Supported olefin polymerization catalyst comprising substituted 2-hydroxythiophene compound

Abstract

Disclosed is a supported catalyst system comprising a substituted 2-hydroxythiophene compound and a support material; and a process for preparing the supported catalyst system; also disclosed is a gas phase or slurry phase polymerization process employing the supported catalyst system; and a polyolefin prepared by the gas phase or slurry phase polymerization process. The substituted 2-hydroxythiophene compound and a pre-catalyst comprising the substituted 2-hydroxythiophene compound, a metal atom, and a leaving group are also disclosed. Methods of preparing the pre-catalyst and the substituted 2-hydroxythiophene compound are also disclosed.

Description

Technical Field

[0001] Catalysts, materials and methods for olefin polymerization. Background Technology

[0002] Polyolefins are prepared by methods generally known, which involve polymerizing one or more olefin monomers in a solution phase catalyzed by a homogeneous catalyst or in a slurry or gas phase catalyzed by a heterogeneous catalyst.

[0003] Homogeneous catalysis generally refers to a reaction in which the soluble catalyst and the reactants it interacts with are in the same phase (the same state of matter) and in unrestricted contact. This is almost always a liquid phase. At standard temperature and pressure (23°C, 101 kPa), the pure form of the catalyst and the pure form of the reactants can be solid or gas, but when the catalyst and reactants are dissolved in the same solution, they are both in the liquid phase.

[0004] Liquid-phase olefin polymerization refers to solution reactions in which the homogeneous olefin polymerization catalyst and reactants (one or more olefin monomers) are dissolved in the same hydrocarbon solvent and react in the same hydrocarbon solvent. When the olefin monomer includes ethylene, polymerization is carried out in a hydrocarbon solution at temperatures ranging from 120°C to 250°C, typically from 150°C to 190°C, which is higher than the melting temperature range of polyethylene (115°C to 135°C).

[0005] Homogeneous olefin polymerization catalysts must be at least partially soluble in hydrocarbon solvents, such that at relatively low catalyst concentrations and high temperatures, the entire amount of catalyst dissolves in solution. In practice, these catalysts are free (unsupported) ligand-metal complex molecules, and the hydrocarbon solvent is an alkane or an aromatic hydrocarbon.

[0006] The structure of free ligand-metal complex molecules can be characterized using small molecule structure characterization techniques such as proton-nuclear and carbon-nuclear magnetic resonance (NMR). 1 H-NMR and / or 13 The structure can be precisely determined using C-NMR spectroscopy or X-ray crystallography. This knowledge allows researchers to make reasonable design modifications to homogeneous catalysts to study their structure-activity relationships and structure-product property relationships.

[0007] Heterogeneous catalysis typically refers to reactions in which an insoluble catalyst and its reactants are in different phases (different states of matter). The reaction occurs at the interface between the phases.

[0008] Heterogeneous catalysts can be prepared using a general strategy of heterogeneously combining a homogeneous catalyst or homogeneous precatalyst and an activator onto a solid support to produce heterogeneous catalyst systems. Different supported catalyst systems may require different support materials. For example, Ziegler-Natta catalysts use magnesium chloride, while supported metallocene catalysts use silica. The structure of the supported catalyst cannot be precisely determined.

[0009] In gas-phase / solid-phase olefin polymerization, also known as gas-phase polymerization, the supported catalyst system (heterogeneous olefin polymerization catalyst) is in the solid phase, while the reactants (one or more olefin monomers) are in the gas or vapor phase. The reaction occurs at the solid / gas interface.

[0010] In liquid / solid phase olefin polymerization, known as slurry-phase polymerization, the supported catalyst system (heterogeneous olefin polymerization catalyst) is in the solid phase, and the reactants (one or more olefin monomers) are dissolved in a hydrocarbon solvent to form a solution constituting the liquid phase. The reaction occurs at the solid / liquid interface.

[0011] When the olefin monomer includes ethylene, gas-phase and slurry-phase polymerization is carried out at 75°C to 120°C (below the melt temperature of most polyethylene).

[0012] For these and other reasons, supported catalyst systems produce significantly different performance results and product properties compared to their corresponding homogeneous olefin polymerization catalysts. Therefore, homogeneous olefin polymerization catalysis / solution phase polymerization cannot predict heterogeneous olefin polymerization catalysis / gas phase or slurry phase polymerization. Summary of the Invention

[0013] We claim protection for a supported catalyst system comprising a substituted 2-hydroxythiophene compound and a support material; and a method for preparing the supported catalyst system. We also claim protection for a gas-phase or slurry-phase polymerization method using the supported catalyst system; and a polyolefin prepared by the gas-phase or slurry-phase polymerization method. Furthermore, we claim protection for a substituted 2-hydroxythiophene compound and a precatalyst comprising the substituted 2-hydroxythiophene compound, a metal atom, and a leaving group. We also claim protection for a method for preparing the precatalyst and the substituted 2-hydroxythiophene compound. Attached Figure Description

[0014] Figure 1 Scheme 1 involving the synthesis of intermediate compounds is shown.

[0015] Figure 2 Scheme 2 is shown, which involves the synthesis of a substituted 2-hydroxythiophene compound (I).

[0016] Figure 3 Scheme 3 is shown, which involves the synthesis of the precatalyst of formula (II).

[0017] Figure 4 Scheme 4 is shown, which involves preparing a spray-dried supported catalyst system (III) or a conventionally dried supported catalyst system (IV).

[0018] Figure 5 Scheme 5 is shown, which involves the synthesis of bis(iodophenoxy)methylene-germanium compounds.

[0019] Figure 6 Diagrams of representative chain structures of LLDPE, LDPE, and HDPE. Detailed Implementation

[0020] We claim protection for a supported catalyst system comprising a substituted 2-hydroxythiophene compound and a support material; and a method for preparing the supported catalyst system. We also claim protection for a gas-phase or slurry-phase polymerization method using the supported catalyst system; and a polyolefin prepared by the gas-phase or slurry-phase polymerization method. Furthermore, we claim protection for a substituted 2-hydroxythiophene compound and a precatalyst comprising the substituted 2-hydroxythiophene compound, a metal atom, and a leaving group. We also claim protection for a method for preparing the precatalyst and the substituted 2-hydroxythiophene compound.

[0021] Synthesis of supported catalyst systems

[0022] There are two general strategies for preparing supported catalyst systems containing substituted 2-hydroxythiophene compounds. The first strategy involves heterogenizing a homogeneous olefin polymerization precatalyst containing a substituted 2-hydroxythiophene compound (“homogeneous precatalyst”). The second strategy involves heterogenizing a homogeneous olefin polymerization catalyst containing a substituted 2-hydroxythiophene compound (“homogeneous catalyst”).

[0023] For the first heterogeneity strategy, which involves heterogenizing the homogeneous precatalyst, there are two main contact pathways. The first pathway involves contacting a solution of the homogeneous precatalyst in a hydrocarbon solvent onto a solid support that has been pretreated with an activator (also known as a cocatalyst) to obtain a supported catalyst system. An example of a solid support pretreated with an activator is spray-dried methylaluminoxane / hydrophobic pyrolytic silica (“SMAO”), which can be used as a convenient method for preparing supported catalyst systems for slurry-phase polymerization. The second pathway involves contacting an activator with a solid support that has been pretreated with the homogeneous precatalyst to obtain a supported catalyst system.

[0024] The third contact pathway is used in conjunction with a second heterogeneity strategy that heterogeneously transforms the homogeneous catalyst. This third pathway involves contacting a solution of the homogeneous precatalyst in a hydrocarbon solvent with an activator to obtain a homogeneous catalyst dissolved in the hydrocarbon solvent, and then contacting the solution with a solid support to obtain a supported catalyst system.

[0025] The second and third contact pathways are unfavorable for use with solid supports that produce side reactions with homogeneous pre-catalysts or homogeneous catalysts. First heterogeneity strategies that include the first contact pathway are generally unaffected by this potential problem.

[0026] Heterogeneity strategies and contact pathways independently enable supported catalyst systems to be suspensions of their solid particles in a liquid consisting essentially of a hydrocarbon solvent and any hydrocarbon-soluble compounds. Hydrocarbon-soluble compounds may include unreacted activators (e.g., methylaluminoxane or triethylaluminum) and / or by-products / side products from heterogeneity and / or activation reactions.

[0027] In some embodiments, a suspension containing any hydrocarbon-soluble compound from the contact pathway is fed into a gas-phase or slurry-phase polymerization reactor to polymerize olefin monomers. Prior to or during the feeding step, the suspension may or may not be stored in a storage tank for a period of time and / or may or may not be diluted with an additional hydrocarbon solvent, which may be the same as or different from the hydrocarbon solvent used in the contact pathway.

[0028] In other embodiments, the suspension from the contact pathway is not fed into the gas-phase or slurry-phase polymerization reactor. Instead, the contact pathway for preparing the supported catalyst system is followed by a separation step that takes place before the supported catalyst system is arbitrarily fed into the gas-phase or slurry-phase polymerization reactor. In such embodiments, the separation step includes physically removing the solids of the supported catalyst system from the liquid portion of the suspension obtained by the contact pathway, or vice versa, physically removing the liquid portion from the solids of the supported catalyst system.

[0029] In some implementations, the separation step includes a filtration step, a decantation step, or an evaporation step. The separation step may also include any combination of two or more separation steps.

[0030] The filtration step may include contacting the suspension with a filter to produce a filtrate consisting of a liquid component and a filter cake consisting of a supported catalyst system (solid). The filter cake may be washed with a fresh hydrocarbon solvent and / or dried.

[0031] The decantation step may include pouring out or aspirating the liquid portion of the suspension, resulting in decanted or aspirated liquid and a supported catalyst system (solid) in the form of a "paste," which consists of the supported catalyst system (solid) and a small amount of remaining undecanted or unaspirated liquid. This paste can be used as is in the polymerization process or dried or slurried with fresh hydrocarbon solvent.

[0032] The drying step may include removing volatile components from the suspension to obtain a supported catalyst system (solid) as a dry powder. Volatile components may include any volatile components of the aforementioned hydrocarbon-soluble compounds, such as any volatile unreacted activators and / or volatile by-products / side products from heterogenization and / or activation reactions. The drying step may include a "conventionally dried" embodiment of slowly evaporating volatile components from the suspension and slowly concentrating the suspension to obtain a dry powder of the supported catalyst system. Alternatively, the drying step may include a "spray-dried" embodiment of spray drying the suspension to rapidly remove (flash evaporate) volatile components from the suspension to obtain a dry powder of the supported catalyst system.

[0033] Any combination of two or more separation steps may include, for example, a decantation step followed by an evaporation step or two consecutive decantation steps.

[0034] Compared to conventional drying of supported catalyst systems in gas-phase polymerization, spray-drying of supported catalyst systems can achieve higher catalyst efficiency, higher catalyst productivity, faster ignition, and can produce polyethylene polymers with different properties in gas-phase polymerization. Therefore, for gas-phase polymerization, spray-drying of supported catalyst systems can be superior to conventional drying. Nevertheless, conventional drying of supported catalyst systems is also perfectly usable and effective for gas-phase polymerization.

[0035] In slurry-phase polymerization, there may be little or no difference between spray-dried supported catalyst systems and conventionally dried supported catalyst systems, or there may be significant differences. However, the performance of any given spray-dried or conventionally dried supported catalyst system in gas-phase polymerization may be completely different from its performance in slurry-phase polymerization.

[0036] All dry powder implementations of supported catalyst systems are applicable to both gas-phase and slurry-phase polymerization because they can be fed as dry powder feedstocks or suspended in alkanes or mineral oils, with the resulting suspensions fed into either the gas-phase or slurry-phase olefin polymerization reactor. Catalyst feeders for both methods are commercially available.

[0037] Supported catalyst systems, regardless of their physical structure (e.g., as dry powder or as powder suspended in a hydrocarbon solvent), can be used to catalyze the gas-phase or slurry-phase polymerization of one or more olefin monomers to prepare polyolefins, such as polyethylene polymers.

[0038] Technological advantages

[0039] Homogeneous olefin polymerization catalysis in solution-phase reactions using corresponding homogeneous catalysts containing substituted 2-hydroxythiophene compounds is entirely different from heterogeneous olefin polymerization catalysis in gas-phase or slurry-phase reactions using supported catalyst systems. The former cannot predict the latter, and the polyolefin products obtained from the latter differ from those obtained from the former in various properties, such as polymer weight-average molecular weight, melt rheology, and branching.

[0040] Compared to corresponding homogeneous catalysts and polyolefins prepared by solution-phase olefin polymerization from homogeneous catalysts, supported catalyst systems and polyolefins prepared by gas-phase or slurry-phase olefin polymerization from supported catalyst systems offer technological advantages. These advantages include one or more of the following: improved catalyst efficiency or productivity, improved behavior in gas-phase reactors, and different product polyolefin polymer properties and morphologies. These advantages lead to different types of unpredictable results: performance differences between the supported catalyst system of the present invention and comparative homogeneous olefin polymerization catalysts; property differences between the polyolefins of the present invention and comparative polyolefins; performance differences between different embodiments of the supported catalyst system of the present invention; and property differences between different embodiments of the polyolefins of the present invention. Furthermore, spray-drying embodiments of supported catalyst systems tend to have more technological advantages than conventionally dried embodiments of supported catalyst systems.

[0041] Unbound by theory, we believe that the technical advantages of the supported catalyst system of the present invention, comprising substituted 2-hydroxythiophene compounds, in gas-phase or slurry-phase polymerization are due to the effect of one or more of the following factors: (a) the effect of the solid support, (b) the performance differences between different embodiments of the supported catalyst system, depending on whether the embodiment is carried out via heterogeneity according to a first, second, or third pathway, (c) the effect of conventional drying methods versus spray drying methods for preparing the dry powder of the supported catalyst system, (d) the effect of differences in process conditions between the solution phase and the gas or slurry phase, (e) the performance differences between different embodiments of the supported catalyst system in terms of their gas-phase reactor behavior, or (f) any combination of two or more of (a) to (e).

[0042] The effect of (a) on the solid support can vary depending on the olefin (olefin monomer containing polar groups) that is particularly sensitive to the solid support, and also varies with the surface chemistry of the solid support, which is affected by whether it has been pretreated with a hydrophobic agent and the hydrophobic agent used.

[0043] The role of (b) in different implementation schemes for heterogenizing homogeneous olefin polymerization catalysts to prepare supported catalyst systems can vary depending on whether a first, second, or third route is used, or a different route is used.

[0044] The role of (c) in the drying method for preparing dry powders of supported catalyst systems can vary depending on whether a drying step is employed and the type of drying step (e.g., conventional drying versus spray drying). In some embodiments, the method of the present invention includes spray drying.

[0045] (d) Differences in process conditions include differences in reaction temperature. Solution-phase polymerization of ethylene is carried out at temperatures ranging from 140°C to 250°C, typically from 150°C to 190°C, while gas-phase and slurry-phase polymerization of ethylene is carried out at lower temperatures ranging from 70°C to 120°C, typically from 75°C to 115°C. These temperature differences affect catalyst efficiency and productivity, as well as polyethylene properties, such as molecular weight (e.g., weight-average molecular weight), which can vary significantly at different reaction temperatures. For example, these differences in relationships are at least partly due to the difference in reaction rates, including the competing reactions of polyethylene chain growth and termination in the solution phase at 150°C to 190°C, compared to the rates of these competing reactions in the gas or slurry phase at 75°C to 115°C. For example, all other things being equal, if the ratio of chain growth rate to chain termination rate increases as the reaction temperature decreases, catalyst efficiency and productivity, as well as molecular weight, will increase (improve), while if this ratio decreases, these relationships will decrease (deteriorate).

[0046] Performance differences between different implementations of the supported catalyst system in (e) gas phase reactor behavior include the kinetics of the supported catalyst system in its ignition kinetics with respect to the fresh feed catalyst, the maximum temperature reached after feeding (the temperature will increase due to the exothermic nature of the olefin polymerization reaction), or the amount of ethylene absorbed per unit weight of catalyst.

[0047] (f) A combination of two or more of factors (a) to (e) is another technical advantage of the present invention for heterogeneous olefin polymerization catalysts containing substituted 2-hydroxythiophene compounds and for the preparation of polyolefins via gas-phase or slurry-phase olefin polymerization catalyzed thereon.

[0048] In some embodiments, the supported catalyst system comprising the substituted 2-hydroxythiophene compound exhibits enhanced activity in gas-phase and slurry-phase polymerization reactions relative to its corresponding homogeneous olefin polymerization catalyst. For example, the enhanced activity may be improved catalyst efficiency and / or improved catalyst productivity. In some embodiments, the supported catalyst system also prepares polyethylene products with one or more improved properties relative to those properties of polyethylene products prepared by solution-phase polymerization using their corresponding homogeneous olefin polymerization catalysts. For example, the improved property may be an increased weight-average molecular weight (M). w Increased content of ultra-high molecular weight (“UHMW”) components, for example, greater than 1,000,000 g / mol of M w ; z-average molecular weight greater than 2,000,000 g / mol; increased long-chain branching (LCB) content; or any combination of two or more of these.

[0049] Other implementation plans

[0050] Another embodiment is a substituted 2-hydroxythiophene compound of formula (I):

[0051] , or its Group 1 or Group 2 metal salt. R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 and R 12 The definition is as follows.

[0052] Another implementation is the precatalyst of formula (II):

[0053] R 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 9 R 10 R 11 R 12 M, X and subscript n are defined as follows.

[0054] Another embodiment is a catalyst prepared by contacting a pre-catalyst of formula (II) with an activator. The catalyst can be used to polymerize one or more olefin monomers.

[0055] Another implementation is a supported catalyst system comprising a precatalyst of formula (II), a support material, and an activator.

[0056] Another embodiment is a method for preparing a supported catalyst system, the method comprising steps (a) or including steps (b) and (c): (a) spray drying a mixture of an inert hydrocarbon solvent, a precatalyst of formula (II), a support material, and an activator to prepare a supported catalyst system; or (b) spray drying a mixture of an inert hydrocarbon solvent, a support material, and an activator to prepare a spray-dried supported activator; and (c) mixing the precatalyst of formula (II) with the spray-dried supported activator and the inert hydrocarbon solvent to prepare a supported catalyst system.

[0057] Another embodiment is a method for polymerizing olefin monomers, which includes contacting the olefin monomers with a supported catalyst system to prepare polyolefins. This method may include gas-phase polymerization in a gas-phase reactor under gas-phase conditions or slurry-phase polymerization in a slurry-phase reactor under slurry-phase conditions.

[0058] Another implementation is a polyolefin prepared by polymerization.

[0059] Independently in equations (I) and (II), R 1 and R 2 Independently, it can be H or halogen. In some implementations, R 1 and R 2 For different, or R 1 and R 2 For the same reason. In some implementations, R 1 and R 2 For H. In other implementations, R 1 and R 2 It is F.

[0060] Independently in equations (I) and (II), R 3 and R 4 Independently H, halogen, (C1-C) 15 ) hydrocarbon group, (C1-C 10 )alkoxy or Si((C1-C 10 )alkyl)3. In some embodiments, R 3 and R 4 For different, or R 3 and R 4 For the same reason. In some implementations, R 3and R 4 Halogen, (C1-C) 15 ) hydrocarbon group, (C1-C 10 )alkoxy or Si((C1-C 10 )alkyl)3. In some embodiments, R 3 and R 4 For H. In other implementations, R 3 and R 4 For F. In some implementations, R 3 and R 4 For (C1-C 15 ) hydrocarbon group. In other embodiments, R 3 and R 4 For (C1-C 10 )alkoxy. In other embodiments, R 3 and R 4 Si((C1-C) 10 )alkyl)3. In some embodiments, R 3 and R 4 All of them are the same and are H, or all of them are F, or all of them are -C(CH3)3, or all of them are -C(CH2CH3)3, or all of them are -C(CH3)2CH2C(CH3)3, or all of them are -OCH3, or all of them are -O(CH2)2C(CH3)3, or all of them are -O(CH2)7CH3, or all of them are 4-(tert-butyl)phenyl, or all of them are 1,3-di(tert-butyl)phenyl, or all of them are -Si(CH3)2(CH2)7CH3. In some embodiments, each (C1-C 15 The hydrocarbon group is independently (C1-C) 15 alkyl, (C1-C5)alkyl, (C6-C 10 )alkyl, (C6-C 15 aryl (e.g., phenyl or naphthyl), (C7-C 15 Aryl groups (e.g., benzyl, 2-phenylethyl, or 1-phenylprop-1-yl) or (C7-C) 15 ) alkylaryl (e.g., 4-methylphenyl or 2,6-diisopropylphenyl).

[0061] Independently in equations (I) and (II), R 5 and R 6 Independently, it can be H or halogen. In some implementations, R 5 and R 6 For different, or R 5 and R 6 For the same reason. In some implementations, R 5 and R 6 For H. In some implementations, R 5 and R6 It is F.

[0062] Independently in equations (I) and (II), R 7 and R 8 Independently, it can be H or halogen. In some implementations, R 7 and R 8 For different, or R 7 and R 8 For the same reason. In some implementations, R 7 and R 8 For H. In some implementations, R 7 and R 8 It is F.

[0063] In some implementation schemes, R 1 R 2 R 3 R 4 R 5 R 6 R 7 and R 8 For H.

[0064] In some implementation schemes, R 3 R 4 R 5 and R 6 Let F be the integer part of the integer part, and R be the integer part of the integer part. 1 R 2 R 7 and R 8 For H. In some implementations, R 1 R 2 R 3 R 4 R 5 and R 6 Let F be the integer part of the integer part, and R be the integer part of the integer part. 7 and R 8 For H. In some implementations, R 3 R 4 R 5 R 6 R 7 and R 8 Let F be the integer part of the integer part, and R be the integer part of the integer part. 1 and R 2 For H.

