WO2001062808A1 - Process for the polymerization of ethylene and a small amount of a diene - Google Patents

Abstract

Disclosed is a polymerization process utilizing a low level of diene to control the polymer product's melt index ratio independently of the melt index and density. The process of the invention produces polymers with enhanced processability. More specifically the process produces ethylene based polymers, prepared in gas phase polymerization processes utilizing bulky ligand metallocene polymerization catalysts, having enhanced melt strength and shear-thinning behaviour.

Description

PROCESS FOR THE POLYMERIZATION OF ETHYLENE AND A SMALL AMOUNT OF A DIENE

FIELD OF THE INVENTION The present invention relates to a polymerization process. In particular, the invention relates to a process for improving the processability of bulky ligand metallocene catalyzed polymers by utilizing low levels of diene, to improve polymer processability and to independently control the polymer's melt index ratio.

BACKGROUND OF THE INVENTION

Polymers produced by bulky ligand metallocene catalysts have excellent properties such as mechanical strength and transparency. However, these polymers are typically more difficult to process. Processability is the ability to economically process and shape a polymer uniformly. Factors of processability include melt strength or the polymer's strength at its extrusion temperature, shear thinning or the ease at which the polymer flows, and whether or not the extrudate is distortion free.

Ethylene based polymers produced by bulky ligand metallocene catalysis (mPe), for example, are generally more difficult to process when compared to low density polyethylenes (LDPE) prepared in a high pressure polymerization process. Typically, mPe's require more motor power and produce higher extrusion pressures to match the extrusion rate of LDPE's. This is typically evident where a polymer exhibits a low melt index ratio (MIR which is the ratio of ratio of I₂₁/I₂ , where. I₂ is the MI measured according to ASTM D-1238, Condition E, at 190°C and where I₂₁ is the flow index measured according to ASTM D-1238, Condition F, at 190°C). In addition, mPE's generally possess a lower melt strength, which adversely affects bubble stability during blown film extrusion, and are prone to melt fracture at commercial shear rates. The relatively low melt strength and relatively low melt viscosity of mPe make the blown bubble extrusion fabrication of film more difficult and lower the rate of production when compared to other types of polymers processed by the same technique. One method to improve the processability (both shear thinning and melt strength) of mPE is to introduce long chain branching (LCB) into the polymer. In LCB, the polymer has branching of sufficient length for chain entanglement, that is the length of a branch is long enough, or contains sufficient carbons, to entangle with other polymer molecules. Generally, long chain branching involves a chain length of at least 6 carbons, and usually contains 10 or more carbons. The long chain branch may be as long as the length of the polymer backbone. Polyethylene containing long chain branching possesses good strength and low viscosity under high shear conditions which peπnits high processing rates. In addition, polyethylene containing long chain branching often exhibits strain hardening, so that films made from such polyethylene tend not to fail during manufacture.

Currently there is no effective way to independently control LCB in polymerization processes, and in particular in gas phase polymerization processes. In addition, present gas phase reactors target only the control of the polymer product's melt index (MI) and density. As a result of this two-dimensional polymer product property control, the product's MLR, which measures the shear thinning capability, is difficult to control independently of the MI and density. This is because the MIR varies with different MI and density targets. For example, the MIR increases with decreasing MI and increasing density. U.S. Patent No. 5,492,986 issued Feb. 20, 1996 to Bai discloses a process for the production of homogeneous polyethylene having superior strain hardening properties by contacting ethylene, one or more alpha olefins, and one or more unconjugated dienes under polymerization conditions utilizing a vanadium catalyst.

European Patent Application EP 0 543 119 A2 discloses a prepolymerization catalyst comprising an α-olefin and a polyene.

European Patent Application EP 0 743 327 A2 discloses polyethylene having enhanced processability prepared utilizing racemic and meso stereoisomers of a bridged metallocene catalyst having facial chirality.

European Patent Application EP 0 784 062 A2 (EP'062) discloses a process for making a polyethylene, having long chain branching, in the presence of a polyene, or hydrocarbon interlinking compound, in an amount sufficient to provide chain entanglement or long chain branching. The EP '062 application describes sufficient amounts of diene levels as from about 8000 to 35,000 ppm. However, this diene concentration produces polymer products with gels. In addition, the EP '062 application does not independently control the diene feed, but rather dissolves the diene in the hexene comonomer and feeds the combined mixture into the reactor. Therefore, the EP'062 application process couples LCB and the density of the polymer product.

Study on Co- and Terpolymerization of Ethylene and Diene Using Metallocene Catalysts, Pietikainene, P. et al., Polymer Technology Publication Series No. 16, (1993) Helsinki Univ. of Technology, Espoo, Finland, generally reviews use of metallocene catalysts in the co- and terpolymerization of ethylene.

Copolymerization of Propene and Nonconjugated Diene Involving Intramolecular Cyclization with Metallocene/Methaluminoxane, Naofumi Naga, et al. Macromolecules, 32 (1999), 1348-1355, discloses the cyclization reaction of incorporated dienes produced by the copolymerization of propene with nonconjugated dienes (1,5 -hexadiene and 1,7- octadiene) utilizing a stereospecific metallocene catalyst.

Copolymerization of Ethylene and non-conjugated dienes with Cp₂ZrCl,/MAO Catalyst System, Pietikainene, P. et al., European Polymer Journal 35 (1999), 1047-1055, discloses the cyclization of hexadiene to from five-member rings in polyethylene produced by metallocene catalysts .

While these polymerization process have been described in the art, a need exists for a process to improve mPe processability, to improve the MIR of mPe, and to provide for independent control the MI, density, and the MIR of polymer products.

SUMMARY OF THE INVENTION

This invention relates to a process for improving the processability of bulky ligand metallocene catalyzed polymers.

In one aspect, the invention provides a process for improving the processability of bulky ligand metallocene catalyzed polyethylenes by utilizing low levels of diene, to enhance the polymer's melt index ratio.

In another aspect, the invention provides a process for controlling the melt index ratio of bulky ligand metallocene catalyzed polyethylenes independently of the melt index and density by the introduction of low levels of diene in gas phase polymerization processes.

DETAILED DESCRIPTION OF THE INVENTION Introduction

The invention relates to the use of a low level of diene to introduce long chain branching into polymers produced in gas phase polymerization processes utilizing bulky ligand metallocene polymerization catalysts. The invention also relates to the use of low level dienes to control the polymer product's melt index ratio independently of the melt index and density. The polymers, specifically polyethylenes, which include ethylene homopolymer, copolymer, and terpolymer, produced by this process possess enhanced melt strength and shear-thinning behavior, which allows for easier processing. This enhanced processability encompasses ease in both extrusion and fabrication processes, such as in blown film, blow molding, extrusion coating and wire and cable extrusion operations.

Bulky Ligand Metallocene Catalyst Compounds

The process of the invention provides polymers of enhanced processability by the addition of a low level of diene during polymerization. Specifically the process of the invention enhances the processability of polyethylene polymers, produced in gas phase polymerization processes catalyzed by bulky ligand metallocene catalyst compounds. Generally, these catalyst compounds include half and full sandwich compounds having one or more bulky ligands bonded to at least one metal atom. Typical bulky ligand metallocene compounds are described as containing one or more bulky ligand(s) and one or more leaving group(s) bonded to at least one metal atom. In one preferred embodiment, at least one bulky ligands is η-bonded to the metal atom, most preferably η⁵-bonded to a transition metal atom.

The bulky ligands are generally represented by one or more open, acyclic, or fused ring(s) or ring system(s) or a combination thereof. The ring(s) or ring system(s) of these bulky ligands are typically composed of atoms selected from Groups 13 to 16 atoms of the Periodic Table of Elements. Preferably the atoms are selected from the group consisting of carbon, nitrogen, oxygen, silicon, sulfur, phosphorous, germanium, boron and aluminum or a combination thereof. Most preferably the ring(s) or ring system(s) are composed of carbon atoms such as but not limited to those cyclopentadienyl ligands or cyclopentadienyl- type ligand structures or other similar functioning ligand structure such as a pentadiene, a cyclooctatetraendiyl or an imide ligand. The metal atom is preferably selected from Groups 3 through 15 and the lanthanide or actinide series of the Periodic Table of Elements. Preferably the metal is a transition metal from Groups 4 through 12, more preferably Groups 4, 5 and 6, and most preferably the transition metal is from Group 4. In one embodiment, low level diene is added to a polymerization process utilizing the bulky ligand metallocene catalyst compounds represented by the formula:

L^AL^BMQ_n (I)

where M is a metal atom from the Periodic Table of the Elements and may be a Group 3 to 12 metal or from the lanthanide or actinide series of the Periodic Table of Elements, preferably M is a Group 4, 5 or 6 transition metal, more preferably M is zirconium, hafnium or titanium. The bulky ligands, L^A and L^B, are open, acyclic or fused ring(s) or ring system(s) and are any ancillary ligand system, including unsubstituted or substituted, cyclopentadienyl ligands or cyclopentadienyl-type ligands, heteroatom substituted and/or heteroatom containing cyclopentadienyl-type ligands. Non-limiting examples of bulky ligands include cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands, indenyl ligands, benzindenyl ligands, fluorenyl ligands, octahydrofluorenyl ligands, cyclooctatetraendiyl ligands, cyclopentacyclododecene ligands, azenyl ligands, azulene ligands, pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125), pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzene ligands and the like, including hydrogenated versions thereof, for example tetrahydroindenyl ligands. In one embodiment, L^A and L^B may be any other ligand structure capable of η -bonding to M, preferably η³- bonding to M and most preferably η⁵-bonding . In yet another embodiment, the atomic molecular weight (MW) of L^A or L^B exceeds 60 a.m.u., preferably greater than 65 a.m.u.. In another embodiment, L^A and L^B may comprise one or more heteroatoms, for example, nitrogen, silicon, boron, germanium, sulfur and phosphorous, in combination with carbon atoms to form an open, acyclic, or preferably a fused, ring or ring system, for example, a hetero-cyclopentadienyl ancillary ligand. Other L^A and L^B bulky ligands include but are not limited to bulky amides, phosphides, alkoxides, aryloxides, imides, carbolides, boroUides, porphyrins, phthalocyanines, corrins and other polyazomacrocycles. Independently, each L^A and L^B may be the same or different type of bulky ligand that is bonded to M. In one embodiment of formula (I) only one of either L^A or L^B is present.

