Process for the production of impact copolymer using a dianionic complex comprising an octadentate chelating ring

Abstract

Impact copolymers can be prepared using bi-anionic complexes with an 8-membered chelate ring. Methods for forming impact copolymers include: mixing a) propylene and optionally b) C2 or C4-C... 20 α-olefins and / or α,ω'-dienes are subjected to first polymerization conditions in the presence of a first polymerization catalyst and optional hydrogen to form matrix polypropylene; and the matrix polypropylene and a) ethylene and C3-C 20 α-olefins, or b) propylene and C2 or C4-C 20 α-olefins are subjected to second polymerization conditions in the presence of a second polymerization catalyst and optionally hydrogen to form an impact copolymer comprising a copolymer phase dispersed within a matrix polypropylene; wherein the second polymerization conditions include gas-phase polymerization conditions and the second polymerization catalyst comprises a dianionic complex of a group 3-6 metal, the dianionic complex comprising two eight-membered chelate rings containing a group 3-6 metal.

Description

Technical Field

[0001] This disclosure relates to impact copolymers, and more specifically, to the production of impact copolymers using metal complexes. Background Technology

[0002] Impact copolymers (ICPs) are specialty polymers containing a crystalline phase and a copolymer phase. The crystalline phase is typically isotactic polypropylene or a propylene-ethylene random copolymer primarily containing propylene-derived monomer units. The copolymer phase can be a rubber or elastomer phase with a low glass transition temperature (Tg), mixed within the crystalline phase as discrete, discontinuous structural domains. The copolymer phase is typically ethylene-propylene rubber (EPR) or ethylene-propylene-diene monomer (EPDM) rubber. Other types of rubber compounds can also be used. The crystalline phase transfers stiffness and hardness to the copolymer, while the copolymer phase acts as an impact modifier and transfers toughness. Due to their impact resistance, ICPs have considerable applications in the automotive industry and other applications requiring these properties.

[0003] ICPs with a broad molecular weight distribution and a copolymer phase with high molecular weight and narrow molecular weight distribution (polydispersity index) and narrow compositional distribution are likely desirable for enhancing ICP performance. Unfortunately, achieving this balance between the crystalline and copolymer phases of ICP using conventional polymerization methods and catalysts is not easy. Furthermore, it may be difficult to form ICPs with a balanced toughness and stiffness using conventional polymerization methods and catalysts.

[0004] ICPs can be prepared by compounding a copolymer phase within a crystalline phase or by growing a copolymer phase within a crystalline phase during a staged polymerization process. Compounding is often difficult and is typically replaced by in-reactor blending via staged polymerization, where both crystalline and copolymer phases are continuously formed. Preparation of ICPs via staged polymerization and in-reactor blending is often carried out using Ziegler-Natta and similar multi-site catalysts in a staged slurry / gas-phase polymerization process, where a crystalline phase is first prepared using slurry polymerization, and then a copolymer phase is grown within the crystalline phase in one or more downstream reactors via gas-phase polymerization in a second polymerization stage. The same polymerization catalyst can promote polymerization in each stage, where the crystalline polymer grows around supported polymer particles in the first polymerization stage, and the supported catalyst continues to promote polymer growth and copolymer phase formation during the second polymerization stage. The properties of ICPs can be tailored, at least in part, by the catalyst structure and by changing the polymerization conditions, including selecting one or more monomers undergoing polymerization. Ziegler-Natta catalysts may be advantageous in the above respects because they can maintain high polymerization activity throughout both polymerization stages. A disadvantage of Ziegler-Natta catalysts when forming impact copolymers is that the multi-site nature of these types of catalysts tends to provide copolymer phases with undesirably broad molecular weight distributions and lower molecular weights, thus impairing impact performance. While metallocene catalysts can sometimes be used as alternatives to Ziegler-Natta catalysts for forming impact copolymers, many metallocene catalysts are expensive and exhibit significantly lower polymerization activity than Ziegler-Natta catalysts, particularly during the second polymerization stage, resulting in incomplete filling of the crystalline phase by the copolymer phase. Summary of the Invention Invention Overview

[0006] In various aspects, this disclosure provides a method for forming an impact copolymer, comprising: making a) propylene and optionally b) C2 or C4-C 20 α-olefins and / or α,ω'-dienes are subjected to first polymerization conditions in the presence of a first polymerization catalyst and optionally hydrogen to form matrix polypropylene; and the matrix polypropylene and a) ethylene and C3-C 20 α-olefins, or b) propylene and C2 or C4-C 20 α-olefins are subjected to second polymerization conditions in the presence of a second polymerization catalyst and optionally hydrogen to form an impact copolymer comprising a copolymer phase dispersed within the matrix polypropylene; wherein the second polymerization conditions include gas-phase polymerization conditions, and the second polymerization catalyst comprises a dianionic complex of a group 3-6 metal, the dianionic complex comprising two eight-membered chelate rings containing a group 3-6 metal.

[0007] These and other features and properties of the systems and methods disclosed in this disclosure, as well as their advantageous applications and / or uses, will become apparent from the detailed description below. Attached Figure Description

[0008] Reference is made to the accompanying drawings to assist those skilled in the art in making and using the subject matter herein. The drawings, included to illustrate certain aspects of this disclosure, should not be considered an exclusive configuration. As will be apparent to those skilled in the art upon reading this disclosure, the disclosed subject matter is capable of numerous modifications, alterations, combinations, and equivalents in form and function.

[0009] Figure 1 This is a graph showing the flexural modulus of the samples from Examples 2-4 as a function of the notch Izod value.

[0010] Figure 2 This is a small-amplitude oscillatory shear plot of the sample from Example 4 compared to a similar sample lacking long-chain branching.

[0011] Figure 3 This is a plot of the tensile viscosity of the sample from Example 4 compared to a similar sample lacking long-chain branching. Invention Details

[0013] This disclosure relates to impact copolymers, and more specifically, to the production of impact copolymers using metal complexes.

[0014] This disclosure provides a polymerization method for producing impact copolymers with desired properties, wherein a dianionic complex of a Group 3-6 metal, such as a bis(phenolate) complex or a similar complex containing two eight-membered chelate rings, can be used to promote polymerization in at least a second polymerization stage, preferably simultaneously in the first and second polymerization stages, to sequentially form a crystalline phase (matrix polypropylene) and a copolymer phase (which may be an elastomer or a rubber phase) to define the impact copolymer. When producing impact copolymers, numerous advantages and operational efficiencies can be achieved by using such a dianionic complex simultaneously during the first and second polymerization stages, as discussed below. At a minimum, by using the same polymerization catalyst simultaneously in the first and second polymerization stages, the risk of incompatibility between the first and second polymerization catalysts and their associated polymerization reaction conditions can be substantially avoided. However, it may sometimes be advantageous to combine the dianionic complex described herein with another type of catalyst, such as metallocene, to provide the desired polymerization properties.

[0015] Bis(phenolate) complexes and similar dianionic complexes are well-suited for forming impact copolymers in segmental polymerization processes. Such complexes are readily compatible with both slurry and gas-phase polymerization conditions and can promote the production of extended catalysts with high catalytic activity under both types of polymerization conditions. Bis(phenolate) complexes and similar dianionic complexes can also provide highly crystalline, predominantly isotactic polypropylene matrices and copolymer phases with high molecular weights. In contrast to some other types of Ziegler-Natta catalysts with multiple catalytic sites, bis(phenolate) complexes and similar dianionic complexes can provide polymers with a relatively limited molecular weight distribution (polydispersity index, Mw / Mn). The preparation of bis(phenolate) complexes and similar dianionic complexes is relatively simple, and they are typically isolated as single isomers, which greatly simplifies their purification. In contrast, many metallocene catalysts used in polypropylene production are isolated as mixtures of diastereomers, leading to complex separation and purification processes. Therefore, the combination of properties available from bis(phenol salts) and similar bianionic complexes may be particularly advantageous for the production of impact copolymers according to this disclosure.

[0016] As another advantage, in addition to propylene, the polymerization mediated by the aforementioned complexes can also utilize higher α-olefins and / or α,ω-dienes as comonomers. The introduction of such comonomers allows for the customization of the properties of the resulting impact copolymer. For example, it may be advantageous to introduce α,ω-diene monomers (e.g., 1,7-octadiene or similar long-chain hydrocarbons with terminal unsaturated portions at both ends of the hydrocarbon chain) into the impact copolymer, particularly within a matrix polypropylene. The resulting matrix polypropylene exhibits long-chain branching and can still effectively fill the copolymer phase during the second polymerization stage. More importantly and surprisingly, the introduction of long-chain branching into the matrix polypropylene can lead to a greater balance between stiffness and toughness in the resulting impact copolymer.

[0017] As another advantage, bis(phenolate) complexes and similar bi-anionic complexes can be used in combination with metallocene catalysts during the formation of impact copolymers according to this disclosure. Metallocene catalysts allow for further customization of the desired properties of the impact copolymer. For example, the significant difference in hydrogen response and initial molecular weight capability between bis(phenolate) catalysts and metallocenes allows for easy customization of the resulting molecular weight distribution. Due to this capability, bimodal and multimodal polymers can be prepared in a single reactor using both catalysts simultaneously on a single support. Furthermore, the inherently different activities of bis(phenolate) catalysts and metallocenes to various comonomers allow for compositional fine-tuning at a given molecular weight distribution, particularly in the dispersed (internal) phase of the impact copolymer. Therefore, this disclosure yields impact copolymers exhibiting step-like performance characteristics and a balance between stiffness and toughness.

[0018] In particular, pairing bis(phenolate) complexes or similar bi-anionic complexes with metallocenes having C1 symmetry may be advantageous in the formation of impact copolymers according to this disclosure. Metallocenes with C1 symmetry are asymmetric, meaning they have no plane of symmetry about any axis. Advantageously, metallocenes with C1 symmetry can efficiently form isotactic polypropylene as the matrix polypropylene and an elastomeric polymer as the copolymer phase under appropriate polymerization conditions, and provide a balance between a sufficiently broad molecular weight distribution of the isotactic polypropylene and a sufficiently narrow molecular weight distribution and high molecular weight of the copolymer phase to provide good impact copolymer properties. Therefore, when used in combination with bis(phenolate) and similar anionic complexes, metallocenes with C1 symmetry can further help tailor the properties of the impact copolymer, for example, promoting a balance between toughness and impact resistance.

[0019] As a final advantage, bis(phenolic) complexes and similar bianionic complexes can be readily incorporated into support materials to simultaneously promote slurry polymerization and gas-phase polymerization processes. When located on a support material, activation of such complexes can be achieved using various types of activators, such as supported aluminoxanes, acidic clays, and more discrete support-bound activators containing tethered aluminum or boron compounds. The latter type of supported activator may be particularly advantageous in avoiding the use of expensive methylaluminoxanes as external activators (which are highly reactive and prone to gelation).

[0020] definition

[0021] For the purposes of this disclosure, a new numbering scheme for the groups of the periodic table is used. In this scheme, groups (columns) are numbered sequentially from 1 to 18 from left to right, excluding 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, including lanthanides and actinides. Ti, Zr, and Hf are, for example, group 4 transition metals.

[0022] In this paper, Mn is the number-average molecular weight, Mw is the weight-average molecular weight, Mz is the z-average molecular weight, wt% is the weight percentage, and mol% is the molar percentage. Molecular weight distribution (MWD) (also known as polydispersity index (PDI)) is defined as Mw divided by Mn. Unless otherwise specified, all molecular weight units (e.g., Mw, Mn, and Mz) are expressed in g / mol (g·mol⁻¹). -1 (in units of )

[0023] For the purposes of this disclosure, when a polymer, copolymer, or oligomer, particularly a polyolefin, is referred to as containing an olefin, the olefin present in such polymer, copolymer, or oligomer is a polymeric form of the olefin. For example, when a copolymer is said to have an "ethylene" content of 0% to 5% by weight, it should be understood that the monomeric units in the copolymer are derived from the monomer ethylene in the polymerization reaction, and said derived units are present at 0% by weight (i.e., absent) to 5% by weight, based on the weight of said copolymer. The terms "polymer" and "oligomer" (and their grammatical variations) as used herein are used interchangeably and refer to a molecule having two or more identical or different monomeric units. The term "to polymerize" (and its grammatical variations, e.g., polymerization) as used herein refers to the process of producing a molecule having two or more identical or different monomeric units from two or more identical or different monomers. A "homopolymer" is a polymer (or oligomer) having identical monomeric units. A "copolymer" is a polymer (or oligomer) having two or more monomeric units that are different from each other. A "terpolymer" is a polymer (or oligomer) having three monomeric units that are different from each other. The term "different" used to refer to monomer units means that the monomer units differ from each other by at least one atom or are isomerically different. Therefore, the definition of copolymer used herein includes terpolymers and similar higher polymers (or oligomers). "Decanene polymer" or "decene copolymer" is, for example, a polymer or copolymer containing at least 50 mol% decene-derived units.

[0024] When referring to selecting multiple items from a given group, the term "independently" means that the selection of the first item does not necessarily affect the selection of any second or subsequent items. In other words, independent selection of multiple items within a given group means that the items can be the same as or different from each other.

[0025] The terms “group,” “base,” and “substituent” are used interchangeably in this document.

[0026] The term "hydrocarbon" refers to a class of compounds having hydrogen atoms bonded to carbon, and encompasses saturated hydrocarbons, unsaturated hydrocarbons, and mixtures of hydrocarbons (saturated and / or unsaturated), including mixtures of hydrocarbons with different numbers of carbon atoms. The term "C"... n "A hydrocarbon" refers to a hydrocarbon (one or more) or hydrocarbon group having n carbon atoms (one or more) per molecule or group, where n is a positive integer. Such hydrocarbon compounds can be one or more of the following: linear, branched, cyclic, acyclic, saturated, unsaturated, aliphatic, and / or aromatic. Cyclic hydrocarbons as used herein may be referred to as "carbocyclic" compounds, which include saturated, unsaturated, and partially unsaturated carbocyclic compounds as well as aromatic compounds. The term "heterocyclic" refers to a carbocyclic ring containing at least one cyclic heteroatom as a substitute for a cyclic carbon atom.

[0027] The terms "hydrocarbyl radical," "hydrocarbyl," and "hydrocarbyl group" are used interchangeably throughout this disclosure and refer to a group containing a hydrogen atom and a carbon atom and having at least one unfilled valence position when removed from the parent compound. In some cases, the hydrocarbon radical may optionally be substituted. A suitable "hydrocarbyl radical" may refer to a C1-C group. 100 A saturated hydrocarbon group, which can be linear, branched, or cyclic, and when cyclic, is aromatic or non-aromatic in nature. Examples of saturated hydrocarbon groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and their substituted analogues.

[0028] A substituted hydrocarbon group is one in which at least one hydrogen atom of the hydrocarbon group is replaced by at least one non-hydrogen group such as a hydrocarbon 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. Substituted groups, or at least one heteroatom of which has been inserted into the hydrocarbon ring or chain, wherein each R Independently hydrogen, hydrocarbon, or halocarboxylic group, or two or more R groups. They can be linked together to form cyclic or polycyclic structures that are substituted or unsubstituted, saturated, unsaturated, partially unsaturated, or aromatic.

[0029] The term "substitution" refers to the replacement of at least one hydrogen or carbon atom in a hydrocarbon or hydrocarbon 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 the substituted hydrocarbon or hydrocarbon group 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, SbR2, SR, BR2, SiR3, GeR3, SnR3, and PbR3, where R is a hydrocarbon group or H. Suitable hydrocarbon groups R may include alkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocyclyl, etc., any of which may optionally be substituted.

[0030] The term "optionally substituted" means that the hydrocarbon or hydrocarbon group may be unsubstituted or substituted. For example, the term "optionally substituted hydrocarbon group" means that at least one hydrogen atom or carbon atom in the hydrocarbon group is replaced by a heteroatom or heteroatom functional group. Unless otherwise specified as explicitly unsubstituted, any hydrocarbon group herein may be optionally substituted.

[0031] The term "saturated hydrocarbon" refers to a hydrocarbon containing zero carbon-carbon double or triple bonds. Saturated hydrocarbons can be linear or cyclic, either of which may optionally be branched. Saturated hydrocarbons can be C2-C... 40 Hydrocarbons, such as C4-C7 hydrocarbons. In at least one embodiment, the C4-C7 hydrocarbon may be isobutane, pentane, cyclopentane, cyclohexane, isopentane, isohexane, hexane, heptane, or mixtures thereof.

[0032] The term "alkyl" refers to a straight-chain, branched, or cyclic hydrocarbon group having only carbon-carbon single bonds. Such alkyl groups can be substituted. Examples of alkyl groups include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, and their substituted analogues.

[0033] The term "alkylene" refers to a divalent alkyl group. For example, methylene is a divalent alkylene group.

[0034] The term "olefin" (or "alkene") refers to a linear, branched, or cyclic compound of carbon and hydrogen having at least one carbon-carbon double bond.

[0035] The term "alkenyl" refers to a straight-chain, branched, or cyclic hydrocarbon group having one or more carbon-carbon double bonds. Alkenyl groups may be optionally substituted. Examples of suitable alkenyl groups include, but are not limited to, vinyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, and their substituted analogues.

[0036] The term "diene" refers to an olefin having two carbon-carbon double bonds. The term "α,ω-diene" refers to an olefin having unsaturated carbon-carbon double bonds at each end of its carbon chain.

[0037] The term "aromatic" refers to a planar unsaturated ring containing atoms stabilized by the interactions of bonds that form the ring. Such compounds are typically six-membered rings, such as benzene and its derivatives. As used herein, the term "aromatic" also refers to quasi-aromatic compounds, which are compounds with similar properties and structures (almost planar) to aromatic compounds, but are not aromatic by definition; similarly, the term "aromatic" also refers to substituted aromatic compounds and groups. Aromatic (but not quasi-aromatic) hydrocarbons follow Hückel's rule and contain a cyclic cloud of 4n + 2π electrons, where n is a positive integer.

[0038] The term "aryl" or "aryl group" refers to a carbon-containing aromatic ring or a variant thereof, including but not limited to phenyl, 2-methylphenyl, xylyl, 4-bromoxylyl, etc. Similarly, the term "heteroaryl" or "heteroaryl group" refers to an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced by a heteroatom (preferably N, O, or S). As used herein, the term "aromatic" also refers to quasi-aromatic heterocycles, which are heterocyclic substituents having properties and structures (almost planar) similar to aromatic heterocyclic groups, but are not aromatic by definition.

