阅读说明：本技术 作为烯烃聚合催化剂活化剂的弱配位阴离子的第iii族阴离子络合物 (Group III anionic complexes of weakly coordinating anions as activators for olefin polymerization catalysts ) 是由 T·D·塞内卡尔 S·穆霍帕迪亚 R·J·基顿 J·克洛西 R·华兹杰 D·M·皮尔森 于 2020-03-24 设计创作，主要内容包括：实施例包括具有根据式(I)的结构的活化剂。(Embodiments include activators having a structure according to formula (I).)

1. An activator having a structure according to formula (I):

wherein:

m is a metal in the +3 oxidation state selected from boron, aluminum, gallium, scandium, yttrium or the lanthanide series;

[Cat]⁺is a cation;

R¹、R²、R³、R⁴ R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵and R¹⁶Independently selected from (C)₁-C₄₀) Alkyl, (C)₆-C₄₀) Aryl, -H, -NR^C ₂、-OR^C、–SR^COr halogen, wherein each R^CIndependently is (C)₁-C₃₀) A hydrocarbyl group or-H, with the proviso that R^1-4And R^5-8And R^9-12And R^13-16One of (A) is fluorine substituted₁-C₄₀) Alkyl, fluoro substituted (C)₆-C₄₀) Aryl or-F; and

R¹⁷and R¹⁸Is (C)₁-C₄₀) Alkyl, (C)₁-C₄₀) Heteroalkyl, fluoro substitutedIs (C)₁-C₄₀) Alkyl or fluoro substituted (C)₆-C₄₀) And (4) an aryl group.

2. The activator of claim 1, wherein R¹、R²、R³、R⁴ R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶Independently is (C)₁-C₁₀) Alkyl, -F or-H, with the proviso that R^1-4And R^5-8And R^9-12And R^13-16One of (A) is fluorine substituted₁-C₁₀) Alkyl or-F.

3. An activator according to claim 1 or claim 2, wherein R is¹⁷And R¹⁸Is (C)₁-C₁₀) An alkyl group.

4. An activator according to any one of claims 1 to 3, wherein [ Cat ™ ]⁺]Is a protonated tertiary amine.

5. An activator according to any one of the preceding claims, wherein [ Cat ™ ]]⁺Is composed of⁺N(H)R^N ₃Wherein each R is^NIndependently is (C)₁-C₂₀) An alkyl group.

6. An activator according to any one of the preceding claims wherein:

R¹、R²、R³and R⁴At least one of which is-F or fluoroalkyl;

R⁵、R⁶、R⁷and R⁸At least one of which is-F or fluoroalkyl;

R⁹、R¹⁰、R¹¹and R¹²At least one of which is-F or fluoroalkyl; and

R¹³、R¹⁴、R¹⁵and R¹⁶At least one of which is-F or fluoroalkyl.

7. An activator according to any one of claims 1 to 5 wherein:

R¹、R²、R³and R⁴At least two of which are-F or fluoroalkyl;

R⁵、R⁶、R⁷and R⁸At least two of which are-F or fluoroalkyl;

R⁹、R¹⁰、R¹¹and R¹²At least two of which are-F or fluoroalkyl; and

R¹³、R¹⁴、R¹⁵and R¹⁶At least two of which are-F or fluoroalkyl groups.

8. An activator according to any one of claims 1 to 5 wherein:

R¹、R²、R³and R⁴At least three of which are-F or fluoroalkyl;

R⁵、R⁶、R⁷and R⁸At least three of which are-F or fluoroalkyl;

R⁹、R¹⁰、R¹¹and R¹²At least three of which are-F or fluoroalkyl; and

R¹³、R¹⁴、R¹⁵and R¹⁶At least three of which are-F or fluoroalkyl groups.

9. An activator according to any one of claims 1 to 5 wherein:

R¹、R²、R³and R⁴At least four of which are-F or fluoroalkyl;

R⁵、R⁶、R⁷and R⁸At least four of which are-F or fluoroalkyl;

R⁹、R¹⁰、R¹¹and R¹²At least four ofis-F or fluoroalkyl; and

R¹³、R¹⁴、R¹⁵and R¹⁶At least four of which are-F or fluoroalkyl groups.

10. A catalyst system comprising an activator according to any one of claims 1 to 9 and a procatalyst, wherein the procatalyst exhibits catalytic activity by contacting the procatalyst with the activator.

11. A process for the polymerization of olefins comprising polymerizing ethylene and optionally (C) in the presence of the catalyst system according to claim 10₃-C₄₀) Alpha-olefins.

Technical Field

Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and methods, and more particularly to catalyst systems including a procatalyst and an anionic yttrium complex or cocatalyst.

Background

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.

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.

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 ferrocene, silver or lead; or a highly lewis acidic cation such as carbonium or silylium.

Disclosure of Invention

Desirable characteristics of activators in polymer systems include increased olefin-based polymer production, increased procatalyst activation rates, increased overall catalyst efficiency to enable the catalyst system to operate at high temperatures, enabling the catalyst system to provide consistent polymer compositions, and the ability of the activators to decompose after olefin polymerization is complete. Derived from the non-coordinating anion tetrakis (pentafluorophenyl) borate^-B(C₆F₅)₄) Capture many of these desirable characteristics.

There is a continuing need for activators that activate metal-ligand procatalysts efficiently and perform well at high temperatures.

Embodiments of the present disclosure include activators having a structure according to formula (I):

in formula (I), M is a metal in the +3 oxidation state, the metal being selected from boron, aluminium, gallium, scandium, yttrium or the lanthanides and [ Cat]⁺Is a cation.

In the formula (I), R¹、R²、R³、R⁴ R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶Is independently selected from(C₁-C₄₀) Alkyl, (C)₆-C₄₀) Aryl, -H, -NR^N ₂、-OR^C、–SR^COr halogen, wherein each R^CAnd each R^NIndependently is (C)₁-C₃₀) A hydrocarbyl group or-H, with the proviso that R^1-4And R^5-8And R^9-12And R^13-16One of (A) is fluorine substituted₁-C₄₀) Alkyl, fluoro substituted (C)₆-C₄₀) Aryl or-F; and each R¹⁷And R¹⁸Is (C)₁-C₄₀) Alkyl, (C)₁-C₄₀) Heteroalkyl, or-F.

Detailed Description

Specific examples of catalyst systems will now be described. It is to be understood that the catalyst systems of the present disclosure may be embodied in different forms and should not be construed as limited to the particular embodiments set forth in the disclosure.

Common abbreviations are listed below:

r, Y, M, L, Q and n: as defined above; me: a methyl group; et: an ethyl group; ph: a phenyl group; bn: a benzyl group; i-Pr: isopropyl group; t-Bu: a tertiary butyl group; t-Oct: tert-octyl (2,4, 4-trimethylpentan-2-yl); tf: trifluoromethanesulfonate; (^tBu^FO)₃Al：Al(OC(CF₃)₃)₃(ii) a KHMDS: potassium hexamethyldisilazane; MTBE: methyl tert-butyl ether; TEA: triethyl aluminum; THF: tetrahydrofuran; et (Et)₂O: diethyl ether; CH (CH)₂Cl₂: dichloromethane; MTBE: methyl tert-butyl ether; CV: column volume (for column chromatography); EtOAc: ethyl acetate; c₆D₆: deuterated benzene or benzene-d 6: CDCl₃: deuterated chloroform; na (Na)₂SO₄: sodium sulfate; MgSO (MgSO)₄: magnesium sulfate; HCl: hydrochloric acid; n-BuLi: butyl lithium; t-BuLi: tert-butyl lithium; n is a radical of₂: nitrogen gas; PhMe: toluene; PPR: parallel polymerization reactors; MAO: methylaluminoxane; MMAO: modified methylaluminoxane; GC: gas chromatography; LC: liquid chromatography; NMR: nuclear magnetic resonance; MS: mass spectrometry; mmol: millimole; mL: ml; m: molar ratio; min or mins: the method comprises the following steps of (1) taking minutes; h or hrs: hours; d: day; r_f(ii) a The fraction is retained; TLC: thin layer chromatography; rpm: rpm.

The term "independently selected" is used herein to indicate an R group, such as R¹、R²、R³、R⁴And R⁵May be the same or different (e.g., R)¹、R²、R³、R⁴And R⁵All may be substituted alkyl or R¹And R²May be substituted alkyl and R³May be aryl, etc.). The chemical name associated with the R group is intended to convey the chemical structure recognized in the art as corresponding to the chemical name. Accordingly, chemical designations are intended to supplement and illustrate rather than to exclude structural definitions known to those skilled in the art.

The term "procatalyst" refers to a compound that has catalytic activity when combined with an activator. 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.

When used to describe certain chemical groups containing carbon atoms, have the form "(C)_x-C_y) The parenthetical expression of "means that the unsubstituted form of the chemical group has from x carbon atoms to y carbon atoms, including x and y. For example, (C)₁-C₅₀) Alkyl is an alkyl group having 1 to 50 carbon atoms in its unsubstituted form. In some embodiments and general structures, certain chemical groups may be substituted with one or more substituents such as R^SAnd (4) substitution. Use of "(C)_x-C_y) "defined in parentheses by R^SThe substituted chemical group may contain more than y carbon atoms depending on any group R^SThe kind of (2). For example, "exactly one radical R^SSubstituted (C)₁-C₅₀) Alkyl radical, wherein R^SIs phenyl (-C)₆H₅) "may contain 7 to 56 carbon atoms. Therefore, in general, when the insert word "(C) is used_x-C_y) "chemical groups definedBy one or more substituents R containing carbon atoms^SWhen substituted, by adding both x and y to the substituents R from all carbon-containing atoms^STo determine the minimum and maximum total number of carbon atoms for the chemical group.

The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom in a corresponding unsubstituted compound or functional group is substituted (e.g., R)^S) And (6) replacing. The term "-H" means a hydrogen or hydrogen group covalently bonded to another atom. "hydrogen" and "-H" are interchangeable and have the same meaning unless explicitly specified otherwise.

The term "halogen-substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom corresponding to an unsubstituted compound or functional group is replaced with a halogen. The terms "halogen-substituted" and "halogenated" are interchangeable. The term "perhalogenated" means that each hydrogen atom (-H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is replaced with a halogen. The term "fluoro substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom in a corresponding unsubstituted compound or functional group is replaced with a fluorine atom. The term "fluoroalkyl" refers to a fluorine substituted (C)₁-C₁₀) Alkyl radical, wherein (C)₁-C₁₀) At least one hydrogen atom bonded to a carbon atom of the alkyl group is replaced by a fluorine atom.

In the present disclosure, the term "halogen atom" or "halogen" means a group of fluorine atom (F) or chlorine atom (Cl). The term "halide" means the anionic form of the halogen atom: fluoride ion (F)^-) Or chloride ion (Cl)^-)。

Term "(C)₁-C₅₀) The hydrocarbon group "means a hydrocarbon group having 1 to 50 carbon atoms, and the term" (C)₁-C₅₀) By hydrocarbylene "is meant a hydrocarbon diradical having from 1 to 50 carbon atoms, wherein each hydrocarbyl group and each hydrocarbon diradical is aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (having three carbon atoms or more and including monocyclic and polycyclic, fused and non-fused polycyclic and bicyclic), or acyclicAnd is substituted by one or more R^SSubstituted or unsubstituted.