[0065] In some implementation schemes, R 1 R 2 R 5 R 6 R 7 and R 8 For H, and R 3 and R 4As defined above, the condition is R. 3 and R 4 Not H.

[0066] Independently in equations (I) and (II), in some implementations, each R 9 For H, and for each R 10 For (C1-C 15 ) hydrocarbon group, which can be replaced by (C1-C) 10 )alkyl or (C1-C5)alkyl, phenyl or substituted phenyl; or each R 10 For H, and for each R 9 For (C1-C 15 ) hydrocarbon group, which can be replaced by (C1-C) 10 Alkyl or (C1-C5) alkyl, phenyl, or substituted phenyl. In other embodiments, each R 9 For H, and for each R 10 -Si((C1-C) 10 )alkyl)3、(C 10 -C 18 )Aryl or substituted (C 10 -C 18 ) aryl; or each R 10 For H, and for each R 9 -Si((C1-C) 10 )alkyl)3、(C 10 -C 18 )Aryl or substituted (C 10 -C 18 ) aryl. Each substituted phenyl group has 1 to 3 independently selected substituents from the following: F, (C1-C 10 )alkyl and (C1-C 10 )alkoxy; or F and (C1-C 10 )alkoxy; or (C1-C 10 )alkyl. In some embodiments, each R 9 For H, and for each R 10 It is tert-butyl, 4-tert-butylphenyl, 4-triethylmethylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl, or 3,5-difluoro-4-octyloxyphenyl. In other embodiments, each R 10 For H, and for each R 9 It is 3,5-di-tert-butylphenyl.

[0067] Independently in equations (I) and (II), R 11 and R 12 Independently for (C1-C) 10 )alkyl; or R 11 and R 12Independently (C1-C5) alkyl; or R 11 and R 12 Independently (C2-C4) alkyl; or R 11 and R 12 Independently (C3) alkyl; or R 11 and R 12 It is isopropyl.

[0068] In some implementation schemes, R 1 and R 2 For different, or R 1 and R 2 For the same; or R 1 and R 2 For H; or R 1 and R 2 For F; or R 3 and R 4 For different, or R 3 and R 4 For the same, or R 3 and R 4 Halogen, (C1-C) 15 ) hydrocarbon group, (C1-C 10 )alkoxy or Si((C1-C 10 )alkyl)3, or R 3 and R 4 For (C1-C 10 )alkyl or (C1-C 10 )alkoxy; or R 5 and R 6 For different, or R 5 and R 6 For the same, or R 5 and R 6 For H, or R 5 and R 6 For F; or R 7 and R 8 For different, or R 7 and R 8 For the same, or R 7 and R 8 For H, or R 7 and R 8 For F; or for each R 9 For H, and for each R 10 It is tert-butyl, 4-tert-butylphenyl, 4-triethylmethylphenyl, 3,5-dimethylphenyl, 3,5-di-tert-butylphenyl or 3,5-difluoro-4-octyloxyphenyl; or each R 10 For H, and for each R 9 It is 3,5-di-tert-butylphenyl; or each R11 and R 12 For the same; or for each R 11 and R 12 For (C1-C 10 )alkyl or (C1-C5)alkyl; or each R 11 and R 12 It is isopropyl; or R 1 To R 12 A combination of the aforementioned definitions.

[0069] Independently in equation (II), M is Ti, Hf, or Zr. In some embodiments, M is Hf or Zr, or M is Ti, or M is Hf, or M is Zr.

[0070] Independently in equation (II), the subscript n is 1 or 2. In some implementations, the subscript n is 2.

[0071] Independently in formula (II), each X is independently a leaving group, and at least one leaving group is replaceable when the precatalyst (II) is contacted with the activator. In some embodiments, each X is independently selected from monodentate ligands, which are independently selected from hydrogen atoms, (C1-C2)... 50 ) hydrocarbon group, (C1-C 50 ) heterohydrocarbon group, (C1-C 50 The heteroatom may be an organic heterogroup, a halogen atom, a dialkylamino group, or a dialkyl carbamate. Each heteroatom in the heteroalkyl or organic heterogroup may be O, N, S, Si, or P. In some embodiments, each heteroatom may be O, N, or Si, or each heteroatom may be Si. In some embodiments, each X may be a halogen, a (C1-C8)alkyl group, a Si((C1-C8)alkyl)3 group, or a CH2Si((C1-C8)alkyl)3 group. 10 (alkyl)3 group or benzyl. In some embodiments, each X is benzyl, or each X is Cl and the subscript n is 2; or each X is benzyl and the subscript n is 2.

[0072] Choose subscripts n and X such that the precatalyst of equation (II) is generally (i.e., formally) electrically neutral.

[0073] Independently in formulas (I) and (II), in some implementations, R 1 and R 2 For the same, R 3 and R 4 For the same, R 5 and R 6 For the same, R 7 and R 8 For the same, each R 9 For the same, each R 10For the same, each R 11 For the same, and each R 12 For the same reason. In some such implementations, R 1 and R 2 For H; R 3 and R 4 Halogen, (C1-C) 15 ) hydrocarbon group, (C1-C 10 )alkoxy or Si((C1-C 10 )alkyl)3;R 5 and R 6 For H; and R 7 and R 8 For H. In some such implementations, R 3 and R 4 As defined above. In some embodiments, each X is the same. In some of these embodiments, M is Hf. In some of these embodiments, M is Zr.

[0074] Independently in formulas (I) and (II), in some implementations, R 1 and R 2 For H, R 3 and R 4 Each is (C1-C) 15 )alkyl or (C1-C 10 )alkoxy, R 5 and R 6 For H, R 7 and R 8 For H, each R 9 For H, each R 10 For the same and being tert-butyl, 4-tert-butylphenyl, 4-triethylmethylphenyl, 3,5-dimethylphenyl, or 3,5-di-tert-butylphenyl, and each R 11 and R 12 It is isopropyl. In other embodiments, R 1 and R 2 For H, R 3 and R 4 It is (C7-C9)alkyl or (C7-C9)alkoxy, R 5 and R 6 For H, R 7 and R 8 For H, each R 9 For H, each R 10 For tert-butyl, and each R 11 and R 12 It is isopropyl. In some embodiments, each R... 3 and R 4It is (CH3)3CCH2C(CH3)2- or CH3(CH2)7O-.

[0075] Independently in formulas (I) and (II), in some implementations, R 1 and R 2 For F, or R 5 and R 6 For F, or R 7 and R 8 It is F, or at least four of them are F.

[0076] Independently in formulas (I) and (II), in some implementations, R 1 and R 2 For the same, R 3 and R 4 For the same, R 5 and R 6 For the same, R 7 and R 8 For the same, each R 9 For the same, each R 10 For the same, R 11 and R 12 They are the same, and in equation (II), each X is the same.

[0077] In some embodiments, the substituted 2-hydroxythiophene compound of formula (I) does not contain a Group 1 or Group 2 metal, i.e., it has the structure shown in formula (I). In other embodiments, the substituted 2-hydroxythiophene compound is a Group 1 or Group 2 metal salt thereof.

[0078] Group 1 or Group 2 metal salts can be prepared by replacing a hydrogen atom of one hydroxyl group of the substituted 2-hydroxythiophene compound in formula (I) with a Group 1 or Group 2 metal atom, or by replacing each hydrogen atom of one of the two hydroxyl groups of the compound. This can be achieved by reacting the compound of formula (I) with a Group 1 or Group 2 metal reactant. The Group 1 or Group 2 metal reactant can be a Group 1 or Group 2 metal hydroxide, a Group 1 or Group 2 metal hydride, a Group 1 or Group 2 metal alkoxide, or an alkyl Group 1 or Group 2 metal. In some embodiments, the Group 1 or Group 2 metal atom is independently Li, Na, K, Ca, or Mg. The amount of the Group 1 or Group 2 metal reactant is chosen such that the Group 1 or Group 2 metal salt of the pre-catalyst of formula (I) is generally (i.e., formally) electrically neutral.

[0079] In some embodiments, the substituted 2-hydroxythiophene compound of formula (I) is selected from the group consisting of compounds 1 to 3 in Table 1.

[0080]

[0081] Where “Cmpd No.” is the compound number, t-Bu is tert-butyl; tert-octyl is (CH3)3CCH2C(CH3)2-; octylO is CH3(CH2)7O-; 35dtBP is 3,5-di-tert-butylphenyl; and i-Pr is isopropyl (i.e., (CH3)2CH-).

[0082] In some implementations, the precatalyst of formula (II) is selected from the group consisting of precatalyst numbers 1 to 6 in Table 2.

[0083]

[0084] In some implementations, the supported catalyst system is selected from the group consisting of spray-dried supported catalyst systems numbered SCS 1 to 7 and undried supported catalyst systems numbered SCS 8 in Table 3.

[0085]

[0086] "HPFS1" refers to hydrophobic pyrolytic silica prepared from untreated pyrolytic silica and hydrophobic agent dichlorodimethylsilane; "MAO" refers to methylaluminoxane; and "SMAO" refers to spray-dried methylaluminoxane / HPFS1, wherein HPFS1 is prepared from untreated pyrolytic silica and hydrophobic agent dichlorodimethylsilane.

[0087] In some embodiments, the supported catalyst system is a supported catalyst system that has been shown to prepare ethylene / 1-hexene copolymers with a weight-average molecular weight greater than 1,000,000 g / mol and / or a z-average molecular weight greater than 2,000,000 g / mol via gas-phase polymerization.

[0088] In some embodiments, the substituted 2-hydroxythiophene compound of formula (I) is compound number 1, 2 or 3; or compound number 1 or 2; or compound number 1; or compound number 2; or compound number 3.

[0089] In some embodiments, the precatalyst of formula (II) is precatalyst number 1, 2, 3, 4, 5, 6, 7, 8 or 9; or precatalyst number 1, 2, 3 or 4; or precatalyst number 5 and 6; or precatalyst number 1; or precatalyst number 2; or precatalyst number 3; or precatalyst number 4; or precatalyst number 5; or precatalyst number 6.

[0090] In some embodiments, the spray-dried supported catalyst system is designated SCS number 1, 2, 3, 4, 5, 6, or 7; or SCS number 1, 2, 3, or 4; or SCS number 5 or 6; or SCS number 1; or SCS number 2; or SCS number 3; or SCS number 4; or SCS number 5; or SCS number 6. In some embodiments, the supported catalyst system is an undried supported catalyst system designated SCS 8, 9, or 10.

[0091] The embodiments also include a method for preparing polyolefins in a gas-phase polymerization process, the method comprising contacting one or more olefin monomers with the above-described supported catalyst system in a gas-phase polymerization reactor under gas-phase polymerization conditions to prepare a polyolefin polymer. In some embodiments, the one or more olefin monomers include ethylene or propylene and optionally a 1-olefin having 4 to 20 carbon atoms (“C4-C…”). 20 The polyolefin polymer prepared includes those selected from polyethylene homopolymers or ethylene / (C4-C4) olefins. 20 )1-olefin copolymers of polyethylene polymers or selected from polypropylene homopolymers or propylene / (C4-C 20 The polyethylene polymer is a 1-olefin copolymer. In some embodiments, one or more olefin monomers include ethylene and 1-butene, 1-hexene, or 1-octene, and the polyethylene polymer is an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer, or an ethylene / 1-octene copolymer. In some of the foregoing embodiments of the preparation of the polyethylene polymer, the polyethylene polymer has a weight-average molecular weight greater than 1,000,000 g / mol and / or a z-average molecular weight greater than 2,000,000 g / mol.

[0092] In some embodiments, the polymerization method includes gas-phase polymerization and has any of the following limitations (i) to (v): (i) wherein the one or more olefin monomers comprise ethylene or a combination of ethylene and propylene, or ethylene and (C4-C5) propylene. 20 The combination of α-olefins, wherein the polyolefin polymer is an ethylene homopolymer or an ethylene / propylene copolymer or an ethylene / (C4-C) copolymer. 20 (ii) wherein one or more olefin monomers comprise ethylene or ethylene and (C4-C) α-olefin copolymers; 20 The combination of α-olefins, and the polyolefin polymer is an ethylene homopolymer or ethylene / (C4-C) 20 α-olefin copolymer; wherein the ethylene homopolymer or ethylene / (C4-C) 20(iii) The α-olefin copolymer has a weight-average molecular weight of 1,000,000 g / mol or greater, or a z-average molecular weight of 2,000,000 g / mol or greater, or both; or (iii) wherein said one or more olefin monomers comprise ethylene and (C4-C 20 The combination of α-olefins, wherein the polyolefin polymer is a broad molecular weight distribution having a weight-average molecular weight to number-average molecular weight ratio (Mw / Mn) greater than or equal to 4.0 or a z-average molecular weight to weight-average molecular weight ratio (Mz / Mw) greater than or equal to 3.5 or both of ethylene / (C4-C) 20 (iv) limiting any one of (i) to (iii), wherein the (C4-C) α-olefin copolymer; 20 (v) restrict the combination of (ii) and (iii) or restrict the combination of (ii), (iii) and (iv).

[0093] The embodiments also include a method for preparing polyolefins in a slurry-phase polymerization process, the method comprising contacting one or more olefin monomers with the aforementioned supported catalyst system in a slurry-phase polymerization reactor under slurry-phase polymerization conditions to prepare a polyolefin polymer. In some embodiments, the method has either of the limitations (i) and (ii): (i) wherein one or more olefin monomers comprise ethylene or a combination of ethylene and propylene, or ethylene and (C4-C5) olefin monomers. 20 Combinations of α-olefins, and polyolefin polymers including ethylene homopolymers or ethylene / propylene copolymers or ethylene / (C4-C) 20 α-olefin copolymers. In some embodiments, one or more olefin monomers include a combination of ethylene and 1-hexene, and the polyolefin polymer includes an ethylene / 1-hexene copolymer.

[0094] Synthesis of compounds of formula (I) and precatalysts of formula (II)

[0095] The compound of formula (I) and the precatalyst of formula (II) can be based on Figures 1 to 4 The structures were synthesized using schemes 1 through 4 shown. The post-reaction processing procedures are standard and will be described later in the examples. The structures were obtained by proton-nuclear magnetic resonance (PNMR) assay. 1 H-NMR spectroscopy and carbon-13 nuclear magnetic resonance (NMR) 13 Characterized by C-NMR spectroscopy.

[0096] Figure 1Synthetic scheme 1, illustrating the transformation of starting material (1) into intermediate compound (5), is described. In scheme 1, methyl 3-bromo-2-hydroxy-thiophene-1-carboxylate (1) was purchased from a commercial supplier. In step A, compound (1) was saponified with sodium hydroxide (NaOH) in an aqueous solution of 1,4-dioxane at 80 °C to give sodium 3-bromo-2-hydroxy-thiophene-1-carboxylate. The formate was heated with concentrated hydrochloric acid at 60 °C to give 3-bromo-2-hydroxythiophene. In step B, 3-bromo-2-hydroxythiophene was reacted at 0 °C with lithium hydroxide monohydrate (LiOH·H2O) and ethoxychloromethane (ClCH2OCH2CH3, also known as chloromethyl ethyl ether) in 1,4-dioxane / tetrahydrofuran (1:4, v / v) to prepare 3-bromo-2-ethoxymethyloxythiophene (2). In step C, 1.0 mol equivalent of compound (2) was reacted at 140 °C in deoxyxylene with 2.20 mol equivalents of carbazole (3), 2.00 mol equivalents of cuprous oxide (Cu2O), 10 mol equivalents of potassium carbonate (K2CO3), 3 mol equivalents of potassium acetate (KOAc), and 4.0 mol equivalents of N,N'-dimethylethylenediamine (“DMEDA”) to prepare 2-ethoxymethyloxy-3-carbazolylthiophene (4). In step D, 1 mol equivalent of compound (4) was reacted at -35 °C with 1.25 mol equivalents of n-butyllithium for 4 hours, followed by the addition of 2.0 mol equivalents of pure isopropoxyboronpinaol ester (“i-PrOBPin”), and the temperature was raised to ambient temperature to prepare intermediate compound (5). Synthesized in Figure 2 Continue in Scheme 2 shown.

[0097] Figure 2 Synthetic scheme 2, illustrating the conversion of intermediate compound (5) into a substituted 2-hydroxythiophene compound of formula (I), is described. In step E, 3 molar equivalents of compound (5) are reacted with 1 molar equivalent of 1,3-bis(iodophenoxy)methylene germanium compound (6) (wherein R... 1 R 2 R 3 R 4 R 5 R 6 R 7 R 8 R 11 and R 12As defined in formula (I), 9 molar equivalents of tripotassium phosphate (K3PO4) are reacted in the presence of a catalyst (e.g., bis(di-tert-butyl(4-dimethylaminophenyl)phosphine)dichloropalladium(II) or “Pd(AmPhos)Cl2”) to prepare a bis(ethoxymethyl)-protected compound. The bis(ethoxymethyl)-protected compound is then used in step F, which involves deprotection hydrolysis at 23 °C under nitrogen with a solution of concentrated hydrochloric acid in dichloromethane / 1,4-dioxane (1:1, v / v) to prepare the substituted 2-hydroxythiophene compound of formula (I).

[0098] Figure 3 Synthetic scheme 3 describes an embodiment of a precatalyst for converting the substituted 2-hydroxythiophene compound of formula (I) to formula (II). In step G, 1.0 molar equivalent of the substituted 2-hydroxythiophene compound of formula (I) is azeotropically dried using toluene. Then, 1.15 molar equivalent of formula M(X) is added dropwise to the solution of compound (I). n+2 The reaction mixture was prepared using a Group 4 metal salt (where M, X, and subscript n are as defined in formula (II)) and stirred at 23°C for 30 minutes. The reaction mixture was then filtered through a 0.45 μm polytetrafluoroethylene filter, and the filtrate was concentrated to obtain the precatalyst of formula (II). Formula M(X) n+2 Examples of Group 4 metal salts are zirconium tetrachloride (ZrCl4), tetrabenzyl zirconium (ZrBn4), dibenzyl zirconium dichloride (ZrBn2Cl2), hafnium tetrachloride (HfCl4), dibenzyl hafnium dichloride (HfBn2Cl2), and tetrabenzyl hafnium (HfBn4). The benzyl group abbreviated as "Bn" is phenylmethyl, a monovalent group of the formula -CH2C6H5. Embodiments for preparing precatalysts of formula (II) using ZrCl4, ZrBn2Cl2, HfCl4, or HfBn2Cl2, wherein M is Zr or Hf, and each X is Cl. These embodiments can be converted into other embodiments of precatalysts of formula (II). For example, embodiments of precatalysts of formula (II) wherein each X is Cl can be reacted with n molar equivalents of alkyl magnesium halide or alkyl lithium to prepare a precatalyst of formula (II) wherein each X is alkyl. An embodiment of the precatalyst of formula (II), wherein M is Zr or Hf and each X is benzyl (Bn), is prepared directly from ZrBn4 or HfBn4. Alternatively, an embodiment of the precatalyst of formula (II), wherein M is Zr or Hf and each X is benzyl (Bn), can be prepared from an embodiment of the precatalyst of formula (II), wherein M is Zr or Hf and each X is Cl, by reacting them with n molar equivalents of benzylmagnesium halide or benzyllithium.

[0099] Figure 4Synthesis scheme 4 is described. In step H of scheme 4, the precatalyst of formula (II) is activated by an activator and supported on a carrier material in an inert hydrocarbon liquid (such as alkanes or toluene) to prepare a supported catalyst system suspended in an inert hydrocarbon liquid. In step I(i), the suspension of the supported catalyst system is spray-dried as described herein to prepare a spray-dried supported catalyst system (“sd-SCS”) embodiment. Alternatively, in step I(ii), the suspension of the supported catalyst system is conventionally dried as described herein to prepare a conventionally dried supported catalyst system (“cd-SCS”) embodiment. The catalyst activity and catalyst productivity of the sd-SCS embodiment prepared from the given precatalyst of formula (II) are different from and generally superior to the catalyst activity and catalyst productivity of the cd-SDS embodiment prepared from the same precatalyst of formula (II).

[0100] Figure 5 Scheme 5 is described. In scheme 5, Figure 2 The 1,3-bis(iodophenoxy)methylene germanium compound (6) shown in Scheme 2 was prepared from phenol (6a) and (6c) and dichloromethyl-diisopropylgermanium (6b) in dimethylformamide (DMF) at 80°C to 100°C in the presence of potassium phosphate (K3PO4).

[0101] Supported catalyst system

[0102] Supported catalyst systems are heterogeneous olefin polymerization catalysts. The preparation of a supported catalyst system by heterogenizing the precatalyst of formula (II) with the support material and activator can be carried out according to any of the heterogenization pathways described above. The supported catalyst system is formulated for gas-phase or slurry-phase polymerization of olefin monomers.

[0103] The supported catalyst system is prepared from the precatalyst of formula (II), the activator, and the solid support. The supported catalyst system may contain additional components, such as by-products / sideproducts of the preparation of the supported catalyst system, and any unreacted activator that may remain in the preparation process using an excess of the activator relative to the amount of the precatalyst of formula (II).

[0104] In supported catalyst systems, the catalyst can be unsupported when in contact with an activator, which can be the same or different for different catalysts. Alternatively, the catalyst can be set onto a solid support material by spray drying before contact with one or more activators. The solid support material can be uncalcined or calcined before contact with the catalyst. The solid support material can be hydrophobic pyrolytic silica (e.g., pyrolytic silica treated with dimethyldichlorosilane (which is (CH3)2SiCl2)), which can be Cabosil. ™ TS-610 pyrolysis silica was purchased from Cabot Corporation. The bimodal (unsupported or supported) catalyst system can be in powder or free-flowing particulate solid form.