[0039] The substituted aryl group is an aryl group in which at least one hydrogen atom of the aryl group has been replaced by at least one non-hydrogen group, such as a hydrocarbon group, a heteroatom or heteroatom-containing group, such as 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 -SiR 3. -GeR -GeR 3. -SnR -SnR 3. -PbR 3-order replacement, where each R Independently hydrogen, hydrocarbon, or halocarboxylic group, or two or more R groups. These can be linked together to form substituted or unsubstituted, saturated, unsaturated, partially unsaturated, or aromatic cyclic or polycyclic ring structures, or in which at least one heteroatom has been inserted into the hydrocarbon ring. For example, 3,5-dimethylphenyl and 2-methylphenyl are substituted aryl groups. The term "aralkyl" refers to an alkyl group in which hydrogen has been replaced by an alkyl or substituted alkyl group. The term "alkylaryl" refers to an alkyl group in which hydrogen has been replaced by an aryl or substituted aryl group. Thus, for example, 2-methylphenyl is an aralkyl or substituted aryl group, and benzyl and phenethyl are alkylaryl groups.

[0040] Any aryl group in this document may be an optionally substituted phenyl group. The terms "substituted phenyl" or "substituted phenyl group" refer to a phenyl group having one or more hydrogen groups, said hydrogen groups being replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom or heteroatom-containing group, such as a halogen (e.g., F, Cl, Br, I) or at least one functional group (e.g., -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, etc.) replacement, where each R Independently hydrogen, hydrocarbon, halogen, or halocarboxylic group, or two or more R groups. They can be linked together to form substituted or unsubstituted, saturated, unsaturated, partially unsaturated, or aromatic cyclic or polycyclic ring structures, or in which at least one heteroatom has been inserted into the hydrocarbon ring.

[0041] The term "heterocycle" refers to a cyclic group in which one or two or three ring carbon atoms have been replaced by heteroatoms such as N, O, or S. A heterocycle is a ring structure containing heteroatoms, as opposed to a ring in which hydrogen atoms on the ring atoms are replaced by heteroatoms. For example, tetrahydrofuran is a heterocycle, and 4-N,N-dimethylaminophenyl is a heteroatom-substituted ring.

[0042] The term "substituted heterocycle" refers to a heterocyclic group in which at least one hydrogen atom of the heterocyclic group has been replaced by at least one non-hydrogen group, such as a hydrocarbon group, a heteroatom or heteroatom-containing group, such as a 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-order replacement, where each R It can be hydrogen, hydrocarbon, or halocarbon.

[0043] The term "ring atom" refers to an atom that belongs to a cyclic ring structure. According to this definition, benzyl has 6 ring atoms and tetrahydrofuran has 5 ring atoms.

[0044] When isomers named alkyl, alkenyl, alkoxide, or aryl (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl), a reference to one member of that group (e.g., n-butyl) should explicitly disclose the remaining isomers in that family (e.g., isobutyl, sec-butyl, and tert-butyl). Similarly, a reference to alkyl, alkenyl, alkoxide, or aryl without specifying a particular isomer (e.g., butyl) specifically discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

[0045] The terms “catalyst productivity” and “catalyst activity” are interchangeable measures of how many grams of polymer (P) are produced in a polymerization catalyst containing W g of catalyst (cat) over a time period of T hours; and can be expressed as: P / (T×W) in gPgcat. -1 hr -1 Units are used to express the total amount of product. Unless otherwise stated, “conversion” is the amount of monomer converted into polymer product and is reported as mol% and calculated based on polymer yield (by weight) and the amount of monomer fed into the reactor. Catalyst activity is a measure of the level of catalyst activity and is reported as the mass of product polymer (P) produced per mass of catalyst (gP / g catalyst).

[0046] The term "catalyst system" refers to a combination of at least one catalyst compound (e.g., at least one bis(phenolate) complex or similar bianionic complex and optionally at least one metallocene, such as a C1 symmetric metallocene) and optionally a support material. A catalyst system may further include at least one activator and / or at least one co-activator. Therefore, a preferred catalyst system may include at least one catalyst compound disposed on a support material in combination with at least one activator. When a catalyst system is described as comprising a neutral, stable form of the above components, it should be understood that the ionic form of the above components is the form in which they react with monomers to produce polymers. For the purposes of this disclosure, "catalyst system" may include both neutral and ionic forms of the components of the catalyst system.

[0047] In this disclosure, "catalyst" can be described as any of a catalyst precursor, a pre-catalyst compound, a catalyst compound, a catalyst, or a transition metal compound or complex, and these terms are used interchangeably herein. "Anionic ligand" is a negatively charged ligand that contributes one or more electron pairs to a metal ion. "Neutral donor ligand" is a neutrally charged ligand that contributes one or more electron pairs to a metal ion.

[0048] The term "hydroxyl group" refers to a C1-C group that is bonded to oxygen. 40 The physical form of a hydrocarbon group. Hydrocarbon groups can be straight-chain, branched, or cyclic, and can be saturated or unsaturated, including aromatic groups. Therefore, the terms "alkoxy" and "alkoxide" refer to alkyl or aryl ether groups. Examples of alkoxy ether groups include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenoxy, etc.

[0049] The term "complex" refers to a molecule in which an auxiliary ligand is coordinated to a central metal atom. The ligand is stably bonded to the metal atom to maintain its influence during the use of the complex in a catalytic process (e.g., polymerization). The ligand can coordinate to the metal atom via covalent bonds and / or electron-donating coordination or intermediate bonds. Metal complexes can undergo activation using activators to perform their catalytic function, such as in polymerization, which are believed to generate cations by removing anionic groups (commonly referred to as leaving groups) from the metal atom.

[0050] The term "metallocene" refers to a metallocene having at least one Bonded cyclopentadienyl structural moiety or substituted cyclopentadienyl structural moiety (e.g., substituted or unsubstituted cyclopentadienyl (Cp) and / or indyl (Ind)) and more often two (or three) Organometallic compounds with a bonded cyclopentadienyl moiety or a substituted cyclopentadienyl moiety. The terms "metallocene" and "metallocene catalyst" are used interchangeably herein.

[0051] The term "phenol salt" refers to a complex in which at least one phenolic anion forms a covalent bond with a metal ion. "Die (phenol salt)" refers to a complex in which two phenolic anions form a covalent bond with a metal ion. Optionally, the two phenolic anions can be linked together by a linking group to create a chelate ring of the desired size.

[0052] The term "scavenger" refers to a compound that can be added to a catalyst system to promote polymerization by removing impurities. Some scavengers can also act as activators and can be called co-activators. Co-activators that are not scavengers can also be used in combination with activators to form an active catalyst system. In at least one embodiment, the co-activator can be premixed with the complex to form an alkylated metal complex.

[0053] The term "continuous" refers to a system that operates without interruption or cessation over a period of time. For example, a continuous process for producing polymers may continuously introduce monomers into one or more reactors and continuously remove polymer products from them.

[0054] The terms "bulk polymerization" or "slurry-phase polymerization" refer to a polymerization method in which the monomers and / or comonomers undergoing polymerization are used as solvents or diluents, with little or no use of inert solvents or diluents, and where supported catalyst particles are dispersed in the solvent or diluent. A small portion of the inert solvent may be used as a carrier for the catalyst and scavenging agent. Slurry-phase polymerization contains less than about 25% by weight of inert solvent or diluent, for example, less than about 10% by weight, for example, less than about 1% by weight, for example, 0% by weight. The polymerization conditions associated with slurry polymerization may include operating under sufficient pressure to keep the monomers and / or comonomers in a liquid state.

[0055] The term "gas-phase polymerization" refers to a polymerization method in which monomers and / or comonomers are present in the gaseous state and supported catalyst particles are fluidized in a reactor.

[0056] When used in this disclosure, the following abbreviations may be used: dme is 1,2-dimethoxyethane, Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is n-propyl, cPr is cyclopropyl, Bu is butyl, iBu is isobutyl, tBu is tert-butyl, p-tBu is p-tert-butyl, nBu is n-butyl, sBu is sec-butyl, TMS is trimethylsilyl, TIBAL is triisobutylaluminum, TNOAL is tri(n-octyl)aluminum, MAO is methylaluminoxane, sMAO is supported methylaluminoxane, Bn is benzyl (i.e., CH2Ph), THF is also called tetrahydrofuran, RT is room temperature (and is 23°C unless otherwise stated), tol is toluene, EtOAc is ethyl acetate, and Cy is cyclohexyl.

[0057] Bi-anionic complex

[0058] Suitable bianionic complexes, such as bis(phenolate) complexes, that effectively promote the formation of impact copolymers according to the present invention may contain Group 3-6 metals, preferably Group 4 metals (e.g., Ti, Zr, or Hf), more preferably Zr. More generally, when properly activated, bianionic complexes can effectively promote the polymerization of olefinic unsaturated compounds (e.g., one or more α-olefins or similar hydrocarbons containing at least one olefinic group) under a range of polymerization reaction conditions, preferably wherein the bianionic complex is arranged in combination with at least one activator on a support material. Bianionic complexes can further effectively promote the polymerization of at least one α-olefin (e.g., propylene) (optionally in combination with ethylene) in combination with at least one α,ω-diene monomer to introduce long-chain branching into at least one of the copolymer phases of the matrix polypropylene and / or the impact copolymer. Further details regarding the activation of bianionic complexes and their polymerization are provided below.

[0059] The bis(phenolic salt) complexes suitable for use in this disclosure may have a structure represented by the following formula 1.

[0060]

[0061] Formula 1

[0062] in:

[0063] M is a metal from Groups 3 to 6, preferably a metal from Group 4;

[0064] E and E' are independently O, S, or NR. 9 , where each R 9 Independently, it is hydrogen, C1-C 40 Optional substituted hydrocarbon groups or heteroatom-containing groups;

[0065] Z is a group 14-16 atom that forms a coordinate bond with M;

[0066] A 1 ZA 1’ It is part of a heterocyclic Lewis base designated as B, containing 4 to 40 non-hydrogen atoms, which connects A via a 3-atom bridge. 2 With A 2’ The connection, where Z is the central atom of the 3-atom bridge;

[0067] A 1 and A 1' Independently C, N, or CR 22 , where each R 22 It is hydrogen or an optional substituted C1-C 20 Hydrocarbon groups, such as optionally substituted C1-C 20 alkyl;

[0068] It is a divalent group, optionally, part of an optionally substituted hydrocarbon ring or optionally substituted heterocycle, containing 2 to 40 non-hydrogen atoms, which connect A via a 2-atom bridge. 1 It is connected to a first aryl group, wherein the first aryl group has an E bonded thereto;

[0069] It is a divalent group, optionally, part of an optionally substituted hydrocarbon ring or optionally substituted heterocycle, containing 2 to 40 non-hydrogen atoms, which connect A via a 2-atom bridge. 1' It is connected to a second aryl group, the second aryl group having an E' bonded to it;

[0070] Each L is a Lewis base;

[0071] Each X is an anionic ligand;

[0072] n is 1, 2, or 3;

[0073] m is 0, 1, or 2;

[0074] n+m is not greater than 4; and

[0075] R 1 R 2 R 3 R 4 R 1' R 2' R 3' and R 4' Independently hydrogen, optionally substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group, or R 1 and R 2 R 2 and R 3 R 3 and R 4 R1' and R 2' R 2' and R 3' or R 3' and R 4' One or more pairs of rings are connected to form one or more optionally substituted hydrocarbon rings or optionally substituted heterocycles, each ring having 5, 6, 7 or 8 ring atoms, and optionally, said optionally substituted hydrocarbon rings or said optionally substituted heterocycles are fused to one or more additional rings.

[0076] in:

[0077] When m is 2, any two L groups may optionally be linked together to form a bidentate Lewis base; or

[0078] X is optionally linked to L to form a monoanionic bidentate ligand bonded to M; or

[0079] When n is 2 or 3, any two Xs may be optionally linked together to form a bi-anion ligand bonded to M.

[0080] In a more specific instance, the dianionic complex contains a Group 4 metal. Preferably, the Group 4 metal M is zirconium.

[0081] Preferably, E and E' are each O. Therefore, the preferred dianionic complexes of this disclosure can be bis(phenolate) complexes. When E and E' are S or NR... 9 When the complex is in this case, it can be called a bis(phenothiolate) or bis(anilide) complex.

[0082] When E or E' is NR 9 At that time, R 9 Independently, it is hydrogen, C1-C 40 Optional substituted hydrocarbon group or heteroatom-containing group. Preferably, R 9 It is C1-C 20 Alkyl or C6-C 10 Aryl groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecyl, phenyl, naphthyl, etc., any of which may be optionally substituted.

[0083] 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, etc. The heterocyclic Lewis base may be a azole, a thiazole, or a furan, any one of which may optionally be substituted or fused with another ring. More preferably, the Z of the heterocyclic Lewis base is N. Even more preferably, the heterocyclic Lewis base may be an optionally substituted pyridine.

[0084] In a more specific example, the heterocyclic Lewis base is a 2,6-disubstituted pyridine ring, wherein... and They are bonded to the 2- and 6-positions of the pyridine ring, respectively, and the nitrogen atom (A) of the pyridine ring... 1 ZA 1' Z) in M ​​forms a coordinate bond with M.

[0085] and Each is preferably a diatomic linking group, wherein the diatomic part of the linking group refers to the number of atoms to which the heterocyclic Lewis base is linked to an aryl group containing E or E'. and Examples of diatomic linkers that can be selected independently include optionally substituted arylene, optionally substituted heteroarylene, or optionally substituted vinylene. Other examples of suitable diatomic linkers may include non-aromatic groups, such as optionally substituted ethylene, optionally substituted cycloalkylene, optionally substituted heterocyclic groups, etc.

[0086] In some instances, and Each may be an optionally substituted phenylene (e.g., an optionally substituted o-phenylene), an optionally substituted cycloalkylene, or an optionally substituted heteroaryl, any of which may optionally be fused with an additional aromatic or non-aromatic ring. For example, in one or more embodiments, and The atom can be independently selected from optionally substituted o-phenylene, optionally substituted 1,2-thienyl, or optionally substituted 1,2-furanyl, any of which can be fused with an additional aromatic or non-aromatic ring. Preferably, and They are the same.

[0087] In some instances, R 2 R 4 R 2’ and R 4’ Each is hydrogen.

[0088] In some instances, R 3 and R 3' Independently hydrogen, optionally substituted C1-C 40 Hydrocarbon group or halogen (e.g., F). More preferably, R 3 and R 3' It can be independently selected from the optionally substituted C1-C 10 Alkyl, halogen, or any combination thereof. 3 and R 3' They can be the same or different, but R is preferred. 3 and R 3' Same. Applicable to R3 and R 3’ Examples of hydrocarbon groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, adamantyl, and 2-phenylisopropyl. , (-Dimethylbenzyl), 1,1,3,3-Tetramethylbutyl, etc.

[0089] In some instances, R 1 and R 1' Independently selected from optionally substituted C1-C 40 Hydrocarbon group, more preferably an optionally substituted C4-C 16 Hydrocarbon group or optional substituted C6-C 16 Hydrocarbon group. More preferably, R 1 and R 1' Each can be an optionally substituted bulky alkyl group (including tertiary alkyl groups), such as optionally substituted tert-butyl, optionally substituted cyclohexyl, optionally substituted 1-methylcyclohexyl, optionally substituted norbornel, optionally substituted adamantyl, optionally substituted 1,1,3,3-tetramethylbutyl, 2-phenylisopropyl, etc. More preferably, R 1 and R 1' Each is independently an optionally substituted tertiary alkyl group, such as optionally substituted adamantyl or optionally substituted tert-butyl. Optionally substituted adamantyl groups include 1-adamantyl and 2-adamantyl, such as 3,5-dimethyl-1-adamantyl or 3,5,7-trimethyl-1-adamantyl. R 1 and R 1’ They can be the same or different, but R is preferred. 1 and R 1’ same.

[0090] Non-limiting examples of X include, but are not limited to, optionally substituted C1-C 40 Hydrocarbon groups (e.g., optionally substituted C1-C) 20 Hydrocarbon group), optionally substituted C4-C 62 Aryl, optionally substituted C4-C 62 Heteroaryl, hydride, amide, alkoxide, sulfide, phosphide, halide, or combinations thereof. For example, each X can independently be a halogen or a C1-C6 alkyl group or a C1-C6 alkyl group. 10A hydrocarbon group, such as methyl or benzyl, either of which may be further optionally substituted. In some embodiments, each X may be independently selected from chlorine, bromine, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl. In some embodiments of this disclosure, one or more X groups may form part of a fused ring or a ring system when combined with another X or with L.

[0091] In some instances, n is 2. In some or other instances, m is 0.

[0092] Therefore, in a more specific instance, a suitable bis(phenolic) complex for use in this disclosure may be a bis(phenolic) complex (E=E'=O) having a structure represented by any one of the following formulas 2A-2E.

[0093]

[0094]

[0095] in:

[0096] R 1 R 1’ R 3 R 3’ R 22 X and M are as defined above, Q is an optional substituent at any open ring position, and further optionally, two Qs can be linked to define a carbocyclic, heterocyclic, aromatic, or heteroaromatic ring fused with the phenyl, thiophene, furanyl, pyrrol, or cyclohexyl ring systems of formulas 2A-2E. For the benzene ring of formula 2A, the variable r is 0, 1, 2, 3, or 4; for the thiophene, furanyl, and pyrrol rings of formulas 2B-2D, the variable r is 0, 1, or 2; and for the cyclohexenyl ring system of formula 2E, the variable r is 0, 1, 2, 3, 4, 5, 6, 7, or 8. The variable q is 0, 1, 2, or 3, preferably 0 or 1. When present, Q is an optional substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group, or one or two or more Q-connected groups to define the above-described carbocyclic, heterocyclic, aromatic or heteroaromatic ring, wherein such ring may have 5, 6, 7 or 8 ring atoms and may optionally be fused with one or more additional rings.

[0097] More preferably, R 1 and R 1' Each is independently selected from tertiary alkyl or tertiary alkyl aryl, such as adamantyl (e.g., optionally substituted 1-adamantyl), optionally substituted tertiary butyl, optionally substituted 2-phenylisopropyl, or optionally substituted 1,1,3,3-tetramethylbutyl; R 3 and R 3' Each selected from C1-C 10Alkyl, C1-C 10 Alkyl or aryl group or halogen (e.g., F); M is a Group 4 metal, preferably Zr. In a more specific example, R 1 and R 1' Each is independently a optionally substituted 1-adamantyl or optionally substituted tert-butyl, R 3 and R 3' C1-C independently of optional substitution 10 Alkyl or F; M is a Group 4 metal, preferably Zr. Preferably, R 1 and R 1' Same as R 3 and R 3' same.

