阅读说明：本技术 烯烃官能化活化剂 (Olefin functionalized activators ) 是由 R·J·基顿 O·V·奥泽罗夫 赖清恒 J·克洛辛 M·J·莱斯尼亚克 D·M·皮尔森 于 2020-04-30 设计创作，主要内容包括：聚烯烃的聚合方法和活化剂的合成。聚合方法包括在至少一种催化剂和至少一种助催化剂的存在下聚合一种或多种(C-(2)-C-(12))α-烯烃单体以产生聚烯烃。助催化剂包括阳离子和阴离子,其中阴离子具有具有乙烯基封端的烯烃、一个硼原子或一个以上的硼原子以及至少四个卤素原子的结构。将助催化剂的阴离子结合到聚烯烃的聚合物链中。(A method for polymerization of polyolefins and synthesis of activators. The polymerization process comprises polymerizing one or more (C) s in the presence of at least one catalyst and at least one cocatalyst 2 ‑C 12 ) Alpha-olefin monomers to produce polyolefins. The cocatalyst comprises a cation and an anion, wherein the anion has a structure having a vinyl terminated olefin, one boron atom or more than one boron atom, and at least four halogen atoms. The anion of the cocatalyst is incorporated into the polymer chain of the polyolefin.)

1. A polymerization process comprising:

polymerizing one or more (C) in the presence of at least one catalyst and at least one cocatalyst₂-C₁₂) An alpha-olefin monomer to produce a polyolefin;

wherein the cocatalyst comprises a cation and an anion, wherein the anion has a structure having a vinyl terminated olefin, one boron atom or more than one boron atom, and at least four halogen atoms; and

inserting the anion of the cocatalyst into a polymer chain of the polyolefin;

wherein the polymer comprises a polymer of the group,

(1) greater than 0 and less than 1 mole percent of the anion of the co-catalyst, based on the molar composition of the polyolefin, and

(2) at 0.853 to 0.920g/cm³A density within the range of (a) a,

2. a polymerization process comprising:

polymerizing one or more (C) in the presence of at least one catalyst and at least one cocatalyst₂-C₁₂) An alpha-olefin monomer to produce a polyolefin;

wherein the cocatalyst comprises a cation and an anion, the anion having a structure according to formula (I):

wherein R is¹Is unsaturated (C) of olefins having vinyl termination₂-C₂₀) A hydrocarbyl group; and each X is independently a halogen atom; and

inserting the anion of the cocatalyst into a polymer chain of the polyolefin.

3. The process according to claim 2, wherein the dissipation factor of the polyolefin is less than that of the corresponding polyolefin composition produced under the same polymerization conditions, except that the molar amount of the anion of formula (I) is replaced by a comparative anion having formula (Ia):

4. a polymerization process comprising:

reacting ethylene monomer and one or more (C) s in the presence of at least one catalyst and at least one cocatalyst₃-C₁₂) Alpha-olefin monomers are copolymerized to produce polyolefins,

wherein the cocatalyst comprises a cation and an anion, the anion according to formula (II):

^-BR²R³R⁴R⁵ (II)

wherein

R²、R³、R⁴And R⁵Is selected from (C)₁-C₄₀) A hydrocarbon group of each (C)₁-C₄₀) The hydrocarbon group is substituted with at least one halogen, and at least one of (C)₁-C₄₀) The hydrocarbyl group is substituted with a vinyl terminated olefin; and

inserting the anion of the cocatalyst into the polymer chain of the polyolefin,

wherein the polyolefin comprises less than 1 mole% of the anion of the co-catalyst.

5. The polymerization process of any one of claims 1 to 3, wherein the vinyl terminated olefin has a structure according to formula (III):

wherein n is an integer of 1 to 10.

6. The polymerization process of any one of claims 1 to 3, wherein the vinyl terminated olefin has a structure according to formula (V):

wherein y is an integer from 1 to 10 and x is 0, 1, 2 and 3.

7. The polymerization process of claim 5, wherein the vinyl terminated olefin according to formula (V) has a structure according to formula (IV):

wherein y and x are as defined in claim 5.

8. The polymerization process of any one of the preceding claims, wherein the ethylene-based polymer has a dissipation factor of less than 0.10 at a frequency of 100Hz and a temperature of 130 ℃.

9. The polymerization process of any one of the preceding claims, wherein the ethylene-based polymer has a dissipation factor of less than 1.00 at a frequency of 10Hz and a temperature of 130 ℃.

10. The polymerization process of any one of the preceding claims, wherein the ethylene-based polymer has a dissipation factor of less than 10 at a frequency of 1.0Hz and a temperature of 130 ℃.

11. The polymerization process of any one of the preceding claims, wherein the ethylene-based polymer has a dissipation factor of less than 100 at a frequency of 0.10Hz and a temperature of 130 ℃.

12. The polymerization process of any one of the preceding claims, wherein the cation of the cocatalyst is⁺N(H)R^N ₃Wherein each R is^NIs selected from (C)₁-C₂₀) Alkyl or (C)₆-C₂₀) And (4) an aryl group.

13. The polymerization process of any one of the preceding claims, wherein the cation of the cocatalyst is⁺N(H)R^N ₃Wherein at least two R^NIs selected from (C)₁₀-C₂₀) An alkyl group.

14. The polymerization process of any one of the preceding claims, wherein the cation of the cocatalyst is⁺C(C₆H₅)₃。

15. The polymerization process of any one of the preceding claims, wherein the cation of the cocatalyst is⁺C(C₆H₄R^C)₃Wherein R is^CIs (C)₁-C₂₀) An alkyl group.

16. The polymerization process of any one of claims 1-15, wherein the polyolefin is polyethylene.

17. The polymerization process of any one of claims 1-15, wherein the polyolefin is polyoctene.

18. The polymerization process of any one of claims 1-15, wherein the polyolefin is an ethylene-based copolymer.

19. The polymerization process of any one of claims 1 to 14, wherein the process polymerizes ethylene and at least one (C)₃-C₁₂) An alpha-olefin monomer.

20. The polymerization process of any one of claims 1-14, wherein the process polymerizes ethylene and 1-octene.

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

22. The polymerization process of claim 2 or claim 4, wherein the polyolefin comprises greater than 0 and less than 1 mole%.

23. The polymerization process of claim 2 or claim 4, wherein the polyolefin comprises greater than 0 and less than 0.1 mole percent.

24. The polymerization process of claim 2 or claim 4, wherein the polyolefin comprises greater than 0 and less than 0.1 mole percent.

25. The polymerization process of any one of claims 2-24, wherein the polyolefin is contained in the range of from 0.853 to 0.920g/cm³Density within the range.

Technical Field

Embodiments of the present disclosure generally relate to olefin functionalized activators, synthesis of activators, and olefin polymerization processes employing the same.

Background

Olefin-based polymers, such as ethylene-based polymers and propylene-based polymers, are produced via a variety of catalyst systems. The selection of such catalyst systems can be an important factor contributing to the characteristics and performance of olefin-based polymers. The catalyst system used to produce the polyethylene-based polymer may include a chromium-based catalyst system, a Ziegler-Natta catalyst system or a molecular (metallocene or non-metallocene) catalyst system.

Activators are typically used in conjunction with a metal procatalyst to form an activated catalyst ion pair for subsequent use in olefin polymerization. As part of the catalyst composition in an alpha olefin polymerization reaction, the activator can have characteristics that facilitate production of the alpha olefin polymer, as well as the final polymer composition comprising the alpha olefin polymer. Activator characteristics that increase the production of alpha-olefin polymers include, but are not limited to: rapid procatalyst activation, high catalyst efficiency, high temperature performance, consistent polymer composition and selective deactivation.

As part of the catalyst system, the molecular polymerization procatalyst is activated to generate a catalytically active species for polymerization, and this can be accomplished by any number of means. One such method employs an activator or cocatalyst, a bronsted acid. Bronsted acid salts containing weakly coordinating anions are commonly used to activate molecular polymerization procatalysts, particularly such procatalysts comprising a group IV metal complex. Fully ionized bronsted acid salts are capable of transferring protons to form cationic derivatives of such group IV metal complexes.

For activators such as bronsted acid salts, the cationic component may include a cation capable of transferring a hydrogen ion, such as ammonium, sulfonium, or phosphonium; or an oxidative cation, such as a ferrocene, silver (I) or lead (II) cation; or a highly lewis acidic cation such as carbonium or silylium.

However, once the cation of the activator or cocatalyst activates the procatalyst, the activator may remain in the polymer composition. As a result, cations and anions may affect the polymer composition. Since not all ions diffuse equally, different ions have different effects on the polymer composition. In particular, the size of the ions, the charge of the ions, the interaction of the ions with the surrounding medium, and the dissociation of the ions from available counter-ions can affect the ability of the ions to diffuse through the surrounding medium (e.g., solvent, gel, or polymeric material).

Conventional olefin polymerization activators include weakly coordinating or non-coordinating anions. It has been shown that a weak coordination of the anion leads to an increase in the catalytic efficiency of the cationic catalyst. However, because the non-nucleophilic nature of the non-coordinating anion also increases diffusion, residual activator anions in the resulting polymer can decrease the resistance of the polymer, thereby increasing electrical losses, and thereby decreasing the insulating ability of the resulting polymer.

Disclosure of Invention

It is desirable to be able to prepare activators or cocatalysts that do not diffuse or otherwise adversely affect the polymerization properties of the resulting polymer while maintaining the catalytic efficiency of weakly coordinating anions. Embodiments of the present disclosure include polymerization processes. In one or more embodiments, the polymerization process comprises polymerizing one or more (C) s in the presence of at least one catalyst and at least one cocatalyst₂-C₁₂) Alpha-olefin monomers to produce polyolefins and then the anion of the cocatalyst intercalates into the polymer chain of the polyolefin. The polyolefin comprises (1) greater than 0 mole% and less than 1 mole%, based on the total mole% of the polyolefin, of a cocatalyst anion, and (2) from 0.853 to 0.920g/cm³Density within the range.

The cocatalyst includes a cation and an anion. The anion has a structure comprising one vinyl terminated olefin, one or more boron atoms, and at least four halogen atoms.

In embodiments, the polymerization process comprises polymerizing one or more (C) in the presence of at least one catalyst and at least one cocatalyst₂-C₁₂) Alpha-olefin monomers to produce polyolefins. The anion of the cocatalyst then intercalates into the polymer chain of the polyolefin.

The cocatalyst comprises a cation and an anion, the anion having a structure according to formula (I):

in the formula (I), R¹Is unsaturated (C) of olefins having vinyl termination₂-C₂₀) A hydrocarbyl group; and X is a halogen selected from the group consisting of fluorine, chlorine, bromine and iodine.

