Process for delivering non-aromatic solutions to polymerization reactors

Abstract

In some embodiments, the method includes introducing a catalyst solution into a reactor via a first pipeline. The catalyst solution includes a catalyst and a first non-aromatic diluent. The method includes introducing an activator solution into the reactor via a second pipeline. The activator solution includes an activator and a second non-aromatic diluent. The second non-aromatic diluent is the same as or different from the first non-aromatic diluent. The method includes operating the reactor under process conditions and obtaining an effluent from the reactor. The effluent includes a polyolefin. The first pipeline and the second pipeline are connected to the reactor.

Description

[0001] Inventor : Aaron H. Reed; Chase A. Eckert; Bradley T. Payne; Catherine A. Faler

[0002] CROSS-REFERENCE TO RELATED APPLICATIONS

[0003] This application claims the benefit of priority to USSN 63 / 063,596, filed August 10, 2020, which is incorporated herein by reference.

[0004] field

[0005] The present disclosure relates to methods of delivering non-aromatic solutions to polymerization reactors.

[0006] background

[0007] Supplying catalyst to polymerization reactor and achieving high catalyst efficiency while minimizing undesirable results is a challenge for many commercial processes. The problems encountered depend on the form of the catalyst (i.e., solid, size of particles, liquid, type of diluent, etc.) and the polymerization process used. The problems encountered may arise from catalyst degradation, poor control of catalyst feed rate, blocking of feed lines, poor mixing of catalyst with monomers and other polymerization media, introduction of undesirable amounts of supporting media into the process, poor solubility of the polymerization medium or supporting diluent, and problems with residual diluent in the product.

[0008] Homogeneous catalysts are used in solution polymerization methods. Many olefin polymerization methods are carried out in the presence of inert liquid organic diluents, and the polymers produced are dissolved in the inert organic diluents. In olefin solution polymerization, a solution of catalyst and activator is usually dissolved in a support medium (usually an aromatic solvent such as benzene, toluene, xylene or ethylbenzene) and is transferred to a polymerization reactor in the form of a solution. The catalyst solution is then mixed with monomers and other polymerization media and polymerization occurs in a liquid state. The support medium can be identical to the diluent used for polymerization, or different types of diluents with better solvency can be used.

[0009] Aliphatic hydrocarbon diluents are commonly used in solution polymerization of olefins. Relatively speaking, aromatic diluents are commonly used as supporting media due to the poor solubility of catalysts and activators in aliphatic hydrocarbon diluents. It is recognized that the use of aromatic diluents is advantageous because good solubility improves catalyst efficiency. However, the use of aromatic diluents can increase the additional requirements / costs of separating the diluent from the high molecular weight polymer product and recovering and recycling the diluent back to the polymerization reactor. Prolonged exposure of the catalyst to the supporting medium (e.g., hydrocarbon diluent) can lead to catalyst deactivation or cause process defects.

[0010] There is a need for polymerization processes in polymerization reactors while achieving high catalyst efficiencies.

[0011] Overview

[0012] The present disclosure relates to methods of delivering non-aromatic solutions to polymerization reactors.

[0013] In some embodiments, the method includes introducing a catalyst solution into a reactor via a first pipeline. The catalyst solution includes a catalyst and a first non-aromatic diluent. The method includes introducing an activator solution into the reactor via a second pipeline. The activator solution includes an activator and a second non-aromatic diluent. The second non-aromatic diluent is the same as or different from the first non-aromatic diluent. The method includes operating the reactor under process conditions and obtaining an effluent from the reactor. The effluent includes a polyolefin. The first pipeline and the second pipeline are connected to the reactor.

[0014] BRIEF DESCRIPTION OF THE DRAWINGS

[0015] In order to understand the above-mentioned features of the present disclosure in detail, a more specific description of the disclosure briefly summarized above can be obtained by reference to the embodiments. Certain aspects of some embodiments are illustrated in the accompanying drawings. However, it should be noted that the accompanying drawings only illustrate exemplary embodiments and are therefore not considered to be limiting, and other equally effective embodiments may be admitted.

[0016] Figure 1 is a schematic diagram of a solution polymerization facility according to an embodiment.

[0017] Figure 2A is the reactor setup of Experiment A according to an embodiment.

[0018] Figure 2B is the reactor setup of Experiment B according to an embodiment.

[0019] Figure 3 is a graph illustrating reactor temperature versus time according to an embodiment.

[0020] Figure 4 is a graph illustrating catalyst efficiency over time according to an embodiment.

[0021] To facilitate understanding, identical reference numerals have been used, where possible, to designate identical elements that are common to the figures. It is contemplated that elements and features of one embodiment may be beneficially incorporated in other embodiments without further recitation.

[0022] Details

[0023] definition

[0024] Unless otherwise indicated, all molecular weights are weight average (Mw). Unless otherwise indicated, all molecular weights are reported in g / mol. Melt index (MI, also known as I2) reported in g / 10 min is measured according to ASTM D-1238, 190°C, 2.16 kg load. High load melt index (HLMI, also known as I2) reported in g / 10 min is measured according to ASTM D-1238, 190°C, 2.16 kg load. 21 ) is measured according to ASTM D-1238, 190°C, 21.6 kg load. Melt Index Ratio (MIR) is the MI divided by the HLMI, measured according to ASTM D1238.

[0025] The specification describes a catalyst that may be a transition metal complex. The term complex is used to describe a molecule in which an auxiliary ligand is coordinated to a central transition metal atom. Transition metal complexes are usually activated using an activator to exert their polymerization function, which is believed to generate cations from the transition metal due to the removal of anionic groups (commonly referred to as leaving groups).

[0026] For purposes of this disclosure, the numbering scheme for the Periodic Table Groups is the "new" notation as described in Chemical and Engineering News, 63(5), p. 27 (1985). Thus, a "Group 8 metal" is an element from Group 8 of the Periodic Table such as Fe, etc.

[0027] The following abbreviations are used throughout the specification: Me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is n-propyl, Bu is butyl, iBu is isobutyl, tBu is tert-butyl, p-tBu is p-tert-butyl, nBu is n-butyl, sBu is sec-butyl, p-Me is p-methyl, Bn is benzyl (i.e., CH2Ph), RT is room temperature (and is 23°C unless otherwise indicated), tol is toluene, MeCy is methylcyclohexane, Cy is cyclohexyl, Ind is indenyl and Flu is fluorenyl.

[0028] Unless otherwise indicated (e.g., the definition of “substituted hydrocarbon”, etc.), the term “substituted” means that at least one hydrogen atom has been replaced by at least one non-hydrogen group, such as a hydrocarbon group, a heteroatom, or a 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, etc., wherein each R* is independently a hydrocarbon group or a halogenated hydrocarbon group, and two or more R* can be joined together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or wherein at least one heteroatom has been inserted into the ring structure.

[0029] The terms "hydrocarbyl radical," "hydrocarbyl," and "hydrocarbyl group" may be used interchangeably in this disclosure. Likewise, the terms "group," "radical," and "substituent" may also be used interchangeably in this disclosure. For the purposes of this disclosure, a "hydrocarbyl radical" is defined as a C1-C1 residue of carbon and hydrogen. 100 The term "radical" refers to a radical which may be linear, branched or cyclic and may be aromatic or non-aromatic when cyclic. Examples of such radicals may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc.

[0030] A substituted hydrocarbyl group is a group in which at least one hydrogen atom of the hydrocarbyl group has been replaced by a heteroatom, or a group containing a heteroatom, 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, etc., wherein each R* is independently a hydrocarbyl or a halogenated hydrocarbyl group, and two or more R* may be joined together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or wherein at least one heteroatom has been inserted into the hydrocarbyl ring.

[0031] A haloalkyl group (also referred to as a haloalkyl, a haloalkyl group, or a haloalkyl substituent) is a group in which one or more of the hydrocarbyl hydrogen atoms has been replaced by at least one halogen (also referred to as a "halo"), such as F, Cl, Br, I, or a halogen-containing group, such as CF3. A substituted haloalkyl group is a group in which at least one haloalkyl hydrogen or halogen atom has been replaced by 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, etc., or in which at least one non-carbon atom or group has been inserted into the haloalkyl group, such as --O--, --S--, --Se--, --Te--, --O--, --S--, --Se--, --Te--, --S ... --N(R*)--, =N--, ​​--P(R*)--, =P--, --As(R*)--, =As--, --Sb(R*)--, =Sb--, --B(R*)--, =B--, --Si(R*)2--, --Ge(R*)2--, --Sn(R*)2--, --Pb(R*)2--, etc., wherein R* is independently a hydrocarbon group or a halogenated hydrocarbon group, provided that at least one halogen atom remains on the original halogenated hydrocarbon group. In addition, two or more R* can be joined together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.

[0032] A hydrocarbylsilyl group (also referred to as a silylcarbyl group) (also referred to as a hydrocarbylsilyl group) is a group in which one or more hydrocarbyl hydrogen atoms have been substituted by at least one group containing SiR*3, or in which at least one -Si(R*)2- has been inserted into a hydrocarbyl group, wherein R* is independently a hydrocarbyl or a halogenated hydrocarbyl, and two or more R* may be joined together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure. A silylcarbyl group may be bonded via a silicon atom or a carbon atom.

[0033] Substituted silyl hydrocarbyl groups are silyl hydrocarbyl groups in which at least one hydrogen atom is replaced by at least one functional group such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, GeR*3, SnR*3, PbR3, etc., or in which at least one non-hydrogen atom or group such as --O--, --S--, --Se--, --Te--, --N(R*)--, =N--, --P(R*)--, etc. is replaced by at least one functional group such as NR*2, OR*, SeR*, TeR*, PR*2, AsR*2, SbR*2, SR*, BR*2, GeR*3, SnR*3, PbR3, etc. )--, =P--, --As(R*)--, =As--, --Sb(R*)--, =Sb--, --B(R*)--, =B--, --Ge(R*)2--, --Sn(R*)2--, --Pb(R*)2--, etc. have been inserted into the silyl hydrocarbon group, wherein R* is independently a hydrocarbon group or a halogenated hydrocarbon group, and two or more R* can be joined together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure.

[0034] The terms "alkyl group" and "alkyl" are used interchangeably in this disclosure. For the purposes of this disclosure, an "alkyl group" is defined as a C1-C 100 Alkyl, which may be linear, branched or cyclic. Examples of such groups may include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, octyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, etc. A substituted alkyl group is a group in which at least one hydrogen atom of the alkyl group has been replaced by at least one non-hydrogen group such as a hydrocarbon group, a heteroatom, or a group containing a heteroatom, 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, etc., wherein each R* is independently a hydrocarbon group or a halogenated hydrocarbon group, and two or more R* can be joined together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or wherein at least one heteroatom has been inserted into the hydrocarbon ring.

[0035] The term "branched alkyl" means that the alkyl group contains a tertiary or quaternary carbon (a tertiary carbon is a carbon atom bonded to three other carbon atoms). A quaternary carbon is a carbon atom bonded to four other carbon atoms. For example, 3,5,5 trimethylhexylphenyl is an alkyl group (hexyl) having three methyl branches (thus one tertiary carbon and one quaternary carbon) and is therefore a branched alkyl group bonded to a phenyl group. Unless otherwise indicated, a branched alkyl group includes all isomers thereof.

[0036] The term "alkenyl" means a straight, branched or cyclic hydrocarbon group having one or more carbon-carbon double bonds. These alkenyl groups may be substituted. Examples of suitable alkenyl groups may include vinyl, propenyl, allyl, 1,4-butadienyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cyclooctenyl, etc.

[0037] The term "aralkenyl" means an aryl group in which a hydrogen has been replaced by an alkenyl or substituted alkenyl group. For example, styrylindenyl is an indene substituted with an aralkenyl group (styryl group).

[0038] The term "alkoxy", "alkoxyl" or "alkoxide" means an alkyl ether or aryl ether group, wherein the terms "alkyl" and "aryl" are as defined herein. Examples of suitable alkyl ether groups may include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenoxy, and the like.

[0039] The term "aryl" or "aryl group" means an aromatic ring containing carbon, such as phenyl. Likewise, heteroaryl means an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced by a heteroatom, such as N, O or S. As used herein, the term "aromatic" also refers to pseudoaromatic heterocycles, which are heterocyclic substituents that have similar properties and structure (almost planar) to aromatic heterocyclic ligands, but are not aromatic by definition.

[0040] Heterocyclic means a cyclic group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced by a heteroatom such as N, O or S. A heterocyclic ring is a ring having heteroatoms in the ring structure, as opposed to a heteroatom-substituted ring in which hydrogens on the ring atoms are replaced by heteroatoms. For example, tetrahydrofuran is a heterocyclic ring and 4-N,N-dimethylamino-phenyl is a heteroatom-substituted ring.

[0041] 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 a group containing a heteroatom, 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, etc., wherein each R* is independently a hydrocarbon group or a halogenated hydrocarbon group.

[0042] Substituted aryl 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 a group containing a heteroatom, 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, etc., wherein each R* is independently a hydrocarbon group or a halogenated hydrocarbon group, and two or more R* can be joined together to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic ring structure, or wherein at least one heteroatom has been inserted into the hydrocarbon ring, for example 3,5-dimethylphenyl is a substituted phenyl.

[0043] The term "substituted phenyl" or "substituted phenyl group" means a phenyl group in which one or more hydrogen groups have been replaced by a hydrocarbon group, a substituted hydrocarbon group, a heteroatom or a 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, etc., wherein each R* is independently a hydrocarbon group, a halogen group or a halogenated hydrocarbon group. Preferably, the "substituted phenyl" group is represented by the following formula:

[0044]

[0045] Where R 17 , R 18 , R 19 , R 20 and R 21 Each of which is independently selected from hydrogen, C1-C 40 Hydrocarbon or C1-C 40 substituted hydrocarbon group, heteroatom such as halogen, or group containing heteroatom (provided that R 17 , R 18 , R 19 , R 20 and R 21 At least one of them is not H).

[0046] "Fluorophenyl" or "fluorophenyl group" is a phenyl group substituted with one, two, three, four or five fluorine atoms.

[0047] "Fluorinated aryl" or "fluoroaryl group" is an aryl group substituted with at least one fluorine atom, e.g., the aryl group is perfluorinated. The term "aralkyl" means an aryl group in which a hydrogen has been replaced by an alkyl or substituted alkyl group. For example, 3,5'-di-tert-butylphenylindenyl is an indene substituted with an aralkyl group. When an aralkyl group is a substituent on another group, it is bonded to the group through the aryl group. For example, in formula (AI), the aryl moiety is bonded to E.

[0048] The term "alkaryl" means an alkyl group in which a hydrogen has been replaced by an aryl or substituted aryl group. For example, phenethylindenyl is an indene substituted with an ethyl group bonded to a phenyl group. When an alkaryl group is a substituent on another group, it is bonded to that group through the alkyl group. For example, in formula (AI), the alkyl portion is bonded to E.

[0049] Unless otherwise stated, reference to an alkyl, alkenyl, alkoxy or aryl group (eg, butyl) without specifying a particular isomer specifically discloses all isomers (eg, n-butyl, isobutyl, sec-butyl and tert-butyl).

[0050] The term "ring atoms" means atoms that are part of a cyclic ring structure. Thus, benzyl has 6 ring atoms and tetrahydrofuran has 5 ring atoms.

[0051] For the purposes of this disclosure, a "catalyst system" is a combination of at least one catalyst compound, an activator, and an optional support material. The catalyst system may also include one or more additional catalyst compounds. For the purposes of this disclosure, when a catalyst system is described as comprising a neutral stable form of a component, it will be well understood by those of ordinary skill in the art that the ionic form of the component is the form that reacts with the monomer to produce a polymer. The catalysts of the disclosure represented by a chemical formula and the activators represented by a chemical formula are intended to include ionic forms in addition to the neutral form of the compound.

[0052] As used herein, "complex" is also often referred to as catalyst precursor, procatalyst, catalyst, catalyst compound, transition metal compound or transition metal complex. These terms can be used interchangeably.

[0053] Scavengers are compounds that are typically added to promote polymerization by removing impurities. Some scavengers can also serve as activators and can be referred to as co-activators. Co-activators (which are not scavengers) can also be used in conjunction with activators to form active catalysts. In some embodiments, co-activators can be premixed with transition metal compounds to form alkylated transition metal compounds.

[0054] In the description herein, catalysts may be described as catalyst precursors, procatalyst compounds, catalyst compounds, or transition metal compounds, and these terms may be used interchangeably. A polymerization catalyst system is a catalyst system that can polymerize monomers into polymers. An "anionic ligand" is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. A "neutral donor ligand" is an electrically neutral ligand that donates one or more pairs of electrons to a metal ion.

[0055] Metallocene catalysts are defined as organometallic compounds having at least one π-bonded cyclopentadienyl moiety or substituted cyclopentadienyl moiety (e.g. substituted or unsubstituted Cp, Ind or Flu) and more often two (or three) π-bonded cyclopentadienyl moieties or substituted cyclopentadienyl moieties (e.g. substituted or unsubstituted Cp, Ind or Flu). (Cp = cyclopentadienyl, Ind = indenyl, Flu = fluorenyl).

[0056] For the purposes of this disclosure, with respect to catalyst compounds, the term "substituted" means that a hydrogen group has been replaced with a hydrocarbyl group, a heteroatom, or a heteroatom-containing group. For example, methylcyclopentadiene (Cp) is a Cp group substituted with a methyl group.

[0057] Catalyst efficiency is the steady state average amount of polymer produced per average amount of metallocene / post-metallocene (metallocene only not the complete catalyst system of metallocene+activator+scavenger) used, on a weight basis. This definition is for steady state operation in a continuous polymerization reactor.

[0058]

[0059] Monomer conversion rate (f 单体 ) refers to the amount of monomer converted to polymer in the reactor (either on a mass or molar basis). More specifically, conversion can be in terms of ethylene conversion, propylene conversion, or any other α-olefin added to the reactor.

[0060]

[0061] The monomer conversion rate in a continuous reactor is related to the monomer concentration in the reactor at steady state. The higher the steady state monomer conversion rate, the lower the steady state monomer concentration in the reactor. The monomer conversion rate in a batch reactor is related to the degree of reaction in the batch reactor, where the monomer concentration in the batch reactor decreases over time as the monomer is converted to polymer.

[0062] For purposes herein, an "olefin" or "alkene" is a linear, branched or cyclic compound containing carbon and hydrogen having at least one double bond. For purposes of this specification and the appended claims, when a polymer or copolymer is referred to as containing an olefin, the olefin present in such a polymer or copolymer is the polymerized form of the olefin. For example, when a copolymer is said to have a "propylene" content of 35% to 55% by weight, it is understood that the monomer units in the copolymer are derived from propylene in the polymerization reaction, and the derived units are present at 35% to 55% by weight based on the weight of the copolymer.

[0063] For purposes herein, a "polymer" has two or more identical or different monomer ("mer") units. A "homopolymer" is a polymer having identical monomer units. A "copolymer" is a polymer having two or more monomer units that are different from each other. A "terpolymer" is a polymer having three monomer units that are different from each other. "Different" with respect to monomer units indicates that the monomer units differ from each other by at least one atom or are isomerically different. Thus, as used herein, copolymers may include terpolymers, etc. An "ethylene polymer" or "ethylene copolymer" is a polymer or copolymer comprising at least 50 mole % ethylene-derived units, a "propylene polymer" or "propylene copolymer" is a polymer or copolymer comprising at least 50 mole % propylene-derived units, and the like.

[0064] As used herein, Mn is the number average molecular weight, Mw is the weight average molecular weight, and Mz is the z average molecular weight, wt% is the weight percent and mol% is the mole percent. Molecular weight distribution (MWD), also known as polydispersity index (PDI), is defined as Mw divided by Mn.

[0065] The term "continuous" means a system that operates for a period of time without interruption or stopping, such as where reactants are continuously fed to a reaction zone and products are continuously or periodically withdrawn without stopping the reaction in the reaction zone. For example, a continuous process for making a polymer would be a process where reactants are continuously introduced into one or more reactors and polymer product is continuously withdrawn.

[0066] "Solution polymerization" means a polymerization process in which the polymerization is carried out in a liquid polymerization medium, such as an inert solvent or monomer(s) or a blend thereof. Solution polymerization is typically homogeneous. Homogeneous polymerization is a polymerization in which the polymer product is dissolved in the polymerization medium. Such systems are typically not turbid, as described in Oliveira, JV et al. (2000), "High-Pressure Phase Equilibria for Polypropylene-Hydrocarbon Systems," Ind. Eng. Chem. Res., Vol. 39, pp. 4627-4633.

[0067] Bulk polymerization refers to a polymerization process in which the monomers and / or comonomers being polymerized are used as solvents or diluents, with little or no use of inert solvents or diluents. A small portion of the inert solvent may be used as a carrier for the catalyst and scavenger. The bulk polymerization system contains less than about 25% by weight of an inert solvent or diluent, such as less than about 10% by weight, such as less than about 1% by weight, such as 0% by weight.

[0068] As used herein, "elastomer" or "elastomeric composition" refers to a polymer or composition of polymers (eg, blends of polymers) that conforms to the definition of ASTM D 1566. Elastomers include mixed blends of polymers, such as melt mixed and / or reactor blends of polymers.

[0069] As used herein, "plastomer" shall mean a polymer having a density of about 0.85 to 0.915 g / cm 3 Ethylene-based copolymers within the range of ASTM D 4703 Method B and ASTM D 1505. The plastomers described herein include copolymers of ethylene derived units and higher alpha-olefin derived units such as propylene, 1-butene, 1-hexene and 1-octene.

[0070] The present disclosure relates to a method for delivering a non-aromatic solution to a polymerization reactor. In some embodiments, the method includes introducing a catalyst solution into the reactor via a first pipeline. The catalyst solution includes a catalyst and a first non-aromatic diluent. The method includes introducing an activator solution into the reactor via a second pipeline. The activator solution includes an activator and a second non-aromatic diluent. The second non-aromatic diluent is the same as or different from the first non-aromatic diluent. The method includes operating the reactor under process conditions and obtaining an effluent from the reactor. The effluent includes a polyolefin. The first pipeline and the second pipeline are connected to the reactor.

[0071] It has been found that the activator of the present disclosure can be partially or completely dissolved in a non-aromatic diluent. However, it has also been found that premixing the activator and catalyst before introducing the activator and catalyst into the reactor results in poor reactor temperature control and inconsistency of the polymer products (and their polymer properties) obtained. It has been found that the independent direct injection of the activator in the non-aromatic solvent and the direct injection of the catalyst in the non-aromatic solvent into the reactor provides reduced or eliminated temperature variations during polymerization. Once in the reactor, the concentration of the activated catalyst complex produced is low enough to prevent precipitation. Surprisingly, although the direct injection of the catalyst and activator in the non-aromatic solvent provides a very dilute concentration of the catalyst and activator in the reactor before the activated catalyst, the catalyst efficiency is also maintained or improved (compared to the polymerization using the premixing of the catalyst and activator in toluene before the mixture / activated catalyst is injected into the reactor). Due to the reduced temperature variation of the method (compared to conventional polymerization methods), the method of the present disclosure can also provide uniform polymer properties in addition to the low aromatic content of the formed polymer.

[0072] Continuous solution polymerization facility

[0073] Figure 1 It is a facility for continuous solution polymerization. The polymerization feed enters the polymerization reactor (8) through a conduit (2), a refrigerator or cooler (6), and a centrifugal pump (3). The feed may contain: A) a diluent such as isohexane, B) a main monomer such as ethylene or propylene, and optionally C) a comonomer, which may be any suitable polymerizable α-olefin, and optionally D) a diene or other polyene or cyclic copolymerizable material. The feed passes through a refrigerator or cooler (6), where the feed is optionally cooled to a low temperature for subsequent polymerization in one or more continuous stirred tank reactors (8). In some embodiments, two or more continuous stirred tank reactors may be operated in series or in parallel (however, for simplicity, in Figure 1 Only one reactor is depicted).

[0074] An activator solution (7) is introduced into the reactor (one or more) (8), and a catalyst solution (5) is introduced into the reactor (one or more) (8). The activator solution includes an activator and a non-aromatic diluent. The catalyst solution includes a catalyst and a diluent (e.g., a non-aromatic diluent). The activator solution (7) and the catalyst solution (5) are introduced into the reactor (one or more) (8) independently without premixing the activator and the catalyst prior to introducing the activator and the catalyst into the reactor (one or more) (8). It has been found that the activators of the present disclosure can be partially or completely dissolved in the non-aromatic diluent. However, it has also been found that premixing the activator and the catalyst in the non-aromatic diluent prior to introducing the activator and the catalyst into the reactor results in poor reactor temperature control and inconsistency in the polymer products obtained (and their polymer properties). Without being bound by theory, it is believed that during premixing, the activator and the catalyst can form an active catalyst complex that is insoluble in the non-aromatic diluent at the concentration used for injection into the polymerization reactor. It has been found that independently injecting the activator in a non-aromatic diluent directly and the catalyst in a non-aromatic diluent directly into the reactor provides reduced or eliminated temperature variations during polymerization (e.g., provides consistent polymerization with a low temperature delta, as described in more detail below). Once in the reactor, the concentration of the activated catalyst complex produced is low enough to prevent precipitation. Surprisingly, although injecting the catalyst and activator directly before activating the catalyst provides very dilute concentrations of the catalyst and activator in the reactor, the catalyst efficiency is also maintained or improved (compared to polymerizations using premixing of the catalyst and activator in toluene before injecting the mixture / activated catalyst into the reactor). In other words, the catalyst and activator can easily form an activated catalyst even under very dilute conditions.

[0075] The concentration of the activator in the activator solution may be from about 0.01 wt % to about 20 wt %, such as from about 0.05 wt % to about 5 wt %, such as from about 0.1 wt % to about 1 wt %, such as from about 0.1 wt % to about 0.5 wt %, such as from about 0.15 wt % to about 0.3 wt %, such as about 0.2 wt %. The feed rate of the activator solution entering the reactor may be from about 0.01 kg / hr to about 40 kg / hr, such as from about 0.2 kg / hr to about 23 kg / hr. In some embodiments, the feed rate of the activator solution entering the reactor is from about 0.02 L / hr to about 60 L / hr, such as from about 0.28 L / hr to about 34 L / hr.

[0076] The concentration of the catalyst in the catalyst solution may be from about 0.01 wt % to about 20 wt %, for example, from about 0.01 wt % to about 5 wt %, for example, from about 0.01 wt % to about 1 wt %, for example, from about 0.02 wt % to about 0.25 wt %, for example, from about 0.05 wt % to about 0.1 wt %, for example, about 0.08 wt %. The feed rate of the catalyst solution entering the reactor may be from about 0.003 kg / hr to about 40 kg / hr, for example, from about 0.06 kg / hr to about 7 kg / hr. In some embodiments, the feed rate of the catalyst solution entering the reactor is from about 0.004 L / hr to about 60 L / hr, for example, from about 0.09 L / hr to about 10 L / hr.

[0077] A scavenger such as an aluminum alkyl, for example triisobutylaluminum or tri-n-octylaluminum, may be added via conduit (4) to minimize the effect of poisons in the feed and reactor on catalyst activity.

[0078] To supplement the molecular weight control provided by controlling the polymerization temperature, hydrogen may be added to one or both reactors (8) via a conduit (not shown).

[0079] The polymerization mixture containing the polymer exiting the reactor (8) via conduit (11) may first be treated with a catalyst killer such as water, sorbitan monooleate and / or methanol added at (10). In some embodiments, the catalyst killer may be introduced into the system as a molecular solution in isohexane diluent to terminate the polymerization reaction.

[0080] The heat exchanger (12) may be arranged as part of a heat integration arrangement and provides an initial increase in the temperature of the polymer-containing polymerization reactor effluent in the conduit (11) by heating the polymer-lean phase emerging from the upper layer (20) of the liquid phase separator (14). A trim heat exchanger (16), which may be heated by steam, hot oil or other high temperature fluid, also raises the temperature of the polymer-containing polymerization reactor effluent to a level suitable for liquid phase separation. The solution then passes through a pressure relief valve (18) wherein a pressure drop is created which causes the polymer-containing polymerization reactor effluent to separate into a polymer-lean phase (20) and a polymer-rich phase (22).

[0081] The density of the polymer-rich phase may be at least 40 kg / m higher than the density of the polymer-poor phase. 3 , or at least 50kg / m 3 , or at least 60kg / m 3, thus allowing the polymer-rich phase to settle by gravity in the liquid-liquid separator. The polymer-poor phase can have a residence time in the liquid-liquid separator of at least 5 minutes, or at least 10 minutes. The polymer-rich phase can have a residence time in the liquid-liquid separator of at least 10 minutes, or at least 15 minutes, or at least 20 minutes.

[0082] In some embodiments, the liquid-liquid separator can be designed to have a conical bottom to enhance the discharge of the polymer-rich phase. In some embodiments, the vessel wall of the liquid-liquid separator can be heated (e.g., by steam jacketing) to further enhance phase separation and reduce the viscosity of the boundary between the two phases.

[0083] Can detect the interface between the polymer-rich phase and the polymer-poor phase in the liquid-liquid separator by acoustic wave detector or by nuclear density meter.In the embodiment using nuclear density meter therein, can there be the radiation source array arranged in the inner side of the inner tube well, it extends parallel to the wall of separator, and the detector array arranged in the outer side of the container along the wall, it and the radiation source radial collinear.The radiation source can be partially shielded in such a way that as much radiation as possible is directed towards the detector paired with it.Described pairing can be horizontally aligned, but can also have staggered alignment so that the radiation source aiming position is above or below the detector it aims at.

[0084] After being cooled by the heat exchanger (12), the lean phase (20) can be further cooled by a cooling device (24) and passed through a buffer tank (26) suitable for stripping out pollutants such as hydrogen. Fresh monomer or comonomer can be added through a conduit (25) and used as a stripping vapor in the buffer tank (26). The cooled lean phase can enter a collector (41) and then pass through a conduit (43) and can enter a dryer (32). A fresh feed (30) of diluent and monomer can be added to the conduit (43) to provide the desired concentration for the polymerization reaction. The dryer (32) can be used to remove any unreacted methanol used as a catalyst deactivator or other pollutants present in the fresh feed supplied or any impurities in the recycled diluent and monomer. The recycled feed from the dryer (32) can then pass through the conduit (2) back to the polymerization reactor (8).

[0085] Vapor from the conduit at the top of the surge tank (26) can be sent to the reflux drum (39) of the column (36). The vapor can be processed to recover valuable components, such as monomers such as ethylene and propylene, through the fractionation column (36) and its overhead vapor compression / condensation system. The recovered components can be recycled to the inlet side of the dryer (32) through the conduit (43). Alternatively, the excess components (112) can be vented or burned.

[0086] Returning to the liquid phase separator (14), the concentrated polymer-rich phase (22) may enter a low pressure separator (34) where evaporated diluent and monomer are separated from the more concentrated polymer solution exiting the liquid phase separator (14).

[0087] The evaporated diluent and monomer phases may be passed in the vapor phase through conduit (35) to a purification / fractionation column (36) which may operate by distillation to separate the unreacted ethylene and propylene and light fractions of the highly volatile diluent from the heavier, less volatile components such as any toluene and hexane used to dissolve the catalyst or activator and unreacted diene-type comonomers.

[0088] A gear pump (38) can convey the concentrated polymer in the low pressure separator (34) to a vacuum devolatilization extruder or mixer (40), where the gas phase is again removed for purification, condensed, and then pumped to a purification column (50). The vacuum devolatilizer can be as described in PCT Publication WO 2011 / 087730. The heavy fraction of toluene used as a catalyst diluent and any used comonomer are recovered by this purification column (50). The recovered comonomer can be recycled through outlet (54), and in some embodiments excess comonomer can be stored in a separate storage container (55), (56). The recycled comonomer can then be reintroduced into the polymerization reactor via conduit (58).

