WO2019156968A1 - Supported catalysts systems and polymerization processes for using the same - Google Patents

Abstract

The present disclosure provides catalyst systems including Group 4 compounds supported on silica with an electron-withdrawing group. The present disclosure also provides for polyolefins and processes for producing polyolefin compositions including contacting at least one olefin with the catalyst system.

Description

SUPPORTED CATALYST SYSTEMS AND POLYMERIZATION PROCESSES FOR

USING THE SAME

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of Serial No. 62/627,402, filed on February 7, 2018, the disclosure of which is hereby incorporated by reference in its entirety.

FIELD OF THE INVENTION

[0002] The present disclosure relates to supported catalyst systems including, for example, phenolate transition metal complexes, and processes for using such catalyst systems in polymerization processes such as ethylene polymerization processes.

BACKGROUND OF THE INVENTION

[0003] Olefin polymerization catalysts and catalyst systems are of great use in industry. Hence there is interest in finding new catalyst systems that increase the commercial usefulness of the catalyst and allow the production of polymers having improved properties. Catalysts for olefin polymerization have been based on bisphenolate complexes as catalyst precursors, which are typically activated with an alumoxane or with an activator containing a non-coordinating anion.

[0004] Diamine bis(phenolate) Group 4 complexes have been used as transition metal components in the copolymerization of ethylene and hexene, see for example, Macromolecules 2005, 38, 2552-2558, and in the homopolymerization of 1 -hexene, see for example J. Am. Chem. Soc. 2000, 122, 10706, and propylene, see for example, Macromolecules 2010, 43, 1689.

[0005] WO 2002/036638 and WO 2012/098521 disclose diamine bis(phenolate) compounds for use as alpha olefin polymerization catalysts.

[0006] WO 2012/027448 and WO 2003/091262 disclose bridged bis(phenyl phenol) compounds for olefin polymerization catalysts.

[0007] Patent Application No. 62/368,247 discloses phenolate transition metal complexes, production, and use as olefin polymerization catalysts.

[0008] WO 2017/058388 Al discloses supported catalysts.

[0009] Conventional supported metallocene catalysts exhibit limitations in the molecular weight and comonomer incorporation capability as well as ¾ response in ethylene/l -hexene copolymerization. Such limitations have hindered access to LLDPE resin compositions having desirable properties for linear low density polyethylene (“LLDPE”) films, such as high tear strength, good bubble stability and easy melt processing.

[0010] There still is a need in the art for new and improved catalyst systems for the polymerization of olefins in order to achieve specific polymer properties such as broader scope in molecular weight, to increase conversion and/or comonomer incorporation, or to alter comonomer distribution without deteriorating the resulting polymer’s properties. Further, there is a need in the art for new catalyst systems having hydrogen response and comonomer response.

SUMMARY

[0011] The present disclosure relates to methods for olefin polymerization. More specifically, the present disclosure relates to the synthesis of polymers using bridged bis(phenolate) Group 4 compounds supported on silica and fluorided silica.

[0012] In an embodiment, the present disclosure provides a catalyst system including a support material comprising an electron withdrawing group; and

a catalyst represented by formula (I):

wherein,

M is a Group 4 transition metal;

each Q is a neutral donor group comprising at least one atom from Group 15 or Group 16, and each of R² and R³ is not present when Q is a Group 16 atom;

L is -(C)_y(R⁴)(R⁵)- and is not part of an aromatic ring;

L* is -(C)_Z(R⁴*)(R⁵*)- and is not part of an aromatic ring;

y is greater than or equal to 2;

z is greater than or equal to 2; each of X¹ and X² is independently a univalent Ci to C20 hydrocarbyl radical, a Ci to C20 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or X¹ and X² join together to form a C4 to C62 cyclic, polycyclic or heterocyclic structure;

R¹ is a divalent Ci to C40 hydrocarbyl radical or a divalent substituted hydrocarbyl radical comprising a portion that comprises a linker backbone comprising from 1 to 18 carbon atoms linking or bridging between the two Q groups;

each of R^a, R^b, R^c, R^d, R^a*, R^b*, R^c*, and R^d* is independently a hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical, a heteroatom or a heteroatom- containing group, or two or more of R^a, R^b, R^c, R^d, R^a*, R^b*, R^c*, and R^d* may independently join together to form a C4 to C62 cyclic, polycyclic or heterocyclic structure, or a combination thereof; and

each of R² and R³ is independently a hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical, a heteroatom, or a heteroatom-containing group.

[0013] In at least one embodiment, a catalyst system is provided. The catalyst system includes (a) a catalyst system of the present disclosure; and (b) a bridged or unbridged catalyst other than the catalyst of (a).

[0014] In at least one embodiment, a catalyst system is provided. The catalyst system includes a catalyst represented by formula (I); a support material; and an activator and an activator.

[0015] In at least one embodiment, a method of polymerizing olefins to produce at least one polyolefin composition is provided. The method includes contacting at least one olefin with a catalyst system of the present disclosure; and obtaining a polyolefin.

[0016] In at least one embodiment, an ethylene, alpha-olefin copolymer is provided. The copolymer is obtained by contacting ethylene, at least one alpha-olefin, and the catalyst system of a catalyst system of the present disclosure, the copolymer having a C6 wt% of from about 0 wt% to about 30 wt%.

[0017] In at least one embodiment, an ethylene, alpha-olefin copolymer is provided. The copolymer is an ethylene alpha-olefin copolymer obtained by contacting ethylene, at least one alpha-olefin, and the catalyst system of the present disclosure in the presence of about 0 ppm hydrogen, the copolymer having an Mw from about 5,000 g/mol to about 2,500,000 g/mol.

[0018] In at least one embodiment, an ethylene, alpha-olefin copolymer is provided. The copolymer is an ethylene alpha-olefin copolymer obtained by contacting ethylene, at least one alpha-olefin, and a catalyst system of the present disclosure in the presence of about 300 ppm hydrogen, the copolymer having an Mw from about 5,000 g/mol to about 2,500,000 g/mol. BRIEF DESCRIPTION OF THE FIGURES

[0019] FIG. 1 is a representative plot of activity (kgmol^h ¹) versus mol ratio of 1 -hexene (C6) to ethylene (C2) in liquid phase in the presence of about 0 ppm Fk for selected catalysts.

[0020] FIG. 2 is a representative plot of activity (kgmof'h ¹) versus mol ratio of 1 -hexene (C6) to ethylene (C2) in liquid phase in the presence of about 300 ppm Ff for selected catalysts.

[0021] FIG. 3 is a representative plot of Mw versus mol ratio of l-hexene (C6) to ethylene (C2) in liquid phase in the presence of about 0 ppm Fh for selected catalysts.

[0022] FIG. 4 is a representative plot of Mw versus mol ratio of l-hexene (C6) to ethylene (C2) in liquid phase in the presence of about 300 ppm Fk for selected catalysts.

[0023] FIG. 5 is a representative plot of l-hexene incorporation (C6 wt%) versus mol ratio of l-hexene (C6) to ethylene (C2) in liquid phase in the presence of about 0 ppm Fk for selected catalysts.

[0024] FIG. 6 is a representative plot of l-hexene incorporation (C6 wt%) versus mol ratio of l-hexene (C6) to ethylene (C2) in liquid phase in the presence of about 300 ppm Fh for selected catalysts.

DETAILED DESCRIPTION OF THE INVENTION

[0025] Catalyst systems of the present disclosure include at least one supported bridged bis(phenolate) Group 4 compound and a support material having an electron withdrawing group. Catalyst systems and methods of the present disclosure are highly active and show increased conversion, and produce polymers with broader scope in molecular weight, comonomer incorporation, and/or altered comonomer distribution. Further, the catalyst systems and methods show improved Fh response and improved comonomer response as compared to commercial metallocene catalysts.

[0026] The catalyst systems and the methods of the present disclosure offer several advantages over conventional techniques. In at least one embodiment, the catalyst system has an activity of about 50 kgmoHh ¹ to about 100,000 kgmol^h ¹ in the presence of about 0 ppm hydrogen and an activity of 50 kgmof'h ¹ to about 100,000 kgmol ¹h ¹ in the presence of about 300 ppm hydrogen. In at least one embodiment, in the presence of about 0 ppm hydrogen, the catalyst system produces ethylene alpha-olefin copolymer having a comonomer content (e.g., hexene (C6 wt%)) from about 0 wt% to about 30 wt%, more preferably from about 1 wt% to about 20 wt%. In at least one embodiment, in the presence of about 300 ppm hydrogen, the catalyst system produces ethylene alpha-olefin copolymer having a comonomer content (e.g., hexene (C6 wt%)) from about 0 wt% to about 30 wt%, more preferably from about 1 wt% to about 20 wt%. In at least one embodiment, in the presence of about 0 ppm hydrogen, the catalyst system produces ethylene alpha-olefin copolymer having an Mw from about 5,000 g/mol to 2,500,000 g/mol. In at least one embodiment, in the presence of about 300 ppm hydrogen, the catalyst system produces ethylene alpha-olefin copolymer having an Mw from 5,000 g/mol to 2,500,000 g/mol.

[0027] For purposes herein, the numbering scheme for the Periodic Table Groups is used as described in CHEMICAL AND ENGINEERING NEWS, 63(5), pg. 27 (1985). For example, a “Group 4 metal” is an element from Group 4 of the Periodic Table, e.g., Hf, Ti, or Zr.

[0028] As used herein,“high molecular weight” is defined as a number average molecular weight (Mn) value of 25,000 g/mol or more.“Low molecular weight” is defined as a Mn value of less than 25,000 g/mol.

[0029] The comonomer content of a polyolefin (e.g., wt% of comonomer incorporated into a polyolefin backbone) can influence the properties of the polyolefin (and composition of the copolymers) and is dependent on the identity of the polymerization catalyst. As used herein, “low comonomer content” is defined as a polyolefin having less than about 1 wt% of comonomer based upon the total weight of the polyolefin. As used herein,“high comonomer content” is defined as a polyolefin having greater than or equal to about 1 wt% of comonomer based upon the total weight of the polyolefin.

[0030] Catalyst activity is a measure of how active the catalyst is and is reported as the mass of product polymer (P) produced per mole of catalyst (cat) used (kgP/molcat).

[0031] “Catalyst productivity” is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T x W) and expressed in units of gPgcaf ¹hr ¹. “Conversion” is the amount of monomer that is converted to polymer product, and is reported as mol% and is calculated based on the polymer yield and the amount of monomer fed into the reactor. “Catalyst activity” is a measure of the level of activity of the catalyst and is reported as the mass of product polymer (P) produced per mole (or mmol) of catalyst (cat) used (kgP/molcat or kgPmof'cat). and catalyst activity can also be expressed per unit of time, for example, per hour (hr).

[0032] As used herein, an“olefin,” alternatively referred to as“alkene,” is a linear, branched, or cyclic compound of carbon and hydrogen having at least one double bond. For purposes of this specification and the claims appended thereto, when a polymer or copolymer is referred to as comprising an olefin, the olefin present in such polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have an“ethylene” content of 35 wt% to 55 wt%, it is understood that the monomer (“mer”) unit in the copolymer is derived from ethylene in the polymerization reaction and said derived units are present at 35 wt% to 55 wt%, based upon the weight of the copolymer.

[0033] A“polymer” has two or more of the same or different monomer (“mer”) units. A “homopolymer” is a polymer having mer units that are the same. A“copolymer” is a polymer having two or more mer units that are different from each other. A“terpolymer” is a polymer having three mer units that are different from each other. “Different” as used to refer to mer units indicates that the mer units differ from each other by at least one atom or are different isomerically. Accordingly, the definition of copolymer, as used herein, includes terpolymers. An“ethylene polymer” or“ethylene copolymer” is a polymer or copolymer having at least 50 mol% ethylene derived units, a“propylene polymer” or“propylene copolymer” is a polymer or copolymer having at least 50 mol% propylene derived units, and so on.

[0034] For the purposes of this disclosure, ethylene shall be considered an a-olefm.

[0035] As used herein, the term“substituted” means that a hydrogen group has been replaced with a heteroatom, or a heteroatom-containing group. For example, a“substituted hydrocarbyl” is a radical made of carbon and hydrogen where at least one hydrogen is replaced by a heteroatom or heteroatom-containing group.

[0036] As used herein, Mn is number average molecular weight, Mw is weight average molecular weight, and Mz is z average molecular weight, wt% is weight percent, and mol% is mole percent. Molecular weight distribution (MWD), also referred to as polydispersity (PDI), is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, Mz) are g/mol.

[0037] Copolymers (and terpolymers) of polyolefins have a comonomer, such as propylene, incorporated into the polyethylene backbone. These copolymers (and terpolymers) provide varying physical properties compared to polyethylene alone and are typically produced in a low pressure reactor, utilizing, for example, solution, slurry, or gas phase polymerization processes. The comonomer content of a polyolefin (e.g., wt% of comonomer incorporated into a polyolefin backbone) influences the properties of the polyolefin (and composition of the copolymers) and is dependent on the identity of the polymerization catalyst.

[0038] “Linear” means that the polymer has few, if any, long chain branches and typically has a g'vis value of 0.97 or above, such as 0.98 or above.

[0039] The term“cyclopentadienyl” refers to a 5-member ring having delocalized bonding within the ring and typically being bound to M through r|⁵-bonds. carbon typically making up the majority of the 5-member positions. [0040] As used herein, a“catalyst” includes a single catalyst, or multiple catalysts with each catalyst being conformational isomers or configurational isomers. Conformational isomers include, for example, conformers and rotamers. Configurational isomers include, for example, stereoisomers.

[0041] The term“complex,” may also be referred to as catalyst precursor, precatalyst, catalyst, catalyst compound, transition metal compound, or transition metal complex. These words are used interchangeably. Activator and cocatalyst are also used interchangeably.

[0042] Unless otherwise indicated, the term“substituted” generally means that a hydrogen of the substituted species has been replaced with a different atom or group of atoms. For example, methyl-cyclopentadiene is cyclopentadiene that has been substituted with a methyl group. Likewise, picric acid can be described as phenol that has been substituted with three nitro groups, or, alternatively, as benzene that has been substituted with one hydroxy and three nitro groups.

[0043] The following abbreviations may be used herein: dme is l,2-dimethoxy ethane, Me is methyl, Et is ethyl, Pr is propyl, cPr is cyclopropyl, nPr is normal propyl, iPr is isopropyl, Bu is butyl, nBu is normal butyl, iBu is isobutyl, sBu is sec-butyl, tBu is tert-butyl, p-tBu is para-tert-butyl, Ph is phenyl, Bn is benzyl (i.e., CFbPh), Oct is octyl, Cy is cyclohexyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is tri(n-octyl)aluminum, MAO is methylalumoxane, p-Me is para-methyl, THF (also referred to as thf) is tetrahydrofuran, RT is room temperature (and is 23°C unless otherwise indicated), tol is toluene, and EtOAc is ethyl acetate.

[0044] An“anionic ligand” is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. A“neutral donor ligand” is a neutrally charged ligand which donates one or more pairs of electrons to a metal ion.

[0045] An“electron-withdrawing group” includes an atom or atoms that withdraw electron density from a neighboring atom. An electron-withdrawing group can include an electron- withdrawing anion or an anionic ligand, and the terms may be used interchangeably.

[0046] As used herein, a“catalyst system” includes at least one catalyst compound and a support material. A catalyst system of the present disclosure can further include an activator and an optional co-activator. For the purposes of this disclosure and claims thereto, when catalyst systems are described as comprising neutral stable forms of the components, it is well understood by one of ordinary skill in the art, that the ionic form of the component is the form that reacts with the monomers to produce polymers. Furthermore, catalysts of the present disclosure represented by a Formula are intended to embrace ionic forms thereof of the compounds in addition to the neutral stable forms of the compounds. Furthermore, activators of the present disclosure are intended to embrace ionic/reaction product forms thereof of the activator in addition to ionic or neutral form.

[0047] A scavenger is a compound that can be added to a reactor to facilitate polymerization by scavenging impurities. Some scavengers may also act as chain transfer agents. Some scavengers may also act as activators and may be referred to as co-activators. A co-activator, that is not a scavenger, may also be used in conjunction with an activator in order to form an active catalyst. In some embodiments, a co-activator can be pre-mixed with the transition metal compound to form an alkylated transition metal compound. Examples of scavengers include trialkylaluminums, methylalumoxanes, modified methylalumoxanes, MMAO-3A (Akzo Nobel), bis(diisobutylaluminum)oxide (Akzo Nobel), tri(n- octyl)aluminum, triisobutylaluminum, and diisobutylaluminum hydride.