In one or more embodiments, the dissipation factor of the polyolefin is less than that of a corresponding polyolefin composition produced under the same polymerization conditions, except that the molar amount of anion of formula (I) is replaced by the same molar amount of a comparative anion having formula (Ia):

in some embodiments, the polymerization process comprises reacting ethylene monomer and one or more (C) in the presence of at least one catalyst and at least one cocatalyst₃-C₁₂) Alpha-olefin monomers are copolymerized to produce polyolefins. The anion of the cocatalyst intercalates into the polymer chain of the polyolefin. The polyolefin comprises greater than 0 mole% and less than 1 mole% of a cocatalyst anion, based on the molar composition of the polyolefin.

The cocatalyst comprises a cation and an anion, the anion according to formula (II):

BR²R³R⁴R⁵ (II)

in the formula (II), R²、R³、R⁴And R5 is independently selected from (C)₁-C₄₀) A hydrocarbyl group. Each (C)₁-C₄₀) The hydrocarbon group being substituted by at least one halogen and at least one (C)₁-C₄₀) The hydrocarbyl group is substituted with a vinyl terminated olefin.

Drawings

FIG. 1 is a negative mode mass spectrum of flow injection analysis of polyoctene produced from procatalyst P1 and alkene substituted carborane activator cocatalyst 5.

FIG. 2 is an expanded mass spectrum of mass to charge ratio (m/z) of about 786.056 for negative flow injection analysis of polyoctene produced from procatalyst P1 and alkene substituted carborane activator cocatalyst 5.

FIG. 3 is [ C ]₂₀H₃₇B₁₁Cl₁₁]^-The product was polymerized from anions of cocatalyst 5 and two 1-octene monomer units, wherein the activated procatalyst P2 is the catalyst.

Fig. 4 is a negative mode mass spectrum of flow injection analysis of polyoctene produced from catalyst P1 and a cocatalyst according to embodiments of the present disclosure.

FIG. 5 is a negative mode mass spectrum of flow injection analysis of polyoctene produced by catalyst P1 compared to a hydrogen substituted (non-olefin) carborane activator of C3.

FIG. 6 is a plot of dissipation factor as a function of frequency for two comparative examples of polyoctene produced by procatalyst P3 and comparative cocatalysts C1 or C2 and polyoctene produced by procatalyst P3 and cocatalysts 1, 2, 3 or 4.

FIG. 7 is a plot of dissipation factor as a function of frequency for two comparative examples of polyoctene produced by procatalyst P3 and comparative cocatalysts C1 or C3 and polyoctene produced by procatalyst P3 and cocatalysts 5, 6, 7.

FIG. 8 is a plot of dissipation factor as a function of frequency for two comparative examples of ethylene-octene copolymers produced by procatalyst P3 and comparative cocatalysts C1 or C3 and ethylene-octene copolymers produced by procatalyst P3 and cocatalyst 7.

FIG. 9 is a plot of dissipation factor as a function of frequency for two comparative examples of ethylene-octene copolymers produced by procatalyst P2 and comparative cocatalysts C1 or C3 and ethylene-octene copolymers produced by procatalyst P2 and cocatalyst 7.

Detailed Description

The term "polyolefin" refers to a polymer compound prepared by polymerizing the same or different types of alpha-olefins. Thus, the generic term polymer encompasses the term "homopolymer", which is commonly used to refer to polymers prepared from only one type of monomer, and "copolymer", which refers to polymers prepared from two or more different monomers. The term "interpolymer" as used herein refers to a polymer prepared by the polymerization of at least two different types of monomers. Thus, the generic term interpolymer encompasses copolymers, and polymers prepared from more than two different types of monomers, such as terpolymers.

"polyethylene" or "ethylene-based polymer" shall mean a polymer comprising greater than 50 mole percent (mol%) units derived from ethylene monomer. This includes polyethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of polyethylene known in the art comprise: low Density Polyethylene (LDPE); linear Low Density Polyethylene (LLDPE); ultra Low Density Polyethylene (ULDPE); very Low Density Polyethylene (VLDPE); a single-site catalyzed linear low density polyethylene comprising both a linear low density resin and a substantially linear low density resin (m-LLDPE); medium Density Polyethylene (MDPE); and High Density Polyethylene (HDPE).

Embodiments of the present disclosure include polymerization processes. In one or more embodiments, the polymerization process comprises polymerizing one or more (C) s in the presence of at least one catalyst and at least one cocatalyst₂-C₁₂) Alpha-olefin monomers to produce polyolefins. The cocatalyst has an anion and a cation. The cation of the cocatalyst is inserted into the polymer chain of the polyolefin. The anion of the cocatalyst has a structure comprising a vinyl terminated olefin, one or more boron atoms, and at least four halogen atoms. In some embodiments, the anion of the cocatalyst has two vinyl-terminated olefin groups. In some embodiments, the polymerization process includes two co-catalysts, wherein both co-catalysts have an anion having a structure comprising a vinyl terminated olefin, one or more boron atoms, and at least four halogen atoms.

The term "vinyl terminated olefin" refers to placement of a double bond on a hydrocarbon. The vinyl-terminated olefin being a terminal double bond, e.g. R^EHC＝CH₂Wherein R is^EIs a hydrocarbyl group.

Scheme 1: schematic representation of anions inserted or covalently bound into the polymer chain of a polyolefin.

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 description of scheme 1 illustrates the manner in which the anion of the cocatalyst is inserted or covalently bonded into the polymer chain of the polyolefin. The anionic vinyl terminated olefin of the cocatalyst acts as an olefin and polymerizes into a polymer chain. Scheme 1 is illustrative and not intended to be limiting. For example, scheme 1 describes a catalyst, namely a metal-ligand catalyst (L-M). However, any catalyst activated by an activator or co-catalyst may be suitable in the methods of the present disclosure.

The term "activator" refers to a compound that chemically reacts with a procatalyst in a manner that converts the procatalyst into a catalytically active catalyst. As used herein, the terms "cocatalyst" and "activator" are interchangeable terms. The term "procatalyst" refers to a compound that has catalytic activity when combined with an activator.

As previously mentioned, residual activator anion in the resulting polymer can reduce the electrical resistance of the polymer, thereby increasing electrical losses and reducing the insulating ability of the resulting polymer. Without being bound by theory, it is believed that migration or diffusion of the cocatalyst anion is reduced throughout the polyolefin composition due to the anion being incorporated into the polymer chain. Thus, the polyolefin produced by the process comprising incorporating the anion of the co-catalyst into the polymer chain of the polyolefin has better electrical properties than expected, e.g., a lower dissipation factor when compared to a comparative polymer produced under similar conditions (except that the co-catalyst is not incorporated into the polymer chain of the comparative polymer).

In embodiments, the polymerization process comprises polymerizing one or more (C) in the presence of at least one catalyst and at least one cocatalyst₂-C₁₂) Alpha-olefin monomers to produce polyolefins. Then, the anion of the cocatalyst is inserted into the polymer chain of the polyolefin.

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

in the formula (I), R¹Is unsaturated (C) of olefins having vinyl termination₂-C₂₀) A hydrocarbon group, and X is a halogen atom. In some embodiments, each X is chloro. In other embodiments, each X is bromo.

One of ordinary skill in the art will recognize that the structures of formula (I) and formula (Ia) are carborane anions. When each X is chlorine, the structure of formula (I) has the formula-B₁₁CR¹Cl₁₁Wherein B is a boron atom, C is a carbon atom, Cl is a chlorine atom, R is¹As previously defined. Each boron atom is represented by a sphere in formula (I). Each chlorine atom of formula (I) is bonded to a boron atom.

In one or more embodiments, the dissipation factor of the polyolefin is less than that of a corresponding polyolefin composition produced under the same polymerization conditions, except that the molar amount of anion of formula (I) is replaced by the same molar amount of a comparative anion having formula (Ia):

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 performed in the reactor producing the polyolefin of the present disclosure, nor does it limit the polymerization process to the same location. For example, if the polyolefin produced by the cocatalyst having an anion of formula (I) is polymerized in a batch reactor, the corresponding polyolefin composition produced by the cocatalyst having an anion of formula (Ia) is also polymerized in a batch reactor. Furthermore, "same conditions" means that each reactor is charged with the same molar amount of: catalyst, cocatalyst, comonomer (if present), hydrogen (if present), and ethylene pressure (if present); and charging the same volume of solvent; and each reactor was heated to the same temperature at the same ramp rate.

In some embodiments, the polymerization process comprises polymerizing one or more (C) in the presence of at least one catalyst and at least one cocatalyst₂-C₁₂) Alpha-olefin monomers to produce polyolefins. The anion of the cocatalyst intercalates into the polymer chain of the polyolefin. The polyolefin comprises less than 1 mole% of cocatalyst anions. The structure of formula (Ia) is also carborane and has an empirical formula B₁₁CCl₁₁H. Each atom is defined in formula (I) except H is a hydrogen atom bonded to a carbon atom.

In some embodiments, the cocatalyst comprises a cation and an anion, the anion according to formula (II):

BR²R³R⁴R⁵ (II)

in the formula (II), R²、R³、R⁴And R⁵Independently selected from (C)₁-C₄₀) A hydrocarbyl group. Each (C)₁-C₄₀) The hydrocarbon group being substituted by at least one halogen and at least one (C)₁-C₄₀) The hydrocarbyl group is substituted with a vinyl terminated olefin.

In embodiments of the present disclosure, the anion of the cocatalyst has one vinyl terminated olefin. In one or more embodiments, the vinyl terminated olefin has a structure according to formula (III):

in formula (III), n is an integer of 1 to 10; in some embodiments, n is 1, 2, or 3;

in various embodiments, the vinyl terminated olefin has a structure according to formula (IV):

in formula (V), subscript y is an integer of 1 to 10, and subscript x is 0, 1, 2, and 3. As shown in formula (IV), the two substituents (i.e., the groups associated with subscript x and subscript y) may be ortho, meta, or para with respect to each other.

In one or more embodiments, the vinyl terminated olefin according to formula (IV) has a structure according to formula (V):

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

In one or more embodiments, the polyolefin comprises greater than 0 mole percent (mol%) and less than 1 mol% of the cocatalyst anion, based on the molar composition of the polyolefin. In some embodiments, the polyolefin comprises greater than 0 mol% and less than 0.5 mol% of the cocatalyst anion. In other embodiments, the polyolefin comprises greater than 0 and less than 0.1 mol% of cocatalyst anion. In various embodiments, the polyolefin comprises greater than 0 mol% and less than 0.01 mol% of the cocatalyst anion, based on the molar composition of the polyolefin.

