Alkene functionalization activator

Abstract

Process for polymerizing polyolefins and synthesis of activators. The polymerization process comprises the step of polymerizing one or more (C2-C6) olefins in the presence of at least one catalyst and at least one cocatalyst to produce polyolefins. 12 The process involves polymerizing α-olefin monomers using a cocatalyst containing a cation and an anion, the anion having a structure containing a vinyl-terminated alkene, one or more boron atoms, and at least four halogen atoms. The cocatalyst anion is incorporated into the polymer chain of the polyolefin.

Description

Technical Field

[0001] Cross - reference to related applications This application claims priority to U.S. Provisional Patent Application No. 62 / 840,887, filed on April 30, 2019, the entire disclosure of which is incorporated herein by reference.

[0002] Embodiments of the present disclosure generally relate to alkene functionalized activators, the synthesis of activators, and their application to olefin polymerization processes.

Background Art

[0003] Olefin polymers such as ethylene - based polymers and propylene - based polymers are produced via various catalyst systems. The selection of such catalyst systems can be an important factor contributing to the characteristics and properties of olefin polymers. Examples of catalyst systems for producing polyethylene - based polymers include chromium - based catalyst systems, Ziegler - Natta catalyst systems, or molecular (either metallocene or non - metallocene) catalyst systems.

[0004] Activators are typically used in combination with metal precatalysts to form activated catalyst ion pairs, which are then used in the polymerization of olefins. As part of the catalyst composition in α - olefin polymerization reactions, activators can have beneficial characteristics for the production of α - olefin polymers and the final polymer composition containing α - olefin polymers. Characteristics of activators that increase the production of α - olefin polymers include, but are not limited to, rapid activation of the precatalyst, high catalyst efficiency, high - temperature capability, consistent polymer composition, and selective deactivation.

[0005] To generate catalytically active species for the coincidence, the molecular polymerization procatalyst as part of the catalyst system is activated, and this activation can be achieved by any number of means. One such method uses an activator or cocatalyst that is a Bronsted acid. To activate a molecular polymerization procatalyst, particularly such a procatalyst containing a Group IV metal complex, generally Bronsted acid salts containing weakly coordinating anions are utilized. A fully ionized Bronsted acid salt is capable of moving a proton to form a cationic derivative of such a Group IV metal complex.

[0006] In an activator such as a Bronsted acid salt, as the cation component, for example, cations capable of moving hydrogen ions such as ammonium, sulfonium, or phosphonium, or oxidation cations such as ferrocenium, silver(I), or lead(II) cations, or highly Lewis acidic cations such as carbonium or silylium can be mentioned.

[0007] However, when the cation of the activator or cocatalyst activates the procatalyst, the activator may remain in the polymer composition. As a result, the cations and anions may affect the polymer composition. Since not all ions diffuse equally, different ions have different effects on the polymer composition. Specifically, the size of the ion, the charge of the ion, the interaction of the ion with the surrounding medium, and the dissociation energy of the ion with the available counterion will affect the ability of the ion to diffuse through the surrounding medium such as a solvent, gel, or polymer material.

[0008] Conventional olefin polymerization activators include weakly coordinating or non-coordinating anions. It has been shown that the weak coordination of the anion results in an increase in the catalytic efficiency of the cationic catalyst. However, since the non-nucleophilic character of the non-coordinating anion also increases diffusion, the activator anion remaining in the produced polymer will reduce the electrical resistance of the polymer, thereby increasing electrical losses and reducing the insulating ability of the produced polymer.

SUMMARY OF THE INVENTION

[0009] There is a continuing need to create an activator or cocatalyst that maintains the catalytic efficiency of the weakly coordinating anion without spreading or adversely affecting the polymer properties of the produced polymer. Embodiments of the disclosure include a polymerization process. In one or more embodiments, the polymerization process comprises, to produce a polyolefin, one or more (C 2 -C 12 ) α-olefin monomers in the presence of at least one catalyst and at least one cocatalyst, and then inserting the anion of the cocatalyst into the polymer chain of the polyolefin. The polyolefin comprises (1) an anion of the cocatalyst greater than 0 mole percent and less than 1 mole percent of the total mole percent of the polyolefin, and (2) a density in the range of 0.853 to 0.920 g / cm 3 .

[0010] The cocatalyst comprises a cation and an anion. The anion has a structure comprising one vinyl-terminated alkene, one boron atom or two or more boron atoms, and at least four halogen atoms.

[0011] In an embodiment, the polymer process comprises polymerizing one or more (C 2 -C 12 ) α-olefin monomers in the presence of at least one catalyst and at least one cocatalyst to produce a polyolefin. The anion of the cocatalyst is then inserted into the polymer chain of the polyolefin.

[0012] The cocatalyst contains a cation and an anion, and the anion has a structure according to formula (I).

Chemical formula

[0013] In formula (I), R 1 is an unsaturated (C 2 -C 20 ) hydrocarbyl having a vinyl-terminated alkene, and X is a halogen selected from the group consisting of fluorine, chlorine, bromine, and iodine.

[0014] In one or more embodiments, the polyolefin has a lower dielectric tangent than the corresponding polyolefin composition produced under the same polymer conditions, except that the molar amount of the anion of formula (I) is replaced by the same molar amount of a comparative anion having formula (Ia).

Chemical formula

[0015] In some embodiments, the polymerization process comprises copolymerizing ethylene monomer and one or more (C 3 -C 12 ) α-olefin monomers in the presence of at least one catalyst and at least one cocatalyst. The anion of the cocatalyst is inserted into the polymer chain of the polyolefin. The polyolefin contains an anion of the cocatalyst greater than 0 mole percent and less than 1 mole percent based on the molar composition of the polyolefin.

[0016] The cocatalyst contains a cation and an anion, and the anion is according to formula (II). - BR 2 R 3 R 4 R 5 (II)

[0017] In formula (II), R 2 , R3 , R 4 , and R 5 are each independently selected from (C 1 -C 40 ). Each (C 1 -C 40 ) hydrocarbyl is substituted with at least one halogen, and at least one (C 1 -C 40 ) hydrocarbyl is substituted with a vinyl-terminated alkene.

Brief Description of the Drawings

[0018]

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DETAILED DESCRIPTION OF THE INVENTION

[0019] The term "polymer" refers to polymer compounds prepared by polymerizing α-olefins, regardless of the same or different types. Thus, the general term "polymer" includes the term "homopolymer", which is usually used to refer to polymers prepared from only one type of monomer, and "copolymer", which refers to polymers prepared from two or more different monomers. As used herein, the term "interpolymer" refers to polymers prepared by polymerizing at least two different types of monomers. Thus, the general term "interpolymer" includes copolymers and polymers prepared from three or more different types of monomers such as terpolymers.

[0020] "Polyethylene" or "ethylene polymer" shall mean a polymer containing units derived from ethylene monomer in an amount exceeding 50 mole percent (mol%). This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of polyethylene known in the art include low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra low density polyethylene (ULDPE), very low density polyethylene (VLDPE), single site catalyst linear low density polyethylene (m-LLDPE) including both linear and substantially linear low density resins, medium density polyethylene (MDPE), and high density polyethylene (HDPE).

[0021] The disclosed embodiments include a polymerization process. In one or more embodiments, the polymerization process comprises polymerizing one or more (C 2 -C 12 )α-olefin monomers in the presence of at least one catalyst and at least one cocatalyst to produce a polyolefin. The cocatalyst has an anion and a cation. The cation of the cocatalyst is inserted into the polymer chain of the polyolefin. The anion of the cocatalyst has a structure comprising a vinyl-terminated alkene, one boron atom or two or more boron atoms, and at least four halogen atoms. In some embodiments, the anion of the cocatalyst has two vinyl-terminated alkene groups. In some embodiments, the polymerization process includes two cocatalysts, both of which have an anion having a structure comprising one vinyl-terminated alkene, one boron atom or two or more boron atoms, and at least four halogen atoms.

[0022] The term "vinyl-terminated alkene" refers to the placement of a double bond on a hydrocarbon. A vinyl-terminated alkene is a terminal double bond, e.g., R E HC=CH 2 , wherein R E is a hydrocarbyl. Scheme 1: Examples of anions inserted into or covalently incorporated into the polymer chain of a polyolefin. [Chemical formula]

[0023] In Scheme 1, "A" is the anion of the cocatalyst, "P" is the polymer chain, "M" is the metal center of the catalyst, and "L" is the ligand of the catalyst. The depiction in Scheme 1 illustrates the means by which the anion of the cocatalyst is inserted into or covalently incorporated into the polymer chain of the polyolefin. The vinyl-terminal alkene of the anion of the cocatalyst functions as an olefin and is polymerized into the polymer chain. Scheme 1 is illustrative and not intended to be limiting. For example, Scheme 1 depicts a catalyst that is a metal-ligand catalyst (L-M). However, any catalyst activated by an activator or cocatalyst may be suitable in the processes of the present disclosure.

[0024] The term "activator" refers to a compound that chemically reacts with a precatalyst to convert the precatalyst into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable terms. The term "precatalyst" refers to a compound that has catalytic activity when combined with an activator.

[0025] As described above, the residual activator anion in the resulting polymer will reduce the electrical resistance of the polymer, thereby increasing the electrical loss and thereby reducing the insulating ability of the resulting polymer. Without intending to be bound by theory, it is believed that the migration or diffusion of the anion of the cocatalyst is reduced throughout the composition of the polyolefin because the anion is incorporated into the polymer chain. Thus, a polyolefin produced from a process that includes incorporating the anion of the cocatalyst into the polymer chain of the polyolefin has electrical properties that are better than expected, such as a lower dielectric tangent, when compared to a comparative polymer produced under similar conditions except that the cocatalyst was not incorporated into the polymer chain of the comparative polymer.

[0026] In an embodiment, the polymer process comprises polymerizing one or more (C 2 -C 12 )α-olefin monomers in the presence of at least one catalyst and at least one cocatalyst to produce a polyolefin. Subsequently, the anion of the cocatalyst is inserted into the polymer chain of the polyolefin.

[0027] The cocatalyst comprises a cation and an anion. The anion has a structure according to formula (I).

Chemical formula

[0028] In formula (I), R 1 is an unsaturated (C 2 -C 20 ) hydrocarbyl having a vinyl terminal alkene, and X is a halogen atom. In some embodiments, each X is chlorine. In other embodiments, each X is bromine.

[0029] Those skilled in the art will recognize that the structures of formula (I) and (Ia) are carborane anions. When each X is chlorine, the structure of formula (I) has an empirical formula of - B 11 CR 1 Cl 11 , where B is a boron atom, C is a carbon atom, Cl is a chlorine atom, and R 1 is as previously defined. Each boron atom is represented by a round ball in formula (I). Each chlorine atom of formula (I) is bonded to a boron atom.