[0105] carrier material

[0106] The support material used in supported catalyst systems can be an inorganic oxide solid. As used herein, the terms “support,” “solid support,” “support material,” and “solid support material” refer to the same substance and refer to porous inorganic or organic matter. In some embodiments, the support material can be an inorganic oxide, including, alternatively, Group 13 or 14 metal oxides, of which Group 2, 3, 4, 5, 13, or 14 metal oxides are preferred. Examples of inorganic oxide-type support materials are silica, magnesium oxide, aluminum oxide, titanium dioxide, zirconium oxide, thorium oxide, and mixtures of any two or more of these inorganic oxides. Examples of such mixtures are silica-chromium, silica-alumina, and silica-titanium dioxide. The support material can be untreated, or it can be treated with a hydrophobic agent. In some embodiments, the support material is hydrophobic pyrolytic silica.

[0107] The inorganic oxide support material is porous and has variable surface area, pore volume, and average particle size. In some embodiments, the surface area is 50 square meters per gram (m²). 2 / g) to 1000m 2 / g, and an average particle size of 1 micrometer (μm) to 300 μm, alternatively 20 μm to 300 μm. Alternatively, the pore volume is 0.5 to 6.0 cubic centimeters per gram (cm³). 3 / g), and a surface area of ​​200 to 600 m² 2 / g. Alternatively, the pore volume is 1.1cm³. 3 / g to 1.8cm 3 / g, and the surface area is 245m² 2 / g to 375m 2 / g. Alternatively, the pore volume is 2.4 cm³. 3 / g to 3.7cm 3 / g, and the surface area is 410m² 2 / g to 620m 2 / g. Alternatively, the pore volume is 0.9 cm³. 3 / g to 1.4cm 3 / g, and the surface area is 390m² 2 / g to 590m 2 / g. Each of the above properties is measured using conventional techniques known in the art.

[0108] The carrier material may include silica, alternatively amorphous silica (not quartz), or alternatively high surface area amorphous silica (e.g., 500 to 1000 m²). 2 / g). This type of silica is commercially available from several sources, including Davison Chemical Division of WRGrace and Company (e.g., Davison 952 and Davison 955 products) and PQ Corporation (e.g., ES70 product). Silica can be in the form of spherical particles obtainable through a spray drying process. Alternatively, the MS3050 product is unspray-dried silica from PQ Corporation. As obtained, this silica is not calcined (i.e., not dehydrated). Calcined silica purchased prior to purchase can also be used as a carrier material.

[0109] In some embodiments, the solid support is hydrophobic pyrolytic silica. Hydrophobic pyrolytic silica is prepared by contacting untreated pyrolytic silica having a surface containing silicon-bonded hydroxyl groups (Si-OH groups) with a hydrophobic agent described later. In some embodiments, the hydrophobic agent is a silicon-based hydrophobic agent containing, on average, one or more functional groups per molecule that react with Si-OH groups, to obtain hydrophobic pyrolytic silica. Silicon-based hydrophobic agents can be selected from (CH3)2SiCl2, polydimethylsiloxane, hexamethyldisilazane (HMDZ), and (Cl-C) 10 )alkylSi((C1-C 10 (e.g., octyltrialkoxysilane, such as octyltriethoxysilane, i.e., CH3(CH2)7Si(OCH2CH3)3). In some embodiments, the silicon-based hydrophobic agent is dimethyldichlorosilane, i.e., (CH3)2SiCl2. In some embodiments, the carrier material is dimethyldichlorosilane-treated pyrolytic silica, such as pyrolytic silica sold as product TS-610 from Cabot Corporation.

[0110] The support material can be uncalcined or calcined. A calcined support material is prepared by heating it in air to obtain a calcined support material before contact with a pre-catalyst, activator, and / or hydrophobic agent. Calcination involves heating the support material at a peak temperature of 350°C to 850°C, alternatively 400°C to 800°C, alternatively 400°C to 700°C, or alternatively 500°C to 650°C, for a period of 2 hours to 24 hours, alternatively 4 hours to 16 hours, alternatively 8 hours to 12 hours, or alternatively 1 hour to 4 hours, thereby preparing a calcined support material. If the support material is not heated in this manner, it is an uncalcined support material.

[0111] hydrophobic agent

[0112] Hydrophobic agents are organic or organosilicon compounds that form stable reaction products with the surface hydroxyl groups of pyrolytic silica. Organosilicon compounds can be polydiorganosiloxane compounds or organosilicon monomers containing silicon-bonded leaving groups (e.g., Si-halogen, Si-acetoxy, Si-oxime (Si-ON=C<), Si-alkoxy, or Si-amino groups) that react with the surface hydroxyl groups of untreated pyrolytic silica to form Si-O-Si bonds, while simultaneously losing water molecules as a byproduct. Polydiorganosiloxane compounds (such as polydimethylsiloxane) contain a main-chain Si-O-Si group, wherein the oxygen atom can form stable hydrogen bonds with the surface hydroxyl groups of pyrolytic silica. Silicon-based hydrophobic agents can be trimethylsilyl chloride, dimethyldichlorosilane, polydimethylsiloxane fluid, hexamethyldisilazane, octyltrialkoxysilane (e.g., octyltrimethoxysilane), and combinations of any two or more of these.

[0113] Activator

[0114] The activator used in the heterogeneity method can be any compound capable of reacting with the precatalyst of formula (II) to produce an active olefin polymerization catalyst. The activator can be a Lewis acid, a noncoordinate ion activator, an ionizing activator, or a Lewis base.

[0115] In some embodiments, the activator is an aluminum-based activator. The molar ratio of the metal (Al) of the activator to the metal (Group 4 metal, e.g., Ti, Zr, or Hf) of the specific catalyst compound can be from 7,000:1 to 0.5:1, alternatively from 3,500:1 to 1:1, alternatively from 1,000:1 to 0.5:1, alternatively from 300:1 to 1:1, or alternatively from 150:1 to 1:1. Suitable activators are commercially available. In some embodiments, the aluminum-based activator is an alkylaluminoxane or alkylalumoxane. Any alkyl group can be used. In some embodiments, each alkyl group of the alkylaluminoxane or alkylalumoxane can independently be (C1-C8) alkyl, alternatively (C1-C7) alkyl, alternatively (C1-C6) alkyl, or alternatively (C1-C4) alkyl.

[0116] Alkyl aluminum can be trialkyl aluminum, alkyl aluminum halides, or alkyl aluminum alkoxides (diethylethoxyaluminum). Trialkyl aluminum can be trimethylaluminum, triethylaluminum (“TEAl”), tripropylaluminum, or tris(2-methylpropyl)aluminum. Alkyl aluminum halides can be diethylaluminum chloride. Alkyl aluminum alkoxides can be diethylethoxyaluminum.

[0117] Alkyl aluminum oxanes can be methyl aluminum oxane (MAO), ethyl aluminum oxane, 2-methylpropyl-aluminum oxane, or modified methyl aluminum oxane (MMAO).

[0118] In some implementations, the activator is MAO.

[0119] Supported catalyst system

[0120] Once the precatalyst and activator of formula (II) come into contact with each other, the active catalyst material and activator material are prepared in situ, regardless of the presence of a solid support, depending on the first, second, or third heterogeneous pathway described above. The active catalyst material comprises a ligand derived from a substituted 2-hydroxythiophene compound of formula (I) and an activator material. The activator material has a different structure or composition than the activator from which it is derived. The activation reaction may also produce one or more byproducts. The corresponding activator materials may be Lewis acids, noncoordinate ionic activators, ionized activators, Lewis bases, derivatives of alkylaluminum or alkylaluminoxanes, respectively. An example of a derivative of a byproduct is a methylaluminoxane material formed by devolatation during spray drying of a supported catalyst system prepared with methylaluminoxane.

[0121] Supported catalyst systems can be prepared via the heterogeneity pathways described above. These pathways typically involve using inert hydrocarbon liquids as solvents or supports.

[0122] In some embodiments, the precatalyst and the support material are brought together in an inert hydrocarbon liquid to obtain a suspension of the supported precatalyst in the inert hydrocarbon liquid. The suspension is then brought together with an activator to obtain a suspension of the supported catalyst system in the inert hydrocarbon liquid. The inert hydrocarbon liquid is then removed to obtain the supported catalyst system.

[0123] In other embodiments, the precatalyst and activator are brought together in an inert hydrocarbon liquid to obtain a solution of the catalyst in the inert hydrocarbon liquid, and then the solution is brought into contact with a support material to obtain a suspension of the supported catalyst system in the inert hydrocarbon liquid. The inert hydrocarbon liquid is then removed to obtain the supported catalyst system.

[0124] In other embodiments, the activator and the support material are brought together in an inert hydrocarbon liquid to obtain a suspension of the supported activator in the inert hydrocarbon liquid. The suspension is then brought into contact with a pre-catalyst to obtain a suspension of the supported catalyst system in the inert hydrocarbon liquid. The inert hydrocarbon liquid is then removed to obtain the supported catalyst system.

[0125] In other embodiments, the precatalyst, activator, and support material are simultaneously brought into contact in an inert hydrocarbon liquid to obtain a suspension of the supported catalyst, and then the inert hydrocarbon liquid is removed to obtain the supported catalyst system.

[0126] Removing inert hydrocarbon liquid from a suspension of a supported catalyst system may include the step of decanting some of the inert hydrocarbon liquid from the suspension. In some embodiments, the decanting method includes pouring off excess inert hydrocarbon liquid from the suspension to obtain a concentrated suspension of the supported catalyst system.

[0127] Removing inert hydrocarbon liquids from a suspension of a supported catalyst system may include a step of drying the supported catalyst system. The drying step may include conventional drying methods or spray drying methods.

[0128] Conventional drying methods involve slowly increasing the mass or molar amount of the lower volatile chemical component per unit volume of a continuous mixture containing both higher and lower volatile chemical components by gradually removing the higher volatile chemical component from the lower volatile component of the continuous mixture, resulting in a concentrate with a higher mass or molar amount of the lower volatile chemical component per unit volume than the continuous mixture. The rate of gradual removal is limited by a relatively small evaporation surface area to mass ratio (compared to spray drying). The concentrate may be a precipitated solid.

[0129] Spray drying involves rapidly forming particulate solids containing the lower volatile chemicals by drawing a bulk mixture of lower and higher volatile chemicals through a sprayer using hot gas. Compared to concentration, this method forms particles with a generally large evaporation surface area to mass ratio. The particle size and shape of the particulate solids formed by spray drying can differ from those of precipitated solids.

[0130] In some embodiments, the spray-dried supported catalyst system can be prepared on a laboratory scale in a nitrogen-purged glove box according to the following spray-drying procedure: Anhydrous deoxytoluene and a solid support material are loaded into an oven-dried glass jar. The contents are stirred at room temperature until fully dispersed into a slurry. A 10% by weight solution of methylaluminoxane (MAO) in toluene is added to the slurry. The resulting mixture is stirred for 15 minutes, and then a certain amount of the precatalyst of formula (II) is added. The resulting reaction mixture is stirred at room temperature for another 30 to 60 minutes to activate the precatalyst, resulting in a supported catalyst system suspended in toluene. The suspension is spray-dried using a spray dryer (e.g., a Büchi miniature spray dryer model B-290 from BUCHI Corporation, NewCastle, Delaware, USA) with the following parameters: set temperature 140°C, outlet temperature 75°C (minimum), ejector set to 95 rpm, and pump speed 150 rpm. The spray-drying process produces a spray-dried supported catalyst system as an anhydrous solid powder. In some embodiments, the solid carrier material has been treated with a hydrophobic agent, such as hydrophobic pyrolytic silica treated with dimethyldichlorosilane. The aforementioned procedure can be scaled up to manufacturing scale using commonly known methods.

[0131] Compare the advantages of undried, conventionally dried, and spray-dried implementation schemes for supported catalyst systems.

[0132] This invention considers embodiments of conventionally dried supported catalyst systems, spray-dried supported catalyst systems, and decanted but not dried supported catalyst systems. The decanted but not dried supported catalyst system embodiment can be used for catalyzing slurry-phase polymerization and is a convenient form for adding supported catalyst systems to slurry-phase reactors.

[0133] Compared to unsupported catalysts prepared from the same precatalyst and activator in the absence of a support material, conventional dry supported catalyst systems can achieve higher catalyst efficiency and thus higher polyolefin production rates.

[0134] Compared to conventionally dried supported catalyst systems, spray-dried supported catalyst systems can achieve higher catalyst efficiency, and therefore higher polyolefin production rates. Thus, compared to a comparative unsupported catalyst prepared from the same precatalyst and activator in the absence of a support material, spray-dried supported catalyst systems can still achieve higher catalyst efficiency, and therefore still achieve higher polyolefin production rates.

[0135] Many spray-dried supported catalyst system embodiments also produce polyolefins with improved resin properties. For example, some spray-dried supported catalyst system embodiments produce polyolefins with increased long-chain branching (LCB) content, while other spray-dried supported catalyst system embodiments and conventionally dried catalyst system embodiments do not produce such polyolefins. In another example, some spray-dried supported catalyst system embodiments produce polyolefins with ultra-high molecular weight content, while other spray-dried supported catalyst system embodiments and conventionally dried catalyst system embodiments do not produce such polyolefins.

[0136] Supported catalyst systems can be used in slurry-phase or gas-phase olefin polymerization reactions to increase the polymerization rate of monomers and / or comonomers. In some aspects, olefin polymerization reactions are carried out in the gas phase in a gas-phase reactor or in the slurry phase in a slurry-phase reactor.

[0137] Methods for polymerizing one or more olefin monomers

[0138] In embodiments of a method for polymerizing olefin monomers, the method includes contacting the olefin monomers with a supported catalyst system to prepare a polyolefin, wherein the olefin polymerization is carried out in a gas-phase reactor under gas-phase process conditions, or in a slurry-phase reactor under slurry-phase conditions. In some embodiments, the method includes polymerizing only ethylene to prepare a polyethylene homopolymer. In other embodiments, the method includes polymerizing ethylene and propylene to prepare an ethylene / propylene copolymer, or polymerizing ethylene and (C4-C8)α-olefins to prepare an ethylene / (C4-C8)α-olefin copolymer. In some embodiments, the (C4-C8)α-olefin is 1-butene, 1-hexene, or 1-octene; or 1-butene or 1-hexene; or 1-butene; or 1-hexene; or 1-octene; and the ethylene / (C4-C8)α-olefin copolymer is an ethylene / 1-butene copolymer, an ethylene / 1-hexene copolymer, or an ethylene / 1-octene copolymer; or an ethylene / 1-butene copolymer or an ethylene / 1-hexene copolymer; or an ethylene / 1-butene copolymer; or an ethylene / 1-hexene copolymer; or an ethylene / 1-octene copolymer.

[0139] Polymerization reactor and process conditions

[0140] The method for polymerizing olefin monomers can be carried out in any gas-phase olefin polymerization reactor or slurry-phase olefin polymerization reactor and under any gas-phase polymerization process conditions or slurry-phase polymerization conditions.

[0141] Reactors and process conditions for gas-phase and slurry-phase olefin polymerization are well known. For example, slurry-phase reactors and process conditions include those described in US 3,324,095. Gas-phase polymerization reactors and process conditions may employ stirred-bed gas-phase polymerization reactors (SB-GPP reactors) or fluidized-bed gas-phase polymerization reactors (FB-GPP reactors). Gas-phase reactors and process conditions may include induced condensation agents and proceed with polymerization in a condensation mode, as described in US 4,453,399, US 4,588,790, US 4,994,534, US 5,352,749, US 5,462,999, and US 6,489,408. The gas-phase reactor and process conditions can be fluidized bed reactors / methods as described in US 3,709,853, US 4,003,712, US 4,011,382, US 4,302,566, US 4,543,399, US 4,882,400, US 5,352,749, US 5,541,270, EP-A-0 802 202, and Belgian Patent No. 839,380. These patents disclose gas-phase polymerization methods in which the polymerization medium is mechanically stirred or fluidized by the continuous flow of gaseous monomers and diluents. Other available gas-phase methods include tandem or multi-stage polymerization methods, such as those described in US 5,627,242, US 5,665,818, US 5,677,375, EP-A-0 794 200, EP-B1-0 649 992, EP-A-0 802 202, and EP-B-634421.

[0142] In some implementations, the gas phase reactor and process conditions include a single gas phase reactor and a single set of process conditions.

[0143] In other embodiments, the gas-phase reactor and process conditions include two gas-phase reactors in series and two sets of process conditions. In such embodiments, the first olefin polymerization is carried out in the first gas-phase reactor under the first gas-phase process conditions, and then the resulting polyolefin is transferred to a second gas-phase reactor, where the second olefin polymerization reaction is carried out under the second set of process conditions. The supported catalyst system can be used for the first olefin polymerization but not for the second olefin polymerization, or for the second olefin polymerization but not for the first olefin polymerization, or for both the first and second olefin polymerizations. The supported catalyst systems used for both the first and second olefin polymerizations can be the same embodiment or different embodiments.

[0144] In some embodiments, olefin polymerization includes tandem slurry-phase reactors and process conditions, and gas-phase reactors and process conditions, or vice versa. In some embodiments, the first olefin polymerization is carried out in a slurry-phase reactor under slurry-phase process conditions, then the slurry-phase polyolefin is transferred to a gas-phase reactor, and the second olefin polymerization is carried out under gas-phase conditions. Supported catalyst systems may be used for the first olefin polymerization but not for the second olefin polymerization, or for the second olefin polymerization but not for the first olefin polymerization, or for both the first and second olefin polymerizations. Supported catalyst systems used for both the first and second olefin polymerizations may be the same embodiment or different embodiments.

[0145] Polyolefins

[0146] The product of olefin polymerization is polyolefin.

[0147] In some implementations, the polyolefin is low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE), or high-density polyethylene (HDPE). These polyethylenes have different polymer chain structures, such as... Figure 6 The diagram illustrates the different polymerization conditions and initiators or catalysts used to prepare them. Generally, the difference between LLDPE and LDPE lies in the polymerization conditions and initiators or catalysts used to prepare them, which leads to differences in the amount of long-chain branching. LDPE is prepared under high pressure via a free radical polymerization process (e.g., initiated by a small amount of organic peroxide), and therefore LDPE inherently possesses a high degree of long-chain branching, such as... Figure 6 As shown. LLDPE prepared using conventional Ziegler-Natta catalysts, which do not produce long-chain branching, is linear and without long-chain branching, as... Figure 6 As illustrated. Typically, the difference between LLDPE and HDPE lies in density and the amount of short-chain branching (SCB). LLDPE has a density of less than 0.940 g / cm³. 3 The density of HDPE is greater than or equal to 0.940 g / cm³. 3 The density. Furthermore, LLDPE has a large amount of short-chain branching, while HDPE has a much smaller amount of short-chain branching; see [link to relevant documentation]. Figure 6 .

[0148] In some embodiments, polyethylene may not have a detectable long-chain branching content, i.e., 0 long-chain branches (“LCB”) / 1000 carbon atoms. In other embodiments, polyethylene may have a long-chain branching content of 0.01 to 2 long-chain branches (“LCB”) / 1000 carbon atoms (LCB / 1000C), alternatively 0.01 to 1.0 LCB / 1000C, or alternatively 0.1 to 1.0 LCB / 1000C. As used herein, having an LCB content means having a detectable long-chain branching content. 13 The detection limit for long-chain branching by C-NMR spectroscopy is currently 0.004 LCB / 1000C. This paper excludes LCB content ranging from greater than 0.000 LCB / 1000C to less than 0.010 LCB / 1000C.

[0149] The long-chain branching content of the polyolefins of the present invention can be characterized directly or indirectly by any of the following measurements (i) to (iv): (i) directly by carbon-13 nuclear magnetic resonance (NMR) spectroscopy; (ii) indirectly by the melt flow ratio (I) described below. 21 (iii) Characterized by the equation / I2); (iii) Indirectly determined by the melt flow ratio (I 21 / I2) Range characterization; or (iv) Mark-Houwink analysis using triple detector gel permeation chromatography (triple detector GPC). In some embodiments, characterization may include a combination of measurement results (i) and (ii), a combination of measurement results (i) and (iv), a combination of measurement results (i) and (iii), a combination of measurement results (ii) and (iv), a combination of measurement results (iii) and (iv), or a combination of measurement results (i), (ii), (iii) and (iv).

[0150] In some embodiments, the polyethylene may have an ultra-high molecular weight (“UHMW”) content. In some embodiments, the polyethylene may have a UHMW tail in the GPC plot. The UHMW content of these polyethylene embodiments can be measured by GPC and is a polymer weight-average molecular weight of 1,000,000 g / mol or greater. The UHMW tail is limited to any one of (i) to (iii): (i) a z-average molecular weight of 1,000,000 g / mol or greater, (ii) a z-average molecular weight to weight-average molecular weight ratio (Mz / Mw) of 3.5 or greater, or (iii) both (i) and (ii).

[0151] Polyolefins can be formulated with one or more additives that can be used in polyethylene articles, such as, but not limited to, additives for polyethylene films, additives for polyethylene pipes, or additives for blow-molded polyethylene articles. In some embodiments, one or more additives include additives for films, such as one or more antioxidants, one or more ultraviolet (UV) light stabilizers, one or more colorants, and / or one or more antimicrobial agents.

[0152] definition

[0153] Activator: A compound used to convert a pre-catalyst with no or negligible catalytic activity into a catalyst with orders of magnitude higher catalytic activity.

[0154] α-olefin: as shown in formula Terminal monoolefins, where the subscript k is an integer of 0 or greater, or 1 or greater; abbreviated as "α-olefin".

[0155] Biphenyl: Compounds with this structure and position number: .

[0156] Carbazole: a compound having the following structure and position numbering: .

[0157] Drying: Precatalysts, activators, catalysts, and calcined support materials may have a water content of 0 parts per million to less than 5 parts per million based on total weight. When used to describe embodiments of supported catalyst systems in the form of dry powders, drying may also refer to the absence of organic solvents, such as toluene or hexane.

