WO2025117379A1

WO2025117379A1 - Formation of branched polypropylenes using dianionic complexes having eight-membered chelate rings

Info

Publication number: WO2025117379A1
Application number: PCT/US2024/057107
Authority: WO
Inventors: Nikola S. LAMBIC; An Ngoc-Michael Nguyen; Carlos R. Lopez-Barron; Jo Ann M. Canich
Original assignee: ExxonMobil Technology and Engineering Co
Current assignee: ExxonMobil Technology and Engineering Co
Priority date: 2023-12-01
Filing date: 2024-11-22
Publication date: 2025-06-05
Anticipated expiration: 2026-06-01

Abstract

Branched polypropylene copolymers may be prepared using dianionic complexes having 8-membered chelate rings. Methods for forming branched polypropylene copolymers may comprise: exposing a) propylene and b) a a,w-diene to polymerization reaction conditions in the presence of a polymerization catalyst system and optionally hydrogen; wherein the polymerization catalyst system comprises a support material, a dianionic complex of a Group 3-6 metal disposed upon the support material, and an activator for the dianionic complex disposed upon the support material; wherein the dianionic complex comprises two eight-membered chelate rings containing the Group 3-6 metal; and forming a branched polypropylene copolymer having long-chain branching under the polymerization reaction conditions.

Description

FORMATION OF BRANCHED POLYPROPYLENES USING DIANIONIC COMPLEXES HAVING EIGHT-MEMBERED CHELATE RINGS

FIELD

[0001] The present disclosure relates to branched polypropylenes and, more particularly, in-reactor production of branched polypropylenes having long-chain branching.

BACKGROUND

[0002] Linear polypropylenes may exhibit a low melt strength. The low melt strength may result in poor foaming performance as a result of cell walls produced during foaming becoming susceptible to rupture during ongoing cell growth. The low melt strength may be problematic for other applications beyond foaming as well.

[0003] To address the low melt strength of as-produced linear polypropylenes, blends of polypropylenes may sometimes be utilized in foaming applications. Post-synthesis chemical modification of linear polypropylenes may also sometimes be performed, such as by electron beam irradiation or melt processing with a radical initiator, either of which may introduce long-chain branches to the polypropylene. Branched polypropylenes having long-chain branching may exhibit increased extensional hardening compared to their linear counterparts, which may improve their melt strength. The increased melt strength, in turn, may improve foaming or thermoforming performance in comparison to as-formed linear polypropylenes. Although effective, post-synthesis chemical modifications of polypropylenes may oftentimes be costly or time-consuming to perform.

SUMMARY

[0004] In various aspects, the present disclosure provides methods for forming branched polypropylene copolymers, comprising: exposing a) propylene and b) a a, co -diene to polymerization reaction conditions in the presence of a polymerization catalyst system and optionally hydrogen; wherein the polymerization catalyst system comprises a support material, a dianionic complex of a Group 3-6 metal disposed upon the support material, and an activator for the dianionic complex disposed upon the support material; wherein the dianionic complex comprises two eight-membered chelate rings containing the Group 3-6 metal; and forming a branched polypropylene copolymer having long-chain branching under the polymerization reaction conditions.

[0005] These and other features and attributes of the disclosed systems and methods of the present disclosure and their advantageous applications and/or uses will be apparent from the detailed description which follows. BRIEF DESCRIPTION OF THE DRAWINGS

[0006] To assist those of ordinary skill in the relevant art in making and using the subject matter hereof, reference is made to the appended drawings. The following figures are included to illustrate certain aspects of the disclosure, and should not be viewed as exclusive configurations. The subject matter disclosed is capable of considerable modifications, alterations, combinations, and equivalents in form and function, as will occur to those skilled in the art and having the benefit of this disclosure. [0007] FIG. l is a plot of complex viscosity as a function of angular frequency for various samples (11-18).

[0008] FIG. 2 is a corresponding plot of phase angle as a function of complex modulus for various samples (11-18).

[0009] FIG. 3 is a corresponding plot of tan(delta) as a function of angular frequency for various samples (11-18).

[0010] FIGS. 4A-4D are plots of extensional viscosity for samples 12-14 and 17, respectively. [0011] FIG. 5 is a plot of tensile stress as a function of g’vis for selected samples among 11-110. [0012] FIG. 6 is a plot of flexural modulus as a function of g\i_s for selected samples among II -110. DETAILED DESCRIPTION

[0013] The present disclosure relates to branched polypropylenes and, more particularly, in-reactor production of branched polypropylenes having long-chain branching.

[0014] The present disclosure provides polymerization methods for in-reactor production of branched polypropylenes copolymers having long-chain branching (also referred to herein as branched polypropylenes), in which a dianionic complex of a Group 3-6 metal, such as a bis(phenolate) complex or similar complex containing two eight-membered chelate rings, may be utilized to promote polymerization of propylene with an oc, co -diene to introduce the long-chain branches. In-reactor introduction of the long-chain branches may be advantageous in terms of avoiding time-consuming and costly post-synthesis chemical modification of an as-produced linear polypropylene. Advantageously, the dianionic complexes described herein may readily incorporate a, CD -dienes into a polypropylene backbone with high activities and in an amount effective to enhance one or more physical properties as a consequence of the resulting long-chain branching. For example, long-chain branches may increase stiffness and shear-thinning performance for applications such as thing-wall injection molding.

[0015] Bis(phenolate) complexes and similar dianionic complexes are readily compatible with both slurry-phase and gas-phase polymerization reaction conditions, as well as capable of facilitating extended catalyst production with high catalytic activities under both types of polymerization reaction conditions. Other types of Ziegler-Natta catalysts may exhibit limited capabilities for incorporating a, o -dienes (e.g., 1,7-octadiene or similar long-chain hydrocarbyl groups having terminal unsaturation at both ends of the hydrocarbyl chain) during polymerization of propylene to afford long- chain branching. Moreover, in contrast to some other types of Ziegler-Natta catalysts having multiple catalytic sites, bis(phenolate) complexes and similar dianionic complexes may afford branched polypropylene copolymers with a relatively limited molecular weight distribution (poly dispersity index, Mw/Mn), which may be advantageous in certain instances. Bis(phenolate) complexes and similar dianionic complexes are relatively simple to prepare and are typically isolated as a single isomer, which greatly simplifies their purification. By contrast, many metallocene catalysts used in polypropylene production are isolated as mixtures of diastereomers, thus leading to complicated isolation and purification processes.

[0016] To facilitate slurry-phase and gas-phase polymerization reactions, bis(phenolate) complexes and similar dianionic complexes may be readily incorporated upon a support material in combination with an activator. While located upon the support material, activation of such complexes may be realized using various types of activators, such as supported alumoxanes, acidic clays, and more discrete support-bound activators containing tethered aluminum or boron compounds. The latter supported activator may be particularly advantageous in avoiding use of costly methylalumoxane as an external activator, which is highly reactive and also prone to gelation. Activation with a combination of an organoaluminum compound containing a haloaryl group (e.g., pentafluorophenyl) and a tertiary aryl amine may be especially advantageous for copolymerizing a,co-dienes, since such monomers may lead to reduced catalytic activities in some cases. Such activation chemistry may be especially advantageous for slurry-phase or gas-phase polymerization of a,co-dienes.

[0017] Slurry-phase polymerization may be particularly advantageous for affording afford branched polypropylene copolymers in the disclosure herein. One major advantage of using a dianionic complex upon a support material for in-reactor preparation of long-chain branched polypropylene via a,co-diene copolymerization is more ready operability compared to conventional solution polymerization process. Long-chain branches inevitably leads to formation of ultra-high molecular weight fractions, which have a tendency to precipitate out of the reactor medium and cause fouling and reactor shutdown in solution polymerization processes. By using a supported catalyst in a slurryphase polymerization, high molecular weight chain fractions may grow within a polymer particle and thereby eliminate fouling risks. Definitions

[0018] For the purposes of the present disclosure, the new numbering scheme for groups of the Periodic Table is used. In said numbering scheme, the groups (columns) are numbered sequentially from left to right from 1 through 18, excluding the f-block elements (lanthanides and actinides). Under this scheme, the term “transition metal” refers to any atom from Groups 3-12 of the Periodic Table, inclusive of the lanthanide and actinide elements. Ti, Zr, and Hf are Group 4 transition metals, for example.

[0019] 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 poly dispersity index (PDI), is defined to be Mw divided by Mn. Unless otherwise noted, all molecular weight units (e.g., Mw, Mn, and Mz) are in units of g/mol (g’mof¹). Procedures for determining polymer molecular weights are specified below.

[0020] For purposes of this disclosure, when a polymer or copolymer, particularly a polyolefin, is referred to as comprising an olefin, the olefin present in such polymer, copolymer, or oligomer is the polymerized form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 0 wt% to 5 wt%, it is to be understood that the mer unit in the copolymer is derived from the monomer ethylene in the polymerization reaction and said derived units are present at 0 wt% (i.e., absent) to 5 wt%, based upon the weight of the copolymer. As used herein, the terms “polymer” and oligomer” (and grammatical variations thereof) are used interchangeably to refer to a molecule having two or more of the same or different mer units. As used herein, the term “polymerize” (and grammatical variations thereof, e.g., polymerization) is used to refer to a process of generating a molecule having two or more of the same or different mer units from two or more of the same or different monomers. A “homopolymer” is a polymer (or oligomer) having mer units that are the same. A “copolymer” is a polymer (or oligomer) having two or more mer units that are different from each other. A “terpolymer” is a polymer (or oligomer) 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 and like higher polymers (or oligomers). A "decene polymer" or "decene copolymer," for example, is a polymer or copolymer comprising at least 50 mol% decene- derived units. [0021] A “straight-chain polypropylene” or “linear polypropylene” comprises a polymer backbone resulting from polymerization of polymerization of propylene and optionally one or more additional ethylenically unsaturated monomers, and at least methyl group branches extending from the polymer backbone, wherein the methyl group branches originate from the propylene. A “branched polypropylene” contains further branches in addition to the methyl group branches. Branched polypropylenes of the present disclosure may have a branching index, as measured by a g’™ value (discussed herein), lower than the branching index resulting from homopolymerization of propylene under similar conditions.

[0022] The term “independently,” when referenced to selection of multiple items from within a given group, means that the selected choice for a first item does not necessarily influence the choice of any second or subsequent item. That is, independent selection of multiple items within a given group means that the individual items may be the same as or different from one another.

[0023] The terms “group,” “radical,” and “substituent” may be used interchangeably herein.

[0024] The term “hydrocarbon” refers to a class of compounds having hydrogen bound to carbon, and encompasses saturated hydrocarbon compounds, unsaturated hydrocarbon compounds, and mixtures of hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different numbers of carbon atoms. The term “C_n” refers to hydrocarbon(s) or a hydrocarbyl group having n carbon atom(s) per molecule or group, wherein n is a positive integer. Such hydrocarbon compounds may be one or more of linear, branched, cyclic, acyclic, saturated, unsaturated, aliphatic, and/or aromatic. As used herein, a cyclic hydrocarbon may be referred to as “carbocyclic,” which includes saturated, unsaturated, and partially unsaturated carbocyclic compounds, as well as aromatic compounds. The term “heterocyclic” refers to a carbocyclic ring containing at least one ring heteroatom as a replacement for a ring carbon atom.

[0025] The terms “hydrocarbyl radical,” “hydrocarbyl,” and “hydrocarbyl group” may be used interchangeably throughout this disclosure and refer to a group containing hydrogen atoms and carbon atoms and bearing at least one unfilled valence position when removed from a parent compound. Hydrocarbyl radicals may be optionally substituted in some cases. Suitable “hydrocarbyl radicals” may refer to Ci-Cioo radicals that may be linear, branched, or cyclic, and when cyclic, aromatic or non-aromatic in nature. Examples of saturated hydrocarbyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like including, their substituted analogues. [0026] Substituted hydrocarbyl radicals are radicals in which at least one hydrogen atom of the hydrocarbyl radical has been substituted with at least a non-hydrogen group, such as a hydrocarbyl group, a halogen (e.g., Br, Cl, F or I), or at least one functional group such as NR*2, OR*, SeR*, TeR*, PR*2, ASR*2, SbR*2, SR*, BR*2, SiR*3, GeR*3, SnR*3, PbR*3, and the like, or where at least one heteroatom has been inserted within a hydrocarbyl ring or chain, wherein each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical, or two or more R* may join together to form a substituted or unsubstituted, saturated, unsaturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure.

[0027] The term “substituted” refers to replacement of at least one hydrogen atom or carbon atom of a hydrocarbon or hydrocarbyl group with a heteroatom or heteroatom functional group. Heteroatoms may include, but are not limited to, B, O, N, S, P, F, Cl, Br, I, Si, Pb, Ge, Sn, As, Sb, Se, and Te. Heteroatom functional groups that may be present in substituted hydrocarbons or hydrocarbyl groups include, but are not limited to, functional groups such as O, S, S=O, S(=O)2, NO2, F, Cl, Br, I, NR₂, OR, SeR, TeR, PR₂, AsR₂, SbR^ SR, BR^ SiR₃, GeR₃, SnR₃, PbR^, where R is a hydrocarbyl group or H. Suitable hydrocarbyl R groups may include alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, and the like, any of which may be optionally substituted.