Independently, each L^A and L^B may be unsubstituted or substituted with a combination of substituent groups R. Non-limiting examples of substituent groups R include one or more from the group selected from hydrogen, or linear, branched alkyl radicals, or alkenyl radicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkyltliio radicals, dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonyl radicals, carbomoyl radicals, alkyl- or dialkyl- carbamoyl radicals, acyloxy radicals, acylamino radicals, aroylamino radicals, straight, branched or cyclic, alkylene radicals, or combination thereof. In a preferred embodiment, substituent groups R have up to 50 non-hydrogen atoms, preferably from 1 to 30 carbon, that can also be substituted with halogens or heteroatoms or the like. Non- limiting examples of alkyl substituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, including all their isomers, for example tertiary butyl, isopropyl, and the like. Other hydrocarbyl radicals include fluoromethyl, fluroethyl, difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbyl substituted organometalloid radicals including trimethylsilyl, trimethylgermyl, methyldiethylsilyl and the like; and halocarbyl-substiruted organometalloid radicals including tris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl, bromomethyldimethylgermyl and the like; and disubstitiuted boron radicals including dimethylboron for example; and disubstituted pnictogen radicals including dimethylamine, dimethylphosphine, diphenylamine, methylphenylphosphine, chalcogen radicals including methoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfϊde. Non-hydrogen substituents R include the atoms carbon, silicon, boron, aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and the like, including olefins such as but not limited to olefinically unsaturated substituents including vinyl-terminated ligands, for example but-3- enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two R groups, preferably two adjacent R groups, are joined to form a ring structure having from 3 to 30 atoms selected from carbon, nitrogen, oxygen, phosphorous, silicon, germanium, aluminum, boron or a combination thereof. Also, a substituent group R group such as 1-butanyl may form a carbon sigma bond to the metal M. Other ligands may be bonded to the metal M, such as at least one leaving group Q. For the purposes of this patent specification and appended claims the term "leaving group" is any ligand that can be abstracted from a bulky ligand metallocene catalyst compound to form a bulky ligand metallocene catalyst cation capable of polymerizing one or more olefϊn(s). In one embodiment, Q is a monoanionic labile ligand having a sigma-bond to M. Depending on the oxidation state of the metal, the value for n is 0, 1 or 2 such that formula (I) above represents a neutral bulky ligand metallocene catalyst compound.

Non-limiting examples of Q ligands include weak bases such as amines, phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals having from 1 to 20 carbon atoms, hydrides or halogens and the like or a combination thereof. In another embodiment, two or more Q's form a part of a fused ring or ring system. Other examples of Q ligands include those substituents for R as described above and including cyclobutyl, cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene, pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy, bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and the like.

In a preferred embodiment, low level diene is added to a polymerization process utilizing the bulky ligand metallocene catalyst compounds of formula (II) where L^A and L^B are bridged to each other by at least one bridging group, A, as represented in the following formula:

L^AAL^BMQ_n (II)

These bridged compounds represented by formula (II) are known as bridged, bulky ligand metallocene catalyst compounds. L^A, L^B, M, Q and n are as defined above. Non- limiting examples of bridging group A include bridging groups containing at least one Group 13 to 16 atom, often referred to as a divalent moiety such as but not limited to at least one of a carbon, oxygen, nitrogen, silicon, aluminum, boron, germanium and tin atom or a combination thereof. Preferably bridging group A contains a carbon, silicon or germanium atom, most preferably A contains at least one silicon atom or at least one carbon atom. The bridging group A may also contain substituent groups R as defined above including halogens and iron. Non-limiting examples of bridging group A may be represented by R'₂C, R'₂Si, R'₂Si R'₂Si, R'₂Ge, R'P, where R' is independently, a radical group which is hydride, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, hydrocarbyl-substituted organometalloid, halocarbyl-substituted organometalloid, disubstituted boron, disubstituted pnictogen, substituted chalcogen, or halogen or two or more R' may be joined to form a ring or ring system. In one embodiment, the bridged, bulky ligand metallocene catalyst compounds of formula (II) have two or more bridging groups A (EP 664 301 Bl).

In another embodiment, the bulky ligand metallocene catalyst compounds are those where the R substituents on the bulky ligands L^A and L^B of formulas (I) and (II) are substituted with the same or different number of substituents on each of the bulky ligands. In another embodiment, the bulky ligands L^A and L^Bof formulas (I) and (II) are different from each other.

Other bulky ligand metallocene catalyst compounds and catalyst systems useful in the invention may include those described in U.S. Patent Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022, 5,276,208, 5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401, 5,723,398, 5,753,578, 5,854,363, 5,856,547 5,858,903, 5,859,158, 5,900,517 and 5,939,503 and PCT publications WO 93/08221, WO 93/08199, W0 95/07140, WO 98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO 99/14221 and European publications EP-A-0 578 838, EP-A-0 638 595, EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834, EP-B1-0 632 819, EP-B1-0 748 821 and EP-B1-0 757 996, all of which are herein fully incorporated by reference.

In another embodiment, bulky ligand metallocene catalysts compounds useful in the t invention include bridged heteroatom, mono-bulky ligand metallocene compounds. These types of catalysts and catalyst systems are described in, for example, PCT publication WO 92/00333, WO 94/07928, WO 91/ 04257, WO 94/03506, WO96/00244, WO 97/15602 and

WO 99/20637 and U.S. 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 herein fully incorporated by reference.

In this embodiment, low level diene is added to a polymerization process utilizing the bulky ligand metallocene catalyst compound represented by formula (III): L^cAJMQ_n (πi)

where M is a Group 3 to 16 metal atom or a metal selected from the Group of actinides and lanthanides of the Periodic Table of Elements, preferably M is a Group 4 to 12 transition metal, and more preferably M is a Group 4, 5 or 6 transition metal, and most preferably M is a Group 4 transition metal in any oxidation state, especially titanium; L^c is a substituted or unsubstituted bulky ligand bonded to M; J is bonded to M; A is bonded to M and J; J is a heteroatom ancillary ligand; and A is a bridging group; Q is a univalent anionic ligand; and n is the integer 0,1 or 2. In formula (III) above, L^c, A and J form a fused ring system. In an embodiment, L^c of formula (III) is as defined above for L^A, A, M and Q of formula (III) are as defined above in formula (I).

In formula (III) J is a heteroatom containing ligand in which J is an element with a coordination number of three from Group 15 or an element with a coordination number of two from Group 16 of the Periodic Table of Elements. Preferably J contains a nitrogen, phosphorus, oxygen or sulfur atom with nitrogen being most preferred.

In another embodiment, low level diene is added to a polymerization process where the bulky ligand type metallocene catalyst compound utilized is a complex ofa metal, preferably a transition metal, a bulky ligand, preferably a substituted or unsubstituted pi-bonded ligand, and one or more heteroallyl moieties, such as those described in U.S. Patent Nos. 5,527,752 and 5,747,406 and EP-B1-0 735 057, all of which are herein fully incorporated by reference.

In another embodiment, low level diene is added to a polymerization process utilizing bulky ligand metallocene catalyst compounds represented formula IV:

L^DMQ₂(YZ)X_n (IV)

where M is a Group 3 to 16 metal, preferably a Group 4 to 12 transition metal, and most preferably a Group 4, 5 or 6 transition metal; L^D is a bulky ligand that is bonded to M; each Q is independently bonded to M and Q₂(YZ) forms a unicharged polydentate ligand; A or Q is a univalent anionic ligand also bonded to M; X is a univalent anionic group when n is 2 or X is a divalent anionic group when n is 1; n is l or 2.

In formula (IV), L and M are as defined above for formula (I). Q is as defined above for formula (I), preferably Q is selected from the group consisting of -O-, -NR-, -CR2- and -S-; Y is either C or S; Z is selected from the group consisting of -OR, - NR2, -CR3, -SR, -S1R3, -PR2, -H, and substituted or unsubstituted aryl groups, with the proviso that when Q is -NR- then Z is selected from one of the group consisting of -OR, -NR2, -SR, -S1R3, -PR2 and-H; R is selected from a group containing carbon, silicon, nitrogen, oxygen, and/or phosphorus, preferably where R is a hydrocarbon group containing from 1 to 20 carbon atoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is an integer from 1 to 4, preferably 1 or 2; X is a univalent anionic group when n is 2 or X is a divalent anionic group when n is 1; preferably X is a carbamate, carboxylate, or other heteroallyl moiety described by the Q, Y and Z combination. In another embodiment of the invention, the bulky ligand metallocene- type catalyst compounds are heterocyclic ligand complexes where the bulky ligands, the ring(s) or ring system(s), include one or more heteroatoms or a combination thereof. Non-limiting examples of heteroatoms include a Group 13 to 16 element, preferably nitrogen, boron, sulfur, oxygen, aluminum, silicon, phosphorous and tin. Examples of these bulky ligand metallocene catalyst compounds are described in WO 96/33202, WO 96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874 005 and U.S. Patent No. 5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417, and 5,856,258 all of which are herein incorporated by reference.

