Olefin polymerization catalyst system and polymerization process

Abstract

The olefin polymerization process is carried out in the presence of a catalyst system comprising a prepolymerization catalyst, a boron-based catalyst activator, an alkylaluminoxane cocatalyst, and a hindered phenol compound. The prepolymerization catalyst is a titanium complex in which an indenoindolyl ligand is bridged to a phenoxy ligand through a silyl group. The catalyst system is effective in polymerizing ethylene with alpha-olefins in a solution phase polymerization process at high temperatures to produce ethylene copolymers having high molecular weights and high degrees of alpha-olefin incorporation.

Description

[Technical field]

[0001] The olefin polymerization catalyst system polymerizes ethylene with alpha-olefins to produce ethylene copolymers having high molecular weight and a high degree of short chain branching. [Background technology]

[0002] A wide variety of single-site catalysts have been developed for the polymerization of olefins, including metallocene polymerization catalysts supported by indenoindolyl ligands, and polymerization catalysts having cyclopentadienyl-type ligands containing indenoindolyl ligands bonded to phenoxy-type ligands, so-called "half-sandwich" complexes.

[0003] There is a continuing desire to improve the performance of single-site catalysts for use in high temperature olefin polymerization processes, such as solution phase olefin polymerization. Summary of the Invention

[0004] We report here an olefin polymerization catalyst system in which ligand derivatization is combined with a specific activation strategy to improve the catalytic activity for the polymerization of ethylene, optionally with alpha-olefins, in solution phase at elevated temperatures.

[0005] In one embodiment, i) A prepolymerized catalyst having structure I or II: [ka] (In the formula, R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 10A , R 11A and R 12Aare each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R 1A , R 2A , R 3A and R 4A or R 5A , R 6A , R 7A and R 8A or R 9A , R 10A , R 11A and R 12A Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; R 1B , R 2B , R 3B , R 4B , R 5B , R 6B , R 7B , R 8B , R 9B , R 10B , R 11B and R 12B are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R 1B , R 2B , R 3B and R 4B or R 5B , R 6B , R 7B and R 8B or R 9B , R 10B , R 11B and R 12B Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; R 13A is a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; R 13B is a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; Each R 14A are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen;14A the groups may optionally be joined to form a ring; Each R 14B are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; 14B the groups may optionally be joined to form a ring; each X is an activatable ligand; ii) a boron-based catalyst activator; iii) an alkylaluminoxane cocatalyst; iv) hindered phenol compounds; An olefin polymerization catalyst system comprising:

[0006] In one embodiment, i) A prepolymerized catalyst having structure I or II: [ka] (In the formula, R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 10A , R 11A and R 12A are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R 1A , R 2A , R 3A and R 4A or R 5A , R 6A , R 7A and R 8A or R 9A , R 10A , R 11A and R 12A Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; R 1B , R 2B , R3B , R 4B , R 5B , R 6B , R 7B , R 8B , R 9B , R 10B , R 11B and R 12B are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R 1B , R 2B , R 3B and R 4B or R 5B , R 6B , R 7B and R 8B or R 9B , R 10B , R 11B and R 12B Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; R 13A is a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; R 13B is a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; Each R 14A are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; 14A the groups may optionally be joined to form a ring; Each R 14B are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; 14B the groups may optionally be joined to form a ring; each X is an activatable ligand; ii) a boron-based catalyst activator; iii) an alkylaluminoxane cocatalyst; iv) hindered phenol compounds; ethylene is optionally condensed into one or more C3-C 12 and an alpha-olefin.

[0007] In an embodiment, the polymerization process comprises polymerizing ethylene with an alpha-olefin selected from the group consisting of 1-butene, 1-hexene, 1-octene, and mixtures thereof.

[0008] In an embodiment, the polymerization process comprises polymerizing ethylene with 1-octene.

[0009] In certain embodiments, the polymerization process is a solution phase polymerization process carried out in a solvent.

[0010] In certain embodiments, the polymerization process is a continuous solution phase polymerization process carried out in a solvent.

[0011] In one embodiment, the continuous solution phase polymerization process is carried out in at least one continuous stirred tank reactor.

[0012] In one embodiment, the continuous solution phase polymerization process is carried out at a temperature of at least 160°C.

[0013] In one embodiment, R 1A , R 2A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 11A , R 1B , R 2B , R 4B , R 5B , R 6B , R 7B , R 8B , R 9B and R 11B is hydrogen.

[0014] In one embodiment, R 3A and R 3B is a hydrocarbyl group.

[0015] In one embodiment, R 3A and R 3Bis an alkyl group.

[0016] In one embodiment, R 10A and R 10B is a hydrocarbyl group.

[0017] In one embodiment, R 10A and R 10B is an alkyl group.

[0018] In one embodiment, R 10A and R 10B is a heteroatom-containing hydrocarbyl group.

[0019] In one embodiment, R 10A and R 10B is an alkoxy group.

[0020] In one embodiment, R 12A and R 12B is a hydrocarbyl group.

[0021] In one embodiment, R 12A and R 12B is an alkyl group.

[0022] In one embodiment, R 13A and R 13B is a hydrocarbyl group.

[0023] In one embodiment, R 13A and R 13B is an alkyl group.

[0024] In one embodiment, R 13A and R 13B is an arylalkyl group.

[0025] In one embodiment, each R 14A and each R 14B is a hydrocarbyl group.

[0026] In one embodiment, each R 14A and each R14B is an alkyl group.

[0027] In one embodiment, each R 14A and each R 14B is an aryl group.

[0028] In certain embodiments, each X is methyl or chloride.

[0029] In certain embodiments, the boron-based catalyst activator is selected from the group consisting of N,N-dimethylanilinium tetrakispentafluorophenylborate ("[Me2NHPh][B(C6F5)4]") and triphenylmethylium tetrakispentafluorophenylborate ("[Ph3C][B(C6F5)4]").

[0030] In one embodiment, the boron-based catalyst activator is triphenylmethylium tetrakispentafluorophenylborate ("[Ph3C][B(C6F5)4]").

[0031] In one embodiment, the hindered phenol compound is 2,6-di-tert-butyl-4-ethylphenol.

[0032] One embodiment is a compound of formula VI: [ka] 1. A method for making an organometallic complex having the formula: The following reaction is carried out in a single reaction vessel: (i) Formula V: [ka] or a double bond isomer of a cyclopentadienyl-containing compound having formula V, is combined with a base and subsequently reacted with a cyclopentadienyl-containing compound having formula VII: [ka] adding a compound represented by: (ii) optionally an excess of a trialkylamine compound, (R F ) in the presence of at least 2 molar equivalents of an alkyllithium reagent, (R E ) adding Li; (iii) Formula TiCl2(X ε )2(D) n adding a Group IV transition metal compound having (iv) optionally, a compound of formula Cl x Si(R ε ) 4-x (In the formula, each R ε The groups are independently C 1~20 adding a silane compound having an alkyl group; (v) optionally, a compound of formula (R G )M, (R G )(R H )Mg or (R G ) adding an alkylating agent having 2Zn; (vi) Optionally, switching the reaction solvent during any of the previous steps. A method comprising the steps of: (In the formula, R A , R B , R C and R D are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R A , R B , R C and R D Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; R 9 , R 10 , R 11 and R 12 are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R 9 , R 10 , R 11 and R 12Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; Each R 14 are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; 14 the groups may optionally be joined to form a ring; each X is an activatable ligand; X ε is halide, C 1~20 an alkoxy group or a group of the formula -NR', where each R' group is independently 1~30 Alkyl group or C 6~10 an amide group having an aryl group; R E is C 1~20 is a hydrocarbyl group; R F is C 1~10 is an alkyl group; R G is C 1~20 is a hydrocarbyl group; R H is C 1~20 Hydrocarbyl group, halide or C 1~20 is an alkoxy group; M is Li, Na or K; D is an electron donor compound; (n=1 or 2). [Brief description of the drawings]

[0033] [Figure 1] FIG. 1 shows the Oak Ridge Thermal Ellipsoid Plot (ORTEP) of an organometallic complex of the present disclosure, Invention Example 28. The ORTEP is a representation of the molecular structure of an organometallic complex of the present disclosure as determined by X-ray diffraction. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0034] As used herein, the term "monomer" refers to a small molecule that can chemically react and become chemically bonded with itself or other monomers to form a polymer.

[0035] As used herein, the term "α-olefin" or "alpha-olefin" is used to describe a monomer having a linear hydrocarbon chain containing 3 to 20 carbon atoms with a double bond at one end of the chain. An equivalent term is "linear α-olefin." As used herein, the term "polyethylene" or "ethylene polymer" refers to a polymer made from ethylene monomer and optionally one or more additional monomers, regardless of the particular catalyst or the particular process used to make the ethylene polymer. In the polyethylene field, the one or more additional monomers are called "comonomers" and often include α-olefins. The term "homopolymer" refers to a polymer containing only one type of monomer. An "ethylene homopolymer" is made using only ethylene as the polymerizable monomer. The term "copolymer" refers to a polymer containing two or more types of monomers. An "ethylene copolymer" is made using ethylene and one or more other types of polymerizable monomers. Common polyethylenes include high density polyethylene (HDPE), medium density polyethylene (MDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE), ultralow density polyethylene (ULDPE), plastomers and elastomers. The term polyethylene also includes polyethylene terpolymers, which may contain two or more comonomers in addition to ethylene. The term polyethylene also includes combinations or blends of the above polyethylenes.

[0036] As used herein, the terms "hydrocarbyl," "hydrocarbyl radical," or "hydrocarbyl group" refer to straight-chain or branched aliphatic, olefinic, acetylenic, and aryl (aromatic) radicals that contain hydrogen and carbon and are deficient in one hydrogen. The term "cyclic hydrocarbyl group" refers to a hydrocarbyl group that contains a cyclic moiety and may have one or more cyclic aromatic rings, and / or one or more non-aromatic rings. The term "acyclic hydrocarbyl group" refers to a hydrocarbyl group that does not have a cyclic moiety, such as an aromatic or non-aromatic ring structure, present therein.

[0037] As used herein, the phrase "heteroatom" includes any atom other than carbon and hydrogen that can be bonded to carbon. The term "heteroatom-containing" or "heteroatom-containing hydrocarbyl group" means that one or more non-carbon atoms can be present in the hydrocarbyl group. Some non-limiting examples of non-carbon atoms that can be present in the heteroatom-containing hydrocarbyl group are N, O, S, P, and Si, as well as halides such as Br and metals such as Sn. Some non-limiting examples of heteroatom-containing hydrocarbyl groups include, for example, aryloxy groups, alkoxy groups, alkylaryloxy groups, and arylalkoxy groups. Further non-limiting examples of heteroatom-containing hydrocarbyl groups generally include, for example, imines, amine moieties, oxide moieties, phosphine moieties, ethers, ketones, heterocycles, oxazolines, thioethers, and the like.

[0038] In certain embodiments of the present disclosure, the heteroatom-containing hydrocarbyl group is a hydrocarbyl group containing from 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen and sulfur.

[0039] The term "cyclic heteroatom-containing hydrocarbyl" or "heterocyclic" refers to a ring system having a carbon skeleton further containing at least one heteroatom selected from the group consisting of, for example, boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen, and sulfur.

[0040] In certain embodiments of the present disclosure, the cyclic heteroatom-containing hydrocarbyl group is a cyclic hydrocarbyl group containing from 1 to 3 atoms selected from the group consisting of boron, aluminum, silicon, germanium, nitrogen, phosphorus, oxygen and sulfur.

[0041] As used herein, "alkyl radical" or "alkyl group" includes straight-chain, branched, and cyclic paraffin radicals that are missing one hydrogen radical. Non-limiting examples include methyl (-CH3) and ethyl (-CH2CH3) radicals. The term "alkenyl radical" or "alkenyl group" refers to straight-chain, branched, and cyclic hydrocarbons that contain at least one carbon-carbon double bond that is missing one hydrogen radical. The term "alkynyl radical" or "alkynyl group" refers to straight-chain, branched, and cyclic hydrocarbons that contain at least one carbon-carbon triple bond that is missing one hydrogen radical.

[0042] As used herein, the term "aryl radical" or "aryl group" includes phenyl, naphthyl, pyridyl and other radicals, the molecules of which have an aromatic ring structure. Non-limiting examples include naphthalene, phenanthrene and anthracene. An "alkylaryl" group is an alkyl group having an aryl group pending therefrom. Non-limiting examples include benzyl, phenethyl and tolylmethyl. An "arylalkyl" is an aryl group having one or more alkyl groups pending therefrom. Non-limiting examples include tolyl, xylyl, mesityl and cumyl.

[0043] An "alkoxy group" is an oxy group having an alkyl group pending therefrom, such as, for example, methoxy, ethoxy, isopropoxy, etc. An "alkylaryloxy group" is an oxy group having an alkylaryl group pending therefrom (for clarity, the alkyl moiety is bonded to the oxy moiety and the aryl group is bonded to the alkyl moiety).

[0044] An "aryloxy" group is an oxy group having an aryl group pending therefrom, such as, for example, a phenoxy group. An "arylalkyloxy group" is an oxy group having an arylalkyl group pending therefrom (for clarity, the aryl moiety is bonded to the oxy moiety and the alkyl moiety is bonded to the aryl moiety).

[0045] In this disclosure, the hydrocarbyl group or heteroatom-containing hydrocarbyl group may be more specifically defined as unsubstituted or substituted. As used herein, the term "unsubstituted" means that a hydrogen radical is attached to the molecular group referred to by the term unsubstituted. The term "substituted" means that the group referred to by this term has one or more moieties substituted with one or more hydrogen radicals at any position within the group. Non-limiting examples of moieties include halogen radicals (F, Cl, Br), alkyl groups, alkylaryl groups, arylalkyl groups, alkoxy groups, aryl groups, aryloxy groups, amido groups, silyl groups or germanyl groups, hydroxyl groups, carbonyl groups, carboxyl groups, amine groups, phosphine groups, phenyl groups, naphthyl groups, C1-C2 alkyl groups, aryl ... 10 Alkyl groups, C2-C 10 alkenyl groups and combinations thereof.

[0046] In embodiments of the present disclosure, any hydrocarbyl group and / or any heteroatom-containing hydrocarbyl group may be unsubstituted or substituted.

[0047] The polymerization catalysts or complexes described herein require activation by one or more cocatalyst or catalyst activator species to provide polymers from olefins. Thus, an unactivated polymerization catalyst or complex may be described as a "pre-polymerization catalyst."

[0048] In embodiments, the prepolymerized catalysts described and used in this disclosure have improved activity when combined with a boron-based catalyst activator, an alkylaluminoxane cocatalyst, and a hindered phenol compound.

[0049] Accordingly, one embodiment of the present disclosure is an olefin polymerization catalyst system comprising: i) a prepolymerized catalyst; ii) a boron based catalyst activator; iii) an alkylaluminoxane cocatalyst; and iv) a hindered phenol compound.

[0050] Another embodiment of the present disclosure relates to a process for the polymerization of ethylene, optionally with one or more C3-C olefins, in the presence of an olefin polymerization catalyst system comprising: i) a prepolymerization catalyst; ii) a boron based catalyst activator; iii) an alkylaluminoxane cocatalyst; and iv) a hindered phenol compound. 12 and an alpha-olefin.

[0051] Prepolymerization Catalyst The prepolymerization catalysts used in this disclosure may generally be considered to be so-called "single-site catalysts", although the term "single-site catalyst" is used herein to distinguish the polymerization catalysts from those considered to be traditional multi-site polymerization catalysts, such as Ziegler-Natta catalysts or chromium-based catalysts. Those skilled in the art will appreciate that, for example, metallocene catalysts, constrained geometry catalysts, and phosphinimine catalysts are all generally considered to be "single-site catalysts", but each of these "single-site catalysts" may also exhibit, under certain conditions, behavior that may be considered to be multi-site catalyst behavior. This is also true for the prepolymerization catalysts used in this disclosure, so the term "single-site catalyst" is not meant to exclude prepolymerization catalysts that may exhibit aspects of multi-site behavior.

[0052] In certain embodiments of the present disclosure, the prepolymerized catalyst has the structure I or II: [ka] (In the formula, R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 10A , R 11A and R 12A are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R 1A , R 2A , R 3A and R 4A or R 5A , R 6A , R 7A and R 8A or R 9A , R 10A , R 11A and R 12AAdjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; R 1B , R 2B , R 3B , R 4B , R 5B , R 6B , R 7B , R 8B , R 9B , R 10B , R 11B and R 12B are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R 1B , R 2B , R 3B and R 4B or R 5B , R 6B , R 7B and R 8B or R 9B , R 10B , R 11B and R 12B Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; R 13A is a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; R 13B is a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; Each R 14A are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; 14A The groups may optionally be joined to form a ring (i.e., two R 14A The groups may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; Each R 14B are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; 14B The groups may optionally be joined to form a ring (i.e., two R 14BThe groups may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; Each X is an activatable ligand.

[0053] In one embodiment, R 1A and R 1B is hydrogen.

[0054] In one embodiment, R 2A and R 2B is hydrogen.

[0055] In one embodiment, R 3A and R 3B is hydrogen.

[0056] In one embodiment, R 4A and R 4B is hydrogen.

[0057] In one embodiment, R 5A and R 5B is hydrogen.

[0058] In one embodiment, R 6A and R 6B is hydrogen.

[0059] In one embodiment, R 7A and R 7B is hydrogen.

[0060] In one embodiment, R 8A and R 8B is hydrogen.

[0061] In one embodiment, R 9A and R 9B is hydrogen.

[0062] In one embodiment, R 10A and R 10B is hydrogen.

[0063] In one embodiment, R 11Aand R 11B is hydrogen.

[0064] In one embodiment, R 12A and R 12B is hydrogen.

[0065] In one embodiment, R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 10A , R 11A , R 1B , R 2B , R 3B , R 4B , R 5B , R 6B , R 7B , R 8B , R 9B , R 10B and R 11B is hydrogen.

[0066] In one embodiment, R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 11A , R 1B , R 2B , R 3B , R 4B , R 5B , R 6B , R 7B , R 8B , R 9B and R 11B is hydrogen.

[0067] In one embodiment, R 1A , R 2A , R 4A , R 5A , R 6A , R 7A , R8A , R 9A , R 10A , R 11A , R 1B , R 2B , R 4B , R 5B , R 6B , R 7B , R 8B , R 9B , R 10B and R 11B is hydrogen.

[0068] In one embodiment, R 1A , R 2A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 11A , R 1B , R 2B , R 4B , R 5B , R 6B , R 7B , R 8B , R 9B and R 11B is hydrogen.

[0069] In certain embodiments of the present disclosure, the prepolymerized catalyst has the structure III or IV: [ka] (In the formula, R 3A , R 10A and R 12A are each independently a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; R 3B , R 10B and R 12B are each independently a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; R 13A is a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; R 13Bis a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; Each R 14A are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; 14A The groups may optionally be joined to form a ring (i.e., two R 14A The groups may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; Each R 14B are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; 14B The groups may optionally be joined to form a ring (i.e., two R 14B The groups may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; Each X is an activatable ligand.

[0070] In one embodiment, R 3A and R 3B is a hydrocarbyl group.

[0071] In one embodiment, R 3A and R 3B is an alkyl group.

[0072] In one embodiment, R 3A and R 3B is an aryl group.

[0073] In one embodiment, R 3A and R 3B is a straight chain alkyl group having 2 to 12 carbon atoms.

[0074] In one embodiment, R 3A and R 3B is a branched alkyl group having 3 to 20 carbon atoms.

[0075] In one embodiment, R 3A and R 3Bis selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl and n-octyl.

[0076] In one embodiment, R 3A and R 3B is a methyl group.

[0077] In one embodiment, R 3A and R 3B is an alkylaryl group.

[0078] In one embodiment, R 3A and R 3B is an arylalkyl group.

[0079] In one embodiment, R 3A and R 3B is a heteroatom-containing hydrocarbyl group.

[0080] In one embodiment, R 3A and R 3B is an alkoxy group.

[0081] In one embodiment, R 3A and R 3B is an aryloxy group.

[0082] In one embodiment, R 3A and R 3B is a methoxy group.

[0083] In one embodiment, R 10A and R 10B is a hydrocarbyl group.

[0084] In one embodiment, R 10A and R 10B is an alkyl group.

[0085] In one embodiment, R 10A and R10B is an aryl group.

[0086] In one embodiment, R 10A and R 10B is a straight chain alkyl group having 2 to 12 carbon atoms.

[0087] In one embodiment, R 10A and R 10B is a branched alkyl group having 3 to 20 carbon atoms.

[0088] In one embodiment, R 10A and R 10B is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl and n-octyl.

[0089] In one embodiment, R 10A and R 10B is a methyl group.

[0090] In one embodiment, R 10A and R 10B is an alkylaryl group.

[0091] In one embodiment, R 10A and R 10B is an arylalkyl group.

[0092] In one embodiment, R 10A and R 10B is a heteroatom-containing hydrocarbyl group.

[0093] In one embodiment, R 10A and R 10B is an alkoxy group.

[0094] In one embodiment, R 10A and R 10B is an aryloxy group.

[0095] In one embodiment, R 10A and R 10B is a methoxy group.

[0096] In one embodiment, R 12A and R 12B is a hydrocarbyl group.

[0097] In one embodiment, R 12A and R 12B is an alkyl group.

[0098] In one embodiment, R 12A and R 12B is an aryl group.

[0099] In one embodiment, R 12A and R 12B is a straight chain alkyl group having 2 to 12 carbon atoms.

[0100] In one embodiment, R 12A and R 12B is a branched alkyl group having 3 to 20 carbon atoms.

[0101] In one embodiment, R 12A and R 12B is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl and n-octyl.

[0102] In one embodiment, R 12A and R 12B is a methyl group.

[0103] In one embodiment, R 12A and R 12B is a tert-butyl group.

[0104] In one embodiment, R 12A and R 12B is a 1-adamantyl group.

[0105] In one embodiment, R 12A and R 12B is an alkylaryl group.

[0106] In one embodiment, R 12A and R 12B is an arylalkyl group.

[0107] In one embodiment, R 12A and R 12B is a heteroatom-containing hydrocarbyl group.

[0108] In one embodiment, R 12A and R 12B is an alkoxy group.

[0109] In one embodiment, R 12A and R 12B is an aryloxy group.

[0110] In one embodiment, R 13A and R 13B is a hydrocarbyl group.

[0111] In one embodiment, R 13A and R 13B is an alkyl group.

[0112] In one embodiment, R 13A and R 13B is an aryl group.

[0113] In one embodiment, R 13A and R 13B is a straight chain alkyl group having 2 to 12 carbon atoms.

[0114] In one embodiment, R 13A and R 13B is a branched alkyl group having 3 to 20 carbon atoms.

[0115] In one embodiment, R13A and R 13B is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl and n-octyl.

[0116] In one embodiment, R 13A and R 13B is a methyl group.

[0117] In one embodiment, R 13A and R 13B is an alkenyl group.

[0118] In one embodiment, R 13A and R 13B is an alkylaryl group.

[0119] In one embodiment, R 13A and R 13B is an arylalkyl group.

[0120] In one embodiment, R 13A and R 13B is a 3,5-di-tert-butyl-phenyl group.

[0121] In one embodiment, R 13A and R 13B is an n-pentyl group.

[0122] In one embodiment, R 13A and R 13B is an n-pentenyl group (-CH2CH2CH2CH=CH2).

[0123] In one embodiment, R 13A and R 13B is a heteroatom-containing hydrocarbyl group.

[0124] In one embodiment, each R 14A and each R 14B is a hydrocarbyl group.

[0125] In one embodiment, each R 14A and each R 14B is an alkyl group.

[0126] In one embodiment, each R 14A and each R 14B is a straight chain alkyl group having 2 to 12 carbon atoms.

[0127] In one embodiment, R 14A and R 14B is a branched alkyl group having 3 to 20 carbon atoms.

[0128] In one embodiment, each R 14A and each R 14B is selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl and n-octyl.

[0129] In one embodiment, each R 14A and each R 14B is ethyl.

[0130] In one embodiment, each R 14A and each R 14B is an alkylaryl group.

[0131] In one embodiment, each R 14A and each R 14B is a substituted or unsubstituted benzyl group.

[0132] In one embodiment, each R 14A and each R 14B is an arylalkyl group.

[0133] In one embodiment, each R 14A and each R 14B is an aryl group.

[0134] In one embodiment, each R 14A and each R 14B is a substituted or unsubstituted phenyl group.

[0135] In one embodiment, one R 14A and one R 14B is hydrogen, and the other R 14A and the other R 14B is a hydrocarbyl group. In one embodiment, one R 14A and one R 14B is hydrogen, and the other R 14A and the other R 14B is an alkyl group. In one embodiment, one R 14A and one R 14B is hydrogen, and the other R 14A and the other R 14B is an aryl group. In one embodiment, one R 14A and one R 14B is hydrogen, and the other R 14A and the other R 14B is an alkylaryl group. In one embodiment, one R 14A and one R 14B is hydrogen, and the other R 14A and the other R 14B is an arylalkyl group.

[0136] In one embodiment, each R 14A and each R 14B is a heteroatom-containing hydrocarbyl group.

[0137] In one embodiment, two R 14A The groups are bonded together to form a ring, and the two R 14B The groups are joined together to form a ring (i.e., two R 14A The groups form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group, and two R 14B The groups form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group.

[0138] Those skilled in the art will know that when there is no plane of symmetry involving the metal center, two enantiomeric forms (enantiomeric isomers) or two diastereomeric forms (diastereomeric isomers) may be available, depending on which face of the cyclopentadienyl moiety is coordinated to the metal center. If the two isomeric forms are non-superimposable mirror images of each other, they are enantiomers of each other. If the two isomeric forms are non-superimposable and are not mirror images of each other, they are diastereomeric of each other.

[0139] In the present disclosure, the cyclopentadienyl moiety does not have mirror symmetry with respect to the metal center, so those skilled in the art will recognize that R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 10A , R 11A , R 12A , R 13A , R 14A , R 1B , R 2B , R 3B , R 4B , R 5B , R 6B , R 7B , R 8B , R 9B , R 10B , R 11B , R 12B , R 13B , R 14B It will be appreciated that depending on the nature of the groups, the catalysts shown in Structure I or Structure II may exist in two enantiomeric or two diastereomeric forms.

[0140] For example, different substituents may be present on the silyl bridging moiety or elsewhere on the ligand backbone (e.g., R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R7A , R 8A , R 9A , R 10A , R 11A , R 12A , R 13A , R 14A , R 1B , R 2B , R 3B , R 4B , R 5B , R 6B , R 7B , R 8B , R 9B , R 10B , R 11B , R 12B , R 13B , R 14B In the presence of one or more chiral groups located at one or more of the chiral group positions, two diastereomeric forms of the catalyst (two diastereoisomers) are available, depending on which face of the cyclopentadienyl moiety is coordinated to the metal center.