[0158] Pyrolytic silica: Silica produced in a flame through pyrolysis. Amorphous silica powder is manufactured by agglomerating tiny droplets into branched, chain-like three-dimensional secondary particles, which are then aggregated into tertiary particles. It is not quartz.

[0159] Heteroatoms: As used herein, a general organic group containing heteroatoms, where one or more specific heteroatoms are not explicitly or implicitly indicated, such as “heteroalkyl” groups and “organoheteroalkyl” groups, inherently contains one or more heteroatoms selected from the group consisting of: O, S, N, P, and Si; or O, S, N, and Si; or O, N, and Si; or O and N; or O; or N; or Si or S; or P. In contrast, examples of organic groups containing heteroatoms where heteroatoms are explicitly or implicitly indicated are: alkoxy groups where the heteroatom is implicitly O' and amino groups where the heteroatom is implicitly N; alkyl O- groups where the heteroatom is explicitly O; and -CH2Si(alkyl)3 groups where the heteroatom is explicitly Si.

[0160] Hydrocarbon groups, heterocarbon groups, and organic heterocarbon groups have their IUPAC Gold Book meanings. A hydrocarbon group is a monovalent group in an unsubstituted embodiment consisting of one or more carbon atoms and hydrogen atoms, wherein the monovalent group is on a carbon atom. Examples are alkyl and aryl groups. A heterocarbon group is a monovalent group in an unsubstituted embodiment consisting of one or more carbon atoms and at least one heteroatom, wherein the monovalent group is a carbon atom. Examples are ethoxymethyl and -CH2Si(alkyl)3. An organic heterocarbon group is a monovalent group in an unsubstituted embodiment consisting of one or more carbon atoms and at least one heteroatom, wherein the monovalent group is a heteroatom. Examples are alkoxy and -Si(alkyl)3.

[0161] Inert: Not (significantly) reactive. The term "inert" applied to purge gas or olefin monomer feed means a molecular oxygen (O2) content of 0 parts per million to less than 5 parts per million based on the total weight of the purge gas or olefin monomer feed. When applied to (unsubstituted) hydrocarbon solvents, it means free of carbon-carbon double and triple bonds, free of molecular oxygen (0 ppm to less than 5 ppm O2), and free of moisture ("dry," 0 ppm to less than 5 ppm H2O). Examples are hydrocarbon solvents that can be inertized (dried and O2 removed) and are unsubstituted alkanes (e.g., hexane and heptane), unsubstituted aromatics (e.g., benzene and naphthalene), and unsubstituted alkyl aromatics (e.g., toluene, xylene, and fluorene).

[0162] Metallocene catalysts. Homogeneous or heterogeneous molecules containing unsubstituted or substituted cyclopentadienyl ligands-metal complexes that enhance the rate of olefin polymerization. Regarding the number of catalytic sites, unsupported metallocene catalyst molecules are typically single-site or two-site, while supported metallocene catalysts are multi-site, meaning two or more sites or substances are formed. The unsubstituted cyclopentadienyl group is of the formula [C5H5]. - The monoanion. As used herein, “substituted cyclopentadienyl” includes monocyclic derivatives of cyclopentadienyl, such as propylcyclopentadienyl and pentamethylcyclopentadienyl, and polycyclic derivatives of cyclopentadienyl, such as the bicyclic derivatives indenyl and tetrahydroindenyl, and the tricyclic derivatives fluorenyl, tetrahydrofluorenyl and octahydrofluorenyl, and their substituted derivatives. Examples of substituted cyclopentadienyl ligands are unsubstituted indene, alkyl-substituted indene, unsubstituted 4,5,6,7-tetrahydroindene, alkyl-substituted 4,5,6,7-tetrahydroindene, unsubstituted fluorenyl and alkyl-substituted fluorenyl, unsubstituted 1,2,3,4-tetrahydrofluorenyl, alkyl-substituted 1,2,3,4-tetrahydrofluorenyl, unsubstituted 1,2,3,4,5,6,7,8-octahydrofluorenyl and alkyl-substituted 1,2,3,4,5,6,7,8-octahydrofluorenyl.

[0163] m-Triphenyl: Also known as 3-phenyl-1,1'-biphenyl, it is a compound with this structure and position number: .

[0164] The peak states of the molecular weight distribution of polyolefins are indicated in a plot of dW / dLog(MW) on the y-axis and Log(MW) on the x-axis for molecular weights greater than 1,000 g / mol (Log(MW) > 3.0) and less than 10,000,000 g / mol (Log(MW) < 7.0). This provides the properties of the molecular weight distribution of polyolefins for gel permeation chromatography (GPC) chromatograms, where Log(MW) and dW / dLog(MW) are as defined herein and measured by a high-temperature gel permeation chromatography (GPC) test method described later. Only peaks between log(MW) 3.0 and log(MW) 7.0 are counted for peak states. The peak states of polyolefins can be singlet (only one peak between log(MW) 3.0 and log(MW) 7.0) or multi-peak (two or more peaks between log(MW) 3.0 and log(MW) 7.0). The peak states of multimodal polyolefins can be bimodal (only two peaks between log(MW) 3.0 and log(MW) 7.0), trimodal (only three peaks between log(MW) 3.0 and log(MW) 7.0), or higher (four or more peaks between log(MW) 3.0 and log(MW) 7.0). Any two peaks between log(MW) 3.0 and log(MW) 7.0 can be separated by a distinguishable local minimum between them, or one peak can be simply a shoulder on another peak. Deconvolution of the GPC plot between log(MW) 3.0 and log(MW) 7.0 can be used to determine if any hidden peaks exist, and then they are counted against the peak states.

[0165] Multisite catalysts: Preparation of polydispersity index (PDI, M w / M n Any catalyst for polyethylene with a thickness greater than 2.0.

[0166] Olefin monomers: Unsubstituted hydrocarbons containing carbon-carbon double bonds.

[0167] Polyolefins: straight-chain or branched macromolecules, or multiple macromolecules, consisting of carbon and hydrogen, and having six or more constituent units derived by polymerizing olefin monomers or two or more olefin comonomers.

[0168] Precatalyst: A catalyst precursor compound, also known as a "precatalyst". The precatalyst itself has little or no catalytic activity, but upon contact with an activator, it transforms into a catalyst compound. Precatalysts can be ligand-metal complexes, such as the precatalysts described herein.

[0169] Preliminary embodiments. Embodiments that have not actually been prepared but can be readily prepared from the teachings provided herein and that the inventors anticipate will have the described inventive features and advantages, and are included to support the scope of the claims.

[0170] A single-site catalyst. An organic ligand-metal complex suitable for increasing the polymerization rate of olefin monomers, and having at most two discrete binding sites at the metal, which can be used to coordinate with olefin monomer molecules before insertion into the growing polymer chain.

[0171] Single-site non-metallocene catalysts. Single-site catalysts without unsubstituted or substituted cyclopentadienyl ligands.

[0172] System (chemicals): The arrangement of different chemical components in order to form a functional whole.

[0173] Ziegler-Natta catalyst: a titanium catalyst supported on magnesium dichloride solid and optionally silica.

[0174] In cases where the chemical name does not match its structure, the structure controls and determines the identity of the compound in question. This is determined by the chemical name and its reference formula (I) or (II) and the substituent group R. # (For example, R) 1 R 2 In cases where the descriptions of (etc.) and X are inconsistent, refer to formula (I) or (II) and substituent R. # The description of the X group controls and identifies the compounds under discussion.

[0175] Experimental methods

[0176] Preparation of test substrates, sheets or specimens: See ASTM D4703-10, Standard Practice for Compression Molding Thermoplastic Materials into Test Specimens, Plaques, or Sheets.

[0177] Density test method: Measured according to ASTM D792-13, Standard Test Methods for Density and Specific Gravity (Relative Density) of Plastics by Displacement, Method B (for testing solid plastics in liquids other than water, such as in liquid 2-propanol). Units are grams per cubic centimeter (g / cm³). 3 ).

[0178] Long-chain branching (LCB) value testing method: The amount of LCB present in EB LLDPE resin can be measured using a combination of nuclear magnetic resonance (NMR) techniques described in the following literature: Z. Zhou, S. Pesek, J. Klosin, M. Rosen, S. Mukhopadhyay, R. Cong, D. Baugh, B. Winniford, H. Brown, K. Xu, “Long chainbranching detection and quantification in LDPE with special solvents, polarization transfer techniques, and inverse gated 13 C NMR spectroscopy", Macromolecules, 2018, 51, 8443; Z. Zhou, C.Anklin, R. Cong, X. Qiu, R. Kuemmerle, "Long-chain branch detection and quantification in ethylene-hexene LLDPE with 13 C NMR", Macromolecule, 2021, 54, 757; and Z. Zhou, C. Anklin, R. Kuemmerle, R. Cong, X. Qiu, J. DeCesare, M. Kapur, R. Patel, "Very sensitive 13"C10⁻¹⁵ NMR method for the detection and quantification of long-chain branches in ethylene-hexene LLDPE", Macromolecule, 2021, 54, 5985. The chemical shifts used for LCB calculations range from 38.12 ppm to 38.22 ppm.

[0179] Melt flow test method. The melt flow index of polyethylene is measured at 190°C under specified temperature, load, piston position and duration in the barrel, using a melt indexer and according to the test method of ASTM D1238-13, via the extrusion rate of molten polymer through a die of specified length and diameter. Loads are 2.16 kg (“I2”), 5.0 kg (“I5”), or 21.6 kg (“I…”). 21 (”).

[0180] Differential scanning calorimetry (DSC) method. Melt temperature is determined by differential scanning calorimetry according to ASTM D 3418-08. Typically, a scan rate of 10 °C / min is used for a 10 mg sample, and a second heating cycle is employed to determine T. m .

[0181] Gel permeation chromatography (GPC) test method :

[0182] Weight-average molecular weight (M w Number-average molecular weight (M) n ) and z-average molecular weight (M z The M value was measured using high-temperature gel permeation chromatography (Polymer Laboratories) equipped with a differential refractive index detector (DRI). w and M n The value is used to calculate the Polydispersity Index (PDI), where Three Polymer Laboratories PLgel 10µm Mixed-B columns were used. The nominal flow rate was 1.0 mL / min, and the nominal injection volume was 300 μL. All transfer lines, columns, and differential refractometers (DRI detectors) were housed in an oven maintained at 160 °C. The solvent for the experiments was prepared by dissolving 6 g of butylated hydroxytoluene as an antioxidant in 4 L of Aldrich reagent-grade 1,2,4-trichlorobenzene (TCB). The TCB mixture was then filtered through a 0.1 μm Teflon filter. The TCB was then degassed using an in-line degasser before entering the GPC instrument. The polymer solution was prepared by placing the dried polymer in a glass vial, adding the required amount of TCB, and then heating the mixture at 160 °C for approximately 2 h with continuous shaking. All quantities were measured by gravimetric analysis. Injection concentrations ranged from 0.5 mg / mL to 2.0 mg / mL, with lower concentrations used for higher molecular weight samples. The DRI detector was purged before each sample run. The flow rate in the apparatus was then increased to 1.0 mL / min, and the DRI was stabilized for 8 hours before injecting the first sample. Molecular weight was determined by combining a universal calibration relationship with column calibration, which was performed using a series of monodisperse polystyrene (PS) standards. MW per elution volume was calculated using the following equation:

[0183]

[0184] Variables with the subscript "X" represent test samples, while those with the subscript "PS" represent PS. In this method, and ,at the same time and It was obtained from publicly published literature. Specifically, it pertains to (PE). And for PP, it is 0.705 / 0.0002288.

[0185] The concentration c at each point in the chromatogram is calculated using the following equation by subtracting the baseline DRI signal from the IDRI: Where KDRI is a constant determined by calibrating DRI, and (dn / dc) is the refractive index increment of the system. Specifically, for polyethylene, Mass recovery is calculated as the ratio of the integral area of ​​the concentration chromatography to the elution volume and the injection mass, which is equal to the predetermined concentration multiplied by the injection ring volume. Unless otherwise specified, all molecular weights are reported in g / mol. If there is a conflict between the GPC-DRI procedure and the “Rapid GPC” procedure, the GPC-DRI procedure immediately preceding it should be used. The comonomer content (i.e., 1-hexene) incorporating the polymer is determined by rapid FT-IR spectroscopy of the dissolved polymer during GPC measurements (wt%). The comonomer content can be determined by using an infrared detector (such as an IR5 detector) with respect to the polymer molecular weight in gel permeation chromatography, as described in Analytical Chemistry 2014, 86(17), 8649-8656. Dean Lee, Colin Li Pi Shan, David M. Meunier, John W. Lyons, Rongjuan Cong, and A. Willem deGroot, “Toward Absolute Chemical Composition Distribution Measurement of Polyolefins by High-Temperature Liquid Chromatography Hyphenated with Infrared Absorbance and Light Scattering Detectors”.

[0186] For some polymer samples, the weight-average molecular weight (Mb) was measured using a chromatographic system consisting of a PolymerChar GPC-IR (Valencia, Spain) high-temperature GPC chromatograph equipped with an internal IR5 infrared detector (IR5) connected to a PrecisionDetectors (now Agilent Technologies) 2-angle laser scattering (LS) detector model 2040 and four capillary viscometers (DV). w Number-average molecular weight (M) n ) and z-average molecular weight (M zFor all absolute light scattering measurements, a 15-degree angle was used. The autosampler oven chamber was set to 165 degrees Celsius, and the column chamber and detector were set to 155 degrees Celsius. The column used was a mixed-pore size column with 4 TOSOH TSKgel GMHHR-H (30) HT 30-micron particle size. The chromatographic solvent used was 1,2,4-trichlorobenzene containing 200 ppm butylated hydroxytoluene (BHT). The solvent source was nitrogen injection. The injection volume used was 200 μL, and the flow rate was 1.0 mL / min.

[0187] GPC column calibration was performed using 21 polystyrene standards with narrow molecular weight distributions, ranging from 580 to 8,400,000, arranged in six "cocktail" mixtures, with each individual molecular weight separated by at least tenfold. The standards were purchased from Agilent Technologies. For molecular weights equal to or greater than 1,000,000, 0.025 g of polystyrene standard was prepared in 50 mL of solvent; for molecular weights less than 1,000,000, 0.05 g of polystyrene standard was prepared in 50 mL of solvent. Individually prepared polystyrene standards (both from Agilent Technologies) at concentrations of 10,000,000 g / mol and 15,000,000 g / mol were also prepared, at concentrations of 0.5 mg / mL and 0.3 mg / mL, respectively. The polystyrene standards were pre-dissolved at 80 °C with gentle stirring for 30 min, then cooled, and the room temperature solution was transferred to a 160 °C autosampler dissolution oven for further cooling for 30 min. Use Equation 1 to convert the peak molecular weight of polystyrene standards to the molecular weight of polyethylene (as described in Williams and Ward, J. Polym.Sci., Polym.Let., 6, 621 (1968)).

[0188] (Equation 1), where M is the molecular weight, A has a value of 0.3992, and B equals 1.0.

[0189] The third-order multi-vertex method is used to fit the corresponding polyethylene equivalent calibration points.

[0190] Total plate counts of the GPC column were performed using decane, which was introduced into the blank sample via a micropump controlled by a PolymerChar GPC-IR system. For a mixed pore size column with 4 TOSOH TSKgel GMHHR-H (30) HT 30 μm particle size, the plate count of the chromatographic system should be greater than 12,000.

[0191] Samples were prepared semi-automatically using PolymerChar Instrument Control software, with a target sample weight of 1 mg / ml. Solvent (containing 200 ppm BHT) was added to a pre-bubbled, diaphragm-capped vial via a PolymerChar high-temperature autosampler. The sample was then dissolved at 165°C for 3 hours with low-speed shaking.

[0192] Based on the GPC results, using the internal IR5 detector (measurement channel) of the PolymerChar GPC-IR chromatograph, according to Equations 2 to 4, the PolymerChar GPCOne was used. ™ The software calculates the Mn content based on the baseline-subtracted IR chromatograms at each equidistant data collection point (i) and the polyethylene equivalent molecular weight obtained from the narrow standard calibration curve at point (i) according to Equation 1. (GPC) Mw (GPC) and Mz (GPC) The calculation.

[0193] (Equation 2).

[0194] (Equation 3).

[0195] (Equation 4).

[0196] To monitor deviations over time, a flow rate marker (decane) was introduced into each sample via a micropump controlled by a PolymerChar GPC-IR system. This flow rate marker (FM) was used to linearly correct the pump flow rate (nominal flow rate) for each sample by comparing the RV (RV(FM sample)) of the corresponding decane peak within the sample with the RV (RV(FM calibrated)) of the decane peak within the narrow standard calibration. It was then assumed that any variation in the decane marker peak time was linearly related to the flow rate (effective flow rate) throughout the run. The effective flow rate (relative to the narrow standard calibration) was calculated according to Equation 5 after calibration based on the flow marker peak system. (via PolymerChar GPCOne) ™ The software processes the flow marker peaks. Acceptable flow rate correction ensures that the effective flow rate is within + / - 0.5% of the nominal flow rate.

[0197] (Equation 5).

[0198] For polymer samples prepared via slurry polymerization in a parallel pressure reactor (PPR), high-temperature GPC analysis was performed using a Dow Robot Assisted Delivery (RAD) system equipped with a PolymerChar infrared detector (IR5) and an Agilent PLgel Mixed A column. Decane (10 µL) was added to each sample as an internal flow marker. Samples were first diluted in 300 ppm butylated hydroxytoluene (BHT)-stabilized 1,2,4-trichlorobenzene (TCB) at a concentration of 10 mg / mL and dissolved by stirring at 160 °C for 120 min. Prior to injection, the samples were further diluted to a concentration of 2 mg / mL using BHT-stabilized TCB. The sample (250 µL) was eluted through a PL-gel 20 µm (50 mm × 7.5 mm) guard column, followed by elution through two PL-gel 20 µm (300 mm × 7.5 mm) Mixed-A columns maintained at 160 °C. TCB was stabilized with BHT at a flow rate of 1.0 mL / min. The total run time was 24 min. To calibrate the molecular weight (MW), Agilent EasiCal polystyrene standards (PS-1 and PS-2) were analyzed to create a third-order MW calibration curve. The molecular weight units were converted from polystyrene (PS) to polyethylene (PE) using a daily Q factor (approximately 0.4, calculated using the average of five Dow 38-4 reference samples with known MW). Hexene incorporation was determined using a linear calibration developed by analyzing copolymer samples with known compositions.

[0199] Liquid chromatography-mass spectrometry (LC-MS) measurements were performed using a Waters e2695 separation module coupled to a Waters 2424 ELS detector, a Waters 2998 PDA detector, and a Waters 3100 ESI mass detector. LC-MS separations were performed on an XBridge C18 3.5 μm 2.1 mm × 50 mm column using a gradient of acetonitrile to water from 5:95 to 100:0, with 0.1% formic acid as the ionizing agent. HRMS analysis was performed using an Agilent 1290 Infinity LC with a Zorbax Eclipse Plus C18 1.8 μm 2.1 mm × 50 mm column coupled to an Agilent 6230 TOF mass spectrometer with electrospray ionization.

[0200] Nuclear magnetic resonance (NMR) spectra were recorded on Bruker 400 NMR, Bruker 500 NMR, Varian 400-MR and VNMRS-500 spectrometers. 1The H NMR data are reported as follows: chemical shifts (multiplicity (br=broad, s=singlet, d=doublet, t=triplet, q=quadruplet, p=quintruplet, sex=sext, sept=septruple and m=multiplicity), integration, and assignment). Low-field data from the inner tetramethylsilane (TMS, scale δ) are reported using the protons remaining in the deuterated solvent as a reference. 1 Chemical shifts (in ppm) from HNMR data. 1 H-decoupling method was used to determine 13 C NMR data were presented, and chemical shifts were reported from the front field of tetramethylsilane (TMS, scale δ) relative to the protons remaining in the deuterated solvent as a reference.

[0201] Example

[0202] Actual examples are not indicated in this way, while contemporaneous examples (if any) are labeled as contemporaneous. Synthesis of commercially available compounds is not shown. Unless otherwise stated, the following conditions are used. Anhydrous toluene, hexane, tetrahydrofuran, and diethyl ether are purified by passing them through activated alumina and, in some cases, through Q-5 reactants. Solvents used for experiments conducted in a nitrogen-filled glove box are further dried by storage on activated 3Å molecular sieves. Glassware used for humidity-sensitive reactions is dried overnight in an oven before use.

[0203] Example 1: Synthesis of 3-bromo-2-hydroxythiophene (Example of step A) .

[0204]

[0205] NaOH (50.000 g, 1.250 mol, 29.6 equivalents) was added in a single addition to a suspension of methyl 3-bromo-2-hydroxythiophene-1-carboxylate (1) (10.020 g, 42.267 mmol, 1.00 equivalent) in 1,4-dioxane (100 mL) and H2O (450 mL) under nitrogen atmosphere. The pale yellow mixture was fitted with a reflux condenser and placed in a hood (i.e., a heating hood) heated to 80 °C. After stirring (500 rpm) for 2.5 hours, thin-layer chromatography (TLC) of the resulting golden yellow solution showed that (1) was completely converted to a solution with a lower R fThe product was obtained by removing the reaction mixture from the jar and allowing it to cool gradually to 23°C, then placing it in an ice-water bath for 60 minutes. Then, concentrated HCl (175 mL, 37%) was added over 10 minutes, and the resulting white heterogeneous mixture was removed from the ice-water bath and placed in a jar heated to 60°C with vigorous stirring (1000 rpm) for 5 hours. The now pale golden-yellow solution was removed from the jar and allowed to cool gradually to 23°C, diluted with Et₂O (100 mL), stirred vigorously for 2 minutes, poured into a separatory funnel, and partitioned. The organic matter was washed with an aqueous HCl solution (2 × 100 mL, 1 equivalent (“N”), and the remaining organic matter was extracted from the aqueous layer with Et₂O (2 × 50 mL), dried over solid Na₂SO₄, decanted, and Et₂O removed by rotary evaporation to give 3-bromo-2-hydroxythiophene as a 1,4-dioxane solution (100 mL). The solution of 3-bromo-2-hydroxythiophene was used in step B without concentration or purification. Aliquots were removed, completely concentrated under vacuum, and the NMR was consistent with that of pure 3-bromo-2-hydroxythiophene as a mixture of keto-enol tautomers, where * indicates keto-enol tautomers: 1 ¹H NMR (400MHz, chloroform-d) δ (8.34 (s, 1H)*), 7.12 (d, J = 3.7Hz, 1H), 6.43 (d, J = 3.7Hz, 1H), 5.49 (s, 1H), (3.72 (s, 2H)*). 13 C NMR (101MHz, chloroform-d) δ (210.23*), 195.46, 160.19, (149.69*), 121.43, (111.65*), (103.07*), 100.24, (37.05*).

