BRPI9816180B1 - ethylene and alpha olefin copolymer and film - Google Patents

Abstract

ethylene copolymers and film made of it. The present invention relates to ethylene copolymers having a polymodal cd, a m / w value of 2.5 to 7, and a density of 0.905 to 0.95 g / cc. The invention is also directed to films made of said copolymers.

Description

(54) Title: COPYLINER OF ETHYLENE AND ALPHA-OLEFINE AND FILM (51) Int.CI .: C08F 4/642; C08F 210/16; C08J 5/18 (30) Unionist Priority: 12/08/1997 US 08 / 986,696 (73) Holder (s): UNIVATION TECHNOLOGIES, LLC (72) Inventor (s): MOSES OLUKAYODE JEJELOWO; SUN-CHUEH KAO; DONALD R. LOVEDAY (85) National Phase Start Date: 12/21/2004

1/54 “COPYLIMER OF ETHYLENE AND ALPHA-OLEFINE AND FILM“ Divided from PI 9813438-8, deposited on 12/08/1998

BACKGROUND OF THE INVENTION

Field of the Invention [001] The invention relates to catalysts, catalyst systems and their use in olefin polymerization. The invention more particularly relates to catalytic compounds of the substituted hafnium metallocene type, catalyst systems thereof, their use in a polymerization process, their polymer products and articles thereof. Description of the Related Art [002] The use of transition metal catalyst compounds with mass ligand in polymerization processes to produce a diverse formation of new polymers for use in a wide variety of applications and products is well known in the art. Typical mass-ligand transition metal compounds, known as metallocene-type compounds, are generally described as containing one or more ligands capable of η-5 bonding on the transition metal atom, usually ligands or portions derived from cyclopentadienyl , in combination with a transition metal selected from Group 4,5 or 6 or from the lanthanide and actinide series of the Periodic Table of the Elements. Predominantly in the literature, the transition metal is Group 4, particularly titanium, zirconium or hafnium, and the ligand or portion derived from cyclopentadienyl is replaced with various radicals, typically alkyl radicals, or two or more cyclopentadienyl ligands are joined by one structural bridge, usually an organic or inorganic group, typically a group containing carbon atom or silicon.

Petition 870180023462, of 03/23/2018, p. 7/64

2/54 [003] Other forms of these metallocene-type catalyst compounds contain a ligand or portion derived from cyclopentadienyl and a group containing heteroatom ligand in a transition metal, typically titanium, where the ligand or portion of cyclopentadienyl and the group containing the heteroatom they are joined by a structural bridge, usually a group containing silicon atom. These and other metallocene-type catalyst compounds in combination with an activator form metallocene-type catalyst systems capable of polymerizing various olefin (s), alone or in combination with other olefin (s). The development of these

and other types of compounds catalysts like metallocene and systems catalysts are described in Patent U.S. Nos 5,017,714 , 5,055,438, 5,096,867.5 .198,401, 5,229,478, 5,264,405 , 5,278,119, 5,324,800.5 .384,299, 5,408,017, 5,491,207 and 5,621,126, all of which are here

completely incorporated by reference.

[004] It is well known in the art, although not fully understood, that where the transition metal of these metallocene-type catalyst compounds is hafnium, often called as a hafnocene, hafnocene catalyst systems generally, among other characteristics, function relatively poorly in compared to their titanium equivalents, especially zirconium, often referred to as zirconocene. Although hafnocene typically polymerize polymers having higher molecular weights than their zirconocene counterparts under similar polymerization conditions, their poor general activity makes them lower polymerization catalysts. European patent EP 0 284 707 B1 granted in

Petition 870180023462, of 03/23/2018, p. 8/64

August 3/54, 1995, which is incorporated herein by reference, describes a process for polymerizing olefins using a catalyst system, in liquid form, containing a hafnium metallocene catalyst compound with a chiral steroride bridge and an aluminum compound.

[005] Thus, it would be highly advantageous to have a hafnium metallocene type catalyst system capable of polymerizing olefin (s) with improved catalyst performance.

SUMMARY OF THE INVENTION [006] This invention relates to a catalyst compound of the metallocene type with hafnium transition metal with substituted mass ligand and a catalyst system thereof. The invention also relates to a polymerization process for polymerizing one or more olefin (s) using the metallocene-type catalyst compound with transition metal with hafnium with substituted mass ligand.

[007] In one embodiment, the invention provides a catalyst system for a metallocene-type compound with hafnium with a mass ligand where at least one mass ligand is replaced by a substituent having at least 3 or more atoms without hydrogen, and an activator . Preferably, the bulk ligand is replaced by a substituent having at least 3 or more carbon atoms or silicon atoms or combinations thereof.

[008] In a preferred embodiment, the invention provides an activated catalyst system of a catalyst complex of the metallocene type with hafnium with mass ligand where the mass ligand is capable of binding η-5 in the transition metal

Petition 870180023462, of 03/23/2018, p. 9/64

4/54 hafnium and is substituted by an alkyl substituent having 3 or more carbon atoms, preferably where the alkyl substituent has 3 to 5 carbon atoms, more preferably the alkyl substituent is linear alkyl. In a preferred embodiment, the alkyl substituent is at least one n-butyl group, more preferably at least one n-propyl group, substituted for at least one of the bulk ligands.

[0010] In yet another embodiment, the invention is directed to a process for polymerizing, preferably in a continuous process, one or more monomer (s) in the presence of the activated catalyst system or catalyst complex described above.

[0011] In a preferred embodiment, the process above the invention is a gas phase or continuous slurry polymerization process. In another embodiment, the invention is directed to a polymer product produced using the hafnocene or complex catalyst systems described above, where the polymer product contains less than 5ppm hafnium, preferably less than 2ppm hafnium. DETAILED DESCRIPTION OF THE INVENTION

Introduction [0012] The invention is directed to a metallocene-type catalyst system with hafnium transition metal to polymerize one or more olefin (s). It has been surprisingly discovered that appropriately replacing the cyclopentadienyl ligand or portion of a hafnocentium results in an improved catalyst system. Unexpectedly where the substituent on the ligand or bulky portion is a substituent having 3 or more atoms without hydrogen, preferably 3 or

Petition 870180023462, of 03/23/2018, p. 10/64

5/54 plus carbon atoms, preferably an alkyl substituent, for example, n-propyl or n-butyl, the catalyst activity of the hafnocene metallocene catalyst system is substantially improved. Along with a sufficiently acceptable activity from a commercial point of view, the Hafnosocene catalyst systems of the invention produce polymers having higher molecular weights compared to their zirconocene equivalents under the same or similar polymerization conditions. It was surprising that the substituted hafnocene of the invention will tend to produce polymer products with a density lower than its zirconocene equivalent at substantially the same molecular weight.

Catalyst Components and Catalyst Systems [0013] Preferred metallocene catalysts of the invention, for example, are typically those mass transition ligand transition metal complexes described by formula (I):

{[(LP) _m M (A ^q ) n] * ^k } h [B '] i where L is a substituted mass ligand attached to Μ, p is the anionic charge of L em is the number of ligands L em is 1,2 or 3; at least one L is replaced by at least one substituent having 3 or more atoms without hydrogen, preferably having 3 or more carbon atoms or silicon atoms or a combination thereof; A is a ligand attached to M and capable of inserting an olefin between the MA bond, q is the anionic charge of A and n is the number of ligands A and n is 1,2,3 or 4, M is a transition metal of which 95 mole% or more is hafnium (HI), preferably more than 97 mole% HI, more preferably more than 98 mole% HI, and more preferably still in the range of more than 99 mole% HI

Petition 870180023462, of 03/23/2018, p. 11/64

6/54 less than 100 mole% HI, and (pxm) + (qxn) + k corresponds to the formal oxidation state of the metal center, where k is the charge in the cation and k is 1,2,3 or 4 , and B 'is a chemically stable non-nucleophilic anionic complex, preferably having a molecular diameter of 4 A or greater and j is the anionic charge in B', h is the number of charge cations k, and the number of charge anions j such that hxk = jx i. [0014] Any two ligands L and / or A can be bridged to each other and / or not bridged. The catalyst compound may be composed of fully compressed tablets having two or more L ligands, which include cyclopentadienyl derived ligands or substituted cyclopentadienyl derived ligands, or sandwich sandwich compounds having an L ligand, which is a cyclopentadienyl derived ligand or cyclopentadienyl derived ligand substituted with heteroatom or ligand or hydrocarbyl-substituted cyclopentadienyl-derived portion such as an indenyl ligand, a benzindenyl ligand or a fluorenyl ligand and the like including hydrogenated versions thereof or any other ligand capable of η-5 bonding on the metal atom transition. One or more of these mass ligands is x-linked at the transition metal atom. At least one L is substituted with at least one substituent having 3 or more atoms without hydrogen, preferably having 3 or more carbon atoms or 3 or more atoms without hydrogen of which at least one is a silicon atom; in addition, L can be substituted with a combination of additional substituents, which can be the same or different. Non-limiting examples of atoms without hydrogen include silicon, germanium, tin, oxygen, nitrogen or carbon and combinations thereof. Examples no Petition 870180023462, of 03/23/2018, p. 12/64

Additional limiting substituents include hydrogen or a linear, branched or cyclic alkyl, alkenyl or aryl radical, or a combination thereof having 1 to 30 carbon atoms. The at least one substituent or additional substituents may also be substituted with hydrogen or a linear, branched or cyclic aryl, alkenyl or aryl radical having from 1 to 30 carbon atoms or atoms without hydrogen. L can also be other types of bulk ligands including but not limited to amides, phosphides, alkoxides, aryloxides, imides, carbolides, borolides, porphyrins, phthalocyanines, corrinas and other polyazomacrocycles. Other ligands can be attached to the hafnium transition metal, such as a starting group, such as - but not limited to weak bases - such as amines, phosphines, ether and the like. In addition to the transition metal, these ligands can be optionally linked to A or L. Non-limiting examples of catalyst components and catalyst systems are discussed, for example, in

Patents U.S. Nos. 4,530,914, 4,871,705, 4,937,299, 5,124,418, 5,017,714, 5,120,867, 5,210,352, 5,278,264, 5,278,119, 5,304,614, 5,324,800, 5,347,025, 5,350,723, 5,391,790, 5,391,789, 5,399,636, 5,539,124, 5,455,366, 5,534,473, 5,684,098 and 5,693,730, all Which are they

incorporated here completely by reference. Also, descriptions of European publications EP-A-0 591 756, EP-A-0 520 732, EP-A-0 420 436, EP-B1 0 485 822, EP-B1 0 485 823 and EP-A2-0 743 324 and PCT publications WO 91/04257, WO 92/00333, WO 93/08221, WO 93/08199, WO 94/01471, WO 96/20233, WO 97/15582 and WO 97/19959 are all incorporated herein by reference .