[0141] In the present disclosure, only one enantiomeric or diastereomeric form may be represented by the exemplified structures I or II (or structures III or IV), however, the present disclosure is meant to include either of the two possible enantiomeric or diastereomeric forms. 14A When the groups are different in Structure I or R 14B When the groups are different in structure II, or when the two R 14A When the groups together form a ring without mirror symmetry containing a metal center, or when two R 14B When the groups together form a ring without mirror symmetry involving the metal center, or are located anywhere on the ligand backbone (e.g., R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 10A , R 11A , R 12A , R 13A , R14A , R 1B , R 2B , R 3B , R 4B , R 5B , R 6B , R 7B , R 8B , R 9B , R 10B , R 11B , R 12B , R 13B , R 14B When a chiral group located at one or more of the group positions disrupts the mirror symmetry with the metal center, two diastereomeric forms (two diastereoisomeric isomers) are available. For clarity, the two possible enantiomeric or diastereomeric forms (diastereoisomeric isomers) of structure I can be represented by structures IA and IB, in which different faces of the cyclopentadienyl moiety are coordinated to the metal center: [ka]

[0142] Similarly, the two possible enantiomeric or diastereomeric forms of structure II can be represented by structures IIA and IIB, in which different faces of the cyclopentadienyl moiety are coordinated to the metal center: [ka]

[0143] In the present disclosure, the term "activatable ligand" means that the ligand X can be cleaved from the metal center (titanium, Ti) via a protonation reaction or abstracted from the metal center by a suitable acidic or electrophilic catalyst activator compound (also known as a "cocatalyst" compound), examples of which are described below. The activatable ligand X can also be converted to another ligand that is cleaved or abstracted from the metal center (e.g., a halide can be converted to an alkyl group). Without wishing to be bound by any single theory, the protonation or abstraction reaction generates an active "cationic" metal center that can polymerize olefins.

[0144] In an embodiment of the present disclosure, the activatable ligand X is a hydrogen atom, a halogen atom, C 1~20 Hydrocarbyl group, C 1~20 Alkoxy groups, and C 6~20 Each of the hydrocarbyl, alkoxy, aryl or aryloxide groups may be unsubstituted or further substituted. Two X ligands may also be joined together to form a delocalized heteroatom-containing group, such as, for example, a substituted or unsubstituted diene ligand (i.e., 1,3-butadiene) or an acetate group.

[0145] In certain embodiments of the present disclosure, each X is a halide atom, C 1~4 is independently selected from the group consisting of an alkyl radical and a benzyl radical.

[0146] In certain embodiments, each X is a halogen atom (eg, chloride) or a hydrocarbyl group (eg, methyl, benzyl).

[0147] In certain embodiments, each X is chloride or methide.

[0148] In certain embodiments, each X is chloride.

[0149] In certain embodiments, each X is a benzyl group.

[0150] In certain embodiments, each X is a methide.

[0151] Method for preparing organometallic complexes (prepolymerization catalysts) One embodiment of the present disclosure is a method for making an organometallic complex (prepolymerized catalyst) using a single reaction vessel.

[0152] Certain embodiments of the present disclosure include compounds of formula VI: [ka] A method for preparing an organometallic complex (prepolymerization catalyst) having the following structure: The following reaction is carried out in a single reaction vessel: (i) Formula V: [ka] or a double bond isomer of a cyclopentadienyl-containing compound having formula V, is combined with a base and subsequently reacted with a cyclopentadienyl-containing compound having formula VII: [ka] adding a compound represented by: (ii) optionally an excess of a trialkylamine compound, (R F ) in the presence of at least 2 molar equivalents of an alkyllithium reagent, (R E ) adding Li; (iii) Formula TiCl2(X ε )2(D) n adding a Group IV transition metal compound having (iv) optionally, a compound of formula Cl x Si(R ε ) 4-x (In the formula, each R ε The groups are independently C 1~20 adding a silane compound having an alkyl group; (v) optionally, a compound of formula (R G )M, (R G )(R H )Mg or (R G ) adding an alkylating agent having 2Zn; (vi) Optionally, switching the reaction solvent during any of the previous steps. A method comprising the steps of: (In the formula, R A , R B , R C and R D are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R A , R B , R C and R D Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; R 9 , R 10 , R 11 and R 12 are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R 9 , R 10 , R 11 and R 12 Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; Each R 14 are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; 14 The groups may optionally be joined to form a ring (i.e., two R 14A The groups may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; each X is an activatable ligand; X ε is halide, C 1~20 an alkoxy group or a group of the formula -NR', where each R' group is independently 1~30 Alkyl group or C 6~10 an amide group having an aryl group; R E is C 1~20 is a hydrocarbyl group; R F is C 1~10 is an alkyl group; R G is C 1~20 is a hydrocarbyl group; R H is R G Same or different C 1~20 Hydrocarbyl group, halide or C 1~20 is an alkoxy group; M is Li, Na or K; D is an electron donor compound; (n=1 or 2).

[0153] Electron donor compounds are well known to those of skill in the art, and in certain embodiments of the present disclosure, D can be an ether compound, such as tetrahydrofuran, or diethyl ether.

[0154] In embodiments, bases that may be used in the preparation of organometallic complexes include organolithium compounds such as organoalkali metal compounds, for example, methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, lithium trimethylsilylacetylide, lithium acetylide, trimethylsilylmethyllithium, vinyllithium, phenyllithium, and allyllithium.

[0155] In embodiments, the amount of base used may range from 0.5 to 5 moles of base per mole of the cyclopentadienyl-containing compound having formula V or its double bond isomer. In further embodiments, the amount of base used may range from 1.0 to 3.0 moles of base per mole of the cyclopentadienyl-containing compound having formula V or its double bond isomer; or may range from 1.5 to 2.5 moles of base per mole of the cyclopentadienyl-containing compound having formula V or its double bond isomer; or may range from 1.8 to 2.3 moles of base per mole of the cyclopentadienyl-containing compound having formula V or its double bond isomer; or may be about 2 moles of base per mole of the cyclopentadienyl-containing compound having formula V or its double bond isomer.

[0156] In some embodiments, base can be used in combination with amine compound.Such amine compound includes primary amine compound such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, tert-butylamine, n-octylamine, n-decylamine, aniline and ethylenediamine, secondary amine compound such as dimethylamine, diethylamine, di-n-propylamine, di-n-butylamine, di-tert-butylamine, di-n-octylamine, di-n-decylamine, pyrrolidine, hexamethyldisilazane and diphenylamine, and tertiary amine compound such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, diisopropylethylamine, tri-n-octylamine, tri-n-decylamine, triphenylamine, N,N-dimethylaniline, N,N,N',N'-tetramethylethylenediamine, N-methylpyrrolidine and 4-dimethylaminopyridine.

[0157] In the embodiment of the present disclosure, the amount of such an amine compound used is in the range of 10 moles or less, 0.5 to 10 moles, or 1 to 3 moles of the amine compound per mole of the base.

[0158] The metallation reaction, step (iii), is generally carried out in an inert solvent. In embodiments, such solvents include aprotic solvents, such as aromatic hydrocarbon solvents such as benzene or toluene, aliphatic hydrocarbon solvents such as hexane or heptane, ether solvents such as diethyl ether, tetrahydrofuran or 1,4-dioxane, amide solvents such as hexamethylphosphoramide or dimethylformamide, polar solvents such as acetonitrile, propionitrile, acetone, diethyl ketone, methyl isobutyl ketone and cyclohexanone, and halogenated solvents such as chlorobenzene or dichlorobenzene. In embodiments, these solvents can be used alone or as a mixture of two or more of them.

[0159] In embodiments, the organometallic complex can be obtained from the reaction mixture using conventional methods, for example, by filtering off the formed precipitate or removing the solvent under vacuum to obtain the organometallic complex as a product, which can be optionally washed with a solvent.

[0160] In embodiments, the activatable ligand X is a hydrogen atom, a halogen atom, C 1~20 Hydrocarbyl group, C 1~20 Alkoxy groups, and C 6~20 Each of the hydrocarbyl, alkoxy, aryl or aryloxide groups may be unsubstituted or further substituted. Two X ligands may also be joined together to form a delocalized heteroatom-containing group, such as, for example, a substituted or unsubstituted diene ligand (i.e., 1,3-butadiene) or an acetate group.

[0161] In certain embodiments, each X is a halide atom, C 1~4 is independently selected from the group consisting of an alkyl radical and a benzyl radical.

[0162] In certain embodiments, each X is a halogen atom (eg, chloride) or a hydrocarbyl group (eg, methyl, benzyl).

[0163] In certain embodiments, each X is chloride or methide.

[0164] In certain embodiments, each X is chloride.

[0165] In certain embodiments, each X is a benzyl group.

[0166] In certain embodiments, each X is a methide.

[0167] Catalyst Activators and Cocatalysts In certain embodiments of the present disclosure, the prepolymerized catalyst is used in combination with a boron-based catalyst activator and an alkylaluminoxane cocatalyst to form an active polymerization catalyst system for olefin polymerization. Boron-based catalyst activators, also known as "ionic activators," are well known to those skilled in the art. Alkylaluminoxanes are likewise well known to those skilled in the art.

[0168] In certain embodiments of the present disclosure, the polymerization catalyst system comprises, in addition to the prepolymerization catalyst, at least one boron-based catalyst activator and at least one alkylaluminoxane cocatalyst.

[0169] In certain embodiments of the present disclosure, the polymerization catalyst system comprises, in addition to the prepolymerization catalyst, a boron-based catalyst activator and an alkylaluminoxane cocatalyst.

[0170] In some embodiments of the present disclosure, the polymerization catalyst system may further include an organoaluminum compound as a cocatalyst.

[0171] Without wishing to be bound by theory, aluminum-based cocatalyst species, such as alkylaluminoxanes and organoaluminum compounds, may themselves act as catalyst activators (and therefore may also be considered "catalyst activators"), and / or as alkylating agents, and / or as scavenging compounds (e.g., reacting with species that adversely affect the polymerization activity of the titanium-based catalyst complex and that may be present in the polymerization reactor).

[0172] Alkylaluminoxane Without wishing to be bound by theory, the alkylaluminoxanes used in the present disclosure are of the formula: RAl 1 O(RAl 1 O) m Al 1 R2 (wherein each R is C 1~20 and m is 3 to 50.

[0173] In one embodiment of the present disclosure, R of the alkylaluminoxane is a methyl radical and m is 10-40.

[0174] The alkylaluminoxane is typically used in substantial molar excess relative to the amount of Group 4 transition metal in the single-site catalyst (e.g., prepolymerized catalyst). 1 The molar ratio of Group 4 transition metal to Group 4 transition metal can be from about 5:1 to about 10,000:1, or from about 10:1 to about 1000:1, or from about 30:1 to about 500:1.

[0175] In certain embodiments of the present disclosure, the alkylaluminoxane cocatalyst is methylaluminoxane (MAO).

[0176] In certain embodiments of the present disclosure, the alkylaluminoxane cocatalyst is modified methylaluminoxane (MMAO).

[0177] It is well known in the art that alkylaluminoxanes can serve multiple roles as catalyst alkylating agents, catalyst activators, and scavengers. Thus, alkylaluminoxane activators are often used in combination with activatable ligands such as halogens.

[0178] Boron-based catalyst activator Boron-based catalyst activators (also known in some embodiments as “ionic activators”) are characterized by: (i) a compound of the formula [R 1 ]+ [B(R 2 )4] - (wherein B is a boron atom, R 1 is cyclic C 5~7 An aromatic cation or a triphenylmethyl cation, and each R 2 is unsubstituted or substituted by a fluorine atom, C 1~4 a phenyl radical substituted with 3 to 5 substituents selected from the group consisting of alkyl or alkoxy radicals; and a radical of the formula --Si--(R * )3(in the formula, each R * is a hydrogen atom and C 1~4 (ii) a compound of the formula [(R 3 ) t ZH] + [B(R 2 )4] - (wherein B is a boron atom, H is a hydrogen atom, Z is a nitrogen atom or a phosphorus atom, t is 2 or 3, and R 3 is C 1~30 Alkyl radical, unsubstituted or with up to 3 C 1~4 phenyl radicals substituted by alkyl radicals or one R 3 may combine with the nitrogen atom to form an anilinium radical, R 2 is as defined above); and (iii) compounds of formula B (R 2 )3(wherein, R 2 is as defined above).

[0179] In some embodiments, in the above compounds, preferably, R 2 is a pentafluorophenyl radical, and R 1 is a triphenylmethyl cation, Z is a nitrogen atom, and R 3 is C 1~4 an alkyl radical or one R 3together with the nitrogen atom to form an anilinium radical (e.g., two R 3 Radicals, e.g. two C 1~4 PhR substituted with alkyl radicals 3 2NH + ) is formed.

[0180] Examples of boron-based catalyst activator compounds that can ionize single-site catalysts (e.g., prepolymerized catalysts) and that can be used in embodiments of the present disclosure include the following: triethylammonium tetra(phenyl)boron, tripropylammonium tetra(phenyl)boron, tri(n-butyl)ammonium tetra(phenyl)boron, trimethylammonium tetra(p-tolyl)boron, trimethylammonium tetra(o-tolyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tripropylammonium Tetra(o,p-dimethylphenyl)boron, tributylammonium tetra(m,m-dimethylphenyl)boron, tributylammonium tetra(p-trifluoromethylphenyl)boron, tributylammonium tetra(pentafluorophenyl)boron, tri(n-butyl)ammonium tetra(o-tolyl)boron, N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)boron, N,N-diethylanilinium tetra(phenyl)n-butylboron, N,N-2,4,6-pentamethane Chilanilinium tetra(phenyl)boron, di-(isopropyl)ammonium tetra(pentafluorophenyl)boron, dicyclohexylammonium tetra(phenyl)boron, triphenylphosphonium tetra(phenyl)boron, tri(methylphenyl)phosphonium tetra(phenyl)boron, tri(dimethylphenyl)phosphonium tetra(phenyl)boron, tropylium tetrakis pentafluorophenylborate, triphenylmethylium tetrakis pentafluorophenylborate, benzene(diazonium) tetrakis pentafluorophenylborate tetrafluorophenylborate, tropylium phenyl tris-pentafluorophenylborate, triphenylmethylium phenyl-tris-pentafluorophenylborate, benzene(diazonium)phenyl tris-pentafluorophenylborate, tropylium tetrakis(2,3,5,6-tetrafluorophenyl)borate, triphenylmethylium tetrakis(2,3,5,6-tetrafluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropylium tetrakis(3,4,5-trifluorophenyl)borate, benzene(diazonium)tetrakis(3,4,5-trifluorophenyl)borate, tropylium tetrakis(1,2,2-trifluoroethenyl)borate, trophenylmethylium tetrakis(1,2,2-trifluoroethenyl)borate, benzene(diazonium)tetrakis(1,2,2-trifluoroethenyl)borate, tropylium tetrakis(2,3,4,5-tetrafluorophenyl)borate, triphenylmethylium tetrakis(2,3,4,5-tetrafluorophenyl)borate and benzene(diazonium)tetrakis(2,3,4,5-tetrafluorophenyl)borate.,

[0181] Further specific examples of boron-based catalyst activator compounds capable of ionizing single-site catalysts (e.g., prepolymerized catalysts) and that may be used in embodiments of the present disclosure are disclosed in U.S. Pat. Nos. 5,919,983, 6,121,185, 10,730,964, and 11,041,031.

[0182] In certain embodiments of the present disclosure, the boron-based catalyst activator comprises N,N-dimethylanilinium tetrakispentafluorophenylborate ("[Me2NHPh][B(CF5)4]") or triphenylmethylium tetrakispentafluorophenylborate ("[Ph3C][B(CF5)4]") and / or trispentafluorophenylboron.

[0183] In certain embodiments of the present disclosure, the boron-based catalyst activator comprises N,N-dimethylanilinium tetrakispentafluorophenylborate ("[Me2NHPh][B(CF5)4]") or triphenylmethylium tetrakispentafluorophenylborate ("[Ph3C][B(CF5)4]") or trispentafluorophenylboron.

[0184] In certain embodiments of the present disclosure, the boron-based catalyst activator comprises an ionic activator selected from the group consisting of N,N-dimethylanilinium tetrakispentafluorophenylborate ("[Me2NHPh][B(CF5)4]") and triphenylmethylium tetrakispentafluorophenylborate ("[Ph3C][B(CF5)4]").

[0185] In one embodiment of the present disclosure, the boron-based catalyst activator is N,N-dimethylanilinium tetrakispentafluorophenylborate ("[Me2NHPh][B(C6F5)4]").

[0186] In one embodiment of the present disclosure, the boron-based catalyst activator is triphenylmethylium tetrakispentafluorophenylborate ("[Ph3C][B(C6F5)4]").

[0187] In embodiments, the boron-based catalyst activator may be used in an amount to provide a molar ratio of Group 4 transition metal (i.e., titanium in the prepolymerized catalyst) to boron of from about 1:0.5 to about 1:10, or from about 1:1 to about 1:6.

[0188] Organoaluminum Compounds Optionally, in an embodiment of the present disclosure, the polymerization catalyst system comprises a catalyst having the formula: Al 2 (R 4 ) m (OR 5 ) n (X * ) p (In the formula, R 4 and R 5 are independent of each other, C1~C 20 is a hydrocarbyl group; X * is a halide; m+n+p=3; m≧1) The aluminum compound may further comprise an organoaluminum compound defined by:

[0189] In one embodiment of the present disclosure, the organoaluminum compound used has the formula: Al3 R 6 x (OR 7 ) y (wherein x is 1 to 3, x+y=3, and R 6 is C1~C 10 is a hydrocarbyl group, R 7 is an alkyl or aryl group) is defined as follows:

[0190] In certain embodiments, the organoaluminum compounds include triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, and diethylaluminum ethoxide.

[0191] Hindered phenol compounds In an embodiment of the present disclosure, the hindered phenol compound is used in combination with a prepolymerized catalyst, a boron based catalyst activator and an alkylaluminoxane cocatalyst to provide an olefin polymerization catalyst system.

[0192] Generally, hindered phenolic compounds (or "sterically hindered" phenolic compounds) are phenols that bear one or more bulky substituents, such as sterically bulky hydrocarbyl groups (non-limiting examples of which include tert-butyl and 1-adamantyl groups).

[0193] In an embodiment of the present disclosure, the hindered phenol compound has a sterically bulky hydrocarbyl group on at least one or both of the carbon atoms adjacent to the carbon atom bonded to the hydroxy group (e.g., the bulky hydrocarbyl group is located at one or both of the 2- and 6-positions of the hindered phenol moiety).

[0194] In an embodiment of the present disclosure, the hindered phenol compound comprises a 2,6-dihydrocarbyl group-substituted hindered phenol moiety.

[0195] In an embodiment of the disclosure, the hindered phenol compound comprises a 2,6-dihydrocarbyl group-substituted hindered phenol moiety, which is optionally further substituted at one or more of the 3-, 4-, and 5-positions with hydrocarbyl or heteroatom-containing hydrocarbyl groups.

[0196] Non-limiting examples of hindered phenol compounds that may be used in embodiments of the present disclosure include butylated phenol antioxidants, butylated hydroxytoluene; 2,6-di-tert-butyl-4-ethylphenol; 4,4'-methylenebis(2,6-di-tert-butylphenol); 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene, and octadecyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate.

[0197] In embodiments, the hindered phenol compound is preferably present in an alkylaluminoxane cocatalyst having a molar ratio of aluminum to hindered phenol compound (i.e., Al 1 :hindered phenol compound ratio).

[0198] Optionally, in embodiments, a hindered phenol compound is added to the alkylaluminoxane cocatalyst prior to contacting the alkylaluminoxane with one or more other components of an olefin polymerization catalyst system (e.g., a prepolymerization catalyst).

[0199] Polymerization method The olefin polymerization catalyst system of the present disclosure can be used in any conventional olefin polymerization process, such as gas phase polymerization, slurry phase polymerization, or solution phase polymerization. The use of a "heterogeneous" catalyst system is preferred for use in gas phase and slurry phase polymerization, while a homogeneous catalyst is preferred for use in solution phase polymerization. The heterogeneous catalyst system can be formed by supporting a prepolymerized catalyst, optionally with a boron-based catalyst activator, an alkylaluminoxane, and a hindered phenol compound, on a carrier, such as a silica carrier. Silica carrier materials, as well as suitable alternative carrier materials, are well known to those skilled in the art.

[0200] In an embodiment of the present disclosure, the polymerization process comprises ethylene optionally with one or more C3-C 12 This involves polymerizing with an alpha-olefin.

[0201] In certain embodiments of the present disclosure, the polymerization process includes polymerizing ethylene with one or more alpha-olefins selected from the group consisting of 1-butene, 1-hexene, 1-octene, and mixtures thereof.

[0202] In some embodiments of the present disclosure, the polymerization process includes polymerizing ethylene with 1-octene.

[0203] When gas phase polymerization is used, in various embodiments the pressure used may range from 1 to 1000 psi, or 50 to 400 psi, or 100 to 300 psi; while in various embodiments the temperature used may range from 30° C. to 130° C., or 65° C. to 110° C. For gas phase polymerization processes, stirred bed or fluidized bed gas phase reactor systems may be used in embodiments of the present disclosure. Such gas phase processes have been widely described in the literature (see, for example, U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228). One or more reactors may be used and may be configured in series with one another.

[0204] Generally, fluidized bed gas phase polymerization reactors use a "bed" of polymer and catalyst that is fluidized by a flow of monomer, comonomer, and other optional components that are at least partially gaseous. Heat is generated by the enthalpy of polymerization of the monomer (and comonomer) flowing through the bed. Unreacted monomer, comonomer, and other optional gaseous components exit the fluidized bed and contact a cooling system to remove this heat. The cooled gas stream containing monomer, comonomer, and optional other components (such as condensable liquids) is then recycled through the polymerization zone along with "make-up" monomer (and comonomer) to replace that polymerized in the previous pass. At the same time, polymer product is removed from the reactor. As will be appreciated by those skilled in the art, the "fluidized" nature of the polymerization bed helps to distribute / mix the heat of reaction evenly, thereby minimizing the formation of localized temperature gradients.

[0205] The polymerization is generally carried out substantially in the absence of catalyst poisons. Organometallic compounds, such as organoaluminum compounds, can be used as poison scavengers to enhance catalyst activity. Some specific non-limiting examples of scavengers are metal alkyls, including aluminum alkyls, such as triisobutylaluminum. Conventional adjuvants may be included in the process, so long as they do not interfere with the operation of the polymerization catalyst in forming the desired polyolefin. For example, hydrogen or metal or nonmetal hydrides (e.g., silyl hydrides) can be used as chain transfer agents in the process. Hydrogen can be used in amounts up to about 10 moles of hydrogen per mole of total monomer feed.

[0206] Detailed descriptions of slurry phase polymerization processes have been widely reported in the patent literature. A slurry phase polymerization process in which the temperature is maintained below the temperature at which the polymer goes into solution, also known as "particle form polymerization", is described in U.S. Pat. No. 3,248,179. Slurry processes include those that use loop reactors and those that utilize a single stirred reactor or multiple stirred reactors in series, parallel, or combinations thereof. Non-limiting examples of slurry phase polymerization processes include continuous loop or stirred tank processes. Further examples of slurry phase polymerization processes are described in U.S. Pat. No. 4,613,484.

[0207] The slurry process is carried out in the presence of a hydrocarbon diluent, such as an alkane (including isoalkanes), aromatic or cycloalkane. The diluent may also be an alpha olefin comonomer used in the copolymerization. Alkane diluents include propane, butane (i.e., normal butane and / or isobutane), pentane, hexane, heptane and octane. The monomer may be soluble (or miscible) in the diluent, but the polymer is not soluble (under polymerization conditions). In an embodiment, the polymerization temperature may be from about 5° C. to about 200° C. In a further embodiment, the polymerization temperature is less than about 120° C., or from 10° C. to about 100° C. The slurry phase polymerization reaction temperature is selected such that the polymer (e.g., ethylene copolymer) is produced in solid particulate form. The reaction pressure is affected by the selection of the diluent and reaction temperature. For example, in embodiments, the pressure may range from 15 to 45 atmospheres (about 220 to 660 psi or about 1500 to about 4600 kPa) when isobutane is used as the diluent, and approximately double that, from 30 to 90 atmospheres (about 440 to 1300 psi or about 3000 to 9100 kPa) when propane is used (see, e.g., U.S. Pat. No. 5,684,097). Pressure in slurry phase polymerization processes is generally maintained high enough to keep at least a portion of the polymerizable monomer (e.g., ethylene) in the liquid phase.

[0208] In an embodiment, the slurry phase polymerization reaction is carried out in a jacketed closed loop reactor with an internal agitator (e.g., impeller) and further containing at least one settling leg. The polymerization catalyst components (suspended or non-suspended), monomer and diluent can be fed to the slurry phase polymerization reactor as a liquid or suspension. The slurry circulates through the loop reactor and the jacket is used to control the reactor temperature. The slurry enters the settling leg through a series of let-down valves and is then reduced in pressure to flash the diluent and unreacted monomer and recover the product polymer, typically in a cyclone. The diluent and unreacted monomer are recovered and recycled to the reactor.

[0209] In certain embodiments of the present disclosure, the polymerization process is a solution phase polymerization process carried out in a solvent.

[0210] In certain embodiments of the present disclosure, the polymerization process is a continuous solution phase polymerization process carried out in a solvent.

[0211] Solution polymerization processes for the homopolymerization of ethylene or the copolymerization of ethylene with one or more alpha-olefins are well known in the art (see, for example, U.S. Pat. Nos. 6,372,864 and 6,777,509). These processes are carried out in an inert hydrocarbon solvent, typically a C 2 -based solvent, even if unsubstituted. 1~4 C optionally substituted with an alkyl group 5~12 The reaction is carried out in the presence of a hydrocarbon, such as pentane, methylpentane, hexane, heptane, octane, cyclohexane, methylcyclohexane and hydrogenated naphtha. An example of a suitable solvent that is commercially available is "Isopar E" (C 8~12 Aliphatic solvents, Exxon Chemical Co.

[0212] The polymerization temperature in a conventional solution phase process can be from about 80° C. to about 300° C. In some embodiments of the present disclosure, the polymerization temperature in a solution phase polymerization process is from about 120° C. to about 250° C. In further embodiments, the solution phase polymerization process is carried out at a temperature of at least 140° C., or at least 160° C., or at least 170° C., or at least 180° C., or at least 190° C.

[0213] The polymerization pressure in the solution phase polymerization process may be a "medium pressure process", meaning that the pressure in the reactor is less than about 6,000 psi (about 42,000 kilopascals or kPa). In an embodiment of the present disclosure, the polymerization pressure in the solution phase polymerization process may be from about 10,000 to about 40,000 kPa, or from about 14,000 to about 22,000 kPa (i.e., from about 2,000 psi to about 3,000 psi).

[0214] Suitable monomers for copolymerization with ethylene include C 3~20Alpha-olefins, including mono- and diolefins. Some non-limiting examples of comonomers that may be copolymerized with ethylene in embodiments of the present disclosure include those that are unsubstituted or have up to two C 1~6 C substituted by alkyl radicals 3~12 Alpha-olefins; unsubstituted or C 1~4 C substituted with up to two substituents selected from the group consisting of alkyl radicals 8~12 vinyl aromatic monomers; and unsubstituted or C 1~4 C substituted by alkyl radicals 4~12 Included are linear or cyclic diolefins. Illustrative non-limiting examples of such alpha-olefins are one or more of propylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene, styrene, alpha-methylstyrene and constrained cyclic olefins such as cyclobutene, cyclopentene, dicyclopentadiene norbornene, alkyl-substituted norbornene, alkenyl-substituted norbornene, and the like (e.g., 5-methylene-2-norbornene, 5-ethylidene-2-norbornene and bicyclo-(2,2,1)-hepta-2,5-diene).