[0089] The polymer melt exiting the vacuum devolatilizing extruder or mixer (40) can then be pelletized in an underwater pelletizer, fed with water cooled at (42), washed at (44) and spin dried to form pellets suitable for bagging or baling at (46).

[0090] The vapor from the devolatilizer (40) may be processed to recover and recycle the diluent. In some embodiments, the vapor may pass through a scrubber, a refrigerated heat exchanger and then through a series of compressors and pumps.

[0091] Some of the equipment parts described above may contain an outer sheath for heating or cooling the circulation of the fluid. The equipment may also contain a central axis or adjacent axes for conveying and / or stirring a polymer solution or polymer melt in the equipment. Metal projections may also be provided along the barrel wall, such as a breaker bar or other fixed elements that help to mix, convey and / or heat or cool the contents. In some embodiments, the equipment may have holes filled with pressurized nitrogen or other inert gases in the stationary and / or moving parts of the machine. Then, a pressure detector may be used to monitor the equipment, and a decrease in nitrogen pressure indicates damage or rupture in the equipment. Alternatively, a flow metering device may be used to monitor the flow of inert gases. In some embodiments, helium or other inert components that are not usually present in the device may be used to pressurize the holes in the stationary and / or moving parts of the machine. In such an embodiment, the concentration of helium may be measured by a helium analyzer in the stream leaving the equipment. The presence of helium in the stream will indicate damage or rupture of the machine.

[0092] Polymerization to produce polymers

[0093] Refer to Table 1 for further explanation Figure 1 Table 1 provides examples of polymerization processes for making (1) plastomers, (2) elastomers, such as ethylene-propylene-diene rubbers, and (3) propylene-based polymers.

[0094] Table 1 : Method conditions for facilities / methods in different operating modes

[0095]

[0096] Reference Figure 1and Table 1, the method described herein can be used to prepare plastomers. For example, the temperature of the feed introduced into the reactor (8) can be reduced to a temperature of 50°C to -15°C, such as about 0°C, by a refrigerator (6). The pressure of the feed can be raised to about 120 bar by a centrifugal pump (3). The feed containing most of the diluent and up to about 50 bar of ethylene and comonomers such as butene, hexene or octene is then introduced into the reactor (8) (or if two reactors are used, into the first of two series reactors). Catalysts and activators are added to the reactor (8) in an amount to produce a desired polymerization temperature, which in turn is related to the desired molecular weight. The heat of polymerization raises the temperature to about 130°C to 200°C, or about 150°C to about 200°C. Plastomers can be formed with or without the use of hydrogen. At the outlet of the reactor (or if two reactors are used in series, the second reactor), the polymer concentration can be 7% by weight to 22% by weight, or 15-22% by weight. Heat exchanger (12) may be used to initially raise the temperature, and then an additional heat exchanger (16) may cause a further temperature increase to within about 50°C of the critical temperature. When the polymerization mixture passes through the pressure relief valve (18) and enters the liquid phase separator (14), a rapid pressure drop occurs, with the pressure rapidly dropping from a pressure in the range of about 100-130 bar to a pressure in the range of about 30-45 bar. In some embodiments, the pressure difference between the outlet of the pump (3) and the outlet of the pressure relief valve (18) is the only reason that causes the feed and polymerization mixture to flow through the reactor (8) and conduit (11) including heat exchangers (12) and (16). An upper lean phase is formed inside the separator (14), having less than about 0.3% by weight polymer, or less than about 0.1% by weight polymer, and a lower polymer-rich phase having about 25 to 40% by weight polymer, or about 30% to 40% by weight polymer. Further removal of diluent and monomer from the polymer-rich phase may be performed in a low pressure separator (34) and an extruder / devolatilizer (40). Polymers containing less than 1 wt. %, preferably 0.3 wt. % or less, even more preferably less than 0.1 wt. % volatiles (including water) may be removed from the apparatus. Other general conditions for producing plastomers are described in WO 1997 / 22635 and WO 1999 / 45041.

[0097] Reference Figure 1With Table 1, the elastomers can be prepared using the methods described herein. As seen in Table 1, although the polymerization temperature for producing elastomers can be lower than the polymerization temperature for producing plastomers, and the polymer concentration coming out of the reactor can also be lower (however, the viscosity of the polymer concentration will be similar to that of plastomers), the separation method, catalyst injection method, and / or activator injection method are the same. Therefore, the feed introduced into the reactor can be at a temperature of about 50°C to about -15°C, such as about 0°C. The pressure of the feed can be increased to about 120 bar. The feed containing most of the diluent and up to about 50 bar of ethylene and comonomers such as propylene and optional diene partial pressures then enters the reactor (or if two reactors are used, the first of the two series reactors). The heat of polymerization raises the temperature to about 85°C to 150°C, or about 95°C to about 130°C.

[0098] The maximum fluctuation of temperature during polymerization (after the initial temperature rise when polymerization begins) is referred to herein as "temperature δ". In at least one embodiment, temperature δ is from about 0°C to about 20°C, such as from about 0°C to about 10°C, such as from about 0.5°C to about 5°C, such as from about 1°C to about 3°C. The temperature δ of the present disclosure is lower than the temperature δ of conventional methods. The method of the present disclosure provides a low temperature δ for a method using a non-aromatic solvent. In contrast, a method with a high temperature δ promotes inconsistent polymer properties of polymers formed during polymerization. Therefore, the method of the present disclosure can provide uniform polymer properties and low aromatic content of the formed polymer. For example, a polymer formed using the method of the present disclosure may have an aromatic content (e.g., toluene content) of 1% by weight or less, such as 0.5% by weight or less, such as 0.1% by weight or less, such as 0% by weight, based on the weight of the polymer (e.g., pelletized polymer).

[0099] At the outlet of the reactor (or the second reactor if two reactors are used in series), the polymer concentration may be 8 wt%-15 wt%, or 10-15 wt%. A heat exchanger (12) may be used to initially raise the temperature, and then an additional heat exchanger (16) may cause a further temperature increase to within 50°C of the critical temperature. When the polymerization mixture passes through the pressure relief valve (18) into the liquid phase separator (14), a rapid pressure drop occurs, with the pressure dropping rapidly from a pressure of about 100-130 bar to a pressure within 50 psig of the critical temperature, such as a pressure of about 30 to 45 bar. An upper lean phase is formed inside the separator (14), having less than about 0.3 wt% polymer, or less than about 0.1 wt% polymer, and a lower polymer-rich phase having about 20 to 40 wt% polymer, or about 30 wt% to 40 wt% polymer. The upper lean phase may have an aromatic diluent content of less than 1 wt%, such as less than 0.5 wt%, such as less than 0.1 wt%, such as less than 0.05 wt%, such as less than 0.01 wt%, such as 0 wt%, based on the weight of the upper lean phase. The lower polymer-rich phase may have an aromatic diluent content of less than 1 wt%, such as less than 0.5 wt%, such as less than 0.1 wt%, such as less than 0.05 wt%, such as less than 0.01 wt%, such as 0 wt%, based on the weight of the lower polymer-rich phase.

[0100] Polymers containing less than 1 wt. %, such as having 0.3 wt. % or less, such as less than 0.1 wt. %, of volatiles (including water) may be withdrawn from the facility. Other general conditions for producing elastomers using two reactors in series are described in WO99 / 45047. Typically, in a series reactor process the first reactor may be operated at a temperature of 0°C-110°C, or 10°C-90°C, or 20°C-79°C, and the second reactor may be operated at 40°C-140°C, or 50°C-120°C, or 60°C-110°C. The activator solution(s) and catalyst solution(s) as described herein may be used in one or more reactors in series or in parallel.

[0101] General conditions for producing propylene-based polymers are also described in WO 00 / 01745. Compared with the methods for producing plastomers and elastomers described in Table 1, the polymerization temperature can be reduced when producing propylene-based polymers. Therefore, the feed introduced into the reactor can be at a temperature of about 50°C to about -35°C, for example about 0°C. The pressure of the feed can be increased to about 120 bar. The feed containing most of the diluent and up to about 50 bar of propylene and comonomers such as ethylene and optional dienes then enters the reactor (or multiple reactors if two parallel reactors are used). The heat of polymerization increases the temperature to about 50°C to 80°C, or about 55°C to about 75°C. After this initial temperature increase, in at least one embodiment, the temperature δ is about 0°C to about 20°C, for example about 0°C to about 10°C, for example about 0.5°C to about 5°C, for example about 1°C to about 3°C. At the outlet of the reactor (or the second reactor if two reactors are used in series), the polymer concentration can be 5% by weight to 15% by weight, or 7% by weight to 12% by weight. Heat exchanger (12) may be used to initially raise the temperature, and then additional heat exchanger (16) may cause a further temperature increase to within 50°C of the critical temperature. When the polymerization mixture passes through pressure relief valve (18) into liquid phase separator (14), a rapid pressure drop occurs, from a pressure in the range of about 100-130 bar to a pressure within 50 psig of the critical temperature, such as a pressure in the range of about 30 to 45 bar. An upper lean phase is formed inside separator (14), having less than about 0.3 wt% polymer, or less than about 0.1 wt% polymer, and a lower polymer-rich phase having about 20 to about 40 wt% polymer, or about 30 wt% to about 40 wt% polymer. A polymer containing less than 1 wt%, such as 0.3 wt% or less, such as less than 0.1 wt% volatiles (including water) may be withdrawn from the facility.

[0102] The method of the present disclosure is described as being carried out as a solution polymerization. In some embodiments, the method of the present disclosure may be carried out as a gas phase polymerization or a slurry phase polymerization. For example, a catalyst solution and an activator solution may be introduced independently into a gas phase polymerization reactor or a slurry phase polymerization reactor. In such an embodiment, the catalyst solution includes a supported catalyst (a catalyst supported on a carrier such as silica, alumina, etc.). Due to the presence of the carrier, additional solvents and / or increased flow rates of the catalyst solution and / or activator solution may be used compared to a solution polymerization method. In such a method, after the initial polymerization temperature is increased, the temperature δ may be from about 0°C to about 20°C, for example, from about 0°C to about 10°C, for example, from about 0.5°C to about 5°C, for example, from about 1°C to about 3°C.

[0103] Gas Phase Polymerization

[0104] Typically, in a gas fluidized bed process for producing polymers, a gaseous stream containing one or more monomers is continuously circulated through a fluidized bed in the presence of a catalyst under reactive conditions. The gaseous stream is withdrawn from the fluidized bed and recycled back to the reactor. Simultaneously, polymer product is withdrawn from the reactor and fresh monomer is added to replace the polymerized monomer. (See, e.g., U.S. Pat. Nos. 4,543,399; 4,588,790; 5,028,670; 5,317,036; 5,352,749; 5,405,922; 5,436,304; 5,453,471; 5,462,999; 5,616,661 and 5,668,228, all of which are incorporated herein by reference in their entirety.

[0105] Slurry Phase Polymerization

[0106] Slurry polymerization processes are typically operated at pressures ranging from 1 to about 50 atmospheres (15 psi to 735 psi, 103 kPa to 5068 kPa) or even greater and at temperatures ranging from 0°C to about 120°C. In slurry polymerization, a suspension of solid particulate polymer is formed in a liquid polymerization diluent medium to which monomers and comonomers are added along with a catalyst. The suspension including the diluent is intermittently or continuously removed from the reactor, wherein the volatile components are separated from the polymer (optionally after distillation) and recycled to the reactor. The liquid diluent used in the polymerization medium is typically an alkane having 3-7 carbon atoms, such as a branched alkane. The medium employed should be liquid and relatively inert under polymerization conditions. When a propane medium is used, the process must be operated above the critical temperature and pressure of the reaction diluent. For example, a hexane or isobutane medium is employed.

[0107] In at least one embodiment, the polymerization process is a particle form polymerization, or a slurry process, in which the temperature is kept below the temperature at which the polymer enters the solution. Such techniques are well known in the art and are described in, for example, U.S. Pat. No. 3,248,179, which is fully incorporated herein by reference. The temperature in the particle form process may be from about 85°C to about 110°C. Two example polymerization processes for slurry processes are those using a loop reactor and those using a plurality of stirred reactors in series, in parallel, or a combination thereof. Non-limiting examples of slurry processes include continuous loop or stirred tank processes. In addition, other examples of slurry processes are described in U.S. Pat. No. 4,613,484, which is fully incorporated herein by reference.

[0108] In another embodiment, the slurry process is carried out continuously in a loop reactor. The catalyst (either as a slurry in isohexane or as a dry free-flowing powder) is regularly injected into a reactor loop which is itself filled with a circulating slurry of polymer particles grown in an isohexane diluent containing monomer and optional comonomer. Optionally, hydrogen may be added as a molecular weight control. (In one embodiment, 50 ppm to 500 ppm, e.g., 100 ppm to 400 ppm, e.g., 150 ppm to 300 ppm of hydrogen is added.)

[0109] The reactor can be maintained at a pressure of 2,000 kPa to 5,000 kPa, such as 3620 kPa-4309 kPa, and a temperature of about 60°C to about 120°C, depending on the desired polymer melt characteristics. Since most of the reactor is in the form of a double-jacketed tube, the heat of reaction is removed through the loop wall. The slurry is allowed to leave the reactor at regular intervals or continuously, in sequence to a heated low-pressure flash vessel, a rotary dryer, and a nitrogen purge column to remove the isohexane diluent and all unreacted monomers and comonomers. The resulting hydrocarbon-free powder is then compounded for various applications.

[0110] If desired, other additives may also be used in the polymerization, such as one or more scavengers, promoters, modifiers, chain transfer agents (eg, diethyl zinc), reducing agents, oxidizing agents, hydrogen, aluminum alkyls, or silanes.

[0111] Useful chain transfer agents are typically alkylaluminoxanes, compounds represented by the formula AlR3, ZnR2 (wherein each R is independently a C1-C8 hydrocarbon group, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl or isomers thereof). Examples may include diethylzinc, methylaluminoxane, trimethylaluminum, triisobutylaluminum, trioctylaluminum or combinations thereof.

[0112] catalyst

[0113] The catalyst compounds of the present disclosure may be stored in a storage tank by themselves or dissolved in a hydrocarbon diluent (s) such as an aliphatic hydrocarbon at a suitable concentration, i.e., a "catalyst solution". The catalyst solution may be measured using liquid measurement techniques including the use of a flow meter to measure the amount of catalyst solution added to or removed from the storage tank. Additionally or alternatively, a weight scale on the storage tank may be used to determine the amount of catalyst solution added to the reactor.

[0114] The catalyst can be diluted (e.g., dissolved) in a hydrocarbon diluent at a suitable concentration in a storage tank, a mixing tank, or an in-line mixer. Dissolution can be accomplished by determining the flow rate or weight of the catalyst and adding an appropriate amount of hydrocarbon diluent. Suitable hydrocarbon diluents include aliphatic and aromatic hydrocarbons. Although aromatic hydrocarbons are suitable diluents, their use can be reduced or eliminated because the production of polyolefins without aromatic hydrocarbons increases the value of the polymer and reduces the cost of polymer devolatilization. Suitable hydrocarbon diluents include non-coordinating inert liquids. Examples of diluents can include straight and branched hydrocarbons, such as 2-methyl-pentane, isobutane, butane, n-pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as commercially available (Isopar TM ); perhalogenated hydrocarbons, such as perfluorinated C4-C 10 Alkanes, chlorobenzenes, and aromatic compounds and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene and xylene. Suitable diluents can also include liquid olefins, which can serve as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene and their mixtures. In at least one embodiment, aliphatic hydrocarbon diluents such as isobutane, butane, n-pentane, isopentane, hexane, isohexane, heptane, octane, dodecane or their mixtures are used; and / or cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane or their mixtures. In another embodiment, the diluent is not aromatic, e.g., the aromatic compound is present in the diluent at less than 1 wt %, e.g., less than 0.5 wt %, e.g., less than 0.1 wt %, e.g., less than 0.05 wt %, e.g., less than 0.01 wt %, e.g., 0 wt %, based on the total weight of the diluent present.

[0115] The system of the present disclosure (e.g. Figure 1 The equipment) may include a storage tank suitable for storing the catalyst or catalyst solution ( Figure 1 In at least one embodiment, the catalyst storage tank is fluidly connected to the polymerization reactor (e.g., via catalyst solution line (5) and reactor (8)). In another embodiment, the catalyst storage tank is fluidly connected to a pump station (not shown), which is fluidly connected to the polymerization reactor (e.g., via catalyst solution line (5) and reactor (8)). It may be advantageous to allow dilution of the catalyst or catalyst solution to allow small amounts of catalyst to be accurately introduced into the polymerization reactor. Dilution may occur in a mixing vessel, an in-line mixer, a feed vessel, or by diluting the activator directly in the storage tank.

[0116] The methods of the present disclosure may use any catalyst system capable of polymerizing the monomers disclosed herein if the catalyst system is sufficiently active under the polymerization conditions disclosed herein. In some embodiments, the catalyst compound is a metallocene catalyst compound, which may be part of a catalyst system.

[0117] The catalyst system of the present disclosure can be formed as follows: combining the catalyst with an activator, including supporting the catalyst system for use in a slurry or gas phase polymerization. The catalyst system can also be added to or produced in a solution polymerization or bulk polymerization (in monomer, i.e., little or no solvent).

[0118] Transition metal compounds capable of catalyzing polymerization when activated using an activator as described above are suitable for use in the polymerization reactors of the present disclosure. Transition metal compounds known as metallocenes are exemplary catalyst compounds according to the present disclosure.

[0119] In at least one embodiment, the present disclosure provides a catalyst system including a catalyst compound with a metal atom. The catalyst compound may be a metallocene catalyst compound. The metal may be a metal atom from the 3rd to the 12th family, such as a metal atom from the 3rd to the 10th family or a lanthanide atom. The catalyst compound with a metal atom from the 3rd to the 12th family may be monodentate or polydentate, such as bidentate, tridentate or tetradentate, wherein the heteroatoms of the catalyst such as phosphorus, oxygen, nitrogen or sulfur are chelated to the metal atom of the catalyst. Non-limiting examples include bis(phenolates). In at least one embodiment, the metal atom from the 3rd to the 12th family is selected from the metal atom from the 5th family, the 6th family, the 8th family or the 10th family. In at least one embodiment, the metal atom from the 3rd to the 10th family is selected from Cr, Sc, Ti, Zr, Hf, V, Nb, Ta, Mn, Re, Fe, Ru, Os, Co, Rh, Ir and Ni. In at least one embodiment, the metal atom is selected from the metal atom from the 4th family, the 5th family and the 6th family. In at least one embodiment, the metal atom is a Group 4 metal atom selected from Ti, Zr or Hf. The oxidation state of the metal atom can be from 0 to +7, such as +1, +2, +3, +4, or +5, such as +2, +3, or +4.

[0120] Metallocene catalyst compounds

[0121] A "metallocene" catalyst compound is a transition metal catalyst compound having one, two or three, typically one or two, substituted or unsubstituted cyclopentadienyl ligands (e.g., substituted or unsubstituted Cp, Ind or Flu) bound to a transition metal. Metallocene catalyst compounds include metallocenes including Group 3 to Group 12 metal complexes, such as Group 4 to Group 6 metal complexes, such as Group 4 metal complexes. The metallocene catalyst compound of the catalyst system of the present disclosure may be an unbridged metallocene catalyst compound represented by the formula: Cp A Cp B M'X' n , where each Cp A and Cp B independently selected from cyclopentadienyl ligands (e.g., Cp, Ind or Flu) and ligands isolobal to cyclopentadienyl, one or two Cp A and Cp B It may contain heteroatoms and one or two Cp A and Cp B may be substituted with one or more R" groups; M' is selected from atoms of Groups 3 to 12 and lanthanide atoms; X' is an anion leaving group; n is 0 or an integer of 1-4; each R" is independently selected from alkyl, substituted alkyl, heteroalkyl, alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, aryloxy, alkylthio, arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocyclic, heteroaryl, heteroatom-containing groups, hydrocarbon, substituted hydrocarbon, heterohydrocarbon, silyl, boryl, phosphino, phosphine, amino, ether and thioether.

[0122] In at least one embodiment, each Cp A and Cp B independently selected from cyclopentadienyl, indenyl, fluorenyl, indacenyl, tetrahydroindenyl, cyclopentaphenanthryl, benzoindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthroindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopenta[a]acenaphthylenyl, 7-H-dibenzofluorenyl, indeno[1,2-9]anthrene, thienoindenyl, thienofluorenyl, hydrogenated and substituted versions thereof. Each Cp A and Cp B and may independently be indacenyl or tetrahydroindenyl.

[0123] The metallocene catalyst compound may be a bridged metallocene catalyst compound represented by the formula: Cp A(T)Cp B M'X' n , where each Cp A and Cp B independently selected from cyclopentadienyl ligands (e.g., Cp, Ind or Flu) and ligands isolobal to cyclopentadienyl, wherein one or two Cp A and Cp B It may contain heteroatoms and one or two Cp A and Cp B may be substituted with one or more R" groups; M' is selected from atoms of Groups 3 to 12 and lanthanide atoms, such as Group 4; X' is an anion leaving group; n is 0 or an integer of 1-4; (T) is selected from divalent alkyl, divalent substituted alkyl, divalent heteroalkyl, divalent alkenyl, divalent substituted alkenyl, divalent heteroalkenyl, divalent alkynyl, divalent substituted alkynyl, divalent heteroalkynyl, divalent alkoxy, divalent aryloxy, divalent alkylthio, divalent arylthio, divalent aryl, divalent substituted aryl, divalent heteroaryl, divalent aralkyl, divalent aralkylene, divalent alkaryl, divalent alkarylene, divalent haloalkyl, divalent haloalkenyl, divalent haloalkynyl, divalent heteroalkyl, divalent heterocycle, divalent heteroaryl, The bridging group of the present invention is a divalent heteroatom-containing group, a divalent hydrocarbon group, a divalent substituted hydrocarbon group, a divalent heterohydrocarbon group, a divalent silyl group, a divalent boryl group, a divalent phosphine group, a divalent phosphine group, a divalent amino group, a divalent ether, and a divalent thioether. R" is selected from the group consisting of alkyl, substituted alkyl, heteroalkyl, alkenyl, substituted alkenyl, heteroalkenyl, alkynyl, substituted alkynyl, heteroalkynyl, alkoxy, aryloxy, alkylthio, arylthio, aryl, substituted aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocycle, heteroaryl, heteroatom-containing group, hydrocarbon group, substituted hydrocarbon group, heterohydrocarbon group, silyl, boryl, phosphine group, phosphine, amino, germanium, ether, and thioether.

[0124] In at least one embodiment, Cp A and Cp B Each of Cp is independently selected from cyclopentadienyl, indenyl, fluorenyl, cyclopentaphenanthryl, benzoindenyl, fluorenyl, octahydrofluorenyl, cyclooctatetraenyl, cyclopentacyclododecene, phenanthroindenyl, 3,4-benzofluorenyl, 9-phenylfluorenyl, 8-H-cyclopenta[a]acenaphthene, 7-H-dibenzofluorenyl, indeno[1,2-9]anthracenyl, thienoindenyl, thienofluorenyl, hydrogenated and substituted versions thereof, such as cyclopentadienyl, n-propylcyclopentadienyl, indenyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl and n-butylcyclopentadienyl. Each Cp A and Cp B and may independently be indacenyl or tetrahydroindenyl.

[0125] (T) is a bridging group containing at least one element of Group 13, 14, 15 or 16 (particularly boron) or a Group 14, 15 or 16 element, for example, wherein (T) is O, S, NR' or SiR'2, wherein each R' is independently hydrogen or C1-C 20 Hydrocarbon.

[0126] In another embodiment, the metallocene catalyst compound is represented by the formula:

[0127] T y Cp m MG n X q

[0128] wherein Cp is independently a substituted or unsubstituted cyclopentadienyl ligand (e.g., substituted or unsubstituted Cp, Ind, or Flu) or a substituted or unsubstituted ligand isolobal to the cyclopentadienyl group; M is a Group 4 transition metal; and G is a ligand of the formula JR* z A heteroatom group represented by wherein J is N, P, O or S, and R* is a linear, branched or cyclic C1-C 20 a hydrocarbon group; z is 1 or 2; T is a bridging group; y is 0 or 1; X is a leaving group; m = 1, n = 1, 2 or 3, q ​​= 0, 1, 2 or 3, and the sum of m + n + q is equal to the coordination number of the transition metal.

[0129] In at least one embodiment, J is N, and R* is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, cyclooctyl, cyclododecyl, decyl, undecyl, dodecyl, adamantyl, or isomers thereof.

[0130] In at least one embodiment, the catalyst compound is represented by formula (II) or formula (III):

[0131]

[0132] Wherein in each of formula (II) and formula (III):

[0133] M is a metal center and is a Group 4 metal such as titanium, zirconium or hafnium, for example zirconium or hafnium when L1 and L2 are present and titanium when Z is present;

[0134] n is 0 or 1;

[0135] T is an optional bridging group, which, if present, is a bridging group containing at least one element of Group 13, 14, 15 or 16 (particularly boron) or a bridging group of Group 14, 15 or 16 (for example, wherein T is selected from dialkylsilyl, diarylsilyl, dialkylmethyl, ethylene (—CH2—CH2—) or alkylethylene, wherein one, two, three or four of the hydrogen atoms of the ethylene are replaced by alkyl groups, wherein the alkyl groups are independently C1-C 16 alkyl or phenyl, tolyl, xylyl, etc.), and when T is present, the catalyst represented may be in the racemic or meso form;

[0136] L1 and L2 are independently cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl, optionally substituted, each of which is bound to M, or L1 and L2 are independently cyclopentadienyl, indenyl, tetrahydroindenyl or fluorenyl, optionally substituted, wherein two adjacent substituents on L1 and L2 are optionally joined to form a substituted or unsubstituted saturated, partially unsaturated or aromatic cyclic or polycyclic substituent;

[0137] Z is nitrogen, oxygen, sulfur or phosphorus (e.g. nitrogen);

[0138] q is 1 or 2 (e.g., wherein q is 1 when Z is N);

[0139] R' is a cyclic, linear, or branched C1-C 40 an alkyl or substituted alkyl group;

[0140] X1 and X2 are independently hydrogen, halogen, a hydride group, a hydrocarbon group, a substituted hydrocarbon group, a halogenated hydrocarbon group, a substituted halogenated hydrocarbon group, a silyl hydrocarbon group, a substituted silyl hydrocarbon group, a germyl hydrocarbon group or a substituted germyl hydrocarbon group; or X1 and X2 are joined or combined with a metal atom to form a metal ring containing about 3 to about 20 carbon atoms; or the two together can be an olefin, a diene or an arylacene ligand.

[0141] In some embodiments, T is present and is a bridging group containing at least one element of Group 13, 14, 15 or 16 of the Periodic Table, particularly Group 14. Examples of suitable bridging groups include P(=S)R', P(=Se)R', P(=O)R', 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, R' 2SiOSiR'2, R'2CSiR'2CR'2, R'2SiCR'2SiR'2, R'C=CR'SiR'2, R'2CGeR'2, R'2GeGeR'2, R'2CGeR'2CR'2, R'2Ge CR'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'2C–Se–CR'2CR'2, R'2C–Se–CR'=CR', R'2C–N=CR', R'2C–NR'–C R'2, R'2C–NR'–CR'2CR'2, R'2C–NR'–CR'=CR', R'2CR'2C–NR'–CR'2CR'2, R'2C–P=CR', R'2C–PR'–CR'2, O, S, Se, Te, NR', PR', AsR', SbR', OO, SS, R'N-NR', R'P-PR', OS, O-NR', O-PR', S-NR', S-PR' and R'N-PR', where R' is hydrogen or contains C1-C 20The hydrocarbon, substituted hydrocarbon, halogenated hydrocarbon, substituted halogenated hydrocarbon, silyl hydrocarbon or germyl hydrocarbon substituent and optionally two or more adjacent R' can be joined to form a substituted or unsubstituted, saturated, partially unsaturated or aromatic, cyclic or polycyclic substituent. Examples of bridging groups T include CH2, CH2CH2, SiMe2, SiPh2, SiMePh, Si(CH2)3, Si(CH2)4, O, S, NPh, PPh, NMe, PMe, NEt, NPr, NBu, PEt, PPr, Me2SiOSiMe2 and PBu.

[0142] In some embodiments of the formulae of the present disclosure, T is represented by the formula R a 2J or (R a 2J)2, where J is C, Si or Ge, and each R a are independently hydrogen, halogen, C1-C 20 A hydrocarbon group (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl) or a C1-C 20 substituted hydrocarbon group, and both R a Cyclic structures can be formed, including aromatic, partially saturated or saturated cyclic or fused ring systems. In some embodiments, T is a bridging group including carbon or silicon (silica), such as a dialkylsilyl group, for example, wherein T is selected from CH2, CH2CH2, C(CH3)2, SiMe2, SiPh2, SiMePh, silylcyclobutyl (Si(CH2)3), (Ph)2C, (p-(Et)3SiPh)2C, Me2SiOSiMe2 and cyclopentasilylene (Si(CH2)4).

[0143] In at least one embodiment, the catalyst compound has a symmetry of C2 symmetry.

[0144] Suitable metallocenes include, but are not limited to, those disclosed and referred to in the above-referenced U.S. patents and those disclosed and referred to in U.S. Patent Nos. 7,179,876; 7,169,864; 7,157,531; 7,129,302; 6,995,109; 6,958,306; 6,884,748; 6,689,847, U.S. Patent Publication No. 2007 / 0055028 and published PCT applications WO 97 / 22635; WO 00 / 699 / 22; WO 01 / 30860; WO 01 / 30861; WO 02 / 46246; WO 02 / 50088; WO 04 / 026921 and WO 06 / 019494, all of which are incorporated by reference. Additional suitable catalysts include those mentioned in U.S. Pat. Nos. 6,309,997; 6,265,338; U.S. Patent Publication No. 2006 / 019925 and the following articles: Resconi, L. et al. (2000) "Selectivity in Propene Polymerization with Metallocene Catalysts," Chem. Rev., Vol. 100(4), pp. 1253-1346; Gibson, VC et al. (2003) "Advances in Non-Metallocene Olefin Polymerization Catalysis," Chem. Rev., Vol. 103(1), pp. 283-316; Nakayama, Y. et al. (2006) "MgCl2 / R' n Al(OR) 3-n:An Excellent Activator / Support for Transition-Metal Complexes for Olefin Polymerization,” Chem.Eur.J., Volume 12, Pages 7546-7556; Nakayama, Y et al. (2004), “Olefin PolymerizationBehavior of bis(phenoxy-imine)Zr, Ti, and V complexes with MgCl2-basedCocatalysts,” J.Mol.Catalysis A:Chemical, Volume 213, Pages 141-150; Nakayama, Y. et al. (2005), Propylene Polymerization Behavior of Fluorinated Bis(phenoxy-imine)TiComplexes with an MgCl2-Based Compound(MgCl2-Supported Ti-Based Catalysts)," Macromol. Chem. Phys., Vol. 206(18), pp. 1847-1852; and Matsui, S. et al. (2001) "A Family of Zirconium Complexes Having Two Phenoxy-Imine Chelate Ligands for Olefin Polymerization," J. Am. Chem. Soc., Vol. 123(28), pp. 6847-6856.