In one or more embodiments, the promoter comprises an anion according to formula (I) and a cation having a formal charge of positive (+ 1). In some embodiments of the cocatalyst, a cationThe ions being selected from protonated tris [ (C)₁-C₄₀) Hydrocarbyl radical]An ammonium cation. In some embodiments the cation is one or two (C) on the ammonium cation₁₄-C₂₀) Protonated trialkylammonium cations of alkyl groups. In one or more embodiments, the cation is⁺N(H)R^N ₃Wherein each R is^NIs selected from (C)₁-C₂₀) Alkyl or (C)₆-C₂₀) And (4) an aryl group. In one or more embodiments, the cation is⁺N(H)R^N ₃Wherein at least two R^NIs selected from (C)₁₀-C₂₀) An alkyl group. In one or more embodiments, the cation is⁺N(H)R^N ₃Wherein R is^NIs (C)₁₆-C₁₈) An alkyl group. In one or more embodiments, the cation is⁺N(CH₃)HR^N ₂Wherein R is^NIs (C)₁₆-C₁₈) An alkyl group. In some embodiments, the cation is selected from a methyldioctadecyl ammonium cation, a methyldioctadecyl (hexadecyl) ammonium cation, a methyldiocetyl ammonium cation, or a methyldietetradecyl ammonium cation. The methyldioctadecyl ammonium cation, the methyloctadecylhexadecyl ammonium cation, the methyldiocetyl ammonium cation, or the methylditetradecyl ammonium cation are collectively referred to herein as the aminium cation. By reacting (e.g. with anhydrous HCl in diethyl ether) a commercially available product as Armeen^TME.g. Armeen^TMM2HT Methyldioctadecyl, Methyldioctadecyl (hexadecyl), Methyldihexadecyl, or Methylditetradecyl amine, available from Akzo-Nobel (Akzo), is protonated to readily form ionic compounds with an aminium cation. In other embodiments, the cation is a triphenylmethyl carbocation (C:)⁺C(C₆H₅)₃) Also known as trityl. In one or more embodiments, the cation is a trisubstituted triphenylmethyl carbocation, such as⁺C(C₆H₄R^C)₃Wherein each R is^CIndependently selected from (C)₁-C₃₀) Alkyl radical. In other embodiments, the cation is selected from aniline, ferrocene, or metallocenes. The aniline cation is a protonated nitrogen cation, e.g. [ HN (R)^S)(R^N)₂]⁺Wherein R is^NIs (C)₁-C₂₀) Alkyl or H and R^SIs selected from (C)₆-C₂₀) Aryl, and each alkyl OR aryl group may additionally be treated with-OR^CSubstituted, e.g. C₆H₅NMe₂H⁺. The metallocenes being aluminium cations, e.g. R^S ₂Al(THF)₂ ⁺Wherein R is^SIs selected from (C)₁-C₃₀) An alkyl group.

In illustrative embodiments, the catalyst system may include one or more cocatalysts comprising an anion and a counter cation, wherein the anion is according to formula (I). Counter cations complexed with anions of formula (I) are not included in the illustrative embodiments. Illustrative embodiments of the anion of formula (I) include the following structures:

electrical properties of polymers

The insulating medium should be as effective as possible. Electrical losses reduce the dielectric's insulating efficiency in the presence of an electric field. For both Alternating Current (AC) and Direct Current (DC) systems, the resistance should be as high as possible, since resistance is inversely related to power or electrical losses.

In DC systems (e.g., photovoltaic encapsulants), energy loss manifests as current leakage from the encapsulant to the external environment. The current (I) is represented by the equation (I) V × R^-1Is directly related to the voltage (V) and inversely related to the resistance (R) of the insulating medium. Thus, the higher the resistance, the lower the current and leakage current.

In AC systems (e.g., cable insulation), losses manifest as absorption of energy by the medium in the presence of an electric field.Measured in power (P), the loss is given by the equation P ═ V²X ω × C × ∈ '× tan δ, where ω is angular frequency, ∈' is relative dielectric constant, C is capacitance, and tan δ is dissipation factor, tan ∈ ═ C × R × ω^-1To obtain the equation P ═ V²×ε′×R^-1. Since resistance is inversely related to power loss, the higher the resistance, the lower the power loss.

One physical effect of reducing the resistance of a medium is ion diffusion due to an electric field. In systems where ion diffusion dominates the electrical response, the resistance is given by the equation R ═ 6 × pi × epsilon' × epsilon₀×η×r×C^-1×q^-2×N^-1Associated with diffusing ions, wherein epsilon₀Dielectric constant of vacuum (8.854X 10)^-12F·m^-1) η is the dynamic viscosity of the medium, r is the hydrodynamic radius of the ion, q is the charge of the ion, and N is the concentration of the ion. The reduction in ion concentration diffused through the medium reduces energy loss since the increased resistance reduces energy loss, and the reduction in ion concentration increases resistance.

In addition to size and charge, the interaction of an ion with the surrounding medium and its dissociation energy from the available counter-ions will affect its ability to diffuse through a given medium. The ability of the ions to diffuse in the activator is an important property because not all ions diffuse equally. Without being bound by theory, it is believed that when the anion and counter cation of the co-catalyst of formula (I) of the present disclosure have reduced diffusion, the resulting polymer of the co-catalyst of the present disclosure has reduced energy loss, which provides good electrical properties.

In one or more embodiments, the polyolefin produced by any of the methods of the present disclosure has a dissipation factor of less than 0.10 at a frequency of 100Hz and a temperature of 130 ℃. In various embodiments, the polyolefin has a dissipation factor of less than 1.00 at a frequency of 10Hz and a temperature of 130 ℃. In other embodiments, the polyolefin has a dissipation factor of less than 10 at a frequency of 1.0Hz and a temperature of 130 ℃. In some embodiments, the polyolefin has a dissipation factor of less than 100 at a frequency of 0.10Hz and a temperature of 130 ℃.

Dissipation factor is related to the electrical properties of the resin. The reduction in dissipation factor results in a material that can be used as a dielectric (e.g., cable insulation or electronic sealant). When the dissipation factor is primarily caused by ions in the resin, removing or immobilizing these ions can reduce the dissipation factor and improve the electrical properties of the resin.

On a small scale, the dissipation factor of the polymer produced with the cocatalyst having the anion of formula (I) is ten times smaller than that of the standard polymer we produced with the comparative cocatalyst C1. Without being bound by theory, it is believed that the dissipation factor of the polyolefin produced by the cocatalyst having an anion of formula (I) will be ten times less than the comparative cocatalyst C1 when the polyolefin is produced on an industrial scale. The dissipation factor of a standard poly (ethylene-octene) copolymer is about 1.0. Thus, we predict that polyolefin polymers produced with cocatalysts having the anion of formula (I) will exhibit a dissipation factor of 0.1 or less at 60 hertz (Hz).

Catalyst system components

The catalyst system may include a procatalyst. The procatalyst may be made catalytically active by contacting or combining the complex with: cocatalysts of the present disclosure having anions and cations of formula (I), anions and cations of formula (II), or anions and cations of formulae (I) and (II). The procatalyst may be selected from group IV metal-ligand complexes (group IVB according to CAS or group 4 according to IUPAC naming convention), such as titanium (Ti) metal-ligand complexes, zirconium (Zr) metal-ligand complexes, or hafnium (Hf) metal-ligand complexes. Without intending to be limiting, examples of procatalysts can be found in the following references: US 8372927; WO 2010022228; WO 2011102989; US 6953764; US 6900321; WO 2017173080; US 7650930; US 6777509WO 99/41294; US 6869904; WO 2007136496. These references are incorporated herein by reference in their entirety.

In one or more embodiments, the group IV metal-ligand complex comprises a bis (phenylphenoxy) group IV metal-ligand complex or a constrained geometry group IV metal-ligand complex.

According to some embodiments, the bis (phenylphenoxy) metal-ligand complex has a structure according to formula (X):

in formula (I), M is a metal selected from titanium, zirconium or hafnium, the metal being in the formal oxidation state of +2, +3 or + 4. The subscript n of (X) n is 0, 1 or 2. When subscript n is 1, X is a monodentate ligand or a bidentate ligand, and when subscript n is 2, each X is selected from the group consisting of monodentate ligands. L is a diradical selected from the group consisting of: (C)₁-C₄₀) Alkylene, (C)₁-C₄₀) Heterohydrocarbylene, -Si (R)^C)₂-、-Si(R^C)₂OSi(R^C)₂-、-Si(R^C)₂C(R^C)₂-、-Si(R^C)₂Si(R^C)₂-、-Si(R^C)₂C(R^C)₂Si(R^C)₂-、-C(R^C)₂Si(R^C)₂C(R^C)₂-、-N(R^N)C(R^C)₂-、-N(R^N)N(R^N)-、-C(R^C)₂N(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) -and-C (O) N (R) -and-N (R)^C) C (O) -. Each Z is independently selected from-O-, -S-, -N (R)^N) -or-P (R)^P)-；R¹To R¹⁶Independently selected from the group consisting of: -H, (C)₁-C₄₀) Hydrocarbyl radical, (C)₁-C₄₀) Heterohydrocarbyl, -Si (R)^C)₃、-Ge(R^C)₃、-P(R^P)₂、-N(R^N)₂、-OR^C、-SR^C、-NO₂、-CN、-CF₃、R^CS(O)-、R^CS(O)₂-、-N＝C(R^C)₂、R^CC(O)O-、R^COC(O)-、R^CC(O)N(R)-、(R^C)₂Nc (o) -, halogen, a group of formula (XI), a group of formula (XII) and a group of formula (XIII):

in the formulae (X1), (XII) and (XIII), R³¹-R³⁵、R⁴¹-R⁴⁸And R⁵¹-R⁵⁹Each independently selected from-H, (C)₁-C₄₀) Hydrocarbyl radical, (C)₁-C₄₀) Heterohydrocarbyl, -Si (R)^C)₃、-Ge(R^C)₃、-P(R^P)₂、-N(R^N)₂、-OR^C、-SR^C、-NO₂、-CN、-CF₃、R^CS(O)-、R^CS(O)₂-、(R^C)₂C＝N-、R^CC(O)O-、R^COC(O)-、R^CC(O)N(R^N)-、(R^C)₂NC (O) -or halogen, provided that R¹Or R¹⁶Is a group of formula (XI), a group of formula (XII) or a group of formula (XIII).

In one or more embodiments, each X can be a monodentate ligand that is halogen, unsubstituted (C) independent of any other ligand X₁-C₂₀) Hydrocarbyl, unsubstituted (C)₁-C₂₀) Hydrocarbyl C (O) O-or R^KR^LN-, wherein R^KAnd R^LEach of which is independently unsubstituted (C)₁-C₂₀) A hydrocarbyl group.

