Organometallic compounds for use as chain transfer agents and methods of making the same

Abstract

Embodiments are directed to an organometallic compound represented by the general formula, M[CH2CH(R1SiMe2X)(R2SiMe2X)]a, wherein M includes a zinc atom or an aluminum atom; R1 and R2 are independently a hydrocarbon chain comprising from 1 to 20 carbon atoms, X is a hydrogen atom or a vinyl group, and a is 2 or 3. Further embodiments are directed to methods for making the organometallic compound and methods for making polyolefin compounds utilizing the organometallic compound.

Description

86262-WO-PCT / DOW 86262 WO1ORGANOMETALLIC COMPOUNDS FOR USE AS CHAIN TRANSFER AGENTS AND METHODS OF MAKING THE SAMECROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims priority to U.S. Provisional Application Serial No. 63 / 714,243 filed October 31, 2024, the entire disclosure of which is hereby incorporated by reference.TECHNICAL FIELD

[0002] Embodiments described herein generally relate to organometallic compounds and, more specifically, to organometallic compounds for use as chain transfer agents, methods of making the same, and methods of making polyolefin compounds that utilize the same.BACKGROUND

[0003] In recent years, advances in polymer design have been seen with the use of compositions capable of chain transfer. For example, chain transfer agents (CTA) may cause termination of polymer chain growth and amounts to a transfer of a growing polymer from a catalyst to the CTA. CTAs may enable the production of novel olefin block copolymers (OBCs) through transfer of growing polymer chains back and forth between catalyst(s) and CTA. Compositions capable of chain transfer may be simple metal alkyls, such as diethylzinc and triethylaluminum. CTAs are important in the production of polyolefins, as CTAs enable the synthesis of polyolefins having desirable functional groups and / or architectures.

[0004] Accordingly, there is a need for improved organometallic compounds that may be used as CTAs to enable production of such polyolefins, as well as methods of making such organometallic compounds.SUMMARY

[0005] The embodiments of the present disclosure meet this need by utilizing a bifunctional organometallic compound. This results in a CTA that provides for the production polyolefins having relatively complex architectures as compared to polyolefins produces using monofunctional CTAs. As described herein, according to one or more embodiments, the organometallic compound may be bifunctional.86262-WO-PCT / DOW 86262 WO2

[0006] In one embodiment, an organometallic compound is represented by the general formula M[CH2CH(RiSiMe2X)(R2SiMe2X)]a, wherein: M comprises a zinc atom or an aluminum atom; Ri and R2 are independently a hydrocarbon chain comprising from 1 to 20 carbon atoms; X is a hydrogen atom or a vinyl group; and a is 2 or 3.

[0007] Additional features and advantages of the embodiments will be set forth in the detailed description and, in part, will be readily apparent to persons of ordinary skill in the art from that description, which includes the accompanying drawing and claims, or recognized by practicing the described embodiments.

[0008] It is to be understood that both the preceding general description and the following detailed description describe various embodiments and are intended to provide an overview or framework for understanding the nature and character of the claimed subject matter.

[0009] The drawings are included to provide a further understanding of the embodiments and, together with the detailed description, serve to explain the principles and operations of the claimed subject matter. However, the embodiments depicted in the drawings are illustrative and exemplary in nature, and not intended to limit the claimed subject matter.BRIEF DESCRIPTION OF THE DRAWINGS

[0010] The following detailed description may be better understood when read in conjunction with the following drawing, in which:

[0011] FIG. 1A depicts a nuclear magnetic resonance (NMR) spectrum of Example 1, according to one or more embodiments of the present disclosure;

[0012] FIG. IB depicts a NMR spectrum of Example 1, according to one or more embodiments of the present disclosure;

[0013] FIG. 2 depicts a gas chromatography-mass spectrometry (GC-MS) spectrum of Example 1, according to one or more embodiments of the present disclosure;

[0014] FIG. 3 depicts a NMR spectrum of Example 2, according to one or more embodiments of the present disclosure; and86262-WO-PCT / DOW 86262 WO3

[0015] FIG. 4. depicts a GC-MS spectrum of Example 2, according to one or more embodiments of the present disclosure.

[0016] Reference will now be made in greater detail to various embodiments, some of which are illustrated in the accompanying drawing.DETAILED DESCRIPTION

[0017] Specific embodiments of the present application will now be described. The disclosure may be embodied in different forms and should not be construed as limited to the embodiments set forth in this disclosure. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0018] DEFINITIONS

[0019] Unless stated to the contrary, implicit from the context, or customary in the art, all test methods are current as of the filing date of this disclosure.

[0020] It is noted that the various details described in this disclosure should not be taken to imply that these details relate to elements that are essential components of the various embodiments described in this disclosure, even in cases where a particular element is illustrated in each of the drawings that accompany the present description. Unless specifically identified as such, no feature disclosed and described herein should be construed as “essential”. Contemplated embodiments of the present technology include those that include some or all of the features of the appended claims.

[0021] For the purposes of describing and defining the present disclosure it is noted that the term “about” are utilized in this disclosure to represent the inherent degree of uncertainty that may be attributed to any quantitative comparison, value, measurement, or other representation. The term “about” are also utilized in this disclosure to represent the degree by which a quantitative representation may vary from a stated reference without resulting in a change in the basic function of the subject matter at issue.

[0022] The terms "comprising", "including", "having”, and their derivatives, are not intended to exclude the presence of any additional component, step or procedure, whether the same is86262-WO-PCT / DOW 86262 WO4 specifically disclosed. In order to avoid any doubt, all compositions claimed through use of the term "comprising" may include any additional additive, adjuvant, or compound, whether polymeric or otherwise, unless stated to the contrary. In contrast, the term, "consisting essentially of’ excludes from the scope of any succeeding recitation any other component, step or procedure, excepting those that are not essential to operability. The term "consisting of’ excludes any component, step or procedure, not specifically delineated or listed.

[0023] It is noted that one or more of the following claims and the detailed description utilize the terms “where” or “wherein” as a transitional phrase. For the purposes of defining the present technology, it is noted that this term is introduced in the claims as an open-ended transitional phrase that is used to introduce a recitation of a series of characteristics of the structure and should be interpreted in like manner as the more commonly used open-ended preamble term “comprising.”

