BRPI0818825B1 - Process for improving film fog of a polymer - Google Patents

Abstract

"process for improving film fog of a polymer". The present invention relates to a process for the polymerization of olefin (s) using a cyclic bridged metallocene catalyst system to produce polymers with improved properties. the catalyst system may include a cyclic bridged metallocene, la (r'sir ') lbzrq2, activated by an activator, the activator comprising aluminoxane, a modified aluminoxane, or a mixture thereof, and supported by a support, where: la and 1b are independently an unsubstituted cyclopentadienyl binder or a zr linked substitute defined by formula (c5h4-drd), where r is hydrogen, a hydrocarbyl substituent, a substituted hydrocarbyl substituent, or a heteroatom substituent, and where d is 0, 1, 2, 3 or 4; la and lb are connected to each other with a cyclic silicon bridge, r'sir ', where r' are independently hydrocarbyl or substituted hydrocarbyl substituents that are connected to each other to form a silicyclic ring; and each q is a labile hydrocarbyl binder or a substituted hydrocarbyl.

Description

[001] This request claims the benefit of Serial N °

60 / 999,903, filed on October 22, 2007, the description of which is incorporated by reference in its entirety. FIELD OF THE INVENTION [002] The present invention relates to processes for polymerizing olefin (s) in order to produce polymers having improved properties. In addition, the invention is directed to a metallocene catalyst compound and catalyst system for use in the polymerization of olefin (s) in order to produce polymers having improved properties. In particular, the invention is directed to a system of cyclic chain catalysts, their use in a polymerization process, and products produced therefrom. BACKGROUND OF THE INVENTION [003] Processability is the ability to economically process and form a polymer uniformly. Processability involves such elements as how easily the polymer flows, resistance to melting, and whether the extrudate is free of distortion or not. Typical metallocene catalyzed polyethylene (mPE) is somewhat more difficult to process than low density polyethylene (LDPE) made in a high pressure polymerization process. Generally, mPEs require more driving force and produce higher extrusion pressures to match the LDPEs extrusion rate. Typical mPEs also have lower melt strength which, for example, adversely affects bubble stability during film extrusion, and they are prone to melt fracture at shear rates

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2/64 commercial. On the other hand, however, mPEs exhibit superior physical properties when compared to LDPEs.

[004] It is not uncommon in the industry to add various levels of LDPE A to an mPE to increase melt strength, to increase shear sensitivity, that is, to increase flow at commercial shear rates; and to reduce the tendency to fusion fracture. However, these mixtures generally have poor mechanical properties when compared to liquid mPE.

[005] Traditionally, metallocene catalysts produce polymers having a poor molecular weight distribution. Deficient molecular weight distribution polymers tend to be more difficult to process. The broader the molecular weight distribution of the polymer the easier the polymer to process. One technique for improving the processability of mPEs is to expand the product molecular weight (MWD) distribution by mixing two or more mPEs with significantly different molecular weights, or by switching to a polymerization catalyst or mixture of catalysts that produce wide MWD polymers.

[006] In the art, the characteristics of specific metallocene catalyst compounds have been shown to produce polymers that are easier to process. For example, U.S. Patent No. 5,281,679 discusses metallocene catalyst compounds in which the linker is substituted with a substituent having a secondary or tertiary carbon atom for the production of broader molecular weight distribution polymers.

The U.S. Patent

No. 5,470,811 describes the use of a metallocene catalyst mixture to produce easily processed polymers

In addition

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3/64

US Patent No. ^s 5,798,427 addresses the production of polymers having enhanced processability using a metallocene compound catalyst wherein the ligands are specifically substituted indenyl ligands.

[007] US Patent No. 6,339,134 (Crowther et al.) And US Patent No. 6,388,115 (Crowther et al.), Describe a binder metallocene catalyst compound represented by the formula L ^A L ^B MQ _n , where MQ _n can be, among other things, zirconium dichloride, and L ^A and L ^B can be, among other things, open, acyclic, or fused ring (s) or ring system (s) (rings) such as unsubstituted or substituted cyclopentadienyl ligands, ligands or ligands of the cyclopentadienyl type, substituted heteroatom and / or heteroatom containing cyclopentadienyl type ligands. Q linkers include hydrocarbyl radicals having 1 to 20 carbon atoms.

[008] Metallocenes of ligands particularly useful for improving processability, contain ligands L ^A and L ^B. that connect cyclic bridges. These metallocene supported catalysts prepared, as reported in US Patent No. ^s 6,339,134 (Crowther et al.) And U.S. Patent No. 6,388,115 (Crowther et al.), Suffer from low productivity (prod = max

1066 ^g polymer / g cat supported x h) in polymerizations in phase in gas. [009] Metallocene, with cyclic bridges connecting the ligands L ^A and L ^B , what contain two groups of departure in methyl, were supported in combinations many different in support / activator in WO 03/064433, WO 03/064433 and in the Order in

US Patent Publication No. 2005-049140 ^s.

[010] The PCT Publication No. WO 03/064433 ^s (Holtcamp, MW)

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4/64 refers to polymerization catalyst activator compounds that are neutral or ionic and include a group of 13 atoms, preferably boron or aluminum, attached to at least one halogenated or partially halogenated heterocyclic linker. The publication states that such activator compounds can be used to activate metallocene catalyst compositions. Two metallocenes, with cyclic bridges connecting L ^A and L ^B ligands, were separately examined with this activator in the solution. These were cyclotetramethylenesilila (tetramethyl cyclopentadienyl) (indenyl) zirconium dimethyl ((C ₄ H ₈ ) Si (C ₅ Me ₄ ) (C ₉ H ₇ ) ZrMe ₂ ) and cyclotrimethylenosilila (tetramethyl cyclopentadienyl) (indenyl) zirconium dimethyl (6) dimethyl (6) Si (C5Me4) (C9H7) ZrMe2). These combinations of metallocene activators suffered from low activity (the maximum activity was 393 g polymer / mmol cat hour). No example of these metallocenes supported in a vehicle has been given.

[011] US Patent Publication No. 2005-049140 ^s (Holtcamp,

MW), refers to a polymerization catalyst activator support system that employs dialuminoxanes in combination with boranes containing halogenated aryl groups and dehydrated silica. A metallocene, with a cyclic bridge connecting the ligands L ^A and L ^B, was examined with this activator in a slurry polymerization: cyclotetramethylenesilila (tetramethyl cyclopentadienyl) (indenyl) zirconium dimethyl ((C4H8) Si (C5Me4) (C9H7) Zr2) .

[012] PCT Publication No. WO 03/064435 ^s (Holtcamp) relates to polymerization catalyst activator compounds employing combinations of diol and halogenated aryl group metal compounds 13. Two metallocenes, with

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5/64 cyclic bridges connecting the ligands L ^A and L ^B were separately examined with this activated in the solution. These were cyclotetramethylenesilila (cyclopentadienyl tetramethyl) (indenyl) dimethyl zirconium ((C ₄ H ₈ ) Si (C ₅ Me ₄ ) (C ₉ H ₇ ) ZrMe ₂ ) and cyclotrimethylenosilila (cyclopentadienyl tetramethyl) (indenyl) zirconium ( ₃ ) dimethyl ( ₃₎ H ₆ ) Si (C ₅ Me ₄ ) (C ₉ H ₇ ) ZrMe ₂ ). These metallocene activator combinations were examined in solution and suffered from low activity (the maximum activity was 37.8 g polymer / mmol cat hour). No example of these metallocenes supported on the vehicle has been given.

[013] hypothetical bisindenila dimethyl zirconocene complexes employing cyclic silicon bridges are mentioned in US Patent Application Publication No. 2007-055028A1 ^s (Casty, G. et. Al.), US Patent Application ° PublicaçãoN

2004-220359 A1 (Abhari, R, et. Al.), US Patent Application Publication No. 2004-152851 A1 ^s (Weng, W., et. Al.), WO 2004/046214 A2 (Jiang, P., et . al.), WO 2004 / 026923A2 (Arjunan, P., et. al.), WO 2004/026921 A1 (Brant, P., et. al.), WO 2002/002575 A1 (Kuchta, M., et al.). These metallocenes were not prepared.

SUMMARY OF THE INVENTION [014] This invention generally relates to polymerization processes using a cyclic chain metallocene catalyst to produce polymer products that have improved properties. In addition, the invention is directed to improving bridged catalyst compounds having a cyclic bridge, catalyst system comprising those compounds, and polymerization processes using these compounds.

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6/64 [015] In accordance with an aspect of the present invention, an olefin polymerization catalyst system comprising a cyclic bridged metallocene, LA (R'SiR ') LBZrQ ₂ , is activated by an activator, the activator comprising an aluminoxane and supported by a support.

[016] Cyclic bridged metallocene, L ^A (R'SiR ') L ^B ZrQ2, is comprised of L ^A and L ^B connected to each other with a cyclic silicon bridge, R'SiR', where each R ' it is independently hydrocarbyl or substituted hydrocarbyl substituents that are connected to each other to form a silacyclic ring. Each of the ligands is attached to a zirconium atom. The L ^A and L ^B ligands are unsubstituted or substituted cyclopentadienyl ligands as described by the formula (C5H4-dRd), where d is an integer selected from 0, 1, 2, 3 or 4 and R is hydrogen, the hydrocarbyl substituent, a substituted hydrocarbyl substituent or a heteroatom substituent. The two starting groups

Q are labile hydrocarbyl or substituted hydrocarbyl binders.

The terms support or vehicle are used interchangeably and are any support material, preferably a porous support material, for example, talc, inorganic oxides, inorganic chlorides. Other vehicles include resinous support materials such as functionalized or crosslinked organic polystyrene supports, such as benzene polyolefins divinyl polystyrene or polymeric compounds, zeolites, clays, or any other organic or inorganic support material and the like, or mixtures thereof.

[018]

The catalyst system can be formed first

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7/64 combining the activator with the support, and then adding L ^A (R'SiR ') L ^B ZrQ ₂ to that end.

[019] An advantage of this polymerization catalyst is the improved productivity with respect to other combinations of catalyst / activator / support of cyclic bridge metallocene in fluidization processes or gas phase.

[020] The catalyst system can be used in the manufacture of a polymer comprising, as monomers, ethylene, an olefin monomer having from 3 to 8 carbon atoms, and optionally one or more olefin monomers having from 2 to 30 atoms carbon such as hexane or butene. The use can be to control the melting index of the product, to control the molecular weight distribution, or to control the dry mist of the film. The polymer product can have a density of 0.910 to 0.945 g / cc, or 0.915 to 0.935 g / cc.