[0048] As used herein,“alkoxides” include those where the alkyl group is a Ci to Cio hydrocarbyl. The alkyl group may be straight chain, branched, or cyclic. The alkyl group may be saturated or unsaturated. In some embodiments, the alkyl group may include at least one aromatic group.

[0049] The terms “hydrocarbyl radical,” “hydrocarbyl,” “hydrocarbyl group,” “alkyl radical,” and“alkyl” are used interchangeably throughout this document. Likewise, the terms “group,”“radical,” and“substituent” are also used interchangeably in this document. For purposes of this disclosure,“hydrocarbyl radical” refers to Ci-Cioo radicals, that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic. Examples of such radicals include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso amyl, hexyl, octyl cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and their substituted analogues. Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least one halogen (such as Br, Cl, F or I) or at least one functional group such as C(0)R*, C(0)NR*2, C(0)OR*, NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, and PbR*3 (where R* is independently a hydrogen or hydrocarbyl radical, and two or more R* may join together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure), or where at least one heteroatom has been inserted within a hydrocarbyl ring.

[0050] The term“alkenyl” means a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more double bonds. These alkenyl radicals may be optionally substituted. Examples of suitable alkenyl radicals include ethenyl, propenyl, allyl, 1 ,4-butadienyl cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, including their substituted analogues.

[0051] The term“alkoxy” or“alkoxide” means an alkyl ether or aryl ether radical wherein the term alkyl is as defined above. Examples of suitable alkyl ether radicals include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, and phenoxyl.

[0052] The term“aryl” or“aryl group” includes a C4-C20 aromatic ring, such as a six carbon aromatic ring, and the substituted variants thereof, including phenyl, 2-methyl-phenyl, xylyl, 4-bromo-xylyl. Likewise heteroaryl means an aryl group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, preferably N, O, or S. As used herein, the term“aromatic” also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic; likewise the term aromatic also refers to substituted aromatics.

[0053] Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, iso-butyl, iso-butyl, and tert-butyl) reference to one member of the group (e.g., n-butyl) shall expressly disclose the remaining isomers (e.g., iso-butyl, sec-butyl, and tert-butyl) in the family. Likewise, reference to an alkyl, alkenyl, alkoxide, or aryl group without specifying a particular isomer (e.g., butyl) expressly discloses all isomers (e.g., n-butyl, iso-butyl, sec-butyl, and tert-butyl).

[0054] For any particular compound disclosed herein, any general or specific structure presented also encompasses all conformational isomers, regioisomers, and stereoisomers that may arise from a particular set of substituents, unless stated otherwise. Similarly, unless stated otherwise, the general or specific structure also encompasses all enantiomers, diastereomers, and other optical isomers whether in enantiomeric or racemic forms, as well as mixtures of stereoisomers, as would be recognized by a skilled artisan.

[0055] The term“ring atom” means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has six ring atoms and tetrahydrofuran has 5 ring atoms.

[0056] A heterocyclic ring is a ring having a heteroatom in the ring structure as opposed to a heteroatom-substituted ring where a hydrogen on a ring atom is replaced with a heteroatom. For example, tetrahydrofuran is a heterocyclic ring and d-A V-di methyl amino-phenyl is a heteroatom-substituted ring.

[0057] As used herein the term“aromatic” also refers to pseudoaromatic heterocycles which are heterocyclic substituents that have similar properties and structures (nearly planar) to aromatic heterocyclic ligands, but are not by definition aromatic; likewise, the term aromatic also refers to substituted aromatics.

[0058] The term“continuous” means a system that operates without interruption or cessation. For example a continuous process to produce a polymer would be one where the reactants are continually introduced into one or more reactors and polymer product is continually withdrawn during a polymerization process.

[0059] “Catalyst productivity” is a measure of how many grams of polymer (P) are produced using a polymerization catalyst comprising W g of catalyst (cat), over a period of time of T hours; and may be expressed by the following formula: P/(T x W) and expressed in units of gPgcar'hr¹. “Conversion” is the amount of monomer that is converted to polymer product, and is reported as mol% and is calculated based on the polymer yield and the amount of monomer fed into the reactor. “Catalyst activity” is a measure of the level of activity of the catalyst and is reported as the mass of product polymer (P) produced per mole (or mmol) of catalyst (cat) used (kgP/molcat or gP/mmolCat), and catalyst activity can also be expressed per unit of time, for example, per hour (hr).

Catalysts

[0060] In at least one embodiment, the present disclosure relates to a catalyst system. The catalyst system includes a supported bridged bis(phenolate) Group 4 compound, where the supporting material comprises an electron withdrawing group.

[0061] Preferably, the bridged bis(phenolate) Group 4 catalyst is represented by formulas

(I) or (II):

wherein:

M is a Group 4 transition metal (preferably Hf, Zr, or Ti, preferably Hf or Zr); each Q is independently a neutral donor group comprising at least one atom from Group 15 or Group 16, preferably comprising O, N, S, or P (preferably O or N), and each of R² and R³ is not present when Q is a Group 16 atom;

L is -(C)_y(R⁴)(R⁵)- and is not part of an aromatic ring;

L* is -(C)_Z(R⁴*)(R⁵*)- and is not part of an aromatic ring;

y is greater than or equal to 2, e.g., 2, 3, 4, 5, or 6;

z is greater than or equal to 2, e.g., 2, 3, 4, 5, or 6;

each of X¹ and X² is independently a univalent Ci to C20 hydrocarbyl radical, a Ci to C20 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or X¹ and X² join together to form a C4 to C62 cyclic, polycyclic or heterocyclic ring structure (preferably benzyl, methyl, ethyl, chloro, or bromo);

R¹ is a divalent C 1-C40 (alternately Ci to C20) hydrocarbyl radical or a divalent substituted hydrocarbyl radical comprising a portion that comprises a linker backbone comprising from 1 to 18 carbon atoms linking or bridging between the two Q groups, preferably R¹ is a -(CR⁶2)n- group, where n is 2, 3, 4, 5, or 6, (preferably 2 or 3) each R⁶ is H, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical, a heteroatom or a heteroatom- containing group, or multiple R⁶ groups may join together to form a C4 to C62 cyclic or polycyclic ring structure (preferably a benzene ring, substituted benzene ring, cyclohexyl, substituted cyclohexyl, cyclooctyl, or substituted cyclooctyl), preferably each R⁶ is, independently, a Ci to C20 hydrocarbyl radical, preferably a Ci to C20 alkyl radical, preferably each R⁶ is independently hydrogen, methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicosyl;

each of R^a, R^b, R^c, R^d, R^a*, R^b*, R^c*, and R^d* is independently a hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or two or more adjacent R^a, R^b, R^c, R^d, R^a*, R^b*, R^c*, and R^d* groups may independently join together to form a C4 to C62 cyclic or polycyclic ring structure, or a combination thereof, preferably each of R^a, R^b, R^c, R^d, R^a*, R^b*, R^c*, and R^d* is independently a Ci to C20 hydrocarbyl radical, preferably a Ci to C20 alkyl or aromatic radical, preferably each of R^a, R^b, R^c, R^d, R^a*, R^b*, R^c*, and R^d* is independently hydrogen, methyl, ethyl, ethenyl or isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, adamantyl, substituted adamantyl, cyclohexyl, substituted cyclohexyl phenyl, substituted phenyl, fluorenyl, substituted fluorenyl, carbazolyl, substituted carbazolyl, naphthyl, substituted naphthyl, phenanthryl, substituted phenanthryl, anthracenyl, substituted anthracenyl, indanyl, substituted indanyl, indenyl, substituted indenyl;

each of R⁴, R⁵, R⁴*, and R⁵* is independently a hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or two or more adjacent R⁴, R⁵, R⁴*, and R⁵* groups may independently join together to form a C4 to C62 cyclic or polycyclic ring structure, or a combination thereof, provided that such cyclic or polycyclic ring structure is not aromatic, preferably each of R⁴, R⁵, R⁴*, and R⁵* is independently a Ci to C20 hydrocarbyl radical, preferably a Ci to C20 alkyl radical, preferably each of R⁴, R⁵, R⁴*, and R⁵* is independently hydrogen, methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicosyl; and

each of R² and R³ is independently a hydrogen, a Ci to C40 hydrocarbyl radical, a

Ci to C40 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, preferably a Ci to C20 hydrocarbyl radical, preferably a Ci to C20 alkyl radical, preferably each of R² and R³ is independently hydrogen, methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and eicosyl, phenyl, or substituted phenyl.

[0062] In at least one embodiment, each of R^a and R^a* is independently carbazolyl, substituted carbazolyl, naphthyl, substituted naphthyl, anthracenyl, substituted anthracenyl, phenanthryl, substituted phenanthryl, phenyl, substituted phenyl, adamantyl, substituted adamantyl, cyclohexyl, substituted cyclohexyl, indolyl, substituted indolyl, indolinyl, substituted indolinyl, imidazolyl, substituted imidazolyl, indenyl, substituted indenyl, indanyl, substituted indanyl, fluorenyl, or substituted fluorenyl.

[0063] In at least one embodiment, the bridged bis(phenolate) Group 4 catalyst represented by formulas (I) or (II) where R^a and/or R^a* (preferably R^a and R^a*) are independently a carbazolyl radical or substituted carbazolyl radical is represented by formula (III):

wherein each of R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ is independently a hydrogen, a C1-C40 hydrocarbyl radical, a functional group comprising elements from Group 13 to 17 of the periodic table of the elements, or two or more of R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ may independently join together to form a C₄ to 0, cyclic or polycyclic ring structure, or a combination thereof, preferably each of R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ is hydrogen.

[0064] For purposes herein, any hydrocarbyl radical (and any alkyl radical) may be independently a methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, heneicosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl, hexacosenyl, heptacosenyl, octacosenyl, nonacosenyl, triacontenyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, eicosynyl, heneicosynyl, docosynyl, tricosynyl, tetracosynyl, pentacosynyl, hexacosynyl, heptacosynyl, octacosynyl, nonacosynyl, and triacontynyl.

[0065] In any embodiment of the catalysts described herein M may be Hf, Ti or Zr, preferably Hf or Zr.

[0066] In any embodiment of the catalysts described herein, each of X¹ and X² is independently hydrocarbyl radicals having from 1 to 20 carbon atoms (such as methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl), hydrides, amides, alkoxides having from 1 to 20 carbon atoms, sulfides, phosphides, halides, sulfoxides, sulfonates, phosphonates, nitrates, carboxylates, carbonates, or combinations thereof, preferably each of X¹ and X² is independently halide (F, Cl, Br, I), unsubstituted or substituted alkyl radicals having from 1 to 10 carbon atoms (methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and isomers thereof), unsubstituted or substituted benzyl radicals, or a combination thereof.

[0067] In any embodiment of the catalysts described herein, R¹ is a divalent C1-C40 hydrocarbyl radical or divalent substituted hydrocarbyl radical comprising a portion that comprises a linker backbone comprising from 1 to 18 carbon atoms linking or bridging between Q and Q. In an embodiment, R¹ is ethylene (-CH2CH2-), 1, 2-cyclohexylene and 1,2- phenylene. In an embodiment, R¹ is -CH2CH2CH2- derived from propylene. In an embodiment, R¹ is Ci to C20 alkyl groups, such as divalent methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, or eicosyl. [0068] In at least one embodiment, each of R^a, R^b, R^c, R^d, R^a*, R^b*, R^c*, and R^d* is independently hydrogen, C1-C20 hydrocarbyl radical, substituted C i to C20 hydrocarbyl radical, or two or more of R^a, R^b, R^c, R^d, R^a*, R^b*, R^c*, and R^d* may independently join together to form a C4 to C62 cyclic or polycyclic ring structure, or a combination thereof.

[0069] In at least one embodiment, two or more of R¹, R², R⁴, R⁵, R³, R⁴*, R⁵*, R⁶, R¹¹, R¹², R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, and R¹⁸ may independently join together to form a C4 to C62 cyclic or polycyclic ring structure, or a combination thereof.

[0070] In any embodiment of the catalysts described herein, each of R^a, R^b, R^c, R^d, R^a*, R^b*. R^c*, and R^d* is independently hydrogen, halogen, Ci to C30 hydrocarbyl radical, Ci to C20 hydrocarbyl radical, or Ci to C 10 hydrocarbyl radical (such as methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, and their substituted analogs).

[0071] In any embodiment of the catalysts described herein, each of R^a, R^b, R^c, R^d, R^a*, R^b*. R^c*, and R^d* is independently a substituted Ci to C30 hydrocarbyl radical, substituted Ci to C20 hydrocarbyl radical, or substituted Ci to C10 hydrocarbyl radical (such as 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-methoxyphenyl, 4-trifluoromethylphenyl, 4- dimethylaminophenyl, 4-trimethylsilylphenyl, 4-triethylsilylphenyl, trifluoromethyl, fluoromethyl, trichloromethyl, chloromethyl, mesityl, methylthio, phenylthio, (trimethylsilyl)methyl, or (triphenylsilyl)methyl).

[0072] In any embodiment described herein, one or more of each of R^a, R^b, R^c, R^d, R^a*, R^b*, R^c*, and R^d* is a methyl radical, fluoride, chloride, bromide, iodide, methoxy, ethoxy, isopropoxy, trifluoromethyl, dimethylamino, diphenylamino, adamantyl, phenyl, pentafluorophenyl, naphthyl, anthracenyl, dimethylphosphanyl, diisopropylphosphanyl, diphenylphosphanyl, methylthio, and phenylthio, or a combination thereof.

[0073] In any embodiment of the catalysts described herein, Q is preferably a neutral donor group comprising at least one atom from Group 15 or Group 16, preferably Q is NR', O, S, or PR', where R' is as defined for R^a and R^a* (preferably R' is independently a hydrogen, a Ci to C40 hydrocarbyl radical, or a Ci to C40 substituted hydrocarbyl radical, preferably R' is methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl or linked together to form a five-membered ring such as pyrrolidinyl or a six-membered ring such as piperidinyl), preferably the -(-Q-R'-Q- )- fragment can form a substituted or unsubstituted heterocycle which may or may not be aromatic and may have multiple fused rings. [0074] In any embodiment of the catalysts described herein, Q is preferably NR', where R' is methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl or linked together to form a five- membered ring such as pyrrolidinyl or a six-membered ring such as piperidinyl.

[0075] In at least one embodiment of the catalysts described herein, R^a and/or R^a* are the same, preferably R^a and R^a* are C-R'" and C-R'"*, respectively, where each of R'" and R'"* is independently H or a Ci to C12 hydrocarbyl or substituted hydrocarbyl (such as methyl, ethyl, ethenyl and isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, trifluoromethylphenyl, tolyl, phenyl, methoxyphenyl, tertbutylphenyl, fluorophenyl, diphenyl, dimethylaminophenyl, chlorophenyl, bromophenyl, iodophenyl, (trimethylsilyl)phenyl, (triethylsilyl)phenyl, (trimethylsilyl)methyl, and (triethylsilyl)methyl). In at least one embodiment of the catalysts described herein, R^a and R^a* are different.

[0076] In at least one embodiment of the catalysts described herein, R^a and R^a* are the same, preferably R^a and R^a* are carbazolyl, substituted carbazolyl, naphthyl, substituted naphthyl, anthracenyl, substituted anthracenyl, phenanthryl, substituted phenanthryl, phenyl, substituted phenyl, adamantyl, substituted adamantyl, cyclohexyl, substituted cyclohexyl, indolyl, substituted indolyl, indolinyl, substituted indolinyl, imidazolyl, substituted imidazolyl, indenyl, substituted indenyl, indanyl, substituted indanyl, fluorenyl, or substituted fluorenyl. In at least one embodiment of the catalysts described herein, R^a and R^a* are different.

[0077] In an embodiment, M is Zr or Hf; X¹ and X² are benzyl radicals; and R¹ is ethylene (-CH2CH2-).

[0078] In an embodiment, M is Zr or Hf; X¹ and X² are benzyl radicals; R^c and R^c* are methyl radicals; R^b, R^d, R^b*, and R^d* are hydrogen; and R¹ is ethylene (-CH2CH2-), each Q is an O-containing group, R^a and R^a* are carbazolyl or fluorenyl.

[0079] In an embodiment, M is Zr or Hf; X¹ and X² are benzyl radicals; R^c and R^c* are methyl radicals; R^b, R^d, R^b*, and R^d* are hydrogen; and R¹ is ethylene (-CH2CH2-), each Q is an N-containing group, R^a and R^a* are carbazolyl or fluorenyl.

[0080] In a particularly preferred embodiment of the present disclosure, the catalyst is one or more of:

[0081] In at least one embodiment, the catalyst system includes: (a) a catalyst system of the present disclosure; and (b) a bridged or unbridged catalyst other than the catalyst of (a).