Petition 870180023462, of 03/23/2018, p. 13/64

8/54 [0015] In one embodiment, the activated catalyst of the invention is formed from a haphenocene catalyst compound represented by the general formula (II):

(LP) m M (Aq) n (Er) o where L is a mass ligand substituted by at least one substituent having 3 or more atoms without hydrogen, preferably 3 or more carbon atoms, preferably an alkyl substituent having 3 or more carbon atoms, even more preferably a linear alkyl substituent having 3 or more carbon atoms, M is HI, A, ep, m, qen are as defined above and E is an anionic leaving group such as, but not - limited to hydrocarbyl, hydride, halide or a combination thereof or any other anionic ligands, r is the anionic charge of E and o is the number of E ligands and o is 1,2,3 or 4 such that (pxm) + ( qxn) + (rxo) is equal to the formal oxidation state of the metal center; and aluminum alkyl, alumoxane, modified alumoxane or any other organometallic compound containing oxy or uncoordinated ionic activators, or a combination thereof.

[0016] In one embodiment of the invention, the substituted hafnocene catalyst compound of the invention includes monocyclopentadienyl-heteroatom ligand containing metallocene-type compounds with hafnium transition metal. This metallocene-type compound is activated by an alumoxane, modified alumoxane, an uncoordinated ionic activator, a Lewis acid or a combination of these to form an active polymerization catalyst system. These types of catalyst systems are described, for example, in PCT publication WO 92/00333, WO 94/07928, WO 91/04257, WO 94/03506,

Petition 870180023462, of 03/23/2018, p. 14/64

9/54

W096 / 00244 and WO 97/15602 and US Patent Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401, 5,227,440 and 5,264,405 and European publication EP-A-0 420 436, all of which are here fully incorporated by reference. Additionally, it is within the scope of this invention that the metallocene catalysts described

5,149,819, be these

5,145,819, 5,296,434, and catalyst systems can in U.S. Patent Nos. 5,064,802,

5,243,001, 5,239,022, 5,276,208,

5,321,106, 5,329,031, 5,304,614 and 5,677,401, and publications

PCT WO 93/08221, WO 93/08199 and WO 95/07140 and European publications EP-A-0 578 838 and EP-A-0 638 595, all of which are incorporated herein completely by reference. [0017] In another embodiment, the catalyst component is represented by the formula (III):

(C ₅ H5- (j-fR _d ) eR'fMQg-e where M is a HI transition metal, (Cs H5-d- [Rd) is a substituted or unsubstituted cyclopentadienyl ligand attached to M, where at minus one (Cs-5-d- (Rd) has at least one R which is an alkyl substituent having 3 or more carbon atoms, each additional R, which can be the same or different is hydrogen or a substituted or unsubstituted hydrocarbyl -substituted having 1 to 30 carbon atoms or combinations of the same or two or more carbon atoms are joined to form a part of a substituted or unsubstituted ring or ring system having 4 to 30 carbon atoms, R 'is one or more or a combination of carbon, germanium, silicon, phosphorous or nitrogen atoms containing radical by bridging two rings (Cs Hs-df Rd), or by bridging a ring of (C5 5-df Rd) in M; each Q which can be the same or different is a hybrid hydrocarbyl,

Petition 870180023462, of 03/23/2018, p. 15/64

10/54 substituted or unsubstituted having from 1 to 30 carbon atoms, haiogen, alkoxides, aryloxides, amides, phosphides or any other univalent anionic ligand or combination thereof; also, two Q's together form an alkylidene ligand or cyclometallated hydrocarbyl ligand or another divalent anionic chelating ligand, where g is an integer corresponding to the formal oxidation state of M, d is 0,1,2,3,4 or 5 , f is 0 or 1 and e is 1,2 or 3.

[0018] In another preferred embodiment of this invention, the catalyst component is represented by the formula (IV):

(JR '*:.,)

- where M is HI; (5 H5-yx Rx) and useful U of cyclopentadienyl which is substituted with at least one to 5 substituent groups of R, x is 1,2,3,4 or 5 denoting the degree of substitution, and at least one R is one atom without hydrogen, preferably R is at least 3 carbon atoms or silicon atoms or a combination thereof, more preferably R is an alkyl having 3 or more carbon atoms, for example n-propyl or n-butyl, and each group An additional substituent of R is, independently, a radical selected from a group consisting of C1-C20 hydrocarbyl radicals, C1-C20 hydrocarbyl substituted radicals where one or more hydrogen atoms is replaced by a haiogen atom, metalloid radicals COM substituted C1-C20 hydrocarbyl, where the metalloid is selected from Group 14 of the Periodic Table of the Elements, and haiogen radicals or (C5H5-y-xRx) is a cyclopentadienyl ring in which two adjacent E groups are

Petition 870180023462, of 03/23/2018, p. 16/64

11/54 joined to form the C4-C2o ring to provide a saturated or unsaturated polycyclic cyclopentadienyl ligand such as indenyl, tetrahydroindenyl, fluorenyl or octahidrofluorenyl;

- (JR 'z-1-y) is a heteroatom ligand in which J is an element with a coordination number of three in Group 15 or an element with a coordination number of two in Group 16 of the Periodic Table of Elements, preferably nitrogen, phosphorus, oxygen or sulfur with nitrogen being preferred, and each R 'is, independently, a radical selected from the group consisting of C1-C20 hydrocarbyl radicals where one or more hydrogen atoms is replaced by a halogen atom, y is 0 or 1, and z is the coordination number of element J;

- each Q is, independently, any univalent anionic ligand such as halogen, hydride, or substituted or unsubstituted C1-C3o hydrocarbyl, alkoxide, aryloxide, amide or phosphide, as long as two Q's may be an alkylidene, a cyclometallated hydrocarbyl or any another bivalent anionic chelating ligand;

- A is a covalent bridging group containing a Group 15 or 14 element such as, but not limited to, a dialkyl, alkylaryl or diaryl silicon or germanium radical, phosphine radical or alkyl or aryl amine, or a hydrocarbyl radical such as methylene, ethylene and the like;

- L 'is a Lewis base such as diethyl ether, tetraethylammonium chloride, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine, n-butylamine, and the like; and w is a number from 0 to 3. Additionally, L 'can be joined to any one of

Petition 870180023462, of 03/23/2018, p. 17/64

12/54

R, R 'or Q.

[0019] In an embodiment of the catalyst compounds of the metallocene type with hafnium transition metal with mass ligand described above, at least one mass ligand is substituted with a substituent having 3 or more carbon atoms, preferably 3 to 20 carbon atoms. carbon, more preferably 3 to 10 and most preferably 3 to 5 carbon atoms. In another preferred embodiment, the metallocene-type catalyst system with hafnium transition metal has two mass ligands which are each substituted with linear or branched, preferably linear, alkyl having 3 or more carbon atoms, preferably 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms, where at least one bulk ligand is a ligand derived from cyclopentadienyl, preferably a cyclopentadienyl ring. In a preferred embodiment, the mass ligands of the metallocene with transition metal are both cyclopentadienyl hafnium rings at least one of which is substituted with one or more branched or linear alkyls having 3 or more carbon atoms, preferably both carbon rings. cyclopentadienyl are replaced with at least one nn-butyl, isobutyl, n-pentyl,

In a more preferred modality of the metallocene type with hafnium transition metal it has two mass ligands which are each substituted with n-propyl, n-butyl or n-pentyl or a combination thereof, in the same or different positions, preferably in the same position in bulk ligands.

[0020] In another preferred embodiment, the propyl, isopropyl system, combination of the same catalyst compound or the

in

Petition 870180023462, of 03/23/2018, p. 18/64

13/54 metallocene type catalyst with hafnium transition metal has two mass ligands which are each replaced with a linear or branched, preferably linear silyl, having 3 or more atoms without hydrogen, preferably 3 to 10 atoms without hydrogen, more preferably 3 to 5 atoms without hydrogen, where at least one mass ligand is a ligand derived from cyclopentadienyl, preferably a cyclopentadienyl ring. In a preferred embodiment, the mass ligands of the metallocene with hafnium transition metal are both cyclopentadienyl rings, at least one of which is substituted with one or more branched or linear silylalkyls having 3 or more atoms without hydrogen. In one embodiment, the substituent has at least 3 or more non-hydrogen atoms of which at least one is a silicon atom, for example, trimethyl silyl alkyl, tributyl silyl alkyl or tripropyl silyl alkyl or even cyclopropyl silyl. Other substituent atoms without hydrogen include oxygen and / or nitrogen.

[0021] It is envisaged that the mass substituted ligands of the metallocene type with the metal of the invention are asymmetrically substituted in terms of additional substituents or types of substituents, and / or unbalanced in terms of the number of additional substituents in the mass ligands.

[0022] Non-limiting examples of hafnocene of the invention include bis hafnium dichloride (cyclopentadienyl n-propyl), dimethyl or dihydride, bis dichloride hafnium dimethyl transition compound or cyclopentadian dimethyl (n-butyl) dimethyl , bis hafnium (cyclopentadienyl n-pentyl), hafnium dichloride or dimethyl (nPetition 870180023462, 23/03/2018, page 19/64

14/54 cyclopentadienyl propyl) (cyclopentadienyl n-butyl), hafnium dichloride or dimethyl bis [(2-trimethylsilylethyl) cycloopentadienyl], dichloride or dimethyl or hafnium bis dihydride (trimethylsilane or cyclopentyl) 2-n-propenyl indenyl), dichloride or dimethyl bis (2-n-butyl indenyl), dichloride or dimethyl hafnium dimethylsilyl bis (n-butyl cyclopentadienyl), dichloride or dimethyl hafnium bis (9-npropyl fluorenyl), dichloro rectum or dimethyl of hafnium bis (9-n-butyl fluorenyl), dichloride or dimethyl of hafnium (9n-propyl fluorenyl) (2-n-propyl indenyl), dichloride or dimethyl of hafnium bis (1,2-n-propyl, methyl cyclopentadienyl), hafnium dichloride or dimethyl (cyclopentadienyl npropyl) (1,3-n-propyl, cyclopentadienyl n-butyl) and the like.