[0028] The term “optionally substituted” means that a hydrocarbon or hydrocarbyl group can be unsubstituted or substituted. For example, the term “optionally substituted hydrocarbyl” refers to replacement of at least one hydrogen atom or carbon atom in a hydrocarbyl group with a heteroatom or heteroatom functional group. Unless otherwise specified as being expressly unsubstituted, any of the hydrocarbyl groups herein may be optionally substituted.

[0029] The term “saturated hydrocarbon” means a hydrocarbon that contains zero carbon-carbon double bonds or carbon-carbon triple bonds. The saturated hydrocarbon can be a linear or cyclic hydrocarbon, either of which may be optionally branched. The saturated hydrocarbon can be a C2- C40 hydrocarbon, such as a C4-C7 hydrocarbon. In at least one embodiment, a C4-C7 hydrocarbon may be isobutane, pentane, cyclopentane, cyclohexane, isopentane, isohexane, hexane, heptane, or mixtures thereof.

[0030] The term “alkyl” means a straight-chain, branched-chain, or cyclic hydrocarbon radical having only carbon-carbon single bonds. Such alkyl radicals may be substituted. Examples of alkyl radicals include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, iso-amyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and the like, including their substituted analogues. [0031] The term “alkylene” means a divalent alkyl radical, such as a C1-C12 alkylene radical having open valence positions at each end of a carbon chain. For example, a methylene group is a divalent alkylene radical.

[0032] The term “olefin” (alternately referred to as “alkene”) means a linear, branched, or cyclic compound of carbon and hydrogen having at least one double carbon-carbon bond.

[0033] The term “alkenyl” means a straight-chain, branched-chain, or cyclic hydrocarbon radical having one or more carbon-carbon double bonds. The alkenyl radicals may be optionally substituted. Examples of suitable alkenyl radicals include, but are not limited to, ethenyl, propenyl, allyl, 1,4- butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloctenyl, and the like, including their substituted analogues.

[0034] The term “diene” refers to an alkene having two carbon-carbon double bonds. The term “a, o -diene” refers to an alkene having an unsaturated carbon-carbon double bond at each end of a carbon chain.

[0035] The term “aromatic” means a hydrocarbyl compound or group containing a planar unsaturated ring of atoms that is stabilized by interaction of the bonds forming the ring. Such compounds are often six-membered rings such as benzene and its derivatives. As used herein, the term “aromatic” also refers to pseudoaromatics which are compounds that have similar properties and structures (nearly planar) to aromatics, but are not by definition aromatic; likewise, the term aromatic also refers to substituted aromatic compounds and radicals. Aromatic (but not pseudoaromatic) hydrocarbons obey the Hiickel Rule and contain a cyclic cloud of 4n+2 ^-electrons, where n is a positive integer.

[0036] The term “aryl” or “aryl group” means a carbon-containing aromatic ring or substituted variants thereof, including but not limited to, phenyl, 2-methylphenyl, xylyl, 4-bromoxylyl, and the like. Likewise, the term “heteroaryl” or “heteroaryl group” 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 groups, but are not by definition aromatic.

[0037] A substituted aryl is an aryl group where at least one hydrogen atom of the aryl radical has been substituted with at least a non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom -containing group, such as halogen (e.g., Br, Cl, F or I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*₂, -AsR*₂, -SbR*₂, -SR*, -BR*₂, -SiR*, -SiR*₃, -GeR*, -GeR*3, -SnR*, -SnR*3, -PbR*3, and the like, where each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical, or two or more R* may join together to form a substituted or unsubstituted, saturated, unsaturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, or where at least one heteroatom has been inserted within a hydrocarbyl ring. For example, 3, 5 -dimethylphenyl and 2-methylphenyl are substituted aryl groups. The term “arylalkyl” may also refer to an aryl group where a hydrogen has been replaced with an alkyl or substituted alkyl group. The term “alkylaryl” means an alkyl group where a hydrogen has been replaced with an aryl or substituted aryl group. Thus, for example, 2-methylphenyl is an arylalkyl or substituted aryl group, and benzyl and phenethyl are alkylaryl groups.

[0038] Any aryl group herein may be an optionally substituted phenyl group. The term “substituted phenyl,” or “substituted phenyl group” means a phenyl group having one or more hydrogen groups replaced by a hydrocarbyl, substituted hydrocarbyl, heteroatom, or heteroatom-containing group, such as halogen (e.g., F, Cl, Br, I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*,-PR*₂, -AsR*₂, -SbR*₂, -SR*, -BR*₂, -SiR*, -SiR*₃, -GeR*, -GeR*₃, -SnR*, -SnR*3, -PbR*3, and the like, where each R* is independently hydrogen, a hydrocarbyl, halogen, or halocarbyl radical, or two or more R* may join together to form a substituted or unsubstituted, saturated, unsaturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure, or where at least one heteroatom has been inserted within a hydrocarbyl ring.

[0039] The term “heterocyclic” means a cyclic group where a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom, such as N, O, or S. 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 4-N,N-dimethylaminophenyl is a heteroatom-substituted ring.

[0040] The term “substituted heterocyclic” means a heterocyclic group where at least one hydrogen atom of the heterocyclic radical has been substituted with at least a non-hydrogen group, such as a hydrocarbyl group, a heteroatom, or a heteroatom-containing group, such as halogen (e.g, F, Cl, Br, I) or at least one functional group such as -NR*2, -OR*, -SeR*, -TeR*, -PR*2, -AsR*2, -SbR*₂, -SR*, -BR*2, -SiR*, -SiR*₃, -GeR*, -GeR*₃, -SnR*, -SnR*₃, -PbR*3, and the like, where each R* is independently hydrogen, a hydrocarbyl or halocarbyl radical.

[0041] The term “optionally substituted heterocycle” or “optionally substituted heterocyclic” means a heterocyclic group wherein a non-hydrogen group substitution may or may not be present. Unless otherwise specified, any heterocyclic group herein may be optionally substituted. [0042] The term “ring atom” means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has 6 ring atoms and tetrahydrofuran has five ring atoms.

[0043] Where isomers of a named alkyl, alkenyl, alkoxide, or aryl group exist (e.g., n-butyl, isobutyl, sec-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).

[0044] The terms “catalyst productivity” and “catalyst activity” interchangeably refer to 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*W) and expressed in units of gPgcat ¹ hr 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 (weight) 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 mass of catalyst (gP/g catalyst).

[0045] The term “catalyst system” refers to a combination of at least one catalyst compound (e.g., at least one bis(phenolate) complex or similar dianionic complex) and an optional support material. The catalyst system may further include at least one activator and/or at least one co-activator. Accordingly, preferable catalyst systems may include at least one catalyst compound disposed upon a support material in combination with at least one activator. When catalyst systems are described as comprising neutral stable forms of the foregoing components, it is to be understood that the ionic form of the component is the form that reacts with monomers to produce polymers. For purposes of the present disclosure, a “catalyst system” may include both neutral and ionic forms of the components of the catalyst system.

[0046] In the present disclosure, a “catalyst” may be described as any of a catalyst precursor, a precatalyst compound, catalyst compound, a catalyst, or a transition metal compound or complex, and these terms are used interchangeably herein. An “anionic ligand” is a negatively charged ligand which donates one or more pairs of electrons to a metal atom. A “neutral donor ligand” is a neutrally charged ligand which donates one or more pairs of electrons to a metal atom. Such ligands may be monodentate or polydentate in nature.

[0047] The term “alkoxide” means entities containing a Ci to C40 hydrocarbyl group bound to oxygen. The hydrocarbyl group may be straight-chain, branched, or cyclic, and be saturated or unsaturated, including aromatic. The terms “alkoxy” and “alkoxide” therefore refer to an alkyl ether or aryl ether radical. Examples of hydrocarbyl ether radicals include, but are not limited to, methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy, phenoxy, and the like. [0048] The term “complex” means molecules in which an ancillary ligand is coordinated to a central metal atom. The ligand is stably bonded to the metal atom so as to maintain its influence during use of the complex during a catalytic process, such as polymerization. The ligand may be coordinated to the metal atom by a covalent bond and/or electron donation coordination or intermediate bonds. The bonding to the metal atom may be a dative bond, for instance. Metal complexes may be subjected to activation to perform their catalytic function, such as polymerization, using an activator which is believed to create a cation as a result of the removal of an anionic group, often referred to as a leaving group, from the metal atom.

[0049] The term “phenolate” means a complex in which at least one phenol anion forms a covalent bond to metal atom. A “bis(phenolate)” refers to a complex in which two phenol anions form covalent bonds to a metal atom. Optionally, the two phenol anions (phenolates) may be joined together by a linker group to create a chelate ring of a desired size.

[0050] The term “scavenger” refers to a compound that may be added to a catalyst system to facilitate polymerization by scavenging impurities. 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 system. In at least one embodiment, a co-activator can be pre-mixed with a complex to form an alkylated metal complex.

[0051] The term “continuous” means a system that operates without interruption or cessation for a period of time. For example, a continuous process to produce a polymer may continually introduce monomer into one or more reactors, and polymer product is continually withdrawn therefrom.

[0052] The term “bulk polymerization” or “slurry-phase polymerization” means a polymerization process in which the monomers and/or co-monomers being polymerized are used as a solvent or diluent using little or no inert solvent or diluent, wherein supported catalyst particles are dispersed in the solvent or diluent. A small fraction of inert solvent might be used as a carrier for catalyst and scavenger. A slurry -phase polymerization contains less than about 25 wt% of inert solvent or diluent, such as less than about 10 wt%, such as less than about 1 wt%, such as 0 wt%. The polymerization reaction conditions associated with a slurry polymerization may include operation at a sufficient pressure to maintain the monomers and/or co-monomers in a liquid state. [0053] The term “gas-phase polymerization” refers to a polymerization process in which monomers and/or co-monomers are present in a gaseous state during polymerization and supported catalyst particles are fluidized within a reactor.

[0054] When used in the present disclosure, the following abbreviations may be used: dme is 1,2- dimethoxy ethane, Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is normal propyl, cPr is cyclopropyl, Bu is butyl, iBu is isobutyl, tBu is tertiary butyl, p-tBu is para-tertiary butyl, nBu is normal butyl, sBu is sec-butyl, TMS is trimethylsilyl, TIB AL is triisobutylaluminum, TNOAL is tri(n-octyl)aluminum, MAO is methylalumoxane, sMAO is supported methylalumoxane, Bn is benzyl (/. « , CTLPh), THF (also referred to as tetrahydrofuran, RT is room temperature (and is 23°C unless otherwise indicated), tol is toluene, EtOAc is ethyl acetate, and Cy is cyclohexyl.

Dianionic Complexes

[0055] Suitable dianionic complexes, such as bis(phenolate) complexes, effective for promoting formation of branched polypropylene copolymers according to the disclosure herein may comprise a Group 3-6 metal, preferably a Group 4 metal (e.g., Ti, Zr, or Hf), more preferably Zr. When suitably activated, the dianionic complexes may be effective for promoting polymerization of propylene and other ethylenically unsaturated compounds, including oc, co -dienes under a range of polymerization reaction conditions, preferably wherein the dianionic complexes are disposed upon a support material in combination with at least one activator. Further details regarding activation of the dianionic complexes and polymerization therewith is provided hereinbelow.

[0056] Bis(phenolate) complexes suitable for use in the present disclosure may have a structure represented by Formula 1.

Formula 1 wherein:

[0057] M is a Group 3-6 metal, preferably a Group 4 metal;

[0058] E and E' are independently O, S, or NR⁹, wherein each R⁹ is independently hydrogen, a C1-C40 optionally substituted hydrocarbyl, or a heteroatom-containing group; [0059] Z is a Group 14-16 atom forming a dative bond to M;

[0060] A^A¹ is part of a heterocyclic Lewis base, designated as B, containing 4 to 40 nonhydrogen atoms that links A² to A² via a 3 -atom bridge, with Z being the central atom of the 3 -atom bridge;

[0061] are independently C, N, or CR²², wherein each R²² is hydrogen or optionally

substituted C1-C20 hydrocarbyl, such as optionally substituted C1-C20 alkyl;

[0062] is a divalent group, optionally part of an optionally substituted hydrocarbyl

ring or optionally substituted heterocyclic ring, containing 2 to 40 non-hydrogen atoms that links A¹ to a first aryl group via a 2-atom bridge, the first aryl having E bonded thereto;

[0063]

_a divalent group, optionally part of an optionally substituted hydrocarbyl ring or optionally substituted heterocyclic ring, containing 2 to 40 non-hydrogen atoms that links A¹ to a second aryl group via a 2-atom bridge, the second aryl group having E’ bonded thereto;

[0064] each L is a Lewis base;

[0065] each X is an anionic ligand;

[0066] n is i, 2, or 3;

[0067] m is 0, 1 , or 2;

[0068] n+m is not greater than 4; and

[0069] R¹, R², R³, R⁴, R¹ , R², R³, and R⁴' are independently hydrogen, optionally substituted

C1-C40 hydrocarbyl, a heteroatom, or a heteroatom-containing group or one, or more of R¹ and R², R² and R³, R³ and R⁴, R¹ and R², R² and R³ , R³ and R⁴ are joined to form one or more optionally substituted hydrocarbyl rings or optionally substituted heterocyclic rings, each ring having 5, 6, 7, or 8 ring atoms, and optionally wherein the optionally substituted hydrocarbyl rings or optionally substituted heterocyclic rings are fused to one or more additional rings;

[0070] wherein:

[0071] when m is 2, any two L groups are optionally joined together to form abidentate Lewis base; or

[0072] an X is optionally joined to an L to form a monoanionic bidentate ligand bound to M; or

[0073] when n is 2 or 3, any two X are optionally joined together to form a dianionic ligand bound to M. [0074] In more specific examples, the dianionic complex comprises a Group 4 metal. Preferably, the Group 4 metal M is zirconium.

