SA02230281B1 - MIXED METALLOCENE CATLYST SYSTEMS CONTAINING INCORPORATOR FOR A WEAK COMMONER AND A GOOD COMMONER - Google Patents

Abstract

Abstract: The present invention provides catalyst compounds for the polymerization process, and catalyst systems include these catalyst compounds, and provides for their use in the process of polymerization of ethylene and at least one comonomer. Specifically, the invention provides a catalytic system that ignites on a weakly incorporating comonomer catalyst and a well incorporating comonomer catalyst. Preferably, the two catalytic compounds that weakly incorporate the co-monomer should be a metallocene containing at least one cyclopentadienyl ligand bearing or without substituents constitutively oriented towards the front of the molecule, which contains a long bridging group. or contains a methyl substitution pattern related to the incorporation of weak covalent monomers. The invention also provides methods for telling a metallocene that incorporates a weak copolymer in order to couple it with a metallocene that incorporates a copolymer well in order to produce polymers that are easily processable to obtain a variety of materials, particularly polyethylene-based films, that have improved properties. ,

Description

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Mixed metallocene catalyst systems contain weak mixed metallocene catalyst systems and a co-comonomer sad gal incorporator with a good cofactor Full description BACKGROUND The present invention relates to catalysts Compounds for the polymerization process and Jad catalyst systems use these catalyst compounds in the polymerization of ethylene and at least one comonomer 0. Specifically; The invention relates to a catalyst system comprising a catalytic compound that incorporates a Gale monomer weakly and a catalytic compound that incorporates a covalent monomer well. Preferably, the catalyst complex incorporating the JS weak comonomer is a metallocene containing at least one cyclopentadienyl ligand with or without substituents constitutively oriented towards the front of the 0 molecule; which contains a long bridging group; or contains a bisindenyl ligand bearing a substituent at position 1 that has been determined to be weakly related to co-monomer incorporation. The invention also relates to methods for selecting metallocene 1106 that is poorly incorporating the comonomer in order to couple it with metallocene that is well incorporating the comonomer; It further relates to polymers prepared using the Way catalytic vo systems of the invention; with materials derived from polymers; Especially the polyethylene Auld film has improved properties.

v Background of the invention that metallocene catalyst compounds What metallocene catalyst compounds show Bale incorporates a weakly covalent monomer with very low efficiency. In addition to that; They are molecules and have a more crystalline crystalline. Lagan polymers that have a low copolymer percentage are high; This is not recommended in the uses of melting temperature o that polymers ost clarity and softness such as membranes where the ductility produced by these weak adsorbents is desirable in the preparation of polymeric blends. These combinations include; For example; Two polymers where each polymer has the same weight of the comonomer. And usually Calida, but each of them has an emolecular molecular weight content. These combinations have mechanical properties; Improved physical and/or chemical yields manufactured materials 0 with preferred properties. for example. The as-prepared polymeric blends are known to have broad bimodal composition distributions that have highly bimodal compositional distributions for membranes. Tear af two tight assemblies have favorable properties as Stehling and collaborators Stehling 077877700 US Patent No. 11 of linear ethylene interpolymers discloses combinations of linear ethylene interpolymers 1 components that can have the same molecular weight but different co-monomer contents; or the same co-monomer contents but different molecular weights ; Or the contents of the co-monomer increase with increasing molecular weight. Resconi and his collaborators The US Patent No. 1061978 in the name of Resconi containing two rings of cyclopentadienyl metallocene reveals a class of metallocene 0 alkylidene compounds bearing two linked substituents Bridged by the cyclopentadienyl rings, where the groups can be indenyl groups 1 (#»4::.

Sua bearing cyclopentadienyl cyclopentadienyl groups (i) that the metallocenes metalocene or hydrogen contain hydrogen 1 while the site contains hydrogen at the site? Non-hydrogen bridge group phrase (ii) 'condensed benzene ring' be part of a condensed benzene ring Yo A

of a methylene bridge group bearing substituents; The cyclopentadienyl groups bear identical substituents. These catalyst structures are used in the polymerization of olefin, especially propylene, but it is generally known that catalysts that contain short bridge groups such as methylene © bridge groups, especially those that contain indenyl ligands, Or cflourenyl has a high ability, Tan, to incorporate the co-monomer. b The reference Angew.

Chem. 101 (1989) No. 11, 1536 Herrman, Rohrmann et al metallocene 8 compounds contain a bis-indenyl bridged with four atoms. There is a need in industry to be able to characterize polymerization catalyst compounds that can incorporate Lely weak co-monomers with improved efficiency to produce polymers and polymer blends with improved properties. In addition to that; There is a need in industry for catalyst systems used to produce polymers with improved properties imparted by catalytic systems comprising catalysts incorporating co-monomer ve weakly to produce polymers; using more than one single Jolie gd catalyst. GENERAL DESCRIPTION OF THE INVENTION The present invention is directed towards polymerization catalytic systems comprising a well-covalently incorporating ad ga catalyst complex and a metallocene weakly covalently incorporating a monomer; Contains at least one cyclopentadienyl vo-incorporated ligand Incorporated cial As directed toward catalyst systems used in olefins polymerization processes The metallocene weakly incorporating comonomer contains a ligand one or more cyclopentadienyl-based fused rings that may be hydrogenated or bear substituents; It may or may not be bridged to another ligand. The invention also directs towards selecting Galea Tai go gradi lia compounds weakly (ge vo) in order to combine them with catalyst compounds that incorporate Lele's coenzyme well to form catalyst systems.

° Polymerization of olefin(s) to produce polymers with improved properties and ease of processing; Especially for the production of polymeric films with improved properties. As for the preferred polymerization processes, they are processes that take place in a gas phase or a slurry phase, and most are processes that take place in a gas phase. Especially when the catalytic system is portable.

e In one embodiment; The invention provides a polymerization process for the polymerization of ethylene in combination with one or more other olefin comonomers in the presence of a catalytic system comprising a metallocene catalytic complex incorporating a weakly co-monomer and a catalytic complex incorporating a co-monomer well. 0

In another embodiment a catalytic system comprising a co-monomer integrator is used

0 0 weak according to the invention and at least one second catalyst compound for the preparation of polymers in a single reactor

gas-phase reactor -single gas phase reactor In another embodiment the catalytic system Ga, of the invention essentially comprises the rac isomer; or all of the racemic, isomers, and intermediates, meso isomers, or the middle isomer of metallocene catalyst compounds 06510086 in essence; The middle flute is preferred

Vo of a metallocene catalyst that weakly incorporates the co-monomer.

Brief explanation of fees

Figure 1: It represents a top view of a metallocene, Cy metallocene, an axis located on the metal atom M between easily removable groups 0 and a bridge group CA, an axis “located on the metal atom 14 and bisects the easily removed groups?;

7 and the angle » that is determined by the intermediate centers of the massive ligand and the metal atom.

Figure 1: Lal, Lau) represents the mole ratio of the copolymer (hexene to ethylene) versus the density of polyethylene produced when using several catalyst compounds of metallocene

Y14¢

the shape ? : Lily Lousy represents the Temperature Rising Elution Fractionation (TREF) of the example polymer Ag. Figures ait: represent graphs of TREF for example polymers "c". Figure LO: represent graphs of 1887 for example polymer DG. Fig. d: represent graphs of the weight distribution ed Molecular Weight Distrubution (MWD) Detailed description a.d. The polymerization catalyst systems according to the invention comprise a metallocene catalyst complex 01 weakly incorporating a co-monomer and a metallocene catalyst complex incorporating a well-monomer. Weak on at least one cyclopentadienyl-based ligand with or without substituents Preferably, the catalyst systems according to the invention are used in the polymerization of ethylene and at least one co-monomer Vo and for the purposes of this patent specification indicate the term “catalyst” to a metallic compound 48 meet; When combined with activator 800780 polymerizes olefins The term “dade aL” is used interchangeably with the term “co-catalyst” The term “catalyst system” refers to a combination of 0 catalyst and optionally a -support material and defines the term 'poor incorporator | 3 is added additionally to this statement and refers to a polymerization catalyst; A catalyst is preferred for the polymerization of metallocene, which produces polyethylene (lef polyethylene) in density; under the same processing media; When compared with zirconium dichloride (inl) .bis(indenyl) zirconium dichloride The term “good incorporator” used in this statement is a relative term meaning the incorporation of a greater amount of co-monomer than ye | For the "weak integrating substance" that is associated with it. Y14¢

The process of the invention demonstrates a method for obtaining polymers with A Gul compositional distributions and improved properties in a single reactor using a catalytic system comprising both a well comonomer incorporating catalyst and a weak comonomer incorporating catalyst. The large difference in the incorporation ability of the co-monomers between the good binder and the poor M binder will result in a more widely separated dimer polymeric structure, which in turn further improves the overall polymer properties. We estimate the degree of ability to incorporate the co-monomer into a polymerization process from the gram-molecular ratio of the co-monomer concentration to the ethylene concentration needed in the polymerization medium to obtain a given polymeric density or average co-monomer content. In a gas-phase polymerization process, it can be derived from the concentrations of the co-monomer and the monomer in the gas phase. In a slurry phase polymerization process, it can be derived from the concentrations of the co-monomer and the monomer in the liquid diluent phase. In a homogeneous solution phase polymerization process, it can be derived from the co-monomer and monomer concentrations in the solution phase. Figure oF and Tables 1 and ¥ describe a gas-phase process using an ai se co-cofactor of Cus hexene requiring a catalytic system comprising a 000(:2:01) gram-molecular ratio of the co-monomer to the monomer of about 0094 to yield a polymer of density +.4Y g/cm.” A catalyst comprising a weak enthalpy of O(Me;Silnd),ZrCl, racemic requires a co-monomer to monomer ratio of about 0668 to produce a polymer of similar density.Thus, the molar ratio of co-monomer to monomer required for the weak adsorbent to produce a polymer of target density of 1971 g/cm' is greater than twice the molar ratio needed for the good adsorbent.In the catalysts of the invention it is preferably The copolymer-to-moner molar ratio required for the weak copolymer sorbent component of the catalyst to produce a vo-polymer of density 1.970 g/cm” is at least twice the value of the monomer molar ratio

A

g/cm"; 0.971 covalent to the monomer needed for a good binder to produce a polymer whose density is greater than ¥ times this value; the best is also greater than ; times this value; the best is also greater than © times this value Weakly incorporating metallocene monomer A catalyst compound of metallocene of the invention contains Gay metallocene catalyst compounds The catalyst system includes a weakly covalently incorporated metallocene The weak binder includes sandwich compounds containing full sandwich compounds and half sandwich compounds cyclopentadienyl on at least one; preferably two; cyclopentadietyl-based; and at least one removable group bonded to a metal atom. They are those ligands that include a cyclopentadienyl base with a cyclopentadienyl base, Ve, with or without substituents, and which share a pair of cyclopentadienyl group, an aromatic structure or a cyclic structure with a carbon ring structure of carbon atoms. Others. Incorporated cyclopentadienyl The ring usually consists of the cyclopentadienyl-based ligand of the periodic table for the distribution of 01 to 1 “rings from atoms selected from the atoms of the ye carbon groups, and it is preferable that the atoms be selected from carbon cPeriodic Table of Elements Phosphorous sulfur silicon coxygen oxygen cnitrogen nitrogen or a combination thereof. It is more preferable that aluminum and aluminum boron are phosphorous with cyclopentadienyl rings. The ring in the cyclopentadienyl ligand is also formed in the cyclopentadienyl ligand, and the ligands that are cyclopentadienyl carbon include Y carbon atoms. The cyclooctatetraendiyl epentadiene structures of other ligands that have the same function such as the imide pentadine ligand or the cyclooctatetraendiyl imide to 10 and from the Y series of lanthanides. It is preferable to choose the metal atom from the groups of the periodic table for the distribution of elements. It is preferred that the actinides be sl lanthanides a and better than VY from groups 4 to transition metal. The metal is a transition metal 4. The metal must be chosen from the group Sain and the most 0 of groups For the purposes of the patent specification “leaving group de pend” and these and the appended claims mean any ligand that can be extracted from the metallocene catalyst cation according to the invention to form one or more metallocene °C cations olefin capable of polymerizing olefin incorporating metallocene monomer metallocene catalyst complex Fray embodiments;

0 | where M is 58 of group 11 YF or a thc atom of the lanthanide series

M from the periodic table of element distribution; Preferably actinides or lanthanides

Z is a transition metal from the group of © or 0, and it is better that it represents 14 transition metals from the group; It is better for 14 zirconium to be represented by hafnium or titanium, and it is more preferable for it to be represented by 14 zirconium.

m and *1 and 12 separately represent large ligands; Linked to 04 where it represents at least one of the 14 or 18 large cyclopentadienyl ligands fused to rings. Large ligands are defined in this statement as an open ring (or rings) or ring system (or systems); Acyclic or fused (Fie) cyclopentadienyl ligands or cyclopentadienyl-based ligands bearing substituted or unterminated or ligands

Y. contain heteroatoms and/or carry substitutions of heteroatoms.

Nonspecific examples of large ligands include cyclopentadientyl ligands

cyclopentadienyl ligands sindenyl ligands benzindenyl ligands

Fluorenyl 800:01 coctahydrofluorenyl ligands

cyclooctatetraendiyl cazenyl ligands cazulene

ve pentalin ligands “pentalenc phosphoyl ligand cphosphoyl ligand pyrrolyl ligand