[0023] In a preferred embodiment, the hafnoceniums of the invention are mono- and bishafnocenees not joined by bridges where a structural bridge is not necessary for stereorigidity. It is also considered that in one embodiment, the hafnocene of the invention includes its structural or optical isomers and mixtures.

[0024] For the purposes of that patent application and appended claims, the term activator is defined as any compound or component that can activate a metallocene catalyst compound with transition metal with mass ligand as described above, for example, a Lewis acid or an uncoordinated ionic activator or ionization activator or any other compound that can convert a neutral metallocene catalyst component to a metallocene cation. It is within the scope of this invention

Petition 870180023462, of 03/23/2018, p. 20/64

15/54 use alumoxane or modified alumoxane as an activator, and / or also use ionization activators, neutral or ionic, such as tri (n-butyl) ammonium tetracis (pentafluorophenyl) boron or a metalloid precursor of trisperfluorophenyl boron that ionizes the compound neutral metallocene.

[0025] There are a variety of methods for preparing alumoxane and modified alumoxanes, non-limiting examples of which are described in U.S. Patent 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 and European publications EP-A-0 561 476, EP-B1-0 279 586 and EP-A-0 594,218 and PCT publication WO 94/10180, all of which are incorporated herein completely by reference.

[0026] Ionization compounds may contain an active proton, or some other cation associated with, but not coordinated or only negligently coordinated in the remaining ion of the ionization compound. Such compounds and the like are described in European publications EP-A-0

570 982, EP-A-0 520 732, EP-A-0 495 375, EP-A-0 426 637, EPA-500 944, EP-A-0 277 003 and EP-A-0 277 004 and US Patent Nos 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025,

5,387,568, 5,384,299 and 5,502,124 and U.S. Patent Application No. Serial 08 / 285,380, filed August 3, 1994, all of which are incorporated herein completely by reference. Combinations of activators are also considered by the invention, for example, alumoxanes and ionization activators in combinations, see, for example, PCT publications WO 94/07928 and WO 95/14044 and U.S. Patent Nos. 5,153,157 and 5,453,410, all

Petition 870180023462, of 03/23/2018, p. 21/64

16/54 which are hereby fully incorporated by reference. [0027] In one embodiment of the invention, two or more catalyst compounds of the metallocene type with hafnium transition metal with mass ligand as described above can be combined to form a catalyst system Useful in the invention. For example, those mixed catalysts described in U.S. Patent Nos. 5,281,679, 5,359,015 and

5,470,811, all of which are incorporated herein by reference. In another embodiment of the catalyst system of the invention, combinations of one or more of the catalyst components of formulas (III) and / or (IV) are considered.

[0028] In one embodiment, the metallocene catalyst components can be combined to form the mixing compositions as described in PCT publication WO 90/03414 published on April 5, 1990, hereby fully incorporated by reference. In yet another embodiment of the invention, mixed metallocenes as described in US Patent Nos. 4,937,299 and 4,935,474, both of which are fully incorporated herein by reference, can be used to produce polymers having a wide molecular weight distribution and / or a distribution multimodal in molecular weight. As a particular aspect of this embodiment of the invention, hafnium metallocene is a hafnium bis dichloride or dimethyl (npropylcyclopentadienyl) comprising at least 95 mole% of the transition metal catalyst component and the balance is a zirconium dichloride or dimethyl bis (npropylcyclopentadienyl) comprising at least 0.1 mole% of the transition metal catalyst component.

[0029] In one embodiment, an ethylene / alpha copolymerPetition 870180023462, of 03/23/2018, p. 22/64

17/54 olefin having a density in the range of approximately 0.87 g / cm ³ to approximately 0.940 g / cm ³ is produced by the catalyst system of the invention. In a preferred embodiment, the ethylene alpha-olefin copolymers of the invention have a density of at least approximately 0.910 g / cm ³ . These copolymers produced by a catalyst system of this invention are especially well suited for filmmaking having a new balance of film properties when compared to films hitherto produced from commercially available metallocene resins such as Dow ELITE and / or Exxon resins EXCEEDTM of similar densities and casting index (MI) values. [0030] In another embodiment of the invention, at least one metallocene catalyst of the invention can be combined with a traditional catalyst or catalyst system without metallocene or Ziegler-Natta, or catalysts or catalyst systems based on chromium, non-limiting examples are described in US Patent Nos. 4,159,965, 4,325,837,

4,701,432, 5,124,418, 5,077,255, 5,183,867, 5,391,660,

5,395,810 and 5,691,264, all of which are incorporated herein completely by reference.

[0031] It is within the scope of this invention that the N2 + and Pd2 + complexes described in the articles by Johnson, et al., New Pd (11) - and Ni (ll) - Based Catalysts for Polymerization of Ethylene and a-olefins, J. Am.Chem.Soc., 1995, 117, 6414-6415 and Copolymerization of Ethylene and Propylene with Functionalized Vinyl Monomers by Palladium (II) Catalysts, J.Am.Chem.Soc., 1996, 118, 267-268, and WO 96/23010 published on August 1, 1996, which are all incorporated herein entirely by reference, can be used as

Petition 870180023462, of 03/23/2018, p. 23/64

18/54 catalysts in combination with the hafnocene of the invention. These complexes can be adducts of dialkyl ether, or alkylated reaction products from the described dihalide complexes that can be activated to a cationic state by the activators of this invention. It is also within the scope of the process of this invention that the complexes described above can be combined with one or more of the catalyst compounds represented by formula (III) and (IV), with one or more activators, and with one or more supporting materials using one of the support methods that are described below. [0032] For the purposes of this patent specification the terms carrier or support are interchangeable and can be any support material, preferably a porous support material, for example, talc, inorganic oxides, inorganic chlorides, and magnesium chloride, and materials resinous support materials such as polystyrene or polystyrene divinyl benzene polyolefins or polymeric compounds or any other organic or inorganic support material and the like, or mixtures thereof.

[0033] Preferred support materials are inorganic oxide materials, which include those from Groups 2,3,4,5,13 or 14 of the metal oxides. In a preferred embodiment, the catalyst support materials include silica, alumina, silica-alumina, and mixtures thereof. Other inorganic oxides that can be used alone or in combination with silica, alumina or silica-alumina and magnesium, titanium, zirconia and the like.

[0034] It is preferred that the catalyst carrier of this invention has a surface area in the range of approximately 10 to approximately 700 m ² / g, the volume of

Petition 870180023462, of 03/23/2018, p. 24/64

19/54 pore in the range of approximately 0.1 to approximately 4.0 cc / g and average particle size in the range of approximately 10 to approximately 500 pm. More preferably, the surface area is in the range of approximately 50 to approximately

500 m ² / g pore volume of approximately 0.5 to approximately 3.5 cm ³ / g and average particle size of approximately 20 approximately to 500Å,

200

More to approximately preferably still, the range of the surface area is approximately 100 to approximately 400 m ² / g, pore volume of approximately 0.8 to approximately 3.0 cm ³ / g and average particle size is approximately 20 to approximately 100pm on. The average pore size of the carrier of the invention typically has a pore size in the range of

1000À, preferably 50 to and most preferably 75 to approximately 350À.

[0035] The catalyst system of the invention can be manufactured and used in a variety of different ways as described below. In one embodiment, the catalyst is not supported, preferably in liquid form as described in U.S. Patent Nos. 5,317,036 and 5,693,727 and European publication EP-A-0 593 083, all of which are incorporated herein by reference. [0036] In the preferred embodiment, the catalyst system of

invention is supported. Examples of system support catalyst used in invention are described in the Patent U.S. Nos. 4,701,432, 4,808,561, 4,912,075, 4,925,821, 4,937,217, 5,008,228, 5,238,892, 5,240,894, 5,332,706, 5,346,925, 5,422,325, 5,466,649, 5,466,766, 5,468,702, 5,529,965, 5,554,704, 5,629,253, 5,639,835, 5,625,015.5 .643,847 and 5,665,665 and U.S. Order Serials 271,598 filed on 7

Petition 870180023462, of 03/23/2018, p. 25/64

20/54

July 1994 and 788,736, filed on January 23, 1997 and PCT publications WO 95/32995, WO 95/14044, WO 96/06187 and WO 97/02297, all of which are incorporated herein by reference.

[0037] In an another modality, O system catalyst invention contains a ligand stuck with polymer as described in the Patent U.S . No. 5,473,202, what is here completely incorporated per reference. In an modality, the system

catalyst of the invention is spray dried as described in U.S. Patent No. 5,648,310, which is fully incorporated herein by reference. In one embodiment, the support of the invention is functionalized as described in European publication EP-A-0 802 203 or at least one substituent or starting group is selected as described in US Patent No. 5,688,880, both of which are incorporated herein. completely by reference. [0038] In one embodiment of the process of the invention, the olefin (s), preferably olefin (s) or alpha-olefin (s) C2 to C30, preferably ethylene or propylene or their combinations are prepolymerized in the presence of the catalyst or system catalyst of the invention before main polymerization. Prepolymerization can be carried out in batches or continuously in gas phase, solution or slurry including at high pressures. Prepolymerization can take place with any alpha-olefin monomer or combination and / or in the presence of any molecular weight control agent such as hydrogen. For details on prepolymerization see U.S. Patent Nos. 4,923,833, 4,921,825 and 5,283,278 and European publication EP-B-0279 863, all of which are incorporated herein by reference.

[0039] In another embodiment of the invention, the system

Petition 870180023462, of 03/23/2018, p. 26/64

21/54 supported catalyst of the invention includes an antistatic agent or surface modifier, for example, those described in U.S. Patent No. 5,283,278 and PCT publication WO 96/11960 which are incorporated herein completely by reference. Non-limiting examples of antistatic agents and surface modifiers include alcohol, thiol, silanol, diol, ester, ketone, aldehyde, acid, amine, and ether compounds. Tertiary amines, ethoxylated amines, and polyether compounds are preferred. The antistatic agent can be added at any stage in the formation of the supported catalyst system of the invention, however, it is preferred that it be added after the supported catalyst system of the invention is formed, in a slurry or dry state.