In another embodiment, the bulky ligand metallocene catalyst compounds are those complexes known as transition metal catalysts based on bidentate ligands containing pyridine or quinoline moieties, such as those described in U.S. Application Serial No. 09/103,620 filed June 23, 1998, which is herein incorporated by reference. In another embodiment, the bulky ligand metallocene catalyst compounds are those described in PCT publications WO 99/01481 and WO 98/42664, which are fully incorporated herein by reference. In another embodiment, low level diene is added to a polymerization process utilizing the bulky ligand metallocene catalyst compounds represented by formula V:

((Z)XA_t(YJ))_qMQ_n (V)

where M is a metal selected from Group 3 to 13 or lanthanide and actinide series of the Periodic Table of Elements; Q is bonded to M and each Q is a monovalent, bivalent, or trivalent anion; X and Y are bonded to M; one or more of X and Y are heteroatoms, preferably both X and Y are heteroatoms; Y is contained in a heterocyclic ring J, where J comprises from 2 to 50 non-hydrogen atoms, preferably 2 to 30 carbon atoms; Z is bonded to X, where Z comprises 1 to 50 non-hydrogen atoms, preferably 1 to 50 carbon atoms, preferably Z is a cyclic group containing 3 to 50 atoms, preferably 3 to 30 carbon atoms; t is 0 or 1; when t is 1, A is a bridging group joined to at least one of X,Y or J, preferably X and J; q is 1 or 2; n is an integer from 1 to 4 depending on the oxidation state of M. In one embodiment, where X is oxygen or sulfur then Z is optional. In another embodiment, where X is nitrogen or phosphorous then Z is present. In an embodiment, Z is preferably an aryl group, more preferably a substituted aryl group.

It is also within the scope of this invention, in one embodiment, that the bulky ligand metallocene catalyst compounds include complexes of Ni²⁺ and Pd²⁺ described in the articles Johnson, et al., "New Pd(II)- and Ni(II)- Based Catalysts for Polymerization of Ethylene and a-Olefins", J. Am. Chem. Soc. 1995, 117, 6414-6415 and Johnson, et al., "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 August 1, 1996, WO 99/02472, U.S. Patent Nos. 5,852,145, 5,866,663 and 5,880,241, which are all herein fully incorporated by reference. These complexes can be either dialkyl ether adducts, or alkylated reaction products of the described dihalide complexes that can be activated to a cationic state by the activators of this invention described below. Also included as bulky ligand metallocene catalyst are those diimine based ligands of Group 8 to 10 metal compounds disclosed in PCT publications WO 96/23010 and WO 97/48735 and Gibson, et. al., Chem. Comm, pp. 849-850 (1998), all of which are herein incorporated by reference.

Other bulky ligand metallocene catalysts are those Group 5 and 6 metal imido complexes described in EP-A2-0 816 384 and U.S. Patent No. 5,851,945, which is incorporated herein by reference. In addition, bulky ligand metallocene catalysts include bridged bis(arylamido) Group 4 compounds described by D.H. McConville, et al., in Organometallics 1195, 14, 5478-5480, which is herein incorporated by reference. In addition, bridged bis(amido) catalyst compounds are described in WO 96/27439, which is herein incorporated by reference. Other bulky ligand metallocene catalysts are described as bis(hydroxy aromatic nitrogen ligands) in U.S. Patent No. 5,852,146, which is incorporated herein by reference. Other metallocene catalysts containing one or more Group 15 atoms include those described in WO 98/46651, which is herein incorporated herein by reference. Still another metallocene bulky ligand metallocene catalysts include those multinuclear bulky ligand metallocene catalysts as described in WO 99/20665, which is incorporated herein by reference.

It is also contemplated that in one embodiment, the bulky ligand metallocene catalysts of the invention described above include their structural or optical or enantiomeric isomers (meso and racemic isomers, for example see U.S. Patent No. 5,852,143, incorporated herein by reference) and mixtures thereof.

Activator Compositions

The above described bulky ligand metallocene polymerization catalyst compounds are typically activated in various ways to yield compounds having a vacant coordination site that will coordinate, insert, and polymerize olefin(s). For the purposes of this patent specification and appended claims, the term "activator" is defined to be any compound or component or method which can activate any of the bulky ligand metallocene catalyst. Non-limiting activators, for example, may include a Lewis acid or a non-coordinating ionic activator or ionizing activator or any other compound including Lewis bases, aluminum alkyls, conventional-type cocatalysts and combinations thereof that can convert a neutral bulky ligand metallocene catalyst to a catalytically active bulky ligand metallocene catalyst cation. It is witliin the scope of this invention to use as alumoxane or modified alumoxanes as an activator. There are a variety of methods for preparing alumoxane and modified alumoxanes, non-limiting examples of which are described in U.S. Patent No. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734, 4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801, 5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,693,838, 5,731,253, 5,731,451, 5,744,656, 5,847,177, 5,854,166, 5,856,256 and 5,939,346 and European publications EP-A-0 561 476, EP-B1-0 279 586, EP-A-0 594-218 and EP-B1-0 586 665, and PCT publication WO 94/10180, all of which are herein fully incorporated by reference. In one embodiment aluminoxanes or modified alumoxanes are combined with catalyst compound(s). In another embodiment modified methyl alumoxane in heptane (MMAO3A), commercially available from Akzo Chemicals, Inc., Holland, under the trade name Modified Methylalumoxane type 3 A , (see for example those aluminoxanes disclosed in U.S. Patent No. 5,041,584, which is herein incorporated by reference) is combined with the catalyst compound(s) to form a catalyst system.

Organoaluminum compounds useful as activators include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum and the like.

It is within the scope of this invention to use an ionizing or stoichiometric activator, neutral or ionic, such as tri (n-butyl) ammonium tetrakis (pentafluorophenyl) boron, a trisperfluorophenyl boron metalloid precursor or a trisperfluoronaphtyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983) or combination thereof, that would ionize the neutral bulky ligand metallocene catalyst compound. It is also within the scope of this invention to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.

Examples of neutral stoichiometric activators include tri-substituted boron, tellurium, aluminum, gallium and indium or mixtures thereof. The three substituent groups are each independently selected from alkyls, alkenyls, halogen, substituted alkyls, aryls, arylhalides, alkoxy and halides. Preferably, the three groups are independently selected from halogen, mono or multicyclic (including halosubstituted) aryls, alkyls, and alkenyl compounds and mixtures thereof, preferred are alkenyl groups having 1 to 20 carbon atoms, alkyl groups having 1 to 20 carbon atoms, alkoxy groups having 1 to 20 carbon atoms and aryl groups having 3 to 20 carbon atoms (including substituted aryls). More preferably, the three groups are alkyls having 1 to 4 carbon groups, phenyl, napthyl or mixtures thereof. Most preferably, the neutral stoichiometric activator is trisperfluorophenyl boron or trisperfluoronapthyl boron.

Ionic stoichiometric activator compounds may contain an active proton, or some other cation associated with, but not coordinated to, or only loosely coordinated to, the remaining ion of the ionizing compound. Such compounds and the like are described in European publications EP-A-0 570 982, EP-A-0 520 732, EP-A-0 495 375, EP-B1-0 500 944, EP-A-0 277 003 and EP-A-0 277 004, and U.S. Patent Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197, 5,241,025, 5,384,299 and 5,502,124 and U.S. Patent Application Serial No. 08/285,380, filed August 3, 1994, all of which are herein fully incorporated by reference.

In a preferred embodiment, the stoichiometric activators include a cation and an anion component, and may be represented by the following formula:

(L-H)_d ⁺ (A^d) (VI)

wherein L is an neutral Lewis base; H is hydrogen;

(L-H)⁺is a Bronsted acid

A^d~ is a non-coordinating anion having the charge d- d is an integer from 1 to 3.

The cation component, (L-H)_d ⁺ may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an akyl or aryl, from the bulky ligand metallocene or Group 15 containing transition metal catalyst precursor, resulting in a cationic transition metal species.

The activating cation (L-H)_d ⁺ may be a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N- dimethylaniline, methyldiphenylamine, pyridine, p-bromo N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxomiuns from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethyl thioethers and tetrahydrothiophene and mixtures thereof. The activating cation (L-H)_d ⁺ may also be an abstracting moiety such as silver, carboniums, tropylium, carbeniums, ferroceniums and mixtures, preferably carboniums and ferroceniums. Most preferably (L-H)_d ⁺ is triphenyl carbonium. The anion component A^d" include those having the formula [M^k+Q_n]^d" wherein k is an integer from 1 to 3; n is an integer from 2-6; n - k = d; M is an element selected from Group 13 of the Periodic Table of the Elements and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted-hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q a halide. Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group.

Most preferably, the ionic stoichiometric activator (L-H)_d ⁺ (A^d") is N,N- dimethylanilinium tetra(perfluorophenyl)borate or triphenylcarbenium tetra(perfluorophenyl)borate.