[0030] In one or more embodiments, the polyolefin has a lower dielectric tangent than the corresponding polyolefin composition produced under the same polymer conditions, except that the molar amount of the anion of formula (I) is replaced by the same molar amount of a comparative anion having formula (Ia).

Chemical formula

[0031] The phrase "under the same polymer conditions" means that the polymerization process occurs under the same conditions in the same type of reactor. "The same type of reactor" does not limit the polymerization process to be carried out in the reactor that produced the polyolefin of the present disclosure, nor does it limit the polymerization process to the same location. For example, when a polyolefin produced by a cocatalyst having an anion of formula (I) is polymerized in a batch reactor, the corresponding polyolefin composition produced by a cocatalyst having an anion of formula (Ia) is also polymerized in a batch reactor. Further, "the same conditions" means that each reactor is filled with the same molar amounts of catalyst, cocatalyst, comonomer (if a comonomer is present), hydrogen (if hydrogen is present), and ethylene pressure (if ethylene is present), filled with the same volume amount of solvent, and each reactor is heated to the same temperature at the same rate of temperature increase.

[0032] In some embodiments, the polymerization process comprises polymerizing one or more (C 2 -C 12 )α-olefin monomers in the presence of at least one catalyst and at least one cocatalyst to produce a polyolefin. The anion of the cocatalyst is inserted into the polymer chain of the polyolefin. The polyolefin contains less than 1 mole percent of the anion of the cocatalyst. The structure of formula (Ia) is also a carborane, having the empirical formula - B 11 CCl 11 H. Each atom is defined by formula (I), except that H is a hydrogen atom bonded to a carbon atom.

[0033] In some embodiments, the cocatalyst comprises a cation and an anion, and the anion is according to formula (II). - BR 2 R 3 R 4 R 5 (II)

[0034] In formula (II), R 2 , R 3 , R 4 , and R 5 are each independently selected from (C 1 -C 40 ) hydrocarbyls. Each (C 1 -C 40 ) hydrocarbyl is substituted with at least one halogen, and at least one (C 1 -C 40 ) hydrocarbyl is substituted with a vinyl-terminated alkene.

[0035] In embodiments of the present disclosure, the anion of the cocatalyst has one vinyl-terminated alkene. In one or more embodiments, the vinyl-terminated alkene has a structure according to formula (III).

Chemical formula

[0036] In formula (III), n is an integer from 1 to 10. In some embodiments, n is 1, 2, or 3.

[0037] In various embodiments, the vinyl-terminated alkene has a structure according to formula (IV).

Chemical formula

[0038] In formula (V), the subscript y is an integer from 1 to 10, and the subscript x is 0, 1, 2, and 3. As shown in formula (IV), the two substituents, the groups associated with the subscripts x and y, can be ortho, meta, or para to each other.

[0039] In one or more embodiments, the vinyl-terminated alkene according to formula (IV) has a structure according to formula (V).

Chemical formula

[0040] In formula (V), the subscripted letter x and the subscripted letter y are as defined in formula (IV). In formula (V), the two substituents, the groups associated with the subscripted letter x and the subscripted letter y, are para to each other.

[0041] In one or more embodiments, the polyolefin comprises anions of a cocatalyst that are greater than 0 mole percent (mol%) and less than 1 mol% based on the molar composition of the polyolefin. In some embodiments, the polyolefin comprises anions of a cocatalyst that are greater than 0 mol% and less than 0.5 mol%. In further embodiments, the polyolefin comprises anions of a cocatalyst that are greater than 0 and less than 0.1 mol%. In various embodiments, the polyolefin comprises anions of a cocatalyst that are greater than 0 mol% and less than 0.01 mol% based on the molar composition of the polyolefin.

[0042] In one or more embodiments, the cocatalyst comprises an anion according to formula (I) and a cation having a formal charge of plus one (+1). In some embodiments of the cocatalyst, the cation is selected from protonated tri[(C 1 -C 40 )hydrocarbyl]ammonium cations. In some embodiments, the cation is a protonated trialkylammonium cation containing one or two (C 14 -C 20 )alkyl groups on the ammonium cation. In one or more embodiments, the cation is + N(H)R N 3 wherein each R N is selected from (C 1 -C 20 )alkyl or (C 6 -C 20 )aryl. In one or more embodiments, the cation is + N(H)R N 3 wherein at least two of the R N are selected from (C 10 -C 20 )alkyl. In one or more embodiments, the cation is +N(H)R N 3 wherein R N is (C 16 -C 18 )alkyl. In one or more embodiments, the cation is + N(CH 3 )HR N 2 wherein R N is (C 16 -C 18 )alkyl. In some embodiments, the cation is selected from methyldioctadecylammonium cation, methyloctadecyl(hexadecyl)ammonium cation, methyldihexadecylammonium cation, or methylditetradecylammonium cation. Methyldioctadecylammonium cation, methyloctadecyl(hexadecyl)ammonium cation, methyldihexadecylammonium cation, or methylditetradecylammonium cation are collectively referred to herein as an armeenium cation. An ionic compound having an armeenium cation is formed readily by protonating, for example, methyldioctadecylamine, methyloctadecyl(hexadecyl)amine, methyldihexadecylamine, or methylditetradecylamine, which are available under the trade name Armeen™ from Akzo-Nobel, with, for example, anhydrous HCl in ether. In other embodiments, the cation is a tritylphenylmethylcarbocation, also referred to as trityl ( + C(C 6 H 5 ) 3 ). In one or more embodiments, the cation is + C(C 6 H 4 R C ) 3 such as a trisubstituted triphenylmethylcarbocation, wherein each R C is independently (C 1 -C 30) It is selected from alkyl. In other embodiments, the cation is selected from anilinium, ferrocenium, or aluminocenium. The anilinium cation is a protonated nitrogen cation such as [HN(R S )(R N ) 2 + , where R N is (C 1 -C 20 )alkyl or H, and R S is selected from (C 6 -C 20 )aryl, and each alkyl or aryl may be further substituted with -OR C , for example C 6 H 5 NMe 2 H + . The aluminocenium is an aluminum cation such as R S 2 Al(THF) 2 + , where R S is selected from (C 1 -C 30 )alkyl.

[0043] In an exemplary embodiment, the catalyst system may include one or more cocatalysts comprising an anion and a countercation, and the anion is according to formula (I). The countercation that forms a complex with the anion of formula (I) is included in the exemplary embodiments. Exemplary embodiments of the anion of formula (I) include the following structures.

Chemical formula

[0044] Electrical properties of the polymer The insulating medium should be as efficient as possible. Electrical losses reduce the efficiency with which the medium insulates in the presence of an electric field. Since resistance is inversely correlated with power or electrical losses, the resistance should be as high as possible in both alternating current (AC) and direct current (DC) systems.

[0045] ​In a DC system (e.g., a photovoltaic encapsulant), energy loss appears as leakage current from the encapsulated device to the external environment. This current (I) correlates with the voltage (V) and is inversely correlated with the resistance (R) of the insulating medium via the equation I = V × R -1 Thus, the higher the resistance, the lower the current and leakage current.

[0046] In an AC system (e.g., a cable insulator), the loss appears as energy absorption by the medium in the presence of an electric field. This loss, measured by the power (P), is determined by the equation P = V 2 × ω × C × ε′ × tan δ, where ω is the angular frequency, ε’ is the relative permittivity, C is the capacitance, tan δ is the dielectric loss tangent, and tan δ = (C × R × ω) -1 and results in the equation P = V 2 × ε′ × R -1 Since the resistance is inversely correlated with the power loss, the higher the resistance, the lower the power loss.

[0047] One physical effect that reduces the resistance of a medium is ion diffusion caused by an electric field. In a system where ion diffusion dominates the electrical response, the resistance is related to the diffusing ions via the equation R ∝ 6 × π × ε′ × ε 0 × η × r × C -1 × q -2 × N -1 where ε 0 is the permittivity of free space (8.854 × 10 -12 F·m -1 ), η is the dynamic viscosity of the medium, r is the hydrodynamic radius of the ion, q is the charge of the ion, and N is the concentration of the ion. Since an increase in resistance reduces energy loss and a decrease in ion concentration increases resistance, a reduction in the concentration of ions diffusing through the medium reduces energy loss.

[0048] In addition to size and charge, the interaction of the ion with the surrounding medium, as well as the dissociation energy of the ion with the available counterions, will affect the ability of the ion to diffuse through a given medium. Since not all ions diffuse equally, the ability of the ions in the activator to diffuse is an important characteristic. Without intending to be bound by theory, if the anions and countercations of the cocatalyst of the present disclosure of formula (I) have reduced diffusion, the resulting polymer of the cocatalyst of the present disclosure will have reduced energy loss, which is believed to provide good electrical properties.

[0049] In one or more embodiments, the polyolefin produced by any process of the present disclosure has a dielectric tangent of less than 0.10 at a frequency of 100 Hz and a temperature of 130 °C. In various embodiments, the polyolefin has a dielectric tangent of less than 1.00 at a frequency of 10 Hz and a temperature of 130 °C. In other embodiments, the polyolefin has a dielectric tangent of less than 10 at a frequency of 1.0 Hz and a temperature of 130 °C. In some embodiments, the polyolefin has a dielectric tangent of less than 100 at a frequency of 0.10 Hz and a temperature of 130 °C.

[0050] The dielectric tangent relates to the electrical properties of the resin. Reduction of the dielectric tangent produces materials that can be used as dielectric media (e.g., cable insulators or electronic encapsulants). If the dielectric tangent is mainly caused by ions in the resin, removal or immobilization of these ions can reduce the dielectric tangent and improve the electrical properties of the resin.

[0051] On a small scale, the polymers produced with the cocatalyst having the anion of formula (I) exhibit a dielectric tangent that is one-tenth of our standard polymer produced with comparative cocatalyst C1. Without being bound by theory, it is believed that polyolefins produced with the cocatalyst having the anion of formula (I) will have a dielectric tangent that is one-tenth of comparative cocatalyst C1 when the polyolefins are produced on an industrial scale. The dielectric tangent of a standard poly(ethylene-octene) copolymer is approximately 1.0. Thus, we predict that polyolefin polymers produced with the cocatalyst having the anion of formula (I) will exhibit a dielectric tangent of 0.1 or less at 60 Hertz (Hz).