[021] The catalyst system can be used to produce a polymer product with wide or bimodal distribution in molecular weight or melt index, in a single reactor, comprising, as monomers, ethylene, an olefin monomer having from 3 to 8 carbon atoms, and optionally one or more other olefin monomers having from 2 to 30 carbon atoms, changing the proportion of comonomer, terpolymer, or polymer in a controlled manner. The catalyst system can be used to produce a polymer product with wide or bimodal distribution in density in a single reactor, comprising, as monomers, ethylene, an olefin monomer having 3 to 8 carbon atoms, and optionally one or more other olefin monomers having from 2 to 30 carbon atoms, in a controlled manner. The

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8/64 monomers can be ethylene and butene. The monomers can be ethylene, butene and another olefin monomer having from 2 to 30 carbon atoms.

[022] The polymer product can have a molecular weight distribution (Mw / Mn) of no more than about 4.2, or about 3.6 to about 4.2.

[023] In another aspect, use is made of a lesser amount, 1% to about 50% by weight, or about 5 to about 20% by weight, of a polymer comprising, as monomers, ethylene, a monomer of olefin having from 3 to 8 carbon atoms, and optionally one or more other olefin monomers having from 2 to 30 carbon atoms made using LA (R'SiR ') LBZrQ ₂ as a catalyst, to mix with another polymer comprising monomer of olefins having from 2 to 30 carbon atoms, to improve the dry mist of the film.

[024] In one embodiment, the invention relates to the preparation of a high productivity supported cyclic bridge metallocene catalyst for the production of ethylene polymers and other olefins. In one embodiment, the cyclic bridge metallocene catalyst comprises (CH ₂ ) ₄ Si (C ₅ Me ₄ ) (C ₅ H ₄ ) Zr (CH ₃ ) ₂ , methyl aluminoxane and silica (average particle size 40 μ , average surface area 300 m ² / g, dehydrated at 600 ° C). This catalyst system was highly productive for the preparation of copolymers of ethylene and butene in a gas phase process. The productivity of at least 1786 g Polymer / (g cat hour) or partial pressure greater than 70 ° C and 170 psi of ethylene was greater than any productivity previously seen for cyclic chain metallocene supported in a process of

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9/64 fluidization or gas phase. This higher productivity is still under adverse conditions of lower ethylene pressure and partial temperature than in previously described systems. [025] Other aspects and characteristics of the present invention will be evident to those skilled in the art upon review of the following description of specific modalities of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS [026] The modalities of the present invention will now be described, by way of example only, with reference to the attached figures, in which:

[027] Figures 1 and 2 contain graphs of strain hardening of an HP-LDPE polymer ExxonMobil LD103.09; and a polymer made using (C ₄ H ₈ ) Si (C ₅ Me ₄ ) (C ₅ H ₄ ) ZrMe ₂ as the catalyst, respectively.

[028] Figure 3 is a graph of MFR v. MI for polymers of the present invention modalities and comparative polymers.

[029] Figure 4 is a contraction graph for Area Retramat v. MD Plastic Tension for polymers of the present invention and comparative polymers; and [030] Figure 5 is a graph of molecular weight g 'v. for polymers of the present invention and comparative polymers.

DETAILED DESCRIPTION [031] As the present compounds, components, compositions and / or methods are disclosed and described, it should be understood that unless otherwise indicated, this invention is not limited to compounds, components, compositions, reagents, conditions of reaction, binders,

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10/64 specific or similar metallocene structures, which as such may vary, unless otherwise specified. It should be understood that the terminology used here at present for the purpose of describing particular modalities only and is not intended to be limiting.

[032] It should be noted that, as used in the specification and in the appended claims, the forms in the singular one, one and the include the plural referring to unless otherwise specified. Thus, for example, reference to a leaving group as in a portion substituted with a leaving group includes more than one leaving group, such that the portion can be replaced with two or more of such groups. Similarly, the reference to a halogen atom as in a moiety substituted with a halogen atom includes more than one halogen atom, such that the moiety can be replaced with two or more halogen atoms, the reference to a substituent includes one or more substituents, reference to a linker includes one or more linkers, and the like.

[033] As used here in the present, all references to the Periodic Table of the Elements and groups of moments are given in the NEW OBSERVATION published in HAWLEY'S CONDENSED CHEMICAL DICTIONARY, Third Edition, John Wiley & Sons, Inc., (1997) (reproduced here with permission from IUPAC).

Cyclic Bridged Metallocene Catalysts [034] Cyclic Bridged Metallocene Catalysts according to a modality of the invention at the moment are comprised of cyclic bridged metallocene, as shown in equation I, an activator, and a support.

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11/64

L ^A (R'SiR ') L ^B ZrQ ₂ (I) [035] Cyclic bridge metallocenes are shown in equation I. They contain two ligands L ^A and L ^B connected to each other with a cyclic silicone bridge, R 'SiR'. Each of the ligands is attached to a zirconium atom. In a preferred embodiment, at least one linker is η-attached to a metal atom, more preferably η-attached to the metal atom. Two starting groups Q are attached to the zirconium atom.

[036] In a preferred embodiment, the L ^A and L ^B ligands are unsubstituted or substituted cyclopentadienyl ligands as described by the formula (C5H4-dRd), where d is an integer selected from 0, 1, 2, 3 or 4 and R is hydrogen, a hydrocarbyl substituent, a substituted hydrocarbyl substituent or a heteroatom substituent. At least two R groups, preferably two adjacent R groups, can come together to form a ring structure. In addition, a substituent of the R group such as 1-butanyl can form a sigma bond of carbon bound to zirconium.

[037]

Hydrocarbyl substitutes are made of between 1 and 100 carbon atoms, the rest being hydrogen. Non-limiting examples of hydrocarbyl substituents include branched or cyclic alkyl radicals; alkyl radicals; alkenyl radicals; alkynyl radicals;

cycloalkyl radicals; aryl radicals; alkylene radicals; or a combination of them. Non-limiting examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl; olefinically unsaturated substituents including vinyl-terminated binder (eg, but-3-enyl, prop-2-enyl, hex-5-enyl and

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12/64 similar), benzyl or phenyl groups and the like, including all their isomers, for example tertiary butyl, isopropyl, and the like.

[038] Substituted hydrocarbyl substituents are made from 1 to 100 carbon atoms, the rest being hydrogen, fluorine, chlorine, bromine, iodine, oxygen, sulfur, nitrogen, phosphorus, boron, silicon, germanium or tin atoms. Substituted hydrocarbyl substituents are carbon-based radicals. Non-limiting examples of the trifluoromethyl radical of substituted hydrocarbyl substituents, trimethylsilyl, trimethylsilanemethyl (MeaSiCH2-) radicals.

[039] Heteroatom substitutes are radicals based on fluorine, chlorine, bromine, iodine, oxygen, sulfur, nitrogen, phosphorus, boron, silicon, germanium or tin. Thus, heteroatom substituents include organometalloid radicals. Non-limiting examples of heteroatom substituents include, methoxy radical, amino diphenyl radical, thioalkyl, thioalkenyl, methyltrimethylsilyl radical, dimethyl aluminum, tri (perflourophenyl) boron radicals and the like.

[040] Non-limiting examples of linkers include cyclopentadienyl linkers, indenyl linkers, benzindenyl linkers, fluorenyl linkers, octahydrofluorenyl linkers, including hydrogenated versions thereof, for example, tetrahydroindenyl linkers. In one embodiment, L ^A to L ^B can be any other linker structure capable of η-bonding to M, preferably η-bonding to M, and more preferably η-bonding to M.

[041] In another modality, L ^A and L ^B can comprise a

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13/64 or more heteroatoms, for example, nitrogen, silicon, boron, germanium, sulfur and phosphorus, in combination with carbon atoms to form an open, acyclic, or preferably fused ring or ring system, for example, a ancillary hetero-cyclopentadienyl.

[042] In one embodiment, the bridged metallocene cyclic catalyst compounds are those in which the substituents of R in the ligands LA and LB, (C ₅ H _4-d R _d ) of formula (I) are substituted with the same or different number of substituents on each of the linkers. In another embodiment, the ligands L ^A and L ^B , (C5H4-dRd) of formula (I) are different from each other.

[043] In a preferred embodiment, the binders of the metallocene catalyst compounds of formula (I) are asymmetrically substituted. In another preferred embodiment, at least one of the ligands L ^A and L ^B , (C5H4-dRd) of formula (I) is unsubstituted. More preferably, L ^A is C5Me4, where Me is methyl, and L ^B is C5H4.

[044] The two linkers are joined with a cyclic bridged group (R'SiR ') in which R' are independently hydrocarbyl or substituted hydrocarbyl substituents that are connected to each other to form a silicate ring. Non-limiting examples of cyclic bridged groups include cyclo-tri or tetra-alkylene silyl groups. Non-limiting examples of cyclic bridged groups are represented by the following structures:

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14/64 [045] is a silicycle ring is preferred

Preferably

Silicycle ring (silicycle) from one to 5 elements. More preferably, the 4-a ring includes cyclotetramethylenesilyl.

silyl cyclotetramethylenes.

[046]

The two element groups. Bridging groups plus silyl cyclotrimethylenes or most preferred outlet Q are ligands of

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Labile hydrocarbyl or substituted hydrocarbyl. Q may also include hydrocarbyl groups having ethylenic or aromatic _z 3 unsaturation thereby forming a η a bond

Zr. Also, two Q's can be an alkylidene, or a cyclomethylated hydrocarbyl. Also, two Q's can be a coordinated diene or polyene such as butadiene or isoprene.

Preferably,

Q originates from butadiene or isoprene. More preferably,

Q is allyl, benzyl, trimethylsilylmethyl, or methyl. More preferably, Q is methyl.

In a preferred embodiment, the metallocene catalyst compounds of the invention include cyclotrimethylene silyl (tetramethyl cyclopentadienyl) (cyclopentadienyl) zirconium dimethyl, cyclotetramethylenylsilyl (tetramethyl cyclopentadienyl) (cyclopentadienyl) zirconium dimethylethylethylethyl, cyclotrimethylethylmethyl (cyclotrimethyl) -cycletrimethyl (tetramethyl cyclopentadienyl) (3-methyl cyclopentadienyl) zirconium dimethyl, cyclotrimethylenesilyl bis (2-methyl indenyl) zirconium dimethyl, cyclotrimethylenesilyl (tetramethyl cyclopentadienyl) cyclopentadienyl) cyclopentadienyl) dimethyl zirconium.

In the most preferred embodiment, the metallocene catalyst compound is cyclotetramethylenesilyl (tetramethyl dimethyl.

Activator and Activation Methods for Compounds

Metallocene Catalysts

The cyclic bridged metallocene catalyst compounds described above can be activated with an activator

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16/64 comprising an aluminoxane or the product of an aluminoxane and a support or vehicle. This activation yields catalyst compounds capable of polymerizing olefins.