In the present disclosure, (C)₁-C₅₀) The hydrocarbon radical may be unsubstituted or substituted (C)₁-C₅₀) Alkyl, (C)₃-C₅₀) Cycloalkyl group, (C)₃-C₂₀) Cycloalkyl- (C)₁-C₂₀) Alkylene, (C)₆-C₄₀) Aryl or (C)₆-C₂₀) Aryl radical- (C)₁-C₂₀) Alkylene (e.g. phenyl (-CH)₂-C₆H₅))。

Term "(C)₁-C₅₀) Alkyl "and" (C)₁-C₁₈) Alkyl "means unsubstituted or substituted by one or more R^SSubstituted saturated straight or branched hydrocarbon groups having 1 to 50 carbon atoms and saturated straight or branched hydrocarbon groups having 1 to 18 carbon atoms. Unsubstituted (C)₁-C₅₀) Examples of alkyl groups are unsubstituted (C)₁-C₂₀) An alkyl group; unsubstituted (C)₁-C₁₀) An alkyl group; unsubstituted (C)₁-C₅) An alkyl group; a methyl group; an ethyl group; 1-propyl group; 2-propyl; 1-butyl; 2-butyl; 2-methylpropyl; 1, 1-dimethylethyl; 1-pentyl; 1-hexyl; 1-heptyl; 1-nonyl; and a 1-decyl group. Substituted (C)₁-C₄₀) Examples of alkyl groups are substituted (C)₁-C₂₀) Alkyl, substituted (C)₁-C₁₀) Alkyl, trifluoromethyl, and [ C₄₅]An alkyl group. The term "[ C ]₄₅]Alkyl "means that up to 45 carbon atoms are present in the group comprising the substituent, and is, for example, independently (C)₁-C₅) One R of alkyl^SSubstituted (C)₂₇-C₄₀) An alkyl group. Each (C)₁-C₅) The alkyl group may be methyl, trifluoromethyl, ethyl, 1-propyl, 1-methylethyl or 1, 1-dimethylethyl.

Term "(C)₆-C₅₀) Aryl "means unsubstituted or substituted with 6 to 40 carbon atoms (one or more R)^S) Substituted monocyclic, bicyclic or tricyclic aromatic hydrocarbon radicals having at least 6 to 14 carbon atomsIs an aromatic ring carbon atom. Monocyclic aromatic hydrocarbon groups include one aromatic ring; the bicyclic aromatic hydrocarbon group has two rings; and the tricyclic aromatic hydrocarbon group has three rings. When a bicyclic or tricyclic aromatic hydrocarbon group is present, at least one of the rings of the group is aromatic. The other ring or rings of the aromatic group may independently be fused or unfused and aromatic or non-aromatic. Unsubstituted (C)₆-C₅₀) Examples of aryl groups include: unsubstituted (C)₆-C₂₀) Aryl, unsubstituted (C)₆-C₁₈) An aryl group; a phenyl group; a fluorenyl group; a tetrahydrofluorenyl group; indacenyl (indacenyl); hexahydroindacenyl; an indenyl group; a dihydroindenyl group; a naphthyl group; tetrahydronaphthyl; and phenanthrene. Substituted (C)₆-C₄₀) Examples of aryl groups include: substituted (C)₁-C₂₀) An aryl group; substituted (C)₆-C₁₈) An aryl group; 2, 4-bis ([ C ]₂₀]Alkyl) -phenyl; 2- (C)₁-C₅) Alkyl-phenyl; a polyfluorophenyl group; pentafluorophenyl; and fluoren-9-on-1-yl.

Term "(C)₃-C₅₀) Cycloalkyl "means unsubstituted or substituted by one or more R having from 3 to 50 carbon atoms^SA substituted saturated cyclic hydrocarbyl group. Other cycloalkyl groups (e.g., (C)_x-C_y) Cycloalkyl) are defined in an analogous manner as having x to y carbon atoms and being unsubstituted or substituted by one or more R^SAnd (4) substitution. Unsubstituted (C)₃-C₄₀) Examples of cycloalkyl are unsubstituted (C)₃-C₂₀) Cycloalkyl, unsubstituted (C)₃-C₁₀) Cycloalkyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, and cyclodecyl. Substituted (C)₃-C₄₀) Examples of cycloalkyl are substituted (C)₃-C₂₀) Cycloalkyl, substituted (C)₃-C₁₀) Cycloalkyl, cyclopentanone-2-yl and 1-fluorocyclohexyl.

(C₁-C₅₀) Examples of the alkylene group include unsubstituted or substituted (C)₆-C₅₀) Arylene, (C)₃-C₅₀) Cycloalkylene and (C)₁-C₅₀) Alkylene (e.g., (C)₁-C₂₀) Alkylene). The diradicals can be located at the same carbon atom (e.g., -CH)₂-) or on adjacent carbon atoms (i.e., 1, 2-diradicals), or separated by one, two, or more intervening carbon atoms (e.g., 1, 3-diradicals, 1, 4-diradicals, etc.). Some diradicals include 1, 2-diradicals, 1, 3-diradicals, 1, 4-diradicals or alpha, omega-diradicals and other 1, 2-diradicals. An α, ω -diradical is a diradical having the greatest carbon backbone spacing between the carbons of the group. (C)₂-C₂₀) Some examples of alkylene alpha, omega-diyl include ethylene-1, 2-diyl (i.e., -CH)₂CH₂-), propan-1, 3-diyl (i.e., -CH₂CH₂CH₂-), 2-methylpropan-1, 3-diyl (i.e., -CH₂CH(CH₃)CH₂-)。(C₆-C₅₀) Some examples of arylene α, ω -diyl groups include phenyl-1, 4-diyl, naphthalene-2, 6-diyl, or naphthalene-3, 7-diyl.

Term "(C)₁-C₅₀) Alkylene "means unsubstituted or substituted by one or more R having from 1 to 50 carbon atoms^SSubstituted saturated straight or branched chain diradicals (i.e., groups that are not on a ring atom). Unsubstituted (C)₁-C₅₀) Examples of alkylene are unsubstituted (C)₁-C₂₀) Alkylene radicals including unsubstituted-CH₂CH₂-、-(CH₂)₃-、-(CH₂)₄-、-(CH₂)₅-、-(CH₂)₆-、-(CH₂)₇-、-(CH₂)₈-、-CH₂C*HCH₃And- (CH)₂)₄C*(H)(CH₃) Wherein "C" denotes a carbon atom from which a hydrogen atom is removed to form a secondary or tertiary alkyl group. Substituted (C)₁-C₅₀) Examples of alkylene are substituted (C)₁-C₂₀) Alkylene, -CF₂-, -C (O) -and- (CH)₂)₁₄C(CH₃)₂(CH₂)₅- (i.e., 6-dimethyl-substituted n-1, 20-eicosyl). Due to two R as mentioned previously^SCan be put together to form (C)₁-C₁₈) Alkylene radicals, thus substituted (C)₁-C₅₀) Examples of alkylene also include 1, 2-bis (methylene) cyclopentane, 1, 2-bis (methylene) cyclohexane, 2, 3-bis (methylene) -7, 7-dimethyl-bicyclo [2.2.1]Heptane and 2, 3-bis (methylene) bicyclo [2.2.2]Octane.

Term "(C)₃-C₅₀) Cycloalkylene "means cyclic having 3 to 50 carbon atoms, unsubstituted or substituted with one or more R^SAnd (3) substituted. Both groups of the cyclic diradical are on a ring atom of the cyclic diradical.

The term "heteroatom" refers to an atom other than hydrogen or carbon. Examples of groups containing one or more than one heteroatom include O, S, S (O), S (O)₂、Si(R^C)₂、P(R^P)、N(R^N)、-N＝C(R^C)₂、-Ge(R^C)₂-or-Si (R)^C) -, wherein each R^CAnd each R^PIs unsubstituted (C)₁-C₁₈) A hydrocarbyl group or-H, and wherein each R^NIs unsubstituted (C)₁-C₁₈) A hydrocarbyl group. The term "heterohydrocarbon" refers to a molecule or molecular framework in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. Term "(C)₁-C₅₀) Heterohydrocarbyl "means a heterohydrocarbyl group having 1 to 50 carbon atoms, and the term" (C)₁-C₅₀) Heterohydrocarbylene "means a heterohydrocarbyl diradical having 1 to 50 carbon atoms. (C)₁-C₅₀) Heterohydrocarbyl or (C)₁-C₅₀) The heterohydrocarbons of the heterohydrocarbylene group have one or more heteroatoms. The group of heterohydrocarbyl groups may be on a carbon atom or a heteroatom. The two groups of the heterohydrocarbylene group can be on a single carbon atom or on a single heteroatom. In addition, one of the two groups of the divalent group may be on a carbon atom and the other group may be on a different carbon atom; one of the two groups may be on a carbon atom and the other on a heteroatom; or one of the two groups may be on a heteroatom and the other group on a different heteroatom. Each (C)₁-C₅₀) A heterohydrocarbyl radical and (C)₁-C₅₀) The heterohydrocarbylene group may be unsubstituted or may be substituted with (one or more R)^S) Substituted, aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

Term "(C)₁-C₅₀) Heterohydrocarbon anion "means an anionic heterohydrocarbon having from 1 to 50 carbon atoms and a formal charge of minus one (-1). Formal charges may be associated with heteroatoms, provided that there is more than one heteroatom in the anionic heterohydrocarbon. The heterohydrocarbon anion is aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (having three or more carbons, and including monocyclic and polycyclic, fused and non-fused polycyclic and bicyclic) or acyclic and substituted with one or more R^SSubstituted or unsubstituted. When the heteroaromatic anion is aromatic ("(C)₁-C₅₀) Heteroaromatic anion "), at least one heteroatom is in the aromatic system. The lone pair of electrons of the anion of the heteroaromatic anion is not part of an aromatic system and can be used to form an ionic or coordinate covalent bond.

(C₁-C₅₀) The heterocarbyl group may be unsubstituted or substituted. (C)₁-C₅₀) Non-limiting examples of heterocarbyl groups include (C)₁-C₅₀) Heteroalkyl group, (C)₁-C₅₀) alkyl-O-, (C)₁-C₅₀) alkyl-S-, (C)₁-C₅₀) alkyl-S (O) -, (C)₁-C₅₀) alkyl-S (O)₂-、(C₁-C₅₀) hydrocarbyl-Si (R)^C)₂-、(C₁-C₅₀) hydrocarbyl-N (R)^N)-、(C₁-C₅₀) hydrocarbyl-P (R)^P)-、(C₂-C₅₀) Heterocycloalkyl group, (C)₂-C₁₉) Heterocycloalkyl- (C)₁-C₂₀) Alkylene, (C)₃-C₂₀) Cycloalkyl- (C)₁-C₁₉) Heteroalkylene, (C)₂-C₁₉) Heterocycloalkyl- (C)₁-C₂₀) Heteroalkylene, (C)₁-C₅₀) Heteroaryl, (C)₁-C₁₉) Heteroaryl- (C)₁-C₂₀) Alkylene, (C)₆-C₂₀) Aryl radical- (C)₁-C₁₉) Heteroalkylene or (C)₁-C₁₉) Heteroaryl- (C)₁-C₂₀) A heteroalkylene group.

Term "(C)₄-C₅₀) Heteroaryl "means unsubstituted or substituted (one or more R)^S) Substituted monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon groups having 4 to 50 total carbon atoms and 1 to 10 heteroatoms. Monocyclic heteroaromatic hydrocarbon groups include one heteroaromatic ring; the bicyclic heteroaromatic hydrocarbon group has two rings; and the tricyclic heteroaromatic hydrocarbon group has three rings. When a bicyclic or tricyclic heteroaromatic hydrocarbyl group is present, at least one of the rings of the group is heteroaromatic. The other ring or rings of the heteroaromatic group may independently be fused or non-fused and aromatic or non-aromatic. Other heteroaryl groups (e.g., (C)_x-C_y) Heteroaryl radicals are typically, e.g., (C)₄-C₁₂) Heteroaryl) is defined in an analogous manner as having x to y carbon atoms (e.g., 4 to 12 carbon atoms) and being unsubstituted or substituted with one or more than one R^SAnd (3) substituted. The monocyclic heteroaromatic hydrocarbon group is a 5-membered ring or a 6-membered ring.

