Alkene functionalized activators

Abstract

To provide processes of polymerizing polyolefins.SOLUTION: Processes of polymerizing polyolefins include polymerizing one or more (C2-C12)α-olefin monomers in the presence of at least one catalyst and at least one co-catalyst to produce a polyolefin. The co-catalyst includes a cation and an anion, and the anion has a structure having a vinyl terminated alkene, one boron atom or two or more boron atoms, and at least four halogen atoms. The anion of the co-catalyst is incorporated into a polymer chain of the polyolefin.SELECTED DRAWING: Figure 4

Description

Technical Field

[0001] Cross - Reference to Related Applications This application claims priority to U.S. Provisional Patent Application No. 62 / 840,88 7, 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, synthesis of activators, and their application to olefin polymerization processes.

Background Art

[0003] Olefin - based polymers, such as ethylene - based polymers and propylene - based polymers, are produced via various catalyst systems. The selection of such a catalyst system can be an important factor contributing to the characteristics and properties of the olefin - based polymer. Catalyst systems for producing polyethylene - based polymers can include chromium - based catalyst systems, Ziegler - Natta catalyst systems, or molecular (either metallocene or non - metallocene) catalyst systems. 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 catalytic efficiency, high - temperature capability, consistent polymer composition, and selective deactivation.

[0004]

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

[0006] For activators such as Bronsted salts, as the cation component, for example, cations capable of moving hydrogen ions such as ammonium, sulfonium, or phosphonium, or oxidative cations such as ferrocenium, silver(I), or lead(II) cations, or highly Lewis acidic cations such as carbonium or silylium can be mentioned.

Summary of the Invention

Problems to be Solved by the Invention

[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 ions, the charge of the ions, the interaction of the ions with the surrounding medium, and the ions with available counterions ​​​The dissociation energy with respect to N will affect the ability of the ions to diffuse through the surrounding medium such as a solvent, gel, or polymeric material. It will affect the ability of the ions to diffuse through the surrounding medium such as a solvent, gel, or polymeric 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, the non-nucleophilic character of the non-coordinating anion also increases diffusion, so the activator anion remaining in the resulting polymer lowers the electrical resistance of the polymer, thereby increasing electrical losses and reducing the insulating ability of the resulting polymer. It will lower the electrical resistance of the polymer, thereby increasing electrical losses and reducing the insulating ability of the resulting polymer. It will lower the electrical resistance of the polymer, thereby increasing electrical losses and reducing the insulating ability of the resulting polymer. There is a continuing need to create activators or cocatalysts that maintain the catalytic efficiency of weakly coordinating anions without spreading or adversely affecting the polymer properties of the resulting polymer. The disclosed embodiments include a polymerization process. In one or more embodiments, the polymerization process includes polymerizing one or more (C

[0009] -C )α-olefin monomers in the presence of at least one catalyst and at least one cocatalyst to produce a polyolefin, and then inserting the anion of the cocatalyst into the polymer chain of the polyolefin. The polyolefin includes (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 0.92 There is a continuing need to create activators or cocatalysts that maintain the catalytic efficiency of weakly coordinating anions without spreading or adversely affecting the polymer properties of the resulting polymer. The disclosed embodiments include a polymerization process. In one or more embodiments, the polymerization process includes polymerizing one or more (C -C )α-olefin monomers in the presence of at least one catalyst and at least one cocatalyst to produce a polyolefin, and then inserting the anion of the cocatalyst into the polymer chain of the polyolefin. The polyolefin includes (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 0.92 2 -C 12 )α-olefin monomers in the presence of at least one catalyst and at least one cocatalyst to produce a polyolefin, and then inserting the anion of the cocatalyst into the polymer chain of the polyolefin. The polyolefin includes (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 0.92 g / cm g / cm 0g / cm 3

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

[0011] In an embodiment, the polymer process is used to produce a polyolefin in the presence of at least one catalyst and at least one cocatalyst, and polymerizes one or more (C 2 -C 12 )α-ole fin monomers. Subsequently, the anion of the cocatalyst is 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 ) hydrocarbon rubyl having a vinyl-terminal 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 polymerization 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 (I a).

Chemical formula

[0015] In some embodiments, the polymerization process is used to produce a polyolefin with at least In the presence of at least one catalyst and at least one cocatalyst, ethylene monomer and one or more (C 3 -C 12 )α-olefin monomers are copolymerized. The anion of the cocatalyst is inserted into the polymer chain of the polyolefin. The polyolefin is greater than 0 mole percent and less than 1 mole percent of the cocatalyst based on the molar composition of the polyolefin. Contains anions.

[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 , R 3 , R 4 , and R 5 are independently selected from (C 1 -C 40 )hydro Selected from localbils. Each (C 1 -C 40 )hydrocarbyl is substituted with at least one ha rogen, and at least one (C 1 -C 40 )hydrocarbyl is substituted with vinyl terminal a lukene.

Brief Description of the Drawings

[0018]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

DETAILED DESCRIPTION OF THE INVENTION

[0019] The term "polymer" refers to a polymer compound prepared by polymerizing α-olefins, regardless of whether they are of the same or different types. Thus, the general term "polymer" encompasses the term "homopolymer", which is commonly used to refer to a polymer prepared from only one type of monomer, and the term "copolymer", which refers to a polymer prepared from two or more different monomers. As used herein, the term "interpolymer" refers to a polymer 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. The term "polyethylene" or "ethylene-based 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), linear and

[0020] ​​​​​​​​​​​A single-site catalyst linear low-density polyethylene (m-LLDPE) that includes both a calling and a substantially linear low-density resin ), 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 is to polymerize at least one (C - C 2 - C 12 ) α-olefin monomer in the presence of at least one catalyst and at least one cocatalyst . 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 that includes 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, and both cocatalysts have an anion with a structure that includes one vinyl-terminated alkene, one boron atom or two or more boron atoms, and at least four halogen atoms. The term "vinyl-terminated alkene" refers to the arrangement of a double bond on a hydrocarbon. A vinyl - terminated alkene is a terminal double bond, e.g., R

[0022] HC=CH , where R E is hydro 2 carbyl. E is hydro carbyl. Scheme 1: Examples of anions that are 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 of Scheme 1 illustrates the means by which the anion of the cocatalyst is inserted 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 reduces the electrical resistance of the polymer, thereby increasing electrical losses and thereby reducing the insulating ability of the resulting polymer. Without intending to be bound by theory, since the anion is incorporated into the polymer chain, the migration or diffusion of the anion of the cocatalyst is thought to decrease throughout the composition of the polyolefin. Thus, the anion of the cocatalyst A polyolefin produced from a process that includes incorporation into the polymer chain of the co-catalyst 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 co-catalyst was not incorporated into the polymer chain of the comparative polymer. 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 co-catalyst

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

[0027] The co-catalyst includes a cation and an anion. The anion has a structure according to formula (I). 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 co-catalyst

Chemical formula

[0028] In formula (I), R 1 is an unsaturated (C 2 -C 20 ) hydrocarbon radical 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. 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 co-catalyst

[0029] One of ordinary skill in the art will recognize that the structures of formulas (I) and (Ia) are carborane anions. When each X is chlorine, the structure of formula (I) has the 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 co-catalyst - B 11 CR 1 Cl 11 experimental formula, where B is a boron atom, C is a carbon atom, and Cl is a chlorine atom. exists, and R 1 has been previously defined. Each boron atom is represented by a round ball in formula (I). Each chlorine atom in 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 polymerization 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). a). The phrase "under the same polymerization 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 carried out in the reactor that produced the polyolefins 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.