[0052] Catalyst system components As the catalyst system, a procatalyst can be mentioned. The procatalyst can be catalytically activated by contacting or combining a complex with the cocatalyst of the present disclosure having an anion and a cation of formula (I), an anion and a cation of formula (II), or both anions and cations of formulas (I) and (II). The procatalyst can be selected from Group IV metal (Group IVB according to CAS, or Group 4 according to IUPAC nomenclature)-ligand complexes such as titanium (Ti) metal-ligand complexes, zirconium (Zr) metal-ligand complexes, or hafnium (Hf) metal-ligand complexes. By way of non-limiting example, examples of procatalysts can be found in the following references: US8372927, WO2010 / 022228, WO2011 / 102989, US6953764, US6900321, WO2017 / 173080, US7650930, US6777509, WO99 / 41294, US6869904, WO2007 / 136496. These references are hereby incorporated by reference in their entirety into this specification.

[0053] In one or more embodiments, the Group IV metal-ligand complex includes a bis(phenylphenoxy) Group IV metal-ligand complex, or a constrained geometry Group IV metal-ligand complex.

[0054] According to some embodiments, the bis(phenylphenoxy) metal-ligand complex has a structure according to formula (X). [Chemical Formula]

[0055] In formula (I), M is a metal selected from titanium, zirconium, or hafnium, and the metal is in a formal oxidation state of +2, +3, or +4. (X) n The subscript n of is 0, 1, or 2. When the subscript n is 1, X is a monodentate ligand or a bidentate ligand, and when the subscript n is 2, each X is selected from monodentate ligands. L is (C 1 -C 40 ) hydrocarbylene, (C 1 -C 40 ) heterohydrocarbylene, -Si(R C ) 2 -Si(R C ) 2 OSi(R C ) 2 -Si(R C ) 2 C(R C ) 2 -Si(R C ) 2 Si(R C ) 2 -Si(R C ) 2 C(R C ) 2 Si(R C ) 2 -C(R C ) 2 Si(R C ) 2 C(R C ) 2 -N(R N )C(R C ) 2 -N(R N )N(R N )-C(R C ) 2 N(R N )C(R C ) 2-, -Ge(R C ) 2 -, -P(R P )-, -N(R N )-, -O-, -S-, -S(O)-, -S(O) 2 -, -N=C(R C )-, -C(O)O-, -OC(O)-, -C(O)N(R)-, and -N(R C )C(O)- selected from the group consisting of is a diradical. Each Z is independently selected from -O-, -S-, -N(R N )-, or -P(R P )-, R 1 -R 16 is independently selected from -H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )heterohydrocarbyl, -Si(R C ) 3 , -Ge(R C ) 3 , -P(R P ) 2 , -N(R N ) 2 , -OR C , -SR C , -NO 2 , -CN, -CF 3 , R C S(O)-, R C S(O) 2 -, -N=C(R C ) 2 , R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C ) 2 NC(O)-, halogen, a radical having formula (XI), a radical having formula (XII), and a radical having formula (XIII).

Chemical formula

[0056] In formula (XI), (XII), and (XIII), R 31 -R35 , R 41 -R 48 , and R 51 -R 59 Each of is independently -H, (C 1 -C 40 ) hydrocarbyl, (C 1 -C 40 ) heterohydrocarbyl, -Si(R C ) 3 , -Ge(R C ) 3 , -P(R P ) 2 , -N(R N ) 2 , -OR C , -SR C , -NO 2 , -CN, -CF 3 , R C S(O)-, R C S(O) 2 -, (R C ) 2 C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C ) 2 NC(O)-, or selected from halogen, provided that at least one of R 1 or R 16 is a radical having formula (XI), a radical having formula (XII), or a radical having formula (XIII).

[0057] In one or more embodiments, each X can be a monodentate ligand that is independent of any other ligand X and is halogen, unsubstituted (C 1 -C 20 ) hydrocarbyl, unsubstituted (C 1 -C 20 ) hydrocarbyl C(O)O-, or R K R L N-, where each of R K and R L is independently unsubstituted (C 1 -C 20 ) hydrocarbyl.

[0058] Exemplary bis(phenylphenoxy)metal-ligand complexes that can be used in the practice of the present invention include (2’,2”-(Propane-1,3-diylbis(oxy))bis(5’-chloro-3-(3,6-di-tert-octyl-9H-carbazol-9-yl)-3’-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3’-chloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))bis(3’-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5’-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3’-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))bis(5’-cyano-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3’-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))bis(5’-dimethylamino-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3’-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))bis(3’,5’-dimethyl-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))bis(5’-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3’-ethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3’-methyl-5’-tert-butyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5’-fluoro-3’-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))bis(3-(9H-carbazol-9-yl)-5’-chloro-3’-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3’-methyl-5’-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(2,2-dimethyl-2-silapropane-1,3-diylbis(oxy))bis(3’,5’-dichloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’2”-(2,2-Dimethyl-2-silapropane-1,1-diylbis(oxy))bis(5’-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3’-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))bis(3’-bromo-5’-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))-(5’-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3’-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)-(3”,5”-dichloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5’-fluoro-3’-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Butane-1,4-diylbis(oxy))bis(5’-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3’-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Ethane-1,2-diylbis(oxy))bis(5’-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3’-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))bis(5’-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3’-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-zirconium, (2’,2”-(Propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3’,5’-dichloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-titanium, and (2’,2”-(Propane-1,3-diylbis(oxy))bis(5’-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3’-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-titanium are exemplified.

[0059] According to some embodiments, the Group IV metal-ligand complex may include a cyclopentadienyl pro-catalyst according to formula (XIV).

[0060] Lp i MX m X’ n X’ p or a dimer of (XIV).

[0061] In formula (XIV), Lp is an anionic delocalized π-bonding group bonded to M, containing up to 50 non-hydrogen atoms. In some embodiments of formula (XIV), two Lp groups may be bonded together to form a cross-linked structure, and optionally, one Lp may be bonded to X.

[0062] In formula (XIV), M is a Group 4 metal of the Periodic Table in a formal oxidation state of +2, +3, or +4. X is an optional divalent substituent of up to 50 non-hydrogen atoms that forms a metallacycle containing M together with Lp. X’ is an optional neutral ligand having up to 20 non-hydrogen atoms, and each X’’ is independently a monovalent, anionic moiety having up to 40 non-hydrogen atoms. Optionally, two X” groups may be covalently bonded together to form a divalent dianion moiety where both valences are bonded to M, or optionally, two X” groups may be covalently bonded together to form a neutral, conjugated, or non-conjugated diene π-bonded to M where M is in the +2 oxidation state. In other embodiments, one or more X’’ and one or more X’ groups may be bonded together to thereby form a moiety that is covalently bonded to M and coordinated by a Lewis base functional group. Lp i The subscript i of n is 0, 1, or 2, and the subscript n of X’ m is 0, 1, 2, or 3, and the subscript m of X p is 0 or 1, and the subscript p of X” p is 0, 1, 2, or 3. The sum of i + m + p is equal to the formal oxidation state of the formula of M.

[0063] Exemplary Group IV metal-ligand complexes include cyclopentadienyl procatalysts, which can be used in the practice of the present invention, cyclopentadienyltitanium trimethyl, cyclopentadienyltitanium triethyl, cyclopentadienyltitanium triisopropyl, cyclopentadienyltitanium triphenyl, cyclopentadienyltitanium tribenzyl, cyclopentadienyltitanium-2,4-dimethylpentadienyl, cyclopentadienyltitanium-2,4-dimethylpentadienyl·triethylphosphine, cyclopentadienyltitanium-2,4-dimethylpentadienyl·trimethylphosphine, cyclopentadienyltitanium dimethyl methoxide, Cyclopentadienyltitanium dimethyl chloride, Pentamethylcyclopentadienyltitanium trimethyl, Indenyltitanium trimethyl, Indenyltitanium triethyl, Indenyltitanium tripropyl, Indenyltitanium triphenyl, Tetrahydroindenyltitanium tribenzyl, Pentamethylcyclopentadienyltitanium triisopropyl, Pentamethylcyclopentadienyltitanium tribenzyl, Pentamethylcyclopentadienyltitanium dimethyl methoxide, Pentamethylcyclopentadienyltitanium dimethyl chloride, Bis(η 5 -2,4-dimethylpentadienyl)titanium, Bis(η 5 -2,4-dimethylpentadienyl)titanium·trimethylphosphine, Bis(η 5 -2,4-dimethylpentadienyl)titanium·triethylphosphine, Octahydrofluorenyltitanium trimethyl, Tetrahydroindenyltitanium trimethyl, Tetrahydrofluorenyltitanium trimethyl, (tert-Butylamide)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilane titanium dimethyl, (tert-Butylamide)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilane titanium dimethyl, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilane titanium dibenzyl, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilane titanium dimethyl, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)-1,2-ethanediyltitanium dimethyl, (tert-Butylamide)(tetramethyl-η 5 -indenyl)dimethylsilanetitanium dimethyl, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(III) 2-(dimethylamino)benzyl, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(III) allyl, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(III) 2,4-dimethylpentadienyl, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II) 1,3-pentadiene, (tert-Butylamide)(2-methylindenyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene, (tert-Butylamide)(2-methylindenyl)dimethylsilanetitanium(II) 2,4-hexadiene, (tert-Butylamide)(2-methylindenyl)dimethylsilanetitanium(IV) 2,3-dimethyl-1,3-butadiene, (tert-Butylamide)(2-methylindenyl)dimethylsilanetitanium(IV) isoprene, (tert-Butylamide)(2-methylindenyl)dimethylsilanetitanium(IV) 1,3-butadiene, (tert-Butylamide)(2,3-dimethylindenyl)dimethylsilanetitanium(IV) 2,3-dimethyl-1,3-butadiene, (tert-Butylamide)(2,3-dimethylindenyl)dimethylsilanetitanium(IV) isoprene, (tert-Butylamide)(2,3-dimethylindenyl)dimethylsilanetitanium(IV) dimethyl, (tert-Butylamide)(2,3-dimethylindenyl)dimethylsilanetitanium(IV) dibenzyl, (tert-Butylamide)(2,3-dimethylindenyl)dimethylsilanetitanium(IV) 1,3-butadiene, (tert-Butylamide)(2,3-dimethylindenyl)dimethylsilanetitanium(II) 1,3-pentadiene, (tert-Butylamide)(2,3-dimethylindenyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene, (tert-Butylamide)(2-methylindenyl)dimethylsilanetitanium(II) 1,3-pentadiene, (tert-Butylamide)(2-methylindenyl)dimethylsilanetitanium(IV) dimethyl, (tert-Butylamide)(2-methylindenyl)dimethylsilanetitanium(IV) dibenzyl, (tert-Butylamide)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene, (tert-Butylamide)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 1,3-pentadiene, (tert-Butylamide)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 2,4-hexadiene, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethyl-silanetitanium(IV) 1,3-butadiene, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(IV) 2,3-dimethyl-1,3-butadiene, (tert-Butylamide)(tetramethyl-η 5(Cyclopentadienyl)dimethylsilane titanium(IV) isoprene, (tert-Butylamide)(tetramethyl-η 5 (Cyclopentadienyl)dimethylsilane titanium(II) 1,4-dibenzyl-1,3-butadiene, (tert-Butylamide)(tetramethyl-η 5 (Cyclopentadienyl)dimethylsilane titanium(II) 2,4-hexadiene, (tert-Butylamide)(tetramethyl-η 5 (Cyclopentadienyl)dimethylsilane titanium(II) 3-methyl-1,3-pentadiene, (tert-Butylamide)(2,4-dimethylpenta-3-enyl)dimethylsilane titanium dimethyl, (tert-Butylamide)(6,6-dimethylcyclohexadienyl)dimethylsilane titanium dimethyl, (tert-Butylamide)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilane titanium dimethyl, (tert-Butylamide)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilane titanium dimethyl, (tert-Butylamide)(tetramethyl-η 5 (Cyclopentadienyl)methylphenylsilane titanium(IV) dimethyl, (tert-Butylamide)(tetramethyl-η 5 (Cyclopentadienyl)methylphenylsilane titanium(II) 1,4-diphenyl-1,3-butadiene, 1-(tert-Butylamide)-2-(tetramethyl-η 5 (Cyclopentadienyl)ethanediyl titanium(IV) dimethyl, 1-(tert-Butylamide)-2-(tetramethyl-η 5 (Cyclopentadienyl)ethanediyl titanium(II) 1,4-diphenyl-1,3-butadiene.