[0215] In solution polymerization, the monomer is dissolved / dispersed in a solvent before being fed to the reactor (or for gaseous monomers, the monomer can be fed to the reactor so that it is dissolved in the polymerization reaction mixture). Before mixing, the solvent and monomer are generally purified to remove potential catalyst poisons such as water, oxygen or metal impurities. Purification of the feedstock can use standard well-known practices in the art such as, for example, the use of molecular sieves, alumina beds and oxygen removal catalysts, all known to be useful in purifying polymerizable monomers. The solvent (e.g., methylpentane, cyclohexane, hexane or toluene) itself can also be similarly treated to remove potential catalyst poisons.

[0216] Feedstock monomers or other solution process components (eg, solvent) may be heated or cooled prior to being fed to the solution phase polymerization reactor.

[0217] In embodiments of the present disclosure, the olefin polymerization catalyst system components (e.g., prepolymerization catalyst, boron-based catalyst activator, alkylaluminoxane, and hindered phenol compound) may be premixed in the solvent used in the polymerization reaction or fed to the polymerization reactor as separate streams. In some embodiments, premixing may be desirable to provide reaction time for the olefin polymerization catalyst system components before entering the polymerization reaction zone (e.g., polymerization reactor). Examples of such "in-line mixing" techniques are described in several patents, such as U.S. Pat. No. 5,589,555.

[0218] In certain embodiments of the present disclosure, the solution phase polymerization process is a continuous process. The term "continuous process" means that a polymerization process stream (e.g., solvent, ethylene, optional alpha-olefin comonomer, olefin polymerization catalyst system components, etc.) is continuously fed to a polymerization zone (e.g., polymerization reactor) where a polymer (e.g., ethylene homopolymer or ethylene copolymer) is formed and from which the polymer is continuously removed via a process stream effluent vapor.

[0219] In certain embodiments of the present disclosure, the solution phase polymerization process is carried out in at least one continuous stirred tank reactor ("CSTR").

[0220] In one embodiment of the present disclosure, the solution phase polymerization process is carried out in at least two continuous stirred tank reactors arranged in series (the process stream is transferred from a first, upstream CSTR reactor to a second, downstream CSTR).

[0221] In some embodiments, a continuous solution phase polymerization process includes a first stirred tank polymerization reactor having an average reactor temperature of about 100° C. to about 140° C. and a second stirred tank polymerization reactor having an average temperature at least about 20° C. higher than the average reactor temperature of the first reactor.

[0222] In certain embodiments of the present disclosure, the solution phase polymerization process is carried out in at least one tubular reactor.

[0223] In one embodiment of the present disclosure, a solution phase polymerization process is carried out in two continuous stirred tank reactors arranged in series and a pipe reactor that receives a process stream from the second continuous stirred tank reactor.

[0224] In a solution phase polymerization process, the reactor is generally operated under conditions to achieve thorough mixing of the reactants, and the residence time (or "hold-up time") of the olefin polymerization catalyst (e.g., an activated single-site catalyst complex) in the reactor depends on the design and capacity of the reactor.

[0225] In embodiments, the residence time of the olefin polymerization catalyst (e.g., activated single-site catalyst complex) in a given reactor will be from a few seconds to about 20 minutes. In further embodiments, the residence time of the olefin polymerization catalyst (e.g., activated single-site catalyst complex) in a given reactor will be less than about 10 minutes, or less than about 5 minutes, or less than about 3 minutes.

[0226] In an embodiment of the present disclosure, at least 60 weight percent (wt%) of the ethylene fed to the CSTR reactor is polymerized into ethylene homopolymers or ethylene copolymers by the olefin polymerization catalyst system. In further embodiments, at least 70 wt%, or at least 80 wt%, or at least 85 wt%, or at least 90 wt% of the ethylene fed to the CSTR reactor is polymerized into ethylene homopolymers or ethylene copolymers by the olefin polymerization catalyst system.

[0227] When two or more CSTRs are used, olefin polymerization catalyst system components can be added to each of the CSTRs in order to maintain high polymer production rates in each reactor.

[0228] When more than one CSTR is used, the olefin polymerization catalyst used in each CSTR may be based on the same type of polymerization catalyst or may be based on different types of polymerization catalyst.

[0229] In certain embodiments of the present disclosure, the same type of olefin polymerization catalyst is used in each CSTR of the two or more CSTR reactors.

[0230] In some embodiments, a mixed catalyst system is used where one olefin polymerization catalyst is a single-site catalyst (e.g., an olefin polymerization catalyst system described in accordance with the present disclosure) and one olefin polymerization catalyst is a Ziegler-Natta catalyst, and a single-site catalyst is used in a first CSTR and a Ziegler-Natta catalyst is used in a second CSTR.

[0231] The term "tubular reactor" refers to its conventional meaning, i.e., a simple tube that is not generally stirred using impellers, agitators, or the like, unlike a CSTR. In an embodiment, the tubular reactor has a length / diameter (L / D) ratio of at least 10 / 1. In an embodiment, the tubular reactor is operated adiabatically. As a general, non-limiting explanation, without wishing to be bound by theory, in a tubular reactor, as the polymerization reaction proceeds, more and more monomer (e.g., ethylene) and / or comonomer (e.g., alpha-olefin) is consumed, and the temperature of the solution increases along the length of the tube (which may improve the efficiency of separating unreacted comonomer from the polymer solution). In an embodiment, the temperature increase along the length of the tubular reactor may be greater than about 3° C. In an embodiment, the tubular reactor is located downstream of the CSTR, and the discharge temperature from the tubular reactor may be at least about 3° C. higher than the discharge temperature from the CSTR (from which the process stream is fed to the tubular reactor).

[0232] In an embodiment, the tubular reactor may have feed ports for adding additional polymerization catalyst system components, such as single-site prepolymerized catalyst, Ziegler-Natta catalyst components, catalyst activators, cocatalysts and hindered phenol compounds, or for adding monomers, comonomers, hydrogen, etc. In an alternative embodiment, no additional polymerization catalyst components are added to the tubular reactor.

[0233] In certain embodiments, the total volume of the tubular reactor used in combination with the at least one CSTR is at least about 10 volume percent (vol%) of the volume of the at least one CSTR, or from about 30 volume% to about 200 volume% of the at least one CSTR (for clarity, if the volume of the at least one CSTR is 1000 liters, the volume of the tubular reactor is at least about 100 liters, or from about 300 to 2000 liters).

[0234] In embodiments, upon leaving the reactor system, non-reactive components may be removed (and optionally recovered), and the resulting polymer (e.g., ethylene copolymer or ethylene homopolymer) may be finished in a conventional manner (e.g., using a devolatilization process). In some embodiments, a two-stage devolatilization process may be used to recover the polymer composition from the polymerization process solvent.

[0235] The following examples are presented for the purpose of illustrating selected embodiments of the present disclosure, with it being understood that the presented examples are not intended to limit the scope of the presented claims. EXAMPLES

[0236] example General Experimental methods for general examples All reactions involving air- and / or moisture-sensitive compounds were carried out under nitrogen using standard Schlenk and glovebox techniques. Reaction solvents were purified using a commercially available solvent purification system essentially according to the methods described by Grubbs et al. (Pangborn, AB; Giardello, MA; Grubbs, RH; Rosen RK; Timmers, FJ Organometallics 1996, 15, 1518-1520) and then stored over activated molecular sieves in an inert atmosphere glovebox.

[0237] Tetrakis(dimethylamido)titanium(IV) was purchased from Strem Chemicals and used as received. MMAO-7 (7 wt % solution in Isopar-E) and TIBAL (25 wt % solution in hexane) were purchased from Akzo Nobel / Nouryon and used as received. Triphenylcarbenium tetrakis(pentafluorophenyl)borate was purchased from Albemarle Corp. and used as received. 5,5,8,8-Tetramethyl-2,3,5,6,7,8-hexahydro-1H-cyclopenta[b]naphthalen-1-one was purchased from Ambeed, Inc. and used as received. All other materials were purchased from Aldrich and used as received. Deuterated solvents were purchased from Sigma Aldrich (toluene-d8, CD2Cl2, CDCl3) and stored over 4 Å molecular sieves prior to use. NMR spectra were obtained on a Bruker 400 MHz spectrometer (400.1 MHz 1 1 H NMR (NMR).

[0238] Bis(dimethylamido)dichlorotitanium(IV), Ti(NMe2)2Cl2, was prepared essentially as described by Benzing, E. and Kornicker, W., Chem. Ber. 1961, 94, 2263-2267. Thus, tetrakis(dimethylamido)titanium (10.19 g, 45.0 mmol) was dissolved in toluene (80 mL) in a 200 mL Schlenk flask and cooled to 0° C. for 15 min. A bright orange solution of titanium(IV) chloride (8.54 g, 45.0 mmol) in toluene (20 mL) was added, resulting in a red suspension. The reaction mixture was stirred overnight and then filtered. The filter cake was further extracted with toluene until the filtrate was colorless. The combined filtrates were removed under reduced pressure. The residue was slurried in pentane (100 mL) for 10 min and filtered. The filter cake was dried under vacuum to give the desired product as a brick red powder (17.56 g, 94% yield). 1 H NMR (400 MHz, toluene-d8) δ 3.02 (s, 12H, NMe2).

[0239] Copolymer samples from semi-batch copolymerization experiments were analyzed using a Polymer Char GPC-IR4 instrument equipped with three GPC columns to determine the polymer M. wwas rapidly determined. Therefore, polymer samples (5-7 mg) were weighed into sample vials and loaded into an autosampler. The vials were filled with 6 ml of 1,2,4-trichlorobenzene (TCB) and heated to 160 °C with shaking for 160 min. To stabilize the polymer against oxidative degradation, 2,6-di-tert-butyl-4-methylphenol (BHT) was added to the TCB at a concentration of 250 ppm. The sample solution was chromatographed at 140 °C on a Polymer Char GPC-IR4 chromatography unit equipped with three GPC columns (e.g., PL mixed B) using TCB as the mobile phase at a flow rate of 1.0 mL / min, with Infrared IR4 as the concentration detector. To protect the SEC column from oxidative degradation, BHT was added to the mobile phase at a concentration of 250 ppm. The sample injection volume was 200 μL. The SEC raw data was processed using an Excel spreadsheet. The SEC column was calibrated with narrow distribution polystyrene standards. Polystyrene molecular weights were converted to polyethylene molecular weights using the Mark-Houwink equation as described in ASTM standard test method D6474.

[0240] Molecular weight of continuous solution copolymerization experiment (GPC-RI M w , M n and M. z (g / mol)) and molecular weight distribution (GPC-RI M w / M n) data were obtained using conventional size-exclusion (gel permeation) chromatography (SEC, or GPC). Thus, polymer sample solutions (1-2 mg / mL) were prepared by heating the polymer in 1,2,4-trichlorobenzene (TCB) and rotating it on a wheel in an oven at 150 °C for 4 h. To stabilize the polymer against oxidative degradation, an antioxidant (2,6-di-tert-butyl-4-methylphenol (BHT) was added to the mixture. The BHT concentration was 250 ppm. The sample solution was chromatographed at 140° C. on a PL 220 high temperature chromatography unit equipped with four SHODEX® columns (HT803, HT804, HT805 and HT806) using TCB as the mobile phase at a flow rate of 1.0 mL / min, equipped with a differential refractive index (DRI) detector as the concentration detector. To protect the SEC column from oxidative degradation, BHT was added to the mobile phase at a concentration of 250 ppm. The sample injection volume was 200 μL. The SEC raw data was processed with CIRRUS® GPC software. The SEC column was calibrated with narrow distribution polystyrene standards. The Mark-Houwink equation was used to convert polystyrene molecular weights to polyethylene molecular weights as described in ASTM standard test method D6474.

[0241] The melt index of the polymer was determined using ASTM D1238 (August 1, 2013). Melt index I2, I6, I 10 and I 21 were measured at 190° C. using weights of 2.16 kg, 6.48 kg, 10 kg and 21.6 kg, respectively. In this disclosure, melt index is expressed using units of gram / 10 minutes or g / 10 min or dg / minute or dg / min, which are equivalent.

[0242] FTIR branching frequency (CH3 / 1000C) was determined from polymer plaques on a Thermo-Nicolet 750 Magna-IR spectrophotometer using the method described in ASTM standard test method D6645. Polymer plaques are prepared using a compression molding apparatus (Wabash-Genesis Series press) based on ASTM standard test method D1928 (now replaced by D4703).

[0243] Titanium prepolymerization catalyst complex (present invention) [ka] [ka] Titanium prepolymerization catalyst complex (comparison) [ka] Titanium complex (prepolymerization catalyst) Titanium prepolymerized catalysts were prepared using the method described below. Example 1 [ka] 8-Methyl-5,10-dihydroindeno[1,2-b]indole: [ka] This material was prepared essentially as described by Grandini, C. et al., Organometallics, 2004, 23, 344-360. 1-Indanone (5.02 g, 38.0 mmol), p-tolylhydrazine hydrochloride (6.03 g, 38.0 mmol) and p-toluenesulfonic acid monohydrate (0.3 g) were suspended in i-PrOH (150 mol) in a 250 mL round bottom flask. A condenser was attached and the mixture was refluxed for 45 min during which time the reaction mixture became a yellow-orange suspension. The reaction mixture was cooled to 0° C. for 15 min and filtered. The filter cake was rinsed with i-PrOH until the filtrate was colorless. Residual volatiles were removed under reduced pressure to give the desired product as a white solid (7.45 g, 89% yield). 1 H NMR(400MHz,CDCl3)δ 8.01(br,1H,NH),7.37(d,1H,ArH),7.28(m,2H,ArH),7.20-7.09(m,3H,ArH),7 .05(t,1H,ArH),6.85(d,1H,ArH),3.54(s,2H,indene-CH2),2.31(s,3H,ArCH3).

[0244] 5,8-Dimethyl-5,10-dihydroindeno[1,2-b]indole: [ka] 8-Methyl-5,10-dihydroindeno[1,2-b]indole (1.73 g, 7.88 mmol) and potassium tert-butoxide (885 mg, 7.88 mmol) were dissolved in THF (60 mL) in a 100 mL Schlenk flask, and the translucent yellow solution was stirred for 1 h. Iodomethane (0.49 mL, 1.12 g, 7.88 mmol) was added via syringe, and a white precipitate formed immediately. After 30 min, the reaction mixture was poured into saturated aqueous NH4Cl (100 mL) and extracted with CHCl (100 mL). The organic extract was rinsed with water (2×50 mL), brine (50 mL), dried over anhydrous Na2SO4, filtered, and removed under reduced pressure to give a pale yellow solid. The crude product was purified by recrystallization from hot heptane to give the desired product as an off-white solid (1.64 g, 89% recrystallization yield). 1 H NMR(400MHz,CDCl3)δ 7.66(d,1H,ArH),7.55(d,1H,ArH),7.45(s,1H,ArH),7.36(t,1H,ArH),7.31-7.20(m,1H ,ArH),7.08(d,1H,ArH),4.04(s,3H,NCH3),3.70(s,2H,indene-CH2),2.51(s,3H,ArCH3).

[0245] 2-Bromo-6-(tert-butyl)-4-methylphenol: [ka] This material was prepared essentially as described in Katayama, H. et al. (Sumitomo), PCT Application WO 97 / 03992, 1997. 2-(tert-Butyl)-4-methylphenol (26.58 g, 161.8 mmol) was dissolved in acetonitrile (300 mL) in a 500 mL round bottom flask to give a pale yellow solution. The flask was cooled to 0° C. for 15 min, after which N-bromosuccinimide (31.68 g, 178.0 mmol) was added in portions. The reaction mixture was stirred overnight. The volatiles were removed under reduced pressure to give a yellow sticky residue. The residue was extracted with diethyl ether (200 mL), rinsed with H2O (4×200 mL), brine (20 mL), dried over anhydrous Na2SO4, and filtered to give a golden yellow filtrate. Evaporation of the volatiles gives the desired product as a thick yellow oil. (37.89 g, 96% yield). Distillation under reduced pressure gave a colorless oil, but the crude product was spectroscopically pure by NMR and could be used without further purification. 1 H NMR(400MHz,CDCl3)δ 7.29(s,1H,ArH),7.12(s,1H,ArH),5.73(m,1H,ArOH),2.37(3H,s,ArCH3),1.51(s,9H,t-Bu).

[0246] 2-(allyloxy)-1-bromo-3-(tert-butyl)-5-methylbenzene: [ka] This material was prepared essentially as described by Hanaoka, H. et al., J. Organomet. Chem. 2007, 692, 4059-4066. 2-Bromo-6-(tert-butyl)-4-methylphenol (9.93 g, 40.83 mmol), potassium carbonate (approximately 10 g), acetone (100 mL), and allyl bromide (4.24 mL, 49 mmol) were charged to a 250 mL round-bottom flask equipped with a stir bar. A condenser was attached and the reaction mixture was refluxed overnight. The reaction mixture, a white suspension, was concentrated under reduced pressure, extracted with pentane, and filtered to give a clear, colorless filtrate. Evaporation afforded the desired product as a thick, colorless oil (11.40 g, 99% yield). 1 H NMR (400 MHz, CDCl3) δ 7.28 (m, 1H, ArH), 7.10 (m, 1H, ArH), 6.28 (m, 1H, O-allyl), 5.52 (dq, 1H, O-allyl), 5.32 (dq, 1H, O-allyl), 4.60 (m, 2H, O-allyl), 2.30 (s, 3H, ArCH3), 1.42 (s, 9H, Ar-t-Bu).

[0247] (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodiethylsilane: [ka] This material was prepared essentially as described by Senda, T. et al., Macromolecules 2009, 42, 8006-8009. 2-(allyloxy)-1-bromo-3-(tert-butyl)-5-methylbenzene (0.94 g, 3.3 mmol) was dissolved in toluene (50 mL) in a 100 mL Schlenk flask. The flask was cooled to -78 °C and n-BuLi solution (1.6 M in hexanes, 2.27 mL, 3.63 mmol) was added quantitatively via cannula with toluene rinses (3 x 3 mL). The reaction mixture was allowed to stir and gradually warm, maintaining the mixture below -15 °C. After 2 h, the reaction mixture, a clear pale yellow solution, was cooled to -78 °C and Et2SiCl2 (1.555 g, 9.9 mmol) was added. The reaction mixture was allowed to warm to ambient temperature over 2 h and then heated to 50 °C for 1 h. The volatiles were removed under reduced pressure and the oily residue was extracted with pentane and filtered through Celite to give a clear, colorless filtrate. The volatiles were removed to give the desired product as a thick, colorless oil (0.85 g, 79% yield). 1 H NMR (400 MHz, toluene-d8) δ 7.53 (d, 1H, ArH), 7.25 (d, 1H, ArH), 5.85 (m, 1H, O-allyl), 5.50 (dq, 1H, O-allyl), 5.15 (dq, 1H, O-allyl), 4.32 (m, 2H, O-allyl), 2.19 (s, 3H, ArCH3), 1.42 (s, 9H, Ar-t-Bu), 1.30-1.05 (m, 10H, SiEt2).

[0248] 10-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diethylsilyl)-5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole: [ka] 5,8-Dimethyl-5,10-dihydroindeno[1,2-b]indole (1.64 g, 7.04 mmol) was dissolved in THF (30 mL) in a 100 mL Schlenk flask. With vigorous stirring, n-BuLi solution (1.6 M in hexanes, 4.62 mL, 7.39 mmol) was added and the dark red reaction mixture was stirred for 1 h. Slow bubbling (butane) was observed initially but subsided over time. After 1 h, (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodiethylsilane (2.29 g, 7.04 mmol) was added to give a dark orange-red solution. The reaction mixture was stirred for 1 h and then the volatiles were removed under reduced pressure to give a sticky yellow solid. The crude material was slurried in pentane (20 mL) and cooled to -30 °C. The solid was then collected on a sintered glass funnel and dried under reduced pressure (2.20 g, 60% yield). 1 H NMR (400MHz, toluene-d8)δ 7.52(m,2H,ArH),7.35(m,1H,ArH),7.27(t,1H,ArH),7.18-7.00(m,4H,ArH) ,6.73(s,1H,ArH),5.85(m,1H,Allyl-H),5.58(dq,1H,Allyl-H),5.18(dq,1H,ArH) Allyl-H),4.49(s,1H,Si-CH),4.34(qd,1H,Allyl-H),3.45(s,3H,NCH3),2.44(s,3 H,ArCH3),2.20(s,3H,ArCH3),1.51(s,9H,t-Bu),1.49-0.70(m,10H,SiEt2).

[0249] Example 1 : 10-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diethylsilyl)-5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole (2.20 g, 4.216 mmol) was dissolved in toluene (40 mL) in a 100 mL Schlenk flask and cooled to −78° C. for 15 min. NEt3 (2.64 mL, 1.92 g, 18.97 mmol) and n-BuLi solution (1.6 M in hexanes, 5.93 mL, 9.49 mmol) were added successively. The pale yellow solution was allowed to warm to ambient temperature and stirred for an additional 2 h, after which the reaction mixture was cooled again to −78° C. for 15 min. Ti(NMe2)2Cl2 (1.05 g, 5.06 mmol) was added as a slurry in toluene and the reaction mixture was allowed to warm to ambient temperature over 10 min and subsequently heated to 90 °C for 3 h to give a dark red-brown solution. The volatiles were removed under reduced pressure and the residue was extracted with toluene and filtered through Celite to give a dark brown filtrate. Extraction was continued until the filtrate was colorless and then the combined extracts were sealed in a 100 mL flask with a vacuum headspace. Chlorotrimethylsilane (1.07 mL, 0.92 g, 8.43 mmol) was added via syringe and the mixture was heated to 85 °C for 5 h. The volatiles were removed and the residue was recrystallized from hot heptane to give the desired product as a dark red-brown solid. (1.96 g, 78% recrystallization yield). 1 H NMR (400MHz, toluene-d8)δ 7.93(d,1H,ArH),7.79(d,1H,ArH),7.48(s,1H,ArH),7.40-7.20(m,3H,ArH),7.05(m,1H,ArH),6.83(d,1H,ArH),6.47(s,1H, ArH),3.62(s,3H,NCH3),2.44(s,3H,ArCH3),2.13(s,3H,ArCH3),1.70-1.30(m,4H,SiEt2),1.20-1.00(m,15H,SiEt2+t-Bu).

[0250] Example 2 [ka] Example 2 : Example 1 (1.05 g, 1.75 mmol) was dissolved in toluene (35 mL) in a 100 mL Schlenk flask. MeMgBr solution (3.0 M in diethyl ether, 1.28 mL, 3.85 mmol) was added and the resulting red-brown solution was stirred for 2 h. The volatiles were removed under reduced pressure and the residue was extracted with toluene and filtered through Celite. The bright orange filtrate was collected and concentrated under reduced pressure to give an amorphous orange residue. This was redissolved in pentane and concentrated under reduced pressure to give the desired product as a bright orange powder (806 mg, 83% yield). 1 H NMR (400MHz, toluene-d8)δ 7.91(d,1H,ArH),7.79(d,1H,ArH),7.45(s,1H,ArH),7.32(s,1H,ArH),7.30-6.90(m,3H,ArH),6.80(d,1H,ArH),6.55(s,1H,ArH),3.57(s ,3H,NCH3),2.45(s,3H,ArCH3),2.12(s,3H,ArCH3),1.31(s,9H,t-Bu),1.30-1.05(m,10H,SiEt2),0.23(s,3H,TiCH3),0.03(s,3H,TiCH3).

[0251] Example 3 : [ka] 2-Methyl-5,6-dihydroindeno[2,1-b]indole: [ka] This material was prepared essentially as described by Grandini, C. et al., Organometallics, 2004, 23, 344-360. 2-Indanone (5.95 g, 45.0 mmol) and p-tolylhydrazine hydrochloride (7.14 g, 45.0 mmol) were slurried in i-PrOH (300 mL) in a 500 mL round bottom flask. A Vigreux column was attached and the reaction mixture was refluxed for 2 h and then poured into saturated aqueous NaHCO3 (300 mL). The precipitate was collected on a sintered glass funnel and rinsed with i-PrOH and water. The crude material was dissolved in CHCl (200 mL), shaken with brine (50 mL), dried over anhydrous NaSO4, filtered, and concentrated under reduced pressure to give the desired product (7.76 g, 79% yield). 1 H NMR(400MHz,CDCl3)δ 8.20(br s,1H,NH),7.70-7.60(m,2H,ArH),7.43(d,1H,ArH),7.35(t,1H,ArH),7.28(m,1H,A rH),7.09(t,1H,ArH),7.04(d,1H,ArH),3.72(s,2H,indene-CH2),2.52(s,3H,ArCH3).

[0252] 2,5-Dimethyl-5,6-dihydroindeno[2,1-b]indole: [ka] 2-Methyl-5,6-dihydroindeno[2,1-b]indole (7.76 g, 35.4 mmol) was dissolved in THF (150 mL) in a 250 mL round bottom flask. Potassium tert-butoxide (3.97 g, 35.4 mmol) was added, resulting in a color change from dark green to dark red. After stirring for 1 h, the flask was immersed in a water bath and iodomethane (2.20 mL, 5.02 g, 35.4 mmol) was added slowly, resulting in a mild exotherm and a brown suspension. The reaction mixture was stirred overnight and then poured into aqueous NH4Cl (57 g in 300 mL water), resulting in a suspended precipitate. The slurry was stirred for 30 min, then the solid was collected on a sintered glass funnel and rinsed with water. This material was dissolved in CH2Cl2 (200 mL), shaken with brine (50 mL), dried over anhydrous Na2SO4, filtered, and concentrated under reduced pressure to give a dark greenish-brown solid (7.63 g, 93% yield). 1 H NMR(400MHz,CDCl3)δ 7.70-7.60(m,2H,ArH),7.45(d,1H,ArH),7.35(t,1H,ArH),7.25(m,1H,ArH),7.10 -7.02(m,2H,ArH),3.81(s,3H,NCH3),3.72(s,2H,indene-CH2),2.53(s,3H,ArCH3).

