Preparation of non-polar-polar block copolymers via vinyl-terminated polyolefins

Abstract

The present disclosure includes a method for preparing a non-polar-polar diblock copolymer. The method involves polymerizing one or more olefin monomers in the presence of an alkylaluminum chain transfer agent to form a polymerylaluminum species, which is then heated to form a vinyl-terminated polyolefin. A thiol compound is reacted with the vinyl-terminated polyolefin to form a sulfide-containing polyolefin intermediate. The thiol compound comprises a terminal hydroxyl or a protected terminal amine. A macroinitiator is produced by reacting the sulfide-containing polyolefin intermediate with a linker, the linker comprising an acyl halide and a halogen atom attached to the alpha carbon to the acyl halide. The macroinitiator, a radical reagent, and a CH═CH—(X) monomer (where X is —C(O)OR, —CN, or —C(O)NHR, and R is —H, a linear (C1-C 18 ) alkyl, or branched chain (C1-C 18 ) alkyl) react via a reversible deactivation radical polymerization reaction to produce a non-polar-polar diblock copolymer.

Description

[Technical Field]

[0001] SUMMARY OF THE DISCLOSURE Embodiments of the present disclosure generally relate to processes for producing non-polar-polar block copolymers using vinyl-terminated olefin polymers. [Background technology]

[0002] Over the past few decades, block copolymers have emerged as a class of polymeric materials with a wide range of technological applications. Due to their highly tunable chemical structure (i.e., morphology, architecture, and domain size), block copolymers have been utilized as surfactants, thermoplastic elastomers, nanotemplates, membranes, etc.

[0003] Polyolefin is generally 70 x 10 6 Polyolefins are commercially produced on a metric ton / year scale by catalytic insertion (co)polymerization of ethylene with linear α-olefins. The crystallinity of polyolefins can be tailored to achieve a variety of properties, including, but not limited to, toughness, elasticity, and solvent resistance. Therefore, incorporating polyolefins into block copolymers offers significant value. However, due to the highly oxygen-philic nature of the early transition element catalysts used in industrial polyolefin production, commercially available polyolefin block copolymers have been limited to those containing only nonpolar comonomers. Therefore, the preparation of functionalized block copolymers containing both polyolefin segments and polymer segments derived from polar comonomers remains a synthetic challenge.

[0004] Some researchers have synthesized functionalized vinyl polymers to produce block copolymers containing polyolefin segments. Functionalized vinyl polymers can be produced by natural molecular weight control based on catalytic or peroxide decomposition of polypropylene. However, the reagents used to produce functionalized vinyl polymers are not controlled, resulting in the production of functionalized vinyl-terminated polyolefin polymers with a wide range of molecular weights and low polyolefin block dispersity. Summary of the Invention

[0005] There is a continuing need to develop methods for producing high purity polyolefins with polar functional groups, such as non-polar-polar block copolymers. This method requires control of the molecular weight or molecular weight distribution of the polyolefin, and thus the polyolefin blocks of the block copolymer. Furthermore, this method requires control of the polar segments of the block copolymer.

[0006] An embodiment of the present disclosure includes a method for preparing a non-polar-polar diblock copolymer. The method includes polymerizing one or more olefin monomers in the presence of an alkylaluminum chain transfer agent to produce a polymeryl aluminum species. The polymeryl aluminum species is heated to produce a vinyl-terminated polyolefin. A thiol compound is reacted with the vinyl-terminated polyolefin to form a sulfide-containing polyolefin intermediate. The thiol compound comprises a terminal hydroxyl or a protected terminal amine. The sulfide-containing polyolefin intermediate is reacted with a linker to produce a macroinitiator. The linker comprises an acyl halide and a halogen atom attached to the alpha carbon to the acyl halide. The macroinitiator, a radical reagent, and a CH═CH—(X) monomer are reacted via a reversible deactivation radical polymerization reaction to produce a non-polar-polar diblock copolymer. In the formula of the CH═CH—(X) monomer, X is independently —C(O)OR, —CN, or —C(O)NHR (where R is —H, linear (C-C 18 ) alkyl, or branched chain (C1-C 18 ) alkyl). [Brief explanation of the drawings]

[0007] [Figure 1] 1 is a proton NMR ( 1 H NMR) spectrum of a vinyl-terminated polyolefin. [Figure 2A]1 is a graph of the integral of the proton NMR ( 1 H NMR) signal of the tert-butyl resonance from the polar block or the methylene (CH 2 ) resonance from the non-polar block as a function of the gradient 2 / 1000. [Figure 2B] The proton signals are tert-butyl resonances from the polar block and methylene (CH2) resonances from the non-polar block. DETAILED DESCRIPTION OF THE INVENTION

[0008] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In case of conflict, the present specification, including definitions, will control.