07702011 carbazolyl ligands borabenzene ligands and the like; Including hydrogenated forms terminated for example -tetrahydroindenyl ligands Unspecified examples of a cyclopentadienyl-based ligand incorporated ° rings include sindenyl ligands ¢benzindenyl ligands fluorenyl ligands “fluorenyl ligands” 'octahydrofluorenyl' cyclooctatetraendiyl ligands 'cazenyl ligands' azulene ligands cazulene and the like ell including hydrogenated forms terminated for example -tetrahydroindenyl ligand 01 In one embodiment it is possible that 14 and GLP be another ligand structure capable of binding to 14 at the eta site; Preferably it binds to 4 at the eta site oF and most preferably to bind to 0” at the eta site H where at least one of *1 or 17 is a cyclopentadienyl ligand. In another embodiment, both 1′ and IB can be homo- or different cyclopentadienyl-based ligands fused to rings. In one embodiment; At least one of them is +1 or 1B and preferably both are indenyl moieties with or without substituents. In another embodiment; *1 and 8 can contain one hetero atom or SS for example; nitrogen, silicon, boron, germanium, Y. sulfur and phosphorous in combination with carbon atoms to form a ring or an open ring system; acyclic or preferably built-in; For example; An additional -hetero-cyclopentadienyl ligand includes other bulky ligands of SLY | 18 to name a few; Large ligands of amides phosphides 010501065 Calkoxides Aryloxides Caryloxides Imides Cimides Carbolides

11’ phthalocyanines porphyrins 00m phthalocyanines borollides borollides other carbolides polyazamacrocycjes multiple massive aza rings corring i and can carry both +1 and 12 separately; as described above; A combination of groups on the Lal R group may be devoid of it. Non-specific examples of substituent JiR groups include | alkenyl radicals alkyl zoase or alkenyl chydrogen one or more selected from hydrogen df oyeloatkyr radicals cycloalkyl radicals linear or branched alkynyl; 'aryloxy' roots 'alkoxy' aroyl roots cacy] acyl roots alkoxycarbutyl roots 'dialkylamino yin dialkyl radicals calkylthio alkyl thio roots 08700001 carbomoyl radicals 'aryloxycarbony] alkoxycarbony] 'acyloxy acyloxy radical 'dialkyl-carbamoy] dialkyl carbamoyl alkyl radical alkylene oryl amino M7071 alkyl radical 'acylamino acyl amino radical or a combination thereof. Branched or - 'methyl' Non-specific examples of alkyl groups include: substituent c methyl groups Jy hexyl 'pentyl 'butyl' 'propyl' cethyl ethyl and the like that; Including phenyl or phenyl benzyl benzyl 'cyclohexyl' cyclopentyl Vo and 'isopropyl isopropyl' tertiary, all of its colleagues, for example, butyl trigonal such as hydrocarby] and the like . Other substituent C groups include the difluoroethyl iodopropyl hydrocarbyl radicals [fluoroethy] fluoromethy fluoromethyl and para-organic radicals [‘chlorobenzy]bromohexyl [¢iodopropy] methyl oN comprising the hydrocarby] of hydrocarbyl Sy bearing metallic organometalloid radicajs yy, descendant of Jl 'trimethylgermy] Jaa' trimethylsilyl descendant of halocerbyl Sa, and semi-metallic organic radicals bearing ay and the like methyldiethylsity 0 tris(trifluoromethyl)sity including tri(trifluoromethyl) silyl halocarby] bromomethyl difluoromethy 'methyl-bis(difluoromethy)sity Jal (difluoromethy) 03 bearing two substituents including bi-boron and the like; and boron roots 'bromomethyldimethylgermy] Yo

1 for example; And 001010860 pentogen radicals bear two substitutes include dimethyl boron methyl boron amine Jib (= “dimethylphosphine” dimethylamine amine chalcogen includes chalcogen radicals ’methylphenylphosphine methylphenylphosphine cdiphenylamine sulfide Methyl 'phenoxy' PTOPOXY '0'; ethoxy 'elastic'; propoxy -ethylsulfide methylsulfide © boron ssilicon carbon Other substituent C groups include carbon atoms oxygen oxygen 'phosphorous' nitrogen 'aluminum' ¢boron

R Groups also include cally and the like germanium sulfur tin tin to name a few olefinic substituents other than Jia olefins other alternative olefins ligands with a vinyl reflux Jai olefinically unsaturated saturated substituents > 0 hexenyl ¢prop-2-enyl ( Y ) sbut-3-enyl propenyl (*) e.g. butetyl ligands at least two; preferably rR and the like. The two hex-5-enyl 0 groups are also linked to an atom of Fe carbon, two adjacent groups of 8, to form a cyclic structure with © to silicon 'phosphorous' phosphorous 'oxygen' oxygen 'nitrogen' carbon or a combination thereof. as well; boron may boron “aluminum aluminum cgermanium germanium Vo carbon Lary bond 1 -butanyl linatoweb-1 JR group by group formation

M lal with carbon sigma bond is one embodiment; gM each © separately represents an easily removable group attached to a monoanionic labile ligand is an unstable monoanionic ligand Q is amines and includes Non-specific examples of ligands of N weak bases. M. amines M. sigma with Y. monoatomic bases tethers and ethers dienes phosphines 1M010 Dienes containing hydrocarbyl radicals scarboxylates such as monoanionic bases carboxylates and so on Similar halogens or hidrides are carbon hydrides 01 to 1 carbon atom of two or more groups part of a ring or that JT or a combination thereof. In another embodiment described above, R includes a built-in loop system. Other examples of © ligatures include those alternatives 0m

1 ok cyclohexyl cyclohexyl cyclobutyl moiety cyclobutyl moiety 'pentamethylene' tetramethylene strifluromethyl fluoromethyl ethoxy 'elastomer'_propoxy 0:00 phenoxy < methoxy cmethylidene cdimethylamide dimethylamide “bis(N-methylanilide) (17-methylanilide) (sD “phenoxy and the like. dimethylphosphide methylphosphide > 0 ( I) so that the formula represents 1 or 1 on the oxidation state of 04 with a value of “yellow sly” neutral. The above metallocene is a catalytic compound of metallocene, it represents a bonded bridge group A is an optional group. When there is A and represents groups containing an atom A b 18 414. Non-specific examples of the bridge group often with double moieties include Ja ay to 11 at least one of the atoms of groups 0 for example no Exclude at least one atom of carbon Jie divalent moieties, boron, aluminum pia sl silicon, silicon, nitrogen, coxygen, oxygen, carbon, or a combination thereof. It is preferable that the group contain tin and tin. germanium germatium 000 and it is better that -germanium or germanium silicon bridge silicon ccarbon M on at least one carbon atom preferably two silicon atoms on a silicon atom A the bridge group ye contains A contains at least one al. And in the embodiment of carbon, a silicon carbon atom, two CAF atoms; more than two atoms are preferred; preferably who? to ; and most preferred

AT to 1” substituent groups as defined by R on groups A and in another embodiment; The bridge group contains

A can represent the bridge group iron and iron halogens above including halogens | 2. Where 1 is R,'Si-ORySi or Ry/Si-NR'-Ry'Si min Ry'Ge R,'SiR,'Si R;'Si R,C —, alkyl Alkyl hydrocarbyl hydride is preferred, each separately representing a radical representing a hydride bearing substituents; halocarbyl hydrocarbyl carbon carbon atoms A to 1 contains of organometalloid a semi-metallic organic compound 0 bearing substituents hydrocarbyl the halocarbyl of halocarbyl Sua a semi-metallic organic compound bearing chalocarbyl It carries a yo-hydrocarbyl substituent.

Ve chalcogen carries substitutes pnictogen chalcogen carries substitutes; A chalocarbyl boron pentogen, or two or more L groups can be linked to form a halogene ring carrying substituents; or metallocene halogen or ring system. In another embodiment the compounds of the catalysts may contain metallocene

A bridging by formula (1) on two or more bridging groups which incorporates the metallocene monomer comprising the metallocene catalyst compound AT and in an embodiment of °

HI) weakly contributing form (1) form L°AIMQ,

SIE or a metal chosen from group 11, where 14 represents a metal atom from group © to

M preferably represents 0 of the periodic table of the distribution of the elements actinides and actinides © lanthanides and preferably represents a transition metal from group 4; VY is a transition metal from the group; to from the group; in any oxidation state. and most LIE or ; It is more preferable to represent 0 metal - hafnium or zirconium mfnium, preferably to represent 14 cyclopentadienyl zirconium with 4, which is a massive ligand based on cyclopentadienyl LC and is linked to the compact rings as I knew above; It can carry variants of # or not, as mentioned above. On J represents [ an additional ligand containing a hetero-atom bonded to 14. It contains Ve or element 0 and belongs to the group Vo late reporting coordination number An element that has a coordinate number of 11 from the periodic table for the distribution of elements. It belongs to group 1. It has a consistency of dae or 'oxygen' phosphorous 'oxygen' phosphorous 'nitrogen' on a nitrogen atom J It is preferable that it contains 'nitrogen' and most preferably nitrogen sulfur .1m as defined above, which is a bridge group linked to 17 and 7 laren and represents the cunivalent anionic ligand and represents a monovalent anionic ligand 1 or 1 valid Jha reporting | integrated. In an embodiment, Lala is the LS JT system button <a ode] (I) and in the form

MA mentioned above. In another embodiment; The symbols A in formula (11) denote the same meaning as − (1) and 0 in formula (0) have the meanings mentioned above in formula + vo incorporates a metallocene monomer and in another embodiment the invention provides a metallocene catalyst It has at least one weakly covalent metallocene ligand where the structure of the metallocene includes icosahedral ligands; preferably two ligands that are directed in a substantial cyclopentadienyl-based form towards the anterior part of the molecule as will be defined below.

J) Ae pend Aa Uy J A 4, the front part of the molecule by the group 0 substituent groups). Referring to Figure 11 which represents an overhead view of an embodiment of metallocene incorporating a Gy weakly covalent monomer of the present invention Coa metal 14 is in the plane of the sheet; There is a first ligand; In this case the cindenyl ligands are above (dashed lines) and below (solid lines) the plane of the page. And the axis > « passes through the metal atom 04; which are located at the page level; It does justice to easy-to-remove Q groups. The * axis passes through the metal atom 04 which lies in the plane of the sheet and cuts the y axis at an angle of 110.” The front part of the molecule is identified as towards easily removable © groups. Although the bridge group A is present in gay However, it is recognized that the bridge group A is facultative and may or may not exist.The ligands, which are represented by + indenyl groups 100821 in Fig. + is a projection in the plane of the bal page drawn between the intermediate center 28 of the linked ring “ll, in this case the cyclopentadienyl ring, and the intermediate center of the incorporated ring; in this case a benzyl ring attached to the cyclopentadienyl ring -cyclopentadienyl Y. It is understood that if two cyclopentadienyl-based ligands are fused; referring again to Figure 1, the angle “of the fused ring above the plane of the sheet can be the same or different from the angle” of the fused ring below Page plane Sa angle determination » by Xray crystallography and/or calculated from molecular modeling techniques, 1; as is known in the technique. In one embodiment; Referring also to the figure techniques ve

be “greater than Fe, preferably greater than 45”, preferably greater than “V, preferably between 1 and less than 40”, preferably from about +0 to about 0. In another embodiment, there are two pentadienyl ligands cyclopentadienyl ils are fused to the rings and they are bridged by “at least atoms chosen from groups 1 to 10 m of the periodic table of the distribution of elements; where the angle” of the first ligand ranges from about 0 to about 40 “and where the angle is » The second bond is greater than 11 . In another embodiment, the invention provides a metallocene catalyst incorporating a weakly copolymer in which the metallocene structure includes at least one cyclopentadienyl-based cyclopentadienyl ligand bridged to a 01-sal cyclopentadienyl ligand as shown. Shown above in formula 1 where the bridge group A is a long bridge group defined as a bridge group containing 2 or more atoms preferably 0 or more atoms The long bridge group A preferably contains oxygen atoms coxygen silicon silicon and carbon (carbon, and the best; that the long bridge group A contains a group of 901 Cua that carries silicon Sb silicon from the group R as 0 - defined above; it is preferable that the R group be It contains alkyl nitrogen 'nitrogen' and the long bridge group A can contain SENSE where nitrogen and silicon atoms carry 100 substituents; it is preferable to carry substituents from the R groups defined above; and the best R being an alkyl group and non-specific examples of suitable metallocenes that incorporate a weakly covalent monomer and contain a long + bridge group include ZrCl, “O(Me;Silnd),ZrCl,” (Fluorenyl “O(Me;SiFluorenyl),ZrC1, O(Me,Si RN(Me,Silnd),ZrCl,” O(Ph;Silnd),ZrCl, “O(MeSi[Me;Cp]),ZrCl,” O(Me,Silnd),HCl, -O(Me,Si[Me;Cp])(Me,Silnd)ZrCl, 5 Preferably, these weak integrants are found in racemic or intermediate form, or a combination thereof. It is better to exist in the image of the middle class in an essential way. without wanting to be bound by any theory; The inventors believe that the structures of the ve crystals exposed to X-rays show that the two long bridge groups oscillate around the part

1 and that it is in “steric hinderance, which constitutes a steric obstruction of the anterior metallocene of the metalocene from the two rings of Kal ag Jad: (0048:5:1:0-middle; for example, ZrCl, group case) Towards the front part of the molecule, which makes it more crowded.Therefore, large indenyls, such as alpha-olefins, do not prefer the proximity of alpha-olefin steric features to these stereoscopic features, or more, and carbon is more preferred. ANY contains alpha-olefin an alpha-olefin e0 of a ccarbon atom and better than that more than © cf carbon atoms of “; and better than the central metal which leads to a decrease in its ability to incorporate Metallocene A Referring again to Fig. 1, the long bridge group provides a weak incorporation of the co-monomer.In one embodiment, there are two ring-integrated metallocene ligands bridged by ?cyclopentadienyl atoms based on cyclopentadienyl 01. From the periodic table of the distribution of elements, where 11 to 1 “at least choose from groups up to about 40, and where the angle value in the first band is 0 from about the angle” in the second band is negative. and in one embodiment “for the purposes of the present application; A weak binder to the monomer with a density higher than that of the contributing polyethylene is defined in this statement as a polymerization catalyst that produces polyethylene ve bis indenyl zirconium dichloride (Ind),ZrCl, if diindenyl zirconium dichloride is used