[0253] 6-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diethylsilyl)-2,5-dimethyl-5,6-dihydroindeno[2,1-b]indole: [ka] 2,5-Dimethyl-5,6-dihydroindeno[2,1-b]indole (467 mg, 2.0 mmol) was weighed into a 100 mL Schlenk flask and dissolved in THF (40 mL). n-BuLi solution (1.6 M in hexanes, 1.38 mL, 2.2 mmol) was added via syringe and the reaction mixture was stirred for 2 h. The volatiles were removed under reduced pressure and the residue was redissolved in diethyl ether (40 mL). (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodiethylsilane (650 mg, 2.0 mmol) was weighed into a vial and added quantitatively via diethyl ether rinses (3 x 3 mL) to give a precipitate. The brown suspension was stirred overnight. The volatiles were removed under reduced pressure and the residue was extracted with toluene and filtered to give a clear dark brown filtrate. The filtrate was concentrated under reduced pressure, triturated with pentane, and then concentrated again to give the product as a brown glassy residue (1.04 g, 99% yield). 1 H NMR (400 MHz, toluene-d8) δ 7.90-6.90 (m, 9H, ArH), 5.85 (m, 1H, allyl-H), 5.55 (d, 1H, allyl-H), 5.19 (d, 1H, allyl-H), 4.28 (m, 2H, allyl-H), 4.19 (s, 1H, Si-CH), 3.00 (s, 3H, NCH3), 2.55 (s, 3H, ArCH3), 2.17 (s, 3H, ArCH3), 1.46 (s, 9H, Ar-t-Bu), 1.10-0.50 (m, 10H, SiEt2).

[0254] Example 3 : 6-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diethylsilyl)-2,5-dimethyl-5,6-dihydroindeno[2,1-b]indole (1.08 g, 1.99 mmol) was dissolved in toluene (20 mL) in a 100 mL Schlenk flask. Triethylamine (1.25 mL, 8.943 mmol, 4.5 equiv) was added to the flask and the reaction mixture was cooled to -78 °C for 15 min. n-BuLi solution (1.6 M in hexanes, 2.79 mL, 4.47 mmol, 2.25 equiv) was added quantitatively from a Hypo-Vial via toluene rinses (3 x 3 mL) and the reaction mixture was allowed to stir and warm to ambient temperature over 2 h. The reaction mixture was cooled to -78 °C for 15 min and Ti(NMe2)2Cl2 (493 mg, 2.38 mmol, 1.2 equiv) was added as a solution in toluene (10 mL). The cold bath was removed after 30 min and replaced with an oil bath. The reaction mixture was heated to 90 °C for 3 h to give a dark red-brown mixture. The volatiles were removed and the residue was extracted with pentane and filtered to give a clear dark brown filtrate. The volatiles were removed from the filtrate and the residue was redissolved in toluene (30 mL). Chlorotrimethylsilane (0.51 mL, 3.974 mmol, 2 equiv) was added and the mixture was heated to 80 °C overnight. The volatiles were removed from the dark red-brown solution and the sticky residue was triturated with pentane. The residue was purified via recrystallization from hot heptane to give the desired product as a red-brown crystalline powder (580 mg, 49% yield). 1 H NMR (400MHz, toluene-d8)δ 8.06(d,1H,ArH),7.95(s,1H,ArH),7.59(d,1H,ArH),7.34(s,1H,ArH),7.28(s,1H,ArH),7.20-6.80(m,4H,ArH),3.27(s,3H,NCH3),2.39(s,3H,A rCH3),2.36(s,3H,ArCH3),1.45(m,2H,SiCH2CH3),1.33(s,9H,Ar-t-Bu),1.12(t,3H,SiCH2CH3),1.05(t,3H,SiCH2CH3),0.95(m,2H,SiCH2CH3).

[0255] Example 4 [ka] Example 4 : Example 3 (461 mg, 0.770 mmol) was dissolved in toluene (5 mL) in a vial. A solution of MeMgBr (3.0 M in diethyl ether, 0.54 mL, 1.618 mmol) was added with stirring, resulting in a color change from dark red-brown to dark tan. After 2 h, the volatiles were removed and the residue was extracted with toluene and filtered to give a dark tan filtrate. The volatiles were removed and the residue was triturated with pentane and concentrated once more to give the desired product as a tan powder (355 mg, 83% yield). 1 H NMR (400MHz, toluene-d8)δ 8.06(d,1H,ArH),7.89(s,1H,ArH),7.80(d,1H,ArH),7.30-7.00(m,5H,ArH),6.72(d,1H,ArH),2.91(s,3H,NCH3),2.48(s, 3H,ArCH3),2.36(s,3H,ArCH3),1.51(s,9H,Ar-t-Bu),1.40-0.90(m,10H,SiEt2),0.30(s,3H,TiCH3),0.21(s,3H,TiCH3).

[0256] Example 5 [ka] 5-Pentyl-8-methyl-5,10-dihydroindeno[1,2-b]-indole: [ka] 8-Methyl-5,10-dihydroindeno[1,2-b]indole (3.00 g, 13.7 mmol) and potassium tert-butoxide (14.4 g, 13.7 mmol) were dissolved in THF (35 mL) in a 100 mL Schlenk flask, and the opaque orange solution was stirred for 1 h. Degassed 1-bromopentane (1.87 mL, 15.1 mmol) was added via syringe. The reaction was refluxed at 80 °C for 18 h. After cooling to ambient temperature, the reaction mixture was poured into water (100 mL) and extracted with CHCl (100 mL). The organic extract was rinsed with water (2 x 50 mL), brine (50 mL), dried over anhydrous NaSO, filtered, and concentrated under reduced pressure to give a brown solid (2.66 g, 67% yield). 1 H NMR (400 MHz, CDCl3) δ 7.55 (t, 2H, ArH), 7.43 (t, 1H, ArH), 7.35 (s, tH, ArH), 7.24 (t, 1H, ArH), 7.04 (m, 1H, ArH), 4.39 (t, 1H, pentane-H), 3.74 (s, 3H, CH2), 2.48 (s, 3H, CH3), 1.91 (m, 2H, pentane-H), 1.37 (m, 5H, pentane-H), 0.90 (t, 3H, pentane-H).

[0257] 10-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diethylsilyl)-5-pentyl-8-dimethyl-5,10-dihydroindeno[1,2-b]indole: [ka] 5-Pentyl-8-methyl-5,10-dihydroindeno[1,2-b]-indole (0.89 g, 3.06 mmol) was dissolved in THF (30 mL) in a 100 mL Schlenk flask. With stirring, n-BuLi solution (1.6 M in hexanes, 2.3 mL, 3.67 mmol) was added resulting in effervescence and a bright red color. After 24 h, (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodiethylsilane (0.994 g, 3.06 mmol) was added. The dark orange solution was stirred overnight resulting in the formation of a white precipitate. The volatiles were removed under reduced pressure and the brown oil was triturated with toluene, filtered through Celite, and concentrated again to a brown oil. The resulting crude material was used directly in the subsequent step.

[0258] Example 5 : 10-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diethylsilyl)-5-pentyl-8-methyl-5,10-dihydroindeno[1,2-b]indole (0.850 g, 1.47 mmol) was dissolved in toluene (30 mL) in a 100 mL Schlenk flask and cooled to −78° C. for 15 min. Triethylamine (0.92 mL, 6.61 mmol) and n-BuLi solution (1.6 M in hexanes, 2.10 mL, 3.31 mmol) were added successively. The pale yellow solution was allowed to warm to ambient temperature and stirred for an additional 2 h, after which the reaction mixture was cooled again to −78° C. for 15 min. Ti(NMe2)2Cl2 (0.367 g, 1.76 mmol) was added as a slurry in toluene and the reaction mixture was allowed to warm to ambient temperature over 10 min, then heated to 90° C. for 3 h to give a dark red-brown solution. The volatiles were removed under reduced pressure and the residue was extracted with toluene and filtered through Celite to give a dark brown filtrate. Extraction was continued until the filtrate was colorless and the combined filtrate was sealed in a 100 mL flask with evacuated headspace. Chlorotrimethylsilane (0.373 mL, 0.319 g, 2.94 mmol) was added via syringe and the mixture was heated to 85° C. overnight. The volatiles were removed and the residue was slurried in cold pentane and filtered. A black solid was recovered from the filter. (0.336 g, 35% yield).1 H NMR (400MHz, toluene-d8)δ 7.93(t,2H,ArH),7.45(s,1H,ArH),7.31(m,3H,ArH),6.49(s,1H,ArH),4.45(dq,2H,NCH2),2.41(s,3H,ArCH3),1 .59(m,4H,SiEt3),1.36(m,4H,SiEt2),1.08(s,12H,ArCH3+tBu),1.01(t,3H,CH3),1.50-0.73(m,6H,pentyl-CH2).

[0259] Example 6 [ka] Example 6 : Example 5 (0.336 g, 0.50 mmol) was dissolved in toluene (10 mL) in a 100 mL Schlenk flask and MeMgBr solution (3.0 M in diethyl ether, 0.60 mL, 1.80 mmol) was added. The red-brown solution was stirred for 2 h. The volatiles were removed under reduced pressure and the residue was extracted with toluene and filtered through Celite. The bright red filtrate was collected and concentrated under reduced pressure to give a red sticky solid (186 mg, 61% yield). 1 H NMR (400MHz, toluene-d8) δ 7.99(d,1H,ArH),7.97(d,1H,ArH),7.40(d,1H,ArH),7.24(d,1H,ArH),7.18(dt,2 H,ArH),6.96(s,1H,ArH2),6.93(s,1H,ArH),6.59(s,1H,ArH)4.21(dq,2H,NCH2),2 .42(s,3H,ArCH3),1.68(m,2H,pentyl-CH2),1.31(s,9H,tBuCH),1.20-1.06(m,15H, Pentyl-CH2+SiEt2), 0.77(t,3H,pentyl-CH3),0.24(s,3H,TiCH3),0.07(s,3H,TiCH3).

[0260] Example 7 [ka] (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodiphenylsilane: [ka] 2-(allyloxy)-1-bromo-3-(tert-butyl)-5-methylbenzene (5.04 g, 17.8 mmol) was weighed into a 100 mL flask and 50 mL of dry toluene was added. The solution was cooled to -78°C and n-BuLi solution (12.2 mL, 19.5 mmol, 1.6 M, hexane) was added dropwise. The mixture was allowed to warm slowly to -15°C over 2 hours and maintained at that temperature for 30 minutes. The solution was cooled to -78°C and neat Ph2SiCl2 (12.6 mL, 12.37 mmol) was rapidly injected into the mixture. The flask was allowed to warm to ambient temperature overnight. The volatiles were removed under reduced pressure while heating to 40°C to give a thick, slightly orange liquid. Pentane was added and the mixture was filtered through a Celite plug. The volatiles were removed and the mixture was distilled under dynamic vacuum at 120°C. A thick off-white liquid was obtained (4.50 g, 60% yield, approximately 90% purity by NMR). 1 H NMR (400 MHz, toluene-d8) δ 7.78 (m, 4H, ArH), 7.60 (m, 1H, ArH), 7.48 (m, 2H, ArH), 7.27 (d, 1H, ArH), 7.12 (d, 4H, ArH), 5.36 (m, 1H, allyl-H), 4.97 (dq, 1H, allyl-H), 4.80 (dq, 1H, allyl-H), 4.16 (m, 2H, allyl-H) 1.46 (s, 3H, CH3), 1.39 (s, 9H, C(CH3)3.

[0261] 10-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diphenylsilyl)-5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole: [ka] 5,8-Dimethyl-5,10-dihydroindeno[1,2-b]indole (1.00 g, 4.31 mmol) was dissolved in THF (30 mL) and cooled to −30° C. in a freezer. After 1 h, n-BuLi solution (2.8 mL, 1.6 M, 4.5 mmol, 1.05 equiv.) was added dropwise, immediately forming a dark orange solution. After stirring at ambient temperature for 3 h, the solution was again placed in the freezer and (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodiphenylsilane (1.85 g, 4.4 mmol) was dissolved in THF (20 mL) and also placed in the freezer. After 1 h, the chlorosilane solution was added dropwise to the lithiated indenoindolyl precursor and the mixture was stirred at ambient temperature for 48 h. The volatiles were removed under dynamic vacuum and the product was extracted with heptane, filtered through a plug of Celite and the volatiles removed leaving 2.4 g of a pale yellow-orange foamy solid which was used without further purification.

[0262] Example 7 : Crude 10-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diphenylsilyl)-5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole (2.40 g, 3.88 mmol) was dissolved in toluene (40 mL) and triethylamine (2.45 mL, 15.5 mmol) was added to the flask. The flask was cooled to -78 °C and n-BuLi solution (5.5 mL, 1.6 M hexane, 8.8 mmol) was added slowly via syringe. The mixture was allowed to warm slowly to ambient temperature over 1 h and left for an additional 1 h. The mixture was then cooled to -78 °C and Ti(NMe2)2Cl2 (964 mg, 4.66 mmol) in toluene (20 mL) was added via cannula followed by 2 additional aliquots of toluene (5 mL each) for rinsing. The mixture was stirred at -78°C for 10 minutes, then allowed to warm to ambient temperature and then heated to 90°C for 2 hours to give a black mixture. The volatiles were removed under reduced pressure while heating to 45°C and 50 mL of toluene was added. The mixture was filtered through Celite, after which the solution was placed under static vacuum, chlorotrimethylsilane (1.5 mL, 11.6 mmol, 3 equiv) was injected into the flask and the mixture was heated to 80°C overnight. The volatiles were removed under dynamic vacuum, heptane was added, the flask was heated to 90°C and the solution was transferred to a Hypo-Vial which was then placed in the freezer. Filtration gave a green crystalline compound (1.11 g, 41.3% yield). 1 H NMR (400MHz, toluene-d8)δ 7.98(m,2H,ArH),7.86(m,2H,ArH),7.71(d,1H,ArH),7.52(s,1H,ArH),7.26(m,ArH,3H),7.20(m,4H,ArH),7.05(d,1H,ArH),6. 91(dd,2H,ArH),6.84(d,2H,ArH),6.56(s,1H,ArH),3.63(s,3H,CH3),2.15(s,3H,CH3),1.94(s,3H,CH3),1.18(s,9H,C(CH3)3).

[0263] Example 8 [ka] Example 8 : Example 7 (932 mg) was dissolved in toluene (20 mL) and MeMgBr solution (0.95 mL, 3 M in diethyl ether, 2.1 equiv.) was poured into the solution with rapid stirring. The mixture was allowed to stir at ambient temperature overnight. The volatiles were removed under dynamic vacuum, toluene was added (20 mL) and the volatiles were once again removed under vacuum. Toluene was added and the mixture was warmed and then filtered through Celite. The volatiles were removed to give an orange powder (745 mg). Recrystallization from cold pentane gave an orange semicrystalline powder (430 mg, 0.66 mmol, 49% yield). 1 H NMR (400MHz, toluene-d8) δ 7.98(m,2H,ArH),7.92(m,2H,ArH),7.83(d,1H,ArH),7.45(d,1H,ArH),7.27(d,1H ,ArH),7.16(m,4H,ArH),7.12(m,2H,ArH),7.05(m,2H,ArH),6.95(d,1H,ArH),6.8 2(d,1H,ArH),6.78(m,1H,ArH),6.36(s,1H,ArH),3.58(s,3H,CH3),2.17(s,3H,CH 3),1.94(s,3H,CH3),1.39(s,9H,C(CH3)3),0.09(s,3H,TiCH3),0.05(s,3H,CH3).

[0264] Example 9 [ka] 2-((3r,5r,7r)-adamantan-1-yl)-6-bromo-4-methylphenol: [ka] 2-((3r,5r,7r)-adamantan-1-yl)-4-methylphenol (2.0 g, 8.25 mmol) was slurried in acetonitrile (100 mL) in a 250 mL round bottom flask and cooled to 0 °C for 15 min. N-bromosuccinimide (1.62 g, 9.08 mmol) was added. The pale yellow reaction mixture was stirred and allowed to warm to ambient temperature overnight to give a pale yellow suspension. The volatiles were removed under reduced pressure and the residue was partitioned between CHCl and water (150 mL each). The organic layer was collected and combined with an additional CHCl extract of the aqueous layer (2 x 100 mL), rinsed with water (2 x 100 mL), brine (50 mL), dried over anhydrous NaSO, and filtered. The filtrate was concentrated under reduced pressure to give a pale yellow solid (2.63 g, 8.20 mmol, 99% yield). 1 H NMR(400MHz,CDCl3)δ 7.15(d,1H,ArH),6.95(d,1H,ArH),5.63(s,1H,ArOH),2.25(s,3H,ArCH3),2.15-2.01(br,9H,AdH),1.77(br s,6H,AdH).

[0265] (3r,5r,7r)-1-(2-(allyloxy)-3-bromo-5-methylphenyl)adamantane: [ka] 2-((3r,5r,7r)-adamantan-1-yl)-6-bromo-4-methylphenol (2.63 g, 8.20 mmol), potassium carbonate (4.53 g, 16.39 mmol) and acetone (70 mL) were combined in a 100 mL round bottom flask and fitted with a condenser. The mixture was stirred for 10 minutes and then allyl bromide (2.84 mL, 16.39 mmol) was added. The reaction mixture was refluxed for 5 hours, cooled to ambient temperature and filtered through Celite. The clear yellow filtrate was concentrated to dryness, triturated with pentane and concentrated once more to give an off-white powder (2.80 g, 95% yield). 1H NMR (400 MHz, CDCl3) δ 7.25 (m, 1H, ArH), 7.03 (d, 1H, ArH), 6.14 (m, 1H, allyl-H), 5.54 (dq, 1H, allyl-H), 5.32 (dq, 1H, allyl-H), 4.59 (m, 1H, allyl-H), 2.28 (3H, ArCH3), 2.07 (br, 9H, AdH), 1.76 (br, 6H, AdH).

[0266] (3-((3r,5r,7r)-adamantan-1-yl)-2-(allyloxy)-5-methylphenyl)chlorodiethylsilane: [ka] (3r,5r,7r)-1-(2-(allyloxy)-3-bromo-5-methylphenyl)adamantane (1.40 g, 3.88 mmol) was dissolved in anhydrous diethyl ether (80 mL). The reaction mixture was cooled to -78°C for 15 min and n-BuLi solution (1.6 M in hexanes, 2.54 mL, 4.07 mmol) was added. The reaction mixture was stirred at -78°C for 3 h, after which dichlorodiethylsilane (1.52 g, 9.69 mmol) was added. The reaction mixture was allowed to warm to ambient temperature overnight to give a tan suspension. The volatiles were removed and the residue was extracted with pentane and filtered through Celite to give a brown solution. The volatiles were removed to give the crude product as a thick oil which was used without further purification (1.28 g, 82% yield, approx. 90% purity by NMR). 1 H NMR (400 MHz, toluene-d8,) δ 7.50 (d, 1H, ArH), 7.18 (d, 1H, ArH), 5.80 (m, 1H, allyl-H), 5.53 (dq, 1H, allyl-H), 5.13 (dq, 1H, allyl-H), 4.31 (m, 2H, allyl-H), 2.19 (s, 3H, ArCH3), 2.07 (br m, 6H, AdH), 2.01 (br, 3H, AdH), 1.74 (br, 6H, AdH), 1.23-1.03 (m, 10H, SiEt2).

[0267] 10-((3-((3r,5r,7r)-adamantan-1-yl)-2-(allyloxy)-5-methylphenyl)diethylsilyl)-5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole: [ka] 5,8-Dimethyl-5,10-dihydroindeno[1,2-b]indole (0.74 g, 3.18 mmol) was dissolved in THF (30 mL) in a 100 mL Schlenk flask. With stirring, a solution of n-BuLi (1.6 M in hexanes, 2.09 mL, 3.34 mmol) was added resulting in effervescence and a bright red color. After 30 min, a solution of (3-((3r,5r,7r)-adamantan-1-yl)-2-(allyloxy)-5-methylphenyl)chlorodiethylsilane (1.28 g, 3.18 mmol) in THF (10 mL) was added via cannula. After stirring the dark orange solution overnight, the volatiles were removed under reduced pressure and the foamy residue was triturated with pentane and concentrated under reduced pressure to give an off-white powder. This was extracted with toluene, filtered, and concentrated under reduced pressure. Purification via column chromatography (silica gel, 9:1 heptane:ethyl acetate) afforded a sticky pale yellow solid (1.39 g, 73% yield). The material thus isolated was used without further purification.

[0268] Example 9 : 10-((3-((3r,5r,7r)-adamantan-1-yl)-2-(allyloxy)-5-methylphenyl)diethylsilyl)-5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole (1.39 g, 2.32 mmol) was dissolved in toluene (30 mL) and treated with triethylamine (1.46 mL, 10.46 mmol) to give a yellow suspension. The flask was cooled to -78 °C for 15 min and then n-BuLi solution (1.6 M in hexanes, 3.27 mL, 5.23 mmol) was added. The reaction mixture was warmed to ambient temperature and stirred for 1 h to give a clear orange solution. The flask was cooled again to -78 °C for 15 min. Ti(NMe2)2Cl2 (577 mg, 2.79 mmol) was added as a toluene solution and the reaction mixture was dark brown. The cold bath was removed and the mixture was heated to 90° C. for 3 h. The mixture was cooled, concentrated under reduced pressure, and the residue was extracted with toluene and filtered through Celite to remove dark solids from the dark red-brown solution. The filtrate was heated overnight with chlorotrimethylsilane (0.59 mL, 4.65 mmol) in a sealed flask under static vacuum. Volatiles were removed under reduced pressure. The residue was stirred with hot heptane (20 mL) and the resulting slurry was cooled in a glove box freezer. The cold mixture was decanted and the resulting solid was isolated and dried under reduced pressure to give a dark green powder (768 mg, 49% yield). 1 H NMR (400MHz, toluene-d8)δ 7.88(d,1H,ArH),7.73(d,1H,ArH),7.45(m,1H,ArH),7.31(m,1H,ArH),7.24(m,1H,ArH),7.19(m,1H,ArH),6.81(d,1H,ArH),6.44(s,1H, ArH),3.59(s,3H,NCH3),2.46(s,3H,ArCH3),2.11(s,3H,ArCH3),1.76(m,12H,AdH+ArCH3),1.54(m,3H,AdH),1.40-0.83(m,10H,SiEt2).

[0269] Example 10 [ka] Example 10 : Example 9 (768 mg, 1.135 mmol) was dissolved in toluene (30 mL) in a 100 mL Schlenk flask and MeMgBr solution (3.0 M in diethyl ether, 0.83 mL, 2.50 mmol) was added. No initial color change was observed. The mixture was stirred overnight to give a dark greenish-brown suspension. The volatiles were removed under reduced pressure, the residue was extracted with heptane, filtered through Celite to remove dark solids from the dull orange-green filtrate, and the filtrate was concentrated under reduced pressure to give a dark green-black solid. Trituration with pentane afforded the desired product as a red-brown powder (533 mg, 0.838 mmol, 74%). 1 H NMR (400MHz, toluene-d8) δ 7.86(d,1H,ArH),7.74(d,1H,ArH),7.39(m,1H,ArH),7.23-7.11(m,3H,ArH),6 .94(d,1H,ArH),6.78(d,1H,ArH),6.57(s,1H,ArH),3.54(s,3H,NCH3),2.45(s, 3H,ArCH3),2.15-2.09(m,6H,ArCH3+AdH),2.00-1.86(m,6H,AdH),1.79-1.59( m,6H,AdH),1.30-1.01(m,10H,SiEt2),0.20(s,3H,TiCH3),0.01(s,3H,TiCH3).

[0270] Example 11 [ka] 2-Bromo-6-(tert-butyl)-4-methoxyphenol: [ka] 2-(tert-Butyl)-4-methoxyphenol (1.80 g, 10 mmol) was dissolved in CHCl (100 mL) in a 250 mL round bottom flask to give a clear, colorless solution. The solution was immersed in an ice-water bath for 15 min. With vigorous stirring, a slurry of N-bromosuccinimide (1.87 g, 10.5 mmol) in CHCl (approximately 50 mL) was added dropwise to control the Br concentration. Once all of the NBS had been added (with a CHCl rinse), the pale yellow solution was allowed to warm to ambient temperature. After 2 h, the reaction mixture was rinsed with saturated aqueous NaSO (50 mL), water (3×50 mL), brine (50 mL), and dried over anhydrous sodium sulfate. The dried organic phase was filtered. The clear pale yellow filtrate was concentrated under reduced pressure to give the product as a thick amber oil (2.23 g, 8.59 mmol, 86% yield, approximately 95% purity by NMR). 1 H NMR(400MHz,CDCl3)δ 6.91(m,2H,ArH),5.51(s,1H,ArOH),3.77(s,3H,ArOMe),1.43(s,9H,t-Bu).

[0271] 2-(allyloxy)-1-bromo-3-(tert-butyl)-5-methoxybenzene: [ka] NaH (144 mg, 6.0 mmol) was slurried in THF (50 mL) in a Schlenk flask. With vigorous stirring, 2-bromo-6-(tert-butyl)-4-methoxyphenol (1.04 g, 4.0 mmol) was added dropwise as a solution in THF (5 mL), resulting in foaming and a dark yellow-green suspension. The reaction mixture was stirred for 1 h, after which allyl bromide (0.52 mL, 6 mmol) was added via syringe. The dark yellow-green reaction mixture was stirred for 3 days. The reaction mixture was concentrated under reduced pressure, slurried in pentane (50 mL), neutralized by dropwise addition of saturated aqueous NH4Cl (50 mL), and the organic layer was rinsed with brine (10 mL) and dried over anhydrous Na2SO4. The dried extract was filtered and concentrated under reduced pressure to give an amber oil (787 mg, 2.63 mmol, 66% yield). 1H NMR (400 MHz, CDCl3) δ 6.96 (d, 1H, ArH), 6.86 (d, 1H, ArH), 6.13 (m, 1H, allyl-H), 5.49 (dq, 1H, allyl-H), 5.30 (dq, 1H, allyl-H), 4.55 (dt, 2H, allyl-H), 3.76 (s, 3H, OMe), 1.38 (s, 9H, t-Bu).

[0272] (2-(allyloxy)-3-(tert-butyl)-5-methoxyphenyl)chlorodiethylsilane: [ka] 2-(Allyloxy)-1-bromo-3-(tert-butyl)-5-methoxybenzene (5.39 g, 18 mmol) was diluted with Et2O (50 mL) in a Schlenk flask. The flask was cooled to -78 °C for 15 min, then n-BuLi solution (1.6 M in hexanes, 11.8 mL, 18.9) was added, initially giving a dark green coloration, then a yellow suspension when the addition was complete. The reaction mixture was stirred for 1 h, then Et2SiCl2 (7.07 g, 45 mmol) was added, giving a dull yellow suspension. This was stirred and allowed to warm to ambient temperature over 2 h. The volatiles were removed under reduced pressure. The yellow residue was extracted with pentane and filtered through Celite to remove the white solids from the clear yellow filtrate. The filtrate was evaporated to give the product as a thick amber oil (5.77 g, 16.92 mmol, 94% yield). 1 H NMR (400 MHz, toluene-d8) δ 7.23 (d, 1H, ArH), 7.06 (d, 1H, ArH), 5.79 (m, 1H, allyl-H), 5.47 (dq, 1H, allyl-H), 5.11 (dq, 1H, allyl-H), 4.26 (m, 2H, allyl-H), 3.43 (s, 3H, OMe), 1.35 (s, 9H, t-Bu), 1.20-0.98 (m, 10H, SiEt2).

