Catalyst system for forming multi-block copolymers

Abstract

The present disclosure relates to a catalyst system for forming a multi-block copolymer containing two or more segments or blocks that differ in chemical or physical properties; a polymerization process using the catalyst system; and the resulting polymer, wherein the composition comprises a mixture or reaction product produced by combining: (A) a first olefin polymerization procatalyst; (B) a second olefin polymerization procatalyst that is capable of producing a polymer that differs in chemical or physical properties from a polymer produced by procatalyst (A) under equivalent polymerization conditions; (C) an activator; and (D) a chain shuttling agent.

Description

[0001] This application is a divisional application of the Chinese invention patent application with application number 201880027869.1 (application date: March 14, 2018, invention name: catalyst system for forming multi-block copolymers). Technical Field

[0002] Embodiments relate to olefin polymerization catalysts, their preparation, and the use of specific catalyst compositions to produce polyolefins, including the use of chain shuttling agents in olefin polymerization processes. Background Art

[0003] The properties and applications of polyolefins depend to varying degrees on the specific characteristics of the catalysts used in their preparation. The specific catalyst composition, activation conditions, steric and electronic characteristics, etc. can all be factored into the characteristics of the resulting polymer products. Indeed, many polymer characteristics, such as comonomer incorporation, molecular weight, polydispersity and long-chain branching, as well as related physical properties (e.g., density, modulus, melt properties, tensile characteristics and optical properties), can be influenced by catalyst design.

[0004] In recent years, the use of well-defined molecular procatalysts has generally led to increased control over polymer properties, including branching architecture, stereochemistry, and block copolymer construction. This latter aspect of polymer design, in which "hard" (semi-crystalline or high glass transition temperature) blocks and "soft" (low crystallinity or amorphous, low glass transition temperature) blocks are assembled into polymer chains, is particularly challenging. Progress in block copolymer formation has been seen through the use of chain shuttling agents (CSAs), which enable growing polymer chains to exchange between different catalytic sites so that parts of a single polymer molecule can be synthesized by at least two different catalysts. In this way, block copolymers can be prepared from a common monomer environment by using a mixture of catalysts with different selectivities (such as different stereoselectivities or monomer selectivities). Efficient chain shuttling can, under the right conditions, produce multi-block copolymers characterized by a random distribution of hard blocks with random lengths and soft blocks.

[0005] Even if CSA and dual catalyst combinations are present in a multi-block copolymer production process, the process can be further improved. One improvement to the process is to increase the reactor temperature, which will increase the production rate and reduce energy consumption while still producing the desired olefin block copolymer architecture with commercially acceptable catalyst efficiency and process control. Such improvements have not yet been demonstrated in the prior art. Summary of the invention

[0006] In certain embodiments, the present disclosure relates to compositions comprising a mixture or reaction product resulting from combining:

[0007] (A) a first olefin polymerization procatalyst,

[0008] (B) a second olefin polymerization procatalyst, and

[0009] (C) chain shuttling agents,

[0010] Wherein the second olefin polymerization procatalyst comprises a metal-ligand complex of formula (I):

[0011]

[0012] wherein M is titanium, zirconium or hafnium;

[0013] wherein each Z1 is independently a neutral, monoanionic or dianionic monodentate or polydentate ligand, wherein nn is an integer, and wherein Z1 and nn are selected so that the metal-ligand complex of formula (I) is overall neutral;

[0014] Each Q 1 and Q 10 Independently selected from the group consisting of: (C6-C 40 ) aryl, substituted (C6-C 40 ) aryl, (C3-C 40 )heteroaryl, and substituted (C3-C 40 ) heteroaryl;

[0015] Each Q 2 , Q 3 , Q 4 , Q 7 , Q 8 and Q 9 are independently selected from the group consisting of: hydrogen, (C1-C 40 ) alkyl, substituted (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, substituted (C1-C 40 ) heteroalkyl, halogen and nitro (NO2);

[0016] Each Q 5 and Q 6 Independently selected from the group consisting of: (C1-C 40 ) alkyl, substituted (C1-C 40 )alkyl, and [(Si) 1- (C+Si) 40 ] substituted organosilyl;

[0017] wherein each N is independently nitrogen;

[0018] Optionally, Q 1-5Two or more of the groups are combined together to form a ring structure having from 5 to 16 atoms in the ring, excluding any hydrogen atoms; and

[0019] Optionally, Q 6-10 Two or more of the groups can be combined together to form a ring structure having from 5 to 16 atoms in the ring, excluding any hydrogen atoms.

[0020] In certain embodiments, the present disclosure relates to a composition for the polymerization of at least one addition polymerizable monomer to form a multi-block (segmented) copolymer containing two or more blocks or segments that differ in one or more chemical or physical properties, the composition comprising a mixture or reaction product produced by combining:

[0021] (A) a first olefin polymerization procatalyst,

[0022] (B) a second olefin polymerization procatalyst, and

[0023] (C) chain shuttling agents,

[0024] The second olefin polymerization procatalyst comprises a metal-ligand complex of formula (I).

[0025] In certain embodiments, the present disclosure relates to a composition for the polymerization of ethylene and at least one copolymerizable comonomer other than ethylene to form a multi-block (segmented) copolymer containing two or more blocks or segments differing in one or more chemical or physical properties, the composition comprising a mixture or reaction product produced by combining:

[0026] (A) a first olefin polymerization procatalyst,

[0027] (B) a second olefin polymerization procatalyst, and

[0028] (C) chain shuttling agents,

[0029] The second olefin polymerization procatalyst comprises a metal-ligand complex of formula (I).

[0030] In certain embodiments, the present disclosure is directed to an olefin polymerization catalyst system comprising:

[0031] (A) a first olefin polymerization procatalyst,

[0032] (B) a second olefin polymerization procatalyst, and

[0033] (C) chain shuttling agents,

[0034] The second olefin polymerization procatalyst comprises a metal-ligand complex of formula (I).

[0035] In other embodiments, the present disclosure is directed to a method of preparing a multi-block (segmented) copolymer, the method comprising contacting one or more addition polymerizable monomers with a composition under addition polymerizable conditions, the composition comprising a mixture or reaction product resulting from combining:

[0036] (A) a first olefin polymerization procatalyst,

[0037] (B) a second olefin polymerization procatalyst, and

[0038] (C) chain shuttling agents,

[0039] The second olefin polymerization procatalyst comprises a metal-ligand complex of formula (I).

[0040] In other embodiments, the present disclosure is directed to a method of preparing a multi-block (segmented) copolymer comprising ethylene and at least one copolymerizable comonomer other than ethylene, the method comprising contacting ethylene and one or more addition polymerizable monomers other than ethylene with a composition under addition polymerizable conditions, the composition comprising a mixture or reaction product produced by combining:

[0041] (A) a first olefin polymerization procatalyst,

[0042] (B) a second olefin polymerization procatalyst, and

[0043] (C) chain shuttling agents,

[0044] The second olefin polymerization procatalyst comprises a metal-ligand complex of formula (I).

[0045] In other embodiments, the present disclosure is directed to a method for preparing a multi-block (segmented) copolymer, the method comprising contacting one or more addition polymerizable monomers with an olefin polymerization catalyst system under addition polymerizable conditions, the olefin polymerization catalyst system comprising:

[0046] (A) a first olefin polymerization procatalyst,

[0047] (B) a second olefin polymerization procatalyst, and

[0048] (C) chain shuttling agents,

[0049] The second olefin polymerization procatalyst comprises a metal-ligand complex of formula (I).

[0050] In other embodiments, the present disclosure is directed to a method for preparing a multi-block (segmented) copolymer comprising ethylene and at least one copolymerizable comonomer other than ethylene, the method comprising contacting ethylene and one or more addition polymerizable monomers other than ethylene with an olefin polymerization catalyst system under addition polymerizable conditions, the olefin polymerization catalyst system comprising:

[0051] (A) a first olefin polymerization procatalyst,

[0052] (B) a second olefin polymerization procatalyst, and

[0053] (C) chain shuttling agents,

[0054] The second olefin polymerization procatalyst comprises a metal-ligand complex of formula (I).

[0055] In certain embodiments, the above method takes the form of a continuous solution process, using multiple catalysts that cannot be converted into each other to form block copolymers, such as multi-block copolymers (preferably, two or more monomers (especially ethylene and C 3-20 Olefins or cycloolefins, and most especially ethylene and C 3-20 The method is ideally suited for polymerizing a monomer mixture at high monomer conversion under continuous solution polymerization conditions. Under these polymerization conditions, shuttling from the chain shuttling agent to the catalyst becomes favorable compared to chain growth, and multi-block copolymers, especially linear multi-block copolymers according to the present disclosure, are formed efficiently.

[0056] In another embodiment of the present invention, segmented copolymers (multi-block copolymers) are provided, especially copolymers comprising ethylene in polymerized form, wherein the copolymer contains two or more (preferably three or more) segments that differ in comonomer content or density or other chemical or physical properties. The copolymer preferably has a molecular weight distribution Mw / Mn of equal to or less than 10.0 (e.g., equal to or less than 9.0, equal to or less than 8.0, equal to or less than 7.0, equal to or less than 6.0, equal to or less than 5.0, equal to or less than 4.0, equal to or less than 3.0, equal to or less than 2.8, etc.). Most preferably, the polymer of the present disclosure is an ethylene multi-block copolymer.

[0057] In yet another embodiment of the present disclosure, a functionalized derivative of the aforementioned segmented or multi-block copolymer is provided.

[0058] The present invention also relates to the following embodiments:

[0059] 1. An olefin polymerization catalyst system, comprising:

[0060] (A) a first olefin polymerization procatalyst,

[0061] (B) a second olefin polymerization procatalyst, and

[0062] (C) chain shuttling agents,

[0063] Wherein the second olefin polymerization procatalyst comprises a metal-ligand complex of formula (I):

[0064]

[0065] wherein M is titanium, zirconium or hafnium;

[0066] wherein each Z1 is independently a neutral, monoanionic or dianionic monodentate or polydentate ligand, wherein nn is an integer, and wherein Z1 and nn are selected in such a way that the metal-ligand complex of formula (I) is neutral overall;

[0067] Each Q 1 and Q 10 Independently selected from the group consisting of: (C6-C 40 ) aryl, substituted (C6-C 40 ) aryl, (C3-C 40 )heteroaryl, and substituted (C3-C 40 ) heteroaryl;

[0068] Each Q 2 , Q 3 , Q 4 , Q 7 , Q 8 and Q 9 are independently selected from the group consisting of: hydrogen, (C1-C 40 ) alkyl, substituted (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, substituted (C1-C 40 ) heteroalkyl, halogen and nitro (NO2);

[0069] Each Q 5 and Q 6 Independently selected from the group consisting of: (C1-C 40 ) alkyl, substituted (C1-C 40 )alkyl, and [(Si) 1- (C+Si) 40 ] substituted organosilyl;

[0070] wherein each N is independently nitrogen;

[0071] Optionally, Q 1-5Two or more of the groups are combined together to form a ring structure having from 5 to 16 atoms in the ring, excluding any hydrogen atoms; and

[0072] Optionally, Q 6-10 Two or more of the groups can be combined together to form a ring structure having from 5 to 16 atoms in the ring, excluding any hydrogen atoms.

[0073] 2. The catalyst system according to item 1, further comprising (D) an activator.

[0074] 3. The catalyst system according to item 1 or 2, wherein each Z1 is independently Me, Bn or Cl.

[0075] 4. A catalyst system according to any one of the preceding items, wherein Q 1 and Q 10 is a substituted phenyl group, as shown in formula (II):

[0076]

[0077] Among them J 1 -J 10 Each independently selected from R s A substituent and hydrogen; and each R S are independently halogen atoms, polyfluorinated, perfluorinated, unsubstituted (C1-C 18 ) alkyl, (C6-C 18 )aryl, F3C, FCH2O, F2HCO, F3CO, (R C1 )3Si、(R C1 )3Ge、(R C1 )O、(R C1 )S、(R C1 )S(O),(R C1 )S(O)2、(R C1 )2P、(R C1 )2N、(R C1 )2C=N、NC、NO2、(R C1 )C(O)O、(R C1 )OC(O),(R C1 )C(O)N(R C1 ) or (R C1 )2NC(O), or two of the R S together to form an unsubstituted (C1-C 18 ) alkylene, wherein each R S are independently unsubstituted (C1-C 18 )alkyl, and

[0078] Each R C1 are independently hydrogen, unsubstituted (C1-C 18 ) alkyl or unsubstituted (C1-C 18 ) is a heteroalkyl group, or is absent (eg, absent when N comprises -N=).

[0079] 5. The catalyst system according to claim 4, wherein J 1 , J 5 , J 6 and J 10 Each is independently selected from the group consisting of a halogen atom, a (C1-C8) alkyl group, and a (C1-C8) alkoxy group.

[0080] 6. A catalyst system according to any one of the preceding items, wherein Q 5 and Q 6 Each independently is (C1-C 40 ) is a primary or secondary alkyl group.

[0081] 7. A catalyst system according to any one of the preceding items, wherein Q 5 and Q 6 Each is independently propyl, isopropyl, neopentyl, hexyl and benzyl.

[0082] 8. The catalyst system according to any one of the preceding items, wherein the metal-ligand complex of formula (I) is selected from the group consisting of:

[0083]

[0084] 9. The catalyst system according to any of the preceding items, wherein M is zirconium or hafnium.

[0085] 10. The catalyst system according to any one of the preceding items, wherein the first olefin polymerization procatalyst (A) and the second olefin polymerization procatalyst (B) have corresponding reaction ratios r 1A and r 1B , so that the ratio (r 1A / r 1B ) is 0.5 or less.

[0086] 11. The catalyst system according to any one of the preceding items, wherein the first olefin polymerization procatalyst (A) comprises a metal-ligand complex of formula (III):

[0087] in:

[0088] R 20is independently at each occurrence a divalent aromatic or inertly substituted aromatic group containing 5 to 20 atoms, excluding hydrogen;

[0089] T 3 is a divalent hydrocarbon or silane radical having 3 to 20 atoms, excluding hydrogen, or an inert substituted derivative thereof;

[0090] R D is independently at each occurrence a monovalent ligand group having 1 to 20 atoms, excluding hydrogen, or two R D The groups together form a divalent ligand group having 1 to 20 atoms excluding hydrogen.

[0091] 12. The catalyst system according to any one of the preceding items, wherein the metal-ligand complex of formula (III) has the following structure:

[0092] in:

[0093] Ar 4 C independently at each occurrence 6-20 Aryl or its inertly substituted derivatives, in particular 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl, naphthyl, anthracen-5-yl, 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl;

[0094] T 4 is independently at each occurrence propene-1,3-diyl, bis(alkylene)cyclohexane-1,2-diyl, or an inert substituted derivative thereof substituted with 1 to 5 alkyl, aryl or aralkyl substituents each having up to 20 carbons;

[0095] R 21 is independently at each occurrence hydrogen, halo, hydrocarbyl having up to 50 atoms excluding hydrogen, trihydrocarbylsilanyl, trihydrocarbylsilylhydrocarbyl, alkoxy, or amino;

[0096] R D is independently at each occurrence a halo group or a hydrocarbyl or trihydrocarbylsilyl group having up to 20 atoms, not counting hydrogen, or 2 R D The radicals together form a divalent hydrocarbylene, hydrocarbyli or trihydrocarbylisilyl radical having up to 40 atoms, not counting hydrogen.

[0097] 13. The catalyst system according to any one of the preceding items, wherein the metal-ligand complex of formula (III) has the following structure:

[0098] in

[0099] Ar 4is independently at each occurrence 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl, or anthracen-5-yl,

[0100] R 21 is independently at each occurrence hydrogen, halo, hydrocarbyl having up to 50 atoms excluding hydrogen, trihydrocarbylsilanyl, trihydrocarbylsilylhydrocarbyl, alkoxy, or amino;

[0101] T 4 is propane-1,3-diyl or bis(methylene)cyclohexane-1,2-diyl; and

[0102] R D is independently at each occurrence a halo group or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms, not counting hydrogen, or 2 R D The radicals together form a hydrocarbylene, hydrocarbyldiyl or hydrocarbylsilanediyl radical having up to 40 atoms not counting hydrogen.

[0103] 14. The catalyst system according to any one of the preceding items, wherein the metal-ligand complex of formula (III) is selected from the group consisting of:

[0104]

[0105]

[0106] 15. A process for preparing a multi-block copolymer comprising contacting one or more addition polymerizable monomers with a catalyst system according to any one of the preceding items under addition polymerization conditions, wherein the process is a continuous solution process conducted at a temperature greater than 125°C.

[0107] 16. The method according to claim 15, wherein the method is carried out at a temperature of about 150°C and comprises more than 400 kg 聚合物 / g 金属 The efficiency of the combined catalyst.

[0108] 17. The method according to claim 15, wherein the method is carried out at a temperature of about 150°C to about 170°C and comprises more than 200 kg 聚合物 / g 金属 The efficiency of the combined catalyst.

[0109] 18. A multi-block copolymer prepared by the method according to any one of items 15 to 17, wherein the multi-block copolymer comprises a polymerized form of ethylene and one or more copolymerizable comonomers, and the copolymer contains two or more segments or blocks that differ in comonomer content, crystallinity, stereoisomerism, homogeneity, density, melting point or glass transition temperature.

[0110] 19. The multi-block copolymer of item 18, wherein the copolymer comprises a molecular weight distribution Mw / Mn of less than 3.0.

[0111] 20. The multi-block copolymer of clause 18, wherein the copolymer comprises a melt index (ASTM D 1238 (190°C / 2.16kg)) of less than 1.0.

[0112] 21. The multi-block copolymer of clause 18, wherein the copolymer comprises a thermomechanical resistance greater than 100°C. BRIEF DESCRIPTION OF THE DRAWINGS

[0113] Figure 1 The chain shuttling process that occurs in the polymerization method of the present disclosure is illustrated.

[0114] Figure 2-4 A CEF curve is provided, which demonstrates that an olefin block copolymer was produced in the examples of the present disclosure.

[0115] Figure 5 Incorporation ratios of exemplary procatalysts of the present disclosure are provided. DETAILED DESCRIPTION

[0116] definition

[0117] All references to the periodic table of the elements refer to the periodic table of the elements published and copyrighted by CRC Press, Inc. in 2003. In addition, any reference to one or more groups should be the one or more groups reflected in such periodic table using the IUPAC system for numbering the groups. Unless otherwise stated, implied by the context, or customary in the art, all parts and percentages are by weight, and all test methods are current as of the filing date of this disclosure. For the purpose of U.S. patent practice, the contents of any cited patent, patent application, or disclosure are incorporated by reference in their entirety (or their equivalent U.S. versions are so incorporated by reference in their entirety), especially with respect to the following disclosures: synthetic techniques, product and process design, polymers, catalysts, definitions (to the extent not inconsistent with any definitions specifically provided in this disclosure) and common knowledge in the art.

[0118] The numerical ranges in the present disclosure and as they relate to the compositions disclosed herein are approximate and therefore may include values ​​outside of the range unless otherwise indicated. Numerical ranges include all values ​​from and including lower and upper values ​​and include fractions or decimals.

[0119] The terms "chain shuttling agent" and "chain transfer agent" refer to those agents known to those of ordinary skill in the art. The term "shuttling agent" or "chain shuttling agent" refers to a compound or mixture of compounds that, under polymerization conditions, is capable of causing polymer radicals to transfer between different active catalyst sites. That is, polymer fragments are transferred to and from active catalyst sites in a convenient and reversible manner. In contrast to shuttling agents or chain shuttling agents, agents that act only as chain transfer agents (such as some main group alkyl compounds) can exchange alkyl groups on the chain transfer agent with polymer chains that are growing on the catalyst, which generally causes the growth of the polymer chain to terminate. In this case, the main group center can act as a reservoir of dead polymer chains, rather than reversibly transferring with the catalyst site in the manner that chain shuttling agents do. It is desirable that the intermediate formed between the chain shuttling agent and the polymer radical chain is not sufficiently stable relative to the exchange between this intermediate and any other growing polymer radical chain, so that chain termination is relatively rare.

[0120] As used herein, the term "procatalyst" or "catalyst precursor" refers to a transition metal species that is capable of polymerizing unsaturated monomers once combined with an activating cocatalyst. For example, Cp2Zr(CH3)2 is a catalyst precursor that, when combined with an activating cocatalyst, becomes an active catalyst species "Cp2Zr(CH3) + For simplicity, the terms "procatalyst", "transition metal catalyst", "transition metal catalyst precursor", "catalyst", "catalyst precursor", "polymerization catalyst or catalyst precursor", "metal complex", "complex", "metal-ligand complex" and similar terms are interchangeable in the present disclosure. Catalysts or procatalysts include those known in the art and those disclosed in the following documents: WO 2005 / 090426, WO 2005 / 090427, WO 2007 / 035485, WO 2009 / 012215, WO 2014 / 105411, U.S. Patent Publication Nos. 2006 / 0199930, 2007 / 0167578, 2008 / 0311812, and U.S. Patent Nos. 7,355,089 B2, 8,058,373 B2, and 8,785,554 B2, all of which are incorporated herein by reference in their entirety.

[0121] "Cocatalyst" or "activator" refers to those agents known in the art, such as those disclosed in WO 2005 / 090427 and US Pat. No. 8,501,885 B2, which are capable of activating a procatalyst by combining or contacting with the procatalyst to form an active catalyst composition.

[0122] Common abbreviations used here are as follows:

[0123] Me: methyl; Ph: phenyl; Bn: benzyl; i-Pr: isopropyl; t-Bu: tert-butyl; n-Oct: 1-octyl; Cy: cyclohexyl; Mesityl: 2,4,6-trimethylphenyl; DI water: deionized water; THF: tetrahydrofuran; DME: dimethoxyethane; CH2Cl2: dichloromethane; CBr4: carbon tetrabromide; TCB: trichlorobenzene; EtOAc: ethyl acetate; C6D6: deuterated benzene; benzene-d6: deuterated benzene; C7D8: deuterated toluene; CDCl3: deuterated chloroform; dba: dibenzylideneacetone; PCy3: tricyclohexylphosphine; CyPF-t-Bu (Josiphos), having the structure: BINAP: 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl; Acac: acetylacetonate; Mg(OH)2: magnesium hydroxide; NaO t Bu: sodium tert-butoxide; K3PO4: tripotassium phosphate; Brine: saturated sodium chloride aqueous solution; n-BuLi: n-butyllithium; MeMgBr: methylmagnesium bromide; HfCl4: hafnium(IV) chloride; HfBn4: tetrabenzylhafnium(IV); ZrCl4: zirconium(IV) chloride; ZrBn4: tetrabenzylzirconium(IV); Pd(OAc)2: palladium(II) acetate; Pd2dba3: tris(dibenzylideneacetone)dipalladium(0); Ni(Acac)2: nickel(II) acetylacetonate; NiBr2 (DME): nickel(II) bromide dimethyl glycol ether complex; DEZ: diethylzinc; MMAO, MMAO-3A: modified methylaluminoxane; BHT: butylated hydroxytoluene; GPC: gel permeation chromatography; HT-GPC: high temperature gel permeation chromatography; PDI: polydispersity index; GC / MS: gas chromatography / mass spectrometry; NMR: nuclear magnetic resonance; MHz: megahertz; g: gram; mg: milligram; mmol: millimole; mL: milliliter; min: minute; h: hour; d: day; RT: room temperature.

[0124] The terms "addition polymerizable conditions," "polymerization conditions," and similar terms refer to conditions known to those of ordinary skill in the art for the polymerization of unsaturated monomers.

[0125] "Polymer" refers to a compound prepared by polymerizing monomers (whether of the same or different types). The general term polymer therefore encompasses the term homopolymer (usually used to refer to polymers prepared from only one type of monomer) and the term interpolymer as defined below. It also encompasses all forms of interpolymers, such as random, block, homogeneous, heterogeneous, etc. "Interpolymer" and "copolymer" refer to polymers prepared by polymerizing at least two different types of monomers. These general terms include classical copolymers (i.e., polymers prepared from two different types of monomers), and polymers prepared from more than two different types of monomers, such as terpolymers, tetrapolymers, etc. The term "polyethylene" includes ethylene homopolymers and copolymers of ethylene and one or more C3-8 alpha-olefins, wherein ethylene accounts for at least 50 mol%. The term "crystalline" (if employed) refers to a polymer having a first order transition or crystalline melting point (Tm), as determined by differential scanning calorimetry (DSC) or equivalent techniques. The term can be used interchangeably with the term "semi-crystalline". The term "amorphous" refers to a polymer that lacks a crystalline melting point as determined by differential scanning calorimetry (DSC) or equivalent technique.

[0126] The terms "olefin block copolymer (OBC)", "block copolymer", "multi-block copolymer" and "segmented copolymer" refer to polymers comprising two or more chemically distinct regions or segments (referred to as "blocks") preferably linked in a linear manner, i.e., polymers comprising chemically distinct units linked end-to-end (covalently bonded) with respect to polymeric functionality, rather than in pendant or grafted fashion. Blocks may differ in the amount or type of comonomer incorporated therein, density, amount of crystallinity, type of crystallinity (e.g., polyethylene versus polypropylene), crystallite size attributable to polymers of such composition, type or degree of stereoisomerism (isotactic or syndiotactic), regioregularity or regioirregularity, amount of branching (including long chain branching or hyperbranching), homogeneity, and / or any other chemical or physical property. For example, the olefin block copolymers may contain "hard blocks" (semi-crystalline or high glass transition temperature) with lower comonomer content and "soft blocks" (low crystallinity or amorphous, low glass transition temperature) with higher comonomer content. Compared to prior art block copolymers (including copolymers produced by sequential monomer addition, stereolabile catalysts, or anionic polymerization techniques), the block copolymers of the present disclosure are characterized by a unique distribution of polymer polydispersity (PDI or Mw / Mn), block length distribution, and / or block number distribution, which, in a preferred embodiment, is attributed to the effect of a shuttling agent in combination with a catalyst. More specifically, when produced in a continuous process, the block copolymers desirably have a PDI of 1.0 to 10.0 (e.g., 1.0 to 9.0, 1.0 to 8.0, 1.0 to 7.0, 1.0 to 6.0, 1.0 to 5.0, 1.0 to 4.0, 1.0 to 3.5, 1.0 to 3.0, 1.7 to 2.9, 1.8 to 2.5, 1.8 to 2.2, and / or 1.8 to 2.1). When produced in a batch or semi-batch process, the block polymers preferably have a PDI of 1.0 to 10.0 (e.g., 1.0 to 9.0, 1.0 to 8.0, 1.0 to 7.0, 1.0 to 6.0, 1.0 to 5.0, 1.0 to 4.0, 1.0 to 3.5, 1.0 to 3.0, 1.7 to 2.9, 1.8 to 2.5, 1.8 to 2.2, and / or 1.8 to 2.1).

[0127] The term "ethylene multi-block copolymer" means a multi-block copolymer comprising ethylene and one or more copolymerizable comonomers, wherein ethylene comprises a plurality of polymerized monomer units of at least one block or segment in the polymer, preferably at least 90 mol%, more preferably at least 95 mol%, and most preferably at least 98 mol% of the block. The ethylene multi-block copolymers of the present disclosure preferably have an ethylene content of 25 to 97 wt%, more preferably 40 to 96 wt%, even more preferably 55 to 95 wt%, and most preferably 65 to 85 wt%, based on the total polymer weight.

[0128] Since two of the multiple monomers form corresponding distinguishable segments or blocks linked into a single polymer chain, the polymer cannot be completely fractionated using standard selective extraction techniques. For example, a polymer containing relatively crystalline regions (high density segments) and relatively amorphous regions (lower density segments) cannot be selectively extracted or fractionated using different solvents. In a preferred embodiment, the amount of extractable polymer using a dialkyl ether or alkane solvent is less than 10% by weight of the total polymer, preferably less than 7%, more preferably less than 5% and most preferably less than 2%.

[0129] In addition, the multi-block copolymers of the present disclosure preferably have a PDI that fits the Schulz-Flory distribution rather than the Poisson distribution. The products produced using the polymerization process of the present invention have a polydisperse block distribution and a polydisperse distribution of block sizes. This forms a polymer product with improved and distinguishable physical properties. The theoretical benefits of a polydisperse block distribution have been previously modeled and discussed in Potemkin, Physical Review E (1998) 57 (6), pp. 6902-6912, and Dobrynin, Journal of Chemical Physics (J. Chem. Phvs.) (1997) 107 (21), pp. 9234-9238.

[0130] In another embodiment, the polymers of the present disclosure, in particular those made in a continuous solution polymerization reactor, have a most probable distribution of block lengths.Exemplary copolymers according to the present disclosure are multi-block copolymers containing 4 or more blocks or segments, including terminal blocks.

[0131] The following mathematical treatment of the resulting polymers is based on theoretically derived parameters that are believed to be applicable to the polymers of the present disclosure and demonstrate that, particularly in a steady-state, continuous, well-mixed reactor, the block lengths of the resulting polymers produced using two or more catalysts will each conform to a most probable distribution derived as follows, where p iis the probability of growth from catalyst i for a block sequence. The theoretical treatment is based on standard assumptions and methods known in the art and is used to predict the effects of polymerization kinetics on molecular structure, including the use of mass action reaction rate expressions that are not affected by chain length or block length. Such methods have been previously disclosed in WHRay, J. Macromol. Sci., Rev. Macromol. Chem. C8, 1 (1972), and AEHamielec and JFMacGregor, Polymer Reaction Engineering, KHReichert and W. Geisler, eds., Hanser, Munich, 1983. In addition, it is assumed that adjacent sequences formed by the same catalyst form a single block. For catalyst i, the fraction of sequences of length n is given by X i [n] is given, where n is an integer from 1 to infinity representing the number of monomer units in the block.

[0132] X i [n] = (1-p i ) i (n-1) The most probable distribution of block lengths

[0133] Number average block length

[0134] Each catalyst has a growth probability (p i ) and form polymer segments with unique average block lengths and distributions. In a most preferred embodiment, the growth probability is defined as:

[0135] For each catalyst i = {1, 2...}, in

[0136] Rp[i] = monomer consumption rate of catalyst i (mol / L),

[0137] Rt[i] = the total rate of chain transfer and termination of catalyst i (mol / L),

[0138] Rs[i] = chain shuttling rate of dormant polymer with other catalysts (mol / L), and

[0139] [C i ] = concentration of catalyst i (mol / L).

[0140] Dormant polymer chains are those that are attached to the CSA. The total monomer consumption or polymer growth rate Rp[i] is given by using the apparent rate constant Multiply by the total monomer concentration [M] to define:

[0141]

[0142] The total chain transfer rate, including values ​​for chain transfer to hydrogen (H2), beta hydrogen elimination, and chain transfer to a chain shuttling agent (CSA) is given as follows: The reactor residence time is given by θ and each subscript k value is a rate constant.

[0143] Rt[i]=θk H2i [H2][C i ]+θk βi [C i ]+θk ai [CSA][C i ]

[0144] For the dual catalyst system, the polymer chain shuttling rate between catalysts 1 and 2 is given by:

[0145] Rs[1]=Rs[2]=θk a1 [CSA]θk a2 [C1][C2].

[0146] If more than two catalysts are used, this results in additional terms for Rs[i] and complexity of the theoretical relationship, but the ultimate conclusion that the resulting block length distribution is the most probable is not affected.

[0147] As used herein with respect to compounds, unless otherwise specifically stated, the singular includes all isomeric forms, and vice versa (e.g., "hexane" includes all isomers of hexane, individually or collectively). The terms "compound" and "complex" are used interchangeably herein to refer to organic compounds, inorganic compounds, and organometallic compounds. The term "atom" refers to the smallest constituent of an element, regardless of ionic state, i.e., whether it carries an electric charge or a partial charge or is bonded to another atom. The term "heteroatom" refers to an atom other than carbon or hydrogen. Preferred heteroatoms include: F, Cl, Br, N, O, P, B, S, Si, Sb, Al, Sn, As, Se, and Ge.

[0148] The term "hydrocarbyl" refers to a monovalent substituent containing only hydrogen and carbon atoms, including branched or unbranched, saturated or unsaturated, cyclic, polycyclic or acyclic materials. Examples include alkyl-, cycloalkyl-, alkenyl-, dienyl-, cycloalkenyl-, cycloalkadienyl-, aryl- and alkynyl-. "Substituted hydrocarbyl" refers to a hydrocarbyl substituted with one or more non-hydrocarbyl substituents. The term "heteroatom-containing hydrocarbyl" or "heterohydrocarbyl" refers to a monovalent group in which at least one atom other than hydrogen or carbon is present together with one or more carbon atoms and one or more hydrogen atoms. The term "heterohydrocarbyl" refers to a group containing one or more carbon atoms and one or more heteroatoms and no hydrogen atoms. The bond between a carbon atom and any heteroatom and the bond between any two heteroatoms may be a single or multiple covalent bond or a coordination bond or other donor bond. Thus, alkyl groups substituted by: heterocycloalkyl-, aryl-substituted heterocycloalkyl-, heteroaryl-, alkyl-substituted heteroaryl-, alkoxy-, aryloxy-, dihydrocarbylboryl-, dihydrocarbylphosphino-, dihydrocarbylamino-, trihydrocarbylsilanyl-, hydroxythio-, or hydrocarbylseleno- fall within the scope of the term heteroalkyl. Examples of suitable heteroalkyl groups include cyanomethyl-, benzoylmethyl-, (2-pyridyl)methyl-, and trifluoromethyl-.