Illustrative bis (phenylphenoxy) metal-ligand complexes useful in the practice of the present invention include:

(2 ', 2 "- (propane-1, 3-diylbis (oxy)) bis (5 ' -chloro-3- (3, 6-di-tert-octyl-9H-carbazol-9-yl) -3 ' -methyl-5- (2, 4, 4-trimethylpent-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (propane-l, 3-diylbis (oxy)) bis (3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -3' -chloro-5- (2, 4, 4-trimethylpent-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-trimethylpent-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (propane-l, 3-diylbis (oxy)) bis (3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -3' -methyl-5- (2, 4, 4-trimethylpent-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-trimethylpent-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (propane-l, 3-diylbis (oxy)) bis (5 ' -dimethylamino-3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -3 ' -methyl-5- (2, 4, 4-trimethylpent-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (propane-l, 3-diylbis (oxy)) bis (3 ', 5 ' -dimethyl-3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -5- (2, 4, 4-trimethylpent-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (propane-1, 3-diylbis (oxy)) bis (5 ' -chloro-3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -3 ' -ethyl-5- (2, 4, 4-trimethylpent-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (propane-1, 3-diylbis (oxy)) bis (3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -3 ' -methyl-5 ' -tert-butyl-5- (2, 4, 4-trimethylpentan-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (propane-1, 3-diylbis (oxy)) bis (3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -5 ' -fluoro-3 ' -methyl-5- (2, 4, 4-trimethylpentan-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (propane-1, 3-diylbis (oxy)) bis (3- (9H-carbazol-9-yl) -5 ' -chloro-3 ' -methyl-5- (2, 4, 4-trimethylpentan-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (propane-1, 3-diylbis (oxy)) bis (3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -3 ' -methyl-5 ' -trifluoromethyl-5- (2, 4, 4-trimethylpentan-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (2, 2-dimethyl-2-silapropane-1, 3-diylbis (oxy)) bis (3 ', 5 ' -dichloro-3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -5- (2, 4, 4-trimethylpentan-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ' 2 "- (2, 2-dimethyl-2-silapropan-1-diylbis (oxy)) bis (5 ' -chloro-3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -3 ' -methyl-5- (2, 4, 4-trimethylpentan-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (propane-1, 3-diylbis (oxy)) bis (3 ' -bromo-5 ' -chloro-3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -5- (2, 4, 4-trimethylpent-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (propane-l, 3-diylbis (oxy)) - (5 ' -chloro-3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -3 ' -fluoro-5- (2, 4, 4-trimethylpent-2-yl) biphenyl-2-ol) - (3", 5 "-dichloro-3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -5- (2, 4, 4-trimethylpent-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (propane-1, 3-diylbis (oxy)) bis (3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -5 ' -fluoro-3 ' -trifluoromethyl-5- (2, 4, 4-trimethylpentan-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (butane-1, 4-diylbis (oxy)) bis (5 ' -chloro-3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -3 ' -methyl-5- (2, 4, 4-trimethylpentan-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (ethane-1, 2-diylbis (oxy)) bis (5 ' -chloro-3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -3 ' -methyl-5- (2, 4, 4-trimethylpent-2-yl) biphenyl-2-ol) dimethyl-hafnium;

(2 ', 2 "- (propane-l, 3-diylbis (oxy)) bis (5 ' -chloro-3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -3 ' -methyl-5- (2, 4, 4-trimethylpent-2-yl) biphenyl-2-ol) dimethyl-zirconium;

(2 ', 2' - (propane-l, 3-diylbis (oxy)) bis (3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -3 ', 5' -dichloro-5- (2, 4, 4-trimethylpent-2-yl) biphenyl-2-ol) dimethyl-titanium, and

(2 ', 2 "- (propane-1, 3-diylbis (oxy)) bis (5 ' -chloro-3- (3, 6-di-tert-butyl-9H-carbazol-9-yl) -3 ' -methyl-5- (2, 4, 4-trimethylpent-2-yl) biphenyl-2-ol) dimethyl-titanium.

According to some embodiments, the group IV metal-ligand complex may include a cyclopentadienyl procatalyst according to formula (XIV):

Lp_iMX_mX′_nX″_por a dimer of (XIV) thereof.

In formula (XIV), Lp is an anionic, delocalized, pi-bonded group containing up to 50 non-hydrogen atoms bonded to M. In some embodiments of formula (XIV), two Lp groups may be joined together to form a bridging structure, and further optionally, one Lp may be bonded to X.

In formula (XIV), M is a metal of group 4 of the periodic Table of the elements, which is in the formal oxidation state of +2, +3, or + 4. X is an optional divalent substituent having up to 50 non-hydrogen atoms which together with Lp forms a metallocycle with M. X' is an optional neutral ligand having up to 20 non-hydrogen atoms; each X "is independently a monovalent, anionic moiety having up to 40 non-hydrogen atoms. Optionally, two X "groups can be covalently bonded together forming a divalent dianionic moiety with both valences bonded to M, or optionally, two X" groups can be covalently bonded together to form a neutral, conjugated or non-conjugated diene pi-bonded to M, where M is in the +2 oxidation state. In other embodiments, one or more X "and one or more X' groups may be bonded together, thereby forming a moiety that is both covalently bonded to M and coordinated thereto by means of a lewis base functional group. Lp_iSubscript i of (a) is 0, 1, or 2; x'_nSubscript n of (a) is 0, 1, 2, or 3; x_mSubscript m of (a) is 0 or 1; and X ″)_pSubscript p of (a) is 0, 1, 2, or 3. The sum of i + M + p is equal to the formulaic oxidation state of M.

Illustrative group IV metal-ligand complexes can include cyclopentadienyl procatalysts useful in the practice of the invention, including:

cyclopentadienyl titanium trimethyl;

cyclopentadienyl triethyl titanium;

cyclopentadienyl titanium triisopropylate;

cyclopentadienyl titanium triphenyl;

cyclopentadienyl titanium tribenzyl;

cyclopentadienyl-2, 4-dimethylpentadienyl titanium;

cyclopentadienyl-2, 4-dimethylpentadienyltitanium triethylphosphine;

cyclopentadienyl-2, 4-dimethylpentadienyltitanium-trimethylphosphine;

cyclopentadienyl titanium dimethylmethoxide;

cyclopentadienyl titanium dimethyl chloride;

pentamethylcyclopentadienyltrimethyltitanium;

indenyl trimethyl titanium;

indenyl triethyl titanium;

indenyl tripropyl titanium;

indenyl triphenyltitanium;

tetrahydroindenyl titanium tribenzyl;

pentamethylcyclopentadienyl triisopropyltitanium;

pentamethylcyclopentadienyltribenzyltitanium;

pentamethylcyclopentadienyldimethylmethaneuritanium;

pentamethylcyclopentadienyldimethyl titanium chloride;

bis (eta)⁵-2, 4-dimethylpentadienyl) titanium;

bis (eta)⁵-2, 4-dimethylpentadienyl) titanium trimethylphosphine;

bis (eta)⁵-2, 4-dimethylpentadienyl) titanium triethylphosphine;

octahydrofluorenyltrimethyltitanium;

tetrahydroindenyl trimethyl titanium;

tetrahydrofluorenyl trimethyl titanium;

(tert-butylamido) (1, 1-dimethyl-2, 3, 4, 9, 10-. eta. -1, 4, 5, 6, 7, 8-hexahydronaphthalenyl) dimethylsilanedimethyltitanium;

(tert-butylamido) (1, 1, 2, 3-tetramethyl-2, 3, 4, 9, 10-. eta. -1, 4, 5, 6, 7, 8-hexahydronaphthalenyl) dimethylsilanedimethyltitanium;

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienyl) dimethylsilane dibenzyltitanium;

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienyl) dimethylsilanedimethyltitanium;

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienyl) -1, 2-ethanediyldimethyltitanium;

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-indenyl) dimethylsilanetitanyl dimethyl;

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienyl) dimethylsilanetitanium (III)2- (dimethylamino) benzyl;

(tert-butylamido) (tetramethyl-⁵-cyclopentadienyl) dimethylsilanetitanium (III) allyl;

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienyl) dimethylsilane 2, 4-dimethylpentadienyl titanium (III);

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienyl) dimethylsilane titanium 1, 4-diphenyl-1, 3-butadiene (II);

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienyl) dimethylsilane 1, 3-pentadienyltitanium (II);

(tert-butylamido) (2-methylindenyl) dimethylsilane titanium (II) 1, 4-diphenyl-1, 3-butadiene;

(tert-butylamido) (2-methylindenyl) dimethylsilane 2, 4-hexadienitanium (II);

(tert-butylamido) (2-methylindenyl) dimethylsilane titanium (IV)2, 3-dimethyl-1, 3-butadiene;

(tert-butylamido) (2-methylindenyl) dimethylsilaneisoprenium titanium (IV);

(tert-butylamido) (2-methylindenyl) dimethylsilane titanium (IV) 1, 3-butadiene;

(tert-butylamido) (2, 3-dimethylindenyl) dimethylsilane titanium (IV)2, 3-dimethyl-1, 3-butadiene;

(tert-butylamido) (2, 3-dimethylindenyl) dimethylsilaneisoprenium titanium (IV);

(tert-butylamido) (2, 3-dimethylindenyl) dimethylsilanedimethyltitanium (IV);

(tert-butylamido) (2, 3-dimethylindenyl) dimethylsilane dibenzyltitanium (IV);

(tert-butylamido) (2, 3-dimethylindenyl) dimethylsilane titanium (IV) 1, 3-butadiene;

(tert-butylamido) (2, 3-dimethylindenyl) dimethylsilane titanium 1, 3-pentadiene (II);

(tert-butylamido) (2, 3-dimethylindenyl) dimethylsilane 1, 4-diphenyl-1, 3-butadiene titanium (II);

(tert-butylamido) (2-methylindenyl) dimethylsilane titanium (II) 1, 3-pentadiene;

(tert-butylamido) (2-methylindenyl) dimethylsilanedimethyltitanium (IV);

(tert-butylamido) (2-methylindenyl) dimethylsilanedibenzyltitanium (IV);

(tert-butylamido) (2-methyl-4-phenylindenyl) dimethylsilane 1, 4-diphenyl-1, 3-butadiene titanium (II):

(tert-butylamido) (2-methyl-4-phenylindenyl) dimethylsilane titanium 1, 3-pentadiene (II);

(tert-butylamido) (2-methyl-4-phenylindenyl) dimethylsilane 2, 4-hexadienitanium (II);

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienyl) dimethylsilane titanium 1, 3-butadiene (IV);

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵Cyclopentadienyl) dimethylsilane 2, 3-dimethyl-1, 3-butadienetitanium (IV)2

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienyl) dimethylsilane titanium Isoprene (IV);

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienyl) dimethylSilane titanium 1, 4-dibenzyl-1, 3-butadiene (II);

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienyl) dimethylsilane 2, 4-hexadienitanium (II);

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienyl) dimethylsilane 3-methyl-1, 3-pentadienyltitanium (II);

(tert-butylamido) (2, 4-dimethylpentadien-3-yl) dimethylsilanedimethyltitanium;

(tert-butylamido) (6, 6-dimethylcyclohexadienyl) dimethylsilanedimethyltitanium;

(tert-butylamido) (1, 1-dimethyl-2, 3, 4, 9, 10-. eta. -1, 4, 5, 6, 7, 8-hexahydronaphthalen-4-yl) dimethylsilanedimethyltitanium;

(tert-butylamido) (1, 1, 2, 3-tetramethyl-2, 3, 4, 9, 10-. eta. -1, 4, 5, 6, 7, 8-hexahydronaphthalen-4-yl) dimethylsilanedimethyltitanium;

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienylmethylphenylsilane dimethyltitanium (IV);

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienylmethylphenylsilane titanium (II) 1, 4-diphenyl-1, 3-butadiene;

1- (tert-butylamido) -2- (tetramethyl-. eta.⁵-cyclopentadienyl) ethanediyldimethyl titanium (IV);

1- (tert-butylamido) -2- (tetramethyl-. eta.⁵-cyclopentadienyl) ethanediyl-1, 4-diphenyl-1, 3-butadienetitanium (II);

each illustrative cyclopentadienyl procatalyst may include zirconium or hafnium in place of the titanium metal center of the cyclopentadienyl procatalyst.