A 5-membered monocyclic heteroaromatic hydrocarbon group having 5 minus h carbon atoms, wherein h is the number of heteroatoms and may be 1,2 or 3; and each heteroatom may be O, S, N or P. Examples of the 5-membered heterocyclic aromatic hydrocarbon group include pyrrol-1-yl; pyrrol-2-yl; furan-3-yl; thiophen-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazol-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2, 4-triazol-1-yl; 1,3, 4-oxadiazol-2-yl; 1,3, 4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl.

The 6-membered monocyclic heteroaromatic hydrocarbon group has 6-minus h carbon atoms, wherein h is the number of heteroatoms and may be 1 or 2, and the heteroatoms may be N or P. Examples of the 6-membered heterocyclic aromatic hydrocarbon group include pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl.

The bicyclic heteroaromatic hydrocarbon group can be a fused 5, 6-or 6, 6-ring system. Examples of fused 5, 6-ring system bicyclic heteroaromatic hydrocarbon groups are indol-1-yl; and benzimidazol-1-yl. Examples of fused 6, 6-ring system bicyclic heteroaromatic hydrocarbon radicals are quinolin-2-yl; and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon group may be a fused 5,6, 5-ring system; a 5,6, 6-ring system; a 6,5, 6-ring system; or a 6,6, 6-ring system. An example of a fused 5,6, 5-ring system is 1, 7-dihydropyrrolo [3,2-f ] indol-1-yl. An example of a fused 5,6, 6-ring system is 1H-benzo [ f ] indol-1-yl. An example of a fused 6,5, 6-ring system is 9H-carbazol-9-yl. An example of a fused 6,5, 6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6, 6-ring system is acridin-9-yl.

Term "(C)₁-C₅₀) Heteroalkyl "means a saturated straight or branched chain radical containing from one to fifty carbon atoms and one or more heteroatoms. Term "(C)₁-C₅₀) Heteroalkylidene "means a saturated straight or branched chain diradical containing 1 to 50 carbon atoms and one or more than one heteroatom. The heteroatom of the heteroalkyl or heteroalkylene group may include Si (R)^C)₃、Ge(R^C)₃、Si(R^C)₂、Ge(R^C)₂、P(R^P)₂、P(R^P)、N(R^N)₂、N(R^N)、N、O、OR^C、S、SR^CS (O) and S (O)₂Wherein each of the heteroalkyl and heteroalkylene is unsubstituted or substituted with one or more R^SAnd (4) substitution.

Unsubstituted (C)₂-C₄₀) Examples of heterocycloalkyl groups include unsubstituted (C)₂-C₂₀) Heterocycloalkyl, unsubstituted (C)₂-C₁₀) Heterocycloalkyl, aziridin-1-yl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophen-S, S-dioxido-2-yl, morpholin-4-yl, 1, 4-dioxan-2-yl, hexaazaphen-4-yl, 3-oxa-cyclooctyl, 5-thio-cyclononyl and 2-aza-cyclodecyl.

The term "saturated" means free of carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double bonds. By one or more substituents R in saturated chemical groups^SIn the case of substitution, one or more double bonds and/or threeA bond may optionally be present in substituent R^SIn (1). The term "unsaturated" means containing one or more carbon-carbon double or carbon-carbon triple bonds or (in heteroatom containing groups) one or more carbon-nitrogen double, carbon-phosphorus double or carbon-silicon double bonds, excluding substituents R which may be present in the substituent^SIf any, or a double bond in an aromatic ring or in a heteroaromatic ring, if any.

Embodiments of the present disclosure include activators, catalyst systems including activators, and methods for polymerizing olefins. In embodiments, the activator has a structure according to formula (I):

in formula (I), M is a metal in the +3 oxidation state, the metal being selected from boron, aluminum, gallium, scandium, yttrium or the lanthanides.

In the formula (I), R¹、R²、R³、R⁴ R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶Independently selected from (C)₁-C₄₀) Alkyl, (C)₆-C₄₀) Aryl, -H, -NR^N ₂、-OR^C、–SR^COr halogen, wherein each R^CAnd each R^NIndependently is (C)₁-C₃₀) A hydrocarbyl group or-H, with the proviso that R^1-4And R^5-8And R^9-12And R^13-16One of (A) is fluorine substituted₁-C₄₀) Alkyl, fluoro substituted (C)₆-C₄₀) Aryl or-F; and each R¹⁷And R¹⁸Is (C)₁-C₄₀) Alkyl or (C)₁-C₄₀) A heteroalkyl group.

In one or more embodiments, activator complexes include, for example, [ Cat [ ]]⁺The indicated cations. [ Cat]⁺In the form of electricity having a positive one (+1)A charged cation. In some embodiments of the activator, [ Cat]⁺Selected from protonated tris [ (C)₁-C₄₀) Hydrocarbyl radical]An ammonium cation. In some embodiments, [ Cat]⁺To contain one or two (C) on the ammonium cation₁₄-C₂₀) Protonated trialkylammonium cations of alkyl groups. In one or more embodiments, [ Cat]⁺Is composed of⁺N(H)R^N ₃Wherein each R is^NIndependently is (C)₁-C₂₀) An alkyl group. In some embodiments, [ Cat]⁺Is composed of⁺N(CH₃)HR^N ₂Wherein R is^NIs (C)₁₆-C₁₈) An alkyl group. In some embodiments, [ Cat]⁺Selected from the group consisting of a methyldioctadecylammonium cation or a methyldiocetylammonium cation. The methyldioctadecyl ammonium cation or the methyldichexadecyl ammonium cation are collectively referred to herein as the aminium cation. The ionic compound having an aminium cation may be given the trade name Armeen^TMM2HT was purchased from Akzo Nobel. In other embodiments, [ Cat]⁺Is triphenylmethyl carbocation (Ph)₃C⁺) Also known as trityl. In one or more embodiments, [ Cat]⁺Is a trisubstituted triphenylmethyl carbocation, e.g.⁺C(C₆H₄R^C)₃Wherein each R is^CIndependently selected from (C)₁-C₃₀) An alkyl group. In other embodiments, [ Cat]⁺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 and R^SIs selected from (C)₁-C₃₀) Alkyl, (C)₆-C₂₀) Aryl group, (C)₅-C₂₀) Heteroaryl OR-H, and each alkyl, aryl OR heteroaryl may additionally be subjected to-OR^CAnd (4) substitution. 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 one or more implementationsIn the examples, R¹、R²、R³、R⁴ R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶Independently is (C)₁-C₁₀) Alkyl, -F or-H, with the proviso that R^1-4And R^5-8And R^9-12And R^13-16One of (A) is fluorine substituted₁-C₁₀) Alkyl or-F.

In some embodiments, R¹、R⁸、R⁹、R¹⁶Is (C)₁-C₁₀) An alkyl group. In various embodiments, R¹、R⁸、R⁹、R¹⁶Selected from methyl, ethyl, n-propyl, 2-propyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, n-octyl, t-octyl, nonyl or decyl.

In one or more embodiments, R¹、R²、R³And R⁴At least one of which is-F or fluoroalkyl, R⁵、R⁶、R⁷And R⁸At least one of which is-F or fluoroalkyl, R⁹、R¹⁰、R¹¹And R¹²At least one of which is-F or fluoroalkyl, and R¹³、R¹⁴、R¹⁵And R¹⁶At least one of which is-F or fluoroalkyl.

In some embodiments, R¹、R²、R³And R⁴At least two of which are-F or fluoroalkyl, R⁵、R⁶、R⁷And R⁸At least two of which are-F or fluoroalkyl, R⁹、R¹⁰、R¹¹And R¹²At least two of which are-F or fluoroalkyl, and R¹³、R¹⁴、R¹⁵And R¹⁶At least two of which are-F or fluoroalkyl groups. In other embodiments, R¹、R²、R³And R⁴At least three of (a) are-F or fluoroalkyl, R⁵、R⁶、R⁷And R⁸At least three of (a) are-F or fluoroalkyl, R⁹、R¹⁰、R¹¹And R¹²At least three of (a) are-F or fluoroalkyl, and R¹³、R¹⁴、R¹⁵And R¹⁶At least three of which are-F or fluoroalkyl groups.

In which R is¹、R²、R³、R⁴ R⁵、R⁶、R⁷、R⁸、R⁹、R¹⁰、R¹¹、R¹²、R¹³、R¹⁴、R¹⁵And R¹⁶In embodiments where any of (a) is a fluoroalkyl group, the fluoroalkyl group can include, but is not limited to, -C (CF)₃)₃、-CF₃、-CF₂(CF₂)_nCF₃Wherein n is 0 to 10.

In illustrative embodiments, the activator has a structure according to formula (I). Illustrative embodiments of activators of formula (I) include the following structures:

catalyst system Components

Embodiments of the present disclosure include catalyst systems. In one or more embodiments, the catalyst system comprises an activator according to formula (I) and a procatalyst. The procatalyst may exhibit catalytic activity by contacting the complex with an activator having formula (I) or combining the complex with the activator. 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 such procatalysts include the procatalysts disclosed in the following references: US 8372927; WO 2010022228; WO 2011102989; US 6953764; US 6900321; WO 2017173080; US 7650930; US 6777509 WO 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-biphenyl phenoxy group IV metal-ligand complex or a constrained geometry group IV metal-ligand complex.

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

in formula (X), M is a metal selected from titanium, zirconium or hafnium, said metal being in a formal oxidation state of +2, +3 or + 4. (X)_nSubscript n of (a) 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 a monodentate ligand. 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 (XI), (XII) and (XIII), R³¹-R³⁵、R⁴¹-R⁴⁸And R⁵¹-R⁵⁹Each of which is 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 of formula (X) can be a monodentate ligand that is halogen, unsubstituted (C) independent of any other ligands 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-biphenyl phenoxy 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-trimethylpentan-2-yl) biphenyl-2-ol) hafnium dimethyl;

(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) hafnium dimethyl;

(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) hafnium dimethyl;

(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) hafnium dimethyl;

(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) hafnium dimethyl;

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

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

(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) hafnium dimethyl;

(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) hafnium dimethyl;

(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) hafnium dimethyl;

(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) hafnium dimethyl;

(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) hafnium dimethyl;

(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) hafnium dimethyl;

(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) hafnium dimethyl;

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

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

(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) hafnium dimethyl;

(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) hafnium dimethyl;

(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) hafnium dimethyl;

(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) dimethylzirconium;

(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) dimethyltitanium, 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) dimethyltitanium.

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

Lp_iMX_mX'_nX"_por a dimer of (XV) thereof.

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

In formula (XV), 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 to form a moiety that is both covalently bonded to M and coordinated thereto by means of a lewis base functional group.

In embodiments of the catalyst system, the procatalyst may comprise any of the following illustrative group IV complexes having a geometry-constrained structure:

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) dimethylsilanedimethyltitanium;

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienyl) dimethylsilane 2- (dimethylamino) benzyltitanium (III);

(Tert-butylamido) (tetramethyl-. eta.) (Tetramethyl-. eta.)⁵-cyclopentadienyl) dimethylsilanoallyl titanium (III);

(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-butyl)Amido) (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.)⁵-cyclopentadienyl) dimethylsilane titanium 2, 3-dimethyl-1, 3-butadiene (IV);

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

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

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

In addition to the activator having formula (I), the catalyst system 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 combination with the activators described in this disclosure correspond to the formula T¹ ₂AlOT²Or T₁Al(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 radicals or aryl-substituted (C)₁-C₃₀) Alkyl groups, such as 2, 6-di (tert-butyl) -4-methylphenyl, 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 activator 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 activators described in this disclosure.