[0098] Illustrative examples of bis(phenolic salt) complexes having a structure represented by formula 2A-2E (M=Hg Zr) may include, but are not limited to:

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107] and

[0108] .

[0109] Any of the aforementioned bianionic complexes can be introduced into a catalyst system comprising a support material, an optional activator, an optional co-activator, and an optional scavenger. Preferably, the activator is present and arranged in combination with the bianionic complex on the support material. The activator and optional co-activator can convert the bianionic complex into a form that effectively promotes olefin polymerization under suitable polymerization conditions to form an impact copolymer, as described in further detail below.

[0110] Metallocene complexes

[0111] The aforementioned bianionic complexes, including bis(phenolate) complexes, disclosed herein can be used in combination with metallocenes on a support material to define a catalyst system containing both types of catalysts. While any metallocene with suitable polymerization activity can be used, the metallocene may preferably have C1 symmetry. Further descriptions of suitable metallocenes with C1 symmetry are provided below. It should be noted that in metallocenes expressed by the following formula, the variable definitions are exclusive to the metallocenes in this section. For example, R is defined for the aforementioned bianionic complexes. 1 The definition and the R specified for the following metallocene complexes 1 The definitions are mutually exclusive.

[0112] Suitable metallocenes exhibiting C1 symmetry and effectively promoting the formation of impact copolymers according to the present invention may comprise group 3-6 metals, preferably group 4 metals (e.g., Ti, Zr, or Hf). When properly activated, metallocenes combined with at least one dianionic complex, such as a bis(phenolate) complex, can also effectively promote the polymerization of olefinic unsaturated compounds, as described above. C1-symmetric metallocenes can also be arranged on a support material in combination with at least one dianionic complex.

[0113] Metallocenes with C1 symmetry and applicable to this disclosure may have a structure represented by the following Equation 3.

[0114]

[0115] Formula 3

[0116] In C1-symmetric metallocene:

[0117] M is a transition metal in group 3, 4 or 5 of the periodic table, such as group 4 metals, such as Zr, Hf or Ti;

[0118] T is a bridge base;

[0119] X 1 and X 2 Each is a monovalent anionic ligand, or X 1 and X 2 Linked to form metallocycle rings, chelate ligands, diene ligands, or alkylidenes;

[0120] R 1 It is hydrogen, halogen, or optionally substituted C1-C 40 Alkyl, optionally substituted C6-C 14 Aryl, optionally substituted C3-C 13 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R"-SiR'3, where R" is C1-C10 Alkylene, and each R' is hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl; preferably, R 1 It is C1-C 10 Alkyl, and more preferably, R 1 It is methyl;

[0121] R 2 and R 6 Independently hydrogen, halogen, or optionally substituted C1-C 40 Alkyl, optionally substituted C6-C 14 Aryl, optionally substituted C3-C 13 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R"-SiR'3, where R" is C1-C 10 Alkylene, and each R' is hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl; preferably, R 2 and R 6 At least one of them is hydrogen, and more preferably, R 2 and R 6 They are all hydrogen;

[0122] R 3 C1-C is an optional substitute 40 Alkyl, optionally substituted C6-C 18 Aryl or optionally substituted C3-C 13 heteroaryl; more preferably, R 3 It is a bulky alkyl group, such as optionally substituted cyclohexyl, optionally substituted norbornel, optionally substituted adamantyl, or optionally substituted tert-butyl, such as cyclohexyl, 1-adamantyl, 2-adamantyl, (1s,4s)-bicyclo[2.2.1]hept-7-oxide, (1R,4S)-bicyclo[2.2.1]hept-2-oxide, or (1s,4s)-bicyclo[2.2.1]hept-1-oxide; or R 3 It is an aryl group that is optionally substituted, more preferably an phenyl group that is optionally substituted; even more preferably R 3 It is an optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted anthraquinone;

[0123] R 4 and R 5 Independently, it is H, R"', or OR"', where R"' is an optionally substituted C1-C 40 Alkyl, or R 4 and R 5 Connect to form C3-C 62Substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structures, or combinations thereof; and

[0124] R 7 R 8 R 9 and R 10 Independently hydrogen, halogen, or optionally substituted C1-C 40 Alkyl, optionally substituted C6-C 14 Aryl, optionally substituted C3-C 13 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R''-SiR'3, where R'' is C1-C 10 Alkylene and R' are hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl, or R 5 and R 6 R 6 and R 7 or R 7 and R 8 One or more pairs are connected to form C3-C 62 A cyclic or polycyclic structure, or a combination thereof, that is substituted or unsubstituted, saturated or unsaturated; preferably, R 7 R 8 R 9 and R 10 It is a methyl group.

[0125] As a non-restrictive statement, in Equation 3, when R 4 and R 5 When linked to form a polycyclic structure, the polycyclic structure may contain a 5- or 6-membered ring, preferably a 5- or 6-membered carbon ring without heteroatoms as ring atoms. For example, indacenyl ligand contains such a 5-membered carbon ring, and hexahydrobenz[f]indenyl ligand contains such a 6-membered carbon ring.

[0126]

[0127] The carbocyclic ring in the indole ligand or hexahydrobenzo[f]indenyl ligand can be substituted or unsubstituted, and can be part of a polycyclic group, wherein the additional cyclic group can be saturated or unsaturated, and substituted or unsubstituted. Typical substituents on the carbocyclic ring can include optionally substituted C1 to C2 groups. 40A hydrocarbon group, a heteroatom (e.g., a halogen, including Br, F, Cl, or I), a heteroatom-containing group (e.g., a halocarboxylic group), or two or more substituents linked together to form a cyclic or polycyclic ring structure (which may contain saturated and / or unsaturated rings), or a combination thereof. One or more of such substituents may be present. Wherein R 4 and R 5 Exemplary ligands that fuse to form a carbon ring include those having a structure represented by the following formulas 4-6:

[0128]

[0129]

[0130] The wavy line indicates the connection with M (e.g., with Zr or Hf) and T (e.g., Me2Si or Ph2Si) in Formula 3. Corresponding ligands without methyl substitution on the unsaturated carbide ring also apply here. In any of the above, R 3 It can be a bulky alkyl group, preferably a optionally substituted cyclohexyl, optionally substituted norbornel, optionally substituted adamantyl, or optionally substituted tert-butyl, or optionally substituted aryl, such as optionally substituted phenyl. In any of the above, R 3 It may preferably be an optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted anthraquinone.

[0131] When R 4 and R 5 When not connected to form a multi-ring structure, R is preferred. 4 and R 5 Both can be hydrogen, or R 4 It can be OR"' and R 5 It can be R"', where each R"' is chosen independently. In a specific instance, R 4 It can be OR"', preferably OCH3, and R 5 It could be hydrogen.

[0132] In some embodiments of this disclosure, X 1 and X 2 Each of the C1-Cs can be substituted independently. 40 Hydrocarbon groups (e.g., optionally substituted C2-C) 20 Hydrocarbon group), optionally substituted C4-C 62 Aryl, optionally substituted C4-C 62 Heteroaryl, hydrogen, amino, hydroxyl, thio, phosphorus, halogen, diene, amine, phosphine, ether, or combinations thereof. For example, X 1 and X 2 Each of these can be independently a halogenated group or a C1-C6 hydrocarbon group or a C1-C6 hydrocarbon group. 10Hydrocarbon group, such as methyl. In some embodiments, X 1 and X 2 Each of these components is independently chlorine, bromine, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl. In some embodiments of this disclosure, X 1 and X 2 It can form a fused ring or part of a ring system, which can define a metal cyclization, chelate ligand, or diene ligand bonded to M.

[0133] In some implementations, T is derived from formula (R) 2G) g This indicates that each G is C, Si, or Ge, g is 1 or 2, and each R... Independently hydrogen, optionally substituted C1-C 20 Hydrocarbon group (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or phenyl), or two or more R groups. The bridging groups are linked to form substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structures. In some embodiments, the bridging groups can be represented by the following formulas: R'2C, R'2Si, R'2Ge, R'2CCR'2, R'2CCR'2CR'2, R'2CCR'2CR'2CR'2, R'C=CR', R'C=CR'CR'2, R'2CCR'=CR'CR'2, R'C=CR'CR'=CR', R'C=CR'CR'2CR'2, R'2CSiR'2, R' 2SiSiR'2, R2CSiR'2CR'2, R'2SiCR'2SiR'2, R'C=CR'SiR'2, R'2CGeR'2, R'2GeGeR'2, R'2CGeR '2CR'2, R'2GeCR'2GeR'2, R'2SiGeR'2, R'C=CR'GeR'2, R'B, R'2C–BR', R'2C–BR'–CR'2, R'2C–O –CR’2, R’2CR’2C–O–CR’2CR’2, R’2C–O–CR’2CR’2, R’2C–O–CR’=CR’, R’2C–S–CR’2, R’2CR’2C– S–CR'2CR'2, R'2C–S–CR'2CR'2, R'2C–S–CR'=CR', R'2C–Se–CR'2, R'2CR'2C–Se–CR'2CR'2, R'2 C–Se–CR2CR'2, R'2C–Se–CR'=CR', R'2C–N=CR', R'2C–NR'–CR'2, R'2C–NR'–CR'2CR'2, R'2C–NR'–CR'=CR', R'2CR'2C–NR'–CR'2CR'2, R'2C–P=CR' or R'2C–PR'–CR'2, wherein each R' is independently hydrogen or optionally substituted C1-C 20 Hydrocarbon groups (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, or phenyl), C1-C 20 Halogenated carbon-based, C1-C 20 Silyl carbon-based or C1-C 20 A germanyl carbonyl substituent, or two or more adjacent R's, are linked to form a substituted or unsubstituted, saturated, partially unsaturated, or aromatic cyclic or polycyclic ring structure. In some embodiments of this disclosure, T can be CH2, CH2CH2, C(CH3)2, (Ph)2C, (p-(Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, or Si(CH2)4. Preferably, T is CH2 or SiMe2, more preferably SiMe2 or SiPh2.

[0134] In any of the choices herein, suitable alkyl groups may optionally be substituted and are independently selected from, but not limited to, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, octadecyl, nonadecanyl, triadecyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecanyl, octadecenyl, and nonadecanenyl. Eicosyl, 21-carbon-alkenyl, 22-carbon-alkenyl, 23-carbon-alkenyl, 24-carbon-alkenyl, 25-carbon-alkenyl, 26-carbon-alkenyl, 27-carbon-alkenyl, 28-carbon-alkenyl, 29-carbon-alkenyl, 30-carbon-alkenyl, propynyl, butynyl, pentynyl, hexynyl, heptyynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, tridecynyl, tetradecynyl, pentadecynyl, hexadecynyl, heptadecynyl, octadecynyl, nonadecynyl, 20-carbon-alkenyl, 21-carbon-alkenyl, 22-carbon-alkenyl, 23-carbon-alkenyl, 24-carbon-alkenyl, 25-carbon-alkenyl, 26-carbon-alkenyl, 27-carbon-alkenyl, 28-carbon-alkenyl, 29-carbon-alkenyl, 30-carbon-alkenyl, butadienyl, pentadienyl, hexadienyl, heptaadienyl, octaadienyl, nonadienyl, and decanadienyl.

[0135] In any of the choices herein, a suitable aryl group may optionally be substituted and independently selected from, but not limited to, phenyl, 1-naphthyl, 2-naphthyl, 9-anthrayl, 2-biphenyl, 3-biphenyl, 4-biphenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,5-trimethylphenyl, 3,4,5-trimethylphenyl, 2,3,4,5,6-pentamethylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-diethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 2,6- Diethylphenyl, 3,4-diethylphenyl, 3,5-diethylphenyl, 2-isopropylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 3,5-diisopropylphenyl, 2,5-diisopropylphenyl, 2-tert-butylphenyl, 3-tert-butylphenyl, 4-tert-butylphenyl, 3,5-di-tert-butylphenyl, 3,5-di-tert-butyl-4-methoxyphenyl, 3,5-di-tert-butyl-4-dimethylaminophenyl, 2,5-di-tert-butylphenyl, 2-trimethylsilylphenyl, 3-trimethylsilylphenyl, 4-trimethylsilylphenyl, 3,5-bis(trimethylsilyl)phenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl and 3,5-bis(trifluoromethyl)phenyl.

[0136] In any of the choices herein, suitable cycloalkyl groups may be optionally substituted and are independently selected from, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, cycloheptyl, norbornel, adamantyl, etc.

[0137] In a more specific example, the metallocene suitable for forming the impact copolymers disclosed herein can have a structure represented by Formula 3 and in R 3 Large-volume alkyl substitutions can include variables as defined below:

[0138] M is a Group 4 metal; preferably, zirconium or hafnium;

[0139] T is a bridging base; preferably, CR 11 R 12 or SiR 11 R 12 , where R 11 and R 12 Independently hydrogen, optionally substituted C1-C 40 Hydrocarbon group or optional substituted C6-C 62 Aryl, or R 11 and R 12 Linked to form substituted or unsubstituted C4-C 62A saturated or unsaturated cyclic or polycyclic ring structure; more preferably, T is CH2, CH2CH2, C(CH3)2, (Ph)2C, (p-(Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4 or Si(CH2)4; even more preferably, T is CH2 or SiMe2, or more preferably, T is SiMe2 or SiPh2;

[0140] X 1 and X 2 Each is a monovalent anionic ligand, or X 1 and X 2 Linkage to form metal cyclic rings, chelate ligands, diene ligands, or alkylidenes, preferably X 1 and X 2 It is independently a halogen (F, Cl, Br, I) or a C1-C6 hydrocarbon group, such as a C1-C6 alkyl or phenyl group, more preferably methyl;

[0141] R 1 It is hydrogen, halogen, or optionally substituted C1-C 40 Hydrocarbon group, optional substituted C4-C 62 Aryl, optionally substituted C4-C 62 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R"-SiR'3, where R" is C1-C 10 Alkylene and R' are hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl; preferably, R 1 It is C1-C 10 Alkyl; more preferably, R 1 It is methyl;

[0142] R 2 and R 6 Independently hydrogen, halogen, or optionally substituted C1-C 40 Hydrocarbon group, optional substituted C4-C 62 Aryl, optionally substituted C4-C 62 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R"-SiR'3, where R" is C1-C 10 Alkylene and R' are hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl; preferred R 2 It is hydrogen; R is preferred. 2 and R 6 Each is hydrogen, or R 2 It is hydrogen and R 6It is a hydrogen or optionally substituted phenyl group;

[0143] R 3 It is a bulky alkyl group; preferably, R 3 It is optionally substituted cyclohexyl, optionally substituted norbornel, optionally substituted adamantyl (e.g., 1-adamantyl, 2-adamantyl, (1s,4s)-bicyclo[2.2.1]hept-7-yl, (1R,4S)-bicyclo[2.2.1]hept-2-yl, (1s,4s)-bicyclo[2.2.1]hept-1-yl) or optionally substituted tert-butyl;

[0144] R 4 and R 5 Independently, it is H, R''', or OR''', where R''' is an optionally substituted C1-C 40 Alkyl, or R 4 and R 5 Connect to form C3-C 62 Substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structures, or combinations thereof; and

[0145] R 7 R 8 R 9 and R 10 Independently hydrogen, halogen, or optionally substituted C1-C 40 Hydrocarbon group, optional substituted C4-C 62 Aryl, optionally substituted C4-C 62 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R"-SiR'3, where R" is C1-C 10 Alkylene and R' are hydrogen, C1-C 10 Alkyl or C6-C 10 aryl, or R 5 and R 6 R 6 and R 7 、or R 7 and R 8 One or more pairs of C4-C are linked to form substituted or unsubstituted C4-C 62 A saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof; preferably, R 5 R 6 R 7 and R 8 Each is C1-C 10 Alkyl; more preferably, R 5 R 6 R 7 and R 8 Each is a methyl group.

[0146] If R 4 and R 5 If the ring structure is not connected to form a ring or multiple rings, then R is preferred. 4 and R 5 Both can be hydrogen, or R 4 It can be OR"' and R 5 It can be R"', where each R"' is chosen independently. In a specific instance, R 4 It can be OR"', preferably OCH3, and R 5 It could be hydrogen, or R 4 It can be OR"', preferably OCH3, and R 5 It can be an alkyl group, preferably tert-butyl.

[0147] Therefore, in some implementations, it has C1 symmetry and in R 3 Suitable metallocenes of bulky alkyl groups can have structures represented by the following formula 7:

[0148]

[0149] Formula 7

[0150] in:

[0151] M is a Group 4 metal, preferably Zr or Hf, more preferably Hf;

[0152] X 1 and X 2 Independently a halogroup (F, Cl, Br, I) or a C1-C6 alkyl group; preferably X 1 and X 2 Each is either a chloride group or a methyl group;

[0153] R 1 It is C1-C 10 Alkyl groups, preferably methyl groups;

[0154] R 3 It is a bulky alkyl group, preferably a substituted cyclohexyl, a substituted norbornel alkyl, a substituted adamantyl alkyl, or a substituted tert-butyl alkyl; preferred groups include 1-adamantyl, 2-adamantyl, (1s,4s)-bicyclo[2.2.1]hept-7-oxide, (1R,4S)-bicyclo[2.2.1]hept-2-oxide, or (1s,4s)-bicyclo[2.2.1]hept-1-oxide;

[0155] R 4 and R 5 Independently, it is H, R''', or OR''', where R''' is an optionally substituted C1-C 40 Alkyl, or R 4and R 5 Connect to form C3-C 62 A cyclic structure, whether substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic, or a combination thereof;

[0156] R 6 It is hydrogen, halogen, or optionally substituted C1-C 40 Alkyl, optionally substituted C6-C 14 Aryl, optionally substituted C3-C 13 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R"-SiR'3, where R" is C1-C 10 Alkylene, and each R' is hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl; preferred R 6 It is a hydrogen or optionally substituted phenyl;

[0157] R 7 R 8 R 9 and R 10 Independently hydrogen, halogen, or optionally substituted C1-C 40 Hydrocarbon group, optional substituted C4-C 62 Aryl, optionally substituted C4-C 62 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R"-SiR'3, where R" is C1-C 10 Alkylene and R' are hydrogen, C1-C 10 Alkyl or C6-C 10 aryl, or R 5 and R 6 R 6 and R 7 、or R 7 and R 8 One or more pairs of C4-C are linked to form substituted or unsubstituted C4-C 62 A saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof; preferably, R 5 R 6 R 7 and R 8 Each is C1-C 10 Alkyl; more preferably, R 5 R 6 R 7 and R 8 Each is a methyl group; and

[0158] R 11 and R 12 C1-C independently of optional substitution10 Alkyl or optionally substituted C6-C 10 aryl, or R 11 and R 12 Connect to form substituted or unsubstituted C2-C 22 Saturated or unsaturated cyclic or polycyclic ring structures; preferably, R 11 and R 12 Each is either methyl or phenyl, and more preferably, R 11 and R 12 Each is a methyl group.

