阅读说明：本技术 用于烯烃聚合的联芳基苯氧基第iv族过渡金属催化剂 (Biarylphenoxy group IV transition metal catalysts for olefin polymerization ) 是由 E·苏罗米 D·D·德沃尔 R·D·J·费勒泽 A·L·克拉索夫斯基 孙立新 K·A·弗雷 于 2018-06-18 设计创作，主要内容包括：实施例涉及一种包含金属配体络合物的催化剂系统和用于聚烯烃聚合的方法,所述方法使用具有以下结构的金属配体络合物进行：<Image he="574" wi="590" file="DDA0002290867360000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(Embodiments relate to a catalyst system comprising a metal-ligand complex and a method for polyolefin polymerization using a metal-ligand complex having the following structure:)

1. A catalyst system comprising a metal-ligand complex according to formula (I):

wherein

M is a metal selected from titanium, zirconium or hafnium, said metal having a formal oxidation state of +2, +3 or + 4;

each X is a monodentate or bidentate ligand independently selected from: unsaturated (C)₂-C₂₀) Hydrocarbon, unsaturated (C)₂-C₅₀) Heterohydrocarbons, (C)₁-C₅₀) Hydrocarbyl radical, (C)₆-C₅₀) Aryl group, (C)₆-C₅₀) Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C)₄-C₁₂) Diene, halogen, -N (R)^N)₂and-NCOR^C；

n is 1, 2 or 3;

m is 1 or 2;

the metal-ligand complex has 6 or fewer metal-ligand bonds;

each Y is independently selected from oxygen or sulfur;

each R¹、R²、R³And R⁴Independently selected from the group consisting of: (C)₁-C₅₀) Hydrocarbyl radical, (C)₁-C₅₀) Heterohydrocarbyl, (C)₆-C₅₀) Aryl group, (C)₄-C₅₀) Heteroaryl, -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)-、(R^C)₂NC (O) -, halogen and-H;

each R⁵Independently selected from (C)₁-C₅₀) Hydrocarbyl radical, (C)₁-C₅₀) Heterohydrocarbyl, (C)₆-C₅₀) Aryl group, (C)₄-C₅₀) Heteroaryl, -Si (R)^C)₃and-Ge (R)^C)₃And when m is 2, two R⁵Optionally covalently linked;

for containing a group z₁、z₂And z₃Each individual ring of (a), z₁、z₂And z₃Each independently selected from the group consisting of sulfur, oxygen, -N (R)^R) -or-C (R)^R) -a group of compositions with the proviso that z₁、z₂And z₃At least one and not more than two of which are-C (R)^R) -, wherein R^Ris-H or (C)₁-C₃₀) Hydrocarbyl groups in which any two R's bonded to adjacent atoms^RThe groups are optionally linked;

each R in the formula (I)^C、R^NAnd R^PIndependently is (C)₁-C₃₀) A hydrocarbyl group.

2. The catalyst system of claim 1, wherein:

m is zirconium or hafnium;

each X is independently selected from (C)₆-C₂₀) Aryl group, (C)₄-C₂₀) Heteroaryl, (C)₄-C₁₂) A diene or halogen;

each Y is oxygen;

each R¹Independently selected from (C)₁-C₅₀) Aryl group, (C)₄-C₅₀) A heteroaryl group; and is

Each R²、R³And R⁴Independently selected from (C)₁-C₅₀) Hydrocarbyl radical, (C)₁-C₄₀) Heterohydrocarbyl, (C)₆-C₄₀) Aryl group, (C)₄-C₅₀) Heteroaryl, halo, and-H.

3. The catalyst system according to claim 1 or 2, wherein for a group containing z₁、z₂And z₃Each individual ring of (a), z₁、z₂And z₃Is a sulfur atom, and z₁、z₂And z₃Two of which are-C (H) -.

4. The catalyst system of any one of claims 1 to 3, wherein each R¹Is a carbazolyl group, each R²Is methyl, and each R³Is methyl.

5. The catalyst system of any one of claims 1 to 3, wherein each R¹Is a 3, 6-di-tert-butylcarbazol-9-yl group.

6. The catalyst system of any one of claims 1 to 3, wherein each R¹Is 3, 5-di-tert-butylphenyl.

7. The catalyst system of any one of claims 1, 2, 3, 5, or 6, wherein R²Is a tert-octyl group.

8. The catalyst system of claim 1, wherein m is 2 and the metal-ligand complex has a structure according to formula (II):

wherein R is¹、R²、R³、R⁴、R⁵、z₁、z₂、z₃Y and X are as defined in formula (I); and n is 1 or 2.

9. The catalyst system of claim 8, wherein:

m is zirconium or hafnium;

each X is independently selected from (C)₆-C₅₀) Aryl group, (C)₆-C₅₀) Heteroaryl, (C)₄-C₁₂) A diene or halogen;

each Y is oxygen;

each R¹、R²、R³And R⁴Independently selected from (C)₁-C₅₀) Hydrocarbyl radical, (C)₁-C₅₀) Heterohydrocarbyl, (C)₆-C₅₀) Aryl group, (C)₄-C₅₀) Heteroaryl, halogen and hydrogen.

10. The catalyst system of claim 8, wherein z for a group containing₁、z₂And z₃Each individual ring of (a), z₁、z₂And z₃Is a sulfur atom, and z₁、z₂And z₃Two of which are-C (H) -.

11. The catalyst system according to claim 9 or 10, wherein n is 2 and each X is benzyl.

12. The catalyst system of any one of claims 8 to 11, wherein each R¹Is a carbazolyl group, each R²Is methyl, and each R³Is methyl.

13. The catalyst system of any one of claims 8 to 11, wherein each R¹Is 3, 6-di-tert-butylcarbazol-9-yl or 2, 7-di-tert-butylcarbazol-9-yl.

14. The catalyst system of any one of claims 8, 9, 10, 11, or 13, wherein each R is³Is a tert-octyl group.

15. The catalyst system of any one of claims 8 to 11, wherein each R¹Is 3, 5-di-tert-butylphenyl.

16. The catalyst system according to any one of claims 8 to 15, wherein two groups R⁵Covalently linked, whereby the metal-ligand complex comprises a group R linked by the two covalent bonds⁵A divalent group Q of composition, and the metal-ligand complex has a structure according to formula (III):

wherein:

q is (C)₁-C₁₂) Alkylene, (C)₁-C₁₂) Heteroalkylidene, (-CH)₂Si(R^C)₂CH₂-)、(-CH₂CH₂Si(R^C)₂CH₂CH₂-)、(-CH₂Ge(R^C)₂CH₂-) or (-CH₂CH₂Ge(R^C)₂CH₂CH₂-^CIs (C)₁-C₃₀) A hydrocarbyl group;

R^1-4、Y、X、M、z₁、z₂and z₃As defined in formula (I); and is

n is 1 or 2.

17. The catalyst system of claim 16, wherein Q is-CH₂Si(CH₃)₂CH₂-。

18. A polymerization process for making an ethylene-based polymer, the polymerization process comprising:

polymerizing ethylene with at least one additional alpha-olefin in the presence of the catalyst system of any one of claims 1 to 17 and at least one activator to form a polymer,

wherein the polymer exhibits:

0.860g/cm measured according to ASTM D792³To 0.973g/cm³(ii) a density of (d);

a molecular weight distribution of 1 to 20; and

less than 20% octene incorporation.

19. The polymerization process of claim 17, wherein the density is 0.880g/cm³To 0.920g/cm³。

20. The polymerization process of claim 17, wherein the activator comprises MMAO, bis (hydrogenated tallowalkyl) methylammonium, tetrakis (pentafluorophenyl) borate, or tris (pentafluorophenyl) borane.

Technical Field

Embodiments of the present disclosure relate generally to olefin polymerization catalyst systems and methods, and more particularly, to the synthesis of biarylphenoxy group IV transition metal catalysts for olefin polymerization, and to olefin polymerization processes incorporating the catalyst systems.

Background

Olefin-based polymers, such as polyethylene and/or polypropylene, are made by various catalyst systems. The selection of such catalyst systems for use in the polymerization process of olefin-based polymers is an important factor affecting the characteristics and properties of such olefin-based polymers.

Polyethylene and polypropylene are manufactured for use in a variety of articles. Polyethylene and polypropylene polymerization processes can be varied in many ways to produce a variety of resulting polyethylene resins having different physical properties that make the various resins suitable for different applications. Ethylene monomer and optionally one or more comonomers are present in a liquid diluent, such as an alkane or isoalkane, for example isobutane. Hydrogen may also be added to the reactor. The catalyst system used to make polyethylene may typically comprise a chromium-based catalyst system, a Ziegler-Natta catalyst system or a molecular (metallocene or non-metallocene) catalyst system. The reactants in the diluent and the catalyst system are circulated around the reactor at an elevated polymerization temperature to produce a polyethylene homopolymer or copolymer. Periodically or continuously, a portion of the reaction mixture, including the polyethylene product dissolved in the diluent, as well as unreacted ethylene and one or more optional comonomers, is removed from the reactor. When removed from the reactor, the reaction mixture may be processed to remove polyethylene product from the diluent and unreacted reactants, which are typically recycled back to the reactor. Alternatively, the reaction mixture may be sent to a second reactor, for example a reactor connected in series to the first reactor, in which a second polyethylene fraction may be produced.

Despite the research efforts in developing catalyst systems suitable for olefin polymerization (e.g., polyethylene or polypropylene polymerization), there remains a need for procatalysts and catalyst systems that exhibit higher efficiencies than comparable catalyst systems, which are capable of producing polymers having high molecular weights and narrow molecular weight distributions.

Disclosure of Invention

According to some embodiments, the catalyst system comprises a metal-ligand complex according to formula (I):

in formula (I), M is a metal selected from titanium, zirconium or hafnium, said metal having a formal oxidation state of +2, +3 or + 4. Each X is a monodentate or bidentate ligand independently selected from: (C)₁-C₅₀) Hydrocarbon, (C)₁-C₅₀) Heterohydrocarbons, (C)₁-C₅₀) Hydrocarbyl radical, (C)₆-C₅₀) Aryl group, (C)₆-C₅₀) Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C)₄-C₁₂) Diene, halogen, -N (R)^N)₂and-NCOR^C. Subscript n is 1, 2, or 3; subscript m is 1 or 2; the metal-ligand complex has 6 or less metal-ligand bonds and is charge neutral as a whole.

In embodiments of formula (I), each Y is independently selected from oxygen or sulfur. Each R¹、R²、R³And R⁴Independently selected from the group consisting of: (C)₁-C₅₀) Hydrocarbyl radical, (C)₁-C₅₀) Heterohydrocarbyl, (C)₆-C₅₀) Aryl group, (C)₄-C₅₀) Heteroaryl, -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)-、(R^C)₂NC (O) -, halogen and-H. Each R⁵Independently selected from (C)₁-C₅₀) Hydrocarbyl radical, (C)₁-C₅₀) Heterohydrocarbyl, (C)₆-C₅₀) Aryl group, (C)₄-C₅₀) Heteroaryl, -Si (R)^C)₃and-Ge (R)^C)₃And when m is 2, two R⁵Optionally covalently linked.

In the examples of formula (I), for radicals containing z₁、z₂And z₃Each individual ring of (a), z₁、z₂And z₃Each independently selected from the group consisting of sulfur, oxygen, -N (R)^R) -or-C (R)^R) -a group of and z₁、z₂And z₃At least one and not more than two of which are-C (R)^R) -, wherein R^Ris-H or (C)₁-C₃₀) Hydrocarbyl groups in which any two R's bonded to adjacent atoms^RThe groups are optionally linked. In the formula (I), each R in the formula (I)^C、R^NAnd R^PIndependently is (C)₁-C₃₀) A hydrocarbyl group.

Detailed Description

Specific embodiments of the catalyst system will now be described. It is understood that the catalyst system of the present disclosure may be embodied in different forms and should not be construed as limited to the specific embodiments set forth in the disclosure. Rather, the embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

Common abbreviations are as follows:

r, Z, M, X and n: as defined above; me: a methyl group; et: ethyl radical(ii) a 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; THF: tetrahydrofuran; et (Et)₂O: diethyl ether; CH (CH)₂Cl₂: dichloromethane; 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: hydrogen chloride; t-BuLi: tert-butyl lithium; cs₂CO₃: cesium carbonate; HfCl₄: hafnium (IV) chloride; HfBn₄: hafnium (IV) tetrabenzyl; ZrCl₄: zirconium (IV) chloride; ZrBn₄: tetrabenzyl zirconium (IV); n is a radical of₂: nitrogen gas; PhMe: toluene; PPR: a parallel polymerization reactor; 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: the method comprises the following steps of (1) taking minutes; h: hours; d: and (5) day.