TUS when used in conditions similar to the process. For example, with reference to and contains 0.971, the density of polyethylene is polyethylene (Ind), ZrCl, and Table (1); Produces, in comparison; .., 104 with a gram molecular ratio of ethylene Call hexene hexene Dichloride (pentadienyl) (indenyl) zirconium requires a gram molecular ratio of (pentamethylcyclopentadienyl) (indenyl) zirconium dichloride with an amount of 0776 to produce polyethylene (13 )/hexene with a density of 7, therefore it is known in this statement as a polyethylene weak binder of the co-monomer. And on the contrary; Requires di(7-tetrahydrindenyl)zirconia Teo dimethylsilane di(4;ye) chloride

VA

A fine molecular ratio of dimethylsilylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride polyethylene for the production of polyethylene +, 0 0 V is an amount of ethylene from hexane p «m »5 / ethylene, and therefore it is known in this Indicated as a good binder for the copolymer. 4,90 Y with a density of 4.90 Y. In another embodiment; A weak binder is defined in this statement as a polymerization catalyst that produces polyethylene polyethylene (Ind), ZrCl, with a density of m when used under process conditions; Where it produces and preferably higher than 60.9, and the best is higher than 0.9700, which is 0157.; a polymer with a density higher than better than 1,948 ef and better than 1,940 8, Sel; The best incorporates a metallocene monomer and in another embodiment; The invention provides a metallocene catalyst. 6 on a weakly covalent metallocene base ligand where the structure includes metallocene and preferably two ligands; The best “JY” is a single-ring incorporator on cyclopentadienyl cyclopentadienyl cyclo-0, and it is more preferable to contain two cindenyl-based ligands and an indenyl-based ligand bearing substituents to control the incorporation of the co-monomer. It has been determined that di-indenyl compounds carry substituents in situ bisindenylzirconium dichloride zirconium Jy JP BE chloride compared to ethylene that contributes to the reactions of ethylene polymerization pad gall Tam They are weak binders 1 and metallocene compounds 1 Which carry dichloride substituents on site with other 1 ve 1 and 9 of dichloride compounds that are not bridged together. While the substitutions may affect the metallocenes at the site, impair the incorporation of the co-monomer.1 on the effectiveness; It was determined that the substituents present in the site that weaken the incorporation of the co-monomer groups 1 and the appropriate substitutions in the site include propyl and propyl ethyl methyl groups 60.1 ethyl alkyl alkyl usually requires dichloride dichloride ( 1-Methylindenyl) zirconium JA sabil + carried on silica “(1-Melnd), ZrCl, with the formula “bis(1-methylindenyl) zirconium dichloride 70.76 with a percentage of Zr containing zirconium Davison 948 4 (Davison type silica) Molecular ratio (VV Ye) of (1-Melnd),ZrCl, to MAO by weight; with a gram molecular ratio of ?+; in the gas phase ethylene to ethylene hexene grams of hexene 5196 with a volume of 1.17 and a density of melt index MD) to form a polymer having a melt index vo

and Tafa in a gas-phase reactor. (J Ally would normally require bis(1-propylindenyl)zirconium dichloride with the formula (1-Prind),ZrCl, ratio molarity of hexene to ethylene of 4 to form a polymer with a melt index of 1.6148 and a density of mAYEY + g/cm. otherwise; Di(7-methylindenyl)zirconium dichloride, ¢bis(2-methylindenyl)zirconium dichloride with the formula ¢(2-Melnd),ZrCl, requires only a hexene to ethylene gram molecular ratio of of V0 4.0 to form a polymer having a melting index of 0.£Y and a density of 0.1176 g/cm". Typically, bis(2-propylindenyl)zirconia dichloride does not require ) zirconium dichloride of the formula (2-Prind),zrCl,V also has a gram molecular ratio of hexene to ethylene of 1.004 to form a polymer with a melting point of 5.15 and a density of AYYO © g/cm. Lad sale bis(propylcyclopentadienyl)zirconium dichloride with the formula o(Pr-Cp),ZrCl, requires only a Vo molecular ratio of hexene to ethylene ethylene of 0015 to form a polymer having a melting index of , FA and a density of 0.914 Fafa and not requiring dichloride (1;7-methylbutylcyclopentadienyl zirconium, 3-methylbutylcyclopentadienyl) zirconium 1 of formula ,3-MeBuCp),ZrCl, 1)” only has a gram molecular ratio of hexene to ethylene of 12014 to form polymer© with a melt index of 0.1; and a density of AVY g/cm '. Well-incorporating comonomer-incorporating catalyst complex Jad The catalytic system Gy of the invention is based on a well-conjugated comonomer-incorporating catalyst complex with the metallocene poorly incorporating comoner catalyst mentioned above. The term “good incorporator” means the catalyst compound that

Y. with which the “poor incorporator” binds the copolymer to a greater extent than the “weak binder” with it. The catalyst with which the “poor incorporator” binds well embodiments Jia; asl and in (10): In the form (1m) LALPMQ, °

V represents a metal atom from the periodic table for the distribution of elements and may be a metal from group M where from the periodic table actinides or actinides lanthanides or from the lanthanide series VY to or; Better yet, © of to distribute the elements; It is preferable that 8 transition metals from the ezirconium group represent a transition metal from the group ;; Even better, 14 zirconium 1 represents titanium or hafnium Ve (or ring systems) or open ring (or rings); Amorphous or Gala and 18 systems 1 + Bays its “soundness”; It has a built-in ligand system as any additional ligand system bearing a cyclopentadienyl or a cyclopentadienyl ligand having a substituent of a cyclopentadienyl atom or without a cyclopentadienyl ligand terminator contrast and/or contain it. Unlimited examples of huge spirals include the 10 Scyclopentaphenanthrenyl rabuets of the penthentinil rich ccyclopentadienyl my throat «Fluorenyl Florinil CBENZINDENY) ctahydrofluoreny! Octahydroflurenyl ligands Cyclododecene ligand Gy Gay <cyclooctatetraendiyl ligand phosphoyl cpentalene pentalene ligand cazulene azulene ligand cazenyl azenyl Y. 34/4075 (See international patent application phosphinimine No. “phosphoyl epymrolyl pyrosolyl ligand is incorporated into this release for reference); pyrrolyl ligands and the like; borabenzene borabenzene ligand ccarbazolyl ligand carbazolyl ligand 0201 and in-tetrahydroindenyl tetrahydroindenyl ligand Mie including hydrogenated forms eg one or more terminated and 1 hetero atoms; Nitrogen 0150860 Silicon 1A May include 0 other embodiments ve

In “phosphorous and sulfur” germanium boron “silicon” to form a ring or open ring system, acyclic or preferably combined; carbon combination with additional bonding carbon atoms of pentadienyl Ring-mixed 116160-070100©0180101. Se ligands include camides phosphides, to name a few; Other IB bulk amides 1 f

phosphides ° alkoxides aryloxides caryloxides imides 011165 Carbolides cborollides dadg yss ccarbolides porphyrins cporphyrins phthalocyanines ccorrins and other polyazomacrocycles. independently; Joey may both 14 and LP have a large Bilas or Calida ligand that binds to 34. In one embodiment of the oI formula there is only one ligand "1" or 1.

1 independently; LA and 1 may both be free of substituents or carry a substituent from a combination of substituent R Cle senses. The R substituent groups include but are not limited to one or more groups of the chosen class of chydrogens or linear or branched alkyl radicals; or alkenyl radicals alkynyl radicals 1oa1a; cycloalkyl radicals or aryl radicals; cacyl dad roots orwell roots 1 radata; alkoxy roots

alkoxy ve caryloxy radicals alkylthio radicals dialkylamino radicals calkoxycarbonyl radicals sda caryloxycarbonyl carbomoyl ccarbomoyl alkyl-carbamoyl or dialkyl-carbamoyl cacyloxy radical acylamino radical caroylamino radical alkylene straight; branched or cyclic

© or a combination thereof. In a preferred embodiment; The LR substituent groups have no more than 950 non-atoms

chydrogen preferably 1 to ye atom; It can also carry Soa of halogens

R alkyl or hetero-atoms or the like. Non-specific examples of alkyl substituents include halogenes

methyl groups cethyl propyl butyl pentyl pentyl hexyl

Hexyl cyclopentyl cyclohexyl benzyl or phenyl etc.

ve similar; Including, for example, all his colleagues; Butyl 0 ctertiary butyl isopropyl alcohol

YY

Other fluoromethyl hydrocarbyl and the like. The hydrocarbyl radicals include 500:01 iodopropyl Al0(e:m000; difluroethyl efluroethyl fluoromethyl) and cchlorobenzyl chlorobenzyl chlorobenzyl bromohexyl radicals comprising trimethylsilane hydrocarbyl bearing a hydrocarbyl substituent of 10 methyldiethylsilyl ctrimethylgermyl trimethylsilyl ° including tri-halocarbyl and the like; (trifluoromethyl)-silyl (trifluoromethyl)-silyl en as a rubber band; difluoromethyl)silyl bearing two substituents including boron and the like; and cbromomethyldimethylgermyl boron radicals bearing two substituents including dimethyl prictogen For example; dimethylboron radicals

Jil sulfide “phenoxy” propoxy cethoxy emethoxy oS fia on hydrogen other than hydrogen R and the alternatives include ethylsulfide and methylsulfide. boron boron ¢silicon carbon atoms 2 silicon \o germanium sulfur sulfur etin tin coxygen oxygen phosphorous phosphorous “nitrogen to name but not limited to substitutes olefins and the like; including germanium olefins e.g. vinyl-terminated ligands unsaturated olefins including vinyl-terminated ligands and the like hex-5-enyl (©) hexenyl cprop-2-enyl (Y) propenyl cbut -3-enyl )( at least two biotinyl R; two contiguous groups of R are preferred. Two ©nitrogen groups of carbon 8:00 Ye JER T5350 Ye are also bonded to form a cyclic structure with © to aluminium, cgermanium, germanium, ssilicon, silicon, phosphorous, coxygen, an alternative oxygen such as the R group or a combination thereof. Also, the boron group may form aluminum .14 boron with the metal carbon sigma bond 1 -butanyl linatoweb-1

YY

Such as one easily removable © group on M and other ligands may bond with the lesser metal. In one embodiment; © represents an unstable unary anionic ligand linked by a sigma bond with (I) or ? So that it represents the formula 1 and depending on the oxidation state of the metal, the value is “yellow.” 4. Neutral and contains a huge ligand. Amines, phosphines, cphosphines, ethers, cethers, carboxylates, dienes, hydrocarbyl radicals that have from 1 to Yo a carbon atom, hydrides or halogenes and the like or their terminated combination and in another embodiment <3 JZ two or more moieties of Q fe ja of a compact ring system or compact ring. Other examples of © ligatures include those of . The R substituents described above include cyclobutyl radicals cyclohexyl (gla cheptyl ctolyl ctrifluromethyl tetrafluoromethyl 1652716111606 pentamethylene ¢methylidene cethoxy (oS gd ¢methoxy propoxy 0007 ¢phenoxy di(17-methylanilide) ¢bis(N-methylanilide) =(methylamide ¢dimethylamide dimethylphosphide and the like. vo In one embodiment, the catalyst compound well incorporating the co-monomer may include such compounds of formula (I) where “1” and LP are bridged through at least one bridge group 4; as 5 J7 of formula (17): (IV) Formula | L*ALPMQ, with bridging catalyst compounds (IV) bridging compounds represented by formula 038 Cpe 25 0” - from metallocene and the symbols M (LB (LA) © and Non-specific examples of A bridge group include bridge groups containing at least one atom from group 17 to 06 often referred to as a divalent moiety such as; but not limited to atom at least one of carbon oxygen nitrogen germanium boron tinned aluminum boron esilicon silicon ¢nitrogen tin or a combination thereof. Preferably, the A bridge group contains a carbon atom

Yi

carbon, silicon, or germanium, and it is preferable that A contains at least one silicon atom or at least one carbon atom. The bridge group A may also contain substituent R groups as specified above Lay including halogenes and iron 0:. Non-specific examples of the MB bridge group may be RY Cus (RP (Ry'Ge «R,'Si R,'Si »Ry'Si (RC©) independently representing a radical group representing the hydrocarbyl chydride Hydrocarbyl carries a substituent of halocarbyl halocarbyl halocarbyl carries Sud a semi-metallic organic compound that carries a substituent of hydrocarbyl chydrocarbyl a semi-metallic organic compound that carries a substituent of halocarbyl boron boron that carries two substituents » a pentogen pnictogen carries 2 substituents a chalcogen carries 0 substituents or a halogene or two or more than 3 may bond to form a ring or ring system.In one embodiment the metallocene bridge catalysts containing a large ligand in formula (IV) on two or more A-bridge groups (see patent