[0159] In some embodiments, R 4 and R 5 It can form a 5-membered carbon ring. In R 3 R has a large volume alkyl group and is fused into a 5-membered carbon ring. 4 and R 5 A specific example of this metallocene can have a structure represented by Equation 8A, preferably wherein R 6 It is a hydrogen or optionally substituted phenyl group, and more preferably R is present in the form of hydrogen. 6 It is hydrogen. The metallocene represented by Formula 8B lacks the 5-membered carbon ring fused to the indenyl group.

[0160]

[0161] In Equation 8A:

[0162] Q is an optional C1-C6 alkyl group, and q is 0, 1, 2, 3, 4, 5, or 6. When present (q≠0), the optional substitution Q can exist in the form of R. 4 and R 5 At any non-aromatic carbon atom of the defined 5-membered ring. Preferably, Q is a methyl group each time it appears.

[0163] Illustrative examples of metallocenes having structures represented by Equations 7, 8A, and 8B may include, but are not limited to:

[0164]

[0165] .

[0166] In other specific examples, the metallocene suitable for forming the impact copolymers disclosed herein can have a structure represented by Formula 3, and in R 3 The part has an optionally substituted aryl group, preferably an optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted anthraquinone, which may include variables as defined below.

[0167] M is a Group 4 metal; preferably, zirconium or hafnium;

[0168] T is a bridging base; preferably, CR 11 R 12 or SiR 11 R 12 , where R 11 and R 12 Independently hydrogen, optionally substituted C1-C 40 Hydrocarbon group or optional substituted C6-C 62 Aryl, or R 11 and R 12 Linked to form substituted or unsubstituted C4-C 62 A saturated or unsaturated cyclic or polycyclic ring structure; more preferably, T is CH2, CH2CH2, C(CH3)2, (Ph)2C, (p-(Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4 or Si(CH2)4; even more preferably, T is CH2 or SiMe2, and even more preferably, T is SiMe2 or SiPh2;

[0169] X 1 and X 2 Each is a monovalent anionic ligand, or X 1 and X 2 Linkage to form metal cyclic rings, chelate ligands, diene ligands, or alkylidenes, preferably X 1 and X 2 It is independently a halogen (F, Cl, Br, I) or a C1-C6 hydrocarbon group, such as a C1-C6 alkyl or phenyl group, more preferably methyl;

[0170] R 1 It is hydrogen, halogen, or optionally substituted C1-C 40 Hydrocarbon group, optional substituted C4-C 62 Aryl, optionally substituted C4-C 62 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R"-SiR'3, where R" is C1-C 10 Alkylene and R' are hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl; preferably, R 1 It is C1-C 10 Alkyl; more preferably, R 1 It is methyl;

[0171] R 2 and R 6 Independently hydrogen, halogen, or optionally substituted C1-C 40 Hydrocarbon group, optional substituted C4-C 62 Aryl, optionally substituted C4-C62 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R"-SiR'3, where R" is C1-C 10 Alkylene and R' are hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl; preferred R 2 It is hydrogen; R is preferred. 2 and R 6 Each is hydrogen, or R 2 It is hydrogen and R 6 It is a hydrogen or optionally substituted phenyl group;

[0172] R 3 It is an optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted anthraquinone;

[0173] R 4 and R 5 Independently, it is H, R''', or OR''', where R''' is an optionally substituted C1-C 40 Alkyl, or R 4 and R 5 Connect to form C3-C 62 Substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic ring structures, or combinations thereof; and

[0174] R 7 R 8 R 9 and R 10 Independently hydrogen, halogen, or optionally substituted C1-C 40 Hydrocarbon group, optional substituted C4-C 62 Aryl, optionally substituted C4-C 62 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R"-SiR'3, where R" is C1-C 10 Alkylene and R' are hydrogen, C1-C 10 Alkyl or C6-C 10 aryl, or R 5 and R 6 R 6 and R 7 、or R 7 and R 8 One or more pairs of C4-C are linked to form substituted or unsubstituted C4-C 62 A saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof; preferably, R 5 R 6 R 7 and R 8 Each is C1-C10 Alkyl; more preferably, R 5 R 6 R 7 and R 8 Each is a methyl group.

[0175] Therefore, in some implementations, it has C1 symmetry and in R 3 Suitable metallocenes of arbitrarily substituted phenyl groups can have structures represented by Formula 9:

[0176]

[0177] Formula 9

[0178] in:

[0179] R 13 -R 17 Independently hydrogen, optionally substituted C1-C 40 Hydrocarbon group, optional substituted C4-C 62 Aryl, optionally substituted C4-C 62 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R"-SiR'3, where R" is C1-C 10 Alkyl groups, and each R' is hydrogen, halogen, C1-C 10 Alkyl or C6-C 10 aryl, or R 13 and R 14 R 14 and R 15 R 15 and R 16 、or R 16 and R 17 Or any combination thereof, connected to form a cyclic or polycyclic structure that is substituted or unsubstituted, saturated, partially unsaturated or aromatic;

[0180] M is a Group 4 metal, preferably Zr or Hf;

[0181] X 1 and X 2 Independently a halogroup (F, Cl, Br, I) or a C1-C6 alkyl group; preferably X 1 and X 2 Each is either chloro or methyl;

[0182] R 1 It is C1-C 10 Alkyl groups, preferably methyl groups;

[0183] R 4 and R 5Independently, it is H, R''', or OR''', where R''' is an optionally substituted C1-C 40 Alkyl, or R 4 and R 5 Connect to form C3-C 62 A cyclic structure, whether substituted or unsubstituted, saturated or unsaturated, cyclic or polycyclic, or a combination thereof;

[0184] R 6 It is hydrogen, halogen, or optionally substituted C1-C 40 Alkyl, optionally substituted C6-C 14 Aryl, optionally substituted C3-C 13 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R"-SiR'3, where R" is C1-C 10 Alkylene, and each R' is hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl; preferred R 6 It is a hydrogen or optionally substituted phenyl;

[0185] R 7 R 8 R 9 and R 10 Independently hydrogen, halogen, or optionally substituted C1-C 40 Hydrocarbon group, optional substituted C4-C 62 Aryl, optionally substituted C4-C 62 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R"-SiR'3, where R" is C1-C 10 Alkylene and R' are hydrogen, C1-C 10 Alkyl or C6-C 10 aryl, or R 5 and R 6 R 6 and R 7 、or R 7 and R 8 One or more pairs of C4-C are linked to form substituted or unsubstituted C4-C 62 A saturated or unsaturated cyclic or polycyclic ring structure, or a combination thereof; preferably, R 5 R 6 R 7 and R 8 Each is C1-C 10 Alkyl; more preferably, R 5 R 6 R 7 and R 8 Each is a methyl group; and

[0186] R 11 and R 12 C1-C independently of optional substitution 10 Alkyl or optionally substituted C6-C 10 aryl, or R 11 and R 12 Connect to form substituted or unsubstituted C2-C 22 Saturated or unsaturated cyclic or polycyclic ring structures; preferably, R 11 and R 12 Each is either methyl or phenyl, and more preferably, R 11 and R 12 Each is a methyl group.

[0187] In some embodiments, R 4 and R 5 It can form a 5-membered carbon ring. In R 3 The R group has an optionally substituted phenyl group and is fused into a 5-membered carbon ring. 4 and R 5 A specific example of this metallocene can have a structure represented by formula 10A, preferably wherein R 6 It is a hydrogen or optionally substituted phenyl group, and more preferably R is present in the form of hydrogen. 6 It is hydrogen. The metallocene represented by formula 10B lacks the 5-membered carbon ring fused to the indenyl group.

[0188]

[0189] In Equation 10A:

[0190] Q is an optional C1-C6 alkyl group, and q is 0, 1, 2, 3, 4, 5, or 6. When present (q≠0), the optional substitution Q can exist in the form of R. 4 and R 5 At any non-aromatic carbon atom of the defined 5-membered ring. Preferably, Q is a methyl group each time it appears.

[0191] Illustrative examples of metallocenes having a structure represented by Equation 9, 10A, or 10B may include, but are not limited to:

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199] Hf can replace Zr in any of the aforementioned metallocenes.

[0200] For naming purposes, the following numbering scheme is used for the indenyl ring. It should be noted that the indenyl ring can be considered as a cyclopentadienyl group fused with a benzene ring. Draw the following structure and name it the anion.

[0201]

[0202] Indene

[0203] For clarity, the following ring structures are substituted indenyl groups, where substitution at the 5- and 6-positions collectively defines the ring structure. These ligands are described below for specific compound nomenclature purposes. Similar numbering and naming schemes are used for these types of substituted indenyl groups, including indaradinyl, cyclopentadieno[b]naphthyl, heterocyclopentadienonaphthyl, heterocyclopentadienoindenyl, etc., as shown below. Each structure is drawn and named an anion.

[0204]

[0205] 1,2,3-Trihydro-S-indaryl-5,6,7,8-Tetrahydro-cyclopentadienyl[b]naphthyl

[0206]

[0207] Cyclopentadieno[b]naphthyl 5,8-dihydro-cyclopentadieno[b]naphthyl

[0208]

[0209] 7,8-Dihydro-cyclopentadien[b]naphthyl

[0210] Any of the aforementioned metallocenes can be introduced into a catalyst system containing the dianionic complex described herein and comprising a support material, optional activator, optional co-activator, and optional scavenger. Preferably, the activator is present and arranged on the support material in combination with the metallocene and the dianionic complex. The activator and optional co-activator can convert the metallocene into a form that effectively promotes olefin polymerization under suitable polymerization conditions to form impact copolymers, as described in further detail below.

[0211] carrier material

[0212] When performing a polymerization reaction to form the impact copolymer according to this disclosure, a bianionic complex, such as a bis(phenolate) complex, and optionally a metallocene, can be arranged on a carrier material. When used, at least one activator can also be combined with the bianionic complex and the metallocene, optionally further combined with a co-activator and / or a scavenger, and arranged on the carrier material. A suitable activator can be arranged on the carrier material by contacting the carrier material with a solution containing the activator, or the activator can be formed in situ on the carrier material. Furthermore, the activator can be covalently bonded to the carrier material and / or otherwise chemically modified. Additional details regarding the activator are provided below.

[0213] The support material can be a finely fragmented inorganic oxide, such as silica, alumina, talc, zeolite, clay, organoclay, etc., each having a highly porous structure. According to this disclosure, suitable inorganic oxides, including group 2, 4, 13, or 14 metal oxides such as silica, alumina, and mixtures thereof, can be disposed thereon. Other inorganic oxides, such as magnesium oxide, titanium oxide, zirconium oxide, etc., can be used alone or in combination with silica or alumina. Particularly useful support materials may include magnesium oxide, titanium oxide, zirconium oxide, montmorillonite, layered silicates, zeolite, talc, silica, clay, silica clay, silica clay, etc. Combinations of these support materials can be used, such as silica-chromium, silica-alumina, silica-titanium oxide, etc. In at least one embodiment, the support material may be selected from Al2O3, ZrO2, SiO2, SiO2 / Al2O3, silica clay, silica / clay, or mixtures thereof. Other suitable carrier materials may also be used, such as finely chopped functionalized polyolefins, such as finely chopped polyethylene, polypropylene, and polystyrene, which have water-absorbing functional groups (e.g., oxygen- or nitrogen-containing groups, such as -OH, -RC=O, -OR, and -NR2). Other organic or inorganic carrier materials may also be used appropriately.

[0214] The carrier material can be optionally treated with electron-withdrawing anions. Compared to untreated carrier material, electron-withdrawing anions can increase the Lewis or Brønsted acidity of the carrier material. Electron-withdrawing anions can be derived from salts, acids, or other compounds, such as volatile organic compounds, which act as sources or precursors of electron-withdrawing anions. Electron-withdrawing anions can include sulfate, bisulfate, fluoride, chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate, trifluoroacetate, trifluoromethanesulfonate (trifluoromethanesulfonate), fluorozirconate, fluorotitanate, phosphotungstic acid, or any combination thereof. A specific acidity of the carrier material can be tailored to a desired level using combinations of one or more different electron-withdrawing anions in varying proportions. Such combinations of electron-withdrawing anions can be contacted with the carrier material simultaneously or individually and in any order to provide the desired specific acidity.

[0215] The support material can optionally be fluorinated by introducing fluorine-containing anions. For example, the fluorinated support can be a silica support, wherein a portion of the silica hydroxyl groups has been replaced by fluorine or a fluorine-containing compound. Suitable fluorine-containing compounds include, but are not limited to, inorganic and / or organic fluorine-containing compounds, any of which can be used to provide fluorine to the support material. Illustrative inorganic fluorine-containing compounds that can be used to fluorinate the support material include, for example, NH4BF4, (NH4)2SiF6, NH4PF6, NH4F, (NH4)2TaF7, NH4NbF4, (NH4)2GeF6, (NH4)2SmF6, (NH4)2TiF6, (NH4)2ZrF6, MoF6, ReF6, GaF3, SO2ClF, F2, SiF4, SF6, ClF3, ClF5, BrF5, IF7, NF3, HF, BF3, NHF2, NH4HF2, and combinations thereof.

[0216] Non-limiting examples of cations suitable for combination with electron-withdrawing anions in this disclosure include ammonium, trialkylammonium, tetraalkylammonium, and tetraalkylammonium. H + [H(OEt2)2] + [HNR3] + (R is C1-C) 20 Hydrocarbon groups (which may be the same or different and optionally substituted) or combinations thereof.

[0217] Methods for contacting the carrier material with electron-withdrawing anions may include, but are not limited to, gelation, co-gelation, impregnation of one compound onto another compound, or combinations thereof. Following a specific contact method, the treated carrier material may then be calcined.

[0218] The carrier material, such as inorganic oxides, more preferably silicon dioxide, can have a thickness of about 10 μm. 2 / g to approximately 800m 2 / g, or approximately 10m 2 / g to approximately 500m 2 / g, or approximately 10m 2 / g to approximately 100m 2 / g, or approximately 10m 2 / g to approximately 50m 2 / g, or approximately 50m 2 / g to approximately 800m 2 / g, or approximately 50m 2 / g to approximately 500m 2 / g, or approximately 50m 2 / g to approximately 100m 2 / g, or approximately 100mg 2 / g to approximately 800m 2 / g, or approximately 100mg 2 / g to approximately 500m 2 / g or approximately 500m 2 / g to approximately 800m 2 / g of surface area.

[0219] The support material, such as an inorganic oxide, 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 Å to about 1000 Å, or about 10 Å to about 500 Å, or about 10 Å to about 100 Å, or about 100 Å to about 1000 Å, or about 100 Å to about 500 Å, or about 500 Å to about 1000 Å.

[0220] The carrier material, such as an inorganic oxide, more preferably silicon dioxide, may have an average particle size of about 5 μm to about 500 μm, or about 5 μm to about 100 μm, or about 5 μm to about 50 μm, or about 50 μm to about 500 μm, or about 50 μm to about 100 μm or about 100 μm to about 500 μm.

[0221] Before using the support material in the polymerization reaction or before depositing the bianionic complex thereon, the support material may be free of or substantially free of absorbed water. Drying of the support material can be achieved 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 can be heated to at least about 200°C, preferably about 200°C to about 850°C, more preferably about 400°C; and sustained for about 1 minute to about 100 hours, or about 12 hours to about 72 hours, or about 24 hours to about 60 hours. After calcination, the support material can be contacted with the bianionic complex and optionally an activator to produce a catalyst system.

[0222] To achieve the above objectives, the support material can be slurried in a nonpolar solvent and contacted with a solution of a dianionic complex, optionally a metallocene, and optionally an activator. In some embodiments, the slurry of the support material can be contacted with the activator 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 the dianionic complex is arranged thereon. Alternatively, the slurry of the support material can be contacted with the dianionic complex 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 contact with the activator. Once the metallocene and the activator have been contacted with each other, the catalyst system can optionally be aged at 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 for the polymerization reaction.

[0223] Suitable nonpolar solvents for loading dianionic complexes, optional metallocenes, and optional activators onto a support material may include those in which the dianionic complexes, optional metallocenes, and optional activators are at least partially soluble and are liquid at the reaction temperature. While preferred nonpolar solvents are alkanes, such as isopentane, hexane, n-heptane, octane, nonane, and decane, various other substances including cycloalkanes, such as cyclohexane, may also be used. Aromatic hydrocarbons, such as benzene, toluene, and ethylbenzene, may also be used.

[0224] Activator

[0225] In most cases, at least one activator is present on the support material in combination with a dianionic complex and optionally a metallocene. Suitable activators may include, for example, aluminoxanes (e.g., methylaluminoxane-MAO), noncoordinate anions, or any combination thereof.

[0226] Aluminoxanes are typically oligomers containing an -Al(R)-O- subunit, where R is an alkyl group. Examples of aluminoxanes include methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethylaluminoxane, and isobutylaluminoxane. Alkylaluminoxanes and modified alkylaluminoxanes are suitable as catalyst activators, especially when the abstractable ligand is alkyl, halogen, alkyloxy, or amide. Mixtures of different aluminoxanes and modified aluminoxanes can also be used. Visually transparent methylaluminoxanes are preferred. Turbid or gelled aluminoxanes can be filtered to prepare a clear solution or a clear aluminoxane can be decanted from the turbid solution. A useful aluminoxane is type 3A modified methylaluminoxane (MMAO) cocatalyst (commercially available from Akzo Chemicals, Inc. under the trade name type 3A modified methylaluminoxane, described in U.S. Patent No. 5,041,584). Another useful aluminum oxane is the solid polymethyl aluminum oxane described in U.S. Patents 9,340,630; 8,404,880 and 8,975,209.

[0227] When the activator is an aluminoxane (modified or unmodified), some embodiments can select a maximum activating dose, typically up to 5000 times molar excess (Al / M) of the catalyst compound (per metal catalytic site). The minimum activator-to-metal ratio is 1:1 molar ratio. Suitable ranges can include 1:1 to 500:1, or 1:1 to 200:1, or 1:1 to 100:1, or 1:1 to 50:1.

[0228] Other suitable activators include compounds containing noncoordinate anions, especially boranes and borate compounds. Particularly useful boranes and borate compounds containing noncoordinate anions or similar entities include, for example, B(C6F5)3 and [PhNMe2H]. + [B(C6F5)4] - [Ph3C] + [B(C6F5)4] - and [PhNMe2H] + [B(C 10 F7)4] - .