[049] It is well known in the art that aluminoxanes contain a wide distribution of structures formed from the reaction of R3Al or mixtures of R3Al, where R is hydrogen or a similar or different hydrocarbyl with water. This is in contrast to dialuminoxanes which have a specific structure. It is also well recognized that aluminoxanes may contain alanes, R3Al, remaining from an incomplete hydrolysis reaction.

[050] There are a variety of methods for the preparation of aluminoxane and modified aluminoxanes, the non-limiting examples of which are described in U.S. Patent Nos.

4,665,208,. 952,540,

4,924,018,

5,248,801,

5,391,529,

5,091,352,

4,908,463,

5,235,081,

5,693,838,

5,206,199,

4,968,827,

5,157,137,

5,731,253,

5,204,419,

5,308,815,

5,103,031,

5,731,451

4,874,734,

5,329,032,

5,391,793,

5,744,656, European publications N ^s s EP-A-0 561

476,

EP-B1-0 279 586 and

EP-A-0 594-218, and PCT publication No. WO 94/10180.

[051] Activation can also occur in the presence of aluminoxanes combined in series or in parallel with other activators capable of converting cyclic bridged metallocenes into olefin polymerization catalysts.

[052] Additional non-limiting activators, for example, may include a Lewis acid or a non-coordinating ionic activator or ionization activator or any other compound that includes Lewis bases, aluminum alkyls, conventional type cocatalysts or a support of activator and combinations of them that can

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17/64 convert a neutral metallocene catalyst compound into a catalytically active metallocene cation. It is within the scope of this invention to use aluminoxane or modified aluminoxane as an activator, and / or also to use ionization activators, neutral or ionic, such as the metalloid precursor of tri (n-butyl) ammonium tetraquis (pentafluorophenyl) boron or trisperfluorophenyl boron or a metalloid precursor of trisperfluoronafile boron that would ionize the neutral metallocene catalyst compound.

[053] In one embodiment, an additional activation method using ionizing ionic compounds not containing an active proton, but capable of producing both a metallocene catalyst cation and a non-coordinating anion is also contemplated, and is also described in EP- A-0 426 637, EP-A-0 573 403 and US Pat. No. 5,387,568.

[054] Additional ionization compounds may contain an active proton, or some other cations associated with but not coordinated with or only weakly coordinated with the remaining ion of the ionization compound. Such compounds and the like are described in European publications No. EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-A-500 944, EP-A-0 277 003 and EP-A-0277004, US patent 5153157 ^s s, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124.

[055] Other additional activators include those described in WO 98/07515 such as tris (2, 2 ', 2nonafluorobiphenyl) fluoroaluminate. Combinations of activators are also contemplated by the invention, for example, aluminoxanes and ionization activators in combination, see for example, WO 94/07928 and WO 95/14044, and the

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18/64 U.S. Patent Nos. 5,153,157 and 5,453,410. WO 98/09996 describes the activation of 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'-bisphenylditrimethylsilicate). 4THF as an activator for the metallocene catalyst compound. Also, activation methods such as using radiation (see EP-B1-0 615 981), electrochemical oxidation, and the like are also contemplated as activation methods for the purposes of imparting the neutral metallocene catalyst compound or precursor to a metallocene cation capable of polymerizing olefins.

[056] It is further contemplated that other catalysts can be combined with the cyclic bridged metallocene catalyst compounds of modalities of the present invention. For example, see U.S. Patent Nos. 4,937,299, 4,935,474, 5,281,679, 5,359,015, 5,470,811, and 5,719,241.

[057] In another embodiment, one or more metallocene catalyst compounds or catalyst systems can be used in combination with one or more conventional type catalyst compounds or catalyst systems. Non-limiting examples of mixed catalysts and catalyst systems are described in U.S. 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, 5,691,264, 5,723,399 and

5,767,031.

and WO 96/23010.

Support method [058] The cyclic metallocene catalyst compounds described above and catalyst systems can be combined with one or more support materials or vehicles using one of the

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19/64 support methods well known in the art or as described below. In the preferred embodiment, the one embodiment method of the invention uses a polymerization catalyst in a supported form. For example, in a more preferred embodiment, a metallocene catalyst compound or catalyst system is in a supported form, for example, deposited on, bonded to, contacted with, or incorporated into, adsorbed or absorbed into, or on a support or vehicle .

[059] The terms support or vehicle are used interchangeably and are any support material, preferably a porous support material, for example, talc, inorganic oxides and inorganic chlorides. Other vehicles include resinous support materials such as polystyrene, functionalized or cross-linked 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.

[060] Preferred carriers are inorganic oxides which include group 2, 3, 4, 5, 13 or 14 metal oxides. Preferred supports include silica, alumina, silica-alumina, magnesium chloride, and mixtures thereof. Other useful supports include magnesia, titania, zirconia, montmorillonite (EP-B1 0 511 665) and the like. Also, combinations of these support materials can be used, for example, silica-chromium, silica-alumina, silica-titania and the like.

[061] It is preferred that the vehicle, more preferably an inorganic oxide, has a surface area in the range of about 10 to about 700 m ² / g, pore volume in the range of about 0.1 to about 4 , 0 cc / g and average particle size

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20/64 in the range of about 5 to about 500 pm. More preferably, the vehicle's surface area is in the range of about 50 to about 500 m ² / g, pore volume of about 0.5 to about 3.5 cc / g and average particle size of about 10 at about 200 pm. More preferably, the vehicle's surface area is in the range of about 100 to about 400 m ² / g, pore volume of about 0.8 to about 3.0 cc / g and average particle size is about from 5 to about 100 pm. The average vehicle pore size of the embodiments of the invention can have a pore size in the range of 10 to 1000 Å, preferably 50 to about 500 Å, and more preferably 75 to about 350 Å.

[062] Examples of supporting the metallocene catalyst systems of embodiments of the invention are described in US Patent 4,701,432 ^s s, 4,808,561, 4,912,075,

4,925,821,

4,937,217,

5,346,925,

5,529,965,

5,643,847,

5,723,402,

5,008,228,

5,422,325,

5,554,704,

5,665,665,

5,731,261,

5,238,892,

5,466,649,

5,629,253,

5,698,487,

5,759,940,

5,240,894,

5,466,766,

5,639,835,

5,714,424,

5,767,032,

5,332,706,

5,468,702,

5,625,015,

5,723,400,

WO

5,770,664,

95/32995, WO 95/14044, WO 96/06187 and WO 97/02297.

[063] In one embodiment, the cyclic bridged metallocene catalyst compounds of the embodiments of the invention can be deposited on the same or separate supports together with the activator, or the activator can be used in an unsupported form, or can be deposited on a support different from the supported metallocene catalyst compounds of an embodiment of the invention, or any combination thereof.

[064] There are several other methods in the art for

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21/64 support a catalyst compound or polymerization catalyst system of an embodiment of the invention. For example, the metallocene catalyst compound is a cyclic bridge embodiment of the invention may contain a polymer bound ligand as described in U.S. Patent ^Nos 5,473,202 and 5,770,755 are, the metallocene catalyst system of an embodiment of the invention can be spray dried as described in US patent ^Nos 5,648,310, the support used with the metallocene catalyst system in a cyclic bridge embodiment of the invention is functionalized as described in European publication ^No's EP-a-0802203, or by at least one substituent or leaving group is selected as described in US patent ^Nos 5,688,880.

[065] In a preferred embodiment, there is provided a supported metallocene catalyst system in cyclic bridge that includes an antistatic agent or surface modifier that is used in preparing the supported catalyst system as described in PCT Publication ^Nos WO 96/11960. Catalyst systems of an embodiment of the invention can be prepared in the presence of an olefin, for example, hexene-1. [066] A preferred method for producing the cyclic bridged metallocene catalyst system of an embodiment of the invention is described below and is described in WO 96/00245 and WO 96/00243. In this preferred method, cyclic bridged metallocene catalyst compound is fluidized in 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 the cyclic and / or cyclic bridged metallocene catalyst compounds

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22/64 activator of an embodiment of the invention. In the most preferred embodiment, the liquid is an aliphatic or aromatic cyclic hydrocarbon, more preferably toluene. Cyclic bridged metallocene catalyst compound and activating solutions are mixed together and added to a porous support or the porous support is added to solutions such as the total volume of the metallocene catalyst compound solution and the activating solution or metallocene catalyst compound and the activating 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. Another preferred method is to pre-react the porous support with an activator in a hydrocarbon diluent. The cyclic bridged metallocene hydrocarbon solution is added later to complete the preparation of the catalyst.

[067] Procedures for measuring the total pore volume of a porous support are well known in the art. The details of one of these procedures are discussed in Volume 1, Experimental Methods in Catalitic Research (Academic Press, 1968) (especially 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 Catalists By Liquid Titration, Vol. 28, No. 3, Analitical Chemistry 332-334 (March, 1956).

[068] The molar ratio of the metal of the activating component to the metal of the cyclic bridged metallocene catalyst compounds is in the range of 0.3: 1 to

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1000: 1, preferably 20: 1 to 800: 1, and more preferably 50: 1 to 500: 1. Where the activator is an ionization activator such as those based on the tetrakis anion (pentafluorophenyl) boron, the metal molar ratio of the activator component to the metal component of the cyclic bridged metallocene catalyst is preferably in the range between 0.3: 1 to 3: 1.

[069] In a preferred embodiment, the catalyst system comprises a catalyst as described hereinafter activated by methylaluminoxane (MAO) and supported by silica. Although conventionally, MAO is combined with a metallocene and then the combination is deposited on silica, as shown in the examples, the preference hereinafter is to first combine the activator (eg, MAO) and the support (eg, silica) and then add the catalyst to the combination. Modified MAO (MMAO) or a combination of MAO and MMAO can also be used.

[070] In one embodiment of the invention, olefin (s), preferably C2 to C30 olefin (s) or alpha-olefin (s), preferably ethylene or propylene or combinations thereof are prepolymerized in the presence of the metallocene catalyst system in cyclic bridge of one embodiment of the invention prior to main polymerization. Prepolymerization can be carried out in batches or continuously in the gas, solution or slurry phase including at high pressures.

Prepolymerization can take place with any olefin monomer or combination and / or in the presence of any molecular weight control agent such as hydrogen.

For examples of prepolymerization procedures, see US Patents 4748221 N ^Y Y,

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4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578, European publication ^No's EP-B-0279 863 and PCT Publication ^Nos WO 97/44371.

[071] In one embodiment, the cyclic bridged metallocene catalysts of the embodiments of the invention can be combined with a carboxylic acid salt of a metal ester, for example, aluminum carboxylates such as aluminum mono-, di- and tristearates, aluminum octoates, oleates and cyclohexylbutyrates, as described in the US patent

6,300,436.