[0145] Exemplary metallocene compounds include:

[0146] Bis(cyclopentadienyl)zirconium dichloride,

[0147] Bis(n-butylcyclopentadienyl)zirconium dichloride,

[0148] Bis(n-butylcyclopentadienyl)zirconium dimethyl,

[0149] Bis(pentamethylcyclopentadienyl)zirconium dichloride,

[0150] Bis(pentamethylcyclopentadienyl)zirconium dimethyl,

[0151] Bis(pentamethylcyclopentadienyl)hafnium dichloride,

[0152] Bis(pentamethylcyclopentadienyl)zirconium dimethyl,

[0153] Bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride,

[0154] Bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,

[0155] Bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride,

[0156] Bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,

[0157] Bis(indenyl)zirconium dichloride,

[0158] Bis(indenyl)zirconium dimethyl,

[0159] Bis(tetrahydro-1-indenyl)zirconium dichloride,

[0160] Bis(tetrahydro-1-indenyl)zirconium dimethyl,

[0161] (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)zirconium dichloride, and

[0162] (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)zirconium dimethyl.

[0163] In at least one embodiment, the catalyst compound may be selected from:

[0164] Dimethylsilylbis(tetrahydroindenyl)MX n ,

[0165] Dimethylsilylbis(2-methylindenyl)MX n ,

[0166] Dimethylsilylbis(2-methylfluorenyl)MX n ,

[0167] Dimethylsilylbis(2-methyl-5,7-propylindenyl)MX n ,

[0168] Dimethylsilylbis(2-methyl-4-phenylindenyl)MX n ,

[0169] Dimethylsilylbis(2-ethyl-5-phenylindenyl)MX n ,

[0170] Dimethylsilylbis(2-methyl-4-biphenylindenyl)MX n ,

[0171] Dimethylsilylenebis(2-methyl-4-carbazolylindenyl)MX n ,

[0172] MX n ,

[0173] Diphenylmethylene(cyclopentadienyl)(fluorenyl)MX n ,

[0174] Bis(methylcyclopentadienyl)MX n ,

[0175] MX n ,

[0176] Dimethylsilylbis(indenyl)MX n ,

[0177] rac-meso-diphenylsilyl-bis(n-propylcyclopentadienyl)MX n ,

[0178] 1,1'-Bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tert-butyl-1-fluorenyl)MX n (the bridge is considered as 1 position),

[0179] Bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(di-tert-butylfluorenyl)MXn,

[0180] Bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(fluorenyl)MXn,

[0181] Bisphenylmethylene (cyclopentadienyl) (dimethylfluorenyl) MXn,

[0182] Bis(n-propylcyclopentadienyl)MX n ,

[0183] Bis(n-butylcyclopentadienyl)MX n ,

[0184] Bis(n-pentylcyclopentadienyl)MX n ,

[0185] (n-propylcyclopentadienyl)(n-butylcyclopentadienyl)MX n ,

[0186] Bis[(2-trimethylsilylethyl)cyclopentadienyl]MX n ,

[0187] Bis(trimethylsilylcyclopentadienyl)MX n ,

[0188] Dimethylsilylbis(n-propylcyclopentadienyl)MX n ,

[0189] Dimethylsilylbis(n-butylcyclopentadienyl)MX n ,

[0190] Bis(1-n-propyl-2-methylcyclopentadienyl)MX n ,

[0191] (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)MX n ,

[0192] Bis(1-methyl,3-n-butylcyclopentadienyl)MX n ,

[0193] Bis(indenyl)MX n ,

[0194] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)MX n ,

[0195] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)MX n ,

[0196] μ-(CH3)2Si(cyclopentadienyl)(1-adamantylamino)MX n ,

[0197] μ-(CH3)2Si(3-tert-butylcyclopentadienyl)(1-adamantylamino)MX n ,

[0198] μ-(CH3)2(Tetramethylcyclopentadienyl)(1-adamantylamino)MX n ,

[0199] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-adamantylamino)MX n ,

[0200] μ-(CH3)2C(Tetramethylcyclopentadienyl)(1-adamantylamino)MX n ,

[0201] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-tert-butylamino)MX n ,

[0202] μ-(CH3)2Si(fluorenyl)(1-tert-butylamino)MX n ,

[0203] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-cyclododecylamino)MX n ,

[0204] μ-(C6H5)2C(Tetramethylcyclopentadienyl)(1-cyclododecylamino)MX n ,

[0205] μ-(CH3)2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tert-butylamino)MX n ,

[0206] Wherein M is selected from Ti, Zr and Hf; Wherein X is selected from the following: halogen, hydrogen, C 1-12 Alkyl, C 2-12 Alkenyl, C 6-12 Aryl, C 7-20 Alkyl aryl, C 1-12 Alkoxy, C 6-16 Aryloxy, C 7-18 Alkyl aryloxy, C 1-12 Fluoroalkyl, C 6-12 Fluoroaryl and C 1-12 Heteroatom-containing hydrocarbons, their substituted derivatives and combinations thereof, and wherein n is zero or an integer from 1 to 4, for example, wherein X is selected from halogen (e.g., bromo, fluoro, chloro) or C1-C 20 Alkyl (eg, methyl, ethyl, propyl, butyl, and pentyl) and n is 1 or 2.

[0207] In other embodiments, the catalyst is one or more of the following:

[0208] Bis(1-methyl, 3-n-butylcyclopentadienyl)M(R)2,

[0209] Dimethylsilylbis(indenyl)M(R)2,

[0210] Bis(indenyl)M(R)2,

[0211] Dimethylsilylbis(tetrahydroindenyl)M(R)2,

[0212] Bis(n-propylcyclopentadienyl)M(R)2,

[0213] Dimethylsilyl (tetramethylcyclopentadienyl) (cyclododecylamino) M (R) 2,

[0214] Dimethylsilyl (tetramethylcyclopentadienyl) (cyclododecylamino) M (R) 2,

[0215] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)M(R)2,

[0216] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)M(R)2,

[0217] μ-(CH3)2Si(cyclopentadienyl)(1-adamantylamino)M(R)2,

[0218] μ-(CH3)2Si(3-tert-butylcyclopentadienyl)(1-adamantylamino)M(R)2,

[0219] μ-(CH3)2(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2,

[0220] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2,

[0221] μ-(CH3)2C(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2,

[0222] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-tert-butylamino)M(R)2,

[0223] μ-(CH3)2Si(fluorenyl)(1-tert-butylamino)M(R)2,

[0224] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2,

[0225] μ-(C6H5)2C(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2,

[0226] μ-(CH3)2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tert-butylamino)M(R)2,

[0227] wherein M is selected from Ti, Zr and Hf; and R is selected from halogen or C1-C5 alkyl.

[0228] In at least one embodiment, the catalyst compound is one or more of the following:

[0229] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)dimethyltitanium,

[0230] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)dimethyltitanium,

[0231] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)dimethyltitanium,

[0232] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)dimethyltitanium,

[0233] μ-(CH3)2Si(cyclopentadienyl)(1-adamantylamino)dimethyltitanium,

[0234] μ-(CH3)2Si(3-tert-butylcyclopentadienyl)(1-adamantylamino)dimethyltitanium,

[0235] μ-(CH3)2(tetramethylcyclopentadienyl)(1-adamantylamino)dimethyltitanium,

[0236] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-adamantylamino)dimethyltitanium,

[0237] μ-(CH3)2C(tetramethylcyclopentadienyl)(1-adamantylamino)dimethyltitanium,

[0238] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-tert-butylamino)dimethyltitanium,

[0239] μ-(CH3)2Si(fluorenyl)(1-tert-butylamino)dimethyltitanium,

[0240] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-cyclododecylamino)dimethyltitanium,

[0241] μ-(C6H5)2C(tetramethylcyclopentadienyl)(1-cyclododecylamino)dimethyltitanium, and / or

[0242] μ-(CH3)2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tert-butylamino)dimethyltitanium.

[0243] In at least one embodiment, the catalyst is rac-dimethylsilyl-bis(indenyl)hafnium dimethyl and / or 1,1'-bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tert-butyl-1-fluorenyl)hafnium dimethyl.

[0244] In at least one embodiment, the catalyst compound is one or more of the following:

[0245] Bis(1-methyl,3-n-butylcyclopentadienyl)hafnium dimethyl,

[0246] Bis(1-methyl,3-n-butylcyclopentadienyl)zirconium dimethyl,

[0247] Dimethylsilylbis(indenyl)zirconium dimethyl,

[0248] Dimethylsilylbis(indenyl)hafnium dimethyl,

[0249] Bis(indenyl)zirconium dimethyl,

[0250] Bis(indenyl)dimethylhafnium,

[0251] Dimethylsilylbis(tetrahydroindenyl)zirconium dimethyl,

[0252] Bis(n-propylcyclopentadienyl)zirconium dimethyl,

[0253] Dimethylsilylbis(tetrahydroindenyl)hafnium dimethyl,

[0254] Dimethylsilylbis(2-methylindenyl)zirconium dimethyl,

[0255] Dimethylsilylbis(2-methylfluorenyl)zirconium dimethyl,

[0256] Dimethylsilylbis(2-methylindenyl)hafnium dimethyl,

[0257] Dimethylsilylbis(2-methylfluorenyl)hafnium dimethyl,

[0258] Dimethylsilylbis(2-methyl-5,7-propylindenyl)zirconium dimethyl,

[0259] Dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl,

[0260] Dimethylsilylbis(2-ethyl-5-phenylindenyl)zirconium dimethyl,

[0261] Dimethylsilylbis(2-methyl-4-biphenylindenyl)zirconium dimethyl,

[0262] Dimethylsilylene bis(2-methyl-4-carbazolylindenyl)zirconium dimethyl,

[0263] Racemic-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benzo(f)indene)dimethylhafnium,

[0264] Hafnium diphenylmethylene (cyclopentadienyl)(fluorenyl) dimethyl,

[0265] Bis(methylcyclopentadienyl)zirconium dimethyl,

[0266] Racemic-dimethylsilylbis(2-methyl,3-propylindenyl)dimethylhafnium,

[0267] Dimethylsilylbis(indenyl)hafnium dimethyl,

[0268] Dimethylsilylbis(indenyl)zirconium dimethyl,

[0269] Dimethyl racemic-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benzo(f)indene)dimethylhafnium,

[0270] rac-meso-diphenylsilyl-bis(n-propylcyclopentadienyl)dimethylhafnium,

[0271] 1,1'-Bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tert-butyl-1-fluorenyl)hafnium X n (the bridge is considered as 1 position),

[0272] Bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(di-tert-butylfluorenyl)dimethylhafnium,

[0273] Bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(fluorenyl)dimethylhafnium,

[0274] Bisphenylmethylene(cyclopentadienyl)(dimethylfluorenyl)hafnium dimethyl,

[0275] Bis(n-propylcyclopentadienyl)hafnium dimethyl,

[0276] Bis(n-butylcyclopentadienyl)hafnium dimethyl,

[0277] Bis(n-pentylcyclopentadienyl)hafnium dimethyl,

[0278] (n-propylcyclopentadienyl)(n-butylcyclopentadienyl)hafnium dimethyl,

[0279] Bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium dimethyl,

[0280] Bis(trimethylsilylcyclopentadienyl)hafnium dimethyl,

[0281] Dimethylsilylbis(n-propylcyclopentadienyl)hafnium dimethyl,

[0282] Dimethylsilylbis(n-butylcyclopentadienyl)hafnium dimethyl,

[0283] Bis(1-n-propyl-2-methylcyclopentadienyl)hafnium dimethyl,

[0284] (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium dimethyl,

[0285] Bis(n-propylcyclopentadienyl)hafnium dimethyl,

[0286] Bis(n-butylcyclopentadienyl)hafnium dimethyl,

[0287] Bis(n-pentylcyclopentadienyl)hafnium dimethyl,

[0288] (n-propylcyclopentadienyl)(n-butylcyclopentadienyl)hafnium dimethyl,

[0289] Bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium dimethyl,

[0290] Bis(trimethylsilylcyclopentadienyl)hafnium dimethyl,

[0291] Dimethylsilylbis(n-propylcyclopentadienyl)hafnium dimethyl,

[0292] Dimethylsilylbis(n-butylcyclopentadienyl)hafnium dimethyl,

[0293] Bis(1-n-propyl-2-methylcyclopentadienyl)hafnium dimethyl,

[0294] (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium dimethyl, and

[0295] Dimethylsilyl(3-n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dimethyl.

[0296] Non-metallocene catalyst compounds

[0297] The transition metal complex used in the polymerization process may include an olefin polymerization catalyst. Suitable catalyst components may include "non-metallocene complexes," which are defined as transition metal complexes that are not characterized by a cyclopentadienyl anion or a substituted cyclopentadienyl anion donor (e.g., cyclopentadienyl, fluorenyl, indenyl, methylcyclopentadienyl). Examples of suitable non-metallocene complex families may include late transition metal pyridylbisimines (e.g., US 7,087,686), Group 4 pyridyldiaminos (e.g., US 7,973,116), quinolyldiaminos (e.g., US Publication No. 2018 / 0002352A1), pyridylaminos (e.g., US 7,087,690), phenoxyimines (e.g., Accounts of Chemical Research 2009, 42, 1532-1544), and bridged biaromatic complexes (e.g., US 7,091,292), the disclosures of which are incorporated by reference.

[0298] Catalyst complexes suitable for use in combination with an activator include: pyridyl diamino complexes; quinolyl diamino complexes; phenoxyimine complexes; bisphenolate complexes; cyclopentadienyl-amidinate complexes; and pyridyl bis(imine) iron complexes or combinations thereof, including any suitable combination with a metallocene complex.

[0299] The term "pyridyl diamino complex", "pyridyl diamine complex" or "pyridyl diamino catalyst" or "pyridyl diamine catalyst" refers to a class of coordination complexes described in U.S. Pat. Nos. 7,973,116 B2, US 2012 / 0071616 A1, US 2011 / 0224391 A1, US 2011 / 0301310 A1, US 2015 / 0141601 A1, US 6,900,321 and US 8,592,615, characterized by a dianionic tridentate ligand coordinated to a metal center via a neutral Lewis basic donor atom (e.g., a pyridine group) and a pair of anionic amino or phosphino (i.e., deprotonated amine or phosphine) donors. In these complexes, the pyridyl diamino ligand is coordinated to the metal to form a five-membered chelate ring and a seven-membered chelate ring. Additional atoms of the pyridyl diamino ligand may be coordinated to the metal without interfering with the catalyst function upon activation; an example of such a combination would be a cyclometalated substituted aryl group forming an additional bond to the metal center.

[0300] The term "quinolinyl diamino complex" or "quinolinyl diamino catalyst" or "quinolinyl diamine complex" or "quinolinyl diamine catalyst" refers to the related class of pyridyl diamino complexes / catalysts described in US 2018 / 0002352, in which a quinolinyl moiety is present in place of the pyridyl moiety.

[0301] The term "phenoxyimine complex" or "phenoxyimine catalyst" refers to a class of coordination complexes described in EP 0874 005, characterized by a monoanionic bidentate ligand coordinated to a metal center via a neutral Lewis basic donor atom (e.g., an imine moiety) and an anionic aryloxy (i.e., deprotonated phenoxy) donor. Typically, two of these bidentate phenoxyimine ligands coordinate to a Group 4 metal to form a complex useful as a catalyst component.

[0302] The term "bisphenolate complex" or "bisphenolate catalyst" refers to a class of coordination complexes described in US 6,841,502, WO 2017 / 004462 and WO 2006 / 020624, characterized by a di-anionic tetradentate ligand coordinated to a metal center via two neutral Lewis basic donor atoms (e.g., oxygen bridging moieties) and two anionic aryloxy (i.e., deprotonated phenoxy) donors.

[0303] The term "cyclopentadienyl-amidinate complex" or "cyclopentadienyl-amidinate catalyst" refers to a class of coordination complexes described in US Pat. No. 8,188,200 that generally feature a Group 4 metal in combination with a cyclopentadienyl anion, a bidentate amidinate anion, and several other anionic groups.

[0304] The term "pyridylbis(imine)iron complexes" refers to a class of iron coordination complexes described in US 7,087,686, which generally feature an iron metal center coordinated to a neutral tridentate pyridylbis(imine) ligand and two other anionic ligands.

[0305] The non-metallocene complexes may include iron complexes of tridentate pyridyldiimine ligands, zirconium and hafnium complexes of pyridylamino ligands, zirconium and hafnium complexes of tridentate pyridyldiamino ligands, zirconium and hafnium complexes of tridentate quinolinyldiamino ligands, zirconium and hafnium complexes of bidentate phenoxyimine ligands, and zirconium and hafnium complexes of bridged biaromatic ligands.

[0306] Suitable non-metallocene complexes may include zirconium and hafnium non-metallocene complexes. In at least one embodiment, the non-metallocene complexes of the present disclosure include Group 4 non-metallocene complexes including two anionic donor atoms and one or two neutral donor atoms. Suitable non-metallocene complexes of the present disclosure include Group 4 non-metallocene complexes including anionic amino donors. Suitable non-metallocene complexes of the present disclosure include Group 4 non-metallocene complexes including anionic aryloxy donor atoms. Suitable non-metallocene complexes of the present disclosure include Group 4 non-metallocene complexes including two anionic aryloxy donor atoms and two additional neutral donor atoms.

[0307] The catalyst compound may be a quinolyl diamino (QDA) transition metal complex represented by formula (BI), such as by formula (BII), such as by formula (BIII):

[0308]

[0309] in:

[0310] M is a Group 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 metal, such as a Group 4 metal;

[0311] J is a group including a three-atom-long bridge between the quinoline and amino nitrogen, such as a group containing up to 50 non-hydrogen atoms;

[0312] E is carbon, silicon or germanium;

[0313] X is an anionic leaving group (e.g., a hydrocarbyl group or a halogen);

[0314] L is a neutral Lewis base;

[0315] R 1 and R 13 independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, and silyl groups;

[0316] R 2 , R 3, R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 10’ , R 11 , R 11’ , R 12 and R 14 are independently hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyl, halo or phosphino;

[0317] n is 1 or 2;

[0318] m is 0, 1, or 2, where

[0319] n+m is not greater than 4; and

[0320] Two R groups (e.g. R 1 and R 2 , R 2 and R 3 , R 10 and R 11 etc.) can be joined to form substituted hydrocarbon groups, unsubstituted hydrocarbon groups, substituted heterocyclic groups or unsubstituted heterocyclic groups, saturated or unsaturated rings, wherein the rings have 5, 6, 7 or 8 ring atoms, and wherein the substituents on the rings can be joined to form additional rings;

[0321] Two X groups can be joined together to form a dianionic group;

[0322] Two L groups can be joined together to form a bidentate Lewis base; and

[0323] The X group may be joined to the L group to form a monoanionic bidentate group.

[0324] In at least one embodiment, M is a Group 4 metal, such as zirconium or hafnium, for example, M is hafnium.

[0325] Representative non-metallocene transition metal compounds that can be used to form the poly(α-olefins) of the present disclosure also include tetrabenzylzirconium, tetrakis(trimethylsilylmethyl)zirconium, oxotris(trimethlsilylmethyl)vanadium, tetrabenzylhafnium, tetrabenzyltitanium, bis(hexamethyl disilazido)dimethyl titanium, tris(trimethylsilylmethyl)niobium dichloride, and tris(trimethylsilylmethyl)tantalum dichloride.

[0326] In at least one embodiment, J is an aromatic substituted or unsubstituted hydrocarbon group having 3 to 30 non-hydrogen atoms, for example, J is represented by the following formula:

[0327] For example, J is

[0328] Where R 7 , R 8 , R 9 , R 10 , R 10 '、R 11 , R 11 '、R 12 , R 14 and E are as defined above, and the two R groups (e.g. R 7 and R 8 , R 8 and R 9 , R 9 and R 10 , R 10 and R 11 The ring may be joined to form a substituted or unsubstituted hydrocarbon or heterocyclic ring, wherein the ring has 5, 6, 7 or 8 ring atoms (e.g., 5 or 6 atoms), and the ring may be substituted or unsubstituted (e.g., partially unsaturated or aromatic), for example, J is aralkyl (e.g., arylmethyl, etc.) or dihydro-1H-indenyl or tetrahydronaphthyl.

[0329] In at least one embodiment, J is selected from the following structures:

[0330]

[0331] in Indicates connection with the complex.

[0332] In at least one embodiment, E is carbon.

[0333] X can be an alkyl group (e.g., an alkyl group having 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and isomers thereof), an aryl group, a hydrogen group, an alkylsilane group, a fluoro group, a chloro group, a bromo group, an iodo group, a triflate group, a carboxylate group, an amino group (e.g., NMe2), or an alkylsulfonate group.

[0334] In at least one embodiment, L is an ether, an amine, or a thioether.

[0335] In at least one embodiment, R 7 and R 8 The six-membered aromatic ring is formed by joining the R 7 / R 8The group is -CH=CHCH=CH-.

[0336] R 10 and R 11 can be joined to form a five-membered ring, wherein the joined R 10 R 11 The group is -CH2CH2-.

[0337] In at least one embodiment, R 10 and R 11 The six-membered ring is formed by joining 10 R 11 The group is -CH2CH2CH2-.

[0338] R 1 and R 13 The phenyl groups may be independently selected from phenyl groups substituted with 0-5 substituents, including F, Cl, Br, I, CF3, NO2, alkoxy, dialkylamino, aryl and alkyl groups having 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and isomers thereof.

[0339] In at least one embodiment, the QDA transition metal complex is represented by formula (II) above, wherein:

[0340] M is a Group 4 metal (e.g., hafnium);

[0341] E is selected from carbon, silicon or germanium (eg carbon);

[0342] X is an alkyl group, an aryl group, a hydrogen group, an alkylsilane group, a fluoro group, a chloro group, a bromo group, an iodo group, a trifluoromethanesulfonate group, a carboxylate group, an amino group, an alkoxo group, or an alkylsulfonate group.

[0343] L is an ether, an amine or a thioether;

[0344] R 1 and R 13 independently selected from the group consisting of a hydrocarbyl group, a substituted hydrocarbyl group, and a silyl group (eg, an aryl group);

[0345] R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 and R 12 are independently hydrogen, hydrocarbyl, alkoxy, silyl, amino, aryloxy, substituted hydrocarbyl, halo or phosphino;

[0346] n is 1 or 2;

[0347] m is 0, 1, or 2;

[0348] n+m is 1-4;

[0349] Two X groups can be joined together to form a dianionic group;

[0350] Two L groups can be joined together to form a bidentate Lewis base;

[0351] The X group can be joined to the L group to form a monoanionic bidentate group;

[0352] R 7 and R 8 can be joined to form a ring (e.g., an aromatic ring, a six-membered aromatic ring, wherein the joined R 7 R 8 The group is -CH=CHCH=CH-); and

[0353] R 10 and R 11 can be joined to form a ring (e.g., a five-membered ring, wherein the joined R 10 R 11 The group is -CH2CH2-, a six-membered ring in which the R 10 R 11 The group is -CH2CH2CH2-).

[0354] In at least one embodiment of Formulas (BI), (BII) and (BIII), R 4 , R 5 and R 6 are independently selected from the group consisting of hydrogen, hydrocarbon, substituted hydrocarbon, alkoxy, aryloxy, halogen, amino, and silyl, and wherein adjacent R groups (R 4 and R 5 and / or R 5 and R 6 ) are joined to form a substituted hydrocarbyl, unsubstituted hydrocarbyl, unsubstituted heterocyclic ring, or substituted heterocyclic ring, wherein the ring has 5, 6, 7, or 8 ring atoms and the substituents on the ring can be joined to form additional rings.

[0355] In at least one embodiment of Formulas (BI), (BII) and (BIII), R 7 , R 8 , R 9 and R 10 are independently selected from the group consisting of hydrogen, hydrocarbon, substituted hydrocarbon, alkoxy, halogen, amino, and silyl, and wherein adjacent R groups (R7 and R 8 and / or R 9 and R 10 ) can be joined to form a saturated substituted hydrocarbon, unsubstituted hydrocarbon, unsubstituted heterocyclic ring, or substituted heterocyclic ring, wherein the ring has 5, 6, 7, or 8 ring carbon atoms and the substituents on the ring can be joined to form additional rings.

[0356] In at least one embodiment of Formulas (BI), (BII) and (BIII), R 2 and R 3 Each is independently selected from the group consisting of hydrogen, hydrocarbon, and substituted hydrocarbon, alkoxy, silyl, amino, aryloxy, halogen, and phosphine, R 2 and R 3 can be joined to form a saturated, substituted or unsubstituted hydrocarbon ring, wherein the ring has 4, 5, 6 or 7 ring carbon atoms and wherein the substituents on the ring can be joined to form additional rings, or R 2 and R 3 The rings may be joined to form a saturated heterocyclic ring or a saturated substituted heterocyclic ring, wherein substituents on the rings may be joined to form additional rings.

[0357] In at least one embodiment of Formulas (BI), (BII) and (BIII), R 11 and R 12 Each is independently selected from the group consisting of hydrogen, hydrocarbon, and substituted hydrocarbon, alkoxy, silyl, amino, aryloxy, halogen, and phosphine, R 11 and R 12 can be joined to form a saturated, substituted or unsubstituted hydrocarbon ring, wherein the ring has 4, 5, 6 or 7 ring carbon atoms and wherein the substituents on the ring can be joined to form additional rings, or R 11 and R 12 may be joined to form a saturated heterocyclic ring or a saturated substituted heterocyclic ring, wherein the substituents on the ring may be joined to form an additional ring, or R 11 and R 10 The rings may be joined to form a saturated heterocyclic ring or a saturated substituted heterocyclic ring, wherein substituents on the rings may be joined to form additional rings.

[0358] In at least one embodiment of Formulas (BI), (BII) and (BIII), R 1 and R 13Independently selected from phenyl groups substituted with 0-5 substituents, said substituents including F, Cl, Br, I, CF3, NO2, alkoxy, dialkylamino, aryl and alkyl groups having 1 to 10 carbons, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and their isomers.

[0359] In at least one embodiment of Formula (BII), suitable R 12 -ER 11 The groups include CH2, CMe2, SiMe2, SiEt2, SiPr2, SiBu2, SiPh2, Si(aryl)2, Si(alkyl)2, CH(aryl), CH(Ph), CH(alkyl) and CH(2-isopropylphenyl), where alkyl is C1-C 40 Alkyl groups (e.g. C1-C 20 Alkyl is one or more of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and isomers thereof), aryl is C5-C 40 Aryl groups (e.g. C6-C 20 Aryl groups such as phenyl or substituted phenyl, such as phenyl, 2-isopropylphenyl or 2-tert-butylphenyl).

[0360] In at least one embodiment of Formula (BIII), R 11 , R 12 , R 9 , R 14 and R 10 are independently selected from the group consisting of hydrogen, hydrocarbon, substituted hydrocarbon, alkoxy, halogen, amino, and silyl, and wherein adjacent R groups (R 10 and R 14 and / or R 11 and R 14 and / or R 9 and R 10 ) can be joined to form a saturated, substituted hydrocarbyl, unsubstituted hydrocarbyl, unsubstituted heterocyclic ring, or substituted heterocyclic ring, wherein the ring has 5, 6, 7, or 8 ring carbon atoms and the substituents on the ring can be joined to form additional rings.

[0361] The above R groups (e.g. R 2 To R 14 The above R groups (e.g. R 2 To R 14Respectively) and other R groups mentioned below may be independently selected from the group comprising hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, trimethylsilyl and -CH2-Si(Me)3.

[0362] In at least one embodiment, the quinolyl diamino complex is linked to one or more additional transition metal complexes, such as quinolyl diamino complexes or another suitable non-metallocene, via the R group in such a way as to make a bimetallic, trimetallic or multimetallic complex that can be used as a catalyst component for olefin polymerization. The linker R-group in such a complex may contain 1 to 30 carbon atoms.

[0363] In at least one embodiment, E is carbon and R 11 and R 12 Independently selected from phenyl groups substituted with 0, 1, 2, 3, 4 or 5 substituents selected from the group consisting of F, Cl, Br, I, CF3, NO2, alkoxy, dialkylamino, hydrocarbyl and substituted hydrocarbyl groups having 1-10 carbons.

[0364] In at least one embodiment of Formula (BII) or (BIII), R 11 and R 12 Independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, -CH2-Si(Me)3 and trimethylsilyl.

[0365] In at least one embodiment of Formula (BII) or (BIII), R 7 , R 8 , R 9 and R 10 Independently selected from hydrogen, methyl, ethyl, propyl, isopropyl, phenyl, cyclohexyl, fluoro, chloro, methoxy, ethoxy, phenoxy, -CH2-Si(Me)3 and trimethylsilyl.

[0366] In at least one embodiment of Formulas (BI), (BII) and (BIII), R 2 , R 3 , R 4 , R 5 and R 6 Independently selected from the group consisting of hydrogen, hydrocarbyl, alkoxy, silyl, amino, substituted hydrocarbyl, and halogen.

[0367] In at least one embodiment of Formula (BIII), R 10 , R 11 and R 14 Independently selected from hydrogen, methyl, ethyl, phenyl, isopropyl, isobutyl, -CH2-Si(Me)3 and trimethylsilyl.

[0368] In at least one embodiment of Formulas (BI), (BII) and (BIII), each L is independently selected from Et2O, MeOtBu, Et3N, PhNMe2, MePh2N, tetrahydrofuran and dimethylsulfanyl.

[0369] In at least one embodiment of formula (BI), (BII) and (BIII), each X is independently selected from methyl, benzyl, trimethylsilyl, neopentyl, ethyl, propyl, butyl, phenyl, hydrogen, chloro, fluoro, bromo, iodo, dimethylamino, diethylamino, dipropylamino and diisopropylamino.

[0370] In at least one embodiment of Formulas (BI), (BII) and (BIII), R 1 It is 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2,6-diisopropyl-4-methylphenyl, 2,6-diethylphenyl, 2-ethyl-6-isopropylphenyl, 2,6-bis(3-pentyl)phenyl, 2,6-dicyclopentylphenyl or 2,6-dicyclohexylphenyl.

[0371] In at least one embodiment of Formulas (BI), (BII) and (BIII), R 13 It is phenyl, 2-methylphenyl, 2-ethylphenyl, 2-propylphenyl, 2,6-dimethylphenyl, 2-isopropylphenyl, 4-methylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, 4-fluorophenyl, 3-methylphenyl, 4-dimethylaminophenyl or 2-phenylphenyl.

[0372] In at least one embodiment of Formula (BII), J is dihydro-1H-indenyl and R 1 It is a 2,6-dialkylphenyl group or a 2,4,6-trialkylphenyl group.

[0373] In at least one embodiment of Formulas (BI), (BII) and (BIII), R 1 is 2,6-diisopropylphenyl and R 13 is a hydrocarbyl group containing 1, 2, 3, 4, 5, 6 or 7 carbon atoms.

[0374] An exemplary catalyst for the polymerization of the present disclosure is (QDA-1)HfMe2 as described in U.S. Publication No. 2018 / 0002352 A1.

[0375]

[0376] In at least one embodiment, the catalyst compound is a bis(phenolate) catalyst compound represented by formula (CI):

[0377]

[0378] M is a Group 4 metal such as Hf or Zr. 1 and X 2 Independently for unit price C1-C 20 Hydrocarbon, C1-C 20 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or X 1 and X 2 Joined together to form C4-C 62 Cyclic or polycyclic ring structure. 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 are independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 substituted hydrocarbon group, heteroatom or heteroatom-containing group, or R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 and R 10 Two or more of them join together to form C4-C 62 Cyclic or polycyclic ring structure, or a combination thereof; Q is a neutral donor group; J is a heterocyclic group, a substituted or unsubstituted C7-C 60 A fused polycyclic group in which at least one ring is aromatic and in which at least one ring (which may or may not be aromatic) has at least five ring atoms; G is as defined for J or may be hydrogen, C2-C 60 Hydrocarbon, C1-C 60 The substituted hydrocarbon group may be independently 6 , R 7 or R 8 or their combination to form C4-C 60 Cyclic or polycyclic ring structure; Y is a divalent C1-C 20 Hydrocarbon or divalent C1-C 20 The substituted hydrocarbon groups or (-QY-) together form a heterocyclic ring; and the heterocyclic ring may be aromatic and / or may have a plurality of condensed rings.