[0075] Preferably, E and E’ are each O. As such, preferred dianionic complexes of the present disclosure may be bis(phenolate) complexes. When E and E’ are S or NR⁹, the complexes may be referred to as bis(phenothiolate) or bis(anilide) complexes.

[0076] When E or E’ is NR⁹, R⁹ is independently hydrogen, Cj-Qo optionally substituted hydrocarbyl, or a heteroatom-containing group. Preferably, R⁹ is a Ci-Cao alkyl group or a Ce-Cio aryl, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl, naphthyl, or the like, any of which may be optionally substituted.

[0077] Preferably, the heterocyclic Lewis base is a 5- or 6-membered heteroaromatic ring. Examples of such heterocyclic Lewis bases may include, for example, pyridine, pyrazine, pyrimidine, triazine, thiazole, imidazole, thiophene, oxazole, thiazole, and furan, any of which may be optionally substituted or fused to another ring. More preferably, Z of the heterocyclic Lewis base is N. Still more preferably, the heterocyclic Lewis base may be an optionally substituted pyridine.

[0078] In more specific examples, the heterocyclic Lewis base is a 2,6-disubstituted pyridine ring, wherein A³ — A² and A² — A^J are bonded to the 2- and 6-positions of the pyridine ring, respectively, and the nitrogen atom of the pyridine ring (Z in A’ZA¹ ) forms the dative bond to M.

[0079] A’— A- and A —A ’ are each preferably a two-atom linker group, wherein the two-atom portion of the linker group refers to the number of atoms linking the heterocyclic Lewis base to an aryl group bearing E or E’. Example two-atom linker groups from which A^J — A² and A² — A^J may be independently selected include optionally substituted arylene, optionally substituted heteroarylene, or optionally substituted vinylene. Other examples of suitable two-atom linker groups may include non-aromatic groups, such as optionally substituted ethylene, optionally substituted cycloalkylene, optionally substituted heterocyclene, and the like.

3 Q 2* 3’

[0080] In some examples, A ^A'and A —A _may each be an optionally substituted phenylene (e.g., an optionally substituted o-phenylene), an optionally substituted cycloalkylene, or an optionally substituted heteroarylene, either of which may be optionally fused to additional aromatic or non-

3 2 2' A 3' aromatic rings. For example, in one or more embodiments, A ^Z22;A and A —A may be independently selected from an optionally substituted o-phenylene, an optionally substituted 1,2- thienyl group, or an optionally substituted 1,2-furanyl group, any of which may be fused to an additional aromatic or non-aromatic ring. Preferably, A^3zzzzA² and A² — A^J are the same.

[0081] In some examples, R², R⁴, R² , and R⁴ are each hydrogen.

[0082] In some examples, R³ and R³ are independently hydrogen, an optionally substituted C1-C40 hydrocarbyl group, or a halogen (e.g., F). More preferably, R³ and R³ may be independently selected from an optionally substituted C1-C10 alkyl group, a halogen, or any combination thereof. R³ and R³ may be the same or different, but preferably R³ and R³ are the same. Examples of suitable hydrocarbyl groups for R³ and R³ include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, adamantyl, 2-phenylisopropyl (a,oc-dimethylbenzyl), 1, 1,3,3- tetramethylbutyl, and the like.

[0083] In some examples, R¹ and R¹ are independently selected from among optionally substituted C1-C40 hydrocarbyl groups, more preferably optionally substituted C4-C16 hydrocarbyl groups or optionally substituted C6-C16 hydrocarbyl groups. Still more preferably, R¹ and R¹ may each be an optionally substituted bulky alkyl group (inclusive of tertiary alkyl groups or tertiary alkylaryl groups), such as optionally substituted t-butyl, optionally substituted cyclohexyl, optionally substituted 1 -methylcyclohexyl, optionally substituted norbomanyl, optionally substituted adamantanyl, optionally substituted 1,1,3,3-tetramethylbutyl, 2-phenylisopropyl, and the like. More preferably, R¹ and R¹ are each independently an optionally substituted tertiary alkyl group, such as an optionally substituted adamantyl group or an optionally substituted t-butyl group. Optionally substituted adamantyl groups include 1-adamantyl and 2-adamantyl, such as 3,5-dimethyl-l- adamantyl or 3,5,7-tiimethyl-l-adamantyl. R¹ and R¹ may be the same or different, but preferably R¹ and R¹ are the same.

[0084] Non-limiting examples of X include, but are not limited to, an optionally substituted C1-C40 hydrocarbyl (such as an optionally substituted C1-C20 hydrocarbyl), an optionally substituted C4-C62 aryl, an optionally substituted C4-C62 heteroaryl, hydride, amide, alkoxide, sulfide, phosphide, halide, or a combination thereof. For example, each X may be independently a halide or a Ci-Ce hydrocarbyl or a C1-C10 hydrocarbyl, such as methyl or benzyl, either of which may be further optionally substituted. In some embodiments, each of X may be independently selected from chloro, bromo, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl. In some embodiments of the present disclosure, one or more X may form a part of a fused ring or a ring system when combined with another X or with L. [0085] In some examples, n is 2. In some or other examples, m is 0.

[0086] Accordingly, in more specific examples, suitable dianionic complexes for use in the present disclosure may be bis(phenolate) complexes (E=E’=O) having a structure represented by Formulas 2A-2E below

Formula 2C

Formula 2E wherein:

[0087] R¹, R³, R²², and M are defined as above, Q is optional substitution at any open ring position, and further optionally two Q may be joined to define a carbocyclic, heterocyclic, aromatic, or heteroaromatic ring fused to the phenyl, thienyl, furanyl, pyrrolyl, or cyclohexyl ring system of Formulas 2A-2E. Variable r is 0, 1, 2, 3, or 4 for the phenyl rings of Formula 2A; 0, 1 , or 2 for the thienyl, furanyl, and pyrrolyl rings of Formulas 2B-2D; and 0, 1, 2, 3, 4, 5, 6, 7, or 8 for the cyclohexyl ring system of Formula 2E. Variable q is 0, 1, 2, or 3, preferably 0 or 1. When present, Q is optionally substituted C1-C40 hydrocarbyl, a heteroatom, or a heteroatom-containing group or one, or two or more Q are joined to define the above-referenced carbocyclic, heterocyclic, aromatic, or heteroaromatic rings, wherein such rings may have 5, 6, 7, or 8 ring atoms and may be optionally fused to one or more additional rings.

[0088] More preferably, R¹ and R¹’ are each independently selected from a tertiary alkyl group or a tertiary alkylaryl group, such as an adamantyl group (e.g., an optionally substituted 1-adamantyl group), an optionally substituted t-butyl group, an optionally substituted 2-phenylisopropyl group, or an optionally substituted 1,1,3,3-tetramethylbutyl group; R³ and R³ are each selected from among a C1-C10 alkyl group, a C1-C10 alkylaryl group, or a halogen e.g., F); and M is a Group 4 metal, preferably Zr. In more specific examples, R¹ and R¹ are each independently an optionally substituted 1-adamantyl group or an optionally substituted t-butyl group; R³ and R³ are independently an optionally substituted C1-C10 alkyl group or F; and M is a Group 4 metal, preferably Zr. Preferably, R¹ and R¹ are the same, and R³ and R³ are the same. [0089] Illustrative examples of bis(phenolate) complexes having a structure represented by

Formulas 2A-2E (M = Zr or Hf) may include, but are not limited to

and

Preferably, in any of the foregoing, M is Zr.

[0090] In more particular examples, the dianionic complex may be

Hf may replace Zr in any of the foregoing bis(phenolate) complexes. [0091] Any of the foregoing dianionic complexes may be incorporated in catalyst systems comprising a support material, preferably an activator upon the support material, optionally a coactivator, and optionally a scavenger. Preferably, the activator is present and disposed upon the support material in combination with the dianionic complex. The activator and optional co-activator may convert the dianionic complex into a form effective for promoting olefin polymerization under suitable polymerization reaction conditions to form an impact copolymer, as described in further detail hereinbelow.

Support Materials

[0092] In conducting polymerization reactions to form a branched polypropylene copolymer according to the present disclosure, the dianionic complex, such as a bis(phenolate) complex, may be disposed upon a support material. At least one activator may also be disposed upon the support material in combination with the dianionic complex, optionally in further combination with a coactivator and/or a scavenger. Suitable activators may be disposed upon the support material by contacting the support material with a solution containing the activator or the activator may be formed in situ upon the support material. Further, the activator may be covalently bonded to the support material and/or otherwise chemically modify the support material. Additional activator details are provided below.

[0093] The support material may be an inorganic oxide in a finely divided form, such as silica, alumina, talc, zeolites, clays, organoclays, and the like, each having a highly porous structure. Suitable inorganic oxides upon which dianionic complexes may be disposed in accordance with the present disclosure include Groups 2, 4, 13, or 14 metal oxides, such as silica, alumina, and mixtures thereof. Other inorganic oxides may be employed, either alone or in combination with the silica or alumina, such as magnesia, titania, zirconia, or the like. Particularly useful support materials may include magnesia, titania, zirconia, montmorillonite, phyllosilicate, zeolites, talc, silica, clays, silica clay, silicon oxide clay, and the like. Combinations of these support materials may be used such as, for example, silica-chromium, silica-alumina, silica-titania, and the like. In at least one embodiment, the support material may be selected from AI2O3, ZrCh, SiCL, SiO^AhCh, silica clay, silicon oxide/clay, or mixtures thereof. Other suitable support materials may be employed as well such as, for example, finely divided functionalized polyolefins, such as finely divided polyethylene, polypropylene, and polystyrene with functional groups that are able to absorb water, (e.g., oxygen- or nitrogen-containing groups such as -OH, -RC=O, -OR, and -NR2). Still other organic or inorganic support materials may also be suitably used.

[0094] The support material may be optionally treated with an electron-withdrawing anion. The electron-withdrawing anion may increase the Lewis or Bronsted acidity of the support material, as compared to the support material that is not treated. The electron-withdrawing anion may be derived from a salt, an acid, or other compounds, such as a volatile organic compound, that serve as a source or precursor for the electron-withdrawing anion. Electron-withdrawing anions may include sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, tri fluoroacetate, triflate (trifluoromethanesulfonate), fluorozirconate, fluorotitanate, phosphotungstate, or any combination thereof. Combinations of one or more different electronwithdrawing anions, in varying proportions, may be used to tailor the specific acidity of the support material to a desired level. Such combinations of electron-withdrawing anions may be contacted with the support material simultaneously or individually and in any order that provides a desired specific acidity.

[0095] The support material may be optionally fluorided by introducing a fluoride-containing anion. For example, a fluorided support may be a silicon dioxide support wherein a portion of the silica hydroxyl groups have been replaced with fluorine or a fluorine-containing compound. Suitable fluorine-containing compounds include, but are not limited to, inorganic fluorine-containing compounds and/or organic fluorine-containing compounds, either of which may be utilized for providing fluorine to the support material. Illustrative inorganic fluorine-containing compounds that may be used for fluoriding a support material include, for example, NH4BF4, (NFL^SiFe, NFUPFe, NH₄F, (NH₄)₂TaF₇, NH₄NbF₄, (NH₄)₂GeF₆, (NH₄)₂SmF₆, (NH₄)₂TiF₆, (NH₄)₂ZrF₆, MoF₆, ReF₆, GaFs, SO₂C1F, F₂, SiF4, SFe, CIF3, CIF5, BrFs. IF7, NF3, HF, BF3, NHF₂, NH4HF₂, and combinations thereof.

[0096] Non-limiting examples of cations suitable for use in the present disclosure in combination with the electron-withdrawing anion include ammonium, trialkylammonium, tetraalkylammonium, tetraalkylphosphonium, H⁺, [H(OEt₂)₂]⁺, [HNR.3]⁺(R is a Ci-C₂o hydrocarbyl group, which may be the same or different and optionally substituted), or combinations thereof.

[0097] The method by which the support material is contacted with the electron-withdrawing anion, may include, but is not limited to, gelling, co-gelling, impregnation of one compound onto another, the like, or combinations thereof. Following a particular contacting method, the treated support material may then be calcined.