European Patent No. YON BI 174). In one embodiment; Compounds of catalysts that well incorporate the comonomer include 1tk compounds where the R substituents on the large ligands LA and LP bear the formulas (mm) and a similar fae(IV) or lida of Alternates on both large ligaments. In another embodiment, the two massive ligands LA and LB of formulas (21) and (IV) are different from each other

andl and other catalyst systems that are metallocene and may include metallocene catalyst compounds ly are suitable for use in this invention as a good binder for the co-monomer in the catalytic system ©; F1 of the invention described in the US patents are MCF numbers TACOLA 1 * KH Umm Lama’a Naham Kaf Al-Ithaham 4 Al-A’aaf Fadada Al-Ala Fala 46 Fala Al-1 MF £TYE 47 AD Al-Moha’im Dave 410/6 Daf 011 . 0 and 057955807 and publications in patents 08771/9 of the Patent Cooperation Treaty International Gig Invention Numbers vo

Yo. Mtakhaf. words “FAL EARRED” (A—. YA 040 and 447 87 NO 81-0; all of which are incorporated in their entirety into this 81-6 YEA AYY (BJ) statement for reference. 0 and in one embodiment; may include The catalyst compounds that well incorporate the co-monomer metallocene and are suitable for use in this invention contain bridge compounds of the type metalocene in Nia containing a large single ligand and a heteroatom.The types and systems of these catalysts have been described; Patent Nos. Tidy International Patent Publications LAM ADDED 4 ../HV Machine Code (AE[.VAYA TRANSFORMED 0 ATATY] and 19/7577 and US Patent Nos. 5FM and 0774405 and EP No. 0777440 819846 are included in this release for reference. Wal sine has all incorporated fully <1 71 £1 containing a metallocene ligand and in this embodiment; the catalyst has metalocene 7:) ( massive in the form vo (v) L°AIMQ, from the group of lanthanides JER T1508 or 11 represents a metal atom from group to M where M from the periodic table of the distribution of elements and preferably represents actinides The lanthanides actinides 0 are a transition metal from group 4; M, and it is better that VY represents a transition metal from the group; to transition from the group; In any oxidation state TBM and most preferably 1 or © represents a large ligand with or without substituents LE titanium especially titanium cooxidation state represents an additional ligand of a hetero-atom; and TJ correlates with 14 and A tM correlates with J correlates with 84; integer Tae represents a bridge group; © represents a monovalent anionic ligand; And “A” represents a loop-integrated system. and in one of the J m and LS forms adel (7) and in the form .1 or 1 yellow vi and © in 14 A above for “1 and Da is the embodiments; ©1 in formula (7) is as (I) above in formula a as (V) formula contains an element with a number J Cus representing a ligand containing a hetero-J atom J and in formula (7) From 11 of group 1 of group 10, or an element with a harmonic number of Vol laa, phosphorus, enitrogen, is coordinated to a nitrogen atom, J, of the periodic table of element distribution. nitrogen and nitrogen sulfur or “phosphorous” coxygen and in an embodiment of the invention; catalyst compounds that well incorporate the co-monomer include bulky ligands; the Cus ring is heterocyclic ligand complexes (or rings), ring system(s), one or more heterotoms, or a combination thereof. to 371 and preferably 1” Unspecified examples of heterotoms include a group 1 element <aluminum coxygen oxygen ¢ sulfur nitrogen «©01508; boron 00:00; sulfur compounds catalysts iP tin and phosphorous silicon «511100» phosphorous these large ligand-containing compounds have been described in patent applications metallocene International Metalocene No. 70777/T 4071/District 4 and 174871/14 and Patent No. 179717556 and American Patent No. 0-1 AVE © European No. 01 Lah and 2881780 incorporated 4411 177144 4M Dalal Adaf 1H All Qalaf are included in this statement for reference. In one embodiment; The catalyst compounds that well incorporate the co-monomer are those complexes known as transition metal catalysts based on bidental ligands such as those described < quinoline or pyridine quinoline containing bidentate ligands Filed on 077700/19 in US Patent Application Serial Number and incorporated into this statement for referral 1017817 which is registered as US Patent No. 44) 2 of which the metallocene catalyst compounds of metallocene AT are referred to as a reference . and in an embodiment it contains a bulky ligature in those described in the two publications of the two international patent applications

To Gay PCT No. VEAY 9/0 and No. AAJEXTTE are fully incorporated into this release by reference. In another embodiment, the catalyst compound that incorporates the comonomer well is a metal complex, preferably a transition metal; a huge ligature; A picbonded 0-by-linked ligand carrying Jay or devoid of substitutions” and one or more Jia cheteroallyl moieties described in US Patents Nos. 5577757 and 074974079 and EP 00517 is preferred. 7735 31-0 are all fully incorporated into this statement for reference. In another embodiment, the other metallic compound or the second metallic compound is 0 a metallocene catalytic compound containing a large ligand represented by the formula (71): (VI)LPMQ,(YZ)X, where M It represents a metal from group 9 to NT and preferably 138 transitions from the group ; to 11 and preferably a group 4 transition metal; 0 or “; Bia LP is a bulky ligand that binds to IM and each Q binds separately to 14 and forms (0:072 ligand; a single-charged vo multi-dentate ligand is preferred; A or Q is a monovalent anionic ligand Load is associated with XM representing a monovalent anion group when “¥ or Bas X reaches a divalent anion group Loveie” represents 1; “ represents 1 or 1 and in the formula ( VI) 1 14 and © as defined above for formula (I) preferably Jaa © from the set consisting of -0» -CRy- ¢-NR- and -58-; 7 represents either © or ¢S 7 choose .ve from the group consisting of -H “PR; ¢-SiR; ¢-SR ¢-CR; NR, ¢-OR and aryl groups with or without a substituent, provided that when Q represents -1088 then JEEZ is from the group consisting of SiR; -SR ¢-NR; ¢-OR B-77 and 17; JES ZR is from the group containing carbon-silicon carbon esilicon nitrogen cnitrogen oxygen coxygen and/or phosphorous “preferably R” represents a hydrocarbon group containing from 1 Yo to Ye carbon atom carbon and the best is de gana alkyl calkyl A cycloalkyl or Y14¢

Ya

or?; 7 represents group 1 to 4; Preferably 1 integer ranging from fae Bian tanyl aryl representing a divalent anion group when “X equals a monovalent anion when “or” or non-alyl moiety “carboxylate” carbamate “carbamate” X preferably representing 1; 2.a and “Q” is described by a homogeneous AT heteroallyl synthesis and in one embodiment the copolymer binder is weakly mixed with the material preferably in 1:1 ratios To 1:01 the copolymer binds well with molar ratios ranging from Ve and in another embodiment Ve and better 0 , and better yet VV preferably _ to 0 moles of Weak copolymer is present with a higher molar ratio 01 metallocene polymerization catalyst FIN metallocene polymerization usually activates compounds that incorporate the co-monomer well and those that incorporate the co-monomer poorly; JIA mentioned above; in various ways to produce compounds that have a coordinate site and for the purposes of the current patent specification and elements .olefin(s) polymerize olefin(s) of Ll activated "as any compound that can activate sald" ancillary protection; The term Vo defines the aforementioned catalyst compounds by converting the neutral catalyst compound into a catalytically effective catalytic compound cation “alumoxanes UL go olf catalytically. Stimulants include; For example, but not limited to, 107121708 activators and ionizing activators may be caluminum alkyls or ionic alkyls. A According to one embodiment; Alumoxanes are used as activators in the catalyst synthesis (Gy) of the invention. And alumoxanes are generally oligomeric compounds (i.e. short chain) containing subunits of -16-0” where R represents an allyl group Examples of alumoxanes include ¢methylalumoxane (MAO) modified methylalumoxane (MMAO) Yo ethylalumoxane and isobutyl

1 hydrolysis by hydrolysis of alumoxanes and may produce isobutylalumoxane. Triisobutylaluminum compounds, such as triisobutylaluminum, may be produced by trialkylaluminum.

oo is soluble in aliphatic solvents and more stable during storage. It includes alkylaluminum or organoalumnium compounds that can be used as materials ok Aa Sie methylaluminum ctrimethylaluminum triethylaluminum triisobutylaluminum triisobutylaluminum tri-p--hexylaluminum tri- n-hexylaluminum (where p denotes (gale Ve) tri-n-octylaluminum and the like. Also within the scope of this invention is the use of an ionizing doping substance or a controlled doping substance “stoichiometric activator, whether neutral or ionic, such as tetrafluoroethyl boron (n-butyl) ammonium tetrakis (pentafluorophenyl) boron 01 metalloid precursor Vo from triperfluorophenylboron trisperfluorophenyl boron or a metal-like source of ctrisperfluoronapthyl boron polyhalogenated heteroborane anions (see International Patent Application No. AA/EYAAY) boric acid (see US patent) 4) or a combination thereof. It is within the scope of this invention Lad the use of © > neutral or ionic activators alone or in combination with alumoxane activators or Jara alumoxane hus se sl + examples of neutral controlled activators include boron tellurium compounds ctellurium, aluminum, caluminum, gallium, and indium, three substituents, or mixtures of Jee, and the three substituent groups are selected separately from the alkyl groups 11915H.” Alkenyl groups Yo calkenyls <halogene Alkyl groups bearing “Ja” aryl groups caryls v. and halides 65 . It is preferable to choose alkoxy carylhalides Ji} single groups or aryl groups aryl chalogene the three groups separately from the halogen aryl groups (polycyclic halogene (including Those that carry a halogen substitute and terminating mixtures and prefer alkenyl groups and alkyl compounds [cary] to 1 alkyl groups have from alkyl alkyl Cle gana carbon carbon atom 71 to 1 Having from alkenyl alkynyl 0 carbon Ye to 1 carbon alkoxy groups Ye carbon (including aryl groups carbon 01 and aryl groups 1 e contains from “7 to alkyl substituents). From 12108602160 aryl of that; that the three groups are halogenated aryl groups 01 and the most preferred; that the activated substance be fluorinated aryl and preferably fluorinated aryl groups oh or trisperfluoropheny! trisperfluoronapthyl boron active pyrofluoronapthyl boron; or proton compounds of the ionic disciplined activator may contain a proton weakly with the ion GRE conjugated; but not symmetrically associated with; or attached to the AT cation of the remaining vo of the ionizing compound. Such and similar compounds are described in patent publications

TEE Av £90 75 European Patent Nos. 487 Lah Right 27 .7m RH and US Patent Nos. >. YVY .H and YVY Burn A O04. 7/6759 Sada Aghath oY VAY / Shhhhhhh “©YAAE ¢YoeYioy and 2©07174; They are all incorporated into this statement in full for reference. vy. In a preferred embodiment; Controlled stimulants include a cationic and anionic component; it may be represented by the following formula: (x) (L-H)s" Lewis base, where 1 represents the Lewis base thydrogen H Yo

(L-H)* ‘Bronsted acid’ m represents a non-symmetrically bonded Gayl with charge fd and d represents an integer ranging from 1 to ? The cationic component may include; (LH), Jie Bronsted acids df protons ° protonated Lewis bases or ALG reducible Lewis acids capable of providing protons or removing 33″ such as an alkyl alkyl or aryl 1<; From a metallocene bulk ligand or transition metal catalyst containing a group 10 element resulting in the production of cationic transition metal molecules. The activated cation (L-H)g" may be a Bronsted acid capable of donating a proton to the transition metal catalyst source (Lape) to a transition metal cation that includes ammoniums, coxoniums, and phosphonium compounds 5M10 Psyllium 5 compounds and mixtures of terminators, preferably ammoniums of methylamine, aniline, caniline, dimethylamine, diethylamine, 77-methyl N-methylaniline (pti-diphenylamine) diphenylamine Vo trimethylamine triethylamine 1137-dimethylaniline ¢N,N-dimethylaniline methyldiphenylamine cmethyldiphenylamine pyridine para-bromo-11:27 -as dimethylaniline ¢p-bromo N,N-dimethylaniline para- (SE NN= 5 5 methyl CL ja cp-nitro-N,N-dimethylaniline (stil phosphoniums) from diethylphosphine ctriethylphosphine AUS, ctriphenylphosphine Y. diphenylphosphine oxoniums of Jia ethers dimethyl ether and diethyl ether tetrahydrofuran And dioxane “dioxane” sulfur moieties 5 of CY yu of cthioethers such as diethyl thioethers and tetrahydrothiophene and mixtures thereof. The activated cation (LH) may also be a mere vo radical such as silver asilver carboniums < carboniums tropylium compounds