[0379] In at least one embodiment, the catalyst compound represented by formula (CI) is represented by formula (CII) or formula (CIII):

[0380]

[0381]

[0382] M is Hf, Zr or Ti. 1 , X 2 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and Y are as defined in formula (CI). 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 are independently hydrogen, C1-C 40 Hydrocarbon, C1-C 40 Substituted hydrocarbon groups, including functional groups from elements of Groups 13 to 17, or R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21, R 22 , R 23 , R 24 , R 25 , R 26 , R 27 and R 28 Two or more of them can be independently joined together to form C4-C 62 Cyclic or polycyclic ring structure, or a combination thereof; R 11 and R 12 can be joined together to form a five- to eight-membered heterocyclic ring; Q* is a Group 15 or 16 atom; z is 0 or 1; J* is CR" or N and G* is CR" or N, wherein R" is C1-C 20 Hydrocarbon or carbonyl-containing C1-C 20 and z=0 if Q* is a Group 16 atom, and z=1 if Q* is a Group 15 atom.

[0383] In at least one embodiment, the catalyst is an iron complex represented by formula (DI):

[0384]

[0385] in:

[0386] A is chlorine, bromine, iodine, -CF3 or -OR 11 ;

[0387] R 1 and R 2 Each of them is independently hydrogen, C1-C 22 -alkyl, C2-C 22 -Alkenyl, C6-C 22 - aryl, arylalkyl in which the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms, or a five-membered, six-membered or seven-membered heterocyclic group comprising at least one atom selected from N, P, O and S;

[0388] Where R 1 and R 2 Each of which is optionally substituted by halogen, -NR 11 2. -OR 11 Or-SiR 12 3 Replacement;

[0389] Where R 1 Optionally with R 3 bonding, and R 2 Optionally with R 5 bonded, in each case independently to form a five-, six-, or seven-membered ring;

[0390] R 7 It is C1-C 20alkyl;

[0391] R 3 , R 4 , R 5 , R 8 , R 9 , R 10 , R 15 , R 16 and R 17 Each of them is independently hydrogen, C1-C 22 -alkyl, C2-C 22 -Alkenyl, C6-C 22 -aryl, arylalkyl wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms, -NR 11 2, -OR 11 , halogen, -SiR 12 3, or a five-membered, six-membered or seven-membered heterocyclic group comprising at least one atom selected from N, P, O and S;

[0392] Where R 3 , R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 15 , R 16 and R 17 Optionally halogen, -NR 11 2. -OR 11 Or-SiR 12 3 Replacement;

[0393] Where R 3 Optionally with R 4 Bonding, R 4 Optionally with R 5 Bonding, R 7 Optionally with R 10 Bonding, R 10 Optionally with R 9 Bonding, R 9 Optionally with R 8 Bonding, R 17 Optionally with R 16 bonding, and R 16 Optionally with R 15 bonded to form, independently in each case, a five-, six- or seven-membered carbocyclic or heterocyclic ring comprising at least one atom selected from N, P, O and S;

[0394] R 13 It is a C1-C2-yl group bonded to the aromatic ring through a primary or secondary carbon atom. 20-alkyl;

[0395] R 14 It is chlorine, bromine, iodine, -CF3 or -OR bonded to an aromatic ring 11 , or C1-C 20 -alkyl;

[0396] Each R 11 are independently hydrogen, C1-C 22 -alkyl, C2-C 22 -Alkenyl, C6-C 22 -aryl, arylalkyl wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms, or -SiR 12 3, where R 11 Optionally substituted with halogen, or both R 11 The groups are optionally bonded to form a five- or six-membered ring;

[0397] Each R 12 are independently hydrogen, C1-C 22 -alkyl, C2-C 22 -Alkenyl, C6-C 22 - aryl, an arylalkyl group in which the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms, or two R 12 The groups are optionally bonded to form a five- or six-membered ring;

[0398] E 1 、E 2 and E 3 where each is independently carbon, nitrogen or phosphorus;

[0399] If E 1 、E 2 and E 3 is nitrogen or phosphorus, then each u is independently 0, if E 1 、E 2 and E 3 is carbon, then each u is independently 1;

[0400] Each X is independently fluorine, chlorine, bromine, iodine, hydrogen, C1-C 20 -alkyl, C2-C 10 -Alkenyl, C6-C 20 -aryl, arylalkyl wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms, -NR 18 2. -OR 18 、-SR 18 、-SO3R 18 、-OC(O)R 18 , -CN, -SCN, β-diketonate, -CO, -BF4- 、-PF6 - or bulky non-coordinating anions, and the groups X can bond to each other;

[0401] Each R 18 are independently hydrogen, C1-C 20 -alkyl, C2-C 20 -Alkenyl, C6-C 20 -aryl, arylalkyl wherein the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms, or -SiR 19 3, where R 18 may be substituted by halogen or nitrogen- or oxygen-containing groups, and both R 18 The groups are optionally bonded to form a five- or six-membered ring;

[0402] Each R 19 are independently hydrogen, C1-C 20 -alkyl, C2-C 20 -Alkenyl, C6-C 20 - aryl or arylalkyl in which the alkyl group has 1 to 10 carbon atoms and the aryl group has 6 to 20 carbon atoms, wherein R 19 may be substituted with halogen or nitrogen- or oxygen-containing groups, or both R 19 The groups are optionally bonded to form a five- or six-membered ring;

[0403] s is 1, 2, or 3;

[0404] D is a neutral donor; and

[0405] t is 0 to 2.

[0406] In another embodiment, the catalyst is a phenoxyimine compound represented by formula (EI):

[0407]

[0408] wherein M represents a transition metal atom selected from metals of Groups 3 to 11 of the periodic table; k is an integer from 1 to 6; m is an integer from 1 to 6; R a To R f may be the same or different from each other, and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, a heterocyclic compound residue, an oxygen-containing group, a nitrogen-containing group, a boron-containing group, a sulfur-containing group, a phosphorus-containing group, a silicon-containing group, a germanium-containing group or a tin-containing group, wherein 2 or more groups may be combined with each other to form a ring; when k is 2 or more, R a Group, R b Group, R c Group, R d Group, R e Group or R fThe groups may be the same or different from each other. a To R f A group in the other ligand and R a To R f One of the groups can form a linking group or a single bond, and R a To R f The heteroatom contained in may coordinate or combine with M; m is a number that satisfies the chemical valence of M; Q represents a hydrogen atom, a halogen atom, an oxygen atom, a hydrocarbon group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group, a boron-containing group, an aluminum-containing group, a phosphorus-containing group, a halogen-containing group, a heterocyclic compound residue, a silicon-containing group, a germanium-containing group or a tin-containing group; when m is 2 or greater, a plurality of groups represented by Q may be the same or different from each other, and a plurality of groups represented by Q may be combined with each other to form a ring.

[0409] In another embodiment, the catalyst is a bis(imino)pyridyl represented by formula (FI):

[0410]

[0411] in:

[0412] M is Co or Fe; each X is an anion; n is 1, 2 or 3, such that the total number of negative charges on the one or more anions is equal to the oxidation state of the Fe or Co atoms present in (FI);

[0413] R 1 , R 2 and R 3 Each is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;

[0414] R 4 and R 5 Each is independently hydrogen, a hydrocarbyl group, an inert functional group, or a substituted hydrocarbyl group;

[0415] R 6 is formula (IX);

[0416] and R 7 It is formula (X):

[0417]

[0418] R 8 and R 13 Each is independently a hydrocarbyl, a substituted hydrocarbyl, or an inert functional group;

[0419] R 9 , R 10 , R 11 , R 14, R 15 and R 16 Each is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;

[0420] R 12 and R 17 Each is independently hydrogen, hydrocarbyl, substituted hydrocarbyl, or an inert functional group;

[0421] And the condition is that the R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 and R 17 Two of them together can form a ring.

[0422] In at least one embodiment, the catalyst compound is represented by formula (GI):

[0423]

[0424] M 1 is selected from the group consisting of titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten. 1 It's zirconium.

[0425] Q of formula (GI) 1 , Q 2 , Q 3 and Q 4 In at least one embodiment, Q 1 , Q 2 , Q 3 and Q 4 At least one of them is oxygen, optionally Q 1 , Q 2 , Q 3 and Q 4 It's all oxygen.

[0426] R of formula (GI) 1 and R 2 are independently hydrogen, halogen, hydroxyl, hydrocarbon, or substituted hydrocarbon (e.g., C1-C 10 Alkyl, C1-C 10 Alkoxy, C6-C 20 Aryl, C6-C 10 Aryloxy, C2-C 10 Alkenyl, C2-C 40 Alkenyl, C7-C 40 Aralkyl, C7-C 40Alkyl, C8-C 40 an arylalkenyl, or a conjugated diene, which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl or tri(hydrocarbyl)silylhydrocarbyl groups, the diene having up to 30 atoms other than hydrogen). R 1 and R 2 can be a halogen selected from fluorine, chlorine, bromine or iodine. In at least one embodiment, R 1 and R 2 It's chlorine.

[0427] Alternatively, R of formula (GI) 1 and R 2 They can also be joined together to form 1 Coordinated alkanediyl groups or conjugated C4-C 40 Diene ligand. 1 and R 2 It may also be the same or different conjugated dienes, optionally substituted by one or more hydrocarbyl, tri(hydrocarbyl)silyl or tri(hydrocarbyl)silylhydrocarbyl groups, the dienes containing up to 30 atoms not counting hydrogen and / or having a carbonyl group with M 1 Formation of π-complex.

[0428] Suitable for R of formula (GI) 1 and / or R 2 Exemplary groups of may include 1,4-diphenyl, 1,3-butadiene, 1,3-pentadiene, 2-methyl 1,3-pentadiene, 2,4-hexadiene, 1-phenyl, 1,3-pentadiene, 1,4-dibenzyl, 1,3-butadiene, 1,4-xylyl-1,3-butadiene, 1,4-bis(trimethylsilyl)-1,3-butadiene, and 1,4-dinaphthyl-1,3-butadiene. 1 and R 2 Can be the same and are C1-C3 alkyl or alkoxy, C6-C 10 Aryl or aryloxy, C2-C4 alkenyl, C7-C 10 Aralkyl, C7-C 12 Alkaryl or halogen.

[0429] R of formula (GI) 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R18 and R 19 Each of which is independently hydrogen, halogen, C1-C 40 Hydrocarbon or C1-C 40 Substituted hydrocarbon groups (e.g. C1-C 10 Alkyl, C1-C 10 Alkoxy, C6-C 20 Aryl, C6-C 10 Aryloxy, C2-C 10 Alkenyl, C2-C 40 Alkenyl, C7-C 40 Aralkyl, C7-C 40 Alkyl, C8-C 40 an arylalkenyl or conjugated diene, which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl or tri(hydrocarbyl)silylhydrocarbyl groups, the diene having up to 30 atoms other than hydrogen), -NR'2, -SR', -OR, -OSiR'3, -PR'2, wherein each R' is hydrogen, halogen, C1-C 10 Alkyl or C6-C 10 Aryl, or R 4 and R 5 , R 5 and R 6 , R 6 and R 7 , R 8 and R 9 , R 9 and R 10 , R 10 and R 11 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 16 and R 17 , R 17 and R 18 , and R 18 and R 19 One or more pairs of C1-C2-C4-C6-C7-C8-C9-C10-C11-C12-C13-C14-C15-C16-C18-C19 ... 40 The hydrocarbon radical is selected from the group consisting of methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, and sec-decyl. In at least one embodiment, R 11 and R 12 It is C6-C 10Aryl, such as phenyl or naphthyl, optionally substituted with C1-C 40 Hydrocarbon groups such as C1-C 10 In at least one embodiment, R 6 and R 17 It is C 1-40 Alkyl groups such as C1-C 10 alkyl.

[0430] In at least one embodiment, R of formula (GI) 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 and R 19 Each of which is independently hydrogen or C1-C 40 In at least one embodiment, C1-C 40 The hydrocarbon radical is selected from the group consisting of methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl, and sec-decyl. In at least one embodiment, R 6 and R 17 Each of C1-C 40 Hydrocarbon and R 4 , R 5 , R 7 , R 8 , R 9 , R 10 , R 13 , R 14 , R 15 , R 16 , R 18 and R 19 is hydrogen. In at least one embodiment, C1-C 40 The hydrocarbon radical is selected from the group consisting of methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl and sec-decyl.

[0431] R of formula (GI) 3 It is C1-C 40Unsaturated alkyl or substituted C1-C 40 Unsaturated alkyl (e.g. C1-C 10 Alkyl, C1-C 10 Alkoxy, C6-C 20 Aryl, C6-C 10 Aryloxy, C2-C 10 Alkenyl, C2-C 40 Alkenyl, C7-C 40 Aralkyl, C7-C 40 Alkyl, C8-C 40 an arylalkenyl or conjugated diene, which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl or tri(hydrocarbyl)silylhydrocarbyl groups, the diene having up to 30 atoms other than hydrogen).

[0432] In at least one embodiment, R of formula (GI) 3 is a hydrocarbon group including a vinyl moiety. The terms "vinyl" and "vinyl moiety" are used interchangeably and include, for example, a vinyl moiety consisting of the structure Represents a terminal olefin. 3 The hydrocarbon group may also be substituted (e.g. C1-C 10 Alkyl, C1-C 10 Alkoxy, C6-C 20 Aryl, C6-C 10 Aryloxy, C2-C 10 Alkenyl, C2-C 40 Alkenyl, C7-C 40 Aralkyl, C7-C 40 Alkyl, C8-C 40 an arylalkenyl or conjugated diene, which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl or tri(hydrocarbyl)silylhydrocarbyl groups, the diene having up to 30 atoms excluding hydrogen). In at least one embodiment, R 3 C1-C for vinyl 40 Unsaturated alkyl or vinyl substituted C1-C 40 Unsaturated alkyl. 3 It can be represented by the structure –R'CH=CH2, where R' is C1-C 40 Hydrocarbon or C1-C 40 Substituted hydrocarbon groups (e.g. C1-C 10 Alkyl, C1-C 10 Alkoxy, C6-C 20 Aryl, C6-C 10 Aryloxy, C2-C 10 Alkenyl, C2-C 40 Alkenyl, C7-C40 Aralkyl, C7-C 40 Alkyl, C8-C 40 an arylalkenyl or conjugated diene, which is optionally substituted with one or more hydrocarbyl, tri(hydrocarbyl)silyl or tri(hydrocarbyl)silylhydrocarbyl groups, the diene having up to 30 atoms excluding hydrogen). In at least one embodiment, C1-C 40 The hydrocarbon radical is selected from the group consisting of methyl, ethyl, propyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, sec-pentyl, n-hexyl, isohexyl, sec-hexyl, n-heptyl, isoheptyl, sec-heptyl, n-octyl, isooctyl, sec-octyl, n-nonyl, isononyl, sec-nonyl, n-decyl, isodecyl and sec-decyl.

[0433] In at least one embodiment, R of formula (GI) 3 It is 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 1-heptenyl, 1-octenyl, 1-nonenyl or 1-decenyl.

[0434] In at least one embodiment, the catalyst is a Group 15 metal-containing compound represented by formula (XII) or (XIII):

[0435]

[0436] Wherein M is a transition metal of Groups 3 to 12 or a metal of the main group 13 or 14, a metal of Groups 4, 5 or 6. In some embodiments, M is a metal of Group 4, such as zirconium, titanium or hafnium. Each X is independently a leaving group such as an anionic leaving group. The leaving group may include hydrogen, a hydrocarbon group, a heteroatom, a halogen, or an alkyl group; y is 0 or 1 (group L' is absent when y is 0). The term "n" is the oxidation state of M. In various embodiments, n is +3, +4 or +5. In some embodiments, n is +4. The term "m" represents the formal charge of the YZL or YZL' ligand, and is 0, -1, -2 or -3 in various embodiments. In some embodiments, m is -2. L is an element of Groups 15 or 16, such as nitrogen or oxygen; L' is an element of Groups 15 or 16 or contains a group of Groups 14, such as carbon, silicon or germanium. Y is an element of Groups 15 such as nitrogen or phosphorus. In some embodiments, Y is nitrogen. Z is a Group 15 element such as nitrogen or phosphorus. In some embodiments, Z is nitrogen. 1 and R 2 Independently C1-C 20 A hydrocarbon group, a heteroatom-containing group having up to 20 carbon atoms, silicon, germanium, tin, lead or phosphorus. 1 To R 2 It is C2-C 20 Alkyl, aryl or aralkyl groups, such as C2-C 20Linear, branched or cyclic alkyl groups or C2-C 20 Hydrocarbyl group. 1 and R 2 They can also be connected to each other. 3 R may not exist or may be a hydrocarbon group, hydrogen, a halogen, or a heteroatom-containing group. 3 , for example, if L is oxygen or hydrogen or a linear, cyclic or branched alkyl group having 1 to 20 carbon atoms. 4 and R 5 R is independently an alkyl group, an aryl group, a substituted aryl group, a cycloalkyl group, a substituted cycloalkyl group, a cyclic aralkyl group, a substituted cyclic aralkyl group, or a polycyclic ring system, often having up to 20 carbon atoms. 4 and R 5 Has 3 to 10 carbon atoms, or is C1-C 20 Hydrocarbon, C1-C 20 Aryl group or C1-C 20 An aralkyl group or a group containing a heteroatom. 4 and R 5 Can be connected to each other. 6 and R 7 R is independently absent, hydrogen, an alkyl group, a halogen, a heteroatom, or a hydrocarbyl group, such as a linear, cyclic, or branched alkyl group having 1 to 20 carbon atoms. 6 and R 7 R* may be absent or may be hydrogen, a group containing a Group 14 atom, a halogen, or a heteroatom-containing group.

[0437] The term "formal charge of the YZL or YZL' ligand" means the charge of the entire ligand without the metal and leaving group X. 1 and R 2 can also be connected to each other" means R l and R 2 They may be directly bonded to each other or may be bonded to each other through other groups. 4 and R 5 can also be connected to each other" means R 4 and R 5Can directly combine with each other or can combine with each other through other groups.Alkyl group can be linear, branched alkyl group, alkenyl group, alkynyl group, cycloalkyl group, aryl group, acyl group, aroyl group, alkoxy group, aryloxy group, alkylthio group, dialkylamino group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkyl-or dialkyl-carbamoyl group, acyloxy group, acylamino group, aroylamino group, straight chain, branched or cyclic alkylene group or their combination.Aralkyl group is defined as substituted aryl group.

[0438] In one or more embodiments, R of formula (XII) or (XIII) 4 and R 5 is independently a group represented by structure (XIV):

[0439]

[0440] Where R 8 To R 12 Each is independently hydrogen, C1-C 40 An alkyl group, a halogen group, a heteroatom, a heteroatom-containing group containing up to 40 carbon atoms. 8 To R 12 It is C1-C 20 A linear or branched alkyl group, such as a methyl, ethyl, propyl or butyl group. Two of the R groups may form a cyclic group and / or a heterocyclic group. The cyclic group may be aromatic. In at least one embodiment, R 9 , R 10 and R 12 is independently a methyl, ethyl, propyl or butyl group (including all isomers). In another embodiment, R 9 , R 10 and R 12 is a methyl group and R 8 and R 11 It's hydrogen.

[0441] In one or more embodiments, R of formula (XII) or (XIII) 4 and R 5 is a group represented by the structure (XV):

[0442]

[0443] wherein M is a Group 4 metal, such as zirconium, titanium, or hafnium. In at least one embodiment, M is zirconium. Each of L, Y, and Z may be nitrogen. 1 and R 2 Each of R may be -CH2-CH2-.3 may be hydrogen, and R may be absent 6 and R 7 .

[0444] In one or more embodiments, the catalyst compounds described in PCT / US2018 / 051345, filed September 17, 2018, can be used with an activator, including the catalyst compounds described on pages 16 to 32 of the filed application.

[0445] In some embodiments, the co-activator is combined with a catalyst compound (e.g., a halogenated catalyst compound described above) to form an alkylated catalyst compound. Organic aluminum compounds that can be used as co-activators include, for example, trialkylaluminum compounds such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum, tri-n-octylaluminum, etc., or aluminoxanes.

[0446] Various catalysts

[0447] In some embodiments, two or more different catalyst compounds are present in the catalyst system. In some embodiments, two or more different catalyst compounds are present in the reaction zone where the polymerization process(es) are performed. The two or more different catalyst compounds can be introduced into the reactor (e.g., catalyst solution line (5) and one or more additional lines (not shown) in fluid communication (e.g., directly connected) with the reactor (8) separately via two or more pipelines (e.g., catalyst solution line (5) and one or more additional lines (not shown) in fluid communication (e.g., directly connected) with the reactor (8) Figure 1 Reactor (8)). Two or more different catalysts may be stored in two or more storage tanks. Alternatively, two or more catalysts are combined in a single storage tank, diluted with one or more diluents, and introduced together via a pipeline into the reactor (e.g., via catalyst solution pipeline (5)).

[0448] When two catalysts based on transition metal compounds are used in one reactor as a mixed catalyst system, the two transition metal compounds can be selected so that the two are compatible. Simple screening methods can be used, for example by 1 H or 13 C NMR is used to determine which transition metal compounds are compatible. It is preferred to use the same activator for the transition metal compounds, however, two different activators may be used in combination. If one or more of the transition metal compounds contains an anionic ligand that is not a hydride, hydrocarbyl, or substituted hydrocarbyl group as a leaving group, the aluminoxane or other aluminum alkyl is typically contacted with the transition metal compound prior to adding the non-coordinating anionic activator.

[0449] Two transition metal compounds (procatalysts) can be used in any suitable ratio. The molar ratio of (A) transition metal compound to (B) transition metal compound can be 1:1000-1000:1, 1:100-500:1, 1:10-200:1, 1:1-100:1, 1:1-75:1 or 5:1-50:1. The specific ratio selected will depend on the exact procatalyst selected, the activation method and the final product. In a particular embodiment, when two procatalysts (wherein both are activated using the same activator) are used, the available molar percentage is 10 to 99.9mol%A to 0.1 to 90mol%B, 25 to 99mol%A to 0.5 to 50mol%B, 50 to 99mol%A to 1 to 25mol%B or 75 to 99mol%A to 1 to 10mol%B based on the molecular weight of the procatalyst.

[0450] Activator

[0451] The activator compounds of the present disclosure may be stored by themselves in a storage tank or dissolved in a hydrocarbon diluent(s), such as an aliphatic hydrocarbon, at a suitable concentration, i.e., an "activator solution". The activator solution may be measured using liquid measurement techniques including the use of a flow meter to measure the amount of activator solution added to or removed from the storage tank. Additionally or alternatively, a weight scale on the storage tank may be used to determine the amount of activator solution added to the reactor.

[0452] The activator can be diluted (e.g., dissolved) in a hydrocarbon diluent at a suitable concentration in a storage tank, a mixing tank, or an in-line mixer. Dissolution can be accomplished by determining the flow rate or weight of the activator and adding an appropriate amount of hydrocarbon diluent. Suitable hydrocarbon diluents include aliphatic and aromatic hydrocarbons. Although aromatic hydrocarbons are suitable diluents, their use can be reduced or eliminated because the production of polyolefins without aromatic hydrocarbons increases the value of the polymer and reduces the cost of polymer devolatilization. Suitable hydrocarbon diluents include non-coordinating inert liquids. Examples of diluents can include straight and branched hydrocarbons, such as 2-methyl-pentane, isobutane, butane, n-pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons, such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof, such as commercially available (Isopar TM ); perhalogenated hydrocarbons, such as perfluorinated C4-C 10Alkanes, chlorobenzenes, and aromatic compounds and alkyl-substituted aromatic compounds, such as benzene, toluene, mesitylene and xylene. Suitable diluents can also include liquid olefins, which can serve as monomers or comonomers, including ethylene, propylene, 1-butene, 1-hexene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-octene, 1-decene and their mixtures. In at least one embodiment, aliphatic hydrocarbon diluents such as isobutane, butane, n-pentane, isopentane, hexane, isohexane, heptane, octane, dodecane or their mixtures are used; and / or cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane or their mixtures. In another embodiment, the diluent is not aromatic, e.g., the aromatic compound is present in the diluent at less than 1 wt %, e.g., less than 0.5 wt %, e.g., less than 0.1 wt %, e.g., less than 0.05 wt %, e.g., less than 0.01 wt %, e.g., 0 wt %, based on the total weight of the diluent present.

[0453] The system of the present disclosure (e.g. Figure 1 The facility (of the invention) may include a storage tank (not shown) suitable for storing the activator or activator solution. In at least one embodiment, the activator storage tank is fluidly connected to the polymerization reactor (e.g., via the activator solution pipeline (7) and the reactor (8)). In another embodiment, the activator storage tank is fluidly connected to a pump station (not shown), which is fluidly connected to the polymerization reactor (e.g., via the activator solution pipeline (7) and the reactor (8)). It may be advantageous to allow dilution of the activator or activator solution to allow small amounts of activator to be accurately introduced into the polymerization reactor. The dilution may occur in a mixing vessel, an in-line mixer, a feed container, or by diluting the activator directly in the storage tank.

[0454] In some embodiments, the activator is stored in a container at concentrations up to nearly 100% by weight (although pure forms and highly concentrated solutions are very viscous). In some embodiments, the activator is stored in a storage container at a concentration of about 10% by weight to about 50% by weight. The activator solution can be diluted to less than 1% by weight during the polymerization process (e.g., in a mixing tank) to increase the volume flow rate to a reasonable flow rate for most pumps. If the concentration of the activator solution is too high, the flow rate to the reactor may be too small to be accurately metered.

[0455] In the present disclosure, activators are described that feature an ammonium group with a long chain aliphatic hydrocarbon group, thereby having improved solubility of the activator in aliphatic solvents compared to conventional activator compounds. Boronate groups useful in the present disclosure include fluoroaryl groups (e.g., fluoronaphthyl borate and / or fluorophenyl borate).

[0456] The terms "cocatalyst" and "activator" are used interchangeably herein and are compounds that can activate any of the catalyst compounds of the present disclosure by converting a neutral catalyst compound into a catalytically active catalyst compound cation. The activator of the present disclosure has one or more non-coordinating anions (NCA). Non-coordinating anions (NCA) mean anions that are not coordinated with a catalyst metal cation or are only weakly coordinated with a metal cation. The term NCA is also defined as including multi-component activators such as tetrakis(perfluorophenyl)borate N,N-dimethylanilinium, which contain an acidic cationic group and a non-coordinating anion. The term NCA is also defined as including neutral Lewis acids such as tris(perfluorophenyl)boron, which can react with the catalyst to form an activated substance by capturing anionic groups. The NCA coordination is weak enough so that a neutral Lewis base such as an olefinic or acetylenic 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 contained in the non-coordinating anion. Suitable metals may include aluminum, gold, and platinum. Suitable metalloids may include boron, aluminum, phosphorus, and silicon.The term non-coordinating anion activator includes neutral activators, ionic activators, and Lewis acid activators.

[0457] "Compatible" non-coordinating anions may be those that are not degraded to neutrality when the initially formed complex decomposes. In addition, the anion will not transfer anionic substituents or fragments to the cation so that it forms a neutral transition metal compound and neutral byproducts from the anion. Non-coordinating anions useful in accordance with the present disclosure are those that are compatible, stabilize the transition metal cation in the sense of balancing its ionic charge at +1, and yet remain sufficiently labile to allow displacement during polymerization.

[0458] The present disclosure provides activators such as ammonium or A metallate or metalloid activator compound, the activator comprising (1) ammonium or A group and a long chain aliphatic hydrocarbon group and (2) a metal acid salt or a metalloid anion such as a borate or an aluminate. When the activator of the present disclosure is used together with one or more catalyst compounds in olefin polymerization, a polymer can be formed. In addition, it has been found that the activator of the present disclosure is soluble in aliphatic solvents.

[0459] With respect to solubility, in one or more embodiments, a 10 wt % mixture (e.g., a 20 wt % mixture) of the activator compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear, homogeneous solution at 25° C., for example, a 30 wt % mixture of the compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear, homogeneous solution at 25° C.

[0460] In one or more embodiments, a 10 wt % mixture (e.g., a 20 wt % mixture) of the catalyst system in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear homogeneous solution at 25°C, for example, a 30 wt % mixture of the compound in n-hexane, isohexane, cyclohexane, methylcyclohexane, or a combination thereof forms a clear homogeneous solution at 25°C.

[0461] In some embodiments, an activating agent described herein has a solubility in methylcyclohexane (MeCy) greater than 10 mM (or greater than 20 mM or greater than 50 mM) at 25°C (stirring for 2 hours).

[0462] In some embodiments, an activating agent described herein has a solubility in isohexane at 25°C (stirring for 2 hours) of greater than 1 mM (or greater than 10 mM or greater than 20 mM).

[0463] In some embodiments, the activators described herein have a solubility in methylcyclohexane greater than 10 mM (or greater than 20 mM or greater than 50 mM) at 25°C (stirring for 2 hours) and a solubility in isohexane greater than 1 mM (or greater than 10 mM or greater than 20 mM) at 25°C (stirring for 2 hours).

[0464] In some embodiments, the catalyst systems described herein have a solubility in methylcyclohexane greater than 10 mM (or greater than 20 mM or greater than 50 mM) at 25°C (stirring for 2 hours) and a solubility in isohexane greater than 1 mM (or greater than 10 mM or greater than 20 mM) at 25°C (stirring for 2 hours).

[0465] The catalyst system used herein preferably contains 0 ppm (optionally less than 1 ppm, alternatively less than 1 ppb) of aromatic hydrocarbons. For example, the catalyst system used herein contains 0 ppm (optionally less than 1 ppm, alternatively less than 1 ppb) of toluene.

[0466] The present disclosure provides activator compounds represented by formula (AI):

[0467] [R 1 R 2 R 3 EH] d + [M k+ Q n ] d- (AI)

[0468] in:

[0469] E is nitrogen or phosphorus, preferably nitrogen;

[0470] Each d is the same and is 1, 2 or 3 (preferably 3); k is 1, 2 or 3 (e.g. 3); n is 1, 2, 3, 4, 5 or 6 (e.g. 4, 5 or 6); nk = d (preferably d is 1, 2 or 3, k is 3, n is 4, 5 or 6, preferably when M is B, n is 4);

[0471] R 1 , R 2 and R 3 wherein each is independently H, optionally substituted C1-C 40 Alkyl (e.g. branched or linear alkyl) or optionally substituted C5-C 50 -Aryl (or R 1 , R 2 and R 3 Each of which is independently unsubstituted or substituted by at least one of the following: halogen, C5-C 50 Aryl, C6-C 35 Arylalkyl, C6-C 35 Alkaryl, and in C5-C 50 In the case of aryl groups, C1-C 50 alkyl); wherein R 1 , R 2 and R 3 Contains 15 or more carbon atoms in total;

[0472] M is an element selected from Group 13 of the Periodic Table, preferably B or Al, preferably B; and

[0473] Each Q is independently hydrogen, a bridged or unbridged dialkylamino, a halo, an alkoxy, an aryloxy, a hydrocarbyl, a substituted hydrocarbyl, a halohydrocarbyl, a substituted halohydrocarbyl or a halo-substituted hydrocarbyl group, preferably a fluorinated aryl group, such as fluoro-phenyl or fluoro-naphthyl, more preferably perfluorophenyl or perfluoronaphthyl.

[0474] In some embodiments of the activator compound represented by Formula (AI), R 1 , R 2 and R 3 At least one of them is a linear or branched C3-C 40 Alkyl (optionally linear or branched C7-C 40 alkyl).