[0064] Each of the exemplary cyclopentadienylpro catalysts may contain zirconium or hafnium instead of the titanium metal center of the cyclopentadienylpro catalyst.

[0065] Other catalysts, specifically catalysts containing other Group IV metal-ligand complexes, will be apparent to those skilled in the art.

[0066] The catalyst system of the present disclosure may include a cocatalyst or activator in addition to the cocatalyst of the present disclosure having the anion and countercation of formula (I). Such additional cocatalysts include, for example, tri(hydrocarbyl)aluminum compounds having 1 to 10 carbons in each hydrocarbyl group, oligomeric or polymeric alumoxane compounds, di(hydrocarbyl)(hydrocarbyloxy)aluminum compounds having 1 to 20 carbons in each hydrocarbyl or hydrocarbyloxy group, or mixtures of the foregoing compounds. It is usually useful to use these aluminum compounds for their beneficial ability to scavenge impurities such as oxygen, water, aldehydes, etc. from the polymerization mixture.

[0067] The di(hydrocarbyl)(hydrocarbyloxy)aluminum compound that can be used in combination with the activator described in the present disclosure has the formula T 1 2 AlOT 2 , or T 1 1 Al(OT 2 ) 2 wherein T 1 is a secondary or tertiary (C 3 -C 6 ) alkyl such as isopropyl, isobutyl, or tert-butyl, and T 2 is an alkyl-substituted (C 6 -C such as 2,6-di(tert-butyl)-4-methylphenyl, 2,6-di(tert-butyl)-4-methylphenyl, 2,6-di(tert-butyl)-4-methyltolyl, or 4-(3’,5’-di-tert-butyltolyl)-2,6-di-tert-butylphenyl30 ) an aryl radical or an aryl-substituted (C 1 -C 30 ) alkyl radical.

[0068] Additional examples of aluminum compounds include [C 6 trialkylaluminum compounds, specifically those in which the alkyl group is ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or isopentyl, dialkyl(aryloxy)aluminum compounds containing 1 to 6 carbons in the alkyl group and 6 to 18 carbons in the aryl group (specifically, (3,5-di(t-butyl)-4-methylphenoxy)diisobutylaluminum), methylalumoxane, modified methylalumoxane, and diisobutylalumoxane.

[0069] In the catalyst system according to an embodiment of the present disclosure, the molar ratio of the cocatalyst of the present disclosure to the Group IV metal-ligand complex can be 1:10,000 to 1000:1, for example, 1:5000 to 100:1, 1:100 to 100:1, 1:10 to 10:1, 1:5 to 1:1, or 1.25:1 to 1:1, etc. The catalyst system can include a combination of one or more cocatalysts of the complexes of the present disclosure described in the present disclosure.

[0070] Polyolefin The catalyst systems described in the previous paragraphs are utilized for the polymerization of olefins, mainly ethylene and 1-octene. In some embodiments, only a single type of olefin or α-olefin is present during the polymerization scheme, generating a homopolymer. However, additional α-olefins may be incorporated into the polymerization procedure. The additional α-olefin comonomers typically have 20 or fewer carbon atoms. For example, the α-olefin comonomer may have 3 to 10 carbon atoms, or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene. For example, one or more α-olefin comonomers can be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively from the group consisting of 1-hexene and 1-octene.

[0071] Polyolefins, such as homopolymers and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers, α-olefins, etc., can contain monomer units derived from at least 50 mole percent (mol%) of ethylene. All individual values and subranges subsumed within "from at least 50 mol%" are disclosed herein as separate embodiments. For example, ethylene-based polymers, homopolymers of ethylene, and / or interpolymers (including copolymers) of ethylene and optionally one or more comonomers such as α-olefins can contain at least 60 mol% of monomer units derived from ethylene, at least 70 mol% of monomer units derived from ethylene, at least 80 mol% of monomer units derived from ethylene, or 50 to 100 mol% of monomer units derived from ethylene, or 80 to 100 mol% of units derived from ethylene.

[0072] In some embodiments, the polyolefin produced from the processes of the present disclosure can include units derived from at least 90 mole percent ethylene. All individual values and subranges from at least 90 mole percent are included herein and are disclosed herein as separate embodiments. For example, an ethylene-based polymer can include at least 93 mole percent units derived from ethylene, at least 96 mole percent units, at least 97 mole percent units derived from ethylene, or alternatively, 90 to 100 mole percent units derived from ethylene, 90 to 99.5 mole percent units derived from ethylene, or 97 to 99.5 mole percent units derived from ethylene.

[0073] In some embodiments of the ethylene-based polymer, the amount of additional α-olefin is less than 50 mol%, other embodiments include at least 0.5 mol% to 25 mol%, and in further embodiments, the amount of additional α-olefin includes at least 5 mol% to 10 mol%. In some embodiments, the additional α-olefin is 1-octene.

[0074] An ethylene-based polymer may be produced using any conventional polymerization process. Such conventional polymerization processes include, for example, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof that use one or more conventional reactors such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors, etc. in parallel, series, or any combination thereof, but are not limited thereto.

[0075] In one embodiment, the ethylene-based polymer can be produced via solution polymerization in a dual reactor system, such as a dual loop reactor system, in which ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein and optionally one or more cocatalysts. In another embodiment, the ethylene-based polymer can be produced via solution polymerization in a dual reactor system, such as a dual loop reactor system, in which ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein in the present disclosure and optionally one or more other catalysts. The catalyst system described herein can be used in the first reactor or the second reactor, optionally in combination with one or more other catalysts. In one embodiment, the ethylene-based polymer can be produced via solution polymerization in both reactors of a dual reactor system, such as a dual loop reactor system, in which ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein.

[0076] In another embodiment, the ethylene-based polymer can be produced via solution polymerization in a single reactor system, such as a single loop reactor system, in which ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described within the present disclosure and optionally one or more of the cocatalysts described in the preceding paragraph.

[0077] The ethylene-based polymer may further contain one or more additives. Such additives include, but are not limited to, antistatic agents, color intensifiers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, ultraviolet stabilizers, and combinations thereof. The ethylene-based polymer may contain any amount of additives. The ethylene-based polymer may contain a total amount of such additives of about 0 to about 10 weight percent, based on the weight of the ethylene-based polymer and one or more additives. The ethylene-based polymer may further contain a filler, and examples of such filler include, but are not limited to, organic or inorganic fillers. The ethylene-based polymer may contain, for example, about 0 to about 20 weight percent of a filler such as calcium carbonate, talc, or Mg(OH) 2 etc., based on the total weight of the ethylene-based polymer and all additives or fillers. The ethylene-based polymer can be further blended with one or more polymers to form a blend.

[0078] In some embodiments, the polymerization process for producing a polyolefin polymer can include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system, which incorporates at least one metal-ligand complex, at least one cocatalyst of the present disclosure, and optionally a scavenger. The polyolefin obtained from such a catalyst system incorporating a metal-ligand complex and a cocatalyst has a density, for example, of 0.853 to 0.920 g / cm 3 , 0.870 g / cm 3 ~0.920 g / cm 3 , 0.870 g / cm 3 ~0.910 g / cm 3 , or 0.870 g / cm 3 ~0.900 g / cm 3 in accordance with ASTM D792 (incorporated herein by reference in its entirety).

[0079] In another embodiment, the polymer obtained from a catalyst system comprising a metal-ligand complex and a cocatalyst of the present disclosure having an anion of formula (I) has a melt flow ratio (I 10 / I 2 has a melt index I 2 which is measured at 190 °C and a load of 2.16 kg in accordance with ASTM D1238 (incorporated herein by reference in its entirety), and the melt index I 10 is measured at 190 °C and a load of 10 kg in accordance with ASTM D1238. In other embodiments, the melt flow ratio (I 10 / I 2 ) is from 5 to 10, and in others, the melt flow ratio is from 5 to 9.

[0080] In some embodiments, the polymer obtained from the catalyst system comprising the metal-ligand complex has a molecular weight distribution (MWD) of from 1 to 25, where the MWD is defined as M w / M n , where M w is the weight average molecular weight and M n is the number average molecular weight. In other embodiments, the polymer obtained from the catalyst system has an MWD of from 1 to 6. Another embodiment includes an MWD of from 1 to 3, and other embodiments include an MWD of from 1.5 to 2.5.

[0081] The embodiments of the catalyst system described in this disclosure result in unique polymer properties as a result of the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer.

[0082] Add experiments on dielectric tangent Batch reactor procedure The experiments in the batch reactor were carried out in a 1 gallon continuous stirred tank reactor. After filling the reactor with Isopar-E hydrocarbon solvent, hydrogen, and an appropriate amount of octene comonomer, it was heated to a specific temperature and pressurized to 450 psi with ethylene. Polymerization was initiated by adding an activated catalyst solution containing the procatalyst, the cocatalyst of this disclosure, the solvent, and a triethylaluminum scavenger while the reactor was under pressure. The polymerization was allowed to proceed for 10 minutes while maintaining the temperature and pressure of the reactor. After the reaction was complete, the polymer was collected, dried in a vacuum oven overnight, and then analyzed.