[0040] A preferred method for producing the catalyst of the invention is described below and can be found in US Order No. Serials 265,533, filed June 24, 1994 and 265,532, filed June 24, 1994 and PCT publications WO 96/00245 and WO 96/00243, both published on January 4, 1996, all of which are incorporated herein by reference. In a preferred embodiment, the metallocene-type catalyst component is slurried into a liquid to form a metallocene solution and a separate solution is formed containing an activator and a liquid. The liquid can be any compatible solvent or other liquid capable of forming a solution or the like with at least one metallocene catalyst component and / or at least one activator. In the preferred embodiment, the liquid is a cyclic aliphatic or aromatic hydrocarbon, more preferably toluene. The metallocene and activator solutions are mixed and added in a porous support or support

Petition 870180023462, of 03/23/2018, p. 27/64

22/54 porous is added to the solutions, such that the total volume of the metallocene solution and the activator solution or the metallocene and the activator solution is less than four times the pore volume of the porous support, more preferably less than three times, even more preferably less than twice; preferred ranges being in the range of 1.1 to 3.5 times and more preferably in the range of 1.2 to 3 times.

[0041] Procedures for measuring the total pore volume of a porous support are well known in the art. Details of one of these procedures are discussed in Volume 1, Experimental Methods in Catalytic Research (Academic Press, 1968) (specifically see pages 67-96). This preferred procedure involves the use of a classic BET device for nitrogen absorption. Another method well known in the art is described in Innes, Total Porosity and Particle Density of Fluid Catalysis By Liquid Titration, Vol. 28, Nos. 3, Analytical Chemistry 332-334 (March, 1956).

[0042] The mole ratio of the metal of the activator component to the transition metal of the metallocene component is in the range of 0.3: 1 to 1000: 1, preferably 20: 1 to 800: 1, and more preferably 50: 1 to 500: 1. Where the activator is an aluminum-free ionization activator such as those based on the tetracis (pentafluorophenyl) boron anion, the metal mole ratio of the activator component to the transition metal component is preferably in the ratio range of 0.3 : 1 to 3: 1.

[0043] In another embodiment, the catalyst load in millimoles (mmol) of metallocene for weight of the supporting catalyst in grams (g) is in the range of approximately 0.001 to approximately 2.0 mmoles of metallocene per g of the

Petition 870180023462, of 03/23/2018, p. 28/64

23/54 support, preferably from approximately 0.005 to approximately 1.0, more preferably from approximately 0.005 to 0.5 and most preferably from approximately 0.01 to 0.05.

[0044] In one embodiment, the catalyst of the invention has a catalyst productivity greater than 1000 grams of polymer per gram of the metallocene catalyst, preferably greater than 1400 grams of polymer per gram of the metallocene catalyst, more preferably

greater than 1800 grams of polymer by catalyst grass metallocene, even more preferably greater than what 2000 grams in polymer per gram of the catalyst in metallocene, and up until even more preferably greater than what 2500 grams of polymer per gram of the catalyst in metallocene. Polymerization Process of Invention

[0045] The catalyst compounds of the metallocene type with hafnium transition metal with substituted mass ligand and catalyst systems of this invention are suitable for the polymerization of monomers, and optionally one or more comonomers, in any polymerization process, solution phase, gas phase or slurry phase, more preferably a gas phase or slurry process is used.

[0046] In one embodiment, this invention is directed to the solution phase, slurry or gaseous polymerization or copolymerization reactions involving the polymerization of one or more of the monomers having from 2 to 30 carbon atoms, preferably 2-12 atoms carbon, and more preferably 2 to 8 carbon atoms. The invention is

Petition 870180023462, of 03/23/2018, p. 29/64

24/54 particularly well suited for copolymerization reactions involving the polymerization of one or more of the monomers, for example, ethylene alpha-olefin, propylene, butene-1, pentene-1, 4-methyl-pentene-1 monomers, hexene-1, octene-1, decene-1, and cyclic olefins such as cyclopentene and styrene or a combination thereof. Other monomers can include polar vinyl monomers, diolefins such as dienes, polyenes, norbornene, norbornadiene, acetylene and aldehyde monomers. Preferably a copolymer of ethylene or propylene is produced. Preferably, the comonomer is an alpha-olefin having 3 to 15 carbon atoms, preferably 4 to 12 carbon atoms and more preferably 4 to 8 carbon atoms. In another embodiment, ethylene or propylene is polymerized with at least two different comonomers to form a terpolymer and the like, the preferred comonomers are a combination of alpha-olefin monomers having 3 to 10 carbon atoms, more preferably 4 to 8 carbon atoms. carbon. [0047] In another embodiment, ethylene or propylene is polymerized with at least two different comonomers to form a terpolymer and the like, the preferred comonomers are a combination of alpha-olefin monomers having 3 to 10 carbon atoms, more preferably 3 to carbon atoms 8 carbon atoms, optionally with at least one diene monomer. Preferred terpolymers include combinations such as ethylene / butene-1 / hexene-1, ethylene / propylene / butene-1, propylene / ethylene / butene-1, propylene / ethylene / hexene-1, ethylene / propylene / norbornadiene and the like.

[0048] In the most preferred embodiment, the process of the invention refers to the polymerization of ethylene and at least one

Petition 870180023462, of 03/23/2018, p. 30/64

25/54

4,543,399, 5,405,922, comonomer having 4 to 8 carbon atoms. In particular, comonomers are butene-1, 4-methylpentene-1, hexene-1 and octene-1, the most preferred being hexene-1. Typically, in a gas phase polymerization process, a continuous cycle is used where in a part of a reactor cycle, a cyclic gas stream, otherwise known as a recycle stream or fluidizing vehicle, is heated in the reactor by the heat of polymerization. This heat is removed in another part of the cycle by a cooling system external to the reactor. See, for example, U.S. Patent Nos. 4,588,790, 5,028,670, 5,317,036, 5,352,749,

5,436,304, 5,453,471, 5,462,999, 5,616,661 and

5,668,228, all of which are incorporated herein by reference.)

[0049] Generally, in a gas fluidized bed process for the production of polymers, a gas stream containing one or more monomers is continuously circulated through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is removed from the fluidized bed and recycled back into the reactor. Simultaneously, the polymer product is removed from the reactor and fresh monomer is added to replace the polymerized monomer. The reactor pressure can vary from approximately 680 kPag (100 psig) to approximately 3448 kPag (500 psig), preferably in the range of approximately 1379 kPag (200 psig) to approximately 2759 kPag (400 psig), more preferably in the range of approximately 1724 kPag (250 psig) at approximately 2414 kPag (350 psig). The reactor temperature can vary between approximately 60 ° C and approximately 120 ° C, preferably approximately 60

Petition 870180023462, of 03/23/2018, p. 31/64

26/54 ° C to approximately 115 ° C, and more preferably in the range of approximately 70 ° C to 110 ° C, and most preferably in the range of approximately 70 ² C to 95 ° C. The mass density deposited for the polymers produced by the process of the invention is in the range of approximately 160 to 561 kg / m ³ (10 to 35 lb / ft ³ ), preferably approximately 193 to 561 kg / m ³ (12 to 35 lb / ft) foot ³ ) more preferably from approximately 224 to 513 kg / m ³ (14 to 32 lb / foot ³ ) and most preferably from approximately 240 to 481 kg / m ³ (15 to 30 lb / foot ³ ).

[0050] Other gas phase processes considered by the process of the invention include those described in US Patent Nos. 5,627,242, 5,665,818 and 5,677,375, and European publications EP-A-0 794 200, EP-A-0 802 202 and EP-B-634 421, all of which are incorporated herein completely by reference.

[0051] A preferred process of the invention is where the process preferably a slurry or gaseous phase process, more preferably a gaseous phase process, is operated in the absence of or essentially free of any cleaners, such as triethyl aluminum, trimethyl aluminum, triisobutylaluminum and tri-n-hexylaluminum and diethyl aluminum chloride and the like. This preferred process is described in PCT publication WO 96/08520, which is incorporated herein completely by reference.

[0052] A slurry polymerization process generally uses pressures in the range of approximately 1 to approximately 50 atmospheres and even higher and temperatures in the range of 0 ° C to approximately 200 ° C. In a slurry polymerization, a polymer suspension

Petition 870180023462, of 03/23/2018, p. 32/64

27/54 solid, particulate, is formed in a liquid polymerization vehicle to which ethylene and comonomers and often hydrogen together with catalyst are added. The liquid used in the polymerization vehicle can be alkane or cycloalkane, or an aromatic hydrocarbon such as toluene, ethylbenzene or xylene. The vehicle used must be liquid under the conditions of polymerization and relatively inert. Preferably, a hexane or isobutane vehicle is employed.

[0053] In one embodiment, a preferred polymerization technique of the invention is called as a particle form, or slurry process where the temperature is kept below the temperature at which the polymer becomes a solution. Such a technique is well known in the art, see, for example, U.S. Patent No. 3,248,179, which is fully incorporated herein by reference. The preferred temperature in the particle form process is within the range of approximately 185 ° F (85 ° C) to approximately 230 ° F (110 ° C). Two preferred polymerization methods for the slurry process are those employing a loop reactor and those using a plurality of reactors agitated in series, in parallel or combinations thereof. Non-limiting examples of slurry processes include continuous loop or agitated reservoir processes. Also, other examples of the slurry process are described in U.S. Patent No. 4,613,484, which is hereby fully incorporated by reference.

[0054] It is also considered in one embodiment of the invention, that the process is a multi-stage polymerization process where a reactor is operating in the slurry phase

Petition 870180023462, of 03/23/2018, p. 33/64

28/54 which feeds into a reactor operating in a gaseous phase as described in U.S. Patent No. 5,684,097, which is fully incorporated herein by reference.

[0055] In one embodiment, the reactor used in the present invention is capable of producing more than 227 Kg / h (500 lbs / h) to approximately 90,900 Kg / h (200,000 lbs / h) or more of polymer, preferably more than than 455 Kg / h (1000 lbs / h), more preferably more than 4540 Kg / h (10,000 lbs / h), even more preferably more than 11,300 Kg / h (25,000 lbs / h), even more preferably more than 15,900 Kg / h (35,000 lbs / h), even more preferably more than 22,700 Kg / h (50,000 lbs / h) and more preferably more than 29,000 Kg / h (65,000 lbs / h) more than than 45,500 Kg / h (100,000 lbs / h).