[0024] It should be understood that any two quantitative values assigned to a property may constitute a range of that property, and all combinations of ranges formed from all stated quantitative values of a given property are contemplated in this disclosure. Where multiple ranges for a quantitative value are provided, these ranges may be combined to form a broader range, which is contemplated in the embodiments described herein.

[0025] All references to the Periodic Table of Elements refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 1990. Also, any references to a Group or Groups shall be to the Group or Groups reflected in this Periodic Table of Elements using the IUPAC system for numbering groups. Unless stated to the contrary, implicit from the context, or customary in the art, all parts and percents are based on weights and all test methods are current as of the filing date of this disclosure.

[0026] Number ranges in this disclosure and as they relate to the composition having the formula (I) are approximate, and thus may include values outside of the range unless otherwise indicated. Number ranges include all values from and including the lower and upper values, including fractional numbers or decimals.

[0027] As used in this disclosure, the term “chain transfer agent” refers to a compound, such as some main-group alkyl compounds, that may exchange, for example, an alkyl group on the86262-WO-PCT / DOW 86262 WO5 chain transfer agent with the growing polymer chain on the catalyst, which generally results in termination of the polymer chain growth.

[0028] As used in this disclosure, the term “catalyst precursor” refers to a transition metal species that, once combined with an activator, is capable of polymerization of unsaturated monomers. The terms "catalysts", "catalyst precursors", "procatalysts", "metal complexes," and like terms are to be interchangeable in the present disclosure, as known to those skilled in the art.

[0029] As used in this disclosure, the term “organometallic compound” refers to any compound that contains a metal-carbon bond, R-M, and includes those known in the art as it relates to the present disclosure.

[0030] As used in this disclosure, “bifunctional” refers to the presence of two functional groups in a molecule, such as the two silyl functional groups at the end of the chains in the organometallic compounds of the present disclosure.

[0031] As used in this disclosure, the term “activator” refers to compounds that can activate the catalyst precursor to form an active catalyst composition. “Co-catalyst” and like terms are used interchangeably with “activator”.

[0032] As used in this disclosure, “polymer” refers to a compound prepared by polymerizing monomers whether of the same or a different type. The generic term “polymer” thus embraces the term “homopolymer”, usually employed to refer to polymers prepared from only one type of monomer, and the term interpolymer as defined below. It also embraces all forms of interpolymers, e.g., random, block, homogenous, heterogenous, etc.

[0033] EMBODIMENTS

[0034] Organometallic Compound

[0035] Embodiments of the present disclosure are directed to bifunctional organometallic compounds for use as CTAs in the production polyolefins having relatively complex architectures as compared to polyolefins produces using monofunctional CTAs. According to one or more embodiments, an organometallic compound may be represented by the general formula M[CH2CH(RiSiMe2X)(R2SiMe2X)]a, wherein:86262-WO-PCT / DOW 86262 WO6M comprises a zinc atom or an aluminum atom;Ri and R2 are independently a hydrocarbon chain comprising from 1 to 20 carbon atoms;X is a hydrogen atom or a vinyl group; and a is 2 or 3.

[0036] In one or more embodiments, the organometallic compound may be a metal alkyl comprising M. M may comprise a divalent metal, such as zinc (Zn) or a trivalent metal, such as aluminum (Al).

[0037] In one or more embodiments, Ri and R2 are independently a hydrocarbon chain comprising from 1 to 20 carbon atoms. For example, Ri, R2, or both may be a hydrocarbon chain comprising from 1 to 19, from 1 to 18, from 1 to 17, from 1 to 16, from 1 to 15, from 1 to 14, from 1 to 13, from 1 to 12, from 1 to 11, from 1 to 10, from 1 to 9, from 1 to 8, from 1 to 7, from 1 to 6, from 1 to 5, from 1 to 4, from 1 to 3, from 1 to 2, from 2 to 20, from 3 to 20, from 4 to 20 ,from 5 to 20, from 6 to 20, from 7 to 20, from 8 to 20, from 9 to 20, from 10 to 20, from 11 to 20, from 12 to 20, from 13 to 20, from 14 to 20, from 15 to 20, from 16 to 20, from 17 to 20, from 18 to 20, from 19 to 20, from 2 to 18, from 4 to 16, from 6 to 14, from 8 to 12 carbon atoms, or any combinations of these ranges.

[0038] In one or more embodiments, X may be a hydrogen atom or a vinyl group. In some embodiments, X may be a hydrogen atom that is attached to the silicon atom, such that the organometallic compound has one or more terminal groups with the formula -Si-H. In other embodiments, X may be a vinyl group. A vinyl group is a functional group that has the formula: -CH=CH2. The vinyl group may be attached to the silicon atom, such that the organometallic compound has one or more terminal groups with the formula: -Si-CH=CH2.

[0039] In some embodiments, M may be an aluminum atom and a may be 3. In such embodiments, the organometallic compound may be represented by the structure:86262-WO-PCT / DOW 86262 WO7

[0040] In some embodiments, M may be represented by the formula, (NB)bM, wherein:NB is a norbornyl group derived from norbornene (NB), ethylidene norbornene(ENB), or dicyclopentadiene (DCPD); and b is 1 or 2.

[0041] In some embodiments, the norbornene compound may be represented by the structure:

[0042] In some embodiments, M may be represented by the general formula (NB)bAl and a + b is 3. In such embodiments, the organometallic compound may be represented by the below structure, where x may be 1 or 2.

[0043] In some embodiments, M is represented by the general formula (NB)bZn, where b is 1 and a is 1. In such embodiments, the organometallic compound may be represented by the structure below, where x is 1.

[0044] Method of Making an Organometallic Compound86262-WO-PCT / DOW 86262 WO8

[0045] The present disclosure further relates to methods for preparing the organometallic compounds described herein.