[0229] The term "noncoordinate anion" (NCA) refers to an anion that is not coordinated to the cation or is only weakly coordinated to the cation, thus remaining sufficiently unstable to be replaced by a neutral Lewis base. The term NCA is defined as including activators containing multicomponent NCAs, such as N,N-dimethylphenylammonium tetra(pentafluorophenyl)boronic acid and N,N-dimethylphenylammonium tetra(heptafluoronaphthyl)boronic acid, which contain acidic cation groups and noncoordinate anions. The term NCA is also defined as including neutral Lewis acids, such as tris(pentafluorophenyl)boron, which can react with the catalyst to form an activating group through the extraction of the anionic group. Typically, the NCA is weakly coordinated enough that a neutral Lewis base, such as an alkene or alkyne unsaturated monomer, can displace it from the catalyst center. Any metal or metalloid that can form a compatible, weakly coordinated complex can be used or included in the noncoordinate 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 noncoordinate anion includes neutral activators, ionic activators, and Lewis acid activators.

[0230] "Compatible" noncoordinate anions are those that do not degrade to neutral when the initially formed complex decomposes. Furthermore, this anion does not transfer anionic substituents or fragments to the cation, causing it to form neutral transition metal compounds and neutral byproducts derived from the anion. Noncoordinate anions that can be used according to this disclosure are anions that are compatible, stabilize the transition metal cation at +1 in the sense of balancing its ionic charge, and still retain sufficient instability to allow displacement during polymerization. Useful ionizing activators here typically include NCAs, especially compatible NCAs.

[0231] The use of ionized, neutral, or ionic activators, such as tris(n-butyl)ammonium tetra(pentafluorophenyl)borate, trifluorophenylboron metalloid precursors or trifluoronaphthylboron metalloid precursors, polyhalogenated heteroborane anions (WO 98 / 43983), boric acid (US Patent No. 5,942,459), or any combination thereof, is within the scope of this disclosure. The use of neutral or ionic activators alone or in combination with aluminoxane or modified aluminoxane activators is also within the scope of this disclosure. Other useful activators may include those described in US Patents 8,658,556 and 6,211,105.

[0232] In a preferred embodiment, a boron-containing NCA activator represented by formula 11 can be used.

[0233] Z d + (A d- )

[0234] Formula 11

[0235] Where Z is (LH) or a reducible Lewis acid; L is a neutral Lewis base; H is hydrogen; (LH) is a Brønsted acid; A d- It is a boron-containing noncoordinate anion with charge d-; d can be 1, 2, or 3.

[0236] Cation component Z d + It may include Brønsted acids, such as protonated or protonated Lewis bases or reducible Lewis acids, which can be protonated or have structural moieties extracted from metal-ligand complexes to provide cationic metal-ligand complexes.

[0237] Cation component Z d + It could also be something like silver, (tropylium), carbon Diocene The structural components of the mixture thereof, preferably carbon And Erocene Suitable reducible Lewis acids include any triaryl carbon. (where the aryl group can be substituted or unsubstituted, for example, from formula (Ar3C) + Those represented by ) where Ar is an aryl group or surrounded by heteroatoms, C1 to C 40 Hydrocarbon group or substituted C1 to C 40 (Alkyl groups substituted with hydrocarbon groups). Preferably, the reducible Lewis acids of Formula 9 above, defined as "Z", include those represented by the following formula: (Ph3C), where Ph is a substituted or unsubstituted phenyl group, preferably substituted by C1 to C2. 40 Hydrocarbon substitution, or substitution of C1 to C2. 40 Hydrocarbon group, preferably C1 to C 20 Alkyl or aromatic or substituted C1 to C2 20 Alkyl or aromatic groups, and preferably Z d + It is triphenyl carbon .

[0238] When Z d + It is an activated cation (LH). d + In this case, it is preferably a Brønsted acid, which can donate protons to transition metal catalytic precursors, thereby generating transition metal cations, including ammonium and oxygen. , silane Mixtures thereof, preferably methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, trimethylamine, triethylamine, N,N-dimethylaniline, methyldiphenylamine, pyridine, p-bromo-N,N-dimethylaniline, ammonium p-nitro-N,N-dimethylaniline, and derived from triethylphosphine, triphenylphosphine, and diphenylphosphine. Derived from ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and diethyl ether. oxygen of alkane Sulfonium derived from sulfides such as diethyl sulfide, tetrahydrothiophene, and mixtures thereof.

[0239] Anionic component A d- Including those with the formula [M] k+ G] d- Those, where k is 1, 2, or 3; g is 1, 2, 3, 4, 5, or 6 (preferably 1, 2, 3, or 4); gk = d; M is an element selected from Group 13 of the periodic table, preferably boron or aluminum; G is independently a hydrogen group, a bridged or unbridged dialkylamido group, a halogen group, an alkyloxy group, an aryloxy group, a hydrocarbon group, a substituted hydrocarbon group, a halocarbon group, a substituted halocarbon group, and a haloalkyl group, wherein G has at most 20 carbon atoms, provided that G is a halogen group no more than once. Preferably, each G is a fluorinated hydrocarbon group containing 1 to 20 carbon atoms, more preferably, each G is a fluorinated aryl group, and most preferably, each G is a pentafluoroaryl group. Suitable A d- Examples also include diboron compounds such as those disclosed in U.S. Patent No. 5,447,895, which is incorporated herein by reference in its entirety.

[0240] Illustrative but non-limiting examples of boron compounds that can be used as activators are those compounds described as activators in U.S. Patent 8,658,556 (and in particular those specifically listed as activators), the boron compounds disclosed therein of which are incorporated herein by reference.

[0241] Most preferably, activator Z d + (A d- It is one or more of the following substances: N,N-dimethylphenylammonium tetra(perfluorophenyl)boronic acid, N,N-dimethylphenylammonium tetra(perfluoronaphthyl)boronic acid, N,N-dimethylphenylammonium tetra(perfluorobiphenyl)boronic acid, N,N-dimethylphenylammonium tetra(3,5-bis(trifluoromethyl)phenyl)boronic acid, and triphenylcarbon tetra(perfluoronaphthyl)boronic acid. Triphenylcarbon tetra(perfluorobiphenyl)borate Triphenylcarbon tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid Or triphenylcarbon tetra(perfluorophenyl)borate In any embodiment, the noncoordinating anion may be selected from: N,N-dimethylphenylamine tetra(perfluoronaphthyl)boronic acid, N,N-dimethylphenylamine tetra(perfluorobiphenyl)boronic acid, N,N-dimethylphenylamine tetra(perfluorophenyl)boronic acid, N,N-dimethylphenylamine tetra(3,5-bis(trifluoromethyl)phenyl)boronic acid, and triphenylcarbon tetra(perfluoronaphthyl)boronic acid. Triphenylcarbon tetra(perfluorobiphenyl)borate Triphenylcarbon tetrakis(3,5-bis(trifluoromethyl)phenyl)boronic acid Triphenylcarbon tetra(perfluorophenyl)borate 、[Me3NH + [B(C6F5)] 4- 1-(4-(tris(pentafluorophenyl)boronic acid)-2,3,5,6-tetrafluorophenyl)pyrrolidine ;[Me3NH + [B(C6F5)] 4- 1-(4-(tris(pentafluorophenyl)borate)-2,3,5,6-tetrafluorophenyl)pyrrolidine Salts, sodium tetra(pentafluorophenyl)borate, potassium tetra(pentafluorophenyl)borate, and 4-(tris(pentafluorophenyl)boronic acid)-2,3,5,6-tetrafluoropyridine Preferably, the noncoordinate anion can be N,N-dimethylphenylammonium tetra(perfluoronaphthyl)boronic acid.

[0242] Massive activators can also be used here as NCAs. As used herein, "massive activator" refers to anionic activators represented by formula 12 or 13 below.

[0243]

[0244] In equations 12 and 13, each R 1a Ar is independently a halogen group, preferably a fluoride group; Ar is a substituted or unsubstituted aryl group (preferably a substituted or unsubstituted phenyl group), preferably substituted at C1 to C2. 40 Hydrocarbon group, preferably C1 to C 20 Alkyl or aromatic group substitution; each R 2a Independently, it is a halogenated group, C6 to C6. 20 Substituted aromatic hydrocarbon groups or –O-Si-R a Silyloxy group, wherein R a It is C1 to C 20 Hydrocarbon or alkylsilyl (preferably R) 2a (It is a fluorinated or perfluorinated phenyl); each R 3a It is a halogenated group, C6 to C 20 Substituted aromatic hydrocarbon groups or –O-Si-R a Silyloxy group, wherein Ra It is C1 to C 20 Hydrocarbon or alkylsilyl (preferably, R) 3a It is a fluorinated or C6 perfluorinated aromatic hydrocarbon group; wherein R 2a and R 3a One or more saturated or unsaturated substituted or unsubstituted rings can be formed (preferably, R). 2a and R 3a (Forms a perfluorinated phenyl ring); and L is a neutral Lewis base; (LH) + It is a Brønsted acid; d is 1, 2 or 3; wherein the anion has a molecular weight greater than 1020 g / mol; wherein at least three of the substituents on the B atom each have a molecular volume greater than 250 cubic Å, greater than 300 cubic Å or greater than 500 cubic Å, as described below.

[0245] Preferably, (Ar3C) d + It is (Ph3C) d + Ph is a substituted or unsubstituted phenyl group, preferably substituted with C1 to C2. 40 Hydrocarbon group or substituted C1 to C 40 Hydrocarbon group, preferably C1 to C2 20 Alkyl or aromatic or substituted C1 to C2 20 Alkyl or aromatic groups.

[0246] In some or other instances, activation can be carried out using organoaluminum compounds having a halogenated aryl group (such as pentafluorophenyl), and the cationic group (neutral form) can be introduced together with the support material at a molar ratio of about 0.01:1 to about 1:1, based on the molar concentration of the organoaluminum compound having the halogenated aryl group or the cationic group (neutral form) relative to the molar concentration of hydroxyl groups on the support material, respectively. Within this range, molar ratios less than or equal to about 1:1, for example less than or equal to about 0.5:1, or less than or equal to about 0.25:1, can be used. The amount of hydroxyl groups on the support material can be determined, for example, by attenuated total reflectance infrared spectroscopy (ATRIR), X-ray photoelectron spectroscopy (XPS), NMR, or secondary ion mass spectrometry (SIMS).

[0247] Organoaluminum compounds having halogenated aryl groups can be substantially dispersed over the total surface area of ​​a carrier material, wherein the coverage on the carrier material can be at least about 75% or at least about 90% of the total surface area of ​​the carrier material.

[0248] After introducing organoaluminum compounds into the support material, residual hydroxyl groups may remain on the support material, which can be detrimental to the overall catalyst activity. To prevent catalyst deactivation, compounds with the formula Al(R) can be used. 1 (R)2 (R) 3 The remaining hydroxyl groups are treated with a second aluminum compound, wherein R 1 For C1-C 40 Alkyl, substituted or unsubstituted C6-C 40 aryl or hydrogen, and R 2 and R 3 Independently for C1-C 40 Alkyl, alkyloxy, heteroalkyl, or substituted or unsubstituted C6-C 40 Aryloxy or heteroaryl.

[0249] The second aluminum compound may contain simple components, such as alkylaluminum and phenolic derivatives, such as BHT. The proton deactivation reaction between the alkylaluminum or aluminum hydride and the surface hydroxyl groups deactivates the hydroxyl groups via the release of hydrocarbons or hydrogen, resulting in the second aluminum compound anchoring to the support material. This effectively reduces or eliminates the possibility of active protons interfering with catalyst activity.

[0250] The second aluminum compound can be introduced into the activator-bound support at a molar ratio of about 0.1:1 to about 10:1, said molar ratio being based on the molar concentration of the antioxidant (BHT) relative to the molar concentration of hydroxyl groups on the support material before treatment with the organoaluminum compound containing a haloaryl group. Within this range, molar ratios less than or equal to about 5:1, for example less than or equal to about 2:1, and most preferably less than or equal to about 1:1 can be used. In some embodiments, within these ranges, the molar ratio of the second aluminum compound relative to the 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.

[0251] In more specific instances, the noncoordinate anionic activator can be formed in situ on the support material as a reaction product of an organoaluminum compound containing electron-withdrawing substituents, preferably three electron-withdrawing substituents, preferably one or more haloaryl groups (e.g., pentafluorophenyl) and a tertiary amine (e.g., N,N-diethylaniline or similar amines). The reaction product can further complex with surface hydroxyl groups or a portion thereof on the support material. Tris(pentafluorophenyl)aluminum can be a suitable organoaluminum compound for achieving the foregoing. Tris(pentafluorophenyl)aluminum or similar organoaluminum compounds can complex surface hydroxyl groups via aluminum atoms to form oxygen anions, wherein the negative charge is balanced by the resulting protonated tertiary aryl amine. The remaining surface hydroxyl groups can be blocked using a second organoaluminum compound without electron-withdrawing substituents, such as (BHT)2AlEt or a similar second organoaluminum compound as described above, wherein the remaining surface hydroxyl groups are blocked with a (BHT)2Al complex.

[0252] "Molecular volume" is used in this paper as an approximation of the three-dimensional volume of an activator molecule in solution. The comparison of substituents with different molecular volumes allows for the consideration that a substituent with a smaller molecular volume is "not too large" compared to a substituent with a larger molecular volume. Conversely, a substituent with a larger molecular volume can be considered "larger" than a substituent with a smaller molecular volume. Molecular volume can 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 cubic Å) is calculated using the following formula: MV = 8.3V s V s It's scaling the volume. V s It is the sum of the relative volumes of the constituent atoms, and is calculated from the molecular formulas of the substituents specified below. For fused rings, V s Reduced by 7.5% / fused ring. The calculated total MV of the anion is the sum of the MVs of each substituent; for example, the MV of a perfluorophenyl is 183 Å. 3 The calculated total MV of tetra(perfluorophenyl)borate is four times 183 Å. 3 Or 732Å 3 .

[0253]

[0254] For a list of particularly useful bulk activators, see U.S. Patent 8,658,556, the disclosure of which is incorporated herein by reference.

[0255] In any embodiment, the NCA activator can be an activator as described in U.S. Patent No. 6,211,105. The NCA activator to catalyst ratio can be from about 1:1 molar ratio to about 1000:1 molar ratio, including 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. Particularly useful ranges are from about 0.5:1 to about 10:1, preferably from about 1:1 to about 5:1.

[0256] Within the scope of this disclosure, the bianionic complex can be activated by a combination of aluminoxane and NCA (see, for example, U.S. Patents 5,153,157 and 5,453,410; EP 0 573 120 B1; and International Patent Application Publications WO 94 / 07928 and WO 95 / 14044, which discuss the use of combinations of aluminoxane with ionizing activators). Therefore, in some embodiments, NCA can be a co-activator of the aluminoxane, or vice versa.

[0257] In addition to activators, scavengers or co-activators can also be used. Alkyl aluminum or organoaluminum compounds that can be used as scavengers or co-activators include, for example, trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, ethylaluminum dichloride, diethylaluminum chloride, and diethylzinc.

[0258] Chain transfer agents can also be used in the compositions and / or methods described herein. Useful chain transfer agents are typically alkylaluminoxanes, i.e., compounds represented by the formula AlR3,ZnR2 (where each R is independently a C1-C8 aliphatic group, preferably methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or isomers thereof) or combinations thereof, such as diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum or combinations thereof.

[0259] In any embodiment, the aluminoxane, such as MAO, can be mixed in an inert solvent such as toluene and then slurried with a support material such as silica. Aluminoxane deposition on the support material can occur at temperatures of about 60°C to 120°C, or about 80°C to 120°C, or about 100°C to 120°C. Depositions occurring below 60°C (including room temperature deposition) may also be effective. NCA can be deposited on the support material in a similar manner.

[0260] catalyst system

[0261] This disclosure further provides a catalyst system comprising a support material; a dianionic complex, such as a bis(phenolate) complex; and an optional metallocene disposed on the support material; and an activator selected from aluminoxanes or NCAs, also disposed on the support material. Preferably, the activator may be an NCA formed from tris(pentafluorophenyl)aluminum or a similar Lewis acid. The dianionic complex, the optional metallocene, and the activator may be disposed on the support material in any order (including simultaneously). Suitable ratios of the activator to the metal and / or optional metallocene of the dianionic complex include the Al:M ratio specified above.

[0262] Aggregation methods

[0263] The polymerization method for preparing the impact copolymer according to this disclosure may include: mixing a) propylene with optional C2 or C4-C20 α-olefins and / or α,ω-dienes are subjected to first polymerization conditions in the presence of a first polymerization catalyst and optionally hydrogen to form matrix polypropylene; and the matrix polypropylene and a) ethylene and C3-C 20 α-olefins, or b) propylene and C2 or C4-C 20 α-olefins undergo second polymerization conditions in the presence of a second polymerization catalyst and optionally hydrogen to form an impact copolymer comprising a copolymer phase dispersed within the matrix polypropylene. The second polymerization conditions include gas-phase polymerization conditions, and at least the second polymerization catalyst comprises a dianionic complex containing a Group 3-6 metal, wherein the dianionic complex comprises two eight-membered chelate rings containing a Group 3-6 metal. Suitable dianionic complexes have been discussed in more detail above. Preferably, the dianionic complex comprises a Group 4 metal, more preferably Zr, as described in more detail above. The dianionic complex may be present on a support material, preferably in combination with an activator, to define the catalyst system. Optionally, metallocenes, such as metallocenes with C1 symmetry, may also be present in the catalyst system.

[0264] The first polymerization reaction conditions may include slurry-phase polymerization reaction conditions or gas-phase polymerization reaction conditions. When the first polymerization reaction conditions include gas-phase polymerization reaction conditions, the first polymerization reaction conditions may be the same as or different from the second polymerization reaction conditions. Preferably, the first polymerization reaction conditions are slurry-phase polymerization reaction conditions. Suitable slurry-phase polymerization reaction conditions and gas-phase polymerization reaction conditions will be discussed later.