[0475] The present disclosure also provides an activator compound represented by Formula (AI) described above, wherein R 1 It is C1-C 30 Alkyl groups (preferably C1-C 10 alkyl group, preferably C1-C2 alkyl, preferably methyl), wherein R 1 is optionally substituted, and

[0476] R 2 and R 3 Each of which is independently an optionally substituted branched or linear C1-C 40 an alkyl group or a meta- and / or para-substituted phenyl group, wherein the meta- and para-substituents are independently optionally substituted C1-C 40 A hydrocarbon group, an optionally substituted alkoxy group, an optionally substituted silyl group, a halogen, or a halogen-containing group, wherein R 1 , R 2 and R 3 contains a total of 15 or more carbon atoms (e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 40 or more carbon atoms), and R 1 , R 2 and R 3 At least one of them is a linear or branched alkyl group (e.g. C3-C 40 Branched alkyl, optionally C7-C 40 branched alkyl).

[0477] The present disclosure also provides a catalyst system comprising an activator compound represented by Formula (AI) as described above, wherein R 1 is methyl; and R 2 and R 3 Each of which is independently C1-C 40 Branched or linear alkyl or C5-C 50 -aryl, where R 1 , R 2 and R 3 Each of which is independently unsubstituted or substituted by at least one of the following: halogen, C5-C 50 Aryl, C6-C 35 Arylalkyl, C6-C 35 Alkaryl, and in C5-C 50 In the case of aryl groups, C1-C 50 Alkyl; wherein R 1 , R 2 and R 3 Contains a total of 15 or more carbon atoms (e.g., 18 or more carbon atoms, e.g., 20 or more carbon atoms, e.g., 22 or more carbon atoms, e.g., 25 or more carbon atoms, e.g., 30 or more carbon atoms, e.g., 35 or more carbon atoms, e.g., 40 or more carbon atoms).

[0478] The present disclosure also provides a catalyst system having an activator compound represented by formula (I):

[0479] [R 1 R 2 R 3 EH] + [BR 4 R 5 R 6 R 7 ] - (I)

[0480] in:

[0481] E is nitrogen or phosphorus;

[0482] R 1 , R 2 and R 3 Each of which is independently C1-C 40 Linear or branched alkyl or C5-C 50 -Aryl (e.g. C5-C 22 ), where R 1 , R 2 and R 3 Each of which is independently unsubstituted or substituted by at least one of the following: halogen, C5-C 50 Aryl, C6-C 35 Arylalkyl, C6-C 35 Alkaryl, and in C5-C 50 In the case of aryl groups, C1-C 50 Alkyl; wherein R 1 , R 2 and R 3 Contains 15 or more carbon atoms in total (e.g. 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms); and

[0483] R 4 , R 5 , R 6 and R 7 Each of them is phenyl or naphthyl, wherein R 4 , R 5 , R 6 and R 7 At least one of them is substituted by 1 to 7 fluorine atoms.

[0484] In some embodiments, R 1 , R 2 and R 3 At least one of them is a linear or branched C3-C 40 Alkyl (e.g. linear or branched C7-C40 alkyl).

[0485] The present disclosure also provides a catalyst system comprising an activator compound represented by Formula (AI) as described above, wherein R 1 , R 2 and R 3 Each of which is independently C1-C 40 Linear or branched alkyl, C5-C 50 -Aryl (e.g. C5-C 22 ), where R 1 , R 2 and R 3 Each of which is independently unsubstituted or substituted by at least one of the following: halogen, C5-C 50 Aryl, C6-C 35 Arylalkyl, C6-C 35 Alkaryl, and in C5-C 50 In the case of aryl groups, C1-C 50 Alkyl; wherein R 1 , R 2 and R 3 In some embodiments, R 1 , R 2 and R 3 At least one of the following is a linear or branched alkyl group (e.g., a linear or branched C3-C 40 Alkyl), such as R 1 , R 2 and R 3 At least two of them are branched alkyl groups (e.g. C3-C 40 Branched alkyl), such as R 1 , R 2 and R 3 Each of which is a branched alkyl group (e.g., C 10 -C 40 branched alkyl).

[0486] In at least one embodiment of formula (AI) or (I) herein, M is an element selected from Group 13 of the Periodic Table of the Elements, preferably boron or aluminum, preferably B.

[0487] In at least one embodiment of formula (AI) or (I) herein, each Q is independently hydrogen, bridged or unbridged dialkylamino, halo, alkoxy, aryloxy, hydrocarbyl, substituted hydrocarbyl, halohydrocarbyl, substituted halohydrocarbyl or halogen substituted hydrocarbyl group. Preferably, each Q is a fluorinated hydrocarbyl group having 1 to 30 carbon atoms, more preferably each Q is a fluorinated aryl (e.g., phenyl or naphthyl) group, and most preferably each Q is a perfluorinated aryl (e.g., phenyl or naphthyl) group.

[0488] In at least one embodiment of Formula (AI) herein, suitable [M k+ Q n ] d- Examples also include diboron compounds as disclosed in US Pat. No. 5,447,895, which is incorporated herein by reference in its entirety.

[0489] In at least one embodiment, the activator is represented by formula (I):

[0490] [R 1 R 2 R 3 EH] + [BR 4 R 5 R 6 R 7 ] - (I)

[0491] in:

[0492] E is nitrogen or phosphorus, preferably nitrogen;

[0493] R 1 , R 2 and R 3 Each of which is independently C1-C 40 Linear or branched alkyl, C5-C 22 - an aryl group, an aralkyl group in which the alkyl group has 1 to 30 carbon atoms and the aryl group has 6 to 20 carbon atoms, or a five-membered, six-membered or seven-membered heterocyclic group containing at least one atom selected from N, P, O and S, wherein R 1 , R 2 and R 3 Each of which is optionally substituted by halogen, wherein R 2 Optional with R 5 Combined to independently form a five-membered, six-membered or seven-membered ring, preferably wherein R 1 , R 2 and R 3A total of 15 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms; R 4 , R 5 , R 6 and R 7 wherein each is independently hydrogen, a bridged or unbridged dialkylamino, a halo, an alkoxy, an aryloxy, a hydrocarbyl, a substituted hydrocarbyl, a halohydrocarbyl, a substituted halohydrocarbyl or a halogen-substituted hydrocarbyl group, preferably R 4 , R 5 , R 6 and R 7 wherein each Q is independently a fluorinated hydrocarbon group having 1-30 carbon atoms, more preferably each Q is a fluorinated aryl (e.g. phenyl or naphthyl) group (substituted by 1-7 fluorine atoms), and most preferably each Q is a perfluorinated aryl (e.g. phenyl or naphthyl) group.

[0494] In some embodiments of the activator represented by formula (I), R 1 , R 2 and R 3 At least one of them is a branched alkyl group (e.g. C7-C 40 branched alkyl), optionally R 1 , R 2 and R 3 At least two of them are branched alkyl groups (e.g. C7-C 40 branched alkyl), optionally R 1 , R 2 and R 3 All three of them are branched alkyl groups (e.g. C7-C 40 branched alkyl).

[0495] In at least one embodiment, the activator is an ammonium or Borates:

[0496] [R 1 R 2 R 3 EH] + [BR 4 R 5 R 6 R 7 ] - (I)

[0497] in:

[0498] E is nitrogen or phosphorus;

[0499] R1 It is C1-C 40 A linear alkyl group, preferably a methyl group;

[0500] R 2 and R 3 Each of which is independently C1-C 40 Linear or branched alkyl, C5-C 22 -Aryl, C5-C 50 Aralkyl, wherein the alkyl has 1-30 carbon atoms and the aryl has 6-20 carbon atoms, or a five-membered, six-membered or seven-membered heterocyclic group containing at least one atom selected from N, P, O and S, wherein R 1 , R 2 and R 3 Each of which is optionally substituted by halogen, wherein R 2 Optional with R 5 Combined to independently form a five-membered, six-membered or seven-membered ring, preferably wherein R 1 , R 2 and R 3 Contains a total of 15 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms; and

[0501] R 4 , R 5 , R 6 and R 7 Each of the above is independently a fluorinated hydrocarbon group having 1 to 30 carbon atoms, more preferably R 4 , R 5 , R 6 and R 7 wherein each is independently a fluorinated aryl (eg, phenyl or naphthyl) group, and most preferably R 4 , R 5 , R 6 and R 7 Each of them is independently a perfluoroaryl (eg, phenyl or naphthyl) group, wherein R 4 , R 5 , R 6 and R 7 At least one of them is substituted by 1 to 7 fluorine atoms.

[0502] The present disclosure also provides a catalyst system comprising an activator compound represented by formula (I):

[0503] [R 1 R 2 R 3 EH] +[BR 4 R 5 R 6 R 7 ] - (I)

[0504] in:

[0505] E is nitrogen or phosphorus, preferably nitrogen;

[0506] R 1 , R 2 and R 3 Each of which is independently C1-C 40 Linear or branched alkyl, C5-C 50 -aryl, where R 1 , R 2 and R 3 Each of which is independently unsubstituted or substituted by at least one of the following: halo, C1-C 50 Alkyl, C5-C 50 Aryl, C6-C 35 Arylalkyl, or C6-C 35 Alkaryl, where R 1 , R 2 and R 3 contains a total of 15 or more carbon atoms, such as 18 or more carbon atoms, such as 20 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms, provided that R 1 , R 2 and R 3 At least one of them is C3-C 40 Branched alkyl, optionally R 1 , R 2 and R 3 At least two of them are C3-C 40 A branched alkyl group; and R 4 , R 5 , R 6 and R 7 Each of them is naphthyl, wherein R 4 , R 5 , R 6 and R 7 At least one of them is substituted with 1 to 7 fluorine atoms, preferably 7 fluorine atoms.

[0507] In a preferred aspect, the activator is an ionic ammonium borate represented by formula (I):

[0508] [R 1 R 2 R 3 EH]+ [BR 4 R 5 R 6 R 7 ] - (I)

[0509] in:

[0510] E is nitrogen or phosphorus;

[0511] R 1 is a methyl group;

[0512] R 2 It is C6-C 50 Aryl, which is optionally substituted by at least one of the following: halogen, C1-C 35 Alkyl, C5-C 15 Aryl, C6-C 35 Arylalkyl and C6-C 35 Alkaryl;

[0513] R 3 It is C1-C 40 A branched alkyl group, which is optionally substituted by at least one of the following: a halogen group, a C1-C 35 Alkyl, C5-C 15 Aryl, C6-C 35 Arylalkyl and C6-C 35 Alkaryl, where R 2 Optional with R 3 Combine to independently form a five-membered, six-membered or seven-membered ring, and R 2 and R 3 contains a total of 20 or more carbon atoms, such as 21 or more carbon atoms, such as 22 or more carbon atoms, such as 25 or more carbon atoms, such as 30 or more carbon atoms, such as 35 or more carbon atoms, such as 40 or more carbon atoms, and

[0514] R 4 , R 5 , R 6 and R 7 Each of them is independently a fluorinated hydrocarbon group having 1 to 30 carbon atoms, wherein R 4 , R 5 , R 6 and R 7 At least one of them is independently substituted by 1, 2, 3, 4, 5, 6, or 7 fluorine atoms, more preferably R 4 , R 5 , R 6 and R 7 wherein each is independently a fluorinated aryl (eg, phenyl or naphthyl) group, and most preferably R 4, R 5 , R 6 and R 7 wherein each is independently a perfluoroaryl (eg, phenyl or naphthyl) group.

[0515] The cationic moieties of formula (AI) and (I) and their anionic moieties (which are NCAs) are further described below.Any combination of cations and NCAs disclosed herein is suitable for use in the methods of the present disclosure and is therefore incorporated herein.

[0516] Activator-Cation

[0517] The cationic component of the activators described herein (e.g., those of Formulas (AI) and (I) above) is a protonated Lewis base that can be capable of protonating a moiety, such as an alkyl or aryl group, from a transition metal compound. Thus, upon release of a neutral leaving group (e.g., an alkane produced by the combination of a proton provided by the cationic component of the activator and an alkyl substituent of the transition metal compound), a transition metal cation is produced, which is a catalytically active species.

[0518] In at least one embodiment of Formula (I) or (AI), wherein the cation is [R 1 R 2 R 3 EH] + , E is nitrogen or phosphorus, preferably nitrogen; R 1 , R 2 and R 3 Each of which is independently hydrogen, C1-C 40 Branched or linear alkyl or C5-C 50 -aryl, where R 1 , R 2 and R 3 Each of which is independently unsubstituted or substituted by at least one of the following: halo, C5-C 50 Aryl, C6-C 35 Arylalkyl, C6-C 35 Alkaryl, and in C5-C 50 In the case of aryl groups, C1-C 50 Alkyl; wherein R 1 , R 2 and R 3 In some embodiments, R 1 , R 2 and R3 At least one (or one, two or three) is a linear or branched alkyl group (e.g. a linear or branched C3-C 40 Alkyl, optionally for example linear or branched C7-C 40 alkyl).

[0519] In at least one embodiment of Formula (I) or (AI), wherein the cation is [R 1 R 2 R 3 EH] + , E is nitrogen or phosphorus, and R 1 , R 2 and R 3 Each of which is independently C1-C 40 Linear or branched alkyl, C5-C 50 -Aryl (e.g. C5-C 22 - aryl, preferably aralkyl (wherein the alkyl has 1 to 10 carbon atoms and the aryl has 6 to 20 carbon atoms) or a five-, six- or seven-membered heterocyclic group containing at least one atom selected from N, P, O and S, wherein R 1 , R 2 and R 3 Each of which is optionally substituted by halo, -NR'2, -OR' or -SiR'3 (wherein R' is independently hydrogen or C1-C 20 Hydrocarbon), where R 2 Optionally with R 5 Combine to independently form a five-membered, six-membered, or seven-membered ring. 1 , R 2 and R 3 In some embodiments, R 1 , R 2 and R 3 At least one of them is a linear or branched C3-C 40 Alkyl, optionally R 1 , R 2 and R 3 At least two of them are linear or branched C3-C 40 alkyl.

[0520] In at least one embodiment of Formula (I) or (AI) described herein, R 1 , R 2 and R 3One, two or three of them can be independently represented by formula (AIII):

[0521]

[0522] Where R A and R E Each of which is independently H, C1-C 40 Linear or branched alkyl or C5-C 50 -aryl, where R A and R E Each of which is optionally substituted by one or more of the following: halogen, C5-C 50 Aryl, C6-C 35 Arylalkyl, C6-C 35 Alkaryl, and in C5-C 50 In the case of aryl groups, C1-C 50 alkyl, provided that at least one (R A -CR E ) group, R A and R E One or both of them are not H; and

[0523] R C , R B and R D is hydrogen; and Q is an integer from 5 to 40.

[0524] In at least one embodiment of the activator of formula (I) or (AI) herein, R 1 , R 2 and R 3 One, two or three of them can be independently represented by formula (IV), wherein:

[0525]

[0526] Where R 17 , R 18 , R 19 , R 20 and R 21 Each of which is independently selected from hydrogen, C1-C 40 Hydrocarbon or C1-C 40 Substituted hydrocarbon groups, heteroatoms such as halogens, groups containing heteroatoms, such as R 17 , R 18 , R 19 , R 20 and R 21 At least one of them is not hydrogen.

[0527] In at least one embodiment of Formula (I) or (AI), R 1 , R 2and R 3 One, two or three of them may be independently represented by formula (AIII) or (IV):

[0528]

[0529] Where R A and R E Each of which is independently selected from H, C1-C 40 Linear or branched alkyl or C5-C 50 -aryl, where R A and R E Each of which is optionally substituted by one or more of the following: halogen, C5-C 50 Aryl, C6-C 35 Arylalkyl, C6-C 35 Alkaryl, and in C5-C 50 In the case of aryl groups, C1-C 50 alkyl, provided that at least one (R A -CR E ) group, R A and R E One or both are not H;

[0530] R C , R B and R D is hydrogen; and

[0531] Q is an integer between 5 and 40.

[0532] R 17 , R 18 , R 19 , R 20 and R 21 Each of which is independently selected from hydrogen, C1-C 40 Hydrocarbon or C1-C 40 substituted hydrocarbon group, heteroatom such as halogen, heteroatom-containing group, or represented by formula (AIII). 17 , R 18 , R 19 , R 20 and R 21 At least one of them is a linear or branched alkyl group, for example, R 17 , R 18 , R 19 , R 20 and R 21 One, two, three, four or five of them are represented by formula (AIII).

[0533] In at least one embodiment, the branched alkyl group can have 1 to 30 tertiary or quaternary carbons, alternatively 2 to 10 tertiary or quaternary carbons, alternatively 2 to 4 tertiary or quaternary carbons, or the branched alkyl group has 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 or 30 tertiary or quaternary carbons.

[0534] In at least one embodiment of Formula (I) or (AI), R 1 , R 2 and R 3 Each of which can be independently selected from:

[0535] 1) optionally substituted linear alkyl (e.g., methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl or n-triacontyl);

[0536] 2) optionally substituted branched alkyl groups (e.g., alkyl-butyl, alkyl-pentyl, alkyl-hexyl, alkyl-heptyl, alkyl-octyl, alkyl-nonyl, alkyl-decyl, alkyl-undecyl, alkyl-dodecyl, alkyl-tridecyl, alkyl-tetradecyl, alkyl-pentadecyl, alkyl-hexadecyl, alkyl-heptadecyl, alkyl-octadecyl, alkyl-nonadecyl, alkyl-eicosyl (including polyalkyl analogs, i.e., dialkyl-butyl, dialkyl-pentyl, dialkyl-hexyl, dialkyl-heptyl, dialkyl-octyl, dialkyl-nonyl, dialkyl-decyl, dialkyl-undecyl, dialkyl-dodecyl, dialkyl-tridecyl, di ... trialkyl-octyl, trialkyl-nonadecyl, trialkyl-eicosyl, trialkyl-butyl, trialkyl-pentyl, trialkyl-hexyl, trialkyl-heptyl, trialkyl-octyl, trialkyl-nonyl, trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl, trialkyl-tridecyl, trialkyl-tetradecyl, trialkyl-pentadecyl, trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl, and trialkyl-eicosyl, and the like), and isomers thereof, wherein each alkyl group is independently C1-C 40 (or C2-C 30 , or C3-C20 ) linear, branched or cyclic alkyl groups), preferably the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or triacontyl);

[0537] 3) optionally substituted aralkyl groups, for example (methylphenyl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, tridecylphenyl, tetradecylphenyl, pentadecylphenyl, hexadecylphenyl, heptadecylphenyl, octadecylphenyl, nonadecylphenyl, eicosylphenyl, heneicosylphenyl, docosylphenyl, tricosylphenyl, tetracosylphenyl, pentacosylphenyl, hexacosylphenyl, heptacosylphenyl, octacosylphenyl, nonacosylphenyl, triacontylphenyl, 3,5,5-trimethylhexylphenyl, dioctylphenyl, 3,3,5-trimethylhexylphenyl, 2,2,3,3,4-pentamethylpentylphenyl, etc.);

[0538] 4) optionally substituted silyl, such as trialkylsilyl, wherein each alkyl group is independently an optionally substituted C1-C 20 Alkyl (e.g., trimethylsilyl, triethylsilyl, tripropylsilyl, tributylsilyl, trihexylsilyl, triheptylsilyl, trioctylsilyl, trinonylsilyl, tridecylsilyl, tri-undecylsilyl, tri-dodecylsilyl, tri-tridecylsilyl, tri-tetradecylsilyl, tri-pentadecylsilyl, tri-hexadecylsilyl, tri-heptadecylsilyl, tri-octadecylsilyl, tri-nonadecylsilyl, tri-eicosylsilyl);

[0539] 5) optionally substituted alkoxy (e.g., -OR*, wherein R* is an optionally substituted C1-C 20 Alkyl or aryl (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, phenyl, alkylphenyl (e.g., methylphenyl, propylphenyl, etc.), naphthyl or anthracenyl);

[0540] 6) halogen (such as Br or Cl); and

[0541] 7) Halogen-containing groups (eg bromomethyl, bromophenyl, etc.).

[0542] In at least one embodiment of Formula (I) or (AI), R 1 It's methyl.

[0543] In at least one embodiment of Formula (I) or (AI), R 2 is unsubstituted phenyl or substituted phenyl. In at least one embodiment, R 2 is phenyl, methylphenyl, n-butylphenyl, n-octadecylphenyl, or isomers thereof, preferably R 2 It is meta- or para-substituted phenyl, for example meta- or para-substituted alkyl-substituted phenyl.

[0544] In at least one embodiment of Formula (I) or (AI), R 3is a linear or branched alkyl group such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, isopropyl, isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isonadecyl, isoeicosyl, isoheneicosyl, isodocosyl, isotricosyl, isotetracosyl, isopentacosyl, isohexadecyl, isoheptacosyl, isooctacosyl, isonocosyl, or isotriacontyl, alkyl-butyl, alkyl-pentyl, alkyl-hexyl, alkyl-heptyl, alkyl-octyl, alkyl-nonyl, alkyl-decyl, alkyl-undecane alkyl-dodecyl, alkyl-tridecyl, alkyl-tetradecyl, alkyl-pentadecyl, alkyl-hexadecyl, alkyl-heptadecyl, alkyl-octadecyl, alkyl-nonadecyl, alkyl-eicosyl (including polyalkyl analogs, i.e., dialkyl-butyl, dialkyl-pentyl, dialkyl-hexyl, dialkyl-heptyl, dialkyl-octyl, dialkyl-nonyl, dialkyl-decyl, dialkyl-undecyl, dialkyl-dodecyl, dialkyl-tridecyl, dialkyl-tetradecyl, dialkyl-pentadecyl, dialkyl-hexadecyl, dialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl, trialkyl-eicosyl, trialkyl-butyl, trialkyl-pentyl, trialkyl-hexyl, trialkyl-heptyl, trialkyl-octyl, trialkyl-nonyl, trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl, trialkyl-tridecyl, trialkyl-tetradecyl, trialkyl-pentadecyl, trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl and trialkyl-eicosyl, etc.), and isomers thereof, wherein each alkyl group is independently C1-C 40 (or C2-C 30 , or C3-C 20 ) linear, branched or cyclic alkyl groups), preferably the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or triacontyl).

[0545] In at least one embodiment of Formula (I) or (AI), R 1 is methyl and R 2 is phenyl, methylphenyl, n-butylphenyl, n-octadecylphenyl, or isomers thereof, preferably R 2 is meta- or para-substituted phenyl, such as meta- or para-substituted alkyl-substituted phenyl, and R 3 It is a linear or branched alkyl group.

[0546] In at least one embodiment of Formula (I) or (AI), R 1 is methyl and R 2 is a branched alkyl group and R 3 It is a linear or branched alkyl group.

[0547] In a preferred embodiment, R 1 is methyl, R 2 is a substituted phenyl group, R 3 It is C 10 -C 30 Linear or branched alkyl.

[0548] In some embodiments, R 2 is not meta-substituted phenyl. 2 It is not an ortho-substituted phenyl group.

[0549] In at least one embodiment, R 1 is methyl, R 2 It is C1-C 35 Alkyl substituted phenyl (preferably ortho- or meta-substituted), R 3 It is C8-C 30 Branched alkyl.

[0550] In at least one embodiment, R 1 It is C1-C 10 Alkyl, R 2 It is C1-C 35 Alkyl substituted phenyl (preferably para-substituted phenyl), R 3 It is C8-C 30 Linear or branched alkyl.

[0551] In at least one embodiment, R 1 is methyl, R 2 It is C1-C 35Alkyl-substituted phenyl groups, for example methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecylphenyl, n-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecylphenyl, n-eicosylphenyl, n-heneicosylphenyl, n-docosylphenyl, n-tricosylphenyl, n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl, n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl, n-triacontylphenyl, and R 3 It is C8-C 30Linear or branched alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, isopropyl, alkyl-butyl, alkyl-pentyl, alkyl- alkyl-hexyl, 2-alkyl-heptyl, 2-alkyl-octyl, 2-alkyl-nonyl, 2-alkyl-decyl, 2-alkyl-undecyl, 2-alkyl-dodecyl, 2-alkyl-tridecyl, 2-alkyl-tetradecyl, alkyl-pentadecyl, alkyl-hexadecyl, alkyl-heptadecyl, alkyl-octadecyl, alkyl-nonadecyl and alkyl-eicosyl (e.g., 2-alkyl-pentyl, 2- ... 2-alkyl-tetradecyl, 2-alkyl-pentadecyl, 2-alkyl-hexadecyl, 2-alkyl-heptadecyl, 2-alkyl-octadecyl, 2-alkyl-nonadecyl, 2-alkyl-eicosyl or polyalkyl analogs, i.e., dialkyl-butyl, dialkyl-pentyl, dialkyl-hexyl, dialkyl-heptyl, dialkyl-octyl, dialkyl-nonyl, dialkyl-decyl, dialkyl-undecyl, dialkyl-dodecyl, dialkyl-tridecyl, dialkyl-tetradecyl, dialkyl-pentadecyl, dialkyl-hexadecyl, dialkyl-heptadecyl, dialkyl- trialkyl-octadecyl, dialkyl-nonadecyl, dialkyl-eicosyl, trialkyl-butyl, trialkyl-pentyl, trialkyl-hexyl, trialkyl-heptyl, trialkyl-octyl, trialkyl-nonyl, trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl, trialkyl-tridecyl, trialkyl-tetradecyl, trialkyl-pentadecyl, trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl and trialkyl-eicosyl, etc.), or isomers thereof, wherein each alkyl group is independently C1-C 40 (or C2-C 30 , or C3-C 20 ) linear, branched or cyclic alkyl groups), preferably the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or triacontyl).

[0552] In some embodiments, R 2 It is C1-C 35 Alkyl-substituted phenyl, for example methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecylphenyl, n-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecylphenyl, n-eicosylphenyl, n-heneicosylphenyl, n-docosylphenyl, n-tricosylphenyl, n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl, n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl, n-triacontylphenyl, and R3 is C8-C8 30Linear or branched alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, isopropyl, alkyl-butyl, alkyl-pentyl, alkyl- alkyl-hexyl, 2-alkyl-heptyl, 2-alkyl-octyl, 2-alkyl-nonyl, 2-alkyl-decyl, 2-alkyl-undecyl, 2-alkyl-dodecyl, 2-alkyl-tridecyl, 2-alkyl-tetradecyl, alkyl-pentadecyl, alkyl-hexadecyl, alkyl-heptadecyl, alkyl-octadecyl, alkyl-nonadecyl and alkyl-eicosyl (e.g., 2-alkyl-pentyl, 2- ... 2-alkyl-tetradecyl, 2-alkyl-pentadecyl, 2-alkyl-hexadecyl, 2-alkyl-heptadecyl, 2-alkyl-octadecyl, 2-alkyl-nonadecyl, 2-alkyl-eicosyl or polyalkyl analogs, i.e., dialkyl-butyl, dialkyl-pentyl, dialkyl-hexyl, dialkyl-heptyl, dialkyl-octyl, dialkyl-nonyl, dialkyl-decyl, dialkyl-undecyl, dialkyl-dodecyl, dialkyl-tridecyl, dialkyl-tetradecyl, dialkyl-pentadecyl, dialkyl-hexadecyl, dialkyl-heptadecyl, dialkyl- trialkyl-octadecyl, dialkyl-nonadecyl, dialkyl-eicosyl, trialkyl-butyl, trialkyl-pentyl, trialkyl-hexyl, trialkyl-heptyl, trialkyl-octyl, trialkyl-nonyl, trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl, trialkyl-tridecyl, trialkyl-tetradecyl, trialkyl-pentadecyl, trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl and trialkyl-eicosyl, etc.), or isomers thereof, wherein each alkyl group is independently C1-C 40 (or C2-C 30 , or C3-C 20 ) linear, branched or cyclic alkyl groups), preferably the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or triacontyl).

[0553] In at least one embodiment of Formula (I), R 1 is methyl, R 2 is a substituted phenyl group, R 3 It is C8-C 30 Branched alkyl and R 4 , R 5 , R 6 , R 7 It is perfluoronaphthyl.

[0554] In at least one embodiment of Formula (AI), R 1 is methyl, R 2 is a substituted phenyl group, R 3 It is C8-C 30 A linear or branched alkyl group, E is nitrogen and each Q is perfluoronaphthyl.

[0555] In a preferred embodiment, R 1 is methyl, R 2 It is C1-C 35 Alkyl-substituted phenyl, for example methylphenyl, ethylphenyl, n-propylphenyl, n-butylphenyl, n-pentylphenyl, n-hexylphenyl, n-heptylphenyl, n-octylphenyl, n-nonylphenyl, n-decylphenyl, n-undecylphenyl, n-dodecylphenyl, n-tridecylphenyl, n-tetradecylphenyl, n-pentadecylphenyl, n-hexadecylphenyl, n-heptadecylphenyl, n-octadecylphenyl, n-nonadecylphenyl, n-eicosylphenyl, n-heneicosylphenyl, n-docosylphenyl, n-tricosylphenyl, n-tetracosylphenyl, n-pentacosylphenyl, n-hexacosylphenyl, n-heptacosylphenyl, n-octacosylphenyl, n-nonacosylphenyl, n-triacontylphenyl, R 3 is a linear or branched alkyl group (e.g. C 10 -C 30The alkyl radicals are branched) or are methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, isopropyl, alkyl-butyl, alkyl-pentyl, alkyl-hexyl, alkyl-pentyl, 2-alkyl-hexyl, 2-alkyl-heptyl, 2-alkyl-octyl, 2-alkyl-nonyl, 2-alkyl-decyl, 2-alkyl-undecyl, 2-alkyl-dodecyl, 2-alkyl-tridecyl, 2-alkyl-tetradecyl, alkyl-pentadecyl, alkyl-hexadecyl, alkyl-heptadecyl, alkyl-octadecyl, alkyl-nonadecyl and alkyl-eicosyl (e.g., 2-alkyl-pentyl, 2-alkyl-hexyl, 2-alkyl-heptyl, 2-alkyl-octyl, 2-alkyl-nonyl, 2-alkyl-decyl, 2-alkyl-undecyl, 2-alkyl-dodecyl, 2-alkyl-tridecyl, 2-alkyl- 2-alkyl-pentadecyl, 2-alkyl-hexadecyl, 2-alkyl-heptadecyl, 2-alkyl-octadecyl, 2-alkyl-nonadecyl, and 2-alkyl-eicosyl or polyalkyl analogs, i.e., dialkyl-butyl, dialkyl-pentyl, dialkyl-hexyl, dialkyl-heptyl, dialkyl-octyl, dialkyl-nonyl, dialkyl-decyl, dialkyl-undecyl, dialkyl-dodecyl, dialkyl-tridecyl, dialkyl-tetradecyl, dialkyl-pentadecyl, dialkyl-hexadecyl, dialkyl-heptadecyl, dialkyl- trialkyl-octadecyl, dialkyl-nonadecyl, dialkyl-eicosyl, trialkyl-butyl, trialkyl-pentyl, trialkyl-hexyl, trialkyl-heptyl, trialkyl-octyl, trialkyl-nonyl, trialkyl-decyl, trialkyl-undecyl, trialkyl-dodecyl, trialkyl-tridecyl, trialkyl-tetradecyl, trialkyl-pentadecyl, trialkyl-hexadecyl, trialkyl-heptadecyl, trialkyl-octadecyl, trialkyl-nonadecyl, trialkyl-eicosyl, etc.), or isomers thereof, wherein each alkyl group is independently C1-C 40 (or C2-C 30 , or C3-C 20 ) linear, branched or cyclic alkyl groups), preferably the alkyl group is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl or triacontyl); and R 4 , R 5, R 6 , R 7 wherein each is a perfluoronaphthyl group.