[0098] The support material, such as an inorganic oxide and more preferably silica, may have a surface area about 10 m²/g to about 800 m²/g, or about 10 m²/g to about 500 m²/g, or about 10 m²/g to about 100 m²/g, or about 10 m²/g to about 50 m²/g, or about 50 m²/g to about 800 m²/g, or about 50 m²/g to about 500 m²/g, or about 50 m²/g to about 100 m²/g, or about 100 m²/g to about 800 m²/g, or about 100 m²/g to about 500 m²/g, or about 500 m²/g to about 800 m²/g. [0099] The support material, such as an inorganic oxide and more preferably silica, may have a pore volume of about 0.1 cc/g to about 4.0 cc/g, or about 0.1 cc/g to about 1 cc/g, or about 1 cc/g to about 4 cc/g. The average pore size of the support material may be about 10 A to about 1000 A, or about 10 A to about 500 A, or about 10 A to about 100 A, or about 100 A to about 1000 A, or about 100 A to about 500 A, or about 500 A to about 1000 A.

[0100] The support material, such as an inorganic oxide and more preferably silica, may have an average particle size of about 5 pm to about 500 pm, or about 5 pm to about 100 pm, or about 5 pm to about 50 pm, or about 50 pm to about 500 pm, or about 50 pm to about 100 pm, or about 100 pm to about 500 pm.

[0101] Before employing the support material in a polymerization reaction or before disposing a dianionic complex thereon, the support material may be free or substantially free of absorbed water. Drying of the support material can be realized by heating or calcining at about 100°C to about 1000°C, preferably at least about 200°C. When the support material is silica, the silica may be heated to at least about 200°C, preferably about 200°C to about 850°C, and more preferably at about 400°C; and for a time of about 1 minute to about 100 hours, or from about 12 hours to about 72 hours, or from about 24 hours to about 60 hours. After calcination, the support material may be contacted with a dianionic complex and optionally an activator to produce a catalyst system.

[0102] To accomplish the foregoing, the support material may be slurried in a non-polar solvent and contacted with a solution of the dianionic complex and optionally an activator. In some embodiments, the slurry of the support material may first be contacted with the activator for about 0.5 hours to about 24 hours, or from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours before disposing the dianionic complex thereon. Alternately, the slurry of the support material may first be contacted with the dianionic complex for about 0.5 hours to about 24 hours, or from about 2 hours to about 16 hours, or from about 4 hours to about 8 hours before being contacted with an activator. Once the metallocene and the activator have been contacted with each other, the catalyst system may be aged, optionally with heating up to about 70°C, for about 0.5 hours to about 24 hours, or about 2 hours to about 16 hours, or about 4 hours to about 8 hours before being used to conduct a polymerization reaction.

[0103] Suitable non-polar solvents for loading the dianionic complex and the optional activator upon the support material may include those in which the dianionic complex and the optional activator 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. Aromatic hydrocarbons, such as benzene, toluene, and ethylbenzene, may also be employed.

Activators

[0104] In most cases, at least one activator is present upon the support material in combination with the dianionic complex. Suitable activators may include, for example, alumoxanes (e.g., methylalumoxane-MAO), non-coordinating anions, or any combination thereof.

[0105] Alumoxanes are generally oligomeric compounds containing -A1(R)-O- sub-units, where R 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 can 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, described in U.S. Patent No. 5,041,584). Another useful alumoxane is solid polymethylaluminoxane as described in US Patents 9,340,630; 8,404,880; and 8,975,209.

[0106] When the activator is an alumoxane (modified or unmodified), some embodiments may select the maximum amount of activator at up to a 5000-fold molar excess Al/M over the catalyst compound (per metal catalytic site). The minimum activator-to-metal ratio is a 1 :1 molar ratio. Suitable ranges may include from 1 : 1 to 500: 1, or from 1 : 1 to 200: 1, or from 1 : 1 to 100: 1, or from 1 : 1 to 50:1.

[0107] Other suitable activators include compounds containing a non-coordinating anion, especially borane and borate compounds. Particularly useful borane and borate compounds containing a noncoordinating anion or similar entity include, for example, B(C6Fs)3, [PhNMe2H]⁺[B(C6F5)4]', [Ph₃C]⁺[B(C6F₅)4]-, and [PhNMe2H]⁺[B(CioF₇)4]’.

[0108] The term “non-coordinating anion” (NCA) means an anion which either does not coordinate to a cation or which is only weakly coordinated to a cation thereby remaining sufficiently labile to be displaced by a neutral Lewis base. The term NCA is defined to include multicomponent NCA- containing activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate and N,N- dimethylanilinium tetrakis(heptafluoronaphthyl)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. Typically, NCAs coordinate weakly enough that a neutral Lewis base, such as an olefmically or acetyl eni cal ly 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, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, aluminum, phosphorus, and silicon. The term non-coordinating anion includes neutral activators, ionic activators, and Lewis acid activators.

[0109] “Compatible” non-coordinating anions are those which are not degraded to neutrality when the initially formed complex decomposes. Further, the anion will 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 the 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. Ionizing activators useful herein typically comprise an NCA, particularly a compatible NCA.

[0110] It is within the scope of the present disclosure to use an ionizing, neutral, or ionic activator, such as tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, a tris perfluorophenylboron metalloid precursor or a trisperfluoronaphthylboron metalloid precursor, polyhalogenated heteroborane anions (WO 98/43983), boric acid (U.S. Patent No. 5,942,459), or any 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. Other useful activators may include those described in US Patents 8,658,556 and 6,211,105.

[0U1] In preferred embodiments, boron-containing NCA activators represented by Formula 4 below may be used,

Formula 4 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 boron-containing non-coordinating anion having the charge d’; and d is 1, 2, or 3. [0112] The cation component Za⁺ may include Bronsted acids such as protons or protonated Lewis bases or reducible Lewis acids capable of protonating or abstracting a moiety from the metal-ligand complexes to afford a cationic metal-ligand complex.

[0113] The cation component Za⁺ may also be a moiety such as silver, tropylium, carboniums, ferroceniums and mixtures thereof, preferably carboniums and ferroceniums. Suitable reducible Lewis acids include any triaryl carbonium (where the aryl can be substituted or unsubstituted, such as those represented by the formula: (ArsC⁺), where Ar is aryl or aryl substituted with a heteroatom, a Ci to C40 hydrocarbyl, or a substituted Ci to C40 hydrocarbyl). Preferably, the reducible Lewis acids in Formula 9 above defined as "Z" include those represented by the formula: (PhiC), 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, and preferably Zd⁺ is triphenylcarbonium.

[0114] When Za⁺ 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-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline, p-nitro-N,N-dimethylaniline, phosphoniums from triethylphosphine, triphenylphosphine, and diphenylphosphine, oxoniums from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane, sulfoniums from thioethers, such as diethyl thioethers, tetrahydrothiophene, and mixtures thereof.

[0115] The anion component A^d" includes those having the formula [M^k+G]^d“ wherein k is 1, 2, or 3; g is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4); g - k = d; M is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum, and G is independently a hydride, bridged or unbridged dialkylamido, halide, alkoxide, aryloxide, hydrocarbyl, substituted hydrocarbyl, halocarbyl, substituted halocarbyl, and halo- substituted hydrocarbyl radicals, said G having up to 20 carbon atoms with the proviso that in not more than 1 occurrence is G a halide. Preferably, each G is a fluorinated hydrocarbyl group having 1 to 20 carbon atoms, more preferably, each G is a fluorinated aryl group, and most preferably, each G is a pentafluoroaryl group. Examples of suitable A^d' also include diboron compounds as disclosed in U.S. Patent No. 5,447,895, which is fully incorporated herein by reference with respect to the diboron compounds disclosed therein. [0116] Illustrative but not limiting examples of boron compounds which may be used as an activator are the compounds described as (and particularly those specifically listed as) activators in U.S. Patent 8,658,556, which is incorporated by reference herein with respect to the boron compounds disclosed therein.

[0117] Most preferably, the activator Za⁺ (A^d‘) is one or more of N,N-dimethylanilinium tetra(perfluorophenyl)borate, N,N-dimethylanilinium 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, or triphenylcarbenium tetra(perfluorophenyl)borate. In any embodiment, the non-coordinating anion may be selected from N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate, N,N-dimethylanilinium tetrakis(perfluorobiphenyl)borate, N,N- dimethylanilinium tetrakis(perfluorophenyl)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 tetrakis(perfluorophenyl)borate, [Me3NH⁺][B(C6F5)⁴'], l-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl) pyrrolidinium; [Me3NH⁺][B(C6Fs)⁴'], l-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl) pyrrolidinium, sodium tetrakis(pentafluorophenyl)borate, potassium tetrakis(pentafluorophenyl)borate, and 4- (tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluoropyridinium. Preferably, the non-coordinating anion may be N,N-dimethylanilinium tetrakis(perfluoronaphthyl)borate.

[0118] Bulky activators are also useful herein as NCAs. "Bulky activator" as used herein refers to anionic activators represented by Formulas 5 or 6 below.

Formula 5 Formula 6

In Formulas 5 and 6, each R^la is, independently, a halide, preferably a fluoride; Ar is a substituted or unsubstituted aryl group (preferably a substituted or unsubstituted phenyl), preferably substituted with Cj to C₄₀ hydrocarbyls, preferably Cj to C₂₀ alkyls or aromatics; each R^2a is, independently, a halide, a C₆ to C₂₀ substituted aromatic hydrocarbyl group or a siloxy group of the formula -O-Si-R^a, where to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferably R^2a is a fluoride or a perfluorinated phenyl group); each R^3a is a halide, C₆ to C₂₀ substituted aromatic hydrocarbyl group or a siloxy group of the formula -O-Si-R^a, where R^a is a Cj to C₂₀ hydrocarbyl or hydrocarbylsilyl group (preferably R^3a is a fluoride or a C₆ perfluorinated aromatic hydrocarbyl group); wherein R^2a and R^3a can form one or more saturated or unsaturated, substituted or unsubstituted rings (preferably R^2a and R^3a 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; wherein at least three of the substituents on the B atom each have a molecular volume of greater than 250 cubic A, greater than 300 cubic A, or greater than 500 cubic A, as specified below.

[0119] Preferably, (ArsC)d⁺ is (PhsC)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.

[0120] In some or other examples, activation may take place with an organoaluminum compound having haloaryl groups, such as a pentafluorophenyl group, and a cationic group (in neutral form) may be introduced with the support material at a molar ratio of about 0.01: 1 to about 1 : 1, based on the molar concentration of, respectively, the organoaluminum compound having haloaryl groups or the cationic group (in neutral form) relative to a molar concentration of hydroxyl groups upon the support material. Within this range, a molar ratio of less than or equal to about 1 : 1 can be employed, such as less than or equal to about 0.5: 1, or less than or equal to about 0.25:1 . The amount of hydroxyl groups upon the support material may be determined, for example, by Attenuated Total Reflectance Infrared Spectroscopy (ATRTR), X-ray Photoelectron Spectroscopy (XPS), NMR, or Secondary Ion Mass Spectroscopy (SIMS).

[0121] The organoaluminum compound having haloaryl groups may be substantially dispersed over the total surface area of the support material, wherein an amount of coverage upon the support material may be at least about 75%, or at least about 90% of the total surface area of the support material.

[0122] After the organoaluminum compound has been introduced to the support material, there may be remaining hydroxyl groups on the support material, which may be detrimental to overall catalyst activity. To prevent catalyst deactivation, the remaining hydroxyl groups can be treated with a second aluminum compound having a formula of A1(R³)(R²)(R³), wherein R¹ is C1-C40 alkyl, a substituted or unsubstituted C6-C40 aryl, or hydride, and R² and R³ are independently, C1-C40 alkyl, alkoxy, heteroalkyl, or a substituted or unsubstituted C6-C40 aryloxy or heteroaryl group.

[0123] The second aluminum compound may contain simple components, such as an alkyl aluminum, and phenolic derivatives, such as BHT. A protonolysis reaction between an aluminum alkyl or aluminum hydride and surface hydroxyl groups results in deactivation of the hydroxyl groups via release of hydrocarbon or hydrogen, and leads to anchoring of the second aluminum compound on the support material. This effectively reduces or eliminates the possibility of active protons interfering with the catalyst activity.

[0124] The second aluminum compound may be introduced to the activator-bound support at a molar ratio of about 0.1 :1 to about 10: 1, based on the molar concentration of, respectively, the antioxidant (BHT) relative to the molar concentration of hydroxyl groups on the support material before treatment with the organoaluminum compound containing haloaryl groups. Within this range, a molar ratio of less than or equal to about 5: 1 can be employed, such as less than or equal to about 2: 1, and most preferably less than or equal to about 1 : 1. In some embodiments within these ranges, a molar ratio of the second aluminum compound relative to hydroxyl groups can be less than or equal to about 0.9: 1, or less than or equal to about 0.8: 1, or less than or equal to 0.5: 1, or less than or equal to about 0.25: 1.