Polyolefins

According to some embodiments, a method of polymerizing olefins includes polymerizing ethylene and (C) in the presence of a catalyst system including a group IV metal-ligand complex and an activator having a structure according to formula (I)₃-C₄₀) The alpha-olefin comonomer.

The catalytic system described in the preceding paragraph is used to polymerize olefins, mainly ethylene and propylene. In some embodiments, the polymerization process includes polymerizing a single type of olefin or a-olefin in the scheme to form 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.

Ethylene-based polymers, such as 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 examples; 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 ethylene-based polymer 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 examples. For example, the ethylene-based polymer may comprise at least 93 mole percent of units derived from ethylene; at least 96 mole percent 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 percent of 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%; other embodiments include at least 0.5 mol% 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 can be produced by solution polymerization in a dual reactor system (e.g., a dual ring 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. The catalyst system as described herein may be used in the first reactor or the second reactor, optionally in combination with one or more other catalysts. In one embodiment, the ethylene-based polymer can be produced by solution polymerization in a dual reactor system (e.g., a dual ring reactor system), wherein ethylene and optionally one or more alpha olefins are polymerized in both reactors in the presence of a catalyst system as described herein.

In another embodiment, the polymerization process may comprise a 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 combined weight of such additives, based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may further comprise a filler, which may include, but is 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.

Batch reactor procedure

Batch reactor experiments were conducted in a continuous stirred tank reactor (1 gallon capacity reactor in table 1, 2L capacity reactor in tables 2-4). The reactor was loaded with Isopar-E hydrocarbon solvent, hydrogen, and appropriate amount of octene comonomer prior to heating to the specified temperature and pressurizing with ethylene to the specified psi. Polymerization is initiated by adding an activated catalyst solution consisting of catalyst, cocatalyst and triethylaluminium 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.

Examples of the invention

Examples 1 to 22 are synthetic procedures for activator intermediates, activator cations, comparative activators and activators themselves. Example 23 provides the polymerization results. One or more features of the present disclosure are illustrated by way of example as follows:

EXAMPLE 1 Synthesis of bis [6,6' - ((((2- (dimethylamino) ethyl) azepinyl) bis (methylene)) bis (2, 4-di-tert-butylphenol) ] Yttrium

Based on reference Clark, l.; cushinon, m.g.; dyer, h.e.; schwarz, a.d.; duchateau, r.; 2010,46,273, "chemical communication (chem.Commun"). In a glove box filled with nitrogen, a solution of 6,6' - (((2- (dimethylamino) ethyl) azepinyl) bis (methylene)) bis (2, 4-di-tert-butylphenol) (1.03g, 1.96mmol, 2.0 equivalents) in toluene (10mL) was added to a vial containing tris (bis (trimethylsilyl) amino) yttrium (0.560g, 0.982mmol, 1 equivalent). The vial of 6,6' - ((2- (dimethylamino) ethyl) azepinyl) bis (methylene)) bis (2, 4-di-tert-butylphenol) was rinsed with additional toluene (2x10mL) and added to the reaction. The reaction was stirred at room temperature for 16 hours. The solution was clear. The solution was passed through a 0.45 μm syringe filter and concentrated in vacuo. A clear viscous oil was obtained. Hexane (15mL) was added, resulting in a clear solution. However, upon mixing, it became cloudy. The turbid solution was passed through a 0.45 μm syringe filter. The filter was rinsed with additional hexane (5 mL). The hexane solution was stored in a refrigerator at-30 ℃ for 3 days. Only a small amount of material precipitated out of solution. All volatiles were removed in vacuo. The solid was wet milled with hexane (15mL) for 30 minutes. The solid was filtered, washed with hexanes (3 × 2mL), and dried in vacuo to give an off-white powder (0.675g, 61% yield).

¹H NMR (400MHz, benzene-d)₆)δ8.70(br s,1H),7.62(d,J＝2.5Hz,1H),7.60(d,J＝2.6Hz,1H),7.48(d,J＝2.5Hz,1H),7.41(d,J＝2.5Hz,1H),7.08–7.02(m,2H),7.00(d,J＝2.5Hz,1H),6.93(d,J＝2.5Hz,1H),6.67(d,J＝2.4Hz,1H),6.59(d,J＝11.2Hz,1H),4.58(d,J＝13.1Hz,1H),4.27(d,J＝12.3Hz,1H),3.24(t,J＝10.8Hz,1H),3.02–2.78(m,3H),2.70(d,J＝12.2Hz,1H),1.84(s,9H),1.72(s,9H),1.63(s,9H),1.48(s,9H),1.42(s,9H),1.41(s,9H),1.40(s,12H),1.31(s,9H),1.26(s,9H)。¹³C NMR (101MHz, benzene-d)₆)δ162.89(d,J_Y-C＝1.7Hz),162.43(d,J_Y-C＝4.6Hz),162.26(d,J_Y-C＝2.8Hz),162.07(d,J_Y-C＝4.3Hz),139.10,138.42,136.72,136.67,136.09,135.84,135.59,134.12,126.81,126.17,125.92,125.84,125.22,124.89,124.62,124.58,124.44,124.02,120.40,65.62,64.29,62.90,62.31,60.25,55.33,51.05,47.63,44.30,35.80,35.56,35.52,35.43,34.55,33.79,33.77,33.65,31.94,31.88,31.83,31.58,31.56,31.38,30.88,30.65。

Example 2 potassium yttrium bis [6,6' - (((2- (dimethylamino) ethyl) azepinyl) bis (methylene)) bis (2, 4-di-tert-butylphenol) ] to compare the synthesis of the C2 precursor

In a glove box filled with nitrogen, bis [6,6' - (((2- (dimethylamino) ethyl) azepinyl) bis (methylene)) bis (2, 4-di-tert-butylphenol)]Yttrium (0.300g, 0.264mmol, 1 equiv.) and toluene (5mL) were charged to the reaction pot. A solution of KHMDS (52.7mg, 0.264mmol, 1 eq) in toluene (5mL) was added dropwise to the yttrium solution. KHMDS vials were rinsed with toluene (2.5mL) and added to the yttrium solution. The reaction was stirred at room temperature for 45 minutes, yielding a clear solution. All volatiles were removed in vacuo to yield a white powder (0.327 g). Substances only sparingly soluble in benzene-d₆. NMR showed residual H-HMDS and toluene. The contents of the NMR tube were transferred back to the reaction. The solid was wet milled with hexane (10mL) for 30 minutes. Removal of all volatiles in vacuoTo yield a white solid (0.305g, 98% yield).

¹H NMR (400MHz, benzene-d)₆)δ7.40(d,J＝2.3Hz,2H),7.38(d,J＝2.3Hz,2H),7.24(d,J＝2.3Hz,2H),7.21(d,J＝2.3Hz,2H),4.58(d,J＝12.1Hz,2H),3.84(d,J＝12.4Hz,2H),3.54(d,J＝12.2Hz,2H),3.46(d,J＝12.5Hz,2H),3.26–3.12(m,2H),2.89–2.69(m,4H),2.62(dt,J＝11.0,5.4Hz,2H),2.10(s,12H),1.41(s,18H),1.40(s,18H),1.38(s,18H),1.33(s,18H)。¹³C NMR (101MHz, benzene-d)₆)δ162.21(d,J_Y-C＝2.7Hz),160.56(d,J_Y-C＝1.4Hz)。136.71,136.62,135.75,134.43,126.90,125.10,123.72,123.52,123.44,121.77,60.45,60.00,49.80,45.98,43.45,35.09,34.88,33.83,33.76,31.88,31.68,30.08,30.00。

EXAMPLE 3 Synthesis of Dimethylbenzylammonium chloride

Dimethylaniline (10mL, 78.9mmol, 1 eq.) was dissolved in hexane (60mL) in a glove box filled with nitrogen. A2M solution of HCl in ether (39.4mL, 78.9mmol, 1 equiv.) was added dropwise to the stirred dimethylaniline solution, causing immediate precipitation of a white solid. The suspension was filtered, washed with hexanes (3 × 20mL), and dried in vacuo to give the product as a white solid (7570-a, 6.017g, 48% yield). A large amount of matter sticks to the tank wall; no scraping was attempted.

¹H NMR (400MHz, chloroform-d) δ 14.37(br s,1H),7.75(d, J ═ 7.3Hz,2H), 7.49-7.37 (m,3H),3.14(s, 6H).¹³C NMR (101MHz, chloroform-d) delta 142.85,130.45,130.15,120.73, 46.51.

EXAMPLE 4 Synthesis of N-methyl-dioctyl ammonium chloride

In a glove box filled with nitrogen, N-methyl-dioctylamine (7.0mL, 21.7mmol, 1 eq) was dissolved in hexane (100 mL). A 2M solution of HCl in ether (10.9mL, 21.7mmol, 1 eq) was slowly added dropwise to the stirred amine solution, causing immediate precipitation of a white solid. The suspension was stirred at room temperature for 45 minutes. The suspension was filtered, washed with hexanes (3 × 20mL), and dried in vacuo to give the product as an off-white solid (6.02g, 95% yield). Upon initial drying, the solids initially agglomerate into solid waxy lumps. However, it can be pulverized into a free-flowing powder.

¹H NMR (400MHz, chloroform-d) δ 11.85(br s,1H),2.92(tq, J ═ 9.6,4.7Hz,2H),2.82(tt, J ═ 11.8,5.4Hz,2H),2.65(d, J ═ 5.0Hz,3H), 1.83-1.61 (m,4H), 1.29-1.08 (m,20H),0.76(t, J ═ 6.7Hz, 6H).¹³C NMR (101MHz, chloroform-d) delta 55.62,39.65,31.52,28.90,28.87,26.66,23.53,22.43, 13.93.

EXAMPLE 5 Synthesis of Armeenium M2HT chloride

Armeen M2HT (5.36g, 10.0mmol, 1 eq.) was dissolved in hexane (150mL) in a nitrogen-filled glove box. A 2M solution of HCl in ether (5.0mL, 10.0mmol, 1 eq) was slowly added dropwise to the stirred amine solution, causing immediate precipitation of a white solid. The suspension was stirred at room temperature for 15 minutes. The precipitated solids are large and fine, resulting in a viscous, gelatinous suspension. Attempting to filter the suspension; however, it does not pass through the filter. The suspension was transferred back into a glass jar and dried in vacuo to yield a white solid (4.76g, 83% yield).

¹H NMR (400MHz, toluene-d)₈)δ13.02–12.71(m,1H),2.90(dtd,J＝43.2,12.4,6.8Hz,4H),2.67(d,J＝4.7Hz,3H),1.72(ddt,J＝50.3,13.3,6.7Hz,4H),1.32(d,J＝22.5Hz,60H),0.91(t,J＝6.6Hz,6H)。¹³C NMR (101MHz, toluene-d)₈)δ54.75,39.08,32.03,30.00,29.98,29.95,29.92,29.86,29.53,29.48,27.04,23.62,22.77,13.96。

Example 6-2-methyl-N- (Tris (pyrrolidin-1-yl) -Lambda⁵Synthesis of (phosphino) -propane-2-ammonium chloride (C-P1 cation)

In a glove box filled with nitrogen, N-tert-butyl-1, 1, 1-tris (pyrrolidin-1-yl) -lambda was added^5-Phosphinimine (5.0mL, 16.4mmol, 1 eq.) was dissolved in hexane (100 mL). A2M solution of HCl in ether (8.2mL, 16.4mmol, 1 eq.) was slowly added dropwise to the stirring amine solution. A white solid precipitated out of solution immediately. During the addition, some of the solids agglomerated to a slightly sticky off-white layer at the bottom. The reaction was stirred at room temperature for 30 minutes. The flask walls were scraped to loosen the solids. The solid was filtered, washed with hexanes (3 × 20m), and dried in vacuo to give the product as an off-white solid (4.20g, 74% yield).¹H NMR (400MHz, chloroform-d) delta 6.40(br s,1H), 3.24-3.17 (m,12H), 1.84-1.78 (m,12H),1.28(d, J)_P-H＝0.9Hz,9H)。¹³C NMR (101MHz, chloroform-d) delta 52.44(d, J)_P-C＝1.8Hz),47.63(d,J_P-C＝4.8Hz),31.43(d,J_P-C＝4.6Hz),26.05(d,J_P-C＝8.2Hz)。³¹P NMR (162MHz, chloroform-d) delta 22.21.