[0149] As used herein, the term "aromatic" refers to a polyatomic cyclic conjugated ring system containing (4δ+2) π electrons, where δ is an integer greater than or equal to 1. The term "fused" as used herein with respect to a ring system containing two or more polyatomic rings means that, for at least two of its rings, both rings include at least one pair of adjacent atoms. "Aryl" means a monovalent aromatic substituent, which may be a single aromatic ring, or multiple aromatic rings fused together, covalently bonded, or bonded to a common group (such as a methylene or ethylene moiety). Examples of one or more aromatic rings include phenyl, naphthyl, anthracenyl, biphenyl, and the like.

[0150] "Substituted aryl" refers to an aryl group in which one or more hydrogen atoms bonded to any carbon are replaced by one or more functional groups, such as alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, halogen, alkyl halide (e.g., CF3), hydroxyl, amino, phosphate, alkoxy, amino, thio, nitro, and saturated and unsaturated cyclic hydrocarbons fused to an aromatic ring, covalently linked, or linked to a common group (e.g., a methylene or ethylene moiety). The common linking group can also be a carbonyl in benzophenone, an oxygen in diphenyl ether, or a nitrogen in diphenylamine.

[0151] For a copolymer prepared by a given catalyst, the relative amounts of comonomer and monomer in the copolymer, and hence the copolymer composition, is determined by the relative reaction rates of the comonomer and monomer. Mathematically, the molar ratio of comonomer to monomer is given by

[0152]

[0153] Here, R p2 With R p1 are the polymerization rates of the comonomer and monomer, respectively, and F2 and F1 are the mole fractions of each in the copolymer. Since F2+F1=1, we can rearrange this equation to

[0154]

[0155] The individual polymerization rates of the comonomer and monomer are usually a complex function of temperature, catalyst, and monomer / comonomer concentration. In the limiting case where the comonomer concentration in the reaction medium is reduced to zero, R p2 drops to zero, F2 becomes zero, and the polymer consists of pure monomer. In the limiting case where there is no monomer in the reactor, R p1 becomes zero, and F2 is 1 (provided that the comonomer can be polymerized alone).

[0156] For most homogeneous catalysts, the comonomer to monomer ratio in the reactor determines to a large extent the polymer composition as determined by either the terminal copolymerization model or the near-terminal copolymerization model.

[0157] For random copolymers where the properties of the last intercalated monomer determine the rate of subsequent intercalation, the terminal copolymerization model is used. In this model, the type of intercalation reaction

[0158]

[0159] Among them C * Represents catalyst, M i represents monomer i, and k ij is the rate constant with the rate equation

[0160]

[0161] The comonomer mole fraction (i=2) in the reaction medium is defined by the following equation:

[0162]

[0163] A simplified equation for the comonomer composition can be derived as disclosed by George Odian, Principles of Polymerization, 2nd edition, John Wiley and Sons, 1970, and is as follows:

[0164]

[0165] According to this equation, the comonomer mole fraction in the polymer depends only on the comonomer mole fraction in the reaction medium and two temperature-dependent reaction ratios defined in terms of the embedding rate constant:

[0166]

[0167] Alternatively, in the quasi-terminal copolymerization model, the properties of the last two monomers embedded in the growing polymer chain determine the rate at which subsequent monomers are embedded. The polymerization reaction takes the form

[0168]

[0169] and the individual rate equations are:

[0170]

[0171] Comonomer content can be calculated as follows (again as disclosed by George Odian, supra):

[0172]

[0173] where X is defined as:

[0174]

[0175] And the reaction ratio is defined as:

[0176]

[0177] Also for this model, the polymer composition is a function only of the temperature-dependent reaction ratio and the comonomer mole fraction in the reactor. This is also true when reverse comonomer or monomer insertion may occur or in the case of interpolymerization of more than two monomers.

[0178] The reaction ratios used in the aforementioned models can be predicted using well-known theoretical techniques or derived empirically from actual polymerization data. Suitable theoretical techniques are disclosed in, for example, BG Kyle, Chemical and Process Thermodynamics, 3rd edition, Prentice-Hall, 1999 and Redlich-Kwong-Soave (RKS) equation of state, Chemical Engineering Science, 1972, pp. 1197-1203. The use of commercially available software programs can help derive the reaction ratios from experimentally derived data. An example of such software is Aspen Plus, available from Aspen Technologies, Ten Canal Park, Cambridge, MA 02141-2201 USA.

[0179] Based on the foregoing theoretical considerations, the present disclosure may alternatively be directed to a composition or catalyst system for the polymerization of two or more addition polymerizable monomers, in particular ethylene and at least one copolymerizable comonomer, to form a high molecular weight segmented copolymer (multi-block copolymer) containing two or more (preferably three or more) segments or blocks differing in one or more chemical or physical properties, as further disclosed herein; the catalyst system or composition comprising a mixture or reaction product resulting from the combination of:

[0180] (A) a first olefin polymerization procatalyst,

[0181] (B) a second olefin polymerization procatalyst capable of producing a polymer having chemical or physical properties different from those of the polymer produced by the first olefin polymerization procatalyst (A) under equivalent polymerization conditions, and

[0182] (C) chain shuttling agents;

[0183] in:

[0184] The first olefin polymerization procatalyst has a r1(r 1A ),and

[0185] The second olefin polymerization procatalyst has a r1(r 1B ),

[0186] The reaction ratio (r 1A / r 1B ) is 0.5 or less (e.g., 0.25 or less, 0.125 or less, 0.08 or less, 0.04 or less).

[0187] Additionally, there is now provided a process, preferably a solution process (and most preferably a continuous solution process), for the polymerization of two or more addition polymerizable monomers (particularly ethylene and at least one copolymerizable comonomer) to form a high molecular weight segmented copolymer (multi-block copolymer) containing two or more (preferably three or more) segments or blocks differing in one or more chemical or physical properties, as further disclosed herein; said process comprising the step of combining the two or more addition polymerizable monomers (particularly ethylene and at least one copolymerizable comonomer) with a catalyst system or composition under polymerization conditions, said catalyst system or composition comprising a mixture or reaction product resulting from combining:

[0188] (A) a first olefin polymerization procatalyst,

[0189] (B) a second olefin polymerization procatalyst capable of producing a polymer having chemical or physical properties different from those of the polymer produced by the first olefin polymerization procatalyst (A) under equivalent polymerization conditions, and

[0190] (C) chain shuttling agents;

[0191] in:

[0192] The first olefin polymerization procatalyst has a r1(r 1A ),and

[0193] The second olefin polymerization procatalyst has a r1(r 1B ),

[0194] The reaction ratio (r 1A / r 1B ) is 0.5 or less (e.g., 0.25 or less, 0.125 or less, 0.08 or less, 0.04 or less).

[0195] Additionally, there is provided a composition or catalyst system for the polymerization of two or more addition polymerizable monomers (referred to as monomers and comonomers, respectively), in particular the polymerization of ethylene and at least one copolymerizable comonomer, to form a high molecular weight segmented copolymer (multi-block copolymer) containing two or more (preferably three or more) segments or blocks differing in one or more chemical or physical properties, as further disclosed herein; the catalyst system or composition comprising a mixture or reaction product produced by combining:

[0196] (A) a first olefin polymerization procatalyst,

[0197] (B) a second olefin polymerization procatalyst capable of producing a polymer having chemical or physical properties different from those of the polymer produced by the first olefin polymerization procatalyst (A) under equivalent polymerization conditions, and

[0198] (C) a chain shuttling agent; wherein

[0199] The comonomer content (mole percent) in the copolymer produced by the first olefin polymerization procatalyst (F1) and

[0200] the comonomer content (mole percent) in the copolymer produced by the second olefin polymerization procatalyst (F2),

[0201] is selected so that the ratio (F1 / F2) under polymerization conditions is 2 or greater (eg, 4 or greater, 10 or greater, 15 or greater, and 20 or greater).

[0202] Additionally, there is provided a process, preferably a solution process (more preferably a continuous solution process), for the polymerization of two or more addition polymerizable monomers (referred to as monomers and comonomers, respectively), especially the polymerization of ethylene and at least one copolymerizable comonomer, to form a high molecular weight segmented copolymer (multi-block copolymer), wherein the copolymer contains two or more (preferably three or more) segments or blocks differing in one or more chemical or physical properties, as further disclosed herein; the process comprising the steps of combining under polymerization conditions:

[0203] (A) a first olefin polymerization procatalyst,

[0204] (B) a second olefin polymerization procatalyst capable of producing a polymer having chemical or physical properties different from those of the polymer produced by the first olefin polymerization procatalyst (A) under equivalent polymerization conditions, and

[0205] (C) a chain shuttling agent; wherein

[0206] The comonomer content (mole percent) in the copolymer produced by the first olefin polymerization procatalyst (F1) and

[0207] the comonomer content (mole percent) in the copolymer produced by the second olefin polymerization procatalyst (F2),

[0208] is selected so that the ratio (F1 / F2) under polymerization conditions is 2 or greater (e.g., 4 or greater, 10 or greater, 15 or greater, and 20 or greater); and

[0209] The polymer product is recovered.

[0210] monomer

[0211] Monomers suitable for preparing the olefin block copolymer or multi-block copolymer of the present disclosure include ethylene and one or more addition polymerizable monomers (i.e., comonomers) other than ethylene. Examples of suitable comonomers include linear or branched α-olefins having 3 to 30, preferably 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene; cyclic olefins having 3 to 30, preferably 3 to 20 carbon atoms; Olefins, such as cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene, tetracyclododecene and 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a,5,8,8a-octahydronaphthalene; diolefins and polyolefins, such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,3-octadiene, 1,4- Octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, ethylidene norbornene, vinyl norbornene, dicyclopentadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, and 5,9-dimethyl, 4,8-decatriene; aromatic vinyl compounds such as mono- or poly-alkylstyrenes (including styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene), and derivatives containing functional groups such as methoxystyrene, ethoxystyrene, vinylbenzoic acid, methyl vinylbenzoate, vinylbenzyl acetate, hydroxystyrene, o-chlorostyrene, p-chlorostyrene, divinylbenzene, 3-phenylpropylene, 4-phenylpropylene, α-methylstyrene, vinyl chloride, 1,2-difluoroethylene, 1,2-dichloroethylene, tetrafluoroethylene and 3,3,3-trifluoro-1-propylene.

[0212] Chain Shuttling Agent (CSA)

[0213] The term "shuttling agent" refers to a compound or mixture of compounds employed in the compositions / catalyst systems / methods of the present disclosure that, under polymerization conditions, is capable of causing the exchange of polymer groups between at least two active catalyst sites of the catalyst included in the compositions / catalyst systems / methods. That is, polymer fragments are transferred to and from one or more active catalyst sites. In contrast to shuttling agents, "chain transfer agents" cause the termination of polymer chain growth and are equivalent to a one-time transfer of the growing polymer from the catalyst to the transfer agent. Preferably, the activity of the shuttling agent is greater than R A-B / R B-Ais from 0.01 to 100, more preferably from 0.1 to 10, most preferably from 0.5 to 2.0 and most highly preferably from 0.8 to 1.2, wherein R A - B is the rate at which the polymer radical is transferred from the active site of catalyst A to the active site of catalyst B through the shuttling agent, and R B-A is the rate of polymer radical back transfer, i.e., the rate of exchange from the active site of catalyst B to the active site of catalyst A via the shuttling agent. It is desirable that the intermediate formed between the shuttling agent and the polymer chain is sufficiently stable that chain termination is relatively rare. It is desirable that less than 90%, preferably less than 75%, more preferably less than 50%, and most preferably less than 10% of the shuttling polymer product terminate before 3 distinguishable polymer segments or blocks are obtained. Ideally, the chain shuttling rate (defined by the time required for a polymer chain to transfer from a catalyst site to a chain shuttling agent and then back to a catalyst site) is similar to or faster than the polymer termination rate, even up to 10 or even 100 times faster than the polymer termination rate. This allows polymer blocks to form on the same time scale as polymer growth.

[0214] The chain shuttling agents suitable for use herein include those containing at least one C 1-20 Hydrocarbyl-substituted Group 1, 2, 12 or 13 metal compounds or complexes, preferably hydrocarbyl-substituted magnesium, aluminum, gallium or zinc compounds, containing 1 to 12 carbon atoms in each hydrocarbyl group; and reaction products thereof with a proton source. Preferred hydrocarbyl groups are alkyl groups, preferably straight or branched C 2-8 The most preferred shuttling agents for use in the present invention are trialkylaluminum and dialkylzinc compounds, especially triethylaluminum, tri(isopropyl)aluminum, tri(isobutyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum, triethylgallium or diethylzinc. Other suitable shuttling agents include those obtained by reacting the aforementioned organometallic compounds (preferably tri(C 1-8 ) alkylaluminum or di(C 1-8The invention relates to a reaction product or mixture of an alkyl zinc compound, particularly triethylaluminum, tri(isopropyl)aluminum, tri(n-butyl)aluminum, tri(n-hexyl)aluminum, tri(n-octyl)aluminum or diethylzinc, and a less than stoichiometric amount (relative to the number of hydrocarbyl groups) of a secondary amine or hydroxy compound, particularly bis(trimethylsilyl)amine, tert-butyl(dimethyl)siloxane, 2-hydroxymethylpyridine, di(n-pentyl)amine, 2,6-di(tert-butyl)phenol, ethyl(1-naphthyl)amine, bis(2,3,6,7-dibenzo-1-azacycloheptaneamine) or 2,6-diphenylphenol. Sufficient amine or hydroxy reagent is used so that one hydrocarbyl group remains per metal atom. The major reaction products of the foregoing combinations that are most useful as shuttling agents in the present disclosure are n-octylbis(bis(trimethylsilyl)aluminum amide), isopropylbis(dimethyl(tert-butyl)aluminum silanol), and n-octylbis(aluminum pyridyl-2-methoxide), isobutylaluminum bis(dimethyl(tert-butyl)siloxane), isobutylbis(bis(trimethylsilyl)aluminum amide), n-octylbis(aluminum pyridine-2-methoxide), isobutylbis(di(n-pentyl)aluminum amide), n-octylbis(2,6-ditert-butyl)silanol, and n-octylbis(aluminum pyridyl-2-methoxide). The following are some of the following: ethylbis(tert-butylaluminum silanol), ethylbis(bis(trimethylsilyl)aluminum amide), ethylbis(2,3,6,7-dibenzo-1-azacycloheptanealuminum amide), n-octylbis(2,3,6,7-dibenzo-1-azacycloheptanealuminum amide), n-octylbis(dimethyl(tert-butyl)silanolaluminum, ethyl(zinc 2,6-diphenylphenol) and ethyl(zinc tert-butyloxide).

[0215] In other embodiments of the present disclosure, suitable chain shuttling agents include metal alkyls containing divalent metals (e.g., Zn), trivalent metals (e.g., Al), or mixtures of divalent and trivalent metals. In certain embodiments, the chain shuttling agent is a divalent metal alkyl, such as a dialkyl zinc. In certain embodiments, the chain shuttling agent is a trivalent metal alkyl, such as a trialkyl aluminum. In certain embodiments, the organometallic compound is a mixture of a divalent metal alkyl (e.g., a dialkyl zinc) and a trivalent metal alkyl (e.g., a trialkyl aluminum). In certain embodiments, the chain shuttling agent is a mixture of a trivalent metal and a divalent metal, with a trivalent / divalent metal ratio of 99:1 to 1:99 (e.g., 95:5 to 50:50, 90:10 to 80:20, 90:10 to 70:30, etc.). In certain embodiments, the chain shuttling agent is a metal alkyl containing a mixture of aluminum and zinc metals with an aluminum / zinc ratio of 99:1 to 1:99 (eg, 95:5 to 50:50, 90:10 to 80:20, 90:10 to 70:30, etc.).

[0216] The skilled artisan will appreciate that a shuttling agent that is suitable for one catalyst or catalyst combination may not necessarily be as good or even satisfactory for a different catalyst or catalyst combination. Some potential shuttling agents may adversely affect the performance of one or more catalysts and may not be desirable for that reason. Therefore, the activity of the chain shuttling agent is preferably balanced with the catalytic activity of the catalysts to achieve the desired polymer properties. In some embodiments of the present disclosure, optimal results may be obtained by using a shuttling agent whose chain shuttling activity (as measured by chain transfer rate) is less than the maximum possible rate.

[0217] However, in general, preferred shuttling agents have the highest polymer transfer rates as well as the highest transfer efficiency (reduced incidence of chain termination). Such shuttling agents can be used at reduced concentrations and still achieve the desired degree of shuttling. In addition, such shuttling agents result in the shortest possible polymer block lengths. It is highly desirable to use chain shuttling agents with a single exchange site because the effective molecular weight of the polymer in the reactor is reduced, thereby reducing the viscosity of the reaction mixture and thus reducing operating costs.

[0218] First olefin polymerization procatalyst (A)

[0219] Suitable procatalysts falling within the scope of the first olefin polymerization procatalyst (A) of the present disclosure include catalysts / complexes discussed below, which are suitable for preparing polymers of the desired composition or type and capable of reversible chain transfer by a chain shuttling agent. As described above, the terms "procatalyst", "catalyst", "metal complex" and "complex" used herein are interchangeable. In certain embodiments, the first olefin polymerization procatalyst (A) is a soft block / segment catalyst (i.e., a high comonomer incorporating agent) of the olefin block copolymer of the present disclosure.

[0220] Both heterogeneous and homogeneous catalysts can be used. Examples of heterogeneous catalysts include the well-known Ziegler-Natta compositions, in particular Group 4 metal halides or mixed halides and alkoxides supported on Group 2 metal halides, and the well-known catalysts based on chromium or vanadium. Preferably, the catalyst used herein is a homogeneous catalyst comprising a relatively pure organometallic compound or metal complex, in particular a compound or complex based on a metal selected from Groups 3-15 of the Periodic Table of the Elements or the lanthanide series.

[0221] The metal complex used herein may be selected from Groups 3 to 15 of the Periodic Table of Elements containing one or more delocalized π-bonded ligands or multivalent Lewis base ligands. Examples include metallocenes, semi-metallocenes, constrained geometry and multivalent pyridylamines, or other polychelate base complexes. The complex is generally depicted by the formula: MK k X x Zz or a dimer thereof, wherein:

[0222] M is a metal selected from Groups 3-15, preferably Groups 3-10, more preferably Groups 4-10 and most preferably Group 4 of the Periodic Table of Elements;

[0223] K is independently at each occurrence a group containing a delocalized π electron or one or more electron pairs, K is bound to M via said delocalized π electron or one or more electron pairs, said K group contains up to 50 atoms excluding hydrogen atoms, optionally two or more K groups may be linked together to form a bridged structure, and further optionally, one or more K groups may be bound to Z, X, or both Z and X;

[0224] X is independently at each occurrence a monovalent anionic moiety having up to 40 non-hydrogen atoms; optionally, one or more X groups may be bonded together to form a divalent or multivalent anionic group; and further optionally, one or more X groups and one or more Z groups may be bonded together to form a moiety that is both covalently bound to and coordinated to M; or two X groups together form a divalent anionic ligand group of up to 40 non-hydrogen atoms or together become a conjugated diene having 4 to 30 non-hydrogen atoms bonded to M by means of delocalized π electrons, wherein M is in the +2 formal oxidation state, and

[0225] Z, at each occurrence, is independently a neutral Lewis base donor ligand having up to 50 non-hydrogen atoms, containing at least one unshared electron pair through which Z is coordinated to M;

[0226] k is an integer from 0 to 3; x is an integer from 1 to 4; z is a number from 0 to 3; and

[0227] The sum of k+x equals the formal oxidation state of M.

[0228] Suitable metal complexes include those containing 1 to 3 π-bonded anionic or neutral ligand groups, which may be cyclic or acyclic delocalized π-bonded anionic ligand groups. Examples of such π-bonded groups are conjugated or non-conjugated, cyclic or acyclic dienes and dienyl groups, allyl groups, borophenyl groups, phosphazolyls, and arenes. The term "π-bonded" means that the ligand group is bonded to the transition metal by sharing electrons from a partially delocalized π bond.

[0229] Each atom in the delocalized π-bonded group may be independently substituted with a group selected from the group consisting of hydrogen, halogen, hydrocarbyl, halogenated hydrocarbyl, and hydrocarbyl-substituted heteroatom, wherein the heteroatom is selected from Groups 14-16 of the Periodic Table of Elements and such hydrocarbyl-substituted heteroatom groups are further substituted with moieties containing heteroatoms from Groups 15 or 16. In addition, two or more such groups may together form a fused ring system, including partially or fully hydrogenated fused ring systems, or they may form a metal ring with a metal. The term "hydrocarbyl" includes C 1-20 Straight chain, branched chain and cyclic alkyl groups, C 6-20 Aromatic groups, C 7-20 Alkyl substituted aromatic group, and C 7-20 Aryl substituted alkyl. Suitable hydrocarbyl substituted heteroatom groups include mono-, di- and tri-substituted groups of boron, silicon, germanium, nitrogen, phosphorus or oxygen, wherein each hydrocarbyl contains 1 to 20 carbon atoms. Examples include N,N-dimethylamino, pyrrolidinyl, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, methyldi(tert-butyl)silyl, triphenylgermanyl and trimethylgermanyl. Examples of moieties containing heteroatoms of Groups 15 or 16 include amino, phosphino, alkoxy or alkylthio moieties or divalent derivatives thereof, such as amides, phosphides, alkyleneoxy or alkylenethio, which are bonded to transition metals or lanthanide metals and bonded to hydrocarbyl, π-bonded groups, or hydrocarbyl substituted heteroatoms.

[0230] Examples of suitable delocalized π-bonded anionic groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl, phosphazolyl and borazolyl, and inertly substituted derivatives thereof, particularly C 1-10 Hydrocarbyl-substituted or tri(C 1-10 Preferred delocalized π-bonded anionic groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, 1-dicyclopentadienylphenyl, 3-pyrrolidinol-indenyl-1-yl, 3,4-(cyclopenta(l)phenanthren-1-yl) and tetrahydroindenyl.

[0231] Borabenzylidene ligands are anionic ligands that are boron-containing analogs of benzene. They are previously known in the art and have been described in G. Herberich et al., Organometallics, 14, 1, 471-480 (1995). Preferred borobenzylidene ligands correspond to the following formula:

[0232]

[0233] Where R 1 is an inert substituent, preferably selected from the group consisting of hydrogen, hydrocarbon, silane, halogen or germyl, wherein R 1 has at most 20 atoms excluding hydrogen, and optionally, two adjacent R 1 The groups may be linked together. In complexes involving divalent derivatives of such delocalized π-bonded groups, one atom thereof is bonded to another atom of the complex via a covalent bond or a covalently bonded divalent group, thereby forming a bridged system.

[0234] Phosphazolides are anionic ligands that are phosphorus-containing analogs of cyclopentadienyl. They are previously known in the art and have been described in WO 98 / 50392 and elsewhere. Preferred phosphazolide ligands correspond to the following formula:

[0235]

[0236] Where R 1 As defined previously.

[0237] The transition metal complexes suitable for use herein correspond to the formula: MK k X x Z z or a dimer thereof, wherein:

[0238] M is a Group 4 metal;

[0239] K is a group containing delocalized π electrons, K is bonded to M via the delocalized π electrons, and the K group contains up to 50 atoms excluding hydrogen atoms; optionally, two K groups may be linked together to form a bridge structure, and further optionally, one K may also be bonded to X or Z;

[0240] X, at each occurrence, is a monovalent anionic moiety having up to 40 non-hydrogen atoms, optionally, one or more X and one or more K groups are bonded together to form a metallacycle, and further optionally, one or more X and one or more Z groups are bonded together to form a moiety that is both covalently bound to and coordinated to M;

[0241] Z, at each occurrence, is independently a neutral Lewis base donor ligand having up to 50 non-hydrogen atoms, containing at least one unshared electron pair through which Z is coordinated to M;

[0242] k is an integer from 0 to 3; x is an integer from 1 to 4; z is a number from 0 to 3; and the sum of k+x is equal to the formal oxidation state of M.

[0243] Suitable complexes include those containing one or two K groups. The latter complexes include those containing a bridging group connecting the two K groups. Suitable bridging groups are those corresponding to formula (ER'2) e wherein E is silicon, germanium, tin or carbon, R′ at each occurrence is independently hydrogen or a group selected from silane, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R′ having up to 30 carbon atoms or silicon atoms, and e is 1 to 8. Illustratively, R′ at each occurrence is independently methyl, ethyl, propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy or phenoxy.

[0244] An example of a complex containing two K groups is a compound corresponding to the formula:

[0245]

[0246] in:

[0247] M is titanium, zirconium or hafnium in the +2 or +4 oxidation state, preferably zirconium or hafnium; R 3 is independently selected at each occurrence from the group consisting of hydrogen, hydrocarbon, silane, germyl, cyano, halide, and combinations thereof, wherein R 3 With up to 20 non-hydrogen atoms, or adjacent R 3 The groups are taken together to form a divalent derivative (i.e., a hydrocarbon diyl, a silane diyl, or a germane diyl) to form a fused ring system, and

[0248] X" is independently at each occurrence an anionic ligand group having up to 40 non-hydrogen atoms, or two X" groups together form a divalent anionic ligand group having up to 40 non-hydrogen atoms or together are a conjugated diene having 4 to 30 non-hydrogen atoms bonded to M by means of delocalized π electrons, wherein M is in the +2 formal oxidation state, and

[0249] R', E and e are as defined above.

[0250] Exemplary bridging ligands containing two π-bonded groups are: dimethylbis(cyclopentadienyl)silane, dimethylbis(tetramethylcyclopentadienyl)silane, dimethylbis(2-ethylcyclopentadien-1-yl)silane, dimethylbis(2-tert-butylcyclopentadien-1-yl)silane, 2,2-bis(tetramethylcyclopentadienyl)propane, dimethylbis(inden-1-yl)silane, dimethylbis(tetrahydroinden-1-yl)silane, dimethylbis(fluoren-1-yl)silane, dimethylbis(tetrahydrofluoren-1-yl)silane, dimethylbis(tetrahydrofluoren-1-yl)silane, dimethylbis(tetrahydrofluoren-1-yl)silane, dimethylbis(cyclopentadi ... dimethyl(cyclopentadienyl)(fluoren-1-yl)silane, dimethyl(cyclopentadienyl)(octahydrofluoren-1-yl)silane, dimethyl(cyclopentadienyl)(tetrahydrofluoren-1-yl)silane, (1,1,2,2-tetramethyl)-1,2-bis(cyclopentadienyl)disilane, (1,2-bis(cyclopentadienyl)ethane) and dimethyl(cyclopentadienyl)-1-(fluoren-1-yl)methane.

[0251] Suitable X" groups are selected from hydrogen, hydrocarbon, silane, germyl, halohydrocarbon, halosilane, silanehydrocarbon and aminohydrocarbon, or two X" groups together form a divalent derivative of a conjugated diene or they otherwise together form a neutral π-bonded conjugated diene. Exemplary X" groups are C 1-20 Hydrocarbon.

[0252] Examples of the metal complex of the above formula used in the present disclosure include:

[0253] Bis(cyclopentadienyl)zirconium dimethyl,

[0254] Bis(cyclopentadienyl)benzhydryl zirconium,

[0255] Bis(cyclopentadienyl)methylbenzylzirconium,

[0256] Bis(cyclopentadienyl)methylphenylzirconium, Bis(cyclopentadienyl)diphenylzirconium,

[0257] Bis(cyclopentadienyl)allyltitanium,

[0258] Bis(cyclopentadienyl)methyl zirconium methoxide, Bis(cyclopentadienyl)methyl zirconium chloride, Bis(pentamethylcyclopentadienyl)zirconium dimethyl, Bis(pentamethylcyclopentadienyl)titanium dimethyl,

[0259] Bis(indenyl)zirconium dimethyl,

[0260] Indenylfluorenylzirconium dimethyl,

[0261] Bis(indenyl)methyl(2-(dimethylamino)benzyl)zirconium, bis(indenyl)methyltrimethylsilylzirconium, bis(tetrahydroindenyl)methyltrimethylsilylzirconium, bis(pentamethylcyclopentadienyl)methylbenzylzirconium, bis(pentamethylcyclopentadienyl)dibenzylzirconium, bis(pentamethylcyclopentadienyl)methylmethoxide zirconium, bis(pentamethylcyclopentadienyl)methylzirconium chloride, bis(methylethylcyclopentadienyl)dimethylzirconium, bis(butylcyclopentadienyl)dibenzylzirconium,

[0262] Bis(tert-butylcyclopentadienyl)zirconium dimethyl, bis(ethyltetramethylcyclopentadienyl)zirconium dimethyl, bis(methylpropylcyclopentadienyl)zirconium dibenzhydryl, bis(trimethylsilylcyclopentadienyl)zirconium dibenzhydryl, dimethylsilylbis(cyclopentadienyl)zirconium dichloride, dimethylsilylbis(cyclopentadienyl)zirconium dimethyl, dimethylsilylbis(tetramethylcyclopentadienyl)allyltitanium(III),

[0263] Dimethylsilylbis(tert-butylcyclopentadienyl)zirconium dichloride,

[0264] Dimethylsilylbis(n-butylcyclopentadienyl)zirconium dichloride,

[0265] (dimethylsilylbis(tetramethylcyclopentadienyl)2-(dimethylamino)benzyltitanium(III),

[0266] (dimethylsilylbis(n-butylcyclopentadienyl)2-(dimethylamino)benzyltitanium(III), dimethylsilylbis(indenyl)zirconium dichloride, dimethylsilylbis(indenyl)zirconium dimethyl,

[0267] Dimethylsilylbis(2-methylindenyl)zirconium dimethyl,

[0268] Dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium dimethyl,

[0269] Dimethylsilylbis(2-methylindenyl)zirconium-1,4-diphenyl-1,3-butadiene, dimethylsilylbis(2-methyl-4-phenylindenyl)zirconium(II)1,4-diphenyl-1,3-butadiene, dimethylsilylbis(4,5,6,7-tetrahydroinden-1-yl)zirconium dichloride, dimethylsilylbis(4,5,6,7-tetrahydroinden-1-yl)zirconium dimethyl, dimethylsilylbis(tetrahydroindenyl)zirconium(II)1,4-diphenyl-1,3-butadiene, dimethylsilylbis(tetramethylcyclopentadienyl)zirconium dimethyl, dimethylsilylbis(fluorenyl)zirconium dimethyl, dimethylsilylbis(tetrahydrofluorenyl)bis(trimethylsilyl)zirconium, ethylenebis(indenyl)zirconium dichloride,

[0270] Ethylenebis(indenyl)zirconium dimethyl,

[0271] Ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dichloride,

[0272] Ethylenebis(4,5,6,7-tetrahydroindenyl)zirconium dimethyl,

[0273] (Isopropylidene)(cyclopentadienyl)(fluorenyl)zirconium dibenzyl, and dimethylsilyl(tetramethylcyclopentadienyl)(fluorenyl)zirconium dimethyl.

[0274] Another class of metal complexes used in the present disclosure corresponds to the above formula: MKZ z X x or a dimer thereof, wherein M, K, X, x and z are as defined above, and Z is a substituent having up to 50 non-hydrogen atoms, said substituent together with K forming a metal ring having M.

[0275] Suitable Z substituents include groups containing up to 30 non-hydrogen atoms, comprising at least one atom directly bonded to K which is oxygen, sulfur, boron or a member of Group 14 of the Periodic Table of the Elements, and a different atom covalently bonded to M selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur.

[0276] More specifically, such Group 4 metal complexes used in accordance with the present invention include "constrained geometry catalysts" corresponding to the formula:

[0277]

[0278] Wherein: M is titanium or zirconium, preferably titanium in the +2, +3 or +4 oxidation state;

[0279] K 1 is a delocalized π-bonded ligand group, which is optionally substituted by 1 to 5 R 2 Group substitution,

[0280] R 2 is independently selected at each occurrence from the group consisting of hydrogen, hydrocarbon, silane, germyl, cyano, halide, and combinations thereof, wherein R 2 With up to 20 non-hydrogen atoms or adjacent R 2 The groups are taken together to form a divalent derivative (i.e., a hydrocarbon diyl, a silane diyl, or a germane diyl), thereby forming a fused ring system,

[0281] Each X is a halide, a hydrocarbon, a heterohydrocarbon, an oxyalkyl or a silane group, the group having up to 20 non-hydrogen atoms, or two X groups together form a neutral C5-30 conjugated diene or a divalent derivative thereof;

[0282] x is 1 or 2,

[0283] Y is -O-, -S-, -NR', -PR'-;

[0284] and X' is SiR'2, CR'2, SiR'2SiR'2, CR'2CR'2, CR'=CR', CR'2SiR'2 or GeR'2, wherein

[0285] R' at each occurrence is independently hydrogen or a group selected from silane, hydrocarbyl, hydrocarbyloxy, and combinations thereof, said R' having up to 30 carbon atoms or silicon atoms.