[0046] The method may comprise two steps: a thermal step and a catalytic step. In some embodiments, the thermal step may comprise combining a silane-containing compound and an aluminum-containing compound at a temperature from 100 °C to 150 °C for a duration from 1 hour to 5 hours to form a monofunctional compound represented by the formula Al(RiSiMe2X)3. In some embodiments, the catalytic step may comprise contacting the monofunctional compound with the silane-containing compound, a catalyst, and an activator to form the organometallic compound.

[0047] The silane-containing compound may comprise 7-octenyldimethylsilane, 5- hexenyldimethylsilane, allyldimethylsilane or combinations thereof. In some embodiments, the silane-containing compound may be represented by the formula: CH2=CH-Ri-SiR3R4X , where Ri and X are as previously described and R3 and R4 may be methyl groups.

[0048] In some embodiments, the aluminum-containing compound may be triisobutyl aluminum or diisobutylaluminum hydride. In additional embodiments, the aluminum compound may include, but is not limited to, tris(2-methylbutyl)aluminum, tris(2- methylpentyl)aluminum, tris(2-ethylbutyl)aluminum, bis(2-methylbutyl)aluminum hydride, bis(2-methylpentyl)aluminum hydride and bis(2-ethylbutyl)aluminum hydride.

[0049] As stated, combining the silane-containing compound and the aluminum-containing compound may be at certain temperatures and durations. The temperature may be from 100 °C to 150 °C. For example, the temperature may be from 105 °C to 150 °C, from 110 °C to 150 °C, from 115 °C to 150 °C, from 120 °C to 150 °C, from 125 °C to 150 °C, from 130 °C to 150°C, from 135 °C to 150 °C, from 140 °C to 150 °C, from 145 °C to 150 °C, from 100 °C to 145°C, from 100 °C to 140 °C, from 100 °C to 135 °C, from 100 °C to 130 °C, from 100 °C to 125°C, from 100 °C to 120 °C, from 100 °C to 115 °C, from 100 °C to 110 °C, from 100 °C to 105°C, from 110 °C to 140 °C, from 120 °C to 130 °C, or any combinations of these ranges. Without being bound by any particular theory, it is believed that heating at these temperatures may cause the removal of branched alkyl groups on aluminum by beta-hydride elimination to form an aluminum hydride species followed by insertion of the vinyl groups of the silane compound to form the desired product. It is believed that temperatures below 100 °C may not86262-WO-PCT / DOW 86262 WO9 be sufficient to cause the beta-hydride elimination reaction and temperatures above 150 °C may render the resulting compound unstable.

[0050] In some embodiments, the silane-containing compound and an aluminum- containing compound may be combined for a duration of from 1 hour to 5 hours. For example, the duration may be from 1.5 hours to 5 hours, from 2 hours to 5 hours, from 2.5 hours to 5 hours, from 3 hours to 5 hours, from 3.5 hours to 5 hours, from 4 hours to 5 hours, from 4.5 hours to 5 hours, from 1 hour to 4.5 hours, from 1 hour to 4 hours, from 1 hour to 3.5 hours, from 1 hour to 3 hours, from 1 hour to 2.5 hours, from 1 hour to 2 hours, from 1 hour to 1.5 hours, from 1.5 hours to 4.5 hours, from 2 hours to 4 hours, from 2.5 hours to 3.5 hours, or any combinations of these ranges. Without being bound by any particular theory, it is believed that durations of less than 1 hour may result in an incomplete reaction. It is also believed that durations of greater than 5 hours may render the resulting compound unstable, particularly at the reaction temperatures described herein.

[0051] Combining the silane-containing compound and the aluminum-containing compound may form a monofunctional compound represented by the formula Al(RiSiMe2X)3. This monofunctional compound may be represented by the structure:

[0052] Now turning to the catalytic step, the catalytic step may comprise contacting the monofunctional compound with the silane-containing compound, a catalyst, and an activator to form the organometallic compound. The silane-containing compound may be the same silane- containing compound that was used in the thermal step and as described herein.

[0053] Catalyst

[0054] According to one or more embodiments, catalysts that may be used to form the organometallic compounds described herein may include any catalyst having good chain transfer ability with organometallic compounds. The catalysts may have no detrimental effect on subsequent polymerization and therefore, may need not be removed from the final solution86262-WO-PCT / DOW 86262 WO10 prior to polymerization. These catalysts may remain as an active catalyst during polymerization reactions, as discussed below.

[0055] The catalyst may be polyvalent Lewis base complexes that include Group 4 metal derivatives, particularly hafnium derivatives of hydrocarbylamine substituted heteroaryl compounds corresponding to the formula:wherein:R11is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, and inertly substituted derivatives thereof containing from 1 to 30 atoms not counting hydrogen or a divalent derivative thereof;T1is a divalent bridging group of from 1 to 41 atoms other than hydrogen, from 1 to 20 atoms other than hydrogen, or a mono- or di- C1.20 hydrocarbyl substituted methylene or silane group; andR12is a C5-20 heteroaryl group containing Lewis base functionality, especially a pyridin-2-yl- or substituted pyridin-2-yl group or a divalent derivative thereof;M is a Group 4 metal, such as hafnium;X1is an anionic, neutral, or dianionic ligand group; x' is a number from 0 to 5 indicating the number of such X1groups; and bonds, optional bonds and electron donative interactions are represented by lines, dotted lines, and arrows, respectively.

[0056] Suitable complexes may be those wherein ligand formation results from hydrogen elimination from the amine group and optionally from the loss of one or more additional groups, especially from R12. In addition, electron donation from the Lewis base functionality, preferably an electron pair, may provide additional stability to the metal center. Suitable metal complexes may correspond to the formula:86262-WO-PCT / DOW 86262 WOwherein:M1, X1, x’, R11, and T1are as previously defined;R13, R14, R15, and R16are hydrogen, halo, or an alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, or silyl group of up to 20 atoms not including hydrogen. In some embodiments, adjacent R13, R14, R15, and R16groups may be joined together to form fused ring derivatives.Bonds, optional bonds, and electron pair donative interactions are represented by lines, dotted lines, and arrows, respectively. Suitable examples of the foregoing metal complexes may be represented by the formula:wherein:M1, X1, and x’ are as previously defined;R13, R14, R15, and R16are as previously defined. In some embodiments, R13, R14, and R15are hydrogen or Ci-4 alkyl, and R16is C6-20 aryl, such as naphthalenyl;Rais independently at each occurrence a C1.4 alkyl and a is 1-5. In some embodiments, Rain two ortho- positions to the nitrogen may be isopropyl or t-butyl;R17, and R18are independently at each occurrence hydrogen, halogen, or a Cl -20 alkyl or aryl group. In some embodiments, one of R17, and R18is hydrogen and the other is a C6-20 aryl group, such as 2-isopropyl, phenyl, or a fused polycyclic aryl group such as an anthracenyl group. Bonds,86262-WO-PCT / DOW 86262 WO12 optional bonds, and electron pair donative interactions are represented by lines, dotted lines, and arrows, respectively.