[0083] General procedure for 1-octene polymerization: In a nitrogen-filled glove box, neat 1-octene (11 mL) was added to a 40 mL vial equipped with a stir bar. The vial was placed on a polyurethane-insulated block positioned on a magnetic stirring plate. A solution of the procatalyst and activator (1.2 - 1.25 equivalents relative to the procatalyst) in toluene was added continuously. The vial was capped and the reactants were stirred for the specified time (3 hours for procatalyst 2 and procatalyst 3, 6 days for procatalyst 3). All volatile substances were removed under reduced pressure to produce a polyoctene resin, which was then characterized by GPC and submitted for electrical testing.

[0084] General procedure for ethylene / 1-octene copolymerization: Ethylene / 1-octene screening is carried out in a high-throughput parallel polymerization reactor (PPR) system. The PPR system consists of a series of 48 single-cell (6×8 matrix) reactors in an inert atmosphere glove box. Each cell is equipped with a glass insert having an internal working liquid volume of approximately 5 mL. Each cell has independent pressure control and is continuously stirred at 800 rpm using a PEEK stirring paddle. The catalyst, ligand, and metal precursor solutions are prepared in toluene. All liquids (i.e., solvent, 1-octene, scavenger, activator, and procatalyst solution) are added via a robotic syringe. The gaseous reagent (i.e., ethylene) is added via a gas injection port. Prior to each run, the reactor is heated to 80 °C, purged with ethylene, and aerated.

[0085] To produce a sufficient amount of polymer for electrical testing, 24 replicates (half of the 48 reactors) are carried out for each procatalyst and activator combination. The polymers obtained from the 24 replicates are then combined.

[0086] The reactor was heated to 100 °C and then pressurized to 25.3 psig with ethylene. A portion of Isopar-E was added. A toluene solution of the reagents was then added to each reactor in the following order: (1) 1-octene (1.10 mL of procatalyst 3, 2.26 mL of procatalyst 2), (2) the scavenger triethylaluminum (TEA) (1 μmol), (3) the activator (comparative cocatalysts C1 - C3 or cocatalysts 1 - 7 (i.e., alkenyl-substituted carboranes) (added in an amount of 1.2 molar equivalents relative to the procatalyst), (4) the procatalyst (20 nmol of procatalyst 3, 80 nmol of procatalyst 2).

[0087] After the addition of each liquid, a small amount of Isopar-E was added to bring the total reaction volume to 5 mL upon final addition. When adding the catalyst, the pressure of each cell was monitored with PPR software. The desired pressure (within approximately 2 - 6 psig) was maintained by supplementary addition of ethylene gas by opening the valve at setpoint minus 2 psi and closing the valve when the pressure was 2 psi higher. All pressure drops were cumulatively recorded as "uptake" or "conversion" of ethylene, either over the course of the run or earlier, whichever occurred first, until the uptake or conversion requirement was reached. Each reaction was then quenched by addition of 10% carbon monoxide in argon at a pressure 40 - 50 psi higher than the reactor pressure for 1 - 4 minutes. To prevent the formation of excessive polymer in any given cell, the reaction was quenched when a predetermined uptake level (50 psig) was reached. After all the reactors were quenched, they were then vented and cooled to 70 °C when the glass tube inserts containing the samples were removed. The polymers from the solutions in 24 reactors containing the same procatalyst and activator solution were combined and left to decant in the draft for several days. The resulting resin was then dried in a vacuum oven in one continuous cycle at 80 °C for 3 hours and 140 °C for 4 hours, weighed to determine the polymer yield, and submitted for GPC analysis.

Example

[0088] Examples 1 to 3 are the synthetic procedures for the cocatalyst intermediate and the cocatalyst itself. Example 4 is the mass spectrometry result. Example 5 is the polymer result.

[0089] The reaction mixture for the mass spectrometry result of Example 4 was prepared at 5 mg / mL in non-inhibiting tetrahydrofuran (THF). Each sample was subjected to negative ion mode flow injection mass spectrometry on an Agilent 1290 Infinity II ultra-high speed liquid chromatograph (UHPLC) and an Agilent 6538 ultra-high resolution accurate mass quadrupole time-of-flight mass spectrometer (QTOF MS). 20 microliters of the analyte solution was injected into the UHPLC in flow injection mode, and the mobile phase was 66.7% non-inhibiting THF and 33.3% methanol with 1 g / L ammonium formate (flow rate 0.3 mL / min). The eluate from the liquid chromatograph was introduced into the MS and ionized in negative ion mode by electrospray ionization. A combination of MS and MS / MS data was collected. The mass spectrum was subjected to external calibration to generate accurate mass information within + / - 10 mDa. After external calibration, accurate mass prediction software (Agilent Masshunter) was utilized to generate the empirical formulas of the MS and fragment ions. The proposed structures were provided using both the predicted empirical formulas and dissociation behavior of each parent ion.

[0090] Unless otherwise specified, all operations were carried out under an Ar atmosphere using standard Schlenk lines of glove box techniques. Toluene, pentane, C 6 D 6 、 and THF were dried over NaK / Ph 2 CO / 18-crown-6, distilled or transferred under vacuum, and stored over molecular sieves in an Ar-filled glove box. NMR spectra were recorded on a Varian Inova 500 spectrometer ( 1 H NMR, 499.703 MHz, 13 C NMR 125.580 MHz), Varian Inova 400 ( 11 B NMR, 128.191 MHz) spectrometers, Bruker 400 (13 C 100, 11 was recorded at 102 MHz. Chemical shifts are reported in δ (ppm). 1 For 1H and 13 13C NMR spectra, the residual solvent peaks were used as internal references ( 1 1H NMR: δ CD 6 Cl3 was 7.16, CD 6 3CN was 1.94, CDCl 3 3 was 7.26, 3 13C NMR: δ CDCl 13 3 was 77.16, CD 3 3CN was 1.32). MALDI mass spectrometric analysis of the carborane anion was performed by the Texas A&M University Laboratory for Biological Mass Spectrometry, and the simulated MALDI(−) spectrum was generated using publicly available isotope distribution calculators and mass spectrometry plotters. 3 For 11B NMR, the spectra were externally referenced to δ = 0 ppm using BF 1 11 3·Et 3 2O. NaH was purchased from Sigma-Aldrich, washed with hexane before use, and 6-bromo-1-hexene, 4-bromo-1-butene, allyl bromide, and 1-iododecane were purchased from Matrix Scientific and used without further purification. 4-Vinylbenzyl chloride was purchased from Sigma Aldrich. [Me 2 NH][CHB 3 11Cl 11 , 11 2 n octyl 2 MeNH]Cl, and [( n 11C 18 6H 37 ) 2 MeNH]Cl were synthesized according to published procedures.

[0091] One or more features of the present disclosure are illustrated in the context of the following examples.

[0092] ​​General procedure for the synthesis of Example 1 - Na[R’CB 11 Cl 11 . A 50 mL Schlenk flask was charged with 500 mg of [Me 3 NH][CHB 11 Cl 11 and 2.5 equivalents of NaH in 20 mL of THF. The resulting suspension was stirred at room temperature for 2 hours until the foaming stopped. All volatile substances were removed under vacuum, and then 20 mL of THF was added with 1.1 equivalents of R’-Hal (allyl bromide, 4-bromo-1-butene, 6-bromo-1-hexene, 4-chloromethylstyrene, or decyl iodide). The suspension was stirred at room temperature overnight. The solution was filtered through a short pad of celite to remove NaCl. All volatile substances were removed under reduced pressure. The residue was washed with cold pentane and further dried under vacuum to obtain Na[R’CB 11 Cl 11 as a white solid. Each of the following examples was characterized by proton nuclear magnetic resonance (H 1 NMR), carbon nuclear magnetic resonance ( 13 C NMR), and boron nuclear magnetic resonance ( 11 B NMR).

Chemical Structure

[0093] Na[allyl-CB 11 Cl 11 : 427 mg (85% yield). 1 H NMR (500 MHz, CD 3 CN): δ 6.10 (ddt, J = 17.2, 9.9, 7.4 Hz, 1H), 5.13 (dq, J = 16.7, 1.4 Hz, 1H), 5.08 - 5.01 (dq, J = 16.7, 1.4 Hz, 1H), 3.01 (d, J = 7.3 Hz, 3H). 11 B{ 1 H}NMR (128 MHz, CD 3 CN): δ -3.03, -10.10, -11.73. 13 C{ 1 H}NMR (100 MHz, CD 3CN): δ 130.5 (s, CHCH 2 ), 120.4 (s, CHCH 2 ), 49.5 (brs, carborane-C), 35.6 (s, CH 2 CHCH 2 ).

Chem.

[0094] Na[butenyl-CB 11 Cl 11 : 427 mg of Na[butenyl-CB 11 Cl 11 (85% yield) 1 1H NMR (500 MHz, CDCl 3 ): δ 5.72 (ddt, J = 17.0, 10.3, 6.6 Hz, 1H), 5.08 (ddd, J = 17.4, 3.1, 1.6 Hz, 1H), 5.03 (ddd, J = 10.2, 3.1 Hz, 1.6 Hz, 1H), 2.69 - 2.61 (m, 2H), 2.37 (t, J = 8.9 Hz, 2H). 11 11B{ 1 1H}NMR (128 MHz, CDCl 3 ): δ -3.87, -10.52, -11.63. 13 13C{ 1 1H}NMR (100 MHz, CD 3 CN): δ 137.6 (s, CH 2 CH 2 CHCH 2 ), 116.6 (s, CHCH 2 ), 50.6 (brs, carborane-C), 31.4 (s, CH 2 CH 2 CHCH 2 ), 29.6 (s, CH 2 CH 2 CHCH 2 ).

Chem.

[0095] Na[hexenyl-CB 11 Cl 11: 300 mg Na[hexenyl-CB 11 Cl 11 (87% yield) 1 H NMR (400 MHz, CD 3 CN): δ 5.77 (ddt, J = 17.0, 10.2, 6.7 Hz, 1H), 4.99 (dq, J = 17.2, 1.7 Hz, 1H), 4.93 (ddt, J = 10.2, 2.3, 1.2 Hz, 1H). 2.30 - 2.20 (m, 2H), 2.07 - 1.97 (m, 2H), 1.90 - 1.75 (m, 2H) 1.32 (p, J = 7.4 Hz, 2H). 11 B{ 1 H}NMR (128 MHz, CD 3 CN): δ -2.94, -9.96, -11.58. 13 C{ 1 H}NMR (100 MHz, CD 3 CN): δ 139.2 (s, CHCH 2 ), 115.3 (s, CHCH 2 ), 51.4 (brs, carborane-C), 33.6 (s, alpha-CH 2 ), 31.8 (s, CH 2 ), 29.9 (s, CH 2 ), 24.6 (s, CH 2 ).

Chem.

