fracture was 30 min and 20 min, respectively. The root cause for the discrepancy with AlSt results from the first Gloucester trial is currently under investigation.

TABLE 8

Film ID 00270- 132 - -021 -031 -041 -051

ZnSt AlSt FX5920 process aid no ne 1000 ppm 1000 ppm 800 ppm

Film Line 2.5" BGE 2.5" BGE 2.5" BGE 2.5" BGE Die Gap (mil) 45 45 45 45

BUR 2.5 2.5 2.5 2.5 Target Gauge

(mil)

Comments

Time for 100% 100 % MF 2 h 100 % MF 1 h MF free film after 2 h after 2 h

Shear rate at die

(S-¹) 262.7 269.8 255.6 279

Film collected after no Film after 2 h after 2 h after 1 h

Temperature

Profile (⁰F)

Feedthroat 85 78 78 85

BZl 315 311 311 311

BZ2 393 400 400 400

BZ3 374 375 375 375

BZ4 330 330 330 330

BZ5 330 330 330 330

Screen Changer 390 390 390 390

Adapter 390 390 390 390

Rotator 391 391 391 391

Lower Die 400 400 400 400

Upper Die 400 400 400 400

Inside Die 423 421 426 420

Melt Temperature

(⁰F) 414 412 417 413

Output (lb/h) 183 190 180 197

Head Pressure

(psi) 5200 4770 4870 4700

Die Pressure (psi) 3500 3300 3500 3370

Motor Load (%) 55.2 60.7 62.5 61.7

Screw Speed

(φm) 60.9 66.5 72.5 65.5

Line Speed (fpm) 166 166 160 159.1

Gauge (mils) 1.063 1.083 1.181 1.22 FLH (in) 21 21 21 24

Air (%) 62.9 62.9 62.5 62.5

ESO (lb/hp-h) 10.25 9.33 7.85 9.22

Spec. Output

(lb/h/rpm) 2.99 2.99 2.59 3 lbs/hr/inch die 9.68 10.57 9.98 10.45

TABLE 9

Film ID 00270-

-021 -031 -041 -051 141 -

ZnSt AlSt Fx5920 process aid none

1000 ppm 1000 ppm 800 ppm

Film Line 22..55"" BBGGEE 2.5" BGE 2.5" BGE 2.5" BGE

Die Gap (mil) 30 30 30 30

BUR 2.5 2.5 2.5 2.5

Target Gauge 1 1 1 1 1

(mil)

Comments

Time for 100% 100 % MF

30 min 20 min 20 min

MF free film after 2 h

Shear rate at die

578 597 607 610 (S-¹)

Film collected no Film after 1 h after 1 h after 1 h after

Temperature Profile (⁰F) Feedthroat 84 77 77 87 BZl 308 308 313 310

BZ2 400 400 400 400

BZ3 375 375 375 375

BZ4 330 330 330 330

BZ5 330 330 330 330

Screen Changer 410 410 410 410

Adapter 410 410 410 410

Rotator 410 410 410 410

Lower Die 410 410 410 410

Upper Die 410 410 410 410

Inside Die 432 439 433 435

Melt Temperature

427 432 427 429 (⁰F)

Output (lb/h) 181 187 190 191

Head Pressure

6070 5980 5710 5580 (psi)

Die Pressure (psi) 4300 4170 4020 4110

Motor Load (%) 62.8 62.6 62.4 62.9

Screw Speed

58.5 75.4 72.5 67.5 (rpm)

Line Speed (fpm) 170.2 170.2 170.2 170.1

Gauge (mils) 0.98 1.02 1.013 0.973

FLH (in) 34 34 34 34

Air (%) 56.2 56.2 56.2 56.2

ESO (lb/hp-h) 9.28 7.56 7.87 8.5

Spec. Output

3.07 2.5 2.59 2.83 (lb/h/rpm) lbs/hr/inchdie 9.57 9.91 10.06 10.14

[00131] Film properties of the films from the second trial are listed in Tables 10 and 11. Specifically, Table 10 indicates mechanical film properties and Table 11 indicates optical and surface film properties for the second Gloucester trial. Films containing metal stearate show better optical properties and about 20 % lower dart impact strength than the film with DYNAMAR FX5920. Other properties are very similar and the differences are not statistically significant.