[0057] In additional embodiments, the catalyst may be represented by the formula:wherein:X1is chosen from a halide, a N,N-dimethylamido, and a Ci-4 alkyl. In some embodiments, X1may be a methyl group;Rfis independently a hydrogen, a halogen, a C1-20 alkyl, or a C6-20 aryl. In some embodiments, adjacent Rfgroups may be joined together to form a ring; f is 1 to 5;Rcis independently a hydrogen, halogen, C1.20 alkyl, or C6-20 aryl. In some embodiments, adjacent Rcgroups may be joined together to form a ring; and c is 1 to 5.

[0058] Suitable examples of metal complexes for use as catalysts according to one or more embodiments may be represented by the formulas:86262-WO-PCT / DOW 86262 WO13 wherein Rxis a C1-4 alkyl or cycloalkyl, such as methyl, isopropyl, t-butyl or cyclohexyl; andX1at each occurrence is a halide, a N,N-dimethylamido, or a C1-4 alkyl, such as methyl.

[0059] Examples of metal complexes used as catalysts according to one or more embodiments may include:[N-(2,6-di(l-methylethyl)phenyl)amido)(o-tolyl)(a-naphthalen-2-diyl(6-pyridin-2- diyl)methane)]hafnium dimethyl;[N-(2,6-di(l-methylethyl)phenyl)amido)(o-tolyl)(a-naphthalen-2-diyl(6-pyridin-2- diyl)methane)]hafhium di(N,N-dimethylamido);[N-(2,6-di(l-methylethyl)phenyl)amido)(o-tolyl)(a-naphthalen-2-diyl(6-pyridin-2- diyl)methane)]hafnium dichloride;[N-(2,6-di(l-methylethyl)phenyl)amido)(2-isopropylphenyl)(a-naphthalen-2-diyl(6-pyridin- 2-diyl)methane)]hafnium di(N,N-dimethylamido);[N-(2,6-di(l-methylethyl)phenyl)amido)(2-isopropylphenyl)(a-naphthalen-2-diyl(6-pyridin- 2-diyl)methane)]hafnium dichloride;[N-(2,6-di(l-methylethyl)phenyl)amido)(phenanthren-5-yl)(a-naphthalen-2-diyl(6-pyridin- 2-diyl)methane)]hafhium dimethyl;[N-(2,6-di(l-methylethyl)phenyl)amido)(phenanthren-5-yl)(a-naphthalen-2-diyl(6-pyridin-2-diyl)methane)]hafhium di(N,N-dimethylamido); and[N-(2,6-di(l-methylethyl)phenyl)amido)(phenanthren-5-yl)(a-naphthalen-2-diyl(6-pyridin- 2-diyl)methane)]hafnium dichloride.

[0060] In some embodiments, the catalyst may be represented by the formula:wherein:86262-WO-PCT / DOW 86262 WO14X1is chosen from a halide, a N,N-dimethylamido, and a C1-4 alkyl; andRi - R? are independently a hydrogen, a halogen, a C1-20 alkyl, or a C6-20 aryl.

[0061] In some embodiments, X1may be a methyl group. In some embodiments, two adjacent R groups (i.e., two of Ri - R7) may be joined together to form a ring.

[0062] The catalyst may be represented by the formula: (N-((6E)-6-(Butylimino-KN)-l- cyclohexen-l-yl)-2,6-bis(l-methylethyl)benzenaminato-KN)trimethyl-hafnium, as shown below.

[0063] In some embodiments, the catalyst may be represented by the formula: (E)-((2,6- diisopropylphenyl)(2-methyl-3-(octylimino)butan- -yljaminojtrimethyl hafnium, as shown below.

[0064] The catalyst may be represented by the formula: [N-(2,6-di(l- methylethyl)phenyl)amido)(2-isopropylphenyl)(a-naphthalen-2-diyl(6-pyridin-2- diyl)methane)]hafnium dimethyl], as shown below.86262-WO-PCT / DOW 86262 WO15

[0065] Activator

[0066] According to one or more embodiments, an activator may be employed during the method of making organometallic compounds described herein. The activator may be any compound or combination of compounds capable of activating a catalyst precursor to form an active catalyst composition or system. Suitable activators include but are not limited to those disclosed in WO 2005 / 090427 and U.S. Pat. No. 8,501,885 B2, which are incorporated by reference herein. In exemplary embodiments of the present disclosure, the activator may be represented by the formula: [HNMe(Ci8H3?)2][B(C6F5)4]. The activator may be a cationforming co-catalyst, a strong Lewis acid, or a combination thereof.

[0067] The catalyst precursors may be rendered catalytically active by combination with a cation forming co-catalyst. Suitable cation forming co-catalysts may include those previously known in the art for metal olefin polymerization complexes. Examples may include neutral Lewis acids, such as C1.30 hydrocarbyl substituted Group 13 compounds, especially tri(hydrocarbyl)aluminum- or tri(hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof, having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri(aryl)boron compounds, and most especially tris(pentafluoro- phenyl)borane; nonpolymeric, compatible, noncoordinating, ion forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium-, phosphonium-, oxonium-, carbonium-, silylium- or sulfonium-salts of compatible, noncoordinating anions, or ferrocenium-, lead- or silver salts of compatible, noncoordinating anions; and combinations of the foregoing cation forming cocatalysts and techniques.