Chemical formula

[0031] Furthermore, "the same conditions" means that each reactor is filled with the same molar amount 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. In some embodiments, the polymerization process uses at least a small amount to produce a polyolefin. 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. Furthermore, "the same conditions" means that each reactor is filled with the same molar amount 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 uses at least a small amount 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. 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 and has the empirical formula The polyolefin contains less than 1 mole percent of the anion of the cocatalyst. The structure of formula (Ia) is also a carborane and has the empirical formula including. Each atom is defined by formula (I), except that H is a hydrogen atom bonded to a carbon atom. - B 11 CCl 11 H. Each atom is defined by formula (I), except that H is a hydrogen atom bonded to a carbon atom. including. Each atom is defined by formula (I), except that H is a hydrogen atom bonded to a carbon atom. is done.

[0033] In some embodiments, the cocatalyst includes a cation and an anion, and the anion is according to formula (II). 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 independently selected from (C 1 -C 40 ) hydro localvyl. Each (C 1 -C 40 ) hydrocarbyl is substituted with at least one halogen, and at least one (C -C 1 -C 40 ) hydrocarbyl is substituted with a vinyl-terminated alkene. is replaced.

[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 subscript x and the subscript 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). has the structure.

Chemical formula

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

[0041] In one or more embodiments, the polyolefin, based on the molar composition of the polyolefin, contains an anion of a cocatalyst greater than 0 mole percent (mol%) and less than 1 mol%. . In some embodiments, the polyolefin is greater than 0 mol% and 0.5 mol% It contains an anion of a cocatalyst less than. In a further embodiment, the polyolefin is greater than 0 and contains an anion of a cocatalyst less than 0.1 mol%. In various embodiments, the polyolefin is greater than 0 mol% and less than 0.01 mol% of an anion of a cocatalyst based on the molar composition of the polyolefin.

[0042] In one or more embodiments, the cocatalyst contains an anion according to formula (I) and a cation having a formal charge of plus 1 (+ 1). In some embodiments of the cocatalyst, the cation is , a protonated tri[(C 1 -C 40 ) hydrocarbyl] ammonium cation. In some embodiments, the cation is a protonated trialkylammonium cation containing one or two (C -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 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 ​​) It is alkyl. 1 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 methyldi(o ctadecyl)ammonium cation, methyl(octadecyl)(hexadecyl)ammoni um cation, methyldi(hexadecyl)ammonium cation, or methyldi(tet radecyl)ammonium cation. Methyldi(octadecyl)ammoni um cation, methyl(octadecyl)(hexadecyl)ammonium cation, methyldi (hexadecyl)ammonium cation, or methyldi(tetradecyl)ammonium cation are collectively referred to herein as armeenium cation . An ionic compound having an armeenium cation is, for example, Armeen (trademark) M2HT available under the trade name Armeen (trademark) from Akzo-Nobel , and is easily formed by protonating methyldi(octadecyl)amine, methyl(octadecyl)(hexadecyl)amine, methyldi(hexadecyl)amine, or methyldi(tetradecyl)amine (e.g., with anhydrous HCl in ether). In other embodiments, the cation is a tritylphenylmethyl carbocation 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 trisubstituted triphenylmethyl carbocations, wherein each R C is independently selected from (C 1 -C 30 )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 ) + wherein , 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 + etc wherein R S is selected from (C 1 -C 30 )alkyl .

[0043] In an exemplary embodiment, the catalyst system may include one or more cocatalysts including an anion and a countercation, the anion being according to formula (I). Countercations that complex with the anion of formula (I) are 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 loss, the resistance should be as high as possible in both alternating current (AC) and direct current (DC) systems. In a DC system (e.g., a photovoltaic encapsulant), the energy loss appears as leakage current from the encapsulated device to the external environment. This current (I) is correlated with the voltage (V) and is inversely correlated with the resistance (R) of the insulating medium via the equation I = V × R. Therefore, the higher the resistance, the lower the current and leakage current. In an AC system (e.g., a cable insulator), the loss appears as the absorption of energy by the medium in the presence of an electric field. This loss, measured as power (P), is determined by the equation P = V × ω × C × ε′ × tan δ, where ω is the angular frequency, ε’ is the relative permittivity, C is the capacitance, and tan δ is the dielectric tangent, and tan δ = (C × R

[0045] × ω), resulting in the equation P = V × ε′ × R. Since resistance is inversely correlated with power loss, the higher the resistance, the lower the power loss. Equation I = V × R -1 One physical effect that reduces the resistance of the medium is ion diffusion caused by the electric field. In a system where ion diffusion dominates the electrical response, the resistance is given by the equation R ∝ 6 × π × ε′ × ε × η × r × C

[0046] × q × ω), resulting in 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, and tan δ is the dielectric tangent, and tan δ = (C × R × ω), resulting in the equation P = V × ε′ × R -1 Equation P = V 2 × ε′ × R -1 Since resistance is inversely correlated with power loss, the higher the resistance, the lower the power loss. One physical effect that reduces the resistance of the medium is ion diffusion caused by the electric field. In a system where ion diffusion dominates the electrical response, the resistance is given by the equation R ∝ 6 × π × ε′ × ε

[0047] × η × r × C × q 0 × η × r × C -1 × q -2×N -1 For the diffusing ion via 0 is the dielectric constant of a vacuum Rate(8.854×10 -12 F m -1 ), η is the dynamic viscosity of the medium, and r is the where q is the hydrodynamic radius of the ion, q is the charge of the ion, and N is the concentration of the ion. Increasing resistance reduces energy loss, and decreasing ion concentration increases resistance, so Reducing the concentration of ions diffusing through the body reduces energy loss.

[0048] In addition to size and charge, the interaction of the ion with the surrounding medium and with the target molecule are also important. The dissociation energy with available counterions affects the ability of an ion to diffuse through a given medium. This will have an effect on the activator because not all ions diffuse equally. The ability of the ions to diffuse is an important characteristic. has reduced diffusion of the anion and countercation of the cocatalyst of the present disclosure of formula (I) The resulting polymers of the cocatalysts of the present disclosure have reduced energy loss, which is a good It is believed to provide electrical properties.