[0096] Na[vinylbenzylCB 11 Cl 11 : 449 mg (89%). 1 H NMR (500 MHz, CD 2 Cl 2 ) δ 7.46 (d, J = 8.2 Hz, 2H), 7.27 (d, J = 8.2 Hz, 2H), 6.69 (dd, J = 17.6, 10.9 Hz, 1H), 5.75 (d, J = 17.6 Hz, 1H), 5.24 (d, J = 11.2 Hz, 1H), 3.67 (s, 2H). 11 B{ 1 H}NMR (128 MHz, CD 2 Cl 2 ): δ -3.32, -10.18, -11.16.13 C{ 1 H} NMR (100 MHz, CD 3 CN): δ 137.5 (s, CHCH 2 ), 137.0 (s, Ph) 134.8 (s, Ph), 131.0 (s, Ph), 125.4 (s, Ph), 114.6 (s, Ph), 49.5 (brs, carborane-C), 36.1 (s, PhCH 2 ).

Chem.

[0097] Na[decylCB 11 Cl 11 : 1.46 g (95%). 1 H NMR (500 MHz, CDCl 3 ): δ 2.27 (t, J = 9.2 Hz, 2H), 2.10 (s, 4H), 1.41 - 1.07 (m, 12H), 0.87 (t, J = 6.9 Hz, 3H). 11 B{ 1 H} NMR (128 MHz, CDCl 3 ): δ -4.14, -10.59, -11.52. 13 C{ 1 H} NMR (100 MHz, CD 3 CN): δ 49.5 (brs, carborane-C), 32.4 (s, decyl CH 2 ), 31.8 (s, decyl CH 2 ), 30.5 (s, decyl CH 2 ), 30.0 (s, decyl CH 2 ), 29.9 (s, decyl CH 2 ), 29.8 (s, decyl CH 2 ), 29.4 (s, decyl CH 2 ), 24.9 (s, decyl CH 2 ), 23.2 (s, decyl CH 2 ), 14.4 (s, decyl CH 3 ).

[0098] Example 2 - n Octyl 2 MeNH][R’CB 11 Cl 11General synthesis of In a 50 mL Schlenk flask, a solution of 300 mg of Na[R’CB 11 Cl 11 in 10 mL of THF was added to a solution of 1.1 equivalents of n octyl 2 MeNH]Cl in 10 mL of THF. Upon mixing, a precipitate immediately formed. The mixture was stirred for an additional 2 hours and then filtered through a short pad of celite. The filtrate was concentrated in vacuo, and the resulting oil was dissolved in toluene. The toluene solution was passed through a short pad of silica gel (to remove excess n octyl 2 MeNH]Cl) and concentrated in vacuo to give the product.

Chemical Structure

[0099] n octyl 2 MeNH][allyl-CB 11 Cl 11 : 360 mg (78%). 1 1H NMR (500 MHz, CDCl 3 ): δ 6.16 (ddt, J = 17.2, 9.9, 7.4 Hz, 1H), 5.20 (dq, J = 16.7, 1.4 Hz, 1H), 5.12 (dq, J = 16.7, 1.4 Hz, 1H), 3.01 (d, J = 7.3 Hz, 3H), 3.15 (vt, J = 7.5 Hz, 4H), 3.08 (d, J = 7.4 Hz, 2H), 2.97 (s, 3H), 1.80 (p, J = 8.0 Hz, 4H), 1.44 - 1.21 (m, 22H), 0.89 (t, J = 7.0 Hz, 3H). 11 11B{ 1 1H} NMR (128 MHz, CDCl 3 ): δ -3.53, -10.47, -11.75. 13 13C{ 1 1H} NMR (126 MHz, CD 3 CN): δ 137.6 (s, CHCH 2 ), 1C), 116.5 (s, CHCH 2 ), 1C), 57.1 (s, alpha-CH 2 ​, 2C), 54.0 (brs, carborane-C, 1C), 40.8 (s, N-Me, 1C), 32.3 (s, CH 2 , 2C), 29.6 (s, CH 2 , 2C), 29.5 (s, CH 2 CHCH 2 , 1C), 26.9 (s, CH 2 , 2C), 24.5 (s, CH 2 , 2C), 23.3 (s, CH 2 , 2C), 14.4 (s, terminal Me, 2C).

Chem.

[0100] n Octyl 2 MeNH][Butenyl-CB 11 Cl 11 : 360 mg (80%). 1 H NMR (500 MHz, CDCl 3 ): δ 6.16 (ddt, J = 17.2, 9.9, 7.4 Hz, 1H), 5.20 (dq, J = 16.7, 1.4 Hz, 1H), 5.12 (dq, J = 16.7, 1.4 Hz, 1H), 3.01 (d, J = 7.3 Hz, 3H), 3.15 (vt, J = 7.5 Hz, 4H), 3.08 (d, J = 7.4 Hz, 2H), 2.97 (s, 3H), 1.80 (p, J = 8.0 Hz, 4H), 1.44 - 1.21 (m, 22H), 0.89 (t, J = 7.0 Hz, 3H). 11 B{ 1 H}NMR (128 MHz, CDCl 3 ): δ -3.81, -10.58, -11.80. 13 C{ 1 H}NMR (126 MHz, CDCl 3 ): δ 136.5 (s, CHCH 2 , 1C), 116.1 (s, CHCH 2 , 1C), 57.7 (s, alpha-CH 2 , 2C), 50.4 (brs, carborane-C, 1C), 41.5 (s, N-Me), 31.5 (s, CH 2 , 2C), 30.4 (s, CH 2 CH​2 CHCH 2 ,(1C), 28.9 (s, CH 2 ,(2C), 28.7 (s, CH 2 CH 2 CHCH 2 ,(1C), 26.2 (s, CH 2 ,(2C), 24.5 (s, CH 2 ,(2C), 22.5 (s, CH 2 ,(2C), 14.0 (s, terminal CH 3 ,(2C). [Chemistry]

[0101] n Octyl 2 MeNH][Hexenyl-CB 11 Cl 11 : 410 mg (85%). 1 H NMR (500 MHz, CDCl 3 ): δ 7.04 (s, 1H), 5.77 (ddt, J = 17.0, 10.2, 6.7 Hz, 1H), 5.00 (dq, J = 17.5, 3.3 Hz, 1H), 4.94 (dq, J = 17.5, 3.3 Hz, 1H), 3.12 (t, J = 8.3 Hz, 4H), 2.93 (s, 3H), 2.28 (t, J = 9.0 Hz, 2H), 2.05 (dd, J = 14.7, 6.9 Hz, 2H), 1.96 - 1.85 (m, 2H), 1.84 - 1.73 (m, 2H), 1.45 - 1.20 (m, 24H), 0.88 (t, J = 6.9 Hz, 6H). 11 B{ 1 H}NMR (128 MHz, CDCl 3 ): δ -3.61, -10.39, -11.70. 13 C{ 1 H}NMR (126 MHz, CDCl 3 ): δ 138.1 (s, CHCH 2 ,(1C), 114.8 (s, CHCH 2 ,(1C), 57.8 (s, alpha-CH 2 ,(2C), 51.1 (brs, carborane-C, 1C), 41.6 (s, N-Me), 33.0 (s, hexyl-CH 2 ​, 1C), 31.6 (s, CH 2 , 2C), 31.0 (s, hexyl-CH 2 , 1C), 29.4 (s, hexyl-CH 2 , 1C), 28.9 (s, CH 2 , 2C), 26.3 (s, CH 2 , 2C), 24.6 (s, CH 2 , 2C), 23.9 (s, hexyl-CH 2 , 1C), 22.6 (s, CH 2 , 2C), 14.1 (s, terminal CH 3 , 2C).

Chem.

[0102] n Octyl 2 MeNH][CH 2 =CHC 6 H 4 CH 2 CB 11 Cl 11 : 500 mg (82%). 1 H NMR (500 MHz, CDCl 3 ) δ 7.46 (d, J = 8.3 Hz, 2H), 7.25 (d, J = 8.3 Hz, 2H), 6.67 (dd, J = 17.7, 10.8 Hz, 1H), 5.73 (d, J = 17.6 Hz, 1H), 5.23 (d, J = 10.9 Hz, 1H), 3.67 (s, 2H), 3.15 (t, J = 8.4 Hz, 4H), 2.97 (s, 3H), 1.84 - 1.71 (m, 4H), 1.43 - 1.18 (m, 22H), 0.88 (t, J = 7.0 Hz, 6H). 11 B{ 1 H}NMR (128 MHz, CDCl 3 ): δ -3.18, -10.42, -11.78. 13 C{ 1 H}NMR (126 MHz, CDCl 3 / CD 3 CN) δ 137.6 (s, sp 2 -C, 1C), 137.2 (s, sp 2 ​-C, 1C), 134.9 (s, Ar, 1C), 131.2 (s, Ar, 1C), 125.5 (s, Ar, 1C), 114.5 (s, Ar, 1C), 57.0 (s, N-CH 2 , 2C), 49.5 (brs, carborane-C, 1C), 40.7 (s, N-Me, 1C), 36.2 (s, benzyl C, 1C), 32.2 (s, CH 2 , 2C), 29.5 (s, CH 2 , 4C), 26.9 (s, CH 2 , 2C), 24.4 (s, CH 2 , 2C), 23.2 (s, CH 2 , 2C), 14.3 (s, CH 2 , 2C).

Chem.

[0103] n Octyl 2 MeNH][Decyl-CB 11 Cl 11 : 400 mg (88%). 1 H NMR (500 MHz, C 6 D 6 ) δ 4.67 (s, 1H), 2.76 (t, J = 8.4 Hz, 2H), 2.33 - 2.17 (m, 4H), 2.10 - 2.00 (m, 2H), 1.90 (d, J = 5.5 Hz, 3H), 1.42 - 1.33 (m, 4H), 1.33 - 1.06 (m, 30H), 0.99 (t, J = 7.2 Hz, 6H), 0.90 (t, J = 7.0 Hz, 3H). 11 B{ 1 H}NMR (128 MHz, CDCl 3 ): δ -3.09, -10.04, -11.72. 13 C{ 1 H}NMR (100 MHz, CD 3 CN) δ 57.3 (s, alpha-CH 2 , 2C), 51.5 (brs, carborane-C, 1C), 41.0 (s, N-Me), 32.6 (s, decyl-alpha-CH 2 , 1C), 32.4 (s, CH 2 , 2C), 32.0 (s, decyl-CH​2 , 1C), 30.6 (s, decyl-CH 2 , 1C), 30.1 (s, decyl-CH 2 , 1C), 30.0 (s, decyl-CH 2 , 1C), 29.9 (s, decyl-CH 2 , 1C), 29.7 (s, CH 2 , 2C), 29.6 (s, CH 2 , 2C), 29.4 (s, decyl-CH 2 , 1C), 27.0 (s, CH 2 , 2C), 25.1 (s, decyl-CH 2 , 1C), 24.8 (s, CH 2 , 2C), 23.4 (s, decyl-CH 2 , 1C), 23.3 (s, CH 2 , 2C), 14.4 (s, terminal CH 3 , 3C).