Examples of suitable A^d" also include diboron compounds as disclosed in U.S. Pat. No. 5,447,895, which is fully incorporated herein by reference.

In one embodiment, an activation method using ionizing ionic compounds not containing an active proton but capable of producing a bulky ligand metallocene catalyst cation and their non-coordinating anion are also contemplated, and are described in EP-A- 0 426 637, EP-A- 0 573 403 and U.S. Patent No. 5,387,568, which are all herein incorporated by reference.

Other activators include those described in PCT publication WO 98/07515 such as tris (2, 2', 2"- nonafluorobiphenyl) fluoroalummate, which publication is fully incorporated herein by reference. Combinations of activators are also contemplated by the invention, for example, alumoxanes and ionizing activators in combinations, see for example, EP-B1 0 573 120, PCT publications WO 94/07928 and WO 95/14044 and U.S. Patent Nos. 5,153,157 and 5,453,410 all of which are herein fully incorporated by reference.

Other suitable activators are disclosed in WO 98/09996, incorporated herein by reference, winch describes activating bulky ligand metallocene catalyst compounds with perchlorates, periodates and iodates including their hydrates. WO 98/30602 and WO 98/30603, incorporated by reference, describe the use of lithium (2,2'-bisphenyl- ditrimethylsilicate)«4THF as an activator for a bulky ligand metallocene catalyst compound. WO 99/18135, incorporated herein by reference, describes the use of organo-boron- aluminum acitivators. EP-B1-0 781 299 describes using a silylium salt in combination with a non-coordinating compatible anion. Also, methods of activation such as using radiation (see EP-B1-0 615 981 herein incorporated by reference), electro-chemical oxidation, and the like are also contemplated as activating methods for the purposes of rendering the neutral bulky ligand metallocene catalyst compound or precursor to a bulky ligand metallocene cation capable of polymerizing olefins. Other activators or methods for activating a bulky ligand metallocene catalyst compound are described in for example, U.S.

Patent Nos. 5,849,852, 5,859,653 and 5,869,723 and WO 98/32775, WO 99/42467

(dioctadecylmethylammonium-bis(tris(pentafluorophenyl)borane) benzimidazolide), which are herein incorporated by reference.

Supports, Carriers and General Supporting Techniques

The above described catalyst and/or activators may be combined with one or more support materials or carriers using one of the support methods well known in the art or as described below to foπn a supported catalyst system. For example, catalyst(s) and/or activator(s) may be deposited on, contacted with, vaporized with, bonded to, or incorporated within, adsorbed or absorbed in, or on, a support or carrier.

The terms "support" or "carrier", for purposes of this patent specification, are used interchangeably and are any support material, preferably a porous support material, including inorganic or organic support materials. Non-limiting examples of inorganic support materials include inorganic oxides and inorganic chlorides. Other carriers include resinous support materials such as polystyrene, functionalized or crosslinked organic supports, such as polystyrene divinyl benzene polyolefins or polymeric compounds, zeolites, talc, clays, or any other organic or inorganic support material and the like, or mixtures thereof.

The preferred carriers are inorganic oxides that include those Group 2, 3, 4, 5, 13 or 14 metal oxides. The 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), phyllosilicate, and the like. Also, combinations of these support materials may be used, for example, silica-chromium, silica-alumina, silica- titania and the like. Additional support materials may include those porous acrylic polymers described in EP 0 767 184 Bl, which is incorporated herein by reference.

It is preferred that the carrier, most preferably an inorganic oxide, has a surface area in the range of from about 10 to about 700 m^/g, pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 5 to about 500 μm. More preferably, the surface area of the carrier is in the range of from about 50 to about 500 m^/g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 μm. Most preferably the surface area of the carrier is in the range is from about 100 to about 400 m^/g, pore volume from about 0.8 to about 3.0 cc/g and average particle size is from about 5 to about 100 μm. The average pore size of the carrier of the invention typically has pore size in the range of from 10 to lOOOA, preferably 50 to about 50θA, and most preferably 75 to about 35θA.

Examples of supporting bulky ligand metallocene catalyst systems are described in U.S. Patent 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, 5,665,665, 5,698,487, 5,714,424, 5,723,400, 5,723,402, 5,731,261, 5,759,940, 5,767,032, 5,770,664, 5,846,895 and 5,939,348 and U.S. Application Serial Nos. 271,598 filed July 7, 1994 and 788,736 filed January 23, 1997 and PCT publications WO 95/32995, WO 95/14044, WO 96/06187 and WO 97/02297, and EP-B1-0 685 494 all of which are herein fully incorporated by reference. There are various other methods in the art for supporting the polymerization catalysts. For example, the bulky ligand metallocene catalyst compound may contain a polymer bound ligand as described in U.S. Patent Nos. 5,473,202 and 5,770,755, which is herein fully incorporated by reference, or may be spray dried as described in U.S. Patent No. 5,648,310, which is herein fully incorporated by reference. The support used with the bulky ligand metallocene catalyst system of the invention may be functionalized as described in European publication EP-A-0 802 203, which is herein fully incorporated by reference, or at least one substituent or leaving group may be selected as described in U.S. Patent No. 5,688,880, which is herein fully incorporated by reference.

In another embodiment, an antistatic agent or surface modifier, that is used in the preparation of the supported catalyst system as described in PCT publication WO 96/11960, which is herein fully incorporated by reference, may be used. The catalyst system may be prepared in the presence of an olefin, for example hexene-1.

In another embodiment, catalyst may be combined with a carboxylic acid salt of a metal ester, for example aluminum carboxylates such as aluminum mono, di- and tri- stearates, aluminum octoates, oleates and cyclohexylbutyrates, as described in U.S. Application Serial No. 09/113,216, filed July 10, 1998.

A preferred method for producing a supported bulky ligand metallocene catalyst system is described below, and is described in U.S. Application Serial Nos. 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 January 4, 1996, all of which are herein fully incorporated by reference. In this preferred method, the catalyst compound is slurried in a liquid to form a catalyst solution or emulsion. A separate solution is formed containing an activator and a liquid. The liquid may be any compatible solvent or other liquid capable of forming a solution or the like with the catalyst compounds and/or activator. In the most preferred embodiment the liquid is a cyclic aliphatic or aromatic hydrocarbon, most preferably toluene. The catalyst compound and activator solutions are mixed together heated and added to a heated porous support or a heated porous support is added to the solutions such that the total volume of the bulky ligand metallocene catalyst compound solution and the activator solution or the bulky ligand metallocene catalyst compound and 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 two times; preferred ranges being from 1.1 times to 3.5 times range and most preferably in the 1.2 to 3 times range. Procedures for measuring the total pore volume ofa porous support are well known in the art. Details of one of these procedures is 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 classical BET apparatus for nitrogen absorption. Another method well known in the art is described in Innes, Total Porosity and Particle Density of Fluid Catalysts By Liquid Titration, Vol. 28, No. 3, Analytical Chemistry 332- 334 (March, 1956).

Diene The addition of a low concentration of diene, is utilized in the polymerization processes, preferably in the gas phase polymerization processes, of the invention to improve product processability. Dienes, as is known in the art, belong to the class of unsaturated hydrocarbons that contain two carbon-carbon double bonds, and are classified as cumulated, conjugated, or isolated according to whether the double bonds constitute a CCC unit, a CC- CC unit, or a CC-(CXY) -CC unit, respectively. In the present invention, a low level of diene is introduced into the reactor to control and improve the polymer product's melt index ratio independently of the products melt index and density, and is believed to independently control long chain branching without gel formation.

Any diene, or mixtures of dienes, containing enough carbon atoms to incorporate long chain branching may be utilized in the process of the invention. Preferably, the diene does not act as a poison to the catalyst, or undergo cyclization which would prevent further chain growth. The diene(s) utilized may be aliphatic, alicyclic or aromatic and is preferably aliphatic. More preferably, the diene is an aliphatic linear diene containing non-conjugated double bonds and most preferably containing isolated double bonds. To facilitate long chain branching, it is most preferable that both of the double bonds of the diene(s) be able to react and insert into growing polymer chains.

For use in gas phase polymerization processes, the diene's vapor pressure and boiling point must be such as to allow sufficient dispersion within the reactor. Failure of the diene to disperse well will result in gel formation and will also present problems in down stream product purging. In addition, diene(s) most suitable for use in the gas phase processes of the invention should not possess a strong odor. Therefore, it is preferable that the diene(s) is an aliphatic linear or branched diene having 5 to 12 carbon atoms and preferably 6 to 10 carbon atoms. Examples of suitable dienes useful in the process of the invention include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7- octadiene, 1,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene and mixtures thereof. In an especially preferred embodiment the diene is a α,ω-diene or one that contains double bonds at both ends. More preferably the diene comprises 1,7-octadiene, 1,8-nonadiene or 1,9- decadiene and most preferably comprises 1,7-octadiene.