Other catalysts, especially catalysts containing other group IV metal-ligand complexes, will be apparent to those skilled in the art.

In addition to the disclosed cocatalysts having an anion of formula (I) and a counter cation, the catalyst systems of the present disclosure may also include a cocatalyst or activator. Such additional cocatalysts may include, for example, tri (hydrocarbyl) aluminum compounds having 1 to 10 carbons in each hydrocarbyl group, oligomeric or polymeric aluminoxane compounds, di (hydrocarbyl) (hydrocarbyloxy) aluminum compounds having 1 to 20 carbons in each hydrocarbyl or hydrocarbyloxy group, or mixtures of the foregoing. These aluminum compounds are usefully employed due to their beneficial ability to scavenge impurities such as oxygen, water and aldehydes from the polymerization mixture.

The di (hydrocarbyl) (hydrocarbyloxy) aluminum compounds that may be used in conjunction with the activators described in this disclosure correspond to the formula T¹ ₂AlOT²Or T¹ ₁Al(OT²)₂Wherein T is¹Is secondary or tertiary (C)₃-C₆) Alkyl groups such as isopropyl, isobutyl or tert-butyl: and T²Is alkyl-substituted (C)₆-C₃₀) Aryl radical or aryl substituted (C)₁-C₃₀) Alkyl groups such as 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.

Additional examples of aluminum compounds include [ C₆]Trialkylaluminum compounds, in particular those in which the alkyl group is ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl or isopentyl, dialkyl (aryloxy) aluminum compounds containing 1 to 6 carbons in the alkyl group and 6 to 18 carbons in the aryl group (in particular (3, 5-di (tert-butyl) -4-methylphenoxy) diisobutylaluminum), methylaluminoxane, modified methylaluminoxane and diisobutylaluminoxane.

In catalyst systems according to embodiments of the present disclosure, the molar ratio of cocatalyst to group IV metal-ligand complex may be 1: 10, 000 to 1000: 1, e.g., 1: 5000 to 100: 1, 1: 100 to 100: 1, 1: 10 to 10: 1, 1: 5 to 1: 1, or 1.25: 1 to 1: 1. The catalyst system may include a combination of one or more co-catalysts of the complexes of the present disclosure described in the present disclosure.

Polyolefins

The olefins (mainly ethylene and 1-octene) are polymerized using the catalytic system described in the preceding paragraph. In some embodiments, only a single type of olefin or alpha-olefin is present in the polymerization scheme, thereby forming a homopolymer. However, additional alpha-olefins may be incorporated into the polymerization procedure. The additional alpha-olefin comonomer typically has no more than 20 carbon atoms. For example, the alpha-olefin comonomer can have 3 to 10 carbon atoms or 3 to 8 carbon atoms. Exemplary alpha-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, the one or more alpha-olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene; or in the alternative, selected from the group consisting of 1-hexene and 1-octene.

Polyolefins, for example homopolymers and/or interpolymers (including copolymers) of ethylene and optionally one or more comonomers, such as alpha-olefins, may comprise at least 50 mole percent (mol%) of monomer units derived from ethylene. All individual values and subranges subsumed by "at least 50 mol%" are disclosed herein as separate embodiments; for example, an ethylene-based polymer, i.e., a homopolymer and/or interpolymer (including a copolymer) of ethylene and optionally one or more comonomers (such as alpha-olefins), can comprise at least 60 mol% of monomer units derived from ethylene; at least 70 mol% of monomer units derived from ethylene; at least 80 mol% of monomer units derived from ethylene; or from 50 to 100 mol% of monomer units derived from ethylene; or from 80 to 100 mol% of units derived from ethylene.

In some embodiments, the polyolefin produced by the process of the present disclosure may comprise 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, the ethylene-based polymer may comprise at least 93 mole percent of units derived from ethylene; at least 96 mole% of units; at least 97 mole percent of units derived from ethylene; or in the alternative, from 90 to 100 mole percent of units derived from ethylene; 90 to 99.5 mole% units derived from ethylene; or 97 to 99.5 mole percent of units derived from ethylene.

In some embodiments of the ethylene-based polymer, the amount of additional alpha-olefin is less than 50 mol%; other embodiments comprise at least 0.5m0 l% to 25 mol%; and in further embodiments, the amount of additional alpha-olefin comprises at least 5 mol% to 10 mol%. In some embodiments, the additional α -olefin is 1-octene.

Any conventional polymerization process can be used to produce the ethylene-based polymer. Such conventional polymerization processes include, but are not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof, for example, using one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, parallel batch reactors, series batch reactors, or any combination thereof.

In one embodiment, the ethylene-based polymer may be produced via solution polymerization in a dual reactor system, such as a double loop reactor system, wherein ethylene and optionally one or more alpha-olefins are polymerized in the presence of a catalyst system as described herein and optionally one or more co-catalysts. In another embodiment, the ethylene-based polymer may be produced via solution polymerization in a dual reactor system, such as a double loop reactor system, wherein ethylene and optionally one or more alpha-olefins are polymerized in the presence of the catalyst system and optionally one or more other catalysts as described herein and in the present disclosure. The catalyst system as described herein may optionally be used in the first reactor or the second reactor in combination with one or more other catalysts. In one embodiment, the ethylene-based polymer may be produced via solution polymerization in a dual reactor system, such as a double loop reactor system, wherein ethylene and optionally one or more alpha-olefins are polymerized in the presence of a catalyst system as described herein in two reactors.

In another embodiment, the ethylene-based polymer may be produced via solution polymerization in a single reactor system (e.g., a single loop reactor system), wherein ethylene and optionally one or more alpha-olefins are polymerized in the presence of a catalyst system as described within this disclosure and optionally one or more co-catalysts as described in the preceding paragraph.

The ethylene-based polymer may further comprise one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene-based polymer may contain any amount of additives. The ethylene-based polymer may comprise from about 0 to about 10% by weight of the total amount of such additives, based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may additionally comprise fillers, which may include, but are not limited to, organic or inorganic fillers. The ethylenic polymer may contain from about 0 to about 20 weight percent of a filler, such as calcium carbonate, talc, or Mg (OH), based on the combined weight of the ethylenic polymer and all additives or fillers₂. The ethylene-based polymer may be further blended with one or more polymers to form a blend.

In some embodiments, a polymerization process for producing a polyolefin polymer may comprise polymerizing ethylene and at least one additional alpha-olefin in the presence of a catalyst system, wherein the catalyst system incorporates at least one metal-ligand complex and at least one co-catalyst of the present disclosure and optionally a scavenger. Polyolefins produced from such catalyst systems incorporating metal-ligand complexes and co-catalysts may have densities of, for example, 0.853g/cm, according to ASTM D792 (incorporated herein by reference in its entirety)³To 0.920g/cm³、0.870g/cm³To 0.920g/cm³、0.870g/cm³To 0.910g/cm³Or 0.870g/cm³To 0.900g/cm³。

In another embodiment, the polymer produced by the catalyst system comprising the metal-ligand complex and the co-catalyst of the present disclosure having an anion of formula (I) has a melt flow ratio (I)₁₀/I₂) Is from 1 to 25, wherein the melt index I₂At 190 ℃ and under a load of 2.16kg according to ASTM D1238 (incorporated herein by reference in its entirety)Measured and melt index I₁₀Measured at 190 ℃ under a 10kg load according to ASTM D1238. In other embodiments, the melt flow ratio (I)₁₀/I₂) From 5 to 10, and in other embodiments, from 5 to 9.

In some embodiments, the polymer produced from the catalyst system comprising the metal-ligand complex has a Molecular Weight Distribution (MWD) of 1 to 25, wherein MWD is defined as M_w/M_nWherein M is_wIs the weight average molecular weight and Mn is the number average molecular weight. In other embodiments, the polymer produced by the catalyst system has a MWD of 1 to 6. Another embodiment comprises an MWD of 1 to 3; and other embodiments comprise an MWD of 1.5 to 2.5.

Embodiments of the catalyst systems described in this disclosure result in unique polymer properties due to the high molecular weight of the polymer formed and the amount of comonomer incorporated into the polymer.

ADD dissipation factor experiment

Batch reactor procedure

Batch reactor experiments were conducted in a 1 gallon continuous stirred tank reactor. The reactor was charged with Isopar-E hydrocarbon solvent, hydrogen and appropriate amount of octene comonomer, then heated to the specified temperature and pressurized with ethylene to 450 psi. Polymerization is initiated by adding an activated catalyst solution comprising a procatalyst, a cocatalyst of the present disclosure, a solvent, and a triethylaluminum scavenger while the reactor is under pressure. The polymerization was allowed to proceed for 10 minutes while maintaining the reactor temperature and pressure. After the reaction was complete, the polymer was collected and dried in a vacuum oven overnight before analysis.

General procedure for polymerization of 1-octene:

in a glove box filled with nitrogen, pure 1-octene (11mL) was added to a 40mL vial equipped with a stir bar. The vial was placed in a polyurethane insulation block, which itself was placed on a magnetic stir plate. The procatalyst and a solution of the activator (1.2-1.25 equivalents relative to the procatalyst) in toluene are added sequentially. The vial was capped and the reaction was stirred for the indicated time (3 hours for procatalyst 2 and procatalyst 3; 6 days for procatalyst 3). All volatiles were removed under reduced pressure to give a polyoctene resin which was then characterized by GPC and submitted to electrical testing.

General procedure for ethylene/1-octene copolymerization:

ethylene/1-octene screening was performed in a high throughput Parallel Polymerization Reactor (PPR) system. The PPR system consisted of an array of 48 single-cell (6x 8 matrix) reactors in an inert atmosphere glove box. Each cell was equipped with a glass insert having an internal working liquid volume of about 5 mL. Each cell was independently pressure controlled and stirred continuously at 800rpm with a PEEK paddle. Catalyst, ligand and metal precursor solutions were prepared in toluene. All liquids (i.e., solvent, 1-octene, scavenger, activator, and procatalyst solution) were added by robotic syringe. The gaseous reagent (i.e., ethylene) is added through a gas injection port. The reactor was heated to 80 ℃, purged with ethylene and vented prior to each run.

In order to produce a sufficient amount of polymer for electrical testing, 24 replicates (half of 48 reactors) were run for each procatalyst and activator combination. The resulting polymers from the 24 repeats were then combined.

The reactor was heated to 100 ℃ and then pressurized to 25.3psig with ethylene and a portion of Isopar-E was added. A toluene solution of the reagents was then added to each reactor in the following order: (1) 1-octene (1.10 mL for procatalyst 3, 2.26mL for procatalyst 2); (2) scavenger Triethylaluminium (TEA) (1. mu. mol); (3) activators (compare cocatalysts C1-C3 or cocatalysts 1-7 (i.e., alkenyl substituted carboranes) (added at 1.2 molar equivalents relative to the procatalyst), and (4) procatalyst (20 nmol procatalyst 3 and 80nmol procatalyst 2).