EXAMPLE 7 Synthesis of N- (bis (dimethylamino) methylene) -2-methylpropan-2-ium chloride

In a glove box filled with nitrogen, 2- (tert-butyl) -1,1,3, 3-tetramethylguanidine (5.0mL, 16.4mmol, 1 eq.) was dissolved in hexane (100 mL). A2M solution of HCl in ether (8.2mL, 16.4mmol, 1 eq.) was slowly added dropwise to the stirring amine solution. A white solid precipitated out of solution immediately. During the addition, some of the solids agglomerated to a slightly sticky off-white layer at the bottom. The reaction was stirred at room temperature for 30 minutes. The flask walls were scraped to loosen the solids. Filtering the solid with hexaneWashed (3 × 20mL) and dried in vacuo to give the product as a white solid (4.00g, 82% yield).¹H NMR (400MHz, chloroform-d) Δ 8.82(br s,1H),3.21(br s,3H),2.84(br s,9H),1.34(s, 9H).¹³C NMR (101MHz, chloroform-d) delta 160.83,56.58,41.07(br), 29.77.

Example 8-comparative C1, 2-methyl-N- (tris (pyrrolidin-1-yl) - λ^5-Phosphino) propan-2-aminebis [6,6' - (((2- (dimethylamino) ethyl) azenediyl) bis (methylene)) bis (2, 4-di-tert-butylphenol)]The synthesis of the yttrium is carried out,

in a glove box filled with nitrogen, 2-methyl-N- (tris (pyrrolidin-1-yl) - λ^5-A solution of phosphino) propane-2-ammonium chloride (53.7mg, 0.154mmol, 1 eq) in toluene (5mL) was added to a solution containing bis [6,6' - ((((2- (dimethylamino) ethyl) azepinyl) bis (methylene)) bis (2, 4-di-tert-butylphenol)]Potassium yttrium (180.5mg, 0.154mmol, 1 eq.) in a reaction flask. 2-methyl-N- (tris (pyrrolidin-1-yl) -lambda⁵The vial of-phosphino) propan-2-ammonium chloride was rinsed with toluene (2 × 2.5ml) and added to the reaction. The reaction was stirred at room temperature for 1 hour, yielding a clear solution. The solution was passed through a 0.45 μm syringe filter in line with a 0.2 μm syringe filter. The vial and syringe filter were washed with additional toluene (1 mL). All volatiles were removed in vacuo to yield a viscous clear oil. The oil was dissolved in toluene (1 mL). Hexane (5mL) was added, resulting in a cloudy solution. All volatiles were removed in vacuo. The viscous oil was wet-milled with hexane (10mL) and concentrated in vacuo. This process is repeated a second time. A clear viscous semisolid (248.8mg) was obtained. The material purity is 90%, and the remaining material is composed of residual solvent

¹H NMR (400MHz, benzene-d)₆)δ7.37(d,J＝2.6Hz,2H),7.36(d,J＝2.6Hz,2H),7.28(d,J＝2.5Hz,2H),7.18(d,J＝2.5Hz,2H),4.94(d,J＝12.0Hz,2H),4.89(d,J＝12.1Hz,2H),3.67(d,J＝12.1Hz,2H),3.56(d,J＝12.3Hz,2H),3.37–3.23(m,2H),3.07–2.98(m,2H),2.88(td,J＝11.0,4.1Hz,2H),2.72(td,J＝11.0,4.4Hz,2H),2.30–2.20(m,12H),2.12(s,12H),1.73(s,18H),1.51(s,18H),1.45(s,18H),1.45(s,18H),1.29–1.24(m,12H),0.71(br s,9H)。¹³C NMR (101MHz, benzene-d)₆)δ163.78(d,J_Y-C＝2.3Hz),163.67(d,J_Y-C＝2.3Hz),135.18,135.12,132.37,132.32,125.80,125.13,123.75,122.68,122.58,122.29,60.30,60.12,50.02,47.03(d,J_P-C＝4.5Hz),45.74,42.48,35.21,35.09,33.80,32.21,32.14,30.89(br),30.42,30.21,25.67(d,J_P-C＝7.8Hz)。³¹P NMR (162MHz, benzene-d)₆)δ20.47。

Example 9-comparative Synthesis of C2, N- (bis (dimethylamino) methylene) -2-methylpropan-2-ammoniumbis [6,6' - (((2- (dimethylamino) ethyl) azepinyl) bis (methylene)) bis (2, 4-di-tert-butylphenol) ] yttrium

In a glove box filled with nitrogen, potassium bis [6,6' - (((2- (dimethylamino) ethyl) azepinyl) bis (methylene)) bis (2, 4-di-tert-butylphenol) ] yttrium (200mg, 0.171mmol, 1 eq) and N- (bis (dimethylamino) methylene) -2-methylpropane-2-ammonium chloride (35.4mg, 0.171mmol, 1 eq) were charged to a reaction flask. Toluene (10mL) was added and the reaction was stirred at room temperature for 1.5 hours, yielding a clear solution. The solution was passed through a 0.45 μm syringe filter in line with a 0.2 μm syringe filter. The vial and syringe filter were washed with additional toluene (1 mL). All volatiles were removed in vacuo to yield a viscous clear oil. The oil was dissolved in toluene (1 mL). Hexane (5mL) was added, resulting in a cloudy solution. Additional hexane (5mL) was added. All volatiles were removed in vacuo to yield a clear, sticky solid with some white precipitate. The material was wet milled with hexane (10 mL). Again, all volatiles were removed in vacuo to yield a white solid with only a small amount of clear, sticky material. Wet milled with hexane (10mL) then dried again repeatedly in vacuo to give the product as a white solid (0.2096g, 94% yield).

¹H NMR (400MHz, benzene-d)₆)δ7.40(d,J＝2.6Hz,2H),7.33(d,J＝2.6Hz,2H),7.27(d,J＝2.5Hz,2H),7.15(d,J＝2.5Hz,2H),4.82(d,J＝12.0Hz,2H),4.67(d,J＝12.3Hz,2H),3.64(d,J＝12.0Hz,2H),3.53(d,J＝12.4Hz,2H),3.29(td,J＝13.1,3.9Hz,2H),3.02–2.91(m,2H),2.87(td,J＝10.9,4.0Hz,2H),2.66(td,J＝10.9,4.0Hz,2H),2.10(s,12H),1.83(s,12H),1.65(s,18H),1.49(s,18H),1.44(s,18H),1.42(s,18H),0.46(s,9H)。¹³C NMR (101MHz, benzene-d)₆)δ163.51(d,J_Y-C＝2.3Hz),163.40(d,J_Y-C＝2.4Hz)。163.52,163.49,163.41,163.38,159.01,135.60,135.37,132.99,132.88,125.89,125.04,123.76,123.06,122.65,122.17,60.03,55.75,49.92,45.58,42.34,39.38,35.18,35.07,33.80,33.78,32.14,32.08,30.30,30.03,29.02。C₉H₂₂N₃[M⁺]Hrms (esi) calculated 172.1808; found 172.1806. C₆₈H₁₀₈N₄O₄Y[M^-]Calculated value of 1133.7435; found 1133.7470

Example 10-comparative C5, 2-methyl-N- (tris (pyrrolidin-1-yl) - λ^5-Synthesis of phosphino) propyl-2-tetrakis (pentafluorophenyl) ammonium borate

In a glove box filled with nitrogen, 2-methyl-N- (tris (pyrrolidin-1-yl) - λ⁵A solution of-phosphinylene) propane-2-ammonium chloride (48.6mg, 0.140mmol, 1 eq) in dichloromethane (5mL) was added to a reaction flask containing potassium tetrakis (pentafluorophenyl) borate (100mg, 0.140mmol, 1 eq). 2-methyl-N- (tris (pyrrolidin-1-yl) -lambda⁵The vial of-phosphinylidine) propan-2-ammonium chloride was rinsed with dichloromethane (2x2.5ml) and added to the reaction. The reaction was stirred at room temperature for 24 hours, resulting in a cloudy solution. The solution was passed through a 0.45 μm syringe filter to give a clear solution. The solution was concentrated in vacuo to give an off-white powder. Toluene (10mL) was added and the suspension was stirred for 5 minutes. The dissolved substances are less; the product appeared to be insoluble in toluene.All volatiles were removed in vacuo. Hexane (10mL) was added, the solid was wet-milled and all volatiles were removed in vacuo to give the product as an off-white solid (0.1311g, 95% yield).

¹H NMR (400MHz, chloroform-d) δ 3.15(td, J ═ 6.7,3.9Hz,12H),2.54(d, J ═ 12H)_P-H＝10.8Hz,1H),1.95–1.83(m,12H),1.28(d,J_P-H＝0.9Hz,9H)。¹³C NMR (101MHz, chloroform-d) delta (several broad resonances centered around 149.34,146.91,139.32,137.38,136.88,134.94,123.74 due to C-F and C-B coupling), 52.91,47.67(d, J)_P-C＝4.6Hz),31.22(d,J_P-C＝4.0Hz),25.99(d,J_P-C＝8.3Hz)。¹⁹F NMR (376MHz, chloroform-d) δ -132.63(d, J ═ 12.6Hz), -163.20(t, J ═ 20.5Hz), -167.00(t, J ═ 18.2 Hz).³¹P NMR (162MHz, chloroform-d) delta 21.20.¹¹B NMR (128MHz, chloroform-d) delta-16.70. C₁₆H₃₄N₄P[M⁺]Hrms (esi) calculated 313.2516; found 313.2516. C₂₄BF₂₀[M^-]Calculated value of 678.9779; found 678.9756.

EXAMPLE 11-Synthesis of comparative C6, N- (bis (dimethylamino) methylene) -2-methylpropane-2-tetrakis (pentafluorophenyl) ammonium borate

In a glove box filled with nitrogen, a solution of N- (bis (dimethylamino) methylene) -2-methylpropane-2-ammonium chloride (28.9mg, 0.140mmol, 1 eq) in dichloromethane (5mL) was added to a reaction flask containing potassium tetrakis (pentafluorophenyl) borate (100mg, 0.140mmol, 1 eq). The vial of N- (bis (dimethylamino) methylene) -2-methylpropane-2-ammonium chloride was rinsed with dichloromethane (2 × 2.5ml) and added to the reaction. The reaction was stirred at room temperature for 2 hours, resulting in a cloudy solution. The solution was passed through a 0.45 μm syringe filter to give a clear solution. The solution was concentrated in vacuo to give an off-white powder. Toluene (10mL) was added and the suspension was stirred for a few minutes. All volatiles were removed in vacuo. The solid was wet milled with hexane (10 mL). All volatiles were removed in vacuo to yield the product as an off-white powder (0.112g, 94% yield).