[0273] 10-((2-(allyloxy)-3-(tert-butyl)-5-methoxyphenyl)diethylsilyl)-5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole: [ka] 5,8-Dimethyl-5,10-dihydroindeno[1,2-b]indole (5.87 g, 25.17 mmol) was dissolved in THF (100 mL). n-BuLi solution (1.6 M in hexanes, 16.5 mL, 26.43 mmol) was added and the dark red mixture was stirred for 1 h. (2-(allyloxy)-3-(tert-butyl)-5-methoxyphenyl)chlorodiethylsilane (8.58 g, 25.17 mmol) was added to give an orange-brown suspension. Volatiles were evaporated after 1.5 h. The residue was triturated with pentane and evaporated once more. The material was extracted with toluene and filtered through Celite to give a dark amber filtrate. The filtrate was concentrated under reduced pressure, after which the residue was dispersed in heptane and concentrated again to a yellow cake. Recrystallization from hot heptane afforded the pure product as a pale yellow powder (4.80 g, 8.92 mmol, 35% recrystallization yield). 1 H NMR (400MHz, toluene-d8)δ 7.51(d,1H,ArH),7.46(d,1H,ArH),7.22(t,1H,ArH),7.12(m,1H,ArH),7.09(td,1H,Ar H),7.02(m,2H,ArH),6.91(s,1H,ArH),6.64(d,1H,ArH),5.78(m,1H,allyl-H),5.56(dq, 1H, allyl-H), 5.15 (dq, 1H, allyl-H), 4.40 (s, 1H, SiCH), 4.23 (m, 2H, allyl-H), 3.38 (s, 3H, OMe), 3.29 (s, 3H, NMe), 2.44 (s, 3H, ArMe), 1.42 (s, 9H, t-Bu), 1.22-0.70 (m, 10H, SiEt2).

[0274] Example 11 : 10-((2-(allyloxy)-3-(tert-butyl)-5-methoxyphenyl)diethylsilyl)-5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole (965 mg, 1.79 mmol) was dissolved in toluene (30 mL) to give a yellow solution. NEt3 (1.13 mL, 8.07 mmol) was added via syringe with no observable change. n-BuLi solution (1.6 M in hexanes, 2.52 mL, 4.04 mmol) was added via syringe with the solution first darkening to a yellow-orange color followed by the formation of a precipitate. The bright yellow suspension was stirred for 1 h. Ti(NMe2)2Cl2 (445 mg, 2.15 mmol) was dissolved in toluene to give a red-brown solution and added to the yellow reaction mixture to give a dark brown suspension. This was heated to 90° C. for 3 hours, after which chlorotrimethylsilane (0.57 mL, 4.49 mmol) was added and the reaction mixture was maintained at 80° C. overnight. The volatiles were removed under reduced pressure. The brown residue was dispersed with hot heptane and the solution was concentrated again. The residue was then extracted with toluene and filtered through Celite to remove dark solids from the brown filtrate. The filtrate was concentrated under reduced pressure. The residue was slurried in minimal hot heptane at 90° C. for 15 minutes, after which the slurry was cooled to −35° C. for 2 hours. The solid was collected on a medium porosity frit, rinsed with minimal pentane, and dried under reduced pressure to give the product as a dark red-brown solid (874 mg, 1.42 mmol, 79% recrystallization yield). 1 H NMR (400MHz, toluene-d8)δ 7.90(d,1H,ArH),7.76(d,1H,ArH),7.32(t,1H,ArH),7.22(m,2H,ArH),7.08(d,1H,ArH),7.00(m,1H,ArH),6.80(d,1H,Ar H),6.50(s,1H,ArH),3.60(s,3H,OMe),3.59(s,3H,NMe),2.12(m,3H,ArMe),1.64-1.05(m,10H,SiEt2),1.04(s,9H,t-Bu).

[0275] Example 12 [ka] Example 11 (1.82 g, 2.96 mmol) was dissolved in toluene (80 mL) to give a dark brown solution. With vigorous stirring, MeMgBr solution (3.0 M in Et2O, 2.17 mL, 6.52 mmol) was added via syringe, which immediately gave an orange-brown color. This was stirred for 30 minutes, after which the reaction mixture was evaporated under reduced pressure. The residue was extracted with toluene, filtered through Celite, and concentrated once more. The residue was slurried in heptane and evaporated once more to give the product as an orange powder (1.47 g, 2.65 mmol, 87% yield). 1 H NMR (400MHz, toluene-d8)δ 7.87(m,1H,ArH),7.73(m,1H,ArH),7.22-7.10(m,4H,ArH),6.94(d,1H,ArH),6.76(d,1H,ArH),6.55(s,1H,ArH),3.62(s,3H,OM e),3.52(s,3H,NMe),2.09(s,3H,ArMe),12.5(s,9H,t-Bu),1.24-1.00(m,10H,SiEt2),0.17(s,3H,TiMe),-0.03(s,3H,TiMe2).

[0276] Example 13 [ka] 3,5-Di-tert-butyliodobenzene: [ka] To a solution of 1-bromo-3,5-di-tert-butylbenzene (5.39 g, 20 mmol) in THF (50 mL) at 78° C., n-BuLi solution (1.6 M in hexanes, 13.12 mL, 21 mmol) was added dropwise over 10 min via cannula. A white precipitate formed and the reaction mixture was stirred vigorously at −78° C. for 1 h. To the resulting slurry, at −78° C., a solution of iodine (5.33 g, 20 mmol) in THF (50 mL) was added slowly over 20 min. Near the end of the addition, the iodine color persisted. The cold bath was removed and the solution was stirred overnight at ambient temperature. The volatiles were removed under reduced pressure and then distilled water (approximately 50 mL) was added to the flask. Saturated aqueous Na2S2O3 (50 mL) was added dropwise to the flask until the iodine color disappeared. The combined aqueous mixture was extracted with diethyl ether, and the organic layer was dried over anhydrous MgSO4, filtered, and then concentrated under reduced pressure. The crude product was dissolved in pentane and passed through a column of activated neutral alumina with several passes of additional pentane. The pentane solution was evaporated to dryness to give a colorless crystalline solid (6.124 g). 1 H NMR(400MHz,CDCl3)δ 7.49(s,1H,ArH),7.28(s,2H,ArH),1.56(s,18H,tBu).

[0277] 5-(3,5-di-tert-butylphenyl)-8-methyl-5,10-dihydroindeno[1,2-b]indole: [ka] 3,5-Di-tert-butyliodobenzene (2.0 g, 6.32 mmol), 8-methyl-5,10-dihydroindeno[1,2-b]indole (1.39 g, 6.32 mmol), potassium phosphate (4.0 g, 18.96 mmol), copper(I) iodide (1.58 g, 1.58 mmol), N,N'-dimethylethylenediamine (500 mg) and toluene (50 mL) were charged to a thick-walled long Kontes flask in a glove box. The flask was sealed and the stirred mixture was heated at 130 °C for 48 h. After cooling the reaction to ambient temperature, the product mixture was filtered and the filter cake was separated with toluene (3 × 10 ml). The solid was rinsed with 10 mL of saturated aqueous ammonium chloride (50 mL) then dried over anhydrous MgSO4, filtered and concentrated under reduced pressure. The solid was redissolved in diethyl ether and the solution passed through a column of activated neutral alumina and washed with more diethyl ether. The diethyl ether solution was concentrated under reduced pressure to approximately 20 mL whereupon the product began to crystallize. After cooling the mixture to -20°C overnight, the crystalline solid was isolated by decantation and dried under reduced pressure to give 1.68 g of material. The mother liquor was evaporated to dryness to give an additional 120 mg of pure product. The combined yield was 1.80 g (70%). 1 H NMR(400MHz,CD2Cl2)δ:7.55-7.51(m,2H,ArH),7.48-7.45(m,1H,ArH),7.41(d,J=2Hz,2H,ArH),7.30(d,J=8.4Hz,1H,ArH),7.19-7.1 4(m,2H,ArH),7.19-7.09(m,1H,ArH),7.00(dd,J=8.5Hz,J=2Hz,1H,ArH),3.78(s,2H,indeno-H),2.47(s,3H,ArCH3),1.40(s,18H,tBu).

[0278] 10-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diethylsilyl)-5-(3,5-di-tert-butylphenyl)-8-methyl-5,10-dihydroindeno[1,2-b]indole: [ka] To a solution of 5-(3,5-di-tert-butylphenyl)-8-methyl-5,10-dihydroindeno[1,2-b]indole (1.32 g, 3.24 mol) in THF (30 mL) was added n-BuLi solution (1.6 M in hexanes, 2.10 mL, 3.36 mmol) at -35°C. The color of the solution became bright orange-red. The solution was stirred at ambient temperature for 3 h, then a solution of (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodiethylsilane (1.052 g, 3.24 mmol) in THF (5 mL) was added. The mixture was stirred overnight at ambient temperature and further stirred at 60°C for 6 h. The reaction mixture was concentrated under reduced pressure, and the residue was redissolved in pentane (40 mL) and passed through a column of activated neutral alumina, rinsing with additional portions of pentane. The volume of the combined pentane eluents was reduced to approximately 5 mL and the solution was cooled overnight to −35° C. The colorless solid was isolated by filtration, washed with cold pentane, and then dried under vacuum to give 1.67 g (74%) of material. 1 H NMR(400MHz,CD2Cl2)δ:7.50(t,J=2Hz,1H,ArH),7.40-7.35(m,1H,ArH),7.33(d,J=2Hz,2H,ArH), 7.25(d,J=8Hz,1H,ArH),7.12-7.04(m,2H,ArH),6.94-6.87(m,2H,ArH),6.45(s,1H,ArH),6.08-6 .97 (m, 1H, allyl H), 5.55 (dq, 1H, allyl H), 5.28 (dq, 1H, allyl H), 4.48 (s, 1H), 4.29 (qm, 2H, allyl H), 2.29 (s, 3H, ArCH3), 2.22 (s, 3H, ArCH3), 1.42 (s, 9H, tBu), 1.38 (s, 18H, tBu), 1.34-0.50 (m, 10H, SiEt2).

[0279] Example 13 : 10-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diethylsilyl)-5-(3,5-di-tert-butylphenyl)-8-methyl-5,10-dihydroindeno[1,2-b]indole (0.81 g, 1.16 mmol) and triethylamine (0.6 g, 4.5-fold excess) were dissolved in toluene (30 mL) and the resulting solution was cooled to -35°C for 0.5 h. n-BuLi solution (1.6 M in hexanes, 2.52 mL, 2.41 mmol) was added to the solution with stirring and the mixture was allowed to warm to ambient temperature and stirred for 2.5 h. The reaction mixture was cooled to -35°C and then solid Ti(NMe2)2Cl2 (240 mg, 1.16 mmol) was added, followed by a small amount of toluene to ensure quantitative addition. The reaction mixture was stirred at ambient temperature overnight and then heated at 90° C. for an additional 3 hours. The red-orange solution was filtered and the filtrate was collected in a separate flask. Chlorotrimethylsilane (350 mg) was added and the sealed flask was heated at 80° C. overnight. The volatiles were removed under reduced pressure and the residue was dissolved in pentane (30 mL). A green-brown solid began to crystallize and the flask was cooled to −35° C. for 4 hours. The precipitate was isolated by filtration and the collected solid was washed several times with cold (−35° C.) pentane. The solid was collected and dried under reduced pressure to give the product as a green-brown solid (0.574 g, 64%). 1 H NMR(400MHz,CD2Cl2)δ:8.14(br.s,1H,ArH),7.93(d,J=8.7Hz,1H,ArH),7.67(d,J=8Hz,1H ,ArH),7.60(s,1H,ArH),7.55(t,J=7.7Hz,1H,ArH),7.50-7.40(m,2H,ArH),7.30(s,1H,ArH ),7.24(s,1H,ArH),7.22(s,1H,ArH),7.12(d,1H,ArH),6.34(s,1H,ArH),2.53(s,3H,ArCH 3),2.08(s,3H,ArCH3),1.41(br.s,18H,tBu),1.35-1.01(m,10H,SiEt2),0.79(s,9H,tBu).

[0280] Example 14 [ka] Example 14 : Example 13 (0.574 g, 0.743 mol) was dissolved in toluene (30 mL) and MeMgBr solution (3.0 M in diethyl ether, 0.75 ml, 2.25 mmol) was added. The mixture was stirred overnight and then evaporated to dryness under reduced pressure. The residue was dissolved in pentane, filtered, and the filtrate was evaporated to dryness to give an orange solid. The solid was dissolved again in pentane and the solution was filtered to remove very small amounts of solid. The filtrate was evaporated to dryness to give a pure orange crystalline solid (489 mg, 90%). 1 H NMR (400MHz, toluene-d8)δ 7.83(d,J=8.5Hz,1H,ArH),7.78(d,J=8.5Hz,1H,ArH),7.75-7.61(br.s,1H,ArH),7.59(m,1H,ArH) ,7.44(m,1H,ArH),7.40(d,J=8.5Hz,1H,ArH),7.32(s,1H,ArH),7.13-7.06(m,1H,ArH),6.96-7.03 (m,1H,ArH),6.91(d,J=8Hz,1H,ArH),6.76(s,1H,ArH),2.43(s,3H,ArCH3),2.09(s,3H,ArCH3),1. 37(s,9H,tBu),1.30(s,18H,tBu),1.28-1.04(m,10H,SiEt2),0.37(s,3H,TiMe),0.24(s,3H,TiMe).

[0281] Example 15 [ka] Dichlorodipropylsilane: Ground magnesium turnings (1.58 g, 65 mmol) were weighed into a 250 mL flask in a glove box and THF (5 mL) was added. A small amount of 1-bromopropane (approximately 0.5 mL from a total of 5.534 g, 45 mmol) was added dropwise with stirring, initiating the reaction within minutes. The reaction mixture was further diluted with additional THF while the remainder of the 1-bromopropane was continuously added to maintain a gentle reflux for approximately 1 h. After stirring for an additional hour, the flask was sealed with a septum and stirred overnight. The resulting mixture was filtered and the excess magnesium turnings were washed with a small amount of THF. The combined filtrate was added dropwise to a solution of silicon tetrachloride (3.822 g, 22.5 mmol) in THF (100 mL) at -78 °C over 1 h. The resulting slurry was stirred overnight while the cold bath (CO2 / EtOH) was allowed to warm slowly to ambient temperature. The reaction mixture was heated to 45°C for 1 h and then the volatiles were removed under reduced pressure. The residue was taken up in pentane, 1,4-dioxane (ca. 1.5 mL) was added and the resulting mixture was stirred for 1 h to precipitate residual magnesium halide salts. The mixture was filtered and the resulting solution was carefully concentrated under reduced pressure and then fractionally distilled under static vacuum (head temperature: 32°C, bath temperature: 45-50°C) to give the product as a clear oil (3.1 g, 74%). 1 H NMR (400 MHz, toluene-d8) δ 1.43-1.30 (m, 2H), 0.83 (t, J=7 Hz, 3H), 0.79-0.73 (m, 2H).

[0282] (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodipropylsilane: [ka] To a solution of 2-(allyloxy)-1-bromo-3-(tert-butyl)-5-methylbenzene (1.415 g, 5 mmol) in Et2O (40 mL) cooled to -78°C, n-BuLi solution (1.6 M in hexanes, 3.27 mL, 5.2 mmol) was added dropwise over 5 min via cannula. After a few minutes, the reaction solution became cloudy and a white slurry formed. The mixture was stirred at -78°C for 2 h, then a solution of dichlorodipropylsilane (2.31 g, 12.5 mmol) in Et2O (5 mL) was added dropwise over 5 min while maintaining the temperature at -78°C. The reaction was stirred overnight while the cold bath (CO2 / EtOH) was allowed to warm slowly to ambient temperature. The volatiles were removed under reduced pressure and the residue was dissolved in pentane. The mixture was filtered through a pad of Celite and the filtrate was concentrated to give the product as a pale orange oil (1.79 g, ca. 100%). 1 H NMR (400 MHz, toluene-d8) δ 7.53 (dd, J = 2 Hz and 1 Hz, 1H), 7.22 (dd, J = 2 Hz and 1 Hz, 1H), 5.87-5.76 (m, 1H), 5.50 (dq, 1H), 5.29 (dq, 1H), 4.30 (m, 2H), 2.166 (s, 3H), 1.60-1.48 (m, 4H), 1.387 (s, 9H), 1.25-1.10 (m, 4H), 0.97 (t, 6H).

[0283] 10-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)dipropylsilyl)-5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole: [ka] To a solution of 5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole (1.157 g, 4.96 mmol) in THF (35 mL) cooled to -35°C was added a solution of n-BuLi (1.6 M in hexanes, 3.10 mL, 4.96 mmol) in hexanes. The resulting solution was stirred for 1 h while warming to ambient temperature. A solution of (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodipropylsilane (1.75 g, 4.96 mmol) in THF (10 mL) was added dropwise over several minutes and the reaction mixture was stirred overnight. The resulting light brown mixture was heated to 55°C for 1 h and then the volatiles were removed under reduced pressure. The residue was dissolved in pentane (approximately 30 mL) and then passed through a calcined neutral alumina plug (calcined at 500° C. overnight and stored under inert atmosphere), which was then rinsed with an additional 15-20 mL of pentane. The pentane solution was concentrated to a volume of approximately 5-6 mL, and a yellow solid began to crystallize. After cooling to −35° C. overnight, the solid material was isolated by filtration, rinsed with a small amount of cold pentane, and then dried under vacuum to give the product as a yellow crystalline solid (1.85 g, 67% yield). 1 H NMR (400 MHz, toluene-d8) δ 7.52 (d, J = 7 Hz, 1H), 7.47 (d, J = 7 Hz, 1H), 7.30 (d, J = 2 Hz, 1H), 7.22 (t, J = 7 Hz, 1H), 7.09 (td, J = 7 Hz and 1 Hz, 1H), 7.06 (d, J = 2 Hz, 1H), 7.00 (d, J = 1 Hz, 2H), 6.71 (s, 1H), 5 .87-5.76(m,1H),5.55(dq,1H),5.15(dq,1H),4.45(s,1H),4.30(qq,2H),3.42(s, 3H), 2.41 (s, 3H), 2.17 (s, 3H), 1.47 (s, 9H), 1.35-1.13 (m, 6H), 1.05-0.85 (m, 8H).

[0284] Example 15 : 10-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)dipropylsilyl)-5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole (1.850 g, 3.364 mmol), triethylamine (2.12 mL, 1.53 g, 15.1 mmol) and toluene (30 mL) were combined in a 200 mL Kontes flask. n-BuLi solution (1.6 M in hexanes, 4.33 mL, 6.93 mmol) was added dropwise with stirring at ambient temperature. The resulting orange solution was stirred for 2 h after which a slurry was formed. To this slurry was added a solution of Ti(NMe2)2Cl2 (0.696 g, 3.364 mmol) in toluene (ca. 50 mL). The mixture was stirred at 60° C. overnight and then at 90° C. for an additional 3 h. The dark orange solution was filtered through a pad of Celite and chlorotrimethylsilane (2.60 g, 23.9 mmol) was added to the filtrate. After briefly applying vacuum to the headspace of the mixture, the flask was sealed and the reaction was stirred at 80° C. overnight. The resulting green-brown solution was evaporated to dryness under reduced pressure and the solid was washed several times with pentane. The solid was dried under vacuum to give the product as a green-brown solid (1.53 g, 72%). 1 H NMR (400MHz, toluene-d8)δ 7.97(d,J=8Hz,1H),7.77(d,J=8Hz,1H),7.51(s,1H),7.33-7.27(m,2H),6.99(d,J=7Hz,1H),7.01(d,J=7Hz,1H),6.79(d,J =7Hz,1H),6.46(s,1H),3.60(s,3H),2.41(s,3H),2.07(t,3H),1.75-1.18(m,8H),0.96(t,J=7Hz,3H),0.87(t,J=7Hz,3H).

[0285] Example 16 [ka] Example 16 : To a solution of Example 15 (1.534 g, 2.38 mmol) in toluene (25 mL) at ambient temperature was added MeMgBr solution (3.0 M in Et2O, 4.0 mL, 12 mmol). The resulting mixture was stirred overnight and then concentrated under reduced pressure. The residue was slurried in pentane (60 mL), stirred for 2 hours, filtered, and the solid cake was washed multiple times with additional pentane (5 x 10 mL). The combined filtrate was reduced in volume to approximately 10 mL under reduced pressure, and a bright orange crystalline solid was deposited, isolated by decantation, washed with cold pentane, and dried under vacuum. The mother liquor was concentrated under reduced pressure and placed in a -35°C freezer in a glove box overnight, where a second crop of solid was deposited, isolated, washed with cold pentane, and dried under vacuum. 1 Analysis of both crops of material by H NMR showed greater than 95% purity. The combined product was isolated as a light orange solid (0.90 g, 63%). 1 H NMR (400MHz, toluene-d8) δ 7.88(dd,J=7Hz and 1Hz,1H),7.83(dd,J=7Hz and 1Hz,1H),7.46(d,J=2Hz,1H),7.29 (d,J=2Hz,1H),7.21-7.12(m,2H),6.95(d,J=8Hz,1H),6.77(d,J=8Hz,1H),6.54(s ,1H),3.54(s,3H),2.43(s,3H),2.08(s,3H),1.68-1.42(m,4H),1.40-1.29(m,4H) ,1.28(s,9H),0.94(t,J=7Hz,3H),0.92(t,J=7Hz,3H),0.22(s,3H),0.002(s,3H).

[0286] Example 17 [ka] (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodimethylsilane: [ka] This material was prepared essentially as described by Senda, T. et al., Macromolecules 2009, 42, 8006-8009. 2-(allyloxy)-1-bromo-3-(tert-butyl)-5-methylbenzene (17.706 g, 60 mmol) was dissolved in diethyl ether (400 mL) in a 2 L, two-necked round-bottom flask equipped with a nitrogen inlet and a rubber septum. The flask was cooled to -78 °C and n-BuLi solution (1.6 M in hexanes, 40 mL, 64 mmol) was added slowly via cannula. The reaction mixture was stirred at -78 °C for 2 h, during which time a fine white solid precipitated. Using a syringe, Me2SiCl2 (25.7 g, 180 mmol) was added rapidly. The reaction mixture was allowed to warm to ambient temperature overnight. The volatiles were removed under reduced pressure and the oily residue was extracted with pentane and filtered through Celite to give a clear, colorless filtrate. The volatiles were removed to give the desired product as a waxy, crystalline solid (17.71 g, 99% yield). 1 H NMR (400 MHz, toluene-d8) δ 7.40 (d, 1H, ArH), 7.22 (d, 1H, ArH), 5.80 (m, 1H, O-allyl), 5.48 (dq, 1H, O-allyl), 5.11 (dq, 1H, O-allyl), 4.34 (m, 2H, O-allyl), 2.14 (s, 3H, ArCH3), 1.38 (s, 9H, Ar-t-Bu), 0.66 (s, 6H, SiMe2).

[0287] 10-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)dimethylsilyl)-5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole: [ka] 5,8-Dimethyl-5,10-dihydroindeno[1,2-b]indole (2.510 g, 10.76 mmol) was dissolved in THF (60 mL) in a 100 mL Schlenk flask. With vigorous stirring, n-BuLi solution (1.6 M in hexanes, 7.0 mL, 11 mmol) was added and the dark red reaction mixture was stirred for 1 h. Slow bubbling (butane) was observed initially but subsided over time. After 4 h, the solution was cooled to -78°C and a solution of (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodimethylsilane (3.401 g, 11.45 mmol) in toluene (50 mL) was added to give a dark orange-red solution. The reaction mixture was allowed to warm overnight and then the volatiles were removed under reduced pressure to give a sticky brown oil. The crude material was dissolved in toluene and passed through a Celite plug. The volatiles were removed under reduced pressure and the solid was dissolved in hot heptane. Upon cooling, a yellow crystalline solid precipitated, which was then collected on a sintered glass funnel and dried under reduced pressure (3.727 g, 67% yield). 1 H NMR(400MHz,CDCl3)δ 7.71(d,1H,ArH),7.36(d,1H,ArH),7.30(m,1H,ArH),7.30(t,1H,ArH),7.10(dt,1H,ArH)7 .05(d,1H,ArH),6.98(dd,1H,ArH),6.46(s,1H,ArH)6.08(m,1H,allyl-H),5.58(dq,1H,allyl-H ),5.32(dq,1H,allyl-H),4.45(qd,1H,allyl-H),4.34(s,1H,Si-CH),4.06(s,3H,NCH3),2.33( s,3H,ArCH3),2.31(s,3H,ArCH3),1.49(s,9H,t-Bu),0.13(s,3H,SiMe),0.02(s,3H,SiMe).

[0288] Example 17 : 10-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)dimethylsilyl)-5,8-dimethyl-5,10-dihydroindeno[1,2-b]indole (3.727 g, 7.14 mmol) was dissolved in toluene (60 mL) in a 100 mL Schlenk flask and cooled to −78° C. for 15 min. Triethylamine (3.2 mL, 2.3 g, 23 mmol) and n-BuLi solution (1.6 M in hexanes, 9.2 mL, 14.7 mmol) were added successively. The pale yellow solution was allowed to warm to ambient temperature and stirred for 2 h, after which the reaction mixture was cooled again to −78° C. for 15 min. Ti(NMe2)2Cl2 (1.700 g, 8.21 mmol) was added as a slurry in toluene and the reaction mixture was allowed to warm to ambient temperature over 30 min and subsequently heated to 90° C. for 30 min to give a dark red-brown slurry. The mixture was cooled to 80° C. and chlorotrimethylsilane (2.3 mL, 2.0 g, 18 mmol) was added via syringe and the mixture was heated to 80° C. overnight. Approximately 1 / 5 of the volatiles were removed under reduced pressure and the mixture was filtered through a Celite pad. The filtrate was stripped of volatiles under reduced pressure and the residue was recrystallized from hot heptane to give a small crop of pure product. Further pure product was obtained by further washing the filter cake with hot toluene (approximately 500 mL total) and then dichloromethane (60 mL) followed by combining the filtrates, concentrating under reduced pressure, and recrystallizing / triturating the resulting solid with hot heptane, isolating the solid by filtration, and then drying under reduced pressure to give the pure product as a green crystalline solid (1.57 g total, 37% recrystallization yield). 1 H NMR (400MHz, toluene-d8)δ 7.82(d,1H,ArH),7.73(d,1H,ArH),7.41(d,1H,ArH),7.29-7.15(m,3H,ArH),6.99(d,1H,ArH),6.78(d,1H,ArH),6.46(s,1H ,ArH),3.58(s,3H,NCH3),2.38(s,3H,ArCH3),2.05(s,3H,ArCH3),1.03(s,9H,t-Bu),0.81(s,3H,SiMe),0.65(s,3H,SiMe).

[0289] Example 18 [ka] Example 18 : To a solution of Example 17 (1.234 g, 2.16 mmol) in toluene (20 mL) was added MeMgBr solution (3.0 M in diethyl ether, 1.50 mL, 4.5 mmol) to give an immediate bright orange solution. The volatiles were removed under reduced pressure and the residue was extracted with toluene and filtered through a Celite pad. The bright orange filtrate was collected and concentrated under reduced pressure to give an amorphous orange residue. The residue was dissolved in pentane and concentrated under reduced pressure to give the desired product as a bright orange powder (1.05 g, 92% yield). 1 H NMR (400MHz, toluene-d8)δ 7.85(d,1H,ArH),7.69(d,1H,ArH),7.39(s,1H,ArH),7.25(s,1H,ArH),7.19 -7.10(m,2H,ArH),6.95(d,1H,ArH),6.77(d,1H,ArH),6.59(s,1H,ArH),3.5 3(s,3H,NCH3),2.39(s,3H,ArCH3),2.07(s,3H,ArCH3),1.28(s,9H,t-Bu),0.70(s,1H,SiMe),0.63(s,1H,SiMe),0.17(s,3H,TiCH3),0.01(s,3H,TiCH3).