[0068] The activator may comprise combinations of neutral Lewis acids, especially the combination of a trialkyl aluminum compound having from 1 to 4 carbons in each alkyl group and a halogenated tri(hydrocarbyl)boron compound having from 1 to 20 carbons in each86262-WO-PCT / DOW 86262 WO16 hydrocarbyl group, especially tris(pentafluorophenyl)borane. Further, the activator may include combinations of such neutral Lewis acid mixtures with a polymeric or oligomeric alumoxane, and combinations of a single neutral Lewis acid, especially tris(pentafluorophenyl)borane with a polymeric or oligomeric alumoxane. Exemplary molar ratios of metal complex:tris(pentafluorophenyl-borane:alumoxane are from 1 :1 :1 to 1 :5:20, such as from 1 :1 :1.5 to 1 :5:10.

[0069] Suitable ion forming compounds useful as activators in some embodiments may comprise a cation that is a Bronsted acid capable of donating a proton, and a compatible, noncoordinating anion, A". As used herein, the term "noncoordinating" refers to an anion or substance which either does not coordinate to the Group 4 metal containing precursor complex and the catalytic derivative derived there from or which is only weakly coordinated to such complexes thereby remaining sufficiently labile to be displaced by a neutral Lewis base. A noncoordinating anion specifically refers to an anion which when functioning as a charge balancing anion in a cationic metal complex does not transfer an anionic substituent or fragment thereof to said cation thereby forming neutral complexes. "Compatible anions" may be anions that are not degraded to neutrality when the initially formed complex decomposes and are noninterfering with desired subsequent polymerization or other uses of the complex.

[0070] Suitable anions may be those containing a single coordination complex comprising a charge -bearing metal or metalloid core which anion is capable of balancing the charge of the active catalyst species (the metal cation) which may be formed when the two components are combined. In addition, said anion should be sufficiently labile to be displaced by olefinic, diolefinic and acetylenically unsaturated compounds or other neutral Lewis bases such as ethers or nitriles. Suitable metals may include, but are not limited to, aluminum, gold and platinum. Suitable metalloids may include, but are not limited to, boron, phosphorus, and silicon.

[0071] Solvent

[0072] The solvent may optionally be used in the thermal step, the catalytic step, or both of the process described above. The solvent may be a hydrocarbon solvent, such as an aromatic solvent or an isoparaffinic hydrocarbon solvent. Suitable solvents may have a boiling point of greater than or equal to 100 °C. For example, suitable solvents may include, but are not limited to, a non-polar aliphatic or aromatic hydrocarbon solvent selected from the group of heptane, octane, nonane, decane, undecane, dodecane, cycloheptane, cyclooctane, decalin, toluene,86262-WO-PCT / DOW 86262 WO17 xylene, an isoparaffinic fluid including but not limited to Isopar™ E, Isopar™ G, Isopar™ H, Isopar™ L, Isopar™ M, a dearomatized fluid including but not limited to Exxsol™ D or isomers and mixtures of two or more thereof. Alternatively, the solvent may be toluene and / or Isopar™ E. The amount of solvent added depends on various factors including the type of solvent selected and the process conditions and equipment that will be used.

[0073] In one or more embodiments, the method of making an organometallic compound may further comprise an additional step of contacting a norbornene compound and dialkylzinc with a catalyst and an activator to form a dinorbonylzinc compound represented by the formula Zn(NB)2. In such embodiments, the monofunctional compound and the dinorbonylzinc compound may be combined with the silane-containing compound, the catalyst, and the activator to form the organometallic compound. The catalyst, activator, and silane-containing compound may be the same as described hereinabove. NB may be a norbornyl group derived from norbornene (NB), ethylidene norbornene (ENB), or dicyclopentadiene (DCPD). In embodiments, NB may be the same as described above with respect to the organometallic compound.

[0074] The dinorbonylzinc compound may be represented by the structure:

[0075] In such embodiments, the organometallic compound produced may be represented by the formula (NB)bZn[CH2CH(RiSiMe2X)(R2SiMe2X)]a,(NB)bAl[CH2CH(RiSiMe2X)(R2SiMe2X)]a, or both. In such embodiments, the molar ratio of Al to Zn may be from 9:1 to 1 :9, such as from 9:2 to 2:9, from 9:3 to 3:9, from 9:4 to 4:9, from 9:5 to 5:9, from 9:6 to 6:9, from 9:7 to 7:9, from 9:8 to 8:9, from 8:1 to 1 :8, from 7:1 to 1 :7, from 6:1 to 1 :6, from 5:1 to 1 :5, from 4:1 to 1 :4, from 3:1 to 1 :3, from 2:1 to 1 :2, or any combinations of these ranges.

[0076] Polyolefin Compounds

[0077] As stated herein, the organometallic compounds of the present disclosure may be utilized to form polyolefin compounds having complex architectures. In some embodiments, a86262-WO-PCT / DOW 86262 WO18 process for making a polyolefin compound may comprise combining olefin monomers, the organometallic compound, a catalyst, and an activator to form the polyolefin compound. The catalyst and the activator may be any catalyst or activator described herein with respect to forming the organometallic compound. The polyolefin compound may be represented by the formula P1CH2CH(RiSiMe2X)(R2SiMe2X) where P1is a polyolefin.

[0078] Specifically, the organometallic compound of the present disclosure may be combined with a catalyst as defined herein, an activator as defined herein, at least one olefin monomer, and optional materials, such as solvents and / or scavengers. Such a polymerization step may be performed under polymerization process conditions known in the art, including but not limited to those disclosed in U.S. Pat. Nos. 7,858,706 and 8,053,529, which are incorporated by reference herein. The polymerization step essentially forms the polyolefin, P1.