Polymerization Process [072] Catalysts and catalyst systems of the embodiments of the invention described above are suitable for use in gas phase or slurry phase processes over a wide range of temperatures and pressures. The most preferred process is a gas phase process. The temperatures can be in the range of -60 ° C to about 280 ° C, preferably from 50 ° C to about 200 ° C, and the pressures employed can be in the range of 1 atmosphere to about 500 atmospheres or more.

[073] The gas phase or slurry phase processes can be conducted in combination with each other or with a solution or high pressure process. Particularly preferred is a gas phase or slurry phase polymerization of one or more olefins at least one of which is ethylene or propylene.

[074] In one embodiment, the process of this invention is directed to a gas phase or slurry polymerization process of one or more olefin monomers having from 2 to carbon atoms, preferably 2 to 12 atoms of

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carbon, and more preferably 2 to 8 atoms in carbon. bad modality gives invention is particularly good adjusted The polymerization two or more monomers in olefin in

ethylene, propylene, butene-1, pentene-1,4,4-methyl-pentene-1, hexene-1, octene-1 and decene-1.

[075] Other monomers useful in the process of the embodiments of the invention include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or unconjugated dienes, polyenes, vinyl monomers and cyclic olefins. Non-limiting monomers useful in an embodiment of the invention can include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes, substituted alkyl styrene, ethylborne norbornene, dicyclopentadiene and cyclopentene.

[076] In a preferred embodiment of the process of the invention, an ethylene copolymer is produced, with ethylene a comonomer having at least one alpha-olefin having from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and more preferably from 4 to 8 carbon atoms, it is polymerized in a gas phase process. In the most preferred embodiment, a copolymer of ethylene and butene is produced.

[077] In another embodiment of the process of the invention, ethylene or propylene is polymerized with at least two different comonomers, optionally one of which may be a diene, to form a terpolymer. In one embodiment, two of the three monomers of the terpolymer are butene and ethylene. In one embodiment, the comonomer content is 1.0 to 20.0% by weight, or 2.0 to 15.0% by weight. As seen in example 5 below, the use of (C ₄ H ₈ ) Si (C ₅ Me ₄ ) (C ₅ H ₄ ) ZrMe ₂ as the catalyst in

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26/64 preparation of an ethylene / butene copolymer, resulted in an acute response to the comonomer ratio. That is, the melting index (MI) changed rapidly and sharply as the comonomer ratio was adjusted. Changes in density were also observed. These changes can be associated with long chain branching. Therefore, polymers having ethylene and butene as two of the monomers can be used to control the melt index of the product. In addition, products with wide or bimodal distribution in molecular weight or fusion index in a single reactor using a single catalyst could be used by changing the comonomer fed in a controlled manner, thus producing polyethylene products with usual designed properties with reactor economy single.

[078] In one embodiment, the invention is directed to a polymerization process, particularly a gas phase or slurry phase process, for the polymerization of propylene alone or with one or more other monomers including ethylene, and / or other olefins having 4 to 12 carbon atoms. Polypropylene polymers may be produced using metallocene catalysts particularly bridged as described in US Patent 5,296,434 and 5,278,264 ^are s.

[079] Typically in a gas phase polymerization process, a continuous cycle is employed in which a part of the cycle of a reactor system, a gas stream in a cycle, otherwise known as a recycle stream or media fluidization, is heated in the reactor by the heat of polymerization. This heat is removed from the recycle composition in another part of the cycle by a cooling system.

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27/64 external to the reactor. Generally, in a gas fluidized bed process for the production of polymers, a gas stream containing one or more monomers is continuously cycled through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is removed from the fluidized bed and recycled again in the reactor. Simultaneously, the polymer product is removed from the reactor and the fresh monomer is added to replace the polymerized monomer. (See, for example, U.S. Patent Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922,

5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228).

[080] The reactor pressure in a gas phase process can vary from about 100 psig (690 kPa) to about 500 psig (3448 kPa), preferably in the range of about 200 psig (1379 kPa) to about 400 psig (2759 kPa), more preferably in the range of about 250 psig (1724 kPa) to about 350 psig (2414 kPa).

[081] The reactor temperature in a phase phase process

gas may vary of fence 30 ° C The about 1 20 ° C, preferably from about 60 ° C at about 115 ° Ç, more preferably in range about 70 ° C at 110 ° C, and more preferably in range of about 70 ° C a about 95 ° Ç. [082] Other processes of phase of gas contemplated fur process of a modality of invention include those

described in U.S. Patent Nos. 5,627,242, 5,665,818 and

5,677,375, and European publications ^s s N EP-A-0794200, EP-A-0

802 202 and EP-B-634 421.

[083] In a preferred embodiment, the reactor used in the present invention is capable of and the process of the invention is producing more than 500 lbs of polymer per hour (227

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Kg / hour) to about 200,000 lbs / h (90,900 kg / h) or more of polymer, preferably greater than 1000 lbs / h (455 kg / h), more preferably greater than 10,000 lbs / h even more preferably greater than 25,000

Kg / h), even more preferably greater than (4540 Kg / h),

35,000 lbs / h (15,900 kg / h), even more preferably greater than 50,000

Kg / h) and more preferably greater than

65,000 lbs / h (29,000 kg / h) more than

100,000 lbs / h (45,500

Kg / h).

A slurry polymerization process generally uses pressures in the range of about 1 to about 50 atmospheres and even more and temperatures in the range of 0 ° C to about

120 ° C. In a slurry polymerization, a solid particulate polymer suspension is formed in a liquid polymerization diluent medium to which ethylene and comonomers and often hydrogen together 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 distillation, to the reactor. The liquid diluent employed in the polymerization medium is typically an alkane having 3 to 7 carbon atoms, preferably a branched alkane. The medium used must be liquid under the conditions of polymerization and relatively inert. When a propane medium is used, the process must be operated above the critical temperature and pressure of the reaction diluent. Preferably, a hexene or isobutene medium is employed.

[085] A preferred polymerization technique of an embodiment of the invention is referred to as a polymerization in the

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29/64 particle form, or a slurry process where the temperature is kept below the temperature at which the polymer goes into the solution. Such a technique is well known in the art, and described, for example, in U.S. Patent No. 3,248,179. Other slurry processes include those that employ a loop reactor and those that use a plurality of series, parallel, or mixed agitated reactors. Non-limiting examples of slurry processes include agitated tank or continuous loop processes. Also, other examples of slurry processes are described in U.S. Patent No. 4,613,484.

[086] In one embodiment, the reactor used in the invention's slurry process is capable of and the process of one embodiment of the invention is producing more than 2000 lbs of polymer per hour (907 kg / h), more preferably more than than 5000 lbs / h (2268 kg / h), and more preferably more than 10,000 lbs / h (4540 kg / h). In another embodiment, the slurry reactor used in the process of one embodiment of the invention is producing more than 15,000 lbs of polymer per hour (6804 kg / h), preferably more than 25,000 lbs / h (11,340 kg / h) at about 100,000 lbs / h (45,500 kg / h).

[087] Examples of solution processes are described in U.S. Patent Nos. 4,271,060, 5,001,205, 5,236,998 and 5,589,555.

[088] A preferred process of an embodiment of the invention is where the process, preferably a gas phase or slurry process is operated in the presence of a cyclic bridged metallocene catalyst system of an embodiment of the invention and in the absence of or essentially free of any scavengers, such as triethyl aluminum,

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30/64 trimethylaluminum, triisobutylaluminum and tri-n-hexylalumin and diethyl aluminum chloride, dibutyl zinc and the like. This preferred process is described in WO 96/08520 and U.S. Patent No. 5,712,352 and 5,763,543. In another preferred embodiment of the process of the invention, the process is operated by introducing a benzyl compound into the reactor and / or contacting a benzyl compound with the metallocene catalyst system of an embodiment of the invention prior to its introduction into the reactor.

Polymer product of embodiments of the invention [089] The properties of the polymers were determined by the test methods listed in Table 1 or described hereinafter.

Table 1: Test methods

Property Units Procedure Fusion indices, Fusion flow ratios dg / min ASTM D-1238 Density g / cc ASTM D-1505 Mist O. % ASTM D-1003 Brightness @ 45 ° O. % ASTM D-2457 Elastic yield @ mPa ASTM D-882 Stretching @ Yield O. % ASTM D-882 1% secant module mPa ASTM D-882 Dart drop impact g / pm ASTM D-1709 (THE) Tear resistance of Elmendorf g / pm ASTM D-1922 Melting resistance cN As described in the specification

[090] The long chain branching index (LCB) for the entire sample (ie, g ' _avg ) and the long slicing branch chain index (SLCB) (ie, g') are

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31/64 described in US Patent No. ^s 6,870,010.

[091] Polymers of the present invention may have improved optical and shrinkage properties, as further discussed below.

[092] Polymers produced by a process of one embodiment of the invention can be used in a wide variety of end-use products and applications. The polymers produced include linear low density polyethylene, plastomers, high density polyethylene, low density polyethylene, polypropylene and polypropylene copolymers. Polymers can be made up of, at least partially, butene, ethylene, and other olefin monomers having from 2 to 20 carbon atoms. For example, the polymers can be copolymers of butene and ethylene, or terpolymers of butene, ethylene, and another olefin monomer.

[093] Polymers, typically ethylene-based polymers, have a density in the range of 0.90 g / cc to 0.97 g / cc, preferably in the range of 0.90 g / cc to 0.965 g / cc , more preferably in the range of 0.90 g / cc to 0.96 g / cc, even more preferably in the range of 0.905 g / cc to 0.95 g / cc, even more preferably in the range of 0.910 g / cc to 0.945 g / cc, and more preferably more than 0.915 g / cc to about 0.935 g / cc.

[094] The melt strength of the polymers produced using the catalyst of an embodiment of the invention are preferably more than 4 cN, preferably more than cN and, preferably less than 10 cN. For the purposes of this patent application and attached claims, melt strength is measured with a capillary rheometer (RHEOTESTER® 1000, Goettfert, Rock Hill, SC) in conjunction with

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32/64 Goettfert Rheotens melting resistance device (RHEOTENS 71,97). A polymeric fusion filament extruded from the capillary matrix is clamped between two counter-rotation wheels on the apparatus. The absorption speed is increased at a constant acceleration of 12 mm / sec ² , which is controlled by the WinRHEO ^® program provided by Goettfert. The maximum buoyant force (in the cN unit) achieved before the filament breaks or begins to show tensile resonance is determined as the melt strength. The rheometer temperature is adjusted to 190 ° C. The barrel has a diameter of 12 mm. The capillary matrix has a length of 30 mm and a diameter of 2 mm. The polymer melt is extruded from the die at a piston speed of 0.49 mm / sec. The apparent shear rate for the melt in the matrix is therefore 70 sec ^-1 and the speed at the exit of the matrix is 17.5 mm / sec. The distance between the die outlet and the wheel contact point must be 125 mm.