[0556] In at least one embodiment herein, the branched alkyl group can be isopropyl, isobutyl, isopentyl, isohexyl, isoheptyl, isooctyl, isononyl, isodecyl, isoundecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, isohexadecyl, isohexadecyl, isoheptadecyl, isooctyl, isononadecyl, isoeicosyl, isohexadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isononadecyl, isoeicosyl, isohexadecyl, isohexadecyl, isotricosyl, isotetracosyl, isopentacosyl, isohexadecyl, isoheptacosyl, isooctacosyl, isohexacosyl, or isotriacontyl.

[0557] In at least one embodiment, R 1 It is o-MePh, R 2 and R 3 It is isooctadecyl.

[0558] In at least one embodiment, R 1 , R 2 and R 3 A total of 20 or more carbon atoms, for example 21 or more carbon atoms, for example 22 or more carbon atoms, for example 25 or more carbon atoms, for example 30 or more carbon atoms, for example 35 or more carbon atoms, for example 37 or more carbon atoms, for example 40 or more carbon atoms, for example 45 or more carbon atoms are contained.

[0559] Activator-Anion

[0560] The anionic component of the activator described herein includes an anionic component of the formula [M k+ Q n ] represented by those wherein k is 1, 2 or 3; n is 1, 2, 3, 4, 5 or 6 (preferably 1, 2, 3 or 4); M is an element selected from Group 13 of the Periodic Table, preferably boron or aluminum, and Q is independently hydrogen, a bridged or unbridged dialkylamino, a halo, an alkoxy, an aryloxy, a hydrocarbyl, a substituted hydrocarbyl, a halohydrocarbyl, a substituted halohydrocarbyl and a halogen-substituted hydrocarbyl group, wherein Q has up to 20 carbon atoms, provided that Q is not more than 1 time a halo. For example, each Q may be a fluorinated hydrocarbyl group, optionally having 1 to 20 carbon atoms, for example, each Q is a fluorinated aryl group, for example, each Q is a perfluoroaryl group. For example, at least one Q is not a substituted phenyl group such as a perfluorophenyl group, for example, all Q are not substituted phenyl groups such as perfluorophenyl groups.

[0561] Alternatively, in at least one embodiment described herein, at least one Q is not substituted phenyl, and alternatively all Q are not substituted phenyl. Alternatively, at least one Q is not fluorine-substituted phenyl, and alternatively all Q are not fluorine-substituted phenyl. Alternatively, at least one Q is not perfluorophenyl, and alternatively all Q are not perfluorophenyl.

[0562] In a preferred embodiment of at least one embodiment of Formula (AI), when R 1 is methyl, R 2 It is C 18 and R 3 It is C 18 When , each Q is not a perfluorophenyl group.

[0563] In at least one embodiment, for the borate portion ([BR 4 R 5 R 6 R 7 ] - ), R 4 , R 5 , R 6 and R 7 Each of the above is independently an aryl group (eg, naphthyl), wherein R 4 , R 5 , R 6 and R 7 At least one of R is substituted by 1 to 7 fluorine atoms. In at least one embodiment, R 4 , R 5 , R 6 and R 7 Each of them is naphthyl, wherein R 4 , R 5 , R 6 and R 7 At least one of them is substituted by 1 to 7 fluorine atoms.

[0564] In at least one embodiment, R 4 , R 5 , R 6 and R 7 wherein each is independently a naphthyl group containing one fluorine atom, two fluorine atoms, three fluorine atoms, four fluorine atoms, five fluorine atoms, six fluorine atoms, or seven fluorine atoms.

[0565] In at least one embodiment of Formula (I), when R 1 is methyl, R 2 It is C 18 and R 3 It is C 18 When R 4 , R 5 , R6 and R 7 Each of which is not a perfluorophenyl group.

[0566] In at least one embodiment, R 4 is a naphthyl group containing one fluorine atom, two fluorine atoms, three fluorine atoms, four fluorine atoms, five fluorine atoms, six fluorine atoms or seven fluorine atoms, and R 5 , R 6 and R 7 wherein each is independently a phenyl group containing one, two, three, four or five fluorine atoms or a naphthyl group containing one, two, three, four, five, six or seven fluorine atoms.

[0567] In at least one embodiment of Formula (I) or (AI), R 4 , R 5 , R 6 and R 7 Each of them is independently naphthyl, wherein R 4 , R 5 , R 6 and R 7 At least one of the groups is naphthyl substituted by one, two, three, four, five, six or seven fluorine atoms.

[0568] In at least one embodiment of Formula (I) or (AI), R 4 , R 5 , R 6 and R 7 Each of them is independently phenyl, wherein R 4 , R 5 , R 6 and R 7 At least one of the phenyl groups is substituted by one, two, three, four or five fluorine atoms.

[0569] Alternatively, in at least one embodiment of formula (I) or (AI), preferably at least one R 4 , R 5 , R 6 and R 7 is not a substituted phenyl group, preferably R 4 , R 5 , R 6 and R 7 In a preferred embodiment, R 1 Not methyl, R 2 Not C 18 and R 3 Not C 18 .

[0570] In at least one embodiment of formula (I) or (AI), preferably all Q or R 4 , R 5 , R 6 and R 7 All of them are not perfluoroaryl groups such as perfluorophenyl groups.

[0571] In at least one embodiment of Formula (I) or (AI), R 4 , R 5 , R 6 and R 7 All of them are naphthyl, among which R 4 , R 5 , R 6 and R 7 At least one, two, three or four of the moieties are substituted by one, two, three, four, five, six or seven fluorine atoms.

[0572] In at least one embodiment, preferably R 4 , R 5 , R 6 and R 7 wherein each is independently a naphthyl group containing one fluorine atom, two fluorine atoms, three fluorine atoms, four fluorine atoms, five fluorine atoms, six fluorine atoms or seven fluorine atoms, preferably seven fluorine atoms.

[0573] In at least one embodiment, R 4 is independently a naphthyl group containing one fluorine atom, two fluorine atoms, three fluorine atoms, four fluorine atoms, five fluorine atoms, six fluorine atoms, or seven fluorine atoms.

[0574] In at least one embodiment, R 4 , R 5 , R 6 and R 7 Each of the above is independently a fluorinated hydrocarbon group having 1 to 30 carbon atoms, more preferably R 4 , R 5 , R 6 and R 7 Each is independently a fluorinated aryl (eg, phenyl, biphenyl [(C6H3(C6H5)2)4B] or naphthyl) group, and most preferably R 4 , R 5 , R 6 and R 7 Each of the R 4 , R 5 , R 6 and R 7 Not perfluorophenyl.

[0575] In at least one embodiment, the borate activator comprises tetrakis(heptafluoronaphthalen-2-yl)borate.

[0576] Anions for use in the non-coordinating anion activators described herein may include those represented by the following Formula 1:

[0577]

[0578] in:

[0579] M* is a Group 13 atom, preferably B or Al, preferably B;

[0580] Each R 11 are independently halo, preferably fluoro;

[0581] Each R 12 are independently halogen, C6-C 20 A substituted aromatic hydrocarbon group or a substituted aromatic hydrocarbon group having the formula -O-Si-R a A silyloxy group, wherein R a It is C1-C 20 A hydrocarbyl or hydrocarbylsilyl group, preferably R 12 is a fluoro or perfluorophenyl group;

[0582] Each R 13 It is a halogen, C6-C 20 A substituted aromatic hydrocarbon group or a substituted aromatic hydrocarbon group having the formula -O-Si-R a A silyloxy group, wherein R a It is C1-C 20 A hydrocarbyl or hydrocarbylsilyl group, such as R 13 is a fluorine group or a C6 perfluoroaromatic hydrocarbon group;

[0583] Where R 12 and R 13 It can form one or more saturated or unsaturated, substituted or unsubstituted rings, preferably R 12 and R 13 Preferably, the anion has a molecular weight greater than 700 g / mol, and preferably at least three of the substituents on the M* atom each have a molecular weight greater than The molecular volume of .

[0584] "Molecular volume" is used herein as an approximation of the spatial volume of an activator molecule in solution. Comparing substituents having different molecular volumes allows a substituent having a smaller molecular volume to be considered "less bulky" than a substituent having a larger molecular volume. Conversely, a substituent having a larger molecular volume can be considered "more bulky" than a substituent having a smaller molecular volume.

[0585] Molecular volume can be calculated as reported in Girolami, GS (1994) "A Simple "Back of the Envelope" Method for Estimating the Densities and Molecular Volumes of Liquids and Solids," Journal of Chemical Education, Vol. 71(11), November 1994, pp. 962-964. The following formula is used to calculate the molecular volume: Molecular volume (MV): MV = 8.3V s , where V s is the scaled volume. s is the sum of the relative volumes of the constituent atoms and is calculated from the molecular formula of the substituent using the relative volumes in Table 2 below. For fused rings, each fused ring V s The calculated total MV of an anion is the sum of the MVs of each substituent, for example the MV of perfluorophenyl is And the calculated total MV of tetrakis(perfluorophenyl)borate is four times or

[0586] Table 2

[0587] element Relative volume H 1 The first short period, Li to F 2 Second short cycle, Na to Cl 4 The first long cycle, K to Br 5 The second longest period, Rb to I 7.5 The third longest period, Cs to Bi 9

[0588] Exemplary anions useful herein and their respective scaled volumes and molecular volumes are shown below in Table 3. Imaginary bonds represent bonding to boron.

[0589] Table 3

[0590]

[0591]

[0592] The activator can be added to the polymerization in the form of an ion pair using, for example, [DEBAH] + [NCA] -, where the 4-butyl-N,N-bis(isotridecyl)phenylammonium (benzenaminium) - ("DEBAH")) cation reacts with a basic leaving group on the transition metal complex to form a transition metal complex cation and [NCA] -. Alternatively, the transition metal complex can be reacted with a neutral NCA precursor such as B(C 10 F7)3 reaction, which abstracts anionic groups from the complex to form activated species.

[0593] In at least one embodiment, the activators for the borate activator compounds obtained in their salt form are: lithium tetrakis(heptafluoronaphthalene-2-yl)borate ether (Li-BF28), N,N-dimethylanilinium tetrakis(heptafluoronaphthalene-2-yl)borate (DMAH-BF28), sodium tetrakis(heptafluoronaphthalene-2-yl)borate (Na-BF28) and N,N-dimethylanilinium tetrakis(heptafluoronaphthalene-2-yl)borate (DMAH-BF28).

[0594] In at least one embodiment where the activator is represented by formula (AI), when Q is a fluorophenyl group, then R 2 Not C1-C 40 Linear alkyl groups, such as R 2 is not an optionally substituted C1-C 40 A linear alkyl group (alternatively when Q is a substituted phenyl group, then R 2 Not C1-C 40 A linear alkyl group, preferably R 2 is not an optionally substituted C1-C 40 linear alkyl group). Optionally, when Q is a fluorophenyl group (alternatively when Q is a substituted phenyl group), then R 2 is a meta- and / or para-substituted phenyl group, wherein the meta- and para-substituents are independently optionally substituted C1-C 40 Hydrocarbyl groups (e.g. C6-C 40 Aryl group or linear alkyl group, C 12 -C 30 Aryl group or linear alkyl group, or C 10 -C 20 aryl groups or linear alkyl groups), optionally substituted alkoxy groups or optionally substituted silyl groups. Optionally, each Q is a fluorinated hydrocarbon group with 1-30 carbon atoms, more preferably each Q is a fluorinated aryl (e.g. phenyl or naphthyl) group, and most preferably each Q is a perfluoroaryl (e.g. phenyl or naphthyl) group. Optionally, at least one Q is not substituted phenyl. Optionally all Q are not substituted phenyl. Optionally, at least one Q is not perfluorophenyl. Optionally all Q are not perfluorophenyl.

[0595] In some embodiments, R 1 Not methyl, R 2 Not C 18 Alkyl and R 3 Not C 18 Alkyl, optionally R 1 Not methyl, R 2 Not C 18 Alkyl and R 3 Not C 18The alkyl group and at least one Q are not substituted phenyl, and optionally all Q are not substituted phenyl.

[0596] Cationic components useful in formula (AI) or (I) include those represented by the following formula:

[0597]

[0598]

[0599] Cationic components useful in formula (AI) or (I) include those represented by the following formula:

[0600]

[0601] The activator can be added to the polymerization in the form of an ion pair using, for example, [M2HTH] + [NCA]-, where the di(hydrogenated tallow)methylamine ("M2HTH")) cation reacts with a basic leaving group on the transition metal complex to form a transition metal complex cation and [NCA]-. Alternatively, the transition metal complex can be reacted with a neutral NCA precursor such as B(C6F5)3, which extracts an anionic group from the complex to form an activated species. Useful activators include di(hydrogenated tallow)methylammonium[tetrakis(pentafluorophenyl)borate] (i.e., [M2HTH]B(C6F5)4) and di(octadecyl)toluylammonium[tetrakis(pentafluorophenyl)borate] (i.e., [DOdTH]B(C6F5)4).

[0602] The activator compound may include one or more of the following:

[0603] [Tetra(perfluorophenyl)borate] N,N-di(hydrogenated tallow)methylammonium,

[0604] [Tetrakis(perfluorophenyl)borate] N-methyl-4-nonadecylammonium-N-octadecylanilinium,

[0605] [Tetrakis(perfluorophenyl)borate] N-methyl-4-hexadecyl-N-octadecylanilinium,

[0606] [Tetrakis(perfluorophenyl)borate] N-methyl-4-tetradecyl-N-octadecylanilinium,

[0607] [Tetrakis(perfluorophenyl)borate] N-methyl-4-dodecyl-N-octadecylanilinium,

[0608] [Tetrakis(perfluorophenyl)borate] N-methyl-4-decyl-N-octadecylanilinium,

[0609] [Tetrakis(perfluorophenyl)borate] N-methyl-4-octyl-N-octadecylanilinium,

[0610] [Tetrakis(perfluorophenyl)borate] N-methyl-4-hexyl-N-octadecylanilinium,

[0611] [Tetrakis(perfluorophenyl)borate] N-methyl-4-butyl-N-octadecylanilinium,

[0612] [Tetrakis(perfluorophenyl)borate] N-methyl-4-octadecyl-N-decylanilinium,

[0613] [Tetrakis(perfluorophenyl)borate] N-methyl-4-nonadecylammonium-N-dodecylanilinium,

[0614] [Tetrakis(perfluorophenyl)borate] N-methyl-4-nonadecylammonium-N-tetradecylanilinium,

[0615] [Tetrakis(perfluorophenyl)borate] N-methyl-4-nonadecylammonium-N-hexadecylanilinium,

[0616] [Tetrakis(perfluorophenyl)borate] N-methyl-4-nonadecylammonium-N-octadecylanilinium,

[0617] [Tetrakis(perfluorophenyl)borate] N-ethyl-4-nonadecylammonium-N-octadecylanilinium,

[0618] [Tetrakis(perfluorophenyl)borate] N-methyl-N,N-dioctadecylammonium,

[0619] [Tetrakis(perfluorophenyl)borate] N-methyl-N,N-dihexadecylammonium,

[0620] [Tetrakis(perfluorophenyl)borate] N-methyl-N,N-di(tetradecyl)ammonium,

[0621] [Tetrakis(perfluorophenyl)borate] N-methyl-N,N-didodecylammonium,

[0622] [Tetrakis(perfluorophenyl)borate] N-methyl-N,N-didecylammonium,

[0623] [Tetrakis(perfluorophenyl)borate] N-methyl-N,N-dioctylammonium,

[0624] [Tetrakis(perfluorophenyl)borate] N-ethyl-N,N-dioctadecylammonium,

[0625] [Tetrakis(perfluorophenyl)borate] N,N-dioctadecyltolylammonium,

[0626] [Tetrakis(perfluorophenyl)borate] N,N-dihexadecyltolylammonium,

[0627] [Tetrakis(perfluorophenyl)borate] N,N-di(tetradecyl)tolylammonium,

[0628] [Tetrakis(perfluorophenyl)borate] N,N-di(dodecyl)tolylammonium,

[0629] [Tetrakis(perfluorophenyl)borate] N-octadecyl-N-hexadecyl-tolylammonium,

[0630] [Tetrakis(perfluorophenyl)borate] N-octadecyl-N-hexadecyl-tolylammonium,

[0631] [Tetrakis(perfluorophenyl)borate] N-octadecyl-N-tetradecyl-tolylammonium,

[0632] [Tetrakis(perfluorophenyl)borate] N-octadecyl-N-dodecyl-tolylammonium,

[0633] [Tetrakis(perfluorophenyl)borate] N-octadecyl-N-decyl-tolylammonium,

[0634] [Tetrakis(perfluorophenyl)borate] N-hexadecyl-N-tetradecyl-tolylammonium,

[0635] [Tetrakis(perfluorophenyl)borate] N-hexadecyl-N-dodecyl-tolylammonium,

[0636] [Tetrakis(perfluorophenyl)borate] N-hexadecyl-N-decyl-tolylammonium,

[0637] [Tetrakis(perfluorophenyl)borate] N-tetradecyl-N-dodecyl-tolylammonium,

[0638] [Tetrakis(perfluorophenyl)borate] N-tetradecyl-N-decyl-tolylammonium,

[0639] [Tetrakis(perfluorophenyl)borate] N-dodecyl-N-decyl-tolylammonium,

[0640] [Tetrakis(perfluorophenyl)borate] N-methyl-N-octadecylanilinium,

[0641] [Tetrakis(perfluorophenyl)borate] N-methyl-N-hexadecylanilinium,

[0642] [Tetrakis(perfluorophenyl)borate] N-methyl-N-tetradecylanilinium,

[0643] [Tetrakis(perfluorophenyl)borate] N-methyl-N-dodecylanilinium,

[0644] [tetrakis(perfluorophenyl)borate]N-methyl-N-decylanilinium, and

[0645] [Tetrakis(perfluorophenyl)borate] N-methyl-N-octylanilammonium.

[0646] The activator compound may include one or more of the following:

[0647] N,N-di(hydrogenated tallow)methylammonium tetra(perfluoronaphthalen-2-yl)borate, N-methyl-4-nonadecyl-N-octadecylanilinium tetra(perfluoronaphthalen-2-yl)borate, N-methyl-4-hexadecyl-N-octadecylanilinium tetra(perfluoronaphthalen-2-yl)borate, N-methyl-4-tetradecyl-N-octadecylanilinium tetra(perfluoronaphthalen-2-yl)borate, N-methyl-4-dodecyl-N-octadecylanilinium tetra(perfluoronaphthalen-2-yl)borate Aniline, N-methyl-4-decyl-N-octadecylanilinium tetra(perfluoronaphthalen-2-yl)borate, N-methyl-4-octyl-N-octadecylanilinium tetra(perfluoronaphthalen-2-yl)borate, N-methyl-4-hexyl-N-octadecylanilinium tetra(perfluoronaphthalen-2-yl)borate, N-methyl-4-butyl-N-octadecylanilinium tetra(perfluoronaphthalen-2-yl)borate, N-methyl-4-octadecyl-N-decylbenzene tetra(perfluoronaphthalen-2-yl)borate ammonium, tetrakis(perfluoronaphthalen-2-yl)borate N-methyl-4-nonadecy-N-dodecylanilinium, tetrakis(perfluoronaphthalen-2-yl)borate N-methyl-4-nonadecy-N-tetradecylanilinium, tetrakis(perfluoronaphthalen-2-yl)borate N-methyl-4-nonadecy-N-hexadecylanilinium, tetrakis(perfluoronaphthalen-2-yl)borate N-methyl-4-nonadecy-N-octadecylanilinium, tetrakis(perfluoronaphthalen-2-yl)borate N-ethyl-4-nonadecy N-octadecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate, N-methyl-N,N-dioctadecylammonium tetrakis(perfluoronaphthalen-2-yl)borate, N-methyl-N,N-dihexadecylammonium tetrakis(perfluoronaphthalen-2-yl)borate, N-methyl-N,N-ditetradecylammonium tetrakis(perfluoronaphthalen-2-yl)borate, N-methyl-N,N-didodecylammonium tetrakis(perfluoronaphthalen-2-yl)borate,

[0648] N-Methyl-N,N-dioctylammonium tetrakis(perfluoronaphthalen-2-yl)borate,

[0649] N-ethyl-N,N-dioctadecyl-ammonium tetra(perfluoronaphthalene-2-yl)borate, N,N-dioctadecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N,N-dihexadecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N,N-ditetradecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N,N-didodecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N-octadecyl-N-hexadecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N-octadecyl-N-hexadecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate,

[0650] N-octadecyl-N-tetradecyl-tolylammonium tetrakis(perfluoronaphthalen-2-yl)borate,

[0651] N-octadecyl-N-dodecyl-tolylammonium tetrakis(perfluoronaphthalen-2-yl)borate,

[0652] N-octadecyl-N-decyl-tolylammonium tetrakis(perfluoronaphthalen-2-yl)borate,

[0653] N-hexadecyl-N-tetradecyl-tolylammonium tetrakis(perfluoronaphthalen-2-yl)borate,

[0654] N-hexadecyl-N-dodecyl-tolylammonium tetrakis(perfluoronaphthalen-2-yl)borate,

[0655] N-hexadecyl-N-decyl-tolylammonium tetrakis(perfluoronaphthalen-2-yl)borate,

[0656] N-Tetradecyl-N-dodecyl-tolylammonium tetrakis(perfluoronaphthalen-2-yl)borate,

[0657] N-Tetradecyl-N-decyl-tolylammonium tetrakis(perfluoronaphthalen-2-yl)borate,

[0658] N-dodecyl-N-decyl-tolylammonium tetrakis(perfluoronaphthalen-2-yl)borate,

[0659] N-Methyl-N-octadecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,

[0660] N-Methyl-N-hexadecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,

[0661] N-Methyl-N-tetradecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,

[0662] N-Methyl-N-dodecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,

[0663] N-methyl-N-decylanilinium tetrakis(perfluoronaphthalen-2-yl)borate, and

[0664] N-Methyl-N-octylanilaminium tetrakis(perfluoronaphthalen-2-yl)borate.

[0665] Additional useful activators and their synthesis are described in USSN 16 / 394,166 filed April 25, 2019, USSN 16 / 394,186 filed April 25, 2019, and USSN 16 / 394,197 filed April 25, 2019, which are incorporated herein by reference.

[0666] In at least one embodiment, the activator is not:

[0667]

[0668]

[0669] The typical activator to catalyst ratio, for example, all NCA activators to catalyst ratios are about 1:1 molar ratios. Alternative ranges include 0.1:1-100:1, alternatively 0.5:1-200:1, alternatively 1:1-500:1, alternatively 1:1-1000:1. Particularly useful ranges are 0.5:1-10:1, preferably 1:1 to 5:1.

[0670] It is also within the scope of the present disclosure that the catalyst compound may be combined with a combination of aluminoxanes and activators described herein.

[0671] Synthesis of activating agent

[0672] In at least one embodiment, a two-step method can be used to perform the general synthesis of the activator. In the first step, the amine or phosphine is dissolved in a solvent (e.g., hexane, cyclohexane, methylcyclohexane, ether, dichloromethane, toluene) and an excess (e.g., 1.2 molar equivalents) of hydrogen chloride is added to form an ammonium chloride or phosphonium chloride salt. This salt is typically separated from the reaction medium by filtration and dried under reduced pressure. The separated ammonium chloride or phosphonium chloride is then heated to reflux in a solvent (e.g., cyclohexane, dichloromethane, methylcyclohexane) with about one molar equivalent of an alkali metal salt or metalloid (e.g., borate or aluminate) to form the desired borate or aluminate and a byproduct alkali chloride, which can typically be removed by filtration.

[0673] In at least one embodiment, a two-step process can be used to perform the general synthesis of ammonium borate activators. In the first step, the amine is dissolved in a solvent (e.g., hexane, cyclohexane, methylcyclohexane, ether, dichloromethane, toluene) and an excess (e.g., 1.2 molar equivalents) of hydrogen chloride is added to form an ammonium chloride salt. This salt is typically separated from the reaction medium by filtration and dried under reduced pressure. The separated ammonium chloride is then heated to reflux in a solvent (e.g., cyclohexane, dichloromethane, methylcyclohexane) with about one molar equivalent of an alkali metal borate to form ammonium borate and a byproduct alkali metal chloride, which can typically be removed by filtration.

[0674] In at least one embodiment, the activator of the present disclosure can be dissolved in an aliphatic solvent at a concentration of about 10 mM or greater, such as about 20 mM or greater, such as about 30 mM or greater, such as about 50 mM or greater, such as about 75 mM or greater, such as about 100 mM or greater, such as about 200 mM or greater, such as about 300 mM or greater. In at least one embodiment, the activator of the present disclosure is dissolved in isohexane or methylcyclohexane at 25° C. to form a homogeneous solution at a concentration of at least 10 mM.

[0675] In at least one embodiment, the solubility of the borate or aluminate activators of the present disclosure in aliphatic hydrocarbon solvents increases with the amount of cationic groups (i.e., ammonium or ) increases with the number of aliphatic carbon atoms. In at least one embodiment, an ammonium or polyol having about 21 aliphatic carbon atoms or more, such as about 25 aliphatic carbon atoms or more, such as about 35 carbon atoms or more, is used. The activator of the group achieves a solubility of at least 10 mM.

[0676] In at least one embodiment, the solubility of the ammonium borate activators of the present disclosure in aliphatic hydrocarbon solvents increases with increasing aliphatic carbon number in the ammonium group. In at least one embodiment, a solubility of at least 10 mM is achieved using an activator having an ammonium group of about 21 aliphatic carbon atoms or more, such as about 25 aliphatic carbon atoms or more, such as about 35 carbon atoms or more.

[0677] Useful aliphatic hydrocarbon solvents may be isobutane, butane, n-pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and mixtures thereof; cyclic and alicyclic hydrocarbons such as cyclohexane, cycloheptane, methylcyclohexane, methylcycloheptane, and mixtures thereof. In at least one embodiment, the aromatic compound is present in the solvent at less than 1 wt %, such as less than 0.5 wt %, such as 0 wt %, based on the weight of the solvent. The activator of the present disclosure may be dissolved in one or more additional solvents. Additional solvents include ethereal, halogenated solvents, and N,N-dimethylformamide solvents.

[0678] In at least one embodiment, the aliphatic solvent is isohexane and / or methylcyclohexane.

[0679] Various activators

[0680] In some embodiments, two or more different activators are present in the catalyst system. In some embodiments, two or more different activators are present in the reaction zone where the polymerization process(es) are performed. The two or more different activators can be introduced separately into the reactor (e.g., activator solution line (7) and one or more additional lines (not shown) in fluid communication (e.g., directly connected) with the reactor (8). Figure 1 Reactor (8)). Two or more different activators may be stored in two or more storage tanks. Alternatively, two or more activators are combined in a single storage tank, diluted with one or more diluents, and introduced together via a pipeline into the reactor (e.g., via activator solution pipeline (7)).

[0681] When two activators are used as mixed activator systems in a reactor, two activators can be selected so that the two are compatible. Two activators can be used in any suitable ratio. The molar ratio of (A) activator to (B) activator can be 1:1000-1000:1, 1:100-500:1, 1:10-200:1, 1:1-100:1, 1:1-75:1 or 5:1-50:1. The specific ratio selected will depend on the exact activator, activation method and final product selected. In a particular embodiment, when two activators are used, the available molar percentage is 10 to 99.9mol%A to 0.1 to 90mol%B, 25 to 99mol%A to 0.5 to 50mol%B, 50 to 99mol%A to 1 to 25mol%B or 75 to 99mol%A to 1 to 10mol%B based on the molecular weight of the activator.

[0682] Optional scavenger or co-activator

[0683] In addition to these activator compounds, scavengers or co-activators may be used. Alkyl aluminum or organoaluminum compounds that may be used as scavengers or co-activators include, for example, trimethyl aluminum, triethyl aluminum, triisobutyl aluminum, tri-n-hexylaluminum, tri-n-octylaluminum and diethylzinc.

[0684] In at least one embodiment, little or no scavenger is used in the process for producing ethylene polymers. The scavenger (e.g., trialkylaluminum) may be present at 0 mol%, alternatively the scavenger is present at a molar ratio of scavenger metal to transition metal of less than 100:1, such as less than 50:1, such as less than 15:1, such as less than 10:1.

[0685] polymer

[0686] Any suitable polymer can be produced using the methods of the present disclosure. For example, the polymer can be a propylene-based polymer or an ethylene-based polymer (eg, an elastomer).

[0687] The polymer produced herein may contain 0 ppm (or less than 1 ppm, or less than 1 ppb) of aromatic hydrocarbons. For example, the polymer produced herein contains 0 ppm (or less than 1 ppm, or less than 1 ppb) of toluene.

[0688] Elastomer

[0689] As described above, the methods described herein can be used to form elastomers, such as terpolymers comprising ethylene, alpha-olefins and dienes, also referred to as EODE (ethylene-alpha-olefin-diene elastomer). For example, EODE can have a high Mw and a diene content greater than 0.3 wt%, such as greater than 2.0 wt%. These polymers can be mostly amorphous and have a low or zero heat of fusion. As used herein, the term "EODE" includes elastomeric polymers having ethylene, alpha-olefins and one or more non-conjugated diene monomers. The non-conjugated diene monomer can be a straight chain, branched or cyclic hydrocarbon diene having 6-15 carbon atoms. Examples of suitable non-conjugated dienes are straight-chain acyclic dienes such as 1,4-hexadiene and 1,6-octadiene; branched acyclic dienes such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyricene and dihydroociene; monocyclic alicyclic dienes such as 1,4-cyclohexadiene and 1,5-cyclododecadiene. and polycyclic alicyclic fused-ring and bridged-ring dienes such as tetrahydroindene, methyltetrahydroindene, dicyclopentadiene, 5-ethylidene-bicyclo(2,2,1)-hept-2-enyl, alkylidene, cycloalkylidene norbornenes such as 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, 5-vinyl-2-norbornene and norbornadiene.

[0690] In at least one embodiment, the polymer produced in the polymer production method is ethylene-propylene rubber. For example, the polymer is ethylene-propylene-diene rubber (EPDM). In a preferred embodiment, the plasticized polymer is the ethylene-propylene-diene rubber containing the plasticizer of 10-100phr. As used herein, "phr" refers to parts / one hundred parts of plasticizer and pure polymer ratio. In at least one embodiment, ethylene-propylene-diene rubber contains approximately 15 to approximately 100phr (approximately 13 to approximately 50 % by weight) of plasticizer, for example plasticizer Group I or Group II paraffin oil (for example Sunpar 150, ChevronParamount 6001).

[0691] Among the dienes commonly used to prepare EPDM, some example dienes are 1,4-hexadiene (HD), 5-ethylidene-2-norbornene (ethylidene norbornene, ENB), 5-vinylidene-2-norbornene (VNB), 5-methylene-norbornene (MNB), and dicyclopentadiene (DCPD). In at least one embodiment, the diene is 5-ethylidene-2-norbornene (ENB) and / or 1,4-hexadiene (HD). Example EODE can contain about 20 to about 90 weight percent ethylene, such as about 30 to about 85 weight percent ethylene, such as about 35 to about 80 weight percent ethylene. Alpha-olefins suitable for use in preparing elastomers with ethylene and dienes can be propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and 1-dodecene. Alpha-olefins are typically incorporated into EODE polymers at about 10 to about 80 weight percent, or about 20 to about 65 weight percent. The non-conjugated diene is typically incorporated into the EODE at about 0.5 to about 35 wt%, such as about 20 to about 35 wt%, or about 1 to about 15 wt%, or about 2 to about 12 wt%. If desired, more than one diene, such as HD and ENB, may be incorporated simultaneously, wherein the total diene incorporation is within the range specified above.