[0082] In at least one embodiment, the catalyst system includes: a catalyst system of the present disclosure; and an activator.

Methods to Prepare the Catalysts

[0083] In some embodiments, the catalysts may be prepared by the following general

synthetic routes. Phenol 1, where R may be a carbazole

. or another group as described herein, is allylated via a nucleophilic substitution followed by a Claisen rearrangement to give 3. The resulting allyl-substituted phenol is then protected (for example, as a methyl ether, or a methoxymethyl ether (MOM)), and oxidized with ozone to the corresponding aldehyde 5. Reductive animation of the carbonyl with a diamine (-HN(R")-R- N(R")H-) as described herein, followed by deprotection results in the final ligand 6. Alternatively, the aldehyde 5 can be transformed to the corresponding ethyl bromide compound 7, which is then reacted via nucleophilic substitution with the precursor of the bridging group, e.g., diamine or diol (-HQ(R")-R'-Q(R")H-). Subsequent deprotection provides final ligand

8. The ligand can then undergo metalation.

[0084] In at least one embodiment, an asymmetric ligand may be prepared by the general procedure. The reductive amination reaction, i.e., will have more than one different carbonyl compounds 5. Alternatively, more than one different ethyl bromide compounds 7, can undergo nucleophilic substitution to produce an asymmetric ligand 8 after deprotection. The asymmetric ligand can then undergo metalation as shown below.

[0085] After the catalysts have been synthesized, catalyst systems may be formed by combining the catalysts with activators in any suitable manner including by supporting them for use in slurry or gas phase polymerization. The catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer). The catalyst system typically includes a catalyst as described above and an activator such as alumoxane or a non-coordinating anion.

Support Materials

[0086] In embodiments herein, the catalyst system may comprise an inert support material (with or without activator). Preferably the supported material is a porous support material, for example, talc, and inorganic oxides. Other support materials include zeolites, clays, organoclays, or any other organic or inorganic support material, or mixtures thereof.

[0087] Preferably, the support material is an inorganic oxide in a finely divided form. Suitable inorganic oxide materials for use in catalyst systems herein include Groups 2, 4, 13, and 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides that may be employed either alone or in combination with the silica, or alumina are magnesia, titania, or zirconia. Other suitable support materials, however, can be employed, for example, finely divided functionalized polyolefins, such as finely divided polyethylene. Particularly useful supports include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, and clays. Also, combinations of these support materials may be used, for example, silica- chromium, silica-alumina, and silica-titania. Preferred support materials include AI2O3, Zr0₂, S1O2, and combinations thereof, more preferably S1O2, AI2O3, or S1O2/AI2O3.

[0088] It is preferred that the support material, most preferably an inorganic oxide, has a surface area in the range of from about 10 to about 700 m²/g, pore volume in the range of from about 0.1 to about 4.0 cc/g and average particle size in the range of from about 5 to about 500 pm. More preferably, the surface area of the support material is in the range of from about 50 to about 500 m²/g, pore volume of from about 0.5 to about 3.5 cc/g and average particle size of from about 10 to about 200 pm. Most preferably the surface area of the support material is in the range is from about 100 to about 400 m²/g, pore volume from about 0.8 to about 3.0 cc/g and average particle size is from about 5 to about 100 pm. The average pore size of the support material useful in the present disclosure is in the range of from about 10 to about 1000 A, preferably about 50 to about 500 A, and most preferably about 75 to about 350 A. In some embodiments, the support material is a high surface area, amorphous silica (surface area= about 300 m²/gm; pore volume of about 1.65 cm³/gm). Preferred silicas are marketed under the trade names of DAVISON 952 or DAVISON 955 by the Davison Chemical Division of W.R. Grace and Company. In other embodiments DAVISON 948 is used.

[0089] The support material should be dry, that is, free of absorbed water. Drying of the support material can be effected by heating or calcining at about l00°C to about l000°C, preferably at least about 600°C. When the support material is silica, it is heated to at least about 200°C, preferably about 200°C to about 850°C, and most preferably at about 600°C; and for a time of about 1 minute to about 100 hours, from about 12 hours to about 72 hours, or from about 24 hours to about 60 hours. The calcined support material must have at least some reactive hydroxyl (OH) groups to produce supported catalyst systems of this disclosure. The calcined support material is then contacted with at least one polymerization catalyst system having at least one catalyst compound and an activator.

[0090] The support material, having reactive surface groups, typically hydroxyl groups, is slurried in a non-polar solvent and the resulting slurry is contacted with a solution of a catalyst compound and an activator. In some embodiments, the slurry of the support material is first contacted with the activator for a period of time in the range from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours. The solution of the catalyst compound is then contacted with the isolated support/activator. In some embodiments, the supported catalyst system is generated in situ. In alternate embodiment, the slurry of the support material is first contacted with the catalyst compound for a period of time in the range of from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours. The slurry of the supported catalyst compound is then contacted with the activator solution.

[0091] The mixture of the catalyst, activator and support is heated to about 0°C to about 70°C, preferably to about 23°C to about 60°C, preferably at room temperature. Contact times typically range from about 0.5 hours to about 24 hours, from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours.

[0092] Suitable non-polar solvents are materials in which all of the reactants used herein, i.e., the activator, and the catalyst compound, are at least partially soluble and which are liquid at reaction temperatures. Preferred non-polar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, although a variety of other materials including cycloalkanes, such as cyclohexane, aromatics, such as benzene, toluene, and ethylbenzene, may also be employed.

[0093] The catalyst precursor, activator, coactivator, if needed, suitable solvent, and support may be added in any order or simultaneously. Typically, the complex and activator may be combined in solvent to form a solution. Then the support is added, and the mixture is stirred for 1 minute to 10 hours. The total solution volume may be greater than the pore volume of the support, but some embodiments limit the total solution volume below that needed to form a gel or slurry (about 90% to about 400%, preferably about 100 to about 200% of the pore volume). After stirring, the residual solvent is removed under vacuum, typically at about ambient temperature and over about 10 to about 16 hours. But greater or lesser times and temperatures are possible.

[0094] The complex may also be supported absent the activator; in that case, the activator (and co-activator if needed) is added to a polymerization process’s liquid phase. Additionally, two or more different complexes may be placed on the same support. Likewise, two or more activators or an activator and co-activator may be placed on the same_support.

[0095] Suitable solid particle supports are typically comprised of polymeric or refractory oxide materials, each being preferably porous. Preferably any support material that has an average particle size greater than about 10 pm is suitable. Various embodiments include a porous support material, such as for example, talc, inorganic oxides, inorganic chlorides, for example, magnesium chloride and resinous support materials such as polystyrene polyolefin or polymeric compounds or any other organic support material. Some embodiments include inorganic oxide materials as the support material including Group -2, -3, -4, -5, -13, or -14 metal or metalloid oxides. Some embodiments include the catalyst support materials to include silica, alumina, silica-alumina, and their mixtures. Other inorganic oxides may serve either alone or in combination with the silica, alumina, or silica-alumina. These are magnesia, titania, or zirconia. Lewis acidic materials such as montmorillonite and similar clays may also serve as a support. In this case, the support can, optionally, double as the activator component, however, an additional activator may also be used.

[0096] The support material may be pretreated by any number of methods. For example, inorganic oxides may be calcined, chemically treated with dehydroxylating agents, such as aluminum alkyls, or both.

[0097] As stated above, polymeric carriers will also be suitable in accordance with the present disclosure, see for example the descriptions in WO 95/15815 and US 5,427,991. The methods disclosed may be used with the catalyst complexes, activators or catalyst systems of the present disclosure to adsorb or absorb them on the polymeric supports, particularly if made up of porous particles, or may be chemically bound through functional groups bound to or in the polymer chains.

[0098] Useful supports typically have a surface area of from about 10 to about 700 m²/g, a pore volume of about 0.1 to about 4.0 cc/g and an average particle size of about 10 to about 500 pm. Some embodiments include a surface area of about 50 to about 500 m²/g, a pore volume of 0.5-3.5 cc/g, or an average particle size of 10-200 pm. Other embodiments include a surface area of about 100 to about 400 m²/g, a pore volume of about 0.8 to about 3.0 cc/g, and an average particle size of about 50 to about 100 pm. Useful supports typically have a pore size of about 10 to about 1000 A, alternatively about 50 to about 500 A, or about 75 to about 350 A.

[0099] The catalyst complexes described herein are generally deposited on the support at a loading level of about 10 to about 100 micromoles of complex per gram of solid support; alternately about 20 to about 80 micromoles of complex per gram of solid support; or about 40 to about 60 micromoles of complex per gram of support. But greater or lesser values may be used provided that the total amount of solid complex does not exceed the support's pore volume.

[0100] In at least one embodiment, the support material comprises a support material treated with an electron-withdrawing anion. The support material can be silica, alumina, silica- alumina, silica-zirconia, alumina-zirconia, aluminum phosphate, heteropolytungstates, titania, magnesia, boria, zinc oxide, mixed oxides thereof, or mixtures thereof; and the electron- withdrawing anion is selected from fluoride, chloride, bromide, phosphate, triflate, bisulfate, sulfate, or any combination thereof.

[0101] The electron-withdrawing group used to treat the support material can be any component that increases the Lewis or Bronsted acidity of the support material upon treatment (as compared to the support material that is not treated with at least one electron-withdrawing anion). In at least one embodiment, the electron-withdrawing component is an electron- withdrawing anion derived from a salt, an acid, or other compound, such as a volatile organic compound, that serves as a source or precursor for that anion. Electron-withdrawing anions can be sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, phospho- tungstate, or mixtures thereof, or combinations thereof. An electron-withdrawing anion can be fluoride, chloride, bromide, phosphate, triflate, bisulfate, or sulfate, or any combination thereof, at least one embodiment of this disclosure. In at least one embodiment, the electron- withdrawing anion is sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, triflate, fluorozirconate, fluorotitanate, or combinations thereof.

[0102] Thus, for example, the support material suitable for use in the catalyst systems of the present disclosure can be one or more of fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica- alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or combinations thereof. In at least one embodiment, the activator-support can be, or can comprise, fluorided alumina, sulfated alumina, fluorided silica-alumina, sulfated silica-alumina, fluorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or combinations thereof. In at least one embodiment, the support material includes alumina treated with hexafluorotitanic acid, silica-coated alumina treated with hexafluorotitanic acid, silica-alumina treated with hexafluorozirconic acid, silica-alumina treated with trifluoroacetic acid, fluorided boria-alumina, silica treated with tetrafluoroboric acid, alumina treated with tetrafluoroboric acid, alumina treated with hexafluorophosphoric acid, or combinations thereof. Further, any of these activator-supports optionally can be treated with a metal ion.

[0103] Non-limiting examples of cations suitable for use in the present disclosure in the salt of the electron-withdrawing anion include ammonium, trialkyl ammonium, tetraalkyl ammonium, tetraalkyl phosphonium, H⁺, [H(OEt2)2]⁺, or combinations thereof.

[0104] Further, combinations of one or more different electron-withdrawing anions, in varying proportions, can be used to tailor the specific acidity of the support material to a desired level. Combinations of electron-withdrawing components can be contacted with the support material simultaneously or individually, and in any order that provides a desired chemically- treated support material acidity. For example, in at least one embodiment, two or more electron-withdrawing anion source compounds in two or more separate contacting steps.

[0105] In one embodiment of the present disclosure, one example of a process by which a chemically-treated support material is prepared is as follows: a selected support material, or combination of support materials, can be contacted with a first electron-withdrawing anion source compound to form a first mixture; such first mixture can be calcined and then contacted with a second electron-withdrawing anion source compound to form a second mixture; the second mixture can then be calcined to form a treated support material. In such a process, the first and second electron-withdrawing anion source compounds can be either the same or different compounds.

[0106] The method by which the oxide is contacted with the electron- withdrawing component, typically a salt or an acid of an electron-withdrawing anion, can include gelling, co-gelling, impregnation of one compound onto another, or combinations thereof. Following a contacting method, the contacted mixture of the support material, electron-withdrawing anion, and optional metal ion, can be calcined.

[0107] According to at least one embodiment of the present disclosure, the support material can be treated by a process comprising: (i) contacting a support material with a first electron- withdrawing anion source compound to form a first mixture; (ii) calcining the first mixture to produce a calcined first mixture; (iii) contacting the calcined first mixture with a second electron-withdrawing anion source compound to form a second mixture; and (iv) calcining the second mixture to form the treated support material.

Fluorided Support

[0108] In at least one embodiment, the electron-withdrawing component comprises fluorine. In an embodiment, a fluorided (also referred to as fluoridated) support is used for any catalyst system disclosed herein. The fluorided supports (such as fluorided silica) can be obtained through the addition of a solution of polar solvent (such as water) and fluorine compound (such as (NFU^SiFe) to a slurry of support (such as a toluene slurry of silica). This preparation method contributes to an even distribution of the fluoride compound (such as (NH4)2SiF6) onto the support surface (such as the silica surface), in contrast to a less homogeneous distribution observed when the solid salt is combined with the solid silica as described in US 2002/0123582 Al.

[0109] Fluorine compounds suitable for providing fluorine for the support may be organic or inorganic fluorine compounds and are desirably inorganic fluorine-containing compounds. Such inorganic fluorine-containing compounds may be any compound containing a fluorine atom as long as it does not contain a carbon atom. Particularly desirable are inorganic fluorine containing compounds are selected from the group consisting ofNFUBF^ (NH4)2SiF6, NH4PF6, NH₄F, (NH4)₂TaF₇, NH₄NbF4, ( B^GeFe, (NfB^SmFe, ( B^TiFe, ( B^ZrFe, MoFe, ReFe, GaF₃, SO2CIF, F₂, SiF₄, SFe, C1F₃, ClFs, BrFs, IFv, NF₃, HF, BF₃, NHF2, and NH4HF2. Of these, ammonium hexafluorosilicate and ammonium tetrafluoroborate are useful. Combinations of these compounds may also be used.

[0110] In an embodiment, an aqueous solution of fluorinating agent (such as (N]B)2SiF6) is added to a slurry of support (such as a toluene slurry of silica). Vigorous stirring of the mixture allows the dissolved fluorine compound (in water) to be evenly absorbed onto the hydrophilic support surface. After filtration, the wet support is allowed to air dry until it is free flowing, and then may be calcined (typically at temperatures over about l00°C for at least about 1 h).

[0111] In an embodiment, a solution of polar solvent and fluorinating agent (such as (NlB)2SiF6) is added to a slurry of support (such as a toluene slurry of silica). Vigorous stirring of the mixture allows the dissolved fluorine compound (in water) to be evenly absorbed onto the hydrophilic support surface. After filtration, the wet support is allowed to air dry until it is free flowing, and then may be calcined (typically at temperatures over about l00°C for at least about 1 h).

Activators

[0112] The terms“cocatalyst” and“activator” are used herein interchangeably and are defined to be any compound which can activate any one of the catalyst compounds described above by converting the neutral catalyst compound to a catalytically active catalyst compound cation.

[0113] After the complexes have been synthesized, catalyst systems may be formed by combining the complexes with activators in any suitable manner including by supporting them for use in slurry or gas phase polymerization. The catalyst systems may also be added to or generated in solution polymerization or bulk polymerization (in the monomer). The catalyst system typically includes a complex as described above and an activator such as alumoxane or a non-coordinating anion.

[0114] Non-limiting activators, for example, include alumoxanes, aluminum alkyls, ionizing activators, which may be neutral or ionic, and conventional-type cocatalysts. Preferred activators typically include alumoxane compounds, modified alumoxane compounds, and ionizing anion precursor compounds that abstract a reactive, s-bound, metal ligand making the metal complex cationic and providing a charge-balancing non-coordinating or weakly coordinating anion.

Alumoxane Activators

[0115] In an embodiment, alumoxane activators are utilized as an activator in the catalyst system. The alkylalumoxane may be used with another activator. Alumoxanes are generally oligomeric compounds containing -A^R^-O- sub-units, where R¹ is an alkyl group. Examples of alumoxanes include methylalumoxane (MAO), modified methylalumoxane (MMAO), ethylalumoxane, and isobutylalumoxane. Alkylalumoxanes and modified alkylalumoxanes are suitable as catalyst activators, particularly when the abstractable ligand is an alkyl, halide, alkoxide or amide. Mixtures of different alumoxanes and modified alumoxanes may also be used. It may be preferable to use a visually clear methylalumoxane. A cloudy or gelled alumoxane can be filtered to produce a clear solution or clear alumoxane can be decanted from the cloudy solution. A useful alumoxane is a modified methyl alumoxane (MMAO) cocatalyst type 3A (commercially available from Akzo Chemicals, Inc. under the trade name Modified Methylalumoxane type 3A, covered under US 5,041,584).