[0056] The productivity of the catalyst or catalyst system is influenced by the partial pressure of the main monomer. The preferred mole percentage of the main monomer, ethylene or propylene, preferably ethylene is approximately 25 to 90 percentage moles and the partial pressure of the monomer is in the range of approximately 517 kPa (75 psia) to approximately 2069 kPa (300 psia), which are typical conditions in a gas phase polymerization process.

[0057] In another embodiment of the invention where the hafnocene of the invention is in particular, a non-bridged metallocene catalyst, the process of the invention is capable of producing a polymer product having a melt index of less than 0.1 dg / min without adding hydrogen to the process.

Polymer Product of the Invention [0058] The polymers produced by this invention can be

Petition 870180023462, of 03/23/2018, p. 34/64

29/54 used in a wide variety of end-use products and applications. Polymers typically have a density in the range of 0.86 g / cm ³ to 0.97 g / cm ³ , preferably in the range of 0.88 g / cm ³ to 0.965 g / cm ³ , more preferably in the range of 0.900 g / cm ³ to 0.96 g / cm ³ , even more preferably in the range of 0.905 g / cm ³ to 0.95 g / cm ³ , even more preferably in the range of 0.910 g / cm ³ to 0.940 g / cm ³ , and more preferably still greater than 0.910 g / cm ³ , preferably greater than 0.915 g / cm ³ . The polymers of the invention typically have a narrow molecular weight distribution, an average molecular weight by weight for number average molecular weight (Mw / Mn) greater than 1.5 approximately 4, particularly greater than 2 to approximately 3, more preferably greater than 2.2 to less than 3. Also, the polymers of the invention typically have a narrow composition distribution. In another embodiment, the polymers produced by the process of the invention, particularly in a gaseous and slurry phase process, contain less than 5 ppm hafnium, generally less than 2 ppm hafnium, preferably less than 1.5 ppm of hafnium, more preferably less than 1 ppm of hafnium. In one embodiment, the polymer of the invention contains in the range of approximately 0.01 ppm to approximately 2 ppm of hafnium, preferably in the range of approximately 0.01 ppm to approximately 1.5 ppm of hafnium, more preferably in the range of approximately 0, 01 ppm to 1 or less ppm of hafnium.

[0059] The polymers produced by the process of the invention are useful in such forming operations as extrusion and coextrusion of film, sheet and fiber, as well as molding by

Petition 870180023462, of 03/23/2018, p. 35/64

30/54 blowing, injection molding and rotary molding. Films include blown or fused films formed by coextrusion or lamination, useful as shrink film, bonding film, stretch film, sealing films, oriented films, light meal packaging, heavy duty bags, warehouse bags, packaging of baked and frozen food, medical packaging, industrial linings, membranes, etc., in applications with food contact and without food contact. The fibers include fiber operations with casting rotation, solution rotation and blown casting for use in woven or non-woven form for the manufacture of filters, diaper fabrics, medical garments, geotextiles, etc. Extruded items include medical tubing, wire and cable liners, geomembranes, and tank liners. Molded articles include single or multiple layer constructions in the form of bottles, tanks, wide hollow articles, hard food containers and toys, etc.

[0060] In one embodiment of this invention, the polymerization product is a linear low density polyethylene resin (LLDPE) produced by the polymerization of ethylene and an alpha-olefin comonomer having from 3 to 20 carbon atoms, preferably hexene-1 . The ethylene copolymers of the invention have from 1 to approximately 5 mol% of alpha-olefin comonomer incorporated in the copolymer. For the LLDPE resins of the invention, the ethylene copolymer typically has a polymer density greater than or equal to 0.910 g / cm ³ , preferably greater than or equal to 0.915 g / cm ³ , and an average molecular weight by weight > 25,000. In a preferred embodiment, the ethylene alpha-olefin copolymers of the invention are produced with a catalyst system having a component

Petition 870180023462, of 03/23/2018, p. 36/64

31/54 hafnocene of at least 95 mole% of the entire transition metal compound component and the balance is a comparable ligand structure zirconocene that comprises at least approximately 0.1 mole% of the transition metal compound component of the catalyst. In another embodiment of this invention, the resins, particularly the LLDPE resins thus produced by a catalyst system of that invention, are then converted into an article of manufacture, especially a film. A catalyst component as described above can be produced from an HfCl4 reagent for the production of the catalyst component of the transition metal compound which has at least approximately 0.1 mole% to approximately 5 mole% of a ZrCl4 contaminant, or other ZrCl4 form is added to the HfCl4 reagent in an amount sufficient to make up this mole% requirement for the transition metal compound component of the general catalyst system.

[0061] In one embodiment of this invention, a hafnium metallocene compound as previously described, but having a minor content of a zirconocene compound of comparable structure is used as the transition metal component for a catalyst system in the form supported for the production of the ethylene copolymer of the invention, especially a linear low density polyethylene resin. Typically, the minor amount of zirconium metallocene is in the range of 0.1 to 4 mole% as is typically the concentration of a zirconium tetrachloride contaminant in a hafnium tetrachloride reagent of which the transition metal component to the system catalyst is done. If the zirconium component is present in a

Petition 870180023462, of 03/23/2018, p. 37/64

32/54 insufficient quantity, then the content of this zirconium component in the hafnium reagent for the production of the catalyst can be increased by directly adding the desired amount of zirconium tetrachloride.

[0062] Any of the activators known as previously described can be used to activate the transition metal compound which is predominantly a hafnosocene with a small zirconocean content to an active catalytic state. Although this catalyst system can be used in any mode for polymerization of olefin-solution, solvent, slurry or gaseous phase since slurry and gaseous phase polymerization are preferred modes for the production of LLDPE resins, preferably the catalyst is in the form supported, preferably on a silica support.

[0063] The monomer supplied for the polymerization zone is regulated to produce a ratio of ethylene to alpha-olefin comonomer in proportion to yield a polyethylene of comonomer content, as a mass measure, preferably from approximately 0.5 to approximately 5.0 mole% comonomer, to mass produce a resin preferably density from 0.95 g / cm ³ to approximately 0.915 g / cm ³ . The reaction temperature, the residence time of the monomer, and the molecular weight control agent (such as H2) of the amounts of the catalyst system component are regulated to produce a resin, preferably a medium molecular weight LLDPE resin. by weight of approximately 25,000 to approximately 150,000, a number average molecular weight of approximately 3500 to approximately 60,000, preferably to approximately

Petition 870180023462, of 03/23/2018, p. 38/64

33/54

50,000, in order to produce the resin, preferably an LLDPE resin, a molecular weight distribution value of approximately 2.5 to approximately 7, preferably approximately 3 to 7.

[0064] An ethylene copolymer thus produced with the hafnium-based catalyst system (having 0.1 to 4 mol% of analogous zirconium structure) in a single reactor, preferably a gas phase reactor, had unique molecular characteristics among which are an expanded molecular weight distribution (MWD) and a polymodal CD. Such ethylene copolymers are more easily extruded into film products by blown film or blown film processing techniques with lower engine load, higher throughput speed and reduced inlet pressure when compared to EXCEED resins of comparable comonomer type and density. . Such ethylene copolymers, particularly the LLDPE resins of the invention, have for a comparable M1 a higher average molecular weight by weight and a broader MWD than an EXCEED resin. For the production of film cast with a resin of approximately 2.0 to approximately 5.0 Ml, and preferably approximately 3 Ml, LLDPE has a higher melt strength and higher breaking speed than those of an EXCEED® resin and the cast LLDPE film has a new balance of hardness and rigidity and generally improved shear balance and haul properties. For a resin of approximately 0.5 to approximately 2.0 Ml, and preferably of approximately Ml = 1.0, converted to film by a blown bubble technique, the LLDPE resin has, compared to a blown film produced

Petition 870180023462, of 03/23/2018, p. 39/64

34/54 of an EXCEED® resin, a 1% higher drying module in the transverse direction and improved casting properties. In both cases, the LLDPE resin has a higher specific energy output value (ESO) compared to an EXCEED® resin for converting it to a film.

[0065] Therefore, because of the greater activity of the hafnocene described here, it is now possible to practically produce the ethylene copolymers of the invention, especially the LLDPE resins of the invention, in a single gas phase reactor as described above and such LLDPE resins they are particularly well suited for processing in film articles by cast and blown film procedures.

[0066] Additional characteristics of the LLDPE resins described above that distinguish these LLDPE resins from the EXCEED® type resins is that under analysis of effluent fractionation of elevation of temperature (TREF), these LLDPE resins show two peaks, while a resin EXCEED® type shows only a single peak. In the ethylene copolymers of the invention, particularly the LLDPEs of that invention, the TREF analysis exhibits a low temperature (low T) peak position at 45-75 ° C, and preferably at approximately 65 ° C; a peak separation between the low T and high temperature (high T) peaks of a minimum of approximately 20 ° C and a maximum of approximately 35 ° C with a preferred peak separation of approximately 25 ° C. Using a Gaussian fit for the TREF via the multiple peak method (a generic mathematical model) shows that the low peak T which is also the low density fraction ranges from approximately 10 mole% to a maximum of approximately 90 mole% and in a preferred LLDPE resin the low peak

Petition 870180023462, of 03/23/2018, p. 40/64

35/54 low T is preferably approximately 30 mole% and the peak of high T is approximately 70 mole%. For an LLDPE as described above with hexene as a comonomer, the total comonomer content can vary from approximately 1 to approximately 5 mole% and preferably is approximately 3 mole% (in which its ASTM density is approximately 0.918 g / cm ³ ). LLDPEs as described above with hexene in particular as the comonomer will exhibit an average molecular weight by weight of approximately 25,000 to 150,000 in corresponding MI values ranging from approximately 10 to approximately 0.1 Ml, and preferably the average molecular weight by weight varies from approximately 80,000 to 110,000 within whose range the smelting index respectively ranges from a value of approximately 3 to approximately 1. For such LLDPE resins, the smelting index (MIR) ratio (l21 / 12 when measured by standard ASTM procedures) is greater than 15 to approximately 100, preferably in the range of 18 to 50, more preferably in the range of approximately 20 to less than approximately 40 and most preferably still from approximately 23 to approximately 35; the molecular weight distribution (MWD) is at least approximately 2.5 and at most 7, preferably approximately 3 to 7; and the Mz / Mw ratio is at least 2 and at most approximately 3.5 and is preferably approximately 2.8.