[0049] In one or more embodiments, the polyolefin produced by any of the processes of the present disclosure. The insulator 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 thermal expansion coefficient of 1. In another embodiment, the polyolefin has a dielectric loss tangent of less than 1.00 at a frequency of 1.0 Hz. In some embodiments, the polyimide has a dielectric constant of less than 10 at a temperature of 130° C. Olefins have a dielectric loss tangent of less than 100 at a frequency of 0.10 Hz and a temperature of 130°C. Do.

[0050] The dielectric tangent relates to the electrical properties of the resin. Reduction of the dielectric tangent produces a material (e.g., cable insulator or electronic encapsulant) that can be used as a dielectric medium. When 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. On a small scale, the polymer produced with the cocatalyst having the anion of formula (I) exhibits a dielectric tangent that is one-tenth that of our standard polymer produced with cocatalyst C1. Without being bound by theory, it is believed that the polyolefin produced with the cocatalyst having the anion of formula (I) will have a dielectric tangent that is one-tenth that of cocatalyst C1 when the polyolefin is produced on an industrial scale. The dielectric tangent of a standard poly(ethylene-octene) copolymer is about 1.0. Accordingly, we predict that the polyolefin polymer produced with the cocatalyst having the anion of formula (I) will exhibit a dielectric tangent of 0.1 or less at 60 Hertz (Hz). When 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. On a small scale, the polymer produced with the cocatalyst having the anion of formula (I) exhibits a dielectric tangent that is one-tenth that of our standard polymer produced with cocatalyst C1. Without being bound by theory, it is believed that the polyolefin produced with the cocatalyst having the anion of formula (I) will have a dielectric tangent that is one-tenth that of cocatalyst C1 when the polyolefin is produced on an industrial scale. The dielectric tangent of a standard poly(ethylene-octene) copolymer is about 1.0. Accordingly, we predict that the polyolefin polymer produced with the cocatalyst having the anion of formula (I) will exhibit a dielectric tangent of 0.1 or less at 60 Hertz (Hz).

[0051] On a small scale, the polymer produced with the cocatalyst having the anion of formula (I) exhibits a dielectric tangent that is one-tenth that of our standard polymer produced with cocatalyst C1. Without being bound by theory, it is believed that the polyolefin produced with the cocatalyst having the anion of formula (I) will have a dielectric tangent that is one-tenth that of cocatalyst C1 when the polyolefin is produced on an industrial scale. The dielectric tangent of a standard poly(ethylene-octene) copolymer is about 1.0. Accordingly, we predict that the polyolefin polymer produced with the cocatalyst having the anion of formula (I) will exhibit a dielectric tangent of 0.1 or less at 60 Hertz (Hz). On a small scale, the polymer produced with the cocatalyst having the anion of formula (I) exhibits a dielectric tangent that is one-tenth that of our standard polymer produced with cocatalyst C1. Without being bound by theory, it is believed that the polyolefin produced with the cocatalyst having the anion of formula (I) will have a dielectric tangent that is one-tenth that of cocatalyst C1 when the polyolefin is produced on an industrial scale. The dielectric tangent of a standard poly(ethylene-octene) copolymer is about 1.0. Accordingly, we predict that the polyolefin polymer produced with the cocatalyst having the anion of formula (I) will exhibit a dielectric tangent of 0.1 or less at 60 Hertz (Hz). Without being bound by theory, the polyolefin produced with the cocatalyst having the anion of formula (I) On a small scale, the polymer produced with the cocatalyst having the anion of formula (I) exhibits a dielectric tangent that is one-tenth that of our standard polymer produced with cocatalyst C1. Without being bound by theory, it is believed that the polyolefin produced with the cocatalyst having the anion of formula (I) will have a dielectric tangent that is one-tenth that of cocatalyst C1 when the polyolefin is produced on an industrial scale. The dielectric tangent of a standard poly(ethylene-octene) copolymer is about 1.0. Accordingly, we predict that the polyolefin polymer produced with the cocatalyst having the anion of formula (I) will exhibit a dielectric tangent of 0.1 or less at 60 Hertz (Hz). The dielectric tangent of a standard poly(ethylene-octene) copolymer is about 1.0. Accordingly, we predict that the polyolefin polymer produced with the cocatalyst having the anion of formula (I) will exhibit a dielectric tangent of 0.1 or less at 60 Hertz (Hz). The dielectric tangent of a standard poly(ethylene-octene) copolymer is about 1.0. Accordingly, we predict that the polyolefin polymer produced with the cocatalyst having the anion of formula (I) will exhibit a dielectric tangent of 0.1 or less at 60 Hertz (Hz). The dielectric tangent of a standard poly(ethylene-octene) copolymer is about 1.0. Accordingly, we predict that the polyolefin polymer produced with the cocatalyst having the anion of formula (I) will exhibit a dielectric tangent of 0.1 or less at 60 Hertz (Hz). Accordingly, we predict that the polyolefin polymer 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 the anion and cation of formula (I), the anion and cation of formula (II), or both the anions and cations of formula (I) and (II). The procatalyst is a titanium (Ti) metal-ligand complex, a zirconium (Zr) metal-ligand complex, or a hafnium (Hf) 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 the anion and cation of formula (I), the anion and cation of formula (II), or both the anions and cations of formula (I) and (II). The procatalyst is a titanium (Ti) metal-ligand complex, a zirconium (Zr) metal-ligand complex, or a hafnium (Hf) 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 the anion and cation of formula (I), the anion and cation of formula (II), or both the anions and cations of formula (I) and (II). The procatalyst is a titanium (Ti) metal-ligand complex, a zirconium (Zr) metal-ligand complex, or a hafnium (Hf) 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 the anion and cation of formula (I), the anion and cation of formula (II), or both the anions and cations of formula (I) and (II). The procatalyst is a titanium (Ti) metal-ligand complex, a zirconium (Zr) metal-ligand complex, or a hafnium (Hf) Ti) metal-ligand complex, a zirconium (Zr) metal-ligand complex, or a hafnium (Hf) Group 4 metal-ligand complexes such as (Hf) metal-ligand complexes can be selected from Group IV metals (Group IVB according to CAS, or Group 4 according to the IUPAC nomenclature)-ligand complexes. Although not intended to be limiting, examples of the precatalyst can be found in the following references: US8372927 , WO2010 / 022228, WO2011 / 102989, US6953764, U S6900321, WO2017 / 173080, US7650930, US67775 09, 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 4 metal-ligand complex is a bis(phenylphenoxy) Group 4 metal-ligand complex or a Group 4 metal-ligand complex of constrained geometry .