[0009] Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of various embodiments, the preferred methods and materials are described herein.

[0010] Unless otherwise specified, all percentages, parts, ratios, etc. are by weight. When an amount, concentration, or other value or parameter is given as either a range, a preferred range, or a list of a lower preferred value and an upper preferred value, it should be understood that this specifically discloses all ranges formed from any pairing of any lower range limit or preferred value with any upper range limit or preferred value, regardless of whether the ranges are separately disclosed. When a range of numerical values ​​is recited herein, unless otherwise specified, the range is intended to include its endpoints, and all integers and fractions within the range. It is not intended that the scope of the invention be limited to the specific values ​​recited when defining the range.

[0011] When the term "about" is used in describing values ​​or endpoints of a range, the disclosure should be understood to include the specific value or endpoint referred to.

[0012] As used herein, the terms "comprises," "comprising," "includes," "including," "containing," "characterized by," "has," "having," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that includes a list of elements is not necessarily limited to those elements and may include other elements that are not expressly listed or that are inherent to such process, method, article, or apparatus. Further, unless expressly stated to the contrary, "or" refers to an inclusive or, not an exclusive or.

[0013] The transitional phrase "consisting essentially of" limits the scope of the claim to the specified materials or steps, and those that do not materially affect the basic and novel characteristics of the disclosure. If applicant defines an embodiment or portion thereof with open-ended terms, such as "comprising," the description should be construed as also describing such embodiment(s) using the term "consisting essentially of," unless otherwise noted.

[0014] The use of "a" or "an" is employed to describe elements and components of various embodiments. This is merely for convenience and to give a general sense of the various embodiments. This description should be read to include one or at least one, and it also includes the plural unless it is clear that the singular form means otherwise.

[0015] The term "polymer" refers to a compound prepared by polymerizing monomers, whether of the same or different types. Thus, the generic term polymer encompasses the terms "homopolymer" and "copolymer." The term "homopolymer" refers to a polymer prepared from only one type of monomer, while the term "copolymer" refers to a polymer prepared from two or more different monomers, and for purposes of this disclosure, may include "terpolymer" and "interpolymer."

[0016] The term "block copolymer" refers to a multi-block interpolymer, which comprises one or more monomers in polymerized form, characterized by multiple blocks or segments of two or more polymerized monomer units, the blocks or segments differing in chemical or physical properties. Specifically, the term "block copolymer" refers to a polymer containing two or more chemically distinct regions or segments (called "blocks") linked in a linear chain. A "diblock copolymer" contains only two blocks or segments. For example, a diblock copolymer may contain a polyethylene segment and a polyacrylamide segment. Block copolymers may be characterized by a unique distribution of both polymer dispersities (D or Mw / Mn). The term "diblock copolymer" refers to a copolymer having two chemically distinct regions or segments linked in a linear chain.

[0017] In one or more embodiments, the non-polar-polar diblock copolymer comprises two blocks or segments, a non-polar block and a polar block. In some embodiments, the non-polar block is a polyolefin. The polyolefin can be an ethylene homopolymer or an ethylene / α-olefin copolymer. In some embodiments, the polar block comprises a polyacrylate copolymer. In various embodiments, the polar block comprises units derived from acrylate monomers, t-butyl acrylate, tert-butyl acrylate, acrylamide, acrylonitrile, and vinyl acetate. In one or more embodiments, the non-polar-polar diblock copolymer is a polyethylene-polyacrylate diblock copolymer.

[0018] The term "chain transfer agent" refers to a compound or mixture of compounds that can undergo reversible or irreversible polymeric exchange with an active catalyst site. Irreversible chain transfer refers to the transfer of a growing polymer chain from an active catalyst to a chain transfer agent, resulting in termination of polymer chain growth. Reversible chain transfer refers to the transfer of a growing polymer chain back and forth between an active catalyst and a chain transfer agent. The term "polymeric" refers to a polymer that is missing a hydrogen atom on the carbon at the point of attachment, for example, from the chain transfer agent to aluminum.