[0067] Molten films produced from such LLDPE resins having a Ml of 2 to 4 will have a drying modulus of 1% greater than the 14.5 kpsi (100 kPa) film layer and less than 21 kpsi (145 kPa) ), a shear in the machine direction greater than 100 g / mil and less than 600 g / mil, a

Petition 870180023462, of 03/23/2018, p. 41/64

36/54 shear in the transverse direction greater than 100 g / mil and less than 1000 g / mil, a haul value of 26 greater than 100 g / mil and less than 1400 g / mil. Such cast film will also have a traction in the machine direction at break greater than 7 kpsi (48 kPa) and less than 11 kpsi (76 kPa), a traction in the transverse direction at break greater than 5 kpsi (34 kPa) and less than 6.5 kpsi (45 kPa), an elongation in the machine direction at break greater than 325% and less than 600%, a transverse direction at break greater than 550% and less than 750%. Blown films produced from such LLDPE resins having an Ml of 0.5 to 2.0 will have a secant modulus of 1% greater than 26 kpsi (179 kPa) and less than 33 kpsi (227 kPa) and a haul value 26 ”greater than 1200 g / mil.

EXAMPLES [0068] In order to provide a better understanding of the present invention including its representative advantages, the following examples are offered.

[0069] The properties of the polymer were determined by the following test methods:

[0070] Density is measured according to ASTM-D-1238.MWD, or polydispersity, is a well-known feature of polymers. MWD is generally described as the ratio of the average molecular weight of the weight (Mg) to the average molecular weight of the number (Me). The Mw / Mn ratio can be measured by gel penetration chromatography techniques, or indirectly, by measuring the ratio (MIR) from l21 to 12 (casting index) as described in ASTM D-1238-F and ASTM D1238 -And, respectively.

[0071] In all the Examples below, methylalumoxane (MAO) is

Petition 870180023462, of 03/23/2018, p. 42/64

37/54 a MAO solution of 30 percentage weights in toluene available from Albernarle Corporation, Baton Rouge, Louisiana, Davison 948 silica is available from W.R. Grace, Davison Chemical Division, Baltimore, Maryland, and octadecylamine N, N-bis (2-hydroxyethyl) is available as Kemamine AS990 from ICI Specialties, Wilmington, Delaware. The metallocene components of the examples were prepared according to procedures well known in the art.

Example 1

Preparation of the Catalyst [0072] A solution of methylalumoxane and metallocene was formed by adding 11 cpl of 30 ps% MAO solution in toluene over 0.202 g of bis hafnium dichloride (npropylcyclopentadienyl) in a small bottle. 40 cm3 of fresh toluene was added, and the mixture stirred for 1 hour at 25 ° C. This pre-mixed solution of MAO and metallocene was then added over 10g of dried Davison 948 silica to 600 ° C. The resulting fluid mass was stirred for 1.5 hours at 25 ° C. The final catalyst was then dried to free flowing powder under vacuum at 65 ° C.

Polymerization [0073] A sample of the dry catalyst formed in Example 1 above was then used in an ethylene / 1-butene polymerization process in a 2 liter semi-packed gas phase reactor at 85 ° C. The reactor pressure, approximately 1069 kPag (155 psig), was kept constant by continuously feeding 5 mol-% 1-butene in ethylene to compensate for any pressure changes due to polymerization. After 1 h (hour), the polymer formed was separated from the seed bed material and analyzed for properties

Petition 870180023462, of 03/23/2018, p. 43/64

Molecular 38/54 shown in Table 1 below as Run 1 and 2. Example 2

Preparation of Catalyst [0074] A solution of methylalumoxane and metallocene was formed by adding 66.5 c 3 of 30 ps% toluene MAO solution over 1.21 g bis hafnium dichloride (npropylcyclopentadienyl) in a small bottle 50 cm of fresh toluene was added, and the mixture stirred for 1.5 hours in 2 ² C. This premixed solution of MAO and metallocene was then added over 60 g of dried Davison 948 silica to 600 ° C. The resulting fluid mass was stirred for 1.5 hours at 25 ° C. Then the solution of 0.41 g of N, N-bis (2-hydroxyethyl) octadecylamine in 50 cm @ 2 of toluene was added, and stirring continued for another 30 minutes. The final catalyst was then dried to free flowing powder under vacuum at 65 ° C.

Polymerization [0075] A sample of the dry catalyst formed in Example 2 above was then used in an ethylene / 1-butene polymerization process in a 2 liter semi-stacked gas phase reactor at 85 ° C. The pressure in the reactor, approximately 1089 kPag (158 psig), was kept constant by continuously feeding 5 mol-% 1-butene in ethylene to compensate for any pressure changes due to polymerization. After 1h, the polymer formed was separated from the seed bed material and analyzed for the molecular properties shown as Execution 3 in Table 1 below. Example 3

Preparation of the Catalyst [0076] Methylalumoxane (MAO) (1155 cm3 of 30 ps% solution in

Petition 870180023462, of 03/23/2018, p. 44/64

39/54 toluene) was loaded into a 2-gallon reaction vessel. 1970 cm3 of fresh toluene was added. Then a solution of 20.2 g of bis hafnium dichloride (npropylcyclopentadienyl) in 355 cm3 of toluene was added. The temperature was maintained at 27 ° C and the mixture was stirred for 1.5 hours.

[0077] 1000 g of a Davison 948 silica dehydrated at 600 ° C was loaded into a 2-gallon reaction vessel at 27 ° C. The solution of methylalumoxane and metallocene was added over the silica in two equal portions. Then an additional 250 cpl of toluene was added to the slurry. After 1 hour, a solution of 6.7 g of octadecylamine N, Nbis (2-hydroxyethyl) in 70 cm 3 of toluene was added and stirring continued for another 20 minutes. The final catalyst was then dried to free flowing powder at 68 ° C under vacuum. Polymerization [0078] Each of the dry catalyst samples formed in Example 3 was then used in an ethylene / 1-butene polymerization process in a 2 liter semi-blast gas phase reactor at 85 ° C. The pressure in the reactor, approximately

1089 kPag (158 psig), was kept constant by continuously feeding 5 mol-% 1-butene in ethylene to compensate for any pressure change due to polymerization. After 1h, the polymer formed was separated from the seed bed material and analyzed for the molecular properties shown as runs 4-6 in Table 1 below.

Example 4

Preparation of Catalyst [0079] A solution of methylalumoxane and metallocene was formed by adding 27.8 cm3 of 30 ps% MAO solution in

Petition 870180023462, of 03/23/2018, p. 45/64

40/54 toluene on 0.536g of bis hafnium dichloride (nbutylcyclopentadienyl) in a small bottle. 60 cm3 of fresh toluene was added, and the mixture stirred for 1.5 hours at 25 ° C. This premixed solution of MAO and metallocene was then added over 25 g of dried Davison 948 silica to 600 ° C. The resulting fluid mass was stirred for 1.5 hours at 25 ° C. Then a solution of 0.166 g of N, N-bis (2-hydroxyethyl) octadecylamine in 40 cm of toluene was added, and stirring continued for another 30 minutes. The final catalyst was then dried to free flowing powder under vacuum at 65 ° C.

Polymerization [0080] Each of the dry catalyst samples formed in Example 4 was then used in an ethylene / 1-butene polymerization process in a 2 liter semi-blast gas phase reactor at 85 ° C. The pressure in the reactor, approximately

1069 kPag (155 psig), was kept constant by continuously feeding 5 mol-% 1-butene in ethylene to compensate for any pressure change due to polymerization. After 1h, the polymer formed was separated from the seed bed material and analyzed for the molecular properties shown as Executions 7-9 in Table 1 below.

Comparative Example 5 Preparation of Catalyst [0081] A solution of methylalumoxane and metallocene was formed by adding 27.7 cpl of 30 ps% solution of MAO in toluene over 0.413 g of ₃ bis hafnium dichloride (cyclopentadienyl) in a flask little. 50 cm of fresh toluene was added, and the mixture stirred for 1.5 hours at 25 ° C. This pre-mixed solution of MAO and metallocene was then added over 25g of Davison silica

Petition 870180023462, of 03/23/2018, p. 46/64

41/54

948 dries to 600 ° C. The resulting slurry was stirred for 1.5 hours at 25 ° C. Then a solution of 0.166 g of N, N-bis (2-hydroxyethyl) octadecylamine in 40 cm of toluene was added, and stirring continued for another 30 minutes. The final catalyst was then dried to free flowing powder under vacuum at 65 ° C.

Polymerization [0082] Each of the dry catalyst samples formed in Comparative Example 5 was then used in an ethylene / 1-butene polymerization process in a 2 liter semi-stack gas phase reactor at 85 ° C. The pressure in the reactor, approximately 1089 kPag (158 psig), was kept constant by continuously feeding 5 mol-% 1-butene in ethylene to compensate for any pressure change due to polymerization. After 1h, the polymer formed was separated from the seed bed material and analyzed for the molecular properties shown as Executions C1 and C2 in Table 1 below.

Comparative Example 6 Preparation of Catalyst [0083] A solution of methylalumoxane and metallocene was formed _{3 by} adding 27.8 cm of 30 ps% solution of MAO in toluene over 0.444 g of bis hafnium dichloride (methylcyclopentadienyl) in a flask little. 60 cm3 of fresh toluene was added, and the mixture stirred for 1.5 hours at 25 ° C. This premixed solution of MAO and metallocene was then added over 25 g of dried Davison 948 silica to 600 ° C. The resulting fluid mass was stirred for 1.5 hours at 25 ° C. Then a solution of 0.169g of ₃ octadecylamine N, N-bis (2-hydroxyethyl) in 50 cm of toluene was added, and stirring continued for another 30 minutes.

Petition 870180023462, of 03/23/2018, p. 47/64

42/54

The final catalyst was then dried to free flowing powder under vacuum at 65 ° C.