[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) with the subscript n being 0, 1, or 2. When the subscript n is 1, X is a monodentate ligand n or a bidentate ligand, and when the subscript n is 2, each X is selected from monodentate ligands . L is a (C -C ) hydrocarbylene, (C 1 -C 40 ), (C 1 -C​​40 ) Heterohydrocar Biphenylene, -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 S i(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 )- and R1 -R 16 is independently -H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )he tero-hydrocarbyl, -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 (XI I), and a radical having formula (XIII), and is selected from the group consisting of them.

Chemical formula

[0056] In formulas (XI), (XII), and (XIII), each of R 31 -R 35 , R 41 -R 48 , and R 51 -R 59 is independently -H, (C 1 -C 40 )hydrocarbyl, (C 1 -C 40 )hetero-hydrocarbyl, -Si(RC ) 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 selected from NC(O)-, or a halogen, provided that at least one of R or 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, independently of any other ligand X, can be a monodentate ligand that is a halogen, an unsubstituted (C -C 1 -C 20 ) hydrocarbyl, an 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 an unsubstituted (C -C 1 -C 20 ) hydrocarbyl.

[0058] Exemplary bis(phenylphenoxy)gold that can be used in the practice of the present invention As the metal-ligand complex, (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’-dimethyl Amino-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’-di methyl-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5- (2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-h afnium, (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’-ter t-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-c arbazol-9-yl)-5’-chloro-3’-methyl-5-(2,4,4-trimethyl pentan-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’-trif luoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-o l)dimethyl-hafnium, (2’,2”-(2,2-Dimethyl-2-silapropane-1,3-diylbis(oxy ))bis(3’,5’-dichloro-3-(3,6-di-tert-butyl-9H-carb azol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl -2-ol)dimethyl-hafnium, (2’2”-(2,2-Dimethyl-2-silapropane-1-diylbis(oxy)) bis(5’-chloro-3-(3,6-di-tert-butyl-9H-carbazole-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-carbazole-9-yl) -5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl l-hafnium, (2’,2”-(Propane-1,3-diylbis(oxy))-(5’-chloro-3 -(3,6-di-tert-butyl-9H-carbazole-9-yl)-3’-fluoro -5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)-(3 ”,5”-dichloro-3-(3,6-di-tert-butyl-9H-carbazole-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’-tri Fluoromethyl-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 l-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-th tane, 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 ruthenium. Examples include

[0059] According to some embodiments, the Group IV metal-ligand complex may include a metallocene 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 that contains up to 50 non-hydrogen atoms. In some embodiments of formula (XIV), two Lp groups may be bonded together to form a crosslinked 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 both of whose 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 when M is in the +2 oxidation state. In other embodiments, one or more X’’ and one or more X’ groups are together ​​​​​​​​​​​ which can be joined together, thereby covalently bonding to M and coordinating through a Lewis base functional group to form a moiety. Lp The subscript i of L is 0, 1, or 2, and the subscript n of X’ i is 0, 1, 2, or 3, the subscript m of X n is 0 or 1, and the subscript p of X is 0, 1, 2, or 3. The sum of i + m + p is equal to the formal oxidation state of M. m The subscript m of X 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 M. The sum of i + m + p is equal to the formal oxidation state of M.

[0063] Exemplary Group IV metal-ligand complexes include cyclopentadienylpro catalysts, which can be used in the practice of the present invention, such as 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, 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-2,3,4,9,1 0-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilane titanium di methyl, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethyl silane titanium dibenzyl, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethyl silane titanium dimethyl, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)-1, 2-ethanediyltitanium dimethyl, (tert-Butylamide)(tetramethyl-η 5 -indenyl)dimethylsilane ti Tanjimethyl, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethyl lucirantitanium(III) 2-(dimethylamino)benzyl, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethyl lucirantitanium(III) allyl, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethyl lucirantitanium(III) 2,4-dimethylpentadienyl, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethyl lucirantitanium(II) 1,4-diphenyl-1,3-butadiene, (tert-Butylamide)(tetramethyl-η 5 -cyclopentadienyl)dimethyl lucirantitanium(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)dimethylsila netitanium (II) 1,4-Diphenyl-1,3-butadiene, (tert-Butylamide)(2-methyl-4-phenylindenyl)dimethylsila netitanium (II) 1,3-Pentadiene, (tert-Butylamide)(2-methyl-4-phenylindenyl)dimethylsila netitanium (II) 2,4-Hexadiene, (tert-Butylamide)(tetramethyl-η 5-Cyclopentadienyl)dimethyl Lumichlorotitanium(IV) 1,3-butadiene, (tert-Butylamide)(tetramethyl-η 5 -Cyclopentadienyl)dimethyl Lumichlorotitanium(IV) 2,3-dimethyl-1,3-butadiene, (tert-Butylamide)(tetramethyl-η 5 -Cyclopentadienyl)dimethyl Lumichlorotitanium(IV) isoprene, (tert-Butylamide)(tetramethyl-η 5 -Cyclopentadienyl)dimethyl Lumichlorotitanium(II) 1,4-dibenzyl-1,3-butadiene, (tert-Butylamide)(tetramethyl-η 5 -Cyclopentadienyl)dimethyl Lumichlorotitanium(II) 2,4-hexadiene, (tert-Butylamide)(tetramethyl-η 5 -Cyclopentadienyl)dimethyl Lumichlorotitanium(II) 3-methyl-1,3-pentadiene, (tert-Butylamide)(2,4-dimethylpentadien-3-yl)dimethyl Silachlorotitanium dimethyl, (tert-Butylamide)(6,6-dimethylcyclohexadienyl)dimethylsi Lachlorotitanium dimethyl, (tert-Butylamide)(1,1-dimethyl-2,3,4,9,10-η-1, 4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilachlorotitanium dimeth Lum, (tert-Butylamide)(1,1,2,3-tetramethyl-2,3,4,9,1 0-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilane Titanium dimethyl, (tert-Butylamide)(tetramethyl-η 5-Cyclopentadienylmethylf enylsilane titanium(IV) dimethyl, (tert-Butylamide)(tetramethyl-η 5 -Cyclopentadienylmethylf enylsilane titanium(II) 1,4-diphenyl-1,3-butadiene, 1-(tert-Butylamide)-2-(tetramethyl-η 5 -Cyclopentadienyl yl)ethanediyl titanium(IV) dimethyl, 1-(tert-Butylamide)-2-(tetramethyl-η 5 -Cyclopentadienyl yl)-titanium(II) 1,4-diphenyl-1,3-butadiene are exemplified .

[0064] Each of the exemplary cyclopentadienyl pro-catalysts may contain zirconium or hafnium instead of the titanium metal center of the cyclopentadienyl pro-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 co-catalyst or activator in addition to the anion and counter-cation of the co-catalyst of formula (I) of the present disclosure. Such additional co-catalysts 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 aforementioned compounds. As a beneficial ability to capture impurities such as oxygen, water, and aldehydes from the polymerization mixture, usually, this ​ It is useful to use these aluminum compounds.