[0125] In more specific examples, the non-coordinating anion activator may be formed in situ upon a support material as a reaction product of an organoaluminum compound containing electronwithdrawing substituents, preferably three electron-withdrawing substituents, preferably one or more haloaryl groups (e.g., pentafluorophenyl), and a tertiary arylamine (e.g., N,N-di ethylaniline or similar amines). The reaction product may further complex surface hydroxyl groups or a portion thereof upon the support material. Tris(pentafluorophenyl)aluminum may be a suitable organoaluminum compound for accomplishing the foregoing. Tris(pentafluorophenyl)aluminum or similar organoaluminum compounds may complex surface hydroxyl groups via the aluminum atom to form an oxyanion, with the negative charge being balanced by the resulting protonated tertiary arylamine. Remaining surface hydroxyl groups may be blocked using a second organoaluminum compound lacking electron-withdrawing substituents, such as (BHT)2AlEt or a similar second organoaluminum compound as specified above, wherein the remaining surface hydroxyl groups are blocked with a (BHT^Al complex.

[0126] " 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. 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 = 8.3V_S, where V_s is the scaled volume. V_s is the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formula of the substituent as specified below. For fused rings, the V_s is decreased by 7.5% per fused ring. The Calculated Total MV of the anion is the sum of the MV per substituent, for example, the MV of perfluorophenyl is 183 A³, and the Calculated Total MV for tetrakis(perfluorophenyl)borate is four times 183 A³, or 732 A³.

For a list of particularly useful bulky activators, U.S. Patent 8,658,556, which is incorporated by reference herein with respect to its disclosure of bulk activators, may be consulted.

[0127] In any embodiment, a NCA activator may be an activator as described in U.S. Patent No. 6,211,105. The NCA activator-to-catalyst ratio may be from about a 1 : 1 molar ratio to about a 1000:1 molar ratio, which includes, from about 0.1 :1 to about 100: 1, from about 0.5: 1 to about 200: 1, from about 1 : 1 to about 500: 1, or 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.

[0128] It is also within the scope of this disclosure that the dianionic complex may be activated with combinations of alumoxanes and NCAs (see for example, U.S. Patents 5,153, 157 and 5,453,410; EP 0 573 120 Bl, and International Patent Application Publications WO 94/07928 and WO 95/14044, which discuss the use of an alumoxane in combination with an ionizing activator). Thus, in some embodiments, a NCA may be a co-activator to an alumoxane, or vice versa.

[0129] In addition to activators, scavengers or co-activators can be used. 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, ethylaluminum dichloride, diethylaluminum chloride, and diethyl zinc.

[0130] Chain transfer agents can also be used in the compositions and/or processes described herein. Useful chain transfer agents are typically alkylalumoxanes, a compound represented by the formula AIR3, Z11R2 (where each R is, independently, a Ci-Cs aliphatic radical, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or an isomer thereof) or a combination thereof, such as diethyl zinc, methylalumoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum, or a combination thereof.

[0131] In any embodiment, an alumoxane, such as MAO, may be mixed in an inert solvent, such as toluene, and then be slurried with a support material, such as silica. Alumoxane deposition upon the support material may occur at a temperature from about 60°C to 120°C, or about 80°C to 120°C, or about 100°C to 120°C. Deposition occurring below 60°C, including room temperature deposition, may also be effective. NCAs may be deposited upon the support material in a similar manner.

Catalyst Systems

[0132] The present disclosure further provides catalyst systems comprising a support material; a dianionic complex, such as a bis(phenolate) complex; and an activator selected from an alumoxane or NCA also disposed upon the support material. Preferably, the activator may be an NCA formed from tris(pentafluorophenyl)aluminum or a similar Lewis acid. The dianionic complex and the activator may be disposed upon the support material in any order, including concurrently. Suitable ratios of the activator to metal of the dianionic complex include the A1:M ratios specified above.

Polymerization Methods and Polymer Product

[0133] Polymerization methods for producing branched polypropylene copolymers according to the present disclosure may comprise: exposing a) propylene and b) a a, co -diene to polymerization reaction conditions in the presence of a polymerization catalyst system and optionally hydrogen to form the branched polypropylene copolymer under the polymerization reaction conditions. The polymerization reaction conditions may comprise gas-phase polymerization reaction conditions or slurry-phase polymerization reaction conditions. Suitable dianionic complexes are discussed in more detail above. Preferably, the dianionic complex comprises a Group 4 metal, more preferably Zr, as described in more detail above.

[0134] The polymerization reaction conditions may comprise slurry-phase polymerization reaction conditions or gas-phase polymerization reaction conditions. Preferably, the polymerization reaction conditions comprise slurry-phase polymerization reaction conditions. Suitable slurry-phase polymerization reaction conditions and gas-phase polymerization reaction conditions are discussed subsequently.

[0135] A slurry-phase polymerization process refers to a polymerization process in which a supported catalyst is employed, preferably also containing a supported activator, and monomers are polymerized on the supported catalyst particles such that the supported catalyst particles are retained in the polymer following polymerization, wherein at least one of the monomers undergoing polymerization is in liquid form and constitutes at least a portion of a fluid medium for the slurry. A gas-phase polymerization process refers to a polymerization process in which the monomers undergoing polymerization are in a gaseous state during polymerization, and in which supported catalyst particles, preferably also containing a supported activator, are fluidized in a reactor producing the polymer. Either of such polymerization processes may be run in batch, semi-batch, or continuous mode. The term "continuous" means a system that operates without interruption or cessation, such that a polymer product may be withdrawn as one or more monomers or other reactants are being introduced to the reactor producing the polymer. Batch and semi-batch processes may take place in the same reactor or in different reactors.

[0136] Both slurry-phase polymerizations and gas-phase polymerizations may be conducted in the presence of an aliphatic hydrocarbon solvent/diluent/condensing agent, such as isobutane, butane, pentane, isopentane, hexanes, isohexane, heptane, octane, dodecane, and mixtures thereof; or cyclic aliphatic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. Preferably, aromatics are present in the solvent/diluent/condensing agent at less than 1 wt%, more preferably less than 0.5 wt%, and still more preferably at 0 wt% based upon the weight of the solvents/diluent/condensing agent.

[0137] Slurry-phase polymerization processes may operate at atmospheric pressure or above, preferably in a pressure range of about 140 psi (965 kPa) to about 750 psi (5171 kPa) or even greater and a temperature ranging from about 0°C to about 120°C or about 20°C to about 110°C. Optionally, hydrogen gas may be present to alter the molecular weight of the polymer being produced. In slurryphase polymerization processes, a suspension of polymer particles is formed in a fluid medium comprising at least one of the monomers undergoing polymerization and optionally a hydrocarbon diluent. The suspension, including diluent, is intermittently or continuously removed from the reactor where the volatile components may be separated from the polymer and recycled, optionally after a distillation, and returned to the reactor. Non-limiting examples of slurry-phase polymerization processes include continuous loop or stirred tank processes. Other examples of slurry-phase polymerization processes are described in U.S. Pat. No. 4,613,484, which is incorporated herein by reference.

[0138] Gas-phase polymerization processes may operate by circulating one or more gaseous monomers through a reactor under gas-phase reaction conditions in the presence of a suitable catalyst. The gaseous monomers need not necessarily be introduced to the reactor as a gas (i.e., they may be introduced as a condensed liquid), but they are in a gas state at least while contacting the catalyst system. Typically, the one or more gaseous monomers are withdrawn from the reactor as an effluent stream, which is recycled back to the reactor to increase conversion, and the polymer is collected from the reactor separate from the effluent stream. Illustrative gas-phase polymerization reaction conditions may include a temperature ranging from about 25°C to about 150°C, or about 50°C to about 140°C, or about 60°C to about 110°C, and a pressure of about 10 psi (69 kPa) to about 450 psi (3103 kPa), or about 150 psi (1034 kPa) to about 400 psi (2758 kPa), or about 200 psi (1379 kPa) to about 300 psi (2068 kPa), or even about 330 psi (2275 kPa). Optionally, hydrogen gas may be present to alter the molecular weight of the polymer being produced. Illustrative gasphase polymerization processes are described in U.S. Pat. Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661; and 5,668,228, each of which is incorporated herein by reference.

[0139] Slurry-phase polymerization reactions and gas-phase polymerization reactions may be conducted in the presence or absence of one or more scavengers. Typical scavengers include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, diethyl zinc, or excess alumoxane activator.

[0140] If desired, hydrogen may be added during either of the polymerization reactions to alter the molecular weight of the polymer being produced. In at least one embodiment, hydrogen may be present in the first polymerization reaction and/or the second polymerization reaction at a partial pressure of about 0.001 psig to about 50 psig (0.007 kPa to 345 kPa), or about 0.01 psig to about 25 psig (0.07 kPa to 172 kPa), or about 0.1 psig and 10 psig (0.7 kPa to 70 kPa). When included, hydrogen may be included at an overall concentration of about 600 ppm or less, or about 500 ppm or less, or about 400 ppm or less, or about 300 ppm or less. Tn other embodiments, hydrogen may be included at an overall concentration of at least about 50 ppm, or at least about 100 ppm, or at least about 150 ppm.

[0141] Long-chain branches within the branched polypropylene copolymer are sufficiently long to induce polymer entanglement and may have a molecular weight of about 500 or more, or about 750 or more, or about 1000 or more, or about 1500 or more, or about 2000 or more, or about 2500 or more, or about 3000 or more, or about 4000 or more, or about 5000 or more. A a,® -diene may provide a reactive site remote from the main polymer chain from which the long-chain branch may continue to grow.

[0142] The a,® -diene may be present in the branched polypropylene copolymer in a non-zero amount up to about 10 wt% relative to a total mass of the branched polypropylene copolymer. In some embodiments, the non-zero amount of the at least one oc,® -diene may range from about 0.001 wt% to about 10 wt%, or about 0.01 wt% to about 9.99 wt%, or about 0.1 wt% to about 9.9 wt%, or about 0.5 wt% to about 99.5 wt%, or about 0.1 wt% to about 10 wt%, or any subrange thereof.

[0143] Suitable a,® -dienes that may be utilized to introduce long-chain branching include, but are not limited to 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7 -octadiene, 1,8 -nonadiene, 1,9- decadiene, 1,10-undecadiene, 1,11 -dodecadiene, 1,12-tridecadiene, 1,13 -tetradecadiene, 2-methyl- 1,6-heptadiene, 2-methyl-l,7-octadiene, 2-methyl-l,8-nonadiene, 2-methyl-l,9-decadiene, 2-methyl- 1,10-undecadiene, 2-methyl- 1,11 -dodecadiene, 2-m ethyl- 1,12-tridecadiene, 2 -methyl- 1,13- tetradecadiene, and vinyl norbomene.

[0144] The branched polypropylene copolymer may have a Mw value ranging from about 150,000 to about 1,000,000, or about 200,000 to about 600,000.

[0145] The branched polypropylene copolymer may have a Mn value ranging from about 75,000 to about 150,000, or about 85,000 to about 200,000.

[0146] The branched polypropylene copolymer may have a Mz value ranging from about 250,000 to about 5,000,000, or about 350,000 to about 3,000,000, or about 500,000 to about 1,500,000.

[0147] The branched polypropylene copolymer may have a relatively narrow poly dispersity index (Mw/Mn). In non-limiting examples, the branched polypropylene copolymer may have a Mw/Mn value of about 7 or less or about 4 or less, such as about 2 to about 6, or about 3 to about 5, or about 2 to about 4, or about 2.4 to about 3.8, or about 2.5 to about 3.4, or about 4 to about 4.5.

[0148] In some or other non-limiting examples, the branched polypropylene copolymer may have a Mz/Mw value of about 6 or less, or about 5 or less, or about 2 to about 5. [0149] The branched polypropylene copolymer may have a g’_vis value, as determined by GPC-4D (described herein) of about 0.97 or less, or about 0.9 or less, or about 0.85 or less, or about 0.8 or less. In non-limiting examples, the branched polypropylene copolymer may have a g’vis value, as determined by GPC-4D, of about 0.75 to about 0.97, or about 0.78 to about 0.96, or about 0.80 to about 0.95.

[0150] In non-limiting examples, the branched polypropylene copolymers produced according to the disclosure herein may have a melting point ranging from about 150°C to about 160°C, or about 154°C to about 156°C. If the branched polypropylene copolymers are semi-crystalline, there may be multiple melting points within the foregoing ranges.

[0151] In non-limiting examples, the branched polypropylene copolymers produced according to the disclosure herein may have a crystallization temperature ranging from about 100°C to about 120°C, or about 104°C to about 116°C.

[0152] In non-limiting examples, the branched polypropylene copolymers produced according to the disclosure herein may have a tensile stress at yield ranging from about 30 MPa to about 40 MPa, or about 33 MPa to about 40 MPa, as determined according to ISO 37 (2005) or ASTM D638 (30 mm grip separation and 50.8 mm/min at a temperature of 70°F).

[0153] In non-limiting examples, the branched polypropylene copolymers produced according to the disclosure herein may have a flexural modulus ranging from about 1200 MPa to about 1900 MPa, or about 1300 MPa to about 1800 MPa, as measured by ASTM D790A.

Foamable Compositions, Foaming Agents, Foamed Products, and Foaming Processes

[0154] The present disclosure describes foamable compositions comprising: a branched polypropylene copolymer of the present disclosure; and a foaming agent blended with the branched polypropylene copolymer. Foamed products may be produced by converting the foamable composition to a foamed form. Any of the foregoing branched polypropylene copolymers may be present therein.

[0155] The foamable compositions, foamed products, and foaming processes of the present disclosure invention may utilize a foaming agent to cause expansion of the branched polypropylene copolymers by foaming under specified conditions.