[0116] Another useful alumoxane is solid polymethylaluminoxane as described in US 9,340,630; US 8,404,880; and US 8,975,209. [0117] When the activator is an alumoxane (modified or unmodified), some embodiments include the maximum amount of activator typically at up to about a 5000-fold molar excess Al/M over the catalyst compound (per metal catalytic site). The minimum activator-to- catalyst-compound is about a 1 : 1 molar ratio. Alternate preferred ranges include from about 1: 1 to about 500: 1, alternately from about 1 : 1 to about 200: 1, alternately from about 1 : 1 to about 100: 1, or alternately from about 1 : 1 to about 50: 1. In an alternate embodiment, little or no alumoxane is used in the polymerization processes described herein. Preferably, alumoxane is present at about zero mole%, alternately the alumoxane is present at a molar ratio of aluminum to catalyst compound transition metal less than about 500: 1, preferably less than about 300: 1, preferably less than about 100: 1, preferably less than about 1: 1.

Non-Coordinating Anion Activators

[0118] A non-coordinating anion (NCA) is defined to mean an anion either that does not coordinate to the catalyst metal cation or that does coordinate to the metal cation, but only weakly. The term NCA is also defined to include multicomponent NCA-containing activators, such as

A-di methy 1 an i 1 i n i um tetrakis(pentafluorophenyl)borate, that contain an acidic cationic group and the non-coordinating anion. The term NCA is also defined to include neutral Lewis acids, such as tris(pentafluorophenyl)boron, that can react with a catalyst to form an activated species by abstraction of an anionic group. An NCA coordinates weakly enough that a neutral Lewis base, such as an olefinically or acetylenically unsaturated monomer can displace it from the catalyst center. Any metal or metalloid that can form a compatible, weakly coordinating complex may be used or contained in the non-coordinating anion. Suitable metals include aluminum, gold, and platinum. Suitable metalloids include boron, aluminum, phosphorus, and silicon. A stoichiometric activator can be either neutral or ionic. The terms ionic activator, and stoichiometric ionic activator can be used interchangeably. Likewise, the terms neutral stoichiometric activator, and Lewis acid activator can be used interchangeably. The term non-coordinating anion includes neutral stoichiometric activators, ionic stoichiometric activators, ionic activators, and Lewis acid activators.

[0119] “Compatible” non-coordinating anions can be those which are not degraded to neutrality when the initially formed complex decomposes, and the anion does not transfer an anionic substituent or fragment to the cation so as to cause it to form a neutral transition metal compound and a neutral by-product from the anion. Non-coordinating anions useful in accordance with this present disclosure are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet retain sufficient lability to permit displacement during polymerization. [0120] It is within the scope of the present disclosure to use an ionizing activator, neutral or ionic, such as tri(n-butyl) ammonium tetrakis(pentafluorophenyl)borate, a tris perfluorophenyl boron metalloid precursor or a tris perfluoronaphthyl boron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (US 5,942,459), or combination thereof. It is also within the scope of the present disclosure to use neutral or ionic activators alone or in combination with alumoxane or modified alumoxane activators.

[0121] The catalyst systems of the present disclosure can include at least one non coordinating anion (NCA) activator.

[0122] In a preferred embodiment, boron containing NCA activators represented by the formula below can be used:

Zd⁺ (A^d ),

where: Z is (L-H) or a reducible Lewis acid; L is a neutral Lewis base; H is hydrogen; (L-H)⁺ is a Bronsted acid; A^d is a non-coordinating anion, for example a boron containing non coordinating anion having the charge d-; and d is 1, 2, or 3.

[0123] The cation component, Zd⁺ may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety, such as an alkyl or aryl, from the bulky ligand containing transition metal catalyst precursor, resulting in a cationic transition metal species.

[0124] The activating cation Zd⁺ may also be a moiety such as silver, tropylium, carboniums, ferroceniums and mixtures, preferably carboniums and ferroceniums. Most preferably Zd⁺ is triphenyl carbonium. Preferred reducible Lewis acids can be any triaryl carbonium (where the aryl can be substituted or unsubstituted, such as those represented by the formula: (AnC '). where Ar is Ar is aryl substituted with a Ci to C40 hydrocarbyl or with a substituted Ci to C40 hydrocarbyl, or a heteroaryl substituted with a Ci to C40 hydrocarbyl, or with a substituted Ci to C40 hydrocarbyl; preferably the reducible Lewis acids in“Z” include those represented by the formula: (Ph3C), where Ph is a substituted or unsubstituted phenyl, preferably substituted with Ci to C40 hydrocarbyls or substituted a Ci to C40 hydrocarbyls, preferably Ci to C20 alkyls or aromatics or substituted Ci to C20 alkyls or aromatics, preferably Z is a triphenylcarbonium.

[0125] When Zd⁺ is the activating cation (L-H)d⁺, it is preferably a Bronsted acid, capable of donating a proton to the transition metal catalytic precursor resulting in a transition metal cation, including ammoniums, oxoniums, phosphoniums, silyliums, and mixtures thereof, preferably ammoniums of methylamine, aniline, dimethylamine, diethylamine, N- methylanibne, diphenylamine, trimethylamine, triethylamine, N A-di methy 1 an i 1 i n e. methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline, p-nitro-/V,/V-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers such as dimethyl ether diethyl ether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethyl thioethers, tetrahydrothiophene, and mixtures thereof.

[0126] The anion component A^d includes those having the formula [M^k+Q_n]^d wherein k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4); n - k = d; M is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum, and Q is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halosubstituted- hydrocarbyl radicals, said Q having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is Q a halide. Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably each Q is a fluorinated aryl group, and most preferably each Q is a pentafluoryl aryl group. Examples of suitable A^d also include diboron compounds as disclosed in US 5,447,895, which is fully incorporated herein by reference.

[0127] Examples of boron compounds which may be used as an activating cocatalyst include the compounds described as (and particularly those specifically listed as) activators in US 8,658,556, which is incorporated by reference herein.

[0128] Bulky activators are also useful herein as NCAs. “Bulky activator” as used herein refers to anionic activators represented by the formula:

wherein:

each R¹ is, independently, a halide, preferably a fluoride,

Ar is a substituted or unsubstituted aryl group (preferably a substituted or unsubstituted phenyl), preferably substituted with Ci to C40 hydrocarbyls, preferably Ci to C20 alkyls or aromatics,

each R² is, independently, a halide, a G, to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R^a, where R^a is a Ci to C20 hydrocarbyl or hydrocarbylsilyl group (preferably R² is a fluoride or a perfluorinated phenyl group),

each R³ is a halide, Ce to C20 substituted aromatic hydrocarbyl group or a siloxy group of the formula -0-Si-R^a, where R^a is a Ci to C20 hydrocarbyl or hydrocarbylsilyl group

(preferably R³ is a fluoride or a Ce perfluorinated aromatic hydrocarbyl group); wherein R² and R³ can form one or more saturated or unsaturated, substituted or unsubstituted rings (preferably R² and R³ form a perfluorinated phenyl ring), and

L is a neutral Lewis base; (L-H)⁺is a Bronsted acid; d is 1, 2, or 3,

wherein the anion has a molecular weight of greater than 1020 g/mol, and

wherein at least three of the substituents on the B atom each have a molecular volume of greater than 250 cubic A, alternately greater than 300 cubic A, or alternately greater than 500 cubic A.

[0129] Preferably (Ar3C)d⁺ is (Ph3C)d⁺, where Ph is a substituted or unsubstituted phenyl, preferably substituted with Ci to C40 hydrocarbyls or substituted Ci to C40 hydrocarbyls, preferably Ci to C20 alkyls or aromatics or substituted Ci to C20 alkyls or aromatics.

[0130] “Molecular volume” is used herein as an approximation of spatial steric bulk of an activator molecule in solution. Comparison of substituents with differing molecular volumes allows the substituent with the smaller molecular volume to be considered“less bulky” in comparison to the substituent with the larger molecular volume. Conversely, a substituent with a larger molecular volume may be considered“more bulky” than a substituent with a smaller molecular volume.

[0131] Molecular volume may be calculated as reported in“A Simple‘Back of the Envelope’ Method for Estimating the Densities and Molecular Volumes of Liquids and Solids,” Journal of Chemical Education, Vol. 71, No. 11, November 1994, pp. 962-964. Molecular volume (MV), in units of cubic A, is calculated using the formula: MV = 8.3Vs, where Vs is the scaled volume. Vs is the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent using the following table of relative volumes. For fused rings, the Vs is decreased by 7.5% per fused ring.

[0132] For a list of particularly useful Bulky activators as described in US 8,658,556, which is incorporated by reference herein.

[0133] In at least one embodiment, one or more of the NCA activators is chosen from the activators described in US 6,211,105. [0134] Preferred activators include N, yV-di methyl an i 1 i n i um tetrakis(perfluoronaphthyl)borate, N, yV-di methy land ini um tetrakis(perfluorophenyl)borate, triphenylcarbenium tetrakis(perfluorophenyl)borate, [Ph3C⁺] | B(C\,F 5)4 | ,

[Me3NH⁺] [B(C6F5)4 ], l-(4-(tris(pentafluorophenyl)borate)-2, 3,5,6- tetrafluorophenyl)pyrrolidinium, 4-(tris(pentafluorophenyl)borate)-2, 3,5,6- tetrafluoropyridine.

[0135] In a preferred embodiment, the activator includes a triaryl carbonium (such as triphenylcarbenium tetraphenylborate, triphenylcarbenium tetrakis(pentafluorophenyl)borate, triphenylcarbenium tetrakis-(2, 3,4, 6-tetrafluorophenyl)borate.

[0136] In at least one embodiment, the activator includes one or more of trialky lammonium tetrakis(pentafluorophenyl)borate, /V, ,V-di al ky 1 an i 1 i n i um tetrakis(pentafluorophenyl)borate, iV, iV-di methyl-(2.4.6-tri methy land ini um) tetrakis(pentafluorophenyl)borate, trialkylammonium tetrakis-(2,3,4,6-tetrafluorophenyl)borate, yV, ,V-di al ky l an i 1 i n i u m tetrakis- (2,3,4,6-tetrafluorophenyl)borate, trialkylammonium tetrakis(perfluoronaphthyl)borate, N,N- dialkylanibnium tetrakis(perfluoronaphthyl)borate, trialkylammonium tetrakis(perfluorobiphenyl)borate, N, ,V-di al kyl an i 1 i ni um tetrakis(perfluorobiphenyl)borate, trialkylammonium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, /V, /V- d i al k y 1 an i 1 i n i u m tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, /V,/V-dialkyl-(2.4.6-tri methy land ini um) tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, (where alkyl is methyl, ethyl, propyl, «-butyl, iso-butyl, or /-butyl).

[0137] Most preferably, the ionic activator Zd⁺ (A^d ) is one or more of N,N- dimethylanibnium tetra(perfluorophenyl)borate, N, /V-di methy 1 an i 1 i n i um tetrakis(perfluoronaphthyl)borate, di(hydrogenated tallow)methylammonium tetra(perfluorophenyl)borate, di(hydrogenated tallow)methylammonium tetrakis(perfluoronaphthyl)borate, N, yV-di methy 1 an i li n i um tetrakis(perfluorobiphenyl)borate, N, yV-di methy 1 an i 1 i n i um tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetrakis(perfluoronaphthyl)borate, triphenylcarbenium tetrakis(perfluorobiphenyl)borate, triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, triphenylcarbenium tetra(perfluorophenyl)borate, trimethylammonium tetrakis(perfluoronaphthyl)borate, triethylammonium tetrakis(perfluoronaphthyl)borate, tripropylammonium tetrakis(perfluoronaphthyl)borate, tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate, tri(/-butyl)ammonium tetrakis(perfluoronaphthyl)borate, N, yV-di ethyl ani 1 i n i um tetrakis(perfluoronaphthyl)borate, /V,/V-dimethyl-(2.4/-trimethylanilinium) tetrakis(perfluoronaphthyl)borate, and tropilbum tetrakis(perfluoronaphthyl)borate.

[0138] The typical activator-to-catalyst ratio, e.g., all NCA activators-to-catalyst ratio is about a 1: 1 molar ratio. Alternate preferred ranges include from about 0.1 : 1 to about 100: 1, alternately from about 0.5: 1 to about 200: 1, alternately from about 1 : 1 to about 500: 1, alternately from about 1 : 1 to about 1000: 1. A particularly useful range is from about 0.5: 1 to about 10: 1, preferably about 1 : 1 to about 5: 1.

[0139] It is also within the scope of the present disclosure that the catalyst compounds can be combined with combinations of alumoxanes and NCA’s (see for example, US 5,153,157, US 5,453,410, EP 0 573 120 Bl, WO 94/07928, and WO 95/14044 which discuss the use of an alumoxane in combination with an ionizing activator).

Optional Scavengers or Co-Activators

[0140] In addition to these activator compounds, one or more scavengers or co-activators may be used in the catalyst system. Aluminum alkyl or organoaluminum compounds which may be utilized as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, and diethyl zinc. Those scavenging compounds having bulky or C6-C20 linear hydrocarbyl substituents connected to the metal or metalloid center usually minimize adverse interaction with the active catalyst. Examples include triethylaluminum, but more preferably, bulky compounds such as tri-iso-butyl aluminum, tri-iso-prenyl aluminum, and long-chain linear alkyl-substituted aluminum compounds, such as tri-n-hexyl aluminum, tri-n-octyl aluminum, or tri-n-dodecyl aluminum. When alumoxane is used as the activator, any excess over that needed for activation will scavenge impurities and additional scavenging compounds may be unnecessary. Alumoxanes also may be added in scavenging quantities with other activators, e.g., methylalumoxane, [Me2HNPh]⁺[B(pfp)4]- or B(pfp)3 (perfluorophenyl = pfp = C6F5). In an embodiment, the scavengers are present at less than about 14 wt%, or from about 0.1 to about 10 wt%, or from about 0.5 to about 7 wt%, by weight of the catalyst system.

[0141] Suitable aluminum alkyl or organoaluminum compounds which may be utilized as co-activators include, for example, trimethylaluminum, triethylaluminum, tri-iso- butylaluminum, tri-n-hexylaluminum, or tri-n-octylaluminum. In an embodiment, the co activators are present at less than about 14 wt%, or from about 0.1 to about 10 wt%, or from about 0.5 to about 7 wt%, by weight of the catalyst system. Alternately, the complex-to-co- activator molar ratio is from about 1 : 100 to about 100: 1; about 1 :75 to about 75: 1; about 1:50 to about 50: 1; about 1 :25 to about 25: 1; about 1: 15 to about 15: 1; about 1: 10 to about 10: 1; about 1 :5 to about 5: 1; about 1 :2 to about 2: 1; about 1 :100 to about 1: 1; about 1 :75 to about 1: 1; about 1 :50 to about 1 : 1; about 1 :25 to about 1 : 1; about 1 : 15 to about 1 : 1; about 1 : 10 to about 1: 1; about 1:5 to about 1 : 1; about 1 :2 to about 1 :1; about 1 : 10 to about 2: 1.

Polymerization Processes

[0142] The supported catalysts described herein are useful in polymerizing unsaturated monomers conventionally known to undergo metallocene-catalyzed polymerization such as solution, slurry, gas-phase, and high-pressure polymerization. Typically one or more of the supported catalysts described herein, one or more activators, and one or more monomers are contacted to produce polymer. In certain embodiments, the complexes may be supported and as such will be particularly useful in the known, fixed-bed, moving-bed, fluid-bed, slurry, solution, or bulk operating modes conducted in single, series, or parallel reactors.

[0143] One or more reactors in series or in parallel may be used. The complexes, activator and when required, co-activator, may be delivered as a solution or slurry, either separately to the reactor, activated in-line just prior to the reactor, or preactivated and pumped as an activated solution or slurry to the reactor. Polymerizations are carried out in either single reactor operation, in which monomer, comonomers, catalyst/activator/co-activator, optional scavenger, and optional modifiers are added continuously to a single reactor or in series reactor operation, in which the above components are added to each of two or more reactors connected in series. The catalyst components can be added to the first reactor in the series. The catalyst component may also be added to both reactors, with one component being added to a first reactor and another component to other reactors. In one preferred embodiment, the complex is activated in the reactor in the presence of olefin.

[0144] In a particularly preferred embodiment, the polymerization process is a continuous process.