[0079] Suitable monomers for the polymerization step include any additional polymerizable monomer, generally any olefin or diolefin monomer. Suitable monomers can be linear, branched, acyclic, cyclic, substituted, or unsubstituted. In one aspect, the olefin can be any a- olefin, including, for example, ethylene and at least one different copolymerizable comonomer, propylene and at least one different copolymerizable comonomer having from 4 to 20 carbons, or 4-methyl-l -pentene and at least one different copolymerizable comonomer having from 4 to 20 carbons. Examples of suitable monomers include, but are not limited to, straight-chain or branched ot-olefins having from 2 to 30 carbon atoms, from 2 to 20 carbon atoms, or from 2 to 12 carbon atoms. Specific examples of suitable monomers include, but are not limited to, ethylene, propylene, 1 -butene, 1 -pentene, 3 -methyl- 1 -butene, 1 -hexene, 4-methyl-l -pentene, 3 -methyl- 1 -pentene, 1 -octene, 1 -decene, 1 -dodecene, 1 -tetradecene, 1 -hexadecene, 1- octadecene, and 1-eicosene. Suitable monomers also include cycloolefins having from 3 to 30, from 3 to 20 carbon atoms, or from 3 to 12 carbon atoms. Examples of cycloolefins that can be used include, but are not limited to, norbornene and 5-methyl-2-norbornene. Suitable monomers also include di- and poly-olefins having from 3 to 30, from 3 to 20 carbon atoms, or from 3 to 12 carbon atoms. Examples of di- and poly-olefins that can be used include, but are not limited to, butadiene, isoprene, 4-methyl-l, 3 -pentadiene, 1,3 -pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3 -hexadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6- octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7- methyl-l,6-octadiene, 4-ethylidene-8-methyl-l,7-nonadiene, and 5,9-dimethyl-l,4,8- decatriene. In a further aspect, aromatic vinyl compounds also constitute suitable monomers86262-WO-PCT / DOW 86262 WO19 for preparing the copolymers disclosed here, examples of which include, but are not limited to, styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o- ethylstyrene, m-ethylstyrene, p-ethylstyrene, divinylbenzene and 3 -phenylpropene, provided the monomer is polymerizable under the conditions employed.

[0080] In some embodiments, the polyolefin compound may be represented by the formula A1P1CH2CH(RiSiMe2X)(R2SiMe2X). A1may be selected from the group consisting of a vinyl group, a vinylidene group of the formula CH2=C(Y1)-, a vinylene group of the formula Y1CH=CH-, a mixture of a vinyl group and a vinylene group of the formula Y1CH=CH-, a mixture of a vinyl group and a vinylidene group of the formula CH2=C(Y1)-, a mixture of a vinylidene group of the formula CH2=C(Y1)- and a vinylene group of the formula Y1CH=CH- , and a mixture of a vinyl group, a vinylidene group of the formula CH2=C(Y1)-, and a vinylene group of the formula Y1CH=CH-. In some embodiments, Y1at each occurrence independently may be a Ci to C30 hydrocarbyl group.

[0081] EXAMPLES

[0082] The various embodiments of the present disclosure will be further clarified by the following examples. The examples are illustrative in nature and should not be understood to limit the subject matter of the present disclosure.

[0083] Test Methods

[0084] Nuclear Magnetic Resonance (NMR) Analysis

[0085] 1H NMR spectra were recorded on a Bruker AV-400 spectrometer at ambient temperature. NMR chemical shifts in benzene-de are referenced to 7.16 ppm (CeDsH) relative to TMS (0.00 ppm).

[0086] 13C NMR spectra of polymers were collected using a Bruker 400 MHz spectrometer equipped with a Bruker Dual DUL high-temperature CryoProbe. The polymer samples were prepared by adding approximately 2.6 g of a 50 / 50 mixture of tetrachloroethane- d2 / orthodichlorobenzene containing 0.025M chromium trisacetylacetonate (relaxation agent) to 0.2 g of polymer in a 10 mm NMR tube. The samples were dissolved and homogenized by heating the tube and its contents to 150° C. The data was acquired using 320 scans per data file, with a 7.3 second pulse repetition delay with a sample temperature of 120° C.86262-WO-PCT / DOW 86262 WO20

[0087] Gas Chromatography-Mass Spectroscopy (GC-MS)

[0088] Tandem gas chromatography-low resolution mass spectroscopy using electron impact ionization (El) was performed at 70 eV on an Agilent Technologies 6890N series gas chromatograph equipped with an Agilent Technologies 5975 inert XL mass selective detector and an Agilent Technologies Capillary column (HP1MS, 15 m><0.25 mm, 0.25 micron). The following conditions (programed method) were used: a) Oven Equilibration Time of 0.5 min, b) Oven equilibrated at 50°C at the start of the analysis, then the temperature was ramped up at 25°C / min to 200°C, and maintained at 200°C for 5 minutes, and c) Run Time of 11 minutes.

[0089] Materials

[0090] The following materials were principally used in the examples of the present disclosure.

[0091] Anhydrous toluene was obtained from Sigma-Aldrich and was further dried over alumina, which was activated in a 275 °C oven for about five hours.

[0092] The activator used was [HNMe(Ci8H3?)2][B(C6F5)4] (“borate activator”), and was obtained from Boulder Scientific Co.

[0093] (E)-((2,6-diisopropylphenyl)(2-methyl-3-(octylimino)butan-2-yl)amino)trimethyl hafnium (“catalyst”) was obtained from Boulder Scientific Co. and prepared according to methods known in the art. The structure of the catalyst is illustrated below:

[0094] Diethylzinc (“DEZ” or “ZnEt2”) and triisobutylaluminum (“TIBA”) were obtained from Sigma- Aldrich.

[0095] Isopar™ E was obtained from Exxon.86262-WO-PCT / DOW 86262 WO21

[0096] The following examples are provided as further illustrations of the present disclosure and are not to be construed as limiting. The term “overnight”, if used, refers to a time of approximately 16 to 18 hours. The term “room temperature” refers to a temperature of about 20 °C to 25 °C. In the event the name of a compound herein does not conform to the structural representation thereof, the structural representation shall control.

[0097] The synthesis of all metal complexes and the preparation of all screening experiments were carried out in a dry nitrogen atmosphere using dry box (glove box) techniques, including running reactions entirely within a dry box under a nitrogen atmosphere. All solvents used were HPLC grade and were dried before their use.