[0290] Example 19 [ka] 1,3,8-trimethyl-5,10-dihydroindeno[1,2-b]indole: [ka] 4,6-Dimethyl-2,3-dihydro-1H-inden-1-one (2.288 g, 14.28 mmol) was dissolved in isopropanol (200 mL) in a round bottom flask to give a clear yellow solution. para-Toluenesulfonic acid monohydrate (82 mg, 0.428 mmol) and p-tolylhydrazine hydrochloride (2.265 g, 14.28 mmol) were added and a condenser was attached to the flask. The reaction mixture was heated to 85° C. for 2 h, then concentrated under reduced pressure and cooled to −33° C. The precipitate was collected on a sintered glass frit, rinsed with a minimum amount of cold isopropanol, and residual volatiles were removed under reduced pressure to give the desired product as a white solid (1.82 g, 7.36 mmol, 52% recrystallization yield). 1 H NMR(400MHz,CDCl3)δ 8.25(br,1H,NH),7.43(s,1H,ArH),7.36(d,1H,ArH),7.21(s,1H,ArH),7.00(m,1H,ArH),6 .95(s,1H,ArH),3.67(s,2H,CH2),2.63(s,3H,ArMe),2.49(s,3H,ArMe),2.41(s,3H,ArMe).

[0291] 1,3,5,8-Tetramethyl-5,10-dihydroindeno[1,2-b]indole: [ka] 1,3,8-Trimethyl-5,10-dihydroindeno[1,2-b]indole (1.820 g, 7.358 mmol) was slurried in THF (100 mL) to give a pale yellow cloudy mixture. Sodium tert-butoxide (743 mg, 7.726 mmol) in THF (20 mL) was added and the mixture was stirred for 1 h. Iodomethane (0.48 mL, 7.726 mmol) was added dropwise via syringe and the mixture was stirred overnight. Volatiles were removed from the yellow suspension under reduced pressure. The residue was dissolved in CHCl (100 mL) and washed with water (100 mL). The aqueous layer was extracted with additional CHCl (2×50 mL) and the combined organic layers were rinsed with brine (50 mL), dried over anhydrous NaSO, filtered and the clear yellow filtrate was evaporated to dryness. Recrystallization from hot heptane afforded the desired product as a white solid (1.013 g, 3.876 mmol, 53% recrystallization yield). 1 H NMR(400MHz,CDCl3)δ 7.40(s,1H,ArH),7.27(d,1H,ArH),7.21(s,1H,ArH),7.04(d,1H,ArH),6.96(s,1H,ArH),4 .09(s,3H,NMe),3.64(s,2H,CH2),2.77(s,3H,ArMe),2.49(s,3H,ArMe),2.39(s,3H,ArMe).

[0292] 10-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diethylsilyl)-1,2,5,8-tetramethyl-5,10-dihydroindeno[1,2-b]indole: [ka] 1,3,5,8-Tetramethyl-5,10-dihydroindeno[1,2-b]indole (1.013 g, 3.876 mmol) was dissolved in THF (50 mL). With vigorous stirring, n-BuLi (1.6 M in hexanes, 2.54 mL, 4.070 mmol) was added to give a dark red solution. After 1 h, (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodiethylsilane (1.260 g, 3.876 mmol) was added and the mixture was stirred for 1 h. The volatiles were removed under reduced pressure and the residue was extracted with pentane and filtered through a Celite pad. The clear amber filtrate was evaporated to give the desired product as a yellow sticky solid (1.942 g, 3.532 mmol). 1 H NMR (400MHz, toluene-d8) δ 7.30(d,1H,ArH),7.17(s,1H,ArH),7.04(m,2H,ArH),6.97(d,1H,ArH),6.83(m,2H ,ArH),5.83(m,1H,allyl-H),5.59(dq,1H,allyl-H),5.16(dq,1H,allyl-H),4.43(s,SiC H),4.32(m,2H,Allyl-H),3.51(s,3H,NMe),2.51(s,3H,ArMe),2.42(s,3H,ArMe),2. 31(s,3H,ArMe),2.16(s,3H,ArMe),1.48(s,9H,t-Bu),1.16-0.68(m,10H,SiEt2).

[0293] Example 19 : 10-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diethylsilyl)-1,3,5,8-tetramethyl-5,10-dihydroindeno[1,2-b]indole (1.942 g, 3.532 mmol) was dissolved in toluene (80 mL) in a 200 mL Schlenk flask to give a clear yellow solution. With vigorous stirring, NEt3 (2.22 mL, 15.89 mmol) and n-BuLi (1.6 M in hexanes, 4.97 mL, 7.947 mmol) were added successively. After 2 h, Ti(NMe2)2Cl2 (877 mg, 4.238 mmol) was added as a red-brown solution in toluene (20 mL). The dark brown solution was sealed in the flask, the headspace was briefly evacuated, and the reaction mixture was heated to 90 °C for 3 h. Chlorotrimethylsilane (0.90 mL, 7.064 mmol) was injected into the dark brown solution and the reaction mixture was heated to 80° C. overnight. The volatiles were removed under reduced pressure and the dark green solid residue was extracted with toluene, filtered through a Celite pad and washed several times with additional toluene until the filtrate was colorless. The combined dark green-brown extracts were evaporated to dryness, slurried in hot heptane and stored in a −33° C. freezer overnight. The solid was collected on a medium porosity frit, rinsed with a minimum of cold pentane and dried under vacuum to give the desired product as a dark green solid (1.271 g, 2.029 mmol, 56% yield). 1 H NMR (400MHz, toluene-d8)δ 7.62(s,1H,ArH),7.47(s,1H,ArH),7.28(s,1H,ArH),7.00(m,1H,ArH),6.90(s,1H,ArH),6.82(d,1H,ArH),6.55(m,1H,ArH),3.63(s ,3H,NMe),2.72(s,3H,ArMe),2.41(s,3H,ArMe),2.36(s,3H,ArMe),2.08(s,3H,ArMe),1.71-1.05(m,10H,SiEt2),1.04(s,9H,t-Bu).

[0294] Example 20 [ka] Example 20 : Example 19 (850 mg, 1.357 mmol) was dissolved in toluene (50 mL) to give a dark greenish brown solution. MeMgBr solution (3.0 M in Et2O, 0.97 mL, 2.910 mmol) was added via syringe and the resulting dark orange brown solution was stirred for 2 h. The volatiles were evaporated under reduced pressure and the residue was triturated with heptane and evaporated once more to remove residual Et2O. The dry residue was extracted with toluene and filtered through a Celite pad. The clear orange filtrate was evaporated to dryness to give a light orange powder (677 mg, 1.156 mmol, 85% yield). 1 H NMR (400MHz, toluene-d8)δ 7.55(s,1H,ArH),7.41(m,1H,ArH),7.28(d,1H,ArH),6.96(m,1H,ArH),6.86(s,1H,ArH),6.81(d,1H,ArH),6.65(s,1H,ArH),3.58(s,3H,NMe),2.7 1(s,3H,ArMe),2.42(s,3H,ArMe),2.30(s,3H,ArMe),2.11(m,3H,ArMe),1.45-1.04(m,19H,SiEt2 and t-Bu),0.21(s,3H,TiMe),0.05(s,3H,TiMe).

[0295] Examples 21-28 [ka] 8-Bromo-5,10-dihydroindeno[1,2-b]indole: [ka] Para-toluenesulfonic acid monohydrate (522 mg, 3 mmol), p-bromophenylhydrazine hydrochloride (16.92 g, 76 mmol) and 1-indanone (10.01 g, 76 mmol) were charged to a 500 mL flask followed by isopropanol (155 mL). Some mild exotherm was observed as the suspension was mixed, forming a bright yellow color. The mixture was heated to 84° C. overnight, after which the mixture turned dark brown and a suspension of off-white solids formed. The mixture was cooled to ambient temperature and aqueous NaOH (approximately 2 g in 100 mL) was slowly added to the mixture, forming further crystalline precipitate. The mixture was filtered through a sintered glass frit and the brownish solid collected on the frit was washed with water (20 mL). This solid was then dissolved in ethyl acetate, filtered through a glass frit and the filtrate was dried over anhydrous MgSO4. The dried solution was filtered and the volatiles removed under dynamic vacuum to give an off-white solid. The solid was dried under vacuum to give 16.5 g of crude product. Recrystallization from hot heptane followed by filtration and drying under vacuum afforded the pure product as an off-white free-flowing solid (15.48 g, 72% yield). 1 H NMR(400MHz,CDCl3)δ 8.39(s,1H,NH),7.77(s,1H,ArH),7.56(d,1H,ArH),7.49(d,1H,ArH),7.35(t,1H,ArH),7.31(d,1H,ArH),7.24(d,1H,ArH),3.71(s,2H,CH2).

[0296] 8-Bromo-5-methyl-5,10-dihydroindeno[1,2-b]indole: [ka] To a stirred dark brown solution of 8-bromo-5,10-dihydroindeno[1,2-b]indole (12.80 g, 45 mmol) in THF (100 mL) at ambient temperature was added a solution of NaOtBu (4.34 g, 45 mmol) in THF (100 mL) via cannula. After rapid stirring for 2 h, iodomethane (2.8 mL, 45 mmol) was added dropwise via syringe and the mixture was allowed to stir for an additional 3 h. The volatiles were removed under dynamic vacuum at 45° C. and the residue was taken up and partitioned between dichloromethane (200 mL), deionized water (150 mL) and saturated aqueous NH4Cl (50 mL). The organic layer was separated and the aqueous layer was washed multiple times with additional dichloromethane (2×50 mL). The volatiles were removed using reduced pressure and the resulting solid was dried under vacuum. Recrystallization from a mixture of heptane and ethyl acetate (approximately 3:1), followed by filtration and drying of the solid under vacuum, afforded the pure product as an off-white solid (11.67 g, 87%). 1 H NMR(400MHz,CDCl3)δ 7.75(s,1H,ArH),7.67(d,1H,ArH),7.55(d,1H,ArH),7.35(t,1H,ArH),7.28(m,1H,ArH),7.25(m,2H,ArH),4.05(s,3H,NCH3),3.68(s,2H,CH2).

[0297] 5-Methyl-8-(pyrrolidin-1-yl)-5,10-dihydroindeno[1,2-b]indole: [ka] 8-Bromo-5-methyl-5,10-dihydroindeno[1,2-b]indole (7.79 g, 26 mmol), sodium tert-butoxide (3.76 g, 39.16 mmol), and pyrrolidine (5 mL, 61 mmol) were combined in a 200 mL Schlenk vessel under an inert atmosphere. A solution of palladium acetate (123 mg, 0.5 mmol) and tri-tert-butylphosphine (211 mg, 1 mmol) in 100 mL of toluene was then transferred via cannula to the flask, which was then heated to 80° C. overnight with rapid stirring. The temperature was increased to 100° C. and the mixture was stirred for 20 hours. The volatiles were removed under dynamic vacuum to give a brown solid. Additional toluene was added and the mixture was stirred to partially dissolve the brown solid. The solution was passed through a plug of neutral alumina and the volatiles were removed under dynamic vacuum to leave 5.61 g of crude product. Additional toluene was passed through an alumina plug and the volatiles were removed leaving more solid. The crude material was recrystallized by dissolving in refluxing heptane followed by cooling to ambient temperature to give colorless needles which were isolated by decantation and dried under vacuum (4.82 g, 64%). 1 H NMR(400MHz,CDCl3)δ 7.65(s,1H,ArH),7.55(d,1H,ArH),7.35(t,2H,ArH),7.23(m,2H,ArH),6.74(m,H,Ar H),4.04(s,3H,NCH3),3.70(s,2H,CH2),3.39(s,4H,N(CH2)2),2.08(s,4H,(CH2)2).

[0298] 2,7,7,10,10-Pentamethyl-5,7,8,9,10,12-hexahydrobenzo[5,6]indeno[1,2-b]indole: [ka] Para-tolylhydrazine hydrochloride (793 mg, 5.0 mmol), 5,5,8,8-tetramethyl-2,3,5,6,7,8-hexahydro-1H-cyclopenta[b]naphthalen-1-one (1.212 g, 5.0 mmol), para-toluenesulfonic acid monohydrate (48 mg, 0.25 mmol) and isopropanol (50 mL) were combined in a flask and the mixture was refluxed overnight under an inert atmosphere of nitrogen. The mixture was cooled to ambient temperature and the volatiles were removed under reduced pressure. The tan residue was partitioned between ethyl acetate (100 mL) and water (50 mL). The organic layer was washed with water (2×50 mL), brine (50 mL), dried over anhydrous Na2SO4, then filtered and evaporated to dryness under reduced pressure to give the product as a yellow / brown crystalline solid (1.53 g, 4.66 mmol, 93%). 1 H NMR(400MHz,CDCl3)δ 8.25(1H,s,NH),7.49(1H,s,ArH),7.46-7.37(m,2H,ArH),7.31(d,1H,ArH),6.99(d,1H,ArH),3.66 (s,2H,indeno-CH2),2.48(s,3H,ArCH3),2.06(s,4H,CH2CH2),1.37(s,6H,CMe2),1.36(s,6H,CMe2).

[0299] 2,5,7,7,10,10-Hexamethyl-5,7,8,9,10,12-hexahydrobenzo[5,6]indeno[1,2-b]indole: [ka] To a solution of 2,7,7,10,10-pentamethyl-5,7,8,9,10,12-hexahydrobenzo[5,6]indeno[1,2-b]indole (1.53 g, 4.66 mmol) in THF (40 mL) was added a solution of sodium tert-butoxide (470 mg, 4.89 mmol) in THF (20 mL) with stirring at ambient temperature (water bath) to give a dark red-brown solution. After 30 min, iodomethane (0.938 g, 4.89 mmol) was added and the mixture was stirred overnight. The volatiles were removed under reduced pressure. The residue was partitioned between diethyl ether and water (40 mL each). The organic layer was shaken with brine (20 mL), dried over anhydrous Na2SO4, filtered and the filtrate was evaporated to dryness to give the product as a brown solid (1.28 g, 3.74 mmol, 80%). 1 H NMR(400MHz,CDCl3)δ 7.58(s,1H,ArH),7.49(s,1H,ArH),7.42(br.s,1H,ArH),7.26(d,1H,ArH),7.03(d,1H,ArH),4.04(s,3H,N Me),3.64(s,2H,indeno-CH2),2.49(s,3H,ArMe),1.76(s,4H,CH2CH2),1.40(s,6H,CMe2),1.36(s,6H,CMe2).

[0300] General procedure for one-pot preparation of Examples 21, 23, 25 and 27 : The following synthetic steps were carried out under an inert nitrogen atmosphere using a Chemspeed Technologies automated reactor platform equipped with a 250 mL stainless steel jacketed reactor with mechanical stirring. The required indeno[1,2-b]indole precursor solution (25.2 mL aliquot of THF solution to yield 2.9 mmol) was added to the reactor followed by additional THF (20 mL). n-BuLi solution (1.6 M in hexanes, 1.91 mL, 3 mmol) was added with stirring and the mixture was stirred at ambient temperature for 3 hours. The required chlorosilane precursor solution (17.4 mL aliquot of THF solution to yield 3 mmol) was then added to the reactor and the reaction mixture was stirred overnight. Volatiles were removed from the reactor under dynamic vacuum and then toluene (50 mL) was added. After stirring for 1 hour, triethylamine (2 mL, >4 equiv.) was added followed by n-BuLi solution (1.6 M in hexanes, 3.82 mL, 6.11 mmol). The mixture was stirred for 2 hours, then cooled to 0° C., and Ti(NMe2)Cl2 solution (9 mL aliquot of toluene solution to yield 3.5 mmol) was added. The mixture was stirred at 0° C. for 1 hour, then heated to 90° C. for 3 hours. It was then cooled to 30° C., and chlorotrimethylsilane (7.3 mmol, 1.5 mL) was added. The reactor was sealed and heated to 85° C. for 14 hours. Volatiles were removed under dynamic vacuum at 50° C. Toluene (50 mL) was added to the reactor and heated to 50° C. with stirring.

[0301] The following manipulations were carried out manually in a glove box under an inert nitrogen atmosphere. The reaction mixture was filtered through Celite into a 100 mL Schlenk flask. Volatiles were removed under dynamic vacuum, heptane (30 mL) was added, and the reaction mixture was heated to 80° C. with stirring and then allowed to cool to room temperature. The solid was collected by filtration, rinsed with pentane, and then dried under dynamic vacuum to give the product as a dark green solid.

[0302] Example 21 : Yield: 0.56g, 29%. 11H NMR (400 MHz, toluene-d8) δ 7.88 (d, 1H, ArH), 7.77 (d, 1H, ArH), 7.40 (s, 1H, ArH), 7.30 (m, 1H, ArH), 7.20 (m, 1H, ArH), 7.18 (d, 1H, ArH), 6.87 (d, 1H, ArH), 6.60 (s, 1H, ArH), 6.25 (s, 1H, ArH), 3.64 (s, 3H, NCH3), 2.75 (m, 4H, N(CH2)2), 2.34 (s, 3H, ArCH3), 1.63 (m, 4H, N(CH2)2(CH2)2), 1.57 - 1.20 (m, 6H, SiEt2), 1.10 (s, 9H, t-Bu), 1.09 - 1.05 (m, 4H, SiEt2).

[0303] Example 23 : Yield: 1.32 g, 68%. 1 1H NMR (400 MHz, toluene-d8) δ 7.87 (d, 1H, ArH), 7.78 (d, 1H, ArH), 7.40 (s, 1H, ArH), 7.31 (m, 1H, ArH), 7.21 (m, 1H, ArH), 7.17 (d, 1H, ArH), 6.88 (d, 1H, ArH), 6.62 (dd, 1H, ArH), 6.27 (s, 1H, ArH), 3.64 (s, 3H, NCH3), 3.57 (s, 3H, ArOCH3), 2.81 (m, 4H, N(CH2)2), 1.64 (m, 4H, N(CH2)2(CH2)2), 1.59 - 1.20 (m, 6H, SiEt2), 1.09 (s, 9H, t-Bu), 1.09 - 1.05 (m, 4H, SiEt2).

[0304] Example 25 : Yield: 0.93 g, 45%. 1H NMR (400MHz, toluene-d8)δ 8.08(d,2H,ArH),7.45(s,1H,ArH),7.28(s,1H,ArH),7.00(d,1H,ArH),6.80(d,1H, ArH),6.46(s,1H,ArH),3.73(s,3H,NCH3),2.40(s,3H,ArCH3),2.07(s,3H,ArCH3),1 .80-1.60(m,6H,SiEt2),1.54(s,3H,CCH3),1.42(s,3H,CCH3),1.40(s,3H,CCH3),1. 35(s,3H,CCH3),1.26(m,2H,CH2),1.18-1.09(m,6H,SiEt2+CH2),1.06(s,9H,t-Bu).

[0305] Example 27 : Yield: 0.66g, 32%. 1 H NMR (400MHz, toluene-d8)δ 8.07(d,2H,ArH),7.23(s,1H,ArH),7.08(s,H,ArH),7.00(d,1H,ArH),6.80(d,1H,A rH),6.53(s,1H,ArH),3.73(s,3H,NCH3),2.60(s,3H,ArOCH3),2.11(s,3H,ArCH3),1 .80-1.60(m,6H,SiEt2),1.54(s,3H,CCH3),1.42(s,3H,CCH3),1.41(s,3H,CCH3),1. 35(s,3H,CCH3),1.26(m,2H,CH2),1.17-1.08(m,6H,SiEt2+CH2),1.05(s,9H,t-Bu).

[0306] General Procedure for Preparation of Examples 22, 24, 26 and 28 : To a solution of the appropriate dichloride complex in toluene (approximately 10 mL) was added MeMgBr solution (required amount of 3.0 M solution in Et2O, 2.2 equiv.). After stirring for 30 min, the volatiles were removed under dynamic vacuum. The residue was extracted using a mixture of toluene and heptane and filtered through a Celite plug. The volatiles were then removed under dynamic vacuum to give the dimethyl complex as a light orange-red powder.

[0307] Example 22: Yield: 0.91 g, 82%. 1 H NMR (400 MHz, toluene-d8) δ 7.89 (m, 1H, ArH), 7.77 (d, 1H, ArH), 7.35 (d, 1H, ArH), 7.20 (d, 1H, ArH), 7.17 (m, 2H, ArH), 6.86 (d, 1H, ArH), 6.58 (dd, 1H, ArH), 6.25 (s, 1H, ArH), 3.60 (s, 3H, NCH3), 2.77 (m, 4H, N(CH2)2), 2.37 (s, 3H, ArCH3), 1.63 (m, 4H, N(CH2)2(CH2)2), 1.32 (s, 9H, t-Bu), 1.29 - 1.02 (m, 10H, SiEt2), 0.20 (s, 3H, TiCH3), 0.03 (s, 3H, TiCH3).

[0308] Example 24 : Yield: 0.40 g, 85%. 1 H NMR (400 MHz, toluene-d8) δ 7.90 (m, 1H, ArH), 7.75 (m, 1H, ArH), 7.17 (m, 2H, ArH), 7.12 (d, 1H, ArH), 7.03 (d, 1H, ArH), 6.87 (d, 1H, ArH), 6.59 (dd, 1H, ArH), 6.27 (s, 1H, ArH), 3.61 (s, 3H, NCH3), 3.60 (s, 3H, ArOCH3), 2.82 (m, 4H, N(CH2)2), 1.64 (m, 4H, N(CH2)2(CH2)2), 1.31 (s, 9H, t-Bu), 1.30 - 1.05 (m, 10H, SiEt2), 0.18 (s, 3H, TiCH3), 0.02 (s, 3H, TiCH3).

[0309] Example 26 : Yield: 0.67 g, 85%. 1H NMR (400MHz, toluene-d8)δ 8.12(s,1H,ArH),7.89(s,1H,ArH),7.41(d,1H,ArH),7.28(d,1H,ArH),6.95(d,1H,ArH),6.79(d,1H,ArH) ,6.57(s,1H,ArH),3.67(s,3H,NCH3),2.41(s,3H,ArCH3),2.09(s,3H,ArCH3),1.80-1.60(m,4H,SiEt2),1 .48(s,3H,CCH3),1.42-1.31(m,2H,CH2),1.37(s,3H,CCH3),1.35(s,3H,CCH3),1.32(s,3H,CCH3),1.31-1 .28(m,2H,CH2),1.29(s,9H,t-Bu),1.18-1.09(m,6H,SiEt2+CH2),0.13(s,3H,TiCH3),0.01(s,3H,TiCH3).

[0310] Example 28 : Yield: 0.34 g, 61%. Recrystallization from a toluene / heptane mixture gave dark red crystals suitable for single crystal X-ray diffraction (see Figure 1 and Table 1). 1H NMR (400MHz, toluene-d8)δ 8.12(s,1H,ArH),7.88(s,1H,ArH),7.18(d,1H,ArH),7.11(d,1H,ArH),6.95(d,1H,ArH),6.79(d,1H,ArH) ,6.62(s,1H,ArH),3.67(s,3H,NCH3),3.63(s,3H,ArOCH3),2.11(s,3H,ArCH3),1.80-1.60(m,4H,SiEt2), 1.48 (s, 3H, CCH3), 1.42-1.31 (m, 2H, CH2), 1.37 (s, 3H, CCH3) 1.35 (s, 3H, CCH3) 1.32 (s, 3H, CCH3), 1.31-1.28 (m, 2H, CH2), 1.28 (s, 9H, t-Bu), 1.20-1.09 (m, 6H, SiEt2+CH2), 0.11 (s, 3H, TiCH3), 0.01 (s, 3H, TiCH3). Figure 1 shows a side view of titanium complex Example 28 showing the atom labeling scheme. Only the major (80%) orientations of the disordered diethylsilyl groups are shown. Non-hydrogen atoms are represented by Gaussian ellipsoids with a probability level of 30%. Hydrogen atoms are not shown. [Table 1-1] [Table 1-2]

[0311] Comparative Example 1 [ka] This material was prepared essentially as described by Senda, T., Oda, Y. et al., Macromolecules 2010, 43, 2299-2306.

[0312] (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)(2,7-di-tert-butyl-9H-fluoren-9-yl)diethylsilane: [ka] 2,7-Di-tert-butylfluorene (1.67 g, 6.0 mmol) was dissolved in THF (40 mL). n-BuLi solution (1.6 M in hexanes, 4.13 mL, 6.6 mmol) was added via syringe, resulting in mild effervescence and bright orange coloration. After stirring for 30 min, the volatiles were removed under reduced pressure and the residue was redissolved in diethyl ether (10 mL). (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodiethylsilane was added as a solution in diethyl ether (40 mL) to give a precipitate. The reaction mixture was stirred overnight and then concentrated under reduced pressure to give a foam. The residue was extracted into pentane and filtered to remove white solids from the clear yellow filtrate. The filtrate was concentrated under reduced pressure to give the desired product as a foam and finally as a sticky oil (3.41 g, 100% yield). 1 H NMR (400 MHz, toluene-d8) δ 7.76 (d, 2H, ArH), 7.40-7.30 (m, 6H, ArH), 5.88 (m, 1H, allyl-H), 5.58 (dq, 1H, allyl-H), 5.19 (dq, 1H, allyl-H), 4.55 (s, 1H, fluorene-9H), 4.39 (q, 2H, allyl-H), 2.30 (s, 3H, ArH), 1.52 (s, 9H, t-Bu), 1.34 (s, 18H, t-Bu), 1.05-0.70 (m, 10H, SiEt2).

[0313] Comparative Example 1 : (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)(2,7-di-tert-butyl-9H-fluoren-9-yl)diethylsilane (3.41 g, 6.0 mmol) was dissolved in toluene (30 mL) in a 100 mL Schlenk flask. The flask was cooled to -78 °C for 15 min and triethylamine (3.76 mL, 2.73 g, 27.0 mmol) and n-BuLi solution (1.6 M in hexanes, 8.44 mL, 13.5 mmol) were added successively. The yellow solution was allowed to warm to ambient temperature over 2 h and stirred for an additional 30 min before being cooled again to -78 °C. Ti(NMe2)2Cl2 (1.49 g, 7.2 mmol) was added as a slurry in toluene to give a dark red reaction mixture. The cold bath was replaced with an oil bath and the reaction mixture was heated to 90 °C for 3 h. The volatiles were removed under reduced pressure to give a black tar. The residue was extracted with toluene and filtered through Celite to remove dark insoluble material from the dark brown-black filtrate. The filter cake was rinsed with toluene until the filtrate turned light brown. The combined toluene extracts were concentrated to 50 mL and chlorotrimethylsilane (1.52 mL, 1.30 g, 12.0 mmol) was added. Vacuum was applied briefly to the headspace and the reaction mixture was heated to 80° C. overnight. The volatiles were removed to give the crude product. Recrystallization from hot heptane gave the desired product as a brown solid (2.01 g, 52% yield). 1 H NMR (400MHz, toluene-d8)δ 8.00(d,2H,ArH),7.79(s,2H,ArH),7.46(d,2H,ArH),7.39(s,1H,ArH),7.24(s,1H,ArH) ,2.33(s,3H,ArCH3),1.37(s,9H,t-Bu),1.23(s,18H,t-Bu),1.17-0.80(m,10H,SiEt2).