Polymerization [0084] A sample of the dry catalyst formed in Comparative Example 6 was then used in an ethylene / 1-butene polymerization process in a 2 liter semi-blast gas phase reactor at 85 ° C. The pressure in the reactor, approximately 1062 kPag (154 psig), was kept constant by continuously feeding 5 mol-% 1-butene in ethylene to compensate for any pressure changes due to polymerization. After 1h, the polymer formed was separated from the seed bed material and analyzed for the molecular properties shown as Execution C3 in Table 1 below.

Comparative Example 7 Preparation of Catalyst [0085] A solution of methylalumoxane and metallocene was formed by adding 27.8 cm of 30 ps% solution of MAO in toluene over 0.475 g of ₃ bis hafnium dichloride (ethylcyclopentadienyl) in a flask little. 60 cm of fresh toluene was added, and the mixture stirred for 1.5 hours at 25 ° C. This pre-mixed solution of MAO and metallocene was then added over 25g of dried Davison 948 silica to 600 ° C. The resulting fluid mass was stirred for 1.5 hours at 25 ° C. Then a solution of 0.167 g of N, N-bis (2-hydroxylethyl) octadecylamine in 50 cm 3 of toluene was added, and stirring continued for another 30 minutes. The final catalyst was then dried to free flowing powder under vacuum at 65 ° C.

Polymerization [0086] A sample of the dry catalyst formed above in the

Petition 870180023462, of 03/23/2018, p. 48/64

43/54

Comparative Example 7 was then used in an ethylene / 1-butene polymerization process in a 2 liter semi-blast gas phase reactor at 85 ° C. The pressure in the reactor, approximately 1103 kPag (160 psig), was kept constant by continuously feeding 5 mol-% of 1-butene in ethylene to compensate for any pressure change due to polymerization. After 1h, the polymer formed was separated from the seed bed material and analyzed for the molecular properties shown as Execution C4 in Table 1 below.

Comparative Example 8

Catalyst Preparation [0087] A solution of methylalumoxane and metallocene was formed by adding 28 cm of 30 wt% MAO in toluene solution on 0,585g hafnium dichloride Me 2 Si (lndeniIa) 2 in a _third vial. 60 cm of fresh toluene was added, and the mixture stirred for 1.5 hours at 25 ° C. This premixed solution of MAO and metallocene was then added over 25g of dry Davison 948 silica to 600 ° C. The resulting slurry was stirred for 1.5 hours at 25 ° C. Then a solution of 0.167 g of N, N-bis (2-hydroxyethyl) octa-decylamine in 40 cm @ 3 of toluene was added, and stirring continued for another 30 minutes. The final catalyst was then dried to free flowing powder under vacuum at 65 ° C. Polymerization [0088] Each of the above dry catalyst samples in Comparative Example 8 was then used in an ethylene / 1-butene polymerization process in a 2 liter semi-stack gas phase reactor at 85 ° C. The pressure in the reactor, approximately 1089 kPag (158 psig), was kept constant

Petition 870180023462, of 03/23/2018, p. 49/64

44/54 for continuously feeding 5 mol-% 1-butene in ethylene to compensate for any pressure change due to polymerization. After 1h, the polymer formed was separated from the seed bed material and analyzed for the molecular properties shown as Executions C5-C7 in Table 1 below.

Table 1

Execution dog Catalyst (mg) Polymer yield Activity 1 Density (g / cm3) L2 (dg / min) L21 (dg / min) M _W MWD (nPrCp) 2HdC12 1 100 211 2126 0.9061 0.096 2.26 278942 2.88 2 50 117 2363 0.9025 0.899 2.5 275100 2.61 3 50 136 2674 NM NM 1.83 NM NM 4 50 159 3159 0.9064 NM 1.76 283282 2.82 5 50 117 2325 0.9091 NM 1.77 272925 2.80 6 50 117 2356 0.9081 NM 2.0 316801 2.88 (nBuCp) 2HIC12 7 150 271 1821 0.9057 NM 1.2 322890 2.46 8 150 225 1479 0.9056 NM 0.83 NM NM 9 100 195 1935 0.9070 NM 1, 51 NM NM (Cp) 2HfC12 Cl 300 12 40 0.9310 Nm 0.42 361692 3.98 C2 500 18 36 0.9273 NM 0.67 NM NM (mEcP) 2HiC12 C3 150 17 112 0.934 NM 0.68 291412 3.24 (EtCp) 2HIC12 C4 150 16 107 0.9275 NM 0.36 375772 3.20 Me2Si (Ind) 2HfC C5 150 7 48 0.9365 NM 1.74 232475 3.44 C6 150 6 37 0.9265 NM 1, 21 263758 4.16 C7 500 25 49 0.9239 NM 1.73 239161 3.40

Note 1- Catalyst activity expressed as MPE / (gcAT * h * 150 psi)

NM - Not measured, Ind is indenyl Example 9

Catalyst Preparation [0089] Metilalumoxane (1155 cm ³ of 30 ps% toluene solution) was loaded into a 2-gallon reaction vessel. 1970 cm3 of fresh toluene was added.

Petition 870180023462, of 03/23/2018, p. 50/64

45/54

Then, a solution of 20.17g of a bis transition metal dichloride (n-propyl cyclopentadienyl), where the transition metal comprised 99.1 mole% HI (hafnocentium) and 0.9 mole% Zr (zirconocene) , in 250 cm of toluene was added. The temperature was maintained at 27 ° C and the mixture was stirred for 1-5 hours. 998.8g of a Crossfield 40 / 600C silica (dehydrated at 600 ° C) was loaded into a 2-gallon reaction vessel at 27 ° C. The methylalumoxane and metallocene solution on top was added over the ₃ silica in two equal portions. Then an additional 250 cm of toluene was added to the slurry. After 1 hour, as an antistatic agent, 6.71 g of N, N-bis (2-hydroxyethyl) ₃ octadecylamine in 85 cm of toluene was added and stirring was continued for another 20 minutes. The final catalyst was then dried to a free flowing powder under vacuum for 12 hours of drying time. The theoretical recovery of

bodies solids (Weight dry) is 1337 g; Yield Final current (Weight dry) was 1160, 6g for an recovery of 87%. Of these bodies solids, 11.11 ps% was Al, the molar ratio of Beyond

The transition metal ratio was 125 and the transition metal charge as Hf was 0.66 ps% and as Zr it was 0.003 ps%. Polymerization [0090] Samples of the dry catalyst formed in Example 9 were then used in an ethylene / 1-hexene polymerization process in a pilot plant semi-packed gas phase reactor at 85 ° C under conditions and with results as reported in the Table 2 below.

Petition 870180023462, of 03/23/2018, p. 51/64

46/54

Table 2

Execution number 3-14 3-15 3-16 Reaction temperature ( ² C) 85 85 85 Runtime 58 35 41 Bed edge number 19, 01 5.97 3.35 Feed rate catalyst catalyst 30 26 22 Reaction atmosphere H ₂ (ppm) 508.2 554.9 171, 9 Ethylene (mole%) 70.0 6 9.9 66, 1 1-hexene (mole%) 1.02 1.01 1.02 Nitrogen (mole%) 28, 98 29.09 32.88 Pressure (psig) / (kPag) 300/2067 300/2067 300/2067 Production rate 58.8 / 24 63.5 / 26 59.8 / 24 Specific activity (g / g-h-atm) 60 64 53 Granule properties MI (g / 10min) 1, 11 3.39 0.11 MIR (I21 / I2) 24, 82 23, 17 28, 17 Density (g / cm ³ ) 0.9163 0.9175 0.9115 Bulk density (g / cm ³ ) 0.4088 0.4036 0.4048 Gray (ppm) 243 229 292 Hf (ppm) 1,281 1,263 1,619 Al (ppm) 17, 4 14, 9 19, 9

Example 10 [0091] Amount of granules of the ethylene copolymer resin product produced by Executions 3-14 and 3-15 of Table 2 of Example 9 were taken from a turnover bed mixed with granules taken from other bed edges and then , with an added antioxidant agent, extruded, then cut into pellets. These resin pellets were then analyzed for their molecular properties before the resin pellets were converted into

Petition 870180023462, of 03/23/2018, p. 52/64

47/54 articles of film. The resin pellets of Execution 3-15 having an MI of approximately 2.9 were melted extruded into a film while the resin pellets of Execution 314 having an MI of approximately 1 were transformed into a film by a blown bubble technique.

[0092] For comparative purposes, the approximately 2.9 Ml ethylene copolymer resin of Execution 3-15 was compared with similarly fused films of Dow ELITE® 5200 and Exxon EXCEED® 357 C32, both of which are ethylene copolymers having an Ml of approximately 3. Similarly, for comparative purposes, ethylene copolymer resins of Execution 3-14 having an MI of approximately 1 was compared to similarly produced blown bubble films of Dow ELITE® 5400 and Exxon EXCEED® 350D60, both of which are copolymers of ethylene having an MI of approximately 1.

[0093] This comparison of fused and blown bubble films prepared from the ethylene copolymers of the invention, in particular the LLDPE resins of that invention, with fused and blown bubble films produced from a Dow ELITE® or Exxon EXCEED® density resin of similar resin and MI value is shown below.

[0094] The specific properties of these fused film resins and their resulting film articles when formed, likewise each is aged in time and aged with heat (as in the case of article inventory storage) are reported in Tables 3- 5 below.