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 R⁵May all 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 what is recognized in the art as a chemical structure corresponding to that of the chemical name. Accordingly, the chemical designations are intended to supplement and illustrate, but not 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 atomsWhen has the form ″ (C)_x-C_y) The parenthetical representation 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 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) "R of a chemical group defined in parentheses^SThe substituted form may contain more than y carbon atoms, depending on any group R^SThe identity of (c). For example, "by exactly one group R^SSubstituted (C)₁-C₅₀) Alkyl radical, wherein R^SIs phenyl (-C)₆H₅) ", may contain from 7 to 56 carbon atoms. Therefore, in general, "(C) is used_x-C_y) "chemical groups defined in parentheses by one or more substituents R containing carbon atoms^SWhen substituted, the minimum and maximum total number of carbon atoms of the chemical group is determined by substituting R substituents from all carbon-containing atoms^SThe combined sum of the number of carbon atoms of (a) is added to both x and y.

The term "substituted" means that at least one hydrogen atom (-H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is substituted (e.g., R)^S) And (4) replacement. The term "fully substituted" means that each hydrogen atom (H) bonded to a carbon atom or heteroatom of a corresponding unsubstituted compound or functional group is substituted with a substituent (e.g., R)^S) And (4) replacement. The term "polysubstituted" means that at least two, but less than all, of the carbon atoms or heteroatoms bonded to the corresponding unsubstituted compound or functional group are replaced with substituents. The term "-H" means a hydrogen or hydrogen radical covalently bonded to another atom. "hydrogen" and "-H" are interchangeable and have the same meaning unless explicitly specified.

Term "(C)₁-C₅₀) The hydrocarbon group "means a hydrocarbon group having 1 to 50 carbon atoms, and the term" (C)₁-C₅₀) Alkylene "means a hydrocarbon diradical having 1 to 50 carbon atoms, each of which isThe hydrocarbyl and each hydrocarbyl diradical are 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 are substituted with one or more R^SSubstituted or unsubstituted.

In the present disclosure, (C)₁-C₅₀) The hydrocarbon group 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. benzyl (-CH)₂-C₆H₅))。

Term "(C)₁-C₅₀) Alkyl "and" (C)₁-C₁₈) Alkyl "means a saturated straight-chain or branched-chain hydrocarbon radical of 1 to 50 carbon atoms and a saturated straight-chain or branched-chain hydrocarbon radical of 1 to 18 carbon atoms, respectively, unsubstituted or substituted by one or more R^SAnd (4) substitution. Unsubstituted (C)₁-C₅₀) Examples of alkyl radicals 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 (including substituents) and is, for example, (C) substituted by one Rs₂₇-C₄₀) Alkyl radical, said R^SIs accordingly (C)₁-C₅) 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 by one or more R)^S) A substituted monocyclic aromatic hydrocarbon group, bicyclic aromatic hydrocarbon group or tricyclic aromatic hydrocarbon group of 6 to 40 carbon atoms, wherein at least 6 to 14 of the carbon atoms are aromatic ring carbon atoms. The monocyclic ring system has one ring, which is aromatic; 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 in the group is aromatic. The polycyclic groups are independently fused or non-fused. Unsubstituted (C)₆-C₅₀) Examples of aryl groups include: unsubstituted (C)₆-C₂₀) An aryl group; unsubstituted (C)₆-C₁₈) An aryl group; 2- (C)₁-C₅) Alkyl-phenyl; a phenyl group; a fluorenyl group; a tetrahydrofluorenyl group; dicyclopentadiene acenyl (indacenyl); hexahydro-dicyclopentadiene-o-phenyl; 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; a polyfluorophenyl group; pentafluorophenyl; and fluoren-9-on-1-yl.

Term "(C)₃-C₅₀) Cycloalkyl "means unsubstituted or substituted by one or more R^SSubstituted saturated cyclic hydrocarbon groups of 3 to 50 carbon atoms. Other cycloalkyl groups (e.g., (C)_x-C_y) Cycloalkyl) is 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 radicals 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 radicals are substituted (C)₃-C₂₀) Cycloalkyl, substituted (C)₃-C₁₀) Cycloalkyl, cyclopentanone-2-yl and 1-fluorocyclohexyl.

(C₁-C₅₀) Of alkylene groupsExamples 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 on the same carbon atom (e.g., -CH)₂-) or on adjacent carbon atoms (i.e., a1, 2-diradical), or separated by one, two, or more than two intervening carbon atoms (e.g., a1, 3-diradical, a1, 4-diradical, etc.). Some diradicals include a1, 2-diradical, a1, 3-diradical, a1, 4-diradical or an alpha, omega-diradical, 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) By alkylene "is meant a saturated straight or branched chain diradical of 1 to 50 carbon atoms (i.e., the group is not on a ring atom) that is unsubstituted or substituted with one or more R^SAnd (4) substitution. Unsubstituted (C)₁-C₅₀) Examples of alkylene groups 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" represents 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 groups are substituted (C)₁-C₂₀) Alkylene, -CF₂-, -C (O) -and- (CH)₂)₁₄C(CH₃)₂(CH₂)₅- (i.e. 6, 6-dimethyl-substituted n-1)20-eicosylene). Since, as mentioned previously, two R are^SMay be formed together (C)₁-C₁₈) Alkylene, 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 unsubstituted or substituted with one or more R^SSubstituted cyclic diradicals of 3 to 50 carbon atoms (i.e., the groups are on a ring atom).

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 RP is 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 backbone in which one or more carbon atoms of a hydrocarbon are replaced with a heteroatom. Term "(C)₁-C₅₀) Heterohydrocarbyl "means a heterohydrocarbyl of 1 to 50 carbon atoms, and the term" (C)₁-C₅₀) Heterohydrocarbylene "means a heterohydrocarbadiyl of 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 heterohydrocarbyl groups may be on a single carbon atom or on a single heteroatom. In addition, one of the two groups of the diradical can be on a carbon atom and the other group can 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) AThe heterocarbon groups may be unsubstituted or substituted (by one or more Rs), aromatic or non-aromatic, saturated or unsaturated, straight or branched chain, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic.

(C₁-C₅₀) The heterohydrocarbyl 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) Heteroalkylidene, (C)₂-C₁₉) Heterocycloalkyl- (C)₁-C₂₀) Heteroalkylidene, (C)₁-C₅₀) Heteroaryl, (C)₁-C₁₉) Heteroaryl- (C)₁-C₂₀) Alkylene, (C)₆-C₂₀) Aryl radical- (C)₁-C₁₉) Heteroalkylidene or (C)₁-C₁₉) Heteroaryl- (C)₁-C₂₀) A heteroalkylene group.

Term "(C)₄-C₅₀) Heteroaryl "means 4 to 50 total carbon atoms and 1 to 10 heteroatoms unsubstituted or substituted with (one or more R)^S) A substituted, monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon group. The monocyclic heteroaromatic hydrocarbon group includes 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 in 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., in general, (C)_x-C_y) Heteroaryl, e.g. (C)₄-C₁₂) Heteroaryl) is defined in like manner as having x to y carbon atoms (e.g., 4 to 12 carbon atoms) and is unsubstituted or substituted with one or more than one R^SAnd (4) substitution. The monocyclic heteroaromatic hydrocarbon group is a 5-or 6-membered ring. The 5 membered ring has 5 minus h carbon atoms, where h is the number of heteroatoms, and can 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 ring has 6 minus h carbon atoms, where h is the number of heteroatoms and can be 1 or 2, and the heteroatoms can 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 radical may 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 groups are quinolin-2-yl; and isoquinolin-1-yl. The tricyclic heteroaromatic hydrocarbon group may be a fused 5, 6, 5-; 5, 6, 6-; 6, 5, 6-; 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 group containing one or more of one to fifty carbon atoms, or fewer carbon and 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 heteroalkyl and heteroalkylene are each unsubstituted or substituted with one or more R^SAnd (3) substituted.

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 "halogen atom" or "halogen" means a group of fluorine atom (F), chlorine atom (Cl), bromine atom (Br) or iodine atom (I). The term "halide" means the anionic form of the halogen atom: fluoride ion (F)^-) Chloride ion (Cl)^-) Bromine ion (Br)^-) Or iodide ion (I)^-)。

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. When the saturated chemical group is substituted by one or more substituents R^SWhen substituted, one or more double and/or triple bonds may or may not optionally be present in the substituent R^SIn (1). The term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, or (in heteroatom-containing groups) one or more carbon-nitrogen, carbon-phosphorus or carbon-silicon double bonds, excluding that may be present in the substituent R^SAny such double bonds (if present) or (hetero) aromatic rings (if present).

Embodiments of the present disclosure include a catalyst system comprising a metal-ligand complex according to formula (I):

in formula (I), M is a metal selected from titanium, zirconium or hafnium, said metal having a formal oxidation state of +2, +3 or + 4; each X is a monodentate or bidentate ligand independently selected from the group consisting of: (C)₁-C₅₀) Hydrocarbyl radical, (C)₆-C₂₀) Aryl group, (C)₆-C₂₀) Heteroaryl, cyclopentadienyl, substituted cyclopentadienyl, (C)₄-C₁₂) Dienes, halogens, and amides. (X) number indicating the ligand X bound to or associated with the metal M_nThe subscript n of (a) is an integer of 1, 2 or 3. Subscript m is 1 or 2; the metal-ligand complex has 6 or fewer metal-ligand bonds and may be charge neutral as a whole or may have a positive charge associated with the metal center. Each Y is independently selected from oxygen or sulfur.

In an embodiment, the catalyst system may comprise a metal-ligand complex according to formula (I), wherein each R is¹、R²、R³And R⁴Independently selected from the group consisting of: (C)₁-C₅₀) Hydrocarbyl radical, (C)₁-C₅₀) Heterohydrocarbyl, (C)₁-C₅₀) Aryl group, (C)₁-C₅₀) Heteroaryl, -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)-、(R^C)₂NC (O) -, halogen and-H; and wherein each R⁵Independently selected from (C)₁-C₅₀) Hydrocarbyl radical, (C)₁-C₅₀) Heterohydrocarbyl, (C)₆-C₅₀) Aryl group, (C)₄-C₅₀) Heteroaryl, -Si (R)^C)₃and-Ge (R)^C)₃. Each R in the formula (I)^C、R^NAnd R^PIndependently is (C)₁-C₃₀) A hydrocarbyl group.

In some embodiments, the metal-ligand of formula (I)Chemical groups of body complexes (e.g. X, R)^1-5Y and z_1-3) Any or all of which may be unsubstituted. In other embodiments, the chemical group X, R of the metal-ligand complex of formula (I)^1-5Y and z_1-3None, any or all of which may be substituted by one or more than one R^SAnd (4) substitution. When two or more than two R are present^SEach R of the chemical groups, when bonded to the same chemical group of the metal-ligand complex of formula (I)^SMay be bonded to the same carbon atom or heteroatom or to different carbon atoms or heteroatoms. In some embodiments, the chemical group X, R^1-5Y and z_1-3None, any or all of which may be substituted by R^SAnd (4) full substitution. In at least one position of R^SIn the fully substituted chemical group, each R^SMay all be the same or may be independently selected.

In some embodiments, the catalyst system comprises a metal-ligand complex according to formula (I), wherein M is zirconium or hafnium; each X is independently selected from (C)₆-C₂₀) Aryl group, (C)₆-C₂₀) Heteroaryl, (C)₄-C₁₂) A diene or halogen; each Y is oxygen; each R¹Independently selected from (C)₁-C₅₀) Aryl group, (C)₁-C₅₀) A heteroaryl group; and each R²、R³And R⁴Independently selected from (C)₁-C₅₀) Hydrocarbyl radical, (C)₁-C₅₀) Heterohydrocarbyl, (C)₁-C₅₀) Aryl group, (C)₁-C₅₀) Heteroaryl, halo, and-H.

In some catalyst systems of the present disclosure, the catalyst system may comprise a metal-ligand complex according to formula (I), wherein each individual ring contains a group z₁、z₂And z₃，z₁、z₂And z₃Each independently selected from the group consisting of sulfur, oxygen, -N (R)^R) -or-C (R)^R) -a group of and z₁、z₂And z₃At least one and not more than two of which are-C (R)^R) -, wherein R^Ris-H or (C)₁-C₃₀) A hydrocarbyl group. Any two bonded to adjacent atomsR is^RThe groups are optionally linked. In some embodiments, for containing a group z₁、z₂And z₃Each individual ring of (a), z₁、z₂And z₃Is a sulfur atom, and z₁、z₂And z₃Two of which are-C (H) -.

In some embodiments, each R is¹Can be selected from carbazole, and R^SOr more than one R^SSubstituted carbazol-9-yl, phenyl, substituted by R^SOr more than one R^SSubstituted phenyl, anthracyl or by R^SOr more than one R^SSubstituted anthracen-9-yl radicals, in which R is^SMay be (C)₁-C₃₀) A hydrocarbyl group. In other embodiments, each R¹Can be selected from carbazol-9-yl, 3, 6-di-tert-butylcarbazol-9-yl, 2, 7-di-tert-butylcarbazol-9-yl, anthracen-9-yl, 3, 5-di-tert-butylphenyl, 1': 3 ', 1 "-terphenyl-5 ' -yl, 3", 5, 5 "-tetra-tert-butyl-1, 1 ': 3 ', 1 "-terphenyl-5' -yl.