[0314] Comparative Example 2 : [ka] Comparative Example 2 : Comparative Example 1 (2.01 g, 3.12 mmol) was dissolved in toluene (50 mL) in a 100 mL Schlenk flask. A solution of MeMgBr (2.19 mL, 3.0 M in diethyl ether, 6.56 mmol) was added, causing a color change from dark brown to dull green. After stirring for 2 h, the volatiles were removed under reduced pressure. The residue was extracted with heptane and filtered through Celite to give a clear yellow-green filtrate. The filtrate was concentrated under reduced pressure to give a foam. Recrystallization from hot heptane gave the desired product as a yellow-green powder (1.36 g, 72% yield). 1 H NMR (400MHz, toluene-d8)δ 8.03(d,2H,ArH),7.51(s,2H,ArH),7.38(dd,2H,ArH),7.35(d,1H,ArH),7.28(d,1H,ArH),2.37(s,3H,ArCH3 ),1.55(s,9H,t-Bu),1.40-1.25(m,4H,SiEt2),1.20(s,18H,t-Bu),1.15(t,6H,SiEt2),0.16(s,6H,TiMe2).

[0315] Comparative Example 3 [ka] This material was prepared essentially as described for the known Me2Si bridged analogue in Hanaoka, H., US Pat. No. 7,141,690.

[0316] 1-(1H-inden-3-yl)pyrrolidine: [ka] 1-Indanone (5.42 g, 41.0 mmol), pyrrolidine (3.70 mL, 45.0 mmol) and toluene (200 mL) were heated to 130° C. in a 500 mL round bottom flask in a Dean-Stark apparatus under N2 for 4 days to give a dark brown reaction mixture. Volatiles were removed under reduced pressure to give a residue consisting of a black oil containing solids. The residue was purified by vacuum distillation to give a clear yellow liquid that was stored under nitrogen (5.25 g, 69% yield). 1 H NMR (400 MHz, toluene-d8) δ 7.54 (d, 1H, ArH), 7.28 (d, 1H, ArH), 7.20 (t, 1H, ArH), 7.12 (t, 1H, ArH), 4.98 (t, 1H, inden-2-ylCH), 3.23 (d, 2H, inden-1-ylCH2), 3.18 (m, 4H, NCH2), 1.58 (m, 4H, NCH2CH2).

[0317] 1-(1-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diethylsilyl)-1H-inden-3-yl)pyrrolidine: [ka] 1-(1H-inden-3-yl)pyrrolidine (1.30 g, 7.0 mmol) was diluted in THF (30 mL) in a 100 mL Schlenk flask to give a pale yellow solution. A solution of n-BuLi (1.6 M in hexanes, 4.81 mL, 7.7 mmol) was added, resulting in effervescence and a dark yellow coloration. After 30 min, a solution of (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodiethylsilane (2.28 g, 7.0 mmol) in THF (10 mL) was added, resulting in a dark green color. After stirring for 1 h, the volatiles were removed under reduced pressure to give a red-brown syrup. This was triturated with pentane, concentrated under reduced pressure, extracted once more with pentane, and then filtered through Celite to remove the beige solids from the red-brown filtrate. The filtrate was concentrated under reduced pressure to give the desired product as a thick red-brown oil (3.37 g, 100% yield). 1H NMR (400 MHz, toluene-d8) δ 7.63 (d, 1H, ArH), 7.36 (d, 1H, ArH), 7.26-7.15 (m, 3H, ArH), 7.09 (d, 1H, ArH), 5.85 (m, 1H, allyl-H), 5.56 (dq, 1H, allyl-H), 5.36 (d, 1H, inden-2-yl CH), 5.11 (dq, 1H, allyl-H), 4.36 (m, 2H, allyl-H), 4.00 (d, 1H, inden-1-yl CH),3.21(m,4H,NCH2),2.22(s,3H,ArCH3),1.62(m,4H,NCH2CH2),1.47(s,9H,t-Bu),1.01-0.77(m,10H,SiEt2).

[0318] Comparative Example 3 : 1-(1-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diethylsilyl)-1H-inden-3-yl)pyrrolidine (3.32 g, 7.0 mmol) was dissolved in toluene (30 mL) in a 100 mL Schlenk flask. NEt3 (4.39 mL, 31.5 mmol) was added to the purple-brown solution. The flask was cooled to -78 °C for 15 min, after which n-BuLi solution (1.6 M in hexanes, 9.84 mL, 15.75 mmol) was added via cannula. The reaction mixture was allowed to warm to ambient temperature over 2 h and cooled again to -78 °C for 15 min. A solution of Ti(NMe2)2Cl2 (1.74 g, 8.4 mmol) in toluene (20 mL) was added via cannula and the reaction mixture was gradually warmed to 90 °C and held for 3 h. The volatiles were removed under reduced pressure and the residue was extracted with toluene and filtered through Celite until the filtrate was colorless The combined toluene extracts were sealed in a flask and the headspace was evacuated.

[0319] Chlorotrimethylsilane (2.67 mL, 21.0 mmol) was added and the reaction mixture was heated to 80° C. overnight. The dark brown reaction mixture was concentrated under reduced pressure. The brown-black residue was slurried in hot heptane (40 mL) and stirred for 20 minutes, after which the suspension was cooled in a glove box freezer overnight. The solid was isolated on a frit, rinsed with a minimum of cold pentane, and dried under vacuum to give a dark green-black solid (3.11 g, 81% yield) that was a dark red-brown in toluene solution. 1 H NMR (400MHz, toluene-d8)δ 7.73(m,1H,ArH),7.43(m,1H,ArH),7.29(d,2H,ArH),7.06-6.98(m,2H,ArH),5.45(s,1H,inden-2-ylCH),3.52-3. 25(m,4H,NCH2),2.31(s,3H,ArCH3),1.49(s,9H,t-Bu),1-49-1.45(m,4H,NCH2NCH2),1.31-0.95(m,10H,SiEt2).

[0320] Comparative Example 4 [ka] Comparative Example 4 : Comparative Example 3 (1.50 g, 2.72 mmol) was dissolved in toluene (40 mL). A solution of MeMgBr (3.0 M in diethyl ether, 2.00 mL, 6.00 mmol) was added dropwise to the dull brown-black mixture with vigorous stirring to give a dark red-brown solution. This was stirred overnight and concentrated under reduced pressure to give a dark red-brown residue. The residue was extracted with toluene and filtered through Celite to remove the black solids from the dark red-brown filtrate. The filtrate was stripped under reduced pressure to a sticky paste. Trituration with pentane gave a red powder. (1.11 g, 80% yield). 1H NMR (400MHz, toluene-d8)δ 7.73(d,1H,ArH),7.25(d,2H,ArH),6.91(d,1H,ArH),6.85(m,1H,ArH),6.55(m,1H,ArH),5.60(s,1H,inden-2-ylCH),3.40( m,4H,NCH2),2.32(s,3H,ArCH3),1.61(s,9H,t-Bu),1.56(m,4H,NCH2CH2),1.17-0.85(m,13H,SiEt2+TiCH3),0.24(TiCH3).

[0321] Comparative Example 5 : [ka] 1-(1H-inden-2-yl)pyrrolidine: [ka] This material was prepared essentially as described by Blomquist et al., J. Org. Chem. 1961, 26, 10, 3761-3769. 2-Indanone (3.70 g, 28.0 mmol) was dissolved in toluene (30 mL) in a 100 mL Schlenk flask. Pyrrolidine (2.46 mL, 30 mmol) was added via syringe and the flask was attached to a Dean-Stark apparatus under a stream of N2. The mixture was heated to 130 °C, resulting in initial effervescence. After 2 h of heating was stopped, the Dean-Stark apparatus was removed and the volatiles were removed under reduced pressure. The residue was triturated with pentane followed by concentration under reduced pressure to give the desired product as a beige powder (4.78 g, 92% yield). 1 H NMR (400 MHz, toluene-d8) δ 7.26-7.12 (m, 3H, ArH), 6.93 (td, 1H, ArH), 5.21 (s, 1H, inden-3-ylCH), 2.96 (s, 2H, inden-1-ylCH2), 2.78 (m, 4H, NCH2), 1.48 (m, 4H, NCH2CH2).

[0322] 1-(1-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diethylsilyl)-1H-inden-2-yl)pyrrolidine: [ka] 1-(1H-inden-2-yl)pyrrolidine (2.04 g, 11.0 mmol) was dissolved in THF (100 mL) in a 200 mL Schlenk flask to give a dark brown solution. n-BuLi solution (1.6 M in hexanes, 7.56 ml, 12.1 mmol) was added via syringe and the mixture was stirred for 2 h. After 2 h, the dark brown reaction mixture was cooled to −78° C. for 15 min and a solution of (2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)chlorodiethylsilane (3.58 g, 11.0 mmol) in THF (10 mL) was added via cannula. The mixture was allowed to stir overnight and warm to ambient temperature. The volatiles were then removed under reduced pressure to give a brown foam. This residue was triturated with pentane and concentrated once more under reduced pressure to remove residual THF. The residue was extracted with pentane and filtered. The dark brown filtrate was concentrated under reduced pressure to give a beige suspension, which was then completely removed to give a pale beige sticky solid. This material was suspended in pentane (50 mL), filtered, and the solid was collected on a sintered glass frit. The solid was isolated and dried under vacuum. An additional crop of solid material was obtained by cooling the mother liquor in a glove box freezer (combined yield: 3.12 g, 60% yield). 1 H NMR (400 MHz, toluene-d8) δ 7.24-6.94 (m, 6H, ArH), 6.87 (td, 1H, ArH), 5.87 (m, 1H, allyl-H), 5.56 (dq, 1H, allyl-H), 5.56 (s, 1H, inden-1-ylCH), 5.14 (dq, 1H, allyl-H), 4.32 (qq, 2H, allyl-H), 3.92 (s, 1H, inden-3-ylCH), 2.85 (m, 4H, NCH2), 2.18 (3H, s, ArCH3), 1.50 (m, 4H, NCH2CH2), 1.44 (s, 9H, t-Bu), 1.09-0.73 (m, 10H, SiEt2).

[0323] Comparative Example 5 : 1-(1-((2-(allyloxy)-3-(tert-butyl)-5-methylphenyl)diethylsilyl)-1H-inden-2-yl)pyrrolidine (1.89 g, 3.98 mmol) was dissolved in toluene (30 mL) in a 100 mL Schlenk flask to give an orange-brown solution. Triethylamine (2.50 mL, 17.93 mmol) was added via syringe. The reaction mixture was cooled to -78°C for 15 min, then n-BuLi solution (1.6 M in hexanes, 5.60 mL, 8.97 mmol) was added via cannula. The reaction mixture was stirred and allowed to warm to ambient temperature over 2 h to give a light brown suspension. It was cooled again to -78 °C for 15 min, then a solution of Ti(NMe2)2Cl2 (989 mg, 4.78 mmol) in toluene (15 mL) was added and the mixture was warmed to ambient temperature and heated to 90 °C for 3 h. The reaction mixture was a dark brown-black solution. The volatiles were removed under reduced pressure and the residue was extracted into toluene and filtered through Celite to remove dark solids from the dark brown solution. The filtrate was collected in a 100 mL Schlenk flask equipped with a stir bar, the flask was sealed with a septum and the headspace was briefly evacuated. Chlorotrimethylsilane (1.00 mL, 7.97 mmol) was injected through the septum via syringe and the reaction mixture was heated to 80 °C for 5 h. The volatiles were removed under reduced pressure. The residue was recrystallized from hot heptane / toluene (ca. 50:50) to give the desired product as a dark red-brown crystalline solid (1.42 g, 65% yield). 1 H NMR (400MHz, toluene-d8)δ 7.53(d,1H,ArH),7.41(d,1H,ArH),7.20(m,2H,ArH),6.91(t,1H,ArH),6.80(t,1H,ArH),6.11(s,1H,Indene -1-ylCH), 3.05(m,4H,NCH2),2.27(s,3H,ArCH3),1.38(s,9H,t-Bu),1.37-0.83(m,14H,SiEt2+NCH2CH2).

[0324] Comparative Example 6 [ka] Comparative Example 6 : Comparative Example 5 (800 mg, 1.45 mmol) was dissolved in toluene (50 mL) in a 100 mL Schlenk flask. With stirring, MeMgBr solution (3.0 M in diethyl ether, 1.07 mL, 3.20 mmol) was added dropwise via syringe to the red-brown solution to give a dark green-brown suspension. This was stirred for 3 hours, after which the reaction mixture was concentrated under reduced pressure. The green powdery residue was extracted with pentane (3×50 mL) and filtered through Celite. The clear light yellow filtrate was concentrated under reduced pressure to give a solid foam and finally a yellow powder (490 mg, 66% yield). 1 H NMR (400MHz, toluene-d8)δ 7.54(t,2H,ArH),7.27-6.92(m,4H,ArH),5.96(s,1H,inden-1-ylCH),2.78(m,4H,NCH2),2.26(s ,3H,ArCH3),1.64(s,9H,t-Bu),1.31-0.74(m,17H,SiEt2+NCH2CH2+TiCH3),0.16(s,3H,TiCH3).

[0325] Solution phase polymerization: Semibatch copolymerization experiments at 140°C Semi-batch ethylene / 1-octene copolymerization experiments were conducted in an automated array of 1 L reactors manufactured by Chemspeed Technologies equipped with pitched blade impellers with gas entrainment through the hollow impeller shaft to maximize gas dispersion in the liquid. Baffles were installed in the reactors to enhance turbulence and ensure good mixing in the reactors. Heating of the reactors was controlled with reactor jacketed electric heaters. Reactor cooling was controlled with silicone oil heat transfer fluid circulating in the reactor jacket. The reactors each contained two catalyst injection vessels fixed to the reactor heads and equipped with solenoid operated shutoff valves. The entire system is housed in an MBraun glove box under nitrogen atmosphere to maintain an oxygen and moisture deficient environment during catalyst handling and polymerization process. The reactors use a software-driven programmable logic control (PLC) system as a method of process control.

[0326] After the reactor was charged with cyclohexane (500 mL) and 1-octene (4 mL), the reactor was heated and the catalyst and activator solutions were charged to the catalyst injection chamber. Depending on the aluminum-based cocatalyst (e.g., organoaluminum compounds or alkylaluminoxanes) addition method (listed in Table 2), an aliquot of the aluminum-based cocatalyst solution was added to the reactor in different ways: the aliquot was added directly to the reactor before heating ("Method a"); 90% of the aliquot was added to the reactor before heating and 10% of the aliquot was premixed with the prepolymerized catalyst solution in the injection vessel before injection ("Method b"); or, once the target reactor temperature was reached, the aliquot was added to the reactor via a high-pressure feed vessel ("Method c").

[0327] In some instances where the cocatalyst was an alkylaluminoxane, a hindered phenol compound (BHEB) was also used. The MMAO-7 / BHEB cocatalyst solution was prepared by adding 2,6-di-tert-butyl-4-ethylphenol (BHEB; 0.28 g, 1.2 mmol) to a cyclohexane solution (10 mL) of MMAO-7 (1.54 g of a 0.4 mmol / mL solution in Isopar-E; AkzoNobel / Nouryon). In instances where the cocatalyst was an organoaluminum compound such as TIBAL, an appropriate aliquot volume and target Al / Ti molar ratio of a solution prepared by diluting TIBAL (25 wt % solution in hexane; AkzoNobel / Nouryon) with cyclohexane was added.

[0328] The first catalyst injection vessel was charged with a toluene solution (5 mL) of the inventive or comparative prepolymerized catalyst complex (0.0005 mmol for a target of 1 μM reactor concentration), and the second catalyst injection vessel was charged with a xylene solution (5 mL) of the boron-based catalyst activators triphenylcarbenium tetrakis(pentafluorophenyl)borate ("tritylborate" or "TB" in the tables) or a toluene / 1,2-dichloroethane solution (1:1, 5 mL total) of dimethylanilinium tetrakis(pentafluorophenyl)borate ("aniliniumborate" or "AnB" in the tables) in the appropriate molar ratio.

[0329] The reactor was pre-pressurized with ethylene to 2.5 bara, allowed to equilibrate for 10 minutes, and then heated to the target temperature. The reactor pressure was then set to 8.6 bara and the impeller speed was set to 1000 rpm just prior to catalyst injection. To initiate the reaction, a solution of prepolymerized catalyst and a solution of boron-based catalyst activator were simultaneously injected into the reactor using nitrogen overpressure in the catalyst injection vessel. The slight increase in reactor pressure associated with catalyst injection rapidly decreased as the reaction proceeded, and the reactor pressure was then maintained at the target pressure throughout the reaction by also controlling the reactor temperature near the target temperature for the duration of the experiment while feeding ethylene on demand. Since the reaction is exothermic and often slightly exceeds the control temperature, the average temperature was calculated and listed in Table 3 as "Temperature-Average".

[0330] After 108 seconds, the reaction was stopped by adding an overpressure of CO2 and then cooling the reactor. The quenched reactor contents were removed from the reactor and dried in a Genevac HT-12 centrifugal vacuum oven. The dried polymer was then weighed. [Table 2] [Table 3]

[0331] Examples B1-B6 demonstrate that polymerization catalyst systems based on prepolymerized catalyst complexes of the invention (with either dichloride or dimethyl activatable ligands), TB as a catalyst activator, and MMAO-7 cocatalysts modified with hindered phenols (e.g., BHEB) have high activity and produce high molecular weight copolymers under these polymerization conditions (see Tables 1 and 2). Similar results were obtained using the complex of Example 1 (dichloride) by adding MMAO-7 / BHEB to the reactor before heating and injection of the complex and borate, or by first premixing a portion (10%) of MMAO-7 / BHEB with the complex of Example 1 before injection and adding the other 90% of MMAO-7 / BHEB to the reactor before heating and injection (compare B2 with B1). This suggests that MMAO-7 / BHEB is a robust and compatible cocatalyst for the dichloride complexes of the invention. The complex of Example 2 (dimethyl) gave similar results to the complex of Example 1 (dichloride), but the activity and molecular weight M with the complex of Example 2 was significantly higher. w was somewhat lower under these conditions (compare B3 with B1). Other inventive titanium complexes from Examples 4 and 10 also yielded highly active catalysts when activated with boron-based activators (e.g., TB) and MMAO-7 / BHEB under these conditions, with high M w (compare B5 and B6 with B3).

[0332] Other combinations of titanium prepolymerized catalyst, boron-based activator and aluminum-based cocatalyst without hindered phenolic compounds (e.g., BHEB) resulted in polymerization catalysts with lower activity under these polymerization conditions. When BHEB was removed and the complex of Example 2 was activated with TB and MMAO-7, the polymerization activity was reduced by about 10% under these polymerization conditions (compare B7 with B4). This result predicted a more severe effect on catalyst activity when BHEB was removed during continuous solution polymerization experiments (see below). When both the boron-based catalyst activator and BHEB were removed (i.e., only the complex of Example 2 and MMAO-7 were used), no activity for polymerization was observed (compare Example B8 with Example B4). This result is in contrast to ethylene / 1-olefin copolymerization experiments at 140°C in batch reactors exemplified in CN112,876,519 and CN112,778,376, where the related prepolymerized catalyst complex was shown to be active when activated with MMAO-7 only.

[0333] Activation of the prepolymerized catalyst example 2 of the present invention using AnB and TIBAL and using catalyst / cocatalyst ratios (Al / Ti=500, AnB / Ti=6) as disclosed for the relevant catalysts in WO 2003 / 066641, WO 2006 / 080475 and WO 2006 / 080479 resulted in much lower catalytic activity compared to catalysts activated with TB and MMAO-7 / BHEB (Al / Ti=500, TB / Ti=1.2) (compare Example B9 with Example B4).

[0334] The polymerization catalyst systems derived from the titanium prepolymerized catalyst examples 2, 4 and 10 of the present invention outperformed the polymerization catalyst systems derived from the previously disclosed prepolymerized catalyst complexes Comparative Examples 2 and 4. The prepolymerized catalyst complex of Comparative Example 2, which has a 2,7-di-tert-butylfluorenyl group (a ligand disclosed in WO 2006 / 080479) as the cyclopentadienyl component, gave significantly lower activity than the prepolymerized catalyst complexes of the present invention when activated in the same manner (compare Example B10 with Examples B3, B5 and B6). When either MMAO-7 / BHEB or TIBAL was added to the reactor at the target temperature just before injecting the titanium prepolymerized catalyst and the boron-based catalyst activator to ensure that the cocatalyst material did not decompose during heating of the reactor contents, the activity of the catalyst derived from Comparative Example 2 was still lower than the catalyst of the present invention (compare Example B11 with Example B10, and compare Example B12 with Examples B4 and B9). The prepolymerized catalyst complex of Comparative Example 4, having a 3-pyrrolidinyl-indenyl group (similar ligand to that disclosed in WO 2003 / 066641, except having an Et2Si bridge instead of an Me2Si bridge) as the cyclopentadienyl component, gave a much lower activity than the prepolymerized catalyst complex of Example 2 when activated in the same manner (compare Example B13 with Example B3). This suggests that the good polymerization performance of the polymerization catalyst system using the prepolymerized catalyst complex of Inventive Example 2 is strongly influenced by the structure of the ligand having the indenoindolyl fragment, and is not simply the result of the presence of nitrogen substitution such as the 3-pyrrolidinyl-indenyl fragment.

[0335] It is instructive to note that the branching frequencies (indicating the degree of incorporation of 1-octene comonomer into the copolymer) of the copolymers from the inventive examples and comparative examples B2, B5 and B10 are nearly identical, ranging from 20 to 23 short chain branches per 1000 carbons. Thus, one skilled in the art would understand that it is reasonable to directly compare the copolymer molecular weights rather than correcting for 1-octene content. In most cases, duplicate or triplicate experiments were performed to determine the catalyst activity and copolymer M. wThe percent relative standard deviation (%RSD) was calculated for the copolymer M. The catalytic activity had an RSD between 7 and 27%. w had RSDs between 1 and 19%. This data indicates that the reproducibility was very good and that the differences in polymerization performance discussed above were significantly outside the run-to-run variability in these experiments.

[0336] Solution Phase Polymerization: Continuous Ethylene / 1-Octene Copolymerization Continuous solution phase polymerizations were carried out in a continuous polymerization unit (CPU) using a stirred 71.5 mL reactor operated at 140°C, 160°C, 190°C, 200°C or 210°C using cyclohexane as the solvent. An upstream mixing reactor with a 20 mL volume was operated at a temperature 5°C lower than the polymerization reactor. The mixing reactor was used to preheat the ethylene, octene and make-up solvent streams. The catalyst feed (ortho-xylene or cyclohexane solution of titanium prepolymerized catalyst complex), boron-based catalyst activator, (Ph3C)[B(C6F5)4](TB), aluminum-based cocatalyst (MMAO-7 or TIBAL), hindered phenol (e.g., BHEB), and additional cyclohexane solvent streams were added directly to the polymerization reactor in a continuous process or combined as described below. The aluminum cocatalyst solution was added directly to the polymerization reactor ("in reactor" configuration in Tables 4, 6, and 8) or combined in-line with the solution of titanium prepolymerized catalyst complex prior to injection into the polymerization reactor ("in-line" configuration in Tables 4, 6, and 8). When hindered phenol BHEB was used, the solutions of MMAO-7 and BHEB were combined upstream of the reactor ("in reactor" configuration) or upstream of the mixing point with the solution of titanium prepolymerized catalyst complex ("in-line" configuration). The solution of boron-based catalyst activator was added directly to the reactor ("in reactor" configuration in Tables 4, 6, and 8) or combined with the solution of titanium prepolymerized catalyst complex immediately prior to combination with the solution of aluminum cocatalyst ("in-line" configuration in Tables 4, 6, and 8). A total continuous flow rate of 27 mL / min to the polymerization reactor was maintained. The B / Ti molar ratio was 1.2 unless otherwise noted in the tables.

[0337] Two different strategies for adding the aluminum-based cocatalyst were used in the experiments. For the "constant concentration" (listed as "constant concentration" in Tables 4, 6 and 8), the flow was adjusted to maintain a constant concentration of 20 μM aluminum in the reactor for the purpose of scavenging impurities, and therefore the Al / Ti molar ratio was varied based on the flow of titanium prepolymerization catalyst to the reactor. For the "ratio" control, the Al / Ti was first optimized to achieve the highest Q with the lowest Al / Ti ratio, and then that Al / Ti ratio was maintained when adjusting the flow of the other polymerization catalyst system components. The optimal Al / Ti ratio is listed in the table. When the hindered phenol, BHEB, was used, the BHEB / Al molar ratio was maintained at 0.30 during optimization of the Al / Ti ratio. Once the optimal Al / Ti ratio was found, the BHEB / Al ratio was varied to find the ratio that gave the highest activity. The optimal BHEB / Al ratio is listed in the table.

[0338] Ethylene / 1-octene copolymers were made with a 1-octene / ethylene weight ratio of 0.30. Ethylene was fed at different rates depending on the reactor temperature: 2.10 g / min at 140°C, 2.70 g / min at 160°C, 3.50 g / min at 190°C, 3.80 g / min at 200°C, or 4.10 g / min at 210°C. The CPU system was operated at a pressure of 10.5 MPa. The solvent, monomer and comonomer streams were all purified by purification trains before being fed to the reactor. Polymerization activity k p (mM -1 ·minute -1 ), is defined as follows:

number

[0339] In sequential copolymerization experiments carried out at 140°C, all catalyst compositions of the present invention from titanium prepolymerized catalyst complexes (dichloride or dimethyl activatable ligands) activated with boron-based catalyst activator (TB) and MMAO-7 as cocatalyst, and with hindered phenol (BHEB) as modifier, showed high activity at 90% ethylene conversion (Q) and produced high molecular weight copolymers with high 1-octene content (see polymerization run numbers C1-C19 in Tables 4 and 5). High activity and high molecular weight were obtained with any combination of polymerization catalyst system components (in reactor or inline) (compare polymerization run numbers C1, C2 and C3; and compare polymerization run numbers C4, C5 and C6).