[0067] Di(hydrocarbyl)(hydrocarbyloxy)aluminum compounds that can be used in combination with the activator described in this disclosure have the formula T AlOT 1 2 AlOT 2 or T 1 1 Al(O T 2 ) 2 corresponding to, in which T 1 is a secondary or tertiary (C -C 3 -C 6 ) alkyl such as isopropyl, isobutyl, or tert-butyl, and T 2 is an alkyl-substituted (C -C ) aryl radical 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-butylphenyl, or an aryl-substituted (C -C 6 -C 30 ) alkyl radical. 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, and 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)di carbons, and dialkyl(aryloxy)aluminum compounds containing 6 to 18 carbons in the aryl group (specifically, (3,5-di(t-butyl)-4-methylphenoxy)di 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)di isobutylaluminum), methylalumoxane, modified methylalumoxane, and dii sobutylalumoxane.

[0069] In the catalyst system according to an embodiment of the present disclosure, the molar ratio of the cocatalyst to the Group IV metal-ligand complex of the present disclosure is 1:10,000 to 1000:1, for example, 1:5000 to 100:1, 1:1 00 to 100:1, 1:10 to 10:1, 1:5 to 1:1, or 1.25:1 to 1:1 and the like. The catalyst system may 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 paragraph are utilized in the polymerization of olefins, mainly ethylene and 1-octene. In some embodiments, only a single type of olefin or only α-olefins are present during the polymerization scheme, producing homopolymers. 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 comonomers 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 may 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 ethylene and optionally one or more comonomers, α-olefins, etc., homopolymers and / or interpolymers (including copolymers) may contain monomer units derived from at least 50 mole percent (mol%) of ethylene. All individual values and subranges included in "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 may contain monomer units derived from ethylene at least 60 mol%, at least 70 mol%, at least 80 mol%, or monomer units derived from ethylene 50 - 100 mol%, or units derived from ethylene 80 - 100 mol%. In some embodiments, the polyolefins produced from the processes of the present disclosure may contain at least 90 mole percent of units derived from ethylene. All individual values and subranges from at least 90 mole percent are included herein and disclosed herein as separate embodiments. For example, an ethylene-based polymer may contain at least 93 mole percent, at least 96 mole percent, at least 97 mole percent of units derived from ethylene, or alternatively, units derived from ethylene 90 - 100 mole percent, units derived from ethylene 90 - 99.5 mole percent, or units derived from ethylene 97 - 99.5 mole percent.

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

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

[0074] The 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 using 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 is 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 and optionally one or more other catalysts. The catalyst system described herein can optionally be combined with one or more other catalysts in the first reactor or the second reactor. ​​​​​can be used in. In one embodiment, the ethylene-based polymer is ethylene and optionally one or more α-olefins are polymerized in the presence of the catalyst system described herein in both reactors of a dual reactor system, such as a dual loop reactor system, via solution polymerization.

[0076] In another embodiment, the ethylene-based polymer is 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 cocatalysts described in the preceding paragraph in a single reactor system, such as a single loop reactor system, via solution polymerization.

[0077] The ethylene-based polymer may further comprise 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 comprise a filler, and such fillers can include, but are not limited to, organic or inorganic fillers. The ethylene-based polymer may contain, based on the total weight of the ethylene-based polymer and all additives or fillers, for example, calcium carbonate, talc, or Mg(OH) any of about 0 to about 20 weight percent of the filler. The ethylene-based polymer may have one or more 2 ​​​It can be further blended with the polymer above to form a blend.

[0078] In some embodiments, the polymerization process for producing the polyolefin polymer comprises polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system wherein the catalyst system 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 the metal-ligand complex and the cocatalyst has a density, for example, of 0.853 to 0.920 g / cm in accordance with ASTM D792 (which is incorporated herein by reference in its entirety) 3 , 0 .870 g / cm 3 to 0.920 g / cm 3 , 0.870 g / cm 3 to 0.910 g / c m 3 , or 0.870 g / cm 3 to 0.900 g / cm 3 .

[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 ) of 1 to 25, where the melt index I 2 is measured at 190 °C and a load of 2.16 kg in accordance with ASTM D1238 (which is 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 5 to 10, In other cases, the melt flow ratio is 5 to 9.

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

[0081] The embodiments of the catalyst system described in the present 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 loss 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. When the reactor was under pressure, polymerization was initiated by adding an activated catalyst solution containing a procatalyst, a cocatalyst of the present disclosure, a solvent, and a triethylaluminum scavenger. The polymerization was allowed to proceed for 10 minutes while maintaining the temperature and pressure of the reactor. After the reaction was completed, the polymer was collected and dried in a vacuum oven overnight before analysis.

[0083] General procedure for 1-octene polymerization: In a nitrogen-filled glove box, neat 1-octene (11 mL) was placed with a stir bar It was added to a 40 mL vial equipped with a polyurethane insulated block placed on a magnetic stirring plate. The vial was placed on the block. A solution of the precatalyst and activator (1.2 - 1.25 equivalents relative to the precatalyst) in toluene was added continuously. The vial was capped and the reactants were stirred for the specified time (3 hours for precatalyst 2 and precatalyst 3, 6 days for precatalyst 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 about 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 precatalyst solution) are added via a robotic syringe. Gaseous reagents (i.e., ethylene) are added via a gas injection port. Prior to each run, the reactor is heated to 80 °C, purged, and aerated with ethylene.

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

[0086] The reactor was heated to 100 °C and then pressurized with ethylene to 25.3 psig, and a portion of Isop ar-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 for procatalyst 3 and 2.26 mL for procatalyst 2), (2) the scavenging agent triethylaluminum (TEA) (1 μmol), (3) the activator (comparative cocatalyst C1 -C3 or cocatalyst 1-7 (i.e., alkenyl-substituted carborane) (added in an amount of 1.2 molar equivalents relative to the procatalyst), (4) the procatalyst (20 nmol for procatalyst 3 and 80 nmol for procatalyst 2). After the addition of each liquid, a small amount of Isopar-E was added, and after the final addition, the total reaction volume was brought to 5

[0087] mL. 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 opening the valve at the setpoint minus 2 psi and closing the valve when the pressure reached 2 psi higher, by the make-up addition of ethylene gas . Any pressure drop was cumulatively recorded as the "uptake" or "conversion" of ethylene, either over the course of the run or earlier, whichever occurred first, until the uptake or conversion demand value was reached. Each reaction was then quenched by the 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 excess 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 the glass tube inserts containing the samples were removed. When they were removed, ​​​It was cooled to 70 °C. Polymers containing solutions from 24 reactors containing the same procatalyst and activator solution were combined and stored out of the draft for several days. The resulting resin containing the solution was then dried in a vacuum oven at 80 °C for 3 hours and 140 °C for 4 hours, in one continuous cycle, weighed to determine the polymer yield, and submitted for GPC analysis performed.