[0145] In some embodiments, the activity of the catalyst when the polymerization process is performed with about 0 ppm H₂ is at least about 5 kgmof'h ¹. preferably about 20 or more kgmof'h ¹. preferably about 50 or more kgmof'h ¹. preferably about 500 or more kgmol ¹h ¹, preferably about 5,000 or more kgmoHh ¹. The activity of the catalyst when the polymerization process is performed with about 300 ppm H₂ is at least about 5 kgmol ¹h ¹, preferably about 20 or more kgmol ¹h ¹, preferably about 50 or more kgmoHh ¹, preferably about 500 or more kgmol ¹h ¹, preferably about 5,000 or more kgmol ¹h ¹. In an alternate embodiment, the conversion of olefin monomer is at least about 10%, based upon polymer yield and the weight of the monomer entering the reaction zone, preferably about 20% or more, preferably about 30% or more. [0146] In some embodiments, a method of polymerizing olefins to produce at least one polyolefin composition is provided. The method includes contacting at least one olefin with any catalyst system of the present disclosure; and obtaining a polyolefin. If an activator(s) is used, the catalyst compounds and activator(s) may be combined in any order, and are combined typically prior to contacting with the monomer (such as ethylene).

[0147] Polymerization may be homogeneous (solution or bulk polymerization) or heterogeneous (slurry - in - liquid diluent, or gas phase - in - gaseous diluent). In the case of heterogeneous slurry or gas phase polymerization, the complex and activator may be supported. Supports useful herein are described above. Chain transfer agents may also be used herein.

[0148] The present polymerization processes may be conducted under conditions preferably including a temperature of 0°C to about 300°C, preferably about 30°C to about 200°C, preferably about 60°C to about l95°C, preferably from about 75°C to about l90°C.

[0149] Monomers useful herein include substituted or unsubstituted C2 to C40 alpha olefins, preferably C2 to C20 alpha olefins, preferably C2 to C12 alpha olefins, preferably ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene and isomers thereof, and mixtures thereof. In a preferred embodiment of the present disclosure, the monomer includes propylene and an optional comonomer comprising one or more ethylene or C4 to C40 olefins, preferably C4 to C20 olefins, or preferably G, to C 12 olefins. The C4 to C40 olefin monomers may be linear, branched, or cyclic. The C4 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups. In another preferred embodiment, the monomer includes ethylene and an optional comonomer comprising one or more C3 to C40 olefins, preferably C4 to C20 olefins, or preferably G, to C 12 olefins. The C3 to C40 olefin monomers may be linear, branched, or cyclic. The C3 to C40 cyclic olefins may be strained or unstrained, monocyclic or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.

[0150] Exemplary C2 to C40 olefin monomers and optional comonomers include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbomene, norbomadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbomene, 7-oxanorbomadiene, substituted derivatives thereof, and isomers thereof, preferably hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, l,5-cyclooctadiene, 1 -hydroxy -4-cyclooctene, l-acetoxy-4-cyclooctene, 5- methylcyclopentene, cyclopentene, dicyclopentadiene, norbomene, norbomadiene, and their respective homologs and derivatives, preferably norbomene, norbomadiene, and dicyclopentadiene. [0151] In a preferred embodiment one or more dienes are present in the polymer produced herein at up to about 10 wt%, preferably at about 0.00001 to about 1.0 wt%, preferably about 0.002 to about 0.5 wt%, even more preferably about 0.003 to about 0.2 wt%, based upon the total weight of the composition. In some embodiments about 500 ppm or less of diene is added to the polymerization, preferably about 400 ppm or less, preferably about 300 ppm or less. In other embodiments at least about 50 ppm of diene is added to the polymerization, or about 100 ppm or more, or about 150 ppm or more.

[0152] Preferred diolefm monomers useful in the present disclosure include any hydrocarbon structure, preferably Cr to C30, having at least two unsaturated bonds, wherein at least two of the unsaturated bonds are readily incorporated into a polymer by either a stereospecific or a non-stereospecific catalyst(s). It is further preferred that the diolefm monomers be selected from alpha, omega-diene monomers (i.e. di-vinyl monomers). More preferably, the diolefm monomers are linear di-vinyl monomers, most preferably those containing from 4 to 30 carbon atoms. Examples of preferred dienes include butadiene, pentadiene, hexadiene, heptadiene, octadiene, nonadiene, decadiene, undecadiene, dodecadiene, tridecadiene, tetradecadiene, pentadecadiene, hexadecadiene, heptadecadiene, octadecadiene, nonadecadiene, icosadiene, heneicosadiene, docosadiene, tricosadiene, tetracosadiene, pentacosadiene, hexacosadiene, heptacosadiene, octacosadiene, nonacosadiene, triacontadiene, particularly preferred dienes include l,6-heptadiene, 1,7- octadiene, 1,8 -nonadiene, l,9-decadiene, l,l0-undecadiene, 1,11 -dodecadiene, 1,12- tri decadiene, 1,13 -tetradecadiene, and low molecular weight poly butadienes (Mw less than 1000 g/mol). Preferred cyclic dienes include cyclopentadiene, vinylnorbomene, norbomadiene, ethylidene norbomene, divinylbenzene, dicyclopentadiene or higher ring containing diolefms with or without substituents at various ring positions.

[0153] Most preferred olefins for the methods of polymerizing olefins described herein include ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, 5 -ethylidene-2 -norbomene (ENB), dicyclopentadiene (DCPD), vinyl norbomene (VNB), or mixtures thereof.

[0154] Polymerization processes of the present disclosure can be carried out in any suitable manner known in the art. Any suspension, homogeneous, bulk, solution, slurry, or gas phase polymerization process known in the art can be used. Such processes can be run in a batch, semi-batch, or continuous mode. Homogeneous polymerization processes and slurry processes are preferred. (A homogeneous polymerization process is defined to be a process where at least about 90 wt% of the product is soluble in the reaction media.) A bulk homogeneous process is particularly preferred. (A bulk process is defined to be a process where monomer concentration in all feeds to the reactor is about 70 vol% or more.) Alternately, no solvent or diluent is present or added in the reaction medium, (except for the small amounts used as the carrier for the catalyst system or other additives, or amounts typically found with the monomer; e.g., propane in propylene). According to an embodiment, a method of polymerizing olefins to produce at least one polyolefin composition includes contacting at least one olefin with a catalyst system of the present disclosure; and obtaining a polyolefin. A method of polymerizing olefins can include introducing any catalyst system described herein into a reactor as a slurry.

[0155] Suitable diluents/solvents for polymerization include non-coordinating, inert liquids. Examples include straight and branched-chain hydrocarbons, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as can be found commercially (Isopar™); perhalogenated hydrocarbons, such as perfluorinated C4-C10 alkanes, chlorobenzene, and aromatic and alkylsubstituted aromatic compounds, such as benzene, toluene, mesitylene, and xylene. Suitable solvents also include liquid olefins which may act as monomers or comonomers including ethylene, propylene, 1 -butene, 1 -hexene, l-pentene, 3- methyl-l-pentene, 4-methyl- l-pentene, l-octene, l-decene, and mixtures thereof. In a preferred embodiment, aliphatic hydrocarbon solvents are used as the solvent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In at least one embodiment, the solvent is not aromatic, preferably aromatics are present in the solvent at less than about 1 wt%, preferably less than about 0.5 wt%, preferably less than about 0 wt% based upon the weight of the solvents.

[0156] In a preferred embodiment, the feed concentration of the monomers and comonomers for the polymerization is about 60 vol% solvent or less, preferably about 40 vol% or less, or preferably about 20 vol% or less, based on the total volume of the feedstream. Preferably the polymerization is run in a bulk process.

[0157] Preferred polymerizations can be run at any temperature and/or pressure suitable to obtain the desired ethylene polymers. Typical temperatures and/or pressures include a temperature in the range of from about 0°C to about 300°C, preferably about 30°C to about 200°C, preferably about 60°C to about l95°C, preferably from about 75°C to about l90°C; and at a pressure in the range of from about 0.35 MPa to about 1500 MPa, preferably from about 0.45 MPa to about 100 MPa, preferably from about 0.5 MPa to about 50 MPa, or preferably from about 1.7 MPa to about 30 MPa. In a typical polymerization, the run time of the reaction is up to about 300 minutes, preferably in the range of from about 5 to about 250 minutes, preferably from about 10 to about 120 minutes, or preferably in the range of from about 15 to about 30 minutes.

[0158] In some embodiments, hydrogen is present in the polymerization reactor at a partial pressure of about 0.001 to about 50 psig (about 0.007 to about 345 kPa), preferably from about 0.01 to about 25 psig (about 0.07 to about 172 kPa), more preferably about 0.1 to about 10 psig (about 0.7 to about 70 kPa).

[0159] In a preferred embodiment, little or no alumoxane is used in the process to produce the polymers. Preferably, alumoxane is present at about zero mol%, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than about 500: 1, preferably less than about 300: 1, preferably less than about 100: 1, preferably less than about 1: 1.

[0160] In a preferred embodiment, little or no scavenger is used in the process to produce the ethylene polymer. Preferably, scavenger (such as tri alkyl aluminum) is present at about zero mol%, alternately the scavenger is present at a molar ratio of scavenger metal to transition metal of less than about 100: 1, preferably less than about 50: 1, preferably less than about 15: 1, preferably less than about 10: 1.

[0161] In a preferred embodiment, the polymerization: 1) is conducted at temperatures of about 0 to about 300°C (preferably about 25 to about l50°C, preferably about 80 to about l50°C, preferably about 100 to about l40°C); 2) is conducted at a pressure of atmospheric pressure to about 50 MPa; 3) is conducted in an aliphatic hydrocarbon solvent (such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and abcycbc hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof; preferably where aromatics are preferably present in the solvent at less than about 1 wt%, preferably less than about 0.5 wt%, preferably at about 0 wt% based upon the weight of the solvents); 4) wherein the catalyst system used in the polymerization includes less than about 0.5 mol%, preferably about 0 mol% alumoxane, alternately the alumoxane is present at a molar ratio of aluminum to transition metal less than about 500: 1, preferably less than about 300:1, preferably less than about 100: 1, preferably less than about 1: 1; 5) the polymerization preferably occurs in one reaction zone. Preferably, the polymerization uses a single reactor. Room temperature is about 23°C unless otherwise noted. [0162] Other additives may also be used in the polymerization, as desired, such as one or more scavengers, promoters, modifiers, hydrogen, chain transfer agents (including Zinc and aluminum-based chain transfer agents such as diethyl zinc), reducing agents, oxidizing agents, hydrogen, aluminum alkyls, or silanes.

[0163] Useful chain transfer agents are typically trialkylaluminums and dialkylzincs, which are represented by the formulas AIR3 and ZnFU (where each R is, independently, a Ci- C8 aliphatic radical, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.

Solution Polymerization

[0164] A solution polymerization is a polymerization process in which the polymer is dissolved in a liquid polymerization medium, such as an inert solvent or monomer(s) or their blends. A solution polymerization is typically homogeneous. A homogeneous polymerization is one where the polymer product is dissolved in the polymerization medium. Such systems are preferably not turbid as described in J. Vladimir Oliveira, C. Dariva and J. C. Pinto, Ind. Eng, Chem. Res. 29, 2000, 4627. Generally solution polymerization involves polymerization in a continuous reactor in which the polymer formed and the starting monomer and catalyst materials supplied, are agitated to reduce or avoid concentration gradients and in which the monomer acts as a diluent or solvent or in which a hydrocarbon is used as a diluent or solvent. Suitable processes typically operate at temperatures from about 0°C to about 250°C, preferably from about l0°C to about l50°C and at pressures of about 0.1 MPa or more, preferably about 2 MPa or more. The upper pressure limit is typically about 200 MPa or less, preferably, about 120 MPa or less. Temperature control in the reactor can generally be obtained by balancing the heat of polymerization and with reactor cooling by reactor jackets or cooling coils to cool the contents of the reactor, auto refrigeration, pre-chilled feeds, vaporization of liquid medium (diluent, monomers or solvent) or combinations of all three. Adiabatic reactors with pre-chilled feeds can also be used. The purity, type, and amount of solvent can be optimized for the maximum catalyst productivity for a particular type of polymerization. The solvent can also be introduced as a catalyst carrier. The solvent can be introduced as a gas phase or as a liquid phase depending on the pressure and temperature. Advantageously, the solvent can be kept in the liquid phase and introduced as a liquid. Solvent can be introduced in the feed to the polymerization reactors. Polyolefin Products

[0165] This disclosure also relates to compositions of matter produced by the methods described herein. In a preferred embodiment, the catalyst systems and methods herein produce polyolefins.

[0166] In an embodiment, an ethylene, alpha-olefin copolymer is obtained by contacting ethylene and at least one alpha olefin with any catalyst system of the present disclosure.

[0167] The activity of the catalyst when the polymerization process is performed with about 0 ppm Tk is at least about 5 kgmoP'h ¹. preferably about 20 or more kgmoP'h ¹. preferably about 50 or more kgmoP'h ¹. preferably about 500 or more kgmol ¹h ¹, preferably about 5,000 or more kgmol ¹h ¹. The activity of the catalyst when the polymerization process is performed with about 300 ppmkk is at least about 5 kgmol ¹h ¹, preferably about 20 or more kgmol ¹h ¹, preferably about 50 or more kgmol ¹h ¹, preferably about 500 or more kgmol ¹h ¹, preferably about 5,000 or more kgmol ¹h ¹. In an alternate embodiment, the conversion of olefin monomer is at least about 10%, based upon polymer yield and the weight of the monomer entering the reaction zone, preferably about 20% or more, preferably about 30% or more.

[0168] The copolymer products produced by the present process, when run at about 0 ppm Tk, have an Mw of about 5,000 to about 2,500,000 g/mol, as determined by GPC. The copolymer products produced by the present process (when run at about 300 ppm Tk) may have an Mw of about 5,000 to about 2,500,000 g/mol, as determined by GPC.

[0169] When the process is run at about 0 ppm Tk, the comonomer(s) (i.e., C6) are present at up to about 20 mol%. When the process is run at about 300 ppm Tk, the comonomer(s) (i.e., C6) are present at up to about 20 mol%.

[0170] In some embodiments herein, a multimodal polyolefin composition is produced, comprising a first polyolefin component and at least another polyolefin component, different from the first polyolefin component by molecular weight, preferably such that the GPC trace has more than one peak or inflection point.

[0171] In some embodiments herein, a multimodal polyolefin composition is produced, having a first polyolefin component and at least another polyolefin component, different from the first polyolefin component by molecular weight, preferably such that the GPC trace has more than one peak or inflection point.

[0172] The term“multimodal,” when used to describe a polymer or polymer composition, means“multimodal molecular weight distribution,” which is understood to mean that the Gel Permeation Chromatography (GPC) trace, plotted as Absorbance versus Retention Time (seconds), has more than one peak or at least one inflection point. An“inflection point” is that point where the second derivative of the curve changes in sign (e.g., from negative to positive or vice versa). For example, a polyolefin composition that includes a first lower molecular weight polymer component (such as a polymer having an Mw of about 100,000 g/mol) and a second higher molecular weight polymer component (such as a polymer having an Mw of about 300,000 g/mol) is considered to be a“bimodal” polyolefin composition.

[0173] In a preferred embodiment, and when the process is run at about 0 ppm Fh, the polymer produced has a PDI of from about 1 to about 40, preferably from about 1 to about 20, preferably from about 1 to about 10, preferably about 1 to about 5.

[0174] In a preferred embodiment, and when the process is run at about 300 ppm Fh, the polymer produced has a PDI of from about 1 to about 40, preferably from about 1 to about 20, preferably from about 1 to about 10, preferably about 1 to about 5.

[0175] In a preferred embodiment, and when the process is run at about 0 ppm Fh, the polymer produced has a Tm of from about 50 to about l35°C, preferably from about 80 to about l35°C, preferably about 90 to about l35°C.

[0176] In a preferred embodiment, and when the process is run at about 300 ppm Fh, the polymer produced has a Tm of from about 50 to about l35°C, preferably from about 80 to about l35°C, preferably about 90 to about l35°C.