[0156] Suitable foaming agents may include both physical foaming agents and chemical foaming agents. Chemical foaming agents include, but are not limited to, azodi carbonamide, azodiisobutyronitrile, benzenesulfonhydrazide, 4,4-oxybenzene sulfonyl semicarbazide, p- toluenesulfonyl semi carb azide, barium azodi carb oxy late, N,N'-dimethyl-N,N'- dinitrosoterephthalamide, trihydrazinotriazine, nitroso compounds, such as N,N'-dimethyl-N,N'- dinitrosoterephthalamide and N,N'-dinitrosopentamethylene tetramine; azo compounds, such as azodicarbonamide, azobisisobutylonitrile, azocyclohexylnitrile, azodiaminobenzene, and barium azodicarboxylate; sulfonyl hydrazide compounds, such as benzene sulfonyl hydrazide, toluene sulfonyl hydrazide, p,p'-oxybis(benzene sulfonyl hydrazide), and diphenyl sulfone-3, 3 '-disulfonyl hydrazide; and azide compounds, such as calcium azide, 4,4'-diphenyl disulfonyl azide, and p-toluene sulfonyl azide.

[0157] Suitable chemical foaming agents also include organic foaming agents, including aliphatic hydrocarbons having 1-9 carbon atoms, halogenated aliphatic hydrocarbons, having 1-4 carbon atoms, and aliphatic alcohols having 1-3 carbon atoms. Aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, isobutene, n-pentane, isopentane, neopentane, and the like. Chemical foaming agents also include halogenated hydrocarbons such as chlorofluorocarbons, hydrochlorofluorocarbons, and preferably, fluorinated hydrocarbons. Examples of fluorinated hydrocarbon include methyl fluoride; perfluoromethane; ethyl fluoride; 1,1-difluoroethane (HFC- 152a); 1,1,1-trifluoroethane (HFC-143a); 1,1,1,2-tetrafluoro-ethane (HFC-134a); pentafluoroethane; perfluoroethane; 2,2-difluoropropane; 1,1,1-trifluoropropane; perfluoropropane; perfluorobutane; and perfluorocyclobutane. Partially halogenated chlorocarbons and chlorofluorocarbons for use in this invention include methyl chloride; methylene chloride; ethyl chloride; 1,1,1 -tri chloroethane; 1,1- dichloro-1 -fluoroethane (HCFC-141b); 1 -chloro- 1,1 -difluoroethane (HCFC-142b); 1,1-dichloro- 2,2,2-trifluoroethane (HCFC-123); and 1 -chloro- 1,2, 2, 2-tetrafluoroethane (HCFC-124). Fully halogenated chlorofluorocarbons include trichloromonofluoromethane (CFC-11); dichlorodifluoromethane (CFC-12); trichlorotrifluoroethane (CFC-113); di chlorotetrafluoroethane (CFC-114); chloroheptafluoropropane; and dichlorohexafluoropropane. Fully halogenated chlorofluorocarbons are not preferred. Aliphatic alcohols useful as foaming agents include methanol, ethanol, n-propanol, and isopropanol.

[0158] Suitable inorganic foaming agents include, but are not limited to, carbon dioxide, nitrogen, argon, water, air, nitrogen, and helium, and combinations thereof. Inorganic foaming agents also include sodium bicarbonate; sodium carbonate; ammonium bicarbonate; ammonium carbonate; and ammonium nitrite. Preferably, the foamable compositions may comprise nitrogen, n-butane, isobutane, n-pentane, isopentane, carbon dioxide, or any combination thereof in a suitable amount as a foaming agent. [0159] The amount of foaming agent incorporated into the foamable compositions may range from about 0.01 wt% to about 10 wt%, based on total mass of the foamable composition, and preferably from about 0.1 wt% to about 5 wt%. The amount of foaming agent may be altered to obtain a desired foam density and/or cell size.

[0160] A foaming assistant can be used with the foaming agent. The simultaneous use of the foaming agent with a foaming assistant may contribute to lowering of the decomposition temperature of the foaming agent, acceleration of decomposition and homogenization of bubbles. Examples of the foaming assistant may include organic acids, such as salicylic acid, phthalic acid, stearic acid and nitric acid, urea, and derivatives thereof. The amount of foaming assistant incorporated into the foamable compositions may range from about 0.01 wt% to about 10 wt% and preferably from about 0.1 wt% to about 5 wt%, more preferably about 0.5 wt% to about 3 wt%, based on total mass of the foamable composition.

[0161] The foamed products described herein may have a density of at least about 0.02 kg/cm³. Foam density is determined according to ASTM D1622-08.

[0162] Foamed products may comprise a foamed form having open cells, closed cells, or any combination thereof. The percentage of open or closed cells in a foamed product may be determined according to ASTM D2856-A.

[0163] The foamed product produced using the blends described herein may have an average cell diameter of about 75 pm or less, according to ASTM D3576-04, preferably about 10 pm to about 75 pm, or about 15 pm to about 70 pm.

[0164] The foamed products described herein may have a cell density of about 10⁷ to about 10⁸ cells/cm³ at temperatures from about 120°C to about 180°C, as measured by ASTM D1622-08. The foamed form may have a bulk density of about 0.1 g/cm³.

[0165] In other instances, the foamed products described herein may have an expansion ratio of about 30 to about 40 within a temperature range of about 110°C to about 180°C, determined according to ASTM D792-13. Expansion ratio can be measured by dividing the density of the foamed form by the density of the polypropylene from which it originates. The foamed products may have a maximum expansion ratio within a temperature range of about 130°C to about 155°C.

[0166] Polyolefin foams are commonly made by an extrusion process. Preferably, the extruders are longer than standard types, typically with an overall L/D (length to diameter) ratio>40, in either a single or tandem extruder configuration. Melt temperature is one parameter that may impact foam extrusion. Preferably, the melt temperature is in a range from approximately 130°C to 180°C. [0167] Foamed products may be produced from the foamable compositions by a number of processes, such as compression molding, injection molding, and hybrids of extrusion and molding. The processes may comprise mixing the branched polypropylene copolymers under heat to form a melt, along with foaming agents and other typical additives, to achieve a homogeneous or heterogeneous blend. The ingredients may be mixed and blended by any means known in the art, such as with a Banbury, intensive mixers, two-roll mill, extruder, or the like. Time, temperature, and shear rate may be regulated to ensure optimum dispersion without premature foaming. An adequate temperature is desired to promote good mixing of polymers and the dispersion of other ingredients. The upper temperature limit for safe operation may depend on the onset decomposition temperatures of foaming agents employed. The decomposition temperature of some foaming agents is lower than the melt temperature of the polymer. In this case, the polymers may be melt-blended before being compounded with other ingredient(s). The resultant mixture can be then compounded with the ingredients. Extruders with staged cooling/heating can also be employed. The latter part of the foam extruder is dedicated to the melt cooling and intimate mixing of the polymer-foaming agent system. After mixing, shaping can be carried out. Sheeting rolls or calendar rolls are often used to make appropriately dimensioned sheets for foaming. An extruder may be used to shape the composition into pellets. Foaming can be carried out in a compression mold at a temperature and time to complete the decomposition of foaming agents. Pressures, molding temperature, and heating time may be controlled. Foaming may also be carried out in injection molding equipment by using foam composition in pellet form. The resulting foam can be further shaped to the dimension of finished products by any means known in the art, such as by thermoforming and compression molding.

[0168] Optionally, a nucleating agent may be blended in the polymer melt. The feeding rate of foaming agent and nucleating agent may be adjusted to achieve a relatively low density foam and small cell size, which results in a foam having thin cell walls.

[0169] In non-limiting embodiments, the branched polypropylene copolymers may be utilized for producing injection molded components for automobiles, such as door panels, consoles, armrests, dashboards, seats, and headliners; especially where the component includes a foamed core covered by a soft-feeling, but scratch resistant, skin. Such components can be formed by employing separate injection molding operations to produce the core and the skin or may be produced in a single injection molding operation using commercially available multi-shot injection machinery.

[0170] It will be understood by those skilled in the art that the steps outlined above may be varied, depending upon the desired result. For example, the foamable compositions of the present disclosure may be directly thermoformed or blow molded without cooling, thus skipping a cooling step. Other parameters may be varied as well in order to achieve foamed product having desirable features.

[0171] In addition to foaming, the branched polypropylene copolymers may be useful in injection molding, blown fdm, and fiber spinning applications.

Additional Embodiments

[0172] The present disclosure is further directed to the following non-limiting embodiments.

[0173] Embodiment 1. A method comprising: exposing a) propylene and b) a a, co -diene to polymerization reaction conditions in the presence of a polymerization catalyst system and optionally hydrogen; wherein the polymerization catalyst system comprises a support material, a dianionic complex of a Group 3-6 metal disposed upon the support material, and an activator for the dianionic complex disposed upon the support material; wherein the dianionic complex comprises two eight-membered chelate rings containing the Group 3-6 metal; and forming a branched polypropylene copolymer having long-chain branching under the polymerization reaction conditions.

[0174] Embodiment 2. The method of Embodiment 1, wherein the branched polypropylene copolymer has an Mw/Mn of about 5 or less.

[0175] Embodiment s. The method of Embodiment 2, wherein the branched polypropylene copolymer has a Mw/Mn of about 2 to about 4.5.

[0176] Embodiment 4. The method of any one of Embodiments 1-3, wherein the branched polypropylene copolymer has an Mz/Mw of about 5 or less.

[0177] Embodiment s. The method of any one of Embodiments 1-4, wherein the polymerization reaction conditions comprise slurry-phase polymerization reaction conditions.

[0178] Embodiment 6. The method of any one of Embodiments 1-5, wherein the branched polypropylene copolymer has a g’vis value of about 0.97 or less, as determined by 4D-GPC.

[0179] Embodiment 7. The method of Embodiment 6, wherein the branched polypropylene copolymer has a g’vis value of about 0.75 to about 0.97, as determined by GPC-4D.

[0180] Embodiment 8. The method of any one of Embodiments 1-7, wherein the hydrogen is present when forming the branched polypropylene copolymer under the polymerization reaction conditions. [0181] Embodiment 9. The method of any one of Embodiments 1-8, wherein the ot,<D-diene comprises a diene selected from the group consisting of 1,4-pentadiene, 1,5-hexadiene, 1,6- heptadiene, 1,7-octadiene, 1,8-nonadiene, 1,9-decadiene, 1,10-undecadiene, 1,11 -dodecadiene, 1,12- tridecadiene, 1,13 -tetradecadiene, 2-m ethyl- 1,6-heptadiene, 2-methyl-l,7-octadiene, 2-methyl-l,8- nonadiene, 2-m ethyl- 1,9-decadiene, 2-methyl-l,10-undecadiene, 2-methyl-l,l 1 -dodecadiene, 2- methyl-l,12-tridecadiene, and 2-methyl-l,13-tetradecadiene.

[0182] Embodiment 10. The method of any one of Embodiments 1-9, wherein the branched polypropylene copolymer comprises about 99 wt% or above propylene and a non-zero amount of a,co-diene, based on total mass of the branched polypropylene copolymer.

[0183] Embodiment 11. The method of Embodiment 10, wherein the branched polypropylene copolymer comprises about 0.0001 wt% to about 1 wt% of the a,a>-diene, based on total mass of the branched polypropylene copolymer.

[0184] Embodiment 12. The method of any one of Embodiments 1-11, wherein the dianionic complex has a structure represented by

wherein:

M is the Group 3-6 metal;

E and E' are independently O, S, or NR⁹, wherein each R⁹ is independently hydrogen, a Ci- C40 optionally substituted hydrocarbyl, or a heteroatom-containing group;

Z is a Group 14-16 atom forming a dative bond to M;

A’ZA¹ is part of a heterocyclic Lewis base, designated as B, containing 4 to 40 nonhydrogen atoms that links A² to A² via a 3 -atom bridge, with Z being the central atom of the 3 -atom bridge;

A¹ and A¹' are independently C, N, or CR²², wherein each R²² is independently hydrogen or optionally substituted C1-C20 hydrocarbyl; 3 2

A ²²²² A i_s a divalent group, optionally part of an optionally substituted hydrocarbyl ring or optionally substituted heterocyclic ring, containing 2 to 40 non-hydrogen atoms that links A¹ to a first aryl group via a 2-atom bridge, the first aryl group having E bonded thereto;

2* 3 ’

A —A i_{s a} divalent group, optionally part of an optionally substituted hydrocarbyl ring or optionally substituted heterocyclic ring, containing 2 to 40 non-hydrogen atoms that links A¹' to a second aryl group via a 2-atom bridge, the second aryl group having E’ bonded thereto; each L is a Lewis base; each X is an anionic ligand; n is 1, 2, or 3; m is 0, 1, or 2; n+m is not greater than 4; and

R¹, R², R³, R⁴, R¹ , R², R³', and R⁴ are independently hydrogen, optionally substituted Ci- C40 hydrocarbyl, a heteroatom, or a heteroatom-containing group or one or more of R¹ and R², R² and R³, R³ and R⁴, R¹ and R² , R² and R³ , or R³ and R⁴ are joined to form one or more optionally substituted hydrocarbyl rings or optionally substituted heterocyclic rings, each ring having 5, 6, 7, or 8 ring atoms, and optionally wherein the optionally substituted hydrocarbyl rings or the optionally substituted heterocyclic rings are fused to one or more additional rings; and wherein: when m is 2, any two L are optionally joined together to form a bidentate Lewis base; or an X is optionally j oined to an L to form a monoanionic bidentate ligand bound to M; or when n is 2 or 3, any two X are optionally joined together to form a dianionic ligand bound to M.