[0265] As described above, when producing the impact copolymer according to this disclosure, the matrix polypropylene can be formed under first polymerization reaction conditions involving slurry-phase polymerization, and the copolymer phase can be grown in the matrix polypropylene under second polymerization reaction conditions involving gas-phase polymerization. Slurry-phase polymerization refers to a polymerization method in which a supported catalyst (optionally also containing an activator) is used, and monomers are polymerized on supported catalyst particles such that the supported catalyst particles remain in the polymer after polymerization, wherein at least one of the monomers undergoing polymerization is in liquid form and constitutes at least a portion of the fluid medium for the slurry. Gas-phase polymerization refers to a polymerization method in which the monomers undergoing polymerization are in a gaseous state and wherein the supported catalyst particles (optionally also containing an activator) are fluidized in a reactor producing the polymer. Any of such polymerization methods can be carried out in a batch, semi-batch, or continuous mode. The term "continuous" means a system operating without interruption or stoppage, such that the polymer product can be removed while one or more monomers or other reactants are being introduced into the reactor producing the polymer. In a continuous process for producing an impact copolymer containing a matrix polypropylene and a copolymer phase grown within the matrix polypropylene, the matrix polypropylene can be produced in a first reactor under slurry-phase polymerization conditions, and the copolymer phase can be produced in a second reactor downstream of the first reactor under gas-phase polymerization conditions. Conversely, batch and semi-batch processes can be carried out in the same reactor or in different reactors. Additional details related to slurry-phase polymerization and gas-phase polymerization conditions are discussed further below.

[0266] Therefore, in various instances, the first polymerization reaction conditions and the second polymerization reaction conditions can be provided in a staged manner in a single reactor, or in a staged manner in separate reactors. When carried out in a staged manner in separate reactors, the first reactor can carry out a first polymerization stage under the first polymerization reaction conditions to produce matrix polypropylene, and the second reactor can carry out a second polymerization stage under the second polymerization reaction conditions to produce a copolymer phase within the matrix polypropylene.

[0267] Both slurry-phase polymerization and gas-phase polymerization can be carried out in the presence of aliphatic hydrocarbon solvents / diluents / condensers, such as isobutane, butane, pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; or cyclic aliphatic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. Preferably, the aromatic compound is present in the solvent / diluent / condenser in less than 1% by weight, more preferably less than 0.5% by weight, and even more preferably 0% by weight, based on the weight of the solvent / diluent / condenser.

[0268] Slurry-phase polymerization can be operated at atmospheric pressure or higher, preferably in a pressure range of about 140 psi (965 kPa) to about 750 psi (5171 kPa) or even higher, and in a temperature range of about 0°C to about 120°C or about 20°C to about 110°C. Optionally, hydrogen may be present to alter the molecular weight of the polymer being produced. In slurry-phase polymerization, a suspension of polymer particles (matrix polypropylene) is formed in a fluid medium containing at least one of the monomers undergoing polymerization and optionally a hydrocarbon diluent. The suspension including the diluent is removed from the reactor intermittently or continuously, wherein volatile components may be separated from the polymer and optionally recycled back to the reactor after distillation, or these components may be directly fed into a reactor to form a copolymer phase by gas-phase polymerization. Non-limiting examples of slurry-phase polymerization methods include continuous loop or stirred tank methods. Other examples of slurry-phase polymerization methods are described in U.S. Patent No. 4,613,484, which is incorporated herein by reference.

[0269] Gas-phase polymerization can be operated 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 do not necessarily need to be introduced into the reactor as gases (i.e., they can be introduced as condensates), but they must be in a gaseous state at least while in contact with the catalyst system. Typically, one or more gaseous monomers are discharged from the reactor as an effluent stream, which is then recycled back into the reactor to increase conversion, and the polymer is collected separately from the effluent stream from the reactor. Illustrative gas-phase polymerization reaction conditions may include temperatures of about 25°C to about 150°C, or about 50°C to about 140°C, or about 60°C to about 110°C, and pressures 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 may be present to alter the molecular weight of the polymer being produced. Illustrative gas-phase polymerization methods are described in U.S. Patent Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661 and 5,668,228, each of which is incorporated herein by reference.

[0270] The first polymerization reaction conditions may include pressures higher than those of the second polymerization reaction conditions. In a non-limiting example, the pressure under the second polymerization reaction conditions (i.e., under gas-phase polymerization reaction conditions) may be about 330 psi (2275 kPa) or less, or about 300 psi (2068 kPa) or less, or about 200 psi (1379 kPa) or less, or about 100 psi (690 kPa) or less.

[0271] Slurry-phase polymerization and gas-phase polymerization can be carried out with or without one or more scavenging agents. Typical scavenging agents include trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, diethylzinc, or an excess of aluminum oxane activator.

[0272] If desired, hydrogen may be added during any polymerization reaction to alter the molecular weight of the polymer being produced. In at least one embodiment, hydrogen may be present in the first and / or second polymerization reactions at partial pressures 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 a total 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. In other embodiments, hydrogen may be included at a total concentration of at least about 50 ppm, or at least about 100 ppm, or at least about 150 ppm.

[0273] The dianionic complex, which serves as the second polymerization catalyst in the second polymerization stage, can also be used as the first polymerization catalyst in the first polymerization stage. That is, the first and second polymerization catalysts can be the same. When also used as the first polymerization catalyst, the dianionic complex can be present on a support material (e.g., silica) and subjected to the first polymerization reaction conditions, wherein the dianionic complex (and the support material, and the supported activator) is bound within the particles of the matrix polypropylene. In this aspect, the first polymerization catalyst is provided to the first polymerization reaction conditions (e.g., within a catalyst system), and subsequently to the second polymerization reaction conditions within the matrix polypropylene, thereby becoming the second polymerization catalyst, wherein the first polymerization catalyst (and subsequently the second polymerization catalyst) is arranged on the support material, preferably in combination with at least one activator. Once subjected to the second polymerization reaction conditions, the dianionic complex and optionally a metallocene can continue to promote the formation of a copolymer phase within the matrix polypropylene.

[0274] In a non-limiting example, the matrix polypropylene prepared under the first polymerization conditions may comprise isotactic polypropylene or a propylene / ethylene random copolymer, which is also predominantly isotactic. The polypropylene may be a propylene homopolymer or copolymer. In yet another example, an α,ω-diene combined with propylene may be present in the first polymerization reaction conditions to produce long-chain branched polypropylene. The long-chain branches within the long-chain branched polypropylene are long enough to induce polymer entanglement and may have a molecular weight of about 500 or greater, or about 750 or greater, or about 1000 or greater, or about 1500 or greater, or about 2000 or greater, or about 2500 or greater, or about 3000 or greater, or about 4000 or greater, or about 5000 or greater. The α,ω-diene can provide reactive sites away from the main polymer chain from which the long-chain branches can continue to grow. When used, the α,ω-diene may be present in the matrix polypropylene in an amount of up to about 10% by weight relative to the total mass of the matrix polypropylene. In some embodiments, the non-zero amount of at least one α,ω-diene may be from about 0.001 wt% to about 10 wt%, or from about 0.01 wt% to about 9.99 wt%, or from about 0.1 wt% to about 9.9 wt%, or from about 0.5 wt% to about 99.5 wt%, or from about 0.1 wt% to about 10 wt%, or any subrange thereof.

[0275] Suitable α,ω-dienes that can be used 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-tetracediene, 1,13-tetradecadiene, 2-methyl-1,6-heptadiene, 2-methyl-1,7-octadiene, 2-methyl-1,8-nonadiene, 2-methyl-1,9-decadiene, 2-methyl-1,10-undecadiene, 2-methyl-1,11-dodecadiene, 2-methyl-1,12-tetracediene, 2-methyl-1,13-tetradecadiene, and vinylnorbornene.

[0276] Suitable propylene / ethylene random copolymers within matrix polypropylene may primarily comprise propylene, such as about 95% by weight or more propylene-derived monomer units, or about 97% by weight or more propylene-derived monomer units, or about 99% by weight or more propylene-derived monomer units, and a non-zero amount of ethylene-derived monomer units. Alternatively, matrix polypropylene may comprise propylene (about 90% by weight or more, or 95% by weight or more propylene-derived monomer units) primarily with C4-C 20 A propylene / α-olefin copolymer formed by copolymerization of α-olefins (optionally further combined with ethylene). Up to about 10% by weight of α,ω-diene may also be present in any of the foregoing substances.

[0277] The matrix polypropylene prepared under the first polymerization reaction conditions may have a Mw value of about 5,000 to about 500,000 and exhibit a wide molecular weight distribution (Mw / Mn). In non-limiting examples, the molecular weight distribution of the matrix polypropylene may be about 2 or greater, or about 3 or greater, or about 4 or greater, or about 5 or greater, or about 6 or greater, for example about 2 to about 5 or about 3 to about 6.

[0278] In a non-limiting example, the copolymer phase prepared under the second polymerization reaction conditions can be an elastomer and comprises an ethylene copolymer or a propylene copolymer, including terpolymers thereof. The copolymer phase can be a discrete phase contained within the matrix polypropylene, or the matrix phase can be at least partially dissolved in the matrix polypropylene (miscible with the matrix polypropylene). Suitable ethylene copolymers can primarily comprise ethylene-derived monomer units (e.g., about 70% to about 97% by weight of ethylene-derived monomer units, or about 70% to about 90% by weight of ethylene-derived units), with the remainder comprising propylene-derived monomer units and / or C4-C4 copolymers. 20 The α-olefin-derived monomer units optionally also include monomer units derived from diene monomers, such as butadiene, isoprene, dicyclopentadiene, or ethylene-imide norbornene. Suitable propylene copolymers may primarily comprise propylene-derived monomer units (e.g., about 70% to about 90% by weight of propylene-derived monomer units), with the remainder comprising ethylene-derived monomer units and / or C4 to C6 monomer units. 20 The α-olefin-derived monomer units optionally also include monomer units derived from diene monomers, such as butadiene, isoprene, dicyclopentadiene, or ethylidene norbornene. Therefore, suitable copolymer phases may include C2 / C3 copolymers, C3 / C4 copolymers, C2 / C4 copolymers, C2 / C6 copolymers, C2 / C8 copolymers, C2 / C10 copolymers, C2 / C3 / C4 copolymers, C2 / C3 / C6 copolymers, C2 / C3 / C8 copolymers, C2 / C3 / C10 copolymers, and any combination thereof. Any of the aforementioned copolymers may be elastomers or rubber compounds. In some examples, the copolymer phase may comprise or substantially constitute from about 10 wt% to about 90 wt% ethylene and from about 10 wt% to about 90 wt% propylene, each based on the total mass of the impact copolymer.

[0279] The Mw value of the copolymer phase prepared under the second polymerization reaction conditions can be higher than that of the matrix polypropylene prepared under the first polymerization reaction conditions, and it exhibits a narrow molecular weight distribution (Mw / Mn). In non-limiting examples, the Mw value of the copolymer phase can be up to about 250,000, or up to about 1,000,000, or even up to about 5,000,000, for example, about 50,000 to about 1,000,000, or about 100,000 to about 700,000, or about 200,000 to about 600,000. In non-limiting examples, the molecular weight distribution of the copolymer phase can be about 5 or less, or about 4 or less, or about 3 or less.

[0280] In a non-limiting example, the impact copolymer prepared according to the disclosure herein may comprise about 65% to about 95% by weight of a matrix polypropylene and about 5% to about 35% by weight of a copolymer phase, each based on the total mass of the impact copolymer. Depending on the ratio of the copolymer phase to the matrix polypropylene, the impact copolymer may comprise about 5% to about 50% by weight of non-propylene-derived monomer units. In a more specific example, the impact copolymer may comprise about 5% to about 40% by weight of ethylene-derived monomer units in total.

[0281] In any implementation scheme using α-olefins herein, suitable α-olefins may include substituted or unsubstituted C2 to C3 olefins. 40 α-olefins, or C2 to C 20 α-olefins, or C2 to C 12 α-Olefins, preferably ethylene, propylene, butene, pentene, hexene, hepten, octene, nonene, decene, undecene, dodecane, and their isomers. When butene is used as the α-olefin comonomer, the butene source can be a mixed butene stream containing various butene isomers. In such a mixed stream, the 1-butene monomer is expected to be preferentially consumed by the polymerization process compared to other butene monomers. The use of such mixed butene streams will provide economic benefits because these streams are typically waste streams from refining processes, such as C4 residue streams, and are therefore much cheaper than pure 1-butene.

[0282] In a non-limiting example, the impact copolymer prepared according to the disclosure herein may have a melting point of about 50°C to about 140°C or about 100°C to about 165°C. If the impact copolymer is semi-crystalline, multiple melting points may exist within the above ranges.

[0283] In a non-limiting example, the impact copolymer prepared according to the disclosure herein may have a flexural modulus of about 400 MPa to about 2200 MPa or about 600 MPa to about 1600 MPa, as measured by ASTM D790A. These values ​​are measured with or without a nucleating agent.

[0284] In non-limiting examples, impact copolymers prepared according to the disclosure herein may have a room temperature notched IZOD impact strength of approximately 0.3 ft·lb / in or higher as measured by ASTM D256. Values ​​under test conditions including those without breakage are included within the foregoing range.

[0285] Other implementation plans

[0286] This disclosure further relates to the following non-restrictive implementations:

[0287] Implementation plan 1. Methods, including:

[0288] Make a) propylene and optionally b) C2 or C4-C 20 α-olefins and / or α,ω'-dienes undergo first polymerization conditions in the presence of a first polymerization catalyst and optional hydrogen to form matrix polypropylene; and

[0289] The matrix is ​​polypropylene and a) ethylene and C3-C 20 α-olefins, or b) propylene and C2 or C4-C 20 α-olefins are subjected to second polymerization conditions in the presence of a second polymerization catalyst and optional hydrogen to form an impact copolymer comprising a copolymer phase dispersed within the matrix polypropylene.

[0290] The second polymerization reaction conditions include gas-phase polymerization reaction conditions, and the second polymerization catalyst comprises a dianionic complex of a group 3-6 metal, wherein the dianionic complex comprises two eight-membered chelate rings containing a group 3-6 metal.

[0291] Implementation Scheme 2. The method of Implementation Scheme 1, wherein the matrix polypropylene comprises isotactic polypropylene having a melting point of about 140°C to about 165°C.

[0292] Implementation Scheme 3. The method of Implementation Scheme 1 or Implementation Scheme 2, wherein the α,ω-diene is present and the matrix polypropylene has a g'vis value of about 0.6 to about 0.95 as determined by GPC-4D.

[0293] Implementation Scheme 4. The method of any one of Implementation Schemes 1-3, wherein the first polymerization reaction conditions include slurry-phase polymerization reaction conditions or gas-phase polymerization reaction conditions.

[0294] Implementation Scheme 5. The method of any one of Implementation Schemes 1-3, wherein the first polymerization reaction conditions include slurry phase polymerization reaction conditions.

[0295] Implementation Scheme 6. The method of any one of Implementation Schemes 1-5, wherein the bianionic complex comprises a Group 4 metal.

[0296] Implementation Scheme 7. The method of any one of Implementation Schemes 1-5, wherein the dianionic complex has a structure represented by the following formula.

[0297]

[0298] in:

[0299] M is a Group 4 metal;

[0300] E and E' are independently O, S, or NR. 9 , where each R 9 Independently, it is hydrogen, C1-C 40 Optional substituted hydrocarbon groups or heteroatom-containing groups;

[0301] Z is a group 14-16 atom that forms a coordinate bond with M;

[0302] A 1 ZA 1’ It is part of a heterocyclic Lewis base designated as B, containing 4 to 40 non-hydrogen atoms, which connects A via a 3-atom bridge. 2 With A 2’ The connection, where Z is the central atom of the 3-atom bridge;

[0303] A 1 and A 1' Independently C, N, or CR 22 , where each R 22 Independently hydrogen or optionally substituted C1-C 20 hydrocarbon group;

[0304] It is a divalent group, optionally, part of an optionally substituted hydrocarbon ring or optionally substituted heterocycle, containing 2 to 40 non-hydrogen atoms, which connect A via a 2-atom bridge. 1 It is connected to a first aryl group, wherein the first aryl group has an E bonded thereto;

[0305] It is a divalent group, optionally, part of an optionally substituted hydrocarbon ring or optionally substituted heterocycle, containing 2 to 40 non-hydrogen atoms, which connect A via a 2-atom bridge. 1' It is connected to a second aryl group, the second aryl group having an E' bonded to it;

[0306] Each L is a Lewis base;

[0307] Each X is an anionic ligand;

[0308] n is 1, 2, or 3;

[0309] m is 0, 1, or 2;

[0310] n+m is not greater than 4;

[0311] R 1 R 2 R 3 R 4 R 1' R 2' R 3' and R 4' Independently hydrogen, optionally substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group or R 1 and R 2 R 2 and R 3 R 3 and R 4 R 1' and R 2' R 2’ and R 3' or R 3' and R 4' One or more pairs of rings are linked to form one or more optionally substituted hydrocarbon rings or optionally substituted heterocycles, each ring having 5, 6, 7, or 8 ring atoms, and optionally, said optionally substituted hydrocarbon rings or said optionally substituted heterocycles are fused to one or more additional rings; and

[0312] in:

[0313] When m is 2, any two Ls can optionally be linked together to form a bidentate Lewis base; or

[0314] X is optionally linked to L to form a monoanionic bidentate ligand bonded to M; or

[0315] When n is 2 or 3, any two Xs may be optionally linked together to form a bi-anion ligand bonded to M.

[0316] Implementation Scheme 8. The method of Implementation Scheme 7, wherein the Group 4 metal includes zirconium.

[0317] Implementation scheme 9. The method of implementation scheme 7 or implementation scheme 8, wherein E and E' are each O.

[0318] Implementation Scheme 10. The method of any one of Implementation Schemes 7-9, wherein R 1 and R 1' It is independently a tertiary alkyl or tertiary alkyl aryl.

[0319] Implementation Scheme 11. The method of Implementation Scheme 10, wherein the tertiary alkyl group includes optionally substituted adamantyl alkyl groups.

[0320] Implementation Scheme 12. The method of any one of Implementation Schemes 7-11, wherein and Independently, it is an optionally substituted arylene, optionally substituted heteroarylene, or optionally substituted vinylene.

[0321] Implementation Scheme 13. The method of any one of Implementation Schemes 7-11, wherein and Each is either a substituted phenylene group or a substituted heteroaryl group.

[0322] Implementation Scheme 14. The method of any one of Implementation Schemes 7-13, wherein the heterocyclic Lewis base is a 5- or 6-membered heteroaromatic ring.

[0323] Implementation Scheme 15. The method of any one of Implementation Schemes 7-14, wherein the Z of the heterocyclic Lewis base is N.

[0324] Implementation Scheme 16. The method of any one of Implementation Schemes 7-15, wherein the heterocyclic Lewis base is an optionally substituted pyridine.

[0325] Implementation Scheme 17. The method of any one of Implementation Schemes 1-16, wherein at least the second polymerization catalyst is arranged on a support material and optionally combined with at least one activator to form a catalyst system.

[0326] Implementation Scheme 18. The method of Implementation Scheme 17, wherein a metallocene comprising a Group 4 metal is disposed on the carrier material.