[0286] Specific examples of the aforementioned constrained geometry metal complex include compounds corresponding to the following formula:

[0287]

[0288] in,

[0289] Ar is an aryl group having 6 to 30 atoms excluding hydrogen;

[0290] R 4 is independently at each occurrence hydrogen, Ar, or a non-Ar group selected from the group consisting of hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermanyl, halo, hydrocarbyloxy, trihydrocarbylsiloxy, bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino, hydrocarbyldiylamino, hydrocarbylimino, di(hydrocarbyl)phosphino, hydrocarbyldiylphosphino, hydrocarbylsulfonyl, halohydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, trihydrocarbylsilyl-substituted hydrocarbyl, trihydrocarbylsiloxy-substituted hydrocarbyl, bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl, di(hydrocarbyl)amino-substituted hydrocarbyl, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino-substituted hydrocarbyl, hydrocarbylenephosphino-substituted hydrocarbyl, or hydrocarbylsulfonyl-substituted hydrocarbyl, the R group having up to 40 atoms not counting hydrogen atoms, and optionally, two adjacent R 4 The groups can be linked together to form polycyclic fused ring groups;

[0291] M is titanium;

[0292] X' is SiR 6 2.CR 6 2. SiR 6 2SiR 6 2.CR 6 2CR 6 2.CR 6 =CR 6 , CR 6 2SiR 6 2. BR 6 , BR 6 L" or GeR 6 2;

[0293] Y is -O-, -S-, or -NR 5 -、-PR 5 -、-NR5 2 or -PR 5 2;

[0294] R 5 is independently at each occurrence a hydrocarbyl, a trihydrocarbylsilyl or a trihydrocarbylsilylhydrocarbyl group, said R 5 having up to 20 non-hydrogen atoms and, optionally, two R 5 Group or R 5 Together with Y or Z, it forms a ring system;

[0295] R 6 is independently hydrogen at each occurrence or is selected from the group consisting of hydrocarbyl, hydrocarbyloxy, silanyl, haloalkyl, haloaryl, -NR 5 2 and combinations thereof, the R 6 having up to 20 non-hydrogen atoms and, optionally, two R 6 Group or R 6 Together with Z, it forms a ring system;

[0296] Z is optionally connected to R 5 , R 6 or an X-bonded neutral diene or a monodentate or polydentate Lewis base;

[0297] X is hydrogen, a monovalent anionic ligand group having up to 60 atoms excluding hydrogen, or two X groups are linked together to form a divalent ligand group;

[0298] x is 1 or 2, and

[0299] z is 0, 1 or 2.

[0300] Suitable examples of the aforementioned metal complexes are those in which the 3- and 4-positions of the cyclopentadienyl or indenyl groups are substituted with Ar groups. Examples of the aforementioned metal complexes include:

[0301] (3-phenylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium dichloride,

[0302] (3-phenylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanedimethyltitanium,

[0303] (3-phenylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium(II)1,3-diphenyl-1,3-butadiene;

[0304] (3-(Pyrrol-1-yl)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium dichloride,

[0305] (3-(Pyrrol-1-yl)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanedimethyltitanium,

[0306] (3-(Pyrrol-1-yl)cyclopentadien-1-yl))dimethyl(tert-butylamido)silanetitanium(II)1,4-diphenyl-1,3-butadiene;

[0307] (3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium dichloride,

[0308] (3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanedimethyltitanium,

[0309] (3-(1-methylpyrrol-3-yl)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium(II)1,4-diphenyl-1,3-butadiene;

[0310] (3,4-diphenylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium dichloride,

[0311] (3,4-diphenylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanedimethyltitanium,

[0312] (3,4-diphenylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium(II)1,3-pentadiene;

[0313] (3-(3-N,N-dimethylamino)phenyl)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium dichloride,

[0314] (3-(3-N,N-dimethylamino)phenylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanedimethyltitanium,

[0315] (3-(3-N,N-dimethylamino)phenylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium(II) 1,4-diphenyl-1,3-butadiene,

[0316] (3-(4-methoxyphenyl)-4-methylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium dichloride,

[0317] (3-(4-methoxyphenyl)-4-phenylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanedimethyltitanium,

[0318] (3-4-methoxyphenyl)-4-phenylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium(II)1,4-diphenyl-1,3-butadiene;

[0319] (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium dichloride,

[0320] (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(tert-butylamido)silanedimethyltitanium,

[0321] (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium(II)1,4-diphenyl-1,3-butadiene;

[0322] (3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium dichloride,

[0323] (3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanedimethyltitanium,

[0324] (3-phenyl-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium(II)1,4-diphenyl-1,3-butadiene;

[0325] 2-Methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(tert-butylamido)silane titanium dichloride,

[0326] 2-Methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanedimethyltitanium,

[0327] 2-Methyl-(3,4-di(4-methylphenyl)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium(II) 1,4-diphenyl-1,3-butadiene,

[0328] ((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium dichloride,

[0329] ((2,3-diphenyl)-4-(N,N-dimethylamido)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanedimethyltitanium,

[0330] ((2,3-diphenyl)-4-(N,N-dimethylamino)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium(II)1,4-diphenyl-1,3-butadiene;

[0331] (2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium dichloride,

[0332] (2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanedimethyltitanium,

[0333] (2,3,4-triphenyl-5-methylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium(II) 1,4-diphenyl-1,3-butadiene,

[0334] (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium dichloride,

[0335] (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(tert-butylamido)silanedimethyltitanium,

[0336] (3-phenyl-4-methoxycyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium(II)1,4-diphenyl-1,3-butadiene;

[0337] (2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium dichloride,

[0338] (2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanedimethyltitanium,

[0339] (2,3-diphenyl-4-(n-butyl)cyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium(II)1,4-diphenyl-1,3-butadiene;

[0340] (2,3,4,5-Tetraphenylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanetitanium dichloride,

[0341] (2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(tert-butylamido)silanedimethyltitanium, and (2,3,4,5-tetraphenylcyclopentadien-1-yl)dimethyl(tert-butylamido)titanium(II) 1,4-diphenyl-1,3-butadiene.

[0342] Further examples of suitable metal complexes herein are polycyclic complexes corresponding to the following formula:

[0343]

[0344] wherein M is titanium in the +2, +3 or +4 oxidation state;

[0345] R 7wherein each occurrence is independently hydrogen, hydrocarbyl, silyl, germanyl, halo, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilanylamino, di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino, hydrocarbylenephosphino, hydrocarbylsulfonyl, halohydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substituted hydrocarbyl, hydrocarbylsilanyloxy-substituted hydrocarbyl, hydrocarbylsilanylamino-substituted hydrocarbyl, di(hydrocarbyl)amino-substituted hydrocarbyl, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino-substituted hydrocarbyl, hydrocarbylenephosphino-substituted hydrocarbyl, or hydrocarbylsulfonyl-substituted hydrocarbyl, wherein R 7 The group has up to 40 atoms excluding hydrogen, and optionally, two or more of the aforementioned groups may together form a divalent derivative;

[0346] R 8 is a divalent alkylene group or a substituted alkylene group, which forms a fused system with the rest of the metal complex, wherein R 8 Containing from 1 to 30 atoms, excluding hydrogen;

[0347] X a is a divalent moiety, or a moiety containing a σ-bond and a neutral two-electron pair capable of forming a coordinate-covalent bond with M, wherein X a Contains boron or a member of Group 14 of the Periodic Table and further contains nitrogen, phosphorus, sulfur or oxygen;

[0348] X is a monovalent anionic ligand group having up to 60 atoms, excluding ligand classes of cyclic, delocalized, π-bound ligand groups, and optionally, two X groups together form a divalent ligand group;

[0349] Z, at each occurrence, is independently a neutral coordination compound having up to 20 atoms;

[0350] x is 0, 1, or 2, and

[0351] z is zero or 1.

[0352] Suitable examples of such complexes are 3-phenyl substituted s-indenyl complexes corresponding to the formula:

[0353]

[0354] The 2,3-dimethyl-substituted s-indenyl complex corresponds to the following formula:

[0355]

[0356] or a 2-methyl substituted s-indenyl complex corresponding to the following formula:

[0357]

[0358] Other examples of metal complexes suitable for use as catalysts according to the present invention include those of the formula:

[0359]

[0360] Specific metal complexes include

[0361] (8-methylene-1,8-dihydrodibenzo[e,h]azulene-1-yl)-N-(1,1-dimethylethyl)dimethylsilaneamide titanium(II) 1,4-diphenyl-1,3-butadiene,

[0362] (8-methylene-1,8-dihydrodibenzo[e,h]azulene-1-yl)-N-(1,1-dimethylethyl)dimethylsilaneamide titanium(II) 1,3-pentadiene,

[0363] (8-methylene-1,8-dihydrodibenzo[e,h]azulene-1-yl)-N-(1,1-dimethylethyl)dimethylsilaneamide 2-(N,N-dimethylamino)benzyltitanium(III),

[0364] (8-Methylene-1,8-dihydrodibenzo[e,h]azulene-1-yl)-N-(1,1-dimethylethyl)dimethylsilaneamide Titanium(IV) dichloride

[0365] (8-methylene-1,8-dihydrodibenzo[e,h]azulene-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide dimethyltitanium(IV),

[0366] (8-methylene-1,8-dihydrodibenzo[e,h]azulene-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide dibenzyltitanium(IV),

[0367] (8-Difluoromethylene-1,8-dihydrodibenzo[e,h]azulene-1-yl)-N-(1,1-dimethylethyl)dimethylsilaneamide titanium(II) 1,4-diphenyl-1,3-butadiene,

[0368] (8-Difluoromethylene-1,8-dihydrodibenzo[e,h]azulene-1-yl)-N-(1,1-dimethylethyl)dimethylsilaneamide titanium(II) 1,3-pentadiene,

[0369] (8-Difluoromethylene-1,8-dihydrodibenzo[e,h]azulene-1-yl)-N-(1,1-dimethylethyl)dimethylsilaneamide 2-(N,N-dimethylamino)benzyltitanium(III)

[0370] (8-Difluoromethylene-1,8-dihydrodibenzo[e,h]azulene-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide dichlorotitanium(IV),

[0371] (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulene-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide dimethyltitanium(IV),

[0372] (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulene-1-yl)-N-(1,1-dimethylethyl)dimethylsilanamide dibenzyltitanium(IV),

[0373] (8-methylene-1,8-dihydrodibenzo[e,h]azulene-2-yl)-N-(1,1-dimethylethyl)dimethylsilaneamide titanium(II) 1,4-diphenyl-1,3-butadiene,

[0374] (8-methylene-1,8-dihydrodibenzo[e,h]azulene-2-yl)-N-(1,1-dimethylethyl)dimethylsilaneamide titanium(II) 1,3-pentadiene,

[0375] (8-methylene-1,8-dihydrodibenzo[e,h]azulene-2-yl)-N-(1,1-dimethylethyl)dimethylsilaneamide 2-(N,N-dimethylamino)benzyltitanium(III),

[0376] (8-Methylene-1,8-dihydrodibenzo[e,h]azulene-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide Titanium(IV) dichloride,

[0377] (8-methylene-1,8-dihydrodibenzo[e,h]azulene-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide dimethyltitanium(IV),

[0378] (8-methylene-1,8-dihydrodibenzo[e,h]azulene-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide dibenzyltitanium(IV),

[0379] (8-Difluoromethylene-1,8-dihydrodibenzo[e,h]azulene-2-yl)-N-(1,1-dimethylethyl)dimethylsilaneamide titanium(II) 1,4-diphenyl-1,3-butadiene,

[0380] (8-Difluoromethylene-1,8-dihydrodibenzo[e,h]azulene-2-yl)-N-(1,1-dimethylethyl)dimethylsilaneamide titanium(II) 1,3-pentadiene,

[0381] (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulene-2-yl)-N-(1,1-dimethylethyl)dimethylsilaneamide 2-(N,N-dimethylamino)benzyltitanium(III),

[0382] (8-Difluoromethylene-1,8-dihydrodibenzo[e,h]azulene-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide Titanium(IV) dichloride,

[0383] (8-difluoromethylene-1,8-dihydrodibenzo[e,h]azulene-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide dimethyltitanium(IV),

[0384] (8-Difluoromethylene-1,8-dihydrodibenzo[e,h]azulene-2-yl)-N-(1,1-dimethylethyl)dimethylsilanamide dibenzyltitanium(IV) and mixtures thereof, in particular mixtures of positional isomers.

[0385] Other illustrative examples of metal complexes used according to the invention correspond to the following formula:

[0386]

[0387] wherein M is titanium in the +2, +3 or +4 oxidation state;

[0388] T is -NR 9 -or-O-;

[0389] R 9 is a hydrocarbyl, silanyl, germyl, dihydrocarbylboryl or halohydrocarbyl group having up to 10 atoms, not counting hydrogen;

[0390] R 10 wherein each occurrence is independently hydrogen, hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, germanyl, halo, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino, hydrocarbylenephosphino, hydrocarbylsulfonyl, halohydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substituted hydrocarbyl, hydrocarbylsiloxy-substituted hydrocarbyl, hydrocarbylsilylamino-substituted hydrocarbyl, di(hydrocarbyl)amino-substituted hydrocarbyl, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino-substituted hydrocarbyl, hydrocarbylenephosphino-substituted hydrocarbyl, or hydrocarbylsulfonyl-substituted hydrocarbyl, wherein R 10 The group has up to 40 atoms excluding hydrogen, and optionally, two or more of the aforementioned adjacent R 10 The groups can be combined to form divalent derivatives, thereby forming saturated or unsaturated fused rings;

[0391] X ais a divalent moiety lacking delocalized π electrons, or a moiety containing a σ-bond and a neutral two-electron pair capable of forming a coordinate-covalent bond with M, wherein X a Contains boron or a member of Group 14 of the Periodic Table and further contains nitrogen, phosphorus, sulfur or oxygen;

[0392] X is a monovalent anionic ligand group having up to 60 atoms, excluding the class of ligands that are cyclic ligand groups that are bound to M via delocalized π electrons, or two X groups together form a divalent anionic ligand group;

[0393] Z, at each occurrence, is independently a neutral coordination compound having up to 20 atoms;

[0394] x is 0, 1, 2, or 3;

[0395] And z is 0 or 1.

[0396] Illustratively, T is =N(CH3), X is a halo or hydrocarbyl group, x is 2, X a is dimethylsilane, z is 0, and R 10 is hydrogen, hydrocarbyl, hydrocarbyloxy, dihydrocarbylamino, hydrocarbyleneamino, dihydrocarbylamino-substituted hydrocarbyl, or hydrocarbyleneamino-substituted hydrocarbyl having up to 20 atoms excluding hydrogen, and optionally, two R 10 Groups can be linked together.

[0397] Exemplary metal complexes of the above formula that can be used to practice the present invention further include the following compounds:

[0398] (tert-Butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silanetitanium(II)1,4-diphenyl-1,3-butadiene,

[0399] (tert-Butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silanetitanium(II)1,3-pentadiene,

[0400] (tert-butylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silane 2-(N,N-dimethylamino)benzyltitanium(III),

[0401] (tert-Butylamido)dimethyl-[6,7]benzo-[4,5:2',3'](1-methylisoindol)-(3H)-inden-2-yl)silane titanium(IV) dichloride,

[0402] (tert-Butylamido)dimethyl-[6,7]benzo-[4,5:2',3'](1-methylisoindol)-(3H)-inden-2-yl)silane dimethyltitanium(IV),

[0403] (tert-butylamido)dimethyl-[6,7]benzo-[4,5:2',3'](1-methylisoindol)-(3H)-inden-2-yl)silane dibenzyltitanium(IV),

[0404] (tert-butylamido)dimethyl-[6,7]benzo-[4,5:2',3'](1-methylisoindol)-(3H)-inden-2-yl)silane bis(trimethylsilyl)titanium(IV),

[0405] (Cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2',3'](1-methylisoindol)-(3H)-inden-2-yl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene,

[0406] (Cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silanetitanium(II) 1,3-pentadiene,

[0407] (Cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silane 2-(N,N-)dimethylamino)benzyltitanium(III),

[0408] (Cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silane titanium(IV) dichloride,

[0409] (Cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silane dimethyltitanium(IV),

[0410] (Cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silane dibenzyltitanium(IV),

[0411] (Cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silane bis(trimethylsilyl)titanium(IV),

[0412] (tert-Butylamido)bis(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silanetitanium(II) 1,4-diphenyl-1,3-butadiene,

[0413] (Cyclohexylamido)dimethyl-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silanetitanium(II) 1,3-pentadiene,

[0414] (tert-butylamido)bis(p-methylphenyl)-[6,7]benzo-[4,5:2',3'](1-methylisoindol)-(3H)-inden-2-yl)silane 2-(N,N-dimethylamino)benzyltitanium(III),

[0415] (tert-Butylamido)bis(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silane titanium(IV) dichloride,

[0416] (tert-butylamido)bis(p-methylphenyl)-[6,7]benzo-[4,5:2',3'](1-methylisoindol)-(3H)-inden-2-yl)silane dimethyltitanium(IV),

[0417] (tert-butylamido)bis(p-methylphenyl)-[6,7]benzo-[4,5:2',3'](1-methylisoindol)-(3H)-inden-2-yl)silane dibenzyltitanium(IV),

[0418] (tert-butylamido)bis(p-methylphenyl)-[6,7]benzo-[4,5:2',3'](1-methylisoindol)-(3H)-inden-2-yl)silanebis(trimethylsilyl)titanium(IV),

[0419] (Cyclohexylamido)bis(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silanetitanium(II) 1,4-phenyl-1,3-butadiene,

[0420] (Cyclohexylamido)bis(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silanetitanium(II) 1,3-pentadiene,

[0421] (Cyclohexylamido)bis(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silane 2-(N,N-dimethylamino)benzyltitanium(III),

[0422] (Cyclohexylamido)bis(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silane titanium(IV) dichloride,

[0423] (Cyclohexylamido)bis(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silane dimethyltitanium(IV),

[0424] (cyclohexylamido)bis(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silane dibenzyltitanium(IV); and

[0425] (Cyclohexylamido)bis(p-methylphenyl)-[6,7]benzo-[4,5:2′,3′](1-methylisoindol)-(3H)-inden-2-yl)silanebis(trimethylsilyl)titanium(IV).

[0426] Illustrative Group 4 metal complexes useful in practicing the present disclosure further include:

[0427] (tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthyl)dimethylsilanedimethyltitanium,

[0428] (tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthyl)dimethylsilanedimethyltitanium,

[0429] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilane dibenzyltitanium,

[0430] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanedimethyltitanium,

[0431] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)-1,2-ethanediyldimethyltitanium,

[0432] (tert-butylamido)(tetramethyl-η 5 -indenyl)dimethylsilanedimethyltitanium,

[0433] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilane 2-(dimethylamino)benzyltitanium(III),

[0434] (tert-butylamido)(tetramethyl-η 5-cyclopentadienyl)dimethylsilane allyltitanium(III),

[0435] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilane 2,4-dimethylpentadienyltitanium(III),

[0436] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II)1,4-diphenyl-1,3-butadiene,

[0437] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II)1,3-pentadiene,

[0438] (tert-Butylamido)(2-methylindenyl)dimethylsilanetitanium(II)1,4-diphenyl-1,3-butadiene,

[0439] (tert-Butylamido)(2-methylindenyl)dimethylsilanetitanium(II)2,4-hexadiene,

[0440] (tert-Butylamido)(2-methylindenyl)dimethylsilanetitanium(IV)2,3-dimethyl-1,3-butadiene,

[0441] (tert-Butylamido)(2-methylindenyl)dimethylsilanetitanium(IV)isoprene,

[0442] (tert-Butylamido)(2-methylindenyl)dimethylsilanetitanium(IV)1,3-butadiene,

[0443] (tert-Butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV)2,3-dimethyl-1,3-butadiene,

[0444] (tert-Butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV)isoprene,

[0445] (tert-Butylamido)(2,3-dimethylindenyl)dimethylsilane dimethyltitanium(IV),

[0446] (tert-Butylamido)(2,3-dimethylindenyl)dimethylsilane dibenzyltitanium(IV),

[0447] (tert-Butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV)1,3-butadiene,

[0448] (tert-Butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(II)1,3-pentadiene,

[0449] (tert-Butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(II)1,4-diphenyl-1,3-butadiene,

[0450] (tert-Butylamido)(2-methylindenyl)dimethylsilanetitanium(II)1,3-pentadiene,

[0451] (tert-Butylamido)(2-methylindenyl)dimethylsilanedimethyltitanium(IV),

[0452] (tert-Butylamido)(2-methylindenyl)dimethylsilane dibenzyltitanium(IV),

[0453] (tert-Butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II)1,4-diphenyl-1,3-butadiene,

[0454] (tert-Butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II)1,3-pentadiene,

[0455] (tert-Butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II)2,4-hexadiene,

[0456] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(IV)1,3-butadiene,

[0457] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(IV)2,3-dimethyl-1,3-butadiene,

[0458] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(IV)isoprene,

[0459] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II) 1,4-dibenzyl-1,3-butadiene,

[0460] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II)2,4-hexadiene,

[0461] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II) 3-methyl-1,3-pentadiene,

[0462] (tert-Butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilane dimethyltitanium

[0463] (tert-Butylamido)(6,6-dimethylcyclohexadienyl)dimethylsilanedimethyltitanium,

[0464] (tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanedimethyltitanium,

[0465] (tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanedimethyltitanium,

[0466] (tert-butylamido)(tetramethyl-η 5 -cyclopentadienylmethylphenylsilane dimethyltitanium (IV),

[0467] (tert-butylamido)(tetramethyl-η 5 -Cyclopentadienylmethylphenylsilanetitanium(II)1,4-diphenyl-1,3-butadiene,

[0468] 1-(tert-butylamido)-2-(tetramethyl- 5 -cyclopentadienyl)ethanediyldimethyltitanium(IV), and

[0469] 1-(tert-butylamido)-2-(tetramethyl- 5 -cyclopentadienyl)ethanediyl-titanium(II) 1,4-diphenyl-1,3-butadiene.

[0470] Other delocalized π-bonded complexes, especially those containing other Group 4 metals, will of course be apparent to those skilled in the art and are disclosed elsewhere: WO 03 / 78480, WO 03 / 78483, WO 02 / 92610, WO 02 / 02577, US 2003 / 0004286 and U.S. Patents 6,515,155, 6,555,634, 6,150,297, 6,034,022, 6,268,444, 6,015,868, 5,866,704 and 5,470,993.

[0471] Other examples of metal complexes suitable for use as catalysts are complexes of polyvalent Lewis bases, such as compounds corresponding to the following formula:

[0472] forward

[0473]

[0474] Where T b is a bridging group, preferably containing 2 or more non-hydrogen atoms,

[0475] X b and Y b Each independently selected from the group consisting of nitrogen, sulfur, oxygen and phosphorus; more preferably X b and Y b It's all nitrogen.

[0476] R b and R b ' is independently hydrogen at each occurrence, or optionally contains one or more heteroatoms C 1-50 A hydrocarbon group or an inertly substituted derivative thereof. Suitable R b and R b Non-limiting examples of R groups include alkyl, alkenyl, aryl, aralkyl, (poly)alkylaryl and cycloalkyl, as well as nitrogen, phosphorus, oxygen and halogen substituted derivatives thereof. Suitable R b and R b Specific examples of the ' group include methyl, ethyl, isopropyl, octyl, phenyl, 2,6-dimethylphenyl, 2,6-di(isopropyl)phenyl, 2,4,6-trimethylphenyl, pentafluorophenyl, 3,5-trifluoromethylphenyl, and benzyl;

[0477] g and g' are each independently 0 or 1;

[0478] M b is a metal element selected from Groups 3 to 15 of the Periodic Table of Elements, or a lanthanide element. b is a Group 3-13 metal, more preferably M b It is a Group 4-10 metal;

[0479] L b is a monovalent, divalent or trivalent anionic ligand containing 1 to 50 atoms, excluding hydrogen. Suitable L b Examples of the group include halogen groups; hydrogen; hydrocarbon groups, hydrocarbonoxy groups; di(hydrocarbyl)amide groups, hydrocarbyleneamide groups, di(hydrocarbyl)phosphine groups, hydrocarbylsulfide groups, hydrocarbonoxy groups, tri(hydrocarbylsilyl)alkyl groups; and carboxylic acid esters. More preferred L b The group is C 1-20 Alkyl, C 7-20 Aralkyl and chlorine;

[0480] h and h' are each independently an integer from 1 to 6, preferably from 1 to 4, more preferably from 1 to 3, and j is 1 or 2, wherein the values ​​h xj are selected to provide charge balance;

[0481] Z b It is with M b The preferred Z is a neutral ligand group containing up to 50 atoms excluding hydrogen. bThe groups include aliphatic and aromatic amines, phosphines and ethers, olefins, alkanedienes and inertly substituted derivatives thereof. Suitable inert substituents include halogen, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, di(hydrocarbyl)amine, tri(hydrocarbyl)silyl and nitrile groups. Preferred Z b The groups include triphenylphosphine, tetrahydrofuran, pyridine, and 1,4-diphenylbutadiene;

[0482] f is an integer from 1 to 3;

[0483] T b , R b and R b ' Two or three of them can be linked together to form a single or multi-ring structure;

[0484] h is an integer from 1 to 6, preferably from 1 to 4, more preferably from 1 to 3;

[0485] represents any form of electronic interaction, in particular coordination or covalent bonds, including multiple bonds, arrows represent coordination bonds, and dashed lines represent optional double bonds.

[0486] In one embodiment, preferably R b Relative to X b Has relatively low steric hindrance. In this embodiment, the most preferred R b The group is a straight chain alkyl, a straight chain alkenyl, a branched chain alkyl, wherein the nearest branch point is from X b At least 3 atoms are removed; and halogenated, dialkylamino, alkoxy or trialkylsilyl substituted derivatives thereof. A highly preferred R in this embodiment b The group is C 1-8 Straight chain alkyl.

[0487] At the same time, in this embodiment, R b 'Relative to Y b Preferably, it has relatively high steric hindrance. b Non-limiting examples of groups include alkyl or alkenyl groups containing one or more secondary or tertiary carbon centers, cycloalkyl, aryl, alkaryl, aliphatic or aromatic heterocyclic groups, organic or inorganic oligomeric, polymeric or cyclic groups, and halo, dialkylamino, alkoxy or trialkylsilyl substituted derivatives thereof. In this embodiment, preferred R b The group contains 3 to 40, more preferably 3 to 30 and most preferably 4 to 20 atoms, excluding hydrogen, and is branched or cyclic. b Examples of groups are structures corresponding to the following formula:

[0488]

[0489] in

[0490] Each R d It is C 1-10 A hydrocarbon group, preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a phenyl group, a 2,6-dimethylphenyl group, a benzyl group or a tolyl group. e It is C 1-10 A hydrocarbon group, preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a phenyl group, a 2,6-dimethylphenyl group, a benzyl group or a tolyl group. d or R e Group or R d and R e The mixture of radicals may together form a polyvalent derivative of a hydrocarbyl group, such as 1,4-butylene, 1,5-pentylene, or a polycyclic, fused-ring, polyvalent hydrocarbyl- or heterohydrocarbyl group, such as naphthalene-1,8-diyl.

[0491] Suitable examples of the aforementioned multivalent Lewis base complexes include:

[0492]

[0493]

[0494] Where R d ' is independently selected at each occurrence from the group consisting of hydrogen and a C1-50 hydrocarbon group or an inert substituted derivative thereof which optionally contains one or more heteroatoms, or further optionally, two adjacent R d 'The groups can together form a divalent bridging group;

[0495] d′ is 4;

[0496] M b’ is a Group 4 metal, preferably titanium or hafnium, or a Group 10 metal, preferably Ni or Pd;

[0497] L b’ is a monovalent ligand having up to 50 atoms excluding hydrogen, preferably a halogen or hydrocarbon group, or two L b’ The groups together form a divalent or neutral ligand group, preferably C 2-50 alkylene, alkyldiyl or alkenyl.

[0498] The polyvalent Lewis base complexes used in the present invention include, inter alia, Group 4 metal derivatives, particularly hafnium derivatives corresponding to the hydrocarbylamine-substituted heteroaryl compounds of the formula:

[0499]

[0500] in:

[0501] R 11is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl and inertly substituted derivatives thereof containing 1 to 30 atoms excluding hydrogen, or a divalent derivative thereof;

[0502] T 1 is a divalent bridging group having 1 to 41 non-hydrogen atoms, preferably 1 to 20 non-hydrogen atoms, and most preferably bridging through a mono- or di-C 1-20 a hydrocarbyl-substituted methylene or silyl group; and

[0503] R 12 It is a C containing Lewis base functional group 5-20 Heteroaryl, in particular pyridin-2-yl or substituted pyridin-2-yl or a divalent derivative thereof;

[0504] M 1 is a Group 4 metal, preferably hafnium;

[0505] X 1 is an anionic, neutral or dianionic ligand group;

[0506] x′ is a number from 0 to 5, indicating this type of X 1 The number of groups; and bonds, optional bonds, and electron donor interactions are represented by lines, dashed lines, and arrows, respectively.

[0507] Suitable complexes are formed by ligand elimination of a hydrogen from an amine group, optionally with the loss of one or more other groups, in particular R 12 Those complexes that cause ligand formation. In addition, the electron donor (preferably an electron pair) from the Lewis base functional group provides additional stability to the metal center. Suitable metal complexes correspond to the following formula:

[0508]

[0509] Among them, M 1 , X 1 , x′, R 11 and T 1 As defined above,

[0510] R 13 , R 14 , R 15 and R 16 is hydrogen, halogen, or an alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, or silane radical having up to 20 atoms excluding hydrogen, or an adjacent R 13 , R 14 , R 15 or R 16 The groups may be linked together to form fused ring derivatives, and bonds, optional bonds and electron pair donor interactions are represented by lines, dashed lines and arrows, respectively. Suitable examples of the foregoing metal complexes correspond to the following formula:

[0511]

[0512] in:

[0513] M 1 , X 1 and x′ are defined as before,

[0514] R 13 , R 14 , R 15 and R 16 As defined above, preferably R 13 , R 14 and R 15 is hydrogen or C 1-4 Alkyl, and R 16 It is C 6-20 Aryl, most preferably naphthyl;

[0515] R a Each is independently C 1-4 alkyl, and a is 1-5, most preferably, R at the two ortho positions of nitrogen a is isopropyl or tert-butyl;

[0516] R 17 and R 18 is independently hydrogen, halogen or C 1-20 Alkyl or aryl; most preferably, R 17 and R 18 One of them is hydrogen and the other is C 6-20 Aryl, particularly 2-isopropyl, phenyl or fused polycyclic aromatic groups, most preferably anthracenyl, and bonds, optional bonds and electron pair donor interactions are represented by lines, dashed lines and arrows, respectively.

[0517] Exemplary metal complexes for use as catalysts herein correspond to the following formula:

[0518]

[0519] Where X 1 Each occurrence is halo, N,N-dimethylamido or C 1-4 alkyl, and preferably each occurrence of X 1 It is methyl;

[0520] R f is independently at each occurrence hydrogen, halogen, C 1-20 Alkyl or C 6-20 Aryl, or two adjacent R f The groups are linked together to form a ring, and f is 1-5; and

[0521] Rc is independently at each occurrence hydrogen, halogen, C 1-20 Alkyl or C 6-20 Aryl, or two adjacent R c The groups are linked together to form a ring, and c is 1-5.

[0522] Examples of metal complexes suitable for use as catalysts according to the invention are complexes of the formula:

[0523]

[0524] Where R x It is C 1-4 alkyl or cycloalkyl, preferably methyl, isopropyl, tert-butyl or cyclohexyl; and

[0525] X 1 Each occurrence is halo, N,N-dimethylamido or C 1-4 Alkyl group, preferably methyl group.

[0526] Examples of metal complexes suitable for use as catalysts according to the present invention include:

[0527] [N-(2,6-bis(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]dimethylhafnium;

[0528] [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)](N,N-dimethylamido)hafnium;

[0529] [N-(2,6-bis(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium dichloride;

[0530] [N-(2,6-bis(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]dimethylhafnium;

[0531] [N-(2,6-bis(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]bis(N,N-dimethylamido)hafnium;

[0532] [N-(2,6-bis(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium dichloride;

[0533] [N-(2,6-bis(1-methylethyl)phenyl)amido)(phenanthrene-5-yl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]dimethylhafnium;

[0534] [N-(2,6-bis(1-methylethyl)phenyl)amido)(phenanthrene-5-yl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]bis(N,N-dimethylamido)hafnium; and

[0535] (N-(2,6-bis(1-methylethyl)phenyl)amido)(phenanthrene-5-yl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium dichloride.

[0536] Under the reaction conditions used to prepare the metal complexes used in the present disclosure, the hydrogen at the 2-position of the α-naphthyl group substituted at the 6-position of the pyridin-2-yl group undergoes an elimination reaction to uniquely form a metal complex in which the metal is covalently bonded to both the resulting amide group and the 2-position of the α-naphthyl group and is stabilized by the coordination of the electron pair of the nitrogen atom to the pyridinyl nitrogen atom.

[0537] Other suitable metal complexes of polyvalent Lewis bases for use herein include compounds corresponding to the following formula:

[0538] in:

[0539] R 20 is an aromatic or inertly substituted aromatic group containing 5 to 20 atoms, excluding hydrogen, or a polyvalent derivative thereof;

[0540] T 3 is an alkylene or silane group having 1 to 20 atoms, excluding hydrogen, or an inert substituted derivative thereof;

[0541] M 3 is a Group 4 metal, preferably zirconium or hafnium;

[0542] G is an anionic, neutral or dianionic ligand group; preferably a halide, a hydrocarbyl, a silane, a trihydrocarbylsilylhydrocarbyl, a trihydrocarbylsilyl or a dihydrocarbylamide group having up to 20 atoms excluding hydrogen;

[0543] g is a number from 1 to 5 indicating the number of such G groups; and bonding and electron donor interactions are represented by lines and arrows, respectively.