[0206] Example 2: Synthesis of 3-bromo-2-ethoxymethyloxythiophene (2) (Example of step B) .

[0207]

[0208] The solution of 3-bromo-2-hydroxythiophene from step A in 1,4-dioxane (100 mL) was diluted with non-anhydrous, non-deoxygenated THF (400 mL). Then, H₂O (6 mL) was added. The solution was placed in an ice-water bath and bubbled with nitrogen for 1 hour under a positive nitrogen flow, and then solid lithium hydroxide monohydrate (3.544 g, 84.453 mmol, 2.00 equivalent) was added. The now dark reddish-brown solution was vigorously stirred (1000 rpm) for 1 hour, and then pure chloromethyl ethyl ether (11.8 mL, 126.80 mmol, 3.00 equivalent, "ClCH₂OEt") was added dropwise via syringe. After stirring at 0°C for 2 hours, the dark brown solution was diluted with NaOH aqueous solution (200 mL, 1N), stirred for 2 minutes, and THF was removed under vacuum. The two-phase mixture was diluted with CH2Cl2 (100 mL), filtered through a diatomaceous earth pad, and washed with CH2Cl2 (4 × 50 mL). The dark brown filtrate was poured into a separatory funnel and divided. The organic matter was washed with NaOH aqueous solution (2 × 100 mL, 1N). The residual organic matter was extracted from the aqueous solution with CH2Cl2 (2 × 50 mL). The mixtures were combined, dried over solid Na2SO4, decanted, and carefully concentrated to obtain a golden brown oil. The oil was diluted with CH2Cl2 (25 mL), filtered through a silica gel pad, washed with CH2Cl2 (4 × 50 mL), and the filtrate was concentrated to obtain 3-bromo-2-ethoxymethyloxythiophene (2) (9.534 g, 40.209 mmol, 95% two-step) in a golden yellow oil. The NMR values ​​are consistent with those of compound (2): 1 ¹H NMR (400MHz, chloroform-d) δ 7.15 (d, J = 3.6Hz, 1H), 6.61 (d, J = 3.5Hz, 1H), 5.19 (s, 2H), 3.73 (q, J = 7.1Hz, 2H), 1.22 (t, J = 7.1Hz, 3H). 13 C NMR (101MHz, chloroform-d) δ 151.51, 121.50, 103.84, 101.55, 95.07, 64.53, 15.05.

[0209] Example 3: Synthesis of 2-ethoxymethyloxy-3-(3',6'-di-tert-butylcarbazolyl)thiophene (4) (Step C) (Example) .

[0210]

[0211] Step C. In a nitrogen-purged glove box, a mixture of bromothiophene (2) (5.883 g, 24.811 mmol, 1.00 equivalent), 3,6-di-tert-butylcarbazole (15.252 g, 54.585 mmol, 2.20 equivalent), Cu2O (7.100 g, 49.622 mmol, 2.00 equivalent) and K2CO3 (34.290 g, 248.11 mmol, 10.00 equivalent) was suspended in deoxygenated anhydrous xylene (200 mL), and N,N'-DMEDA (10.7 mL, 99.244 mmol, 4.00 equivalent) was added. The mixture was then equipped with a reflux condenser and a rubber septum, removed from the glove box, and placed under nitrogen atmosphere. The mixture was heated to 140°C and vigorously stirred (1000 rpm) for 48 hours. After removal from the heat chamber, the dark reddish-black mixture was allowed to cool gradually to 23°C. CH2Cl2 (100 mL) was added, and the mixture was stirred for 5 minutes. The mixture was then filtered through a silica gel pad, washed with CH2Cl2 (4 × 75 mL), concentrated, and the golden-brown amorphous solid was suspended in hexane (50 mL). The mixture was placed in a jacket heated to 60°C and stirred (300 rpm) for 1 hour. The golden-brown mixture was then removed from the heating jacket and allowed to cool gradually to 23°C. The mixture was filtered, and the remaining white solid was washed with hexane (4 × 20 mL). The golden-brown filtrate solution was concentrated onto diatomaceous earth and purified using an ISCO chromatography system via silica gel chromatography; 15% CH2Cl2 / hexane purification was used to prepare thiophene-carbazole (4) (7.699 g, 17.673 mmol, 71%) as a white amorphous foam. NMR was consistent with compound (4). 1 H NMR (500MHz, chloroform-d) δ 8.12 (d, J = 1.9Hz, 2H), 7.45 (dd, J = 8.6,2.0Hz, 2H), 7.32 (d, J = 3.6Hz, 1H), 7.20 (d, J = 8.6Hz, 2H), 6.89 (d, J =3.6Hz, 1H), 3.56 (q, J = 7.1Hz, 2H), 1.47 (s, 18H), 1.16 (t, J = 7.1Hz, 3H). 13 C NMR (126MHz, chloroform-d) δ 150.87, 142.60, 139.70, 127.62, 123.44, 123.08, 120.21, 116.07, 109.57, 102.36, 94.78, 64.37, 34.70, 32.03, 15.01.

[0212] Example 4: 2-ethoxymethyloxy-3-(3',6'-di-tert-butylcarbazolyl)-2-pinacolborylthiophene (5) Synthesis (Example of step D) .

[0213]

[0214] Step D. Place the golden solution of thiophene carbazole (4) (3.000 g, 6.887 mmol, 1.00 equivalent) in anhydrous deoxygenated Et2O (75 mL) in a nitrogen-purged glove box in a freezer (-35 °C) and pre-cool it for 14 hours. Then, add the pre-cooled n-butyllithium (n-BuLi) solution (3.50 mL, 8.608 mmol, 1.25 equivalent, titrated with 2.5 M hexane solution) dropwise. Let the light orange solution stand in the freezer for 4 hours, and then add pure isopropoxyboron pinacol ester (“i-PrOBPin”) (2.81 mL, 13.774 mmol, 2.00 equivalent). The present golden yellow solution was stirred at 23°C for 2 hours. The present white heterogeneous mixture was removed from the glove box and diluted with aqueous phosphate buffer (20 mL, pH = 8, 0.05 M). The mixture was concentrated by rotary evaporation. The mixture was diluted with CH2Cl2 (25 mL) and water (25 mL), poured into a separatory funnel, and divided. The organic matter was washed with water (1 × 25 mL). The residual organic matter was extracted with CH2Cl2 (2 × 25 mL). The extracts were combined, dried over solid Na2SO4, decanted, and concentrated. The resulting golden yellow foam was dissolved in CH2Cl2 (10 mL), filtered through a short silica gel pad, washed with CH2Cl2 (4 × 20 mL), and the golden yellow filtrate solution was concentrated to give thiophene-boronpinacol ester (5) (2.581 g, 4.596 mmol, 67%) with light golden yellow foam. The NMR was consistent with that of compound (5) at approximately 72% purity. 1 ¹H NMR (500MHz, chloroform-d) δ 8.11 - 8.08 (m, 2H), 7.62 (d, J = 0.9Hz, 1H), 7.45 (dt, J = 8.6, 1.4Hz, 2H), 7.23 (dd, J = 8.7, 0.7Hz, 2H), 4.88 (d, J = 0.8Hz, 2H), 2.96 -2.88 (m, 2H), 1.46 (s, 18H), 1.38 (s, 12H), 0.58 (t, J = 7.1Hz, 3H). 13C NMR (126MHz, chloroform-d) δ 158.93, 142.70, 139.53, 130.88, 127.58, 123.65, 123.00, 115.86, 109.77, 98.24, 84.20, 64.53, 34.71, 32.03, 24.80, 14.14. 72% pure compound (5) can be used in subsequent reactions without further purification.

[0215] Example 5: Synthesis of 3,5-di-tert-butylpinacolborylbenzene .

[0216]

[0217] A clear, colorless solution of t-BuLi (6.60 mL, 11.143 mmol, 3.00 equivalent, untitrated 1.70 M pentane solution) in pentane (30 mL) was placed in a nitrogen-filled glove box and incubated at -35°C for 14 hours. Then, a pre-cooled solution of 3,5-di-tert-butylphenyl bromide (1.000 g, 3.714 mmol, 1.00 equivalent) in anhydrous deoxygenated Et₂O (10 mL) was added dropwise. The resulting clear, pale yellow mixture was incubated in the freezer for 3 hours. The resulting pale golden yellow mixture was then removed from the freezer and pure i-PrOBPin (1.50 mL, 7.428 mmol, 2.00 equivalent) was added dropwise via syringe. The current pale yellow mixture was vigorously stirred at 23°C (1000 rpm) for 2 hours. After removing it from the glove box, it was neutralized with aqueous phosphate buffer (50 mL, pH = 8, 0.05 M). The white heterogeneous mixture was filtered through a diatomaceous earth filter and washed with CH2Cl2 (4 × 20 mL). The pale yellow biphasic mixture was poured into a separatory funnel and partitioned. The organic matter was separated using aqueous phosphate buffer (2 × 25 mL, pH = 8). Wash with 0.05 M solution. Extract the residual organic matter from the aqueous layer using CH2Cl2 (2 × 25 mL). Combine the extracts, dry with solid Na2SO4, decant, and concentrate to obtain a pale yellow amorphous viscous oil. Dissolve the oil in CH2Cl2 (10 mL), filter through a silica gel pad, wash with CH2Cl2 (4 × 20 mL), and concentrate the pale yellow filtrate to obtain 3,5-di-tert-butylphenylboronol ester (1.021 g, 3.229 mmol, 87%), which appears as white foam. NMR indicates the product. 1 ¹H NMR (500MHz, chloroform-d) δ 7.71 (d, J = 2.0Hz, 2H), 7.58 (t, J = 2.0Hz, 1H), 1.38 (s, 18H), 1.38 (s, 12H). 13C NMR (126MHz, chloroform-d) δ 149.81, 128.79, 125.55, 83.53, 34.82, 31.53, 24.89.

[0218] Example 6: Synthesis of 3,6-bis(3',5'-di-tert-butylphenyl)carbazole .

[0219]

[0220] A mixture of carbazole (1.062 g, 3.267 mmol, 1.00 equivalent), 3,5-di-tert-butylphenylboronine ester (3.100 g, 9.801 mmol, 3.00 equivalent), Pd(PPh3)4 (0.755 g, 0.6534 mmol, 0.20 equivalent), and K3PO4 (6.241 g, 29.403 mmol, 9.00 equivalent) equipped with a reflux condenser was evacuated and then backfilled with nitrogen. The refilling process was repeated three times, with freshly deoxygenated 1,4-dioxane (30 mL) and H2O (5.0 mL) added simultaneously via syringe. The golden mixture was placed in a hood heated to 100°C and vigorously stirred (1000 rpm) for 48 hours. After removal from the hood, it was allowed to cool gradually to 23°C. The golden suspension was filtered through silica gel, washed with CH2Cl2 (4 × 20 mL), and the yellow filtrate was concentrated onto diatomaceous earth and purified by silica gel chromatography; hexane-50% CH2Cl2 / hexane, yielding a white, foamy, disubstituted carbazole (1.551 g, 2.852 mmol, 87%). The NMR was consistent with that of pure 3,6-bis(3',5'-di-tert-butylphenyl)carbazole. 1 ¹H NMR (500MHz, chloroform-d) δ 8.34 - 8.29 (m, 2H), 8.10 (s, 1H), 7.68 (dd, J = 8.4, 1.8Hz, 2H), 7.54 (d, J = 1.7Hz, 4H), 7.51 (d, J = 8.3Hz, 2H), 7.45 (t, J = 1.8Hz, 2H), 1.43 (s, 36H). 13 C NMR (126MHz, chloroform-d) δ 151.03, 141.57, 139.25, 134.55, 126.04, 123.93, 122.02, 120.74, 119.18, 110.71, 35.01, 31.60.

[0221] Example 7: 2-Ethyloxymethyloxy-3-[3,6-bis(3',5'-di-tert-butylphenyl)carbazolyl]thiophene synthesis .

[0222]

[0223] In a nitrogen-purged glove box, a mixture of bromothiophene (2) (1.000 g, 4.218 mmol, 1.00 equivalent), 3,6-bis(3',5'-di-tert-butylphenyl)carbazole (3.485 g, 9.280 mmol, 2.20 equivalent), Cu2O (1.208 g, 8.326 mmol, 2.00 equivalent) and K2CO3 (5.828 g, 42.174 mmol, 10.00 equivalent) was suspended in deoxygenated anhydrous xylene (40 mL), and N,N'-DMEDA (1.80 mL, 16... 0.872 mmol (4.00 equivalents), the mixture was fitted with a reflux condenser and rubber septum, removed from the glove box, placed under nitrogen, and heated to 140°C in a hood with vigorous stirring (1000 rpm) for 48 hours. It was then removed from the hood and allowed to gradually cool to 23°C. CH2Cl2 (100 mL) was added, and the mixture was stirred for 5 minutes. The mixture was filtered through a silica gel sieve, washed with CH2Cl2 (4 × 75 mL), and the golden-brown filtrate was concentrated onto diatomaceous earth. Purification was performed using an ISCO chromatography system via silica gel chromatography; hexane-5% EtOAc / hexane purification yielded a transparent, colorless, amorphous foam of thiophene-carbazole (2.448 g, 3.497 mmol, 83%). NMR was consistent with pure 2-ethyloxymethyloxy-3-[3,6-bis(3',5'-di-tert-butylphenyl)carbazolyl]thiophene. 1 H NMR (400MHz, chloroform-d) δ8.35 (d, J = 1.7Hz, 2H), 7.66 (dd, J = 8.5, 1.7Hz, 2H), 7.55 (d, J = 1.8Hz,4H), 7.48 - 7.43 (m, 3H), 7.37 (d, J = 8.4Hz, 2H), 6.94 (d, J = 3.6Hz, 1H), 5.09 (s, 2H), 3.59 (q, J = 7.0Hz, 2H), 1.44 (s, 36H), 1.18 (t, J = 7.1Hz, 3H). 13 C10 NMR (101 MHz, chloroform-d) δ 151.05, 150.83, 141.62, 141.04, 134.98, 127.09, 125.98, 123.75, 122.08, 120.78, 120.71, 119.09, 110.37, 102.55, 94.83, 64.49, 35.02, 31.61, 15.06. HRMS (ESI): Calculated C10 NMR values. 47 H57 NO2S [M+H] + The value was 700.4183; the measured value was 700.4144.

[0224] Example 8: 2-Ethyloxymethyloxy-3-[3,6-bis(3',5'-di-tert-butylphenyl)carbazole]-1-pin Synthesis of boronic thiophene

[0225]

[0226] A golden solution of 2-ethyloxymethyloxy-3-[3,6-bis(3',5'-di-tert-butylphenyl)carbazolyl]thiophene (2.448 g, 3.497 mmol, 1.00 equivalent) in anhydrous deoxygenated Et₂O (40 mL) was placed in a freezer (-35 °C) and pre-cooled for 14 hours. Then, pre-cooled n-BuLi solution (1.75 mL, 4.371 mmol, 1.25 equivalent, titrated with 2.5 M hexane solution) was added dropwise. The pale orange solution was allowed to stand in the freezer for 4 hours, and then pure isopropoxyboronpinacol ester (1.43 mL, 6.994 mmol, 2.00 equivalent) was added. The current golden yellow solution was stirred at 23°C for 2 hours, then removed from the glove box. The current white heterogeneous mixture was diluted with water (50 mL) and Et2O (50 mL), poured into a separating funnel, and partitioned. The organic matter was washed with water (1 × 25 mL), and the residual organic matter was extracted with Et2O (2 × 25 mL). The solutions were combined, dried over solid Na2SO4, decanted, concentrated, and the golden yellow filtrate was concentrated to give thiophene-boron pinacol ester (2.537 g, 2.641 mmol) with a light golden yellow foam. The NMR was consistent with that of approximately 86% pure 2-ethyloxymethyloxy-3-[3,6-bis(3',5'-di-tert-butylphenyl)carbazolyl]-1-pinacolboronylthiophene. 1 H NMR(400MHz, cdcl3) δ 8.35 - 8.33 (m, 2H), 7.73 (s, 1H), 7.67 (dd, J = 8.5,1.7Hz, 2H), 7.55 (d, J = 1.8Hz, 4H), 7.46 (t, J = 1.8Hz, 2H), 7.41 (d, J =8.5Hz, 2H), 4.98 (s, 2H), 2.96 (q, J = 7.1Hz, 2H), 1.44 (s, 36H), 1.40 (s,12H), 0.60 (t, J = 7.0Hz, 3H). 13C10 NMR (101MHz, cdcl3) δ 158.91, 151.13, 151.06, 141.55, 140.88, 134.99, 130.51, 127.81, 126.13, 123.65, 122.00, 120.80, 118.90, 110.62, 98.41, 84.30, 64.58, 35.02, 31.62, 24.82, 14.20. The product was used in subsequent reactions without further purification.

[0227] Example 9: Synthesis of 2-iodo-4-(1',1',3',3'-tetramethylbutyl)phenol .

[0228]

[0229] A clear, colorless solution of 4-(1',1',3',3'-tetramethylbutyl)phenol (3.324 g, 16.110 mmol, 1.00 equivalent), potassium iodide (KI, 3.477 g, 20.943 mmol, 1.30 equivalent), and NaOH aqueous solution (21 mL, 20.943 mmol, 1.30 equivalent, 1N) in methanol (100 mL) and water (50 mL) was placed in an ice bath and stirred vigorously for 1 hour. Then, pre-cooled commercial aqueous bleach (26 mL, 20.943 mmol, 1.30 equivalent, 5.2% w / w) was added dropwise over 10 minutes. The opaque pale yellow mixture was stirred at 0°C for 2 hours. The mixture was then removed from the ice-water bath and stirred at 23°C for 3 hours. Solid NaH2PO4 (20 g) was then added, followed by water (100 mL) and a saturated aqueous mixture of Na2S2O3 (100 mL) to reduce residual iodine. The mixture was vigorously stirred for 10 minutes, diluted with CH2Cl2 (50 mL), and the two yellow phases were poured into a separatory funnel for partitioning. The organic matter was washed with Na2S2O3 aqueous solution (2 × 50 mL), and the residual organic matter was extracted from the aqueous layer with CH2Cl2 (2 × 50 mL). The extracts were combined, dried over solid Na2SO4, decanted, concentrated onto diatomaceous earth, and purified by silica gel chromatography with hexane-10% CH2Cl2 to obtain 2-iodo-4-(1',1',3',3'-tetramethylbutyl)phenol (3.240 g, 9.340 mmol, 58%) as a transparent, colorless, amorphous foam. The NMR was consistent with that of pure 2-iodo-4-(1',1',3',3'-tetramethylbutyl)phenol. 1¹H NMR (500MHz, chloroform-d) δ 7.60 (d, J = 2.3Hz, 1H), 7.24 (dd, J = 8.5, 2.3Hz, 1H), 6.90 (dd, J = 8.6, 0.5Hz, 1H), 5.11 (s, 1H), 1.68 (s, 2H), 1.32 (s, 6H), 0.73 (s, 9H). 13 C NMR (126MHz, chloroform-d) δ 152.34, 144.65, 135.66, 128.14, 114.23, 85.38, 56.87, 37.93, 32.35, 31.81, 31.55.

[0230] Example 10: Synthesis of 4-Octyloxyphenol .

[0231]

[0232] Add 1-bromooctane (40.8 mL, 236.13 mmol, 1.30 equivalent) to a mixture of hydroquinone (20.000 g, 181.64 mmol, 1.00 equivalent) and K₂CO₃ (100.40 g, 726.56 mmol, 4.00 equivalent) in DMSO (600 mL). Place the mixture under nitrogen atmosphere in a hood heated to 90 °C and stir (500 rpm) for 36 hours. Remove from the hood and allow to cool to ambient temperature. Add water (200 mL) and KH₂PO₄ (100 g) and stir for approximately 10 minutes. Then, EtOAc / hexane (200 mL, 1:1) was added, and the two-phase mixture was poured into a separatory funnel for partitioning. The organic matter was washed with water (3 × 100 mL), and the residual organic matter was extracted from the aqueous solution using EtOAc / hexane (2 × 100 mL, 1:1). The extracts were combined, dried over Na2SO4, decanted, concentrated onto diatomaceous earth, and purified by silica gel chromatography using ISCO; 40%–80% CH2Cl2 / hexane to give 4-octyl ether phenol (16.646 g, 74.871 mmol, 41%) as a light golden-brown solid. NMR indicated the product. 1 H NMR (400MHz, CDCl3) δ6.84 - 6.73 (m, 4H), 5.11 (s, 1H), 3.92 (t, J = 6.6Hz, 2H), 1.78 (p, J =6.8Hz, 2H), 1.46 (p, J = 7.0Hz, 2H), 1.34 (ddd, J = 19.4, 10.1, 5.1Hz, 8H), 0.99 - 0.84 (m, 3H).13 C NMR (101MHz, CDCl3) δ 153.24, 149.44, 116.07, 115.74, 68.91, 31.83, 29.38, 29.26, 26.06, 22.67, 14.11.