In one or more embodiments, each R²Selected from methyl, ethyl, propyl, 2-methylpropyl, n-butyl, tert-butyl (also known as 1, 1-dimethylethyl), pentyl, hexyl, heptyl, tert-octyl (also known as 1, 1, 3, 3-tetramethylbutyl), n-octyl, nonyl, chloro, fluoro or-H.

In some embodiments, each R is³Selected from the group consisting of methylethyl, propyl, 2-methylpropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, t-octyl, n-octyl, nonyl, chloro, fluoro or-H.

In one or more embodiments, R¹May be 3, 6-di-tert-butylcarbazol-9-yl, R²May be tert-octyl, and R³And R⁴May be-H. In some embodiments, R¹May be a carbazolyl group, R²May be methyl, and R³And R⁴May be-H. In other embodiments, R¹May be 3, 5-di-tert-butylphenyl, R²May be methyl, and R³And R⁴May be-H.

In one or more embodiments, the catalyst system comprises a metal-ligand complex according to formula (I), wherein each Y is independently O, S, N (C)₁-C₅₀) Hydrocarbyl or P (C)₁-C₅₀) A hydrocarbyl group. In some embodiments, when m is 2, each Y is different and may be selected from O and N (C)₁-C₅₀) Hydrocarbyl radicals, (e.g. NCH)₃). In other embodiments, when m is 2, each Y may be independently selected from O and S, or independently selected from S and N (C)₁-C₅₀) A hydrocarbyl group. In further embodiments, when m is 2, each Y may be the same and selected from O and S.

In accordance with another embodiment of the present disclosure, a catalyst system includes a metal-ligand complex of formula (I), wherein m is 2 and the metal-ligand complex has a structure according to formula (II):

in the formula (II), R¹、R²、R³、R⁴、R⁵、z₁、z₂、z₃Y and X are as defined in formula (I); and n may be 1 or 2. It should be readily understood that all metal-ligand complexes according to formula (II) are also complexes according to formula (I). Thus, the examples described with respect to the metal-ligand complex according to formula (II) necessarily apply to the complex according to formula (I).

In the examples, when m is 2, each individual ring contains a group z₁、z₂And z₃，z₁、z₂And z₃One of them is sulfur, oxygen, -N (R)^R) -or-C (R)^R) -, wherein R^Ris-H or (C)₁-C₃₀) Hydrocarbyl groups in which any two R's bonded to adjacent atoms^RThe groups are optionally linked. In other embodiments, the catalyst system may comprise a metal-ligand complex according to formula (II) wherein z is for a group containing z₁、z₂And z₃Each individual ring of (a), z₁、z₂And z₃Is a sulfur atom, and z₁、z₂And z₃Two of which are-C (H) -.

In one or more embodiments, the catalyst system can include a metal-ligand complex according to formula (II) wherein M is zirconium or hafnium; each X is independently selected from (C)₁-C₅₀) Hydrocarbyl radical, (C)₆-C₂₀) Aryl group, (C)₆-C₂₀) Heteroaryl, (C)₄-C₁₂) Dienes (such as 1, 3-butadiene) or halogens; each Y is oxygen; each R¹Independently selected from (C)₁-C₅₀) Aryl or (C)₁-C₄₀) A heteroaryl group; and each R²、R³And R⁴Independently selected from (C)₁-C₅₀) Hydrocarbyl radical, (C)₁-C₅₀) Heterohydrocarbyl, (C)₁-C₅₀) Aryl group, (C)₁-C₅₀) Heteroaryl, halogen and hydrogen.

In some embodiments, each X is benzyl, and each R is²Is methyl. In further embodiments, each X is benzyl and each R is²Is methyl, and each R¹Can be 3, 6-di-tert-butylcarbazol-9-yl, 2, 7-di-tert-butylcarbazol-9-yl, carbazolyl or 3, 5-di-tert-butylphenyl. In some embodiments, each X is benzyl and each R is²Is methyl, and each R³It may be tert-octyl or methyl.

The catalyst system according to the different embodiments of formula (II) may also comprise a divalent group Q consisting of two covalently bonded groups R⁵(ii) whereby the metal-ligand complex has a structure according to formula (III):

in the formula (III), R^1-4、z₁、z₂And z₃Y, M, X and n are as defined in formula (II). Reference to two R⁵The term "covalently bonded" means that the two R's of the metal-ligand complex of formula (II)⁵The groups being joined by at least one covalent bond to form the formula (III)) A single diradical unit represented by Q.

Thus, in formula (III), Q represents a single atom (C)₁-C₁₂) Alkylene, (C)₁-C₁₂) Heteroalkylidene or (C)₆-C₁₈) Two R of formula (II) in the arylene form⁵A group. When Q is a diradical unit, e.g. (C)₁-C₁₂) Alkylene or (C)₁-C₁₂) In the case of heteroalkylene groups, the two group-bearing atoms of the diradical unit are separated by one or more intervening carbon atoms such that the two Y atoms of formula (III) are bonded through a group having three to twelve atoms, wherein at least two of the three to twelve atoms are carbon atoms and no more than two of the three to twelve atoms are heteroatoms. In some embodiments, Q is selected from (C)₆-C₁₈) Arylene-1, 4-diyl, (C)₆-C₁₈) Arylene-1, 5-diyl and (C)₆-C₁₈) Arylene 1, 6-diyl; (C)₄-C₂₀) Cycloalkylene-1, 4-diyl group, (C)₄-C₂₀) Cycloalkylene-1, 5-diyl or (C)₄-C₂₀) Cycloalkylene-1, 6-diyl; (C)₃-C₂₀) Alkylene-1, 4-diyl, (C)₃-C₂₀) Alkylene-1, 5-diyl or (C)₃-C₂₀) Alkylene-1, 6-diyl; hept-2, 6-diyl (e.g. CH)₃C*(H)CH₂CH₂CH₂C*(H)CH₃) (ii) a 2, 6-dimethylhept-2, 6-diyl; 3, 3-dimethylpentan-1, 5-diyl; and o-xylylene group. In other embodiments, when Q is (C)₁-C₁₂) When alkylene is hetero, Q is selected from (-CH)₂CH₂Si(Me)₂CH₂CH₂-)；(-CH₂CH₂Si(ⁱPr)₂CH₂CH₂-)；(-CH₂CH₂Si (n-octyl)₂CH₂CH₂-)；(-CH₂CH₂Ge(Me)₂CH₂CH₂-)；(-CH₂CH₂Ge(ⁱPr)₂CH₂CH₂-) according to the formula (I); and (-CH)₂CH₂Ge (n-octyl)₂CH₂CH₂-)。

Examples of formula (I) include examples of formula (II). Similarly, embodiments of formula (I) and formula (II) include embodiments of formula (III). Can be used for

M in the metal-ligand complex of formula (I), (II) or (III) may be a transition metal, such as titanium (Ti), zirconium (Zr) or hafnium (Hf), which may have a formal oxidation state of +2, +3 or + 4. (X) of formula (I) indicating the number of ligands X bound to or associated with the metal M_nThe subscript n of (a) is 1, 2 or 3.

The metal M in the metal-ligand complex of formula (I), (II) or (III) may be derived from a metal precursor which is subsequently subjected to a single or multi-step synthesis to prepare the metal-ligand complex. Suitable metal precursors may be monomeric (one metal center) or dimeric (two metal centers), or may have more than two metal centers, such as 3, 4, 5, or more than 5 metal centers. Specific examples of suitable hafnium and zirconium precursors include, but are not limited to, HfCl₄、HfMe₄、Hf(CH₂Ph)₄、Hf(CH₂CMe₃)₄、Hf(CH₂SiMe₃)₄、Hf(CH₂Ph)₃Cl、Hf(CH₂CMe₃)₃Cl、Hf(CH₂SiMe₃)₃Cl、Hf(CH₂Ph)₂Cl₂、Hf(CH₂CMe₃)₂Cl₂、Hf(CH₂SiMe₃)₂Cl₂、Hf(NMe₂)₄、Hf(NEt₂)₄And Hf (N (SiMe)₃)₂)₂Cl₂；ZrCl₄、ZrMe₄、Zr(CH₂Ph)₄、Zr(CH₂CMe₃)₄、Zr(CH₂SiMe₃)₄、Zr(CH₂Ph)₃Cl、Zr(CH₂CMe₃)₃Cl、Zr(CH₂SiMe₃)₃Cl、Zr(CH₂Ph)₂Cl₂、Zr(CH₂CMe₃)₂Cl₂、Zr(CH₂SiMe₃)₂Cl₂、Zr(NMe₂)₄、Zr(NEt₂)₄、Zr(NMe₂)₂Cl₂、Zr(NEt₂)₂Cl₂、Zr(N(SiMe₃)₂)₂Cl₂、TiBn₄、TiCl₄And Ti (CH)₂Ph)₄. Lewis base adducts of these examples are also suitable as metal precursors, for example ethers, amines, thioethers and phosphines are suitable as lewis bases. Specific examples include HfCl₄(THF)₂、HfCl₄(SMe₂)₂And Hf (CH)₂Ph)₂Cl₂(OEt₂). The activated metal precursor may be an ionic or zwitterionic compound, such as (M (CH)₂Ph)₃ ⁺)(B(C₆F₅)₄ ^-) Or (M (CH)₂Ph)₃ ⁺)(PhCH₂B(C₆F₅)₃ ^-) Wherein M is as defined above as Hf or Zr.

In the metal-ligand complex according to formula (I), each X is bonded to M by a covalent bond, a dative bond, or an ionic bond. When n is 1, X may be a monodentate ligand or a bidentate ligand; when n is 2, each X is an independently selected monodentate ligand and may be the same or different from the other groups X. Generally, when in the form of a procatalyst, the metal-ligand complex according to formula (I) is charge neutral overall. In some embodiments, the monodentate ligand can be a monoanionic ligand. The monoanionic ligand has a net formal oxidation state of-1. Each monoanionic ligand may be independently a hydride, (C)₁-C₄₀) Hydrocarbyl carbanion (C)₁-C₄₀) Heterocarbyl carbanions, halides, nitrates, carbonates, phosphates, sulfates, HC (O) O^-、HC(O)N(H)^-、(C₁-C₄₀) Hydrocarbyl C (O) O^-、(C₁-C₄₀) Hydrocarbyl C (O) N ((C)₁-C₂₀) Alkyl radical)^-、(C₁-C₄₀) Hydrocarbyl C (O) N (H)^-、R^KR^LB-、R^KR^LN^-、R^KO^-、R^KS^-、R^KR^LP^-Or R^MR^KR^LSi^-Wherein each R is^K、R^LAnd R^MIndependently of each other, hydrogen, (C)₁-C₄₀) Hydrocarbyl or (C)₁-C₄₀) Heterohydrocarbyl, or R^KAnd R^LTogether form (C)₂-C₄₀) Alkylene or (C)₁-C₂₀) A heterohydrocarbylene group, and R^MAs defined above.

In other embodiments, at least one monodentate ligand X, independent of any other ligand X, can be a neutral ligand. In particular embodiments, the neutral ligand is a neutral Lewis base, such as R^XNR^KR^L、R^KOR^L、R^KSR^LOr R^XPR^KR^LWherein each R is^XIndependently of each other is hydrogen, [ (C)₁-C₁₀) Hydrocarbyl radical]₃Si(C₁-C₁₀) Hydrocarbyl radical, (C)₁-C₄₀) Hydrocarbyl radical, [ (C)₁-C₁₀) Hydrocarbyl radical]₃Si or (C)₁-C₄₀) A heterohydrocarbyl group, and each R^KAnd R^LIndependently as defined above.

In addition, each X may be a monodentate ligand that is halogen, unsubstituted (C) independently of any other ligand X₁-C₂₀) Hydrocarbyl, unsubstituted (C)₁-C₂₀) A hydrocarbon group C (O) O-, or R^KR^LN-, in which R^KAnd R^LEach independently of the others being unsubstituted (C)₁-C₂₀) A hydrocarbyl group. In some embodiments, each monodentate ligand X of the metal-ligand complex is a chlorine atom, (C)₁-C₁₀) Hydrocarbyl (e.g., (C)₁-C₆) Alkyl or benzyl), unsubstituted (C)₁-C₁₀) Hydrocarbyl C (O) O-or R^KR^LN-, wherein R^KAnd R^LEach independently of the others being unsubstituted (C)₁-C₁₀) A hydrocarbyl group.