Each liquid addition was followed with a small amount of Isopar-E to achieve a total reaction volume of 5mL after final addition. After the catalyst was added, the PPR software started monitoring the pressure of each cell. By opening the valve when the set point minus 2psi and closing the valve when the pressure reaches above 2psi, the desired pressure (within about 2 to 6 psig) is maintained by means of the supplemental addition of ethylene gas. All pressure drops are cumulatively recorded during operation as "absorption" or "conversion" of ethylene, or until the absorption or conversion requirement is reached, whichever occurs first. Each reaction was quenched by the addition of 10% carbon monoxide under argon for 1 to 4 minutes at 40 to 50psi above the reactor pressure. To prevent too much polymer formation in any given cell, the reaction was quenched after a predetermined absorption level (50psig) was reached. After quenching all reactors, they were cooled to 70 ℃, then vented and the glass tube insert containing the sample was removed. The polymer-containing solutions from the 24 reactors containing the same procatalyst and activator solutions were combined and allowed to devolatilize for several days in a fume hood. The resulting resin was then dried in a vacuum oven at 80 ℃ for 3 hours and at 140 ℃ for 4 hours in one continuous cycle, weighed to determine polymer yield and submitted for GPC analysis.

Examples

Examples 1 to 3 are the synthesis procedure of the intermediate of the cocatalyst and the cocatalyst itself. Example 4 is a mass spectrometry result. Example 5 is a polymer result.

The reaction mixture used for the mass spectrometry results of example 4 was prepared at 5mg/mL in uninhibited Tetrahydrofuran (THF). Each sample was subjected to negative ion mode flow injection mass spectrometry on Agilent 1290Infinity II Ultra High Performance Liquid Chromatograph (UHPLC) and Agilent 6538 ultra high definition accurate mass quadrupole time of flight mass spectrometer (QTOF MS). 20 microliters of the analyte solution was injected into the UHPLC in a flow injection mode with a mobile phase of 66.7% uninhibited THF and 33.3% of a 1g/L solution of ammonium formate in methanol (flow rate of 0.3 mL/min). The effluent from the liquid chromatograph is introduced into the MS and ionized in negative ion mode by electrospray ionization. MS and MS/MS data combinations are collected. The mass spectra were subjected to external calibration to generate accurate mass information within +/-10 mDa. After external calibration, empirical equations for MS and fragment ions were generated using accurate mass prediction software (Agilent Masshunter). In the case of using both the predicted empirical formula and the dissociation behavior of each parent ion, a proposed structure for each component has been provided.

All manipulations were performed under Ar atmosphere using standard Schlenk series glove box techniques unless otherwise indicated. Toluene, pentane and C₆D₆And THF at NaK/Ph₂Dried over CO/18-crown-6, distilled or vacuum transferred and stored on molecular sieves in a glove box filled with Ar. NMR spectra were recorded on a Varian Inova 500 spectrometer (¹H NMR，499.703MHz，¹³C NMR 125.580MHz)、Varian Inova 400(¹¹B NMR, 128.191MHz) Spectroscopy, Bruker 400(¹³C 100，¹¹B102 MHz). Chemical shifts are reported in δ (ppm). For the¹H and¹³c NMR spectrum with residual solvent peak as internal reference: (¹H NMR：C₆D₆Is delta 7.16, CD₃CN is 1.94, CDCl₃Is 7.26;¹³C NMR：CDCl₃is delta 77.16, CD₃CN 1.32). MALDI mass spectrometry of carborane anions by Texas A&The M university BioMass Spectrometry laboratory performed simulated MALDI (-) spectra were generated using a publicly available isotope distribution calculator and mass spectrometer plotter.¹For the¹¹B NMR use of BF₃·Et₂O is 0ppm at the external reference δ. NaH was purchased from Sigma-Aldrich and washed with hexane prior to use; 6-bromo-1-hexene, 4-bromo-1-butene, allyl bromide and 1-iodododecane were purchased from Matrix Scientific and used without further purification. 4-vinyl benzyl chloride was purchased from Sigma Aldrich. [ Me ]₃NH][CHB₁₁Cl₁₁]，²[ⁿOctyl₂MeNH]Cl and [ () ]ⁿC₁₈H₃₇)₂MeNH]Cl was synthesized according to the published procedure.

One or more features of the present disclosure are illustrated by means of the following examples:

example 1 Na [ R' CB₁₁Cl₁₁]General procedure for the Synthesis

A50 mL Schlenk flask was charged with 500mg [ Me₃NH][CHB₁₁Cl₁₁]And 2.5 equivalents NaH, to which was added 20mL of THF. The resulting suspension was stirred at room temperature for 2 hours until it stopped foaming. All volatiles were removed under vacuum and then 1.1 equivalents of R 'were added to 20mL THF'-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. NaCl was removed by filtering the solution through a short pad of celite. All volatiles were removed under reduced pressure. The residue was washed with cold pentane and further dried in vacuo to afford Na [ R' CB as a white solid₁₁Cl₁₁]. The following examples are characterized by proton nuclear magnetic resonance (H)¹NMR and carbon nuclear magnetic resonance (¹³CNMR), and boron NMR¹¹B NMR)。

Na [ allyl-CB₁₁Cl₁₁]: 427mg (85% yield).¹H NMR(500MHz，CD₃CN)：δ6.10(ddt，J＝17.2，9.9，7.4Hz，1H)，5.13(dq，J＝16.7，1.4Hz，1H)，5.08-5.01(dq，J＝16.7，1.4Hz，1H)，3.01(d，J＝7.3Hz，3H).¹¹B{¹H}NMR(128MHz，CD₃CN)：δ-3.03，-10.10，-11.73.¹³C{¹H}NMR(100MHz，CD₃CN)：δ130.5(s，CHCH₂)，120.4(s，CHCH₂) 49.5(brs, carborane-C), 35.6(s, CH)₂CHCH₂)。

Na [ butenyl-CB 1₁Cl₁₁]: 427mg Na [ butenyl-CB₁₁Cl₁₁](85% yield)¹H NMR(500MHz，CDCl₃)：δ5.72(ddt，J＝17.0，10.3，6.6Hz，1H)，5.08(ddd，J＝17.4，3.1，1.6Hz，1H)，5.03(ddd，J＝10.2，3.1Hz，1.6Hz，1H)，2.69-2.61(m，2H)，2.37(t，J＝8.9Hz，2H).¹¹B{¹H}NMR(128MHz，CDCl₃)：δ-3.87，-10.52，-11.63.¹³C{¹H}NMR(100MHz，CD₃CN)：δ137.6(s，CH₂CH₂CHCH₂)，116.6(s，CHCH₂) 50.6(brs, carborane-C), 31.4(s, CH)₂CH₂CHCH₂)，29.6(s，CH₂CH₂CHCH₂)。

Na [ hexenyl-CB₁₁Cl₁₁]: 300mg Na [ hexenyl-CB₁₁Cl₁₁](87% yield)¹H NMR(400MHz，CD₃CN)：δ5.77(ddt，J＝17.0，10.2，6.7Hz，1H)，4.99(dq，J＝17.2，1.7Hz，1H)，4.93(ddt，J＝10.2，2.3，1.2Hz，1H).2.30-2.20(m，2H)，2.07-1.97(m，2H)，1.90-1.75(m，2H)1.32(p，J＝7.4Hz，2H).¹¹B{¹H}NMR(128MHz，CD₃CN)：δ-2.94，-9.96，-11.58.¹³C{¹H}NMR(100MHz，CD₃CN)：ε139.2(s，CHCH₂)，115.3(s，CHCH₂) 51.4(brs, carborane-C), 33.6(s, α -CH)₂)，31.8(s，CH₂)，29.9(s，CH₂)，24.6(s，CH₂)。

Na [ vinylbenzyl CB ]₁₁Cl₁₁]：449mg(89％)。¹H NMR(500MHz，CD₂Cl₂)ε7.46(d，J＝8.2Hz，2H)，7.27(d，J＝8.2Hz，2H)，6.69(dd，J＝17.6，10.9Hz，1H)，5.75(d，J＝17.6Hz，1H)，5.24(d，J＝11.2Hz，1H)，3.67(s，2H).¹¹B{¹H}NMR(128MHz，CD₂Cl₂)：ε-3.32，-10.18，-11.16.¹³C{¹H}NMR(100MHz，CD₃CN)：δ137.5(s，CHCH₂) 137.0(s, Ph)134.8(s, Ph), 131.0(s, Ph), 125.4(s, Ph), 114.6(s, Ph), 49.5(brs, carborane-C), 36.1(s, PhCH)₂)。

Na [ decyl CB ]₁₁Cl₁₁]：1.46g(95％)。¹H NMR(500MHz，CDCl₃)δ2.27(t，J＝9.2Hz，2H)，2.10(s，4H)，1.41-1.07(m，12H)，0.87(t，J＝6.9Hz，3H).¹¹B{¹H}NMR(128MHz，CDCl₃)：δ-4.14，-10.59，-11.52.³C{¹H}NMR(100MHz，CD₃CN): Δ 49.5(brs, carborane-C), 32.4(s, decyl CH)₂) 31.8(s, decyl CH)₂) 30.5(s, decyl CH)₂) 30.0(s, decyl CH)₂) 29.9(s, decyl CH)₂) 29.8(s, decyl CH)₂) 29.4(s, decyl CH)₂) 24.9(s, decyl CH)₂) 23.2(s, decyl CH)₂) 14.4(s, decyl CH)₃)。

Example 2 [ alpha ], [ 2 ]ⁿOctyl radical₂MeNH][R′CB₁₁Cl₁₁]General synthesis of (a):

in a 50mL Schlenk flask, 300mg of Na [ R' CB₁₁Cl₁₁]A solution in 10mL of THF is added to 1.1 equivalent of [ 2 ], [ⁿOctyl radical₂MeNH]Cl in 10mL THF. Upon mixing, a precipitate formed immediately. The mixture was stirred for a further 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 [ [ 2 ] ])ⁿOctyl radical₂MeNH]Cl) and concentrated under vacuum to provide the product.

[ⁿOctyl radical₂MeNH][ allyl-CB ]₁₁Cl₁₁]：360mg(78％)。¹H NMR(500MHz，CDCl₃)：δ6.16(ddt，J＝17.2，9.9，7.4Hz，1H)，5.20(dq，J＝16.7，1.4Hz，1H)，5.12(dq，J＝16.7，1.4Hz，1H)，3.01(d，J＝7.3Hz，3H)，3.15(Vt，J＝7.5Hz，4H)，3.08(d，J＝7.4Hz，2H)，2.97(s，3H)，1.80(p，J＝8.0Hz，4H)，1.44-1.21(m，22H)，0.89(t，J＝7.0Hz，3H).¹¹B{¹H}NMR(128MHz，CDCl₃)：δ-3.53，-10.47，-11.75.¹³C{¹H}NMR(126MHz，CD₃CN)：ε137.6(s，CHCH₂，1C)，116.5(s，CHCH₂，1C)，57.1(s，α-CH₂2C), 54.0(brs, carborane-C, 1C), 40.8(s, N-Me, 1C), 32.3(s, CH)₂，2C)，29.6(s，CH₂，2C)，29.5(s，CH₂CHCH₂，1C)，26.9(s，CH₂，2C)，24.5(s，CH₂，2C)，23.3(s，CH₂2C), 14.4(s, end-Me, 2C).