[0098] Comparative Example A

[0099] Comparative Example A was prepared in two steps. In Step 1, in a drybox under a nitrogen atmosphere, TIB A (5.0 mL, 19.8 mmol) was dissolved in 23 mL of toluene. Hex-5 - en-l-ol (2.38 mL, 19.8 mmol) was added dropwise at room temperature while stirring to form (hex-5-en-l-yloxy)diisobutylaluminum solution (0.66 M). In Step 2, in a drybox, DEZ (0.3 mL, 2.9 mmol), borate activator (0.019 mmol) and catalyst (6 mg, 0.012 mmol) were added to 10 mL of toluene in a vial. The (hex-5-en-l-yloxy)diisobutylaluminum solution (17.6 mL, 11.6 mmol) from Step 1 was added slowly to the vial. After 3 hours, one sample was taken for NMR testing and showed no reaction. The vinyl peaks at 4.95 ppm to 5.1 ppm and 5.75 ppm to 5.85 ppm remained unchanged. An additional 10 mg of catalyst and 0.3 mL of the borate activator were added and the reaction was maintained for another 2 hours. The NMR analysis still showed no reaction. Thus, Comparative Example A was unsuccessful at producing functional organometallic compounds.

[0100] Comparative Example B

[0101] Comparative Example B was prepared in two steps. In Step 1, hex-5-en-l-ol (2.8 mL, 23.3 mmol) and triethylamine (4.2 mL, 30.3 mmol) were mixed in 50 mL hexane. MesSiCl (3.87 mL, 30.3 mmol) was added slowly, which immediately formed a thick white suspension. The suspension was stirred overnight. The salt was filtered out and the solvent was removed under vacuum. The product was redissolved in 30 mL of hexane, filtered, and dried under reduced pressure to obtain (hex-5-en-l-yloxy)trimethylsilane. In Step 2, in a drybox (hex-5-en- 1 -yloxy)trimethylsilane (1.94 mmol), methylaluminoxane (MAO) (0.22 mL of 30 wt% solution86262-WO-PCT / DOW 86262 WO22 in toluene, 0.065 mmol Al), DEZ (0.1 mL, 0.97 mmol), and borate activator (0.0155 mmol) were added to toluene (3 mL ). Catalyst (0.013 mmol) was added to initiate the reaction. After 1 hour, one sample was taken for NMR analysis, which showed no reaction. The vinyl peaks at 4.95 ppm to 5.1 ppm and 5.75 ppm to 5.85 ppm remained unchanged. Additions of MAO, borate activator, and catalyst were added and reaction was maintained for another one hour. The NMR analysis still showed no reaction. Thus, Comparative Example B was unsuccessful at producing functional organometallic compounds.

[0102] Inventive Example 1 : Organometallic Compound

[0103] Example 1 was prepared in two steps. In Step 1, in a glovebox under a nitrogen atmosphere, 5-hexenyldimethylsilane (2.0 g, 14.0 mmol) and TIBA (1.18 mL, 4.68 mmol) were added to 8 mL of o-xylene. The mixture was heated to 130 °C with stirring and a small needle on cap for venting. NMR analysis was conducted after Step 1, with results shown in FIG. 1A. After 2 hours, the NMR analysis showed that the vinyl groups were completely consumed as evidenced by the disappearance of vinyl peaks at 4.95 ppm to 5.1 ppm and 5.75 ppm to 5.85 ppm. Thus, a monofunctional aluminosilane compound was formed. The reaction mechanism for Step 1 was as follows:\I / VWSl\AI(viBu)73 + ^^X^X / ^ | -HMo-xy ;lene U HSJi A / V^ VA\ / A\ / \ / z130C, 2h I |

[0104] In Step 2, catalyst (10 mg, 0.017 mmol) was weighed in a separate vial and dissolved in 1 mL toluene. Same amount of HDMS (2.0 g, 14.0 mmol) was added to the reaction mixture from Step 1, followed by addition of borate activator (0.022 mmol) and the catalyst solution. The reaction was maintained overnight. The reaction scheme for Step 2 was as follows:NMR analysis was conducted after Step 2, with results shown in FIG. IB. The NMR analysis showed that all vinyl groups disappeared as evidenced by the disappearance of vinyl peaks at86262-WO-PCT / DOW 86262 WO234.95 ppm to 5.1 ppm and 5.75 ppm to 5.85 ppm. GC-MS testing, shown in FIG. 2, evidenced that the bifunctional groups were made. The bifunctional groups are indicated in FIG. 2 by the peak at m / z = 285 (at 4.5 min). FIG. 2 also shows that some monofunctional groups remained, as shown by the peak at m / z = 143 (at 1.75 min). Thus, the two-step process of Example 1 is successful at creating bifunctional organometallic compounds as described herein.

[0105] Inventive Example 2: Organometallic Compound

[0106] Example 2 was prepared in two steps. In Step 1, in a drybox, ethylidene norbornene (ENB) (0.78 mL, 5.8 mmol), DEZ (0,3 mL, 2.9 mmol) and borate activator (0.27 mL of 0.064M solution in MCH, 0.017 mmol) were added to 7 mL of toluene in a 20 mL glass vial. Catalyst (9 mg, 0.015 mmol dissolved in 2 mL of toluene) was added to initiate the reaction. After 2 hours, the reaction was completed. The solution has [Zn] of 0.3 M and [Hf] of 0.00198 M. Separately, in a drybox, 7-octenyldimethylsilane (4.05 g, 23.78 mmol) and TIB A (2.0 mL, 7.9 mmol) were mixed in 10 mL of p-xylene in a 40 mL glass vial with a stir bar and a venting needle on the cap. The silane-aluminum mixture was heated at 130 °C with stirring. The reaction scheme for Step 1 was as follows:,

[0107] In Step 2, in the drybox, additional 7-octenyldimethylsilane (0.426 g, 2.5 mmol), the silane-aluminum mixture from Step 1 (1.0 mL, 0.5 mmol Al) and the solution from Step 1 (0.33 mL, 0.1 mmol Zn) were mixed in 3 mL of toluene in a 20 mL glass vial. Borate activator (0.31 mL of 0.0644M solution in MCH, 0.02 mmol) was added followed by catalyst (9 mg, 0.015 mmol dissolved in 2 mL of toluene). The reaction scheme for Step 2 was as follows:86262-WO-PCT / DOW 86262 WO24

[0108] Aluminum is trivalent and, as such, when the organometallic compound comprises an aluminum atom, x may be 1 or 2. Zinc is divalent and, as such, when the organometallic compound comprises a zinc atom, x is 1.