[0544] Illustratively, such complexes correspond to the following formula:

[0545] in:

[0546] T 3is a divalent bridging group having 2 to 20 atoms excluding hydrogen, preferably a substituted or unsubstituted C3-6 alkylene group;

[0547] And Ar 2 is independently at each occurrence an arylene group of 6 to 20 atoms, excluding hydrogen, or an arylene group substituted with an alkyl group or an aryl group;

[0548] M 3 is a Group 4 metal, preferably hafnium or zirconium;

[0549] G, at each occurrence, is independently an anionic, neutral, or dianionic ligand group;

[0550] G is a number from 1 to 5 indicating the number of such X groups; and electron donor interactions are indicated by arrows.

[0551] Suitable examples of metal complexes of the foregoing formula include the following compounds:

[0552]

[0553] Among them, M 3 is Hf or Zr;

[0554] Ar 4 It is C 6-20 aryl or an inertly substituted derivative thereof, in particular 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl or anthracen-5-yl, and

[0555] T 4 Include C independently at each occurrence 3-6 Alkylene, C 3-6 Cycloalkylene, or an inertly substituted derivative thereof;

[0556] R 21 is independently at each occurrence hydrogen, halogen, hydrocarbyl having up to 50 atoms excluding hydrogen, trihydrocarbylsilanyl, or trihydrocarbylsilylhydrocarbyl; and

[0557] G at each occurrence is independently halogen, a hydrocarbyl or trihydrocarbylsilyl group having up to 20 atoms not counting hydrogen, or two G groups taken together form a divalent derivative of the foregoing hydrocarbyl or trihydrocarbylsilyl group.

[0558] Suitable compounds are compounds of the formula:

[0559]

[0560] Among them, Ar 4 is 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl or anthracene-5-yl,

[0561] R 21 is hydrogen, halogen or C 1-4 Alkyl groups, especially methyl groups,

[0562] T 4 is propane-1,3-diyl or butane-1,4-diyl, and

[0563] G is chloro, methyl or benzyl.

[0564] Exemplary metal complexes of the foregoing formula are:

[0565]

[0566] Suitable metal complexes for use in accordance with the present disclosure also include compounds corresponding to the following formula:

[0567] in:

[0568] M is zirconium or hafnium;

[0569] R 20 is independently at each occurrence a divalent aromatic or inertly substituted aromatic group containing 5 to 20 atoms, excluding hydrogen;

[0570] T 3 is a divalent hydrocarbon or silane radical having 3 to 20 atoms, excluding hydrogen, or an inert substituted derivative thereof;

[0571] R D is independently at each occurrence a monovalent ligand group having 1 to 20 atoms, excluding hydrogen, or two R D The groups together form a divalent ligand group having 1 to 20 atoms excluding hydrogen.

[0572] This complex may correspond to the following formula:

[0573] in:

[0574] Ar 2 is independently at each occurrence arylene or alkyl, aryl, alkoxy or amino substituted arylene having 6 to 20 atoms excluding hydrogen, or any atom of any substituent;

[0575] T 3 is a divalent hydrocarbon bridging group having 3 to 20 atoms excluding hydrogen, preferably a substituted or unsubstituted divalent C 3-6 an aliphatic, cycloaliphatic or bis(alkylene)-substituted cycloaliphatic group having at least 3 oxygen atoms separating the carbon atoms; and

[0576] R Dis independently at each occurrence a monovalent ligand group having 1 to 20 atoms, excluding hydrogen, or two R D The groups together form a divalent ligand group having 1 to 40 atoms not counting hydrogen.

[0577] Other examples of metal complexes suitable for use herein include compounds of the formula:

[0578] in

[0579] Ar 4 C independently at each occurrence 6-20 Aryl or its inertly substituted derivatives, in particular 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl, naphthyl, anthracen-5-yl, 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl;

[0580] T 4 is independently at each occurrence propene-1,3-diyl, bis(alkylene)cyclohexane-1,2-diyl, or an inert substituted derivative thereof substituted with 1 to 5 alkyl, aryl or aralkyl substituents each having up to 20 carbons;

[0581] R 21 is independently at each occurrence hydrogen, halo, hydrocarbyl having up to 50 atoms excluding hydrogen, trihydrocarbylsilanyl, trihydrocarbylsilylhydrocarbyl, alkoxy, or amino;

[0582] R D is independently at each occurrence a halo group or a hydrocarbyl or trihydrocarbylsilyl group having up to 20 atoms, not counting hydrogen, or 2 R D The radicals together form a divalent hydrocarbylene, hydrocarbyli or trihydrocarbylisilyl radical having up to 40 atoms, not counting hydrogen.

[0583] Exemplary metal complexes are compounds of the formula:

[0584]

[0585] Among them, Ar 4 is independently at each occurrence 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl or anthracen-5-yl,

[0586] R 21 is independently at each occurrence hydrogen, halo, hydrocarbyl having up to 50 atoms excluding hydrogen, trihydrocarbylsilanyl, trihydrocarbylsilylhydrocarbyl, alkoxy, or amino;

[0587] T 4is propane-1,3-diyl or bis(methylene)cyclohexane-1,2-diyl; and

[0588] R D is independently at each occurrence a halo group or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms, not counting hydrogen, or 2 R D The radicals together form a hydrocarbylene, hydrocarbyldiyl or hydrocarbylsilanediyl radical having up to 40 atoms not counting hydrogen.

[0589] Suitable metal complexes according to the present disclosure correspond to the following formula:

[0590]

[0591] Among them, R D is independently at each occurrence chloro, methyl or benzyl.

[0592] Specific examples of suitable metal complexes are the following compounds:

[0593] A) bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyldimethylhafnium(IV),

[0594] Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl hafnium(IV) dichloride,

[0595] Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyldibenzylhafnium(IV),

[0596] Bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyldimethylhafnium(IV),

[0597] Bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyl hafnium(IV) dichloride,

[0598] Bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediyldibenzylhafnium(IV);

[0599] B) bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldimethylhafnium(IV),

[0600] Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyl hafnium(IV) dichloride,

[0601] Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldibenzylhafnium(IV),

[0602] Bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldimethylhafnium(IV),

[0603] Bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyl hafnium(IV) dichloride,

[0604] Bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediyldibenzylhafnium(IV);

[0605] C) bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylhafnium(IV),

[0606] Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyl hafnium(IV) dichloride,

[0607] Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldibenzylhafnium(IV),

[0608] Bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldimethylhafnium(IV),

[0609] Bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyl hafnium(IV) dichloride,

[0610] Bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediyldibenzylhafnium(IV);

[0611] D) bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl dimethyl hafnium(IV),

[0612] Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-(2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl hafnium(IV) dichloride,

[0613] Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-)yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyldibenzyl hafnium(IV),

[0614] Bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl dimethyl hafnium(IV),

[0615] Bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl hafnium(IV) dichloride, and

[0616] Bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyldibenzylhafnium(IV).

[0617] The above metal complexes can be conveniently prepared by standard metallation and ligand exchange procedures involving a transition metal source and a neutral multifunctional ligand source. The techniques employed are the same or similar to those disclosed in USP 6,827,976 and US2004 / 0010103 and elsewhere.

[0618] The metal complex is activated by combining with a cocatalyst to form an active catalyst composition. Activation can occur prior to adding the catalyst composition to the reactor with or without the other components of the reaction mixture, or in situ by adding the metal complex and activating cocatalyst separately to the reactor.

[0619] The above-mentioned multivalent Lewis base complexes are conveniently prepared by standard metalation and ligand exchange procedures involving a source of a Group 4 metal and a source of a neutral multifunctional ligand. Alternatively, the complexes may be prepared starting with the corresponding Group 4 metal tetraamide and a hydrocarbylating agent such as trimethylaluminum by means of amide elimination and hydrocarbylation methods. Other techniques may also be used. These complexes are known from the disclosures of, inter alia, U.S. Patents 6,320,005, 6,103,657, WO 02 / 38628, WO 03 / 40195 and US 04 / 0220050.

[0620] Catalysts with high comonomer incorporation characteristics are also known to reincorporate long chain olefins produced in situ incidentally during polymerization by beta-hydrogen elimination and chain termination or other processes of the growing polymer. The concentration of such long chain olefins is particularly increased by using continuous solution polymerization conditions at high conversions, particularly 95% or greater ethylene conversions, more preferably 97% or greater ethylene conversions. Under such conditions, small but detectable amounts of olefin terminated polymers can be reincorporated into the growing polymer chain, thereby forming long chain branches, that is, branches of greater carbon length that are produced by other intentionally added comonomers. In addition, such chains reflect the presence of other comonomers present in the reaction mixture. That is, depending on the comonomer composition of the reaction mixture, the chains may also include short or long chain branches. Long chain branching of olefin polymers is further described in USP 5,272,236, 5,278,272 and 5,665,800.

[0621] Alternatively, branching, including hyperbranching, can be induced in specific segments of the multi-block copolymers of the present invention by using specific catalysts known to induce "chain walking" in the resulting polymer. For example, branched copolymers can be prepared from single monomers (including ethylene) using certain homogeneous bridged bis-indenyl or partially hydrogenated bis-indenyl zirconium catalysts disclosed in Kaminski et al., J. Mol. Catal. A: Chemical, 102 (1995) 59-65; Zambelli et al., Macromolecules, 1988, 21, 617-622; or Dias et al., J. Mol. Catal. A: Chemical, 185 (2002) 57-64. Higher transition metal catalysts, especially nickel and palladium catalysts, are also known to produce hyperbranched polymers whose branches are also branched, as disclosed in Brookhart et al., J. Am. Chem. Soc., 1995, 117, 64145-6415.

[0622] In one embodiment of the present invention, such branches (long chain branches, 1,3-additions or hyper-branching) present in the polymer of the present invention may be limited to blocks or segments generated by the activity of the first olefin polymerization precatalyst (A). Therefore, in one embodiment of the present disclosure, multi-block copolymers containing blocks or segments in the presence of such branches in combination with other segments or blocks (especially high density or high crystallinity polymer blocks) that are substantially lacking such branches can be made from a reaction mixture containing a single monomer, that is, without the addition of intentionally added comonomers. Very preferably, in a specific embodiment of the present disclosure, multi-block copolymers comprising alternating unbranched ethylene homopolymer segments and branched polyethylene segments (especially ethylene / propylene copolymer segments) can be prepared from an initial reaction mixture that consists essentially of ethylene as an addition polymerizable monomer. The presence of such branches in the multi-block copolymers of the present invention can be detected based on certain physical properties of the resulting copolymers, such as reduced surface defects during melt extrusion (reduced melt fracture), a lower glass transition temperature, Tg (amorphous segments compared to unbranched polymer segments), and / or the presence of 1,3-addition order or hyperbranching, as detected using NMR techniques. The amounts of the foregoing branch types present in the polymers of the present invention (as part of the blocks or segments containing them) are generally from 0.01 to 10 branches per 1,000 carbons.

[0623] Exemplary procatalysts falling within the scope of the first olefin polymerization procatalyst (A) of the present disclosure include, but are not limited to, procatalysts (A1)-(A7), as listed below.

[0624] Catalyst (A1): [N-(2,6-bis(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]dimethylhafnium], prepared according to the teachings of WO 03 / 40195 and WO 04 / 24740 and methods known in the art.

[0625]

[0626] Catalyst (A2): (E)-((2,6-diisopropylphenyl)(2-methyl-3-(octylimino)butan-2-yl)amino)trimethylhafnium, prepared according to methods known in the art.

[0627]

[0628] Precatalyst (A3): [[2',2"'-[1,2-cyclohexanediylbis(methyleneoxy-κO)]bis[3-(9H-carbazol-9-yl)-5-methyl\1,1'-biphenyl]-2-olato-κO]](2-)]dimethylhafnium, prepared according to methods known in the art.

[0629]

[0630] Procatalyst (A4): [[6',6"'-[1,4-butanediylbis(oxy-κO)]bis[3-(9H-carbazol-9-yl)-3'-fluoro-5-methyl-[1,1'-biphenyl]-2-olato-κO]](2-)]-dimethylhafnium, prepared according to methods known in the art.

[0631]

[0632] Procatalyst (A5): [[6',6"'-[1,4-butanediylbis(oxy-κO)]bis[3-(9H-carbazol-9-yl)-3'-fluoro-5-octyl-[1,1'-biphenyl]-2-olato-κO]](2-)]-dimethylhafnium, prepared according to methods known in the art.

[0633]

[0634] Precatalyst (A6): [[6′,6"′-[1,4-butanediylbis(oxy-κO)]bis[3-(9H-carbazol-9-yl)-3′-fluoro-5-(butyldimethylsilyl)-[1,1′-biphenyl]-2-ol-κO]](2-)]-dimethylhafnium, prepared according to methods known in the art.

[0635]

[0636] Procatalyst (A7): (N-((6E)-6-(butylimino-κN)-1-cyclohexen-1-yl)-2,6-bis(1-methylethyl)phenylainate-κN)trimethylhafnium, prepared according to the disclosure of WO2010 / 022228 and methods known in the art.

[0637]

[0638] Second olefin polymerization procatalyst (B)

[0639] The second olefin polymerization procatalyst (B) of the present disclosure comprises a metal-ligand complex of formula (I):

[0640]

[0641] wherein M is titanium, zirconium or hafnium;

[0642] wherein each Z1 is independently a neutral, monoanionic or dianionic monodentate or polydentate ligand, wherein nn is an integer, and wherein Z1 and nn are selected in such a way that the metal-ligand complex of formula (I) is neutral overall;

[0643] Each Q 1 and Q 10 Independently selected from the group consisting of: (C6-C 40 ) aryl, substituted (C6-C 40 ) aryl, (C3-C 40 )heteroaryl, and substituted (C3-C 40 ) heteroaryl;

[0644] Each Q 2 , Q 3 , Q 4 , Q 7 , Q 8 and Q 9 are independently selected from the group consisting of: hydrogen, (C1-C 40 ) alkyl, substituted (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, substituted (C1-C 40 ) heteroalkyl, halogen and nitro (NO2);

[0645] Each Q 5 and Q 6 Independently selected from the group consisting of: (C1-C 40 ) alkyl, substituted (C1-C 40 )alkyl, and [(Si) 1- (C+Si) 40 ] substituted organosilyl;

[0646] wherein each N is independently nitrogen;

[0647] Optionally, Q 1-5 Two or more of the groups are combined together to form a ring structure having from 5 to 16 atoms in the ring, excluding any hydrogen atoms; and

[0648] Optionally, Q 6-10 Two or more of the groups can be combined together to form a ring structure having from 5 to 16 atoms in the ring, excluding any hydrogen atoms.

[0649] In certain embodiments, the second olefin polymerization procatalyst (B) is a hard block / segment catalyst (ie, a low comonomer incorporating agent) of the olefin block copolymers of the present disclosure.

[0650] The metal-ligand complex of formula (I) above and all specific embodiments thereof herein are intended to include every possible stereoisomer, including coordination isomers thereof.

[0651] The metal-ligand complexes of formula (I) described above provide homoleptic as well as heteroleptic procatalyst components.

[0652] In an alternative embodiment, Q 1 , Q 2 , Q 3 , Q 4 , Q 5 , Q 6 , Q 7 , Q 8 , Q 9 and Q 10 Any one or more of (C1-C 40 ) alkyl and (C1-C 40 ) each of the heteroalkyl groups is independently unsubstituted or substituted with one or more R S Substituents, and each R S are independently halogen atoms, polyfluorinated, perfluorinated, unsubstituted (C1-C 18 ) alkyl, (C6-C 18 )aryl, F3C, FCH2O, F2HCO, F3CO, (R C1 )3Si、(R C1 )3Ge、(R C1 )O、(R C1 )S、(R C1 )S(O),(R C1 )S(O)2、(R C1 )2P、(R C1 )2N、(R C1 )2C=N、NC、NO2、(R C1 )C(O)O、(R C1 )OC(O),(R C1 )C(O)N(R C1 ) or (R C1 )2NC(O), or two of the R S together to form an unsubstituted (C1-C 18 ) alkylene, wherein each R S are independently unsubstituted (C1-C 18 )alkyl, and each R C1 are independently hydrogen, unsubstituted (C1-C 18 ) alkyl or unsubstituted (C1-C 18 ) heteroalkyl, or is absent (e.g., absent when N comprises -N=). In certain embodiments, Q 5 and Q 6 With respect to their attachment to the amine nitrogen of the parent ligand structure, each is independently (C1-C 40) primary alkyl or secondary alkyl. The terms primary alkyl and secondary alkyl are given their usual and customary meanings herein; i.e., primary means that the carbon atom directly attached to the ligand nitrogen bears at least two hydrogen atoms, while secondary means that the carbon atom directly attached to the ligand nitrogen bears only one hydrogen atom.

[0653] Optionally, two or more Q 1-5 Group or two or more Q 6-10 Each is independently capable of combining together to form ring structures having from 5 to 16 atoms in the ring excluding any hydrogen atoms.

[0654] In a preferred embodiment, Q 5 and Q 6 Each independently is (C1-C 40 ) a primary or secondary alkyl group and most preferably, Q 5 and Q 6 Each is independently propyl, isopropyl, neopentyl, hexyl, isobutyl and benzyl.

[0655] In certain embodiments, Q in the olefin polymerization procatalyst of formula (I) 1 and Q 10 is substituted by phenyl; as shown in formula (II),

[0656]

[0657] Among them J 1 -J 10 Each independently selected from R s A substituent and hydrogen; and each R S are independently halogen atoms, polyfluorinated, perfluorinated, unsubstituted (C1-C 18 ) alkyl, (C6-C 18 )aryl, F3C, FCH2O, F2HCO, F3CO, (R C1 )3Si、(R C1 )3Ge、(R C1 )O、(R C1 )S、(R C1 )S(O),(R C1 )S(O)2、(R C1 )2P、(R C1 )2N、(R C1 )2C=N、NC、NO2、(R C1 )C(O)O、(R C1 )OC(O),(R C1 )C(O)N(R C1 ) or (R C1 )2NC(O), or two of the R Stogether to form an unsubstituted (C1-C 18 ) alkylene, wherein each R S are independently unsubstituted (C1-C 18 )alkyl, and each R C1 are independently hydrogen, unsubstituted (C1-C 18 ) alkyl or unsubstituted (C1-C 18 ) heteroalkyl, or is absent (e.g., absent when N comprises -N=). More preferably, J in formula (II) 1 , J 5 , J 6 and J 10 are each independently selected from the group consisting of a halogen atom, a (C1-C8) alkyl group, and a (C1-C8) alkoxy group. Most preferably, J in formula (II) 1 , J 5 , J 6 and J 10 Each is independently methyl, ethyl or isopropyl.

[0658] When used to describe certain chemical groups containing carbon atoms (e.g. (C1-C 40 ) alkyl), the bracket expression (C1-C 40 ) can be represented by the form "(Cx-Cy)", which means that the unsubstituted form of the chemical group contains from a number x of carbon atoms to a number y of carbon atoms, wherein each x and y is independently an integer as described for the chemical group. s Depending on the nature of the chemical group, R s Substituted forms may contain more than y carbon atoms. Thus, for example, unsubstituted (C1-C 40 ) alkyl contains 1 to 40 carbon atoms (x = 1 and y = 40). s When substituted with a substituent, the substituted (Cx-Cy) chemical group may contain more than y total carbon atoms; that is, the total number of carbon atoms of the (Cx-Cy) chemical group substituted with one or more carbon-containing substituents is equal to y plus the sum of the number of carbon atoms of each of the one or more carbon-containing substituents. Any atom of a chemical group not specified herein is understood to be a hydrogen atom.

[0659] In some embodiments, the chemical group (e.g., Q 1-10 ) may be unsubstituted, that is, the substituent R S In other embodiments, at least one chemical group in the metal-ligand complex of formula (I) independently contains one or more substituents R SWhen a compound contains two or more substituents R S When each R S independently bonded to the same or different substituted chemical groups. s When bonded to the same chemical group, they are independently bonded to the same or different carbon atoms or heteroatoms (as the case may be) in the same chemical group, up to and including full substitution of the chemical group.

[0660] The term "fully substituted" means that each hydrogen atom (H) bonded to a carbon atom or a heteroatom (as the case may be) in the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S The term "polysubstituted" means that each of at least two, but not all, hydrogen atoms (H) bonded to a carbon atom or a heteroatom (as the case may be) in the corresponding unsubstituted compound or functional group is replaced by a substituent (e.g., R S ) is replaced by a substituent (e.g., R S ) replacement.

[0661] As used herein, the definitions of the terms hydrocarbyl, heterohydrocarbyl, hydrocarbylene, heterohydrocarbylene, alkyl, alkylene, heteroalkyl, heteroalkylene, aryl, arylene, heteroaryl, heteroarylene, cycloalkyl, cycloalkylene, heterocycloalkylene, and heterocycloalkylene are intended to include every possible stereoisomer.

[0662] As used herein, the term "(C1-C 40 )hydrocarbyl" means a hydrocarbon group having 1 to 40 carbon atoms, and the term "(C1-C 40 The term "alkylene" means a hydrocarbon diradical having 1 to 40 carbon atoms, wherein each hydrocarbon group and diradical is independently aromatic (6 carbon atoms or more) or non-aromatic, saturated or unsaturated, straight chain or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic, including bicyclic; 3 carbon atoms or more) or acyclic, or a combination of two or more thereof; and each hydrocarbon group and hydrocarbon diradical is independently the same as or different from another hydrocarbon group and hydrocarbon diradical, and is independently unsubstituted or substituted with one or more R S replace.

[0663] Preferably, (C1-C 40 ) alkyl groups are independently unsubstituted or substituted (C1-C 40 )alkyl, (C3-C 40 )cycloalkyl, (C3-C 20 )cycloalkyl-(C1-C 20 ) alkylene, (C6-C 40) aryl, or (C6-C 20 )aryl-(C1-C 20 ) alkylene. This document includes and discloses (C1-C 40 ) all individual values ​​and subranges of 1 to 40 carbons in the hydrocarbon group; for example (C1-C 40 The upper limit of the range of carbon atoms in the (C1-C1) hydrocarbon group may be 40 carbon atoms, preferably 30 carbon atoms, more preferably 20 carbon atoms, more preferably 15 carbon atoms, more preferably 12 carbon atoms, and most preferably 10 carbon atoms. 40 ) Hydrocarbyl groups include (C1-C 40 ) hydrocarbon group, (C1-C 30 )alkyl) group, (C1-C 20 )alkyl) group, (C1-C 15 )alkyl) group, (C1-C 12 )alkyl) group, (C1-C 10 )alkyl) group, (C 10 -C 30 )alkyl) group, (C 15 -C 40 )alkyl) group, (C5-C 25 )alkyl) group, or (C 15 -C 25 )alkyl) group.

[0664] The term "(C1-C 40 ) alkyl means a saturated straight or branched hydrocarbon group having 1 to 40 carbon atoms, which is unsubstituted or substituted by one or more R S Substituted. Unsubstituted (C1-C 40 Examples of alkyl groups are unsubstituted (C1-C 20 ) alkyl; unsubstituted (C1-C 10 )alkyl; unsubstituted (C1-C5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 2,2-dimethylpropyl, 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 2-ethylhexyl, 1-heptyl; 1-nonyl; and 1-decyl; 2,2,4-trimethylpentyl. Substituted (C1-C5)alkyl; methyl; ethyl; 1-propyl; 2-propyl; 2,2-dimethylpropyl; 1-butyl; 2-butyl; 2-methylpropyl; 1,1-dimethylethyl; 1-pentyl; 1-hexyl; 2-ethylhexyl; 1-heptyl; 1-nonyl; and 1-decyl; 2,2,4-trimethylpentyl. 40 Examples of alkyl groups are substituted (C1-C 20 ) alkyl; substituted (C1-C 10 )alkyl; trifluoromethyl; trimethylsilylmethyl; methoxymethyl; dimethylaminomethyl; trimethylgermanylmethyl; phenylmethyl (benzyl); 2-phenyl-2,2-dimethylethyl; 2-(dimethylphenylsilyl)ethyl; and dimethyl(tert-butyl)silylmethyl.

[0665] The term "(C6-C 40 ) aryl refers to an unsubstituted or substituted (with one or more R s unsubstituted (C6-C 6-substituted) monocyclic, bicyclic or tricyclic aromatic hydrocarbon groups, wherein at least 6 to 14 carbon atoms are aromatic ring carbon atoms, and the monocyclic, bicyclic or tricyclic groups contain 1, 2 or 3 rings, respectively; one of the rings is aromatic and the optional second or third ring is independently fused or unfused and the second or third ring is each independently, optionally aromatic. 40 Examples of aryl groups are unsubstituted (C6-C 20 )aryl; unsubstituted (C6-C 18 )aryl; phenyl; biphenyl; o-terphenyl; m-terphenyl; fluorenyl; tetrahydrofluorenyl; dicyclopentadienylphenyl; hexahydrodicyclopentadienylphenyl; indenyl; dihydroindenyl; naphthyl; tetrahydronaphthyl; phenanthrenyl and triptyl. Substituted (C6-C 40 Examples of aryl groups are substituted (C6-C 20 ) aryl; substituted (C6-C 18 )aryl; 2,6-bis[(C1-C 20 )alkyl]-phenyl; 2-(C1-C5)alkyl-phenyl; 2,6-bis(C1-C5)alkyl-phenyl; 2,4,6-tri(C1-C5)alkyl-phenyl; polyfluorophenyl; pentafluorophenyl; 2,6-dimethylphenyl; 2,6-diisopropylphenyl; 2,4,6-triisopropylphenyl; 2,4,6-trimethylphenyl; 2-methyl-6-trimethylsilylphenyl; 2-methyl-4,6-diisopropylphenyl; 4-methoxyphenyl; and 4-methoxy-2,6-dimethylphenyl.

[0666] The term "(C3-C 40 ) Cycloalkyl refers to a saturated cyclic hydrocarbon group having 3 to 40 carbon atoms, which is unsubstituted or substituted by one or more R S Other cycloalkyl groups (e.g. (C3-C 12 )alkyl) is defined in a similar manner. Unsubstituted (C3-C 40 Examples of cycloalkyl groups are unsubstituted (C3-C 20 )cycloalkyl, unsubstituted (C3-C 10 )cycloalkyl; cyclopropyl; cyclobutyl; cyclopentyl; cyclohexyl; cycloheptyl; cyclooctyl; cyclononyl; cyclodecyl; octahydroindenyl; bicyclo[4.4.0]decyl; bicyclo[2.2.1]heptyl; and tricyclo[3.3.1.1]decyl. Substituted (C3-C 40 Examples of cycloalkyl groups are substituted (C3-C 20 )cycloalkyl; substituted (C3-C 10)cycloalkyl; 2-methylcyclohexyl; and perfluorocyclohexyl.

[0667] (C1-C 40 Examples of alkylene groups are unsubstituted or substituted (C3-C 40 )alkylene; (C6-C 40 ) arylene, (C3-C 40 )cycloalkylene and (C3-C 40 ) alkylene (e.g. (C3-C 20 ) alkylene). In some embodiments, the diradical is located on a terminal atom of the alkylene group, such as a 1,3-α,ω-diradical (e.g., -CH2CH2CH2-) or a 1,5-α,ω-diradical with internal substitution (e.g., -CH2CH2CH(CH3)CH2CH2-). In other embodiments, the diradical is located on a non-terminal atom of the alkylene group, such as in a C72,6-diradical (e.g., ) or a C7 2,6-diyl having an internal substitution (e.g. )middle.

[0668] The term "(C1-C 40 ) heteroalkyl" and "(C1-C 40 ) heteroalkylene" refers to a heteroalkyl or dialkyl having 1 to 40 carbon atoms, each of which independently has one or more heteroatoms or heteroatom groups O, S, N, S(O), S(O)2, S(O)2N, Si(R C1 )2、Ge(R C1 2. P(R C1 )、P(O)(R C1 ) and N(R C1 ), where each R C1 are independently hydrogen, unsubstituted (C1-C 18 ) alkyl or unsubstituted (C1-C 18 ) heteroalkyl or absent (e.g., absent when N comprises -N=). Each (C1-C 40 ) heteroalkyl and (C1-C 40 ) heteroalkylene groups are independently unsubstituted or (substituted by one or more R S ) substituted, aromatic or non-aromatic, saturated or unsaturated, linear or branched, cyclic (including monocyclic and polycyclic, fused and non-fused polycyclic) or acyclic, or a combination of two or more thereof; and each is the same as or different from the other.

[0669] The term "(C1-C 40 ) Alkylene means a group having 1 to 40 carbon atoms which is unsubstituted or substituted with one or more R SSubstituted saturated or unsaturated straight chain or branched diyl. Unsubstituted (C1-C 40 Examples of alkylene groups are unsubstituted (C3-C 20 )alkylene, including unsubstituted 1,3-(C3-C 10 ) alkylene; 1,4-(C4-C 10 )alkylene; -(CH2)3-; -(CH2)4-; -(CH2)5-; -(CH2)6-; -(CH2)7-; -(CH2)8-; and -(CH2)4CH(CH3)-. Substituted (C1-C 40 Examples of alkylene groups are substituted (C3-C 20 )alkylene; -CF2CF2CF2-; and -(CH2) 14 C(CH3)2(CH2)5- (i.e., n-1,20-eicosene substituted with 6,6-dimethyl). As mentioned above, the two R S can be combined to form (C1-C 40 ) alkylene, thus substituted (C1-C 40 Examples of )alkylene groups also include 1,2-bis(methylene)cyclopentane; 1,2-bis(methylene)cyclohexane; 2,3-bis(methylene)-7,7-dimethyl-bicyclo[2.2.1]heptane; and 2,3-bis(methylene)bicyclo[2.2.2]octane.

[0670] The term "(C3-C 40 "Cycloalkylene" refers to a cyclic diradical (i.e., the radical is on a ring atom) having 3 to 40 carbon atoms, which is unsubstituted or substituted by one or more R S Substitution. The chelating substituent is connected to the cycloalkylene group Q of formula (I) 3 The following requirement must also be met on the group: there are at least three atoms in the shortest chain connecting the bridging nitrogen atoms of formula (I). 40 Examples of cycloalkylene are 1,3-cyclobutylene, 1,3-cyclopentylene and 1,4-cyclohexylene. 40 ) Examples of cycloalkylene are 2-trimethylsilyl-1,4-cyclohexylene and 1,2-dimethyl-1,3-cyclohexylene.

[0671] Preferably, (C1-C 40 ) heteroalkyl is independently unsubstituted or substituted (C1-C 40 ) heteroalkyl, (C1-C 40 )alkyl-O-, (C1-C 40 )alkyl-S-, (C1-C 40 )alkyl-S(O)-, (C1-C 40)alkyl-S(O)2-, (C1-C 40 )alkyl-Si(R C1 )2-、(C1-C 40 )alkyl-Ge(R C1 )2-、(C1-C 40 )alkyl-N(R C1 )-、(C1-C 40 )alkyl-P(R C1 )-、(C2-C 40 )heterocycloalkyl, (C2-C 19 )heterocycloalkyl-(C1-C 20 ) alkylene, (C3-C 20 )cycloalkyl-(C1-C 19 )heteroalkylene, (C2-C 19 )heterocycloalkyl-(C1-C 20 )heteroalkylene, (C1-C 40 )heteroaryl, (C1-C 19 )heteroaryl-(C1-C 20 ) alkylene, (C6-C 20 )aryl-(C1-C 19 )heteroalkylene, or (C1-C 19 )heteroaryl-(C1-C 20 )heteroalkylene, wherein each R C1 are independently hydrogen, unsubstituted (C1-C 18 ) alkyl or unsubstituted (C1-C 18 )heteroalkyl, or is absent (e.g., absent when N comprises -N=). The term "(C1-C 40 ) heteroaryl" refers to an unsubstituted or substituted (one or more R S ) substituted monocyclic, bicyclic or tricyclic heteroaromatic hydrocarbon groups, and the monocyclic, bicyclic or tricyclic groups include 1, 2 or 3 rings, respectively, one of which is heteroaromatic, and optionally the second ring and the third ring are independently fused or non-fused; and the second ring or the third ring is optionally and independently heteroaromatic. Other heteroaryl groups (for example (C3-C 12) heteroaryl) is defined in a similar manner. Monocyclic heteroaromatic hydrocarbon groups are 5- or 6-membered rings. The 5-membered rings have 1 to 4 carbon atoms and 4 to 1 heteroatoms, each heteroatom being O, S, N or P, and preferably O, S or N. Examples of 5-membered heteroaromatic hydrocarbon groups are pyrrol-1-yl; pyrrol-2-yl; furan-3-yl; thien-2-yl; pyrazol-1-yl; isoxazol-2-yl; isothiazol-5-yl; imidazole-2-yl; oxazol-4-yl; thiazol-2-yl; 1,2,4-triazole-1-yl; 1,3,4-oxadiazole-2-yl; 1,3,4-thiadiazol-2-yl; tetrazol-1-yl; tetrazol-2-yl; and tetrazol-5-yl. The 6-membered ring has 3 to 5 carbon atoms and 1 to 3 heteroatoms, the heteroatoms being N or P and preferably N. Examples of 6-membered heteroaromatic hydrocarbon groups are pyridin-2-yl; pyrimidin-2-yl; and pyrazin-2-yl, triazinyl. Bicyclic heteroaromatic hydrocarbon groups are preferably fused 5,6- or 6,6-ring systems. Examples of fused 5,6-ring bicyclic heteroaromatic hydrocarbon groups are indol-1-yl; and benzimidazol-1-yl. Examples of fused 6,6-ring bicyclic heteroaromatic hydrocarbon groups are quinolin-2-yl; and isoquinolin-1-yl. Tricyclic heteroaromatic hydrocarbon groups are preferably fused 5,6,5-; 5,6,6-; 6,5,6-; or 6,6,6-ring systems. An example of a fused 5,6,5-ring system is 1,7-dihydropyrrolo[3,2-f]indol-1-yl. An example of a fused 5,6,6-ring system is 1H-benzo[f]indol-1-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,5,6-ring system is 9H-carbazol-9-yl. An example of a fused 6,6,6-ring system is acridin-9-yl.