[0104] Example 3-[( n C 18 H 37 ) 2 MeNH][R’CB 11 Cl 11 General Synthesis: In a 50 mL Schlenk flask, a solution of 300 mg of Na[R’CB 11 Cl 11 in 10 mL of THF was added to a solution of 1.1 equivalents of [( n C 18 H 37 ) 2 MeNH]Cl in 10 mL of THF. Upon mixing, a precipitate immediately formed. The mixture was stirred for an additional 2 hours and then filtered through a short pad of celite. The filtrate was concentrated under vacuum and the resulting oil was dissolved in toluene. The toluene solution was passed through a short pad of silica gel (to remove excess [( n C 18 H 37 ) 2 MeNH]Cl) and concentrated under vacuum to give the product. Each of the following examples / products was characterized by H 1 NMR and C 13 NMR. [Chemical formula]

[0105] [( n C 18 H 37 ) 2 MeNH][allyl-CB 11 Cl 11 : 425 mg (85%). 1 H NMR (500 MHz, C 6 D 6 ): δ 6.40 (brs, NH), 6.05 (ddt, J = 17.2, 9.9, 7.4 Hz, 1H), 5.09 (dq, J = 16.7, 1.4 Hz, 1H), 5.02 (dq, J = 16.7, 1.4 Hz, 1H), 3.14 - 2.96 (m, 6H, N-CH 2 , alpha-CH 2 ), 2.88 (d, J = 5.4 Hz, 3H, N-CH 3 ), 1.75 - 1.66 (m, 4H, CH 2 ), 1.32 - 1.16 (m, 60H, CH 2 ), 0.78 (t, J = 6.9 Hz, 3H, terminal Me). 11 B{ 1 H}NMR (160 MHz, toluene-d 8 ): δ -2.74, -9.58, -10.87. 13 C{ 1 H}NMR (126 MHz, acetone-d 6 ): δ 137.6 (s, CHCH 2 , 1C), 116.5 (s, CHCH 2 , 1C), 57.1 (s, alpha-CH 2 ), 2C), 54.0 (brs, carborane-C, 1C), 40.9 (s, N-Me), 32.6 (s, CH 2 ), 2C), 30.4 - 29.6 (m, CH 2 ), 24C), 29.5 (s, CH 2 CHCH 2 ), 1C), 26.8 (s, CH 2 ), 2C), 24.4 (s, CH 2 ), 2C), 23.3 (s, CH 2, 2C), 14.4 (s, terminal CH 3 , 2C). [Chemical formula]

[0106] [( n C 18 H 37 ) 2 MeNH][butenyl-CB 11 Cl 11 : 300 mg (85%). 1 H NMR (500 MHz, CDCl 3 ): δ 5.70 (ddt, J = 16.9, 10.2, 6.6 Hz, 1H), 5.06 (dq, J = 17.1, 1.5 Hz, 1H), 5.00 (dq, J = 10.2, 1.4 Hz, 1H), 3.14 - 2.96 (m, 6H, N-CH 2 , alpha-CH 2 ), 2.98 (s, 3H, N-CH 3 ), 2.65 - 2.60 (m, 2H, hexyl-CH 2 ), 2.35 (t, J = 8.9 Hz, 2H, hexyl-CH 2 ), 1.82 - 1.76 (m, 4H, CH 2 ), 1.41 - 1.25 (m, 60H, CH 2 ), 0.88 (t, J = 7.0 Hz, 3H, terminal Me). 11 B{ 1 H}NMR (128 MHz, CD 3 CN): δ -2.87, -9.93, -11.60. 13 C{ 1 H}NMR (126 MHz, CDCl 3 ): δ 138.9 (s, CHCH 2 , 1C), 116.2 (s, CHCH 2 , 1C), 57.8 (s, alpha-CH 2 , 2C), 51.2 (brs, carborane-C, 1C), 41.8 (s, N-Me), 32.0 (s, CH 2 , 2C), 30.6 (s, CH 2 CH 2 CHCH 2 , 1C), 30.4 - 29.6 (m, CH2 , 24C), 28.9 (s, CH 2 CHCH 2 , 1C), 26.5 (s, CH 2 , 2C), 24.5 (s, CH 2 , 2C), 22.8 (s, CH 2 , 2C), 14.3 (s, terminal CH 3 , 2C).

Chem.

[0107] [( n C 18 H 37 ) 2 MeNH][hexenyl-CB 11 Cl 11 : 300 mg (83%). 1 H NMR (500 MHz, CDCl 3 ): δ 6.19 (brs, NH), 5.77 (ddt, J = 16.9, 10.2, 6.7 Hz, 1H), 5.00 (dq, J = 17.1, 1.6 Hz, 1H), 4.94 (dq, J = 10.2, 1.2 Hz, 1H), 3.25 - 3.08 (m, 6H, N-CH 2 , alpha-CH 2 ), 2.99 (d, J = 4.9 Hz, 3H, N-CH 3 ), 2.29 (vt, J = 9.6 Hz, 2H, alpha C of hexyl), 2.05 (qt, J = 6.8, 1.3 Hz, 2H, hexyl-CH 2 ), 1.93 - 1.77 (m, 6H, CH 2 ), 1.32 - 1.16 (m, 62H, CH 2 ), 0.88 (t, J = 7.0 Hz, 3H, terminal Me). 11 B{ 1 H}NMR (128 MHz, CD 3 CN): δ -2.97, -9.99, -11.62. 13 C{ 1 H}NMR (126 MHz, CDCl 3 ): δ 13 C{ 1 H}NMR (126 MHz, CDCl 3): δ 138.4 (s, CHCH 2 , 1C), 114.9 (s, CHCH 2 , 1C), 57.9 (s, alpha-CH 2 , 2C), 51.7 (brs, carborane-C, 1C), 41.9 (s, N-Me), 33.2 (s, hexyl-CH 2 , 1C), 32.1 (s, CH 2 , 2C), 31.2 (s, hexyl-CH 2 , 1C), 30.4 - 29.6 (m, CH 2 , 24C), 29.6 (s, hexyl-CH 2 , 1C), 26.4 (s, CH 2 , 2C), 24.5 (s, CH 2 , 2C), 24.0 (s, hexyl-CH 2 , 1C), 22.8 (s, CH 2 , 2C), 14.3 (s, terminal CH 3 , 2C).

Chemical formula

[0108] [( n C 18 H 37 ) 2 MeNH][styrenyl-CB 11 Cl 11 : 330 mg (82%). 1 H NMR (400 MHz, chloroform-d) δ 7.47 (d, J = 8.1 Hz, 2H), 7.24 (d, J = 8.1 Hz, 2H), 6.66 (dd, J = 17.6, 10.9 Hz, 2H), 5.73 (d, J = 17.6 Hz, 1H), 5.23 (d, J = 10.9 Hz, 0H), 3.67 (s, 2H), 3.24 - 2.93 (m, 4H), 2.86 (d, J = 5.1 Hz, 3H, N-Me), 1.35 - 1.26 (m, CH 2 60H), 0.88 (t, J = 6.8 Hz, 6H). 11 B{ 1 H}NMR (128 MHz, CD 3 CN): δ -2.70, -9.95, -11.35. 13 C{ 11H NMR (126 MHz, CDCl 3 ): δ 136.8 (s, CHCH 2 , 1C), 136.5 (s, Ar, 1C), 134.1 (s, Ar, 2C), 130.2 (s, Ar, 1C), 124.9 (s, Ar, 2C), 114.0 (s, CHCH 2 , 1C), 57.5 (s, alpha-CH 2 , 2C), 49.2 (brs, carborane-C, 1C), 41.3 (s, N-Me, 1C), 35.6 (s, benzyl-CH 2 , 1C), 32.0 (s, CH 2 , 4C), 29.8 - 29.6 (m, CH 2 , 22C), 29.5 (s, CH 2 , 2C), 29.4 (s, CH 2 , 2C), 29.3 (s, CH 2 , 2C), 29.0 (s, CH 2 , 2C), 26.3 (s, CH 2 , 2C), 24.4 (s, CH 2 , 2C), 22.7 (s, CH 2 , 2C), 14.2 (s, terminal CH 3 , 2C).

Chem.

[0109] [( n C 18 H 37 ) 2 MeNH][decyl-CB 11 Cl 11 : 340 mg (80%). 1 1H NMR (400 MHz, chloroform-d) δ 6.16 (brs, N-H, 1H), 3.27 - 3.08 (m, N-CH 2 , 4H), 2.99 (d, J = 5.2 Hz, N-Me, 3H), 2.28 - 2.24 (m, alpha-decyl-CH 2 , 2H), 1.87 - 1.74 (m, CH 2 , 6H), 1.41 - 1.26 (m, CH 2 , 76H), 0.87 (t, J = 6.7 Hz, terminal-CH 3, 9H). 11 B{ 1 H} NMR (128 MHz, CD 3 CN): δ -3.22, -10.05, -11.38. 13 C{ 1 H} NMR (126 MHz, CDCl 3 ): δ 58.1 (s, alpha-CH 2 , 2C), 51.5 (brs, carborane-C, 1C), 41.9 (s, N-Me, 1C), 32.01 (s, N-alkyl-CH 2 , 2C) 31.96 (s, decyl-CH 2 , 1C), 31.3 (s, decyl-CH 2 , 1C), 30.3 (s, decyl-CH 2 , 1C), 29.8 - 29.3 (m, CH 2 , 34C), 29.0 (s, CH 2 , 2C), 26.4 (s, CH 2 , 2C), 24.7 (s, CH 2 , 2C), 24.5 (s, decyl-CH 2 , 2C), 22.77 (s, N-alkyl-CH 2 , 2C), 22.74 (s, decyl-CH 2 , 1C), 14.21 (s, N-alkyl terminal CH 3 , 2C), 14.19 (s, decyl terminal CH 3 ).

[0110] Example 4 - Polymerization of 1 - Octene Poly - octene was prepared by mixing a procatalyst 1 and an olefin - substituted cocatalyst 1 in 1 - octene. The average molecular weight of the poly - octene final product was pre - determined to have an Mn of 1449 amu by size - exclusion chromatography. In addition to olefin incorporation, the carborane activator contains 11 boron atoms (black dots in cocatalyst 1), 11 chloride atoms, and a fixed negative charge. To confirm the incorporation of anions in the polyolefin (poly - octene), mass spectrometry was utilized to analyze the reaction mixture and additional controls.