[0327] Implementation Scheme 19. The method of Implementation Scheme 18, wherein the metallocene is a C1-symmetric metallocene.

[0328] Implementation Scheme 20. The method of Implementation Scheme 19, wherein the C1 symmetric metallocene has a structure represented by the following formula.

[0329]

[0330] in:

[0331] M is a Group 4 metal;

[0332] T is a bridge base;

[0333] X 1 and X 2 Each is a monovalent anionic ligand, or X 1 and X 2 Linked to form metal cyclic rings, chelated ligands, diene ligands, or alkylidenes;

[0334] R 1 It is hydrogen, halogen, or optionally substituted C1-C 40 Alkyl, optionally substituted C6-C 14 Aryl, optionally substituted C3-C 13Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R''-SiR'3, where R'' is C1-C 10 Alkylene and R' are hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl;

[0335] R 2 and R 6 Independently hydrogen, halogen, or optionally substituted C1-C 40 Alkyl, optionally substituted C6-C 14 Aryl, optionally substituted C3-C 13 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R''-SiR'3, where R'' is C1-C 10 Alkylene and R' are hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl;

[0336] R 3 It is an optional substitution of C1-C 40 Alkyl or optionally substituted C6-C 18 Aryl;

[0337] R 4 and R 5 Independently, it is H, R''', or OR''', where R''' is an optionally substituted C1-C 40 Alkyl, optionally substituted C6-C 14 Aryl, optionally substituted C3-C 13 heteroaryl, or R 4 and R 5 Connected to form C3-C 62 Substituted or unsubstituted, saturated or unsaturated cyclic or polycyclic structures, or combinations thereof; and

[0338] R 7 R 8 R 9 and R 10 Independently hydrogen, halogen, or optionally substituted C1-C 40 Alkyl, optionally substituted C6-C 14 Aryl, optionally substituted C3-C 13 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R''-SiR'3, where R'' is C1-C 10 Alkylene and R' are hydrogen, C1-C 10 Alkyl or C6-C 10Aryl, or R 5 and R 6 R 6 and R 7 or R 7 and R 8 One or more pairs are connected to form C3-C 62 A cyclic or polycyclic structure, or a combination thereof, that is substituted or unsubstituted, saturated or unsaturated.

[0339] Implementation Scheme 21. The method of Implementation Scheme 20, wherein the Group 4 metal is Hf or Zr; T is selected from CH2, CH2CH2, C(CH3)2, (Ph)2C, (p-(Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4 and Si(CH2)4; X 1 and X 2 It is independently a halogen or a C1-C6 hydrocarbon group; R 3 It is an optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted anthraquinone; R 2 and R 6 It is hydrogen; R 1 It is a methyl group.

[0340] Implementation Scheme 22. The method of any one of Implementation Schemes 17-21, wherein the at least one activator is present and comprises at least one aluminum oxane.

[0341] Implementation Scheme 23. The method of any one of Implementation Schemes 17-21, wherein the at least one activator is present and comprises at least one noncoordinate anion.

[0342] Implementation Scheme 24. The method of Implementation Scheme 23, wherein the noncoordinate anion is surface-bonded to the support material as a reaction product of a surface hydroxyl group and a noncoordinate anion precursor, the noncoordinate anion precursor comprising an organoaluminum compound having a haloaryl group.

[0343] Implementation Scheme 25. The method of any one of Implementation Schemes 17-24, wherein the carrier material comprises silicon dioxide.

[0344] Implementation Scheme 26. The method of any one of Implementation Schemes 1-25, wherein the first polymerization catalyst is provided to a first polymerization reaction condition and subsequently provided to a second polymerization reaction condition within a matrix polypropylene, thereby becoming a second polymerization catalyst.

[0345] Implementation Scheme 27. The method of any one of Implementation Schemes 1-26, wherein the first polymerization reaction conditions include a higher pressure than the second polymerization reaction conditions, and the second polymerization reaction conditions include a pressure of about 330 psi or lower.

[0346] Implementation Scheme 28. The method of any one of Implementation Schemes 1-27, wherein the impact copolymer comprises about 65% to about 95% by weight of the matrix polypropylene and about 5% to about 35% by weight of the copolymer phase, each based on the total mass of the impact copolymer.

[0347] Implementation Scheme 29. The method of any one of Implementation Schemes 1-28, wherein the copolymer phase comprises about 10 wt% to about 90 wt% ethylene and about 10 wt% to about 90 wt% propylene, each based on the total mass of the impact copolymer.

[0348] To aid in a better understanding of the various embodiments of this disclosure, the following examples of preferred or representative embodiments are provided. These examples should in no way be construed as limiting or restricting the entire scope of the invention.

[0349] Example

[0350] Bis(phenolic salt) complexes. The following bis(phenolic salt) complexes are synthesized in a manner similar to that described in U.S. Patents 11,254,763 and 11,225,539, each of which is incorporated herein by reference. The bis(phenolic salt) complexes are used in the polymerization reactions further described below.

[0351]

[0352] Metallocene catalysts. The following metallocenes are used in polymerization reactions described further below.

[0353]

[0354] Metallocene A is synthesized by introducing a substituted phenyl group onto a 6-methyl-1,2,3,5-tetrahydro-s-indaragans via Suzuki coupling of 4-tert-butylphenylboronic acid with the corresponding bromide parent ring system, followed by lithiation, dimethylsilyl bridging, and metallocene formation. Illustrative synthetic procedures for metallocene A can be found in U.S. Patent Application Publication 2022 / 0315680 and International Patent Application Publication WO2023 / 034889, each of which is incorporated herein by reference. Illustrative synthetic procedures for metallocene B can be found in U.S. Patent 9,458,254, which is incorporated herein by reference.

[0355] Preparation of the supported activator. A non-coordinated anionic activator was prepared in situ and deposited on a silica support. 0.21 g (2.85 mmol) of AlMe3 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). After this, the mixture became homogeneous and was stirred uncovered at room temperature for 1 hour, during which time BMe3 was removed as a gas. While stirring, the resulting Al(C6F5)3 solution was transferred to 10 g of silica (PD17062, Ecovyst), followed by the addition of N,N-diethylaniline (0.425 g, 2.85 mmol) in a minimal amount of toluene. The silica slurry was then stirred for another 30 minutes.

[0356] In a separate flask, 0.975 g of triethylaluminum (8.55 mmol) was suspended in toluene (30 mL) and cooled in a refrigerator. While stirring, a solution of 3.77 g (17.1 mmol) of BHT (butylated hydroxytoluene) in toluene (10 mL) was slowly added to the triethylaluminum suspension. After 30 minutes, the resulting triethylaluminum:BHT complex was slowly added to the silica slurry prepared above at room temperature. The combined reaction mixture was then stirred overnight. After 18 hours, the reaction mixture was filtered, and the solid was washed with toluene (2 × 50 mL) and pentane (2 × 50 mL). After vacuum drying, a support material as a white powder was obtained.

[0357] Preparation of supported catalysts. The bis(phenolate) complexes and metallocenes listed above were supported by contacting a toluene solution of one or more catalyst compounds with a supported activator prepared as described above. Briefly, a toluene solution of one or more catalyst compounds (~17-38 μmol) was slowly added to 1.2 g of supported activator slurried in 1 mL of toluene. After shaking for 4 hours, the solid was collected on a glass substrate and washed with toluene (2 × 10 mL) and pentane (2 × 10 mL). After drying under vacuum, the supported catalyst was slurried in mineral oil to prepare a 5 wt% slurry for distribution into the polymerization reactor.

[0358] The general procedure for phased polymerization of slurry and gas phases. Slurry phase polymerization stage.A 2L autoclave reactor equipped with a mechanical stirrer was used for polymer preparation. Before operation, the reactor was purged with nitrogen at 90°C for 30 minutes. After cooling to ambient temperature, propylene (600 mL), a scavenger (0.4 mL of 1M TIBAL, triisobutylaluminum), optional diene comonomer, and optional hydrogen (charged from a 50 mL bomb at the desired pressure) were introduced into the reactor and mixed for 5 minutes. The required amount of the supported catalyst prepared above (typically 12.5–25.0 mg) was then introduced into the reactor by flushing a predetermined amount of 5% by weight catalyst slurry from the catalyst tube with 200 mL of liquid propylene. The reactor was held at room temperature for 5 minutes (prepolymerization stage), and then the temperature was raised to 70°C for the desired duration (typically 20–30 minutes). Propylene remained liquid throughout the polymerization process. Additional polymerization details are described in the table below. Gas-phase polymerization stage. After slurry-phase polymerization, the reactor is vented to the desired propylene pressure (typically 40-160 psi). Once the desired propylene pressure is reached, ethylene gas (typically 80-220 psi) and optional hydrogen are introduced, and the reaction is allowed to continue for typically 10-20 minutes. After completion, the reactor is vented, the polymer is collected, and air-dried overnight. Additional polymerization details are described in the table below.

[0359] Polymer characterization. The obtained polymers are characterized to determine their molecular weight and thermal properties.

[0360] GPC-4D analysis. The molecular weight and comonomer content of the polymer were determined by GPC-4D analysis as detailed and further described below in U.S. Patent Application Publication 2018 / 0059076, which is incorporated herein by reference. Following filtration and reinjection of the GPC eluent, the further analysis described in U.S. Patent Application Publication 2018 / 0059076 was performed to determine the amount of copolymer phase and the C2 content of said copolymer phase in the matrix polypropylene.

[0361] The distribution and fractions of molecular weights (Mw, Mn, Mz, Mw / Mn, etc.), comonomer content, and branching index (g') were determined using high-temperature gel permeation chromatography (Polymer Char GPC-IR) equipped with a multi-channel bandpass filter-based infrared detector IR5 (with a band coverage of approximately 2,700 cm⁻¹). -1 Approximately 3,000 cm -1A multi-channel bandpass filter-based infrared detector assembly (IR5) (representing saturated CH stretching vibration), an 18-angle light scattering detector, and a viscometer are used. Three Agilent PLgel 10 μm mixed-B LS columns are used to provide polymer separation. Reagent-grade 1,2,4-trichlorobenzene (TCB) (from Sigma-Aldrich) containing ~300 ppm of the 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 μL. The entire system, including the delivery lines, columns, and detectors, can be contained in an oven maintained at ~145°C. A given amount of polymer sample is weighed and sealed in a standard finger tube, to which ~10 μL of a flow marker (heptane) is added. After loading the finger tube into the autosampler, the oligomer or polymer can be automatically dissolved in the instrument at ~160°C with ~8 mL of added TCB solvent under continuous oscillation. Sample solution concentrations can range 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 using the following formula, subtracting the baseline IR5 broadband signal (I): c = αI, where α is a mass constant determined using polyethylene or polypropylene standards. The mass recovery can be calculated as the ratio of the integral area of ​​the concentration chromatography over the elution volume to the injection mass, which is equal to the predicted concentration multiplied by the injection loop volume. The conventional molecular weight (IRMW) is determined by combining a universal calibration relationship with column calibration using a series of monodisperse polystyrene (PS) standards ranging from 700 to 10 M gm / mol. MW at each elution volume is calculated using Formula 1:

[0362]

[0363] Formula 1

[0364] Variables with the subscript "PS" represent polystyrene, while those without subscripts are the test samples. In this method, α... PS =0.67 and K PS =0.000175, for other materials α and K are calculated as described in published literature (e.g., Sun, T. et al. (2001) Macromolecules, Vol. 34, p. 6812), only for the purposes of this disclosure and the appended claims, for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, =0.705 and then K=0.0000229, for linear ethylene polymers, =0.695 and K=0.000579, for linear propylene polymers, =0.705 and K=0.0002288, for linear butene polymers, =0.695 and K=0.000181. Unless otherwise stated, concentrations are expressed in g / cm³. 3 The molecular weight is expressed in g / mol, and the intrinsic viscosity (and therefore K in the Mark–Houwink equation) is expressed in dL / g.

[0365] The comonomer composition was determined by proportioning the intensity of an IR5 detector corresponding to the CH2 and CH3 channels, calibrated using a series of PE and PP homopolymer / copolymer standards whose nominal values ​​were predetermined by NMR or FTIR. Specifically, this provides methyl groups per 1,000 total carbons (CH3 / 1,000TC) as a function of molecular weight. The short-chain branching (SCB) content per 1,000TC (SCB / 1000TC) as a function of molecular weight was then calculated as follows: chain-end correction was applied to the CH3 / 1000TC functional groups, assuming each chain was linear and end-capped with a methyl group at each end. The weight % comonomer was then obtained by Equation 2, where for comonomers C3, C4, C6, C8, etc., respectively... The values ​​are 0.3, 0.4, 0.6, 0.8, etc.

[0366]

[0367] Formula 2

[0368] The bulk composition of the polymer analyzed by GPC-IR and GPC-4D was obtained by taking into account the full signals of the CH3 and CH2 channels between the integration limits of the concentration chromatograms. First, the following proportions in Equation 3 were obtained.

[0369]

[0370] Formula 3

[0371] Then, the same calibration for the CH3 and CH2 signal ratios is applied (as previously mentioned in obtaining CH3 / 1000TC as a function of molecular weight) to obtain the basic CH3 / 1000TC. The bulk methyl end / 1000TC (bulk CH3 end / 1000TC) is obtained by weighting the chain-end correction over the molecular weight range. Then, Equations 4 and 5 are applied:

[0372]

[0373] Formula 4

[0374]

[0375] Formula 5

[0376] And convert the SCB / 1000TC onto the original using the same method as described above. .

[0377] The LS detector is an 18-angle Wyatt Technology High Temperature DAWN HELEOSII. The LS molecular weight (M) at each point in the chromatogram was determined by analyzing the LS output value using a Zimm model of static light scattering (Light Scattering from Polymer Solutions; Huglin, MB, Ed.; Academic Press, 1972.), as specified in Formula 6:

[0378]

[0379] Formula 6

[0380] Here, ΔR(θ) is the scattering angle. The measured excess Rayleigh scattering intensity, c is the polymer concentration determined by IR5 analysis, A2 is the second virial coefficient, P(θ) is the shape factor of the monodisperse random coil, and Ko is the optical constant of the system, as specified in Equation 7:

[0381]

[0382] Formula 7

[0383] Where N A dn / dc is Avogadro's constant, and (dn / dc) is the refractive index increment of the system. The refractive index n of TCB at 145℃ and λ=665nm is 1.500. For the analysis of polyethylene homopolymers, ethylene-hexene copolymers, and ethylene-octene copolymers, dn / dc = 0.1048 ml / mg and A2 = 0.0015; for the analysis of ethylene-butene copolymers, dn / dc = 0.1048 × (1 - 0.00126 × w2) ml / mg and A2 = 0.0015, where w2 is the weight percentage of the butene comonomer.

[0384] Specific viscosity was determined using a high-temperature Agilent (or Viscotek Corporation) viscometer, which has four capillaries arranged in a Wheatstone bridge configuration and two pressure sensors. One sensor measures the total pressure drop across the detector, and the other, located between the two sides of the bridge, measures the pressure difference. The specific viscosity η of the solution flowing through the viscometer is... s Calculated from their outputs. The intrinsic viscosity [η] at each point in the chromatogram is given by the formula [η] = η s / c is calculated, where c is the concentration and is measured by the IR5 broadband channel output. The viscosity (MW) at each point is calculated as follows: ,in ps It is 0.67 and K ps It is 0.000175.

[0385] The branching index (g'vis) was calculated using the GPC-IR5-LS-VIS method as follows. The average intrinsic viscosity of the sample [η] 平均 Calculated using Formula 8:

[0386] (where [η]) avg [η] 平均 )

[0387] Formula 8

[0388] The sum is taken from all chromatogram slices i between the integration limits.

[0389] The branching index g'vis is defined as shown in Formula 9:

[0390] ,

[0391] Formula 9

[0392] Where Mv is the viscosity-average molecular weight based on the molecular weight determined by LS analysis, and K and α are for reference linear polymers, wherein for the purposes of this disclosure and the appended claims, for ethylene-propylene copolymers and ethylene-propylene-diene terpolymers, α = 0.705 and K = 0.0000229; for linear ethylene polymers, α = 0.695 and K = 0.000579; for linear propylene polymers, α = 0.705 and K = 0.0002288; and for linear butene polymers, α = 0.695 and K = 0.000181. Unless otherwise stated, concentrations are expressed in g / cm³. 3 The molecular weight is expressed in g / mol, and the intrinsic viscosity (and therefore K in the Mark–Houwink equation) is expressed in dL / g. The w2b value is calculated as discussed above.

[0393] DSC Analysis. The thermal properties of polymers were analyzed by differential scanning calorimetry (DSC). In short, the peak melting point (Tm) and peak crystallization temperature (Tc) were determined using a TA instrument model DSC2500 using the following DSC procedure. A sample weighing approximately 5 mg to 10 mg was sealed in an aluminum sealed sample tray and loaded into the instrument at approximately room temperature. DSC data was recorded by first gradually heating the sample to approximately 200 °C at a rate of 10 °C / min. The sample was held at approximately 200 °C for 5 minutes, then cooled to approximately -50 °C at a rate of approximately 10 °C / min, followed by isothermal holding for approximately 5 minutes, then heated to approximately 200 °C at approximately 10 °C / min, followed by isothermal holding for approximately 5 minutes, and finally cooled to approximately 25 °C at a rate of approximately 10 °C / min. The thermal results of the first and second cycles were recorded. Unless otherwise specified, the Tm and Tc values ​​reported in the table below were obtained during the second heating / cooling cycle.

[0394] Tensile properties. 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 clamp spacing and 50.8 mm / min, at 70℉).

[0395] MFR procedure. Melt flow rate is determined according to ASTM D-1238 conditions L (2.16 kg, 230°C).

[0396] Flexural modulus procedure. Using injection molding of ISO 37-3 type strips, measure the 1% secant flexural modulus (commonly referred to as flexural modulus) according to ASTM D 790 (A, 1.0 mm / min) with a crosshead speed of 1.0 mm / min and a carrier span of 30.0 mm.

[0397] Notched Izod Procedure. Notched Izod impact measurements are performed on notched injection-molded strips at indicated temperatures according to ASTM D256.