[0672] The term "[(Si)1-(C+Si) 40 ] "substituted organosilyl" refers to a substituted silyl group having 1 to 40 silicon atoms and 0 to 39 carbon atoms, such that the total number of carbon plus silicon atoms is between 1 and 40. [(Si)1-(C+Si) 40 Examples of the substituted organosilyl group include trimethylsilyl, triisopropylsilyl, dimethylphenylsilyl, diphenylmethylsilyl, triphenylsilyl and triethylsilyl.

[0673] In some embodiments, (C3-C 40 ) heteroaryl is 2,7-disubstituted carbazolyl or 3,6-disubstituted carbazolyl, more preferably wherein each R SThe phenyl group is independently phenyl, methyl, ethyl, isopropyl or tert-butyl, and still more preferably 2,7-di(tert-butyl)-carbazolyl, 3,6-di(tert-butyl)-carbazolyl, 2,7-di(tert-octyl)-carbazolyl, 3,6-di(tert-octyl)-carbazolyl, 2,7-diphenylcarbazolyl, 3,6-diphenylcarbazolyl, 2,7-bis(2,4,6-trimethylphenyl)-carbazolyl or 3,6-bis(2,4,6-trimethylphenyl)-carbazolyl.

[0674] As used herein, "heteroalkyl" and "heteroalkylene" groups are saturated straight or branched chain groups or diradicals, respectively, containing (C1-C 40 ) carbon atoms and one or more of the following heteroatoms or heteroatom groups: O, S, N, S(O), S(O)2, S(O)2N, Si(R C1 )2、Ge(R C1 2. P(R C1 )、P(O)(R C1 ) and N(R C1 ), as defined above, wherein each of heteroalkyl and heteroalkylene is independently unsubstituted or substituted with one or more R S Replace, and each R C1 are independently hydrogen, unsubstituted (C1-C 18 ) alkyl or unsubstituted (C1-C 18 ) heteroalkyl, or is absent (eg, absent when N comprises -N=). Examples of substituted and unsubstituted heteroalkyl are methoxy; ethoxy; trimethylsilyl; dimethylphenylsilyl; tert-butyldimethylsilyl; and dimethylamino.

[0675] The heteroalkyl group may optionally be cyclic, i.e., heterocycloalkyl. 40 Examples of heterocycloalkyl groups are unsubstituted (C3-C 20 )heterocycloalkyl, unsubstituted (C3-C 10 )heterocycloalkyl, oxetan-2-yl, tetrahydrofuran-3-yl, pyrrolidin-1-yl, tetrahydrothiophene-S,S-dioxide-2-yl, morpholin-4-yl, 1,4-dioxane-2-yl, hexahydroazol-4-yl, 3-oxa-cyclooctyl, 5-thioxo-cyclononyl and 2-aza-cyclodecyl.

[0676] The term "halogen atom" means a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br) or an iodine atom (I) group. Preferably, each halogen atom is independently a Br, F or Cl group, and more preferably a F or Cl group. The term "halide" means a fluoride (F-), chloride (Cl-), bromide (Br-) or iodide (I-) anion.

[0677] Preferably, in the metal-ligand complex of formula (I), except the OS bond in the S(O) or S(O)2 diradical functional group, there is no OO, SS or OS bond. More preferably, in the metal-ligand complex of formula (I), except the OS bond in the S(O) or S(O)2 diradical functional group, there is no OO, PP, SS or OS bond.

[0678] The term "saturated" means lacking carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus, and carbon-silicon double and carbon-nitrogen triple bonds. S When substituted, one or more double bonds and / or triple bonds may or may not be present in the substituent R. S The term "unsaturated" means containing one or more carbon-carbon double bonds, carbon-carbon triple bonds, and (in heteroatom-containing groups) carbon-nitrogen, carbon-phosphorus and carbon-silicon double bonds and carbon-nitrogen triple bonds, excluding those that may be present in the substituent R S any such double or triple bonds in the aromatic ring (if any) or (hetero)aromatic ring (if any).

[0679] M is titanium, zirconium or hafnium. In one embodiment, M is titanium. In another embodiment, M is zirconium. In another embodiment, M is hafnium. In some embodiments, M is in a formal oxidation state of +2, +3 or +4. Each Z1 is independently a neutral, monoanionic or dianionic monodentate or multidentate ligand. Z1 and nn are selected in such a way that the metal-ligand complex of formula (I) is neutral overall. In some embodiments, each Z1 is independently a monodentate ligand. In one embodiment, when there are two or more Z1 monodentate ligands, each Z1 is the same. In some embodiments, the monodentate ligand is a monoanionic ligand. The monoanionic ligand has a net formal oxidation state of -1. Each monoanionic ligand can independently be hydrogen, (C1-C 40 ) Hydrocarbyl carbon anion, (C1-C 40 ) heteroalkyl carbanions, halides, nitrates, carbonates, phosphates, borates, borohydrides, sulfates, HC(O)O-, alkoxides or aryl oxides (RO - )、(C1-C 40 ) hydrocarbon group C(O)O-, HC(O)N(H)-, (C1-C 40 )C(O)N(H)-, (C1-C 40 )alkylC(O)N((C1-C 20 )alkyl)-, R K R L B-, R K R L N-、RK O-、R K S-, R K R L P- or R M R K R L Si-, where each R K , R L and R M are independently hydrogen, (C1-C 40 ) alkyl or (C1-C 40 ) heteroalkyl, or R K and R L Connected together to form (C2-C 40 )alkylene or (C1-C 40 )heteroalkylene and R M As defined above.

[0680] In some embodiments, at least one monodentate ligand of Z1 is independently a neutral ligand. In one embodiment, the neutral ligand is a neutral Lewis base group, i.e., R X1 NR K R L , R K OR L , R K SR L or R X1 PR K R L , where each R X1 are independently hydrogen, (C1-C 40 ) alkyl, [(C1-C 10 )alkyl]3Si, [(C1-C 10 )alkyl]3Si(C1-C 10 ) alkyl or (C1-C 40 ) heteroalkyl, and each R K and R L Independently as defined above.

[0681] In some embodiments, each Z1 is a monodentate ligand which is independently a halogen atom, an unsubstituted (C1-C 20 ) alkyl, unsubstituted (C1-C 20 )C(O)O- or R K R L N-, where R K and R L Each of which is independently unsubstituted (C1-C 20 In some embodiments, each monodentate ligand Z1 is a chlorine atom, (C 1-C10) hydrocarbon group (e.g. (C1-C6) alkyl or benzyl), unsubstituted (C1-C 10 )C(O)O- or R K R L N-, where R K and R L Each of which is independently unsubstituted (C1-C 10 ) hydrocarbon group.

[0682] In some embodiments, there are at least two Z1 and the two Z1 are linked together to form a bidentate ligand. In some embodiments, the bidentate ligand is a neutral bidentate ligand. In one embodiment, the neutral bidentate ligand is of formula (R D1 )2C=C(R D1 )-C(R D1 )=C(R D1 )2, wherein each R D1 R is independently H, unsubstituted (C1-C6) alkyl, phenyl or naphthyl. In some embodiments, the bidentate ligand is a monoanionic-mono(Lewis base) ligand. The monoanionic-mono(Lewis base) ligand can be a 1,3-diketoate ester of formula (D): R E1 -C(O-)=CH-C(=O)-R E1 (D), where each R E1 is independently H, unsubstituted (C1-C6) alkyl, phenyl or naphthyl. In some embodiments, the bidentate ligand is a dianionic ligand. The net formal oxidation state of the dianionic ligand is -2. In one embodiment, each dianionic ligand is independently carbonate, oxalate (i.e., -O2CC(O)O-), (C2-C 40 )alkylene dicarbon anion, (C1-C 40 )heteroalkylene dicarbonyl anion, phosphate or sulfate.

[0683] As mentioned previously, the number and charge (neutral, monoanionic, dianionic) of Z1 are selected according to the formal oxidation state of M such that the metal-ligand complex of formula (I) is neutral overall.

[0684] In some embodiments, each Z1 is the same, wherein each Z1 is methyl; isobutyl; neopentyl; neophenyl; trimethylsilylmethyl; phenyl; benzyl or chlorine. In some embodiments, nn is 2 and each Z1 is the same.

[0685] In some examples, at least two Z1 are different. In some embodiments, each Z1 is different from methyl; isobutyl; neopentyl; neophenyl; trimethylsilylmethyl; phenyl; benzyl; and chlorine.

[0686] In one embodiment, the metal-ligand complex of formula (I) is a mononuclear metal complex. In another embodiment, the olefin polymerization catalyst system of the present invention exhibits reversible chain transfer, indicating that chain shuttling behavior occurs in the presence of an appropriate chain shuttling agent. This combination of properties is of great interest in the preparation of olefin block copolymers. In general, the ability to adjust alpha-olefin incorporation and thereby the distribution of short chain branches is critical to obtaining materials with performance differences.

[0687] In some embodiments, the metal-ligand complex of formula (I) is a metal-ligand complex of formula (II):

[0688]

[0689] Among them J 1 -J 10 Each independently selected from R s A substituent (as defined above) and hydrogen.

[0690] In a specific embodiment, J in formula (II) 1 , J 5 , J 6 and J 10 Each is independently selected from the group consisting of a halogen atom, a (C1-C8) alkyl group and a (C1-C8) alkoxy group.

[0691] The structure of the metal-ligand complex described by formula (I) is shown below:

[0692]

[0693]

[0694]

[0695]

[0696] Co-catalyst / activator

[0697] An activator is an additive that renders the procatalyst active with respect to olefin polymerization by contacting the olefin with the procatalyst or by combining the procatalyst with the olefin. Common activators abstract a monoanionic ligand, typically an alkyl group, in some cases a benzyl or methyl group, thereby forming a cationic metal-ligand complex of the procatalyst with a weakly coordinating or non-coordinating anion derived or present as part of the activator. This type of activator includes, for example, Bronsted acids ( acid), such as [R3NH] +(ammonium) activators, such as N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate); and Lewis acids, such as alkylaluminums, polymeric or oligomeric alumoxanes (also known as aluminoxanes), boranes (such as tris(pentafluorophenyl)borane) or carbon cation species (such as triphenylmethyl tetrakis(pentafluorophenyl)borate). When alumoxane is used alone as an activator, preferably, the number of moles of alumoxane used is at least 100 times the number of moles of the metal-ligand complex. Lower alumoxane loadings do not act as activators, but rather as scavengers. The scavenger chelates impurities in the reactor before the catalyst is added and therefore does not constitute an activator.

[0698] Activating cocatalysts suitable for use herein include alkylaluminums; polymeric or oligomeric alumoxanes (alumoxanes) (also referred to as aluminoxanes); neutral Lewis acids; and non-polymeric, non-coordinating ion-forming compounds (including the use of such compounds under oxidizing conditions). A suitable activation technique is bulk electrolysis. Combinations of one or more of the foregoing activating cocatalysts and techniques are also contemplated. The term "alkylaluminum" means a monoalkylaluminum dihydride or a monoalkylaluminum dihalide, a dialkylaluminum hydride or a dialkylaluminum halide or a trialkylaluminum. Aluminoxanes and their preparation are known, for example, in U.S. Patent No. (USPN) US 6,103,657. Examples of preferred polymeric or oligomeric aluminoxanes are methylaluminoxane, triisobutylaluminum-modified methylaluminoxane, and isobutylaluminoxane.

[0699] Exemplary Lewis acid activating cocatalysts are Group 13 metal compounds containing 1 to 3 hydrocarbyl substituents as described herein. In some embodiments, exemplary Group 13 metal compounds are tri(hydrocarbyl)-substituted aluminum or tri(hydrocarbyl)-boron compounds. In some other embodiments, exemplary Group 13 metal compounds are tri(C1-C 10 )alkyl)aluminum or tri((C6-C 18 In some other embodiments, the exemplary Group 13 metal compound is tri(fluorophenyl)borane, and in other embodiments, tri(pentafluorophenyl)borane. In some embodiments, the activating cocatalyst is tri((C1-C 20 )alkyl)methane borate (e.g. trityltetrakis(pentafluorophenyl)borate) or tris((C1-C 20 )alkyl)ammonium tetra((C1-C 20 ) alkyl) borate (e.g., bis(octadecyl)methylammoniumtetrakis(pentafluorophenyl)borate). As used herein, the term "ammonium" refers to a nitrogen cation, which is ((C1-C 20 )alkyl)4N+, ((C1-C 20 )alkyl)3N(H)+, ((C1-C 20)alkyl)2N(H)2+, (C1-C 20 ) hydrocarbon group N(H)3+ or N(H)4+, wherein each (C1-C 20 ) The hydrocarbon groups may be the same or different.

[0700] Exemplary combinations of neutral Lewis acid activated cocatalysts include mixtures comprising tri((C1-C4)alkyl)aluminum and tri((C6-C 18 In some embodiments, the present invention relates to a combination of a neutral Lewis acid mixture with a polymeric or oligomeric aluminoxane and a combination of a single neutral Lewis acid (especially tris(pentafluorophenyl)borane) with a polymeric or oligomeric aluminoxane. In some embodiments, the molar ratio of (metal-ligand complex):(tris(pentafluoro-phenylborane):(aluminoxane) [e.g., (Group 4 metal-ligand complex):(tris(pentafluoro-phenylborane):(aluminoxane)] is 1:1:1 to 1:10:30, and other exemplary embodiments are 1:1:1.5 to 1:5:10.

[0701] Various activating cocatalysts and activation techniques have been previously taught in conjunction with various metal-ligand complexes in the following USPNs: US 5,064,802; US 5,153,157; ​​US 5,296,433; US 5,321,106; US 5,350,723; US 5,425,872; US 5,625,087; US 5,721,185; US 5,783,512; US 5,883,204; US 5,919,983; US 6,696,379; and US 7,163,907. Examples of suitable hydrocarbyl oxides are disclosed in US 5,296,433. Examples of Bronsted salts suitable for addition polymerization catalysts are disclosed in US 5,064,802; US 5,919,983; US 5,783,512. Examples of salts of cationic oxidants and non-coordinating compatible anions suitable as activating co-catalysts for addition polymerization catalysts are disclosed in US 5,321,106. Examples of carbocation salts suitable as activating co-catalysts for addition polymerization catalysts are disclosed in US 5,350,723. Examples of silanol salts suitable as activating co-catalysts for addition polymerization catalysts are disclosed in US 5,625,087. Examples of suitable complexes of alcohols, thiols, silanols and oximes with tris(pentafluorophenyl)borane are disclosed in US 5,296,433. Some of these catalysts are also described in a portion of US 6,515,155 Bl starting at column 50, line 39 through column 56, line 55, only said portion being incorporated herein by reference.

[0702] In some embodiments, the procatalyst of the present disclosure can be activated by combining with one or more cocatalysts (such as a cationic cocatalyst, a strong Lewis acid, or a combination thereof) to form an active catalyst composition. Suitable cocatalysts include polymeric or oligomeric aluminoxanes, especially methylaluminoxane and inert, compatible, non-coordinating ion-forming compounds. Suitable exemplary cocatalysts include, but are not limited to, modified methylaluminoxane (MMAO), bis(hydrogenated tallow alkyl)methylammonium tetra(pentafluorophenyl)borate, triethylaluminum (TEA), and any combination thereof.

[0703] In some embodiments, one or more of the aforementioned activating cocatalysts are used in combination with one another. A particularly preferred combination is a mixture of tri((C1-C4)hydrocarbyl)aluminum, tri((C1-C4)hydrocarbyl)borane or ammonium borate with an oligomeric or polymeric aluminoxane compound. In an exemplary embodiment of the present disclosure, the cocatalyst is [(C 16-18 H 33-37 )2CH3NH]tetrakis(pentafluorophenyl)borate.

[0704] The ratio of the total moles of one or more catalysts to the total moles of one or more activating cocatalysts is 1:10,000 to 100:1. In some embodiments, the ratio is at least 1:5000, in some other embodiments, at least 1:1000; and 10:1 or less, and in some other embodiments, 1:1 or less. When a single aluminoxane is used as an activating cocatalyst, preferably, the moles of aluminoxane used are at least 100 times the moles of catalyst. When a single tris(pentafluorophenyl)borane is used as an activating cocatalyst, in some other embodiments, the moles of tris(pentafluorophenyl)borane used are 1:0.5 to 1:10, in some other embodiments, 1:1 to 1:6, and in some other embodiments, 1:1 to 1:5 relative to the total moles of one or more catalysts. The remaining activating cocatalyst is typically employed in a mole number approximately equal to the total moles of the one or more catalysts.

[0705] Aggregation methods

[0706] Any conventional polymerization method can be used to produce block copolymers according to the present disclosure. Such conventional polymerization methods include, but are not limited to, solution polymerization methods, gas phase polymerization methods, slurry or particle formation polymerization methods, and combinations thereof, using one or more conventional reactors, such as loop reactors, isothermal reactors, fluidized bed reactors, stirred tank reactors, batch reactors in parallel, in series, and / or any combination thereof.

[0707] In certain embodiments of the present disclosure, a multi-block copolymer is prepared by a solution polymerization process using a first olefin polymerization procatalyst (A), a second olefin polymerization procatalyst (B), one or more cocatalysts, and a chain shuttling agent (C).

[0708] The polymerization method of the present disclosure using the first olefin polymerization procatalyst A, the second olefin polymerization procatalyst B, one or more cocatalysts and the chain shuttling agent C can be further referred to Figure 1 , where there is an illustrative activated catalyst site A 10 which, under polymerization conditions, forms a polymer chain 13 attached to active catalyst site 12. Similarly, active catalyst site B 20 produces a different polymer chain 23 which is attached to active catalyst site 22. Chain shuttling agent C1 attached to polymer chain 14 produced by active catalyst B causes its polymer chain 23 to exchange with polymer chain 13 attached to catalyst site A. Additional chain growth under polymerization conditions results in the formation of a multi-block copolymer 18 attached to active catalyst site A. Similarly, chain shuttling agent C2 attached to polymer chain 24 produced by active catalyst site A causes its polymer chain 13 to exchange with polymer chain 23 attached to catalyst site B. Additional chain growth under polymerization conditions results in the formation of a multi-block copolymer 28 attached to active catalyst site B. The growing multi-block copolymer repeatedly exchanges between active catalyst A and active catalyst B with the aid of shuttling agent C, thereby forming blocks or segments of different nature each time an exchange occurs with an opposite active catalyst site. The growing polymer chain can be recovered while attached to the chain shuttling agent and functionalized if necessary. Alternatively, the resulting polymer can be recovered by cleavage from the active catalyst site or shuttling agent using a proton source or other killing agent.

[0709] It is believed (without wishing to be bound by such belief) that the composition of the respective segments or blocks, especially the composition of the terminal segments of the polymer chains, can be influenced by the selection of process conditions or other process variables. In the polymers of the present invention, the properties of the terminal segments are determined by the relative rates of chain transfer or termination of the respective catalysts and the relative rates of chain shuttling. Possible chain termination mechanisms include, but are not limited to, β-hydrogen elimination, β-hydrogen transfer to monomer, β-methyl elimination, and chain transfer to hydrogen or other chain terminating agents, such as organosilanes or chain functionalizing agents. Thus, when low concentrations of chain shuttling agents are used, a large fraction of the polymer chain ends will be generated in the polymerization reactor by one of the aforementioned chain termination mechanisms, and the relative rates of chain termination of catalysts (A) and (B) will determine the dominant chain termination fraction. That is, the catalyst with the fastest chain termination rate will produce relatively more chain end segments in the finished polymer.

[0710] In contrast, when a high concentration of chain shuttling agent is used, a majority of polymer chains within the reactor and exiting the polymerization zone are attached or bound to the chain shuttling agent. Under these reaction conditions, the relative rates of chain transfer of the polymerization catalysts and the relative rates of chain shuttling of the two catalysts primarily determine the identity of the chain-terminating moieties. If catalyst (A) has a faster chain transfer and / or chain shuttling rate than catalyst (B), then the majority of the chain-ending moieties will be those produced by catalyst (A).

[0711] At moderate concentrations of chain shuttling agents, all three of the above factors contribute to determining the properties of the final polymer blocks. The above methods can be extended to the analysis of multiblock polymers with more than two block types and used to control the average block length and block order of these polymers. For example, a mixture of catalysts 1, 2, and 3 with chain shuttling agents, where each catalyst type forms a different type of polymer block, produces a linear block copolymer with three different block types. In addition, for the three catalysts, if the ratio of shuttling rate to growth rate follows the order 1>2>3, then the average block length of the three block types will follow the order 3>2>1, and the situation where a type 2 block is adjacent to a type 3 block is less than the situation where a type 1 block is adjacent to a type 2 block.

[0712] Thus, it can be seen that there is a method for controlling the block length distribution of different block types. For example, by selecting catalysts 1, 2, and 3 (where 2 and 3 produce essentially the same polymer block type) and a chain shuttling agent, and the shuttling rates follow the order 1>2>3, the resulting polymer will have a bimodal distribution of block lengths produced by the 2nd and 3rd catalysts.

[0713] During polymerization, a reaction mixture containing one or more monomers is contacted with an activated catalyst composition according to any suitable polymerization conditions. The process is characterized by the use of elevated temperature and pressure. If necessary, hydrogen can be used as a chain transfer agent to control the molecular weight according to known techniques. As with other similar polymerization reactions, it is highly desirable that the monomers and solvents used have sufficiently high purity so that catalyst deactivation does not occur. Any suitable monomer purification technique can be used, such as removing volatile components under reduced pressure, contacting with molecular sieves or high surface area alumina, or a combination of the above methods. Those skilled in the art will understand that the ratio of chain shuttling agent to one or more catalysts and / or monomers in the process of the present invention can be varied to produce polymers that differ in one or more chemical or physical properties. In the present invention, particularly in slurry or gas phase polymerization, a support can be used. Suitable supports include solid particulate high surface area metal oxides, metalloid oxides, or mixtures thereof (interchangeably referred to herein as inorganic oxides). Examples include: talc, silica, alumina, magnesia, titania, zirconium oxide, Sn2O3, aluminosilicates, borosilicates, clays, and mixtures thereof. Suitable carriers preferably have a density of 10 to 1000 m 2 / g and preferably 100 to 600 m 2 The surface area of ​​the particles is 1000 μm, preferably 1000 μm, more preferably 1000 μm, and 1000 μm.

[0714] In one embodiment of the present invention, the catalyst composition of the present invention and optional support can be spray dried or otherwise recovered in solid particulate form to provide a composition that is easy to transport and handle. Suitable methods for spray drying liquid-containing slurries are well known in the art and can be effectively used herein. Preferred techniques for spray drying catalyst compositions for use herein are described in US-A's-5,648,310 and 5,672,669.

[0715] The polymerization is preferably carried out as a continuous polymerization, preferably as a continuous solution polymerization, wherein the catalyst components, shuttling agents, monomers and optional solvents, adjuvants, scavengers and polymerization aids are continuously supplied to the reaction zone and the polymer product is continuously removed therefrom. Those processes in which there is intermittent addition of reactants and removal of the product at regular or irregular time intervals so that the overall process is substantially continuous over time fall within the scope of the terms "continuous" and "continuously" as used herein. The catalyst composition can be advantageously used in high pressure, solution, slurry or gas phase polymerization processes. For solution polymerization processes, it is desirable to use a homogeneous dispersion of the catalyst components in a liquid diluent in which the polymer is soluble under the polymerization conditions used. One such process is disclosed in US-A-5,783,512, which utilizes extremely fine silica or a similar dispersant to produce such a homogeneous catalyst dispersion in which only the metal complex of the co-catalyst is poorly soluble. Solution processes, particularly continuous solution processes, for preparing the novel polymers of the present invention are preferably carried out at temperatures between 80°C and 250°C, more preferably between 100°C and 210°C, and most preferably between 110°C and 210°C. High pressure processes are typically carried out at temperatures of 100°C to 400°C and pressures above 500 bar (50 MPa). Slurry processes typically use an inert hydrocarbon diluent and a temperature of 0°C to just below the temperature at which the resulting polymer is substantially soluble in the inert polymerization medium. The preferred temperature for slurry polymerization is 30°C, preferably 60°C to 115°C, preferably up to 100°C. Pressures are typically in the range of atmospheric pressure (100 kPa) to 500 psi (3.4 MPa). In all of the above processes, continuous or substantially continuous polymerization conditions are preferably used. The use of such polymerization conditions, particularly continuous solution polymerization processes using two or more active polymerization catalyst species, allows the use of elevated reactor temperatures, thereby economically producing multi-block or segmented copolymers with high yields and efficiencies. Both homogeneous and plug flow reaction conditions can be used. The latter conditions are preferred where a gradual decrease in block composition is desired.

[0716] Both catalyst compositions (A) and (B) can be prepared as homogeneous compositions by adding the necessary metal complexes to the solvent in which the polymerization is to be carried out or to a diluent that is compatible with the final reaction mixture. Desired cocatalysts or activators and shuttling agents can be combined with the catalyst composition before, simultaneously with, or after combining with the monomers to be polymerized and any additional reaction diluent.

[0717] The individual ingredients as well as any active catalyst composition must be kept away from oxygen and moisture at all times. Therefore, the catalyst components, shuttling agents and activated catalysts must be prepared and stored in an oxygen- and moisture-free atmosphere, preferably a dry inert gas such as nitrogen.

[0718] Without limiting the scope of the invention in any way, one way to carry out such a polymerization process is as follows. The monomer to be polymerized is continuously introduced into a stirred tank reactor together with any solvent or diluent. The reactor contains a liquid phase consisting essentially of the monomer and any solvent or diluent and dissolved polymer. Preferred solvents include C 4-10 Hydrocarbon or its mixture, especially alkane (such as hexane) or alkane mixture, and one or more monomers used in polymerization. The procatalyst is continuously or intermittently introduced into the reactor liquid phase or any recycle part thereof together with the cocatalyst and chain shuttling agent. The reactor temperature and pressure can be controlled by adjusting the solvent / monomer ratio, the catalyst addition rate and by cooling or heating coils, jackets or both. The polymerization rate is controlled by the catalyst addition rate. The ethylene content of the polymer product is determined by the ratio of ethylene to comonomer in the reactor, and the ratio is controlled by manipulating the corresponding feed rates of these components to the reactor. As is well known in the art, the polymer product molecular weight is optionally controlled by controlling other polymerization variables (such as temperature, monomer concentration or the aforementioned chain transfer agent). When leaving the reactor, the effluent is contacted with a catalyst killer (such as water, steam or alcohol). The polymer solution is optionally heated, and the polymer product is recovered by flashing off gaseous monomers and residual solvents or diluents under reduced pressure, and if necessary, volatiles are further removed in equipment such as devolatilization extruders. In a continuous process, the average residence time of the catalyst and polymer in the reactor is generally from 5 minutes to 8 hours, and preferably from 10 minutes to 6 hours.

[0719] Alternatively, the aforementioned polymerization can be carried out in a continuous loop reactor with or without established monomer, catalyst or shuttling agent gradients between different zones, optionally with separate addition of catalyst and / or chain transfer agent and operated under adiabatic or non-adiabatic solution polymerization conditions or a combination of the aforementioned reactor conditions. Examples of suitable loop reactors and various operating conditions suitable therefor are found in USP 5,977,251, 6,319,989 and 6,683,149.

[0720] Although undesirable, the catalyst composition may also be prepared and used as a heterogeneous catalyst by adsorbing the necessary components onto an inorganic or organic inert particulate solid, as disclosed hereinbefore. In a preferred embodiment, the heterogeneous catalyst is prepared by coprecipitating the reaction product of a metal complex and an inert inorganic compound with an activator containing an active hydrogen, particularly the reaction product of a tri(C1.4 alkyl)aluminum compound and an ammonium salt of a hydroxyaryltri(pentafluorophenyl)borate, such as an ammonium salt of (4-hydroxy-3,5-di-tert-butylphenyl)tris(pentafluorophenyl)borate. When prepared in a heterogeneous or supported form, the catalyst composition may be used in slurry or gas phase polymerizations. As a practical limitation, slurry polymerization occurs in a liquid diluent in which the polymer product is substantially insoluble. Preferably, the diluent for the slurry polymerization is one or more hydrocarbons having less than 5 carbon atoms. If desired, a saturated hydrocarbon such as ethane, propane or butane may be used in whole or in part as a diluent. As with solution polymerization, an α-olefin comonomer or a combination of different α-olefin monomers may be used in whole or in part as a diluent. Most preferably, at least a majority of the diluent comprises the α-olefin monomer or monomers to be polymerized.

[0721] Preferably, for use in a gas phase polymerization process, the support material and resulting catalyst has a median particle size of 20 to 200 μm, more preferably 30 to 150 μm and most preferably 50 to 100 μm. Preferably, for use in a slurry polymerization process, the support has a median particle size of 1 to 200 μm, more preferably 5 to 100 μm and most preferably 10 to 80 μm.

[0722] Gas phase polymerization processes suitable for use herein are substantially similar to the known processes used commercially on a large scale to produce polypropylene, ethylene / α-olefin copolymers and other olefin polymers. The gas phase process used may be, for example, of the type using a mechanically stirred bed or a gas fluidized bed as the polymerization reaction zone. Preferred are processes in which the polymerization reaction is carried out in a vertical cylindrical polymerization reactor containing a fluidized bed of polymer particles supported or suspended on a perforated plate or fluidizing grid and flowed by a fluidizing gas.

[0723] The gas used to fluidize the bed contains one or more monomers to be polymerized and is also used as a heat exchange medium to remove the heat of reaction from the bed. The hot gas is usually discharged from the top of the reactor through a stable zone (also called a slowdown zone) that has a wider diameter than the fluidized bed and where fine particles entrained in the gas stream have a chance to move back into the bed. It can also be advantageous to use a cyclone separator to remove ultrafine particles from the hot gas stream. The gas is then typically recycled to the bed by means of a blower or compressor and one or more heat exchangers that remove the heat of polymerization from the gas.

[0724] In addition to cooling provided by the cooled recycle gas, a preferred method of cooling the bed is to supply a volatile liquid to the bed to provide an evaporative cooling effect, commonly referred to as a condensing mode of operation. The volatile liquid used in this case may be, for example, a volatile inert liquid, such as a saturated hydrocarbon having 3 to 8, preferably 4 to 6 carbon atoms. In the case where the monomer or comonomer itself is a volatile liquid, or can be condensed to provide such a liquid, this can be appropriately added to the bed to provide an evaporative cooling effect. The volatile liquid evaporates in the hot fluidized bed to form a gas that mixes with the fluidizing gas. If the volatile liquid is a monomer or comonomer, it will undergo some polymerization in the bed. The evaporated liquid is then discharged from the reactor as part of the hot cycle gas and enters the compression / heat exchange portion of the circulation loop. The recycle gas is cooled in the heat exchanger, and if the temperature of the gas after cooling is below the dew point, the liquid will precipitate from the gas. This liquid is preferably continuously recycled to the fluidized bed. The precipitated liquid can be recycled to the bed in the form of droplets carried in the recycle gas stream. This type of process is described, for example, in EP-89691; US4,543,399; WO-94 / 25495 and US5,352,749. A particularly preferred method for recycling liquid into the bed is to separate liquid from the recirculating gas stream and to reinject this liquid directly into the bed, preferably using a method that produces microdroplets in the bed. This type of process is described in WO-94 / 28032. The polymerization reaction occurring in the gas fluidized bed is catalyzed by continuous or semi-continuous addition of a catalyst composition according to the invention. The catalyst composition may be subjected to a prepolymerization step, for example, by polymerizing a small amount of olefin monomer in a liquid inert diluent to provide a catalyst composite comprising supported catalyst particles also embedded in olefin polymer particles. In the fluidized bed, monomers or a mixture of monomers are polymerized on fluidized particles of the catalyst composition, supported catalyst composition or prepolymerized catalyst composition in the bed to directly produce a polymer. The polymerization reaction is initiated using a bed of preformed polymer particles, preferably similar to the desired polymer, and conditioning the bed by drying with an inert gas or nitrogen prior to introducing the catalyst composition, monomers and any other gases (such as diluent gases), hydrogen chain transfer agents or inert condensable gases (when operating in a gas phase condensing mode) desired in the recycle gas stream. The polymer produced is continuously or semi-continuously withdrawn from the fluidized bed when desired.

[0725] The gas phase process most suitable for practicing the present invention is a continuous process, which allows the continuous supply of reactants to the reaction zone of the reactor and the removal of products from the reaction zone of the reactor, thereby providing a macroscopic steady-state environment in the reaction zone of the reactor. The product is easily recovered by exposure to reduced pressure and optionally elevated temperature (devolatiles) according to known techniques. Typically, the fluidized bed of the gas phase process is operated at a temperature above 50°C, preferably from 60°C to 110°C, more preferably from 70°C to 110°C.

[0726] Examples of gas phase processes suitable for use in the process of the present invention are disclosed in U.S. Patents: 4,588,790; 4,543,399; 5,352,749; 5,436,304; 5,405,922; 5,462,999; 5,461,123; 5,453,471; 5,032,562; 5,028,670; 5,473,028; 5,106,804; 5,556,238; 5,541,270; 5,608,019; and 5,616,661.