In some embodiments, the catalyst system can include a metal-ligand complex according to either formula (I) or formula (II), wherein n is 2 or greater than 2, such that at least two groups X are present, andwherein any two groups X may join to form a bidentate ligand. In illustrative embodiments that include bidentate ligands, the bidentate ligand may be a neutral bidentate ligand. In one embodiment, the neutral bidentate ligand is of formula (R)^D)₂C＝C(R^D)-C(R^D)＝C(R^D)₂Wherein each R is^DIndependently H, unsubstituted (C)₁-C₆) Alkyl, phenyl or naphthyl. In some embodiments, the bidentate ligand is a monoanionic-mono (lewis base) ligand. In some embodiments, the bidentate ligand is a dianionic ligand. Dianionic ligands have a net formal oxidation state of-2. In one embodiment, each dianionic ligand is independently carbonate, oxalate (i.e.,^-O₂CC(O)O^-)、(C₂-C₄₀) Hydrocarbylene dicarbanions, (C)₁-C₄₀) A heterocarbylene dicarbanion, a phosphate, or a sulfate.

In further embodiments, X is selected from methyl; an ethyl group; 1-propyl group; 2-propyl; 1-butyl; 2,2, -dimethylpropyl; trimethylsilylmethyl; a phenyl group; a benzyl group; or chlorine. In some embodiments, n is 2 and each X is the same. In some cases, at least two xs are different from each other. In other embodiments, n is 2 and each X is methyl; an ethyl group; 1-propyl group; 2-propyl; 1-butyl; 2,2, -dimethylpropyl; trimethylsilylmethyl; a phenyl group; a benzyl group; and a different one of chlorine. In one embodiment, n is 2 and at least two X are independently monoanionic monodentate ligands. In some embodiments, n is 2 and two X groups join to form a bidentate ligand. In other embodiments, the bidentate ligand is 2, 2-dimethyl-2-silapropane-1, 3-diyl or 1, 3-butadiene.

In an illustrative embodiment, the catalyst system can include a metal-ligand complex according to any one of formulas (I), (II), or (III) having the structure of any one of procatalysts 1 through 32:

cocatalyst component

The catalyst system comprising the metal-ligand complex of formula (I) may be rendered catalytically active by any technique known in the art for activating metal-based catalysts for olefin polymerization reactions. For example, a metal-ligand complex according to formula (I) may be rendered catalytically active by contacting the complex with an activating cocatalyst or combining the complex with an activating cocatalyst. In addition, the metal-ligand complex according to formula (I) includes both a neutral procatalyst form and a positively charged catalytic form. Activating cocatalysts suitable for use herein include aluminum alkyls; polymeric or oligomeric aluminoxanes (also known as aluminoxanes); a neutral lewis acid; and non-polymeric, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is bulk electrolysis (bulk electrolysis). Combinations of one or more of the foregoing activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means a monoalkylaluminum dihalide or monoalkylaluminum dihalide, a dialkylaluminum hydride or halide, or a trialkylaluminum. Examples of the polymeric or oligomeric aluminoxane include methylaluminoxane, triisobutylaluminum-modified methylaluminoxane, and isobutylaluminoxane.

Lewis acid activating cocatalysts include compounds containing (C) as described herein₁-C₂₀) A hydrocarbyl-substituted group 13 metal compound. In some embodiments, the group 13 metal compound is tris ((C)₁-C₂₀) Hydrocarbyl-substituted aluminium or tris ((C)₁-C₂₀) Hydrocarbyl) -boron compounds. In other embodiments, group 13 metals are combinedThe compound is tri (hydrocarbyl) -substituted aluminum, tri ((C)₁-C₂₀) Hydrocarbyl-boron compound, tris ((C)₁-C₁₀) Alkyl) aluminum, tris ((C)₆-C₁₈) Aryl) boron compounds, and halogenated (including perhalogenated) derivatives thereof. In further embodiments, the group 13 metal compound is tris (fluoro substituted phenyl) borane, tris (pentafluorophenyl) borane. In some embodiments, the activating cocatalyst is tris ((C) borate₁-C₂₀) Hydrocarbon esters (e.g. trityl tetrafluoroborate) or tetrakis ((C)₁-C₂₀) Hydrocarbyl) borane tris ((C)₁-C₂₀) Hydrocarbyl) ammonium (e.g., bis (octadecyl) methylammonium tetrakis (pentafluorophenyl) borane). As used herein, the term "ammonium" means a nitrogen cation which is ((C)₁-C₂₀) Alkyl radical)₄N⁺((C₁-C₂₀) Alkyl radical)₃N(H)⁺、((C₁-C₂₀) Alkyl radical)₂N(H)₂ ⁺、(C₁-C₂₀) Alkyl radicals N (H)₃ ⁺Or N (H)₄ ⁺Wherein when there are two or more, each (C)₁-C₂₀) The hydrocarbyl groups may be the same or different.

Combinations of neutral lewis acid activating cocatalysts include those comprising tris ((C)₁-C₄) Alkyl) aluminum and tris ((C) halide₆-C₁₈) Aryl) boron compounds, especially tris (pentafluorophenyl) borane. Other examples are combinations of such neutral lewis acid mixtures with polymeric or oligomeric alumoxanes, and combinations of a single neutral lewis acid, especially tris (pentafluorophenyl) borane, with polymeric or oligomeric alumoxanes. (metal-ligand complex): (tris (pentafluoro-phenylborane): aluminoxane [ e.g., (group 4 metal-ligand complex): tris (pentafluoro-phenylborane): aluminoxane)]The molar ratio is 1: 1 to 1: 10: 30, and in other embodiments 1: 1.5 to 1: 5: 10.

A catalyst system comprising a metal-ligand complex of formula (I) may be activated to form an active catalyst composition by combination with: one or more promoters, such as a cation forming promoter, a strong lewis acid, or a combination thereof. Suitable activating cocatalysts include polymeric or oligomeric aluminoxanes, especially methylaluminoxane, and inert, compatible, non-coordinating ion-forming compounds. Exemplary suitable cocatalysts include, but are not limited to, Modified Methylalumoxane (MMAO), bis (hydrogenated tallow alkyl) methyl, 1-amine tetrakis (pentafluorophenyl) borate, and combinations thereof.

In some embodiments, more than one of the foregoing activating cocatalysts may be used in combination with each other. A specific example of a combination of cocatalysts is tris ((C)₁-C₄) Hydrocarbyl aluminum, tris ((C)₁-C₄) Hydrocarbyl) borane or ammonium borate with oligomeric or polymeric aluminoxane compounds. The ratio of the total moles of the one or more metal-ligand complexes of formula (I) to the total moles of the one or more activating cocatalysts is from 1: 10,000 to 100: 1. In some embodiments, the ratio is at least 1: 5000, in some other embodiments, at least 1: 1000; and 10: 1 or less, and in some other embodiments, 1: 1 or less. When an aluminoxane is used alone as the activating cocatalyst, it is preferable to use an aluminoxane in a number of moles at least 100 times that of the metal-ligand complex of formula (I). When tris (pentafluorophenyl) borane is used alone as the activating cocatalyst, in some other embodiments, a ratio of moles of tris (pentafluorophenyl) borane to total moles of the one or more metal-ligand complexes of formula (I) is employed of from 0.5: 1 to 10: 1, from 1: 1 to 6: 1, or from 1: 1 to 5: 1. The remaining activating cocatalyst is generally employed in a molar amount approximately equal to the total molar amount of the one or more metal-ligand complexes of formula (I).

Polyolefins

The catalytic system described in the preceding paragraph is used for the polymerization of olefins, mainly ethylene and propylene. In some embodiments, only a single type of olefin or alpha-olefin is present in the polymerization scheme, resulting in 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 may 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, and 4-methyl-1-pentene. 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 ethylene homopolymers and/or interpolymers (including copolymers) of ethylene with optionally one or more comonomers (e.g., alpha-olefins), can comprise at least 50 weight percent of monomer units derived from ethylene. All individual values and subranges subsumed by "at least 50 weight percent" are disclosed herein as separate embodiments; for example, the ethylene-based polymer, ethylene homopolymer, and/or interpolymer (including copolymer) of ethylene with optionally one or more comonomers (e.g., alpha-olefin) may comprise at least 60 weight percent of units derived from ethylene; at least 70% by weight of units derived from ethylene; at least 80% by weight of units derived from ethylene; or from 50 to 100 weight percent of units derived from ethylene; or from 80 to 100 weight percent 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% of units; at least 97 mole percent of units derived from ethylene; or in the alternative, from 90 to 100 mole percent of units derived from ethylene; or from 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 1 mole% (mol%) to 20 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 method can be employed to produce the ethylene-based polymer. For example, such conventional polymerization processes include, but are not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof, using one or more conventional reactors in parallel, series, such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors, or any combination thereof.

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

In another embodiment, the ethylene-based polymer may be produced by solution polymerization in a single reactor system, for example, 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. Ethylene based on the weight of the ethylene-based polymer and the one or more additivesThe polymer may comprise from about 0 to about 10% by weight of the combination of such 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.

In some embodiments, a polymerization process for making an ethylene-based polymer may include polymerizing ethylene and at least one additional alpha-olefin in the presence of a catalyst system, wherein the catalyst system incorporates at least one metal-ligand complex of formulae (I), (II), and (III). The density of the polymer produced from such a catalyst system incorporating a metal-ligand complex of formula (I) according to ASTM D792 (incorporated herein by reference in its entirety) may be, for example, 0.850g/cm³To 0.950g/cm³、0.880g/cm³To 0.920g/cm³、0.880g/cm³To 0.910g/cm³Or 0.880g/cm³To 0.900g/cm³。

In another embodiment, the polymer produced by the catalyst system comprising the metal-ligand complex of formulas (I), (II), and (III) can have a melt flow ratio (I) of 5 to 15₁₀/I₂) Wherein the melt index I₂Measured at 190 ℃ under a load of 2.16kg according to ASTM D1238 (incorporated herein by reference in its entirety), and melt index I₁₀Measured at 190 ℃ under a 10kg load according to ASTM D1238. In other embodiments, the melt flow ratio (I)₁₀/I₂) Is from 5 to 10 and in other embodiments, the melt flow ratio is from 5 to 9.

In some embodiments, the polymer produced by the catalyst system comprising the metal-ligand complex of formulae (I), (II), and (III) has a Molecular Weight Distribution (MWD) of 1 to 10, wherein MWD is defined as M_w/M_nWherein M is_wIs the weight average molecular weight and M_nIs the number average molecular weight. In other embodiments, the polymer produced by the catalyst system has a MWD of 1 to 6. Another embodiment includes1 to 3 MWD; and other embodiments include an MWD of 1.5 to 2.5.

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

General procedure for batch reactor polymerization

The starting materials (ethylene, 1-hexene) and the process solvent (a narrow boiling point range high purity isoparaffinic solvent commercially available from ExxonMobil Corporation under the trade name ISOPAR E) were purified with molecular sieves prior to introduction into the reaction environment. A one gallon (3.79L) stirred autoclave reactor was charged with ISOPAR E and 1-octene. The reactor was then heated to reaction temperature and ethylene was added to bring the total pressure to about 320 psig. By reacting the desired metal-ligand complex with a cocatalyst ([ HNMe (C) in an inert atmosphere in a dry box₁₈H₃₇)₂][B(C₆F₅)₄]Along with Modified Methylaluminoxane (MMAO)) with additional solvent to give a total volume of about 15 to about 20mL to prepare the catalyst composition. The activated catalyst mixture was injected rapidly into the reactor. Reactor pressure and temperature were kept constant by feeding ethylene during the polymerization and cooling the reactor as needed. After 10 minutes, the ethylene feed was stopped and the solution was transferred to a nitrogen purged resin kettle. The polymer was thoroughly dried in a vacuum oven and the reactor was rinsed with hot ISOPAR E between polymerization runs.

General procedure for PPR screening experiments

Polyolefin catalytic screening was performed in a Freescale (formerly Symyx) high throughput Parallel Polymerization Reactor (PPR) system. The PPR system comprises a 48-cell (6 x 8 matrix) array of reactors in an inert atmosphere glove box. Each cell was equipped with a glass insert with an internal working liquid volume of approximately 5 mL. Each cell had independent pressure control and was continuously stirred at 800 rpm. Unless otherwise stated, catalyst, ligand and metal precursor solutions were prepared in toluene. All liquids (i.e., solvent, 1-octene and catalyst solution) were added via a robotic syringe. A gaseous reagent (i.e., ethylene) is added through a gas injection port. Prior to each run, the reactor was heated to 80 ℃, purged with ethylene and vented. A portion of ISOPAR-E was added. The reactor was heated to operating temperature and then the reaction was pressurized to the appropriate psig with ethylene. The toluene solution of the reagents was added in the following order: 1-octene and scavenger MMAO-3A (500 nmol for 120 ℃ run and 750nmol for 150 ℃), activator (bis (hydrogenated tallowalkyl) methylammonium tetrakis (pentafluorophenyl) borate, tris (pentafluorophenyl) borane, etc.), then catalyst. 1-octene: the ethylene molar ratio was 2.24.