[0692] Propylene-based polymers

[0693] As described above, the methods described herein can be used to form propylene-based polymers, such as one or more propylene-based elastomers ("PBE"). The PBE comprises propylene and about 5 to about 30 weight percent of one or more α-olefin derived units, preferably ethylene and / or C4-C 12 α-olefins. For example, the α-olefin derived unit or comonomer can be ethylene, butene, pentene, hexene, 4-methyl-1-pentene, hexene, or decene. In some embodiments, the comonomer is ethylene. In some embodiments, the PBE consists essentially of propylene and ethylene, or consists only of propylene and ethylene. Some embodiments described below are discussed with reference to ethylene as the comonomer, but the embodiments are equally applicable to PBEs with other α-olefin comonomers. In this regard, the copolymers may be referred to simply as propylene-based elastomers with reference to ethylene as the α-olefin.

[0694] The PBE may include at least about 5 wt%, at least about 6 wt%, at least about 7 wt%, at least about 8 wt%, at least about 9 wt%, at least about 10 wt%, at least about 12 wt%, or at least about 15 wt% α-olefin derived units, wherein the percentages by weight are based on the total weight of the propylene derived units and the α-olefin derived units. The PBE may include up to about 30 wt%, up to about 25 wt%, up to about 22 wt%, up to about 20 wt%, up to about 19 wt%, up to about 18 wt%, or up to about 17 wt% α-olefin derived units, wherein the percentages by weight are based on the total weight of the propylene derived units and the α-olefin derived units. In some embodiments, the PBE may contain from about 5 wt% to about 30 wt%, from about 6 wt% to about 25 wt%, from about 7 wt% to about 20 wt%, from about 10 wt% to about 19 wt%, from about 12 wt% to about 18 wt%, or from about 15 wt% to about 17 wt% α-olefin derived units, wherein the percentages by weight are based on the total weight of the propylene derived units and the α-olefin derived units.

[0695] The PBE may include at least about 70 wt%, at least about 75 wt%, at least about 78 wt%, at least about 80 wt%, at least about 81 wt%, at least about 82 wt%, or at least about 83 wt% propylene derived units, wherein the percentages by weight are based on the total weight of the propylene derived units and the α-olefin derived units. The PBE may include up to about 95 wt%, up to about 94 wt%, up to about 93 wt%, up to about 92 wt%, up to about 91 wt%, up to about 90 wt%, up to about 88 wt%, or up to about 85 wt% propylene derived units, wherein the percentages by weight are based on the total weight of the propylene derived units and the α-olefin derived units.

[0696] The PBE can be characterized by a melting point (Tm), which can be determined by differential scanning calorimetry (DSC). For purposes herein, the maximum of the highest temperature peak is considered to be the melting point of the polymer. A "peak" in this context is defined as a change in the overall slope of the DSC curve (heat flow versus temperature) from positive to negative, resulting in a maximum, without a baseline shift, where the DSC curve is drawn so that an endothermic reaction would appear as a positive peak. The Tm of the PBE (as determined by DSC) can be less than about 120°C, less than about 115°C, less than about 110°C, or less than about 105°C.

[0697] The PBE can be characterized by its heat of fusion (Hf), as determined by DSC. The PBE can have an Hf of at least about 0.5 J / g, at least about 1.0 J / g, at least about 1.5 J / g, at least about 3.0 J / g, at least about 4.0 J / g, at least about 5.0 J / g, at least about 6.0 J / g, or at least about 7.0 J / g. The PBE can be characterized by an Hf of less than about 75 J / g, or less than about 70 J / g, or less than about 60 J / g, or less than about 50 J / g.

[0698] As used in this specification, the DSC procedure for determining Tm and Hf is as follows. The polymer is pressed at a temperature of about 200°C to about 230°C in a heated press, and the resulting polymer sheet is suspended in air under ambient conditions to cool. A polymer sheet of about 6 to 10 mg is removed with a die. The 6 to 10 mg sample is annealed at room temperature for about 80 to 100 hours. At the end of this stage, the sample is placed in a DSC (Perkin Elmer Pyris One thermal analysis system) and cooled to about -30°C to about -50°C and maintained at this temperature for 10 minutes. The sample is then heated at 10°C / min to reach a final temperature of about 200°C. The sample is maintained at 200°C for 5 minutes. A second cooling-heating cycle is then performed, in which the sample is cooled again to about -30°C to about -50°C and maintained at this temperature for 10 minutes, and then heated again to a final temperature of about 200°C at 10°C / min. Events from two cycles are recorded. The thermal output is recorded as the area under the melting peak of the sample, which typically occurs between about 0° C. and about 200° C. It is measured in joules, and is a measure of the Hf of the polymer.

[0699] PBE can have 13 The triad tacticity of three propylene units may be 75% or greater, 80% or greater, 85% or greater, 90% or greater, 92% or greater, 95% or greater, or 97% or greater as measured by C NMR (mmm tacticity). For example, the triad tacticity may be in the range of about 75 to about 99%, about 80 to about 99%, about 85 to about 99%, about 90 to about 99%, about 90 to about 97%, or about 80 to about 97%. The triad tacticity is determined as described in U.S. Patent Application Publication No. 2004 / 0236042.

[0700] The PBE may have a tacticity index m / r ranging from a lower limit of 4 or 6 to an upper limit of 8 or 10 or 12. 13C nuclear magnetic resonance ("NMR") determines the stereoregularity index, denoted herein as "m / r". The stereoregularity index (m / r) is calculated as defined by HN Cheng in Volume 17, MACROMOLECULES, pp. 1950-1955 (1984), which is incorporated herein by reference. The designations "m" or "r" describe the stereochemistry of adjacent pairs of propylene groups, with "m" indicating meso and "r" indicating racemic. An m / r ratio of 1.0 generally describes a syndiotactic polymer, and an m / r ratio of 2.0 describes an atactic material.

[0701] The PBE may have a percent crystallinity of about 0.5% to about 40%, about 1% to about 30%, or about 5% to about 25%, as determined by DSC. Crystallinity may be determined by dividing the Hf of the sample by the Hf of a 100% crystalline polymer, which is assumed to be 189 J / g for isotactic polypropylene.

[0702] PBE can have a room temperature of about 0.84 g / cm 3 - About 0.92g / cm 3 , about 0.85g / cm 3 -About 0.90g / cm 3 , or about 0.85 g / cm 3 - About 0.87g / cm 3 The density of the composite as measured in accordance with ASTM D-1505 test method.

[0703] The PBE can have a melt index (MI) (ASTM D-1238, 2.16 kg at 190° C.) of less than or equal to about 100 g / 10 min, less than or equal to about 50 g / 10 min, less than or equal to about 25 g / 10 min, less than or equal to about 10 g / 10 min, less than or equal to about 8 g / 10 min, less than or equal to about 5 g / 10 min, or less than or equal to about 3 g / 10 min.

[0704] The PBE may have a melt flow rate (MFR) greater than about 0.5 g / 10 min, greater than about 1 g / 10 min, greater than about 1.5 g / 10 min, greater than about 2 g / 10 min, or greater than about 2.5 g / 10 min, as measured according to ASTM D-1238 (2.16 kg weight at 230° C.). The PBE may have an MFR less than about 100 g / 10 min, less than about 50 g / 10 min, less than about 25 g / 10 min, less than about 15 g / 10 min, less than about 10 g / 10 min, less than about 7 g / 10 min, or less than about 5 g / 10 min. In some embodiments, the PBE may have an MFR of about 0.5 to about 10 g / 10 min, about 1 to about 7 g / 10 min, or about 1.5 to about 5 g / 10 min.

[0705] The PBE may have a g' index value of 0.95 or greater, or at least 0.97, or at least 0.99, where g' is measured at the Mw of the polymer using the intrinsic viscosity of isotactic polypropylene as a baseline. For use herein, the g' index is defined as:

[0706] g′=ηbηl

[0707] Where ηb is the intrinsic viscosity of the polymer and ηl is the intrinsic viscosity of a linear polymer having the same viscosity average molecular weight (Mv) as the polymer. ηl = KMvα, K and α are measured values ​​for linear polymers and should be obtained on the same instrument as used for g' index measurement.

[0708] The PBE can have a weight average molecular weight (Mw) as measured by DRI of about 50,000 to about 1,000,000 g / mol, or about 75,000 to about 500,000 g / mol, about 100,000 to about 350,000 g / mol, about 125,000 to about 300,000 g / mol, about 150,000 to about 275,000 g / mol, or about 200,000 to about 250,000 g / mol.

[0709] The PBE can have a number average molecular weight (Mn) as measured by DRI of about 5,000 to about 500,000 g / mol, about 10,000 to about 300,000 g / mol, about 50,000 to about 250,000 g / mol, about 75,000 to about 200,000 g / mol, or about 100,000 to about 150,000 g / mol.

[0710] The PBE can have a z-average molecular weight (Mz) as measured by MALLS of about 50,000 to about 1,000,000 g / mol, or about 75,000 to about 500,000 g / mol, or about 100,000 to about 400,000 g / mol, about 200,000 to about 375,000 g / mol, or about 250,000 to about 350,000 g / mol.

[0711] The molecular weight distribution (MWD, equal to Mw / Mn) of the PBE can be about 0.5 to about 20, about 0.75 to about 10, about 1.0 to about 5, about 1.5 to about 4, or about 1.8 to about 3.

[0712] Optionally, the PBE may also include one or more dienes. The term "diene" is defined as a hydrocarbon compound having two sites of unsaturation, i.e., a compound having two double bonds connecting carbon atoms. Depending on the context, the term "diene" as used herein broadly refers to a diene monomer prior to polymerization (e.g., forming part of a polymerization medium), or a diene monomer after polymerization has begun (also referred to as a diene monomer unit or a diene-derived unit). In some embodiments, the diene may be selected from 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, 5-methylene-2-norbornene (MNB), 1,6-octadiene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 1,3-cyclopentadiene, 1,4-cyclohexadiene, vinyl norbornene (VNB), dicyclopentadiene (DCPD), and combinations thereof. In embodiments where the propylene-based elastomeric composition comprises a diene, the diene may be present in the range of 0.05 wt% to about 6 wt%, about 0.1 wt% to about 5.0 wt%, about 0.25 wt% to about 3.0 wt%, about 0.5 wt% to about 1.5 wt% of diene-derived units, wherein the percentages by weight are based on the combined weight of propylene-derived units, α-olefin-derived units, and diene-derived units.

[0713] Optionally, the PBE may be grafted (i.e., "functionalized") using one or more grafting monomers. As used herein, the term "grafted" means that the grafting monomer is covalently bonded to the polymer chain of the PBE. The grafting monomer may be or include at least one ethylenically unsaturated carboxylic acid or acid derivative, such as an anhydride, ester, salt, amide, imide, or acrylate. Illustrative grafting monomers include, but are not limited to, acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, 4-methylcyclohexene-1,2-dicarboxylic anhydride, bicyclo(2.2.2)octene-2,3-dicarboxylic anhydride, 1,2,3,4,5,8,9,10-octahydronaphthalene-2,3-dicarboxylic anhydride, 2-oxa-1,3-diketospiro(4.4)nonene, bicyclo(2.2.1)heptene-2,3-dicarboxylic anhydride, maleopimaric acid, tetrahydrophthalic anhydride, norbornene-2,3-dicarboxylic anhydride, nadic anhydride, methylnadic anhydride, himic anhydride, methyl himic anhydride, and 5-methylbicyclo(2.2.1)heptene-2,3-dicarboxylic anhydride. Other suitable grafting monomers include methyl acrylate and higher alkyl acrylates, methyl methacrylate and higher alkyl methacrylates, acrylic acid, methacrylic acid, hydroxymethyl methacrylate, hydroxyethyl methacrylate and higher hydroxyalkyl methacrylates and glycidyl methacrylate. In at least one embodiment, the grafting monomer includes maleic anhydride. In embodiments where the grafting monomer is maleic anhydride, the maleic anhydride concentration in the grafted polymer may be from about 1 to about 6 weight percent, at least about 0.5 weight percent, or at least about 1.5 weight percent.

[0714] In some embodiments, the PBE is a reactor blend polymer. That is, the PBE is a reactor blend of a first polymer component ("R1") produced in a first solution polymerization reactor and a second polymer component produced in a second solution polymerization reactor, wherein the solution polymerization reactor is as described in reference Figure 1 The description is in a parallel configuration. Thus, the comonomer content of the propylene-based elastomer can be adjusted by adjusting the comonomer content of the first polymer component, adjusting the comonomer content of the second polymer component, and / or adjusting the ratio of the first polymer component to the second polymer component present in the PBE.

[0715] In embodiments where the PBE is a reactor blended polymer, the α-olefin content of the first polymer component may be greater than 5 wt% α-olefin, greater than 7 wt% α-olefin, greater than 10 wt% α-olefin, greater than 12 wt% α-olefin, greater than 15 wt% α-olefin, or greater than 17 wt% α-olefin, wherein the percentages by weight are based on the total weight of the propylene derived units and the α-olefin derived units of the first polymer component. The α-olefin content of the first polymer component may be less than 30 wt% α-olefin, less than 27 wt% α-olefin, less than 25 wt% α-olefin, less than 22 wt% α-olefin, less than 20 wt% α-olefin, or less than 19 wt% α-olefin, wherein the percentages by weight are based on the total weight of the propylene derived units and the α-olefin derived units of the first polymer component. In some embodiments, the α-olefin content of the first polymer component is from about 5 wt% to about 30 wt% α-olefins, from about 7 wt% to about 27 wt% α-olefins, from about 10 wt% to about 25 wt% α-olefins, from about 12 wt% to about 22 wt% α-olefins, from about 15 wt% to about 20 wt% α-olefins, or from about 17 wt% to about 19 wt% α-olefins. Preferably, the first polymer component comprises propylene and ethylene, and in some embodiments the first polymer component consists solely of propylene and ethylene derived units.

[0716] In embodiments where the PBE is a reactor blended polymer, the α-olefin content of the second polymer component ("R2") may be greater than 1.0 wt% α-olefin, greater than 1.5 wt% α-olefin, greater than 2.0 wt% α-olefin, greater than 2.5 wt% α-olefin, greater than 2.75 wt% α-olefin, or greater than 3.0 wt% α-olefin, wherein the percentages by weight are based on the total weight of the propylene derived units and the α-olefin derived units of the second polymer component. The α-olefin content of the second polymer component may be less than 10 wt% α-olefin, less than 9 wt% α-olefin, less than 8 wt% α-olefin, less than 7 wt% α-olefin, less than 6 wt% α-olefin, or less than 5 wt% α-olefin, wherein the percentages by weight are based on the total weight of the propylene derived units and the α-olefin derived units of the second polymer component. In some embodiments, the α-olefin content of the second polymer component can be from about 1 wt% to about 10 wt% α-olefins, or from about 1.5 wt% to about 9 wt% α-olefins, or from about 2 wt% to about 8 wt% α-olefins, or from about 2.5 wt% to about 7 wt% α-olefins, or from about 2.75 wt% to about 6 wt% α-olefins, or from about 3 wt% to about 5 wt% α-olefins. In some embodiments, the second polymer component comprises propylene and ethylene, and in some embodiments the second polymer component consists only of propylene and ethylene derived units.

[0717] In embodiments where the PBE is a reactor blended polymer, the PBE may have from about 1 to about 25 wt % of the second polymer component, from about 3 to about 20 wt % of the second polymer component, from about 5 to about 18 wt % of the second polymer component, from about 7 to about 15 wt % of the second polymer component, or from about 8 to about 12 wt % of the second polymer component, based on the weight of the propylene-based elastomer. The PBE may have from about 75 to about 99 wt % of the first polymer component, from about 80 to about 97 wt % of the first polymer component, from about 85 to about 93 wt % of the first polymer component, or from about 82 to about 92 wt % of the first polymer component, based on the weight of the propylene-based elastomer.

[0718] Commercially available examples of polymers formed by the methods of the present disclosure may include Vistamaxx from ExxonMobil Chemical Company. TM Copolymer, Tafmer from Mitsui Chemicals TM Elastomers and Versify from Dow Chemical Company TM Elastomer.

[0719] For example, Vistamaxx TM It is a propylene-based elastomer that extends the performance and processability of films, compounds, nonwovens and molded / extruded products. Vistamaxx TM The free-flowing granules are easy to incorporate and the wide compatibility allows for dry blending operations. Vistamaxx TM Offering a range of applications such as 1) nonwovens (elasticity, softness and toughness; excellent processing properties); 2) films (elasticity, sealing, toughness and adhesion); 3) polymer modifications and compounds (impact strength, clarity, elasticity / stiffness, softness, higher filler loadings). Vistamaxx TM Copolymers are copolymers of propylene and ethylene. Vistamaxx TM Rich in propylene (>80%) and semi-crystalline materials with high amorphous content. Their synthesis is based on ExxonMobil Chemical's Exxpol TM technology.

[0720] Vistamaxx TM 3980 propylene-ethylene performance polymer ("VM3980") is available from ExxonMobil Chemical Company. VM3980 has an ethylene content of 9 wt. %, with the balance being propylene. The properties of VM3980 include: 0.879 g / cm 3density (ASTM D1505); a melt index of 3.6 g / 10 min (ASTM D1238; 190°C, 2.16 kg); a melt mass flow rate of 8 g / 10 min (230°C, 2.16 kg); a Shore D hardness of 34 (ASTM D2240); and a Vicat softening temperature (VST) of 77.3°C.

[0721] Vistamaxx TM 6502 (VM6502) is a polymer with isotactic propylene repeating units and random ethylene distribution; the polymer has a molecular weight of 0.865 g / cm 3 The melt had a density of 45.2 g / 10 min (230° C., 2.16 kg), and an ethylene content of 13.1 wt %.

[0722] Vistamaxx TM 3000 propylene-ethylene high performance polymer ("VM3000") is available from ExxonMobil Chemical Company. VM3000 has an ethylene content of 11% by weight, with the balance being propylene. The properties of VM3000 include: 0.873 g / cm 3 density (ASTM D1505); a melt index of 3.7 g / 10 min (ASTM D1238; 190°C, 2.16 kg); a melt mass flow rate of 8 g / 10 min (230°C, 2.16 kg); a Shore D hardness of 27 (ASTM D2240); and a Vicat softening temperature (VST) of 65.1°C.

[0723] Vistamaxx TM 3588 propylene-ethylene high performance polymer ("VM3588") is available from ExxonMobil Chemical Company. VM3588 has an ethylene content of 4 wt. %, with the balance being propylene. The properties of VM3588 include: 0.889 g / cm 3 density (ASTM D1505); a melt mass flow rate (230°C, 2.16 kg) of 8 g / 10 min; a Shore D hardness (ASTM D2240) of 50; and a Vicat softening temperature (VST) of 103°C.

[0724] Vistamaxx TM 6202 ("VM6202") is a propylene-ethylene copolymer with a molecular weight of 0.863 g / cm 3 The composite had a density of 9.1 g / 10 min, a melt index of 9.1 g / 10 min (at 190° C., 2.16 kg), an MFR of 20 g / 10 min, and an ethylene content of 15 wt %.

[0725] Vistamaxx TM 6102 ("VM6102") is a propylene-ethylene copolymer with a molecular weight of 0.862 g / cm 3 The composite had a density of 1.4 g / 10 min, a melt index of 2.16 kg at 190° C., an MFR of 3 g / 10 min, and an ethylene content of 16 wt %.

[0726] Vistamaxx TM 3020 ("VM3020") is a propylene-ethylene copolymer with a molecular weight of 0.874 g / cm 3 The composite had a density of 1.1 g / 10 min, a melt index of 1.1 g / 10 min (at 190° C., 2.16 kg), an MFR of 3 g / 10 min, and an ethylene content of 11 wt %.

[0727] Additional aspects

[0728] The present disclosure provides, among other things, the following aspects, each of which may be considered to optionally include any alternative aspects.

[0729] Clause 1. A method comprising:

[0730] introducing a catalyst solution into the reactor via a first line, the catalyst solution comprising a catalyst and a first non-aromatic diluent;

[0731] introducing an activator solution into the reactor via a second line, the activator solution comprising an activator and a second non-aromatic diluent, wherein the second non-aromatic diluent is the same as or different from the first non-aromatic diluent;

[0732] operating the reactor under process conditions; and

[0733] obtaining an effluent from the reactor, the effluent comprising polyolefin,

[0734] The first pipeline and the second pipeline are connected to the reactor.

[0735] Clause 2. The method of Clause 1, wherein the catalyst solution does not contain an activator.

[0736] Clause 3. The method of clause 1 or 2, wherein the activator solution contains no catalyst.

[0737] Clause 4. The process of any one of clauses 1 to 3, wherein the catalyst solution consists of the catalyst and a non-aromatic diluent.

[0738] Clause 5. The method of any one of Clauses 1 to 4, wherein the activator solution consists of an activator and a non-aromatic diluent.

[0739] Clause 6. The process of any of Clauses 1 to 5, wherein the first non-aromatic diluent is selected from the group consisting of 2-methyl-pentane, isobutane, butane, n-pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and one or more mixtures thereof.

[0740] Clause 7. The process of any of Clauses 1 to 6, wherein the first non-aromatic diluent is 2-methyl-pentane.

[0741] Clause 8. The process of any of Clauses 1 to 7, wherein the second non-aromatic diluent is selected from the group consisting of 2-methyl-pentane, isobutane, butane, n-pentane, isopentane, hexane, isohexane, heptane, octane, dodecane, and one or more mixtures thereof.

[0742] Clause 9. The process of any of Clauses 1 to 8, wherein the second non-aromatic diluent is 2-methyl-pentane.

[0743] Clause 10. The process of any of Clauses 1 to 9, wherein the first non-aromatic diluent has about 1 wt % or less aromatics, based on the weight of the first non-aromatic diluent + aromatics.

[0744] Clause 11. The process of any of Clauses 1 to 10, wherein the first non-aromatic diluent has about 0 wt % aromatics, based on the weight of the first non-aromatic diluent + aromatics.

[0745] Clause 12. The process of any of Clauses 1 to 11, wherein the second non-aromatic diluent has about 1 wt % or less aromatic compounds based on the weight of the second non-aromatic diluent + aromatic compounds.

[0746] Clause 13. The process of any of Clauses 1 to 12, wherein the second non-aromatic diluent has about 0 wt % aromatics based on the weight of the second non-aromatic diluent + aromatics.

[0747] Clause 14. The method of any of Clauses 1 to 13, wherein the activator solution comprises the activator in an amount of about 0.01 wt % to about 20 wt % based on the weight of the activator solution.

[0748] Clause 15. The method of any of Clauses 1 to 14, wherein the activator solution comprises the activator in an amount of about 0.15 wt % to about 0.3 wt % based on the weight of the activator solution.

[0749] Clause 16. The process of any of Clauses 1 to 15, wherein introducing the activator solution into the reactor is carried out at a feed rate of about 0.01 kg / hr to about 40 kg / hr, alternatively about 0.02 L / hr to about 60 L / hr.

[0750] Clause 17. The method of any of Clauses 1 to 16, wherein the catalyst solution comprises the catalyst in an amount of about 0.01 wt % to about 20 wt % based on the weight of the catalyst solution.

[0751] Clause 18. The method of any of Clauses 1 to 17, wherein the catalyst solution comprises the catalyst in an amount of about 0.05 wt % to about 0.1 wt % based on the weight of the catalyst solution.

[0752] Clause 19. The process of any of Clauses 1 to 18, wherein introducing the catalyst solution into the reactor is carried out at a feed rate of about 0.003 kg / hr to about 40 kg / hr, alternatively about 0.004 L / hr to about 60 L / hr.

[0753] Clause 20. The process of any one of Clauses 1 to 19, wherein process conditions comprise a temperature delta of from about 0°C to about 20°C during substantially the entire process.

[0754] Clause 21. The process of any one of clauses 1 to 20, wherein the temperature δ is from about 1°C to about 3°C ​​during substantially the entire process.

[0755] Clause 22. The process of any of Clauses 1 to 22, wherein the effluent has an aromatic content of about 1 wt % or less, based on the weight of the effluent.

[0756] Clause 23. The process of any of Clauses 1 to 22, wherein the polyolefin has an aromatic content of about 1 wt % or less, based on the weight of the polyolefin.

[0757] Clause 24. The process of any of Clauses 1 to 23, wherein the polyolefin has an aromatic content of 0 weight percent, based on the weight of the polyolefin.

[0758] Clause 25. The method of any one of clauses 1 to 24, wherein:

[0759] Process conditions include a temperature of about 130°C to about 200°C and a pressure of about 100 bar to about 130 bar, and

[0760] Polyolefins are plastomers.

[0761] Clause 26. The method of any one of clauses 1 to 25, wherein:

[0762] Process conditions include a temperature of about 85°C to about 150°C and a pressure of about 100 bar to about 130 bar, and

[0763] Polyolefins are elastomers.

[0764] Clause 27. The method of any one of clauses 1 to 26, wherein:

[0765] Process conditions include a temperature of about 50°C to about 80°C and a pressure of about 100 bar to about 130 bar, and

[0766] Polyolefins are propylene-based polymers.

[0767] Clause 28. The method of any one of clauses 1 to 27, wherein the catalyst is represented by the formula:

[0768] Cp A Cp B M'X' n

[0769] Each Cp A and Cp B independently selected from cyclopentadienyl ligands or ligands isolobal to cyclopentadienyl, one or two Cp A and Cp B Optionally contains heteroatoms, and one or two Cp A and Cp B Optionally substituted with one or more R" groups; M' is selected from Group 3 to Group 12 atoms and lanthanide atoms; X' is an anion leaving group; n is 0 or an integer from 1 to 4; each R" is independently selected from alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, alkoxy, aryloxy, alkylthio, arylthio, aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocyclyl, silyl, boryl, phosphino, phosphine, amino, ether and thioether.

[0770] Clause 29. The method of any one of clauses 1 to 28, wherein the catalyst is represented by the formula:

[0771] Cp A (T)Cp B M'X' n

[0772] Each Cp A and Cp B independently selected from cyclopentadienyl ligands or ligands isolobal to cyclopentadienyl, one or two Cp A and Cp B Optionally contains heteroatoms, and one or two Cp A and Cp Bis optionally substituted with one or more R" groups; M' is selected from the group consisting of Group 3 to Group 12 atoms and lanthanide atoms; X' is an anion leaving group; n is 0 or an integer from 1 to 4; (T) is selected from the group consisting of a divalent alkyl, a divalent heteroalkyl, a divalent alkenyl, a divalent heteroalkenyl, a divalent alkynyl, a divalent heteroalkynyl, a divalent alkoxy, a divalent aryloxy, a divalent alkylthio, a divalent arylthio, a divalent aryl, a divalent heteroaryl, a divalent aralkyl, a divalent aralkylene, a divalent alkaryl, a divalent alkarylene, a divalent haloalkyl, a divalent haloalkenyl, a divalent a bridging group selected from the group consisting of a haloalkynyl, a divalent heteroalkyl, a divalent heterocyclic radical, a divalent silyl, a divalent boryl, a divalent phosphino, a divalent phosphine, a divalent amino, a divalent ether, and a divalent thioether; and R" is selected from the group consisting of an alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, alkoxy, aryloxy, alkylthio, arylthio, aryl, heteroaryl, aralkyl, aralkylene, alkaryl, alkarylene, haloalkyl, haloalkenyl, haloalkynyl, heteroalkyl, heterocyclic radical, silyl, boryl, phosphino, phosphine, amino, germanium, ether, and thioether.

[0773] Clause 30. The process of any one of clauses 1 to 29, wherein the catalyst is selected from the group consisting of:

[0774] Bis(cyclopentadienyl)zirconium dichloride,

[0775] Bis(n-butylcyclopentadienyl)zirconium dichloride,

[0776] Bis(n-butylcyclopentadienyl)zirconium dimethyl,

[0777] Bis(pentamethylcyclopentadienyl)zirconium dichloride,

[0778] Bis(pentamethylcyclopentadienyl)zirconium dimethyl,

[0779] Bis(pentamethylcyclopentadienyl)hafnium dichloride,

[0780] Bis(pentamethylcyclopentadienyl)zirconium dimethyl,

[0781] Bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dichloride,

[0782] Bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,

[0783] Bis(1-methyl-3-n-butylcyclopentadienyl)hafnium dichloride,

[0784] Bis(1-methyl-3-n-butylcyclopentadienyl)zirconium dimethyl,

[0785] Bis(indenyl)zirconium dichloride,

[0786] Bis(indenyl)zirconium dimethyl,

[0787] Bis(tetrahydro-1-indenyl)zirconium dichloride,

[0788] Bis(tetrahydro-1-indenyl)zirconium dimethyl,

[0789] (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)zirconium dichloride, and

[0790] (n-propylcyclopentadienyl, pentamethylcyclopentadienyl)zirconium dimethyl.

[0791] Clause 31. The process of any one of clauses 1 to 30, wherein the catalyst is selected from the group consisting of:

[0792] Dimethylsilylbis(tetrahydroindenyl)MX n ,

[0793] Dimethylsilylbis(2-methylindenyl)MX n ,

[0794] Dimethylsilylbis(2-methylfluorenyl)MX n ,

[0795] Dimethylsilylbis(2-methyl-5,7-propylindenyl)MX n ,

[0796] Dimethylsilylbis(2-methyl-4-phenylindenyl)MX n ,

[0797] Dimethylsilylbis(2-ethyl-5-phenylindenyl)MX n ,

[0798] Dimethylsilylbis(2-methyl-4-biphenylindenyl)MX n ,

[0799] Dimethylsilylenebis(2-methyl-4-carbazolylindenyl)MX n ,

[0800] MX n ,

[0801] Diphenylmethylene(cyclopentadienyl)(fluorenyl)MX n ,

[0802] Bis(methylcyclopentadienyl)MX n ,

[0803] MX n ,

[0804] Dimethylsilylbis(indenyl)MX n ,

[0805] rac-meso-diphenylsilyl-bis(n-propylcyclopentadienyl)MX n ,

[0806] 1,1'-Bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tert-butyl-1-fluorenyl)MX n (the bridge is considered as 1 position),

[0807] Bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(di-tert-butylfluorenyl)MXn,

[0808] Bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(fluorenyl)MXn,

[0809] Bisphenylmethylene (cyclopentadienyl) (dimethylfluorenyl) MXn,

[0810] Bis(n-propylcyclopentadienyl)MX n ,

[0811] Bis(n-butylcyclopentadienyl)MX n ,

[0812] Bis(n-pentylcyclopentadienyl)MX n ,

[0813] (n-propylcyclopentadienyl)(n-butylcyclopentadienyl)MX n ,

[0814] Bis[(2-trimethylsilylethyl)cyclopentadienyl]MX n ,

[0815] Bis(trimethylsilylcyclopentadienyl)MX n ,

[0816] Dimethylsilylbis(n-propylcyclopentadienyl)MX n ,

[0817] Dimethylsilylbis(n-butylcyclopentadienyl)MX n ,

[0818] Bis(1-n-propyl-2-methylcyclopentadienyl)MX n ,

[0819] (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)MX n ,

[0820] Bis(1-methyl,3-n-butylcyclopentadienyl)MXn ,

[0821] Bis(indenyl)MX n ,

[0822] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamino)MX n ,

[0823] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)MX n ,

[0824] μ-(CH3)2Si(cyclopentadienyl)(1-adamantylamino)MX n ,

[0825] μ-(CH3)2Si(3-tert-butylcyclopentadienyl)(1-adamantylamino)MX n ,

[0826] μ-(CH3)2(Tetramethylcyclopentadienyl)(1-adamantylamino)MX n ,

[0827] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-adamantylamino)MX n ,

[0828] μ-(CH3)2C(Tetramethylcyclopentadienyl)(1-adamantylamino)MX n ,

[0829] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-tert-butylamino)MX n ,

[0830] μ-(CH3)2Si(fluorenyl)(1-tert-butylamino)MX n ,

[0831] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-cyclododecylamino)MX n ,

[0832] μ-(C6H5)2C(Tetramethylcyclopentadienyl)(1-cyclododecylamino)MX n ,and

[0833] μ-(CH3)2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tert-butylamino)MX n ,

[0834] in:

[0835] M is Ti, Zr or Hf;

[0836] Each X is independently selected from the following: halogen, hydrogen, C 1-12 Alkyl, C 2-12 Alkenyl, C 6-12 Aryl, C 7-20 Alkyl, C 1-12 Alkoxy, C 6-16 Aryloxy, C 7-18 Alkyl aryloxy, C 1-12 Fluorinated alkyl and C 6-12 fluorinated aryl, and

[0837] n is zero or an integer from 1 to 4.