YY

And their mixtures, preferably ferroceniums, ccarbeniums (LH) Stay, and ferrocenium 2700©0(5). The most preferred is that carboniums -tripheny] carbonium, which includes the anionic component A is that component of the form *[,14“0] where k is an integer fae m from 1 to ?; le is an integer from ? to 1 nk -l; 14 Represents an element chosen from group VY of the periodic table of the distribution of elements; preferably boron or aluminum and © independently represents a dialkylamido (dialkylamido) hydride bridge or non (Sun chalide) The alkoxide aryloxide chydrocarbyl hydrocarbyl carries “Say” halocarbyl <halocarbyl 1. halocarbyl carries Sa” and hydrocarbyl radicals carry a substituent of chalogene So that the aforementioned Q contains not more than Ye a carbon atom, provided that the existence of 9 does not occur more than once in the form of a halide p81:1.It is preferable that every 0 represents a hydrocarbyl group fluorinated by it from 1 to Yo a carbon atom and preferably each Q represents a fluorinated aryl group; preferably de sane Q US represents pentafluoryl aryl Vo. *m Suitable examples also include diborons as described in US Patent No. 417/885©; which are fully incorporated into this statement for reference. In one embodiment; The controlled ionic activator (*4) (LH) is GEN ON N,N-dimethylanilinium tetra (perfluorophenyl)borate Y. OR tetra(perfluorophenyl)borate GEN ON carbenium -triphenylcarbenium tetra(perfluorophenyl)borate and in one embodiment; Lia uses an activation method using ionic compounds that lack a JZ ab proton but are capable of producing a metallocene catalytic cation containing a large ligand and its asymmetric anion; and are described in EP No. ry 2777818 and No. 6 09/7 M. and US Patent No. 7 £YT H0 are all incorporated herein for reference. Carrying method Metallocene polymerization catalyst compounds can be mixed the comonomer well and the comonomer incorporating poorly; The above-mentioned; with one or more carriers or carriers using one of the carrying methods well known in the art or as described below. and in the Jia precipitate of the invention a polymerization catalyst in a mobile form; Gy is a preferred embodiment; The method is used in contact with or incorporated into; adsorbed or absorbed into or on a carrier or substance; Carrier is interchangeably related to “carrier” or “support” and the two terms “carrier material” are used 01 Tall 1816 oxides “Nia 00:05 support” and represent any carrier, preferably a porous carrier. Other carrier materials include inorganic chlorides and inorganic oxides carrier materials (polystyrene polystyrene (Fie resinous support materials) resinous carriers with added functional or cross-linked groups such as organic support materials organic vinylbenzenes ALD or polymeric compounds of polystyrene polyolefins polyolefins Vo or any carrier clays clays zeolites zeolites «polystyrene divinyl benzene other organic or inorganic And the like; or mixtures thereof. Inorganic, including those oxides, and the preferred carriers are oxides, and the preferred carriers include silica VE or VY 0 of oF oY the metallic elements of the groups “magnesium chloride Magnesium chloride silica-alumina Lise olf silica Y. titania cmagnesia and mixtures thereof. Other useful carriers include magnesia (see European Patent No. montmorillonite ¢zirconia zirconia 81); Zeolitic materials 65: ; and the like. Combinations of + 5 011 silica-alumina, csilica-chromium, silica-chromium, Sle, and the like may also be used. silica-titania vo

Yt

It is preferable that the carrier material be; which is highly preferred to represent an oxide

inorganic oxide surface area in the range from about 01 to about

m aaa of pore volume in the range from about 1.1 to about Ee cm/gm; and aaa average particle size in the range from about * to about

0 00 µm. Better yet; The surface area of the carrier is in the range from about 00 to about pf Tn 00, pore size from about 1.9 to about 700 wef on and average particle size from about 01 to about Yoo μm. Most preferably, the surface area of the carrier is in the range from about 0 to 5060 Ja m'/g; pore size of about 0.8 to about 7.0 cm'/g and an average particle size of about © to

ale of the invention has an average pore size of ado (µm). The carrier has a 0 of about 0 000 angstroms; to about 0 Angstrom (A) 0001 angstroms to 1 0 Who

The best is from Ve to about 0 70 angstroms.

Procedures for measuring the total pore volume of a porous carrier, Tas, are defined in the technique.

One such procedure is detailed in the reference Experimental Methods in Catalytic

volume 7 (Academic Press, 1968) (pages 67-96) Vo.72520727. This preferred procedure involves the use of a conventional BET (Brunauer-Emmett-Teller) nitrogen adsorption apparatus. Another well-known method is described in the Lod technique reported by Innes.

Total Porosity and Particle Density of Fluid Catalysts By Liquid Titration, Vol. 28, in ref

-No. 3, Analytical Chemistry 332-334 (March 1956)

7 and when the mixed catalyst systems Gy of the invention are loaded with laa on the same support using conventional deposition methods; such as activation in toluene contact with the carrier; solvent removal; A catalyst reaction may occur. for example. It often enhances the yield of the binder for the weaker copolymer relative to the better binder; This results in a narrower bimodal distribution of the composition such that the polymer properties are not LB or ve enhanced ALB for polymers produced by single catalyst components alone. and to enhance the ro of the polymer properties by means of the catalyst system according to the invention; The composition distribution is measured and the catalyst system is adjusted to obtain bimodal distributions significantly so that the densities of the largest groups with g/cm' differ and each group includes 01070 not less than Ley high density and low density Ley at least 5 from the installation. Therefore, it is important to choose the two components of the catalyst or a group of its components (Lala separate oF m) whose response curves to the copolymer, as shown in the figure, and activate them; carry them and transfer them to the polymerization process in a way that ensures obtaining the bimodal distribution

Yo desired. The representative data and curves used in Figure 7 and in the two tables show that ethylene is in the process of polymerization of ethylene 1, respectively. Notes from the table

Ya tee combined (indenyl IndCua) (MesCp)IndZrCl, gas phase; It appears as indenyl Ind, and 0048:5:00(2:01) shows the middle (where bam is the covalent monomer and racemic activity 3. O(Me;SiInd),ZrCl, and chun shows weak incorporation (MesCp),21Cl, and the ratio of polymeric groups can be adjusted by means of (MesCp),21Cl. Composition analysis and quantification

Al The relative load of a component. The total molar ratio of aluminum 1 to zirconium:7 can be increased to adjust the polymeric group ratio. The molar ratio may be increased in the process to increase the difference in density of the two ethylene groups of the copolymer to the ethylene copolymer or copolymer groups. For Alda and in a more favorable embodiment; The used polymerization catalysts are placed on a material such as pentane hydrocarbon by quenching a previously carried activator in oil; hydrocarbon © solvent or non-solvent medium; Then add the catalyst in solid form with stirring. It is preferable, 'pentane solubility, that the catalysts be finely fractionated solids. Although the catalysts usually have solubility in the dilution medium, it was found that they are distributed over the support material and are effective for polymerization. P «Aah» M. The diluted substance can be removed by filtration, where (Drakol or Drakol Kaydo veo i) The remaining solid material shows a higher polymerization potential than expected if the catalyst was prepared by toluene methods in toluene methylalumoxane contacting the catalyst with methyl Conventional Jue aluminoxane is contacted with the carrier, then the solvent is removed.If the diluent is volatile as pentane to obtain nitrogen it may be removed in vacuo or by means of a nitrogen clean-up stream (pentane) then one or more catalysts may be applied The Glia contains an active catalyst If more than 0 of the carrier is used at the same time the activator is added and the other compounds are later added in the diluent to the previously formed portable activator If more than one catalyst is added To the pre-formed portable activator in a diluent, it may be added once or sequentially. It is preferable that the mixing time be more than four hours; But prefer short times. This preferred method of loading mentioned above is advantageous when more than one catalyst is used on the carrier as the interactions between two or more molecules of the catalyst are reduced. Therefore; While it is noted that the reactions of a conventionally carried catalyst lead to a higher yield by one of the catalysts relative to the other or a lower difference in the density of the polymer groups produced by two catalysts for the co-monomer; The catalyst produced by using a loaded activator, Tan, with two different incorporation ratios, Ne, previously in a diluent, reduces the deviations of the expected behavior of the catalyst. In addition; The workability of the gas-phase polymerization process is improved. which incorporates metallocene and in one embodiment; Both the metallocene catalyst compound that copolymer is weakly deposited and the catalyst complex that incorporates the comoner well on the same or different carriers with an activator; OR YOU MAY USE THE ACTIVITY MATERIAL IN © OFFLINE FRAMEWORK; or it may be deposited on a carrier different from the metallocene catalyst compounds of the invention; or any combination thereof. The gram-molecular ratio of the metal or metal-like metallocene in the activator component ranges from preferably 1:0001 to 0:0. The metallocene carrier in catalyst compounds ve

di-activators such as those based on the tetrakis(pentafluorophenyl) boron anion. The gram-molecular ratio of the metal or metal-like in the dopant component to the metal component of the metallocene catalyst ranges from 0:0, to AY and in one embodiment; The catalyst system is used in an unmounted form; Preferably in 0 in liquid form as described ie in US Patents Nos. 511767376 and ©4777 and European Patent Publication No. (A= OAT AY) are all incorporated herein for reference. The polymerization catalyst may be fed in liquid form to Reactor as described in PCT Gy International Patent Publication No. 4 which is fully incorporated into this release for reference.

01 and when a non-portable metallocene catalyst system is used; The gram-molecular ratio of the metal or metalloid in the component of the activator to the metal in the metallocene catalyst compound ranges from 0:0 to 00000:1, preferably from 0:001 to 0:2... The most preferred from 0:500 to Aree is the polymerization process

The if of the invention described above for use in Gyvo catalysts and catalyst systems are suitable for polymerization over a wide range of temperatures and pressures. Temperatures may range from, preferably, from 00 C to about 107 C. In one embodiment, a 7860 to about aes m. As the polymerization process takes place at a temperature higher than 11 °C and preferably higher than atmospheric pressure or higher. ©5000 The pressures used range from one atmospheric pressure to about

a Polymerization processes include a process in solution; gaseous phase slurry phase and high pressure, or a combination thereof. A particularly preferred process is a gas-phase or slurry-phase polymerization of one or more Cus olefins, at least one of which is ethylene.

In one embodiment; The Way process of the present invention directs towards a polymerization process conducted in vo solution; lee polymerization under high pressure; A polymerization process that takes place in slurry or gas phase Y14¢

p of one or more olefin monomers with whom? to a 2+ carbon atom and preferably 1 to 11 carbon atoms; and better than? to + nny atbon atoms The invention Lila is particularly suitable for the polymerization of two or more olefin monomers “ethylene: propylene cbutene-1 nitweb-1 propylene 1-pentene aad —J fut 1-pentesene octene-1 OES 1 chexene-1 nicch-1 “4-methyl-pentene-1° and 1-decene .decene-1 Other monomers useful to the process of the invention include unsaturated ethylene monomers 0035 cethylenically unsaturated diolefins of ; to 8 ccarbon dienes, both conjugative and non-conjugative dienes; Polyene compounds, cpolyenes, monomers, vinyl Js, and cyclic olefins. abd includes, but is not limited to, monomers useful in the invention1 norbornene cnorbornadiene isobutylene isoprene vinylbenzocyclobutane vinylbenzocyclobutane styrene 65 compounds Su bears from Ji the “alkyl ethylidene norbornene” dicyclopentadiene and two cyclopentene ve. In the most spall embodiment of the process of the invention; It produces a copolymer of ethylene, where a copolymer containing at least one alpha-olefin has ; to 0 carbon atoms, preferably from ; to 1 atom carbon 0m and most preferably of ; To * carbon atoms, ton of ethylene tyne, a process that takes place in the gas phase. Ye In another embodiment of the invention process; Polymerizes ethylene or propylene with at least two different co-monomers; One of them may optionally be a diene to form a terpolymer. In one of the embodiments; The invention is directed towards a polymerization process”” and in particular a process conducted in a gas phase or a slurry phase; For the polymerization of propylene 6 alone or with another monomer aly 3 = © or more including ethylene and/or other olefins having from ; to ? 1 carbon atom is 1" 64

Ya using catalysts of type polypropylene and special bridging polypropylene-carbon polymers can be produced that contain a bulky ligand as described in the two American Patents Metallocene Metallocene No. 16474 and No. 071874 incorporated in this statement for reference. For reference:

Sales ° uses a continuous cycle in a gaseous phase polymerization process as it is in one of the stages of the ass Jeli system cycle) a cycling gas stream known as a recycle stream or a dilute medium; in the reactor by the heat generated from the polymerization process. This heat is removed from the recycled composition at another stage of the cycle via a cooling system located outside the reactor. And the stream returned

0 gaseous containing one or more monomers in continuous form; In a gaseous fluidized bed process 5 used to produce (i yal gy) through the fluidized bed in the presence of a catalyst exposed to ANTE conditions and the gaseous stream is withdrawn from the fluidized bed and recycled back to the reactor 0 and at the same time; A polymeric product was withdrawn from the reactor and monomer 2 was added

New to replace the polymerized monomer (see eg US Patent Nos. 4M Lamy “etc. HOW TO UPGRADE KMV BGOM MEQ RIARAEE Pf 0617444 STATA oN All of which are fully incorporated into this statement for reference. Reactor pressure may vary in process Conducted in a gas phase from about 0 kPa (Vor) to about 24448 kPa (0 lb/in); preferably in the range from about 4 kPa

(psi” standard); 0 (psi” standard) to approximately 19754 kPa (001)

The best is in the range from about 4 kPa (img Jay YOu Standard) to about

_ lbs/in” standard). TO (08.08 kilopascals).