[095] Polymers of the modalities of the present invention have an exceptionally high shear thinning combination for extrusion, excellent optical film property and excellent shrinkage performance. Historically HD-LDPE is the only product family having most of these attributes. However, the clarity of HP-LDPE is much less than that of the polymers of the embodiments of the present invention. Conventional ZNLLDPE are lacking most of these attributes. Some easy-to-process products (i.e., very broad MWD) from the gaseous and / or slurry phase processes are typically very poor in optical properties. The shrinkage property of these conventional products is also somewhat insufficient for the

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33/64 application of shrinkage. It was found that (C ₄ H ₈ ) Si (C ₅ Me ₄ ) (C ₅ H ₄ ) ZrMe ₂ is very effective in reducing the film fog of various LLDPE (especially for a polymer made using (1,3-Me , n-Bu-Cp) ₂ ZrCl ₂ as the catalyst and for a polymer made using (C5H4-CH2CH2CH3) 2Hf (CH3) 2.

[096] As shown in figure 2, the polymers of the modalities of the present invention exhibited deformation-hardening behavior under the transient uniaxial extensional flow, similar to HP-LDPE. As shown in Table 4, the polymers of the modalities of the present invention have a wide MFR (greater than 100), which is an indicator of good processability. The films in these products have TD shrinkage comparable to, or better than, HP-LDPE, optical properties similar to HP-LDPE. Compared to a high pressure ethylene polymerization process, a gas phase reactor also has the added benefit of lower cost and generally higher capacity.

[097] Hardening by deformation at 150 ° C of the Example

Comparative A (ExxonMobil LD103.09, from Exxon Mobil Chemical Company, Houston, TX) and Example 5 are shown in Figures 1 and 2 respectively. The following two references discuss the polyolefin deformation hardening and the test for measurement of the same: Strain hardening of various polyolefins in uniaxial stretching to flow, The Society of Rheology, Inc. J. Rheol. 47 (3), 619-630 (2003); and Measuring the transient extensional rheology of polyethylene melts using the SER universal testing platform, The Society of

Rheology, Inc. J. Rheol. 49 (3), 585-606 (2005).

RETRAMAT shrinkage test [098] The RETRAMAT shrinkage test used here at

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34/64 following is based on NFT 54-125 and ASTM D 2838-95, procedure A. The DIN 53-369 and ISO / DIS 14616 methods only cover the measurement of the shrinkage force, but do not give guidelines for simultaneous measurement percentages of shrinkage. The ASTM method covers the determination of the plastic shrinkage stress characteristics and related shrinkage. The shrinkage force and orientation release tension from the heat shrinkable film less than 800 pm thick, while the specimen is completely restricted to shrinkage as it is heated. The NFT 54-125 method covers the total shrinking process, with both plastic and thermal shrinking processes.

[099] The method used here is to expose two film samples at a given temperature, for a given time, and to cool them down to room temperature, simulating what happens inside a shrinking installation. For each test sample, a minimum of 10 strips ± 150 mm long and 15 mm wide are prepared for both MD and TD on a sample cutter. Retramat adhesives are applied over the edges of the sample so that the shrinking area of the test specimen measures exactly 100 mm in length. The oven temperature is 190 ° C and the closing time is 45 seconds. During the test, one of the samples is connected to a force transducer, while the other is connected to a displacement transducer. A thermocouple allows the temperature to be monitored in a few millimeters of the sample medium. The three parameters (displacement force - temperature) are displayed continuously on the Retramat and recorded on a lab PC.

[100] Polymers produced by the process of a

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35/64 embodiment of the invention may have a molecular weight distribution, a weight average molecular weight to a numerical average molecular weight (M _w / M _n ) of more than 1.5 to about 15, particularly more than 2 to about from 10, more preferably more than about 2.5 to less than about 8, and more preferably from 3.0 to 8.

[101] The polymers of the present invention in one embodiment have a melt index (MI) or (I2) as measured by ASTM-D1238-E in the range of 0.01 dg / min to 1000 dg / min, more preferably about from 0.01 dg / min to about 100 dg / min, even more preferably from about 0.01 dg / min to about 50 dg / min, even more preferably from about 0.01 dg / min to about 10 dg / min, and more preferably from about 0.05 dg / min to about 10 dg / min.

[102] The polymers of the invention in one embodiment have a melt index ratio (I ₂₁ / I ₂ ) (I ₂ is measured by ASTM-D1238-F) equal to or more than 49.011 x MI ⁽ -0.4304) ⁾ ; more preferably equal to or more than 57.18 x mi ^(-0.4304) ; as shown in figure 3.

[103] In certain embodiments, polymers as described hereinafter may have a limited composition distribution characterized by the fact that the T75-T25 value is less than 25, preferably less than 20, more preferably less than 15 , and more preferably less than 10, where T25 is the temperature at which 25% of the eluted polymer is obtained and T75 is the temperature at which 75% of the eluted polymer is obtained in a TREF experiment as described hereinafter. The TREF-LS data reported here below were measured using an analytical-sized TREF instrument (Polimerchar, Spain), with a column of the following

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36/64 dimension: the internal diameter (ID) of 7.8 mm and the external diameter (OD) of 9.53 mm and a column length of 150 mm. The column was filled with steel beads. 0.5 mL of a solution

polymer to 6.4% (p / v ) in orthodichlorobenzene (ODCB) containing 6 g BHT / 4 L was loaded about the column and cold in 140 ° C a 25 ° C at a rate in cooling constant in 1.0 ° C / min. Subsequently, ODCB was pumped

through the column at a flow rate of 1.0 ml / min, and the column temperature was increased at a constant heating rate of 2 ° C / min to elute the polymer.

[104] Polymers of an embodiment of the invention can be mixed and / or coextruded with any other polymer. Non-limiting examples of other polymers include linear low density polyethylenes produced by conventional Ziegler-Natta and / or metallocene catalysis, elastomers, plastomers, low density and high pressure polyethylene, high density polyethylene, polypropylene and the like .

[105] Polymers produced by the process of an embodiment of the invention and mixtures thereof are useful in such forming operation as film, sheet, and extrusion and coextrusion as well as blow molding, injection molding and rotary molding. Films include blown or cast films formed by monolayer extrusion, coextrusion or bilamination useful as shrink sleeves, shrink wrap, bundle shrink, cling film, extension film, sealing films, oriented films, snack pack, heavy bags of responsibility, heavy bags of responsibility, snacks at the grocery store, packaging of roasted and frozen food in food packaging,

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37/64 medical packaging, industrial coatings, membranes, etc. in food contact and non-food contact applications. Fibers include melt rotation, solution rotation, and melt blown fiber operations for use in woven or non-woven form to make filters, disposable diaper fabrics, medical clothing, geotextiles, etc. Extruded items include medical tubes, wire and cable sheaths, geomembranes, and tank sheaths. Molded articles include single, multi-layered constructions in the form of bottles, tanks, large hollow articles, containers for rigid food and toys, etc.

EXAMPLES [106] It should be understood that although the invention has been described in conjunction with the specific modalities thereof, the foregoing description is intended to illustrate and not to limit the scope of the invention. Other aspects, advantages and modifications will be apparent to those skilled in the technique to which the invention belongs.

[107] Therefore, the following examples are determined to provide those skilled in the art with a complete description and disclosure of how to make and use the compounds of the invention, and are not intended to limit the scope of what the inventors regard as their invention.

[108] In all the examples below, the methylaluminoxane (MAO) used was a 30 wt% MAO solution in toluene (typically 13.5 wt% Aluminum and 28.2 wt% MAO by NMR) available from Albemarle Corporation (Baton Rouge, LA). Davison 948 silica dehydrated at 600 ° C (silica gel) was used and is available from W.R. Grace, Davison

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Chemical Division (Baltimore, MD). Anhydrous oxygen-free solvents were used. The synthesis of (CH ₂ ) ₄ Si (C ₅ Me ₄ (CH ₂ ) ₄ Si (C ₅ Me ₄ ) (C ₅ H ₅ ) ZrCl ₂ is described in US Patent No. 6,388,155.

[109] The preparation of (CH ₂ ) ₄ Si (C ₅ Me ₄ ) (C ₅ H ₅ ) ZrMe ₂ . The comparative supported catalyst (1-Me, 3-Bu Cp) ₂ ZrCl ₂ was prepared as described in US Patent No. 6,680,276.

[110] A 1.6 M solution of methyl lithium and ether (184 mL,

0.294 mol) was added slowly to a stirred mixture of (CH2) 4Si (C5Me4) (C5H5) ZrCl2 (60 g, 0.139 mol) and ether (600 mL) in a 2 L flask. ether was slowly removed with a N ₂ purge following the remaining solids extracted with methylene chloride. The solvent was

removed to give the product (41 g, 0.105 mol). [111] Preparation of mixed aluminum stearate

Snowtex®

[112] A 4 L beaker was loaded with aluminum (200 g) from Crompton Corporation (now Chemtura

Corporation, Middlebury, CT), 30% by weight of the Snowtex® IPA-ST-ZL suspension in isopropanol (164 g) from Nissan Chemical

Industries Inc. (Houston, TX) and methanol (300 ml). the slurry was stirred at room temperature for 2 hours then dried to a slurry with a nitrogen purge. Vacuum and heat (108 ° C) were applied for two days to remove the residual solvent. The solids were crushed and sieved through a mesh screen to give ^N, 25 20% by Snowtex® weight flow aid (Nissan Chemical Industries Inc., Houston, TX) as a fine powder.

Preparation of Catalyst A [113] Crosfield ES757 silica (741 g) (INEOS Silicas

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Limited, Warrington, UK), dehydrated at 600 ° C, was added to a mixture of stirred toluene (2 L) (top mechanical conical stirrer) and 30% by weight of the solution of methyl aluminoxane in toluene (874 g, 4, 52 moles). The silica was chased with toluene (200 ml) then the mixture was heated to 90 ° C for 3 h. After all, the volatiles were removed by applying vacuum and light heating (40 ° C) overnight, then the solid was allowed to cool to room temperature. To a stirred slurry of these solids and toluene (3 L), a solution of (CH ₂ ) ₄ Si (C ₅ Me ₄ ) (C ₅ H ₅ ) ZrMe ₂ (16.8 g, 43.0 mmols) was slowly added ) and toluene (1 L) over a 3 h period. After an additional 3 h, the volatiles were removed by applying vacuum and mild heat (40 ° C) overnight then the solid was allowed to cool to room temperature. This catalyst was mixed dry briefly with a mixture of 20% by weight of Snowtex ^® and 80% by weight of aluminum stearate (7.5% by total weight of the additive).