Examples

[0088] Examples 1 to 3 are the synthesis procedures of 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 performance 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 externally calibrated to generate accurate mass information within + / - 10 mDa. After external calibration, accurate mass prediction software (Agilent ​​​​​Using (t Masshunter), the empirical formulas of MS and fragment ions were generated. Both the predicted empirical formulas and dissociation behaviors of each parent ion were utilized to provide the proposed structure. has been provided.

[0090] Unless otherwise specified, all operations were carried out under an Ar atmosphere using standard Schlenk techniques of the glovebox method. Klein was used. Toluene, pentane, C 6 D 6 and T HF was dried with NaK / Ph 2 CO / 18-crown-6, distilled or transferred under vacuum, and stored over molecular sieves in an Ar-filled glovebox. NMR spectra were recorded on a Varian Inova 500 spectrometer ( 1H NMR, 499.703 MHz, 1 13C NMR 13 125.580 MHz), Varian Inova 400 ( 11B NMR, 128 11 .191 MHz) spectrometer, Bruker 400 ( 13C 100, 13 11B 102 MH 11 z). Chemical shifts are reported in δ (ppm). For 1H and 1 13C NMR 13 spectra, the residual solvent peaks were used as internal references ( 1H NMR: δ 1 CD Cl 6 3 is 7.16, CD 6 3CN is 1.94, CDCl 3 3 is 7.26, 3 13C NMR: 13 δ CDCl 3 is 77.16, CD 3 3CN is 1.32). MALD 3 I mass spectrometric analysis of the carborane anion was performed at the Texas A&M University Laborator y Performed by y for Biological Mass Spectrometry and the simulated MALDI(-) spectra were generated using publicly available isotope distributions and a computer and a mass spectrometry plotter. 1 11 For B NMR the spectra were externally referenced to δ = 0 ppm using BF 3 ·Et 2 O. 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 NH 3 [CHB 11 Cl 11 , 2 n octyl 2 MeNH]Cl, and [( n C 18 H 3 7 ) 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] Example 1 - General Procedure for the Synthesis of 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 bubbled ​​It was stirred at room temperature for 2 hours until it 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 further 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 obtained. 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 (5 00 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). 1 1 B{ 1 H}NMR (128 MHz, CD 3 CN): δ -3.03, -10.10, -1 1.73. 13 C{ 1 H}NMR (100 MHz, CD3 CN): 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 Na[butenyl-CB 11 Cl 11 (85% yield) 1 1H NMR (500 MHz, CDCl 3 ): δ 5.72 (dd t, 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, 1.6H z, 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, car borane-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 (12 8 MHz, CD 3 CN): δ -2.94, -9.96, -11.58. 13 C{ 1 H}N MR (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-C H 2 ), 31.8 (s, CH 2 ), 29.9 (s, CH 2 ), 24.6 (s, CH 2 ).

Chem.

[0096] Na[vinylbenzyl CB 11 Cl 11 : 449 mg (89%).1 1H 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 11B{ 1 1H} NMR (128 MHz, CD 2 Cl 2 ): δ -3 .32, -10.18, -11.16. 13 13C{ 1 1H} NMR (100 MHz, CD 3 Cl N): δ 137.5 (s, CHCH 2 ), 137.0 (s, Ph) 134.8 (s, P h), 131.0 (s, Ph), 125.4 (s, Ph), 114.6 (s, Ph), 4 9.5 (brs, carborane-C), 36.1 (s, PhCH 2 ).

Chem.

[0097] Na[decylCB 11 Cl 11 : 1.46 g (95%). 1 1H NMR (500 M Hz, 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 11B { 1 1H} NMR (128 MHz, CDCl 3 ): δ -4.14, -10.59, -11. 52. 13 13C{ 11H NMR (100 MHz, CD 3 CN): δ 49.5 (brs, car borane-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 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 octyl 2 Me NH]Cl in 10 mL of THF. Upon mixing, a precipitate immediately formed. The mixture was further stirred for 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 formula

[0099] n ​​Octyl 2 MeNH][allyl-CB 11 Cl 11 : 360 mg (78%). 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 (12 8 MHz, CDCl 3 ): δ -3.53, -10.47, -11.75. 13 C{ 1 H} NMR (126 MHz, CD 3 CN): δ 137.6 (s, CHCH 2 , 1C), 11 6.5 (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 , 1 C), 26.9 (s, CH 2 , 2C), 24.5 (s, CH 2 , 2C), 23.3 (s, CH 2 , 2C), 14.4 (s, terminal Me, 2C).

Chemical Structure

[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, 3 H), 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 - 1.2 1 (m, 22H), 0.89 (t, J = 7.0 Hz, 3H). 11 B{ 1 H}NMR (1 28 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), 1 16.1 (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, end -CH 3 , 2C). [Chemical formula]

[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), 3.1 2 (t, J = 8.3 Hz, 4H), 2.93 (s, 3H), 2.28 (t, J = 9.0 H z, 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, CDC l 3 ): δ -3.61, -10.39, -11.70. 13 C{ 1 H}NMR (126 M Hz, CDCl 3 ): δ 138.1 (s, CHCH 2 , 1C), 114.8 (s, CH CH 2 , 1C), 57.8 (s, alpha-CH 2 , 2C), 51.1 (brs, carbonyl​ Lan-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, C H 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).

Chemical formula

[0102] n Octyl 2 MeNH][CH 2 =CHC 6 H 4 CH 2 CB 11 Cl 11 :50 0 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 = 1 7.7, 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 - 1.1 8 (m, 22H), 0.88 (t, J = 7.0 Hz, 6H). 11 B{ 1 H}NMR (1 ​28 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 , 2 C).

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, 2 H), 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 , 1 C), 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 11Cl 11 general Synthesis: In a 50 mL Schlenk flask, 300 mg of Na[R ’CB 11 Cl 11 solution 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 formed immediately. 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 the excess [( n C 18 H 37 ) 2 MeNH]Cl and concentrated under vacuum to obtain the product. Each of the following examples / products was characterized by H NMR and C 1 NMR. 13 NMR. Characterized.

Chemical Structure

[0105] [( n C 18 H 37 ) 2 MeNH][allyl - CB 11 Cl 11 : 425 mg (8 5%). 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 = 1 6.7, 1.4 Hz, 1H), 5.02 (dq, J = 16.7, 1.4 Hz, 1H), 3 .14 - 2.96 (m, 6H, N - CH2 、 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, a lpha-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 Structure

[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 = 1 6.9, 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 ), 2.6 5 - 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 , 2 C), 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, CH 2 , 24C), 28.9 (s, CH 2 CHCH 2 , 1C), 26.5 (s, CH2 , 2C), 24.5 (s, CH 2 , 2C), 22.8 (s, CH 2 , 2C) , 14.3 (s, terminal CH 3 , 2C). [Chemical formula]

[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, 1 H), 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, hex yl's alpha C), 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, C H 2 ), 0.88 (t, J = 7.0 Hz, 3H, terminal Me). 11 B{ 1 H}NMR (1 28 MHz, CD 3 CN): δ -2.97, -9.99, -11.62. 13 C{ 1 H} NMR (126 MHz, CDCl 3 ): δ13 C{ 1 H} NMR (126 MHz, CD Cl 3 ): δ 138.4 (s, CHCH 2 、1C), 114.9 (s, CHCH 2 、1 C), 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 、1 C), 22.8 (s, CH 2 、2C), 14.3 (s, terminal CH 3 、2C).