[0109] After the overnight reaction, NMR analysis, as depicted in FIG. 3, showed that all vinyl groups were consumed as evidenced by the disappearance of vinyl peaks at 4.95 ppm to 5.1 ppm and 5.75 ppm to 5.85 ppm. GC-MS analysis, as depicted in FIG. 4, showed a major peak at m / z = 341 (at around 6.2 min), indicating the creation of bifunctional groups. The peaks with m / z = 170 (at around 3.1 min) are believed to be the octenyldimethylsilane isomers with unreactive internal double bonds. The peak at around 8.6 min is believed to be a trimer, which appears due to the amount of octenyldimethylsilane used. Thus, the two-step process of Example 2 is successful at creating bifunctional organometallic compounds as described herein.

[0110] Inventive Example 3: Polyolefin Compound

[0111] Example 3 is a polyolefin compound that was produced by combining the organometallic compounds of Example 2 with an olefin monomer, the catalyst, and the activator. An example polyolefin compound is shown below:

[0112] It will be apparent to those skilled in the art that various modifications and variations can be made to the presently disclosed technology without departing from the spirit and scope of the technology. Since modifications combinations, sub-combinations and variations of the disclosed embodiments incorporating the spirit and substance of the presently disclosed technology may occur to persons skilled in the art, the technology should be construed to include everything within the scope of the appended claims and their equivalents. Additionally, although some aspects of the present disclosure may be identified herein as favored or particularly advantageous, it is contemplated that the present disclosure is not limited to these aspects.

Claims

86262-WO-PCT / DOW 86262 WO25CLAIMS1. An organometallic compound represented by the general formula, M[CH2CH(RiSiMe2X)(R2SiMe2X)]a, wherein:M comprises a zinc atom or an aluminum atom;Ri and R2are independently a hydrocarbon chain comprising from 1 to 20 carbon atoms;X is a hydrogen atom or a vinyl group; and a is 1, 2, or 3.2 The organometallic compound of claim 1, wherein M is an aluminum atom and a is 3.3 The organometallic compound of claim 1, wherein M is represented by the formula (NB)bM, wherein:NB is a norbornyl group derived from norbornene (NB), ethylidene norbornene (ENB), or dicyclopentadiene (DCPD); and b is 1 or 2.4 The organometallic compound of claim 3, wherein M is represented by the general formula (NB)bAl and a + b is 3.5 The organometallic compound of claim 3, wherein M is represented by the general formula (NB)bZn, where b is 1 and a is 1.6 A method of making the organometallic compound of claim 1, the method comprising: combining a silane-containing compound and an aluminum- containing compound at a temperature from 100 °C to 150 °C for a duration from 1 hour to 5 hours to form a mono functional compound represented by the formula Al(RiSiMe2X)3; and contacting the monofunctional compound with the silane-containing compound, a catalyst, and an activator to form the organometallic compound.7 The method of making the organometallic compound of claim 6, the method further comprising:86262-WO-PCT / DOW 86262 WO26 contacting a norbornene compound and dialkylzinc with a catalyst and an activator to form a dinorbonylzinc compound represented by the formula Zn(NB)2, where NB is a norbornyl group derived from norbornene (NB), ethylidene norbornene (ENB), or dicyclopentadiene (DCPD); and combining the mono functional compound and the dinorbonylzinc compound with the silane- containing compound, the catalyst, and the activator to form the organometallic compound.8 A method for making a polyolefin compound, the method comprising: polymerizing olefins in the presence of the organometallic compound of any one of claims 1 to 5, a catalyst, and an activator to form the polyolefin compound, wherein: the polyolefin compound is represented by the formula,P1CH2CH(RiSiMe2X)(R2SiMe2X), andP1is a polyolefin.9 The method of claim 8, wherein the polyolefin compound is represented by the formula A1P1CH2CH(RiSiMe2X)(R2SiMe2X), wherein:A1is selected from the group consisting of a vinyl group, a vinylidene group of the formula CH2=C(Y1)-, a vinylene group of the formula Y1CH=CH-, a mixture of a vinyl group and a vinylene group of the formula Y1CH=CH-, a mixture of a vinyl group and a vinylidene group of the formula CH2=C(Y1)-, a mixture of a vinylidene group of the formula CH2=C(Y1)- and a vinylene group of the formula Y1CH=CH-, and a mixture of a vinyl group, a vinylidene group of the formula CH2=C(Y1)-, and a vinylene group of the formula Y1CH=CH-; andY1at each occurrence independently is a Ci to C30 hydrocarbyl group.10 The method of any one of claims 6 to 9, wherein the catalyst is represented by the formula:wherein:X1is chosen from a halide, a N,N-dimethylamido, and a Ci-4 alkyl; andRi - R? are independently a hydrogen, a halogen, a C1-20 alkyl, or a Ce-2o aryl.86262-WO-PCT / DOW 86262 WO2711. The method of any one of claims 6 to 10, wherein the catalyst is represented by the formula:

12. The method of any one of claims 6 to 10, wherein the catalyst is represented by the formula:wherein:X1is chosen from a halide, a N,N-dimethylamido, and a Ci-4 alkyl;Rfis a hydrogen, a halogen, a C1-20 alkyl, or a C6-20 aryl; f is 1 to 5;Rcis a hydrogen, halogen, C1.20 alkyl, or C6-20 aryl; and c is 1 to 5.

13. The method of any one of claims 6 or 7, wherein the silane-containing compound comprises7-octenyldimethylsilane, 5-hexenyldimethylsilane, allyldimethylsilane or combinations thereof.

14. The method of any one of claims 6 or 7, wherein the aluminum- containing compound is triisobutylaluminum.

15. The method of any one of claims 6 to 14, wherein the activator is represented by the formula [HNMe(Ci8H37)2][B(C6F5)4].

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