Y14¢

The temperature of the reactor in a gas phase process may vary from about SY to about 101°C preferably from about He to about 70°C and the best in the range from -about 6°C to 10011°C; and most favorably in the range from about 1 lam to about 109 m. Other gaseous phase processes Gig uses for this invention process include 0 processes described in US patents and European patent publications numbers 0 for both ATS AX AX and X.Y rights. 8-774 are all fully incorporated into this statement for reference. In a preferred embodiment; The reactor used in the present invention and process (as of the invention) are capable of producing in excess of YYV kg of polymer per hour (0 00 lb/hr) to about 0 00 kg/hr (lbhr) or JS   Production over £00 kg/hr (0 lb/hr) is preferred; And the best is more than 98 kg/hr (Yours lb/hr); Even better, over 11,701 kg/hr (90 lb/hr); The best is also more than 09,500 kg/hr (Yoru) (lb/hr); Even better Lad over 17700 kg/h (1 1 90 lb/h) and most preferably over Lad +790060 kgh (1900 lb/hr) to over 4050660 kg/h 0....1 (lbs an hour). The slurry polymerization process usually uses Ua gaia ranging in the range from about 1 to about ©0 atmospheric pressure and even higher and temperatures in the range from zero to about 11 C 0 and in Ades slurry polymerization. JS A suspension of Ye solid particulate polymer in a polymerization medium containing a liquid diluent to which ethylene-6 and hydrogen co-monomers Lies with 0 lis are added and the suspension containing the diluted salad is intermittently or continuously removed from the reactor where Jami volatile components are removed from the polymer and optional after distillation are recycled back to the reactor. Usually, the liquid diluent used in the polymerization medium is an alkane of ? to - NY Ye at carbon, preferably a branched alkane, and the medium should be

1 It is propane under polymerization conditions and is relatively inert. When using UL propane medium used critical temperature the process should be run at a temperature higher than the critical temperature of the reaction diluent. Critical pressure and induces a pressure higher than the critical pressure of isobutane or isobutane hexane is preferable to use a medium of hexane to invent polymerization in the form of particles; or Gy process The temperature at a value lower than the temperature at which the polymer turns slurry hia tn is indicated in the technology; It is described, for example, in a patent, whereby Tan is then reduced to a solution. This process, which is fully incorporated into this statement for reference, is known as FY EA VY US Invention No. EA and those utilizing a loop reactor Sle lia Other slurry processes include those using or combinations thereof. Including ¢ J sie oJ sia in the form of stirred reactors 4x" 160 sets of 1 reactor or stirred tank. Gala Examples of slurry processes without specifying continuous processes using a reservoir Other examples of slurry processes in the patent Lad and described which are fully incorporated into this release for reference: 464 embodiments; the reactor used in the slurry process according to the invention and process i lbs); 0 (the invention; can produce more than 107 kg of polymer per hour - lb/hr); most preferably over 0 (and preferably over 1768 kg/hr lb/hr). In another embodiment the slurry reactor used yields 0) kg/hr 0 of the invention in excess of 18604 kg of polymer per hour Gay in process (lbs/hr) to You (lbs/hr); preferably over 150000 kg/hr (lbs/hr). 0 ) approximately 5 kgh x . Examples of processes carried out in solution are described in US Patents Nos. M2.17.M.07711414 and 0/40 00 which are fully incorporated into this statement 4776 for reference. A preferred process according to the invention is a process; preferably a process carried out in a metallocene ligand-containing rod phase in the presence of a Jak or a gaseous Yo metallocene catalyst system.

£yY or without them as scavengers of the invention and in the absence of any bulky ly strimethylaluminum ctriethylaluminum basic; Such as tri-ethyl aluminum, tri-isobutylaluminum, diethyl aluminum chloride, tri-n-hexylaluminum chloride, and the like. This preferred process is described in Dibutyl Zine Zinc 0 and Patent Application Bulletin 976/085710 of the Patent Cooperation Treaty (PCT) Gay International Patents Americas No. 5717787 and 50717547; all of which are fully incorporated into this release for reference. According to the invention polymer product of the invention; The Gy weak copolymer binder is chosen to produce the polymers: 0 and the good copolymer binder so that the two catalysts produce two polymer groups of at least 71/7 composition weight having two different densities and each forming about the polymer. The two catalysts should also be chosen so that they have graphically different co-monomer responses to the co-monomer response curves for Lay catalysts. The figure shows? which represents many Lila in a gaseous phase process; For example, the catalysts (MesCp)PrCpZICl, and MesSi(Helnd),ZeCl, | au 5~O(Me;Silnd),ZrCly 3 (Cp)IndZeCl, (Cp)IndZrCl, necessary separation of polymer group densities; While the catalysts do not provide that. (Me,Cp),ZrCl, and (CpYIdZiCl, of 0401 P2M). The resulting polymers in the process according to the invention can be used in a wide variety of linear, low-density polyethylene. End products and uses include polyethylene 7 polyethylene cplastomers elastomers elastomers low-density rubber polymers; high-density polyethylenes; polyethylenes polypropylene and copolymers of polypropylene propylene Density ranges in Bale ethylene and for polymers; ethylene-based polymers have diploids "to MA g/cm"; preferably in the range from 1.47 g/cm" to AT range from ve ty g/cm' to +21 g/cm'; better than 1,900 g/cm'; best in the range of 1,400 in the range of Lad g/cm'; better than 0.95 AT approx.

° The melt strength of the polymers produced using the Ly catalyst of the invention is greater than ccentiNewton (cN), preferably greater than 7 centinewton, and most preferably A centinewton or greater. For the purposes of this patent application and the appended claims, magma resistance is measured using a capillary rheometer of the type Instron in conjunction with a magma resistor of the type Goettfert Rheotens.

01 polymer melt strand formed by extrusion from the capillary die between

Two counter-rotating wheels in the machine. The take-up speed increases with a constant acceleration of “Laake YE”; set via the Acceleration Programmer (model £09) at a set value of Sobol “4, (VY) maximum pulling force (in two centnewtons) which is achieved before the strand breaks or before 01 begins to show the draw-resonance as the resistance of the magma. The rheometer temperature is set at 8191 C. The capillary mold has a length of 7.04 cm (1 inch). ) and a diameter of 118 cm (0.00 in.) The polymer melt is formed by extruding from the mold at a speed of 7.67 cm/min (in. per minute). The distance between the outlet of the mold and the contact point of the wheel should be 100 mm (7.48 in.) . Ye and the polymers produced by the process according to the invention usually have a weight distribution of 'eux' with a ratio of mean molecular weight to numerical mean molecular weight (MyM) in excess of to about lo and in particular in excess of JY about 10 the best is a ratio of more than about v0 to less than about A and the most preferred is a ratio of * to A and in one of the preferred embodiments; The Ga polymers of the present invention have a ratio of .14/14 vo greater than or equal to oF and a ratio greater than “. And,14 represents the average molecular weight. and at Y14¢

A preferred embodiment “AT.” The polymers Gy of the invention have a MyM ratio greater than or equal to Too to about 4. In another preferred embodiment the ratio MUM, in the range greater than JY is less than 4. The polymers according to the invention, Bale, have a narrow compositional distribution as measured by the Composition Distribution Breadth Index (CDBD). Other details are known about determining the CDBI value of a copolymer for those skilled in the technique. Se hil International Patent Application pursuant to PCT No. 070473/37 dated February 18, 1971, which is fully incorporated into this release for reference.In one embodiment, the Gig polymers of the invention generally have CDBI values In the range Los 0 more than 700 to ©0010 £49 is preferred Preferably in the range 700 to 7485 The best is from 710 to 80 and better than that Values over 770 and better than that Values of more than Ae and in embodiment Others the polymers have a value of 00181 Ji of 0 75, preferably less than 6 and most preferably less than JY dg one embodiment; the polymers of the present invention have a Vo melt index MID) or (L ) as measured by the American Society for Testing Materials (ASTM) D-1238-E in the range of 201 dg/min to 0,001 dg/min; the best is from about 0.101 dg/min to about 001 dg/min; even better, from about 110 dg/min to about 50 dg/min; and most preferably from about -0.1 dg/min to about -01 dg/min. and in embodiment; The polymers according to the invention have a melt index ratio (L/L) (measured as Gy I, according to the ASTM-1238-F method) ranging from Fe to less than 100 and better than about © to less than Or and more preferably from 50 to 16. In a preferred embodiment, the Thy polymers of the invention have a melt index ratio of (1/121) vo (measured as Gyn, according to the ASTM method). -D-1238F Preferably go 5 Better than 0 Better than Ye Better than 0 Better than 0 Better than Lad that of the invention and/or is co-extruded with any Gy polymer and the polymers may be blended with other linear polyethylenes Unspecified examples of other polymers include conventional polyethylene and/or conventional catalyst from Ziegler-Natta Low-density produced by Ziegler-Natta catalyst© polyethylene rubber polymers; ductile polymers; high-density cmetallocene; high-pressure low-density polyethylenes; high-pressure low-density polyethylenes; polyethylene and the like. The invention and combinations thereof are useful in Gy and the polymers produced by the process and extrusion are considered by extrusion fibers and fibers csheets sheets films forming processes such as forming Ve films injection molding blow molding in addition to molding co-extrusion and co-extrusion films include blow molding and rotary molding and injection molding for use as lamination, co-extrusion or sealing 5081”; and sealing films Stretch films Cling films Adhesive films Shrink films Durable bags Snack packaging Wrappers for snacks Cured films Oriented films Vo backed and packaging for baked and frozen foods Grocery sacks groceries <heavy duty bags industrial liners; industrial liners 1 packaging medical packaging “frozen food packaging etc.; In contact and non-contact applications with food. The manufacture of cmembranes and membrane materials includes “solution spinning”, “emelt spinning”, “fibers”, “magma spinning processes”, “filters”, “magma” for use in woven and non-woven form, for the manufacture of vy filters. Geotextiles, cmedical garments, “diaper fabrics for baby diapers”, medical tubing, etc. Extruded materials include medical tubes, geotextiles and geomembranes, geomembrane materials, wire and cable coatings, wires and cables. Molded materials include single- and multi-layer structures in the form of pond liners.

chottles; or large hollow articles, rigid food containers, ctoys, etc.

The following examples are provided for a better understanding of the present invention and its representative advantages.

a1 ay for ASTM method ty and,:1 1, (FI) and flow index (MI) magma index measured °

For materials testing (ASTM D-1238 Case 8 and © respectively. The melt index ratio (MIR) is a ratio of O over Ll, and the density was measured according to the ASTM D1505 3 gall method. ‏

The Compositional Distribution Breadth Index (CDBI) is defined as the weight ratio of the polymer molecules

0 cofactors that have a co-monomer content within +10 of the average total molar co-moner content. The CDBI for linear polyethylene reports; It does not contain a co-monomer + “7) and the 0081 is calculated from data obtained from either temperature metamorphism fractionation (TREF) or crystallization analysis fractionation (CRYSTAF) as known in the technique.

m and for the purposes stated in this statement; Cp denotes cyclopentadienyl ligand 01000180101, CpMe; denotes Jatin J Ae cyclic pentamethylcyclopentadienyl ligand “pentamethylcyclopentadienyl ligand, Ind denotes indenyl ligand 001, n-BuLi denotes -n-buty! lithium a gd 8g c

Standard Schlenk air-sensitive techniques were used to synthesize the compounds

Y. metallocene »1612110 Activation and its carriers and for the treatment of portable catalysts. Dry airless solvents such as those sold commercially from the Aldrich Company were used, provided that the ethereal solvents were free of the inhibitor.

The compound was purchased (0 Vg SET 1; - Tetramethyldisiloxane

<Aldrich of The Aldrich Company (CIMe;SiOSiMe,Cl) 1,3-dichloro-1,1,3,3-tetramethyl disiloxane of Tollytown; State (Gelest City of Milwaukee; State of Wisconsin) or from Gelest Corporation vo

Pennsylvania. (CpMes), ZICl, was purchased from Stream Chemicals of Newburyport; Massachusetts. CPZICl was purchased from the Aldrich Company and A, 200:2:0 was purchased; Dimethylsilene of ( SB 5 6 1-tetrahydroindenyl) O2:0 “dimethylsilylene bis(4,5,6,7 tetrahydroindenyl)ZrC1, di)1-methyl”-p_+-e-butyl (1-methyl, 3-n-butylcyclpentadienyl)ZrC1, ZrCl, LD cdimethylsilylene bis(indenyl) ZrCl, ZrCl, di(7-methyl) indenyl) dimethylsilylene bis (2-methyl indenyl) ZrCl, ZrCl, and ethylenebisindenylzirconium dichloride from Albemarle Corp. of Baton Rouge, Louisiana. The compound methylalumoxane 01 was purchased present at a concentration of Bos ZY in toluene from Albemarle Company and cooled when not in use.(CpMes)IdZrCl was prepared by reacting (CpMes)ZrCly with indenyllithium in toluene, then Filtration; washing and recrystallization in a mixture of cold methylene chloride/pentane as known in the art.(Cp)INdZrCl, prepared according to the method described in International Patent Application No. 60 48/1878. Example 1: A conventional carrying technique prepared carrying catalysts by contacting metallocenes or metallocenes in toluene with methylalumoxane of concentration Boy 0 Y. in toluene (supplied by Albemarle Albemarle Baton Rouge, Louisiana) for at least 10 minutes; Then by adding silica with good mixing and removing the solvent in vacuum or in the presence of a nitrogen purge stream (0p01008). The total amount of SiS solvent was that the volume of liquids should be equal to a value ranging from about 11 to about * times the pore size Carrier The portable catalysts were traditionally prepared so that the catalyst is portable

£A

Al by weight of the final 70 Y that was quenched in the diluent. Loading ratios amounted to about

AVA and a gram-molecular ratio of 1H/:7 amounted to about Zr of Uj / 0.75 and fy Example Ql Preparation of a catalyst system No.

VV at a gram molecular ratio of (MesCp)PrCpZiCl, load 100(:2:01b, 115:01) and 1° using the technique described in Example B.