TABLE 10

Sample ID 00270-141-041 00270-141-031 00270-141-051

800 ppm

1000 ppm ZnSt 1000 ppm AlSt FX5920A

1% Secant Modulus

25117 25366 25574 (psi) MD

1% Secant Modulus

25685 24240 26432 (psi) TD

Yield Strength (psi)

1277 1267 1266 MD

Yield Strength (psi)

1224 1232 1273 TD

Elongation @ Yield

6 5.6 5.8 (%) MD

Elongation @ Yield

5.3 5.5 5.4 (%) TD

Tensile Strength

7431 7283 7485 (psi) MD

Tensile Strength

6025 6081 6075 (psi) TD

Elongation @ Break

510 497 517 (%) MD

Elongation @ Break

575 586 582 (%) TD

Elmendorf Tear 250 263 257 (g/mil) MD

Elmendorf Tear

392 406 375 (g/mil) TD

Dart Drop (g/mil) 435 469 554

Puncture - Method

B

Peak Load (lbs) 9.6 9.5 9.5

Peak/mil (lbs/mil) 9.2 9.1 9.0

Break Energy (in-

22.0 19.7 21.4 Ib)

Break Energy/mil

21.2 19.0 20.4 (in-lb/mil)

Shrink (%) MD 34 47 40

Shrink (%) TD 4 -13 -4

Gauge Mic (mils) 1.04 1.04 1.05

TABLE 1 1

Sample ID 00270-141-041 00270-141-031 00270-141-051

1000 ppm ZnSt 800 ppm

1000 ppm AlSt FX5920A

Gloss (GU) MD 52 62 34

Gloss (GU) TD 53 64 35

Haze(%) 12.6 9.77 22

Clarity 92 94 89

Internal Haze 1.36 1.03 2

Reblock (g) 10 8 8

COF(I/O) Static 0.74 0.77 0.74 COF(I/O) Kinetic 0.69 0.72 0.69

Gauge Mic (mils) 1.04 1.04 1.05

|OO132| For the thermal stability tests, granular mLLDPE feedstock resin was dry blended with VITON Z-IOO, CRODAMIDE ER, WESTON 399 and different quantities of IRGANOX 1076 and ZnSt. The specific formulations are listed in Table 12 below. A Werner & Pfleiderer ZSK 30 mm twin screw extruder was used for compounding and subsequent extrusion of the resins. The temperature profile, screw rpm and output rate for compounding and multipass extrusions are listed in Table 13 below. The initial compounding step was carried out under a nitrogen blanket while subsequent extrusion steps were carried out in air atmosphere.

[00133] The samples for the thermal and color stability tests were obtained according to the following procedure: (1) The granular formulation was introduced into the extruder and a minimum of 10 lbs. were purged prior to capturing a sample of the compounded resin (extrusion pass 0); (2) The compounded resin from step (1) was reintroduced in the extruder and subjected to another extrusion pass (pass 1). The sample was taken after 3 lbs. of resin ran through the extruder to purge it; and (3) The resin from extrusion pass 1 was reintroduced in the extruder and subjected to another extrusion pass (pass 2). A sample was taken after 3 lbs. of resin ran through the extruder to purge it. [00134] The resin was run through the extruder a total of 5 times (passes 1-5) after the compounding step. Table 14 below lists the samples from the compounding and multipass extrusion trial. Samples were taken after each extrusion step, except for pass 4, and analyzed for thermal or melt temperature stability and color stability. TABLE 12

TABLE 13

TABLE 14

[00135] Table 15 below shows melt index (I₂), high load melt index (I₂]), melt index ratio (I₂i/I₂) and yellowness index (YI) of the formulations listed in Table 12 after extrusion passes 1,2,3, and 5. I₂ (melt index) was determined according to ASTM-D-1238-E (190⁰C, 2.16 kg weight) and I₂i (flow index) was determined according to ASTM-D-1238-F (190°C, 21.6 kg weight). With regard to color stability, yellowness index (YI) of the pellets was determined using a HunterLab ColorQuest XE spectrophotometer which is commercially available from Hunter Associates Laboratory, Inc. (11491 Sunset Hills Road, Reston, VA 20190-5280). 100136] Table 15 displays the melt index data of samples designated as 00332-009- 603 and 00332-009-604. According to the present invention, the formulations with zinc stearate provide for much better melt index stability than the formulations with less (and without) zinc stearate after each extrusion pass. Likewise, the formulations with zinc stearate provide for a constant melt index ratio (I₂i /I₂) after each extrusion pass while the formulations with less zinc stearate show a significant increase in melt index ratio. The zinc stearate containing formulations (Examples 00332-009-603 and 00332-009-604) also provide acceptable color stability.