¹H NMR (400MHz, chloroform-d) delta 4.29(br s,1H),2.94(s,12H),1.34(s, 9H).¹⁹F NMR (376MHz, chloroform-d) δ -132.72(d, J ═ 7.6Hz), -162.75(t, J ═ 20.5Hz), -166.80(t, J ═ 18.2 Hz).¹¹B NMR (128MHz, chloroform-d) delta-16.71. C₉H₂₂N₃[M⁺]Hrms (esi) calculated 172.1808; found 172.1809. C₂₄BF₂₀[M^-]Calculated value of 678.9779; found 678.9774.

Example Synthesis of 6-6, 6' - ((Methylazadiyl) bis (methylene)) bis (2, 4-di-tert-butylphenol)

Paraformaldehyde (1.03g, 34.4mmol, 2 equiv.), potassium hydroxide (10mg, 0.172mmol, 1 mol%) and methanol (5mL) were charged to a 100mL round bottom flask. The solution was cooled in an ice bath. 40% w/w aqueous methylamine solution (1.48mL, 17.2mmol, 1 equiv.) was added dropwise to the methanol solution. The ice bath was removed and the reaction was allowed to warm to room temperature. A solution of 2, 4-di-tert-butylphenol (7.10g, 34.4mmol, 2 eq.) in methanol (3mL) was added to the reaction. The phenol vial was rinsed with methanol (2mL) and added to the reaction. The mixture was stirred at reflux for 24 hours. Some solid material precipitated out of solution. All volatiles were removed in vacuo to yield a foamy solid with some viscous oil. Attempts were made to recrystallize the material from toluene, however, little material precipitated out of solution. The material was adsorbed onto silica gel and purified by flash column chromatography (ISCO, 220g silica gel, 1-4% EtOAc/hexanes). The material was initially a viscous oil, but after drying in vacuo, foamed significantly. The product was isolated as a white solid (5.49 g). The bulk material was recrystallized from hexane. Some heating is required to dissolve all the material. A white solid was obtained (3.8113g, 48% yield).

¹H NMR (400MHz, chloroform-d) δ 7.84(br s,2H),7.24(d, J ═ 2.4Hz,2H),6.92(d, J ═ 2.4Hz,2H),3.64(s,4H),2.32(s,3H),1.41(s,18H),1.28(s, 18H).¹³C NMR (101MHz, chloroform-d) delta 152.42,141.51,136.02,124.89,123.55,121.56,59.99,42.03,34.85,34.15,31.62, 29.71. C₃₁H₄₉NO₂[M+1]Hrms (esi) calculated 468.3836; found 468.3792.

Example 13-Synthesis of potassium bis [6,6' - ((methylazadiyl) bis (methylene)) bis (2, 4-di-tert-butylphenol) ] yttrium, a precursor for comparing C3 and C4

In a nitrogen-filled glove box, a solution of 6,6' - ((methylazadiyl) bis (methylene)) bis (2, 4-di-tert-butylphenol) (1.00g, 2.14mmol, 2 equivalents) in toluene (20mL) was added to a reaction pot containing tris (bis (trimethylsilyl) amino) yttrium (0.609g, 1.07mmol, 1 equivalent) and toluene (20 mL). Vials of 6,6' - ((methylazadiyl) bis (methylene)) bis (2, 4-di-tert-butylphenol) were rinsed with additional toluene (2x10mL) and added to the reaction. The reaction was stirred at room temperature for 1.5 hours. All volatiles were removed in vacuo to yield a white solid. The solid was dissolved in toluene (10 mL). Not all substances initially go into solution. A solution of KHMDS (0.213g, 1.07mmol, 1 equiv.) in toluene (10mL) was added. The vial containing the KHMDS solution was rinsed with additional toluene (2x5mL) and added to the reaction. The clear solution was stirred at room temperature for 4 hours. After 5 minutes, all materials dissolved into a clear solution. After stirring for 15 minutes, the solution became slightly cloudy and a large amount of white precipitate formed by stirring for 1 hour. All volatiles were removed in vacuo. The material was wet milled with hexane (30 mL). The sample was additionally dried under vacuum at 40 ℃ for 18 hours to give a white solid (1.16g, quantitative yield).

¹H NMR (400MHz, dichloromethane-d)₂)δ7.27(d,J＝2.1Hz,2H),7.06(d,J＝2.3Hz,2H),6.99(d,J＝2.3Hz,2H),6.84(d,J＝2.1Hz,2H),4.52(d,J＝12.0Hz,2H),4.44(d,J＝12.6Hz,2H),3.12(d,J＝12.7Hz,2H),2.91(d,J＝12.0Hz,2H),2.01(s,6H),1.47(s,18H),1.30(s,18H),1.24(s,18H),0.93(s,18H)。¹³C NMR (101MHz, dichloromethane-d)₂)δ161.89(d,J_Y-C＝2.2Hz),160.02(d,J_Y-C＝1.3Hz),136.89,136.47,134.92,134.51,126.60,125.24,124.26,123.25,122.44,65.08,64.98,39.02,35.11,34.36,33.82,33.56,31.55,31.50,29.81,29.17。C₆₂H₉₄N₂O₄Y[M^-]Hrms (esi) calculated 1019.6278; found 1019.6316.

Example 14-comparative C3, 2-methyl-N- (tris (pyrrolidin-1-yl) - λ^5-Phosphino) propan-2-aminebis [6,6' - ((methylazadiyl) bis (methylene)) bis (2, 4-di-tert-butylphenol)]Synthesis of yttrium

In a glove box filled with nitrogen, bis [6,6' - ((methylazadiyl) bis (methylene)) bis (2, 4-di-tert-butylphenol)]Potassium yttrium (0.300g, 0.283mmol, 1 eq.) was charged to the reaction flask. Reacting 2-methyl-N- (tri (pyrrolidin-1-yl) -lambda⁵A solution of-phosphino) propan-2-ammonium chloride (98.8mg, 0.283mmol, 1 eq) in dichloromethane (5mL) was added to the yttrium complex. 2-methyl-N- (tris (pyrrolidin-1-yl) -lambda⁵The vial of-phosphino) propan-2-ammonium chloride was washed with additional dichloromethane (2x5mL) and added to the vial of yttrium. The solution was stirred at room temperature for 2 hours, yielding a clear solution with a small amount of white precipitate. The solution was passed through a 0.45 μm syringe filter and concentrated in vacuo. The white solid was wet-milled with toluene (5 mL). The material is only slightly soluble in toluene. All volatiles were removed in vacuo. The white powder was wet milled with hexane (5 mL). All volatiles were removed in vacuo to give the product as a white solid (0.3549g, 94% yield).

¹H NMR (400MHz, dichloromethane-d)₂)δ7.13(d,J＝2.5Hz,2H),6.96(d,J＝2.5Hz,2H),6.95(d,J＝2.4Hz,2H),6.84(d,J＝2.5Hz,2H),4.69(d,J＝12.2Hz,2H),4.57(d,J＝11.9Hz,2H),3.17(dq,J＝6.6,3.9Hz,12H),2.94(d,J＝12.3Hz,2H),2.83(d,J＝11.9Hz,2H),2.02(s,6H),1.98–1.88(m,12H),1.44(s,18H),1.33(d,J＝0.7Hz,9H),1.32(s,18H),1.27(s,18H),1.02(s,18H)。¹³C NMR (101MHz, dichloromethane-d)₂)δ163.18(d,J_Y-C＝2.1Hz),163.02(d,J_Y-C＝2.7Hz),134.75,134.48,132.84,132.67,125.32,125.05,124.52,123.16,122.52,65.00,64.81,52.90(d,J_P-C＝1.2Hz),47.77(d,J_P-C＝4.8Hz),38.57,34.85,34.48,33.65,33.53,31.78,31.73,31.32(d,J_P-C＝3.9Hz),29.46,29.36,26.09(d,J_P-C＝8.2Hz)。³¹P NMR (162MHz, dichloromethane-d)₂)δ21.18。C₁₆H₃₄N₄P[M⁺]Hrms (esi) calculated 313.2516; found 313.2514. C₆₂H₉₄N₂O₄Y[M^-]Calculated value of 1019.6278; found 1019.6311.

EXAMPLE 15 Synthesis of N- (bis (dimethylamino) methylene) -2-methylpropan-2-aminebis [6,6' - ((methylazadiyl) bis (methylene)) bis (2, 4-di-tert-butylphenol) ] yttrium

In a glove box filled with nitrogen, potassium bis [6,6' - ((methylazadiyl) bis (methylene)) bis (2, 4-di-tert-butylphenol) ] yttrium (0.300g, 0.283mmol, 1 eq) was charged to the reaction flask. A solution of N- (bis (dimethylamino) methylene) -2-methylpropane-2-ammonium chloride (58.8mg, 0.283mmol, 1 eq) in dichloromethane (5mL) was added. The N- (bis (dimethylamino) methylene) -2-methylpropane-2-ammonium chloride vial was washed with additional dichloromethane (2x5mL) and added to the yttrium vial. The solution was stirred at room temperature for 2 hours, yielding a clear solution with a small amount of white precipitate. The solution was passed through a 0.45 μm syringe filter and concentrated in vacuo. The white solid was wet-milled with toluene (5 mL). The material is only slightly soluble in toluene. All volatiles were removed in vacuo. The white powder was wet milled with hexane (5 mL). All volatiles were removed in vacuo to give the product as a white solid (0.3101g, 92% yield).

¹H NMR (400MHz, dichloromethane-d)₂)δ7.14(d,J＝2.5Hz,2H),6.96(d,J＝2.5Hz,2H),6.95(d,J＝2.5Hz,2H),6.84(d,J＝2.5Hz,2H),4.64(d,J＝12.3Hz,2H),4.54(d,J＝11.8Hz,2H),4.22(br s,1H),2.96(d,J＝12.4Hz,2H),2.84(d,J＝11.9Hz,2H),2.69(br s,12H),2.01(s,6H),1.43(s,18H),1.30(s,18H),1.26(s,27H),1.00(s,18H)。¹³C NMR (101MHz, dichloromethane-d)₂)δ163.06(d,J_Y-C＝2.1Hz),162.91(d,J_Y-C＝2.6Hz),160.68,134.82,134.58,133.20,132.88,125.42,125.03,124.51,122.91,122.70,122.66,64.91,64.63,57.66,40.47,38.40,34.89,34.47,33.67,33.53,31.80,31.70,29.72,29.53,29.33。C₉H₂₂N₃[M⁺]Hrms (esi) calculated 172.1808; found 172.1811. C₆₂H₉₄N₂O₄Y[M^-]Calculated value of 1019.6278; found 1019.6309.

EXAMPLE 16 Synthesis of 2- (tert-butyl) -4-fluorophenol

4-fluorophenol (5.00g, 44.6mmol, 1 equiv.), dichloromethane (80mL), tBuOH (5.9mL, 61.8mmol, 1.39 equiv.), and concentrated H₂SO₄(3.0mL, 56.2mmol, 1.3 equiv.) was charged to the reaction pot. Upon addition of the acid, the color of the solution turned slightly amber. The reaction was stirred at room temperature for 18 hours. With water (100mL) followed by NaHCO₃The solution was washed with a saturated aqueous solution (150 mL). The organic phase is passed over MgSO₄Dried, filtered and concentrated in vacuo to give an amber oil. The material was adsorbed onto silica gel and purified by flash column chromatography (ISCO, 220g silica gel, 5-10% EtOAc/hexanes). The fraction from the first main peak was concentrated in vacuo to give the product as a pale yellow oil (3.75g, 50% yield).