Ql polymerization process using catalyst No. operating shall use catalyst system No. 01 in a gas fluidized bed reactor (inch); diameter VA) 8.1 cm outer diameter Te continuous incorporating shaft type <00 inner 1.4 cm (11.0 in). fluidized bed formed; The ethylene hydrogen present in each reactor of this type; of polymer granules. Gaseous feed streams of ethylene and a mixing tee arrangement of a liquid co-monomer in a t-thread arrangement of aa hydrogen Niske-1 introduced the mixture from a point below the reactor bed to the recycled gas line. Cethylene was used as the co-monomer. The independent flow rates of ethylene 1-hexene Vo and the co-monomer were adjusted to maintain the target stable compositions. And adjust the hydrogen to maintain a constant partial pressure of ethylene ©0:160. Adjust the ethylene concentration to hydrogen to maintain a constant gram-molecular ratio of hydrogen hydrogen on-line and measure the concentration of all gases by continuous gas chromatography and with ethylene to ensure a relatively stable composition in The gaseous stream is recycled. and inject metallocene Y chromatograph purified mobile solid nitrogen directly into the fluidized bed using metallocene nitrogen (lb/hr). The reactant bed of 0 (0 0 kg/h) TA at a rate of growing polymer particles was maintained in a fluidized state by the continuous flow of superficial gas and recycled gas through the reaction zone. Apparent gas velocity is used to ? ft/sec) to achieve 1) 91.4 cm/sec to 01.9 cm/sec that ranged from Yo velocity

Y14¢

£4 for this purpose. The reactor was operated at a total pressure of 4 kPa (Fe (lbs/in' standard); At a temperature of 5°C in the reactor, de ju used the apparent gas of TAT cm/sec (0,70.7 ft/sec) to liquefy the granules. To maintain a constant temperature in the reactor, the temperature of the recycled gas was continuously set to a higher or lower temperature to accommodate any changes in the rate of heat generation from the polymerization process. The fluidized bed was maintained at a constant height by withdrawing part of the bed at a rate equal to the rate of formation of the particulate product. The product was removed semi-continuously by means of a series of valves in a constant-sized chamber; Breathe in at the same time to recycle back into the reactor. This allowed for fairly efficient product removal; With a large portion of the unreacted gases being recycled back into the reactor at the same time. This product was cleaned to remove suspended hydrocarbons and treated with a stream containing a small amount of wet nitrogen to inactivate any trace amounts of residual catalyst. Example “A polymer should be produced using a catalyst number Ql vo A polymer with a density of ANY, + g/cm” and a melt index (MI) of “©, showed a well-separated bimodal compositional distribution ( See Fig. “) with the same Ay shal by weight (7 by weight) of each polymer component. Although the individual catalyst components showed similar efficiency to produce a product with a density of 1,914 g/cm” and a melting index (MI) of a value of 1; however, this experiment showed a strong increase in the yield of the weak cementing material (MesCp)PrCpziCl, | 0 relative to the good cementing material -Me;Si(HaInd), ZrCl, example iv Prepare a system Catalyst No. Q2 used the catalyst system described in Example A? except that the molecular ratio of:(115:03,0(:2:0) to (MesCp)PrCpzeCl, was 0:4. In addition ve prepared four different molecular ratios of Zr/Al amounting to 1:57 1:178-VIVIAN and 11080

Example “B Polymerization Process Using Catalyst No. 02 The polymerization processes were carried out in an autoclave reactor of 1 liter stainless steel type Zipperclave ©2100©00187. The reactor was provided with a water jacket © For heating and cooling Injections were typically carried out through a diaphragm inlet or by injection of high pressure nitrogen Before polymerization the reactor was cleaned with nitrogen for several hours at 100 C After catalyst injection fed ethylene Continuously as required while maintaining the reactor pressure, Bl, and the reaction temperature at 1 °C. The reaction was stopped by cooling, depressurizing, and exposing the reactor contents (Yemah-Neske-1) to air. The liquid components were evaporated and the poly(ethylene--0) was dried. -vacuum oven Poly(ethylene co-hexene-1) example:

Q2 Production of a polymer using a catalyst No. showing TREF analysis of polymers; See Figures A-4D; that as the vo increases the molecular ratio is 1e/:2; The contribution of the copolymer binder also increases well. Accordingly; Although the catalysts (i.e., transition metal compounds) that exhibited different co-monomer incorporation features were present at the same molar ratio in all four experiments; However, their relative contributions to the total mass of the resulting polymer became more or less equal with the increase in the molecular ratio [8:2. unwilling to adhere to any particular theory; One possible explanation for these phenomena is that compounds of transition metal catalysts have different equilibrium constants for activation. With this discovery; It adjusts for the relative contributions to the total resulting polymer AES; The catalyst compounds can be carried separately and fed into the polymerization reactor separately or fed as mixtures from separately carried systems.

The example is ¢ catalyst deposition in an oil bearing technique; Or a hydrocarbon or a non-solvent substance prepared as portable catalysts using the dipping method, that is, portable catalyst systems were prepared by contacting (mixing) transition metal compounds in the form of a dry powder with methylalumoxane, previously carried, slurred in a diluent so that it became The final portable catalyst system had a payload of about Lg NY of 1H, 7785 by weight of Zr, and a molecular weight of ZrfAl of about 1:114. The compound was prepared by preloading methylalumoxane using MAO with a concentration of 771 by weight in toluene (supplied by Albemarle and Davison 48 4 400 silica). Contacting methylalumoxane with silica slurred in toluene and removing the solvent resulted in a free flowing powder.For the catalytic pair (CP)IndZrCly and Jan mOMe,SiInd), ZrCl, the catalyst can be deposited on The carrier successively or simultaneously without defects Example fo Vo Preparation of a No. Z catalyst system carrying (Cp)IndZrCl, and aw O(Me,Silnd),ZrCl, with a molecular ratio of 1 : ?Using the technique described in the example as a slurry of about LT concentration in Kaydol (supplied by Witco 177160) Example polymerization using catalyst system #2 Use catalyst system #2 in a gas phase fluidized bed reactor operating continuously as described in example B.

oy example is daj

Z produced a polymer using catalyst No. showed a blown film of resin that had a MI of about 1 and its density ranged from about 1,918 to 1,971 g/cm” (see table (VF). Tear properties; excellent modulus and puncture value compared with a similar commercial metallocene resin (Lady) of table FY and a similar commercial Ziegler-Natta resin (Las , of Table F are known for their improved rupture and extrusion properties. Typical compositions of the resins specified by 1827 are shown; see Fig. do. Fully dimeric compositions using well-separated polymeric groups intended for good and weak co-monomer incorporation catalysts. 0 and arrows Each constituent is typically in at least 771 Gog for products with a density of about AY g/cm” and TREF peaks separated for extreme values greater than 10m. The molecular weight distributions were somewhat broader by about 7.5 to 4,5; see Fig. cco if each catalyst was used separately.

oy 1 Table Data points used in the graph of co-monomer gram-molecular ratio versus density (Fig. /concentration i (MFR) magma (Mi) catalytic gradient (7) C2

YA ¥ oJ A 0.1 oe YY (Me, Cp), 7.1 11 vv "11 GVA (Me.Cp), 1 97 9” 77 ve and (Me, Cp), L — - Vy, YY +,4v¢ 0, EA (Me;Cp), 97 Yv,e +, AQ «48 oe YE (si 5~O(Me,Silnd),

Y, Yo, A 1, Y¢ Avy ved su 5~O(Me, Silnd),

Y,. Yo,A m 11 eff Bu 5~O(Me,Silnd), A Yv,o «(0)5100©-average 0,m off Ye ,) \ Vv 0 2, AR ve 8 My name is _~O(Me, Silnd),

VY ve, 8.7 «,4Y¢ +, +0) my name —O(Me,Silnd), o,A 14,¢ 759 +,4.0 oY) Cp(Ind) 7 91 1 18 DEAR Cp(Ind) ) “7,1 71 1 ne Ye Cp(Ind) A YY,A «40 zero Cp(Ind) 01 6 YyYy,y +,4Y4 oe) Cp(Ind) 9, +” and VY oe) E Cp(Ind) M" of EA 1 vv, +14 Cp2 11 AA 7.8 0.71 (MesCp)Ind oY V4 "9 4 m" (Me; sCp)Ind M YA,0 Y¢,A0 +40. aye (MesCp)Ind 0,4 YAY m7 “aye oe Yo (MesCp)Ind oY 16 aye 10 eM (MesCp)Ind 1,0 Ye Vy, YY «avy 0 YA (MesCp)Cp 1 11,4 ) Al, + Salt A (Ind),

Yy,1 "1 AY YY «avy +14 (Ind), 11 011 7 170 ERR (Ind),

Y,4 VY, YY v 04 A ","M (Ind), 7 0 Vv, 40 0 ,4 1 ¢ Me, Si(H,Ind), vy 6 Y,A1 4%. Zero Me, Si(H,Ind), ¢ , A zero 1 pm 1 zero 484 y Me, Si(H,Ind), v,A Yv,y 0.17 +,40A 0 Me,Si(H,Ind), 79.6 979 0 400 + (No 1151) +: 0 CYA .,40) 0 11 1 , € ¢ a/n ., 944 0 1151) 0 6 a "14 Jeo Me,Si(H,Ind), q,v YY, ¢ 2,1 Lavy veel Me,Si(H,Ind),

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Y Contributory Table 1 (Fig. sai gall) Polynomial equations used to reconcile response data at which the intercept point All catalyst is set Equation Value +41 no = 6.8031x%-1.6044x + 0.96 ( Me Cp),ZrCl, n.d. y =300.75x> - 7.5505 + 0.9566 Me,Si(H,Ind),ZrCl, n.d. 52.58« - 3.7679x + 0.9615 Cp(Ind)ZrCl, +41 y =40.974x% - 2.9269x + 0.96 (Ind),ZrCl, not specified 14.318« - 1.4146x + 0.9523 (MesCp)IndZrCl, +41 y = 7.8436 - 0.8913x + 0.96 —O(Me,Silnd) ZrCl, Table A —_—e ee aa For example Eh Wag * and Comparison 1 Sling 7 bits of a polymer prepared using catalyst No. 7 Comparison la) Comparison lia Z The catalyst is the name of the mixture, the name of the six assays 01 16 A (MI) magma index 7 1 91 (MIR) magma index ratio 1/7 +4190 4 density cut-off coefficient in one direction The machine has a ratio of 7 (lbs / inch) yum malala mm mm cm tte (round per inch) 71 coefficient of incisor in the transverse direction by 0 m. 4. Tew (Jaf) Ballistic Impact

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Claims (1)