[0111] The polyoctene produced from the catalyst and the olefin-substituted carborane activator was subjected to negative-mode flow injection mass spectrometry analysis to determine whether incorporation of carborane into the polyoctene had occurred. In Figure 1, a monovalent distribution of ions was observed at intervals of m / z 112. Further investigation of the exact mass spectrometry of m / z 786.056 (i.e., as indicated by O 2 C in the mass spectrum) was carried out, and it was consistent with the experimental formula of C 20 H 37 B 11 Cl 11 having a mass error of 5 mDa (Figure 2). The experimental formula C 20 H 37 B 11 Cl 11The theoretical isotope modeling was consistent with the isotope profiles and relative abundances of the experimental data (Figure 3). Based on the experimental formula and periodicity of 112 amu, m / z 786.056 was consistent with a carborane activator polymerized with two octene monomers. Subsequent fragmentation of m / z 786.056 was performed to assist in confirming the covalent incorporation of the carborane activator. The initial fragmentation conditions required 70 V of energy to generate fragmentation, but did not have sufficient energy to generate fragment ions (i.e., 35 V). During fragmentation, homolytic cleavage of the carbon-carbon bond in the boron cage olefin linker was observed in the spectrum of Figure 4. This observation, along with substantially higher fragmentation conditions than normal, indicated that the intact olefin-containing carborane starting reagent was not observed as fragment ions, showing that the carborane activator was covalently incorporated into the polyoctene. In addition to this peak, other ion signals in the mass spectrum were investigated. Overall, the m / z 786.056 peak functioned as a representative example of the other ion signals. Accurate mass spectrometry, isotope modeling, and fragmentation of the additional ion signals (m / z 890 - 3100) were consistent with increased polymerization of octene where up to 22 polyoctene chains incorporated with the carborane activator were observed. For comparison purposes, polyoctene generated from catalyst P1 and a hydrogen-substituted (olefin-free) carborane activator comparison C3 (anion having the formula [B 11 Cl 11 CH] - ) was analyzed by flow injection analysis of Figure 5 and the negative mode mass spectrum from the data report. The mass spectrum indicated that comparison C3 was not incorporated into the polymer chain. The only signal in the mass spectrum of Figure 5 was the signal corresponding to the [B 11 Cl 11 CH] - anion.

[0112] Example 5 - Polymerization Results To obtain the data recorded in Table 1, the polymerization was carried out according to the procedure described in the polymerization section of 1-octene. To obtain the data presented in Table 2, the polymerization reaction was carried out according to the procedure in the general procedure section of the aforementioned ethylene / 1-octene copolymerization. The activator efficiency and the resulting polymer characteristics were evaluated for cocatalysts 1-7, and each anion of cocatalysts 1-7 had an anion according to formula (I), and the catalyst (Catalyst 1) was presumed to be formed from a procatalyst (Procatalyst 3, herein "P3") with a bis((phenylphenoxy) structure of formula (X) and two other catalysts previously described in the present disclosure (Procatalyst 1, herein "P1", and Procatalyst 2, herein "P2"). [Chemical formula]

[0113] Each of cocatalysts 1-7 and comparative cocatalysts C1, comparative cocatalyst C2, comparative cocatalyst C3, and comparative cocatalyst C4 (herein "Comparative C1", "Comparative C2", "Comparative C3", and "Comparative C4") was mixed with one of Procatalyst 1, Procatalyst 2, or Procatalyst 3 to form 16 catalyst systems. Comparative C1 was a compound having a tetrakis(pentafluorophenyl)borate anion and + NH(Me)(C 18 H 37 ) 2 as the counter cation. Comparative C1 has been successfully used in industrial-scale olefin polymerization reactions. [Table 1]

[0114] The density of the polymers produced by cocatalysts 1-7 was measured at 0.86 ± 0.05 g / cm 3 .

[0115] To avoid cross - contamination, 1 - octene was polymerized in glass vials. This procedure was described in the previous paragraph. The resulting polyoctene was measured by broadband dielectric spectroscopy. Figures 6 - 9 are graphs of broadband dielectric spectroscopy. Each polymer generated from the catalyst system shows a slope of - 1 at low frequencies, indicating that ionic diffusion is the main factor in the dielectric tangent. The graph in Figure 6 shows that while Comparisons C1 and C2 show similar dielectric tangents, the polymers generated from the catalyst systems containing cocatalysts 1, 2, 3, and 4 show a dielectric tangent that is one - tenth of that of the comparative cocatalyst. The difference between Comparison C2 and cocatalysts 1, 2, 3, and 4 is that cocatalysts 1, 2, 3, and 4 contain vinyl - terminated alkenes at the R 1 position. Comparisons C2 and cocatalysts 1, 2, 3, and 4 are of similar size and would thus be expected to have similar diffusion rates. Thus, the ten - fold decrease in the comparative cocatalyst indicates that each of cocatalysts 1, 2, 3, and 4 is incorporated into the polyoctene backbone and cannot diffuse freely, and thus has a lower dielectric tangent when compared to Comparison C2 which is not incorporated.

[0116] The dielectric tangent tests were carried out with a Novocontrol Alpha A dielectric analyzer and a custom sample cell. The samples were measured at room temperature from 0.01 Hz to 1 MHz at 1.5 VAC. Briefly, the sample cell was first measured with dry air to obtain background measurements. Then, the highly viscous polyoctene sample was placed on one of the electrodes with a clean spatula and the test cell was closed. Excess polyoctene was extruded from the electrode into the adjacent channel as designed. The dielectric tangent of the complete test cell was then measured. The test cell was then cleaned with toluene and dried completely before the next measurement. Five different polyoctene samples were provided, three made with cocatalyst Comparison C1, one with carborane, and one with allyl - substituted carborane. To confirm reproducibility, each sample was measured at least twice.

Table 2

[0117] The equivalence of the cocatalyst to the procatalyst was 1.2.

[0118] The dielectric tangent of the ethylene-octene copolymer recorded in Table 2 was measured, and the obtained spectra are shown in FIGS. 8 and 9. FIG. 8 shows the spectra of two comparative examples of an ethylene-octene copolymer produced from procatalyst P3 and comparative cocatalyst C1 or C3 and an ethylene-octene copolymer produced from procatalyst P3 and cocatalyst 7. The dielectric tangent of the polymer produced by cocatalyst 7 is one-tenth of the dielectric tangent of the polymer produced by comparative cocatalyst C1.

[0119] FIG. 9 shows the spectra of two comparative examples of an ethylene-octene copolymer produced from procatalyst P2 and comparative cocatalyst C1 or C3 and an ethylene-octene copolymer produced from procatalyst P2 and cocatalyst 7. Similar to the dielectric tangent of the polymer produced by cocatalyst 7 and procatalyst P3 shown in FIG. 8, the dielectric tangent of the polymer produced by cocatalyst 7 and procatalyst P2 is one-tenth of the dielectric tangent of the polymer produced by procatalyst P3 and comparative cocatalyst C1 and the dielectric tangent of the polymer produced by procatalyst P3 and comparative cocatalyst C3. The present invention includes the following aspects. Item 1. In the presence of at least one catalyst and at least one cocatalyst, polymerizing one or more (C 2 -C 12 ) α-olefin monomers to produce a polyolefin, wherein the cocatalyst contains a cation and an anion, and the anion has a structure having a vinyl-terminal alkene, one boron atom or two or more boron atoms, and at least four halogen atoms, and polymerizing; inserting the anion of the cocatalyst into the polymer chain of the polyolefin, wherein the polyolefin is (1) Based on the molar composition of the polyolefin, greater than 0 and less than 1 mol% of the anion of the cocatalyst, and (2) A density in the range of 0.853 to 0.920 g / cm 3 including inserting, and a polymerization process. Item 2. To produce a polyolefin, in the presence of at least one catalyst and at least one cocatalyst, one or more (C 2 -C 12 )α-olefin monomers are polymerized, wherein the cocatalyst includes a cation and an anion, and the anion has a structure according to formula (I),

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Chemical formula

Claims

1. In the presence of at least one catalyst and at least one cocatalyst comprising a cation and an anion, one or more (C ２ -C １２ ) polymerizing α-olefin monomers to produce a polyolefin; and inserting said anion of said cocatalyst into a polymer chain of said polyolefin, the anion has a structure according to formula (I): 【Chemistry 1】 In the formula, ● is a boron atom, and R １ but with vinyl terminated alkenes (C ２ -C ２０ ) hydrocarbyl, and each X is independently a halogen atom; said cation is + N(H)R N 3 , + C(C 6 H 5 ) 3 , or + C(C 6 H 4 R C ) 3 , where each R N is selected from (C 1 -C 20 ) alkyl or (C 6 -C 20 ) aryl and each R C is (C 1 -C 20 ) alkyl; The polymerization process wherein the catalyst comprises a procatalyst selected from the group consisting of Procatalyst 1, Procatalyst 2, and Procatalyst 3. 【Chemistry 1A】

2. 2. The process of claim 1, wherein the polyolefin has a lower dielectric loss tangent than a corresponding polyolefin produced under identical polymerization conditions except that the anion of formula (I) is replaced by a comparative anion of formula (Ia). 【Chemistry 2】

3. the vinyl terminated alkene has a structure according to formula (III): 【Chemistry 3】 The polymerization process of claim 1 or 2, wherein n is an integer from 1 to 10.

4. the vinyl terminated alkene has a structure according to formula (V): 【Chemistry 4】 3. The polymerization process of claim 1 or 2, wherein y is an integer from 1 to 10 and x is an integer from 0 to 3.

5. The vinyl terminated alkene according to formula (V) has a structure according to formula (IV): 【Chemistry 5】 5. The polymerization process of claim 4, wherein y and x are as defined in claim 4.

6. 6. The polymerization process of any one of claims 1 to 5, wherein the polyolefin has a dielectric loss tangent of less than 0.10 at a frequency of 100 Hz and a temperature of 130°C, or the polyolefin has a dielectric loss tangent of less than 1.00 at a frequency of 10 Hz and a temperature of 130°C.

7. 6. The polymerization process of any one of claims 1 to 5, wherein the polyolefin has a dielectric loss tangent of less than 10 at a frequency of 1.0 Hz and a temperature of 130°C, or the polyolefin has a dielectric loss tangent of less than 100 at a frequency of 0.10 Hz and a temperature of 130°C.

8. The cation of the cocatalyst is ＋ N(H)R Ｎ ３ wherein at least two R Ｎ However, (C １０ -C ２０ 8. The polymerization process of claim 1, wherein the alkyl is selected from the group consisting of aryl, aryloxy ...

9. The polymerization process of any one of claims 1 to 8, wherein the polyolefin is a polyethylene, a polyoctene, or an ethylene-based copolymer.

10. The polymerization process according to any one of claims 1 to 9, wherein each X is a chlorine atom.

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