[0185] Embodiment 13. The method of any one of Embodiments 1-12, wherein the dianionic complex comprises a Group 4 metal.

[0186] Embodiment 14. The method of Embodiment 13, wherein the Group 4 metal comprises zirconium.

[0187] Embodiment 15. The method of any one of Embodiments 12-14, wherein E and E’ are each O.

[0188] Embodiment 16. The method of any one of Embodiments 12-15, wherein R¹ and R¹ are independently a tertiary alkyl group, or a tertiary alkylaryl group. [0189] Embodiment 17. The method of Embodiment 16, wherein R¹ and R¹ are each a tertiary alkyl group, and the tertiary alkyl group comprises an optionally substituted adamantyl group.

2

[0190] Embodiment 18. The method of any one of Embodiments 12-17, wherein A — A and A —A are independently an optionally substituted arylene, an optionally substituted heteroarylene, an optionally substituted cycloalkylene, or an optionally substituted vinylene.

[0191] Embodiment 19. The method of any one of Embodiments 12-17, wherein A^J — A- and 2’ 3 *

A —A are each an optionally substituted phenylene or an optionally substituted heteroarylene.

[0192] Embodiment 20. The method of any one of Embodiments 12-19, wherein the heterocyclic Lewis base is a 5- or 6-membered heteroaromatic ring.

[0193] Embodiment 21. The method of any one of Embodiments 12-20, Z of the heterocyclic Lewis base is N.

[0194] Embodiment 22. The method of any one of Embodiments 12-21, wherein the heterocyclic Lewis base is an optionally substituted pyridine.

[0195] Embodiment 23. The method of any one of Embodiments 1-22, wherein the at least one activator comprises at least one alumoxane.

[0196] Embodiment 24. The method of any one of Embodiments 1-22, wherein the at least one activator comprises at least one non-coordinating anion.

[0197] Embodiment 25. The method of Embodiment 24, wherein the non-coordinating anion is surface bound to the support material as a reaction product of surface hydroxyl group and a noncoordinating anion precursor, the non-coordinating anion precursor comprising an organoaluminum compound having a haloaryl group.

[0198] Embodiment 26. The method of any one of Embodiments 1-25, wherein the support material comprises silica.

[0199] Embodiment 27. The method of any one of Embodiments 1-26, further comprising: foaming the branched polypropylene copolymer.

[0200] To facilitate a better understanding of the embodiments of the present disclosure, the following examples of preferred or representative embodiments are given. In no way should the following examples be read to limit, or to define, the scope of the invention.

EXAMPLES

[0201] Bis(phenolate) Complex (Inventive). The following bis(phenolate) complex was synthesized in a manner similar to that described in U.S. Patent 11,254,763, which is incorporated herein by reference. Polymerization reactions conducted with the bis(phenolate) complex are designated as Entries II -Il 0 in the data below.

[0202] Metallocene Catalysts (Comparative). The following metallocene was synthesized through introduction of the substituted phenyl group onto 6-methyl-l,2,3,5-tetrahydro-s-indacene via Suzuki coupling of 4-t-butylphenylboronic acid to the corresponding brominated parent ring system, followed by lithiation, dimethylsilyl bridge introduction, and metallocene formation, as described in U.S. Patent Application Publication 2022/0315680. Comparative polymerization reactions were conducted using this metallocene. The comparative polymerization reactions conducted with the metallocene complex are designated as Entries C1-C6 in the data below.

[0203] Supported Activator Preparation. Non-coordinating anion activators were prepared in situ and deposited upon a silica support. 0.21 g (2.85 mmol) of Al Me? in toluene (~5 mL) was slowly added to a stirred slurry of 1.46 g (2.85 mmol) of tris(pentafluorophenyl)boron in toluene or pentane (~30 mL). Upon completion, the mixture became homogenous and was stirred uncapped for 1 hour at room temperature, during which time BMe? was removed as a gas. While stirring, the resulting Al(C6Fs)3 solution was transferred to 10 g of silica (PD17062, PQ Corp.), followed by addition of N,N-diethylaniline (0.425 g, 2.85 mmol) in minimal toluene. The silica slurry was further stirred for an additional 30 minutes.

[0204] In a separate flask, 0.975 g of triethylaluminum (8.55 mmol) was suspended in toluene (30 mL) and cooled in a freezer. While stirring, a solution of 3.77 g (17.1 mmol) of BHT (butylated hydroxytoluene) in toluene (10 mL) was slowly added to the tri ethylaluminum suspension. After 30 minutes, the resulting tri ethylaluminum :BHT complex was slowly added at room temperature to the silica slurry prepared above. The combined reaction mixture was then stirred overnight. After 18 hours, the reaction mixture was filtered, and the solid was washed with toluene (2 x 50 mL) and pentane (2 x 50 mL). After drying in vacuo, the support material was obtained as white powder.

[0205] Comparative Supported Activator Preparation. Silica (DM-L403, Asahi Glass) was calcined at 200°C, and 10.0 g of the calcined silica was suspended in approximately 100 mL of dry toluene and cooled to -20 °C. After approximately 30 minutes of cooling, 15.8 g ofa 30 wt% solution of MAO in toluene was slowly added to the silica mixture over 10 minutes with stirring. The mixture was warmed to room temperature and stirred for 1.5 hours. After 1.5 hours, the mixture was heated to 100°C and stirred for an additional 2.5 hours. The temperature was then decreased to 55°C and filtered through a glass frit. The collected solid was then washed with toluene (2 x 50 mL) and pentane (2 x 50 mL) and was dried in vacuo for 1 hour to afford a white powder (14.1 g).

[0206] Inventive Supported Catalyst Preparation. The bis(phenolate) complex was deposited upon the supported activator by contacting a toluene solution of the bis(phenolate) complex with the supported activator prepared as above. In brief, a toluene solution of the bis(phenolate) complex (21 mg, 17 pmol) was slowly added to 1.2 g of the supported activator slurried in 1 mL toluene. After shaking for 4 hours, the solids were collected on a glass frit, and washed with toluene (2 x 10 mL) and pentane (2 x 10 mL). After drying in vacuo, the supported catalyst was slurried in mineral oil to make a 5 wt% slurry for dispensation to a polymerization reactor.

[0207] Comparative Supported Catalyst Preparation. The above metallocene was supported upon the comparative supported activator by the following procedure. 1.67 g of the comparative supported activator was slurried in 10 mL of toluene, and 0.864 mL of TIB AL (1 M in hexane) was then slowly added. After shaking for 15 minutes, 22 mg of the comparative metallocene catalyst was added as a toluene solution. After an additional 2.5 hours of agitation, the slurry was filtered to collect the comparative supported metallocene catalyst. The comparative supported metallocene catalyst was washed with toluene (2 x 10 mL) and pentane (2 x 10 mL) and dried in vacuo to afford a maroon free-flowing solid. Thereafter, the comparative supported metallocene catalyst was slurried in mineral oil to provide a 5 wt% slurry for dispensation to a polymerization reactor.

[0208] General Procedure for Slurry-Phase Polymerization. A 1 L autoclave reactor equipped with a mechanical stirrer was used for polymer preparation. Prior to the run, the reactor was placed under nitrogen purge at 90°C temperature for 30 minutes. Upon cooling to ambient temperature, propylene (500 mL), scavenger (0.2 mL of 1 M TIB AL, triisobutylaluminum), a specified amount of diene co-monomer, and hydrogen (charged from a 50 mL bomb at a desired pressure) were introduced to the reactor and mixed for 5 minutes. A desired amount of supported catalyst prepared as above (typically 12.5 - 25.0 mg) was then introduced to the reactor by flushing a pre-determined amount of the 5 wt% catalyst slurry from a catalyst tube with 100 mL of liquid propylene. The reactor was kept at room temperature for 5 minutes (pre-polymerization stage), before raising the temperature to 70°C for a desired time period (typically 30 minutes). The propylene was maintained in a liquid state throughout the polymerization process. After the reaction time period, the excess propylene was vented off, and the polymer granules were collected and dried overnight. Additional polymerization details are specified in Table 1 below.

Table 1

[0209] Polymer Characterization. The resulting polymers were characterized to determine molecular weights, mechanical properties, and thermal properties using the procedures outlined below. Polymer characterization data is summarized in Table 2 below.

[0210] Tensile Properties and Flexural Modulus. Tensile properties (ultimate tensile strength, elongation at break, tensile yield, and elongation at yield) were determined according to ISO 37 (2005) or ASTM D638 (30 mm grip separation and 50.8 mm/min at a temperature of 70°F). The 1% secant flexural modulus, generally referred to as flexural modulus, was measured according to ASTM D 790 (A, 1.0 mm/min) using an injection molded ISO 37-Type 3 bar, a crosshead speed of 1 mm/min, and a support span of 30.0 mm.

[0211] Small Amplitude Oscillatory Shear (SAGS) Test: Dynamic shear melt rheological data were measured with an Advanced Rheometrics Expansion System (ARES-G2) from TA Instruments using parallel plates (diameter = 25 mm) in a dynamic mode under nitrogen atmosphere. For all experiments, the rheometer was thermally stable at 190°C for at least 30 minutes before inserting compression-molded sample of resin onto the parallel plates. To determine the samples viscoelastic behavior, frequency sweeps in the range from 0.01 to 628 rad/s were carried out at a temperature of 190°C under constant strain. Depending on the molecular weight and temperature, strains in the linear deformation range verified by strain sweep test were used. A nitrogen stream was circulated through the sample oven to minimize chain extension or cross-linking during the experiments. All the samples were compression molded at 190°C. A sinusoidal shear strain is applied to the material if the strain amplitude is sufficiently small the material behaves linearly. It can be shown that the resulting steadystate stress will also oscillate sinusoidally at the same frequency but will be shifted by a phase angle d with respect to the strain wave. The stress leads the strain by d. For purely elastic materials d=0° (stress is in phase with strain) and for purely viscous materials, d=90° (stress leads the strain by 90° although the stress is in phase with the strain rate). For viscoelastic materials, 0 < d < 90.

[0212] GPC-4D Analysis. Polymer molecular weights were determined by GPC-4D analysis, as described in U.S. Patent Application Publication 2018/0059076, incorporated by reference, and further described below.

[0213] The distribution and the moments of molecular weight (Mw, Mn, Mz, Mw/Mn, etc.), the comonomer content, and the branching index (g¹) were determined by using a high-temperature Gel Permeation Chromatography (Polymer Char GPC-IR) equipped with a multiple-channel band-filter based infrared detector IR5 with a multiple-channel band filter based infrared detector ensemble IR5 with band region covering from about 2,700 cm'¹ to about 3,000 cm'¹ (representing saturated C-H stretching vibration), an 18-angle light scattering detector and a viscometer. Three Agilent PLgel 10- pm Mixed-B LS columns were used to provide polymer separation. Reagent grade 1,2,4- tri chlorobenzene (TCB) (from Sigma-Aldrich) comprising -300 ppm antioxidant BHT can be used as the mobile phase at a nominal flow rate of -1.0 mL/min and a nominal injection volume of -200 pL. The whole system including transfer lines, columns, and detectors can be contained in an oven maintained at ~145°C. A given amount of sample can be weighed and sealed in a standard vial with -10 pL flow marker (heptane) added thereto. After loading the vial in the auto-sampler, the oligomer or polymer may automatically be dissolved in the instrument with -8 mL added TCB solvent at ~160°C with continuous shaking. The sample solution concentration can be from -0.2 to -2.0 mg/ml, with lower concentrations used for higher molecular weight samples. The concentration, c, at each point in the chromatogram can be calculated from the baseline-subtracted IR5 broadband signal, I, using the equation: c=al, where a is the mass constant determined with polyethylene or polypropylene standards. The mass recovery can be 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 10M gm/mole. The MW at each elution volume is calculated with Equation 1 :

Equation 1 where the variables with subscript “PS” stand for polystyrene while those without a subscript are for the test samples. In this method, aps = 0.67 and Kps = 0.000175, a and K for other materials are calculated as described in the published literature (e.g., Sun, T., et al. (2001) Macromolecules, v.34, pg. 6812), except that for purposes of this present disclosure and claims thereto, a = 0.705 and K = 0.0000229 for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, a = 0.695 and K = 0.000579 for linear ethylene polymers, a = 0.705 and K = 0.0002288 for linear propylene polymers, and a = 0.695 and K = 0.000181 for linear butene polymers. 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.