protection elements 1-1 Process for polymerizing olefin(s) olefin(s) to produce cpolymer product Y The process involves contacting ethylene and at least one comonomer 7 with the Cus system catalyst system lia The catalyst system comprises a catalyst compound that poorly incorporates the comonomer and contains at least one 40° cyclopentadienyl ligand incorporating the co-monomer well and a catalyst that incorporates the comonomer well; The polymeric product has a Cua ¢himodal composition distribution 77 The catalyst incorporating the weakly co-monomer is a bisindenylzirconium dihalide 4 bearing a substituent at the Sung site bearing a dihalide Ve bisindenylzirconium dihalide at position Sy 1 of de gana alkyl 11 selected from the group consisting of a methyl group ethyl group VY and a propyl group 1 “- Process according to claim 1 wherein a catalyst compound that weakly incorporates a Y co-monomer comprises at least one cyclopentadienyl-based v-ligand incorporated The rings are oriented towards the anterior part of the ¢ molecule at an angle of »more than 0″. 0 “- Operation Gy of claim 1 where the angle “ is greater than 0 . 0 ;- Operation Gy of claim 1 where the angle » is greater than TA 1 0~ process according to yeaa) protection 1 where the catalyst compound that weakly incorporates the Y comonomer contains an ic gens bridging group with more r of two atoms. 1 1— Operation (Eg of claimant ©Cus representing dana) bridging group Y is selected from the group of Cus (Ry'Si-O-R,'Si 3 «RySi-NR' -R;'Si Each R r separately represents a hydride radical or a 'hydrocarbyl radical' —V 1 process Gg of protective squeezing ¥ where the catalyst compound incorporating Y is involved The comonomer is weakly formed on two 5-ligands with a cyclopentadienyl ¥ fused base; where the angle of one of the two ligands ranges from about 71 to about 4 and where the angle of the second ligand is greater than 11 . =A process Ga, of claim 1 where the angle » of the ligand of the two ligands ranges from L about “701” to about CR and where the angle » of the second ligand is greater than 46 . 1 4 - The lig process of the claimant 1, where the catalyst compound 7 that incorporates Jai gall is chosen to weakly contribute a comonomer from group v consisting of «O(Me,SiInd),ZrCl , :2:0©1:(O(Me,Si Fluorenyl) «O(Me,Si[Me;Cp]),ZrCl, «O(Me,Silnd),HfCl, «O(Me,SiFluorenyl) ),ZrC1, ¢ RN(Me,Silnd),ZrCl, «O(Ph,Silnd),ZrCl, ° and Ss < O(Me;Si[Me;Cp])(Me;Silnd)ZrCl, 1 Ind represents the indenyl group -indenyl -0 1 process pursuant to claim 1 where 8< 2 is the polymer product in Y as film ov where the process is For a process that takes place in phase 1 of the claim i the process -11 0 -gas phase process gaseous Y metallocene catalyst in which there is a metallocene catalyst compound 1 of the claim Gig process 1 -1 ha To weakly in the form of comonomer 00d which fuses the co-monomer 1 and the sracemic meso intermediate from the group consisting of the racemic form 7 . And the intermediate 3 rad that incorporates a compound where the catalyst compound 1 of the protective element Gig requires the process 1 - 1 of the mole ratio weakly. The comonomer co-monomer Y is at least twice greater than the monomer to the comonomer the comonomer v that molecular ratio of the catalyst compound that incorporates the co-monomer in the form of -density having the same density polymer is good for preparing a polymer that catalyst compound Where the catalyst compound 11 of the protectant (hg process 6-1 of the mole ratio is weakly required, the comonomer incorporating comonomer Y is ¥ times larger than the monomer to monomer comonomer comonomer 1 less than that of the molarity of the catalyst compound incorporating the monomer well comonomer ° which catalyst compound where catalyst compound 11 requires operation according to claim 1 -1 of weakly mole ratio comonomer incorporating comonomer Y is greater than b times greater than monomer to comonomer comonomer v less than that of the mole ratio of the catalyst incorporating the copolymer 1 oa is the contributing form of oA 1 - Process (Ey) of claim 11 wherein the catalyst compound which Y incorporates the comonomer weakly requires a mole ratio of the ad gall r comonomer to the monomer is f © times greater at least ¢ than that of the gram-molecular ratio of the catalyst compound that incorporates the co-monomer ° well. —VY 1 Operation Gig of claim 1 in which the catalyst system is prepared by mixing preloaded activator Y in solvent or non-solvent medium to form slurry sslurry 1 and then contacting compound The catalyst compound that incorporates the comonomer ¢ poorly and the catalyst compound that incorporates the cocomoner ¢ well with the slurry. VA process according to claim 117 where the medium is oil or hydrocarbon 7 17000870 1 4- Process Gg of protection element 1, where the catalyst system includes an activator material Y that contains aluminum, and the mole ratio is v for aluminum. to a transition metal is greater than 1:01. 0-1 The process according to Claim 1, where the catalyst system includes a Y activator containing aluminum and the mole ratio is 7 for aluminum to metal Transition metal is greater than .:7001 -71 0 The process Gy of claimant 1 where is the mole ratio of the Y catalyst compound that incorporates the comonomer well to 4 pm 04 v catalyst compound weakly incorporating the co-monomer greater than .:1 YY 1 — process according to claim 1 where is the mole ratio of the 1 catalyst compound whose The comonomer incorporates well into v the catalyst compound which incorporates the co-monomer poorly than NY -YY \ process Ga of protectant 1 where mole ratio of compound Y the catalyst compound which incorporates the jad gall comonomer well to the catalyst compound r which incorporates the comonomer weakly than 1 N10;?- the process according to claim 1 where The catalyst compound that incorporates the Y comonomer well and the catalyst compound that incorporates the copolymer is 5 ald (elie, Sith Comite JS (pl sane Cin JS ' reactor ¢) separately or They are fed in the form of a mixture of catalyst systems ° separately carried. 1 - Process for polymerizing olefin(s) olefin(s) to produce polymer product Y The process involves contacting ethylene and at least one co-monomer 7 with a Cus ccatalyst system lia The catalyst system includes a catalyst compound that weakly incorporates the comonomer and has ° at least one cyclopentadienyl-based ligand incorporating 1-rings and a catalyst incorporating the comonomer in the form of CAM and the polymeric product 7 ¢himodal composition distribution Catalytic compound A weakly incorporating the co-monomer includes at least one cyclopentadienyl-9 ligand fused to the anterior part of the Ve molecule at an angle » Its amount exceeds “10”. -717 1 Process according to claim 77; where contacting takes place in a single reactor Y for the production of the polymer product —YA 0 Process Gig For claim YT where the angle » is greater than 61.—YA 0 Operation Gag for claim 77 where the angle » is greater than 68. -#0 1 Operation (Eg for claim 77 Cun The catalyst compound whose Y weakly incorporates a comonomer contains a bridging group r with more than two atoms. 505 JZ bridging group 1 in the form chosen from the group consisting of (Ry'Si-O-Ry'Si g "Ry'Si-NR'-R,'Si" where v is each "© separately a hydride radical or a 'hydrocarbyl radical YY 1 — process pursuant to claim 77 wherein a catalyst compound whose Y incorporates a co-monomer weakly comprises two base ligands a cyclic cyclopentadienyl; and where the angle a of a ligament of the two ligands ranges from about 70 to about 400 and where the angle a of the second ligand is greater than YO . 0 “©- operation according to claim FY where the angle” of the ligand of the two ligands ranges from about 70” to about 400 and where the angle of the second ligand is greater than 49 . 1#- Process ag of protectant YT where the catalyst compound whose Y fuses a weakly fused a gall comonomer is chosen is the group r 9 of O(MeSi Jy 5 5l8),ZCl , «OMe,SiInd),ZrCly «O(Me,Si[Me;Cp]),ZrCl, «O(Me,Silnd),HfCl, «O(Me;SiFluorenyl),ZrCl, 1 «O (Me,Si[MesCp])(Me;Silnd)ZrCl, s RN(Me;Silnd),ZrCl, «O(Ph,Silnd),ZrCl, o where 1 is the indenyl group of .indenyl —Vo 1 process Gp of protection age 77 where the catalyst compound that weakly incorporates the Y co-monomer is a bisindenylzirconium dihalide bearing an in situ substituent 1.1 11 — Process 6) of claimant YO where AW carries the SLD bisindenylzirconium dihalide Y at position 1 with a substitution of an alkyl group selected from the 1 group consisting of From cmethyl group ethyl group and propyl group t VV 1 — process Gy of claim 77 where polymer product V7 forms film YA process Gig For the protection element YT, where the process is a gas phase process 1 -gas phase process Y14¢ A 1 4 “#- The process according to the claim YT where there is a metallocene catalyst Y 00m that incorporates a weakly co-monomer in the form of Jes v from the group consisting of Racemic form 18066 meso, racemic ¢ and median. -0 1 process according to claim 77 wherein a catalyst compound that weakly incorporates a co-monomer Y requires a mole ratio of 1 comonomer to monomer that is at least twice greater than that of the molar ratio of the catalyst that incorporates the co-monomer ° well to prepare a polymer of the same -density 1) 4 — process with claim 0; where the catalyst is required compound that Y weakly incorporates the comonomer a mole ratio of v comonomer to monomer is at least 0 times greater than 1 of that molecular ratio For the catalyst compound that incorporates the co-monomer ° in the form of oa 1 7- The process according to the protection element £0 where the catalyst compound that incorporates the co-monomer Y weakly requires a mole ratio of v comonomer to monomer is ¢ times greater than at least ¢ that molar ratio of the catalyst compound incorporating co-monomer 0 in the form of o 1 £—process according to claim £0 A catalyst compound that weakly incorporates a comonomer Y requires a mole ratio of ad gall 1 the comonomer to the monomer is b * times greater than at least ¢ that MoR of the catalyst incorporating the monomer ° | for my contribution well. 1 ¢£~ Operation Gig of claim 77 where pT vas catalyst system mixed with 1 preloaded activator in solvent or non-solvent medium to form slurry 7¢slurry Then the contact of the catalyst compound which incorporates the comonomer poorly with the form 3 and the catalyst compound which incorporates the comonomer well with the slurry. 1 20— Operation Gy of claim 4; Where the medium is oil Cu) hydrocarbon -hydrocarbon 7 1 £7— the process according to claim 77 where the catalyst system includes an Y activator containing aluminum The mole ratio v for aluminum to transition metal is greater than 1 1 1 0:1 - Process 88 of the protection element YT, where the catalyst system includes a substance Y is an activator that contains aluminum, and the mole ratio v of aluminum to the transition metal is greater than N: Y eo 1 48- The process is according to the element The protection is YT where the mole ratio of the catalyst compound Y that incorporates the comonomer well to the catalyst compound that incorporates the comonomer poorly is greater than NY Na 1 £4 — process according to claim YT where the mole ratio of the catalyst compound y well incorporating the comonomer to v the catalyst compound incorporating the cocomoner is Weakly greater than 1:7. -*+1 0 Process according to claim 77 where the moll ratio of the Y catalyst compound incorporating the comonomer (JSS) is good to: the catalyst compound incorporating the comonomer is poor Greater than 1:0 -51 1 Process according to claim 77 wherein the catalyst compound incorporating Y comonomer well and the catalyst compound incorporating comonomer v poorly are carried separately and fed to the polymerization reactor ¢:07 separately or fed as a mixture of separately carried catalyst systems °. oY 1 Process for polymerizing olefin(s) to produce cpolymer product Y The process involves contacting ethylene and at least one co-monomer with a Cus catalyst system The catalyst system ¢ comprises a catalyst compound lis poorly incorporating the comonomer and ° containing at least one cyclopentadienyl ligand incorporated/rings and a catalyst compound lis incorporating the comonomer well; The catalyst complex that v incorporates the comonomer weakly contains a bridging group with more than two A atoms; And where the bridging group represents in the form of choosing from 9 the group consisting of (RySi-O-Ry'Si s Ry/Si-NR™-Ry'Si, where each 8 separately represents 1 hydride root or hydrocarbyl root ‎Y14¢ le —0Y 1 Process under claim OF where the catalyst compound weakly incorporating the comonomer comprises at least one cyclopentadienyl-based ¥ ligand oriented towards the front ¢ of the molecule molecule at an angle of more than 10 . —0f 0 Operation Gi of the OF protector where the angle » is greater than 61 . 0 *#- Operation Gi of the OF protector where the angle » is greater than 60 . 1 - Process Gig of claimant “© where the catalyst compound that Y weakly incorporates the comonomer +06 comprises two cyclopentadienyl v-based 5-ligands fused to each other; and where the angle is » A ligand of the two ligands is from about “70” to about Che and where the angle » of the second ligand is greater ° than Yo . \ 1E - the operation according to the claim ol where the angle 0 of the ligand of the two ligands ranges from about 71" to about 40 and where the angle of the second ligand is greater than 46. 0A — 1 the operation according to the claim Cua OF The catalyst compound whose Y weakly incorporates the ai gall comonomer is selected from the group consisting of “O(Me;SiFluorenyl),ZrC1, O(Me,Si Ju 14 5 $18 ), 7rCl, <O(Me,Silnd),ZrCl, v «O(Ph,Silnd),ZrCl, «O(Me,Si[Me;Cp]),ZrCl, «O(Me,Silnd), HfCl, ¢ < RN(Me,Silnd),ZrCl, ° and <O(Me,Si[Me;Cp])(Me,Silnd)ZrCl, where Ind is a .indenyl group ‏ 3+1 4- The process (dy) of the OF protectant where the catalyst compound that weakly incorporates the Y comonomer is ALS diindenyl halide 1 and bisindenylzirconium dihalide a 5236S bears a substituent at position 1.0 1 process according to the claim claim where a di-halide zirconium 06 7 at position Sha 1 of de gana carries a selected alkyl alkyl Of the 7 group consisting of a methyl group, the number of an ethyl group, and a propyl group ¢ -71 1 process Gd of the protective element OF where the polymer product is formed in the form of a film 0 7?+- The process according to claim OY, where the process is a process that takes place in a Y-gas phase process 1 "+- Process 1684 of claim OF, where there is a metallocene catalyst compound metallocene catalyst compound Y which weakly incorporates the comonomer in the form of JAC 3 from the group consisting of the intermediate cracemic form ¢meso p, racemic and intermediate. Protection Gua 0Y A catalyst compound that weakly incorporates the comonomer Y requires a mole ratio r of comonomer to monomer that is 2 times greater than 1 less than that of the molar ratio of the catalyst compound that incorporates the co-monomer 0 well to prepare a polymer having the same density .density Tv 1 5+- process according to [aia] protection 14 where a catalyst compound that weakly incorporates Y requires a comonomer a mole ratio of 7 comonomer to monomer monomer is at least ¥ times greater ¢ than that of the catalyst compound that incorporates the co-monomer ° well. 1 7- The process according to claim 14 where a catalyst compound that weakly incorporates a comonomer requires a mole ratio of v comonomer to monomer that is greater B ; times at least ¢ of that molarity of the catalyst compound that incorporates the comonomer ° well. 1 97+- process according to claim 714 wherein a catalyst compound that 1 weakly incorporates the comonomer requires a mole ratio of 1 comonomer to monomer that is greater b * times at least ¢ than that of the molarity of the catalyst compound that incorporates the co-monomer ° well. 1 8+- Operation Gig of claim 0Y where “any 5” catalyst system by mixing preloaded “Y” activator in solvent or non-solvent medium to form a slurry 0 and then contacting the catalyst compound that incorporates the comonomer poorly and the catalyst compound that incorporates the comonomer well with the slurry. Y14¢ M 0 4+- Process Gy of claim TA where the medium is oil or -hydrocarbon Y -70 1 Process 385) of protectant OF where the catalyst system includes system on an activator material Y that contains aluminum and the mole ratio of 7 for aluminum to the transition metal is greater than 0:11 -171 1 the process According to the protection element (OF) where the catalyst system includes a substance 7 activator containing aluminum aluminum and the mole ratio 7 for aluminum to transition metal is greater than 0:70 —VY 1 process (Ey) of the claimant OY where is the mole ratio of 1 the catalyst compound which fuses the comonomer ©0006 well to v the catalyst compound which The co-monomer incorporates weaker than .:1 1 7- The process (ay of the Cua OF protector) is the mole ratio of the Y catalyst compound that incorporates the comonomer well into and of the catalyst compound that incorporates the cocomoner Weakly larger than NY 0;72- The Gay process of the OF claim where the mole ratio of the Y catalyst compound that incorporates the comonomer well to the catalyst compound r that incorporates The copolymer is weakly greater than 0:1 —Vo 1 Process Gg of protectant OY where is the catalyst compound that integrates the ai gall Y cocomonomer well and the catalyst compound that may be the comonomer 7 weakly carried separately and fed into the polymerization reactor ¢ 07 separately or fed as a mixture of catalyst systems 0 separately carried. 1 +- Process according to claim OF where contact takes place in a single Jolie single reactor to produce Y polymer product VV 1 process Gig of claim YT 1 or 57; wherein the weak incorporator Y is a polymerization catalyst operating when ag Lal v undergoes the process; which then yields (Ind),ZrCl, polyethylene with a density of AR £ g anf to produce a polymer with a density of more than 1.978 g/cm. VA 1 Gay process of the claimant (VY where the weak incorporator is Y is a polymerization catalyst that works when subjected to process conditions; v at which it produces (Ind),ZrCl , polyethylene with a density of 1 0 g/cm', to produce a polymer with a density of more than 0.170 g/cm.