[0838] Clause 32. The method of claim 1, wherein the catalyst is selected from the group consisting of:

[0839] Bis(1-methyl, 3-n-butylcyclopentadienyl)M(R)2,

[0840] Dimethylsilylbis(indenyl)M(R)2,

[0841] Bis(indenyl)M(R)2,

[0842] Dimethylsilylbis(tetrahydroindenyl)M(R)2,

[0843] Bis(n-propylcyclopentadienyl)M(R)2,

[0844] Dimethylsilyl (tetramethylcyclopentadienyl) (cyclododecylamino) M (R) 2,

[0845] Dimethylsilyl (tetramethylcyclopentadienyl) (cyclododecylamino) M (R) 2,

[0846] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)M(R)2,

[0847] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)M(R)2,

[0848] μ-(CH3)2Si(cyclopentadienyl)(1-adamantylamino)M(R)2,

[0849] μ-(CH3)2Si(3-tert-butylcyclopentadienyl)(1-adamantylamino)M(R)2,

[0850] μ-(CH3)2(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2,

[0851] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2,

[0852] μ-(CH3)2C(tetramethylcyclopentadienyl)(1-adamantylamino)M(R)2,

[0853] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-tert-butylamino)M(R)2,

[0854] μ-(CH3)2Si(fluorenyl)(1-tert-butylamino)M(R)2,

[0855] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2,

[0856] μ-(C6H5)2C(tetramethylcyclopentadienyl)(1-cyclododecylamino)M(R)2, and

[0857] μ-(CH3)2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tert-butylamino)M(R)2,

[0858] in:

[0859] M is Ti, Zr or Hf; and

[0860] R is selected from halogen and C1-C5 alkyl.

[0861] Clause 33. The method of any one of clauses 1 to 32, wherein the catalyst is selected from the group consisting of:

[0862] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)dimethyltitanium,

[0863] Dimethylsilyl(tetramethylcyclopentadienyl)(cyclododecylamido)dimethyltitanium,

[0864] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)dimethyltitanium,

[0865] Dimethylsilyl(tetramethylcyclopentadienyl)(tert-butylamino)dimethyltitanium,

[0866] μ-(CH3)2Si(cyclopentadienyl)(1-adamantylamino)dimethyltitanium,

[0867] μ-(CH3)2Si(3-tert-butylcyclopentadienyl)(1-adamantylamino)dimethyltitanium,

[0868] μ-(CH3)2(tetramethylcyclopentadienyl)(1-adamantylamino)dimethyltitanium,

[0869] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-adamantylamino)dimethyltitanium,

[0870] μ-(CH3)2C(tetramethylcyclopentadienyl)(1-adamantylamino)dimethyltitanium,

[0871] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-tert-butylamino)dimethyltitanium,

[0872] μ-(CH3)2Si(fluorenyl)(1-tert-butylamino)dimethyltitanium,

[0873] μ-(CH3)2Si(tetramethylcyclopentadienyl)(1-cyclododecylamino)dimethyltitanium,

[0874] μ-(C6H5)2C(tetramethylcyclopentadienyl)(1-cyclododecylamino)dimethyltitanium, and

[0875] μ-(CH3)2Si(η 5 -2,6,6-trimethyl-1,5,6,7-tetrahydro-s-indacen-1-yl)(tert-butylamino)dimethyltitanium.

[0876] Clause 34. The method of any one of clauses 1 to 33, wherein the catalyst is selected from the group consisting of:

[0877] Bis(1-methyl,3-n-butylcyclopentadienyl)hafnium dimethyl,

[0878] Bis(1-methyl,3-n-butylcyclopentadienyl)zirconium dimethyl,

[0879] Dimethylsilylbis(indenyl)zirconium dimethyl,

[0880] Dimethylsilylbis(indenyl)hafnium dimethyl,

[0881] Bis(indenyl)zirconium dimethyl,

[0882] Bis(indenyl)dimethylhafnium,

[0883] Dimethylsilylbis(tetrahydroindenyl)zirconium dimethyl,

[0884] Bis(n-propylcyclopentadienyl)zirconium dimethyl,

[0885] Dimethylsilylbis(tetrahydroindenyl)hafnium dimethyl,

[0886] Dimethylsilylbis(2-methylindenyl)zirconium dimethyl,

[0887] Dimethylsilylbis(2-methylfluorenyl)zirconium dimethyl,

[0888] Dimethylsilylbis(2-methylindenyl)hafnium dimethyl,

[0889] Dimethylsilylbis(2-methylfluorenyl)hafnium dimethyl,

[0890] Dimethylsilylbis(2-methyl-5,7-propylindenyl)zirconium dimethyl,

[0891] Dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl,

[0892] Dimethylsilylbis(2-ethyl-5-phenylindenyl)zirconium dimethyl,

[0893] Dimethylsilylbis(2-methyl-4-biphenylindenyl)zirconium dimethyl,

[0894] Dimethylsilylene bis(2-methyl-4-carbazolylindenyl)zirconium dimethyl,

[0895] Racemic-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benzo(f)indene)dimethylhafnium,

[0896] Hafnium diphenylmethylene (cyclopentadienyl)(fluorenyl) dimethyl,

[0897] Bis(methylcyclopentadienyl)zirconium dimethyl,

[0898] Racemic-dimethylsilylbis(2-methyl,3-propylindenyl)dimethylhafnium,

[0899] Dimethylsilylbis(indenyl)hafnium dimethyl,

[0900] Dimethylsilylbis(indenyl)zirconium dimethyl,

[0901] Dimethyl racemic-dimethylsilyl-bis-(5,6,7,8-tetrahydro-5,5,8,8-tetramethyl-2-methyl-1H-benzo(f)indene)dimethylhafnium,

[0902] rac-meso-diphenylsilyl-bis(n-propylcyclopentadienyl)dimethylhafnium,

[0903] 1,1'-Bis(4-triethylsilylphenyl)methylene-(cyclopentadienyl)(3,8-di-tert-butyl-1-fluorenyl)hafnium X n (the bridge is considered as 1 position),

[0904] Bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(di-tert-butylfluorenyl)dimethylhafnium,

[0905] Bis-trimethylsilylphenyl-methylene(cyclopentadienyl)(fluorenyl)dimethylhafnium,

[0906] Bisphenylmethylene(cyclopentadienyl)(dimethylfluorenyl)hafnium dimethyl,

[0907] Bis(n-propylcyclopentadienyl)hafnium dimethyl,

[0908] Bis(n-butylcyclopentadienyl)hafnium dimethyl,

[0909] Bis(n-pentylcyclopentadienyl)hafnium dimethyl,

[0910] (n-propylcyclopentadienyl)(n-butylcyclopentadienyl)hafnium dimethyl,

[0911] Bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium dimethyl,

[0912] Bis(trimethylsilylcyclopentadienyl)hafnium dimethyl,

[0913] Dimethylsilylbis(n-propylcyclopentadienyl)hafnium dimethyl,

[0914] Dimethylsilylbis(n-butylcyclopentadienyl)hafnium dimethyl,

[0915] Bis(1-n-propyl-2-methylcyclopentadienyl)hafnium dimethyl,

[0916] (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium dimethyl,

[0917] Bis(n-propylcyclopentadienyl)hafnium dimethyl,

[0918] Bis(n-butylcyclopentadienyl)hafnium dimethyl,

[0919] Bis(n-pentylcyclopentadienyl)hafnium dimethyl,

[0920] (n-propylcyclopentadienyl)(n-butylcyclopentadienyl)hafnium dimethyl,

[0921] Bis[(2-trimethylsilylethyl)cyclopentadienyl]hafnium dimethyl,

[0922] Bis(trimethylsilylcyclopentadienyl)hafnium dimethyl,

[0923] Dimethylsilylbis(n-propylcyclopentadienyl)hafnium dimethyl,

[0924] Dimethylsilylbis(n-butylcyclopentadienyl)hafnium dimethyl,

[0925] Bis(1-n-propyl-2-methylcyclopentadienyl)hafnium dimethyl,

[0926] (n-propylcyclopentadienyl)(1-n-propyl-3-n-butylcyclopentadienyl)hafnium dimethyl, and

[0927] Dimethylsilyl(3-n-propylcyclopentadienyl)(tetramethylcyclopentadienyl)zirconium dimethyl.

[0928] Clause 35. The method of any one of clauses 1 to 34, wherein the catalyst is selected from the group consisting of:

[0929] dimethylsilylbis(indenyl)zirconium dimethyl, and

[0930] Dimethylsilylbis(indenyl)hafnium dimethyl.

[0931] Clause 36. The method of any one of clauses 1 to 35, wherein the activator is represented by formula (AI):

[0932] [R 1 R 2 R 3 EH] d + [M k+ Q n ] d- (AI)

[0933] in:

[0934] E is nitrogen or phosphorus;

[0935] Each d is the same and is 1, 2, or 3;

[0936] k is 1, 2, or 3;

[0937] n is 1, 2, 3, 4, 5, or 6;

[0938] nk=d;

[0939] R 1 , R 2 and R 3 Each of which is independently selected from the following: H, C1-C 40 Alkyl, and C5-C 50 -aryl; wherein R 1 , R 2 and R 3 Contains 15 or more carbon atoms in total;

[0940] M is an element selected from Group 13 of the Periodic Table; and

[0941] Each Q is independently selected from the group consisting of hydrogen, bridged or unbridged dialkylamino, halo, alkoxy, aryloxy, hydrocarbyl, and halohydrocarbyl.

[0942] Clause 37. The method of any one of clauses 1 to 36, wherein:

[0943] E is nitrogen,

[0944] M is boron, and

[0945] n is 4.

[0946] Clause 38. The method of any one of Clauses 1 to 37, wherein each Q is a fluorinated aryl group.

[0947] Clause 39. The process of any one of clauses 1 to 38, wherein each Q is perfluoronaphthyl.

[0948] Clause 40. The method of any one of clauses 1 to 39, wherein R of formula (AI) 1 It is C1-C 30 An alkyl group, and R of formula (AI) 2 and R 3 Each of which is independently a branched or linear C1-C 40 an alkyl group or a meta- or para-substituted phenyl group, wherein the meta- or para-substituted groups are independently C1-C 40 A hydrocarbon group, an alkoxy group, a silyl group, a halogen, or a halogen-containing group.

[0949] Clause 41. The method of any one of clauses 1 to 40, wherein R 1 , R 2 and R 3 Together they contain 35 or more carbon atoms.

[0950] Clause 42. The method of any one of clauses 1 to 41, wherein:

[0951] R 1 is selected from the group consisting of methyl, ethyl, propyl, butyl and pentyl, and

[0952] R 2 and R 3 Each of which is independently C1-C 40 Branched or linear alkyl, or C5-C 50 -Aryl.

[0953] Clause 43. The method of any one of clauses 1 to 42, wherein [R 1 R 2 R 3 EH] Selected from the following:

[0954]

[0955] Clause 44. The method of any one of clauses 1 to 43, wherein the activator is selected from the group consisting of: [tetrakis(perfluorophenyl)borate] N,N-di(hydrogenated tallow)methylammonium,

[0956] [Tetrakis(perfluorophenyl)borate] N-methyl-4-nonadecylammonium-N-octadecylanilinium,

[0957] [Tetrakis(perfluorophenyl)borate] N-methyl-4-hexadecyl-N-octadecylanilinium,

[0958] [Tetrakis(perfluorophenyl)borate] N-methyl-4-tetradecyl-N-octadecylanilinium,

[0959] [Tetrakis(perfluorophenyl)borate] N-methyl-4-dodecyl-N-octadecylanilinium,

[0960] [Tetrakis(perfluorophenyl)borate] N-methyl-4-decyl-N-octadecylanilinium,

[0961] [Tetrakis(perfluorophenyl)borate] N-methyl-4-octyl-N-octadecylanilinium,

[0962] [Tetrakis(perfluorophenyl)borate] N-methyl-4-hexyl-N-octadecylanilinium,

[0963] [Tetrakis(perfluorophenyl)borate] N-methyl-4-butyl-N-octadecylanilinium,

[0964] [Tetrakis(perfluorophenyl)borate] N-methyl-4-octadecyl-N-decylanilinium,

[0965] [Tetrakis(perfluorophenyl)borate] N-methyl-4-nonadecylammonium-N-dodecylanilinium,

[0966] [Tetrakis(perfluorophenyl)borate] N-methyl-4-nonadecylammonium-N-tetradecylanilinium,

[0967] [Tetrakis(perfluorophenyl)borate] N-methyl-4-nonadecylammonium-N-hexadecylanilinium,

[0968] [Tetrakis(perfluorophenyl)borate] N-methyl-4-nonadecylammonium-N-octadecylanilinium,

[0969] [Tetrakis(perfluorophenyl)borate] N-ethyl-4-nonadecylammonium-N-octadecylanilinium,

[0970] [Tetrakis(perfluorophenyl)borate] N-methyl-N,N-dioctadecylammonium,

[0971] [Tetrakis(perfluorophenyl)borate] N-methyl-N,N-dihexadecylammonium,

[0972] [Tetrakis(perfluorophenyl)borate] N-methyl-N,N-di(tetradecyl)ammonium,

[0973] [Tetrakis(perfluorophenyl)borate] N-methyl-N,N-didodecylammonium,

[0974] [Tetrakis(perfluorophenyl)borate] N-methyl-N,N-didecylammonium,

[0975] [Tetrakis(perfluorophenyl)borate] N-methyl-N,N-dioctylammonium,

[0976] [Tetrakis(perfluorophenyl)borate] N-ethyl-N,N-dioctadecylammonium,

[0977] [Tetrakis(perfluorophenyl)borate] N,N-dioctadecyltolylammonium,

[0978] [Tetrakis(perfluorophenyl)borate] N,N-dihexadecyltolylammonium,

[0979] [Tetrakis(perfluorophenyl)borate] N,N-di(tetradecyl)tolylammonium,

[0980] [Tetrakis(perfluorophenyl)borate] N,N-di(dodecyl)tolylammonium,

[0981] [Tetrakis(perfluorophenyl)borate] N-octadecyl-N-hexadecyl-tolylammonium,

[0982] [Tetrakis(perfluorophenyl)borate] N-octadecyl-N-hexadecyl-tolylammonium,

[0983] [Tetrakis(perfluorophenyl)borate] N-octadecyl-N-tetradecyl-tolylammonium,

[0984] [Tetrakis(perfluorophenyl)borate] N-octadecyl-N-dodecyl-tolylammonium,

[0985] [Tetrakis(perfluorophenyl)borate] N-octadecyl-N-decyl-tolylammonium,

[0986] [Tetrakis(perfluorophenyl)borate] N-hexadecyl-N-tetradecyl-tolylammonium,

[0987] [Tetrakis(perfluorophenyl)borate] N-hexadecyl-N-dodecyl-tolylammonium,

[0988] [Tetrakis(perfluorophenyl)borate] N-hexadecyl-N-decyl-tolylammonium,

[0989] [Tetrakis(perfluorophenyl)borate] N-tetradecyl-N-dodecyl-tolylammonium,

[0990] [Tetrakis(perfluorophenyl)borate] N-tetradecyl-N-decyl-tolylammonium,

[0991] [Tetrakis(perfluorophenyl)borate] N-dodecyl-N-decyl-tolylammonium,

[0992] [Tetrakis(perfluorophenyl)borate] N-methyl-N-octadecylanilinium,

[0993] [Tetrakis(perfluorophenyl)borate] N-methyl-N-hexadecylanilinium,

[0994] [Tetrakis(perfluorophenyl)borate] N-methyl-N-tetradecylanilinium,

[0995] [Tetrakis(perfluorophenyl)borate] N-methyl-N-dodecylanilinium,

[0996] [tetrakis(perfluorophenyl)borate]N-methyl-N-decylanilinium, and

[0997] [Tetrakis(perfluorophenyl)borate] N-methyl-N-octylanilammonium.

[0998] Clause 45. The method of any one of clauses 1 to 44, wherein the activator is selected from the group consisting of:

[0999] N,N-di(hydrogenated tallow)methylammonium tetra(perfluoronaphthalen-2-yl)borate,

[1000] N-Methyl-4-nonadecylammonium-N-octadecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,

[1001] N-Methyl-4-hexadecyl-N-octadecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,

[1002] N-Methyl-4-tetradecyl-N-octadecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,

[1003] N-Methyl-4-dodecyl-N-octadecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,

[1004] N-Methyl-4-decyl-N-octadecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,

[1005] N-Methyl-4-octyl-N-octadecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,

[1006] N-Methyl-4-hexyl-N-octadecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,

[1007] N-Methyl-4-butyl-N-octadecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,

[1008] N-Methyl-4-octadecyl-N-decylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,

[1009] N-Methyl-4-nonadecyl-N-dodecylanilinium tetra(perfluoronaphthalen-2-yl)borate, N-Methyl-4-nonadecyl-N-tetradecylanilinium tetra(perfluoronaphthalen-2-yl)borate, N-Methyl-4-nonadecyl-N-hexadecylanilinium tetra(perfluoronaphthalen-2-yl)borate, N-Methyl-4-nonadecyl-N-octadecylanilinium tetra(perfluoronaphthalen-2-yl)borate, N-Ethyl-4-nonadecyl -N-octadecylanilinium, N-methyl-N,N-dioctadecylammonium tetra(perfluoronaphthalen-2-yl)borate, N-methyl-N,N-dihexadecylammonium tetra(perfluoronaphthalen-2-yl)borate, N-methyl-N,N-ditetradecylammonium tetra(perfluoronaphthalen-2-yl)borate, N-methyl-N,N-didodecylammonium tetra(perfluoronaphthalen-2-yl)borate, N-methyl-N,N-didecylammonium tetra(perfluoronaphthalen-2-yl)borate,

[1010] N-Methyl-N,N-dioctylammonium tetrakis(perfluoronaphthalen-2-yl)borate,

[1011] N-ethyl-N,N-dioctadecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N,N-dioctadecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N,N-dihexadecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N,N-ditetradecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N,N-didodecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N-octadecyl-N-hexadecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N-octadecyl-N-hexadecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N-octadecyl-N-tetradecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N-octadecyl-N-dodecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N-octadecyl-N-decyl-tolylammonium borate, N-hexadecyl-N-tetradecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N-hexadecyl-N-dodecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N-hexadecyl-N-decyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N-tetradecyl-N-dodecyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N-tetradecyl-N-decyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N-dodecyl-N-decyl-tolylammonium tetra(perfluoronaphthalene-2-yl)borate, N-methyl-N-octadecylanilinium tetra(perfluoronaphthalene-2-yl)borate, N-methyl-N-hexadecylanilinium tetra(perfluoronaphthalene-2-yl)borate, N-methyl-N-tetradecylanilinium tetra(perfluoronaphthalene-2-yl)borate,

[1012] N-Methyl-N-dodecylanilinium tetrakis(perfluoronaphthalen-2-yl)borate,

[1013] N-methyl-N-decylanilinium tetrakis(perfluoronaphthalen-2-yl)borate, and

[1014] N-Methyl-N-octylanilaminium tetrakis(perfluoronaphthalen-2-yl)borate.

[1015] Clause 46. The process of any one of clauses 1 to 45, wherein the polyolefin has:

[1016] About 9% by weight ethylene content, the balance being propylene;

[1017] About 0.879g / cm 3 Density (ASTM D1505),

[1018] Melt index of about 3.6 g / 10 min (ASTM D1238; 190°C, 2.16 kg),

[1019] Melt mass flow index of about 8g / 10min (230℃, 2.16kg),

[1020] A Shore D hardness of approximately 34 (ASTM D2240), and

[1021] Vicat softening temperature (VST) of about 77.3°C.

[1022] Clause 47. The process of any one of clauses 1 to 46, wherein the polyolefin has:

[1023] About 11% by weight ethylene content, the balance being propylene;

[1024] About 0.873g / cm 3 Density (ASTM D1505),

[1025] Melt index of about 3.7 g / 10 min (ASTM D1238; 190°C, 2.16 kg),

[1026] Melt mass flow index of about 8g / 10min (230℃, 2.16kg),

[1027] A Shore D hardness of approximately 27 (ASTM D2240), and

[1028] Vicat softening temperature (VST) of about 65.1°C.

[1029] Clause 48. The process of any one of clauses 1 to 47, wherein the polyolefin has:

[1030] About 4% by weight ethylene content, the balance being propylene;

[1031] About 0.889g / cm 3 Density (ASTM D1505),

[1032] Melt mass flow index of about 8g / 10min (230℃, 2.16kg),

[1033] A Shore D hardness of approximately 50 (ASTM D2240), and

[1034] Vicat softening temperature (VST) of about 103°C.

[1035] Clause 49. The process of any one of clauses 1 to 48, wherein the polyolefin is a propylene-ethylene copolymer having:

[1036] About 0.863g / cm 3 Density (ASTM D1505),

[1037] A melt index of about 9.1 g / 10 min (ASTM D1238; 190°C, 2.16 kg), a melt flow index of about 20 g / 10 min, and

[1038] Ethylene content of about 15% by weight.

[1039] Clause 50. The process of any one of clauses 1 to 49, wherein the polyolefin is a propylene-ethylene copolymer having:

[1040] About 0.862g / cm 3 Density (ASTM D1505),

[1041] A melt index of about 1.4 g / 10 min (ASTM D1238; 190°C, 2.16 kg), a melt flow index of about 3 g / 10 min, and

[1042] Ethylene content of about 16 wt%.

[1043] Clause 51. The process of any of clauses 1 to 50, wherein the polyolefin is a propylene-ethylene copolymer having:

[1044] About 0.874g / cm 3 Density (ASTM D1505),

[1045] Melt index of about 1.1 g / 10 min (ASTM D1238; 190°C, 2.16 kg),

[1046] A melt flow index of about 3 g / 10 min, and

[1047] Ethylene content of about 11 wt%.

[1048] Clause 52. The process of any one of clauses 1 to 51, wherein the polyolefin has:

[1049] Isotactic propylene repeating unit,

[1050] About 0.865g / cm 3 The density of

[1051] A melt mass flow index of about 45.2 g / 10 min (230° C., 2.16 kg), and

[1052] Ethylene content of about 13.1 wt%. Example

[1053] The foregoing discussion may be further described with reference to the following non-limiting examples.

[1054] As used herein, M1 = dimethylsilylbis(indenyl)hafnium dimethyl and was obtained from WR Grace & Co.

[1055] N-methyl-4-nonadecanyl-N-octadecylaniline is made from N-methylaniline.Aniline is alkylated with octadecyl bromide, then formylated in the para position by reacting with dimethylformamide and phosphoryl chloride.The Grignard reaction of octadecyl magnesium chloride is used, followed by hydrogenation to introduce the nonadecanyl group.The amine is dissolved in a solvent, and a slightly excessive ether solution of hydrogen chloride is added to form chlorinated N-methyl-4-nonadecanyl-N-octadecylanilinium.In order to prepare borates, the ammonium chloride separated by heating is refluxed with a molar equivalent of tetrakis (perfluoronaphthalene-2-yl) sodium borate.A solution of 0.2344 wt % tetrakis (perfluoronaphthalene-2-yl) boric acid N-methyl-4-nonadecanyl-N-octadecylanilinium is prepared in a 4L beaker in 2-methyl-pentane, and a separate solution of 0.0765 wt % of M1 (metallocene) in 2-methyl-pentane is prepared in a 4L beaker in a nitrogen environment box of a continuous experimental device. The two solutions were drawn from the 4 L beaker into separate syringe pumps and then pumped through separate feed lines to a mixing tee located approximately 0.5 m from the polymerization reactor.

[1056] In experiment A, the two solutions were mixed together in a tee and injected into the polymerization reactor. In experiment B, the two solutions were injected into the polymerization reactor separately. Figure 2A Describe the arrangement and Figure 2B Describe the arrangement of Experiment B.

[1057] Vistamaxx was produced in the reactor during two experiments according to the reactor conditions given in Table 4. TM3980. (Note: For Table 4, for Experiment A, the catalyst and activator concentrations and feed rates are for injection into the mixing tee. For Experiment B, the catalyst and activator concentrations and feed rates are for direct injection into the reactor.)

[1058] Table 4: Reactor conditions for Experiments A and B

[1059]

[1060]

[1061] Experiment A, premixing of metallocene and activator was performed at about 15:00 on the first day of the run. The switch to experiment B was made at about 18:00 on the second day, by changing the valve arrangement to inject metallocene solution and activator solution separately without stopping the polymerization reaction. Figure 3 This significantly improves reactor temperature control (e.g., small temperature delta), and illustrates the advantage of separate injection of activator and metallocene solutions when non-aromatic solvents are used at concentrations typically used for injection into polymerization reactors. Figure 4 As can be seen in Figure 5, switching from Experiment A to Experiment B improved catalyst efficiency and reduced variation over time, illustrating another advantage of separate injections of the activator and metallocene solutions.

[1062] In general, the present disclosure provides an activator that can be partially or completely dissolved in a non-aromatic diluent. The method of the present disclosure can provide for the independent direct injection of the activator and the direct injection of the catalyst into the reactor, which provides a temperature change that is reduced or eliminated during polymerization. In addition, although the direct injection of the catalyst and the activator provides a very dilute concentration of the catalyst and the activator in the reactor before the activated catalyst, the catalyst efficiency is also maintained or improved compared to the premixing of the catalyst and the activator in toluene. Due to the reduced temperature change of the method (compared to conventional polymerization methods), the method of the present disclosure can also provide uniform polymer properties in addition to the low aromatic content of the formed polymer.

[1063] Unless otherwise specified, the phrases "consisting essentially of" and "consisting essentially of" do not exclude the presence of other steps, elements, or materials, whether or not specifically mentioned in the present specification, as long as such steps, elements, or materials do not affect the basic and novel characteristics of the present disclosure, and further, they do not exclude impurities and variations normally associated with the elements and materials used.

[1064] For the purpose of brevity, only some ranges are explicitly disclosed herein. However, the range from any lower limit can be combined with any upper limit to record the range that is not clearly recorded, and the range from any lower limit can be combined with any other lower limit to record the range that is not clearly recorded, and in the same way, the range from any upper limit can be combined with any other upper limit to record the range that is not clearly recorded. In addition, even if it is not clearly recorded, each point or individual value between its endpoints is included in the scope. Therefore, each point or individual value can serve as their own lower limit or upper limit, combined with any other point or individual value or any other lower limit or upper limit, so as to record the range that is not clearly recorded.

[1065] All documents described herein are incorporated herein by reference, including any priority documents and / or test procedures, as long as they do not contradict this article. As is apparent from the general description and specific embodiments above, although the form of the present disclosure has been set forth and described, various changes can be made without departing from the spirit and scope of the present disclosure. Therefore, it is not intended to limit the present disclosure thereby. Similarly, for the purposes of U.S. law, the term "comprising" is considered to be synonymous with the term "including". Similarly, whenever a composition, element or group of elements is preceded by the conjunction "comprising", it should be understood that we also consider the same composition or group of elements preceded by the conjunction "essentially consisting of...", "consisting of...", "selected from a group consisting of..." or "is", and vice versa.

[1066] Although the disclosure has been described with respect to a number of embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised that do not depart from the scope and spirit of the disclosure.

Claims

1. Methods, including: introducing a catalyst solution into the reactor via a first pipeline, the catalyst solution consisting of a catalyst and a first non-aromatic diluent, wherein the catalyst is a metallocene catalyst; An activator solution is introduced into the reactor via a second pipeline, the activator solution consisting of an activator and a second non-aromatic diluent, wherein the second non-aromatic diluent is the same as the first non-aromatic diluent and the first non-aromatic diluent and the second non-aromatic diluent are selected from the following: butane, n-pentane, isopentane, hexane, heptane, octane, dodecane and one or more mixtures thereof, wherein the activator is represented by formula (AI): [R 1 R 2 R 3 EH] d + [M k+ Q n ] d- (AI) in: E is nitrogen or phosphorus; Each d is the same and is 1, 2, or 3; k is 1, 2, or 3; n is 1, 2, 3, 4, 5, or 6; nk=d; R 1 , R 2 and R 3 Each of which is independently selected from the following: H, C1-C 40 Alkyl, and C5-C 50 -aryl; wherein R 1 , R 2 and R 3 Contains 15 or more carbon atoms in total; M is an element selected from Group 13 of the Periodic Table; and Each Q is independently selected from the following: hydrogen, bridged or unbridged dialkylamino, halo, alkoxy, aryloxy, hydrocarbyl, halohydrocarbyl; operating the reactor under process conditions, wherein the process conditions comprise a temperature delta of 0°C to 20°C during substantially the entire process; and obtaining an effluent from the reactor, the effluent comprising polyolefin, The first pipeline and the second pipeline are connected to the reactor.

2. The process of claim 1, wherein the first non-aromatic diluent and the second non-aromatic diluent are selected from the group consisting of isobutane, isohexane, and mixtures thereof.

3. The method of claim 1, wherein the first non-aromatic diluent and the second non-aromatic diluent are 2-methyl-pentane.

4. The method of claim 1, wherein the catalyst solution does not contain an activator.

5. The method of claim 1, wherein the activator solution does not contain a catalyst.

6. The process of claim 1, wherein process conditions comprise a temperature delta of 0°C to 10°C during substantially the entire process.

7. The method of claim 1, wherein the first non-aromatic diluent and the second non-aromatic diluent have 1 wt% or less of aromatic compounds, based on the weight of the first non-aromatic diluent + aromatic compounds and the second non-aromatic diluent + aromatic compounds, respectively.

8. The process of claim 1, wherein process conditions comprise a temperature delta of 0.5°C to 5°C during substantially the entire process.

9. The method of claim 1, wherein the activator solution comprises the activator in an amount of 0.01 wt% to 20 wt% based on the weight of the activator solution.

10. The method of claim 9, wherein the activator solution comprises the activator in an amount of 0.15 wt% to 0.3 wt% based on the weight of the activator solution.

11. The process according to claim 1, wherein the introduction of the activator solution into the reactor is carried out at the following feed rate: 0.01 kg / hr to 40 kg / hr, or 0.02 L / hr to 60 L / hr.

12. The method of claim 1, wherein the catalyst solution comprises the catalyst in an amount of 0.01 wt% to 20 wt% based on the weight of the catalyst solution.

13. The method of claim 12, wherein the catalyst solution comprises the catalyst in an amount of 0.05 wt% to 0.1 wt% based on the weight of the catalyst solution.

14. The process according to claim 1, wherein the catalyst solution is introduced into the reactor at a feed rate of: 0.003 kg / hr to 40 kg / hr, or 0.004 L / hr to 60 L / hr.

15. The method of claim 1, wherein the process conditions comprise a temperature delta of 1°C to 3°C during substantially the entire process.

16. The process of claim 1, wherein the effluent has an aromatic content of 1 wt% or less based on the weight of the effluent.

17. The method of claim 1, wherein the polyolefin has an aromatic content of 1 wt% or less, based on the weight of the polyolefin.

18. The method of claim 1, wherein: The process conditions include a temperature of 130°C to 200°C and a pressure of 100 bar to 130 bar, and Polyolefins are plastomers.

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