[0019] Embodiments of the present disclosure include a method for preparing a non-polar-polar diblock copolymer. The method includes polymerizing one or more olefin monomers in the presence of an alkylaluminum chain transfer agent to produce a polymerylaluminum species, which is then heated to produce a vinyl-terminated polyolefin. A thiol compound is reacted with the vinyl-terminated polyolefin to form a sulfide-containing polyolefin intermediate. The sulfide-containing polyolefin intermediate is reacted with a linker to produce a macroinitiator. The macroinitiator, a radical reagent, and a CH═CH—(X) monomer are reacted via a reversible deactivation radical polymerization reaction to produce a non-polar-polar diblock copolymer.

[0020] In one or more embodiments, the olefin monomers polymerized in the presence of an alkylaluminum chain transfer agent are (C-C 12 ) α-olefin monomers. In some embodiments, the olefin monomers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, and 1-decadene. In various embodiments, the olefin monomers are ethylene and 1-octene; ethylene and 1-hexene; ethylene and 1-butene; or ethylene and propylene.

[0021] In various embodiments, the olefin monomer is polymerized in the presence of an alkylaluminum chain transfer agent, the alkylaluminum chain transfer agent being AlR, where each R is independently (C-C 12 ) alkyl). In some embodiments, R is methyl, ethyl, n-propyl, 2-propyl, n-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, n-octyl, tert-octyl, nonyl, decyl, undecyl, or dodecyl. Non-limiting examples of alkyl aluminum chain transfer agents include triethyl aluminum, tri(i-propyl) aluminum, tri(i-butyl) aluminum, tri(n-hexyl) aluminum, and tri(n-octyl) aluminum.

[0022] The disclosed method involves polymerizing one or more olefin monomers in the presence of an alkylaluminum chain transfer agent to produce polymerylaluminum species. The alkylaluminum functions as a chain transfer agent, resulting in the formation of polymerylaluminum species. Heating the polymerylaluminum species produces vinyl-terminated polyolefins. The vinyl-terminated polyolefins may be formed via a β-hydride elimination reaction.

[0023] Formula A 1 L 1 A process for preparing a polyolefin component comprising a vinyl-terminated polyolefin according to the method of claim 1, wherein the polyolefin component comprises a olefin selected from the group consisting of ethylene and, optionally, one or more (C3-C 12 ) combining catalyst components including an α-olefin monomer, an alkyl aluminum chain transfer agent, and a procatalyst to form a solution, and polymerizing greater than 10 mol % to 99 mol % of ethylene and the α-olefin monomer in the solution. Heating the solution to a temperature of at least 160°C, holding the solution at a temperature of at least 160°C for at least 30 seconds, and recovering the product. The product is A 1 L 1 The polyolefin component includes an unsaturated polyolefin.

[0024] Formula A1 L 1 Medium, L 1 is a polyolefin, and A 1 is a vinyl group, formula CH2=C(Y 1 )-, a vinylidene group of formula Y 1 Vinylene group, where CH=CH-, vinyl group and formula Y 1 A mixture of vinyl groups with CH=CH- vinyl groups and the formula CH2=C(Y 1 )- with vinylidene groups, the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 Mixtures of vinylene groups with CH=CH- and vinyl groups with the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 and a mixture of CH═CH— and vinylene groups. 1 is C1~C 30 is a hydrocarbyl group of formula A 1 L 1 The unsaturated polyolefin has a weight average molecular weight of 1,000 to 10,000,000 g / mol.

[0025] Without being bound by any particular theory, the alkylaluminum chain transfer agent may be represented by the formula A 1 L 1 contributes to the formation of unsaturated polyolefins.

[0026] The molecular weight of the diblock copolymer varies with the amount of chain transfer agent added to the polyolefin polymerization reaction, for example, as the amount of chain transfer agent increases, the molecular weight decreases compared to a polymer composition polymerized in the presence of a lower amount of chain transfer agent.

[0027] Scheme 1 illustrates a synthetic procedure according to an embodiment of the present disclosure. In Scheme 1, compound 1 is a vinyl-terminated polyolefin produced by the method described above. Compound 1 is mixed with a thiol compound to form compound 2, a sulfide-containing polyolefin intermediate. Compound 2 reacts with a linker to form compound 3, a macroinitiator. Compound 3, a radical reagent, and CH═CH—(X) monomers (i.e., t-butyl acrylate and n-butyl acrylate) are reacted via reversible deactivation radical polymerization to produce compound 4, a nonpolar-polar diblock copolymer. In an optional reaction, the tert-butyl group of the units derived from tert-butyl acrylate is removed via the addition of acid to the reaction or via a thermal reaction to produce an acid nonpolar-polar diblock copolymer.