¹H NMR (400MHz, chloroform-d) δ 6.98(dd, J ═ 10.9,3.1Hz,1H),6.74(ddd, J ═ 8.6,7.5,3.1Hz,1H),6.58(dd,J＝8.6,4.9Hz,1H),4.87–4.78(m,1H),1.39(s,10H)。¹³C NMR (101MHz, chloroform-d) delta 157.04(d, J)_C-F＝236.5Hz),150.09(d,J_C-F＝2.0Hz),138.04(d,J_C-F＝5.8Hz),116.91(d,J_C-F＝8.3Hz),113.96(d,J_C-F＝24.1Hz),112.61(d,J_C-F＝22.9Hz),34.64,29.28。¹⁹F NMR (376MHz, chloroform-d) delta-123.93-124.05 (m).

Example 17 Synthesis of 6,6' - ((Methylazadiyl) bis (methylene)) bis (2- (tert-butyl) -4-fluorophenol

Paraformaldehyde (0.578g, 19.3mmol, 2 equiv.), potassium hydroxide (5.4mg, 0.096mmol, 1 mol%) and methanol (2mL) were charged to a 50mL round bottom flask. The solution was cooled in an ice bath. 40% w/w aqueous methylamine solution (0.83mL, 9.63mmol, 1 equiv.) was added dropwise to the methanol solution. The ice bath was removed and the reaction was allowed to warm to room temperature. The cloudy white solution became clear and homogeneous. 2-tert-butyl-4-fluorophenol (3.24g, 19.3mmol, 2 equivalents) was added dropwise to the reaction. The 2-tert-butyl-4-fluorophenol flask was rinsed four times with 2mL of methanol and the rinse was added to the reaction. The mixture was stirred at reflux (about 80 ℃) for 5 days. The reaction was cooled to room temperature and concentrated in vacuo. NMR showed a mixture of species.¹⁹F NMR showed two main species, the desired product being the major component. The material was adsorbed onto silica gel and purified by flash column chromatography (ISCO, 220g silica gel, 1-7% EtOAc/hexanes) to give a clear oil (3161-C, 2.15 g). The material contained 25% 2-tert-butyl-4-fluorophenol. The material was adsorbed onto silica gel and purified by flash column chromatography (ISCO, 120g silica gel, 10-30% dichloromethane/hexanes gradient) to give a clear glassy semisolid (1.58g, 42% yield).

¹H NMR (400MHz, chloroform-d) δ 7.71(br s,2H),6.97(dd, J ═ 10.9,3.1Hz,2H),6.68(dd, J ═ 7.9,3.1Hz,2H),3.62(s,4H),2.32(s,3H),1.41(s, 18H).¹³C NMR (101MHz, chloroform-d)δ156.04(d,J_F-C＝236.5Hz),150.65(d,J_F-C＝2.0Hz),139.06(d,J_F-C＝6.1Hz),123.18(d,J_F-C＝7.4Hz),113.98(d,J_F-C＝22.9Hz),113.61(d,J_F-C＝23.4Hz),59.38,41.91,34.82,29.39。¹⁹F NMR (376MHz, chloroform-d) delta-124.30-124.61 (m). C₂₃H₃₁F₂NO₂[M+1]Hrms (esi) calculated 392.2396; found 392.2416.

EXAMPLE 18 Synthesis of potassium bis [6,6' - ((methylazadiyl) bis (methylene)) bis (2- (tert-butyl) -4-fluorophenol) ] Yttrium

In a nitrogen-filled glove box, a solution of 6,6' - ((methylazadiyl) bis (methylene)) bis (2- (tert-butyl) -4-fluorophenol) (1.08g, 2.76mmol, 2 equivalents) in toluene (10mL) was added to a reaction tank containing tris (bis (trimethylsilyl) amino) yttrium (0.787g, 1.38mmol, 1 equivalent) and toluene (20 mL). The vial of 6,6' - ((methylazadiyl) bis (methylene)) bis (2- (tert-butyl) -4-fluorophenol was rinsed twice with additional toluene (10mL) and added to the reaction. Upon addition of phenol, the reaction turned yellow. The reaction was stirred at room temperature for 2 hours. All volatiles were removed in vacuo to yield a yellow solid with some clear glassy material near the top. The solid was dissolved in toluene (10 mL). A solution of KHMDS (0.276g, 1.38mmol, 1 eq.) in toluene (10mL) was added. The vial containing the KHMDS solution was rinsed with additional toluene (2x5mL) and added to the reaction. Upon addition of the KHMDS solution, the yellow color of the solution disappeared. However, even during the addition, a white precipitate began to form. Some of the precipitate clumps on the tank wall. All solids were wet milled and additional toluene (15mL) was added. The reaction was stirred at room temperature for 15 hours. The stirring was stopped and the suspension was allowed to settle. A clear supernatant and a white precipitate were observed. All volatiles were removed in vacuo. The material was wet milled with hexane (40 mL). The sample was additionally dried under vacuum at 40 ℃ for 3 hours to give a white solid (1.38 g). The material was dissolved in THF (20mL) and stirred briefly. All volatiles were removed in vacuo. The residue was wet-milled with toluene (20mL) and all volatiles were removed in vacuo to give a white solid

¹H NMR(400MHz,THF-d₈)δ6.72(dd,J＝11.3,3.3Hz,2H),6.60(t,J＝2.9Hz,2H),6.58(d,J＝3.2Hz,2H),6.51(dd,J＝8.6,3.2Hz,2H),4.64(dd,J＝12.0,5.5Hz,4H),2.83(dd,J＝28.1,12.1Hz,4H),2.02(s,6H),1.37(s,18H),1.02(s,18H)。¹³C NMR(101MHz,THF-d₈)δ163.05(d,J_Y-C＝1.9Hz),162.80(d,J_Y-C＝1.9Hz),153.61(d,J_F-C＝226.5Hz),153.49(d,J_F-C＝225.7Hz),138.59(d,J_F-C＝5.6Hz),138.07(d,J_F-C＝5.6Hz),126.08(d,J_F-C＝7.0Hz),125.12(d,J_F-C＝7.3Hz),115.37(d,J_F-C＝15.2Hz),115.16(d,J_F-C＝15.0Hz),113.97(d,J_F-C＝18.5Hz),113.75(d,J_F-C＝18.5Hz),66.23,65.61,40.04,36.40,36.10,30.98,30.98。¹⁹F NMR(376MHz,THF-d₈)δ-134.98(dd,J＝11.2,8.9Hz),-135.52(dd,J＝10.8,8.7Hz)。C₄₆H₅₈F₄N₂O₄Y[M^-]Hrms (esi) calculated 867.3397; found 867.3416.

EXAMPLE 18 Synthesis of N-methyl-dioctylammonium bis [6,6' - ((methylazadiyl) bis (methylene)) bis (2- (tert-butyl) -4-fluorophenol) ] Yttrium

In a glove box filled with nitrogen, potassium bis [6,6' - ((methylazadiyl) bis (methylene)) bis (2- (tert-butyl) -4-fluorophenol) ] yttrium (also containing about 1 equivalent of toluene) (0.300g, 0.300mmol, 1 equivalent) was charged to the reaction flask. A solution of N-methyl-dioctyl ammonium chloride (87.7mg, 0.300mmol, 1 eq) in dichloromethane (5mL) was added. The N-methyl-dioctyl ammonium chloride vial was washed twice with an additional 5mL of dichloromethane and these washes were added to the reaction. The solution was stirred at room temperature for 3 hours. A pale yellow solution with a fine precipitate formed. The suspension was passed through a 0.45 μm syringe filter to give a clear, pale yellow solution. All volatiles were removed in vacuo to give a pale yellow solid with some gelatinous fraction. The residue was wet milled with hexane (10 mL). The viscous oil was separated from the hexane solution. Some toluene (10mL) was used to wash the tank walls and spatula. All volatiles were removed in vacuo to yield a yellow oil. The oil was wet milled with hexane (10mL) and all volatiles were removed in vacuo to yield a pale yellow solid (0.292g, 86% yield).

¹H NMR (400MHz, benzene-d)₆)δ7.88(br s,1H),7.13(dd,J＝11.2,3.3Hz,2H),7.09–7.05(m,2H),6.84(dd,J＝8.3,3.2Hz,2H),6.73(dd,J＝8.0,3.3Hz,2H),4.67(d,J＝12.1Hz,2H),4.32(d,J＝1f1.9 Hz,2H),2.75(d,J＝12.2Hz,2H),2.67(d,J＝12.0Hz,2H),2.10(s,10H),1.91(s,3H),1.42(s,18H),1.35–1.15(m,12H),1.21(s,18H),1.10–1.00(m,4H),0.92(t,J＝7.1Hz,6H),0.87–0.71(m,8H)。¹³C NMR (101MHz, benzene-d)₆)δ160.69–160.60(m),160.01–159.92(m),152.91(d,J_F-C＝230.6Hz),152.66(d,J_F-C＝227.4Hz),138.35(d,J_F-C＝5.4Hz),137.46(d,J_F-C＝5.6Hz),124.83(d,J_F-C＝7.0Hz),123.05(d,J_F-C＝7.3Hz),115.01(d,J_F-C＝21.6Hz),114.33(d,J_F-C＝22.4Hz),114.06(d,J_F-C＝21.8Hz),113.46(d,J_F-C＝22.4Hz),64.64,63.68,55.56,39.66,39.07,35.18,34.63,30.02,29.49,29.03,26.18,23.24,22.64,13.94。¹⁹F NMR (376MHz, benzene-d)₆)δ-129.81,-131.81–-132.28(m)。C₁₇H₃₈N[M⁺]Hrms (esi) calculated 256.2999; found 256.2989. C₄₆H₅₈F₄N₂O₄Y[M^-]Calculated value of 867.3397; found 867.3416.

EXAMPLE 19 Synthesis of 2- (tert-butyl) -3,4, 5-trifluorophenol

In a glove box filled with nitrogen, 3,4, 5-trifluorophenol (3.00g, 20.3mmol, 1 eq.), ZrCl₄(2.36g, 10.1mmol, 0.5 equiv.) and MTBE (5.3mL, 44.6mmol, 2.2 equiv.) were charged to the reaction flask. After addition of MTBE, a significant exotherm was observed. The vial was capped, removed from the glove box, and stirred at 50 ℃ for 4 days. The reaction turned deep red. The reaction was allowed to settle and cooled to room temperature. The mixture was poured into saturated NH₄Aqueous Cl solution (70 mL). 2M aqueous HCl (30mL) was added. The aqueous phase was washed with diethyl ether (3 × 50 mL). Upon quenching, the color changed to light yellow. The organic phase is passed over MgSO₄Dried, filtered and concentrated in vacuo. After concentration the colour turned back dark purple. The material was adsorbed onto silica gel and purified by flash column chromatography (ISCO, 120g silica gel, 20-40% CH)₂Cl₂Hexanes) to give the product as a green solid (2.17g, 16% yield).

¹H NMR (400MHz, chloroform-d) δ 6.31(ddd, J ═ 10.8,6.5,2.4Hz,1H),4.92(s,1H),1.47(d, J ═ 3.2Hz, 9H).¹⁹F NMR (376MHz, chloroform-d) δ -130.25(dtq, J ═ 19.1,6.4,2.9Hz), -139.11(ddd, J ═ 22.1,10.8,7.1Hz), -170.07(ddd, J ═ 21.9,19.3,6.5 Hz).¹³C NMR (101MHz, chloroform-d) delta 151.19(ddd, J)_F-C248.2,10.9,5.0Hz), 149.72-146.66 (m,2 carbons), 135.38(ddd, J)_F-C＝241.5,19.3,14.3Hz),120.18(ddd,J_F-C＝11.0,4.4,3.3Hz),100.43(dd,J_F-C＝19.3,3.1Hz),36.12(dd,J_F-C＝2.9,1.2Hz),30.74(d,J_F-C＝5.9Hz)。C₁₀H₁₁F₃O[M-1]Hrms (esi) calculated 204.0762; found 204.0718.