[0177] Unless otherwise indicated, measurements of the moments of molecular weight, i.e., weight average molecular weight (Mw), number average molecular weight (Mn), and z average molecular weight (Mz) are determined by Gel Permeation Chromatography (GPC) as described in Macromolecules, 2001, Vol. 34, No. 19, pg. 6812, which is fully incorporated herein by reference, including that, a High Temperature Size Exclusion Chromatograph (SEC, Waters Alliance 2000), equipped with a differential refractive index detector (DRI) equipped with three Polymer Laboratories PLgel 10 mm Mixed-B columns is used. The instrument is operated with a flow rate of about 1.0 cmVmin, and an injection volume of about 300 pL. The various transfer lines, columns, and differential refractometer (the DRI detector) are housed in an oven maintained at about l45°C. Polymer solutions are prepared by heating about 0.75 to about 1.5 mg/mL of polymer in filtered 1 ,2, 4-tri chlorobenzene (TCB) containing -1000 ppm of butylated hydroxy toluene (BHT) at about l60°C for about 2 hours with continuous agitation. A sample of the polymer containing solution is injected into to the GPC and eluted using filtered 1,2, 4-tri chlorobenzene (TCB) containing -1000 ppm of BHT. The separation efficiency of the column set is calibrated using a series of narrow MWD polystyrene standards reflecting the expected Mw range of the sample being analyzed and the exclusion limits of the column set. Seventeen individual polystyrene standards, obtained from Polymer Laboratories (Amherst, MA) and ranging from Peak Molecular Weight (Mp) -580 to 10,000,000, were used to generate the calibration curve. The flow rate is calibrated for each run to give a common peak position for a flow rate marker (taken to be the positive inject peak) before determining the retention volume for each polystyrene standard. The flow marker peak position is used to correct the flow rate when analyzing samples. A calibration curve (log(Mp) vs. retention volume) is generated by recording the retention volume at the peak in the DRI signal for each PS standard, and fitting this data set to a 2nd-order polynomial. The equivalent polyethylene molecular weights are determined by using the Mark-Houwink coefficients shown in Table A.

Table A

[0178] In at least some embodiments, the polymer produced is a tactic polymer, preferably an isotactic or highly isotactic polymer. In at least some embodiments, the polymer produced is isotactic polypropylene, such as highly isotactic polypropylene.

[0179] The term“isotactic polypropylene” (iPP) is defined as having at least about 10% or more isotactic pentads. The term“highly isotactic polypropylene” is defined as having about 50% or more isotactic pentads. The term“syndiotactic polypropylene” is defined as having about 10% or more syndiotactic pentads. The term“random copolymer polypropylene” (RCP), also called propylene random copolymer, is defined to be a copolymer of propylene and about 1 to about 10 wt% of an olefin chosen from ethylene and Cr to Cx alpha-olefins. Preferably, isotactic polymers (such as iPP) have at least about 20% (preferably at least about 30%, preferably at least about 40%) isotactic pentads. A polyolefin is“atactic,” also referred to as “amorphous” if it has less than about 10% isotactic pentads and syndiotactic pentads.

[0180] Polypropylene microstructure is determined by ¹³C NMR spectroscopy, including the concentration of isotactic and syndiotactic diads ([m] and [r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]). The designation“m” or“r” describes the stereochemistry of pairs of contiguous propylene groups,“m” referring to meso and“r” to racemic. Samples are dissolved in d2-l,l,2,2-tetrachloroethane, and spectra recorded at l25°C using a 100 MHz (or higher) NMR spectrometer. Polymer resonance peaks are referenced to mmmm = 21.8 ppm. Calculations involved in the characterization of polymers by NMR are described by F. A. Bovey in POLYMER CONFORMATION AND CONFIGURATION (Academic Press, New York 1969) and J. Randall in POLYMER SEQUENCE DETERMINATION, ¹³C-NMR METHOD (Academic Press, New York, 1977).

End Uses

[0181] Articles made using polymers produced herein may include, for example, molded articles (such as containers and bottles, e.g., household containers, industrial chemical containers, personal care bottles, medical containers, fuel tanks, and storage ware, toys, sheets, pipes, tubing) films, and non-wovens. It should be appreciated that the list of applications above is merely exemplary, and is not intended to be limiting.

EXAMPLES

[0182] It is to be understood that while the invention has been described in conjunction with the specific embodiments thereof, the foregoing description is intended to illustrate and not limit the scope of the invention. Other aspects, advantages and modifications will be apparent to those skilled in the art to which the invention pertains.

[0183] Therefore, the following examples are put forth so as to provide those skilled in the art with a complete disclosure and description and are not intended to limit the scope of that which the inventors regard as their invention.

Synthesis of Catalyst A and Catalyst B

[0184] 9-(2-(Allylo\y)-5-methylphenyl)-9//-carba/ole (10). Allyl bromide (19 mL, 220 mmol, l.2 equiv) was added to a solution of compound 2-(9//-carbazol-9-yl)-4- methylphenol (50.0 g, 183 mmol, 1 equiv) and anhydrous potassium carbonate (K2CO3) (50.6 g, 366 mmol, 2 equiv) in acetone (1 L). After refluxing overnight, the reaction was cooled to room temperature, and filtered, washing the filter cake with acetone (500 mL). The filtrate was concentrated under reduced pressure to give compound 10 (53.6 g, 94% yield) as an off white solid which was used subsequently.

[0185] 2-Allyl-6-(9i/-carbazol-9-yl)-4-methylphenol (11). Compound 10 (53.6 g,

171 mmol, 1 equiv) was dissolved in l,2-di chlorobenzene (186 mL) in a 500 mL sealed glass pressure vessel and heated to l80°C for 6 days. The solution was purified over silica gel (1 kg) eluting with a gradient of 0 to 50% toluene in heptanes to give compound 11 (47.4 g, 88% yield) as a tan oil that slowly solidified.

[0186] 9-(3-Allyl-2-metho\y-5-methylphenyl)-9//-carbazole (12). Iodomethane (Mel)

(3.0 mL, 48.8 mmol, 1.5 equiv) was added to a solution of compound 11 (10.2 g, 32.5 mmol, 1 equiv) and anhydrous potassium carbonate (6.7 g, 48.8 mmol, 1.5 equiv) in acetone (200 mL). After refluxing overnight, the reaction was cooled to room temperature and filtered. The filter cake was washed with acetone (50 mL). The filtrate was concentrated under reduced pressure and the residue was partially purified on an AnaLogix column (120 g), eluting with a gradient of 0 to 40% toluene in heptanes. The mixed fractions were purified on an AnaLogix column (20 g) eluting with a gradient of 0 to 40% toluene in heptanes. The clean material from each column was combined to compound 12 (7.7 g, 72% yield) as a colorless oil that slowly solidified.

[0187] 2-(3-(9//-Carba/ol-9-yl)-2-metho\y-5-methyl phenyl (acetaldehyde (13).

Compound 12 (5.9 g, 18 mmol, 1 equiv) was dissolved in dichloromethane (120 mL) and methanol (140 mL) and cooled to -78°C. Ozone (O3) was bubbled through the solution for 50 minutes until a yellow color persisted. The solution was sparged with air for an extra 10 minutes. The solution was quenched with dimethyl sulfide (2.5 mL) and stirred while warming to room temperature for 5 hours. The solution was concentrated under reduced pressure and the residue was partially purified on an AnaLogix column (80 g), eluting with a gradient of 0 to 50% ethyl acetate in heptanes. The mixed fractions were purified on an AnaLogix column (25 g), eluting with a gradient of 0 to 50% ethyl acetate in heptanes. The clean material from each column was combined to give compound 13 (4.2 g, 71% yield) as a white solid. [0188] /V /V^'-Bis(3-(9//-carbazol-9-yl)-2-methoxy-5-methylphenethyl)-/V /V^'- dimethylethane-l, 2-diamine (14). A, A’-Dimethylethane-l, 2-diamine (0.53 mL, 4.9 mmol, 1 equiv) was added to a solution compound 13 (3.9 g, 12 mmol, 2.4 equiv) and sodium cyanoborohydride (NaBLLCN) (1.23 g, 19.6 mmol, 4 equiv) in methanol (156 mL). Acetic acid (CH3COOH) (45 drops) was added and the solution was stirred at room temperature overnight. The solution was concentrated under reduced pressure. The residue was purified on an AnaLogix column (40 g), eluting with a gradient of 0 to 10% methanol in dichloromethane, to give compound 14 (3.7 g, > theoretical yield) as a colorless oil that slowly solidified.

[0189] 6.6'-((Ethane- 1.2-diylbis(methyla/anediyl))bis(ethane-2.1 -diyl))bis(2-(9//- carbazol-9-yl)-4-methylphenol) (15). Boron tribromide (BBn) (3.0 mL, 31 mmol, 6.4 equiv) as added dropwise to solution of compound 14 (3.5 g, 4.9 mmol, 1 equiv) in anhydrous dichloromethane (100 mL) at -78°C. The solution was stirred at -78°C for 4 hours and warmed to room temperature overnight. The solution was carefully diluted with ice water (100 mL). The layers were separated and the aqueous layer was extracted with dichloromethane (100 mL). The combined organic layers were dried over sodium sulfate and concentrated under reduced pressure. The crude reside was dry loaded onto silica (8 g) and partially purified on an AnaLogix column (40 g), eluting with a gradient of 0 to 100% ethyl acetate in heptanes. The mixed fractions from the first column were partially purified on an AnaLogix column (40 g), eluting with a gradient of 0 to 100% methyl tert-butyl ether (MTBE) in heptanes. The mixed fractions from the second column were partially purified in batches, two runs on an AnaLogix Reverse Phase column (100 g) and seven runs on an AnaLogix Reverse Phase column (50 g), eluting each batch with a gradient of 0 to 100% tetrahydrofuran in deionized water. The mixed fractions from the reverse phase columns were partially purified on an AnaLogix column (12 g) eluting isocratically with a solution of 98:2: 1 dichloromethane: methyl tert-butyl ether: ammonia. The mixed fractions were partially purified on an AnaLogix column (25 g), eluting isocratically with a solution of 98:2: 1 dichloromethane: methyl tert-butyl ether: ammonia. The mixed fractions were purified one last time on an AnaLogix column (12 g), eluting isocratically with a solution of 98:2: 1 dichloromethane: methyl tert- butylether: ammonia. All of the clean material was combined to give compound 15 (1.42 g, 42% yield) as a white solid.

[0190] 6,6'-((Ethane-l,2-diylbis(methylazanediyl))bis(ethane-2,l-diyl))bis(2-(9i/- carbazol-9-yl)-4-methylphenoxide) zirconium dibenzyl (A). In the drybox, Zr(CH2Ph)4 (0.0996 g, 0.219 mmol, 1 equiv) was dissolved in toluene (3 mL), and the resulting orange solution was added to a slurry of compound 15 (0.1500 g, 0.2184 mmol, 1 equiv) in toluene (2 mL). The mixture was stirred for 2.5 hours at room temperature then concentrated under a stream of nitrogen. The resulting yellow-orange residue was washed with hexane (5 mL) and dried under vacuum to give catalyst A (0.1836 g, -88% yield) as a yellow powder.

[0191] 6.6'-((Ethane- 1.2-diylbis(methylazanediyl))bis(ethane-2.1 -diyl))bis(2-(9//- carbazol-9-yl)-4-methylphenoxide) hafnium dibenzyl (B). In the drybox, Hf(CH2Ph)4 (0.0786 g, 0.145 mmol, 1 equiv) was dissolved in toluene (3 mL), and the resulting pale yellow solution was added to a slurry of compound 15 (0.0998 g, 0.145 mmol, 1 equiv) in toluene (2 mL). The mixture was stirred for 2.5 hours at room temperature then concentrated under a stream of nitrogen. The resulting pale yellow residue was washed with hexane (5 mL) and dried under vacuum to give catalyst B (0.1262 g, -83% yield) as a cream powder. Synthesis of Catalyst C and Catalyst D

[0192] 9-(3-Allyl-2-(methoxymethoxy)-5-methylphenyl)-9i/-carbazole (16).

Compound 12 (45.4 g, 145 mmol, 1 equiv), chloromethyl methyl ether (MOM-C1, 22 mL, 290 mmol, 2 equiv) and /V A- di i s o p ro py 1 e thy 1 am i n e (50.6 mL, 290 mmol, 2 equiv) were dissolved in dichloromethane (450 mL) and refluxed for 6.5 hours. The solution was diluted with water (400 mL) and the layers were separated. The aqueous layer was extracted with dichloromethane (100 mL). The combined organic layers were concentrated under reduced pressure. The residue was partially purified over silica gel (1 kg), eluting with a gradient of 10 to 50% toluene in heptanes. The mixed fractions from the first column were purified on an AnaLogix column (330 g), eluting with a gradient of 10 to 50% toluene in heptanes. The clean material from each column was combined to give compound 16 (41.7 g, 73% yield) as ayellow oil.

[0193] 2-(3-(9//-Carba/ol-9-yl)-2-(metho\ymetho\y)-5-methyl phenyl (acetaldehyde (17). Compound 16 (30.7 g, 85.9 mmol, 1 equiv) was dissolved in dichloro-methane (600 mL) and methanol (700 mL) and cooled to -78°C. Ozone was bubbled through the solution for 2.5 hours until a yellow color persisted. The solution was sparged with air for an additional 10 minutes. The solution was quenched with dimethyl sulfide (12 mL) and stirred while warming to room temperature for 5 hours. The solution was concentrated under reduced pressure. The residue was purified over silica gel (300 g), eluting with a gradient of 0 to 60% ethyl acetate in heptanes, to give compound 17 (20.5 g, 66% yield) as ayellow oil.

[0194] iV,iV^'-Bis(3-(9//-carba/ol-9-yl)-2-(methoxymethoxy)-5-methylphenethyl)-iV,iV^'- dimethylbenzene-l, 2-diamine (18). Sodium cyanoborohydride (NaBTbCN) (1.8 g, 29.2 mmol, 4 equiv) and acetic acid (CTbCOOH) (3.6 mL, 57 mmol, 7.8 equiv) were added to a solution of compound 17 (6.3 g, 17.6 mmol, 2.4 equiv) and /V,/V’-dimethylbenzene-l,2- diamine (1.0 g, 7.3 mmol, 1 equiv) in methanol (250 mL). The solution was stirred at room temperature overnight. The solution was filtered and the filtrate was partially concentrated under reduced pressure and filtered again. The solids from each filtration were combined, dissolved in dichloromethane and dry loaded onto Celite (10 g). The dry loaded solid was then partially purified on an AnaLogix column (120 g), eluting with a gradient of 0 to 25% ethyl acetate in heptanes. The mixed fractions from the first column were combined and dry loaded onto Celite (5 g) and partially purified on an AnaLogix column (80 g), eluting with a gradient of 0 to 25% ethyl acetate in heptanes. The mixed fractions from the second column were combined and dry loaded onto Celite (5 g) and partially purified on an AnaLogix column (80 g), eluting with a gradient of 0 to 25% ethyl acetate in heptanes. The clean material from each column was combined to give compound 18 (2.5 g, 42% yield) as a white solid.

[0195] 6,6'-((l ,2-Phenylenebis(methylazanediyl))bis(ethane-2, 1 -diyl))bis(2-(9//- carbazol-9-yl)-4-methylphenol) (19). Compound 18 (2.4 g, 3.3 mmol, 1 equiv) was dissolved in a solution of 2.5% v/v concentrated hydrochloric acid in methanol (102.5 mL) and stirred at 45°C for 5 hours. Solid sodium bicarbonate (6.5 g) was added to neutralize the solution to pH 8. The solution was concentrated under reduced pressure. The residue was partitioned between ethyl acetate (200 mL) and water (200 mL). The organic layer was dried over sodium sulfate and concentrated under reduced pressure. The residue was dry loaded onto Celite (5 g) and purified on an AnaLogix column (25 g), eluting with a gradient of 0 to 25% ethyl acetate in heptanes, to give compound 19 (1.5 g, 71% yield) as a white solid.

[0196] 6,6'-((l,2-phenylenebis(methylazanediyl))bis(ethane-2,l-diyl))bis(2-(9i/-carbazol- 9-yl)-4-methylphenoxide) zirconium dibenzyl (C). In the drybox, Zr(CH2Ph)4 (0.0606 g, 0.133 mmol, 1 equiv) was dissolved in toluene (3 mL), and the resulting orange solution was added to a solution of compound 19 (0.0998 g, 0.136 mmol, 1 equiv) in toluene (2 mL). The mixture was stirred for 2.5 hours at room temperature then concentrated under a stream of nitrogen. The resulting yellow-orange residue was stirred in hexane (5 mL), collected in a funnel with a glass frit and dried under vacuum to give catalyst C (0.0983 g, -73% yield) as a yellow powder.