[0233] Example 11: Synthesis of 4-Octyloxyphenol methyl ethyl ether .

[0234]

[0235] A clear, colorless solution of iodophenol (18.405 g, 0.08278 mol, 1.00 equivalent) in 500 mL of THF was bubbled for 15 minutes under a positive nitrogen flow. Then, an aqueous solution of NaOH (13.2 mL, 0.500 mol, 6.00 equivalent, 50% w / w) was added dropwise via syringe. After stirring at 23 °C (500 rpm) for 60 minutes, pure chloromethyl ether (23.0 mL, 0.24835 mol, 3.00 equivalent) was added dropwise via syringe to the clear, pale yellow solution. After stirring at 23°C for 3 hours, the resulting white heterogeneous mixture was diluted with 100 mL of NaOH aqueous solution (1N). THF was removed by rotary evaporation. The resulting white two-phase mixture was diluted with 100 mL of CH2Cl2, poured into a separatory funnel, and partitioned. The organic matter was washed with 2 × 100 mL of NaOH aqueous solution (1N). The remaining organic matter was extracted from the aqueous solution with 2 × 50 mL of CH2Cl2. The extracts were combined, dried over solid Na2SO4, decanted, and concentrated. The resulting pale yellow oil was diluted in 20 mL of CH2Cl2, filtered through a silica gel filter, washed with 4 × 25 mL of CH2Cl2, and the filtrate was concentrated to give a transparent amber oil of phenolic methyl ethyl ether (23.116 g, 0.08244 mol, 99%). NMR indicated the product. 1 H NMR (400MHz, cdcl3) δ 7.00 - 6.92(m, 2H), 6.84 - 6.76 (m, 2H), 5.13 (s, 2H), 3.88 (t, J = 6.6Hz, 2H), 3.71 (q,J = 7.1Hz, 2H), 1.74 (dt, J = 14.6, 6.7Hz, 2H), 1.43 (dq, J = 10.2, 6.0Hz, 2H), 1.37 - 1.24 (m, 8H), 1.21 (t, J = 7.1Hz, 3H), 0.92 - 0.83 (m, 3H). 13C NMR (101MHz, cdcl3) δ 154.19, 151.31, 117.50, 115.26, 94.00, 68.51, 63.99, 31.79, 29.35, 29.22, 26.03, 22.63, 15.09, 14.07.

[0236] Example 12: Synthesis of 2-iodo-4-octyloxyphenol methyl ethyl ether .

[0237]

[0238] Before use, the diether was azeotropically dried using toluene (4 × 10 mL). A clear, colorless solution of the diether (4.359 g, 15.545 mmol, 1.00 equivalent) in anhydrous deoxygenated THF (150 mL) was placed in a freezer (-35 °C) for 16 hours. n-BuLi (10.9 mL, 27.204 mmol, 1.75 equivalent, 2.5 M hexane solution) was added, resulting in a deep amber solution. This solution was then placed in the freezer for 20 hours. Pure 2-iodo-1,1,1-trifluoroethane (3.8 mL, 38.863 mmol, 2.50 equivalent) was added dropwise, resulting in a golden-brown solution. This solution was then kept in the freezer for 30 minutes, removed, stirred (500 rpm) for 4 hours, removed from the glove box, neutralized with H2O (50 mL), and the THF was removed by rotary evaporation. The brown mixture was diluted with 50 mL of CH2Cl2 and 50 mL of water, poured into a separatory funnel, and partitioned. The organic matter was extracted with CH2Cl2 (2 × 50 mL), and the extracts were combined, dried over Na2SO4, decanted, concentrated onto diatomaceous earth, and purified by silica gel chromatography using ISCO. The iodide was purified by hexane-20% CH2Cl2 / hexane to give a transparent, colorless oily product (5.208 g, 12.818 mmol, 82%). NMR indicated the product. 1 H NMR (500MHz, cdcl3) δ 7.31 (d, J = 2.9Hz, 1H), 7.00 (d, J= 8.9Hz, 1H), 6.83 (dd, J = 9.0, 2.9Hz, 1H), 5.19 (s, 2H), 3.88 (t, J =6.6Hz, 2H), 3.78 (q, J = 7.1Hz, 2H), 1.74 (dq, J = 8.9, 6.6Hz, 2H), 1.47 -1.39 (m, 2H), 1.39 - 1.28 (m, 8H), 1.23 (d, J = 7.1Hz, 3H), 0.91 - 0.85 (m,3H).13 C NMR (126MHz, cdcl3) δ 154.71, 150.48, 125.02, 116.25, 115.55, 94.60,87.65, 68.74, 64.55, 31.80, 29.32, 29.24, 29.22, 25.99, 22.65, 15.07, 14.09.

[0239] Example 13: Synthesis of 2-iodo-4-octyloxyphenol .

[0240]

[0241] Under nitrogen atmosphere at 23°C, concentrated HCl (25 mL) was added to a clear, pale yellow solution of iodophenol (17.510 g, 0.04310 mol, 1.00 equivalent) in 1,4-dioxane (50 mL) and CH2Cl2 (50 mL). After stirring (500 rpm) at 23°C for 8 hours, the resulting golden-brown mixture was diluted with water (100 mL) and CH2Cl2 (50 mL), poured into a separatory funnel, and partitioned. The organic matter was extracted from the aqueous solution using CH2Cl2 (2 × 25 mL). The extracts were combined, dried over Na2SO4, decanted, concentrated, and CH2Cl2 (20 mL) was added. The dark brown solution was filtered through a silica gel filter, washed with CH2Cl2 (4 × 25 mL), and the filtrate was concentrated to give iodophenol (14.810 g, 0.04253 mol, 99%) as a clear, amber-colored oil. NMR indicates a product with minor impurities, which can be used in subsequent reactions without further purification. 1 H NMR (400MHz, cdcl3) δ 7.17 (d, J = 2.8Hz, 1H), 6.88 (d, J = 8.9Hz, 1H), 6.80 (dd, J = 8.9, 2.9Hz, 1H), 4.93 (s, 1H), 3.85 (t, J = 6.5Hz, 2H), 1.81 - 1.65 (m, 2H), 1.41 (p, J = 6.9Hz, 2H), 1.37 -1.20 (m, 8H), 0.96 - 0.79 (m, 3H). 13 C NMR (101MHz, cdcl3) δ 153.51, 149.03, 123.45, 116.95, 115.04, 85.07, 68.94, 31.79, 29.32, 29.24, 29.21, 25.98, 22.64, 14.09.

[0242] Example 14: Bis[2-iodo-4-(1',1',3',3'-tetramethylbutyl)phenoxy)methyl]-diisopropylgermanium synthesis .

[0243]

[0244] A solid mixture of 2-iodo-4-tert-octylphenol (1.610 g, 4.845 mmol, 2.50 equivalents) and K3PO4 (1.646 g, 7.752 mmol, 4.00 equivalents) was suspended in DMF (30 mL) under nitrogen atmosphere, pure dichloromethyl diisopropylgermanium (0.500 g, 1.938 mmol, 1.00 equivalents) was added, and the mixture was placed in a hood heated to 80 °C. After stirring (300 rpm) for 16 hours, the golden-brown solution was heated to 100°C and stirred for 2 hours. It was then removed from the hood and allowed to cool to ambient temperature. The resulting golden-brown mixture was diluted with water (25 mL) and hexane (25 mL). The two-phase mixture was poured into a separatory funnel and partitioned. The organic matter was washed with NaOH aqueous solution (2 × 25 mL, 1N). The residual organic matter was extracted with hexane (2 × 25 mL). The extracts were combined, dried over solid Na₂SO₄, decanted, concentrated onto diatomaceous earth, and purified by silica gel chromatography (0%–10% CH₂Cl₂ / hexane) to obtain a transparent, colorless oily substance, bis[2-iodo-4-(1',1',3',3'-tetramethylbutyl)phenoxy)methyl]-diisopropylgermanium (0.985 g, 1.159 mmol, 60%). The NMR was consistent with the compound. 1 H NMR (500MHz, cdcl3) δ 7.70 (d, J =2.3Hz, 2H), 7.29 - 7.26 (m, 2H), 6.91 (d, J = 8.7Hz, 2H), 4.16 (s, 4H), 1.73(p, J = 7.5Hz, 2H), 1.68 (s, 4H), 1.31 (s, 12H), 1.29 (d, J = 7.5Hz, 12H), 0.73 (s, 18H). 13 C NMR (126MHz, cdcl3) δ 157.33, 144.34, 137.02, 126.96,110.23, 85.81, 58.10, 56.83, 37.89, 32.36, 31.87, 31.60, 19.80, 14.00.

[0245] Example 15: Synthesis of bis[2-iodo-4-(octyloxy)phenoxy)methyl]-diisopropylgermanium .

[0246]

[0247] A solid mixture of 2-iodo-4-octyl ether phenol (1.159 g, 3.328 mmol, 2.10 equivalents) and K3PO4 (1.682 g, 7.925 mmol, 5.00 equivalents) was suspended in DMF (30 mL) under nitrogen atmosphere, pure dichloromethyl diisopropylgermanium (0.409 g, 1.585 mmol, 1.00 equivalents) was added, and the mixture was placed in a hood heated to 80 °C. After stirring (300 rpm) for 16 hours, the golden-brown solution was heated to 100°C and stirred for 2 hours. It was then removed from the hood and allowed to cool to ambient temperature. The resulting dark brown / black mixture was diluted with water (25 mL) and hexane (25 mL). The two phases were poured into a separatory funnel and partitioned. The organic matter was washed with NaOH aqueous solution (2 × 25 mL, 1N). The residual organic matter was extracted with hexane (2 × 25 mL). The extracts were combined, dried over solid Na₂SO₄, decanted, concentrated onto diatomaceous earth, and purified by silica gel chromatography (0%–30% CH₂Cl₂ / hexane) to obtain a transparent, pale yellow, amorphous oily diiodide (0.978 g, 1.109 mmol, 70%). NMR indicated the product. 1 HNMR (500MHz, cdcl3) δ 7.31 (d, J = 2.9Hz, 2H), 6.91 (d, J = 9.0Hz, 2H), 6.85(dd, J = 8.9, 2.8Hz, 2H), 4.12 (s, 4H), 3.87 (t, J = 6.6Hz, 4H), 1.78 - 1.67(m, 6H), 1.46 - 1.38 (m, 4H), 1.36 - 1.23 (m, 20H), 1.28 (d, J = 7.5Hz, 12H), 0.92 - 0.86 (m, 6H). 13 C NMR (126MHz, cdcl3) δ 154.18, 153.58, 125.38, 115.27,111.33, 86.03, 68.90, 58.64, 31.82, 29.35, 29.29, 29.25, 26.00, 22.67, 19.80,14.13, 13.98.

[0248] Example 16 (contemplated): Synthesis of bis[2-iodophenoxy)methyl]-di-isopropylgermanium .

[0249]

[0250] A mixture of 2-iodophenol (4.845 mmol, 2.50 equivalents) and K3PO4 (1.646 g, 7.752 mmol, 4.00 equivalents) was suspended in DMF (30 mL) under nitrogen atmosphere, pure dichloromethyl diisopropylgermanium (0.500 g, 1.938 mmol, 1.00 equivalents) was added, and the mixture was placed in a hood heated to 80 °C. After stirring (300 rpm) for 16 hours, the solution was heated to 100°C and stirred for 2 hours. It was then removed from the hood and allowed to cool to ambient temperature. The resulting mixture was diluted with water (25 mL) and hexane (25 mL). The mixture was poured into a separatory funnel, partitioned, and the organic matter was washed with NaOH aqueous solution (2 × 25 mL, 1N). The residual organic matter was extracted with hexane (2 × 25 mL). The extracts were combined, dried over solid Na₂SO₄, decanted, concentrated onto diatomaceous earth, and purified by silica gel chromatography (0%–10% CH₂Cl₂ / hexane) to prepare bis[(2-iodo-phenoxy)methyl]-diisopropylgermanium. NMR was expected to be consistent with the compound.

[0251] Example 17: Synthesis of Compound 1: A compound of formula (I), wherein R 1 R 2 and R 5 To R 9 For H, R 3 and R 4 Each for themselves (CH3)3CCH2C(CH3)2- ("tert-singyl"), each R 10 It is tert-butyl, and R 11 and R 12 Each is isopropyl .

[0252]

[0253] A solid mixture of boron pinacol ester (11.228 g, 13.995 mmol, 3.00 equivalent, approximately 70% pure), diiodide (3.966 g, 4.665 mmol, 1.00 equivalent), Pd(AmPhos)Cl2 (0.661 g, 0.9330 mmol, 0.20 equivalent), and solid K3PO4 (8.912 g, 41.985 mmol, 9.00 equivalent) in a round-bottom flask equipped with a reflux condenser sealed with a rubber septum was evacuated, backfilled with nitrogen, and the evacuation / nitrogen refilling process was repeated 3 times. Then, freshly bubbled deoxygenated 1,4-dioxane (50 mL) and H2O (5.0 mL) were added via syringe, and the resulting pale yellow mixture was placed in a hood heated to 50°C. After stirring (300 rpm) for 36 hours, the resulting black mixture was removed from the diaphragm and cooled to 23°C. It was then diluted with 20 mL of CH₂Cl₂. The two-phase mixture was filtered through a silica gel filter, washed with 4 × 20 mL of CH₂Cl₂, concentrated onto diatomaceous earth, and purified by silica gel chromatography (10%–35% CH₂Cl₂ / hexane) to give a protected coupling product (5.220 g) appearing as a golden-brown foam. NMR indicated a product with minor impurities. The mixture was used in subsequent reactions without further purification.

[0254] Under nitrogen atmosphere at 23°C, the above coupling product (6.220 g) was added to a solution of 1,4-dioxane and CH2Cl2 (50 mL, 1:1) with concentrated HCl aqueous solution (15 mL, 37% w / w). After stirring (300 rpm) for 24 hours, the dark brown mixture was diluted with water (50 mL) and CH2Cl2 (25 mL). The two-phase mixture was poured into a separatory funnel, partitioned, and the residual organic matter was extracted with CH2Cl2 (2 × 25 mL). The extracts were combined, dried over solid Na2SO4, decanted, concentrated onto diatomaceous earth, and purified by silica gel chromatography (10%–30% CH2Cl2 / hexane) to give hydroxythiophene (compound 1) (3.523 g, 2.612 mmol, 56% two-step), which was a light golden amorphous foam. NMR indicated the product. 1 H NMR (500MHz, cdcl3) δ 8.13 (dd, J = 2.0,0.6Hz, 4H), 7.45 - 7.41 (m, 6H), 7.31 (s, 2H), 7.22 (dd, J = 8.6, 0.6Hz, 4H), 7.03 (dd, J = 8.7, 2.5Hz, 2H), 6.91 (s, 2H), 6.59 (d, J = 8.8Hz, 2H), 4.08(s, 4H), 1.73 (s, 4H), 1.45 (s, 36H), 1.36 (s, 12H), 1.36 - 1.28 (m, 2H),0.93 (d, J = 7.5Hz, 12H), 0.75 (s, 18H). 13 C NMR (126MHz, cdcl3) δ 154.05,146.27, 144.07, 142.53, 139.92, 128.26, 127.31, 126.70, 123.47, 123.10,121.11, 119.95, 116.09, 116.00, 112.74, 109.66, 59.56, 56.83, 38.10, 34.71, 32.39, 32.06, 31.91, 31.62, 19.40, 13.92.

[0255] Example 18: Synthesis of Compound 2: A compound of formula (I), wherein R 1 R 2 and R 5 To R 9 For H, R 3 and R 4 Each for themselves Octyloxy, each R 10 It is tert-butyl, and R 11 and R 12 Each is isopropyl .

[0256]

[0257] A solid mixture of boron pinacol ester (1.408 g, 1.504 mmol, 2.80 equivalents, approximately 60% pure), diiodide (0.473 g, 0.5373 mmol, 1.00 equivalents), Pd(AmPhos)Cl2 (76.0 mg, 0.1075 mmol, 0.20 equivalents), and solid K3PO4 (1.026 g, 4.836 mmol, 9.00 equivalents) in a round-bottom flask equipped with a reflux condenser sealed with a rubber septum was evacuated, backfilled with nitrogen, and the evacuation / nitrogen refilling process was repeated 3 times. Then, freshly bubbled deoxygenated 1,4-dioxane (15 mL) and H2O (1.5 mL) were added via syringe, and the resulting pale yellow mixture was placed in a hood heated to 50°C. After stirring (300 rpm) for 36 hours, the resulting black mixture was removed from the hood and cooled to 23°C. It was then diluted with 20 mL of CH₂Cl₂, and the two-phase mixture was filtered through a silica gel filter. The mixture was washed with CH₂Cl₂ (4 × 20 mL), and the filtrate was concentrated onto diatomaceous earth and purified by silica gel chromatography (10%–40% CH₂Cl₂ / hexane) to give a protected coupling product (0.559 g) as a dark purple amorphous foam. NMR indicated a product with minor impurities. The mixture was used in subsequent reactions without further purification. Under nitrogen atmosphere at 23°C, a solution of the coupling product (0.559 g) in 1,4-dioxane and CH₂Cl₂ (10 mL, 1:1) was added to a solution of concentrated HCl (5 mL, 37% w / w). After stirring (300 rpm) for 20 hours, the dark purple-black mixture was diluted with water (25 mL) and CH2Cl2 (25 mL). The two-phase mixture was poured into a separatory funnel, partitioned, and the residual organic matter was extracted with CH2Cl2 (2 × 25 mL). The extracts were combined, dried over solid Na2SO4, decanted, concentrated onto diatomaceous earth, and purified by silica gel chromatography (10%-40% CH2Cl2 / hexane) to obtain hydroxythiophene (compound 2) (0.353 g, 0.2557 mmol, 48% two-step process) as a transparent, colorless, amorphous foam. NMR indicated the product. 1H NMR (500MHz, cdcl3) δ 8.12 (dd, J = 1.9, 0.6Hz, 4H), 7.41 (dd, J = 8.6, 1.9Hz, 4H), 7.31 (s, 2H), 7.21 - 7.17 (m, 6H), 6.96 (dd, J= 2.2, 1.1Hz, 2H), 6.52 (d, J = 2.3Hz, 4H), 3.97 (s, 4H), 3.91 (t, J = 6.5Hz,4H), 1.78 (p, J = 6.7Hz, 4H), 1.44 (s, 36H), 1.42 - 1.22 (m, 22H), 0.95 -0.87 (m, 18H). 13 C NMR (126MHz, cdcl3) δ 154.29, 150.34, 146.59, 142.55,139.85, 127.44, 123.46, 123.10, 123.05, 120.22, 115.99, 115.73, 115.41,115.29, 114.76, 109.66, 68.56, 60.61, 34.70, 32.04, 31.85, 29.42, 29.36,29.29, 26.10, 22.70, 19.34, 14.15, 13.82.

[0258] Example 19 (contemplated): Synthesis of compound 3: a compound of formula (I), wherein R 1 To R 9 For H, each R 10 It is 3. 5-Di(tert-butyl)phenyl ("35dtBP"), and R 11 and R 12 Each is isopropyl .

[0259]

[0260] Compound 3 was prepared using a method similar to that of Example 18.

[0261] Example 20: Synthesis of compound 4: a compound of formula (I), wherein R 1 R 2 and R 5 To R 9 For H, R 3 and R 4 Each for themselves Fluorine, per R 10 It is tert-butyl, and R 11 and R 12 Each is isopropyl .

[0262]

[0263] A mixture of thiophene boron pinacol ester (1.602 g, 2.077 mmol, 4.00 equivalents, NMR purity 72%), K3PO4 (1.323 g, 6.230 mmol, 12.0 equivalents), Pd(AmPhos)Cl2 (74.0 mg, 0.1038 mmol, 0.20 equivalents), and diphenyl iodine (0.294 g, 0.5192 mmol, 1.00 equivalents) was prepared. The mixture was purged and then backfilled with nitrogen. This process was repeated at least three times. Then, deoxygenated 1,4-dioxane (10.0 mL) and deoxygenated water (1.0 mL) were added sequentially via syringe. The mixture was then placed in a hood heated to 50°C. After vigorous stirring (1000 rpm) for 40 hours, the black mixture was removed from the diaphragm and allowed to cool gradually to 23°C. It was then filtered through a silica gel pad, washed with CH2Cl2 (4 × 20 mL), and the clear black filtrate was concentrated. Residual 1,4-dioxane was removed by rotary evaporation azeotropically using toluene (2 × 10 mL). The black mixture was then suspended in CH2Cl2 (20 mL), filtered through a silica gel pad, washed with CH2Cl2 (4 × 20 mL), and the black filtrate was concentrated onto diatomaceous earth. Purification was then performed using an ISCO chromatography system via silica gel chromatography; 10%–55% CH2Cl2 / hexane, yielding an impure dithiophene (0.220 g) exhibiting pale yellow foam. NMR indicated the presence of impurities in the product. The impure material was used in subsequent reactions.