Each liquid addition was followed with a small amount of ISOPAR-E so that the total reaction volume reached 5mL after the final addition. After the catalyst was added, the PPR software monitored the pressure in each cell. The desired pressure (150 psig for 120 ℃ run, and 213psig for 150 ℃ run, within about 2-6 psi) is maintained by opening the valve at the set point minus 1psi, and closing the valve when the pressure reaches 2-6psi, by the supplemental addition of ethylene gas. For the duration of the run or until the desired value of absorption or conversion is reached, all pressure drops are cumulatively recorded as "absorption" or "conversion" of ethylene, whichever occurs first. Each reaction was then quenched by the addition of 10% carbon monoxide under argon at 40-50psi above the reactor pressure for 4 minutes. A shorter "quench time" indicates a higher catalyst activity. To prevent excessive polymer formation in any given compartment, the reaction was quenched when a predetermined absorption level was reached (50 psig for 120 ℃ and 75psig for 150 ℃).

After all the reactors were quenched, they were cooled to 70 ℃. The reactor was vented, purged with nitrogen for 5 minutes to remove carbon monoxide, and the tube removed. The polymer samples were then dried in a centrifugal evaporator at 70 ℃ for 12 hours, weighed to determine polymer yield and provided for IR (1-octene incorporation) and GPC (molecular weight) analysis.

Examples of the invention

One or more features of the present disclosure are illustrated in accordance with the following examples:

example 1: synthesis of 4-bromo-3-methoxythiophene-2-carboxylic acid methyl ester 2

Compound 1(1.000g, 4.22mmol) was dissolved in 40mL of acetone. Potassium carbonate (2.915g, 21.09mmol) was added followed by methyl iodide (2.36mL, 37.96 mmol; d 2.28). The resulting mixture was heated at 60 ℃ for 14 hours. The reaction mixture was cooled to 23 ℃ and then filtered through a pad of celite, which was then rinsed with methane chloride (20 mL). The filtrate was concentrated in vacuo, and the residue was taken up in 80mL of methyl chloride and a small amount of white solid was removed by filtration. The solvent was removed in vacuo to give a yellow solid (1.01g, 95%).

¹H NMR(400MHz，CDCl₃)δ7.39(s，1H)，4.01(s，3H)，3.88(s，3H)。

Example 2: synthesis of 4-bromo-3-methoxythiophene-2-carboxylic acid 3

Compound 2(1.000g, 3.98mmol) was dissolved in 15mL THF and combined with 1.0M aqueous sodium hydroxide (5.2mL, 5.18 mmol). The mixture was stirred at room temperature for 48 h.

Aqueous HCl (1.0M) was added dropwise to the mixture until the pH was about 2. By CH₂Cl₂The acidic mixture was extracted (60 mL. times.2). Brine was added to aid phase separation. The combined organic extracts were concentrated using a rotary evaporator to give a residue, which was combined with 100mL CH₂Cl₂And (4) mixing. Some of the white material remained undissolved. These solids (found to be water soluble) were filtered off. The filtrate was washed with water (60 mL. times.2) and Na₂SO₄Dried and concentrated under reduced pressure to a solid (0.55g, 58%).

¹H NMR(400MHz，CDCl₃)δ7.51(s，1H)，4.08(s，3H)。

Example 3: synthesis of 3-bromo-4-methoxythiophene 4

Compound 3(0.550g, 2.32mmol) was placed in a scintillation vial equipped with a pressure-release membrane lid at 65 ℃ with 15mL of concentrated H₂SO₄The treatment was carried out for 5 hours. (Note: it is important to reduce the pressure using a vented needle or some other method, as this reaction produces CO₂A gas. ) After cooling to room temperature, the mixture was poured into 20mL of crushed ice and extracted with methane chloride (3X 100 mL). The organic extracts were combined and successively saturated NaHCO₃Aqueous solution (2X 80mL) and water (2X 100 mL). The organic layer was passed through a plug of silica gel and concentrated in vacuo to a dark brown oil (0.3g, 67%). Solvent removal needs to be accomplished quickly due to the volatility of the product. GC/MS confirmed the pure desired product (m/z 193).

¹H NMR(400MHz，CDCl₃)δ7.20(d，J＝3.5Hz，1H)，6.25(d，J＝3.5Hz，1H)，3.88(s，3H)。

Example 4: synthesis of ligand L1

Compound 4(0.080g, 0.41mmol) and compound 5(0.200g, 0.41mmol, from Boulderscientific) were dissolved in 4mL THF. Mixing Na₂CO₃(0.264g, 2.49mmol) was dissolved in 1mL deionized water and added to the THF solution to form a biphasic solution, which was then taken up with N₂Bubbling for 30 minutes. Pd (P)^tBu3)₂(0.011g, 0.021mmol) was dissolved in 0.5mL degassed THF in a nitrogen-filled dry box and then added to the reaction mixture by syringe. The two-phase mixture was stirred vigorously at 65C for 14 hours. The reaction mixture was cooled to 25C and the aqueous phase was separated and discarded. The organic phase was diluted with 30mL THF and the solution was passed through a short plug of silica gel. The filtrate was concentrated on a rotary evaporator. The crude protected product was used in the next step without further purification.

¹H NMR(400MHz，C₆D₆)δ8.09(dt，J＝7.6，0.9Hz，2H)，7.37-7.21(m，7H)，7.03(d，J＝3.5Hz，1H)，6.84(d，J＝1.9Hz，1H)，6.27(s，1H)，5.72(d，J＝3.5Hz，1H)，3.01(s，3H)，2.06(s，3H)。

The crude protected product was dissolved in 4mL of an approximately 1: 2 mixture of MeOH and THF, concentrated HCl (4 drops from a Pasteur pipette (Pasteur pipette)) was added, and the solution was stirred at 23 ℃ for 5 hours. The solution was evaporated to dryness in vacuo and the residue was dissolved in 40mL Et₂O, pass through a short silica gel plug, and remove the solvent under vacuum. The brown crude product was purified using Biotage (EtOAc/hexanes gradient: 5% to 10% EtOAc over 8 Column Volumes (CV) then held at 10%). The fractions containing pure product were combined and concentrated on a rotary evaporator. The product was further dried overnight under high vacuum to give L1(0.130g, 81%) as a white solid.

¹H NMR(400MHz，CDCl₃)δ8.20-8.11(m，2H)，7.45-7.38(m，3H)，7.36(d，J＝1.8Hz，1H)，7.31-7.28(m，3H)，7.27-7.26(m，1H)，6.46-6.41(m，2H)，3.90(s，3H)，2.40(s，3H)。¹³CNMR(101MHz，CDCl₃)δ154.84，147.78，141.12，131.41，130.52，129.35，129.31，125.80，125.37，124.30，123.77，123.36，120.23，119.72，110.31，98.19，57.97，20.55。

Example 5: synthesis of ligand L2

Compound 4(0.100g, 0.52mmol) and compound 6(0.262g, 0.52mmol, from Boulder scientific) were dissolved in 4mL THF. Mixing Na₂CO₃(0.329g, 3.11mmol) was dissolved in 1mL deionized water and added to the THF solution to form a biphasic solution, which was then diluted with N₂Bubbling for 30 minutes. Pd (Pt-Bu)₃)₂(0.013g, 0.026mmol) was dissolved in 0.5mL degassed THF in a nitrogen-filled dry box and then added to the reaction mixture via syringe. The two-phase mixture was stirred vigorously at 65 ℃ for 14 hours. Mixing the reactionThe composition was cooled to 25 ℃, and the aqueous phase was separated and discarded. The organic phase was diluted with 30mL THF and the solution was passed through a short plug of silica gel. The filtrate was concentrated on a rotary evaporator. The crude protected product was dissolved in 16mL of an approximately 1: 1 mixture of MeOH and THF, concentrated HCl (4 drops from a Pasteur pipette) was added, and the solution was stirred at 23 ℃ for 4 hours. The solution was evaporated to dryness in vacuo and the residue was dissolved in 100ml of EtOAc/hexanes (10% EtOAc), passed through a short plug of silica gel, and the solvent was removed in vacuo to afford L2 as a beige solid in quantitative yield.

¹H NMR(400MHz，CDCl₃)δ7.45-7.41(m，2H)，7.39(d，J＝1.8Hz，2H)，7.32(d，J＝3.4Hz，1H)，7.14(d，J＝2.7Hz，2H)，6.42(d，J＝3.4Hz，1H)，6.17(s，1H)，3.90(s，3H)，2.36(s，3H)，1.37(s，18H)。¹³C NMR(101MHz，CDCl₃)δ155.32，150.63，147.98，137.35，131.21，130.92，130.56，130.06，129.62，123.89，123.80，122.16，121.28，97.72，57.86，34.94，31.53，31.48，20.56。

Example 6: synthesis of ligand L3

Compound 4(0.055g, 0.28mmol) and compound 7(0.198g, 0.28mmol, from Boulderscientific) were dissolved in 4mL THF. Mixing Na₂CO₃(0.181g, 1.71mmol) was dissolved in 1mL deionized water and added to the THF solution to form a biphasic solution, which was then taken up with N₂Bubbling for 20 minutes. Pd (P)^tBu₃)₂(0.007g, 0.014mmol) was dissolved in 0.8mL of degassed THF in a nitrogen-filled dry box and then added to the reaction mixture by syringe. The two-phase mixture was stirred vigorously at 65 ℃ for 14 hours. The reaction mixture was cooled to 25 ℃, and the aqueous phase was separated and discarded. The organic phase was diluted with 30mL THF and the solution was passed through a short plug of silica gel. The filtrate was concentrated on a rotary evaporator. The crude protected product was dissolved in 16mL of MeOH and THF approximately 1: 1To the mixture, concentrated HCl (4 drops from a pasteur pipette) was added and the solution was stirred at 25 ℃ for 14 hours. The solution was evaporated to dryness in vacuo and the residue was dissolved in 100ml of EtOAc/hexanes (10% EtOAc), passed through a short plug of silica gel and the solvent removed in vacuo to give L3(0.165g, 97%) as a beige solid. LC/MS confirmed the pure desired product (m/z ═ 596).

¹H NMR(400MHz，CDCl₃)δ8.02(d，J＝8.2Hz，2H)，7.59(d，J＝2.4Hz，1H)，7.45(d，J＝3.4Hz，1H)，7.37(d，J＝2.6Hz，1H)，7.34(d，J＝1.7Hz，1H)，7.32(d，J＝1.7Hz，1H)，7.20(d，J＝1.4Hz，2H)，6.45(d，J＝3.4Hz，1H)，6.11(s，1H)，3.94(s，3H)，1.76(s，2H)，1.40(s，6H)，1.37(s，18H)，0.84(s，9H)。¹³C NMR(101MHz，CDCl₃)δ155.36，149.09，147.68，142.59，141.57，129.74，128.82，126.66，124.66，124.23，122.72，121.09，119.64，119.43，118.21，117.66，106.63，106.29，97.81，57.90，57.20，38.24，35.14，32.51，31.90，31.80，31.73，31.58。

Example 7: synthesis of ligand L4

Compound 4(0.059g, 0.31mmol) and compound 8(0.212g, 0.31mmol, from Boulder scientific) were dissolved in 4mL THF. Mixing Na₂CO₃(0.194g, 1.83mmol) was dissolved in 1mL deionized water and added to the THF solution to form a biphasic solution, which was then taken up with N₂Bubbling for 15 minutes. Pd (P)^tBu₃)₂(0.008g, 0.015mmol) was dissolved in 0.8mL of degassed THF in a nitrogen-filled dry box and then added to the reaction mixture by syringe. The two-phase mixture was stirred vigorously at 65 ℃ for 14 hours. The reaction mixture was cooled to 25 ℃, and the aqueous phase was separated and discarded. The organic phase was diluted with 30mL THF and the solution was passed through a short plug of silica gel. The filtrate was concentrated on a rotary evaporator. The crude protected product was dissolved in 16mL MeOH and THFTo the 1: 1 mixture, concentrated HCl (4 drops from a Pasteur pipette) was added and the solution was stirred at 25 ℃ for 14 hours. The solution was evaporated to dryness in vacuo and the residue was dissolved in 100mL EtOAc/hexanes (10% EtOAc), passed through a short plug of silica gel and the solvent was removed in vacuo to give L4(0.170g, 93%) as a beige solid. LC/MS confirmed the pure desired product (m/z ═ 596).