Any amount of diene or mixture of dienes effective to produce LCB and/or to enhance the shear thinning property of bulky ligand metallocene catalyzed polymer products may be utilized. Preferably, in gas phase polymerization processes, the amount of diene utilized is from about 1 to about lOOOppm of diene based upon the total weight of monomer feed to the process, or about 0.255 to about 255 ppm of diene based on total moles of monomer feed. Total weight or moles of monomer feed means the weight or moles of the monomer utilized, for example ethylene, and does not include the weight or moles of comonomer. More preferably the amount of diene utilized is from about 10 to about 900ppm weight or about 2.55 to about 229.5 ppm molar, more preferably from about 15 to about 850ppm weight or about 3.82 to about 216.4 ppm molar , more preferably from about 20 to about 800ppm weight or about 5.1 to about 203.6 ppm molar, more preferably from about 50 to about 750ppm weight or about 12.7 to about 191 ppm molar, more preferably from about 100 to about 700ppm weight or about 25.5 to about 178.2 ppm molar and most preferably from about 150 to about 650ppm weight or about 38.2 to about 165.5 ppm molar diene.

Polymerization Process The addition of diene to control polymer product processability may be utilized in any prepolymerization and/or polymerization process. The polymerization may be conducted in solution, gas phase, slurry phase or in a high pressure process or a combination thereof. Preferred is a gas phase or slurry phase polymerization of one or more olefins at least one of which is ethylene or propylene. Most preferably, polymerization is conducted in a gas phase polymerization process. In the process of the invention, the diene(s) must be properly dispersed within the reactor. Proper dispersion of diene reduces the possibility of gel formation and allows for uniform incorporation of LCB and control of the polymer product's MIR independent of its MI and density. For example, at the same MI and density, it has been found that MIR increases with increasing diene level and the product possesses melt strength similar to the product prepared without diene addition. Therefore, without wishing to be limited by theory, it is believed that the addition of diene generates LCB, which appears to be a star type of branch, since there is significant enhancement in shear thinning and little increases in melt strength of the polymer products. Preferably, the diene is dissolved in a suitable solvent, for example hexane or iso- pentane, to form a diene solution which is then introduced into the reactor. More preferably, the introduction of diene and/or diene solution into the reactor is independently controlled and may be introduced into the reactor by any suitable means as is known in the art. By controlling the reactor diene level, the LCB present in bulky ligand metallocene catalyzed polymer products may be controlled. Most preferably, and to achieve maximum diene dispersion, a controlled amount of the diene or diene solution is first introduced to the comonomer, the inducing condensing agent (ICA) feed, and/or other feeds which are known in the art, before entering the reactor.

In one embodiment, the process of this invention is directed toward utilizing a low level of diene(s) in polymerization or copolymerization reactions involving the polymerization of one or more olefin monomers having from 2 to 30 carbon atoms, preferably 2 tol2 carbon atoms, and more preferably 2 to 8 carbon atoms. The invention is particularly well suited to the polymerization of two or more olefin monomers of ethylene, propylene, butene-1, pentene-1, 4-methyl-pentene-l, hexene-1, octene-1 and decene-1, 3- methyl pentene-1, 3,5,5-trimethyl-hexene-l and cyclic olefins or combinations thereof.

Other monomers useful in the polymerization process of the invention include ethylenically unsaturated monomers, diolefins having 4 to 18 carbon atoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers and cyclic olefins. Other monomers useful in the invention may include norbornene, norbornadiene, isobutylene, isoprene, vinylbenzocyclobutane, styrenes, alkyl substituted styrene, ethylidene norbornene, dicyclopentadiene and cyclopentene. In a preferred embodiment the process of this invention is directed toward utilizing a low level of diene(s) to produce a copolymer of ethylene, where with ethylene, a comonomer having at least one alpha-olefϊn having from 4 to 15 carbon atoms, preferably from 4 to 12 carbon atoms, and most preferably from 4 to 8 carbon atoms, is polymerized in a polymerization process.

In another embodiment of the process of the invention, a low level of diene(s) is utilized when ethylene or propylene is polymerized with at least two different comonomers, to form a terpolymer.

In one embodiment, the invention is directed to utilizing a low level of diene(s) in a polymerization process for polymerizing propylene alone or with one or more other monomers including ethylene, and/or other olefins having from 4 to 12 carbon atoms. Polypropylene polymers may be produced using the particularly bridged bulky ligand metallocene catalysts as described in U.S. Patent Nos. 5,296,434 and 5,278,264, both of which are herein incorporated by reference. In a prefened embodiment ethylene and optionally a comonomer, and the diene compound are contacted with an effective amount of bulky ligand metallocene catalyst, as described above, at a temperature and pressure sufficient to initiate polymerization. In a typically gas phase polymerization process, a continuous cycle is employed where in one part of the cycle of a reactor system, a cycling gas stream, otherwise known as a recycle stream or fluidizing medium, 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 external to the reactor. Generally, in a gas fluidized bed process for producing polymers, a gaseous 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 withdrawn from the fluidized bed and recycled back into the reactor.

Simultaneously, polymer product is withdrawn from the reactor and 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, all of which are fully incorporated herein by reference.) The reactor temperature in a gas phase process may vary from about 30°C to about 120°C, preferably from about 60°C to about 115°C, more preferably in the range of from about 70°C to 110°C, and most preferably in the range of from about 70°C to about 95°C.

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

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

In a preferred embodiment, the reactor utilized in the process of the present invention is capable of producing greater than 500 lbs of polymer per hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg hr) or higher of polymer, preferably greater than 1000 lbs/hr (455 Kg/hr), more preferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferably greater than 25,000 lbs/hr (11,300 Kg hr), still more preferably greater than 35,000 lbs hr (15,900 Kg/hr), still even more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than 65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500 Kg/hr).

Other gas phase processes contemplated by the process of the invention include series or multistage polymerization processes. Also gas phase processes contemplated by the invention include those described in U.S. Patent Nos. 5,627,242, 5,665,818 and 5,677,375, and European publications EP-A- 0 794 200 EP-B1-0 649 992, EP-A- 0 802 202 and EP-B- 634 421 all of which are herein fully incorporated by reference.

A prefereed process of the invention is where the process is operated in the presence of a bulky ligand metallocene catalyst system and in the absence of or essentially free of any scavengers, such as triethylaluminum, trimethylaluminum, tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminum chloride, dibutyl zinc and the like. This preferred process is described in PCT publication WO 96/08520 and U.S. Patent No. 5,712,352 and 5,763,543, which are herein fully incorporated by reference. In one embodiment of the invention, olefϊn(s), preferably C2 to C30 olefin(s) or alpha-olefm(s), preferably ethylene or propylene or combinations thereof are prepolymerized prior to the main polymerization. The prepolymerization can be carried out batchwise or continuously in gas, solution or slurry phase including at elevated pressures. The prepolymerization can take place with any olefin monomer or combination and/or in the presence of any molecular weight controlling agent such as hydrogen. For examples of prepolymerization procedures, see U.S. Patent Nos. 4,748,221, 4,789,359, 4,923,833, 4,921,825, 5,283,278 and 5,705,578 and European publication EP-B-0279 863 and PCT Publication WO 97/44371 all of which are herein fully incorporated by reference. Optionally, unreacted diene may be removed from the polymer product by methods known in the art such as, for example, purging with an inert gas, such as nitrogen, purging with and inert gas and water vapor or oxygen, by heating under vacuum or combinations thereof.

Polymer Products

The polymers produced by the process of the invention can be used in a wide variety of products and end-use applications and may include linear low density polyethylene, elastomers, plastomers, high density polyethylenes, medium density polyethylenes, low density polyethylenes, polypropylene and polypropylene copolymers. The polymers of the present invention, preferably ethylene based polymers, have a melt index (MI) or (I₂) as measured by ASTM-D-1238-E in the range of from less than 0.01 dg/min to 1000 dg/min, more preferably from about less than 0.01 dg/min to about 100 dg/min, even more preferably from about 0.1 dg/min to about 50 dg/min, and most preferably from about 0.1 dg/min to about 10 dg/min. The polymers of the invention in a prefeπed embodiment have a melt index ratio

(I₂₁/I₂) ( I₂₁ is measured by ASTM-D-1238-F) of from preferably greater than 10, more preferably greater than 30, even more preferably greater that 40, still even more preferably greater than 50 and most preferably greater than 65. In one embodiment, the polymer of the invention may have a narrow molecular weight distribution and a broad composition distribution or vice-versa, and may be those polymers described in U.S. Patent No. 5,798,427 incorporated herein by reference. The polymers of the invention, typically ethylene based polymers, have a density in the range of from 0.86g/cc to 0.97 g/cc, preferably in the range of from 0.88 g/cc to 0.965 g/cc, more preferably in the range of from 0.900 g/cc to 0.96 g/cc, even more preferably in the range of from 0.905 g/cc to 0.95 g/cc, yet even more preferably in the range from 0.910 g/cc to 0.940 g/cc, and most preferably greater than 0.915 g/cc, preferably greater than

0.920 g/cc, and most preferably greater than 0.925 g/cc. Density is measured in accordance with ASTM-1505.

In another embodiment the polymer produced herein has a melt strength of 7 cN or more, preferably 9 cN or more, more preferably 10 cN or more, and even more preferably 12 cN or more, as measured with an Instron capillary rheometer in conjunction with the Goettfert Rheotens melt strength apparatus. A polymer melt strand extruded from the capillary die is gripped between two counter-rotating wheels on the apparatus, the take up speed is increased at a constant acceleration of 24 mm/sec², which is controlled by the Acceleration Programmer (Model 45917, at a setting of 12). The maximum pulling force (in cN) achieved before the strand breaks or starts to show draw resonance is determined as the melt strength. The temperature of the rheometer is set at 190°C. The capillary die has a length of one inch (2.54 cm) and a diameter of 0.06 inch( 0.15 cm). The polymer melt is extruded from the die at a piston speed of 3 inch/min (7.62 cm/min). The distance between the die exit and the wheel contact point should be 3.94 inches (100 mm). The polymers produced by the process of the invention typically have a molecular weight distribution, a weight average molecular weight to number average molecular weight (M_w/M_n) of greater than 1 to about 40, preferably greater than 1.5 to about 15, more preferably greater than 2 to about 10, most preferably greater than about 2.0 to about 8.