[0727] As previously mentioned, functionalized derivatives of the multi-block copolymers are also included in the present invention. Examples include metallated polymers where the metal is a residue of the catalyst or chain shuttling agent used, and further derivatives thereof, such as the reaction product of the metallated polymer with an oxygen source, followed by reaction with water to form a hydroxyl terminated polymer. In another embodiment, sufficient air or other quencher is added to cleave some or all of the shuttling agent-polymer bonds, thereby converting at least a portion of the polymer to a hydroxyl terminated polymer. Additional examples include olefin terminated polymers formed by β-hydrogen elimination and olefinic unsaturation in the resulting polymer.

[0728] In one embodiment of the invention, the multi-block copolymers can be functionalized by maleation (reaction with maleic anhydride or its equivalent), metallation (such as using an alkyl lithium reagent, optionally in the presence of a Lewis base (especially an amine such as tetramethylethylenediamine), or incorporation of a diene or masked olefin during the copolymerization process. Following polymerization involving masked olefins, the masking group, such as a trihydrocarbylsilane, can be removed, exposing a residue that is more easily functionalized. Techniques for functionalizing polymers are well known and disclosed, for example, in USP 5,543,458 and elsewhere.

[0729] Since most of the polymer product leaving the reactor is terminated with a chain shuttling agent, further functionalization is relatively easy. The metallated polymer species can be used for well-known chemical reactions, such as those applicable to other alkyl aluminum, alkyl gallium, alkyl zinc or alkyl Group 1 compounds, to form amine-, hydroxyl-, epoxy-, ketone, ester, nitrile and other functionalized terminated polymer products. Examples of suitable reaction techniques suitable for use herein are described in Organometallics in Organic Synthesis, Vol. 1 and Vol. 2, (1980), and other standard textbooks on organometallics and organic synthesis.

[0730] Polymer products

[0731] In certain embodiments, the multi-block copolymers (i.e., olefin block copolymers or OBCs) prepared by the compositions / catalyst systems / methods of the present disclosure are defined as having:

[0732] (A) an Mw / Mn of 1.0 to 10.0 (e.g., 1.0 to 9.0, 1.0 to 8.0, 1.0 to 7.0, 1.0 to 6.0, 1.0 to 5.0, 1.5 to 5.0, 1.5 to 4.0, 1.7 to 3.5, etc.), at least one melting point, Tm (degrees Celsius), and a density, d (g / cm3), wherein the numerical values ​​of Tm and d correspond to the following relationship:

[0733] T m ≧-2002.9+4538.5(d)-2422.2(d) 2 ; and / or

[0734] (B) M from about 1.7 to about 3.5 w / M n , and is characterized by the heat of fusion ΔH (J / g) and the difference ΔT (degrees Celsius, defined as the temperature difference between the highest DSC peak and the highest CRYSTAF peak), where the values ​​of ΔT and ΔH have the following relationship:

[0735] When ΔH is greater than zero and up to 130 J / g, ΔT>-0.1299(ΔH)+62.81,

[0736] When ΔH is greater than 130J / g, ΔT≧48℃,

[0737] wherein the CRYSTAF peak is determined using at least 5% of the cumulative polymer, and if less than 5% of the polymer has an identifiable CRYSTAF peak, then the CRYSTAF temperature is 30°C; and / or

[0738] (C) elastic recovery Re (%) measured at 300% strain and 1 cycle using a compression molded ethylene / α-olefin interpolymer film, and having a density d (g / cm3), wherein when the ethylene / α-olefin interpolymer is substantially free of a crosslinked phase, the values ​​of Re and d satisfy the following relationship:

[0739] Re>1481-1629(d); and / or

[0740] (D) a molecular fraction eluting between 40°C and 130°C when fractionated using TREF, characterized in that the molar comonomer content in said fraction is at least 5% greater than the molar comonomer content of a similar random ethylene interpolymer fraction eluting between the same temperatures, wherein said similar random ethylene interpolymer has the same comonomer(s) and has a melt index, density, and molar comonomer content (based on the whole polymer) within 10% of that of an ethylene / α-olefin interpolymer; and / or

[0741] (E) a storage modulus at 25°C, G'(25°C), and a storage modulus at 100°C, G'(100°C), wherein the ratio of G'(25°C) to G'(100°C) is in the range of about 1:1 to about 9:1; and / or

[0742] (F) a molecular fraction eluting between 40°C and 130°C when fractionated using TREF, characterized in that the fraction has a block index of at least 0.5 and at most 1 and a molecular weight distribution of Mw / Mn greater than 1.3; and / or

[0743] (G) average block index is greater than zero and at most 1.0, and molecular weight distribution Mw / Mn is greater than 1.3. It should be understood that the olefin block copolymer may have one, some, all or any combination of characteristics (A)-(G). The block index can be determined as described in detail in U.S. Patent No. 7,608,668, which is incorporated herein by reference for the purpose. The analytical method for determining characteristics (A) to (G) is disclosed in, for example, U.S. Patent No. 7,608,668, column 31, line 26 to column 35, line 44, which is incorporated herein by reference for the purpose.

[0744] In certain embodiments, the olefin block copolymers prepared by the compositions / catalyst systems / processes of the present disclosure have a density of 0.820 g / cc to 0.925 g / cc (eg, 0.860 g / cc to 0.890 g / cc). In some embodiments, the olefin block copolymers prepared by the compositions / catalyst systems / methods of the present disclosure have a melt index (MI) of 0.1 g / 10 min to 1000 g / 10 min (e.g., 0.1 g / 10 min to 500 g / 10 min, 0.1 g / 10 min to 100 g / 10 min, 0.1 g / 10 min to 50 g / 10 min, 0.1 g / 10 min to 35 g / 10 min, 0.1 g / 10 min to 30 g / 10 min, 0.1 g / 10 min to 20 g / 10 min, and / or 0.1 g / 10 min to 15 g / 10 min), as measured according to ASTM D 1238 (190° C. / 2.16 kg). In certain embodiments, the olefin block copolymers prepared by the compositions / catalyst systems / methods of the present disclosure have a molecular weight of 10,000 to 250,000 g / mol (e.g., 10,000 to 200,000 g / mol and / or 20,000 to 175,000 g / mol). In certain embodiments, the olefin block copolymers prepared by the compositions / catalyst systems / methods of the present disclosure have a residual zinc content of 50 ppm to 1000 ppm (e.g., 50 ppm to 750 ppm, 50 ppm to 500 ppm, and / or 75 ppm to 400 ppm). In certain embodiments, the olefin block copolymers of the present disclosure have a molecular weight distribution (MWD or PDI) of less than 5.0 (e.g., less than 4.0, less than 3.5, less than 3.0, less than 2.9, less than 2.8, etc.). In certain embodiments, the olefin block copolymers of the present disclosure have a thermomechanical resistance (TMA) greater than 100°C.

[0745] Examples

[0746] method

[0747] Combined catalyst efficiency: Combined catalyst efficiency is calculated by dividing the mass (e.g., kg) of the olefin block copolymer produced by 聚合物 )) divided by the mass of metal from the two procatalysts (e.g., total milligrams or grams (g 金属 )) to calculate.

[0748] 3D-GPC: Molecular weights were measured using a high temperature triple detector gel permeation chromatography (3D-GPC) system equipped with a Robotic Assistant Delivery (RAD) system for sample preparation and sample injection. The concentration detector was an infrared concentration detector (IR4, from Polymer Char, Valencia, Spain), which was used to determine molecular weight and molecular weight distribution. The other two detectors were precision detectors (Agilent) 2-angle laser scattering detector model 2040 and 4-capillary differential viscometer detector model 150R from Malvern (Houston, TX). The 15 degree angle of the light scattering detector was used for calculation purposes.

[0749] Data collection was performed using a Polymer Char DM 100 data acquisition box. The carrier solvent was 1,2,4-trichlorobenzene (TCB). The system was equipped with an online solvent degasser from Agilent. The column compartment was operated at 150°C. The column was a 20 micron column of four Mixed A LS 30cm. Samples were prepared using a RAD system at 2.0mg / mL. Chromatographic solvent (TCB) and sample preparation solvent contained 200ppm of butylated hydroxytoluene (BHT), and both solvent sources were sparged with nitrogen. The polyethylene sample was gently stirred for 3 hours at 150°C. The injection volume was 200μl, and the flow rate was 1.0mL / minute. Using a flow marker (a drop of decane added to the sample bottle), the flow rates of all samples were linearly corrected by comparing with the decane peak.

[0750] The data were processed using in-house software. The GPC columns were calibrated using 21 narrow molecular weight distribution polystyrene standards. The molecular weights of the standards ranged from 580 to 8,400,000 g / mol and were prepared as 6 "cocktail" mixtures with at least a ten-fold separation between the individual molecular weights.

[0751] The polystyrene standard peak molecular weight was converted to polyethylene molecular weight using the following equation (J. Polym. Sci., Polym. Let. 1968, 6, 621-624):

[0752] M 聚乙烯 =A(M 聚苯乙烯 ) B (1)

[0753] Here the value of B is 1.0, and the experimentally determined value of A is about 0.39.

[0754] The corresponding polyethylene equivalent calibration points obtained from equation (1) were fit to their elution volume observations using a fifth order polynomial.A true polynomial fit was obtained to relate the logarithm of the polyethylene equivalent molecular weight to the elution volume observations (and associated powers) for each polystyrene standard.

[0755] The number average molecular weight, weight average molecular weight and z average molecular weight were calculated according to the following equations:

[0756]

[0757]

[0758] Among them, Wf i is the weight fraction of the ith component, and M i is the molecular weight of the ith component.

[0759] MWD is expressed as the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn).

[0760] The A value is determined by adjusting the A value in equation (1) until the weight average molecular weight Mw calculated using equation (3) and the corresponding retention volume polynomial agrees with an independently determined value of Mw obtained from a linear homopolymer reference having a known weight average molecular weight of 115,000 g / mol.

[0761] Using the 15° laser scattering signal and the IR concentration detector, the same K as in Equation (5) is used. LS Calibration constant to calculate absolute molecular weight: M PE,I,abs =K LS *(LS i ) / (IR i ). The paired data sets of the ith layer of IR responses and LS responses are adjusted using the determined offsets obtained through systematic method practice:

[0762]

[0763] Among them, K LS =LS-MW calibration constant. As explained above, the response coefficient K of the laser detector LS The molecular weight was determined using the certified weight average molecular weight value of NIST 1475 (52,000 g / mol).

[0764] Differential Scanning Calorimetry (DSC) Analysis: Melting temperature (Tm), glass transition temperature (Tg), crystallization temperature (Tc), and heat of fusion can be measured by differential scanning calorimetry (DSC Q2000, TA Instruments Inc.) using a hot-cold-hot temperature profile. An open pan DSC sample of 3-6 mg of polymer is first heated from room temperature to a set point at 10°C per minute. Traces are individually analyzed using TA Universal analysis software or TA Instruments TRIOS software.

[0765] Density: Density measurements were performed according to ASTM D792.

[0766] Melt index: I2 and I 10 It is measured according to ASTM D-1238 (190°C; 2.16 kg and 10 kg).

[0767] CEF: Comonomer distribution analysis was performed by crystallization elution fractionation (PolymerChar, Spain) (Monrabal et al., Macromol. Symp. 257, 71-79 (2007)) equipped with an IR-4 detector (PolymerChar, Spain) and two angle light scattering detectors model 2040 (Precision Detectors, now Agilent Technologies). An IR-4 or IR-5 detector was used. A 50×4.6 mm 10 or 20 micron guard column (PolymerLab, now Agilent Technologies) was installed just before the IR-4 detector or IR-5 detector in the detector oven. Ortho-dichlorobenzene (ODCB, 99% anhydrous grade) and 2,5-di-tert-butyl-4-methylphenol ("BHT", catalog number B1378-500G, batch number 098K0686) were obtained from Sigma-Aldrich. ODCB was distilled before use. Silica gel 40 (particle size 0.2-0.5 mm, catalog number 10181-3) was also obtained from EMD Chemicals. Silica gel was dried at 160° C. for about two hours before use in a vacuum oven. Eight hundred milligrams of BHT and five grams of silica gel were added to two liters of ODCB. The ODCB can also be sent through one or more columns filled with silica gel to dry the ODCB. For a CEF instrument equipped with an automatic sampler with N2 purge capability, silica gel 40 was filled into two 300×7.5 mm GPC grade stainless steel columns, and the silica gel 40 column was installed at the pump inlet of the CEF instrument to dry the ODCB; and BHT was not added to the mobile phase. This "ODCB containing BHT and silica gel" or ODCB dried over silica gel 40 is now referred to as "ODCB". This ODCB was bubbled with dry nitrogen (N2) for one hour before use. Dry nitrogen was obtained by passing nitrogen at <90 psig through CaCO3 and The nitrogen obtained was obtained from a molecular sieve. The obtained nitrogen should have a dew point of about -73°C. Shake at 160°C for 2 hours, use an autosampler, and prepare samples at 4 mg / ml (unless otherwise stated). The injection volume was 300 μl. The temperature profile of CEF is: crystallization from 110°C to 30°C at 3°C / min; thermal equilibrium at 30°C for 5 minutes (including elution time of soluble elution set to 2 minutes); elution from 30°C to 140°C at 3°C / min. The flow rate during crystallization is 0.052 ml / min. The flow rate during the cooling step is 0.052 ml / min. The flow rate during elution is 0.50 ml / min. Data are collected at one data point / second. According to U.S. Patent No. 8,372,931, the CEF column is filled with 125 μm ± 6% glass beads (MO-SCI Specialty Products) using 1 / 8 inch stainless steel tubes. The column outer diameter (OD) is 1 / 8 inch. The key parameters required to perform the method repeatedly include the column inner diameter (ID) and the column length (L). The selection of ID and L must be such that when filled with 125 μm diameter glass beads, the liquid internal volume is 2.1 to 2.3 mL. If L is 152 cm, then the ID must be 0.206 cm and the wall thickness must be 0.056 cm. Different values ​​of L and ID can be used as long as the glass bead diameter is 125 μm and the internal liquid volume is between 2.1 mL and 2.3 mL. Column temperature calibration is performed using a mixture of NIST standard reference materials linear polyethylene 1475a (1.0 mg / ml) and eicosane (2 mg / ml) in ODCB. CEF temperature calibration consists of the following four steps: (1) calculation of the delay volume, which is defined as the temperature offset between the measured peak elution temperature of eicosane minus 30.00°C; (2) subtracting the temperature offset of the elution temperature from the CEF raw temperature data. It should be noted that this temperature shift is a function of experimental conditions (e.g., elution temperature, elution flow rate, etc.); (3) A linear calibration line was established that scaled the elution temperature over the range of 30.00°C to 140.00°C so that NIST linear polyethylene 1475a had a peak temperature of 101.0°C and eicosane had a peak temperature of 30.0°C; (4) For the soluble fraction measured isothermally at 30°C, the elution temperature was linearly extrapolated using an elution heating rate of 3°C / min. The elution peak temperature report was obtained so that the observed comonomer content calibration curve was consistent with those previously reported in U.S. Patent No. 8,372,931.

[0768] Residual zinc content (ppm) can be measured using standard industry procedures such as mass balance or x-ray fluorescence (XRF) methods.

[0769] TMA: Thermomechanical analysis was used to evaluate the temperature resistance of OBC resins. TMA was performed on a TA Instruments Q400. Small disks of approximately 8 mm in diameter were cut from 3.2 mm thick compression molded plaques. The probe was 1.1 mm in diameter with a rounded tip. The samples were tested at ambient conditions with a temperature ramp rate of 5°C / min. The temperature was recorded at which the probe was recessed 1 mm into the surface under a constant force of 1 N.

[0770] Reactivity Ratio: The reactivity ratio of the olefin polymerization procatalyst can be determined by the above discussion and mathematical formula.

[0771] Working Example

[0772] The following examples illustrate embodiments of the present disclosure but are not intended to be limiting in any way. More specifically, the following non-limiting examples demonstrate that the CSA and dual catalyst combination of the present invention is capable of producing olefin block copolymers with desired properties at commercially acceptable catalyst efficiencies and process control at elevated reactor temperatures (e.g., equal to or greater than 150° C.). As seen below, a comparative CSA and dual catalyst combination representing the state of the art is not capable of producing olefin block copolymers that meet desired product specifications and efficiencies at elevated reactor temperatures (e.g., equal to or greater than 150° C.).

[0773] Procatalyst component

[0774] Exemplary non-limiting procatalysts falling within the scope of the first olefin polymerization procatalyst (A) of the present disclosure (procatalysts (A4), (AB) and (AA1)) have the structure shown below:

[0775]

[0776] Exemplary non-limiting procatalysts falling within the scope of the second olefin polymerization procatalyst (B) of the present disclosure (procatalysts (B10), (B14), and (BB)) have the following structure:

[0777]

[0778] The procatalysts (procatalysts (A1) and (R)) representing the state of the art comparative CSA and dual catalyst combinations have the following structures:

[0779]

[0780] Synthesis of procatalyst (A4)

[0781]

[0782] 2-iodo-4-fluorophenol (14.2 g, 59.6 mmol) and 1,4-dibromobutane (3.6 mL, 30 mmol) were combined in acetone (200 mL) and stirred at reflux for 3 days. The mixture was cooled, filtered and concentrated in vacuo. The residue was dissolved in dichloromethane (150 mL) and washed with KOH (50 mL, 3N) and saturated K2CO3 (2×50 mL). The organic portion was then dried over MgSO4 and concentrated to give a white powder. The white powder was rinsed in hexane and ultrasonicated, cooled, filtered, and dried under vacuum to give the desired product (12.22 g, 77.3%). 1H NMR (400MHz, CDCl3) δ7.49 (dd, J = 7.7, 3.1Hz, 2H), 7.01 (td, J = 8.4, 3.1Hz, 2H), 6.74 (dd, J = 9.0, 4.6Hz, 2H), 4.08 (d, J = 5.3Hz, 4H), 2.16-2.01 (m, 4H).

[0783]

[0784] A solution of bis(aryl iodide) (10.0 g, 18.9 mmol), boric acid ester (18.2 g, 37.7 mmol), THF (200 mL) and Na2CO3 (12.0 g, 113 mmol) in water (50 mL) was placed in a 500 mL 2-necked flask and purged with nitrogen for 15 minutes. The palladium catalyst was added to the THF solution. The reactants were heated to 65 ° C and stirred overnight. The desired protected product precipitated as a white solid during the reaction. The mixture was then cooled, filtered and the white solid was washed with water. The solid was then transferred to a clean flask and suspended in a MeOH / THF mixture. Hydrochloric acid (5 drops) was added to the solution, and the solution was heated to reflux overnight, when the suspension was completely dissolved. The solution was cooled, filtered and concentrated to obtain a brown oil. The remaining free-flowing liquid was decanted and discarded. After standing for several days in methanol, the remaining brown viscous oil slowly crystallized into a brown solid. The solid was collected by filtration, dissolved in dichloromethane and passed through a plug of silica (Rf ~ 1 in dichloromethane). The light red solution produced by the dichloromethane elution was collected and concentrated to give a red solid, which was sonicated with ether, filtered and dried to give the title compound (14.98 g, 96%) as an off-white pink solid. 1H NMR (400MHz, CDCl3) δ8.25-7.99(m,4H),7.29(ddd,J=8.2,7.1,1.3Hz,4H),7.25-7.19(m,6H),7.19-7.12(m,8H),7.00(dd d,J=9.0,7.7,3.1Hz,2H),6.72(dd,J=9.0,4.5Hz,2H),6.10(s,2H),3.88-3.64(m,4H),2.33(s,6H),1.63(t,J=3.2Hz,4H).

[0785]

[0786] At -35 ° C, methylmagnesium bromide (0.812mL, 3M, 2.4mmol) is added to a toluene (20mL) suspension containing hafnium tetrachloride (0.195g, 0.609mmol). The reactant is slightly warmed and stirred for 20 minutes. The solution is then transferred to a solution of the ligand in toluene (10mL). The solution is stirred overnight and then the solvent is removed under high vacuum. The residue is extracted with dichloromethane (15mL) and filtered. Then dichloromethane is removed under high vacuum to obtain a pale solid product (0.325g, 52%). 1 H NMR (400MHz, benzene-d6) δ8.19-8.11(m,2H),8.05(dt,J=7.6,1.0Hz,2H),7.44(tt,J=8.9,0.9Hz,4H),7.32(ddd,J=8.2,7.1,1 .3Hz,2H),7.28-7.20(m,4H),7.21-7.09(m,5H),7.09(dd,J=2.3,0.8Hz,2H),7.02(ddt,J=7.9,1.4,0.7Hz,1H),6.92(dd ,J=2.3,0.8Hz,2H),6.82(dd,J=9.2,3.2Hz,2H),6.57(ddd,J=9.1,7.2,3.2Hz,2H),4.60(dd,J=9.1,4.9Hz,2H),3.89-3. 68(m,2H),3.21(dd,J=11.6,4.4Hz,2H),2.11(d,J=1.4Hz,8H),0.68-0.48(m,2H),0.40(d,J=13.3Hz,2H),-1.17(s,6H).

[0787] Preparation of pre-synthetic catalyst (B10)

[0788]

[0789] Step 1: Synthesis of 2-mesityl-6-bromopyridine. In a glove box, 2,6-dibromopyridine (8.00 g, 33.77 mmol), 2,6-diisopropylphenylimidazolium chloride (0.287 g, 0.68 mmol), nickel bis(acetylacetonate) (0.174 g, 0.68 mmol) and THF (70 mL) were added to a 200 mL wide-mouth bottle. MesMgBr (33.8 mL, 1 M, 33.77 mmol) was slowly added to the solution and the reaction was stirred at room temperature for 2.5 hours. The solution was removed from the glove box and all volatiles were removed. The crude product was dissolved in CH2Cl2 and washed with 1N HCl. The organic layer was collected and all volatiles were removed. The crude product was used for the next reaction without further purification. 1 H NMR (400MHz, CDCl3) δ7.58 (ddd, J=7.9, 7.5, 1.0Hz, 1H), 7.46-7.40 (m, 1H), 7.17 (dt, J=7.4, 1.0Hz, 1H), 6.91-6.87 (m, 2H), 2.29 (s, 3H), 2.02 (s, 6H). 13 C NMR (101MHz, CDCl3) δ161.14,138.42,137.89,135.60,128.32,127.01,126.86,125.91,123.67,21.05,20.13.

[0790]

[0791] Step 2: Synthesis of 2-mesityl-6-neopentylaminopyridine. The crude product from the previous reaction was added to a 250 mL round-bottom flask. Neopentylamine (4.42 g, 50.66 mmol), NaOtBu (7.14 g, 74.30 mmol), Pd2dba3 (0.309 g, 0.34 mmol) and BINAP (0.420 g, 0.68 mmol) were all added to the flask, followed by anhydrous toluene (120 ml). The reactants were heated overnight at 100 ° C under a nitrogen purge. The reactants were cooled to room temperature, and all volatiles were removed. Water and EtOAc were added, and the organic layer was collected. Silica gel was added to the dark crude solution, and all volatiles were removed. The product was purified by column chromatography using a solid support (90: 10 hexane: EtOAc) to obtain a pure product (64% yield, 6.1 g). 1H NMR (400MHz, CDCl3) δ7.46(t,J=7.8Hz,1H),6.89(s,2H),6.50-6.42(m,1H),6.32(d,J=8.4H z, 1H), 4.66 (s, 1H), 3.04 (d, J = 6.2Hz, 2H), 2.29 (s, 3H), 2.07 (s, 6H), 0.97 (d, J = 1.5Hz, 9H). 13 C NMR (101MHz, CDCl3) δ159.31,158.37,137.64,136.86,135.57,128.13,128.07,113.24,102.95,54.16,32.03,27.51,21.03,20.03.

[0792] General procedure for the metalation of 2-aminopyridine ligands.

[0793] In a glove box, HfCl4 or ZrCl4 (0.23mmol) and toluene (5mL) were added to a vial. The solution was cooled to -30°C, and MeMgBr (0.35mL, 3M, 1.04mmol) was then added. The solution was stirred for 2 minutes, and then a suspension of the ligand (0.23mmol) in cold toluene (5mL) was added. The solution quickly turned yellow and was stirred at room temperature for 2 hours. All volatiles were removed, and the residue was wet-ground with hexane. The residue was dissolved in hexane and filtered through a disposable glass frit. The yellow solution was evacuated to dryness and then dissolved in ether. The yellow solution was concentrated and cooled to -30°C to obtain yellow crystals of the product.

[0794] Synthesis of procatalyst (B10)

[0795]

[0796] Use HfCl4, according to General procedure for the metalation of 2-aminopyridine ligands Preparation of procatalyst (B10). Yield: 86%. 1 H NMR(400MHz,C6D6)δ6.96-6.86(m,2H),6.70(s,4H),5.88(d,J=8.7Hz,2H),5.85-5.81(m,2H) ,2.41(s,4H),2.18(s,6H),2.10-1.94(m,6H),1.71-1.51(m,6H),0.95(s,18H),0.47(s,6H). 13C NMR(101MHz,C6D6)δ171.86,155.31,140.05,136.79,136.39,135.94,134.9 7,127.96,109.27,103.49,57.80,54.81,34.23,28.39,20.69,20.31,19.79.

[0797] Synthesis of procatalyst (B14)

[0798]

[0799] Preparation of 2,4-dimesitylpyridine: In a glove box, 2,4-dibromopyridine (25.0 g, 105.5 mmol), NiCl2(PCy3)2 (1.45 g, 2.11 mmol) and THF (500 mL) were added to a 1 L round bottom flask. MesMgBr (1 M in THF, 237.5 mL, 237.5 mmol) was slowly added to the solution via an addition funnel and the reactants were stirred at room temperature for 1 hour (the reaction warmed to reflux, so slow addition was required). The solution was removed from the glove box and quenched with water (100 mL). THF was removed by rotary evaporation, and then 1N HCl (200 mL) and CH2Cl2 (200 mL) were added to the crude product and the organic layer was collected. The dark red CH2Cl2 solution was passed through a silica gel plug and eluted with CH2Cl2 to give the product. All volatiles were removed and the product was collected for the next step (80%, 26.5 g). 1 H NMR (400MHz, CDCl3) δ8.79 (dd, J=5.0, 0.9Hz, 1H), 7.08 (dd, J=5.0, 1.7Hz, 1H), 7.06 (dd, J=1.6, 0.9 Hz,1H),7.02-6.98(m,2H),6.98-6.94(m,2H),2.37(s,3H),2.36(s,3H),2.12(s,6H),2.09(s,6H). 13 C NMR (101MHz, CDCl3) δ160.31,149.83,149.72,137.80,137.42,137.31,136.44 ,135.55,134.99,128.38,128.31,125.68,122.61,21.13,21.07,20.59,20.18.

[0800]

[0801] Preparation of 2-bromo-4,6-di-mesitylpyridine: Dimethylaminoethanol (16.6 mL, 164.5 mmol) and hexane (250 mL) were charged into a 1L round-bottom flask. The flask was purged with nitrogen, and nBuLi (2.5 M in hexane, 131.6 mL, 329.0 mmol) was added dropwise at 0 °C. The reactants were stirred for 1 hour, and then 2,4-di-mesitylpyridine (17.3 g, 54.8 mmol in 130 mL of ether) was added dropwise. The solution became dark brown and stirred for 2 hours. The solution was cooled to -77 °C, and then a solution of CBr4 (63.7 g, 191.9 mmol) in ether (80 mL) was added dropwise. A precipitate was formed and stirred at room temperature overnight. Water was added to quench the reaction, and then ether was added and the organic layer was extracted. All volatiles were removed and the crude product was then passed through a plug of silica gel (eluted with hexanes to remove CBr4 and then with CH2Cl2 to give the product). The crude product was purified by column chromatography (gradient 100% hexanes to 70:30 hexanes:EtOAc). Yield: 14.0 g, 65%. 1 H NMR (400MHz, CDCl3) δ7.28-7.22(m,1H),7.01-6.97(m,1H),6.94(s,3H),6.91(s,3H),2.32(s,3H),2.30(s,3H),2.08(s,6H),2.05(s,6H). 13 C NMR (101MHz, CDCl3) δ161.08,152.53,142.01,137.91,137.86,136.30,135.54 ,134.93,134.85,128.43,128.36,126.57,125.05,21.07,21.02,20.53,20.20.

[0802]

[0803] In a glove box, 2,4-dimesityl-6-bromo-pyridine (0.500 g, 1.27 mmol), NaO t Bu (0.270 g, 2.81 mmol), Pd2dba3 (0.058 g, 0.06 mmol), BINAP (0.039 g, 0.06 mmol), neopentylamine (0.188 g, 2.16 mmol) and toluene (8 mL). The reaction mixture was heated to 100 ° C for 3 hours and then removed from the glove box. Silica gel was added and all volatiles were removed. The solid was purified by column chromatography (hexane: EtOAc 85: 15). Yield: 0.415 g, 82%. 1H NMR (400MHz, CDCl3) δ7.03(s,2H),7.00(s,2H),6.39(d,J=1.2Hz,1H),6.27(d,J=1.1Hz,1H),4.95(t, J=6.2Hz,1H),3.14(d,J=6.2Hz,2H),2.42(s,3H),2.40(s,3H),2.25(s,6H),2.22(s,6H),1.09(s,9H). 13 C NMR (101MHz, CDCl3) δ159.88,158.71,151.28,138.42,137.83,136.88,136.86,135.55,1 35.14,128.29,128.21,114.63,103.60,54.35,32.33,27.62,21.17,21.12,20.50,20.19.

[0804]

[0805]

[0806] Then use HfCl4, as above General procedure for metalation of 2-aminopyridine ligands Preparation of procatalyst (B14). Yield: 87%. 1 H NMR (400MHz, C6D6) δ6.78(d,J=7.6Hz,4H),6.70(d,J=13.1Hz,4H),5.99(s,2H),2.54(d,J=13.5Hz,2H),2.23(m,2H),2. 18(s,4H),2.16(s,6H),2.14(s,6H),2.11(d,J=11.4Hz,6H),2.07-2.02(m,6H),1.97(s,6H),0.93(s,18H),0.47(s,6H). 13 C NMR (101MHz, C6D6) δ172.73,156.01,154.68,138.17,137.17,137.06,136.80,136.13,135.45,135.25,134. 46,128.72,128.47,111.23,104.42,58.20,55.16,34.49,31.93,28.88,25.61,21.12,21.08,20.50,20.19.

[0807] Synthesis of procatalyst (A1)

[0808] Procatalyst (A1) was synthesized according to the procedure described in US Pat. No. 6,953,764 B2, which is incorporated herein by reference in its entirety.

[0809] Synthesis of procatalyst (R)

[0810]

[0811] Salicylaldehyde (2503.0 g, 10.68 mol) and methanol (12 L) were added to a 20 L carboy and the slurry was tumbled for 20 minutes. The temperature was lowered to about 16 °C as the solid dissolved. Amine (1313 g, 11.60 mol) was added in three batches over a two hour period. The reaction was tumbled overnight. The bright yellow solid product was collected by filtration and then vacuum dried in a 12 L round bottom glass flask. 1 H NMR showed the product to be a mixture in about a 3:1 trans:cis ratio with about 2.4 mol% residual MeOH. Yield = 3141 g (89.2%).

[0812]

[0813] A 5-liter three-necked round-bottom flask was equipped with an overhead stirrer in a drying oven under a N2 atmosphere, and the ligand (393 g, 1.19 mol), zirconium tetrachloride (139 g, 0.597 mmol) and anhydrous toluene (3.5 L) were loaded to stir the bright yellow slurry, and a 3.0 M methylmagnesium bromide solution in ether (800 mL, 2400 mmol) was added dropwise over 1 hour. During the addition of the first two equivalents of Grignard reagent, the temperature and methane release were carefully monitored. After stirring for another 1 hour, the ether and toluene were removed in vacuo. The solid was slurried with toluene (4 L), and the magnesium salts were removed on a sinter funnel. The salts were washed with an additional 4 L of toluene, and the filtrate was combined in a B-5 graduated cylinder. The graduated cylinder was sampled for gravimetric analysis and batch reactor evaluation. Typical concentrations were close to 5.4 wt.%, equivalent to about 370 g of complex (80% yield).

[0814] Synthesis of procatalyst (AB):

[0815]

[0816] 4-Bromophenol (15.0 g, 86.7 mmol, 1.0 eq.) and p-toluenesulfonic acid hydrate (165 mg, 0.867 mmol, 0.01 eq.) were dissolved in 35 mL of CHCl. 2中And cooled to 0 ° C. 3,4-dihydro-2H-pyran (11.9mL, 130mmol, 1.5 equivalents) was added dropwise under stirring, and the following measures were taken. Stirred for 1 hour at 0 ° C. Quenched with 100mL 1N NaOH and diluted with 100mL Et2O. The organic layer was separated and the aqueous layer was extracted with another 50mL Et2O. The combined organic extracts were filtered through a silica plug, rinsed with Et2O, and concentrated. Eluted with a 0→10% acetone / hexane gradient and purified by column chromatography. 18.73g of transparent oily product was collected, 84.0% yield, which solidified into a white solid in the freezer. 1 H NMR (400MHz, CDCl3) δ7.41-7.33(m,2H),6.98-6.89(m,2H),5.37(t,J=3.3Hz,1H),3.87(ddd,J=11.4,9.6 ,3.2Hz,1H),3.59(dtd,J=11.4,4.1,1.4Hz,1H),2.05-1.91(m,1H),1.94-1.79(m,2H),1.78-1.52(m,3H). 13 C NMR (101MHz, CDCl3) δ156.17,132.19,118.31,113.83,96.51,62.00,30.26,25.13,18.65.