¹H NMR(400MHz，CDCl₃)δ8.17(d，J＝1.8Hz，2H)，7.56(d，J＝2.4Hz，1H)，7.48(d，J＝1.9Hz，1H)，7.46(d，J＝1.9Hz，1H)，7.43(d，J＝3.4Hz，1H)，7.38(d，J＝2.4Hz，1H)，7.17(s，1H)，7.14(s，1H)，6.43(d，J＝3.4Hz，1H)，6.27(s，1H)，3.90(s，3H)，1.75(s，2H)，1.48(s，18H)，1.39(s，6H)，0.84(s，9H)。¹³C NMR(101MHz，CDCl₃)δ155.19，147.53，142.65，142.53，139.64，129.70，128.70，126.66，124.95，124.19，123.56，123.29，122.68，116.27，109.55，97.90，57.87，57.06，38.21，34.72，32.44，32.06，31.88，31.58。

Example 8: synthesis of 2-bromo-3-methoxythiophene 10

The synthesis of compound 10 was based on 2012, 134(46), 19070 in journal of american society of chemistry (JACS). A solution of N-bromosuccinimide (1.840g, 10.34mmol) in anhydrous DMF (6mL) was added dropwise to a solution of 3-methoxythiophene (1.180g, 10.34mmol) in anhydrous DMF (4 mL). After 1h, the reaction mixture was partitioned between water and dichloromethane (30mL each). The aqueous layer was washed with dichloromethane (30mL), and then the combined dichloromethane layers were washed with brine (2 × 30mL), over Na₂SO₄Dried and the solvent removed under reduced pressure. The crude product was dissolved in 100mL of hexane and passed through a silica gel plug. Solvent removal gave the pure product as a pale yellow liquid (1.500g, 75%).

Important explanation: the pure product is unstable in air at 25 ℃. Significant decomposition occurred within one hour. Stability at low temperature and/or under inert atmosphere was not tested.

¹H NMR(400MHz，CDCl₃)δ7.21(d，J＝6.0Hz，1H)，6.77(d，J＝6.0Hz，1H)，3.90(s，3H)。

Example 9: synthesis of ligand L5

Compound 5(0.228g, 0.47mmol) and Compound 10(0.091g, 0.47mmol) were dissolved in 10mL THF. Mixing Na₂CO₃(0.300g, 2.83mmol) was dissolved in 5mL deionized water and added to the THF solution to form a biphasic solution which was then taken up with N₂Bubbling for 20 minutes. Pd (P)^tBu₃)₂(0.012g, 0.024mmol) was dissolved in 2mL degassed THF in a nitrogen-filled dry box and then added to the reaction mixture via syringe. The reaction mixture was stirred vigorously at 65 ℃ for 14 hours. The reaction mixture was cooled to 25 ℃. The aqueous phase was separated and discarded. The organic phase was washed with 30mL Et₂O was mixed and the solution was passed through a silica gel plug. The solvent was removed in vacuo to give a yellow residue as protected product.

¹H NMR(400MHz，CDCl₃)δ8.20-8.13(m，2H)，7.46-7.36(m，3H)，7.34(d，J＝5.6Hz，1H)，7.32-7.27(m，3H)，7.26-7.23(m，2H)，6.92(d，J＝5.6Hz，1H)，3.92(s，3H)，2.40(s，3H)。

The yellow residue (protected product) was dissolved in 20mL of a 1: 1(v/v) mixture of MeOH and THF, concentrated HCl (5 drops from a pasteur pipette) was added, and the solution was stirred at 25 ℃ for 3 hours to evaporate the reaction mixture to dryness, the residue was dissolved in a mixture of 50mL of diethyl ether and 50mL of hexane, and the solution was passed through a plug of silica gel. Solvent removal under vacuum yielded ligand L5(0.150g, 83%).

¹H NMR(400MHz，C₆D₆)δ8.11(dt，J＝7.7，1.1Hz，2H)，7.48(dd，J＝2.2，0.7Hz，1H)，7.38-7.20(m，7H)，6.87(dt，J＝2.2，0.6Hz，1H)，6.69(d，J＝5.6Hz，1H)，6.21(d，J＝5.6Hz，1H)，2.94(s，3H)，2.02(s，3H)。¹³C NMR(101MHz，CDCl₃)δ151.34，147.93，141.19，130.88，130.53，129.51，126.04，125.69，125.11，123.25，121.87，120.19，119.54，118.31，116.46，110.32，59.43，20.52。

Example 10: synthesis of propane-1, 3-diylbis (trifluoromethanesulfonate) 13

A solution of 1, 3-propanediol (2.9mL, 40.0mmol) and pyridine (6.5mL, 80 mmol; d 0.978) in anhydrous dichloromethane (100mL) was cooled to-78 deg.C under nitrogen and Tf was added dropwise₂O (13.5mL, 80.0 mmol; d 1.677). The reaction mixture was warmed to 25 ℃ and stirred for 1h to give a pink solution with a white precipitate. The reaction mixture was washed rapidly with deionized water (3X 20mL) over anhydrous Na₂SO₄Dried and rapidly filtered through silica gel. The silica gel was washed with dichloromethane (50mL) and the filtrate was combined with the first wash. Removal of the solvent in vacuo afforded compound 13(7.5g, 55%) as a pale red oil. The product should be stored under an inert atmosphere.

¹H NMR(400MHz，CDCl₃)δ4.67(t，J＝5.8Hz，4H)，2.36(p，J＝5.8Hz，2H)。¹³C NMR(101MHz，CDCl₃)δ118.54(q，J＝320.0Hz)，71.43，29.27。

Example 11: synthesis of butane-1, 4-diylbis (trifluoromethanesulfonate) 15

A solution of 1, 4-butanediol (1.000g, 11.10mmol) and pyridine (2.69mL, 33.30 mmol; d 0.978) in anhydrous dichloromethane (60mL) was cooled to-78 deg.C under nitrogen and Tf was added dropwise₂O (4.67mL, 27.74 mmol; d 1.677). The reaction mixture was warmed to 25 ℃ and stirred for 14 hours to give a pink solution with a white precipitate. Will be provided withThe reaction mixture was washed rapidly with deionized water (3X 50mL) over anhydrous Na₂SO₄Dried and filtered through celite. The solvent was removed in vacuo to give the desired product as an oil. Pentane (30mL) was added and a separate phase formed above the oil, which was therefore removed under vacuum. As the system was cooled under vacuum, the oil became an off-white solid (2.3g, 59%). The product was stored under an inert atmosphere at-30 ℃.

¹H NMR(400MHz，CDCl₃)δ4.59(m，4H)，2.02(m，4H)。¹³C NMR(101MHz，CDCl₃)δ118.57(q，J＝319.4Hz)，75.74，25.37。¹⁹F NMR(376MHz，CDCl₃) Delta-74.62 (not calibrated).

Example 12: synthesis of Compound 16

Compound 1(0.100g, 0.42mmol) was dissolved in 5mL acetone (solvent over MgSO)₄Dried). Potassium carbonate (0.291g, 2.11mmol) was added, followed by addition of compound 13(0.070g, 0.21 mmol). The resulting mixture was heated at 65 ℃ for 14 hours. The mixture was filtered and the filter cake was rinsed with dichloromethane (30 mL). The combined filtrates were concentrated in vacuo. Dichloromethane (50mL) was added (some of the material was insoluble) and the mixture was filtered through a pad of celite. The filtrate was evaporated to dryness in vacuo (0.100g, 94%). LC/MS confirmed the product as a sodium addition adduct (m/z 537).

¹H NMR(400MHz，CDCl₃)δ7.38(s，2H)，4.47(t，J＝6.2Hz，4H)，3.87(s，6H)，2.34(p，J＝6.2Hz，2H)。

Example 13: synthesis of Compound 17

Compound 1(0.500g, 2.11mmol) was dissolved in 50mL acetone (solvent over MgSO)₄Dried). Potassium carbonate (1.457g, 10.55mmol) was added, followed by addition of Compound 15(0.366g, 1.0 mmol)3 mmol). The resulting mixture was heated at 65 ℃ for 14 hours. The mixture was filtered and the filter cake was rinsed with dichloromethane (100 mL). The combined filtrates were concentrated in vacuo. Dichloromethane (50mL) was added and the mixture was filtered through a pad of celite. The filtrate was evaporated to dryness in vacuo to give an orange oil (0.526g, 48%).

¹H NMR(400MHz，CDCl₃)δ7.38(s，2H)，4.26(m，4H)，3.87(s，6H)，2.09(m，4H)。¹³CNMR(101MHz，CDCl₃)δ160.76，157.92，127.07，127.01，116.91，108.83，75.22，52.11，26.64。

Example 14: synthesis of Compound 18

The synthesis is based on WO2002038572A1 directed to 3-bromo-4-hexyloxythiophene-2-carboxylic acid. To a solution of compound 16(0.220g, 0.43mmol) in 5mL ethanol (containing 2mL THF to increase solubility) was added a solution of NaOH (0.510g, 12.84mmol) in 3mL water. The mixture was stirred vigorously at 70 ℃ for 14 hours. After cooling the reaction mixture to 25 ℃, it was acidified to pH 1 with concentrated HCl and Et₂O (2X 30 mL). The organic phase was washed with water (3X 50mL) and Na₂SO₄Drying and removal of solvent under reduced pressure gave a white solid (0.200g, 96%). The product is in CDCl₃Medium has low solubility, however, it slowly dissolves in acetone-d₆In (1).

¹H NMR (400MHz, acetone-d₆)δ7.82(s，2H)，4.52(t，J＝6.3Hz，4H)，2.32(p，J＝6.3Hz，2H)。¹³C NMR (101MHz, acetone-d)₆)δ161.49，158.42，128.67，118.19，108.97，73.44，31.80。

Example 15: synthesis of Compound 19

To a mixture of compound 17(0.510g, 0.97mmol) in 10mL ethanol and 8mL THFTo the solution in (1.16g, 28.96mmol) was added a solution of NaOH (1.16g, 28.96mmol) in 6mL of water. The mixture was stirred vigorously at 70 ℃ for 14 hours. After cooling the reaction mixture to 25 ℃, it was acidified to pH 1 with concentrated HCl and Et₂O (2X 80 mL). The organic phase was washed with water (3X 60mL) and Na₂SO₄Drying, filtration through celite, and removal of the solvent under reduced pressure gave an off-white solid (0.440g, 91%). The product was taken to the next step without further purification (decarboxylation).

¹H NMR (400MHz, acetone-d₆)δ7.81(s，2H)，4.31(m，4H)，2.07(m，4H)。

Example 16: synthesis of Compound 20

The synthesis is based on PCT international application 2004033440. Compound 18(0.200g, 0.41mmol) was placed in a 40mL scintillation vial equipped with a pressure-release septum cap at 65 ℃ with 5mL concentrated H₂SO₄The treatment was carried out for 5 hours. During this time, an exhaust needle is used to reduce CO₂The induced pressure is released.

After allowing the reaction mixture to cool to room temperature, it was poured into 50mL of crushed ice and extracted with dichloromethane (3X 40 mL). The combined organic phases are successively treated with H₂O (2X 30mL), saturated NaHCO₃Aqueous (2X 30mL) and brine (2X 40 mL). The organic layer was passed through a short plug of silica gel and concentrated in vacuo (0.135g, 82%). NMR showed slightly impure product. It was taken to the next step without further purification

¹H NMR(400MHz，CDCl₃)δ7.18(d，J＝3.5Hz，2H)，6.30(d，J＝3.5Hz，2H)，4.21(t，J＝6.0Hz，4H)，2.34(p，J＝6.0Hz，2H).¹³C NMR(101MHz，CDCl₃)δ153.40，122.05，103.26，97.66，67.00，28.90。

Example 17: synthesis of Compound 21

Compound 19(0.440g, 0.88mmol) was placed in a 40mL scintillation vial equipped with a pressure-release membrane cap at 65 ℃ with 10mL concentrated H₂SO₄The treatment was carried out for 5 hours. During this time, an exhaust needle is used to reduce CO₂The induced pressure is released. After allowing the reaction mixture to cool to room temperature, it was poured into 100mL of crushed ice and extracted with dichloromethane (3X 60 mL). The combined organic phases were filtered through celite and then successively with H₂O (2X 60mL), saturated NaHCO₃Aqueous (2X 60mL) and brine (2X 60 mL). The organic layer was passed through a short silica gel plug (at this stage some product was lost due to slight overflow) and concentrated in vacuo (0.075 g).

¹H NMR(400MHz，CDCl₃)δ7.18(d，J＝3.5Hz，2H)，6.25(d，J＝3.5Hz，2H)，4.09(m，4H)，2.05(m，4H)。

Example 18: synthesis of ligand L6

Compound 5(0.291g, 0.60mmol) and compound 20(0.120g, 0.30mmol) were dissolved in 10mL THF. Mixing Na₂CO₃(0.383g, 3.62mmol) was dissolved in 2mL of water and added to the THF solution to form a biphasic solution, which was then diluted with N₂Bubbling for 20 minutes. Pd (P)^tBu₃)₂(0.015g, 0.030mmol) was dissolved in 0.8mL of degassed THF in a nitrogen-filled dry box and then added to the reaction mixture by syringe. The reaction mixture was stirred vigorously at 65 ℃ for 14 hours. The reaction mixture was cooled to 25 ℃. The aqueous phase was separated and discarded. The organic phase was diluted with 30mL THF and the solution was passed through a short plug of silica gel. The filtrate was concentrated on a rotary evaporator and the residue was dissolved in a 1: 1(v/v) mixture of 16ml meoh and THF, 4 drops of concentrated HCl were added and the solution was stirred at 25 ℃ for 4 hours. The solution was evaporated to dryness in vacuo, and the residue was dissolved in 150mL EtOAc/hexanes (30% v/v EtOAc), passed through a short silica gel plug, and was removed in vacuoThe solvent was removed to give a beige solid (0.220 g). Biotage purification was performed using a gradient of EtOAc in hexanes as eluent (2% to 20% EtOAc on 11CV then held at 20%). The desired product fractions (first major eluent) were combined and evaporated to dryness in vacuo to give a white solid (0.140g, 61%). Residual acetone was shown in the NMR spectra due to washing of the Biotage tube with acetone, otherwise the product was pure. The solid was taken up in 5mL of dichloromethane and the solvent was removed in vacuo. A high vacuum was applied to the solid overnight, but dichloromethane was still shown in NMR. The product was not completely dissolved in CDCl₃However, it slowly dissolves in C₆D₆In (1).