Example Synthesis of 20-6, 6' - ((Methylazadiyl) bis (methylene)) bis (2- (tert-butyl) -3,4, 5-trifluorophenol)

Paraformaldehyde (0.297g, 9.89mmol, 2 equivalents), potassium hydroxide (2.8mg, 0.0495mmol, 1 mol%) and methanol (1mL) were charged to a 25mL round bottom flask. 40% w/w aqueous methylamine solution (0.43mL, 2.34mmol, 1 equiv.) was added dropwise to the methanol solution. Most of the solid dissolved, but the solution remained cloudy. 2- (tert-butyl) -3,4, 5-trifluorophenol (2.02g, 9.89mmol, 2 equiv.) was added to the reaction. The 2- (tert-butyl) -3,4, 5-trifluorophenol vial was rinsed four times with 1mL of methanol, and the rinse was added to the reaction. The mixture was stirred at reflux (100 ℃) for 4 days, resulting in an orange solution. The solution was concentrated in vacuo, adsorbed onto silica gel, and purified by flash column chromatography (ISCO, 120g silica gel, 3-20% EtOAc/hexanes) to give the product as an orange oil (0.96g, 42% yield).

¹H NMR (400MHz, chloroform-d) δ 8.52(s,2H),3.75(d, J ═ 1.9Hz,4H),2.39(s,3H),1.49(d, J ═ 3.4Hz, 18H).¹⁹F NMR (376MHz, chloroform-d) δ -131.23(dtd, J ═ 20.2,6.6,3.2Hz,2F), -142.88(dd, J ═ 22.7,7.3Hz,2F), -171.09(dd, J ═ 22.6,20.4Hz, 2F).¹³C NMR (101MHz, chloroform-d) delta 150.84(ddd, J)_F-C＝9.7,5.8,3.4Hz),150.50(ddd,J_F-C＝248.4,10.9,5.4Hz),147.35(ddd,J_F-C＝244.9,11.0,6.3Hz),134.77(ddd,J_F-C＝241.1,19.4,15.5Hz),120.47(ddd,J_F-C＝10.1,4.5,3.0Hz),106.54(ddd,J_F-C＝12.5,3.5,1.4Hz),50.29,41.41,30.71(d,J_F-C＝5.9Hz)。C₂₃H₂₇F₆NO₂[M+1]Hrms (esi) calculated 464.2019; found 464.2015.

EXAMPLE 21 Synthesis of potassium bis [6,6' - ((methylazadiyl) bis (methylene)) bis (2- (tert-butyl) -3,4, 5-trifluorophenol) ] yttrium

In a nitrogen-filled glove box, a solution of 6,6' - ((methylazadiyl) bis (methylene)) bis (2- (tert-butyl) -3,4, 5-trifluorophenol) (0.681g, 1.47mmol, 2 equivalents) in toluene (5mL) was added to a reaction tank containing tris (bis (trimethylsilyl) amino) yttrium (0.419g, 0.735mmol, 1 equivalent) and toluene (5 mL). The vial of 6,6' - ((methylazadiyl) bis (methylene)) bis (2- (tert-butyl) -3,4, 5-trifluorophenol) was rinsed three times with an additional 5mL of toluene and added to the reaction. The reaction turned orange immediately after the addition of yellow phenol. The reaction was stirred at room temperature for 2 hours. All volatiles were removed in vacuo to give an orange solid. The solid was dissolved in toluene (15 mL). Addition of a solution of KHMDS (146.6mg, 0.735mmol, 1 eq) in toluene (3mL) caused immediate precipitation of the solid and a yellow color change. KHMDS vials were washed with toluene (3x3mL) and added to the reaction. The reaction was allowed to stir at room temperature for 2 hours. The precipitate still remains. All volatiles were removed in vacuo to yield an off-white powder. The solid was dissolved in THF (15mL) and stirred briefly. All volatiles were removed in vacuo. The solid was wet-milled with toluene (10mL) and all volatiles were removed again in vacuo to give the product as an off-white solid (0.825g, 98% yield). The material contained 0.5 equivalents of toluene and 0.75 equivalents of THF.

¹H NMR(400MHz,THF-d₈)δ4.21(dd,J＝12.8,2.2Hz,4H),3.52(d,J＝12.7Hz,2H),3.43(d,J＝12.5Hz,2H),2.02(s,6H),1.47(d,J＝3.4Hz,18H),1.14(d,J＝3.2Hz,18H)。¹⁹F NMR(376MHz,THF-d₈) δ -137.52(d, J ═ 19.9Hz,4F), -147.66(dddd, J ═ 330.6,23.7,6.2,3.0Hz,4F), -182.73(ddd, J ═ 186.2,23.6,21.3Hz, 4F). Due to the extensive C-F and C-Y coupling,¹³c NMR is very complex. C₄₆H₅₀F₁₂N₂O₄Y[M^-]Hrms (esi) calculated 1011.2643; found 1011.2669.

Example 22-synthesis of activator 2, Armeenium M2HT bis [6,6' - ((methylazadiyl) bis (methylene)) bis (2- (tert-butyl) -3,4, 5-trifluorophenol) ] yttrium-activator 2

In a glove box filled with nitrogen, potassium yttrium bis [6,6' - ((methylazadiyl) bis (methylene)) bis (2- (tert-butyl) -3,4, 5-trifluorophenol) ] (0.200g, 0.174mmol, 1 eq) and armenium M2HT hydrochloride (99.5mg, 0.174mmol, 1 eq) were stirred in toluene (10mL) for 5 days, yielding a cloudy yellow solution. The reaction mixture was passed through a 0.45 μm syringe filter in line with a 0.2 μm syringe filter to yield a clear yellow solution. All volatiles were removed in vacuo to yield a yellow oil. The oil was wet-milled with hexane (5mL) and all volatiles were removed in vacuo (this procedure was repeated a total of two times) to give the product as a yellow oil (0.226g, 84% yield).

¹H NMR (400MHz, toluene-d)₈)δ4.46(d,J＝12.3Hz,4H),3.72(d,J＝12.7Hz,2H),3.64(d,J＝12.5Hz,2H),2.27(s,4H),2.22–2.13(m,4H),1.91(s,2H),1.72(d,J＝3.2Hz,18H),1.43–1.16(m,75H),1.12–1.01(m,4H),0.99–0.80(m,12H)。¹⁹F NMR (376MHz, toluene-d)₈) δ -135.80(d, J ═ 22.1Hz,2F), -136.36(d, J ═ 22.3Hz,2F), -145.37(dd, J ═ 24.1,5.8Hz,2F), -146.59(dd, J ═ 24.2,5.9Hz,2F), -180.34(t, J ═ 23.1Hz,2F), -181.14(t, J ═ 23.0Hz, 2F). Due to the extensive C-F and C-Y coupling,¹³c NMR is very complex. C₃₇H₇₈N[M⁺]Hrms (esi) calculated 536.6129; found 536.6129. C₄₆H₅₀F₁₂N₂O₄Y[M^-]Calculated value of 1011.2643; found 1011.2640.

Example 23 polymerization results

Polymerization was conducted in a batch reactor to evaluate activator efficiency of activators 1-2 and resulting polymer characteristics. The catalyst system for polymerization comprises an activator having a structure according to formula (I) or a comparative activator not having a structure according to formula (I), wherein procatalyst a or procatalyst B is the procatalyst. Procatalyst a is a bis-biphenyl phenoxy procatalyst having a structure according to formula (X) (the structure is shown below).

Activators 1 and 2 of the present invention and comparative C1-C6 were effective. The results are summarized in tables 1, 23 and 4. The data in tables 1,2,3 and 4 were obtained at a polymerization temperature of 140 ℃.

TABLE 1-1 gallon batch reactor results using procatalyst A

Polymerization conditions: 415psig C₂H₄215g octene, 1350g Isopar E; the procatalyst to activator ratio was 1: 1.2.

TABLE 2L batch reactor data Using procatalyst A

Polymerization conditions: 360psig C₂H₄104g octene, 693g Isopar E, 0.75. mu. mol TEA, 0.015. mu. mol procatalyst A; the procatalyst to activator ratio was 1: 1.2.

The addition of fluorine atoms to the yttrium complex increases the efficiency of the activator when compared to yttrium complex without fluorine.

TABLE 3 2L batch reactor data Using procatalyst A

Polymerization conditions: 288psig C₂H₄300g octene, 605g Isopar E, 10. mu. mol TEA, 0.1. mu. mol procatalyst A; the procatalyst to activator ratio was 1: 1.2.

TABLE 4 2L batch reactor data Using procatalyst B

Polymerization conditions: 288psig C₂H₄300g octene, 605g Isopar E, 0. mu. mol TEA, 1. mu. mol procatalyst B; the procatalyst to activator ratio was 1: 1.2.

The calculation method comprises the following steps: the ground state geometry of all anions was optimized at the B971/6-31g x level using Density Functional Theory (DFT). The effective nuclear potential of Y is incorporated by including SDD groups on those atoms. The ground state of the anion is assumed to be in a singlet closed shell structure. The effect of the dielectric is incorporated using a conductor-like polarizable continuum model (cpcm); cyclohexane was chosen as a representative medium. Since the energies of the cations and anions are calculated separately, the electrostatic interaction between them is not considered in these calculations. To account for this, the electrostatic potential at each atom of the reactants (reactant 1 and reactant 2) was calculated using the Merz-Kollman-Singh population analysis, where the radius of each atom was taken from the universal force field (mkuff). These calculations are performed using the G09 suite. Calculating the electrostatic interaction between the anion and the cation using the following steps; first, the charge on each atom of the anion (obtained using the mkuff method) was scaled by 0.5 (the dielectric constant of cyclohexane is 2.0), and the relative distance and orientation between the anion and cation was optimized using a universal force field. For force field calculations, the respective geometries of the anion and cation do not allow relaxation, and the cutoff distances neglecting electrostatic and van der Waals interactions are chosen to beVarious initial conformations were selected by varying the relative orientation and distance between the anion and cation and then subjected to a force field optimization procedure. The conformation with the highest electrostatic interaction (Eelec; most negative) was used to calculate the final energy of the cation-anion pair. The force field calculation is performed using a Forcite module, as implemented in Materials Studio 8.0. All energies are reported in kcal/mol.

Catalytic compositions comprising activators having more than one fluorine atom substituted for each phenolic moiety (in other words, more than 4 in yttrium complex)The catalyst system has a higher efficiency than a catalyst system in which the activator does not have more than one fluorine atom substituted for each phenol moiety. The basis for the increased efficiency of catalyst systems comprising activators having a large number of fluorine atoms in the yttrium complex is due to the Δ E as fluorine atoms are added to the complex_{Protonation of}Increased (table 5). In other words, these calculations indicate the R of the activated catalyst system₃NH⁺The charged species are stabilized by the presence of fluorine atoms. The higher the number of fluorine atoms, the more stable the charged species, which is necessary to activate the procatalyst. Similar calculations (table 6) indicate that cation from activator a (Armeen M2HT was approximated as Et₂NMe) cations from comparative C5 and comparative C6 were expected to perform poorly compared; negative Delta E_{Activation of}Resulting in advantageous activation of the procatalyst.

TABLE 5 calculated anion protonation energy (. DELTA.E) for atom pair F_{Protonation of}) Influence of (2)

TABLE 6 variation of protonation energy (. DELTA.E) of activator to procatalyst-A_{Activation of}) Influence of (2)

Species (II)	ΔEActivation of(kcal/mol)
		Activator A	-16.2
Comparison C6	3.2
		Comparison C5	8.4