Also, the polymers of the invention typically have a narrow composition distribution as measured by Composition Distribution Breadth Index (CDBI). Further details of determining the CDBI of a copolymer are known to those skilled in the art. See, for example, PCT Patent Application WO 93/03093, published February 18, 1993, which is fully incorporated herein by reference.

The polymers of the invention in one embodiment have CDBI's generally in the range of greater than 50%> to 100%, preferably 99%, preferably in the range of 55% to 85%, and more preferably 60% to 80%, even more preferably greater than 60%, still even more preferably greater than 65%.

In another embodiment, polymers produced by the process of the invention have a CDBI less than 50%, more preferably less than 40%, and most preferably less than 30%. In yet another embodiment, propylene based polymers are produced in the process of the invention. These polymers include atactic polypropylene, isotactic polypropylene, hemi-isotactic and syndiotactic polypropylene. Other propylene polymers include propylene block or impact copolymers. Propylene polymers of these types are well known in the art see for example U.S. Patent Nos. 4,794,096, 3,248,455, 4,376,851, 5,036,034 and 5,459, 117, all of which are herein incorporated by reference.

The polymers of the invention may be blended and/or coextruded with any other polymer. Non-limiting examples of other polymers include linear low density polyethylenes produced via conventional Ziegler-Natta and/or bulky ligand metallocene catalysis, elastomers, plastomers, high pressure low density polyethylene, high density polyethylenes, polypropylenes and the like.

Polymers produced by the process of the invention and blends thereof are useful in such forming operations as film, sheet, and fiber extrusion and co-extrusion as well as blow molding, injection molding and rotary molding. Films include blown or cast films formed by coextrusion or by lamination useful as shrink film, cling film, stretch film, sealing films, oriented films, snack packaging, heavy duty bags, grocery sacks, baked and frozen food packaging, medical packaging, industrial liners, membranes, etc. in food-contact and nonfood contact applications. Particularly preferced methods to form the polymers into films include extrusion or coextrusion on a blown or cast film line. Fibers include melt spinning, solution spinning and melt blown fiber operations for use in woven or non-woven form to make filters, diaper fabrics, medical garments, geotextiles, etc. Extruded articles include medical tubing, wire and cable coatings, geomembranes, and pond liners. Molded articles include single and multi-layered constructions in the form of bottles, tanks, large hollow articles, rigid food containers and toys, etc.

In another embodiment, the films produced in the process of the invention may further contain additives such as slip, antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers, antistats, polymer processing aids, neutralizers, lubricants, surfactants, pigments, dyes and nucleating agents. Preferred additives include silicon dioxide, synthetic silica, titanium dioxide, polydimethylsiloxane, calcium carbonate, metal stearates, calcium stearate, zinc stearate, talc, BaSO₄, diatomaceous earth, wax, carbon black, flame retarding additives, low molecular weight resins, hydrocarbon resins, glass beads and the like. The additives may be present in the typically effective amounts well known in the art, such as 0.001 weight % to 10 weight %.

EXAMPLES

In order to provide a better understanding of the present invention including representative advantages thereof, the following examples of polymerization processes and their polymerization results, are offered.

The examples were run in a continuous gas phase fluidized bed reactor. Ten polyethylene polymer products were produced at 6 different diene levels. The process run conditions averaged over a period of time at steady state appear in Table I, and the characteristics of each run's polymer product appear in Table 2. Data obtained from comparative example lb and from four polymer products, which were further processed into film, appears in Tables 3-6. The amount of diene is reported in ppm based upon the total weight of monomer feed as described above.

Comparative Example 1 (2MI/0.920D)

Before diene was introduced into the reactor, a control run, for 2MI/0.920D condition, was performed to establish a baseline. After stable operation for 7.2 Bed Turn Over's (BTO) and collecting one box of product, the tetraethylaluminium (TEAL) pump was flushed with hexane into the reactor. As used herein, BTO (production/bed weight) means the replacement, over time as polymer is being continuously produced and withdrawn from the reactor, the amount of product the reactor may contain at any one time (about 3001bs (136 kg) in the present examples). In addition, as used herein, one box of product means about 600 to 800 pounds (about 272 to 363 kg) of polymer. Due to residual TEAL being flushed into the reactor and to some bed weight control problems, the reactor was killed at 12.3 BTO's due to a product discharge line plug. Catalyst, dimethylsilyl- bis(tetrahydroindenyl) zirconium dichloride, was cut briefly to stabilize the reactor. Catalyst productivity averaged 3,650 g/g (where g/g is g polymer/g catalyst) on 2.23MI/0.918D condition.

Comparative Example lb (Second Startup) The reactor was restarted on 2MI/0.920D condition after the shut down. There were no reactor continuity problems and reactor stayed on this condition for 5.8BTOs. Catalyst productivity averaged 3,366 g/g.

Example 2 (2MI/0.920D, 50ppm Diene) After stabilized on the 2MI/0.920D control condition, the reactor was transitioned to a 50ppm diene condition by starting a 1% 1,7-octadiene solution in hexane using the TEAL pump. Diene was on flow ratio control to ethylene feed to maintain 50ppm diene to ethylene weight ratio. Hydrogen concentration and hexene flow ratio was held constant at the 2MI control condition. The reactor was lined out at 1.5MI with 50ppm diene and one box of product was collected. The diene 50ppm condition was run for 5.6 BTO with 4,130g/g average productivity.

Example 3 (2MI/0.920D, lOOppm Diene)

After finishing the 50ppm condition (Example 2), the reactor was transitioned to a lOOppm condition by increasing the diene flow rate while keeping hydrogen and hexene concentration constant. Bed weight still fluctuated and the reactor was killed at 2.5BTO due to product discharge plug. Catalyst productivity was about 3,850g/g before shutdown.

Comparative Example lc (Third Startup) The reactor was restarted with the control condition (2MI/0.920D) and ran for

4.8BTO's without any skin temperature activity or chip formation. Catalyst productivity was between 3,300 to 3,600g/g. Product MIR was 34 at 1.93MI/0.9178D.

Example 4 (1MI/0.920D 150ppm diene) After stabilizing the reactor on 2MI/0.920D condition, the reactor was transitioned to a 150ppm condition by starting diene flow and increasing hydrogen concentration from 950 to lOOOppm. Catalyst productivity was about 3,750 g/g. One box of product was collected with 50.9 MIR at 0.95MI/0.9181D.

Example 5 (0.75MI/0.920D 150ppm diene) Reactor hydrogen was lowered to 950ppm to get 0.75MI product at 150ppm diene level. There were no continuity problems. ^' Average catalyst productivity was 3,650g/g. One box of product was collected with 54.73 MIR at 0.82MI/0.9179D.

Example 6 (1MI/0.920D 250ppm diene) The reactor was transitioned to a 250ppm diene condition by increasing diene feed.

The diene solution concentration was increased to 8% to maintain pump speed between 200 to 400 cc/hr. Hydrogen level was increased to 1075ppm from 950ppm to compensate for increasing diene level. The reactor was on this condition for 4.47BTO and one box of product collected with 55.53 MIR at 1.01 MI/0.9200D.

Example 7 (0.75MI/0.920D 250ppm diene)

Hydrogen concentration was reduced from 1,075 PPM to l,000ppm to get 0.75MI product at 250ppm diene. Catalyst productivity averaged 3,400 g/g. One box of product was collected with 60.03MIR at 0.86MI/0.9205D.

Example 8 (0.75MI/0.920D 400 ppm diene)

The reactor was transitioned to a 400ppm condition by increasing diene flow at l,000ppm hydrogen. After MI drifted down to 0.56, hydrogen was raised to 1,100 ppm and MI started to come back to 0.71. However, the diene solution ran out for 2 hours. MI responded quickly to diene lose, jumping from 0.71 to 1.41 and finally to 1.67. MI eventually settled down to 0.75g/10min at 1075ppm hydrogen when the diene solution was put back on line. This incidence demonstrated the ability of diene to couple chains and lower MI. Average catalyst productivity was 3,850 g/g, and one box of product was collected with 74.71 MIR at 0.75MI/0.9206D.

Example 9 (0.75MI/0.920D 600ppm diene)

The reactor was transitioned from the 400 ppm to a 600 ppm diene condition by increasing diene flow and raising hydrogen level to 1,200 ppm. Hydrogen level was further raised to 1,300 ppm to get to 0.75MI target. Average catalyst productivity was 3,400 g/g. One box of product was collected with 82.09 MIR at 0.80MI/0.920D.

Example 10 (1MI/0.920D 600ppm diene)

Hydrogen level was further raised to l,400ppm to target IMI product. Due to slow MI response to hydrogen, hydrogen level was raised up to 1,500 ppm. This apparently overshot the hydrogen and MI climbed to 1.49 at one point and finally settled around IMI at 1,350 ppm hydrogen. Average catalyst productivity was 3,800g/g. One box of product was collected with 75.12 MIR at 1.12MI/0.9218D.