[0028] Scheme 1: Polymerization procedure for synthesizing nonpolar-polar diblock copolymers via vinyl-terminated polyolefins [ka]

[0029] The phrase "reversible deactivation radical polymerization" refers to a radical polymerization reaction controlled by a radical reagent. The radical reagent influences the rate and site of polymer propagation. Reversible deactivation radical polymerization differs from conventional radical polymerization due to the ability of the metal complex to control the steady-state concentration of propagating radicals. By controlling the concentration of propagating radicals, the rate of termination by the combination of propagating radicals becomes disproportionate to the rate of propagation. By controlling the rate and location of radical propagation, the amount of branching is also controlled.

[0030] In one or more embodiments, the method of the present disclosure further includes reacting the non-polar-polar diblock copolymer under thermal or acidic conditions to form a non-polar-polar acid diblock copolymer. The non-polar-polar acid diblock copolymer is compound 5 shown in Scheme 1. Reacting the non-polar-polar diblock copolymer under thermal or acidic conditions removes the tert-butyl group from the unit derived from the tert-butyl acrylate monomer in the non-polar-polar diblock copolymer. The phrase "thermal conditions" refers to the amount of energy (i.e., heat) required to produce a reaction product in an endothermic reaction. In some embodiments, the thermal conditions include a temperature greater than 20°C. In various embodiments, the thermal conditions include a temperature greater than 30°C, greater than 40°C, or greater than 50°C. In other embodiments, the thermal conditions include a temperature between 20°C and 190°C.

[0031] As shown in Scheme 1, in some embodiments, the thiol compound comprises a thiol group (—SH) and a terminal hydroxyl group (—OH). In other embodiments, the thiol compound comprises a thiol group and a protected terminal amine —(NHR). The terminal amine is reactive with many groups, including vinyl groups. The terminal amine may comprise a protecting group to prevent the terminal amine from reacting with the vinyl group in a vinyl-terminated polyolefin (e.g., Compound 1) rather than with the thiol group. Because the protecting group is not believed to alter the “terminal functionality” of the terminal amine, as used herein, the term “terminal amine” is considered to encompass terminal amines bearing a protecting group unless expressly stated.

[0032] In some embodiments, the thiol compound has a structure according to Formula (I). [ka]

[0033] In formula (I), the subscript x is 2 to 12, and Y is -NHR B or —OH (wherein R Bis a protecting group). The protecting group may be derived from a BOC-anhydride (di-tert-butyl dicarbonate) to form a BOC-protected amine (-NHBOC). In one or more embodiments, terminal amine protecting groups may include FMOC (9-fluorenylmethylcarbamate), BOC (t-butylcarbamate), Cbz (benzylcarbamate), trifluoroacetamide, and phthalimide.

[0034] In some embodiments, when the thiol compound includes a protected terminal amine, the method further includes deprotecting the protected terminal amine after reacting the thiol compound with the vinyl-terminated polyolefin.

[0035] In some embodiments, a thiol compound reacts with a vinyl-terminated polyolefin to form a sulfide-containing polyolefin intermediate. In some embodiments, the thiol group (—SH) of the thiol compound reacts with the terminal vinyl group of the vinyl-terminated polyolefin to produce the sulfide-containing polyolefin intermediate.

[0036] In embodiments, the macroinitiator is produced by reacting a sulfide-containing polyolefin intermediate with a linker. In some embodiments, the macroinitiator is formed via an esterification or amidation reaction of the linker. In one or more embodiments, the linker comprises an acyl halide and a halogen atom at the alpha carbon to the acyl halide. In some embodiments, the alpha halogen atom of the linker is bromine or iodine.

[0037] In some embodiments, the linker has a structure according to formula (II): [ka]

[0038] In formula (II), X1 is a halogen atom, and X2 is chlorine, bromine, or iodine. 1 and R 2are independently (C1-C 20 ) hydrocarbyl. In some embodiments, R 1 and R 2 are independently (C1-C 12 ) alkyl. In various embodiments, R 1 and R 2 is independently methyl, ethyl, propyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl. 1 and R 2 are independently -(CH2) n [(C6-C 20 )aryl], where the subscript n is 1 to 10. In some embodiments, R 1 and R 2 independently (C6-C 20 ) alkyl.