Preparation of Catalyst B [114] Crosfield ES70 silica (741 g), (INEOS Silicas

Limited, Warrington, UK), dehydrated at 600 ° C, was added to a stirred mixture of toluene (2 L) (top mechanical conical stirrer) and 30% by weight of the solution of methyl aluminoxane in toluene (874 g, 4, 52 moles). The silica was chased with toluene (200 ml) then the mixture was heated to 90 ° C for 3 h. After all, the volatiles were removed by applying vacuum and mild heat (40 ° C) overnight, then the solid was allowed to cool to room temperature. To a stirred slurry of these solids and toluene (3 L), it was slowly added to a

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solution of (CH2) 4 Si (C5Me4) (C5H5 ) ZrMe2 (16.8 g, 43.0 mmols) and toluene ( 1 L) over a period 3 h. After one additional in 3 h, volatiles have been removed by application vacuum and mild heat (40 ° C) during the night to follow O

solid was allowed to cool to room temperature. The solids were mixed dry briefly with 82.48 g of a mixture of 20 wt% SnowTex and 80 wt% aluminum stearate.

Preparation of Methyl Aluminoxane Supported on Silica (SMAO) [115] In a typical procedure, silica (741 g), dehydrated at 600 ° C, was added to a stirred mixture of toluene (2 L) (top mechanical conical stirrer) and 30% by weight of the solution of methyl aluminoxane in toluene (874 g, 4.52 moles). The silica was chased with toluene (200 ml) then the mixture was heated to 90 ° C for 3 h. After all, the volatiles were removed by applying vacuum and mild heat (40 ° C) overnight, then the solid was allowed to cool to room temperature.

Preparation of Catalyst C [116] To a 4.5 mmol / g slurry of methyl aluminoxane supported on Davison 948 silica, dehydrated at 600 ° C, (40 g) and pentane (300 ml) stirred with a top stirrer ( overhead stirrer), was slowly added to a solution of (CH2) 4Si (C5Me4) (C5H5) ZrMe2 (670 mg, 1.72 mmols) and toluene. After stirring for 18h, the mixture was filtered and dried.

Polymerization with Catalyst C [117] These catalysts were tested in a continuous fluid gas bed phase reactor with a nominal reactor diameter of 14, an average bed weight of about

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1900 g, speed d and gas about 1.6 ft / s, rate in production in about 500 g / h. The reactor was operated in an pressure in 300 psig of which ethylene it was 35% in mol . O swing of gas was made with nitrogen , 1-hexene, and

nitrogen as indicated in table 2. Table 2: Polymerization conditions

Catalyst Cat C H ₂ concentration (mol ppm) 945 Hexane concentration (mol%) 0.444 Reactor Temperature (° C) 79

Examples 1 and 2 [118] The polymers of examples 1 and 2 were prepared from ethylene and butene-1 monomers in a pilot scale continuous gas-phase fluidized bed reactor using CAT A. The reactor was operated at 70 ° C. ° C and

0 psi of ethylene partial pressure. The fluidized bed was made of polymer granules and the weight of the average bed was approximately 100 to 170

During the reaction, aluminum distearate was added to the reaction, aluminum distearate was added to the reactors at 20% by weight of slurry in mineral oil in concentrations on a resin base of 6 and 17 ppmw (parts per million weight). The conditions for making the polymers of examples 1 and are listed in table 3.

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Table 3. Polymerization conditions of examples 1 and 2.

Condition Conditions for the polymer of Example 1 Conditions for the polymer of Example 2 Reactor temperature (° C) 70 70 Partial pressure of ethylene (psi) 170 170 H2 / C2 molar ratio 0.00289 0.00413 C4 / C2 molar ratio 0.036 0.039

[119] The reactor granules of examples 1 and 2 were mixed dry with additives before being compounded in a 2.5 Davis-Standard single screw extruder equipped with mixing pins and pelleted underwater at an output rate of approximately 100 lb / h. The pellets composed of examples 1 and 2 were ten films extruded in a 2.5 Gloucester line with 6 oscillating dies and an air ring from Future Design Inc. (Mississauga, Ontario, Canada). The exit rate was about 150 lbs / h (8 lbs / hr- in dead circumference) and the dead opening was 45,000. The caliber of the film was 1 ratio of a thousand. and the explosion (department) varied from 2.5 to 3.5. The height of the frozen line (FLH) was typically 20 to 24. The dead temperature was about 199 ° C (390 ° F).

[120] Table 4 compares the polymer properties of Examples 1 and 2 to be properties of the following reference polymers: Borealis Borstar FB2230 (Borealis A / S, Vienna, Austria). Dow DNDA7340 (The Dow Chemical Company, Midland, MI). Dow DINH-1 (The Dow Chemical Company, Midland, MI). ExxonMobil LD103.09 (from Exxon Mobil Chemical Compani, Houston, TX). The reference films were made under

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Table 4: Properties of the polymers of examples 1 and 2 and Reference polymers

unity s Ex. 1 Ex. 2 Boreali s Borstar FB2230 Dow DNDA7340 Dow DINH-1 ExxonMobi l LD103.09 Polymer produced using Me ₂ Si (H ₄ In) ₂ Zr Cl ₂ as a catalyst Polymer produced using e2Si (H4In) 2ZrC l2 as a catalyst Density grams / cc 0.9215 0.9220 0.9232 0.9230 0.9195 0.9202 0.9194 0.927 I2 (MI) g grams / 10min 0.21 0.79 0.24 0.57 2.04 1.06 0.94 0.59 I21 (FI) g grams / 10min 32.4 66.3 23.3 45.2 102.7 59, 4 35, 8 29, 4 MFR - 157 84 97 79 50 56 38 50 Mn - 22301 20381 9460 10310 14750 17730 24563 30699 Mw - 93130 73968 192800 89730 89840 116410 97355 107489 Mz - 226153 166365 336880 268560 318880 208826 248888 MWD (PDI) (Mw / Mn) - 4.2 3, 6 20.4 8.7 6, 1 6.6 4.0 3.5 LCB ^(g avg vis. Avg.) 0.6 0.70 ~ 1.0 0.97 0.41 0.37 0.99 0.98 LCB (g '@ 100,000 MW) 0.9 0.90 - 0.96 0.48 0.46 1.00 1.00

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Table 4: continuation

Units Ex. 1 Ex. 2 Boreali s Borstar FB2230 Dow DNDA7340 Dow DINH-1 ExxonMobi l LD103.09 Polymer produced using Me ₂ Si (H ₄ In) ₂ Zr Cl ₂ as a catalyst Polymer produced using e2Si (H4In) 2ZrC l2 as a catalyst LCB (g '@ 500,000 MW) 0.71 0.74 - 0.98 0.25 0.25 0.89 0.89 Gap matrix thousand 45, 45 45, 45 50 45, 45 45 30, 60 BUR - 2.5, 3.2 2.5, 3.2 2.5 2.5, 3.5 2.5 3.5, 2.5 caliber thousand 2.12, 2.09 1, 96, 2.09 - 1.95 1, 97, 1.98 1.97 2.05, 2.08 Mist O. % 11, 9.6 6.3, 6.7 29, 7 8.1, 7.54 11.3 10.7, 13.5 Inner fog O. % 1.20, 1.02 1.75, 1.94 2.23 1.09, 1.37 0.70 2.99, 3.27 Normalized internal fog %/ thousand 0.57, 0.49 0.89, 0.93 1, 14 0.55, 0.69 0.36 1.46, 1.57 Clarity O. % 59, 62 74, 70 1 36, 54 31 67, 66 Shrinkage of MD Retromat O. % 6 4, 60 6 6, 60 75 75, 71 79 52, 64 TD Retromat shrinkage O. % 5.0, 19.3 -7.5, 4.3 -10.8 -12.5, 3.3 2.8 4.5, -15.0

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Table 4: continuation

Units Ex. 1 Ex. 2 Boreali s Borstar FB2230 Dow DNDA7340 Dow DINH-1 ExxonMobi l LD103.09 Polymer produced using Me ₂ Si (H ₄ In) ₂ Zr Cl2 as a catalyst Polymer produced using e ₂ Si (H ₄ In) ₂ ZrC l2 as a catalyst Shrinkage of the Retromat area O. % 65, 6 8 63, 62 72 72, 72 79 54, 59 Shrinkage stress of plastic MD MPa 0.080, 0.074 0.065, 0.046 0.155 0.095, 0.083 0.167 0.029, 0.046 MD thermal shrinkage voltage MPa 0.548, 1,099 0.891, 1,074 break 0.697, 0.939 0.921 1,213, 1,216 Thermal shrinkage voltage TD MPa 0.952, 1,110 1.008, 0.984 0.000 0.500, 0.761 0.708 1.335, 0.246 Melting resistance cN 6, 9 4.7 11.2 9.8 12.8 19, 5 5.7 Deformation hardening - no some no no Yes Yes T75 83 81, 6 95, 1 90.3 81, 6 88.2 T25 75.5 73.2 68.3 65, 9 75.3 83.6 T75-T25 7.5 8.4 26, 8 24, 4 6.3 4, 6

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Example 3: Catalyst B [121] As shown in this example, a polymer of one embodiment of the invention can improve the optical properties of other LLDPE polymers when it is mixed as a secondary component. In this example, a polymer of one embodiment of this invention was mixed with 10% (by weight) of the final product using an in-line mixing setting on a Battenfeld Gloucester film line (Gloucester, MA). In this setting, the components of the mixture were weighed separately according to the mixing ratio and added to a mixing chamber, where the components were mixed by stirring before they were discharged into a feed hopper above the extruder. The line was equipped with a 2.5 single screw extruder, 6 oscillating die and air ring from Future Design Inc. (Mississauga, Ontario, Canada). The yield rate was 151 lbs / h (8 lbs / hr-in right circumference) and the matrix gap was 45 mill. The caliber of the film was 1,000 and BUR was kept constant at 2.5. FLH was typically 20 to 24. The matrix temperature was 390 ° F. Table 5 shows these improvements in the mist for different mixtures. This polymer has a density of 0.9220 grams / cc, an MI (I2) of 0.76 grams / 10min and an MFR of 99.3. this was done using CAT B under similar conditions as in examples 1 and 2.

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Table 5: Mist Improvements for LLDPE where 10% by weight of the catalyzed product (C ₄ H ₈ ) Si (CsMe ₄ ) (C ₅ H ₄ ) ZrMe ₂ was added.