Reactor Continuity Reactor continuity was fairly good throughout the example runs. There were no skin temperature excursion and no major sheeting incidence. Some small chips came out occasionally, but the amount was small (0.1-0.2% of product) and did not cause major continuity disruptions. There were two shutdowns in the beginning part of the run, but none of them were directly related to diene injection. The first shutdown occurred before diene condition and was caused by residual tefraethylaluminum (TEAL) being flushed out and by bed weight control problems. The second shutdown happened at the lOOppm diene condition and was probably caused by the bed weight control problem. Most of the conditions (7) were finished after the third startup and the run was completed with a scheduled shutdown. Upon completion of the run, the reactor and cooler were opened for inspections and were found clean. Some coating formed on the expanded section wall and was easily blown off.

Catalyst Productivity

Catalyst productivities were between 3,500g/g to 4,000g/g and there was no major activity loss with diene. Actually, all the diene run activities were higher than the control run at beginning of the diene run, which may have been caused by a difference in catalyst batches.

Gels Gel formation is a major concern especially if the polymer is to be utilized in the production of film. In the preceding examples, the diene solution was dispersed into hexene feed before it entered the reactor to achieve good dispersion. Extra care was taken during the run to avoid getting into the gel region too quickly since it may take a long time for gels to clear up. Gel tape was run at each condition to help deciding next diene level. As shown in Table 2, gel level was at baseline up to 400ppm diene. At 600 ppm, some partially melted gel particles showed up on gel tape. However, after the granules were compounded and pelletized with a twin-screw extruder, the tape was virtually gel free. Since there was only about 0.1 diene per chain even at 600ppm level, the partially melted gels were likely caused by non-uniform dispersion of diene in gas phase, which could be minimized with better diene dispersion.

Purging and Odor Issues

Diene level during the run was monitored for any exposure and/or odor issues. Compared to aromatic dienes (ethylidene norbornene (ENB), etc.), the aliphatic diene used did not have a noticeable odor during processing. In addition, using normal gas phase reactor purging practices, the polymer product had no noticeably odor, and no diene was detected by headspace gas chromatograph analysis of the 600ppm diene run granular product. Product Processibility

Eight products were pelleted by a twin screw extruder with a standard additive package as is known in the art. The MI of the pellets, however, was higher than that of granules with the difference increasing with increasing diene level. This difference was likely caused by a lack of homogeneousness in the melt indexer when measuring the granule MI. The pellet MI was used in characterizing film product. Table 3 lists the characterization results of the pelleted diene products. As diene level increased from 0 to 600 ppm, there was significant increase in weight (M_w) and the Z-averaged molecular weight (M_z) measured by light-scattering and viscometer detectors, as is known in the art, even though number average molecular weight (M was roughly the same or even smaller. While not wishing to be limited by theory, it is thought that since light scattering and viscometer detectors are more sensitive to the high MW fraction, diene re-incorporation mostly likely occurred in the high MW portion. Pellet products from representative examples (lb, 5, 7, 8, 9) were further blown into

1 mil film using a blown film line. A control standard with same Ml/density produced in a commercial reactor with the same catalyst was run under the same conditions. Table 4 compares diene product processability at standard output rate (188 lb/hr or 85.3 kg/hr) on a pilot scale blow film line. At the same MI and density (1MI/0.920D), product processability improves with increasing diene level. Comparing the 400ppm diene product with the control, motor load decreases from 51.6% to 41.7%>, die press decreases from 3460 to 2710 psi (23856 to 18685 kPa), melt temperature decreases from 378°F (192.2°C) to 369 °F (187.2°C). Specific output increases from 11.79 to 13.96 lb/hr (5.35 to 6.33 kg/hr).

Table 5 compares maximum output rates of the different diene products. Since the extruder was not powder limited, the maximum rate was primarily determined by bubble stability. At the maximum output rate, melt temperature and pressure decreased from 385°F (196 °C) and 4440 psig (30613 kPa) for the control standard to 374°F (190 °C) and 2340 psig (15918 kPa) for the 400ppm diene sample, indicating significant shearing with increasing diene level. The maximum output rate is obtained at 400ppm diene level, 323 lb/hr (147 kg/hr) compared with 294 lb/hr (133 kg/hr) for the control. Film Properties

Table 6 compares product characteristics of films produced at 188 lb/hr (85.3 kg/hr) output rate. The best balance of processibility and film properties seem to be achieved from about 250ppm to about 400ppm diene. At 250ppm diene, the processibility increases by 20 to 25%) as measured by maximum rate, specific output (lb/hp-hr), motor load, head pressure and melt temperature. Overall film properties of the 250ppm diene product are similar to the control without diene. Film hardness is basically the same as control (MD/TD modulus, MD/TD yield). Film toughness (MD/TD tensile, puncture force/energy) and film appearance(haze and gloss) are also similar to control standard. Dart impact of 250ppm diene product is slightly better than control (10%). MD and TD tear of the 250ppm diene product is somehow defensive to the control. By changing diene level, product processibility can be significantly enhanced without comprising most of the film properties.

Conclusion

By using small amount diene, shear thinning property of bulky ligand metallocene catalyzed polymer products were enhanced by 50-100% without major impact on process continuity or catalyst productivity. The process provides a new means of controlling product LCB by controlling reactor diene level, and may be utilized to broaden the product window of existing bulky ligand metallocene catalyst. The process of the invention enlarges product property control from the traditional two dimensions (MI and density) to three dimensions (MI, density and LCB). For example at the same MI and density, it has been found that MIR increases with increasing diene level. At 250-600 ppm diene, MIR increases by 50-100% when compared to the product made without diene. For instance, MIR of 1MI/0.920D product increases from 38.2 without diene to 63.2 with 400ppm (wt) diene. Product processibility improves with increasing diene level as measured by specific out put, pressure drop and melt temperature. Product melt strength is similar to the product prepared without diene addition. Most film properties (hardness, toughness and dart impact) are similar to control and MD/TD tear is defensive to control.

Table 1. Diene Run Process Conditions Continued

Table 1. Diene Run Process Conditions Continued

Table 1. Diene Run Process Conditions Continued

Table 2. Diene Run Products (Granular)

Table 3. Diene Run Products (Granule and Pellet)