[0214] The co-monomer 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 values are predetermined by TWTR or FTIR.. In particular, this provides the methyls per 1,000 total carbons (CH3/IOOOTC) as a function of molecular weight. The short-chain branch (SCB) content per l,000TC (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 % co-monomer is then obtained from Equation 2 in which f is 0.3, 0.4, 0.6, 0.8, and so on for C3, C4, Ce, Cs, and so on co-monomers, respectively:

[0215] 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 in Equation 3 is obtained

Equation 3

Then the same calibration of the CH3 and CH2 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 l,000TC (bulk CH3end/1000TC) is obtained by weight-averaging the chainend correction over the molecular-weight range Then Equations 4 and 5 apply

/

Equation 5 and bulk SCB/1000TC is converted to bulk w2 in the same manner as described above.

[0216] 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.), as specified in Equation 6:

Equation 6 Here, AR(0) is the measured excess Rayleigh scattering intensity at scattering angle 0, c is the polymer concentration determined from the IR5 analysis, A2 is the second virial coefficient, P(9) is the form factor for a monodisperse random coil, and K_o is the optical constant for the system, as specified in

Equation 7:

Equation 7 where NA is Avogadro’s number, and (dn/dc) is the refractive index increment for the system. The refractive index, n = 1.500 for TCB at 145°C and X = 665 nm. For analyzing polyethylene homopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn/dc = 0.1048 ml/mg and A2 = 0.0015; for analyzing ethyl ene-butene copolymers, dn/dc = 0.1048*(l-0.00126*w2) ml/mg and A2 = 0.0015 where w2 is weight percent butene comonomer.

[0217] 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, r|_s, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [q], at each point in the chromatogram is calculated from the equation [q]=q_s/c, where c is concentration and is determined from the IR5 broadband channel output. The viscosity MW at each point is calculated as

[0218] The branching index (g¹ . ) is calculated using the output of the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity, [r|]avg> °f the sample is calculated by Equation 8:

Equation 8 where the summations are over the chromatographic slices, i, between the integration limits.

[0219] The branching index g'vis is defined as Equation 9:

Equation 9 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 this present disclosure and claims thereto, a = 0.705 and K = 0.0000229 for ethyl ene-propylene copolymers and ethylene-propylene-diene terpolymers, a = 0.695 and K = 0.000579 for linear ethylene polymers, oc = 0.705 and K = 0.0002288 for linear propylene polymers, oc = 0.695 and K = 0.000181 for linear butene polymers. 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.

[0220] DSC Analysis. Thermal properties of the polymers were assayed by differential scanning calorimetry (DSC). In brief, peak melting point (Tm) and peak crystallization temperature (Tc) were determined by the following DSC procedure using a TA Instruments model DSC2500 device. Samples weighing approximately 5 to 10 mg were sealed in an aluminum hermetic sample pan and loaded into the instrument at about room temperature. The DSC data were recorded by first gradually heating the sample to about 200°C at a rate of about 10°C/minute. The sample was kept at about 200°C for 5 minutes, cooled to about -50°C at a rate of about 10°C/minute, followed by an isothermal hold for about 5 minutes, heating to about 200°C at about 10°C/minute, followed by an isothermal hold for about 5 minutes, and finally cooling to about 25°C at a rate of about 10°C/minute. Both the first and second cycle thermal events were recorded. The Tm and Tc values reported in Table 2 below were obtained during the second heating/cooling cycle unless otherwise noted.

Table 2

[0221] As shown, the inventive supportive catalyst afforded increased long-chain branching (lower g’vis value) as the amount of 1,7-octadiene in the polymerization reaction increased. Relative to the supported comparative polymerization catalysts, the inventive supported polymerization catalysts afforded higher activities and greater 1,7-octadiene incorporation. For samples exhibiting long-chain branching, the poly dispersity index (Mw/Mn) was considerably lower for the bis(phenolate) catalyst relative to the comparative catalyst. In general, the data show improved activities and narrower polydispersity values, with lower required diene loadings, which may collectively provide benefits of lower volatiles and better off-gassing following polymerization, for bis(phenolates) relative to metallocenes. Narrower poly dispersity values may provide additional benefits for fiber spinning applications, where such properties may be advantageous, particularly in combination with improved melt strength. The improved melt strength and narrow poly dispersity values may allow thinner fibers with improved tensile values to be drawn.

[0222] FIG. l is a plot of complex viscosity as a function of angular frequency for various samples (11-18). As shown, as the amount of 1,7-octadiene increased, thereby affording lower g\i_s values, shear-behavior increased, as shown by the larger decrease in complex viscosity from lower angular frequencies to higher angular frequencies. A typical low frequency plateau characterizing the so- called zero-shear viscosity was observed for the sample of Entry II, whereas the other samples showed an increasingly strong viscosity upturn at low frequencies, reflective of their high melt strength resulting from long-chain branching. The shear-thinning index, defined as a ratio of complex viscosity measured at 100 rad/s and complex viscosity measured at 0.1 rad/s become smaller with increasing levels of octadiene in the feed. [0223] FIG. 2 is a corresponding plot of phase angle as a function of complex modulus for samples 11-18, and FIG. 3 is a corresponding plot of tan(delta) as a function of angular frequency for samples 11-18. FIGS. 2 and 3 are likewise reflective of increased long-chain branching with growing incorporation of 1,7-octadiene.

[0224] FIGS. 4A-4D are plots of extensional viscosity for samples 12-14 and 17, respectively. As shown in FIG. 4A, strain hardening was evident at the lowest loading of 1,7-octadiene, and the increased signal strength in FIGS. 4B-4D is indicative of increased strain hardening increased with growing incorporation of 1,7-octadiene. The increased strain hardening is determined based upon the shear-thinning index, which is defined as the complex viscosity at 100 rad/s relative to the complex viscosity at 0.1 rad/s at a given angular frequency from SAGS measurements.

[0225] FIG. 5 is a plot of tensile stress as a function of g’_vis for selected samples among II -110. FIG. 6 is a plot of flexural modulus as a function of g’vis for selected samples among II -Il 0. As shown, both of these mechanical properties increased with increasing long-chain branching (decreasing g’vis). [0226] All documents described herein are incorporated by reference herein for purposes of all jurisdictions where such practice is allowed, 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 disclosure have been illustrated and described, various modifications can be made without departing from the spirit and scope of the disclosure. Accordingly, it is not intended that the disclosure be limited thereby. For example, the compositions described herein may be free of any component, or composition not expressly recited or disclosed herein. Any method may lack any step not recited or disclosed herein. Likewise, the term “comprising” is considered synonymous with the term “including.” Whenever a method, composition, element or 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.

[0227] Unless otherwise indicated, all numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth used in the present specification and associated claims are to be understood as being modified in all instances by the term “about.” Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by one or more embodiments described herein. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claim, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0228] Whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee. Moreover, the indefinite articles “a” or “an,” as used in the claims, are defined herein to mean one or more than one of the element that it introduces.

[0229] One or more illustrative embodiments are presented herein. Not all features of a physical implementation are described or shown in this application for the sake of clarity. It is understood that in the development of a physical embodiment of the present disclosure, numerous implementationspecific decisions must be made to achieve the developer's goals, such as compliance with system- related, business-related, government-related and other constraints, which vary by implementation and from time to time. While a developer's efforts might be time-consuming, such efforts would be, nevertheless, a routine undertaking for one of ordinary skill in the art and having benefit of this disclosure.

[0230] Therefore, the present disclosure is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present disclosure may be modified and practiced in different but equivalent manners apparent to one having ordinary skill in the art and having the benefit of the teachings herein. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. It is therefore evident that the particular illustrative embodiments disclosed above may be altered, combined, or modified and all such variations are considered within the scope and spirit of the present disclosure. The embodiments illustratively disclosed herein suitably may be practiced in the absence of any element that is not specifically disclosed herein and/or any optional element disclosed herein.

Claims

CLAIMS The invention claimed is:

1. A method comprising: exposing a) propylene and b) a oc, co -diene to polymerization reaction conditions in the presence of a polymerization catalyst system and optionally hydrogen; wherein the polymerization catalyst system comprises a support material, a dianionic complex of a Group 3-6 metal disposed upon the support material, and an activator for the dianionic complex disposed upon the support material; wherein the dianionic complex comprises two eight-membered chelate rings containing the Group 3-6 metal; and forming a branched polypropylene copolymer having long-chain branching under the polymerization reaction conditions.

2. The method of claim 1, wherein the branched polypropylene copolymer has an Mw/Mn of about 2 to about 5.

3. The method of any preceding claim, wherein the branched polypropylene copolymer has an Mz/Mw of about 2 to about 5.

4. The method of any preceding claim, wherein the polymerization reaction conditions comprise slurry-phase polymerization reaction conditions.

5. The method of any preceding claim, wherein the branched polypropylene copolymer has a g’vi_s value of about 0.75 to about 0.97, as determined by GPC-4D.

6. The method of any preceding claim, wherein the hydrogen is present when forming the branched polypropylene copolymer under the polymerization reaction conditions.

7. The method of any preceding claim, wherein the a,®-diene comprises a diene selected from the group consisting of 1,4-pentadiene, 1,5 -hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,8-nonadiene, 1 ,9-decadiene, 1,10-undecadiene, 1,11 -dodecadiene, 1,12-tri decadiene, 1,13- tetradecadiene, 2-methyl-l,6-heptadiene, 2-methyl-l,7-octadiene, 2-m ethyl- 1,8-nonadiene, 2- methyl- 1,9-decadiene, 2-methyl- 1,10-undecadiene, 2-methyl-l,l 1 -dodecadiene, 2-methyl- 1,12- tridecadiene, and 2-methyl- 1,13 -tetradecadiene.

8. The method of any preceding claim, wherein the branched polypropylene copolymer comprises about 99 wt% or above propylene and about 0.0001 wt% to about 1 wt% of the a,cn- diene, based on total mass of the branched polypropylene copolymer.

9. The method of any preceding claim, wherein the dianionic complex has a structure represented by

wherein:

M is the Group 3-6 metal;

E and E¹ are independently O, S, or NR⁹, wherein each R⁹ is independently hydrogen, a C1-C40 optionally substituted hydrocarbyl, or a heteroatom-containing group;

Z is a Group 14-16 atom forming a dative bond to M;

A^A¹ is part of a heterocyclic Lewis base, designated as B, containing 4 to 40 nonhydrogen atoms that links A² to A² via a 3 -atom bridge, with Z being the central atom of the 3- atom bridge;

A¹ and A¹' are independently C, N, or CR²², wherein each R²² is independently hydrogen or optionally substituted C1-C20 hydrocarbyl;

A 3 — A 2 is a divalent group, optionally part of an optionally substituted hydrocarbyl ring or optionally substituted heterocyclic ring, containing 2 to 40 non-hydrogen atoms that links A¹ to a first aryl group via a 2-atom bridge, the first aryl group having E bonded thereto; A —A i_{s a} divalent group, optionally part of an optionally substituted hydrocarbyl ring or optionally substituted heterocyclic ring, containing 2 to 40 non-hydrogen atoms that links A¹' to a second aryl group via a 2-atom bridge, the second aryl group having E’ bonded thereto; each L is a Lewis base; each X is an anionic ligand; n is 1, 2, or 3; m is 0, 1, or 2; n+m is not greater than 4; and

R¹, R², R³, R⁴, R¹ , R², R³, and R⁴ are independently hydrogen, optionally substituted C1-C40 hydrocarbyl, a heteroatom, or a heteroatom-containing group or one or more of R¹ and R², R² and R³, R³ and R⁴, R¹ and R² , R² and R³ , or R³ and R⁴ are joined to form one or more optionally substituted hydrocarbyl rings or optionally substituted heterocyclic rings, each ring having 5, 6, 7, or 8 ring atoms, and optionally wherein the optionally substituted hydrocarbyl rings or the optionally substituted heterocyclic rings are fused to one or more additional rings; and wherein: when m is 2, any two L are optionally joined together to form a bidentate Lewis base; or an X is optionally joined to an L to form a monoanionic bidentate ligand bound to M; or when n is 2 or 3, any two X are optionally joined together to form a dianionic ligand bound to M.

10. The method of claim 9, wherein the dianionic complex comprises a Group 4 metal and preferably where in the Group 4 metal comprises zirconium.

11. The method of claim 9, wherein: a) E and E’ are each O; b) R¹ and R¹ are independently a tertiary alkyl group, or a tertiary alkylaryl group; c) R¹ and R¹ are each a tertiary alkyl group, and the tertiary alkyl group comprises an optionally substituted adamantyl group; _are independently an optionally substituted arylene, an optionally

substituted heteroarylene, an optionally substituted cycloalkylene, or an optionally substituted vinylene; e) the heterocyclic Lewis base is a 5- or 6-membered heteroaromatic ring; or, f) any combination of a) through e).

12. The method of claim 11, wherein re each an optionally

substituted phenylene or an optionally substituted heteroarylene.

13. The method of claim 9, Z of the heterocyclic Lewis base is N.

14. The method of any preceding claim, wherein the at least one activator comprises at least one alumoxane.

15. The method of any preceding claim, wherein the at least one activator comprises at least one non-coordinating anion.

16. The method of claim 15, wherein the non-coordinating anion is surface bound to the support material as a reaction product of surface hydroxyl group and a non-coordinating anion precursor, the non-coordinating anion precursor comprising an organoaluminum compound having a haloaryl group.

17. The method of any preceding claim, further comprising: foaming the branched polypropylene copolymer.