Catalyst Medium caliber (thousand) Mist of the movie (%) Inner fog (%) Tear MD (g / mil) Tear TD (g / thousand) Specific performance (lb / hp- hr) 100% (1,3-Me, n-Bu- Cp) 2ZrCl2 0.97 19, 6 1.54 244 355 11.26 90% of (1,3-Me, n-Bu- Cp) 2ZrCl2 / 10% (C4H8) Si (C5Me4) (C5H4) ZrMe2 0.97 3.4 0.97 238 482 12.11 100% LL3001,63 0.98 11.0 2.27 381 588 14.79 90% LL3001,63 / 10% (C4H8) Si (C5Me4) (C5H4) ZrMe2 0.99 9.7 1.94 274 650 14.17 100% C5H4- CH2CH2CH3) 2Hf (CH3) 2 0.97 25, 1 2.46 248 389 14, 63 90% C5H4- CH2CH2CH3) 2Hf (CH3) 2 / 10% (C4H8) Si (C5Me4) (C5H4) ZrMe2 1.00 7.2 1.92 239 489 15.05 100% C5H4- CH2CH2CH3) 2Hf (CH3) 2 0.98 11.5 2.24 304 425 12, 62 90% C5H4- CH2CH2CH3) 2Hf (CH3) 2 / 10% (C4H8) Si (C5Me4) (C5H4) ZrMe2 1.00 6.5 1.79 239 524 13.11 100% (C4H8) Si (C5Me4) (C5H4) ZrMe2 0.99 8.7 0.84 25 324 21, 43

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When a polymer of one embodiment of the invention is mixed with other LLDPE polymers as a secondary component, in addition to the benefit of improving the optical properties of the base polymer, the polymer also improves its tear resistance TD while largely maintaining its tear resistance MD unchanged or causes negligible or minor loss. In contrast, when these LLDPEs are mixed with HP-LDPE to improve optical properties, the loss in hardness is dramatic. In addition, mixing these polymers also improves the extrusion performance of the base polymers, as indicated by the increase in specific yield (lbs / hp-hr), making the extrusion process more energy efficient.

Example 4 [123] Polymers were prepared from ethylene (C ₂ ) and butene-1 (C4) monomers in a pilot scale continuous gas phase fluidized bed reactor using (CH ₂ ) ₄ Si (C ₅ Me ₄ ) ( C ₅ H ₅ ) ZrMe ₂ (CAT A). The reactor was operated at temperatures of 70 ° C and 85 ° C, and partial ethylene pressure of 170 and 220 psi. The fluidized bed was composed of polymer granules and the average bed weight was approximately 100 to 170 lbs. During the reaction, aluminum distearate was added to the reactors at 20% by weight of slurry in mineral oil in concentration on a resin base of 6 and 24 ppmw (parts per million by weight). The concentration of the comonomer in the reactor has been changed; its effect on the product has been recorded, and is shown below in Tables 7 and 8.

[124] For comparative purposes, a polymer was generated using (1-Me, 3-Bu Cp) 2ZrCl2 as the catalyst. The reactor was operating at 85 ° C and 220 psi partial pressure from the

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50/64 ethylene. The comonomer concentration, butene-1, was changed from approximately 1.4 mol% to approximately 4.6 mol%, with other process parameters kept constant. The melt flow index (MI or I ₂ ) of the product only changed from approximately 2.0 to 0.9 g / 10min.

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Table 6: Change of MI using (1,3-Me, n-Bu-Cp) ₂ ZrCl ₂ as catalyst (Comparative)

Time (H) Temperature reactor (° C) Partial pressure of ethylene (psi) H2 / C2 Reason Ethylene (mol%) Butene-1 (% in mol) C4 / C2 reason Product I2 (g / 10min) Product density (g / cc) 1 84, 97 220.29 0.0003 65.51 1.40 0.0213 1.67 0.9230 2 84, 99 221.24 0.0003 65, 69 1.35 0.0206 3 85, 02 219.73 0.0003 65.34 1.33 0.0204 4 84, 98 218.62 0.0003 64, 97 1.32 0.0204 1.93 0.9226 5 85.00 221.23 0.0003 65, 64 1.32 0.0201 6 84, 99 221.28 0.0003 65.68 1.36 0.0206 7 85.00 220.17 0.0003 65.51 1.41 0.0215 2.06 0.9330 8 85, 03 219.94 0.0003 65.35 1.41 0.0215 9 85.00 218.70 0.0003 65.04 1.40 0.0216 10 84, 98 218.86 0.0003 6 4.99 1.40 0.0216 1.90 0.9341 11 84, 99 221.53 0.0003 65.75 1.41 0.0214 12 85.01 221.14 0.0002 65.72 1.41 0.0215 13 84, 98 220.57 0.0002 65, 60 1.41 0.0215 1.73 0.9347 14 85, 06 219.04 0.0002 65.05 1.41 0.0217

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Table 6: continued

Time (H) Temperature reactor (° C) Partial pressure of ethylene (psi) H2 / C2 Reason Ethylene (mol%) Butene-1 (% in mol) C4 / C2 reason Product I2 (g / 10min) Product density (g / cc) 15 85, 02 218.27 0.0002 64.89 1.41 0.0218 16 85.01 218.05 0.0002 64, 88 1.40 0.0216 1.54 0.9341 17 84, 97 220.70 0.0002 65.39 1.42 0.0216 18 85.04 220.92 0.0002 65.51 1.61 0.0245 19 84, 95 220.91 0.0002 65, 46 1.26 0.0192 1.39 0.9333 20 85, 08 218.27 0.0002 64.79 1.96 0.0301 21 84, 93 217.84 0.0002 64.77 2.30 0.0356 22 84, 84 224.06 0.0002 66.23 2.92 0.0439 1.31 0.9311 23 85.30 220.91 0.0002 65, 44 3.42 0.0522 24 84, 91 218.60 0.0002 64.52 3.97 0.0610 25 84, 84 220.58 0.0002 65.72 4.47 0.0681 1.17 0. 9255 26 85.38 219.43 0.0002 65.24 4.55 0.0698 27 84, 85 216.03 0.0002 64.27 4.62 0.0720 28 84, 99 223.20 0.0002 66, 08 4.53 0.0682 0.94 0.9195

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Table 6: continued

Time (H) Temperature reactor (° C) Partial pressure of ethylene (psi) H2 / C2 Reason Ethylene (mol%) Butene-1 (% in mol) C4 / C2 reason Product I2 (g / 10min) Product density (g / cc) 29 84, 99 221.31 0.0002 65, 95 4.59 0.0696 30 84, 96 222.07 0.0002 65, 90 4.58 0.0693 31 85, 07 219.31 0.0002 65.36 4.59 0.0704 0.85 0.9182 32 84, 92 220.94 0.0002 65.73 4.55 0.0693 33 85.01 220.87 0.0003 65.73 4.60 0.0699 34 84, 99 220, 55 0.0003 65, 54 4.58 0698 0.93 0.980

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54/64 [125] (CH ₂ ) 4Si (C ₅ Me ₄ ) (C ₅ H ₅ ) ZrMe ₂ (CAT A) was used to produce the copolymer of ethylene (C ₂ ) and butene-1 (C ₄ ) in a pilot-scale continuous gas-phase fluidized bed reactor. The reactor temperature was 70 ° C and the partial pressure in the ethylene reactor was approximately 150 psi. The concentration of butene-1 was changed from approximately 1.3 mol% to approximately 0.7 mol%, with other process parameters kept constant. The results are shown in Table 7. The melt index (MI or I2) of the product has changed significantly from approximately 5 to 20 g / 10min.

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Table 7: Change of MI using (CH ₂ ) ₄ Si (C ₅ Me ₄ ) (C ₅ H ₅ ) ZrMe ₂ (CAT A) as catalyst

Time (H) Reactor temperature (° C) Partial pressure of ethylene (psi) H2 / C2 Reason Ethylene (mol%) Butene-1 (mol%) C4 / C2 ratio Product I2 (g / 10min) 1 66.89 149.11 0.0031 44.57 1.34 0.0301 2 36.35 150.87 0.0030 45, 07 1.33 0.0298 4.98 3 51.15 154.37 0.0029 45.52 1.31 0.0287 4 70, 12 146.13 0.0028 43, 18 0.93 0.0214 5 70.00 149.45 0.0027 44.24 0.52 0.0119 6 69, 98 154.75 0.0030 45, 82 0.53 0.0115 7 69, 97 151.98 0.0029 45, 12 0.55 0.0120 8 6 9.96 151.65 0.0029 45, 06 0.56 0.0124 3.33 9 70.02 151.81 0.0029 45, 03 0.60 0.0132 10 70.02 151.62 0.0029 45.00 0.61 0.0137 11 70.01 149.30 0.0029 44.26 0.62 0.0141 12 70.02 146.60 0.0030 43, 60 0.63 0.0143 13 6 9.99 147.00 0.0029 4 3.66 0.59 0.0136 14 70.02 148.02 0.0029 43, 90 0.57 0.0131 6, 14 15 70.04 148.15 0.0029 43, 95 0.58 0.0132

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Table 7: Change of MI using (CH ₂ ) ₄ Si (C ₅ Me ₄ ) (C ₅ H ₅ ) ZrMe ₂ (CAT A) as catalyst

Time (H) Reactor temperature (° C) Partial pressure of ethylene (psi) H2 / C2 Reason Ethylene (mol%) Butene-1 (mol%) C4 / C2 ratio Product I2 (g / 10min) 16 70.04 147.77 0.0028 43, 84 0.70 0.0160 17 69, 97 148.89 0.0028 44.00 0.70 0.0160 18 70.00 149.86 0.0029 44, 43 0.71 0.0159 19 70.02 149.44 0.0029 44.29 0.71 0.0160 20 70.00 149.48 0.0029 44.37 0.71 0.0159 16, 41 21 70.01 150.06 0.0029 44, 47 0.70 0.0158 22 70.02 149.90 0.0029 44.52 0.71 0.0159 23 70.04 150.04 0.0029 44, 60 0.71 0.0159 19.70 24 6 9.99 149.73 0.0029 44, 43 0.72 0.0161 25 70.02 148.84 0.0028 44, 18 0.76 0.0170 26 70.01 149.56 0.0027 44.26 0.86 0.0193 19, 98

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57/64 [126] This experiment was repeated once again also using (CH ₂ ) ₄ Si (C ₅ Me ₄ ) (C ₅ H ₅ ) ZrMe ₂ (CAT A) as a catalyst, but under reactor conditions in some way many different. The reactor temperature was the same at 70 ° C, but the partial pressure in the ethylene reactor was 170 psi and the H2 / C2 ratio was approximately 0.0040. The reactor was constantly making approximately 1.0 (g / 10min) of the product's melting index for an extended period of time before the concentration of the comonomer, butene-1, was changed from approximately 2.0 mol% to approximately 0, 55 mol%, with other process parameters kept constant. The results are shown in Table 8. The melt index (MI or I2) of the product has changed dramatically from 1.0 to more than 100 g / 10min. This level of change is very significant and unexpected from other metallocene catalysts such as Me2Si (H4In) 2ZrCl2 given in the comparative example.