Chemical Structure

[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 = 1 7.6, 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 (128M Hz, CD 3 CN): δ - 2.70, - 9.95, - 11.35. 13 C{ 1 H} 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).

Chemical Structure

[0109] [( n C 18 H 37 ) 2 MeNH][Decyl-CB 11 Cl 11 : 340 mg (8 0%). 1 H 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 (1 28 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 , 2 C), 22.77(s, N-alkyl-CH 2 , 2C), 22.74(s, desyl-CH 2 , 1C), 14.21 (s, N-alkyl-terminated CH 3 , 2C), 14.19(s, deci Terminal CH 3 ).

[0110] Example 4-1-Octene Polymerization Polyoctene was produced by mixing procatalyst 1 and olefin-substituted cocatalyst 1 in 1-octene. The average molecular weight of the final polyoctene product was determined by size exclusion chromatograph. The Mn was previously determined to be 1449 amu by olefin incorporation. In addition, the carborane activator contains 11 boron atoms (black dots in cocatalyst 1), Contains 11 chloride atoms and a fixed negative charge. Polyolefin (polyoctene) To confirm the incorporation of the anion in the reaction mixture and Additional controls were analyzed.

[0111] The polyoctene produced from the catalyst and the olefin-substituted carborane activator was The polyoctyltransferase of carborane was analyzed by active-mode flow injection mass spectrometry. In Figure 1, the distribution of singly charged ions at m / z 112 m / z 786.056 (i.e., O in the mass spectrum) 2 The accurate mass analysis of the compound C, denoted as C, was further investigated and found to have a mass error of 5 mDa. 2 0 H 37 B 11 Cl 11 This coincided with the empirical formula (Figure 2).20 H 37 B 11 Cl 1 1 The theoretical isotope modeling of 1 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 786.05 6 was consistent with the carborane activator polymerized with two octene monomers. The subsequent fragmentation of m / z 7 86.056 was carried out to help confirm the covalent incorporation of the carborane activator. The initial fragmentation conditions required 70 V of energy to generate fragmentation, but there was not enough 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, indicates that the intact olefin-containing carborane starting reagent was not observed as fragment ions, so 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 other ion signals . Accurate mass spectrometry, isotope modeling, and fragmentation of additional ion signals (m / z 890 - 3100) were consistent with increased polymerization of octene, where a maximum of 22 polyoctene chains incorporated with the carborane activator were observed. For comparison purposes, catalyst P1 and a hydrogen-substituted (olefin-free) carborane activator comparison C3 ([B C l were used. Since the intact olefin-containing carborane starting reagent was not observed as fragment ions, it indicates 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 other ion signals . Accurate mass spectrometry, isotope modeling, and fragmentation of additional ion signals (m / z 890 - 3100) were consistent with increased polymerization of octene, where a maximum of 22 polyoctene chains incorporated with the carborane activator were observed. For comparison purposes, catalyst P1 and a hydrogen-substituted (olefin-free) carborane activator comparison C3 ([B C l were used. The accurate mass spectrometry, isotope modeling, and fragmentation of additional ion signals (m / z 890 - 3100) were consistent with the increased polymerization of octene, in which a maximum of 22 polyoctene chains incorporated with the carborane activator were observed . For comparison purposes, catalyst P1 and a hydrogen-substituted (olefin-free) carborane activator comparison C3 ([B C 11 C l11 CH] - The polyoctene produced from an anion having the formula) was analyzed by flow injection analysis and negative mode mass spectrum from data reporting as shown in Figure 5 and the mass spectrum indicates that Comparative 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 anion 11 Cl 11 CH] - anion was

[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 ethylene / 1 - octene copolymerization described above and the activator efficiency and the polymer characteristics obtained were evaluated for cocatalysts 1 - 7. Each anion of cocatalysts 1 - 7 has an anion according to formula (I), and the catalyst (Catalyst 1) was presumed to be formed from a procatalyst with a bis((phenylphenoxy) structure according to formula (X) (Procatalyst 3, herein referred to as "P3" ) and two other catalysts previously described in the present disclosure (Procatalyst 1, herein referred to as " P1", and Procatalyst 2, herein referred to as " P2"). ) and two other catalysts previously described in the present disclosure (Procatalyst 1, herein referred to as " P1", and Procatalyst 2, herein referred to as "

Chemical formula

[0113] Each of cocatalysts 1 - 7 and Comparative cocatalysts C1, Comparative cocatalyst C2, Comparative cocatalyst C3, and Comparative cocatalyst C4 (herein referred to as "Comparative C1", "Comparative C2", "Comparative C3", and " Comparative C4") was mixed with one of Procatalyst 1, Procatalyst 2, or Procatalyst 3 ​​​Thus, 16 catalyst systems were formed. Comparative C1 was tetrakis(pentafluorophenyl)borate anion, and as the counter cation + NH(Me)(C 18 H 37 ) 2 and had a compound which was 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 a glass vial. This procedure was described in the previous paragraph. The polyoctene produced was measured by broadband dielectric spectroscopy . Figures 6-9 are graphs of broadband dielectric spectroscopy. Each polymer produced from the catalyst system showed 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 Comparative C1 and Comparative C2 showed similar dielectric tangents, while the polymers produced from the catalyst systems containing cocatalysts 1 , 2, 3, and 4 showed a dielectric tangent that was one-tenth that of the comparative cocatalyst . The difference between Comparative 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. Comparative C2 and cocatalysts 1, 2, 3, and 4 are of similar size and thus would be expected to have similar diffusion rates . Thus, the ten-fold decrease in the comparative cocatalyst is due to cocatalysts 1 Each of 2, 3, and 4 is incorporated into the polyoctene backbone and cannot diffuse freely, and thus has a lower dielectric tangent when compared to comparative C2 which is not incorporated. This is shown by having a lower dielectric tangent when compared to comparative C2 which is not incorporated. This is shown by having a lower dielectric tangent when compared to comparative C2 which is not incorporated.