[0817]

[0818] In a 500 mL oven-dried flask, under N2, the aryl bromide (18.7 g, 72.8 mmol, 1.0 equiv) was dissolved in 146 mL of anhydrous THF. Cooled to -78 °C, n-butyl lithium (2.43 M in hexane, 31.5 mL, 76.5 mmol, 1.05 equiv) was slowly added with stirring. Stirred at -78 °C for 30 minutes, then chloro(dimethyl)octylsilane (18.1 mL, 76.5 mmol, 1.05 equiv) was slowly added. Stirred overnight and allowed to gradually warm to room temperature. Quenched with 100 mL of saturated NH4Cl aqueous solution. 100 mL of Et2O was added and the layers were separated. The aqueous layer was extracted with another 100 mL of Et2O. The combined organic layers were dried over MgSO4, filtered and concentrated. The crude product was of very good purity, but by 1 A small amount of silane-derived byproduct (about 0.1 equivalent) was observed by H NMR. This impurity can be removed by reverse phase column chromatography with a 0→30% THF / MeCN gradient elution. Alternatively, the product can be carried forward to the next step by isolating the crude material according to the subsequent step. The recovery of the product is quantitative. 1H NMR (400MHz, chloroform-d) δ7.42(d,J=8.6Hz,2H),7.04(d,J=8.6Hz,2H),5.45(s,1H),3.91(ddd,J=11.4,9.6,3.1Hz,1H),3.60(dtd,J=11.3,4 .1,1.5Hz,1H),2.07-1.93(m,1H),1.90-1.80(m,2H),1.73-1.58(m,3H),1.26(m,12H),0.87(t,J=6.5Hz,3H),0.70(m,2H),0.22(s,6H).

[0819]

[0820] In a dried 500mL flask, under N2, the substrate (25.4g, 72.8mmol, 1.0 equivalent) dissolved in 146mL THF is cooled to -78°C. n-Butyl lithium (2.43M solution in hexane, 42.0mL, 102mmol, 1.4 equivalent) is added dropwise under stirring. The solution is stirred at -78°C for 30 minutes, then warmed to 0°C and stirred for another 3 hours. Separately, I2 (25.0g, 98.3mmol, 1.35 equivalent) is dissolved in 58mL THF. The reaction flask is cooled to -78°C and I2 solution is added dropwise by a syringe. The mixture is stirred overnight and gradually warmed to room temperature in the process. Quenched with 100mL saturated Na2S2O3 aqueous solution and 100mL H2O. Stir for 30 minutes. Dilute with 100mL Et2O and separate the organic layer. Extract the aqueous phase with another 100mL Et2O. The combined organic fractions were dried over MgSO4, filtered and concentrated. The crude material was filtered through a short plug of silica, eluting with hexanes. The crude material was very pure and the recovery was quantitative. However, the silane-derived impurities present in the previous step were still present. The impurities can be removed by reverse phase chromatography using a 0→30% THF / MeCN gradient elution. 1 H NMR (400MHz, chloroform-d) δ7.85 (d, J=1.5Hz, 1H), 7.37 (dd, J=8.1, 1.5Hz, 1H), 7.05 (d,J=8.1Hz,1H),5.56(t,J=2.9Hz,1H),3.86(td,J=11.1,2.9Hz,1H),3.64- 3.53(m,1H),2.21-2.08(m,1H),2.01-1.94(m,1H),1.91-1.82(m,1H),1.77- 1.60(m,3H),1.26(m,12H),0.87(t,J=6.9Hz,3H),0.70(m,2H),0.21(s,6H).

[0821]

[0822] In an oven-dried 100 mL flask, dissolve the aryl iodide (10.0 g, 21.1 mmol, 1.0 equiv) in 42 mL of toluene under N2. Add carbazole (4.93 g, 29.5 mmol, 1.4 equiv), CuI (161 mg, 0.84 mmol, 0.04 equiv), N,N′-dimethylethylenediamine (0.63 mL, 6.32 mmol, 0.3 equiv) and K3PO4 (8.95 g, 42.1 mmol, 2.0 equiv). Stir the solution at 110°C for 72 h. Cool to room temperature and filter through a plug of silica, eluting with Et2O. Concentrate the eluate and then triturate with hexanes to remove insoluble carbazole. Filter the mixture and rinse with 2×25 mL of hexanes. Concentrate the filtrate. Purify by reverse phase column chromatography eluting with a 30→0% H2O / MeCN gradient, then 0→35% THF / MeCN gradient. Collect 8.66 g of product as a light yellow oil, 80.0% yield. 1 H NMR (400 MHz, chloroform-d) δ 8.14 (d, J = 7.7 Hz, 2H), 7.60 (d, J = 1.6 Hz, 1H), 7.56 (dd, J = 8.1, 1.6 Hz, 1H), 7.43-7.33 (m, 3H), 7.28-7.22 (m, 3H), 7.16 (d, J = 8.2 Hz, 1H), 5.34 (t, J = 2.9 Hz, 1H), 3.61 (td ,J=11.2,2.9Hz,1H),3.50-3.42(m,1H),1.50-1.38(m,1H),1.36-1.21(m,14H),1.18-1.10(m ,1H),1.08-0.98(m,1H),0.87(t,J=6.9Hz,3H),0.79-0.69(m,2H),0.26(s,3H),0.26(s,3H).

[0823]

[0824] In a dried 250mL flask, under N2, the substrate (8.66g, 16.9mmol, 1.0 equivalent) dissolved in 84mL anhydrous THF is cooled to -78°C. n-Butyl lithium (2.50M solution in hexane, 8.8mL, 21.9mmol, 1.3 equivalents) is added dropwise by a syringe and stirred for 15 minutes. The reactant is transferred to a 0°C bath and stirred for 4 hours. The reactant turns yellow and then turns dark green. Isopropoxy (pinacol borane) (4.8mL, 23.6mmol, 1.4 equivalents) is added by a syringe and stirred overnight at room temperature, allowing it to gradually warm to room temperature. The color becomes lighter and is light yellow-green. The reactant is quenched with 50mL saturated NaHCO3 aqueous solution, diluted with 50mL Et2O and layered. The aqueous phase is extracted with another 50mL Et2O. The combined organic matter is washed with 100mL brine. The organic layer was dried over MgSO4, filtered and concentrated to collect a viscous oil. Triturated with MeCN, the mixture was cooled to 0°C and filtered to collect the product as a white powder. 9.01 g of product was collected, 83.5% yield. 1 H NMR (400 MHz, chloroform-d) δ8.13-8.09 (m, 2H), 7.95 (d, J = 1.7 Hz, 1H), 7.60 (d, J = 1.7 Hz, 1H), 7.43-7.34 (m, 2H), 7.29-7.22 (m, 4H), 4.93 (t, J = 2.9 Hz, 1H), 2.67-2.54 (m, 2H), 1.7 0-1.62(m,1H),1.39(s,6H),1.38(s,6H),1.33-1.21(m,14H),1.20-1.06(m,3H),0. 97-0.90(m,1H),0.87(t,J=6.8Hz,3H),0.76-0.70(m,2H),0.25(s,3H),0.24(s,3H).

[0825]

[0826] To a 20 mL vial under N2 was added a bis(aryl bromide) bridge (0.300 g, 0.688 mmol, 1.0 equiv), a borate ester (0.946 g, 1.48 mmol, 2.15 equiv), chloro[(tri-tert-butylphosphine)-2-(2-aminobiphenyl)]palladium(II) (0.018 g, 0.034 mmol, 0.05 equiv), Na2CO3 (0.292 g, 2.75 mmol, 4.0 equiv), 6.4 mL of degassed THF, and 2.1 mL of degassed water. The system was sparged with N2. The reaction was heated to 70 °C for 24 hours and the conversion was monitored by HPLC. The reaction was cooled and the volatiles were removed by rotary evaporation. The residue was dissolved in Et2O, washed with brine, dried over anhydrous magnesium sulfate, filtered through a pad of silica gel, and then concentrated to give the protected ligand. Dissolved in 1:1 THF:MeOH, 1 drop of HCl was added, and stirred at room temperature for 2 hours. The solution was concentrated to a yellow oil. Purified by reverse phase column chromatography using 0→40% THF / MeCN as eluent. The product was collected from two fractions. The later fraction contained a large amount of unidentified impurities and was discarded. The remaining fraction was re-chromatographed under the same conditions. 0.416 g of white powder product was collected with a yield of 53.3%. 1 H NMR (400MHz, chloroform-d) δ8.14 (d, J = 7.7Hz, 4H), 7.54 (m, 2H), 7.46 (m, 2H), 7.32 (dd t,J=8.2,7.1,1.1Hz,4H),7.23(m,4H),7.16(m,6H),7.01(ddd,J=10.3,5.4,2 .8Hz,2H),6.72(dd,J=9.0,4.4Hz,2H),6.20(s,2H),3.71(m,4H),1.62(m,4H) ,1.39-1.16(m,24H),0.84(t,J=7.2Hz,6H),0.78-0.69(m,4H),0.24(s,12H). 19 F NMR (376MHz, CDCl3) δ-121.74.

[0827]

[0828] In a glove box, in a dried 4oz jar with a stirring bar, HfCl4 (0.515 g, 1.61 mmol, 1.0 eq) was suspended in 40 mL of toluene (anhydrous). Cooled to -30°C in a freezer. Removed from the freezer, MeMgBr (3.0 M in Et2O, 2.25 mL, 6.76 mmol, 4.2 eq) was added with stirring. Stirring for 10 minutes, the solution darkened. Added ligand (1.82 g, 1.61 mmol, 1.0 eq), warmed to room temperature and stirred overnight. The solvent was removed in vacuo to give a brown solid. The solid was extracted with about 150 mL of hexane. The extract was concentrated to give 1.30 g of white powder product, 60.4% yield. 1 H NMR (400MHz, benzene-d6) δ8.13(dd,J=7.6,0.9Hz,2H),8.05(d,J=6.9Hz,2H),7.83(d,J=1.7Hz,2H),7.60-7.53(m, 4H),7.46-7.36(m,4H),7.27-7.17(m,6H),6.97(dd,J=9.0,3.2Hz,2H),6.59(ddd,J=9.0,7.2,3.2Hz,2H),4. 64(dd,J=9.1,4.9Hz,2H),3.85(t,J=10.4Hz,2H),3.28(dd,J=11.8,3.6Hz,2H),1.40-1.23(m,24H),0.90-0. 85(m,6H),0.76-0.69(m,4H),0.69-0.61(m,2H),0.55-0.45(m,2H),0.24(s,6H),0.23(s,6H),-1.12(s,6H). 13 C NMR(101MHz,C6D6)δ161.53,159.09,157.27,151.47,151.44,141.59,141.15,135.85,135 .02,134.39,134.31,130.69,130.35,127.59,127.08,125.58,125.49,125.44,125.26,12 2.91,121.08,120.56,120.49,120.05,118.50,118.26,116.65,116.42,112.78,109.10,80.66,49.97,33.94,32.35,29.82,29.73,26.23,24.51,23.09,16.26,14.36,-2.58,-2.76. 19 F NMR (376MHz, C6D6) δ-115.86.

[0829] Synthesis of procatalyst (AA1):

[0830]

[0831] Step 1: Preparation of 2-methyldecene :Methyltriphenylphosphonium bromide (297.18g, 831.9mmol, 1.3 equivalents) and 850mL tetrahydrofuran (THF, anhydrous, 1mL / mmol, through cannula) are loaded into a 2L three-necked flask equipped with a mechanical stirrer, a thermocouple and a nitrogen pad. The white suspension is cooled to 0°C in an ice bath and NaOtBu (79.95g, 831.9mmol, 1.3 equivalents) is added (a slight exotherm is observed, which increases by about 2°C after addition). The resulting reaction mixture (yellow slurry) is stirred at 0°C for 45 minutes. A solution of 2-decanone (100g, 639.9mmol, 1 equivalent) in 150mL THF (anhydrous, 0.23mL / mmol) is slowly added to the suspension within 10 minutes (add at a rate such that the temperature remains <10°C). The resulting reaction mixture is warmed to ambient temperature overnight. After stirring overnight (22 hours), the reaction mixture was sampled (yellow slurry) and filtered through 1 H NMR spectral analysis. 1 H NMR spectrum shows that the starting material is completely consumed. The reaction mixture is filtered through a diatomaceous earth pad, and the filter cake is rinsed with dichloromethane. The filtrate is concentrated by rotary evaporation to obtain a yellow oil. The yellow oil is dissolved in pentane and filtered through a silica gel pad. The filtrate is concentrated by rotary evaporation, and the process is repeated until all solids are removed. A colorless liquid product (95g, according to 1 H NMR pure, 96% yield).

[0832]

[0833] Step 2: Preparation of 4-(2-methyldec-2-yl)phenol:To a 2L four-necked flask equipped with a magnetic stirrer, a thermocouple, a water condenser and a nitrogen pad, phenol (133.5g, 1418mmol, 2 equivalents), 2-methyldecene (109.4g, 709mmol, 1 equivalent) and 709mL 1,2-dichloroethane (DCE) were added. The reaction mixture was bubbled with nitrogen for 30 minutes. Bi(OTf)3 (4.65g, 7.09mmol, 0.01 equivalent) was then added, and the resulting reaction mixture (a yellow solution containing a white solid) was heated to 80°C (setting the temperature to 45°C, and a strong exotherm was observed; the temperature reached about 70°C). Once the temperature stabilized, the temperature was set to 80°C and the reaction mixture was stirred overnight. After stirring overnight (15 hours), a sample of the reaction mixture (orange solution) was taken out and analyzed by GC. The GC trace showed that the olefin was completely consumed. The reaction mixture was cooled to ambient temperature, filtered through a short silica gel pad, and diluted with ethyl acetate (EtOAc, 500mL). The organic layer was washed with 2N NaOH (300 mL x 2), water (300 mL), brine (300 mL) and passed through a silica gel plug topped with Na2SO4. The plug was rinsed with hexane and the filtrate was concentrated by rotary evaporation to give a light brown oily crude product. The crude product was dissolved in hexane and concentrated (repeated 3 times) to remove residual EtOAc. A light brown oily crude product (175 g, GC analysis purity 95.8%, isolated yield 95%) was obtained. 1 H NMR (400MHz, CDCl3) δ7.18(d,J=8.8Hz,2H),6.76(d,J=8.8Hz,2H),4.70(s,1H ), 1.54 (m, 2H), 1.25 (s, 6H), 1.19 (m, 10H), 1.03 (m, 2H), 0.86 (t, J = 7.0Hz, 3H).

[0834]

[0835] Step 3: Preparation of 2-iodo-4-(2-methyldec-2-yl)phenol:4-(2-methyldec-2-yl)phenol (176 g, 678 mmol, 1 eq.), p-toluenesulfonic acid monohydrate (pTSA H2O, 12.9 g, 67.4 mmol, 0.1 eq.) and 1000 mL of acetonitrile were added to a 3L four-necked flask equipped with a mechanical stirrer, a thermocouple and a nitrogen pad. The resulting reaction mixture (pink solution) was stirred at ambient temperature for 30 minutes. The reaction mixture was then cooled to 3-4°C with an ice-water bath, and N-iodosuccinimide (NIS, 160 g, 1.05 eq.) (about 15 g each, 4-5°C) was added in batches. After adding NIS, the reaction mixture was stirred at 5°C for 1 hour, the ice bath was then removed, the flask was covered with foil, and the reaction mixture (orange solution) was stirred at ambient temperature. After stirring for 50 hours, a sample of the reaction mixture was quenched with Na2SO3 (20% aqueous solution) and analyzed by GC. The GC trace showed that the starting material was completely consumed. The reaction mixture was quenched with Na2SO3 (20% aqueous solution, about 150 mL), diluted with water (1500 mL), and stirred at ambient temperature for 1 hour. After stopping stirring, a brown oil precipitated to the bottom of the flask. The solution was decanted from the oil and additional water (1500 mL) was added. The resulting mixture was stirred at ambient temperature for 1 hour and the solution was decanted from the oil (repeated once more). The crude product was dissolved in 1 L of hexane, washed with water (500 mL×2), brine (500 mL), and transferred through a silica gel plug with Na2SO4 on top. The filtrate was concentrated by rotary evaporation and dried in a vacuum oven at 40° C. (20 torr) to give a brown oily crude product (254 g, GC purity about 96%, yield 96%). 1 H NMR (400MHz, CDCl3) δ7.55(s,1H),7.19(d,J=8.5Hz,1H),6.91(d,J=8.5Hz,1H),5.13 (s,1H),1.52(m,2H),1.23(s,6H),1.20(m,10H),1.03(m,2H),0.86(t,J=7.0Hz,3H).

[0836]

[0837] Step 4: Preparation of 2-iodo-1-(methoxymethoxy)-4-(2-methyldec-2-yl)benzene:To a 1 L three-necked flask equipped with a mechanical stirrer, reflux condenser and nitrogen pad was added dimethoxymethane (59 mL, 664.0 mmol, 1.3 equiv. relative to ArOH), anhydrous toluene (250 mL) and Zn(OAc)2 (20 mg, 0.02 mol%). Acetyl chloride (47 mL, 664.0 mmol, 1.3 equiv.) was added via an addition funnel over 45 minutes. An exothermic reaction was observed and the temperature gradually increased to 29°C over the first 15 minutes, at which point a cold water bath was applied to cool the reaction. When the addition of acetyl chloride was complete, the cold water bath was removed and the reaction mixture was stirred at ambient temperature for 4 hours. 2-iodo-4-(2-methyldec-2-yl)phenol (191.2 g, 510.5 mmol, 1 eq) was added in one go (rinsed with 30 mL of anhydrous toluene), followed by iPr2NEt (134 mL, 766.2 mmol, 1.5 eq) via an addition funnel over 53 minutes (a slight exothermic reaction was observed at the beginning, with a temperature increase of about 2 °C). The resulting reaction mixture was stirred at ambient temperature for 1 hour, then heated to 60 °C overnight (15 hours). After the reaction was considered complete by GC analysis, the reaction mixture was cooled to ambient temperature and then cooled in an ice-water bath. Saturated NH4Cl solution (500 mL) was added at a rate to keep the temperature below 30 °C (an exothermic reaction was observed, and an ice-water bath was used to control the temperature). The two-phase reaction mixture was stirred for 2 hours, then diluted with toluene (500 mL) and water (500 mL). The two phases were separated, and the aqueous layer was washed with toluene (500 mL×2). The combined organic phases were washed with brine (500 mL x 3), filtered through a plug of anhydrous MgSO4, and concentrated to dryness under reduced pressure using rotary evaporation to give the desired product as a colorless oil (212.5 g, 95.5% yield). The crude product was used in the next step without further purification. 1 H NMR(400MHz, CDCl3) δ7.69(d,J=2.3Hz,1H),7.24-7.19(m,1H),6.98(d,J=8.6Hz,1H),5.20(s,2H ), 3.52 (s, 3H), 1.58-1.48 (m, 2H), 1.31-1.13 (m, 16H), 1.10-0.98 (m, 2H), 0.86 (t, J = 7.0Hz, 3H).

[0838]

[0839] Step 5:2-iodo-1-(methoxymethoxy)-4-(2-methyldec-2-yl)benzene (323.0 g, 710.3 mmol, 1 eq) and anhydrous toluene (890 mL) were added to a 2L three-necked flask equipped with a mechanical stirrer, a reflux condenser and a nitrogen pad. The solution was bubbled with nitrogen for 30 minutes. Carbazole (124.7 g, 745.8 mmol, 1.05 eq), anhydrous potassium phosphate (powder form, 301.5 g, 1421 mmol, 2.0 eq), copper iodide (CuI, 6.8 g, 35.5 mmol, 0.05 eq) and dimethylethylenediamine (DMEDA, 23 mL, 213.1 mmol, 0.30 eq) were added to the solution. The reaction mixture obtained is heated to 110 ℃ and kept for 21 hours, now adding other CuI (6.8g, 35.5mmol, 0.05 equivalent) and DMEDA (23mL, 213.1mmol, 0.30 equivalent). After 43 hours of total reaction time, GC analysis shows that the initial MOM compound is consumed completely, and reactant is cooled to ambient temperature. After cooling, filter and remove solid by medium glass frit funnel, and transmit filtrate through silica gel pad. Filtrate (about 2L) is divided into two parts of about 1L, concentrate each part. In each flask containing brown solid, add acetonitrile (1500mL). The gained slurries were stirred 15 minutes, filtered and collected light brown solid. The solid collected was wet-milled 15 minutes again with acetonitrile (every batch of solid 1000mL). By filtering and collecting solid, dry in vacuum drying oven (35 ℃), obtain the product (192.9g, 99.8% purity) merging batches. The wet milled filtrates were combined and concentrated to give 174 g of crude product, which was then absorbed onto silica gel (330 g). The crude product on silica was divided into four portions and purified by flash chromatography using a CombiFlash Torrent purification system (2% ethyl acetate / hexane for 5 minutes, then gradient to 5% ethyl acetate over 12 minutes). The relatively pure eluate was concentrated to give 44.6 g of a light pink solid, which was wet milled with acetonitrile (400 mL) for 15 minutes, filtered, and then dried in a vacuum oven (35° C.) to give an additional 27.6 g of a white solid (99.0% purity). The total yield was 220.5 g (67.8%).

[0840] 1H NMR (400MHz, CDCl3) δ8.14(ddd,J=7.8,1.3,0.7Hz,2H),7.42-7.35(m,4H),7.34-7.30(m,1H),7.26(ddd,J=8.1,7.2,1.0Hz,2H),7 .17(dt,J=8.2,0.9Hz,2H),4.93(s,2H),3.16(s,3H),1.60-1.56(m,2H),1.26(d,J=27.1Hz,16H),1.13(s,2H),0.91-0.80(m,3H).

[0841]

[0842] Step 6 : Under nitrogen atmosphere, a 1L three-necked round-bottom flask equipped with a magnetic stirrer, a thermocouple well with a thermal probe, and a nitrogen purge was charged with a DOC-61128 top group (81.0 g, 177 mmol, 1 eq) and anhydrous THF (366 g, via cannula, 18.1 wt% solution). The mixture was cooled to -20 to -15°C in a dry ice acetonitrile bath. While maintaining the internal temperature between -20 and -15°C, a 2.5 M solution of n-butyl lithium in hexane (88.5 mL, 221.3 mmol, 1.25 eq) was added using a syringe pump (3 mL / min). The resulting dark brown solution was stirred and warmed to 10°C over 1.5 hours. A sample of the reaction mixture (0.1 mL) was removed and quenched with D2O, extracted with CDCl3, and filtered through 1H NMR spectroscopy analysis, which shows that the starting material is completely deuterated (confirming that the lithiation step is complete). The reaction mixture is cooled to between -20 and -15 ° C, and 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (iPrOBPin, 49 mL, 239 mmol, 1.35 equivalents) is added at 1 mL / min by a syringe pump. After the addition is complete, the reaction mixture is stirred for 40 minutes and warmed to 0 ° C. The sample is taken out, quenched with saturated NH4Cl, extracted with hexane, diluted with THF, and analyzed by HPLC. The HPLC trace shows 95.6% BPin+boric acid and 1.5% proton deborylation byproducts. About 1 hour after the addition of iPrOBPin is completed, the reaction mixture is warmed to 4 ° C. The light brown slurry reaction mixture is cooled to 0-5 ° C in a dry ice bath, diluted with hexane (200 mL), and ice water (115 mL) is slowly added to keep the temperature below 5 ° C. The mixture was transferred to a 1L separatory funnel and the bottom aqueous layer was removed. The aqueous layer was extracted with hexane (60 mL x 2). The combined organics were washed with saturated NH4Cl (115 mL), water (115 mL) and saturated NaCl (60 mL) and vacuum filtered through anhydrous MgSO4 pad. The filtrate was concentrated by rotary evaporation (20 Torr, 50 ° C) to give a yellow viscous oily crude product (96% purity, 103.7 g, theoretical value = 103.3 g). The crude product was used in the next step without further purification. 1 H NMR (400MHz, CDCl3) δ8.11(d,J=7.7Hz,2H),7.83(s,1H),7.46(s,1H),7.39(t,J=7.7Hz,2H),7.27(d,J=1.0Hz,1H),7.21(d, J=8.2Hz,3H),4.66(s,2H),2.32(s,3H),1.58(d,J=7.6Hz,2H),1.38(s,12H),1.26(d,J=31.9Hz,26H),0.86(t,J=6.9Hz,3H).

[0843]

[0844] Step 7: Preparation of 2-iodo-4-fluorophenol : This step is carried out as seen in the synthesis of procatalyst (A4).

[0845]

[0846] Step 8: This step is carried out as seen in the synthesis of procatalyst (A4).

[0847]

[0848] Step 9: DOC-61128 iodine-bottom group (32 g, 60.4 mmol, 1 equivalent), DOC-61128 top group BPin (87 g, 126.8 mmol, 2.1 equivalents) and THF (300 mL) were loaded into a 1 L four-necked flask equipped with an overhead stirrer, a thermocouple, a water condenser and a nitrogen pad. The reaction mixture was degassed for 1 hour. Then degassed 2N NaOH (181 mL, 362 mmol, 6 equivalents, via cannula) and (Pd(PPh3)4) (2.09 g, 1.8 mmol, 3 mol%) were added to the flask. The resulting reaction mixture (brown biphasic solution) was stirred at 50°C. After stirring for 6 hours, additional DOC-61128 top group BPin (20.7 g, 35.8 wt % solution, 0.2 eq., degassed) and Pd(PPh3)4 (0.7 g, 1 mol %) were added, and the reaction mixture was stirred at 50°C overnight. After stirring overnight (15 hours), a sample of the reaction mixture (brown solution) was taken out and analyzed by HPLC. The HPLC trace showed complete consumption of the single coupling intermediate. The reaction mixture was cooled to ambient temperature and the layers were separated. The aqueous layer was extracted with THF (160 mL×2). The combined organic layers were passed through a filter, then washed with brine (500 mL in total, 5 portions), and placed in a 2L four-necked flask.

[0849] Deprotection step : A 2L four-necked flask equipped with a magnetic stirrer, a water condenser, a thermocouple and a nitrogen pad was charged with THF containing the protected crude product. Methanol (MeOH, 370 mL) and concentrated HCl (31 mL, 362 mmol, 6 eq.) were added, and the reaction mixture (clear red solution) was stirred at 60°C. After stirring for 5 hours, a sample of the reaction mixture was taken out and purified by 19 FNMR spectral analysis. 19 F NMR spectrum showed that the deprotection was almost complete. Water (35 mL) was added and the reaction mixture was stirred at 60 °C until 19 The reaction was completed by F NMR spectrum. After the reaction was completed (about 12 hours), the reaction mixture was cooled to ambient temperature under agitation. After cooling, a precipitate was observed. The precipitate was collected by filtration and rinsed with acetonitrile (500mL). The collected off-white solid was dried in vacuo at 50°C (30 Torr) to obtain the final product (53.68g, HPLC purity 98%, isolated yield 79%) of off-white solid. 1H NMR (400MHz, CDCl3) δ8.14(d,J=7.7Hz,4H),7.40-7.28(m,8H),7.26(s,1H),7.23(d,J=7.6Hz,3H),7.15(d,J=7.8Hz,6H),6.99(td,J=8.4,7. 8, 3.1Hz, 2H), 6.72 (dd, J = 9.0, 4.5Hz, 2H), 6.03 (s, 2H), 3.73 (s, 4H), 1.60 (d, J = 22.6Hz, 8H), 1.25 (d, J = 30.7Hz, 36H), 0.84 (t, J = 6.8Hz, 6H). 19 F NMR (400MHz, CDCl3) δ-121.77 (s, 2F).

[0850]

[0851] Step 10 : In a glove box, HfCl4 (39.428 g, 123.10 mmol) and 5.4 L toluene (anhydrous) were loaded into a glass reactor. The mixture was cooled to -20 ° C, and MeMgBr (172 mL, 517.01 mmol) was then added under stirring. After stirring for 8 minutes, DOC-61128 ligand (135.59 g, 123.10 mmol) was added, and the resulting mixture was warmed to room temperature within 20 minutes. Once room temperature was reached, the reaction mixture was stirred for 4.5 hours. When NMR confirmed that the reaction was complete, the crude mixture was filtered and the solid was rinsed with additional toluene (0.4 L). The filtrate was vacuum dried to obtain a brown solid. The solid was dissolved in anhydrous methylcyclohexane (4.5 L), stirred for 2 hours, and then filtered through a diatomaceous earth pad. The solids were rinsed with additional methylcyclohexane (0.5 L) and the filtrate was dried under vacuum to afford 145.666 g, 90.5% yield, of the desired metal complex. 1H NMR (400MHz, benzene-d6) δ8.15(d,J=7.6Hz,2H),8.05(d,J=7.0Hz 2H),7.60(d,J=2.5Hz,2H),7.55(d,J=8.1Hz,2H),7.47(d,J=8.2Hz,2H),7.40(ddd,J=8.2,7.1,1.2Hz, 2H),7.30(d,J=2.5Hz,2H),7.27-7.18(m,6H),6.96(dd,J=9.0,3.2Hz,2H),6.59(ddd,J=9.0,7.2,3.2H z,2H),4.68(dd,J=9.1,5.0Hz,2H),3.92(t,J=10.3Hz,2H),3.35(d,J=11.5Hz,2H),1.57-1.46(m,4H), 1.25(m,24H),1.22(s,6H),1.19(s,6H),0.90(t,J=6.5Hz,6H),0.84(m,2H),0.75(m,2H),-1.11(s,6H). 19 F NMR(376MHz,C6D6)δ-116.02.

[0852] Synthesis of procatalyst (BB):

[0853] Step 1: Preparation of 2-mesityl-6-bromopyridine as seen in the synthesis of B10

[0854]

[0855] Step 2: Preparation of N-isobutyl-6-mesitylpyridin-2-amine : In a 500mL round-bottom flask, 2-bromo-6-mesitylpyridine (20.0g, 72.4mmol), NaOtBu (20.9g, 217.3mmol), Pd2dba3 (0.33g, 0.36mmol), rac-BINAP (0.45g, 0.72mmol), isobutylamine (10.8mL, 109mmol) and toluene (200mL, anhydrous) were loaded. The reaction mixture was heated to 100°C for 15 hours and then all volatiles were removed. The crude product was washed with water and extracted with EtOAc. The organic layer was collected and all volatiles were removed. The crude brown product was purified by column chromatography to obtain a pure product (hexane: EtOAc 85: 15). Yield: 19.4g, 62%. 1H NMR (400MHz, CDCl3) δ7.47(ddd,J=8.4,7.1,1.2Hz,1H),6.88(s,2H),6.46(dq,J=7.2,0.8Hz,1H),6.30(d,J=8.3Hz,1H),4.74(s, 1H), 3.04 (ddd, J=7.0, 5.9, 1.2Hz, 2H), 2.28 (s, 3H), 2.03 (s, 6H), 1.88 (dpd, J=13.3, 6.7, 1.3Hz, 1H), 0.97 (dd, J=6.6, 1.2Hz, 6H). 13 C NMR (101MHz, CDCl3) δ158.90,137.75,136.92,135.57,128.14,113.36,103.01,50.27,28.33,21.03,20.37,20.04.

[0856]

[0857] Step 3 :In a glove box, HfCl4(8.11g, 25.3mmol) and CH2Cl2(100mL) were added to a 200mL wide-mouth bottle. The suspension was cooled to -25°C, and MeMgBr(3M, in ether, 38.0mL, 114.0mmol) was then added. The solution was stirred for 2 minutes, and then a cold CH2Cl2(50mL) solution of 2-mesitylene-N-neopentylpyridine-2-amine(13.6g, 50.7mmol) was added. The solution quickly turned yellow and was stirred at room temperature for 3 hours. All volatiles were removed, the residue was dissolved in hexane, and filtered through a disposable glass frit. The yellow solution was evacuated to dryness, then dissolved in hexane again and filtered through a 0.2 micron syringe filter. Note: It may be necessary to dissolve in hexane and filter more than twice to remove all salts (proving that salts are problematic and have an adverse effect on the efficiency of the catalyst). The yellow solution was evacuated to dryness and used without further purification (14.5 g, 93%). The compound crystallized readily as a yellow solid. 1 H NMR(400MHz,C6D6)δ6.96(dd,J=8.7,7.2Hz,2H),6.70(s,4H),5.88(dd,J=7.2,0.8Hz,2H),5.75(dd,J=8.7,0.8Hz,2H) ,2.40(d,J=7.1Hz,4H),2.16(s,6H),1.86(s,12H),1.74(dq,J=13.6,6.9Hz,2H),0.93(h,J=6.6Hz,12H),0.50(s,6H). 13C NMR (101MHz, C6D6) δ171.26,155.90,140.68,136.79,136.40,135.46,109.42,102.34,54.83,53.74,28.45,20.65,20.59,19.93.

[0858] Aggregate Instance

[0859] Continuous solution polymerization procedure

[0860] The above exemplary non-limiting procatalysts are used for the polymerization of olefin block copolymers in continuous mixed polymerization. The continuous mixed polymerization is carried out in a 5L or 3.8L continuous stirred tank reactor (CSTR) or a 114L loop reactor according to the following non-limiting procedures and the process conditions of Tables 1-3. The properties of the olefin block copolymers polymerized by the exemplary non-limiting procatalysts of the present disclosure are shown in Table 4.

[0861] Referring to the table, "Catalyst 1" refers to the first olefin polymerization procatalyst (A), "Catalyst 2" refers to the second olefin polymerization procatalyst (B), "Cocatalyst 1" refers to [HNMe(C18H37)2][B(C6F5)4] (an exemplary cocatalyst), "Cocatalyst 2" refers to TEA (an exemplary cocatalyst), and "CSA" refers to DEZ (an exemplary chain shuttling agent). "(A1)", "(A4)", "(B10)", "(B14)" and "(R)" refer to procatalyst (A1), procatalyst (A4), procatalyst (B10), procatalyst (B14) and procatalyst (R), respectively.