[0039] In embodiments, the method for preparing a non-polar-polar diblock copolymer further comprises reacting a macroinitiator, a radical reagent, and a CH═CH—(X) monomer via a reversible deactivation radical polymerization reaction to produce a non-polar-polar diblock copolymer. In the CH═CH—(X) monomer, X is independently —C(O)OR, —CN, or —C(O)NHR (wherein R is —H, linear (C-C 18 ) alkyl, or branched chain (C1-C 18 ) alkyl).

[0040] In one or more embodiments, the acrylate monomer is CH═CHC(O)(OR), where each R is —H, a straight chain (C-C 18 ) alkyl, or branched chain (C1-C 18 ) alkyl), glycidyl acrylate, or a combination thereof. In some embodiments, the acrylate monomer comprises at least one t-butyl acrylate.

[0041] In various embodiments, the radical reagents include CuX, Fe(III)X, and Ru(III)X (wherein each X is selected from the group consisting of 2,2':6',2"-terpyridine (tpy), 2,2'-bipyridine (bpy), 4,4'-di(5-nonyl)-2,2'-bipyridine (dNbpy), N,N,N',N'-tetramethylethylenediamine (TMEDA), N-propyl(2-pyridyl)methanimine (NPrPMI), 4,4',4"-tris(5-nonyl)-2,2':6',2"-terpyridine (tNtpy), N,N,N',N'',N''-pentamethyldiethylenetriamine (PDM), and 4,4',4"-tris(5-nonyl)-2,2':6',2"-terpyridine (tNtpy). The ligand is selected from the group consisting of N,N-bis(2-pyridylmethyl)octylamine (PMDETA), N,N-bis(2-pyridylmethyl)octylamine (BPMOA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA), tris[2-(dimethylamino)ethyl]amine (Me6TREN), tris[(2-pyridyl)methyl]amine (TPMA), 1,4,8,11-tetraaza-1,4,8,11-tetramethylcyclotetradecane (Me4CYCLAM), and N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN).

[0042] In one or more embodiments, the radical reagent comprises a copper(I) halide, wherein the halide is bromine, chlorine, or iodine. In some embodiments, the radical reagent is copper(I) bromide.

[0043] In one or more embodiments, the non-polar block of the non-polar-polar diblock copolymer is a polyolefin. In some embodiments, the non-polar block is a polyethylene copolymer. In various embodiments, the non-polar-polar diblock copolymer comprises at least 40 wt. % (i.e., weight percent) of the non-polar block. In some embodiments, the non-polar-polar diblock copolymer comprises at least 50 wt. % of the non-polar block.

[0044] In one or more embodiments, the non-polar block of the non-polar-polar diblock copolymer has a number average molecular weight (M nIn some embodiments, the non-polar block of the non-polar-polar diblock copolymer has an M n In various embodiments, the non-polar block of the non-polar-polar diblock copolymer has an M n It has.

[0045] In one or more embodiments, the polar block of the non-polar-polar diblock copolymer is a polyacrylate. In various embodiments, the non-polar-polar diblock copolymer comprises 10% to 60% by weight (i.e., weight percent) of the polar block.

[0046] In one or more embodiments, the non-polar-polar diblock copolymer has a number average molecular weight (M n )

[0047] catalyst system In a further embodiment of the present disclosure, olefin monomers are polymerized in the presence of a chain transfer agent and a catalyst system to produce vinyl-terminated polyolefins. The catalyst system comprises one or more procatalysts.

[0048] In further embodiments, the catalyst system comprises a procatalyst and a cocatalyst, whereby an active catalyst is formed by the combination of the procatalyst and cocatalyst. In these embodiments, the catalyst system may have a ratio of procatalyst to cocatalyst of 1:2, or 1:1.5, or 1:1.2.