[0398] Small Amplitude Oscillating Shear (SAOS) Test: Kinematic shear melt rheological data were obtained from TA Instruments' Advanced Rheometrics Expansion System (ARES-G2 type) and measured in dynamic mode under a nitrogen atmosphere using parallel plates (diameter = 25 mm). For all experiments, the resin compression-molded samples were placed in a thermally stable rheometer at 190 °C for at least 30 minutes before being inserted into the parallel plates. To determine viscoelastic behavior, frequency scans were performed at constant strain at 190 °C in the range of 0.01 to 628 rad / s. Depending on the molecular weight and temperature, strains within the linear deformation range validated by strain scan tests were used. Nitrogen gas was circulated through the sample oven to minimize chain elongation or crosslinking during the experiment. All samples were compression-molded at 190 °C. If the strain amplitude was small enough to make the material behave linearly, a sinusoidal shear strain was applied to the material. It can be shown that the resulting steady-state stress will also oscillate sinusoidally at the same frequency, but with a phase shift d relative to the strain wave. Stress leads strain d. For a purely elastic material, d=0 o (Stress and strain are in phase), and for purely viscous materials, d=90 o (Stress leads strain 90) o (Although stress and strain rate are in phase). For viscoelastic materials, 0 < d < 90.

[0399] Extended flow measurement. The sample was thermally equilibrated for 10–15 minutes prior to testing. Analysis was performed using the SER testing platform of the Advanced Rheometrics Expansion System (ARES-G2) from TA Instruments, as described in U.S. Patents 6,578,413 and 6,691,569, which are incorporated herein by reference. A general description of transient uniaxial tensile viscosity measurements is provided, for example, in "Measuring the transient extensional rheology of polyethylene melts using the SERuniversal testing platform", The Society of Rheology, Inc., J. Rheol. Vol. 49(3), 585–606 (2005). Strain hardening can occur when a polymer undergoes extended flow and the transient tensile viscosity increases relative to the linear viscoelastic envelope (EVE), or when subjected to tensile viscosity at a higher rate at a Hengi strain of 1.0 or lower, where the Hengi strain is calculated as the product of the Hengi strain rate and time. Strain hardening is observed as a sharp increase in tensile viscosity on a transient tensile viscosity versus time graph. The strain hardening ratio (SHR) is used to characterize this increase in tensile viscosity and is the ratio described above. When this ratio is greater than 1, strain hardening is present in the material.

[0400] Example 1. Propylene homopolymer. Propylene homopolymers were prepared by slurry-phase polymerization (first stage) using only propylene in the slurry-phase polymerization stage and performing only the polymerization process. Characterization data and additional polymerization details are listed in Table 1 below.

[0401] Table 1

[0402]

[0403] As shown, the individual bis(phenolate) complexes (I3 and I4, entries 3 and 4) provide Mw values ​​comparable to those of the individual tested metallocene catalysts (MCA and MCB, entries 1 and 2), but with surprisingly small polydispersity indices (Mw / Mn). Small changes in Tm and Tc are also observed when using the bis(phenolate) complexes. Compared to the individual bis(phenolate) complexes, using combinations of bis(phenolate) complexes and metallocenes (entries 5-8) increases the polydispersity index, and the Mw value increases significantly, except in the case of entry 8. The broadening of the polydispersity index is thought to be due to the different polymer molecular weights that can be produced by the two catalysts. As further shown, the bis(phenolate) complexes maintain high activity values ​​in all cases.

[0404] Example 2. Ethylene-propylene impact copolymers under constant ethylene pressure were prepared using only propylene in the slurry-phase polymerization stage (first stage) and both propylene and ethylene in the gas-phase polymerization stage (second stage), wherein a fixed amount of ethylene was used in the gas-phase polymerization. Characterization data and additional polymerization details are listed in Tables 2A-2D below.

[0405] Table 2A

[0406]

[0407] Table 2B

[0408]

[0409] Table 2C

[0410]

[0411] =No breakage

[0412] Table 2D

[0413]

[0414] As shown above, in most cases, the catalyst primarily produces an isotactic polypropylene matrix and primarily produces an ethylene-propylene copolymer phase. Narrow polydispersity values ​​for the copolymer phase are achieved in most cases, and no breakage occurs during notched Izod tests in most situations.

[0415] Example 3. Ethylene-propylene impact copolymer under variable ethylene pressure. An ethylene-propylene impact copolymer was prepared using only propylene in the slurry-phase polymerization stage (first stage) and both propylene and ethylene in the gas-phase polymerization stage (second stage), wherein a variable amount of ethylene was used in the gas-phase polymerization. Characterization data and additional polymerization details are listed in Tables 3A-3D below.

[0416] Table 3A

[0417]

[0418] Table 3B

[0419]

[0420] Table 3C

[0421]

[0422] =No breakage

[0423] Table 3D

[0424]

[0425] As shown above, narrow polydispersity indices were achieved for both the overall impact copolymer and the ethylene-propylene copolymer phase, and in some cases, no fracture occurred during the notched Izod test. Increased ethylene introduction occurred at higher ethylene partial pressures. Due to the greater ethylene introduction in the copolymer phase, a slight improvement in stiffness and toughness was also achieved compared to the sample of Example 2.

[0426] Example 4. Ethylene-propylene impact copolymer with long-chain branching in a matrix polypropylene. The ethylene-propylene impact copolymer was prepared using propylene and 1,7-octadiene in the slurry-phase polymerization stage (first stage) and propylene and ethylene in the gas-phase polymerization stage (second stage). Characterization data and additional polymerization details are listed in Tables 4A-4D below.

[0427] Table 4A

[0428]

[0429] Table 4B

[0430]

[0431] Table 4C

[0432]

[0433] =No breakage

[0434] Table 4D

[0435]

[0436] As shown, when 1,7-octadiene is copolymerized with propylene, the total polydispersity index (MFR) widens slightly and the MFR value decreases. These results are consistent with the introduction of long-chain branches resulting from the introduction of 1,7-octadiene into matrix polypropylene.

[0437] This group of impact copolymers is also relatively insensitive to the composition and amount of copolymer phases, thus allowing for adjustable stiffness and toughness. Figure 1This is a graph showing the flexural modulus of the samples from Examples 2-4 as a function of the notched Izod value. As shown, the samples without long-chain branching tend to exhibit a decreasing flexural modulus with increasing notched Izod value (Examples 2 and 3), while the samples with long-chain branching show a small decrease in flexural modulus with increasing notched Izod value (Example 4). Therefore, the ability of bis(phenolate) complexes to introduce long-chain branching into the matrix polypropylene allows for the realization of impact copolymers with a balance of stiffness and toughness.

[0438] Additional rheological data were collected from the long-chain branched sample (Example 4) and compared with similar samples without long-chain branching (Entry 15, Example 2). Small-amplitude oscillatory shear was measured using an ARES-G2 rheometer (TA Instruments) with an 8 mm parallel plate geometry and 1% shear strain. Figure 2 This is a small-amplitude oscillatory shear plot of the sample from Example 4 compared to a similar sample lacking long-chain branching. The plot shows complex viscosity as a function of angular frequency. The complex viscosity plot was constructed by time-temperature superposition (tTS) of various measurements taken at temperatures ranging from 150°C to 250°C. As shown, the gradually increasing amount of 1,7-octadiene in the slurry-phase polymerization leads to improved processability due to the increased shear-thinning behavior. For the sample in Item 12, a typical low-frequency plateau characterizing the so-called zero-shear viscosity was observed, while other samples showed increasingly stronger viscosity increases at low frequencies, reflecting their high melt strength resulting from long-chain branching.

[0439] Figure 3 This is a tensile viscosity plot of the sample from Example 4 compared to a similar sample lacking long-chain branching. Figure 3 In the middle, the dashed line represents passing through 0.0001s -1 The linear viscoelastic envelope (LVE) viscosity (L) was measured at the initial shear rate. Differences in viscosity over long time reflect the higher melt strength of samples containing long-chain branched polymers (Entries 28-32, Example 4). Strain hardening can occur when the polymer undergoes extended flow and the instantaneous tensile viscosity increases relative to the LVE, or when the polymer undergoes tensile viscosity at a higher rate at a Hengyi strain of 1.0 or lower, where the Hengyi strain is calculated as the product of the Hengyi strain rate and time. Strain hardening is observed as a sharp increase in tensile viscosity in a transient tensile viscosity versus time plot. The strain hardening ratio (SHR) is used to characterize the increase in tensile viscosity and is the ratio described above. Strain hardening is present when this ratio is greater than 1. For impact copolymers containing linear matrix polypropylene (Entry 15), the strain hardening ratio is negligible, while significantly large values ​​are observed for long-chain branched samples (Entries 28-32).

[0440] All documents described herein, including any priority documents and / or experimental procedures, are incorporated herein by reference to the full extent permitted by law without conflict with this document. It will be apparent from the foregoing overview and specific embodiments that, while the form of this disclosure has been illustrated and described, various modifications may be made without departing from the spirit and scope of this disclosure. Therefore, it is not intended that this disclosure be limited thereto. For example, the compositions described herein may not contain any components or compositions not specifically listed or disclosed herein. Any method may lack any steps not listed or disclosed herein. Similarly, the term “comprising” is considered synonymous with the term “including.” Whenever a method, composition, element, or group of elements precedes the transitional term “comprising,” it should be understood that the same composition or group of elements preceding the listed composition, element, or elements, and vice versa, is also considered.

[0441] Unless otherwise stated, all numerical values ​​used in the specification and appended claims to indicate the quantity of ingredients, properties such as molecular weight, reaction conditions, etc., shall in all cases be understood to be modified by the term "approximately". Therefore, unless otherwise indicated, the numerical parameters listed in the following specification and appended claims are approximate values ​​that may vary depending on the desired properties sought to be obtained from one or more embodiments described herein. To a minimum, and not to limit, the application of principles equivalent to the scope of the claims, each numerical parameter should be interpreted based at least on the number of significant digits recorded and by applying ordinary rounding techniques.

[0442] Whenever a range of numbers with a lower and upper limit is disclosed, any number falling within that range and any included range are explicitly disclosed. In particular, each range of values ​​disclosed herein (in the form of “from about a to about b” or equivalently “from approximately a to b” or equivalently “from approximately ab”) should be understood as listing every number and range covered by a broader range of numerical values. Furthermore, terms in the claims have their ordinary, normal meaning unless otherwise explicitly and clearly defined by the patentee. Additionally, the indefinite article “a” or “an” used in the claims is defined herein as indicating one or more of the elements it introduces.

[0443] One or more illustrative embodiments are provided herein. For clarity, not all features of the physical implementation are described or shown in this application. It should be understood that in the development of a physical implementation incorporating this disclosure, many implementation-specific decisions must be made to achieve the developer's objectives, such as compliance with system-related, business-related, governmental-related, and other constraints, which depend on the implementation and change from time to time. Although the developer's efforts may be time-consuming, such efforts remain a routine task for those skilled in the art and benefit from this disclosure.

[0444] Therefore, this disclosure is fully adapted to obtain the stated purposes and advantages, and those inherent therein. The specific embodiments disclosed above are merely illustrative, as this disclosure can be modified and practiced in different but equivalent ways that will be apparent to those skilled in the art who benefit from the teachings herein. Furthermore, there is no intention to limit the details of the constructions or designs shown herein except as described in the claims below. Therefore, it will be apparent that the specific illustrative embodiments disclosed above can be altered, combined, or modified, and all such variations are considered to be within the scope and spirit of this disclosure. The embodiments of the illustrative disclosure herein can be properly practiced in the absence of any elements not specifically disclosed herein and / or any optional elements disclosed herein.

Claims

1. Methods, including: Make a) propylene and optionally b) C2 or C4-C 20 α-olefins and / or α,ω'-dienes undergo first polymerization conditions in the presence of a first polymerization catalyst and optional hydrogen to form matrix polypropylene; and The matrix is ​​polypropylene and a) ethylene and C3-C 20 α-olefins, or b) propylene and C2 or C4-C 20 α-olefins are subjected to second polymerization conditions in the presence of a second polymerization catalyst and optional hydrogen to form an impact copolymer comprising a copolymer phase dispersed within the matrix polypropylene. The second polymerization reaction conditions include gas-phase polymerization reaction conditions, and the second polymerization catalyst comprises a dianionic complex of a group 3-6 metal, wherein the dianionic complex comprises two eight-membered chelate rings containing a group 3-6 metal.

2. The method of claim 1, wherein: a) The matrix polypropylene comprises isotactic polypropylene having a melting point of about 140°C to about 165°C. b) The presence of α,ω-diene and the matrix polypropylene having a g'vis value of about 0.6 to about 0.95 as determined by GPC-4D; or c) both a) and b) 3. The method of any of the preceding claims, wherein the first polymerization reaction conditions include slurry-phase polymerization reaction conditions or gas-phase polymerization reaction conditions.

4. The method of any of the preceding claims, wherein the first polymerization reaction conditions include slurry-phase polymerization reaction conditions.

5. The method of any of the preceding claims, wherein the bianionic complex has a structure represented by the following formula: in: M is a Group 4 metal; E and E' are independently O, S, or NR. 9 , where each R 9 Independently, it is hydrogen, C1-C 40 Optional substituted hydrocarbon groups or heteroatom-containing groups; Z is a group 14-16 atom that forms a coordinate bond with M; A 1 ZA 1’ It is part of a heterocyclic Lewis base designated as B, containing 4 to 40 non-hydrogen atoms, which connects A via a 3-atom bridge. 2 With A 2’ The connection, where Z is the central atom of the 3-atom bridge; A 1 and A 1' Independently C, N, or CR 22 , where each R 22 Independently hydrogen or optionally substituted C1-C 20 hydrocarbon group; It is a divalent group, optionally, part of an optionally substituted hydrocarbon ring or optionally substituted heterocycle, containing 2 to 40 non-hydrogen atoms, which connect A via a 2-atom bridge. 1 It is connected to a first aryl group, wherein the first aryl group has an E bonded thereto; It is a divalent group, optionally, part of an optionally substituted hydrocarbon ring or optionally substituted heterocycle, containing 2 to 40 non-hydrogen atoms, which connect A via a 2-atom bridge. 1' It is connected to a second aryl group, the second aryl group having an E' bonded to it; 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 R 1 R 2 R 3 R 4 R 1' R 2' R 3' and R 4' Independently hydrogen, optionally substituted C1-C 40 Hydrocarbon group, heteroatom or heteroatom-containing group or R 1 and R 2 R 2 and R 3 R 3 and R 4 R 1' and R 2' R 2’ and R 3' or R 3' and R 4' One or more pairs of rings are linked to form one or more optionally substituted hydrocarbon rings or optionally substituted heterocycles, each ring having 5, 6, 7, or 8 ring atoms, and optionally, said optionally substituted hydrocarbon rings or said optionally substituted heterocycles are fused to one or more additional rings; and in: When m is 2, any two Ls can be optionally linked together to form a bidentate Lewis base; or X is optionally linked to L to form a monoanionic bidentate ligand bonded to M; or When n is 2 or 3, any two Xs may be optionally linked together to form a bi-anion ligand bonded to M.

6. The method of claim 5, wherein the group 4 metal comprises zirconium.

7. The method of claim 5, wherein E and E' are each O.

8. The method of claim 5, wherein R 1 and R 1' It is independently a tertiary alkyl or tertiary alkyl aryl.

9. The method of claim 8, wherein the tertiary alkyl group comprises optionally substituted adamantyl alkyl group.

10. The method of claim 5, wherein and Independently, it is an optionally substituted arylene, optionally substituted heteroarylene, optionally substituted phenylene, or optionally substituted vinylene.

11. The method of claim 5, wherein the heterocyclic Lewis base is a 5- or 6-membered heteroaromatic ring.

12. The method of claim 11, wherein the Z of the heterocyclic Lewis base is optionally substituted pyridine.

13. The method of any of the preceding claims, wherein at least the second polymerization catalyst is arranged on a support material and optionally combined with at least one activator to form a catalyst system.

14. The method of claim 13, wherein a C1-symmetric metallocene comprising a group 4 metal is further disposed on the carrier material.

15. The method of claim 14, wherein the C1-symmetric metallocene has a structure represented by the following formula: in: M is a Group 4 metal; T is a bridge base; X 1 and X 2 Each is a monovalent anionic ligand, or X 1 and X 2 Linked to form metal cyclic rings, chelated ligands, diene ligands, or alkylidenes; R 1 It is hydrogen, halogen, or optionally substituted C1-C 40 Alkyl, optionally substituted C6-C 14 Aryl, optionally substituted C3-C 13 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R''-SiR'3, where R'' is C1-C 10 Alkylene and R' are hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl; R 2 and R 6 Independently hydrogen, halogen, or optionally substituted C1-C 40 Alkyl, optionally substituted C6-C 14 Aryl, optionally substituted C3-C 13 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R''-SiR'3, where R'' is C1-C 10 Alkylene and R' are hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl; R 3 It is an optional substitution of C1-C 40 Alkyl or optionally substituted C6-C 18 Aryl; R 4 and R 5 Independently, it is H, R''', or OR''', where R''' is an optionally substituted C1-C 40 Alkyl, optionally substituted C6-C 14 Aryl, optionally substituted C3-C 13 heteroaryl, or R 4 and R 5 Connected to form C3-C 62 Substituted or unsubstituted, saturated or unsaturated cyclic or polycyclic structures, or combinations thereof; and R 7 R 8 R 9 and R 10 Independently hydrogen, halogen, or optionally substituted C1-C 40 Alkyl, optionally substituted C6-C 14 Aryl, optionally substituted C3-C 13 Heteroaryl, -NR'2, -SR', -OR', -SiR'3, -OSiR'3, -PR'2 or -R''-SiR'3, where R'' is C1-C 10 Alkylene and R' are hydrogen, C1-C 10 Alkyl or C6-C 10 Aryl, or R 5 and R 6 R 6 and R 7 or R 7 and R 8 One or more pairs are connected to form C3-C 62 A cyclic or polycyclic structure, or a combination thereof, that is substituted or unsubstituted, saturated or unsaturated.

16. The method of claim 15, wherein the group 4 metal is Hf or Zr; T is selected from CH2, CH2CH2, C(CH3)2, (Ph)2C, (p-(Et)3SiPh)2C, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, and Si(CH2)4; X 1 and X 2 It is independently a halogen or a C1-C6 hydrocarbon group; R 3 It is an optionally substituted phenyl, optionally substituted naphthyl, or optionally substituted anthraquinone; R 2 and R 6 It is hydrogen; and R 1 It is a methyl group.

17. The method of any of the preceding claims, wherein the first polymerization reaction conditions include a higher pressure than the second polymerization reaction conditions, and the second polymerization reaction conditions include a pressure of about 330 psi or lower.

18. The method of any of the preceding claims, wherein the impact copolymer comprises about 65% to about 95% by weight of the matrix polypropylene and about 5% to about 35% by weight of the copolymer phase, each based on the total mass of the impact copolymer.

19. The method of any of the preceding claims, wherein the copolymer phase comprises about 10% to about 90% ethylene and about 10% to about 90% propylene, each based on the total mass of the impact copolymer.

Images