[0116] The dielectric tangent test was performed 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, 1.5 VAC. Briefly, the sample cell was first measured with dry air to obtain background measurements. Next, 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 pushed out 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 completely dried before the next measurement. Five different polyoctene samples were provided, three made with cocatalyst comparative C1, one with carborane, and one made 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 tangents of the ethylene-octene copolymers recorded in Table 2 were measured, and the spectra obtained are shown in FIGS. 8 and 9. FIG. 8 shows the spectra of two comparative examples of ethylene-octene copolymers produced from procatalyst P3 and comparative cocatalyst C1 or C3, and ethylene-octene copolymers produced from procatalyst P3 and cocatalyst 7. The dielectric tangents of the ethylene-octene copolymers recorded in Table 2 were measured, and the spectra obtained are shown in FIGS. 8 and 9. FIG. 8 shows the spectra of two comparative examples of ethylene-octene copolymers produced from procatalyst P3 and comparative cocatalyst C1 or C3, and ethylene-octene copolymers produced from procatalyst P3 and cocatalyst 7. from procatalyst P3 and cocatalyst 7. from procatalyst P3 and cocatalyst 7. Therefore, the dielectric tangent of the resulting polymer is one-tenth of the dielectric tangent.

[0119] Figure 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. The dielectric tangent of the polymer produced by cocatalyst 7 and procatalyst P2 is, like the dielectric tangent of the polymer shown in Figure 8 and produced by cocatalyst 7 and procatalyst P3, one-tenth of the dielectric tangent of the polymer produced by procatalyst P3 and comparative cocatalyst C1, and of the polymer produced by procatalyst P3 and comparative cocatalyst C3. ​​​​​

Claims

1. At least one catalyst and at least one co-catalyst are used to produce a polyolefin. In the presence of a catalyst, one or more (C ２ -C １２ ) polymerizing an α-olefin monomer; So, The cocatalyst comprises a cation and an anion, the anion being a vinyl terminated alkoxy group. ketone, one boron atom or two or more boron atoms, and at least four halogens polymerizing a structure having atoms; by inserting the anion of the cocatalyst into the polymer chain of the polyolefin. hand, The polyolefin is (1) greater than 0 and less than 1 mole percent based on the molar composition of the polyolefin the anion of the cocatalyst, and (2) 0.853-0.920g / cm ３ Density range of inserts and , a polymerization process comprising:

2. At least one catalyst and at least one co-catalyst are used to produce a polyolefin. In the presence of a catalyst, one or more (C ２ -C １２ ) polymerizing an α-olefin monomer; So, The cocatalyst comprises a cation and an anion, the anion having a structure according to formula (I): It has a structure, 【Chemistry 1】 In the formula, R １ but with vinyl terminated alkenes (C ２ -C ２０ ) Hydrocarbohydrates and each X is independently a halogen atom; inserting the anion of the cocatalyst into the polymer chain of the polyolefin; , a polymerization process.

3. The polyolefin has a molar amount of the anion of formula (I) having the formula (Ia) The corresponding 3. The process of claim 2 having a lower dissipation factor than the polyolefin composition. 【Chemistry 2】

4. At least one catalyst and at least one co-catalyst are used to produce a polyolefin. In the presence of a catalyst, ethylene monomer and one or more (C ３ -C １２ ) α-Olefin mono copolymerizing a mer, The cocatalyst comprises a cation and an anion, the anion being represented by formula (II): the law of nature, -BR ２ R ３ R ４ R ５ (II) During the ceremony, R ２ , R ３ , R ４ , and R ５ However, (C １ -C ４０ ) Selected from hydrocarbyl And each (C １ -C ４０ ) Hydrocarbyl is substituted with at least one halogen and At least one (C １ -C ４０ ) the hydrocarbyl is substituted with a vinyl terminated alkene; Copolymerizing by inserting the anion of the cocatalyst into the polymer chain of the polyolefin. hand, The polyolefin comprises less than 1 mole percent of the anion of the cocatalyst. , and intercalating.

5. the vinyl terminated alkene has a structure according to formula (III): 【Chemistry 3】 In the formula, n is an integer from 1 to 10. Seth.

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

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

8. The ethylene-based polymer has a molecular weight of less than 0.10 at a frequency of 100 Hz and a temperature of 130° C.

2. The polymerization process of any one of the preceding claims, wherein the polymer has a dissipation factor of less than 1.

9. The ethylene-based polymer has a viscosity of less than 1.00 at a frequency of 10 Hz and a temperature of 130° C.

2. The polymerization process of any one of the preceding claims, wherein the polymerisation has a dielectric loss tangent of

10. The ethylene-based polymer has a vibrational resistance of less than 10 at a frequency of 1.0 Hz and a temperature of 130° C.

2. The polymerization process of any one of the preceding claims, having a dielectric loss tangent.

11. The ethylene-based polymer is a ferroelectric polymer having a molecular weight of less than 100 at a frequency of 0.10 Hz and a temperature of 130° C.

2. The polymerization process of any one of the preceding claims, wherein the polymer has a dissipation factor of less than 1.

12. The cation of the cocatalyst is ＋ N(H)R Ｎ ３ wherein each R Ｎ However, (C １ - C ２０ ) alkyl or (C ６ -C ２０ ) aryl 3. The polymerization process according to claim 1 .

13. The cation of the cocatalyst is ＋ N(H)R Ｎ ３ wherein at least two R Ｎ However, (C １０ -C ２０ ) alkyl as claimed in any one of the preceding claims. Polymerization process.

14. The cation of the cocatalyst is ＋ C (C ６ H ５ ) ３ Any one of the preceding claims, Item 5. The polymerization process according to item 4.

15. The cation of the cocatalyst is ＋ C (C ６ H ４ R Ｃ ) ３ Wherein R Ｃ However, (C １ -C ２０ 2. The polymerization process of any one of the preceding claims, wherein:

16. 16. The method according to claim 1, wherein the polyolefin is polyethylene. Polymerization process.

17. 16. The method according to claim 1, wherein the polyolefin is polyoctene. Polymerization process.

18. 16. The method according to claim 1, wherein the polyolefin is an ethylene-based copolymer. Item 5. The polymerization process according to item 4.

19. The process comprises the steps of: ３ -C １２ ) α-olefin The polymerization process according to any one of claims 1 to 14, wherein a monomer is polymerized.

20. Any of claims 1 to 14, wherein the process polymerizes ethylene and 1-octene.

3. The polymerization process according to claim 1 .

21. 2. The polymerization process of any one of the preceding claims, wherein each X is a chlorine atom.

22. 2. The method of claim 1, wherein the polyolefin comprises greater than 0 and less than 1 mole percent. The polymerization process according to claim 4.

23. 2. The polyolefin comprises greater than 0 and less than 0.1 mole percent.

5. The polymerization process according to claim 4.

24. 2. The polyolefin comprises greater than 0 and less than 0.1 mole percent.

5. The polymerization process according to claim 4.

25. The polyolefin has a viscosity of 0.853 to 0.920 g / cm ３ The range of densities includes 25. The polymerization process according to any one of claims 2 to 24.

Images