¹H NMR(400MHz，C₆D₆)δ8.15-8.09(m，4H)，7.27(pd，J＝7.1，1.4Hz，8H)，7.21-7.17(m，4H)，7.07(dd，J＝2.2，0.5Hz，2H)，6.82(d，J＝3.4Hz，2H)，6.79(dd，J＝2.3，0.6Hz，2H)，6.00(s，2H)，5.40(d，J＝3.4Hz，2H)，3.52(t，J＝5.9Hz，4H)，2.02(s，6H)，1.47(p，J＝5.9Hz，2H)。¹³C NMR(101MHz，C₆D₆)δ154.26，149.15，142.40，132.40，130.73，130.16，129.95，126.52，125.83，124.61，124.57，124.51，121.07，120.58，111.03，99.27，66.95，28.94，20.67。

Example 19: synthesis of ligand L7

Compound 5(0.291g, 0.60mmol) and compound 21(0.120g, 0.30mmol) were dissolved in 10mL THF. Mixing Na₂CO₃(0.383g, 3.62mmol) was dissolved in 4mL of water and added to the THF solution to form a biphasic solution, which was then diluted with N₂Bubbling for 20 minutes. Pd (P)^tBu₃)₂(0.015g, 0.030mmol) was dissolved in 0.8mL of degassed THF in a nitrogen-filled dry box and then added to the reaction mixture by syringe. The reaction mixture was stirred vigorously at 65 ℃ for 14 hours. The reaction mixture was cooled to 25 ℃.The aqueous phase was separated and discarded. The organic phase was diluted with 30mL THF and the solution was passed through a short plug of silica gel. The filtrate was concentrated on a rotary evaporator and the residue was dissolved in a 1: 1(v/v) mixture of 20ml meoh and THF, 5 drops of concentrated HCl were added and the solution was stirred at 25 ℃ for 3 hours. The solution was evaporated onto silica gel for Biotage purification, eluting with a gradient of EtOAc in hexanes as eluent (2% to 20% EtOAc on 11CV then held at 20%). The desired product fractions were combined (final elution) and evaporated to dryness in vacuo to give a dark orange solid (0.072g, 50%). LC/MS confirmed the desired product as a sodium addition adduct (m/z 820). The product was taken up in ether (6mL) and the solvent was removed in vacuo. NMR still showed ether present.

¹H NMR(400MHz，CDCl₃)δ8.13(dt，J＝7.6，0.9Hz，4H)，7.38(d，J＝3.4Hz，2H)，7.36(d，J＝1.2Hz，1H)，7.33(m，6H)，7.24(br s，2H)，7.22(d，J＝1.0Hz，1H)，7.20(m，6H)，6.41(s，2H)，6.24(d，J＝3.4Hz，2H)，3.95(s，4H)，2.35(s，6H)，1.84(s，4H)。¹³C NMR(101MHz，CDCl₃)δ153.60，147.86，141.22，131.54，130.51，129.55，129.41，125.72，125.33，124.08，123.85，123.35，120.24，119.66，110.16，98.93，70.44，25.83，20.50。

Example 20: synthesis of ligand L8

Compound 8(0.286g, 0.41mmol) and compound 22(0.085g, 0.21mmol) were dissolved in 10mL THF. Mixing Na₂CO₃(0.262g, 2.47mmol) was dissolved in 4mL of water and added to the THF solution to form a biphasic solution, which was then diluted with N₂Bubbling for 15 minutes. Pd (P)^tBu₃)₂(0.011g, 0.021mmol) was dissolved in 0.8mL degassed THF in a nitrogen-filled dry box and then added to the reaction mixture by syringe. The reaction mixture was stirred vigorously at 65 ℃ for 14 hours. Allowing the reaction mixture to coolTo 25 ℃. The aqueous phase was separated and discarded. The organic phase is concentrated on a rotary evaporator and the resulting wet residue is dissolved in 50mL Et₂O, and remove a small amount of the aqueous layer with a pipette. The solution was passed through a short silica gel plug. The filtrate was concentrated on a rotary evaporator and the residue was dissolved in 20mL of a 1: 2(v/v) mixture of MeOH and THF, 5 drops of concentrated HCl were added, and the solution was stirred at 25 ℃ for 14 hours. The reaction mixture was evaporated to dryness, redissolved in 50mL THF, and evaporated onto silica gel. Biotage purification was performed using a gradient of EtOAc in hexanes as eluent (2% to 18% EtOAc on 10 CV). The desired product fractions were combined (final elution) and evaporated to dryness in vacuo (0.080g, 32%).

¹H NMR(400MHz，CDCl₃)δ8.16(d，J＝1.6Hz，4H)，7.53(d，J＝2.4Hz，2H)，7.44(d，J＝1.9Hz，2H)，7.41(m，4H)，7.35(d，J＝2.4Hz，2H)，7.11(d，J＝8.6Hz，4H)，6.29(d，J＝3.4Hz，2H)，6.10(s，2H)，4.01(m，4H)，1.91(m，4H)，1.70(s，4H)，1.45(s，36H)，1.35(s，12H)，0.80(s，18H)。¹³C NMR(101MHz，CDCl₃)δ154.16，147.58，142.58，139.66，129.64，128.59，126.66，124.76，124.09，123.51，123.33，122.70，116.28，109.48，98.60，70.22，57.08，38.20，34.71，32.44，32.05，31.89，31.56，25.89。

Example 21: synthesis of Compound 23

Compound 5(1.599g, 3.31mmol) and compound 22(0.800g, 3.31mmol) were dissolved in 20mL THF. Mixing Na₂CO₃(2.103g, 19.84mmol) was dissolved in 10mL of water and added to the THF solution to form a biphasic solution, which was then diluted with N₂Bubbling for 30 minutes. Pd (P)^tBu₃)₂(0.068g, 0.13mmol) was dissolved in 1mL degassed THF in a nitrogen-filled dry box and then added to the reaction mixture via syringe. The reaction mixture was stirred vigorously overnight at 65 ℃. Mixing the reaction mixtureCooled to 25 ℃, and the aqueous phase was separated and discarded. THF phase over Na₂SO₄Dried and then evaporated onto silica gel for Biotage purification using EtOAc in 5% (v/v) hexane as eluent. The product fractions (second eluted material) were combined and the solvent was removed on a rotary evaporator. Et used to transfer product from flask to vial was seen in product NMR even after vacuum drying₂And O. Yield: 0.701g, 41%.

¹H NMR(400MHz，CDCl₃)δ8.15-8.08(m，2H)，7.46-7.41(m，8H)，7.38(d，J＝3.5Hz，1H)，7.35-7.32(m，1H)，7.31-7.27(m，2H)，7.25-7.23(m，1H)，4.42-4.30(m，1H)，2.75-2.64(m，1H)，2.42(s，3H)，1.18-0.80(m，8H)，0.63(d，J＝13.3Hz，1H)。

Example 22: synthesis of ligand L9

In a nitrogen-filled glove box, compound 23(0.400g, 0.77mmol) was dissolved in Et₂O (5mL) and cooled to-35 ℃. A solution of t-BuLi in pentane (0.95mL, 1.62 mmol; 1.70M) was added to the cold solution of 23 and the reaction mixture was allowed to warm to 0 ℃ while stirring and then cooled to-35 ℃ for 30 minutes. Trimethylene bis (thiotosylate) (0.145g, 0.35mmol) was added to the solution, which was then allowed to warm to 25 ℃ and stirred for 14 hours. The reaction mixture was taken up with 20mL of saturated NH₄Cl (aq) and extracted into EtOAc (30 mL). Some white solid was present in the biphasic mixture, which was removed by filtration. The organic phase is passed through Na₂SO₄Dried and passed through a silica gel plug. The solvent was removed under vacuum. The crude THP protected product was subjected to Biotage purification (EtOAc/hexanes gradient: 1% to 10% EtOAc on 11.5CV, then held at 10%).

¹H NMR(400MHz，CDCl₃)δ8.14(dt，J＝7.7，0.9Hz，4H)，7.41-7.36(m，4H)，7.35(d，J＝3.3Hz，2H)，7.31-7.27(m，4H)，7.24-7.23(m，2H)，7.21-7.14(m，4H)，7.05(d，J＝3.3Hz，2H)，5.09(s，2H)，2.79(t，J＝7.0Hz，4H)，2.34(s，6H)，1.80(p，J＝7.0Hz，2H)。

The purified protected product was dissolved in 16mL of a 1: 1(v/v) mixture of THF and MeOH, concentrated HCl (3 drops from a Pasteur pipette) was added, and the solution was stirred at 25 ℃ for 2 hours. The solvent was removed in vacuo to give a white residue which was dissolved in 15mL Et₂O, through a silica gel plug, and evaporated to dryness in vacuo. The product was dried under high vacuum overnight (0.182g, 64%).

¹H NMR(400MHz，C₆D₆)δ8.05(dt，J＝7.7，1.0Hz，4H)，7.37-7.29(m，4H)，7.29-7.19(m，8H)，7.05(dd，J＝2.3，0.6Hz，2H)，6.87(d，J＝3.3Hz，2H)，6.71(dd，J＝2.2，0.7Hz，2H)，6.61(d，J＝3.3Hz，2H)，4.93(s，2H)，2.47(t，J＝7.1Hz，4H)，1.98(s，6H)，1.55(p，J＝7.1Hz，2H)。¹³C NMR(101MHz，CDCl₃)δ147.80，140.97，138.39，131.99，131.66，130.30，129.27，126.09，125.41，124.60，124.23，124.02，123.64，120.35，120.16，110.20，33.56，28.25，20.49。

Example 23: synthesis of ligand L10

In a nitrogen-filled glove box, compound 23(0.293g, 0.57mmol) was dissolved in Et₂O (5mL) and cooled to-35 ℃. A solution of t-BuLi in pentane (0.70mL, 1.19 mmol; 1.70M) was added to the cold solution of 23 and the reaction mixture was allowed to warm to 0 ℃ while stirring and then cooled to-35 ℃ for 30 minutes. Tetramethylenebis (thiotosylate) (0.117g, 0.27mmol) was added to the solution, then the solution was warmed to 25 ℃ and stirred for 14 hours. The reaction mixture was taken up with 20mL of saturated NH₄Cl (aq) and extracted into EtOAc (30 mL). The organic phase was passed through a plug of silica gel and the solvent was removed under vacuum. The crude THP protected product was dissolved in 20mL of a 1: 1(v/v) mixture of THF and MeOH, and concentrated was addedHCl (5 drops from pasteur pipette) and the solution was stirred at 25 ℃ for 3 hours. Solvent removal in vacuo gave a white residue which was dissolved in 100mL of a 1: 1(v/v) mixture of EtOAc and hexane, passed through a plug of silica gel, and evaporated to dryness in vacuo to give L10 as a beige solid in quantitative yield.

¹H NMR(400MHz，CDCl₃)δ8.14(d，J＝7.7Hz，4H)，7.44-7.37(m，4H)，7.35(d，J＝3.3Hz，2H)，7.31-7.29(m，2H)，7.29-7.26(m，4H)，7.22-7.17(m，4H)，7.06(d，J＝3.3Hz，2H)，5.18(s，2H)，2.75-2.64(m，4H)，2.35(s，6H)，1.69-1.60(m，4H)。¹³C NMR(101MHz，CDCl₃)δ147.81，141.00，138.21，131.95，130.28，129.29，126.04，125.43，124.30，124.10，124.00，123.61，120.44，120.33，120.11，110.22，34.22，27.84，20.49。

Example 24: synthesis of Compound 25

A50 mL nitrogen purged round bottom flask was charged with a Turbo Grignard solution (1.70mL, 2.18 mmol; 1.30M in THF) and cooled to-40 ℃ in an acetonitrile dry ice bath. To this cold solution was added dropwise 3, 4-dibromofuran (0.447g, 1.98mmol) dissolved in THF (1mL) to prevent the reaction from undergoing an exotherm. The reaction mixture was allowed to warm to 25 ℃. The reaction mixture was then cooled to 0 ℃ and trimethylene bis (thiotosylate) (370mg, 0.89mmol) dissolved in THF (2mL) was added dropwise at 0 ℃. The reaction mixture was allowed to warm to ambient temperature overnight. A large amount of precipitate formed. To the reaction mixture was added saturated aqueous ammonium chloride (15mL), and the resultant was extracted into ethyl acetate (20 mL). The organics were washed with saturated aqueous ammonium chloride (2 × 15mL), dried over sodium sulfate, filtered and absorbed onto celite in vacuo. This material was purified by flash column chromatography (0 to 20% EtOAc in hexanes) to give the product as a colorless oil (0.145g, 41%).