TABLE 15

IR1076

Sample ID (ppm) Pass# 12 121 121/12 YI

00332-

009-60 IA 0 0.67 25.07 37.5 -3.1 1

00332-

009-60 IB 0 0.57 24.27 42.5 -2.27

00332-

009-601C 0 0.44 22.95 52.4 -2.1 00332- 9-60 I D 0 3 0.35 22.80 64.6 -1.97

00332-09-601E 0 5 0.24 22.55 92.4 -1.62

00332- 9-602A 250 0 0.66 24.75 37.6 -2.86

00332-09-602B 250 1 0.64 24.97 38.8 -1.91

00332-09-602C 250 2 0.64 24.49 38.1 -0.95

00332-09-602D 250 3 0.51 23.31 46.1 -0.24

00332-09-602E 250 5 0.32 21.56 66.7 -0.23

00332-09-603A 250 0 0.66 24.81 37.7 -3.35

00332-09-603B 250 1 0.66 25.1 1 37.8 -2.76

00332-09-603C 250 2 0.68 25.65 37.5 -2.03

00332-09-603D 250 3 0.66 25.62 38.8 -0.42

00332-09-603E 250 5 0.49 23.44 48.0 -0.37

00332-09-604A 500 0 0.66 24.92 37.9 -2.82

00332-09-604B 500 1 0.67 25.04 37.3 -2.78

00332-09-604C 500 2 0.68 25.21 36.9 -2.38

00332-09-604D 500 3 0.69 25.66 37.3 -1.88

00332-09-604E 500 5 0.69 25.93 37.6 1.02 00332- 009-605A 500 0 0.52 19.77 38 -3.55

00332- 009-605B 500 1 0.55 20.70 37.5 -2.5

[00137] The phrases, unless otherwise specified, "consists essentially of and "consisting essentially of do not exclude the presence of other steps, elements, or materials, whether or not, specifically mentioned in this specification, so long as such steps, elements, or materials, do not affect the basic and novel characteristics of the invention, additionally, they do not exclude impurities and variances normally associated with the elements and materials used.

[00138] For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, within a range includes every point or individual value between its end points even though not explicitly recited. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

(00139] All priority documents are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted and to the extent such disclosure is consistent with the description of the present invention. Further, all documents and references cited herein, including testing procedures, publications, patents, journal articles, etc. are herein fully incorporated by reference for all jurisdictions in which such incorporation is permitted and to the extent such disclosure is consistent with the description of the present invention. |00140] While the invention has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the invention as disclosed herein.

Claims

CLAIMSWhat is claimed is:

1. A method for processing a linear low density polyethylene (LLDPE) into a film, the method comprising: contacting LLDPE with a carboxylate metal salt, wherein the LLDPE has: a) a molecular weight (Mw) from 50,000 g/mol to 180,000 g/mol; b) a molecular weight distribution from 1.5 to 3.0; and c) a melt index ratio from 15 to 25; and melt processing the LLDPE and the carboxylate metal salt to form the film.

2. The method of claim 1, wherein the LLDPE is a metallocene catalyzed linear low density polyethylene (mLLDPE).

3. The method of any one of the preceding claims, wherein the carboxylate metal salt is selected from the group consisting of zinc stearate, calcium stearate, aluminum stearate, and combinations thereof.

4. The method of any one of the preceding claims, wherein the carboxylate metal salt is used in amount from 1000 to 2000 parts per million (ppm) based upon the LLDPE and the carboxylate metal salt.

5. The method of any one of the preceding claims, wherein the LLDPE has a density from 0.890 g/cm³ to 0.935 g/cm³.

6. The method of any one of the preceding claims, wherein the LLDPE has a MFR (I₂₎/I₂) from 15 to 20.

7. The method of any one of the preceding claims, wherein the LLDPE has a melt index (MI) or (I₂) from 0.1 dg/min to 3.5 dg/min.

8. The method of any one of claims 1-6, wherein the LLDPE has a melt index (MI) or (I₂) from 0.2 dg/min to 2 dg/min.

9. The method of any one of the preceding claims, wherein the LLDPE has a weight average molecular weight to number average molecular weight (Mw/Mn) from 2.0 to 2.5.