Petition 870180023462, of 03/23/2018, p. 53/64

Table 3A Cast films

48/54

Resin Resin properties Execution 3-15 Elite® 5200 Exceed® 357C32 MI (g / 10 min) 2.9 3.4 3.4 MIR 22.5 23, 0 16.7 Resin density (g / cm ³ ) 0.9177 0.9197 0.9183 Mw (x10 0 0) 94.2 7 6.6 84.8 MWD (M _w / M _n ) 3.48 3.4 2.45 Mg / M _w 2023 2, 6 1.80 Soft hexene% (mass) 3, 6 2.7 3.1 Casting resistance (cN) 1.82 NM 1.2 T.R.E.F. Low Peak T ² C 63 62 AT .est low peak soft T% 73 53 AT . low peak T hexene soft 5.82 6.01 AT Intermediate T peak ² C AT 79 73 .th peak of soft I-T% AT 30 100 . peak I-T hexene soft% AT 2.88 3.91 High peak T ² C 82 90 AT . peak soft H-T% 27 17 AT . peak H-T hexene soft% 2.30 0.83 AT

Petition 870180023462, of 03/23/2018, p. 54/64

Table 3B

49/54

Resin Resin properties Execution 3-14 Elite® 5200 Exceed® 357C32 Film measure (mil) 0.83 0.83 0.83 Film density (g / cm ³ ) 0.9104 0.9121 0.9101 1% Se. Mod. (Psi) MD 15,400 22,300 14,950 TD 18,780 25,250 20,570 Traction (psi) @ Yield MD 821 1,000 954 TD 806 970 938 @ Break MD 9, 982 9, 913 8,896 TD 6.227 5.350 5.154 Stretching (%) @ Yield MD 4.7 5.0 4.4 TD 6 4, 9 4, 6 @ Break MD 365 364 446 TD 673 616 793 Shear ± SD (g / mil) MD 252 ± 43 183 185 ± 26 TD 620 ± 53 773 615 ± 53 Intrinsic shear (g / mil) - 530 here. 460 26 ± SD section (g / mil) 4 60 ± 30 212 ± 31 ^b 6 4 8 ± 7 6 Mist (%) 1 0, 6 2.1 Brightness at 45 ² 92, 6 92 88.8 Rate (lb / h / rpm) 5.90 5.85 ± 6.10 E.S.O. (lb / hp / h) 6, 95 7.37 ± 6.36 Act./max Extr.Amp 204/240 180/240 225/240 Inlet pressure (psi) 3941 2900 ± 4167

[0095] Table 4 below reports the differentiation in the properties of the fused film with 6 months of

Petition 870180023462, of 03/23/2018, p. 55/64

50/54 aging of the inventive and comparative films reported in Table 3B above. In Table 4 the number Δ is the differential value in changing the properties of the film from those of an initial unused aged film.

Table 4

Cast films, six months aged

Film properties Execution 3-15 Exceed® 57C32 Film measure (mil) 0.82 (ΔΟ, ΟΙ) 0.83 (Δ = 0) Film Density (g / cm ³ ) 0.9104 (Δ = 0) 0.9102 (Δ = 0.001) 1% Sec.Mod. (kpsi) MD 16.1 (Δ = 0.7) 16.2 (Δ = 1.25) TD 20.0 (Δ = 1.22) 17.9 (Δ = 2.67) Shear ± SD (g / mil) MD 367 (Δ = 115 ± 20) 166 (Δ = -19 ± 21.5) TD 617 (Δ = -3 ± 44.5) 555 (Δ = -60 ± 46) 26 ± SD section (g / mil) Contraction MD 60 (Δ = + 4) 54 (Δ = -7) TD 16 (Δ = 2 8) 9 (Δ = -10)

[0096] The films produced (of the invention and comparisons) were heat aged by keeping a roll of such film at 64.4 ° C (140 ° F) for 48 hours, and then removing such roll of film for temperature of the room (environment) and balancing it for ASTM conditions (except for the relative humidity). For the cast LLDPE resin films of that invention compared to the cast resin films of Dow ELITE® 5200 and / or Exxon EXCEED® 357C32, similarly fused and heat aged, Table 5 below reports the difference in certain film properties ( that is, in the table, reported as Δ = in either a positive or negative value or against the measured property value for the film initially produced).

Petition 870180023462, of 03/23/2018, p. 56/64

51/54

Table 5

Heat aged cast film

Resin Film properties Execution 3-15 Elite® 5200 Exceed® 357C32 Film measure (mil) 0.83 (Δ = 0) 0.83 (Δ = 0) 0.83 (Δ = 0) Film density (g / cm ³ ) 0.9130 (Δ = 0.0026) 0.9121 (Δ = ΝΜ) 0.9125 (Δ = 0.0024) 1% Sec. Mod. (Kpsi) MD 17.23 (Δ = 1.8) 19.3 (Δ = —3) 15.78 (Δ = 0.83) TD 21.32 (Δ = 2.54) 27.3 (Δ = 2.05) 19.9 (Δ = -0.67) Traction (psi) @ Yield MD 1149 (Δ = 328) 1014 (Δ = 14) 1107 (Δ = 153) TD 1091 (Δ = 285) 970 (Δ = 119) 1037 (Δ = 99) @break MD 9856 (Δ = - 126) 9238 (Δ = -675) 9833 (Δ = 937) TD 6220 (Δ = -7) 5368 (Δ = 18) 7191 (Δ = 2037) Stretching (%) @ Yield MD 7.3 (Δ = 2.6) 4.3 (Δ = -0.7) 7.4 (Δ = 3.0) TD 6.0 (Δ = 0.4) 4.5 (Δ = -0.4) 6.3 (Δ = 1.7) @break MD 370 (Δ = 5) 351 (Δ = —13) 417 (Δ = -29) TD 704 (Δ = 31) 633 (Δ = 17) 711 (Δ = -82) Shear ± SD (g / thousand) MD 138 (Δ = - 114 ± 335) 391 (Δ = 208) 136 (Δ = -49 ± 22) TD 778 (Δ = -158 ± 53) 827 (Δ = 57) 615 (Δ = -0 ± 43) 26 ± SD section (g / mil) 648 (Δ = -188 ± 53) 212 (Δ = —88) 187 (Δ = 461 ± 50)

Petition 870180023462, of 03/23/2018, p. 57/64

52/54 [0097] As also reported by this Example, blown bubble film articles were prepared from a MIul (LLDPE resin from that invention and also comparison of ELITE® and EXCEED® resins from -MI = 1). The specific properties of these blown film resins and their resulting film articles when formed are reported in Table 6 below.

Table 6A Blown films

Resin Resin properties Execution 3-15 Elite® 5200 Exceed® 357C32 MI (g / 10min) 1.0 1.26 0.98 MIR 23.5 1, 6 16.3 Resin density (g / cm ³ ) 0.9137 0.9168 0.9186 Mw (x10 0 0) 131 98, 9 106 (+) MWD (M _w / Mn) 3.28 3.3 1.4 (+) Mg / Mw 2.24 2.4 1.8 (+) Soft hexene% (mass) 3.3 3.5 2, 6 T.R.E.F. Low Peak T ² C 65 58 AT . low peak T soft% 72 37 AT . low peak T hexene soft% 5.44 6.75 AT Intermediate T peak ² C AT 76 76 . peak soft I-T% AT 53 100 . peak I-T hexene soft% AT 3.39 3.38 High peak T ² C 82 90 AT . peak soft H-T% 27 10 AT . peak H-T hexene soft% 2.30 0.76 AT

Petition 870180023462, of 03/23/2018, p. 58/64

Table 6B

53/54

Resin Resin properties Execution 3-14 Elite® 5400 Exceed® 350D60 Film measure (mil) 1.00 0.74 1.00 Film density (g / cm ³ ) 0.9140 0.9142 0.9156 1% Sec. Mod. (Psi) MD 26,400 25,280 28,600 TD 32,100 29,500 30,900 Traction (psi) @ Yield MD 1244 1117 1250 TD 1265 1190 1328 Traction @ Break MD 7782 8863 8485 TD 9755 7856 10.026 Stretching (%) @ Yield MD 4.7 4.2 4.8 TD 4.7 4.4 4, 9 Stretch @ Break MD 424 440 465 TD 624 569 644 Shear ± SD (g / mil) MD 238 ± 22 273 249 ± 24 TD 495 ± 17 526 500 ± 25 Intrinsic shear (g / mil) Ca 390 510 390 26 ± SD section (g / mil) 1238 ± 114 1237 ± 105b 927 ± 84 Mist (%) 13, 1 7.1 12, 6 Brightness at 45 ² 44 58 39 Extrusion properties of the film Rate (lb / h / rpm) (_ / h / rpm) 3.3 6.2 3.2 E.S.O. (lb / h / rpm) (/ h / rpm) 11, 6 13, 4 9.96 Act./max Extr.Amp 68.6 / 125 170/240 74/129 Inlet pressure (psi) 3490 5310 3650

[0099] Although the present invention has been described and illustrated with reference to particular embodiments, those skilled in the art will find that the invention lends itself to variations not necessarily illustrated here. It is considered that the catalyst system of this invention can be used in

Petition 870180023462, of 03/23/2018, p. 59/64

54/54 combination with other catalyst systems comprising more than one catalyst system of the invention. For that reason, then, reference should be made only to the appended claims for purposes of determining the true scope of the present invention. Various changes in the details of the illustrated apparatus and construction and method of operation can be made without departing from the spirit of the invention.

Petition 870180023462, of 03/23/2018, p. 60/64

1/2

Claims (8)

1. Ethylene and alpha-olefin copolymer, characterized by the fact that it has: a bimodal composition distribution, a Mw / Mn value of 2.5 to 7, a density of 0.910 to 0.915 g / cm ³ , the copolymer being under fractionation analysis by high temperature elution (TREF) shows two peaks, a low temperature peak (LTP) between 45 ° C and 75 ° C and a high temperature peak (HTP), the two peaks being separated by 20 ° C at 35 ° C, presenting an I ₂₁ / I ₂ ratio value of 15 to 100, and be produced with a hafnium metallocene catalyst system with bulky binder. 2. Copolymer, according to claim 1, characterized by the fact that under high temperature elution fractionation analysis (TREF) exhibits a low temperature peak position at 65 ° C. 3. Copolymer, according to claim 1, characterized by the fact that under high temperature elution fractionation (TREF) the low temperature peak (LTP) corresponds to a fraction of the ethylene / alpha-olefin copolymer ranging from 10 % to 90% of said copolymer. 4. Copolymer, according to claim 1, characterized by the fact that under high temperature elution fractionation (TREF) the low temperature peak (LTP) corresponds to 30% of the ethylene / alpha-olefin copolymer and the peak high temperature (HTP) corresponds to 70% of said copolymer. 5. Copolymer, according to claim 1, characterized by the fact that it has a Mz / Mw ratio of at least 2. Petition 870180023462, of 03/23/2018, p. 61/64 2/2 6. Copolymer, according to claim 1, characterized by the fact that it is produced in a single reactor. 7. Copolymer, according to claim 6, characterized by the fact that the reactor is a gas phase reactor. 8. Film, characterized by the fact that it is made of a copolymer as defined in any one of claims 1 to 7. Petition 870180023462, of 03/23/2018, p. 62/64 1/1