[ⁿOctyl radical₂MeNH][ butenyl-CB₁₁Cl₁₁]：360mg(80％)。¹H NMR(500MHz，CDCl₃)：ε6.16(ddt，J＝17.2，9.9，7.4Hz，1H)，5.20(dq，J＝16.7，1.4Hz，1H)，5.12(dq，J＝16.7，1.4Hz，1H)，3.01(d，J＝7.3Hz，3H)，3.15(vt，J＝7.5Hz，4H)，3.08(d，J＝7.4Hz，2H)，2.97(s，3H)，1.80(p，J＝8.0Hz，4H)，1.44-1.21(m，22H)，0.89(t，J＝7.0Hz，3H).¹¹B{¹H}NMR(128MHz，CDCl₃)：ε-3.81，-10.58，-11.80.³C{¹H}NMR(126MHz，CDCl₃)：ε136.5(s，CHCH₂，1C)，116.1(s，CHCH₂，1C)，57.7(s，α-CH₂2C), 50.4(brs, carborane-C, 1C), 41.5(s, N-Me), 31.5(s, CH)₂，2C)，30.4(s，CH₂CH₂CHCH₂，1C)，28.9(s，CH₂，2C)，28.7(s，CH₂CH₂CHCH₂，1C)，26.2(s，CH₂，2C)，24.5(s，CH₂，2C)，22.5(s，CH₂2C), 14.0(s, terminal CH)₃，2C)。

[ⁿOctyl radical₂MeNH][ hexenyl-CB ]₁₁Cl₁₁]：410mg(85％)。¹H NMR(500MHz，CDCl₃)：δ7.04(s，1H)，5.77(ddt，J＝17.0，10.2，6.7Hz，1H)，5.00(dq，J＝17.5，3.3Hz，1H)，4.94(dq，J＝17.5，3.3Hz，1H)，3.12(t，J＝8.3Hz，4H)，2.93(s，3H)，2.28(t，J＝9.0Hz，2H)，2.05(dd，J＝14.7，6.9Hz，2H)，1.96-1.85(m，2H)，1.84-1.73(m，2H)，1.45-1.20(m，24H)，0.88(t，J＝6.9Hz，6H).¹¹B{¹H}NMR(128MHz，CDCl₃)：ε-3.61，-10.39，-11.70.¹³C{¹H}NMR(126MHz，CDCl₃)：ε138.1(s，CHCH₂，1C)，114.8(s，CHCH₂，1C)，57.8(s，α-CH₂2C), 51.1(brs, carborane-C, 1C), 41.6(s, N-Me), 33.0(s, hexyl-CH)₂，1C)，31.6(s，CH₂2C), 31.0(s, hexyl-CH)₂1C), 29.4(s, hexyl-CH)₂，1C)，28.9(s，CH₂，2C)，26.3(s，CH₂，2C)，24.6(s，CH₂2C), 23.9(s, hexyl-CH)₂，1C)，22.6(s，CH₂2C), 14.1(s, terminal CH)₃，2C)。

[ⁿOctyl radical₂MeNH][CH₂＝CHC₆H₄CH₂CB₁₁Cl¹ ₁]：500mg(82％).¹H NMR(500MHz，CDCl₃)ε7.46(d，J＝8.3Hz，2H)，7.25(d，J＝8.3Hz，2H)，6.67(dd，J＝17.7，10.8Hz，1H)，5.73(d，J＝17.6Hz，1H)，5.23(d，J＝10.9Hz，1H)，3.67(s，2H)，3.15(t，J＝8.4Hz，4H)，2.97(s，3H)，1.84-1.71(m，4H)，1.43-1.18(m，22H)，0.88(t，J＝7.0Hz，6H).¹¹B{¹H}NMR(128MHz，CDCl₃)：δ-3.18，-10.42，-11.78..¹³C{¹H}NMR(126MHz，CDCl₃/CD₃CN)δ137.6(s，sp²-C，1C)，137.2(s，sp²-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-CH₂2C), 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，CH₂，4C)，26.9(s，CH₂，2C)，24.4(s，CH₂，2C)，23.2(s，CH₂，2C)，14.3(s，CH₂，2C)。

[ⁿOctyl radical₂MeNH][ decyl-CB₁₁Cl₁₁]：400mg(88％)。¹H NMR(500MHz，C₆D₆)δ4.67(s，1H)，2.76(t，J＝8.4Hz，2H)，2.33-2.17(m，4H)，2.10-2.00(m，2H)，1.90(d，J＝5.5Hz，3H)，1.42-1.33(m，4H)，1.33-1.06(m，30H)，0.99(t，J＝7.2Hz，6H)，0.90(t，J＝7.0Hz，3H).¹¹B{¹H}NMR(128MHz，CDCl₃)：δ-3.09，-10.04，-11.72.¹³C{¹H}NMR(100MHz，CD₃CN)δ57.3(s，α-CH₂2C), 51.5(brs, carborane-C, 1C), 41.0(s, N-Me), 32.6(s, decyl-. alpha.c-CH)₂，1C)，32.4(s，CH₂2C), 32.0(s, decyl-CH)₂1C), 30.6(s, decyl-CH)₂1C), 30.1(s, decyl-CH)₂1C), 30.0(s, decyl-CH)₂1C), 29.9(s, decyl-CH)₂，1C)，29.7(s，CH₂，2C)，29.6(s，CH₂2C), 29.4(s, decyl-CH)₂，1C)，27.0(s，CH₂2C), 25.1(s, decyl-CH)₂，1C)，24.8(s，CH₂2C), 23.4(s, decyl-CH)₂，1C)，23.3(s，CH₂2C), 14.4(s, terminal CH)₃，3C)。

Example 3- [, (ⁿC₁₈H₃₇)₂MeNH][R′CB₁₁Cl₁₁]General synthesis of (a):

at 50mL of SchInto a lenk flask, 300mg of Na [ R' CB₁₁Cl₁₁]The solution in 10mL of THF was added to 1.1 equivalents [ ((R))ⁿC₁₈H₃₇)₂MeNH]Cl in 10ml THF. Upon mixing, a precipitate formed immediately. The mixture was stirred for a further 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 [ (ii))ⁿC₁₈H₃₇)₂MeNH]Cl) and concentrated under vacuum to provide the product. Each of the following examples/products is given by H¹NMR and C¹³And (5) NMR characterization.

[(ⁿC₁₈H₃₇)₂MeNH][ allyl-CB ]₁₁Cl₁₁]：425mg(85％)。¹H NMR(500MHz，C₆D₆)：δ6.40(brs，NH)，6.05(ddt，J＝17.2，9.9，7.4Hz，1H)，5.09(dq，J＝16.7，1.4Hz，1H)，5.02(dq，J＝16.7，1.4Hz，1H)，3.14-2.96(m，6H，N-CH₂，α-CH₂)，2.88(d，J＝5.4Hz，3H，N-CH₃)，1.75-1.66(m，4H，CH₂)，1.32-1.16(m，60H，CH₂) 0.78(t, J ═ 6.9Hz, 3H, end-Me).¹¹B{¹H } NMR (160MHz, toluene-d₈)：δ-2.74，-9.58，-10.87.¹³C{¹H } NMR (126MHz, acetone-d₆，)：δ137.6(s，CHCH₂，1C)，116.5(s，CHCH₂，1C)，57.1(s，α-CH₂2C), 54.0(brs, carborane-C, 1C), 40.9(s, N-Me), 32.6(s, CH)₂，2C)，30.4-29.6(m，CH₂，24C)，29.5(s，CH₂CHCH₂，1C)，26.8(s，CH₂，2C)，24.4(s，CH₂，2C)，23.3(s，CH₂2C), 14.4(s, terminal CH)₃，2C)。

[(ⁿC₁₈H₃₇)₂MeNH][ butenyl-CB₁₁Cl₁₁]：300mg(85％)。¹H NMR(500MHz，CDCl₃)：δ5.70(ddt，J＝16.9，10.2，6.6Hz，1H)，5.06(dq，J＝17.1，1.5Hz，1H)，5.00(dq，J＝10.2，1.4Hz，1H)，3.14-2.96(m，6H，N-CH₂，α-CH₂)，2.98(s，3H，N-CH₃) 2.65-2.60(m, 2H, hexyl-CH)₂) 2.35(t, J ═ 8.9Hz, 2H, hexyl-CH₂)，1.82-1.76(m，4H，CH₂)，1.41-1.25(m，60H，CH₂) 0.88(t, J ═ 7.0Hz, 3H, end-Me).¹¹B{¹H}NMR(128MHz，CD₃CN)：δ-2.87，-9.93，-11.60.¹³C{¹H}NMR(126MHz，CDCl₃)：δ138.9(s，CHCH₂，1C)，116.2(s，CHCH₂，1C)，57.8(s，α-CH₂2C), 51.2(brs, carborane-C, 1C), 41.8(s, N-Me), 32.0(s, CH)₂，2C)，30.6(s，CH₂CH₂CHCH₂，1C)，30.4-29.6(m，CH₂，24C)，28.9(s，CH₂CHCH₂，1C)，26.5(s，CH₂，2C)，24.5(s，CH₂，2C)，22.8(s，CH₂2C), 14.3(s, terminal CH)₃，2C)。

[(ⁿC₁₈H₃₇)₂MeNH][ hexenyl-CB₁₁Cl₁₁]：300mg(83％)。¹H NMR(500MHz，CDCl₃)：δ6.19(brs，NH)，5.77(ddt，J＝16.9，10.2，6.7Hz，1H)，5.00(dq，J＝17.1，1.6Hz，1H)，4.94(dq，J＝10.2，1.2Hz，1H)，3.25-3.08(m，6H，N-CH₂，α-CH₂)，2.99(d，J＝4.9Hz，3H，N-CH₃) 2.29(vt, J ═ 9.6Hz, 2H, hexyl α C), 2.05(qt, J ═ 6.8, 1.3Hz, 2H, hexyl-CH)₂)，1.93-1.77(m，6H，CH₂)，1.32-1.16(m，62H，CH₂) 0.88(t, J ═ 7.0Hz, 3H, end-Me).¹¹B{¹H}NMR(128MHz，CD₃CN)：ε-2.97，-9.99，-11.62.¹³C{¹H}NMR(126MHz，CDCl₃，)：δ¹³C{¹H}NMR(126MHz，CDCl₃)：δ138.4(s，CHCH₂，1C)，114.9(s，CHCH₂，1C)，57.9(s，α-CH₂2C), 51.7(brs, carborane-C, 1C), 41.9(s, N-Me), 33.2(s, hexyl-CH)₂，1C)，32.1(s，CH₂2C), 31.2(s, hexyl-CH)₂，1C)，30.4-29.6(m，CH₂24C), 29.6(s, hexyl-CH)₂，1C)，26.4(s，CH₂，2C)，24.5(s，CH₂2C), 24.0(s, hexyl-CH)₂，1C)，22.8(s，CH₂2C), 14.3(s, terminal CH)₃，2C)。