10. A composition comprising the contact product of: a linear low density polyethylene (LLDPE) having: a) a molecular weight (Mw) from 50,000 g/mol to 180,000 g/mol b) a molecular weight distribution froml .5 to 3.0; and c) a melt index ratio from 15 to 25; and a carboxylate metal salt.

1 1. The composition of claim 10, wherein the LLDPE is a metallocene catalyzed linear low density polyethylene (mLLDPE).

12. The composition of any one of claims 10-11, wherein the carboxylate metal salt is selected from the group consisting of zinc stearate, calcium stearate, aluminum stearate, and combinations thereof.

13. The composition of any one of claims 10-12, wherein the LLDPE has a density from 0.890 g/cm³ to 0.935 g/cm³.

14. The composition of any one of claims 10-13, wherein the LLDPE has a MFR (WI₂) from 15 to 20.

15. The composition of any one of claims 10-14, wherein the LLDPE has a melt index (MI) or (I₂) from 0.1 dg/min to 3.5 dg/min.

16. The composition of any one of claims 10-14, wherein the LLDPE has a melt index (MI) or (I₂) from 0.2 dg/min to 2 dg/min.

17. The composition of any one of claims 10-16, wherein the LLDPE has a weight average molecular weight to number average molecular weight (Mw/Mn) from 2.0 to 2.5.

18. A method for processing a linear low density polyethylene (LLDPE) into a film, the method comprising: contacting LLDPE with a carboxylate metal salt, wherein the LLDPE has: a) a molecular weight (Mw) from 50,000 g/mol to 180,000 g/mol; b) a molecular weight distribution from between 1.5 to 5.0; and c) a melt index ratio from 15 to 100; and melt processing the LLDPE and the carboxylate metal salt to form the film.

19. The method of claim 18, wherein the LLDPE is a metallocene catalyzed linear low density polyethylene (mLLDPE).

20. The method of any one of claims 18-19, wherein the carboxylate metal salt is selected from the group consisting of zinc stearate, calcium stearate, aluminum stearate, and combinations thereof.

21. The method of any one of claims 18-20, wherein the carboxylate metal salt is used in an amount from 250 to 500 parts per million (ppm) based on the LLDPE and carboxylate metal salt.

22. The method of any one of claims 18-21, wherein the LLDPE has a MFR (WI₂) from 20 to 100.

23. The method of any one of claims 18-21, wherein the LLDPE has a MFR (WI₂) from 30 to 80.

24. The method of any one of claims 18-21, wherein the LLDPE has a MFR (I₂₁/I₂) from 40 to 80.

25. The method of any one of claims 18-24, wherein the LLDPE has a melt index (MI) or (I₂) from 0.1 dg/min to 3.5 dg/min.

26. The method of any one of claims 18-24, wherein the LLDPE has a melt index (MI) or (I₂) from 0.2 dg/min to 2.0 dg/min.

27. The method of any one of claims 18-26, wherein the LLDPE has a weight average molecular weight to number average molecular weight (Mw/Mn) from 2.5 to 4.0.

28. The method of any one of claims 18-26, wherein the LLDPE has a weight average molecular weight to number average molecular weight (Mw/Mn) from 2.5 to 4.0.

29. The method of any one of claims 18-28, wherein the LLDPE has a MFR (WI₂) of from 15 to 20.

30. The method of any one of claims 18-26 or 29, wherein the LLDPE has a weight average molecular weight to number average molecular weight (Mw/Mn) from 2.0 to 2.5.

31. A composition comprising: a metallocene catalyzed linear low density polyethylene (mLLDPE), wherein the mLLDPE has: a) a molecular weight (Mw) of about 50,000 g/mol to about 180,000 g/mol; b) a molecular weight distribution of between 1.5 and 5.0; and d) a melt index ratio of between 20 and 100; and a carboxylate metal salt.

32. The composition of claim 31 , wherein the mLLDPE has a density from 0.890 g/cm³ to 0.935 g/cm³.

33. The composition of any one of claims 31 -32, wherein the mLLDPE has a MFR (WI₂) from 20 to 80.

34. The composition of any one of claims 31-32, wherein the mLLDPE has a MFR (I₂₁ZI₂) from 30 to 80.

35. The composition of any one of claims 31 -34, wherein the mLLDPE has a melt index (MI) or (I₂) from 0.2 dg/min to 2 dg/min.

36. The composition of any one of claims 31-35, wherein the mLLDPE has a weight average molecular weight to number average molecular weight (Mw/Mn) from 2.5 to 4.0.