[0264] Under nitrogen atmosphere at 23°C, concentrated HCl (3 mL) was added to a solution of impure coupling product in CH₂Cl₂-1,4-dioxane (6 mL, 1:1). The golden-brown solution was stirred (500 rpm) for 20 hours, diluted with 1N HCl (10 mL) and CH₂Cl₂ (10 mL), poured into a separatory funnel, and partitioned. The organic matter was washed with 1N HCl (1 × 10 mL), and the residual organic matter was extracted from the aqueous solution with CH₂Cl₂ (2 × 10 mL). The extracts were combined, dried over solid Na₂SO₄, decanted, concentrated onto diatomaceous earth, and purified by silica gel chromatography using an ISCO system; 10%–75% CH₂Cl₂ / hexane purification, yielding bisthiophene (0.100 g, 0.08617 mmol, 17% two-step process) as a transparent amorphous foam. NMR indicated the purity of the product. 1H NMR (500MHz, chloroform-d) δ 8.16 (dd,J = 1.9, 0.6Hz, 4H), 7.42 (dd, J = 8.6, 1.9Hz, 4H), 7.35 (s, 2H), 7.17 (dd, J= 8.6, 0.7Hz, 4H), 7.12 (dd, J = 9.2, 3.1Hz, 2H), 6.71 (s, 2H), 6.56 (ddd, J= 9.0, 7.7, 3.1Hz, 2H), 6.34 (dd, J = 9.2, 4.6Hz, 2H), 3.94 (s, 4H), 1.47 (s,36H), 1.39 - 1.29 (m, 2H), 0.94 (d, J = 7.5Hz, 12H). 19 F NMR (470MHz, chloroform-d) δ-121.59 (td, J = 8.4, 4.6Hz). 13 C NMR (126MHz, chloroform-d) δ 157.50 (d, J =240.5Hz), 152.50, 146.74, 142.85, 139.78, 127.26, 123.55, 123.25 (d, J =9.3Hz), 123.21, 120.73, 116.49 (d, J = 24.6Hz), 116.08, 115.02 (d, J =22.9Hz), 114.50 (d, J = 8.9Hz), 114.22 (m), 109.59, 60.00, 34.73, 32.04,19.34,13.91.

[0265] Examples 21 and 22: Synthesis of precatalyst 1: precatalyst of formula (II), wherein R 1 R 2 and R 5 To R 9 For H, R 3 and R 4 Each is (CH3)3CCH2C(CH3)2- ("tert-singyl"), each R 10 For tert-butyl, R 11 and R 12 Each is isopropyl, and M is Zr. Each X is benzyl, and the subscript n is 2; and the synthesis of precatalyst 2: the precatalyst of formula (II), wherein R 1 R 2 and R 5 To R 9 For H, R 3 and R 4 Each is (CH3)3CCH2C(CH3)2- ("tert-singyl"), each R 10 For tert-butyl, R 11 and R 12 Each is an isopropyl The base is M, which is Hf, each X is benzyl, and the subscript n is 2. .

[0266]

[0267] Prior to use, the thiophene ligand was azeotropically dried using PhMe (4 × 10 mL). A solution of ZrBn4 (55.8 mg, 0.1223 mmol, 1.10 equivalent) in PhMe (4.46 mL) was added dropwise to a clear, pale golden-yellow solution of thiophene (0.150 g, 0.1112 mmol, 1.00 equivalent) in PhMe (35.5 mL) at 23 °C. After stirring (500 rpm) for 20 min, the pale golden-yellow solution was filtered through a 0.45 µm PTFE submicron filter connected to a 0.20 µm PTFE submicron filter, washed with PhMe (3 × 3 mL), and concentrated to give a zirconium complex (pre-catalyst 1) (0.178 g, 0.1100 mmol, 99%) exhibiting a golden-yellow foam. NMR indicated the product. 1 H NMR (400MHz, C6D6) δ 8.60 (d, J= 1.9Hz, 2H), 8.22 (d, J = 1.8Hz, 2H), 7.60 - 7.50 (m, 6H), 7.47 (d, J =8.5Hz, 2H), 7.25 (d, J = 8.7Hz, 2H), 7.14 - 7.08 (m, 4H), 7.08 - 6.99 (m,2H), 6.90 (s, 2H), 6.88 - 6.81 (m, 2H), 6.35 - 6.30 (m, 4H), 5.53 (d, J =8.6Hz, 2H), 4.52 (d, J = 13.0Hz, 2H), 3.56 (d, J = 13.1Hz, 2H), 1.79 (d, J =14.6Hz, 2H), 1.60 (d, J =14.6Hz, 2H), 1.58 (s, 18H), 1.28 (s, 18H), 1.28 (s,6H), 1.23 (s, 6H), 1.21 (d, J = 12.5Hz, 2H), 0.93 (dt, J = 14.8, 7.4Hz, 2H), 0.75 (s, 18H), 0.74 (d, J = 7.5Hz, 6H), 0.65 (d, J = 7.5Hz, 6H), 0.55 (d, J =12.5Hz, 2H). 13C NMR (101MHz, C6D6) δ 156.48, 152.38, 147.32, 143.05, 142.67,139.77, 139.59, 130.59, 128.47, 128.34, 127.30, 126.40, 125.33, 125.15,124.70, 122.84, 122.44, 120.90, 120.71, 118.22, 117.69, 116.25, 115.64,112.46, 109.16, 75.85, 71.81, 56.72, 38.08, 34.69, 34.40, 32.45, 32.16, 32.07, 31.71, 30.15, 19.34, 19.29, 13.65.

[0268]

[0269] Prior to use, the thiophene ligand was azeotropically dried using PhMe (4 × 10 mL). A solution of HfBn4 (15.8 mg, 0.02899 mmol, 1.15 equivalent) in PhMe (1.27 mL) was added dropwise to a clear, pale golden-yellow solution of thiophene (34.0 mg, 0.02521 mmol, 1.00 equivalent) in PhMe (16.0 mL) at 23 °C. After stirring (500 rpm) for 20 min, the pale golden-yellow solution was filtered through a 0.45 µm PTFE submicron filter connected to a 0.20 µm PTFE submicron filter, washed with PhMe (3 × 3 mL), and concentrated to give a pale golden-yellow foamy hafnium complex (pre-catalyst 2) (42.5 mg, 0.02493 mmol, 99%). NMR indicated the product. 11H NMR (400MHz, c6d6) δ 8.57(d, J = 1.9Hz, 2H), 8.19 (d, J = 1.8Hz, 2H), 7.55 - 7.45 (m, 6H), 7.40 (d, J = 8.5Hz, 2H), 7.13 - 7.06 (m, 6H), 7.06 - 7.00 (m, 2H), 6.83 (s, 2H), 6.77(t, J = 7.3Hz, 2H), 6.29 - 6.23 (m, 4H), 5.49 (d, J = 8.6Hz, 2H), 4.53 (d, J = 13.1Hz, 2H), 3.54 (d, J = 13.2Hz, 2H); 1.75 (d, J = 14.7Hz, 2H), 1.53 (s, 18H), 1.23 (s, 18H), 1.23 (s, 6H), 1.18 (s, 6H), 0.96 (d, J = 13.3Hz, 2H), 0.87 (p, J = 7.5Hz, 2H), 0.71 (s, 18H), 0.67 (d, J = 7.4Hz, 6H), 0.58 (d, J = 7.4Hz, 6H), 0.23 (d, J = 12.9Hz, 2H). 13 C NMR (101MHz, c6d6) δ 156.17, 152.42,147.79, 147.52, 143.04, 142.61, 139.71, 139.50, 128.79, 128.27, 126.99,125.26, 124.65, 122.79, 122.32, 121.19, 120.75, 117.80, 117.46, 116.22,115.58, 112.48, 109.10, 78.51, 72.32, 56.67, 38.04, 34.66, 34.37, 32.14, 32.06, 31.68, 30.09, 19.29, 19.20, 13.67.

[0270] Examples 23 and 24: Synthesis of precatalyst 3: precatalyst of formula (II), wherein R 1 R 2 and R 5 To R 9 For H, R 3 and R 4 Each is CH3(CH2)7O- (octyloxy), each R 10 For tert-butyl, R 11 and R 12 Each is isopropyl, M is Zr, and each X is... Benzyl, and the subscript n is 2; and the synthesis of precatalyst 4: the precatalyst of formula (II), wherein R 1 R 2 and R 5 To R 9 For H, R 3 and R 4 Each is CH3(CH2)7O- (octyloxy), each R 10 For tert-butyl, R 11 and R 12 Each is isopropyl, M is Hf, and each X is... Benzyl, and the subscript n is 2. 。

[0271]

[0272] Prior to use, the thiophene ligand was azeotropically dried using PhMe (4 × 10 mL). A solution of ZrBn4 (15.3 mg, 0.03365 mmol, 1.15 equivalent) in PhMe (1.22 mL) was added dropwise to a clear, pale golden-yellow solution of thiophene (40.4 mg, 0.02926 mmol, 1.00 equivalent) in PhMe (16.8 mL) at 23 °C. After stirring (500 rpm) for 20 min, the golden-yellow solution was filtered through a 0.45 µm PTFE submicron filter connected to a 0.20 µm PTFE submicron filter, washed with PhMe (3 × 3 mL), and concentrated to give a zirconium complex (pre-catalyst 3) (48.0 mg, 0.02905 mmol, 99%) exhibiting a pale golden-brown foam. NMR indicated the product. 1 H NMR (400MHz, C6D6) δ 8.58 - 8.54(m, 2H), 8.31 (dd, J = 1.9, 0.6Hz, 2H), 7.60 - 7.56 (m, 4H), 7.47 - 7.39 (m,4H), 7.14 - 7.10 (m, 4H), 7.03 (d, J = 3.0Hz, 2H), 6.91 (s, 2H), 6.83 (tt, J= 7.3, 1.2Hz, 2H), 6.67 (dd, J = 9.0, 3.1Hz, 2H), 6.48 - 6.44 (m, 4H), 5.55(d, J = 9.0Hz, 2H), 4.47 (d, J = 13.0Hz, 2H), 3.67 (dt, J = 8.9, 6.5Hz, 2H), 3.58 (dt, J = 9.0, 6.4Hz, 2H), 3.51 (d, J = 13.0Hz, 2H), 1.63 - 1.53 (m, 4H), 1.51 (s, 18H), 1.30 (s, 18H), 1.36 - 1.14 (m, 20H), 0.93 (t, J = 7.0Hz, 6H), 0.94 - 0.82 (m, 4H), 0.73 (d, J = 7.4Hz, 6H), 0.70 (d, J = 12.5Hz, 2H), 0.63(d, J = 7.4Hz, 6H). 13C NMR (101MHz, C6D6) δ 156.66, 152.62, 152.02, 147.57,143.25, 142.80, 139.89, 139.66, 128.40, 128.36, 128.31, 127.01, 126.59,126.41, 125.27, 124.70, 122.81, 122.53, 122.50, 120.71, 118.02, 117.71,116.35, 116.12, 115.60, 114.81, 112.49, 109.12, 75.91, 71.67, 68.14, 34.62, 34.46, 32.01, 31.85, 31.75, 29.85, 29.34, 29.28, 29.18, 25.97, 22.73, 19.36, 14.02, 13.79.

[0273]

[0274] Prior to use, the thiophene ligand was azeotropically dried using PhMe (4 × 10 mL). A solution of HfBn4 (22.9 mg, 0.04207 mmol, 1.15 equivalent) in PhMe (1.83 mL) was added dropwise to a clear, pale golden-yellow solution of thiophene (50.5 mg, 0.03658 mmol, 1.00 equivalent) in PhMe (18.2 mL) at 23 °C. After stirring (500 rpm) for 20 min, the pale golden-yellow solution was filtered through a 0.45 µm PTFE submicron filter connected to a 0.20 µm PTFE submicron filter, washed with PhMe (3 × 3 mL), and concentrated to give a pale golden-yellow foamy hafnium complex (pre-catalyst 4) (63.2 mg, 0.03631 mmol, 99%). NMR indicated the product. 1H NMR (400MHz, C6D6) δ 8.59 -8.55 (m, 2H), 8.34 - 8.30 (m, 2H), 7.57 (dd, J = 8.6, 1.9Hz, 4H), 7.44 (d, J= 8.5Hz, 2H), 7.37 - 7.32 (m, 2H), 7.18 - 7.12 (m, 4H), 7.02 (d, J = 3.0Hz,2H), 6.91 (s, 2H), 6.81 (dt, J = 7.3, 1.2Hz, 2H), 6.70 (dd, J = 9.0, 3.1Hz,2H), 6.48 - 6.44 (m, 4H), 5.57 (d, J = 9.0Hz, 2H), 4.52 (d, J = 13.1Hz, 2H),3.68 (dt, J = 9.0, 6.5Hz, 2H), 3.58 (dt, J = 8.9, 6.4Hz, 2H), 3.53 (d, J =13.1Hz, 2H), 1.58 (dd, J = 8.3, 6.2Hz, 4H), 1.51 (s, 18H), 1.31 (s, 18H),1.36 - 1.16 (m, 20H), 1.09 (d, J = 13.3Hz, 2H), 0.93 (t, J = 7.0Hz, 6H), 0.94- 0.81 (m, 2H), 0.72 (d, J = 7.4Hz, 6H), 0.62 (d, J = 7.4Hz, 6H), 0.40 (d, J= 13.4Hz, 2H)。 13C NMR (101MHz, C6D6) δ 156.82, 152.74, 151.73, 148.07, 143.31,142.81, 139.91, 139.65, 128.82, 128.31, 127.05, 126.91, 126.76, 125.33,124.73, 122.80, 122.77, 122.48, 120.81, 118.16, 117.01, 116.33, 116.12,115.54, 114.71, 112.51, 109.10, 78.89, 72.10, 68.15, 34.62, 34.46, 32.01, 31.86, 31.76, 29.34, 29.28, 29.18, 25.97, 22.73, 19.32, 14.02, 13.88.

[0275] Examples 25 and 26 (contemplated): Synthesis of precatalyst 5: precatalyst of formula (II), wherein R 1 To R 9 For H, each R 10 For tert-butyl, R 11 and R 12 Each is isopropyl, M is Zr, each X is benzyl, and the subscript n is 2; and precatalyst 6 Synthesis: The precatalyst of formula (II), wherein R 1 To R 9 For H, each R 10 For tert-butyl, R 11 and R 12 Each is isopropyl, and M is Hf. Each X is benzyl, and the subscript n is 2. .

[0276]

[0277] Precatalysts 5 and 6 were prepared in a manner similar to that of precatalysts 3 and 4.

[0278] Example 27: Synthesis of precatalyst 7: precatalyst of formula (II), wherein R 1 R 2 and R 5 To R 9 For H, R 3 and R 4 each Self-consistent with (CH3)3CCH2C(CH3)2- ("tert-synthetyl"), each R 10 For tert-butyl, R 11 and R 12 Each is isopropyl, M is Zr, and each X It is chlorine, and the subscript n is 2. .

[0279]

[0280] Prior to use, the thiophene ligand was azeotropically dried using PhMe (4 × 10 mL). A solution of ZrBn₂Cl₂ (16.7 mg, 0.03618 mmol, 1.00 equivalent) in PhMe (16.8 mL) was added dropwise to a clear, pale golden-yellow solution of thiophene (48.8 mg, 0.03980 mmol, 1.10 equivalent) in PhMe (1.34 mL) at 23 °C. After stirring (500 rpm) for 15 min, the pale golden-yellow solution was filtered through a 0.45 µm PTFE submicron filter connected to a 0.20 µm PTFE submicron filter, washed with PhMe (3 × 3 mL), and concentrated to give a white, foamy zirconium complex (53.9 mg, 0.0357 mmol, 99%). NMR indicated the product. 11H NMR (400MHz, C6D6) δ 8.57 (d, J = 1.9Hz, 2H), 8.37 (t, J = 1.3Hz, 2H), 7.54 (dd, J = 8.6Hz, 1.9Hz, 2H), 7.45 (d, J = 2.1Hz, 4H), 7.41 (d, J = 8.6Hz, 2H), 7.09 (dd, J = 8.8Hz, 2.4Hz, 2H), 6.87 (s, 2H), 5.82 (d, J = 8.7Hz, 2H), 4.65 (d, J = 13.0Hz, 2H), 3.50 (d, J = 13.1Hz, 2H), 1.72 (d, J = 14.6Hz, 2H), 1.59 (d, J = 14.6Hz, 2H), 1.48 (s, 18H), 1.38 (s, 18H), 1.24 (s, 6H), 1.17 (s, 6H), 0.98 - 0.86 (m, 2H), 0.73 (s, 18H), 0.68 (d, J = 5.9Hz, 6H), 0.60 (d, J = 6.5Hz, 6H). 13 C NMR (101MHz,C6D6) δ 157.52, 152.22, 148.12, 143.27, 142.90, 139.90, 139.77, 128.61,125.93, 125.07, 124.16, 122.50, 122.33, 121.32, 119.13, 117.74, 116.28,115.03, 112.60, 109.23, 73.02, 56.78, 38.06, 34.58, 34.45, 32.18, 31.98,31.94, 31.78, 31.74, 30.42, 29.84, 19.31, 18.99, 13.81.

[0281] Examples 28 and 29: Synthesis of precatalyst 8: precatalyst of formula (II), wherein R 1 R 2 and R 5 To R 9 For H, R 3 and R 4 Each is F (fluorine), and each R 10 For tert-butyl, R 11 and R 12 Each is isopropyl, M is Zr, each X is benzyl, and the subscript n Synthesis of 2; and precatalyst 9: precatalyst of formula (II), wherein R 1 R 2 and R 5 To R 9 For H, R 3 and R 4 Each is F (fluorine). Each R 10 For tert-butyl, R 11 and R 12 Each is isopropyl, M is Hf, each X is benzyl, and the subscript n is 2. 。

[0282] Synthesis of pre-catalyst 8 :

[0283]

[0284] Prior to use, the thiophene ligand was azeotropically dried using PhMe (4 × 10 mL). A solution of ZrBn4 (2.2 mg, 4.74 µmol, 1.10 equivalent) in C6D6 (0.18 mL) was added dropwise to a clear, colorless solution of thiophene (5.0 mg, 4.31 µmol, 1.00 equivalent) in anhydrous C6D6 (1.54 mL) at 23 °C in a nitrogen-filled glove box. After stirring (500 rpm) for 30 min, the solution was filtered through a 0.20 µm PTFE submicron filter to obtain a zirconium complex in C6D6 solution. NMR indicated the product. The same procedure can be used with PhMe as a solvent to prepare pre-catalyst solutions (0.0025 M or 0.0042 M) that can be used directly after filtration in slurry polymerization experiments. 1 H NMR (500MHz, benzene-d6) δ 8.45 (dd, J = 1.9, 0.6Hz,2H), 8.30 (dd, J = 2.0, 0.6Hz, 2H), 7.54 (dd, J = 8.7, 1.9Hz, 2H), 7.49 (dd,J = 8.5, 1.9Hz, 2H), 7.38 (dd, J = 8.7, 0.6Hz, 2H), 7.31 (dd, J = 8.5, 0.6Hz, 2H), 7.07 - 7.02 (m, 2H), 6.99 - 6.95 (m, 4H), 6.83 (s, 2H), 6.77 (tt, J =7.3, 1.2Hz, 2H), 6.61 (ddd, 1.40 (s, 18H), 1.28 (s, 18H), 1.17 (d, J = 12.5Hz, 2H), 0.71 (dp, J =14.1, 6.9Hz, 2H), 0.60 (d, J = 7.2Hz, 6H), 0.57 (d, J = 12.5Hz, 2H), 0.51 (d,J = 7.3Hz, 6H). 19 F NMR (470MHz, benzene-d6) δ -115.87 (td, J = 8.0, 4.8Hz). 13C NMR (126MHz, benzene-d6) δ 159.44 (d, J = 245.5Hz), 154.21, 154.19, 152.80, 146.62,143.27 (d, J = 53.0Hz), 139.67 (d, J = 30.0Hz), 130.56, 128.33, 128.16,126.33, 125.24, 124.59, 122.81, 122.51, 121.20, 119.01, 116.58 (m), 116.35,116.19 (d, J = 17.8Hz), 116.01 (d, J = 16.9Hz), 115.62, 112.27, 108.98, 76.05, 71.65, 34.53, 34.45, 31.89, 31.70, 19.18, 19.13, 13.59.

[0285] Synthesis of pre-catalyst 9 :

[0286]

[0287] Prior to use, the thiophene ligand was azeotropically dried using PhMe (4 × 10 mL). HfBn4 (2.7 mg, 4.93 µmol, 1.10 equivalent) in C6D6 (0.22 mL) was added dropwise to a clear, colorless solution of thiophene (5.2 mg, 4.48 µmol, 1.00 equivalent) in anhydrous C6D6 (1.58 mL) at 23 °C in a nitrogen-filled glove box. After stirring (500 rpm) for 30 min, the pale golden solution was filtered through a 0.20 µm PTFE submicron filter to obtain a hafnium complex as a 0.0025 M C6D6 solution. NMR indicated the product. The same procedure can be used with PhMe as a solvent to prepare a pre-catalyst solution (0.0025 M) for direct use in slurry polymerization experiments after filtration. 11H NMR (500 MHz, benzene-d6) δ 8.46 (dd, J = 2.0, 0.6 Hz, 2H), 8.31 (dd, J = 1.9, 0.6 Hz, 2H), 7.53 (dd, J = 8.7, 1.9 Hz, 2H), 7.48 (dd, J = 8.5, 1.9 Hz, 2H), 7.30 (ddd, J = 11.7, 8.6, 0.6 Hz, 4H), 6.99 - 6.94 (m, 4H), 6.82 (s, 2H), 6.78 - 6.73 (m, 2H), 6.65 (ddd, J = 9.0, 7.2, 3.1 Hz, 2H), 6.52 - 6.48 (m, 2H), 6.40 - 6.35 (m, 4H), 5.44 (dd, J = 9.0, 4.8 Hz, 2H), 4.36 (d, J = 13.0 Hz, 2H), 3.33 (d, J = 13.1 Hz, 2H), 1.40 (s, 18H), 1.28 (s, 18H), 1.03 (d, J = 13.5 Hz, 2H), 0.68 (dq, J = 14.1, 7.2 Hz, 2H), 0.58 (d, J = 7.3 Hz, 6H), 0.49 (d, J = 7.3 Hz, 6H), 0.28 (d, J = 13.7 Hz, 2H). 19 19F NMR (470 MHz, benzene-d6) δ -114.35 - -117.32 (m). 13C NMR (126MHz, benzene-d6) δ 159.63 (d, J = 246.1Hz), 153.86 (d, J = 2.5Hz), 152.93, 147.26, 143.32 (d, J = 61.1Hz), 139.67 (d, J =33.6Hz), 129.89, 128.58, 128.18, 127.17, 126.70, 125.31, 124.49 (d, J =34.8Hz), 123.03 (d, J = 9.2Hz), 122.78, 122.45, 121.24, 119.15, 116.32,116.16 (d, J = 13.5Hz), 115.98 (d, J = 13.4Hz), 115.90, 115.88, 115.53,112.32, 108.97, 83.00, 72.10, 34.53, 34.45, 31.88, 31.70, 19.13, 19.07,13.67.