[0197] 6,6'-((l,2-phenylenebis(methylazanediyl))bis(ethane-2,l-diyl))bis(2-(9i/-carbazol- 9-yl)-4-methylphenoxide) hafnium dibenzyl (D). In the drybox, Hf(CH2Ph)4 (0.0726 g, 0.134 mmol, 1 equiv) was dissolved in toluene (3 mL), and the resulting pale yellow solution was added to a solution of compound 19 (0.0992 g, 0.135 mmol, 1 equiv) in toluene (2 mL). The mixture was stirred for 2.5 hours at room temperature then concentrated under a stream of nitrogen. The resulting pale yellow residue was washed with hexane (5 mL) and dried under vacuum to give catalyst D (0.1180 g, -81% yield) as a cream powder. Synthesis of Catalyst E and Catalyst F

[0198] /V /V -bis(3-(9//-carbazol-9-yl)-2-(methoxymethoxy)-5-methylphenethyl)-/V /V - dimethylpropane- 1,3 -diamine (20). Sodium cyanoborohydride (NaBLLCN) (0.556 g, 8.85 mmol, 4 equiv) and acetic acid (CH3COOH) (10 drops) were added to a solution of compound 17 (1.904 g, 5.30 mmol, 2.4 equiv) and A, A’-dimethylpropane-l, 3-diamine (0.226 g, 2.21 mmol, 1 equiv) in methanol (25 mL). The solution was stirred at room temperature overnight then filtered and concentrated under reduced pressure. The resulting residue was purified on a Biotage SNAP Ultra column (50 g), eluting with a gradient of 0 to 20% ethyl acetate in hexane, to give compound 20 as an off-white solid. The compound was carried over to the next step as isolated.

[0199] 6.6'-(2.2'-(propane- 1.3-diylbis(methyla/anediyl))bis(ethane-2.1 -diyl))bis(2-(9//- carbazol-9-yl)-4-methylphenol) (21). Compound 20 (from previous reaction) was dissolved in 30 mL of methanol and a solution of 2.5% v/v concentrated hydrochloric acid (HC1) in methanol (10.3 mL) and stirred at 45°C for 5 hours. Solid sodium bicarbonate was added to neutralize the solution to pH 8. The solution was concentrated under reduced pressure. The residue was partitioned between ethyl acetate (50 mL) and water (50 mL). The organic layer was washed with water (2 x 50 mL) and brine (1 x 50 mL). The organic layer was separated, dried over sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified on a Biotage SNAP Ultra column (50 g), eluting with a gradient of 0 to 20% ethyl acetate in hexane, to give compound 21 (0.954 g, 62% overall yield) as a white solid.

[0200] 6.6'-(2.2'-(propane- 1.3-diylbis(methylazanediyl))bis(ethane-2.1 -diyl))bis(2-(9//- carbazol-9-yl)-4-methylphenoxide) zirconium dibenzyl (E). In the drybox, Zr(CH2Ph)4 (0.099 g, 0.217 mmol, 1 equiv) was dissolved in toluene (3 mL), and the resulting orange solution was added to a solution of compound 21 (0.152 g, 0.217 mmol, 1 equiv) in toluene (2 mL). The mixture was stirred for 1 hour at room temperature then concentrated under a stream of nitrogen. The resulting yellow-orange residue was stirred in hexane (10 mL), collected in a funnel with a glass frit and dried under vacuum to give catalyst E (0.169 g, 80% yield) as a yellow powder.

[0201] 6,6'-(2,2'-(propane-l,3-diylbis(methylazanediyl))bis(ethane-2,l-diyl))bis(2-(9i/- carbazol-9-yl)-4-methylphenoxide) hafnium dibenzyl (F). In the drybox, Hf(CH2Ph)4 (0.136 g, 0.250 mmol, 1 equiv) was dissolved in toluene (3 mL), and the resulting pale yellow solution was added to a solution of compound 21 (0.175 g, 0.250 mmol, 1 equiv) in toluene (2 mL). The mixture was stirred for 1 hour at room temperature then concentrated under a stream of nitrogen. The resulting off-white residue was stirred in hexane (10 mL), collected in a funnel with a glass frit, washed with hexane, and dried under vacuum to give catalyst F (0.213 g, 80% yield) as a white powder. Preparation of Supported Catalysts

[0202] Preparation of Fluorided Silica Support (F-sMAO). Fluorided silica was prepared as described in WO 2017058386 Al.

[0203] Preparation of Supported Catalyst. In the drybox, 20 pmol of the metal complex was dissolved in 1.0 g of toluene in a 20 ml glass vial. 1.0 g F-sMAO was slurried in 3.0 g of toluene in a 20 ml glass vial. The metal complex toluene solution was added to the sMAO slurry via a pipette. The glass vial was capped with a Teflon-lined cap and vortexed at room temperature for 90 min. The resulting slurry was filtered through an 18 mL polyethylene frit (10 micron), and rinsed with 3 g toluene for 3 times, followed by 2 g of pentane for 3 times. The collected solid was dried under vacuum for 40 min to afford a free flowing yellow or white solid. 1.0 g of supported catalyst was collected. Calculated catalyst loading: 20 pmol/g (catalyst loading = pmol of catalyst/gram of support).

Polymerization Examples

[0204] The following describes the general polymerization procedure used for the present disclosure. The desired temperatures, pressures, quantities of chemicals used (e.g., pre catalysts, activators, scavengers, etc.) will vary from experiment to experiment, and specific values are given in Table 1 (or immediately above or below the Table) where data are presented.

General Polymerization Procedures for Parallel Pressure Reactor

[0205] Solvents, polymerization-grade toluene, and isohexane were supplied by ExxonMobil Chemical Company and purified by passing through a series of columns: two 500 cc Oxyclear cylinders in series from Labclear (Oakland, Calif.), followed by two 500 cc columns in series packed with dried 3 A mole sieves (8-12 mesh; Aldrich Chemical Company), and two 500 cc columns in series packed with dried 5 A mole sieves (8-12 mesh; Aldrich Chemical Company).

[0206] 1 -hexene (C6) (98%, Aldrich Chemical Company) was dried by stirring over NaK overnight followed by filtration through basic alumina (Aldrich Chemical Company, Brockman Basic 1).

[0207] Polymerization-grade ethylene (C2) was used and further purified by passing the gas through a series of columns: 500 cc Oxyclear cylinder from Labclear (Oakland, CA) followed by a 500 cc column packed with dried 3A mole sieves (8-12 mesh; Aldrich Chemical Company) and a 500 cc column packed with dried 5A mole sieves (8-12 mesh; Aldrich Chemical Company). [0208] Polymerization grade propylene (C3) was used and further purified by passing it through a series of columns: 2250 cc Oxiclear cylinder from Labclear followed by a 2250 cc column packed with 3 A mole sieves (8-12 mesh; Aldrich Chemical Company), then two 500 cc columns in series packed with 5 A mole sieves (8-12 mesh; Aldrich Chemical Company), then a 500 cc column packed with Selexsorb CD (BASF), and finally a 500 cc column packed with Selexsorb COS (BASF).

[0209] Slurries of supported catalysts in toluene were prepared in the drybox using 45 mg of the supported catalyst and 15 mL of toluene. The resulting mixture was vortexed for uniform distribution of particles prior to injection.

[0210] For polymerization experiments with supported catalysts, tri-n-octylaluminum (TNOAL, neat, AkzoNobel) was used as a scavenger. Concentration of the TNOAL solution in toluene ranged from 0.5 to 2.0 mmol/L.

[0211] Polymerizations were carried out in a parallel, pressure reactor, as generally described in US 6,306,658; US 6,455,316; US 6,489,168; WO 00/09255; and Murphy et al, J. Am. Chem. Soc., 2003, 125, pp. 4306-4317, each of which is fully incorporated herein by reference. The experiments were conducted in an inert atmosphere (N₂) drybox using autoclaves equipped with an external heater for temperature control, glass inserts (internal volume of reactor = 23.5 mL for C2 and C2/C8; 22.5 mL for C3 runs), septum inlets, regulated supply of nitrogen, ethylene and propylene, and equipped with disposable PEEK mechanical stirrers (800 RPM). The autoclaves were prepared by purging with dry nitrogen at H0°C or 1 l5°C for 5 hours and then at 25°C for 5 hours. Although the specific quantities, temperatures, solvents, reactants, reactant ratios, pressures, and other variables are frequently changed from one polymerization run to the next, the following describes a typical polymerization performed in a parallel, pressure reactor.

[0212] Polymerizations using Supported Catalysts. The reactor is prepared as described above, and then purged with ethylene. Isohexane, 1 -hexene, and TnOAl are added via syringe at room temperature and atmospheric pressure. The reactor is then brought to process temperature (85°C) and charged with ethylene to process pressure (130 psig = 896 kPa) while stirring at 800 RPM. The catalyst metal compound (100 pL of a 3 mg/mL toluene slurry, unless indicated otherwise) is added via syringe with the reactor at process conditions. TnOAl is used as 200 pL of a 20 mmol/L in isohexane solution. No other reagent is used. Ethylene is allowed to enter (through the use of computer controlled solenoid valves) the autoclaves during polymerization to maintain reactor gauge pressure (+/- 2 psig). Reactor temperature is monitored and typically maintained within +/- l°C. Polymerizations are halted by addition of approximately 50 psi 02/ Ar (5 mol% 02) gas mixture to the autoclaves for approximately 30 seconds. The polymerizations are quenched after a predetermined cumulative amount of ethylene had been added or for a maximum of 45 minutes polymerization time. In addition to the quench time for each run, the reactors are cooled and vented. The polymer is isolated after the solvent is removed in-vacuo. Yields reported include total weight of polymer and residual catalyst. Catalyst activity is reported as kilograms of polymer per mmol transition metal compound per hour of reaction time (kg/mmol*hr).

[0213] Polymer Characterization. Polymer sample solutions were prepared by dissolving polymer in 1, 2, 4-tri chlorobenzene (TCB, 99+% purity from Sigma- Aldrich) containing 2,6-di- tertbutyl-4-methylphenol (BHT, 99% from Aldrich) at l65°C in a shaker oven for approximately 3 hours. The typical concentration of polymer in solution was between 0.1 to 0.9 mg/mL with a BHT concentration of 1.25 mg BHT/mL of TCB.

[0214] To determine various molecular weight related values by GPC, high temperature size exclusion chromatography was performed using an automated "Rapid GPC" system as generally described in US 6,491,816; US 6,491,823; US 6,475,391; US 6,461,515; US 6,436,292; US 6,406,632; US 6,175,409; US 6,454,947; US 6,260,407; and US 6,294,388; each of which is fully incorporated herein by reference for US purposes. This apparatus has a series of three 30 cm x 7.5 mm linear columns, each containing PLgel 10 pm, Mix B. The GPC system was calibrated using polystyrene standards ranging from 580 - 3,390,000 g/mol. The system was operated at an eluent flow rate of 2.0 mL/minutes and an oven temperature of l65°C. 1,2, 4-tri chlorobenzene was used as the eluent. The polymer samples were dissolved in 1,2, 4-tri chlorobenzene at a concentration of 0.28 mg/mL and 400 uL of a polymer solution was injected into the system. The concentration of the polymer in the eluent was monitored using an evaporative light scattering detector. The molecular weights presented are relative to linear polystyrene standards and are uncorrected, unless indicated otherwise.

[0215] Differential Scanning Calorimetry (DSC) measurements were performed on a TA- Q100 instrument to determine the melting point (Tm) of the polymers. Samples were pre annealed at 220°C for 15 minutes and then allowed to cool to room temperature overnight. The samples were then heated to 220°C at a rate of l00°C/min and then cooled at a rate of 50°C/min. Melting points were collected during the heating period.

[0216] The weight percent of ethylene incorporated in polymers was determined by rapid FT-IR spectroscopy on a Bruker Equinox 55+ IR in reflection mode. Samples were prepared in a thin film format by evaporative deposition techniques. FT-IR methods were calibrated using a set of samples with a range of known wt% ethylene content. GPC 4D Procedure: Molecular Weight Comonomer Composition and Long Chain Branching

Determination by GPC-IR Hyphenated with Multiple Detectors

[0217] Unless otherwise indicated, the distribution and the moments of molecular weight (Mw, Mn, Mw/Mn, etc.), the comonomer content (C2, C3, C6, etc.) and the branching index (g'vis) are determined by using a high temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based Infrared detector IR5, an 18-angle light scattering detector and a viscometer. Three Agilent PLgel lO-pm Mixed-B LS columns are used to provide polymer separation. Aldrich reagent grade 1, 2, 4-tri chlorobenzene (TCB) with 300 ppm antioxidant butylated hydroxy toluene (BHT) is used as the mobile phase. The TCB mixture is filtered through a 0.1 -pm Teflon filter and degassed with an online degasser before entering the GPC instrument. The nominal flow rate is 1.0 ml/min and the nominal injection volume is 200 pL. The whole system including transfer lines, columns, and detectors are contained in an oven maintained at l45°C. The polymer sample is weighed and sealed in a standard vial with 80-pL flow marker (Heptane) added to it. After loading the vial in the autosampler, polymer is automatically dissolved in the instrument with 8 ml added TCB solvent. The polymer is dissolved at l60°C with continuous shaking for about 1 hour for most PE samples or 2 hour for PP samples. The TCB densities used in concentration calculation are 1.463 g/ml at room temperature and 1.284 g/ml at l45°C. The sample solution concentration is from 0.2 to 2.0 mg/ml, with lower concentrations being used for higher molecular weight samples. The concentration (c). at each point in the chromatogram is calculated from the baseline-subtracted IR5 broadband signal intensity (I), using the following equation: c = ///. where b is the mass constant. The mass recovery is calculated from the ratio of the integrated area of the concentration chromatography over elution volume and the injection mass which is equal to the pre-determined concentration multiplied by injection loop volume. The conventional molecular weight (IR MW) is determined by combining universal calibration relationship with the column calibration which is performed with a series of monodispersed polystyrene (PS) standards ranging from 700 to lOM gm/mole. The MW at each elution volume is calculated with following equation

log {K_PS /K) _,

logM = a ps + 1 logM PS

a + 1 a + 1

where the variables with subscript“PS” stand for polystyrene while those without a subscript are for the test samples. In this method, a^PS = 0.67 and KPS = 0.000175 while a and K are for other materials as calculated and published in literature (Sun, T. et al. Macromolecules 2001,

34, 6812), except that for purposes of the present disclosure, a = 0.695 and K = 0.000579 for linear ethylene polymers, a = 0.705 and K = 0.0002288 for linear propylene polymers, a = 0.695 and K = 0.000181 for linear butene polymers, a is 0.695 and K is 0.000579*(l- 0.0087*w2b+0.0000l8*(w2b)^A2) for ethylene-butene copolymer where w2b is a bulk weight percent of butene comonomer, a is 0.695 and K is 0.000579*(l-0.0075*w2b) for ethylene- hexene copolymer where w2b is a bulk weight percent of hexene comonomer, and a is 0.695 and K is 0.000579*(l-0.0077*w2b) for ethylene-octene copolymer where w2b is a bulk weight percent of octene comonomer. Concentrations are expressed in g/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g unless otherwise noted.

[0218] The comonomer composition is determined by the ratio of the IR5 detector intensity corresponding to CH2 and CH3 channel calibrated with a series of PE and PP homo/copolymer standards whose nominal value are predetermined by NMR or FTIR. In particular, this provides the methyls per 1000 total carbons (CH3/IOOOTC) as a function of molecular weight. The short-chain branch (SCB) content per 1000TC (SCB/1000TC) is then computed as a function of molecular weight by applying a chain-end correction to the CH3/IOOOTC function, assuming each chain to be linear and terminated by a methyl group at each end. The weight % comonomer is then obtained from the following expression in which / is 0.3, 0.4, 0.6, 0.8, and so on for C3, C4, C6, C8, and so on comonomers, respectively.

w2 = / * SCB/1000TC.

[0219] The bulk composition of the polymer from the GPC-IR and GPC-4D analyses is obtained by considering the entire signals of the CH3 and CH2 channels between the integration limits of the concentration chromatogram. First, the following ratio is obtained

Area of CH₃ signal within integration limits

Bulk IR ratio

Area of CH₂ signal within integration limits^'

[0220] Then the same calibration of the Ctb and Cth signal ratio, as mentioned previously in obtaining the CH3/1000TC as a function of molecular weight, is applied to obtain the bulk CH3/1000TC. A bulk methyl chain ends per 1000TC (bulk CH3end/l000TC) is obtained by weight-averaging the chain-end correction over the molecular-weight range. Then

w2b = / * bulk CH3/1000TC,

bulk SCB/1000TC = bulk CH3/1000TC - bulk ^CH3end

1000TC’

and bulk SCB/1000TC is converted to bulk w2 in the same manner as described above.

[0221] The LS detector is the 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering ( Light Scattering from Polymer Solutions ; Huglin, M. B., Ed.; Academic Press, 1972.):

K„c 1

- 2A₂C

AR(o) MR(Q)

[0222] Here, AR(0) is the measured excess Rayleigh scattering intensity at scattering angle Q, c is the polymer concentration determined from the IR5 analysis, A2 is the second virial coefficient, R(q) is the form factor for a monodisperse random coil, and Ko is the optical constant for the system:

where NA is Avogadro’s number, and (dn/dc) is the refractive index increment for the system. The refractive index, n=l.500 for TCB at l45°C and l=665 nm. For analyzing polyethylene homopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn/dc=0.1048 ml/mg and A2=0.00l5; for analyzing ethylene-butene copolymers, dn/dc=0. l048*(l-0.00l26*w2) ml/mg and A2=0.00l5 where w2 is weight percent butene comonomer.