[0340] The combination of Ti prepolymerized catalyst complex of the present invention with boron-based activator, alkylaluminoxane and hindered phenol was necessary for high catalyst activity in high temperature continuous solution phase process. Removal of BHEB from catalyst system composition derived from complex of Example 1 (dichloride precursor) while keeping other catalyst flows constant resulted in a drop in Q from 90% to 51% (compare polymerization run number C20 with C1). When BHEB was removed from catalyst system derived from complex of Example 4 (dimethyl precursor) and catalyst components were combined in-line before the reactor, Q dropped by 6% (compare polymerization run number C24 with C8) and catalyst flow had to be increased by almost 3 times to achieve 90% Q, k pwas much lower (compare polymerization run number C25 with C8). A similar effect was observed when BHEB was omitted from catalyst system compositions derived from prepolymerized catalyst dimethyl precursor examples 8, 10, 12 and 14 of the present invention (compare polymerization run numbers C27, C28, C29 and C30 with polymerization run numbers C10, C11, C12 and C13, respectively). In all cases, the resulting catalyst complex loading levels required to achieve 90% Q without BHEB were high, with k p was much lower than when the hindered phenol compound was present in the catalyst system composition. When both BHEB and TB were removed from the catalyst system composition derived from the prepolymerized catalyst of Example 4 (i.e., activation with MMAO-7 only), the ethylene conversion dropped to less than 10% (compare polymerization run numbers C26 with C8). This result is also in contrast to the ethylene / 1-olefin copolymerization experiments exemplified in CN112,876,519 and CN112,778,376, where the related prepolymerized catalyst complexes were shown to be active when activated with MMAO-7 only in batch reactor experiments.

[0341] As disclosed for the related catalyst system in WO 2006 / 080479, alternative catalyst activation using TB and TIBAL resulted in much lower catalytic activity than the TB and MMAO-7 / BHEB activated system and failed to achieve the target ethylene conversion of 90%Q. WO 2006 / 080479 showed that the borate activators TB and AnB resulted in similar catalytic activity when combined with TIBAL in batch reactor experiments at 130°C, but TB has higher solubility and is therefore more practical for use in continuous solution processes. The catalyst system composition derived from complex example 1 combined with TB and TIBAL components, with all components combined in the reactor, gave much lower activity than the TB and MMAO-7 / BHEB activated system with the same catalyst flow (compare polymerization run number C21 with C1). Increasing the catalyst flow and Al / Ti ratio in the Example 1 / TB / TIBAL system did not result in a polymerization catalyst system active enough to achieve 90% Q (compare polymerization run number C22 with C21 and C1). Repeating the experiment with pre-contacting the Example 1 complex with TIBAL in-line before the reactor did not improve the polymerization activity (compare polymerization run number C23 with C21).

[0342] Polymerization catalyst systems derived from the titanium prepolymerization catalysts of the present invention (e.g., Examples 1, 2, 4, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, and 26) performed much better in the high temperature continuous polymerization process than polymerization catalyst systems derived from previously disclosed prepolymerization catalyst complexes Comparative Examples 1, 2, and 4 and the associated Comparative Example 6. Catalyst systems using the prepolymerization catalyst complexes of Comparative Example 1 (dichloride) and Comparative Example 2 (dimethyl), which have a 2,7-di-tert-butylfluorenyl group (a ligand disclosed in WO 2006 / 080479) as the cyclopentadienyl component, had significantly lower activity and required much higher catalyst concentrations to achieve 90% Q than the catalyst systems of the present invention when activated in the same manner (compare polymerization run number C31 with C3, and compare polymerization run number C32 with C4 and C7). Repeating polymerization run number C32 using Comparative Example 2 but without BHEB did not significantly change the activity, which remained low. The catalyst system derived from Comparative Example 4, which has a 3-pyrrolidinyl-indenyl group as the cyclopentadienyl component, gave much lower activity than the catalyst system derived from Example 2, which has an indeno[1,2-b]indolyl fragment with N-substitution at the same relative position as the silyl bridge (compare polymerization run number C34 with C6). Removal of BHEB from the catalyst system composition resulted in significantly lower activity and failed to achieve 90% Q (compare polymerization run number C35 with C34). Similar results were obtained using Comparative Example 6, which has a 2-pyrrolidinyl-indenyl group, in comparison with Inventive Example 4, which has an indeno[2,1-b]indolyl fragment with N-substitution at the same relative position (compare polymerization run numbers C36 and C37 with polymerization run number C8). These results suggest that the good polymerization performance of the polymerization catalyst system derived from the prepolymerized catalyst complex of the present invention is strongly influenced by the indenoindolyl fragment and is not simply the result of an all-carbon-containing cyclopentadienyl-like fragment or a cyclopentadienyl-like fragment with nitrogen substitution at a specific position.

[0343] Those skilled in the art will note that while all of the examples listed in Tables 4 and 5 produced high molecular weight copolymers with high incorporation of 1-octene comonomer, only the inventive examples produced these types of copolymers with commercially relevant high catalytic activity. [Table 6] [Table 7]

[0344] In continuous copolymerization experiments carried out at 160°C, polymerization catalyst systems containing the titanium prepolymerized catalyst of the present invention (with dichloride or dimethyl activatable ligands), boron-based catalyst activator (TB), alkylaluminoxane (MMAO-7), and hindered phenolic compound (BHEB) all exhibited high activity at 90% ethylene conversion (Q) and produced high molecular weight copolymers with high 1-octene content (see polymerization run numbers C38-C55 in Tables 6 and 7). High activity and high molecular weight were obtained with any combination of polymerization catalyst system components (in-reactor or in-line).

[0345] The polymerization catalyst systems derived from the comparative titanium prepolymerization catalysts (Comparative Examples 1, 2, 6) were able to achieve 90% Q, but the activity was much lower than that of the inventive examples. For example, compare polymerization run number C56 with C38 and C39 (dichloride complexes); compare polymerization run number C57 with C40 and C43 (dimethyl complexes with constant Al concentration); compare polymerization run number C58 with C44 (dimethyl complex). The polymerization catalyst system derived from inventive complex example 8, which has a diphenylsilyl (PhSi) bridging group, while the other inventive complexes have a dialkylsilyl (Et2Si or n-Pr2Si) bridging group, exhibited a lower k than the other inventive catalyst systems. p , but still had higher activity than catalyst systems using comparative prepolymerized catalysts (compare invention polymerization run no. C46 with comparative polymerization run nos. C56, C57, and C58). [Table 8-1] [Table 8-2] [Table 9-1] [Table 9-2]

[0346] In continuous solution phase copolymerization experiments conducted under the more demanding conditions of 190°C and 90%Q, optimal catalytic activity of each of the inventive polymerization catalyst systems was achieved when the polymerization catalyst system contained a titanium prepolymerized catalyst, a boron-based catalyst activator (e.g., TB), an alkylaluminoxane cocatalyst (e.g., MMAO-7), and a hindered phenol compound (e.g., BHEB) (see Tables 8 and 9). All of the inventive polymerization catalyst systems were activated using 100 mM -1 ·minute -1 Exceeds k p (See Polymerization Runs C59-C63 and C66-C78). The polymerization catalyst systems derived from the inventive titanium prepolymerization catalyst of Example 2 also maintained significant polymerization activity and molecular weight at 200° C. and 210° C. (See Polymerization Runs C64 and C65).

[0347] For high activity at 190°C and 90%Q, a hindered phenolic compound (e.g., BHEB) is required. In all examples using catalysts derived from titanium prepolymerized complexes of the present invention (Examples 2, 4, 10, 12, 14, 16, 18, 20), removal of BHEB from the catalyst composition resulted in significantly lower activity (compare polymerization run no. C79 to C62; compare run no. C80 to C66; compare run no. C81 to C69; compare run no. C82 to C70; compare run no. C83 to C71; compare run no. C84 to C72; compare run no. C85 to C73; and compare run no. C86 to C74).

[0348] Polymerization catalyst systems derived from comparable related titanium complexes (Comparative Examples 1, 2, 4, 6) and using a combination of TB as a boron-based activator, MMAO-7 as a cocatalyst, and a hindered phenolic compound (e.g., BHEB) had low activity and were unable to achieve 90±1% Q and / or k p <100mM -1 ·minute -1 (compare polymerization run numbers C87-C91 with the runs using the catalyst of the present invention).

[0349] Those skilled in the art will recognize that while all of the examples listed in Table 9 produced high molecular weight copolymers with high incorporation of 1-octene comonomer, only the inventive examples produced these types of copolymers with commercially relevant catalytic activity.

[0350] Non-limiting embodiments of the present disclosure include: Embodiment A. i) A prepolymerized catalyst having structure I or II: [ka] (In the formula, R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 10A , R 11A and R 12A are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R 1A , R 2A , R 3A and R 4A or R 5A , R 6A , R 7A and R 8A or R 9A , R 10A , R 11Aand R 12A Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; R 1B , R 2B , R 3B , R 4B , R 5B , R 6B , R 7B , R 8B , R 9B , R 10B , R 11B and R 12B are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R 1B , R 2B , R 3B and R 4B or R 5B , R 6B , R 7B and R 8B or R 9B , R 10B , R 11B and R 12B Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; R 13A is a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; R 13B is a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; Each R 14A are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; 14A the groups may optionally be joined to form a ring; Each R 14B are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; 14B the groups may optionally be joined to form a ring; each X is an activatable ligand; ii) a boron-based catalyst activator; iii) an alkylaluminoxane cocatalyst; iv) hindered phenol compounds; ethylene optionally with one or more C3-C 12 A polymerization process comprising polymerizing an alpha-olefin.

[0351] Embodiment B. The polymerization process of embodiment A comprising polymerizing ethylene with an alpha-olefin selected from the group consisting of 1-butene, 1-hexene, 1-octene, and mixtures thereof.

[0352] Embodiment C. The polymerization process of embodiment A comprising polymerizing ethylene with 1-octene.

[0353] Embodiment D. The polymerization process of embodiment A, B or C which is a solution phase polymerization process carried out in a solvent.

[0354] Embodiment E. The polymerization process of any of embodiments A, B, C which is a continuous solution phase polymerization process carried out in a solvent.

[0355] Embodiment F. The polymerization process of embodiment E, wherein the continuous solution phase polymerization process is carried out in at least one continuous stirred tank reactor.

[0356] Embodiment G. The polymerization process of embodiment E or F, wherein the continuous solution phase polymerization process is carried out at a temperature of at least 160° C.

[0357] Embodiment HR 1A , R 2A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 11A , R 1B , R 2B , R 4B , R 5B , R 6B , R 7B , R 8B , R 9B and R 11BThe polymerization method of embodiment A, B, C, D, E, F or G, wherein is hydrogen.

[0358] Embodiment IR 3A and R 3B The polymerization process of embodiment A, B, C, D, E, F, G or H, wherein is a hydrocarbyl group.

[0359] Example JR 3A and R 3B The method of polymerization of embodiment A, B, C, D, E, F, G or H, wherein is an alkyl group.

[0360] Embodiment KR 3A and R 3B The method of polymerization of embodiment A, B, C, D, E, F, G or H, wherein is a methyl group.

[0361] Embodiment LR 10A and R 10B The polymerization process of embodiment A, B, C, D, E, F, G, H, I, J or K, wherein

[0362] EMBODIMENT MR 10A and R 10B The method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J or K, wherein

[0363] Embodiment NR 10A and R 10B The method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J or K, wherein

[0364] Embodiment OR 10A and R 10B The polymerization process of embodiment A, B, C, D, E, F, G, H, I, J or K, wherein

[0365] Implementation example PR 10A and R 10BThe method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J or K, wherein

[0366] Example QR 10A and R 10B The method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J or K, wherein

[0367] Embodiment RR 12A and R 12B The polymerization process of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P or Q, wherein

[0368] SR embodiment 12A and R 12B The method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P or Q, wherein

[0369] Embodiment TR 12A and R 12B The method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P or Q, wherein

[0370] Embodiment UR 12A and R 12B The method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P or Q, wherein

[0371] VR 13A and R 13B The polymerization process of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T or U, wherein

[0372] Embodiment WR 13A and R 13BThe method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T or U, wherein

[0373] Embodiment XR 13A and R 13B The method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T or U, wherein

[0374] Embodiment YR 13A and R 13B The method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T or U, wherein

[0375] Embodiment ZR 13A and R 13B The method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T or U, wherein

[0376] Embodiment AA.R 13A and R 13B The polymerization method of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T or U, wherein is a 3,5-di-tert-butylphenyl group.

[0377] Embodiment BB. Each R 14A and each R 14B is a hydrocarbyl group.

[0378] Embodiment CC. Each R 14A and each R 14B The method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z or AA, wherein

[0379] DD.Each R 14A and each R 14B The method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z or AA, wherein

[0380] Embodiment EE. Each R 14A and each R 14B The method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z or AA, wherein

[0381] Embodiment FF. Each R 14A and each R 14B The method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z or AA, wherein

[0382] Embodiment GG. The method of polymerization of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB, CC, DD, EE, or FF, wherein each X is methyl or chloride.

[0383] Embodiment HH. The polymerization method of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB, CC, DD, EE, FF, or GG, wherein the boron based catalyst activator is selected from the group consisting of N,N-dimethylanilinium tetrakispentafluorophenylborate ("[MeNHPh][B(CF)]") and triphenylmethylium tetrakispentafluorophenylborate ("[PhC][B(CF)]").

[0384] Embodiment II. The polymerization method of embodiment A, B, C, D, E, F, G, H, I, J, K, L, M, N, O, P, Q, R, S, T, U, V, W, X, Y, Z, AA, BB, CC, DD, EE, FF or GG, wherein the hindered phenol compound is 2,6-di-tert-butyl-4-ethylphenol.

[0385] Embodiment JJ.i) A prepolymerized catalyst having structure I or II: [ka] (In the formula, R 1A , R 2A , R 3A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 10A , R 11A and R 12A are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R 1A , R 2A , R 3A and R 4A or R 5A , R 6A , R 7A and R 8A or R 9A , R 10A , R 11A and R 12A Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; R 1B , R 2B , R 3B , R 4B , R 5B , R 6B , R 7B , R 8B , R 9B , R 10B , R 11B and R 12Bare each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R 1B , R 2B , R 3B and R 4B or R 5B , R 6B , R 7B and R 8B or R 9B , R 10B , R 11B and R 12B Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; R 13A is a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; R 13B is a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; Each R 14A are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; 14A the groups may optionally be joined to form a ring; Each R 14B are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; 14B the groups may optionally be joined to form a ring; each X is an activatable ligand; ii) a boron-based catalyst activator; iii) an alkylaluminoxane cocatalyst; iv) hindered phenol compounds; An olefin polymerization catalyst system comprising:

[0386] Embodiment KK.R 1A , R 2A , R 4A , R 5A , R 6A , R 7A , R 8A , R 9A , R 11A , R 1B , R 2B , R4B , R 5B , R 6B , R 7B , R 8B , R 9B and R 11B The method of embodiment JJ, wherein is hydrogen.

[0387] Embodiment LL.R 3A and R 3B The polymerization process of embodiment JJ ​​or KK, wherein is a hydrocarbyl group.

[0388] Embodiment MM.R 3A and R 3B The method of embodiment JJ ​​or KK, wherein is an alkyl group.

[0389] Embodiment NN.R 3A and R 3B The method of embodiment JJ ​​or KK, wherein is a methyl group.

[0390] Embodiment OO.R 10A and R 10B The polymerization process of embodiment JJ ​​or KK, LL, MM or NN, wherein is a hydrocarbyl group.

[0391] Embodiment PP.R 10A and R 10B The polymerization method of embodiment JJ, or KK, LL, MM, or NN, wherein is an alkyl group.

[0392] Embodiment QQ.R 10A and R 10B The method of embodiment JJ ​​or KK, LL, MM or NN, wherein is a methyl group.

[0393] Embodiment RR.R 10A and R 10B The polymerization process of embodiment JJ ​​or KK, LL, MM or NN, wherein is a heteroatom-containing hydrocarbyl group.

[0394] Embodiment SS.R 10A and R10B The method of embodiment JJ ​​or KK, LL, MM or NN, wherein is an alkoxy group.

[0395] Embodiment TT.R 10A and R 10B The method of polymerization of embodiment JJ ​​or KK, LL, MM or NN, wherein is a methoxy group.

[0396] Embodiment UU.R 12A and R 12B The polymerization process of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, or TT, wherein

[0397] Embodiment VV.R 12A and R 12B The polymerization method of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, or TT, wherein is an alkyl group.

[0398] Embodiment WW.R 12A and R 12B The polymerization method of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, or TT, wherein is a tert-butyl group.

[0399] Embodiment XX.R 12A and R 12B The method of polymerization of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS or TT, wherein is a 1-adamantyl group.

[0400] Embodiment YY.R 13A and R 13B The polymerization process of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, TT, UU, VV, WW or XX, wherein

[0401] Embodiment ZZ.R 13A and R 13BThe polymerization method of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, TT, UU, VV, WW or XX, wherein

[0402] Embodiment AAA.R 13A and R 13B The polymerization method of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, TT, UU, VV, WW or XX, wherein

[0403] Embodiment BBB.R 13A and R 13B The polymerization method of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, TT, UU, VV, WW or XX, wherein

[0404] Embodiment CCC.R 13A and R 13B The polymerization method of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, TT, UU, VV, WW, or XX, wherein

[0405] Embodiment DDD.R 13A and R 13B The polymerization method of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, TT, UU, VV, WW or XX, wherein is a 3,5-di-tert-butyl-phenyl group.

[0406] Embodiment EEE. Each R 14A and each R 14B The polymerization process of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, TT, UU, VV, WW, XX, YY, ZZ, AAA, BBB, CCC, or DDD, wherein

[0407] FFF.Each R 14A and each R 14BThe polymerization method of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, TT, UU, VV, WW, XX, YY, ZZ, AAA, BBB, CCC, or DDD, wherein

[0408] Embodiment GGG. Each R 14A and each R 14B The polymerization method of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, TT, UU, VV, WW, XX, YY, ZZ, AAA, BBB, CCC, or DDD, wherein

[0409] Embodiment HHH. Each R 14A and each R 14B The polymerization method of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, TT, UU, VV, WW, XX, YY, ZZ, AAA, BBB, CCC, or DDD, wherein

[0410] Embodiment III. Each R 14A and each R 14B The polymerization method of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, TT, UU, VV, WW, XX, YY, ZZ, AAA, BBB, CCC, or DDD, wherein

[0411] The method of polymerization of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, TT, UU, VV, WW, XX, YY, ZZ, AAA, BBB, CCC, DDD, EEE, FFF, GGG, HHH or III, wherein each X is methyl or chloride.

[0412] The polymerization method of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, TT, UU, VV, WW, XX, YY, ZZ, AAA, BBB, CCC, DDD, EEE, FFF, GGG, HHH, III or JJJ, wherein the boron based catalyst activator is selected from the group consisting of N,N-dimethylanilinium tetrakispentafluorophenylborate ("[MeNHPh][B(CF)]") and triphenylmethylium tetrakispentafluorophenylborate ("[PhC][B(CF)]").

[0413] The polymerization method of embodiment JJ ​​or KK, LL, MM, NN, OO, PP, QQ, RR, SS, TT, UU, VV, WW, XX, YY, ZZ, AAA, BBB, CCC, DDD, EEE, FFF, GGG, HHH, III, JJJ or KKK, wherein the hindered phenol compound is 2,6-di-tert-butyl-4-ethylphenol.

[0414] Embodiment MMM. Formula VI: [ka] 1. A method for making an organometallic complex having the formula: The following reaction is carried out in a single reaction vessel: (i) Formula V: [ka] or a double bond isomer of a cyclopentadienyl-containing compound having formula V, is combined with a base and subsequently reacted with a cyclopentadienyl-containing compound having formula VII: [ka] adding a compound represented by: (ii) optionally an excess of a trialkylamine compound, (R F ) in the presence of at least 2 molar equivalents of an alkyllithium reagent, (R E) adding Li; (iii) Formula TiCl2(X ε )2(D) n adding a Group IV transition metal compound having (iv) optionally, a compound of formula Cl x Si(R ε ) 4-x (In the formula, each R ε The groups are independently C 1~20 adding a silane compound having an alkyl group; (v) optionally, a compound of formula (R G )M, (R G )(R H )Mg or (R G ) adding an alkylating agent having 2Zn; (vi) Optionally, switching the reaction solvent during any of the previous steps. A method comprising the steps of: (In the formula, R A , R B , R C and R D are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R A , R B , R C and R D Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; R 9 , R 10 , R 11 and R 12 are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R 9 , R 10 , R 11 and R 12 Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; Each R 14 are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; 14The groups may optionally be joined to form a ring (e.g., two R 14A The groups may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; each X is an activatable ligand; X ε is halide, C 1~20 an alkoxy group or a group of the formula -NR', where each R' group is independently 1~30 Alkyl group or C 6~10 an amide group having an aryl group; R E is C 1~20 is a hydrocarbyl group; R F is C 1~10 is an alkyl group; R G is C 1~20 is a hydrocarbyl group; R H is C 1~20 Hydrocarbyl group, halide or C 1~20 is an alkoxy group; M is Li, Na or K; D is an electron donor compound; (n=1 or 2). [Industrial Applicability]

[0415] An olefin polymerization catalyst system is provided for polymerizing ethylene with alpha-olefins to produce ethylene copolymers having high molecular weight and a high degree of short chain branching. The olefin polymerization catalyst system may be used in a continuous solution phase polymerization process at elevated temperatures.

Claims

1. i) a prepolymerized catalyst having structure I or II: 【Chemical 1】 (In the formula, R １Ａ , R ２Ａ , R ３Ａ , R ４Ａ , R ５Ａ , R ６Ａ , R ７Ａ , R ８Ａ , R ９Ａ , R １０Ａ , R １１Ａ and R １２Ａ are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R １Ａ , R ２Ａ , R ３Ａ and R ４Ａ or R ５Ａ , R ６Ａ , R ７Ａ and R ８Ａ or R ９Ａ , R １０Ａ , R １１Ａ and R １２Ａ Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; R １Ｂ , R ２Ｂ , R ３Ｂ , R ４Ｂ , R ５Ｂ , R ６Ｂ , R ７Ｂ , R ８Ｂ , R ９Ｂ , R １０Ｂ , R １１Ｂ and R １２Ｂ are each independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, halogen, or hydrogen; R １Ｂ , R ２Ｂ , R ３Ｂ and R ４Ｂ or R ５Ｂ , R ６Ｂ , R ７Ｂ and R ８Ｂ or R ９Ｂ , R １０Ｂ , R １１Ｂ and R １２Ｂ Adjacent groups in the group consisting of may optionally form a cyclic hydrocarbyl group or a cyclic heteroatom-containing hydrocarbyl group; R １３Ａ is a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; R １３Ｂ is a hydrocarbyl group or a heteroatom-containing hydrocarbyl group; Each R １４Ａ are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; １４Ａ the groups may optionally be joined to form a ring; Each R １４Ｂ are independently a hydrocarbyl group, a heteroatom-containing hydrocarbyl group, or hydrogen; １４Ｂ the groups may optionally be joined to form a ring; each X is an activatable ligand; ii) a boron-based catalyst activator; and iii) an alkylaluminoxane cocatalyst; iv) a hindered phenol compound; ethylene optionally with one or more C ３ ~C １２ A polymerization process comprising polymerizing an alpha-olefin.

2. 10. The polymerization process of claim 1, comprising polymerizing ethylene with an alpha-olefin selected from the group consisting of 1-butene, 1-hexene, 1-octene, and mixtures thereof.

3. The polymerization process of claim 1, comprising polymerizing ethylene with 1-octene.

4. 10. The polymerization process of claim 1, which is a solution phase polymerization process carried out in a solvent.

5. 10. The polymerization process of claim 1, which is a continuous solution phase polymerization process carried out in a solvent.

6. 6. The polymerization process of claim 5, wherein the continuous solution phase polymerization process is carried out in at least one continuous stirred tank reactor.

7. 6. The polymerization process of claim 5, wherein the continuous solution phase polymerization process is carried out at a temperature of at least 160°C.

8. R １Ａ , R ２Ａ , R ４Ａ , R ５Ａ , R ６Ａ , R ７Ａ , R ８Ａ , R ９Ａ , R １１Ａ , R １Ｂ , R ２Ｂ , R ４Ｂ , R ５Ｂ , R ６Ｂ , R ７Ｂ , R ８Ｂ , R ９Ｂ and R １１Ｂ 2. The polymerization process of claim 1, wherein is hydrogen.

9. R ３Ａ and R ３Ｂ The polymerization process of claim 1 wherein is a hydrocarbyl group.

10. R ３Ａ and R ３Ｂ The polymerization method of claim 1 , wherein is an alkyl group.

11. R ３Ａ and R ３Ｂ The polymerization method according to claim 1 , wherein is a methyl group.

12. R １０Ａ and R １０Ｂ The polymerization process of claim 1 wherein is a hydrocarbyl group.

13. R １０Ａ and R １０Ｂ The polymerization method of claim 1 , wherein is an alkyl group.

14. R １０Ａ and R １０Ｂ The polymerization method according to claim 1 , wherein is a methyl group.

15. R １０Ａ and R １０Ｂ The polymerization process of claim 1 wherein is a heteroatom-containing hydrocarbyl group.

16. R １０Ａ and R １０Ｂ The polymerization method of claim 1 , wherein is an alkoxy group.

17. R １０Ａ and R １０Ｂ The polymerization method of claim 1 , wherein is a methoxy group.

18. R １２Ａ and R １２Ｂ The polymerization process of claim 1 wherein is a hydrocarbyl group.

19. R １２Ａ and R １２Ｂ The polymerization method of claim 1 , wherein is an alkyl group.

20. R １２Ａ and R １２Ｂ The polymerization method of claim 1, wherein is a tert-butyl group.

21. R １２Ａ and R １２Ｂ The polymerization method according to claim 1, wherein is a 1-adamantyl group.

22. R １３Ａ and R １３Ｂ The polymerization process of claim 1 wherein is a hydrocarbyl group.

23. R １３Ａ and R １３Ｂ The polymerization method of claim 1 , wherein is an alkyl group.

24. R １３Ａ and R １３Ｂ The polymerization method according to claim 1 , wherein is a methyl group.

25. R １３Ａ and R １３Ｂ The polymerization method according to claim 1, wherein is an n-pentyl group.

26. R １３Ａ and R １３Ｂ The polymerization method of claim 1 , wherein is an arylalkyl group.

27. R １３Ａ and R １３Ｂ The polymerization method according to claim 1, wherein is a 3,5-di-tert-butylphenyl group.

28. Each R １４Ａ and each R １４Ｂ The polymerization process of claim 1 wherein is a hydrocarbyl group.

29. Each R １４Ａ and each R １４Ｂ The polymerization method of claim 1 , wherein is an alkyl group.

30. Each R １４Ａ and each R １４Ｂ The polymerization method according to claim 1 , wherein is an ethyl group.

31. Each R １４Ａ and each R １４Ｂ The polymerization method of claim 1 , wherein is an aryl group.

32. Each R １４Ａ and each R １４Ｂ The polymerization method of claim 1 , wherein is a phenyl group or a substituted phenyl group.

33. 10. The polymerization process of claim 1, wherein each X is methyl or chloride.

34. The boron-based catalyst activator is N,N-dimethylanilinium tetrakispentafluorophenylborate ("Me ２ NHPh][B(C ６ F ５ ) ４ ]") and triphenylmethylium tetrakispentafluorophenylborate ("[Ph ３ C] [B(C ６ F ５ ) ４ 2. The polymerization method of claim 1, wherein the hydroxyl group is selected from the group consisting of:

35. 2. The polymerization process of claim 1, wherein the hindered phenol compound is 2,6-di-tert-butyl-4-ethylphenol.

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