[0862] Starting materials (ethylene, 1-octene, butene) and process solvents (SBP100 / 140 purchased from Shell, or narrow boiling range high purity isoparaffin solvents purchased from Exxon Mobil Corp. under the trademark Isopar-E) were purified with molecular sieves before introduction into the reaction environment. Hydrogen was supplied in pressurized cylinders as a high purity gas. Triethylaluminum (TEA) commercially available from Akzo Nobel was used as an impurity scavenger. Diethylzinc (DEZ) commercially available from Akzo Nobel was used as a chain shuttling agent. Individual catalyst components (precatalyst, cocatalyst) were manually diluted in batches with purified solvent to specified component concentrations and added to the reactor under positive nitrogen pressure. The cocatalyst was [HNMe(C18H37)2][B(C6F5)4 commercially available from Boulder Scientific]. All reaction feed flows were controlled by mass flow meters.

[0863] The combined solvent, monomer, comonomer and hydrogen are delivered to the reactor at a controlled temperature between 5°C and 30°C. The reactor is filled with liquids filled with reactor feed (ethylene, 1-octene, hydrogen and process solvent), which enter the reactor from the bottom and leave from the top. The reactor is heated with hot oil, and the normal process pressure is 28 bar. The catalyst is delivered to the reactor to achieve a specified ethylene conversion. The cocatalyst is delivered separately based on a calculated value of a specific molar ratio (1.2 molar equivalents) with the catalyst component. TEA and DEZ share the same pipeline with the cocatalyst. The TEA flow rate is based on the Al concentration in the reactor or a specific molar ratio with the catalyst component. The DEZ flow rate is based on the Zn concentration in the polymer. The effluent from the polymerization reactor (containing solvent, monomer, comonomer, hydrogen, catalyst component and molten polymer) leaves the reactor, and water is injected into the material flow to terminate the polymerization. In addition, various stabilizers or additives, such as antioxidants, are also added at this time. The material flow then passes through a static mixer to evenly disperse the catalyst killer and additives. When leaving the static mixer, the molten polymer is preheated and then enters the first devolatilizer where most of the solvent and unconverted feed are removed by flash evaporation. The solvent-rich polymer is transferred through a second preheater in a vacuum devolatilizer where the remaining solvent is removed. The final polymer is pumped through the static mixer to the pelletizer.

[0864] Table 1

[0865]

[0866] Table 2

[0867]

[0868] Table 3

[0869]

[0870] Table 4

[0871]

[0872] As seen in Comparative Example A, the comparative CSA and dual catalyst combination representing the state of the art cannot meet the desired product specifications (e.g., 0.5I2) of molecular weight and the combined catalyst efficiency at high temperatures. As seen in Comparative Example B, replacing the procatalyst (A1) with only the exemplary procatalyst (A4) produces the desired melt index and sufficient efficiency, but produces an undesirable wider polydispersity. In contrast, as seen in Inventive Examples 1 to 7, the CSA and dual catalyst combination of the present invention can produce olefin block copolymer resins with desired properties (e.g., desired melt index, relatively low I10 / I2, and narrow PDI) at high reactor temperatures up to 170°C with good combined catalyst efficiency. This elevated reactor temperature increases production rates and reduces energy consumption. This is surprising and unexpected because the prior art has not yet demonstrated that the CSA and dual catalyst combination can produce olefin block copolymers with desired properties with commercially acceptable catalyst efficiency and process control at such elevated reactor temperatures.

[0873] In addition, at similar densities, the thermomechanical properties of the inventive examples are improved as measured by TMA. Comparing Inventive Example 4 and Comparative Example A to the inventive procatalyst pair, the OBC resin has higher thermomechanical resistance as measured by TMA, as well as narrow PDI and acceptable Mw. Inventive Examples 1 to 3 and 5 to 7 also have a combination of slightly higher thermomechanical resistance, narrow PDI and higher catalyst efficiency compared to Comparative Example B.

[0874] Figures 2 to 4 The CEF curves seen in further support that the present invention examples prepare olefin block copolymers. Figures 2 to 4 As can be seen, two peaks are observed in the CEF trace of each polymer sample, and the high-temperature peak is often bimodal. The material that elutes first at low temperature (about 30°C) is composed of polymers with a high comonomer content, which will not crystallize from a dilute solution under CEF analysis conditions. This fraction contains mainly polymers produced by soft block catalysts (A1, A4). The material eluted at high temperature (about 60-115°C) is composed of polymers with semi-crystalline segments. This fraction contains polymers with a large portion of segments produced by hard block catalysts (R, B10 or B14). The bimodality of the peak is due to the distribution of block segment lengths and the number of blocks per polymer chain. Polymer chains with a larger portion of "hard" blocks or a longer average "hard" block length elute at higher temperatures. Compared to random copolymers with the same CEF elution temperature in the range of 60-115°C, Figures 2 to 4All of the examples shown in have higher comonomer content at the same elution temperature, indicating the presence of "hard" semi-crystalline blocks and "soft" high comonomer content blocks in the same polymer chain (as evidenced by ATREF analysis in WO 2006 / 101966 A1). The unshuttled blends produced by Catalyst 1 and Catalyst 2 will separate into two CEF peaks, one eluting at about 30°C and one eluting at about 100°C, with the peak areas corresponding to the mass fraction produced by each catalyst. The examples shown have about 75-90 wt% of the segments produced by the "soft" block catalyst Catalyst 1. However, most of the resin elutes in the high temperature region, indicating the presence of olefin block copolymers in all of the examples shown.

[0875] In addition, the reaction ratio (r 1A ) was determined to be 8.83, while the reaction rate (r 1B ) was determined to be 133.46. Therefore, the r of the dual catalyst combination of the precatalyst (A4) and (B14) of the present invention is 1A With r 1B The ratio is less than 0.5. In addition, Figure 5 Incorporation data for the dual catalyst combination of the inventive procatalysts (A4) and (B14) is provided, obtained by plotting the mole percent comonomer in the olefin block copolymer produced versus the mole percent comonomer in the reactor.

[0876] In addition, Examples 8 to 24 of the present invention provided similar results to Examples 1 to 7 of the present invention, as shown in Tables 5 to 12 below:

[0877] Table 5

[0878]

[0879] Table 6

[0880]

[0881] Table 7

[0882]

[0883] Table 8

[0884]

[0885] Table 9

[0886]

[0887] Table 10

[0888]

[0889] Table 11

[0890]

[0891] Table 12

[0892]

[0893] Specific embodiments

[0894] The following are exemplary non-limiting embodiments of the present disclosure and combinations thereof.

[0895] 1. A composition comprising a mixture or reaction product produced by combining:

[0896] (A) a first olefin polymerization procatalyst,

[0897] (B) a second olefin polymerization procatalyst, and

[0898] (C) chain shuttling agents,

[0899] Wherein the second olefin polymerization procatalyst comprises a metal-ligand complex of formula (I):

[0900]

[0901] wherein M is titanium, zirconium or hafnium;

[0902] wherein each Z1 is independently a neutral, monoanionic or dianionic monodentate or polydentate ligand, wherein nn is an integer, and wherein Z1 and nn are selected in such a way that the metal-ligand complex of formula (I) is neutral overall;

[0903] Each Q 1 and Q 10 Independently selected from the group consisting of: (C6-C 40 ) aryl, substituted (C6-C 40 ) aryl, (C3-C 40 )heteroaryl, and substituted (C3-C 40 ) heteroaryl;

[0904] Each Q 2 , Q 3 , Q 4 , Q 7 , Q 8 and Q 9 are independently selected from the group consisting of: hydrogen, (C1-C 40) alkyl, substituted (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, substituted (C1-C 40 ) heteroalkyl, halogen and nitro (NO2);

[0905] Each Q 5 and Q 6 Independently selected from the group consisting of: (C1-C 40 ) alkyl, substituted (C1-C 40 )alkyl, and [(Si) 1- (C+Si) 40 ] substituted organosilyl;

[0906] wherein each N is independently nitrogen;

[0907] Optionally, Q 1-5 Two or more of the groups are combined together to form a ring structure having from 5 to 16 atoms in the ring, excluding any hydrogen atoms; and

[0908] Optionally, Q 6-10 Two or more of the groups can be combined together to form a ring structure having from 5 to 16 atoms in the ring, excluding any hydrogen atoms.

[0909] 2. The composition of embodiment 1, further comprising (D) an activator.

[0910] 3. The composition of any preceding embodiment, wherein each Z1 is independently Me, Bn or Cl.

[0911] 4. The composition of any of the preceding embodiments, wherein Q 1 and Q 10 is a substituted phenyl group, as shown in formula (II):

[0912]

[0913] Among them J 1 -J 10 Each independently selected from R s A substituent and hydrogen; and each R S are independently halogen atoms, polyfluorinated, perfluorinated, unsubstituted (C1-C 18 ) alkyl, (C6-C 18 )aryl, F3C, FCH2O, F2HCO, F3CO, (R C1 )3Si、(R C1 )3Ge、(R C1 )O、(R C1)S、(R C1 )S(O),(R C1 )S(O)2、(R C1 )2P、(R C1 )2N、(R C1 )2C=N、NC、NO2、(R C1 )C(O)O、(R C1 )OC(O),(R C1 )C(O)N(R C1 ), or (R C1 )2NC(O), or two of the R S together to form an unsubstituted (C1-C 18 ) alkylene, wherein each R S are independently unsubstituted (C1-C 18 )alkyl, and

[0914] Each R C1 are independently hydrogen, unsubstituted (C1-C 18 ) alkyl or unsubstituted (C1-C 18 ) is a heteroalkyl group, or is absent (eg, absent when N comprises -N=).

[0915] 5. The composition of embodiment 4, wherein J 1 , J 5 , J 6 and J 10 Each is independently selected from the group consisting of a halogen atom, a (C1-C8) alkyl group, and a (C1-C8) alkoxy group.

[0916] 6. The composition of embodiment 4, wherein J 1 , J 5 , J 6 and J 10 Each is independently methyl; ethyl or isopropyl.

[0917] 7. The composition of any of the preceding embodiments, wherein Q 5 and Q 6 Each independently is (C1-C 40 ) is a primary or secondary alkyl group.

[0918] 8. The composition of any of the preceding embodiments, wherein Q 5 and Q 6 Each is independently propyl, isopropyl, neopentyl, hexyl and benzyl.

[0919] 9. The composition of any of the preceding embodiments, wherein the metal-ligand complex of formula (I) is selected from the group consisting of:

[0920]

[0921] 10. The composition of any of the preceding embodiments, wherein the metal-ligand complex of formula (I) is selected from the group consisting of:

[0922]

[0923] 11. The composition of any of the preceding embodiments, wherein the metal-ligand complex of formula (I) is selected from the group consisting of:

[0924]

[0925] 12. The composition of any preceding embodiment wherein M is zirconium or hafnium.

[0926] 13. The composition of any of the preceding embodiments, wherein the first olefin polymerization procatalyst (A) and the second olefin polymerization procatalyst (B) have a reaction ratio of 1A and r 1B , so that the ratio under polymerization conditions (r 1A / r 1B ) is 0.5 or less.

[0927] 14. The composition of any of the preceding embodiments, wherein the first olefin polymerization procatalyst (A) comprises a metal-ligand complex of formula (III):

[0928] in:

[0929] M is zirconium or hafnium;

[0930] R 20 is independently at each occurrence a divalent aromatic or inertly substituted aromatic group containing 5 to 20 atoms, excluding hydrogen;

[0931] T 3 is a divalent hydrocarbon or silane radical having 3 to 20 atoms, excluding hydrogen, or an inert substituted derivative thereof;

[0932] R D is independently at each occurrence a monovalent ligand group having 1 to 20 atoms, excluding hydrogen, or two R D The groups together form a divalent ligand group having 1 to 20 atoms excluding hydrogen.

[0933] 15. The composition of embodiment 13, wherein the metal-ligand complex of formula (III) has the following structure:

[0934] in:

[0935] Ar 4 C independently at each occurrence 6-20 Aryl or its inertly substituted derivatives, in particular 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl, naphthyl, anthracen-5-yl, 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl;

[0936] T 4 is independently at each occurrence propene-1,3-diyl, bis(alkylene)cyclohexane-1,2-diyl, or an inert substituted derivative thereof substituted with 1 to 5 alkyl, aryl or aralkyl substituents each having up to 20 carbons;

[0937] R 21 is independently at each occurrence hydrogen, halo, hydrocarbyl having up to 50 atoms excluding hydrogen, trihydrocarbylsilanyl, trihydrocarbylsilylhydrocarbyl, alkoxy, or amino;

[0938] R D is independently at each occurrence a halo group or a hydrocarbyl or trihydrocarbylsilyl group having up to 20 atoms, not counting hydrogen, or 2 R D The radicals together form a divalent hydrocarbylene, hydrocarbyli or trihydrocarbylisilyl radical having up to 40 atoms, not counting hydrogen.

[0939] 16. The composition of embodiment 13, wherein the metal-ligand complex of formula (III) has the following structure:

[0940] in

[0941] Ar 4 is independently at each occurrence 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl, or anthracen-5-yl,

[0942] R 21 is independently at each occurrence hydrogen, halo, hydrocarbyl having up to 50 atoms excluding hydrogen, trihydrocarbylsilanyl, trihydrocarbylsilylhydrocarbyl, alkoxy, or amino;

[0943] T 4 is propane-1,3-diyl or bis(methylene)cyclohexane-1,2-diyl; and

[0944] R D is independently at each occurrence a halo group or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms, not counting hydrogen, or 2 R D The radicals together form a hydrocarbylene, hydrocarbyldiyl or hydrocarbylsilanediyl radical having up to 40 atoms not counting hydrogen.

[0945] 17. The composition of embodiment 13, wherein the metal-ligand complex of formula (III) is selected from the group consisting of:

[0946]

[0947]

[0948] 18. The composition of any of the preceding embodiments, wherein the chain shuttling agent is an aluminum, zinc or gallium compound containing at least one hydrocarbyl substituent having 1 to 12 carbons.

[0949] 19. An olefin polymerization catalyst system comprising:

[0950] (A) a first olefin polymerization procatalyst,

[0951] (B) a second olefin polymerization procatalyst, and

[0952] (C) chain shuttling agents,

[0953] Wherein the second olefin polymerization procatalyst comprises a metal-ligand complex of formula (I):

[0954]

[0955] wherein M is titanium, zirconium or hafnium;

[0956] wherein each Z1 is independently a neutral, monoanionic or dianionic monodentate or polydentate ligand, wherein nn is an integer, and wherein Z1 and nn are selected in such a way that the metal-ligand complex of formula (I) is neutral overall;

[0957] Each Q 1 and Q 10 Independently selected from the group consisting of: (C6-C 40 ) aryl, substituted (C6-C 40 ) aryl, (C3-C 40 )heteroaryl, and substituted (C3-C 40 ) heteroaryl;

[0958] Each Q 2 , Q 3 , Q 4 , Q 7 , Q 8 and Q 9 are independently selected from the group consisting of: hydrogen, (C1-C 40 ) alkyl, substituted (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, substituted (C1-C 40) heteroalkyl, halogen and nitro (NO2);

[0959] Each Q 5 and Q 6 Independently selected from the group consisting of: (C1-C 40 ) alkyl, substituted (C1-C 40 )alkyl, and [(Si) 1- (C+Si) 40 ] substituted organosilyl;

[0960] wherein each N is independently nitrogen;

[0961] Optionally, Q 1-5 Two or more of the groups are combined together to form a ring structure having from 5 to 16 atoms in the ring, excluding any hydrogen atoms; and

[0962] Optionally, Q 6-10 Two or more of the groups can be combined together to form a ring structure having from 5 to 16 atoms in the ring, excluding any hydrogen atoms.

[0963] 20. The olefin polymerization catalyst system of embodiment 19, further comprising (D) an activator.

[0964] 21. The olefin polymerization catalyst system of embodiment 19 or 20, wherein each Z1 is independently Me, Bn or Cl.

[0965] 22. The olefin polymerization catalyst system of any one of embodiments 19 to 21, wherein Q 1 and Q 10 is a substituted phenyl group, as shown in formula (II):

[0966]

[0967] Among them J 1 -J 10 Each independently selected from R s A substituent and hydrogen; and each R S are independently halogen atoms, polyfluorinated, perfluorinated, unsubstituted (C1-C 18 ) alkyl, (C6-C 18 )aryl, F3C, FCH2O, F2HCO, F3CO, (R C1 )3Si、(R C1 )3Ge、(R C1 )O、(R C1 )S、(R C1 )S(O),(R C1 )S(O)2、(RC1 )2P、(R C1 )2N、(R C1 )2C=N、NC、NO2、(R C1 )C(O)O、(R C1 )OC(O),(R C1 )C(O)N(R C1 ), or (R C1 )2NC(O), or two of the R S together to form an unsubstituted (C1-C 18 ) alkylene, wherein each R S are independently unsubstituted (C1-C 18 )alkyl, and

[0968] Each R C1 are independently hydrogen, unsubstituted (C1-C 18 ) alkyl or unsubstituted (C1-C 18 ) is a heteroalkyl group, or is absent (eg, absent when N comprises -N=).

[0969] 23. The olefin polymerization catalyst system of embodiment 22, wherein J 1 , J 5 , J 6 and J 10 Each is independently selected from the group consisting of a halogen atom, a (C1-C8) alkyl group, and a (C1-C8) alkoxy group.

[0970] 24. The olefin polymerization catalyst system of embodiment 22, wherein J 1 , J 5 , J 6 and J 10 Each is independently methyl; ethyl or isopropyl.

[0971] 25. The olefin polymerization catalyst system of any one of embodiments 19 to 24, wherein Q 5 and Q 6 Each independently is (C1-C 40 ) is a primary or secondary alkyl group.

[0972] 26. The olefin polymerization catalyst system of any one of embodiments 19 to 25, wherein Q 5 and Q 6 Each is independently propyl, isopropyl, neopentyl, hexyl and benzyl.

[0973] 27. The olefin polymerization catalyst system of any one of embodiments 19 to 26, wherein the metal-ligand complex of formula (I) is selected from the group consisting of:

[0974]

[0975] 28. The olefin polymerization catalyst system of any one of embodiments 19 to 27, wherein the metal-ligand complex of formula (I) is selected from the group consisting of:

[0976]

[0977] 29. The olefin polymerization catalyst system of any one of embodiments 19 to 28, wherein the metal-ligand complex of formula (I) is selected from the group consisting of:

[0978]

[0979] 30. The olefin polymerization catalyst system of any one of embodiments 19 to 29, wherein M is zirconium or hafnium.

[0980] 31. The olefin polymerization catalyst system of any one of embodiments 19 to 30, wherein the first olefin polymerization procatalyst (A) and the second olefin polymerization procatalyst (B) have corresponding reaction ratios r 1A and r 1B , so that the ratio (r 1A / r 1B ) is 0.5 or less.

[0981] 32. The olefin polymerization catalyst system of any one of embodiments 19 to 31, wherein the first olefin polymerization procatalyst (A) comprises a metal-ligand complex of formula (III):

[0982] in:

[0983] M is zirconium or hafnium;

[0984] R 20 is independently at each occurrence a divalent aromatic or inertly substituted aromatic group containing 5 to 20 atoms, excluding hydrogen;

[0985] T 3 is a divalent hydrocarbon or silane radical having 3 to 20 atoms, excluding hydrogen, or an inert substituted derivative thereof;

[0986] R D is independently at each occurrence a monovalent ligand group having 1 to 20 atoms, excluding hydrogen, or two R D The groups together form a divalent ligand group having 1 to 20 atoms excluding hydrogen.

[0987] 33. The olefin polymerization catalyst system of embodiment 32, wherein the metal-ligand complex of formula (III) has the following structure:

[0988] in:

[0989] Ar 4 C independently at each occurrence 6-20 Aryl or its inertly substituted derivatives, in particular 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl, naphthyl, anthracen-5-yl, 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl;

[0990] T 4 is independently at each occurrence propene-1,3-diyl, bis(alkylene)cyclohexane-1,2-diyl, or an inert substituted derivative thereof substituted with 1 to 5 alkyl, aryl or aralkyl substituents each having up to 20 carbons;

[0991] R 21 is independently at each occurrence hydrogen, halo, hydrocarbyl having up to 50 atoms excluding hydrogen, trihydrocarbylsilanyl, trihydrocarbylsilylhydrocarbyl, alkoxy, or amino;

[0992] R D is independently at each occurrence a halo group or a hydrocarbyl or trihydrocarbylsilyl group having up to 20 atoms, not counting hydrogen, or 2 R D The radicals together form a divalent hydrocarbylene, hydrocarbyli or trihydrocarbylisilyl radical having up to 40 atoms, not counting hydrogen.

[0993] 34. The olefin polymerization catalyst system of embodiment 32, wherein the metal-ligand complex of formula (III) has the following structure:

[0994] in

[0995] Ar 4 is independently at each occurrence 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl, or anthracen-5-yl,

[0996] R 21 is independently at each occurrence hydrogen, halo, hydrocarbyl having up to 50 atoms excluding hydrogen, trihydrocarbylsilanyl, trihydrocarbylsilylhydrocarbyl, alkoxy, or amino;

[0997] T 4 is propane-1,3-diyl or bis(methylene)cyclohexane-1,2-diyl; and

[0998] R D is independently at each occurrence a halo group or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms, not counting hydrogen, or 2 RD The radicals together form a hydrocarbylene, hydrocarbyldiyl or hydrocarbylsilanediyl radical having up to 40 atoms not counting hydrogen.

[0999] 35. The olefin polymerization catalyst system of embodiment 32, wherein the metal-ligand complex of formula (III) is selected from the group consisting of:

[1000]

[1001] 36. The olefin polymerization catalyst system of any one of embodiments 19 to 35, wherein the chain shuttling agent is an aluminum, zinc or gallium compound containing at least one hydrocarbyl substituent having 1 to 12 carbons.

[1002] 37. A method of preparing a multi-block copolymer comprising contacting one or more addition polymerizable monomers with the composition of any one of embodiments 1 to 18 or the olefin polymerization catalyst system of embodiments 19 to 36 under addition polymerization conditions.

[1003] 38. A method of preparing a multi-block copolymer comprising contacting ethylene and at least one copolymerizable comonomer other than ethylene with the composition of any one of embodiments 1 to 18 or the olefin polymerization catalyst system of embodiments 19 to 36 under addition polymerization conditions.

[1004] 39. A method of preparing a multi-block copolymer comprising contacting ethylene and a C3-8 alpha-olefin with the composition of any one of embodiments 1 to 18 or the olefin polymerization catalyst system of embodiments 19 to 36 under addition polymerization conditions.

[1005] 40. The method of any one of embodiments 37 to 39, wherein the method is a continuous solution process.

[1006] 41. The method of embodiment 40, wherein the method is performed at a temperature greater than 125°C.

[1007] 42. The method of embodiment 41, wherein the method is carried out at a temperature of about 150°C and comprises more than 400 kg 聚合物 / g 金属 The efficiency of the combined catalyst.

[1008] 43. The method of embodiment 41, wherein the method is carried out at a temperature of about 150°C to about 170°C and comprises more than 200 kg 聚合物 / g 金属 The efficiency of the combined catalyst.

[1009] 44. A multi-block copolymer prepared by the method of any one of embodiments 37 to 43, wherein the multi-block copolymer comprises polymerized forms of one or more addition polymerizable monomers, the copolymer comprising two or more segments or blocks that differ in comonomer content, crystallinity, stereoisomerism, homogeneity, density, melting point, or glass transition temperature.

[1010] 45. The multi-block copolymer of embodiment 44, wherein the multi-block copolymer comprises a polymerized form of ethylene and one or more copolymerizable comonomers, the copolymer comprising two or more segments or blocks that differ in comonomer content, crystallinity, stereoisomerism, homogeneity, density, melting point, or glass transition temperature.

[1011] 46. ​​The multi-block copolymer of embodiment 44, wherein the multi-block copolymer comprises a molecular weight distribution Mw / Mn of less than 3.0.

[1012] 47. The multi-block copolymer of embodiment 44, wherein the multi-block copolymer comprises a melt index (ASTM D 1238 (190°C / 2.16 kg)) of less than 1.0.

[1013] 48. The multi-block copolymer of embodiment 44, wherein the multi-block copolymer comprises a thermomechanical resistance greater than 100°C.

[1014] 49. A functionalized derivative of the multi-block copolymer according to embodiment 44.

[1015] 50. The multi-block copolymer of embodiment 44, comprising the multi-block copolymer in the form of a film, at least one layer of a multilayer film, at least one layer of a laminated article, a foamed article, a fiber, a non-woven fiber, an injection molded article, a blow molded article, a rotationally molded article, or an adhesive.

Claims

1. An olefin polymerization catalyst system, comprising: (A) a first olefin polymerization procatalyst, (B) a second olefin polymerization procatalyst, and (C) chain shuttling agents, Wherein the second olefin polymerization procatalyst comprises a metal-ligand complex of formula (I): wherein M is titanium, zirconium or hafnium; wherein each Z1 is independently a neutral, monoanionic or dianionic monodentate or polydentate ligand, wherein nn is an integer, and wherein Z1 and nn are selected in such a way that the metal-ligand complex of formula (I) is neutral overall; Each Q 1 and Q 10 Independently selected from the group consisting of: C6-C 40 Aryl, substituted C6-C 40 Aryl, C3-C 40 Heteroaryl, and substituted C3-C 40 heteroaryl; Each Q 2 , Q 3 , Q 4 , Q 7 , Q 8 and Q 9 are independently selected from the group consisting of: hydrogen, C1-C 40 Hydrocarbon, substituted C1-C 40 Hydrocarbon, C1-C 40 Heteroalkyl, substituted C1-C 40 Heteroalkyl, halogen and nitro NO2; Each Q 5 and Q 6 Independently selected from the group consisting of: C1-C 40 Alkyl, substituted C1-C 40 Alkyl, and [(Si) 1- (C+Si) 40 ] substituted organosilyl, wherein the "substituted by [(Si) 1- (C+Si) 40 ] "substituted organosilyl" refers to a substituted silyl group having 1 to 40 silicon atoms and 0 to 39 carbon atoms such that the total number of carbon plus silicon atoms is between 1 and 40; wherein each N is independently nitrogen; and Wherein the first olefin polymerization procatalyst comprises a metal-ligand complex of the following formula: Among them, M 3 is Hf or Zr; Ar 4 is 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl or anthracene-5-yl, and T 4 Include C independently at each occurrence 3-6 Alkylene or C 3-6 Cycloalkylene; R 21 is independently at each occurrence hydrogen, halogen, hydrocarbyl having up to 50 atoms excluding hydrogen, trihydrocarbylsilanyl, or trihydrocarbylsilylhydrocarbyl; and G at each occurrence is independently halogen, a hydrocarbyl or trihydrocarbylsilyl group having up to 20 atoms not counting hydrogen, or two G groups taken together form a divalent derivative of the foregoing hydrocarbyl or trihydrocarbylsilyl group.

2. The catalyst system according to claim 1, further comprising (D) an activator.

3. The catalyst system according to claim 1 or 2, wherein each Z1 is independently Me, Bn or Cl.

4. The catalyst system according to claim 1 or 2, wherein Q 1 and Q 10 is a substituted phenyl group, as shown in formula (II): Among them J 1 -J 10 Each independently selected from R s A substituent and hydrogen; and each R S are independently halogen atoms, polyfluorinated C1-C 18 Alkyl, unsubstituted C1-C 18 Alkyl, C6-C 18 Aryl, FCH2O, F2HCO, F3CO, (R C1 )3Si、(R C1 )3Ge、R C1 O.R C1 S, R C1 SO, R C1 S(O)2、(R C1 )2P、(R C1 )2N、(R C1 )2C=N、NC、NO2、R C1 C(O)O、R C1 OCO, R C1 C(O)NR C1 or (R C1 )2NCO, or two of the R S Linked together to form unsubstituted C1-C 18 Alkylene, where each R S are independently unsubstituted C1-C 18 Alkyl, and Each R C1 are independently hydrogen, unsubstituted C1-C 18 Hydrocarbon or unsubstituted C1-C 18 Heteroalkyl.

5. The catalyst system according to claim 4, wherein each R S are independently perfluorinated C1-C 18 alkyl.

6. The catalyst system according to claim 4, wherein each R S Independently is F3C.

7. The catalyst system according to claim 4, wherein J 1 , J 5 , J 6 and J 10 Each is independently selected from the group consisting of a halogen atom, a C1-C8 alkyl group, and a C1-C8 alkoxy group.

8. The catalyst system according to claim 1 or 2, wherein Q 5 and Q 6 Each is independently C1-C 40 A primary or secondary alkyl group.

9. The catalyst system according to claim 1 or 2, wherein Q 5 and Q 6 Each is independently propyl, isopropyl, neopentyl, hexyl and benzyl.

10. The catalyst system according to claim 1 or 2, wherein the metal-ligand complex of formula (I) is selected from the group consisting of:

11. The catalyst system according to claim 1 or 2, wherein M in formula (I) is zirconium or hafnium.

12. The catalyst system according to claim 1 or 2, wherein the first olefin polymerization procatalyst (A) and the second olefin polymerization procatalyst (B) have corresponding reaction ratios r 1A and r 1B , so that the ratio r under polymerization conditions 1A / r 1B is 0.5 or less.

13. The catalyst system according to claim 1 or 2, wherein the first olefin polymerization procatalyst is selected from:

14. A method for preparing a multi-block copolymer, the method comprising contacting one or more addition polymerizable monomers with a catalyst system according to any one of claims 1 to 13 under addition polymerization conditions to prepare the multi-block copolymer, wherein the method is a continuous solution process carried out at a temperature greater than 125°C, The multi-block copolymer comprises polymerized forms of ethylene and one or more copolymerizable comonomers, wherein the copolymer contains two or more segments or blocks that differ in comonomer content, crystallinity, stereoisomerism, homogeneity, density, melting point or glass transition temperature.

15. The process according to claim 14, wherein the process is carried out at a temperature of about 150°C and comprises more than 400 kg 聚合物 / g 金属 The efficiency of the combined catalyst.

16. The process according to claim 14, wherein the process is carried out at a temperature of 150°C to 170°C and comprises more than 200 kg 聚合物 / g 金属 The efficiency of the combined catalyst.

17. The method of any one of claims 14-16, wherein the copolymer comprises a molecular weight distribution Mw / Mn of less than 3.

0.

18. The method of any one of claims 14-16, wherein the copolymer comprises a melt index of less than 1.0, wherein the melt index is measured according to ASTM D 1238 at 190°C and 2.16 kg.

19. The method of any one of claims 14-16, wherein the copolymer comprises a thermomechanical resistance greater than 100°C.

20. A method for preparing a multi-block copolymer by contacting one or more addition polymerizable monomers with a catalyst system under addition polymerization conditions to prepare the multi-block copolymer, wherein the method is a continuous solution process conducted at a temperature greater than 125°C, wherein the multi-block copolymer comprises polymerized forms of ethylene and one or more copolymerizable comonomers, the copolymer comprising two or more segments or blocks differing in comonomer content, crystallinity, stereoisomerism, homogeneity, density, melting point or glass transition temperature, and wherein the catalyst system comprises: (A) a first olefin polymerization procatalyst, (B) a second olefin polymerization procatalyst, and (C) chain shuttling agents, Wherein the second olefin polymerization procatalyst comprises a metal-ligand complex of formula (I): wherein M is titanium, zirconium or hafnium; wherein each Z1 is independently a neutral, monoanionic or dianionic monodentate or polydentate ligand, wherein nn is an integer, and wherein Z1 and nn are selected in such a way that the metal-ligand complex of formula (I) is neutral overall; Each Q 1 and Q 10 Independently selected from the group consisting of: C6-C 40 Aryl, substituted C6-C 40 Aryl, C3-C 40 Heteroaryl, and substituted C3-C 40 heteroaryl; Each Q 2 , Q 3 , Q 4 , Q 7 , Q 8 and Q 9 are independently selected from the group consisting of: hydrogen, C1-C 40 Hydrocarbon, substituted C1-C 40 Hydrocarbon, C1-C 40 Heteroalkyl, substituted C1-C 40 Heteroalkyl, halogen and nitro NO2; Each Q 5 and Q 6 Independently selected from the group consisting of: C1-C 40 Alkyl, substituted C1-C 40 Alkyl, and [(Si) 1- (C+Si) 40 ] substituted organosilyl, wherein the "substituted by [(Si) 1- (C+Si) 40 ] "substituted organosilyl" refers to a substituted silyl group having 1 to 40 silicon atoms and 0 to 39 carbon atoms such that the total number of carbon plus silicon atoms is between 1 and 40; wherein each N is independently nitrogen; and The first olefin polymerization procatalyst comprises a metal-ligand complex of formula (III) in Ar 4 is independently at each occurrence 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl, naphthyl, anthracen-5-yl or 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl, R 21 is independently at each occurrence hydrogen, halo, hydrocarbyl having up to 50 atoms excluding hydrogen, trihydrocarbylsilanyl, trihydrocarbylsilylhydrocarbyl, alkoxy, or amino; T 4 is propane-1,3-diyl or bis(methylene)cyclohexane-1,2-diyl; and R D is independently at each occurrence a halo group or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms, not counting hydrogen, or 2 R D The radicals together form a hydrocarbylene, hydrocarbyldiyl or hydrocarbylsilanediyl radical having up to 40 atoms not counting hydrogen.

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