[0223] A high temperature Agilent (or Viscotek Corporation) viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, q_s, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [h], at each point in the chromatogram is calculated from the equation [h]= qs/c, where c is concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as

M = K_psM^aps+1 /[h\ ,

where a_ps is 0.67 and KPS is 0.000175.

[0224] The branching index (g'_vis) is calculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity, [q]avg, of the sample is calculated by:

where the summations are over the chromatographic slices, i, between the integration limits.

[0225] The branching index g'_vls is defined as

where M_v is the viscosity-average molecular weight based on molecular weights determined by LS analysis and the K and a are for the reference linear polymer, which are, for purposes of the present disclosure, a = 0.695 and K = 0.000579 for linear ethylene polymers, a = 0.705 and K = 0.0002288 for linear propylene polymers, a = 0.695 and K = 0.000181 for linear butene polymers, a is 0.695 and K is 0.000579*(l-0.0087*w2b+0.0000l8*(w2b)^A2) for ethylene- butene copolymer where w2b is a bulk weight percent of butene comonomer, a is 0.695 and K is 0.000579*(l-0.0075*w2b) for ethylene-hexene copolymer where w2b is a bulk weight percent of hexene comonomer, and a is 0.695 and K is 0.000579*(l-0.0077*w2b) for ethylene- octene copolymer where w2b is a bulk weight percent of octene comonomer. Concentrations are expressed in g/cm³, molecular weight is expressed in g/mole, and intrinsic viscosity (hence K in the Mark-Houwink equation) is expressed in dL/g unless otherwise noted. Calculation of the w2b values is as discussed above.

[0226] Experimental and analysis details not described above, including how the detectors are calibrated and how to calculate the composition dependence of Mark-Houwink parameters and the second-virial coefficient, are described by T. Sun, P. Brant, R. R. Chance, and W. W. Graessley ( Macromolecules , 2001, Vol. 34(19), pp. 6812-6820).

[0227] All molecular weights are weight average unless otherwise noted. All molecular weights are reported in g/mol unless otherwise noted.

[0228] Methyl groups per 1000 carbons (Grb/lOOOCarbons) is determined by 'H NMR.

[0229] Melt Index (MI, also referred to as 12) is measured according to ASTM D1238 at l90°C, under a load of 2.16 kg unless otherwise noted. The units for MI are g/lO min or dg/min.

[0230] High Load Melt Index (HLMI, also referred to as 121) is the melt flow rate measured according to ASTM D-1238 at l90°C, under a load of 21.6 kg. The units for HLMI are g/lO min or dg/min.

[0231] Melt Index Ratio (MIR) is the ratio of the high load melt index to the melt index, or 121/12.

[0232] Average wt% of ethylene (C2 content) and 1 -hexene (C6 content) is determined by Ή NMR and ¹³C NMR.

[0233] To determine various molecular weight related values by GPC, high temperature size exclusion chromatography was performed using GPC-IR (Polymer Char). The IV

(intrinsic viscosity) molecular weights presented in the examples are relative to linear polystyrene standards whereas the LS (light scattering) and TR (infrared) molecular weights are absolute.

[0234] Characterization of selected ethylene-hexene copolymers are shown in Table 1. Comparative plots for Catalysts A-F and the reference metallocene (Catalyst G) are shown in FIGs. 1-6. Catalyst G has the following structure:

Table 1 : Catalyst Activity and Composition of Polymers (Run conditions: isohexane as solvent 85°C 130 psi set ethylene pressure variable volume of 1 -hexene)

[0235] The data in Table 1 show molecular weights and compositions of the EH polymers using catalyst systems described herein. Supportation on silica (sMAO) and fluorided silica (F-sMAO) of non-metallocene Group IV complexes with a C2-bridged diamine bis(phenolate) ligand framework (C2-N2O2) resulted in highly active olefin polymerization catalysts based on high-throughput EH slurry experiments.

[0236] FIG. 1 and FIG. 2 are representative plots of activity (kgmol ¹h ¹) versus mol ratio of 1 -hexene (C6) to ethylene (C2) in liquid phase in the presence of about 0 ppm H2 and about 300 ppm H2 for selected catalysts. FIG. 1 and FIG. 2 illustrate that Catalysts A and Catalysts B have comparable activities at moderate hexene/ethylene ratio to the comparative Catalyst G when the polymerization reactions are run in the presence of about 0 ppm H2 and about 300 ppmH2, respectively. Notably, the activity of Catalyst B increased more significantly than did Catalyst G as the concentration of hexene was raised.

[0237] FIG. 3 and FIG. 4 are representative plots of Mw versus mol ratio of 1 -hexene (C6) to ethylene (C2) in liquid phase in the presence of about 0 ppm H2 and about 300 ppm H2 for selected catalysts. FIG. 3 and FIG. 4 illustrate that Mw of up to about 2.4x10⁶ g/mol (Catalyst B) can be achieved, which can be lowered to <l.0xl0⁶ g/mol in the presence of 300 ppm hydrogen (Catalyst G, Mw = 0.5 xlO⁶ g/mol).

[0238] FIG. 5 and FIG. 6 are representative plots of 1 -hexene incorporation (C6 wt%) versus mol ratio of 1 -hexene (C6) to ethylene (C2) in liquid phase in the presence of about 0 ppm H2 and about 300 ppm H2 for selected catalysts. FIG. 5 and FIG. 6 illustrate that hexene incorporation can be increased by using Catalysts A and B (about doubled with Catalyst B) when run under similar conditions as Catalyst G.

[0239] The catalyst systems and methods described herein are highly active and show increased conversion, and produce polymers with broader scope in molecular weight, improved comonomer incorporation, and/or altered comonomer distribution without deteriorating the resulting polymer’s properties. Further, the catalyst systems and methods show improved H2 response and improved comonomer response. The improved response is likely due to the combination of the catalyst and the electron withdrawing character of the support material; here, the support material includes a fluorided silica.

[0240] All documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the present disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the present disclosure. Accordingly, it is not intended that the present disclosure be limited thereby. Likewise, the term “comprising” is considered synonymous with the term“including.” Likewise whenever a composition, an element or a group of elements is preceded with the transitional phrase “comprising,” it is understood that we also contemplate the same composition or group of elements with transitional phrases“consisting essentially of,”“consisting of,”“selected from the group of consisting of,” or“is” preceding the recitation of the composition, element, or elements and vice versa.

Claims

CLAIMS We claim:

1. A catalyst system comprising:

a support material comprising an electron withdrawing group; and

a catalyst represented by formula (I):

wherein,

M is a Group 4 transition metal;

each Q is a neutral donor group comprising at least one atom from Group 15 or Group 16, and each of R² and R³ is not present when Q is a Group 16 atom;

L is -(C)_y(R⁴)(R⁵)- and is not part of an aromatic ring;

L* is -(C)_Z(R⁴*)(R⁵*)- and is not part of an aromatic ring;

y is greater than or equal to 2;

z is greater than or equal to 2;

each of X¹ and X² is independently a univalent Ci to C20 hydrocarbyl radical, a Ci to C20 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or X¹ and X² join together to form a C4 to C62 cyclic, polycyclic or heterocyclic structure;

R¹ is a divalent Ci to C40 hydrocarbyl radical or a divalent substituted hydrocarbyl radical comprising a portion that comprises a linker backbone comprising from 1 to 18 carbon atoms linking or bridging between the two Q groups;

each of R^a, R^b, R^c, R^d, R^a*, R^b*, R^c*, and R^d* is independently a hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical, a heteroatom or a heteroatom- containing group, or two or more of R^a, R^b, R^c, R^d, R^a*, R^b*, R^c*, and R^d* may independently join together to form a C4 to C62 cyclic, polycyclic or heterocyclic structure, or a combination thereof; and each of R² and R³ is independently a hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical, a heteroatom, or a heteroatom-containing group.

2. The catalyst system of claim 1, wherein the catalyst is represented by formula (II):

wherein,

M is a Group 4 transition metal;

each Q is neutral donor group comprising at least one atom from Group 15 or Group 16, and each of R² and R³ is not present when Q is a Group 16 atom;

each of X¹ and X² is independently a univalent Ci to C20 hydrocarbyl radical, a C i to

C20 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or X¹ and X² join together to form a C4 to C62 cyclic, polycyclic or heterocyclic structure;

R¹ is a divalent Ci to C40 hydrocarbyl radical or a divalent substituted hydrocarbyl radical comprising a portion that comprises a linker backbone comprising from 1 to 18 carbon atoms linking or bridging between the two Q groups;

each of R^a, R^b, R^c, R^d, R^a*, R^b*, R^c*, and R^d* is independently a hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical, a heteroatom or a heteroatom- containing group, or two or more of R^a, R^b, R^c, R^d, R^a*, R^b*, R^c*, and R^d* may independently join together to form a C4 to C62 cyclic, polycyclic or heterocyclic structure, or a combination thereof;

each of R⁴, R⁵, R⁴*, and R⁵* is independently a hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group, or two or more adjacent R⁴, R⁵, R⁴*, and R⁵* groups may independently join together to form a C4 to C62 cyclic or polycyclic ring structure, or a combination thereof, provided that such cyclic, polycyclic or heterocyclic structure is not aromatic; and each of R² and R³ is independently a hydrogen, a Ci to C40 hydrocarbyl radical, a Ci to C40 substituted hydrocarbyl radical, a heteroatom or a heteroatom-containing group.

3. The catalyst system of claims 1 or 2, wherein the electron withdrawing group of the support comprises fluorine.

4. The catalyst system of any of claims 1 to 3, wherein each of R^a and R^a* is independently carbazolyl, substituted carbazolyl, naphthyl, substituted naphthyl, anthracenyl, substituted anthracenyl, phenanthryl, substituted phenanthryl, phenyl, substituted phenyl, adamantyl, substituted adamantyl, cyclohexyl, substituted cyclohexyl, indolyl, substituted indolyl, indolinyl, substituted indolinyl, imidazolyl, substituted imidazolyl, indenyl, substituted indenyl, indanyl, substituted indanyl, fluorenyl, or substituted fluorenyl.

5. The catalyst system of any of claims 1 to 4, wherein each of R^a and R^a* is independently a carbazolyl radical or a substituted carbazolyl radical.

6. The catalyst system of any of claims 1 to 5, wherein Q is a neutral donor group comprising at least one atom from Group 15 or Group 16 and the -(-Q-R'-Q-)- fragment can form a substituted or unsubstituted heterocycle which may or may not be aromatic and may have multiple fused rings, preferably wherein Q is NR', O, S, PR', where R' is independently a hydrogen, a Ci to C40 hydrocarbyl radical, or a Ci to C40 substituted hydrocarbyl radical.

7. The catalyst system of any of claims 1 to 6, wherein

R¹ is a -(CR¾n- group, where n is 2 or 3; and

each R⁶ is H, a Ci to C20 hydrocarbyl radical, a Ci to C20 substituted hydrocarbyl radical, or multiple R⁶ groups may join together to form a benzene ring, substituted benzene ring, cyclohexyl, substituted cyclohexyl, cyclooctyl, or substituted cyclooctyl.

8. The catalyst system of any of claims 1 to 7, wherein each of X¹ and X² is independently halide, C1-C10 hydrocarbyl, C1-C10 substituted hydrocarbyl, benzyl, or substituted benzyl.

9. The catalyst system of any of claims 1 to 8, wherein each of R^c and R^c* is independently C1-C20 hydrocarbyl or substituted C1-C20 hydrocarbyl.

10. The catalyst system of any of claims 1 to 9, wherein each of R^c and R^c* is independently substituted or unsubstituted methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, or tert-butyl.

11. The catalyst system of any of claims 1 to 10, wherein M is Hf or Zr.

12. The catalyst of any of claims 1 to 11, wherein:

R¹ = -CH2CH2-; and

Y¹ and Y² are benzyl.

13. The catalyst of claim 11, wherein the catalyst represented by Formula (I) or Formula

(II) is one or more of:

Structure Structure Structure

14. A catalyst system comprising:

(a) the catalyst system of any of claims 1 to 13; and

(b) a bridged or unbridged catalyst other than the catalyst of (a).

15. A catalyst system comprising:

the catalyst system of any of claims 1 to 14; and

an activator.

16. The catalyst system of claim 15, wherein the activator comprises one or more of:

N,N-dimethylanilinium tetra(perfluorophenyl)borate,

N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate,

di(hydrogenated tallow)methylammonium tetra(perfluorophenyl)borate,

di(hydrogenated tallow)methylammonium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate,

N,N-dimethylanilinium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

triphenylcarbenium tetrakis(perfluoronaphthyl)borate,

triphenylcarbenium tetrakis(perfluorobiphenyl)borate,

triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,

triphenylcarbenium tetra(perfluorophenyl)borate,

trimethylammonium tetrakis(perfluoronaphthyl)borate,

triethylammonium tetrakis(perfluoronaphthyl)borate,

tripropylammonium tetrakis(perfluoronaphthyl)borate,

tri(n-butyl)ammonium tetrakis(perfluoronaphthyl)borate,

tri(t-butyl)ammonium tetrakis(perfluoronaphthyl)borate,

N,N-diethylanilinium tetrakis(perfluoronaphthyl)borate,

N,N-dimethyl-(2,4,6-trimethylanibnium) tetrakis(perfluoronaphthyl)borate, and tropillium tetrakis(perfluoronaphthyl)borate.

17. The catalyst system of claims 15 or 16, wherein the activator comprises alkylalumoxane.

18. The catalyst system of any of claims 15 to 17, wherein the support material comprises AI2O3, ZrC , S1O2, or SiC /AkCb.

19. The catalyst system of claim 18, wherein the support material comprises an electron withdrawing group.

20. A method of polymerizing olefins to produce at least one polyolefin composition, the method comprising:

contacting at least one olefin with the catalyst system of any of claims 14 to 19; and obtaining the polyolefin composition.

21. The method of claim 20, further comprising alkylalumoxane present at a molar ratio of aluminum to catalyst group 4 metal of 100: 1 or more.

22. The method of any of claims 20 to 21, wherein the catalyst system further comprises an activator represented by the formula:

(Z)d⁺(A^d ),

wherein Z is (L-H) or a reducible Lewis acid, L is a neutral base; H is hydrogen; (L-H)⁺ is a Bronsted acid; A^d is a non-coordinating anion having the charge d-; and d is an integer from 1 to 3.

23. The method of any of claims 20 to 22, wherein the catalyst system further comprises an activator represented by the formula:

(Z)d⁺(A^d ),

wherein A^d is a non-coordinating anion having the charge d-; and d is an integer from 1 to 3; Z is a reducible Lewis acid represented by the formula: (AnC ¹ ). wherein Ar is aryl substituted with a Ci to C40 hydrocarbyl or with a substituted Ci to C40 hydrocarbyl, or a heteroaryl substituted with a Ci to C40 hydrocarbyl, or with a substituted Ci to C40 hydrocarbyl.

24. The method of any of claims 20 to 23, wherein the method occurs at a temperature of about 0°C to about 300°C, at a pressure in the range of from about 0.35 MPa to about 1500 MPa, and at a time up to about 300 min.

25. The method of any of claims 20 to 24, wherein the olefin comprises ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, isomers thereof, or mixtures thereof.

26. The method of any of claims 20 to 25, further comprising introducing the first catalyst represented by Formula (I) or Formula (II) into a reactor as a slurry.

27. The method of any of claims 20 to 26, wherein the catalyst has an activity of at least about 50 kgmof'h ¹ in the presence of about 0 ppm hydrogen and an activity of at least about 50 kgmoHh ¹ in the presence of about 300 ppm hydrogen.

28. An ethylene alpha-olefin copolymer obtained by contacting ethylene, at least one alpha- olefin, and the catalyst system of any of claims 14 to 19, the copolymer having a Ce wt% of from about 0.01 wt% to about 50 wt%.

29. An ethylene alpha-olefin copolymer obtained by contacting ethylene, at least one alpha- olefin, and the catalyst system of any of claims 14 to 19 in the presence of 0 ppm hydrogen, the copolymer having an Mw from about 5,000 g/mol to about 1,000,000 g/mol.

30. An ethylene alpha-olefin copolymer obtained by contacting ethylene, at least one alpha- olefin, and the catalyst system of any of claims 14 to 19 in the presence of 300 ppm hydrogen, the copolymer having an Mw from about 5,000 g/mol to about 1,000,000 g/mol.