[(ⁿC₁₈H₃₇)₂MeNH][ styryl-CB₁₁Cl₁₁]：330mg(82％)。¹H NMR (400MHz, chloroform-d) δ 7.47(d, J ═ 8.1Hz, 2H), 7.24(d, J ═ 8.1Hz, 2H), 6.66(dd, J ═ 17.6, 10.9Hz, 2H), 5.73(d, J ═ 17.6Hz, 1H), 5.23(d, J ═ 10.9Hz, 0H), 3.67(s, 2H), 3.24-2.93(m, 4H), 2.86(d, J ═ 5.1Hz, 3H, N-Me), 1.35-1.26(m, CH-d), c, H, N-Me), and c₂60H)，0.88(t，J＝6.8Hz，6H).¹¹B{¹H}NMR(128MHz，CD₃CN)：δ-2.70，-9.95，-11.35.¹³C{¹H}NMR(126MHz，CDCl₃)：δ136.8(s，CHCH₂，1C)，136.5(s，Ar，1C)，134.1(s，Ar，2C)，130.2(s，Ar，1C)，124.9(s，Ar，2C)，114.0(s，CHCH₂，1C)，57.5(s，α-CH₂2C), 49.2(brs, carborane-C, 1C), 41.3(s, N-Me, 1C), 35.6(s, benzyl-CH)₂，1C)，32.0(s，CH₂，4C)，29.8-29.6(m，CH₂，22C)，29.5(s，CH₂，2C)，29.4(s，CH₂，2C)，29.3(s，CH₂，2C)，29.0(s，CH₂，2C)，26.3(s，CH₂，2C)，24.4(s，CH₂，2C)，22.7(s，CH₂2C), 14.2(s, terminal CH)₃，2C)。

[(ⁿC₁₈H₃₇)₂MeNH][ decyl-CB₁₁Cl₁₁]：340mg(80％)。¹H NMR (400MHz, chloroform-d) delta 6.16(brs, N-H, 1H), 3.27-3.08(m, N-CH)₂4H), 2.99(d, J ═ 5.2Hz, N-Me, 3H), 2.28-2.24(m, α -decyl-CH)₂，2H)，1.87-1.74(m，CH₂，6H)，1.41-1.26(m，CH₂76H), 0.87(t, J ═ 6.7Hz, terminal — CH)₃，9H).¹¹B{¹H}NMR(128MHz，CD₃CN)：δ-3.22，-10.05，-11.38.¹³C{¹H}NMR(126MHz，CDCl₃)：δ58.1(s，α-CH₂2C), 51.5(brs, carborane-C, 1C), 41.9(s, N-Me, 1C), 32.01(s, N-alkyl-CH)₂2C)31.96(s, decyl-CH)₂1C), 31.3(s, decyl-CH)₂1C), 30.3(s, decyl-CH)₂，1C)，29.8-29.3(m，CH₂，34C)，29.0(s，CH₂，2C)，26.4(s，CH₂，2C)，24.7(s，CH₂2C), 24.5(s, decyl-CH)₂2C), 22.77(s, N-alkyl-CH)₂2C), 22.74(s, decyl-CH)₂1C), 14.21(s, N-alkyl terminal CH)₃2C), 14.19(s, decyl-terminal-CH)₃)。

Example 4 polymerization of 1-octene

Polyoctene is prepared by mixing procatalyst 1 and olefin-substituted cocatalyst 1 in 1-octene. The average molecular weight of the polyoctene end product was previously determined by size exclusion chromatography to have an Mn of 1449 amu. In addition to the olefin incorporation, the carborane activator also contains eleven boron atoms (black dots in cocatalyst 1), eleven chlorine atoms, and a fixed negative charge. To confirm the binding of anions in the polyolefin (polyoctene), the reaction mixture and additional controls were analyzed using mass spectrometry.

Negative mode flow injection mass spectrometry was performed on polyoctenamer produced from the catalyst and alkene-substituted carborane activator to determine if carborane was incorporated into polyoctenamer. In FIG. 1, a single charge distribution of ions is observed with a spacing of m/z 112. M/z 786.056 (i.e., represented as O in the mass spectrum) was studied in one step₂C) And it is associated with C₂₀H₃₇B₁₁Cl₁₁The empirical formula of (2) is consistent, with a mass error of 5 mDa. Empirical formula C₂₀H₃₇B₁₁Cl₁₁The theoretical isotope modeling of (a) was matched to the isotope distribution and relative abundance of the experimental data (fig. 3). According to empirical formula and periodicity of 112amu, m/z 786.056 is consistent with carborane activators polymerized with two octene monomers. The m/z 786.056 was then fragmented to help confirm covalent binding of the carborane activator. The energy of the initial fragmentation conditions is not sufficient to produce fragment ions (i.e. 35V), where 70V is required to produce fragmentation. Upon fragmentation, homolytic cleavage of carbon-carbon bonds at the boron cage olefin-linker was observed in the spectra of fig. 4. This observation, and results significantly higher than normal fragmentation conditions, indicate that the carborane activator has been covalently incorporated into the polyoctene, since no intact alkene-containing carborane starting agent was observed as a fragment ion. In addition to this peak, other ion signals in the mass spectrum were studied. In general, the m/z 786.056 peak serves as a representative example of other ion signals. Accurate mass analysis, isotopic modeling and fragmentation of the additional ion signal (m/z 890-. For comparison purposes, C3 (having the formula [ B ]) was compared by catalyst P1 and a hydrogen-substituted (olefin-free) carborane activator₁₁Cl₁₁CH]^-Anions) were analyzed using the negative mode mass spectrum and data report of the flow injection analysis of figure 5. Mass spectrometry showed that comparative C3 was not incorporated into the polymer chain. The only signal in the mass spectrum in FIG. 5 is that corresponding to [ B ]₁₁Cl₁₁CH]^-Anion(s)Of the signal of (1).

Example 5 polymerization results

To obtain the data recorded in table 1, the polymerization was carried out according to the procedure described in the section of polymerization of 1-octene. To obtain the data shown in table 2, the polymerization was carried out according to the procedure described previously in the general procedure section for ethylene/1-octene copolymerization. The activator efficiencies and resulting polymer characteristics of cocatalysts 1 to 7 were evaluated, each anion in cocatalysts 1 to 7 having an anion according to formula (I) -as well as a catalyst (catalyst 1) putatively formed from a bis ((phenylphenoxy) structure according to formula (X) (procatalyst 3, herein "P3") and two other catalysts as previously described in the disclosure (procatalyst 1, herein "P1", and procatalyst 2, herein "P2").

Each of cocatalysts 1 to 7, as well as comparative cocatalyst C1 and comparative cocatalyst C2, comparative cocatalyst C3 and comparative cocatalyst C4 (herein comparative C1 "," comparative C2 "," comparative C3 ", and" comparative C4 "), were mixed with one of procatalyst 1, procatalyst 2, or procatalyst 3 to form sixteen catalyst systems. Comparative C1 is a compound having a tetrakis (pentafluorophenyl) borate anion and⁺NH(Me)(C₁₈H₃₇)₂a compound as a counter cation. Comparative C1 has been successfully used for olefin polymerization on a commercial scale.

Table 1: polyoctene screening

Wrt means "about"

The density of the polymers produced by cocatalysts 1 to 7 was measured at 0.86. + -. 0.05g/cm³。

To avoid cross-contamination, 1-octene was polymerized in glass bottles. This process is described in the preceding paragraph. The polyoctene produced was measured by broad-band dielectric spectroscopy. FIGS. 6 to 9 show broadband dielectric spectra. Each polymer produced by the catalyst system exhibited a slope of-1 at low frequencies, indicating that ion diffusion is a major contributor to dissipation factor. The graph of fig. 6 shows that comparative C1 and comparative C2 exhibit similar dissipation factors, while polymers produced from catalyst systems comprising cocatalysts 1, 2, 3, and 4 exhibit dissipation factors that are 10 times less than the comparative cocatalysts. The difference between comparing C2 with cocatalysts 1, 2, 3 and 4 is that cocatalysts 1, 2, 3 and 4 are at R¹The sites include vinyl terminated olefins. Comparison C2 and cocatalysts 1, 2, 3 and 4 have similar dimensions, and therefore, this can be expected if they have similar diffusion rates. Thus, a 10-fold smaller drop compared to the comparative co-catalyst indicates that: each of cocatalysts 1, 2, 3 and 4 has been incorporated into the polyoctene backbone, is not free to diffuse, and thus has a lower dissipation factor C2 than the unbound comparative C2.

Dissipation factor testing was performed using a Novocontrol Alpha a dielectric analyzer and custom sample cell. The samples were measured between 0.01Hz and 1MHz at room temperature and 1.5 VAC. Briefly, the sample cell is first measured with dry air to obtain a background measurement. Then, a clean spatula was used to place the high viscosity polyoctene sample on one of the electrodes and the test cell was closed. Excess polyoctene is pushed out of the electrode into the adjacent channel as designed. The dissipation factor of the entire test cell was then measured. Thereafter, the test cell was cleaned with toluene and allowed to dry completely before the next measurement. Five different polyoctene samples were provided; three were made with the cocatalyst comparative C1, one with carborane and one with allyl-substituted carborane. To confirm reproducibility, each sample was measured at least twice.

Table 2: ethylene/octene copolymer screening

The equivalent of cocatalyst to procatalyst was 1.2.

The dissipation factors of the ethylene-octene copolymers recorded in table 2 were measured, and the resulting spectra are shown in fig. 8 and 9. Fig. 8 shows the spectra of two comparative examples of ethylene-octene copolymers produced by procatalyst P3 and comparative cocatalysts C1 or C3 and ethylene-octene copolymers produced by procatalyst P3 and cocatalyst 7. The dissipation factor of the polymer produced by cocatalyst 7 is ten times smaller than the dissipation factor.

Fig. 9 shows spectra of two comparative examples of ethylene-octene copolymers produced by procatalyst P2 and comparative cocatalysts C1 or C3 and ethylene-octene copolymers produced by procatalyst P2 and cocatalyst 7. Similar to the dissipation factors for the polymers produced by cocatalyst 7 and procatalyst P3 and shown in fig. 8, the dissipation factors for the polymers produced by cocatalyst 7 and procatalyst P2 were ten times less than the dissipation factors for the polymers produced by procatalyst P3 and comparative cocatalyst C1 and the polymers produced by procatalyst P3 and comparative cocatalyst C3.