[0288] Examples 30 to 36: Spray drying of pre-catalyst to prepare spray-dried supported catalyst systems .

[0289] The supported catalyst system described in Table 3 above was prepared and spray-dried in a nitrogen-purged glove box. Cabosil was then placed in a wide-mouth flask dried in an oven. ™ TS-610 pyrolytic silica was slurried in toluene until fully dispersed, and then a 10% by weight solution of MAO in toluene was added. The mixture was magnetically stirred at ambient temperature for about 15 minutes, and then the metal-ligand complex was added to the resulting slurry, and the mixture was stirred at ambient temperature for 30 to 60 minutes. The mixture was spray-dried using a Büchi miniature spray dryer B-290 with the following parameters to produce a dried sample: set temperature: 140°C, outlet temperature: 75°C (min), vacuum pump set to 95 rpm, and pump speed at 150 rpm. Table 4 contains the amounts of metal-ligand complex, pyrolytic silica, 10% MAO solution, and toluene for each of the supported catalyst systems 1 to 7 used to prepare the spray-dried sample. The amounts of reagents used are listed in Table 4 below.

[0290]

[0291] Gas-phase polymerization for preparing ethylene / 1-hexene copolymers .

[0292] The spray-dried catalyst described in Table 4 was used to catalyze the gas-phase polymerization of ethylene monomer and 1-hexene comonomer to obtain an ethylene / 1-hexene copolymer (also known as a poly(ethylene-copoly-1-hexene) copolymer). Gas-phase polymerization was carried out in a 2-liter (L) semi-batch stainless steel autoclave gas-phase polymerization reactor equipped with a mechanical stirrer. For each polymerization run, the reactor was first dried (“baked”) for 1 hour by charging it with 200 g of NaCl and heating the reactor contents at 100°C for 30 minutes under dry nitrogen. Then, 5 g of spray-dried methylaluminoxane / pyrolytic silica (“SDMAO”) was added to the reactor under nitrogen pressure to remove any residual water. The reactor was sealed and the contents were stirred. Polymerization was initiated by charging the reactor with hydrogen (H2) and 1-hexene (C6), followed by pressurizing the reactor with ethylene (C2). The feed ratios of hydrogen, 1-hexene, and ethylene are set to achieve predetermined H2 / C2 and C6 / C2 molar ratios in the reactor. Once the reactor reaches steady state, the supported catalyst system is loaded into the reactor at 80°C to initiate polymerization. The reactor temperature is brought to a predetermined polymerization temperature, typically 90°C or 100°C for these experiments, but any temperature from 75°C to 115°C can be used and maintained at this polymerization temperature while keeping the ethylene, 1-hexene, and hydrogen feed ratio consistent for 1 hour. At the end of the 1-hour run, the feed of hydrogen, 1-hexene, and ethylene is stopped, the reactor is cooled, vented, and opened. The resulting product mixture is washed with water and methanol and then dried to obtain the ethylene / 1-hexene copolymer. The weight of the copolymer is recorded. Catalyst productivity (g copolymer / g catalyst-hour) and catalyst efficiency (g copolymer / g catalyst metal (Zr or Hf)) are determined to compare the amount of copolymer produced based on the amount of ethylene and hexene absorbed / consumed relative to the amount of supported catalyst system added to the reactor. The copolymer samples were characterized by DSC, GPC, and melt flow. The polymerization running conditions and results are listed in the table below.

[0293]

[0294]

[0295]

[0296]

[0297] Tables 5 to 8 show that the spray-dried supported catalyst system (“sd-SCS”) of the present invention, comprising a substituted 2-hydroxythiophene compound, successfully prepared ethylene / 1-hexene copolymers under commercially relevant gas-phase polymerization process conditions. This compound contains -CH2Ge(i-Pr2)CH2- bridges between phenolic rings and various substituents on the catalyst backbone. Unexpectedly, the sd-SCS of the present invention exhibits a high catalyst productivity of up to 32,000 gPE / gCat / hr and a high catalyst efficiency of up to 30.3 mm gPE / gM. Based on melt flow data (I2, I5, I... 21 Based on the data and GPC analysis, the sd-SCS of the present invention can produce polyethylene copolymers with high Mw (up to 2,729,300 g / mol in these examples) and / or high Mz (up to 5,286,700 g / mol in these examples) and wide molecular weight distribution (MWD) or polydispersity index (PDI) (up to 8.9 Mw / Mn in these examples); and wide Mz / Mw (up to 5.3 Mz / Mw in these examples). These Mw and Mz can be reduced by increasing the temperature and the H2 / C2 or C6 / C2 ratio used in the reactor. Finally, based on the comonomer consumption in the reactor, GPC analysis and / or T M Several of these sd-SCS of the present invention are advantageously incorporated with high levels of 1-hexene comonomers under industrially relevant high-density process conditions. This combination of high Mw and / or high Mz, a wider Mw / Mn ratio, and a wide Mz / Mw ratio with higher α-olefin comonomer incorporation provides ethylene / α-olefin copolymer resins with advantageous properties.

[0298] Slurry phase polymerization experiment

[0299] Synthesis of an undried supported catalyst system for slurry-phase polymerization. The precatalyst of formula (II) was provided in pure form, either as a solution dissolved in toluene or as a solid, in a nitrogen-purged continuous glove box, wherein the precatalyst was supported on a spray-dried activator / hydrophobic pyrolytic silica solid, wherein the activator was methylaluminoxane. This supported activator is referred to herein as “SMAO” and is white in color. Unless otherwise specified, the unsupported precatalyst was diluted to a concentration of 4.21 mM in anhydrous deoxytoluene and pipetted into oven-dried 4 mL or 8 mL scintillation vials containing a pre-weighed amount of SMAO, such that the resulting slurry contained 45 μmol Zr or Hf atoms per 1.0 g SMAO (as applicable). The slurry was stirred at 300 rpm and heated to 50°C for 30 minutes, then returned to room temperature to obtain a slurry of the undried supported catalyst system (“ud-SCS”) in toluene. The previous white SMAO staining indicated that the pre-catalyst had been loaded and activated. The liquid phase of the slurry... 1 ¹H-NMR experiments showed no residual precatalyst or unsupported active catalyst in the liquid phase, indicating that the precatalyst had been completely converted into an active catalyst in ud-SCS. The ud-SCS slurry at room temperature was vortexed and stirred at 700 rpm to produce a homogeneous dispersion. The ud-SCS slurry was stirred for at least one minute, and while continuing vortexing, aliquots were dispensed into 8 mL vials using a positive displacement pipette tip (PDT). Based on the expected catalytic activity, the aliquots of ud-SCS were diluted with isoparaffin solvent (Isopar E) to a concentration of 50 mmol to 500 nmol per mL. All catalyst materials and aliquots of ud-SCS were stored in a glove box freezer at -30°C until use for slurry-phase polymerization.

[0300] Slurry-phase polymerization reactor units were prepared in a drying oven. One day prior to polymerization, 48 parallel pressure reactor units, each with a modular head and body, were prepared as follows: Oven-dried, pre-weighed glass tubes were manually inserted into the reactor orifices. A polyetheretherketone (“PEEK”) agitator was attached to the modular head, and the modular head to the modular body. The reactor units were heated to 190°C, purged with nitrogen for 10 hours, and cooled to 50°C. On the second day (the day of the experiment), the reactors were purged twice with ethylene and completely vented to purge the feed line. The reactor units were then preheated to 50°C, and the agitator was turned on at a stirring rate of 800 rpm to obtain the prepared reactor units.

[0301] Slurry-phase polymerization was run in the prepared reactor units in a drying oven. The prepared reactor units were partially filled (to the appropriate solvent level) using a machine needle with isoparaffin (“solvent”, Isopar-E from ExxonMobil) and an olefin comonomer (1-hexene for these experiments) to obtain a final total volume of 5 mL in each reactor unit later (once all reagent solutions were added later). After solvent injection, the reactor units were heated to the target initiation polymerization temperature (100 °C in these experiments) and the stirring rate was increased. When the reactor unit reached the initiation polymerization temperature, which required approximately 10–30 minutes of heating, the reactor units were pressurized to the target initiation polymerization pressure with pure ethylene or a gas mixture of ethylene and hydrogen from a gas accumulator, and until the solvent was saturated with either pure ethylene or the gas mixture (as observed by gas absorption). If a gas mixture of ethylene and hydrogen was used, once the solvent was saturated in all units, the gas feed line was switched from the accumulator to pure ethylene for the remaining polymerization run.

[0302] The machine synthesis protocol is then initiated, first by injecting the activator (a slurry of SMAO in solvent), followed by an injection of a slurry of a conventionally dried supported catalyst system. Two injections are completed for a given reactor unit before the robot begins the injection sequence for the next unit. An additional 500 μL of solvent is added for each reagent addition to ensure all reagents have been injected. After each reagent injection, the needle is washed with solvent both inside and outside.

[0303] While injecting the catalyst into each individual unit, a reaction timer was started and the pressure in each unit was monitored. The required pressure (approximately 2-6 psig) was maintained by adding a supplemental amount of ethylene gas, by opening a valve when the target pressure was 2 psi minus the target pressure and closing the valve when the pressure reached 2 psi above the target pressure. All pressure drops in the reactor unit were cumulatively recorded as ethylene absorption over the duration of operation. The slurry-phase polymerization reaction proceeded for 90 minutes or until ethylene absorption reached 90 psi, whichever occurred first, followed by quenching with argon gas containing 10% (v / v) CO2 at a 60 psi overpressure. Data collection for each unit continued for 5 minutes after quenching. After the last unit had completed quenching, any potential gas leaks were identified based on the unit pressure, and the ethylene absorption profile was recorded. The reactor was cooled to 50°C, vented, and the glass tubes were removed from the module. The glass tubes were removed from the drying oven, and volatiles were removed using a rotary evaporator. The glass tubes were re-weighed to obtain the reaction yield, and the obtained polyethylene homopolymer or ethylene / 1-hexene copolymer product was analyzed by high-throughput high-temperature gel permeation chromatography (HT-HT-GPC).

[0304] High-throughput high-temperature gel permeation chromatography (HT-HT-GPC) was performed using a Robot-Assisted Delivery (RAD) system equipped with a PolymerChar infrared detector (IR5) and an Agilent PLgel Mixed A column. Decane (10 µL) was added to each sample as an internal flow marker. Samples were first diluted in 300 ppm butylated hydroxytoluene (BHT)-stabilized 1,2,4-trichlorobenzene (TCB) at a concentration of 10 mg / mL and dissolved by stirring at 160 °C for 120 min. Prior to injection, the samples were further diluted to a concentration of 2 mg / mL using BHT-stabilized TCB. The sample (250 µL) was eluted through a PL-gel 20 µm (50 mm × 7.5 mm) guard column, followed by elution through two PL-gel 20 µm (300 mm × 7.5 mm) Mixed-A columns maintained at 160 °C. TCB was stabilized with BHT at a flow rate of 1.0 mL / min. The total run time was 24 min. To calibrate the molecular weight (MW), Agilent EasiCal polystyrene standards (PS-1 and PS-2) were analyzed to create a third-order MW calibration curve. The molecular weight units were converted from polystyrene (PS) to polyethylene (PE) using a daily Q factor (approximately 0.4, calculated using the average of five reference samples with known MW).

[0305] The table below lists the slurry-phase polymerization conditions: temperature = 100℃, Isopar E = 5 mL, C6 / C2 (molar ratio) in liquid = 0.6 / 1 or 0.4 / 1 in liquid, H2 / C2 (molar ratio) in liquid = 0.0016 / 1.0, run time = maximum 90 minutes (5400 seconds), quench time = time required to absorb 90 psi ethylene; the faster the quench time, the higher the catalyst activity. SCS 8 was prepared as 20 µmol Zr / 1 g SMAO, and SCS 9 and 10 were prepared as 45 µmol Zr or Hf / 1 g SMAO. ND = not determined. The loading of SCS 8 in the slurry-phase reactor was 5 nanomoles (nmol), and the loading of SCS 9 and 10 was 20 nmol. "ud-SCS" refers to an undried supported catalyst system prepared according to the procedure for the synthesis of undried supported catalyst systems for slurry-phase polymerization.

[0306]

[0307] The slurry polymerization results for the undried supported catalyst system (ud-SCS) are shown in Table 17. High activity was defined as a quenching time of 1,000 seconds or less at a catalyst charge of 25 nanomoles (nmol) or less at a loading of 45 µmol Zr or Hf per 1.0 g SMAO. "Quenching time" is the time taken for the polymerization reaction to consume 90 psi of ethylene; the shorter the time, the higher the activity of the ud-SCS. Under process-dependent high-density conditions, the quenching times for ud-SCS8 and ud-SCS9 were 494 seconds and 195 seconds, respectively, indicating high activity for both catalysts. Based on GPC analysis of the resulting polyethylene-hexene copolymers, under these slurry polymerization process conditions, the ud-SCS of the present invention produces polyethylene with a certain range of Mw and Mz. Several ud-SCSs produce ethylene / hexene copolymers with above-average (>100,000 g / mol) to high Mw, average to a wide polydispersity index (PDI, Mw / Mn), and higher 1-hexene incorporation. ud-SCS can prepare polyethylene polymers with a wide range of Mw and / or a wide range of PDI and / or high 1-hexene incorporation. Therefore, these polyethylene polymers have advantageous properties for industrial applications.

[0308] The proposed implementation plan for protection is as follows.

Claims

1. A substituted 2-hydroxythiophene compound of formula (I): , or its Group 1 or Group 2 metal salt, wherein: R 1 and R 2 Independently H or halogen; R 3 and R 4 Independently H, halogen, (C1-C) 20 ) hydrocarbon group, (C1-C 10 )alkoxy or Si((C1-C 10 )alkyl)3; R 5 and R 6 Independently H or halogen; R 7 and R 8 Independently H or halogen; Each R 9 For H, and for each R 10 For (C1-C 20 ) hydrocarbon group; or each R 10 For H, and for each R 9 For (C1-C 20 ) hydrocarbon group; and R 11 and R 12 Independently for (C1-C 10 )alkyl.

2. A precatalyst of formula (II): ； in: M is Ti, Hf, or Zr; The subscript n is 1 or 2; and Each X is independently selected from monodentate ligands, which are independently selected from hydrogen atoms, (C1-C2) and (C2-C3) ligands. 50 ) hydrocarbon group, (C1-C 50 ) heterohydrocarbon group, (C1-C 50 Organic heterogroups, halogen atoms, dialkylamino groups, or dialkyl carbamates; R 1 and R 2 Independently H or halogen; R 3 and R 4 Independently H, halogen, (C1-C) 20 ) hydrocarbon group, (C1-C 10 )alkoxy or Si((C1-C 10 )alkyl)3; R 5 and R 6 Independently H or halogen; R 7 and R 8 Independently H or halogen; Each R 9 For H, and for each R 10 For (C1-C 20 ) hydrocarbon group; or each R 10 For H, and for each R 9 For (C1-C 20 ) hydrocarbon group; and R 11 and R 12 Independently for (C1-C 10 )alkyl.

3. A supported catalyst system comprising a precatalyst of formula (II) according to claim 2, a support material, and an activator.

4. A method for preparing the supported catalyst system according to claim 3, the method comprising step (a) or comprising steps (b) and (c): (a) The supported catalyst system is prepared by spray drying a mixture of an inert hydrocarbon solvent, a precatalyst of formula (II), a support material, and an activator; or (b) Spray drying a mixture of an inert hydrocarbon solvent, the carrier material, and the activator to prepare a spray-dried supported activator, and (c) The precatalyst of formula (II) is mixed with the spray-dried supported activator and inert hydrocarbon solvent to prepare the supported catalyst system.

5. The invention according to any one of claims 1 to 4, wherein: R 1 and R 2 For different, or R 1 and R 2 For the same; or R 1 and R 2 For H; or R 1 and R 2 For F; or R 3 and R 4 For different, or R 3 and R 4 For the same, or R 3 and R 4 Halogen, (C1-C) 20 ) hydrocarbon group, (C1-C 10 )alkoxy or Si((C1-C 10 )alkyl)3, or R 3 and R 4 For (C1-C 20 )alkyl, (C1-C 10 )alkoxy or fluorine; or R 5 and R 6 For different, or R 5 and R 6 For the same, or R 5 and R 6 For H, or R 5 and R 6 For F; or R 7 and R 8 For different, or R 7 and R 8 For the same, or R 7 and R 8 For H, or R 7 and R 8 For F; or Each R 9 For H, and for each R 10 It is tert-butyl, 4-tert-butylphenyl, 4-triethylmethylphenyl, 3,5-dimethylphenyl or 3,5-di-tert-butylphenyl; or each R 10 For H, and for each R 9 It is 3,5-di-tert-butylphenyl; or Each R 11 and R 12 For the same; or for each R 11 and R 12 For (C1-C 10 )alkyl or (C1-C5)alkyl; or each R 11 and R 12 It is isopropyl; or R 1 To R 12 A combination of the aforementioned definitions.

6. The invention according to any one of claims 2 to 5, wherein: M is either Hf or Zr; or The subscript n is 2; or Each X is benzyl, or each X is Cl; or M is Hf or Zr, the subscript n is 2, and each X is benzyl; or M is Hf or Zr, the subscript n is 2, and X is chlorine.

7. The substituted 2-hydroxythiophene compound of formula (I) according to claim 1, wherein the compound is selected from the group consisting of compounds 1 to 3 in Table 1: Where "Cmpd No." is the compound number, t-Bu is tert-butyl; tert-octyl is (CH3)3CCH2C(CH3)2-; octylO is CH3(CH2)7O-; F is fluorine; 3,5-dtBP is 3,5-di-tert-butylphenyl; and i-Pr is isopropyl.

8. The precatalyst of formula (II) according to claim 2, wherein the precatalyst is selected from the group consisting of precatalyst numbers 1 to 9 in Table 2:

9. The supported catalyst system according to claim 3, wherein the supported catalyst system is selected from the group consisting of spray-dried supported catalyst systems numbered SCS 1 to 7 and undried supported catalyst systems numbered SCS 8 to 10 in Table 3: "HPFS1" refers to hydrophobic pyrolytic silica prepared from untreated pyrolytic silica and hydrophobic agent dichlorodimethylsilane; "MAO" refers to methylaluminoxane; and "SMAO" refers to spray-dried methylaluminoxane / HPFS1, wherein HPFS1 is prepared from untreated pyrolytic silica and hydrophobic agent dichlorodimethylsilane.

10. The supported catalyst system according to claim 3, 4 or 9, wherein the supported catalyst system is a supported catalyst system that has been shown to prepare ethylene / 1-hexene copolymers with a weight-average molecular weight greater than 500,000 g / mol and / or a z-average molecular weight greater than 2,000,000 g / mol by gas-phase polymerization.

11. A method for preparing polyolefins in a gas-phase polymerization process, the method comprising contacting one or more olefin monomers with the above-described supported catalyst system in a gas-phase polymerization reactor under gas-phase polymerization conditions to prepare a polyolefin polymer.

12. The method according to claim 11, wherein the method has any of the limitations (i) to (v): (i) The one or more olefin monomers mentioned herein include ethylene or a combination of ethylene and propylene, or ethylene and (C4-C5) propylene. 20 The combination of α-olefins, wherein the polyolefin polymer is an ethylene homopolymer or an ethylene / propylene copolymer or an ethylene / (C4-C) copolymer. 20 α-olefin copolymers; (ii) wherein the one or more olefin monomers comprise ethylene or ethylene and (C4-C) 20 The combination of α-olefins, and the polyolefin polymer is an ethylene homopolymer or ethylene / (C4-C) 20 α-olefin copolymer; wherein the ethylene homopolymer or ethylene / (C4-C) 20 α-olefin copolymers having a weight-average molecular weight of 500,000 g / mol or greater, or a z-average molecular weight of 2,000,000 g / mol or greater, or both; or (iii) The one or more olefin monomers mentioned above include ethylene and (C4-C5) 20 The combination of α-olefins, wherein the polyolefin polymer is a broad molecular weight distribution having a weight-average molecular weight to number-average molecular weight ratio (Mw / Mn) greater than or equal to 4.0 or a z-average molecular weight to weight-average molecular weight ratio (Mz / Mw) greater than or equal to 3.5 or both of ethylene / (C4-C) 20 α-olefin copolymers; (iv) limiting any one of (i) to (iii), wherein the (C4-C 20 The α-olefin is 1-hexene; (v) Restricting the combination of (ii) and (iii) or the combination of (ii), (iii) and (iv).

13. A method for preparing polyolefins in a slurry-phase polymerization process, the method comprising contacting one or more olefin monomers with the above-described supported catalyst system in a slurry-phase polymerization reactor under slurry-phase polymerization conditions to prepare a polyolefin polymer.

14. The method of claim 13, wherein the one or more olefin monomers comprise ethylene or a combination of ethylene and propylene, or ethylene and (C4-C5) propylene. 20 The combination of α-olefins, and the polyolefin polymer includes ethylene homopolymers or ethylene / propylene copolymers or ethylene / (C4-C) olefins. 20 α-olefin copolymer.

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