[0049] The catalyst system can include a procatalyst. The procatalyst can be made catalytically active by contacting the complex with, or combining with, a metal activator having the anion and countercation of the procatalyst. The procatalyst can be selected from Group IV metal-ligand complexes (Group IVB according to CAS, or Group 4 according to IUPAC nomenclature), such as titanium (Ti), zirconium (Zr), or hafnium (Hf) metal-ligand complexes. Non-limiting examples of procatalysts include catalysts, procatalysts, or catalytically active compounds for polymerizing ethylene-based polymers and are disclosed in one or more of U.S. Pat. No. 8,372,927, WO 2010022228, WO 2011102989, U.S. Pat. No. 6,953,764, U.S. Pat. No. 6,900,321, WO 2017173080, U.S. Pat. No. 7,650,930, U.S. Pat. No. 6,777,509, WO 99 / 41294, U.S. Pat. No. 6,869,904, or WO 2007136496, all of which documents are incorporated herein by reference in their entirety.

[0050] Suitable procatalysts include, but are not limited to, those disclosed in WO 2005 / 090426, WO 2005 / 090427, WO 2007 / 035485, WO 2009 / 012215, WO 2014 / 105411, WO 2017 / 173080, U.S. Patent Application Publication Nos. 2006 / 0199930, 2007 / 0167578, 2008 / 0311812, and U.S. Patent Nos. 7,858,706(B2), 7,355,089(B2), 8,058,373(B2), and 8,785,554(B2). When referring to the following paragraphs, the term "procatalyst" is interchangeable with terms such as "catalyst," "precatalyst," "catalyst precursor," "transition metal catalyst," "transition metal catalyst precursor," "polymerization catalyst," "polymerization catalyst precursor," "transition metal complex," "transition metal compound," "metal complex," "metal compound," "complex," and "metal-ligand complex."

[0051] In one or more embodiments, the Group IV metal-ligand procatalyst complexes include bis(phenylphenoxy) Group IV metal-ligand complexes or constrained geometry Group IV metal-ligand complexes.

[0052] According to some embodiments, the Group IV metal-ligand procatalyst complex may include a bis(phenylphenoxy) compound according to formula (X). [ka]

[0053] In formula (X), M is a metal selected from titanium, zirconium, or hafnium, the metal being in the +2, +3, or +4 formal oxidation state. (X) n The subscript n in is 0, 1, or 2. When the subscript n is 1, X is a monodentate or bidentate ligand, and when the subscript n is 2, each X is a monodentate ligand. L is a (C1-C 40 ) hydrocarbylene, (C1-C 40 ) heterohydrocarbylene, -Si(R C )2-, -Si(R C )2OSi(R C )2-, -Si(R C )2C(R C )2-, -Si(R C )2Si(R C )2-, -Si(R C )2C(R C )2Si(R C )2-, -C(R C )2Si(R C )2C(R C )2-, -N(R N )C(R C )2-, -N(R N )N(R N )-, -C(R C )2N(R N )C(R C )2-, -Ge(R C )2-, -P(R P )-, -N(R N)-, -O-, -S-, -S(O)-, -S(O)2-, -N=C(R C )-, -C(O)O-, -OC(O)-, -C(O)N(R)-, and -N(R C )C(O)—. Each Z is independently —O—, —S—, —N(R N )-, or -P(R P )-, and R 2 ~R 4 , R 5 ~R -8 , R 9 ~R 12 , and R 13 ~R 15 are independently -H, (C1-C 40 ) hydrocarbyl, (C 1- C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, -N=C(R C )2, R C C(O)O-, R C OC(O)-, R C C(O)N(R)-, (R C )NC(O)-, and halogen. 1 and R 16 is selected from a radical having formula (XI), a radical having formula (XII), and a radical having formula (XIII). [ka]

[0054] In formulas (XI), (XII), and (XIII), R 31 ~R 35 , R 41 ~R 48 , and R 51 ~R 59each independently represents -H, (C-C 40 ) hydrocarbyl, (C1-C 40 ) heterohydrocarbyl, -Si(R C )3, -Ge(R C )3, -P(R P )2, -N(R N )2, -OR C , -SR C , -NO2, -CN, -CF3, R C S(O)-, R C S(O)2-, (R C )2C=N-, R C C(O)O-, R C OC(O)-, R C C(O)N(R N )-, (R C )2NC(O)-, or halogen.

[0055] In one or more embodiments, each X, independently of any other ligand X, is selected from halogen, unsubstituted (C-C 20 ) hydrocarbyl, unsubstituted [(C-C 20 )hydrocarbyl]C(O)O—, or R K R L N-(wherein, R K and R L each independently is unsubstituted (C-C 20 ) a monodentate ligand that is a hydrocarbyl.