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Table 8: Change of MI using (CH ₂ ) ₄ Si (C ₅ Me ₄ ) (C ₅ H ₅ ) ZrMe ₂ (CAT A) as a catalyst under somewhat different reaction conditions

Time (H) Reactor temperature (C) Partial pressure of ethylene (psi) H2 / C2 Reason Ethylene (mol%) Butene-1 (mol%) C4 / C2 reason Product I2 (g / 10min) Product density (g / cc) 1 6 9.99 166.90 0.0043 49, 63 1.97 0.0398 1.06 0.9217 2 6 9.96 169.27 0.0041 50.25 1.94 0.0387 3 6 9.99 170.68 0.0042 50.58 1.92 0.0379 4 70.02 171.23 0.0042 50.76 1.91 0.0375 0.89 0.9217 5 70.05 169.96 0.0042 50.42 1.88 0.0372 6 70.04 168.85 0.0042 50.11 1.87 0.0372 7 69, 97 169.91 0.0042 50.23 1.88 0.0373 0.95 0.9217 8 70.02 169.44 0.0042 50.38 1.87 0.0372 9 70.04 167.54 0.0042 49, 88 1.85 0.0374 10 70.00 169.18 0.0042 50.22 1.88 0.0374 0.95 0.9219 11 70.10 167.89 0.0042 49, 95 1.95 0.0391 12 69, 97 168.13 0.0042 50.00 1.96 0.0392 13 70.01 169.57 0.0041 50.31 1.96 0.0389 0.97 0.9221

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Table 8: continued

Time (H) Reactor temperature (C) Partial pressure of ethylene (psi) H2 / C2 Reason Ethylene (mol%) Butene-1 (mol%) C4 / C2 reason Product I2 (g / 10min) Product density (g / cc) 14 6 9.96 170.48 0.0042 50.53 1.98 0.0391 15 70.02 170.09 0.0042 50.50 1.97 0.0390 16 70.01 168.75 0.0042 50.22 1.96 0.0391 0.88 0.9216 17 6 9.99 170.69 0.0042 50, 63 1.98 0.0390 18 70.01 170.48 0.0042 50, 60 1.98 0.0390 19 6 9.99 170.17 0.0042 50.49 1.98 0.0390 0.83 0.9213 20 70.03 169.57 0.0042 50.39 1.97 0.0391 21 70.01 168.50 0.0041 50.10 1.95 0.0389 22 70.00 170.52 0.0041 50.56 1.97 0.0389 0.80 0.9209 23 69, 97 169.99 0.0041 50, 61 1.97 0.0391 24 6 9.94 171.83 0.0041 51.08 1.99 0.0389 25 6 9.99 172.83 0.0041 51.10 2.00 0.0389 0.78 0.9204 26 70.04 169.70 0.0042 50, 63 1.98 0.0392 27 69, 98 170.21 0.0042 50.44 1.98 0.0391

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Table 8: continued

Time (H) Reactor temperature (C) Partial pressure of ethylene (psi) H2 / C2 Reason Ethylene (mol%) Butene-1 (mol%) C4 / C2 reason Product I2 (g / 10min) Product density (g / cc) 28 70.02 169.22 0.0042 50.27 1.96 0.0390 0.77 0.9208 29 70.01 169.60 0.0041 50.39 1.81 0.0361 30 69, 95 170.91 0.0040 50.78 0.91 0.0180 31 6 9.99 171.78 0.0039 50, 92 0.59 0.0116 0.91 0.9221 32 70.02 169.48 0.0039 50.38 0.57 0.0113 33 70.02 167.94 0.0038 50.05 0.57 0.0114 34 70.09 168.98 0.0037 50.14 0.55 0.0110 2.56 0.9266 35 69, 91 170.01 0.0037 50.81 0.54 0.0106 36 70.01 172.03 0.0039 51.18 0.55 0.0108 37 69, 98 170.23 0.0040 50.80 0.54 0.0107 14, 07 0.9359 38 70.03 169.92 0.0040 50.87 0.56 0.0110 39 70.00 169.47 0.0040 50.55 0.55 0.0109 40 70.00 170.20 0.0040 50.74 0.55 0.0108 51.41 0.9408 41 70.00 170.15 0.0040 50.75 0.56 0.0110

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Table 8: continued

Time (H) Reactor temperature (C) Partial pressure of ethylene (psi) H2 / C2 Reason Ethylene (mol%) Butene-1 (mol%) C4 / C2 reason Product I2 (g / 10min) Product density (g / cc) 42 70.01 169.70 0.0040 50, 66 0.56 0.0111 43 70.00 169.36 0.0040 50.56 0.56 0.0111 84, 96 0.9432 44 69, 95 171.02 0.0040 50, 94 0.56 0.0109 45 6 9.96 172.51 0.0041 51.32 0.57 0.0111 46 69, 98 172.44 0.0042 51.36 0.57 0.0112 129, 30 0.9454

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Example 5 [127] When subjected to uniaxial extension, the extensional viscosity of a polymer increases the rate of strain rate. The transient uniaxial extensional viscosity of a linear polymer can be predicted as is known to those skilled in the art. Deformation hardening occurs when the polymer is subjected to uniaxial extension and the transient extensional viscosity increases more than is predicted from linear viscoelastic theory.

Figures and 2 show the deformation hardening at

150 ° C ethylene / hexene copolymers of an embodiment of the present invention prepared using a laboratory scale phase reactor

CAT

C as a catalyst (example and figure 2).

This compared to ExxonMobil

LD103.09 (from ExxonMobil

Chemical

Company,

Houston, TX) (figure

1). The samples were composed in the

Haake Polilab system (Term Fisher Scientific, Inc., Waltam,

MA) and cast in films in the Haake-Brabender combination system (Term

Fisher Scientific, Inc., Waltam, MA).

[129] Figure 3 is a graph of MFR v. MI for polymers of modalities of the present invention (use (C ₄ H ₈ ) Si (C ₅ Me ₄ ) (C ₅ H ₄ ) ZrMe ₂ as the catalyst) and comparative polymers. As seen from the figure, polymers of modalities of the present x MI invention (-0.4304) satisfy the following relationships: MFR>

(0.4304) (57.18 x MI.

MFR>

figure is a Retramat versus shrinkage graph

MD

Plastic

Force for films made from the polymers of modalities of the present invention (using (C ₄ H ₈ ) Si (C ₅ Me ₄ ) (C ₅ H ₄ ) ZrMe ₂ as the catalyst) including examples 1 and 2, and comparative films. As seen from

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In the figure, the films of the embodiments of the present invention generally have a Retromat shrinkage area of more than 60% and a DM plastic tension of less than about 0.08 MPa.

[131] Figure 5 is a graph of g 'versus molecular weight for polymers of the modalities of the immediate invention (using (C ₄ H ₈ ) Si (C ₅ Me ₄ ) (C ₅ H ₄ ) ZrMe ₂ as the catalyst) and comparative polymers. As seen from the figure, polymers of the modalities of the immediate invention do satisfy the following ratios: 0.5 <g ' _avg <0.9 and M _w / M _n <4.6.

[132] The phrases, unless otherwise specified, consist essentially of and consist essentially of not excluding the presence of other steps, elements or materials even if or not specifically mentioned in the specification as throughout such steps, elements or materials, they do not exclude the impurities normally associated with the elements and materials used.

[133] For the sake of brevity, only certain scales are explicitly described here. However, it varies from any low limit perhaps combined with any upper limit to report an unexplained reported variation, just as it varies from any upper limit perhaps combined with another any upper limit to report an unexplained reported variation. Additionally, with a variation they include several points or individual values between those points of the same resistant end reported not explained. Then, all individual points or values can serve as their own upper and lower limits combined with other points or values

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64/64 individual or any other lower or upper limit, to report an unexplained reported variation.

[134] All priority documents are fully incorporated by reference for all jurisdictions where such incorporation is not permitted and the extent of such disclosure is consistent with the description of the present invention. But, all documents and references mentioned here, including test procedures, publications, patents, newspaper articles, etc. are incorporated herein by reference for all jurisdictions in which such incorporation is not permitted and to the extent of such disclosure is consistent with the description of the present invention.

[135] While the invention has been described with respect to the number of modalities and examples, those skilled in the art, taking advantage of this description, will appreciate that other modalities can be planned which do not depart from the scope and spirit of the invention as described here.

Claims (8)

1. Process for improving the polymer film haze, characterized by the fact that it comprises: a) forming a polymer by polymerizing ethylene, an olefin monomer having 3 to 8 carbon atoms and, optionally, one or more different olefin monomers having 2 to 30 carbon atoms, under gas phase polymerization conditions, in the presence of a catalyst system comprising a cyclic bridged metallocene activated by an activator, the activator comprising aluminoxane, a modified aluminoxane, or a mixture thereof, and a support, in which the cyclic bridged metallocene is cyclotetramethylenesilila (tetramethylcyclopentadienyl) dimethyl zirconium (cyclopentadienyl); and (ii) mixing from 1 to 50% by weight of the polymeric product with another polymer comprising olefin monomer having 2 to 30 carbon atoms. 2. Process according to claim 1, characterized in that the support comprises a Group 2, 3, 4, 5, 13 or 14 inorganic metal oxide. Process according to either of Claims 1 and 2, characterized in that the support comprises silica, alumina, or silica-alumina. 4. Process according to any one of claims 1 to 3, characterized in that the activator comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), or a combination thereof and the support is silica. 5. Process according to any one of claims 1 to 4, characterized in that the catalyst system is formed by first combining the activator with the support and, in Petition 870180163648, of 12/17/2018, p. 73/80 2/2 followed by the addition of this to cyclotetramethylenesilila (tetramethylcyclopentadienyl) dimethyl zirconium (cyclopentadienyl). Process according to any one of claims 1 to 4, characterized in that the catalyst system is formed by first combining MAO and silica and then by adding it to cyclotetramethylenesilila (tetramethylcyclopentadienyl) dimethyl zirconium (cyclopentadienyl) ). Process according to any one of claims 1 to 6, characterized in that the polymeric product has a density of 0.910 to 0.945 g / cc. 8. Process according to claim 1, characterized in that the amount of the polymeric product in the mixture is 5% to 20% by weight.