¹H NMR(400MHz，CDCl₃)δ7.48(dd，J＝1.7，0.4Hz，2H)，7.42(dd，J＝1.7，0.4Hz，2H)，2.81(t，J＝7.1Hz，4H)，1.78(p，J＝7.1Hz，2H)。¹³C NMR(101MHz，CDCl₃)δ145.68，142.00，117.46，106.23，33.22，28.44。

Example 25: synthesis of ligand L11

In a nitrogen-filled dry box, a vial containing a stir bar was charged with Compound 5(0.237g, 0.49mmol), Compound 25(0.065g, 0.16mmol), and Cs₂CO₃(0.319g, 0.98 mmol). Deoxygenated dioxane (2mL) and PdCl (crotyl) (P) were added^tBu₃) (0.0033g, 0.01mmol), and the vial was sealed with a septum cap and removed from the dry box. Deoxygenated deionized water (0.6mL) was added via syringe. The reaction mixture was heated to 80 ℃ and stirred vigorously for 14 hours. The reaction mixture was cooled to 25 ℃, and the aqueous phase was separated and discarded. The organic phase was evaporated to dryness in vacuo. The residue was taken up in CHCl at 60 ℃ over 2.5 hours with 10 mol% pyridinium p-toluenesulfonate₃And MeOH (6: 1 v/v). The solvent was removed in vacuo and the residue taken up in Et₂In O (about 5mL), pass through a plug of silica gel and evaporate to dryness in vacuo (0.070g, 56%).

¹H NMR(500MHz，CDCl₃)δ8.14(dt，J＝7.7，0.9Hz，1H)，7.73(d，J＝1.7Hz，0H)，7.54(d，J＝1.9Hz，1H)，7.46(d，J＝1.7Hz，0H)，7.38(ddd，J＝8.2，7.2，1.0Hz，1H)，7.28(ddd，J＝7.9，7.4，0.8Hz，1H)，7.21(dt，J＝7.9，0.8Hz，1H)，7.14(d，J＝1.8Hz，0H)，5.36(s，0H)，5.30(s，0H)，2.66(t，J＝7.0Hz，1H)，2.35(s，1H)，1.76(p，J＝7.0Hz，1H)。¹³C NMR(126MHz，CDCl₃)δ147.87，145.19，142.85，140.94，131.33，130.48，128.84，126.17，124.05，123.68，122.85，120.39，120.29，119.75，115.85，110.12，109.70，33.57，28.29，20.55。

Example 26: discrete procatalysts 21 through 30

ZrCl was added in a nitrogen-filled dry box at 25 deg.C₄Or HfCl₄(0.05mmol) was suspended in 2mL of dry degassed toluene and MeMgBr (0.140mL, 0.21mmol, 4.1 equiv.; in Et)₂A 1.5M solution in O) was added to the suspension. Within 30 seconds, a solution of the ligand in 2mL of toluene (0.05mmol) was added and the mixture was stirred at 25 ℃ for 2 hours. (ligands L6 to L10 were used for the synthesis of these procatalysts.) the reaction mixture was evaporated to dryness in vacuo and toluene (5mL) was added. The mixture was filtered (0.45 μm) and the filtrate was evaporated to dryness in vacuo. Toluene addition, filtration and solvent removal under vacuum were repeated once more to give the product. Individual yields and NMR data are provided in table 1.

Table 1: yield and NMR data for procatalyst 21-30

Example 27: in situ procatalysts 1 through 20, 31 and 32

In a nitrogen-filled dry box, appropriate volumes of 0.005M solutions of ligands L1 to L5 and L11 (0.1. mu. mol for procatalysts 1 to 10, 31 and 32; 0.2. mu. mol for procatalysts 11 to 20) were combined with 0.010M HfBn₄Or ZrBn₄The solution (0.1. mu. mol) was mixed at 25 ℃ and injected into the PPR at the appropriate time after half an hour to 3 hours.

The polymers produced from procatalysts 1-20 and 31-32 were prepared according to the PPR screening procedure described above, using the following conditions: 120 ℃, 150psig, 838 μ L of 1-octene, 500nmol of MMAO-3A, 100nmol of catalyst, 150nmol of bis (hydrogenated tallow alkyl) methylammonium tetrakis (pentafluorophenyl) borate, 5mL total liquid volume. All polymerizations were carried out using bis (hydrogenated tallow alkyl) methylammonium tetrakis (pentafluorophenyl) borate as the activator and MMAO as the scavenger. The data for the polymers produced by procatalysts 1-20 are reported in table 2. The data for the polymers produced by the procatalysts 31 and 32 are reported in table 3.

The catalyst activities (in terms of quench time and polymer yield) and the resulting polymer characteristics of procatalysts 1-20 and 31-32 were evaluated. The polymerization is carried out in a Parallel Polymerization Reactor (PPR).

Selected data in table 2 were obtained at a polymerization temperature of 120 ℃. The activator is [ HNMe (C) in an amount of 0.15. mu. mol₁₈H₃₇)₂][B(C₆F₅)₄]. The quench time indicates the time required for ethylene absorption to reach 50 psi. The quench time was measured as the time at which the target absorption occurred or after 1800 seconds quenching the polymerization with CO (whichever occurred first).

Table 2: parallel polymerization reactor data

Octene Mol% or C8/alkene was defined as: (moles of 1-octene/(total moles of 1-octene and ethylene)). times.100.

Polymers produced in polymerization systems including procatalysts 1-20 yield polymers with moderate octene incorporation; the medium octene incorporation is between 3 mol% and 15 mol% incorporation. The zirconium-containing procatalysts 1, 3, 5, 7, 9, 11, 13, 15, 17 and 19 generally have higher efficiencies than the hafnium-based procatalysts 2, 4, 6, 8, 10, 12, 14, 16, 18 and 20, as indicated by shorter quench times and higher polymer yields. Hafnium-based procatalysts generally provide a catalyst having a higher M than the corresponding zirconium analog_wThe polymer of (1).

The data in Table 3 were obtained with varying amounts of activator (act) and procatalyst at either 120 ℃ or 150 ℃ polymerization temperature. The activator used to obtain the data in Table 3 was [ HNMe (C)₁₈H₃₇)₂][B(C₆F₅)₄]. The quench time indicates the time required to reach the target ethylene absorption (50 psi for 120 ℃ run and 75psi for 150 ℃) and was measured as described above.

Table 3: parallel polymerization reactor data-various amounts of activator

Octene Mol% or C8/alkene was defined as: (moles of 1-octene/(total moles of 1-octene and ethylene)). times.100.

The polymers produced in the polymerization system including procatalysts 31 and 32 exhibit very high efficiency as indicated by shorter quench times and higher polymer yields. These procatalysts also produce a catalyst with low M_wAnd a high octene-incorporated polymer; high octene incorporation is at least 15 mol% incorporation.

The data in Table 4 are obtained from 1.2 equivalents of [ HNMe (C) at 120 ℃ polymerization temperature₁₈H₃₇)₂][B(C₆F₅)₄]As an activator in a batch reactor. The run time was 10 minutes and the scavenger was MMAO-3A.

Table 4: batch reactor ethylene and 1-octene copolymerization data

Solvent: 1153g Isopar E, monomer: 280psi ethylene, comonomer: 568g of 1-octene.

The procatalysts 21 through 23 and 25 through 30 exhibit high efficiencies for polymers made in batch reactors, both greater than 800,000 grams polymer per gram metal. Procatalysts 21 through 26 and 28 through 30 produce polymers with high mol% octene incorporation (greater than 15 mol% incorporation). Procatalyst 27 produces a polymer with moderate mol% octene incorporation (greater than 10 mol% incorporation). The polymers produced by the zirconium-based procatalysts 21, 23, 25 and 27 through 29 exhibit higher efficiencies, but lower M's, than the polymers produced by the corresponding hafnium-based procatalysts 22, 24, 26, 28 and 30, respectively_w. Procatalysts 22, 24 and 26 produce high octene-incorporated polymers having relatively high molecular weights (all greater than 200,000g/mol) and greater than 15 mol%, but with procatalysts 21, 23, 25 and 27-30The efficiency is lower than the efficiency. The thioether-bridged procatalysts 27 and 29 provide a catalyst with a significantly lower M than the analogous ether-bridged procatalysts 21 and 23_wThe polymer of (1). Similarly, the thioether-bridged procatalysts 28 and 30 provide a catalyst having a significantly lower M than the analogous ether-bridged procatalysts 22 and 24_wThe polymer of (1).

Measurement standard

Density of

Density-measuring samples were prepared according to ASTM D-1928, which is incorporated herein by reference in its entirety. Measurements were made within one hour of sample pressing using ASTM D-792, method B, which is incorporated herein by reference in its entirety.

Octene content

By taking CH₃Area (1382.7-1373.5 wavenumbers) and CH₂The ratio of the areas (1525 to 1400 wavenumbers), and normalized to a standard curve generated by NMR analysis of poly (ethylene-co-1-octene) standards, determines the mole% (mol%) of 1-octene in each sample.

Gel Permeation Chromatography (GPC)

The properties of the ethylene/α -olefin interpolymers were tested by GPC according to the following procedure. The GPC system consisted of Waters (Milford, Mass), equipped with an on-board differential Refractometer (RI), a 150 ℃ high temperature chromatograph (other suitable high temperature GPC instruments include Polymer Laboratories (Shropshire, UK) model 210 and model 220). Additional Detectors may include IR4 infrared Detectors from Polymer ChAR (Valencia, Spain)), Precision Detectors (Amherst, Mass.) model 2-angle laser light scattering Detectors 2040 and Viscotek (Houston, Tex.) 150R 4 capillary solution viscometers. GPC with the latter two independent detectors and at least one first detector is sometimes referred to as "3D-GPC," while the separate term "GPC" generally refers to conventional GPC. Depending on the sample, either a 15 degree angle or a 90 degree angle light scatter detector is used for calculation purposes.

Data collection was performed using Viscotek TriSEC software version 3 and 4-channel Viscotek Data Manager DM 400. The system was equipped with an on-line solvent degasser from the polymer laboratory (scrapshire, uk). Suitable high temperature GPC columns may be used, such as four 30cm long Shodex HT 80313 micron columns, or four 30cm Polymer Labs columns with 20 micron mixed pore size packing (MixA LS, Polymer laboratories). The sample transfer chamber was operated at 140 ℃ and the chromatography column chamber was operated at 150 ℃. Samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent. The chromatographic solvent and sample preparation solvent contained 200ppm of Butylated Hydroxytoluene (BHT). Both solvents were sparged with nitrogen. The polyethylene sample was gently stirred at 160 ℃ for four hours (4 h). The injection volume was 200 microliters (μ L). The flow rate through GPC was set at 1 ml/min.

Prior to running the examples, the GPC chromatography column set was calibrated by running twenty-one narrow molecular weight distribution polystyrene standards. The molecular weight (Mw) of the standards ranged from 580 to 8,400,000 grams per mole (g/mol), and the standards were contained in 6 "cocktail" mixtures. Each standard mixture has at least a tenfold separation between the individual molecular weights. The standard mixtures were purchased from polymer laboratories (Leishoproshire, UK). For molecular weights equal to or greater than 1,000,000g/mol, polystyrene standards were prepared at 0.025g in 50mL of solvent, and for molecular weights less than 1,000,000g/mol, polystyrene standards were prepared at 0.05g in 50mL of solvent. The polystyrene standards were dissolved at 80 ℃ for 30 minutes with gentle stirring. The narrow standards mixtures were run first, and in order of decreasing highest molecular weight (Mw) components to minimize degradation. The polystyrene standard peak molecular weight was converted to polyethylene Mw using the Mark-Houwink constant. After constants were obtained, these two values were used to construct two linear reference routine calibrations of polyethylene molecular weight and polyethylene intrinsic viscosity as a function of elution column.

Efficiency measurement

The catalytic efficiency is measured in terms of polymer throughput relative to the amount of catalyst used in the solution polymerization process, wherein the polymerization temperature is at least 130 ℃.

It will be apparent to those skilled in the art that various modifications can be made to the described embodiments without departing from the spirit and scope of the claimed subject matter. Thus, it is intended that the present specification cover the modifications and variations of the described embodiments provided such modifications and variations come within the scope of the appended claims and their equivalents.