Example 1b 4 5 6 7 8 9 10

Diene (ppm) 0 150 150 250 250 400 600 600

Ml (granule) 2.00 1.00 0.80 1.00 0.80 0.75 0.75 1.00

Ml (pellet) 1.57 1.07 0.95 1.21 1.05 1.01 1.78 2.13

Density (granule) 0.9180 0.9180 0.9180 0.9200 0.9200 0.9200 0.9210 0.9200

Density (pellet) 0.9193 0.9177 0.9184 0.9209 0.9212 0.9209 0.9224 0.9223

MIR (pellet) 33.79 46.58 50.59 54.45 53.90 63.22 60.06 47.89

DRI Mn 25,280 24,288 26,988 20,590 24,153 20,429 17,254 17,141

DRI Mw 89,863 98,137 100,908 90,824 96,496 99,249 96,893 94,421

DRI Mz 183,932 233,970 240,510 225,684 237,928 278,698 327,449 326,625

DRI Mw/Mn 3.55 4.04 3.74 4.41 4.00 4.86 5.62 5.51

DRI Mz/Mw 2.05 2.38 2.38 2.48 2.47 2.81 3.38 3.46

LS Mn 31,511 32,907 31 ,394 25,366 22,718 31 ,339 31 ,884 18,927

I

LS Mw 84,075 95,384 98,145 91,607 92,929 107,616 113,561 108,355

LS z 181,932 224,872 239,896 257,809 263,864 317,387 481,384 519,230 I

LS Mw/Mn 2.67 2.90 3.13 3.61 4.09 3.43 3.56 5.72

LS Mz/Mw 2.16 2.36 2.44 2.81 2.84 2.95 4.24 4.79

VS Mn 28,423 39,471 36,068 30,829 17,079 27,887 25,918 22,692

VS Mw 104,470 120,028 126,592 110,117 113,140 127,928 127,280 143,597

VS Mz 308,752 817,149 2,465,790 3,421 ,330 375,204 2,607,160 915,941 49,387,800

VS Mw/Mn 3.68 3.04 3.51 3.57 6.62 4.59 4.91 6.33

VS Mw/Mz 2.96 6.81 19.48 31.07 3.32 20.38 7.20 343.93

Vinyl/1000C 0.05 0.02 0.02 0.03 0.04 0.04 0.02 0.04

Vinylenes/1000C 0.13 0.19 0.11 0.07 0.08 0.09 0.07 0.09

Vinyldienes/1000C 0.03 0.03 0.03 0.04 0.06 0.05 0.04 0.04

Trisubstitute IOOOC 0.14 0.08 0.09 0.13 0.07 0.07 0.10 0.04

(vinyl/ 000C)*Mw 4.49 1.96 2.02 2.72 3.86 3.97 1.94 3.78

Methyl/1000C 13.9 15.5 15.2 14.8 13 14.1 14.8 14.7

Hexene wt% 8.3 9.3 9.1 8.9 7.8 8.4 8.9 8.8

Hexene mol% 2.9 3.3 3.2 3.1 2.7 3 3.1 3.1

Intrinsic Tear (g/mil) 383.53 376.14 379 306 291.85 259.9 220 223

Melt Strength (c/N) 5.4 5.05 4.9 4.5

Break Spd (cm/s) 54.5 56.5 60 61.5

I o I

Table 4 Product Processability

Example 1b 5 7 8 9 Control Standard Diene (ppm) 0 150 250 400 600 0 0 0

Ml 1.57 0.95 1.05 1.01 1.78 1.03 1.03 1.03

Density 0.9193 0.9184 0.9212 0.9209 0.9224 0.9227 0.9227 0.9227

MIR (121/12) 33.8 50.6 53.9 63.2 47.9 38.2 38.2 38.2

ACT SPD 58.2 60.4 60.2 61.5 62 59.6 59.7

ACT RATE 187 188 188 190 188 190 188

%Mtr Load 47.2 46.4 43.5 41.7 33.1 51.6 50.6

Press 1 3070 3100 2850 2710 1930 3580 3460

Press2 1990 2080 1890 1790 1250 2310 2290

Melt Temp 372 374 370 369 360 378 378

Lb/HP-hr 12.87 12.69 13.54 13.96 17.28 11.66 11.79

I

Table 5 Maximum Rate

Example 1b 5 7 8 9 Control Standard

Diene (ppm) 0 150 250 400 600 0 0 0

Ml 1.57 0.95 1.05 1.01 1.78 1.03 1.03 1.03

Density 0.9193 0.9184 0.9212 0.9209 0.9224 0.9227 0.9227 0.9227

MIR (121/12) 33.8 50.6 53.9 63.2 47.9 38.2 38.2 38.2

ACT SPD 75.7 102.6 102.2 104.3 86.8 88.9

ACT RATE 243 323 317 323 263 294

%Mtr Load 53.2 58.5 54.9 53.4 39.4 61

Press 1 3550 4170 3760 3590 2380 4440

Press2 2290 2730 2450 2340 1510 2920

Melt Temp 376 383 377 374 360 385

ACT SPD 69.8 96.5 96.0 98.0 80.5 83.0

ACT RATE 224 304 298 304 243 271

%Mtr Load 51.4 57.1 53.6 51.9 38.3 59.3

I

Press 1 3340 3960 3590 3420 2290 4200

Press2 2190 2640 2380 2270 1460 2810 I

Melt Temp 375 382 376 373 360 384

ACT SPD 64 90.5 90.2 92 74.4 77

ACT RATE 206 284 279 284 225 251

%Mtr Load 49.4 55.5 52.1 50.4 36.7 57.5

Press 1 3190 3820 3500 3340 2160 4050

Press2 2090 2560 2300 2200 1390 2700

Melt Temp 374 381 375 373 360 382

ACT SPD 58.2 84.5 84.1 67.4 68.1 71.1

ACT RATE 187 264 260 207 206 229

%Mtr Load 47.2 54.1 50.5 43.6 35.0 55.5

Press 1 3070 3780 3370 2850 2060 3950

Press2 1990 2470 2230 1870 1320 2570

Melt Temp 372 380 374 370 360 381

Example ¹b Control

Standard

ACT SPD 78.4 78.2 61.5 62 65.2 ACT RATE 244 242 190 188 208 %Mtr Load 5522..44 4499..11 4411..77 3333..11 5533..77

Press 1 3570 3240 2710 1930 3740 Press2 2380 2150 1790 1250 2440 Melt Temp 378 373 369 360 379

ACT SPD 72.3 72.1 59.6 59.7 ACT RATE 225 223 190 188 %Mtr Load 50.4 47.4 51.6 50.6 Press 1 3480 3130 3580 3460 Press2 2280 2060 2310 2290 Melt Temp 377 371 378 378

ACT SPD 66.2 66.1

ACT RATE 2 _0„6 2 _0„6

%Mtr Load 4488..55 4455..66 j-.

Press 1 33224400 22998800 ^

Press2 2180 1980

Melt Temp 375 371

ACT SPD 60.4 60.2 ACT RATE 188 188 %Mtr Load 46.4 43.5 Press 1 3100 2850 Press2 2080 1890 Melt Temp 374 370

Table 6 Film Product Charateristics

Example 1b 5 7 8 9 Control Standard

Diene (ppm) 0 150 250 400 600 0 0 0

Ml 1.57 0.95 1.05 1.01 1.78 1.03 1.03 1.03

Density 0.9193 0.9184 0.9212 0.9209 0.9224 0.9227 0.9227 0.9227

MIR (121/12) 33.8 50.6 53.9 63.2 47.9 38.2 38.2 38.2

Observation Haze, gels haze, gels haze, gels haze, gels haze, gels haze, gels haze, gels haze, gels

Gauge 1.03 1.07 1.05 1.11 1.14 1.07 1.07 1.06

Internal Haze 1.7 1 1.4 1.4 1.3 2.1 2.2 2.2

Total Haze 10.1 9.8 11 15.8 25.8 10.2 15.1 10.3

Gloss 59.3 51.5 48.8 37.0 22.0 54.6 36.0 48.5

Shrinkage (MD) 79 78 79 78 77 80 79 79

Shrinkage (TD) -22 -18 -16 -16 -21 -21 -24 -20

TANMOD-MD (ksi) 54.52 43.57 55.93 66.70 60.63 65.40 67.83 70.53

TANMOD-TD (ksi) 73.98 76.70 100.23 95.08 114.17 90.72 93.00 73.12

1%Secmod-MD (ksi) 34.45 31.97 39.95 43.83 44.58 41.68 42.73 42.23

1%Secmod-TD (ksi) 42.44 46.58 56.52 59.88 65.68 53.80 53.15 49.27 I

YLDTNS-MD (psi) 1412 1424.33 1868.33 1656 1704.4 1719.83 1663.67 1692

YLDTNS-TD (psi) 1562.83 1600.4 1637.5 1879.33 2076 1820.8 1891 1783.17 I

YLDENG-MD (%) 6.06 6.06 5.8 5.69 5.78 5.9 5.89 5.91

YLDENG-TD (%) 5.98 5.95 5.98 5.43 5.71 5.95 5.87 5.39

ULTTNS-MD (psi) 8741 8201 7432 6775 5090 9231 8758 9030

ULTTNS-TD (psi) 5993 6674 5514 5592 4968 6079 6714 6558

ULTELG-MD (%) 482 458 647 469 478 442 470 489

ULTELG-TD (%) 665 671 462 655 643 688 700 718

PKLOAD-MD (lb) 9.37 8.28 6.06 7.19 5.32 9.13 9.24 9.42

PKLOAD-TD (lb) 5.81 7.01 7.44 5.55 5.12 6.31 6.49 6.77

Energy-MD (in lb) 41.33 37.4 35.88 36.97 30.5 39.25 42.78 40.83

Energy-TD (in lb) 33.68 38.56 36.22 33.37 32.65 38.94 39.53 43

Puncture PK (lbs/mil) 9.7176 9.7994 9.4642 8.3119 7.1600 9.2616 9.6197 11.3320

Puncture PK (lbs*in/mil) 24.4260 24.8120 19.8700 15.4250 11.9240 21.4310 21.6870 30.4360

Dart Drop (g/mil) 176.7 237.38 140.48 120.72 97.81 129.44 137.85 129.25

Elmendorf Tear-MD (g/mil) 125 59 56 54 51 69 73 74

Elmendorf Tear-TD (g/mil) 710 511 535 484 442 812 797 807

Intrinsic Tear (g/mil) 384 379 292 259 220 360 360 360

While the present invention has been described and illustrated by reference to particular embodiments, those of ordinary skill in the art will appreciate that the invention lends itself to variations not necessarily illustrated herein. For example, more than one diene may be added and/or more than one bulky ligand metallocene type catalyst compound may be utilized. For this reason, then, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.

Claims

CLAIMSWe Claim:

1. A process for polymerizing an ethylene monomer and optionally one or more comonomer comprising introducing an amount of diene into a polymerization reactor where the amount of diene is less than lOOOppm based upon the total weight of the ethylene monomer or is less than 255ppm based on the total moles of ethylene monomer.

2. An olefin(s) polymerization process for independently controlling the melt index ratio of a polymer product comprising introducing an amount of diene into a polymerization reactor where the diene feed is less than lOOOppm diene based upon the total weight or less than 255ppm based on total moles of a monomer to be polymerized.

3. An olefin(s) polymerization process to produce a polyethylene from an ethylene monomer and optionally one or more co-monomer comprising introducing an amount of diene into a polymerization reactor where the diene feed is lOOOppm or less diene based upon the total weight of monomer or less than 255 ppm based on total mole of monomer, and where the diene feed is controlled independently.

4. The process of any one of 1 to 3 where the diene is first introduced into a comonomer feed, an inducing condensing agent (ICA) feed, or another feed prior to introduction into the polymerization reactor.

5. The process of any one of claims 1 to 3 where the diene is an aliphatic diene containing non-conjugated double bonds The process of any one of claims 1 to 3 where polymerization occurs in a gas phase reactor in the presence of a catalyst system comprising a bulky ligand metallocene polymerization catalyst.

The process of any one of claims 1 to 3 wherein the catalyst system comprises a bridged a bulky ligand metallocene polymerization catalyst.

The process of any one of claims 1 to 3 where the diene feed comprises a linear or branched aliphatic diene with 5 to 12 carbon atoms.

The process of any one of claims 1 to 3 where the aliphatic diene is selected from the group consisting of 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,11-dodecadiene and combinations thereof.

A film or injected molded article comprising an produced by a polymerization process comprising introducing an amount of diene into a polymerization reactor where the amount of diene is lOOOppm or less, based upon the total weight of a monomer to be polymerized, or 255 ppm or less based on total mole of monomer to be polymerized.