[0056] Exemplary bis(phenylphenoxy) metal-ligand complexes according to formula (X) include, for example,

[0057] (2',2"-(propane-l,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-octyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0058] (2',2"-(propane-l,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-chloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0059] (2',2"-(propane-l,3-diylbis(oxy))bis(3'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0060] (2',2"-(propane-l,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0061] (2',2"-(propane-l,3-diylbis(oxy))bis(5'-cyano-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0062] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-dimethylamino-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0063] (2',2"-(propane-l,3-diylbis(oxy))bis(3',5'-dimethyl-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0064] (2',2"-(propane-l,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-ethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0065] (2',2"-(propane-l,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5'-tert-butyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0066] (2',2"-(propane-l,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0067] (2',2"-(propane-l,3-diylbis(oxy))bis(3-(9H-carbazol-9-yl)-5'-chloro-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0068] (2',2"-(propane-l,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5'-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0069] (2',2"-(2,2-dimethyl-2-silapropane-l,3-diylbis(oxy))bis(3',5'-dichloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0070] (2'2"-(2,2-dimethyl-2-silapropane-1-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0071] (2',2"-(propane-l,3-diylbis(oxy))bis(3'-bromo-5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0072] (2',2"-(propane-l,3-diylbis(oxy))-(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-fluoro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)-(3",5"-dichloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0073] (2',2"-(propane-l,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-5'-fluoro-3'-trifluoromethyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0074] (2',2"-(butane-l,4-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0075] (2',2"-(ethane-l,2-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-hafnium;

[0076] (2',2"-(propane-l,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-zirconium;

[0077] (2',2"-(propane-1,3-diylbis(oxy))bis(3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3',5'-dichloro-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-titanium; and

[0078] (2',2"-(propane-1,3-diylbis(oxy))bis(5'-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)-3'-methyl-5-(2,4,4-trimethylpentan-2-yl)biphenyl-2-ol)dimethyl-titanium.

[0079] Other bis(phenylphenoxy) metal-ligand complexes that can be used in combination with the metal activators in the catalyst systems of the present disclosure will be apparent to those skilled in the art.

[0080] According to some embodiments, the Group IV metal-ligand complex may comprise a cyclopentadienyl procatalyst according to formula (XIV):

[0081] Lp i MX m X' n X” p or a dimer of (XIV).

[0082] In formula (XIV), Lp is an anionic, delocalized, π-bonded group containing up to 50 non-hydrogen atoms and attached to M. In some embodiments of formula (XIV), two Lp groups may be bonded together to form a bridged structure, and optionally one Lp may be bonded to X.

[0083] In formula (XIV), M is a Group 4 metal of the Periodic Table of the Elements in a formal oxidation state of +2, +3, or +4. X is an optional divalent substituent of up to 50 non-hydrogen atoms that, together with Lp, forms a metallocycle containing M. X' is an optional neutral ligand having up to 20 non-hydrogen atoms, and each X" is independently a monovalent anionic moiety having up to 40 non-hydrogen atoms. Optionally, two X" groups can be covalently bonded together to form a divalent dianionic moiety with both valences bonded to M, or optionally, two X" groups can be covalently bonded together to form a neutral, conjugated, or non-conjugated diene π-bonded to M, wherein M is in the +2 oxidation state. In other embodiments, one or more X" and one or more X' groups can be bonded together, thereby forming a moiety covalently bonded to M and coordinated by a Lewis base functionality. Lp i The subscript i in X' is 0, 1, or 2. n The subscript n is 0, 1, 2, or 3, and X m The subscript m in X” is 0 or 1, p The subscript p in is 0, 1, 2, or 3. The sum of i+m+p equals the formula oxidation state of M.

[0084] Exemplary Group IV metal-ligand complexes that can be used in the practice of the present invention include cyclopentadienyl procatalysts, such as:

[0085] Cyclopentadienyltitanium trimethyl, cyclopentadienyltitanium triethyl, cyclopentadienyltitanium triisopropyl, cyclopentadienyltitanium triphenyl, cyclopentadienyltitanium tribenzyl, cyclopentadienyltitanium-2,4-dimethylpentadienyl, cyclopentadienyltitanium-2,4-dimethylpentadienyl triethylphosphine, cyclopentadienyltitanium-2,4-dimethylpentadienyl trimethylphosphine, cyclopentadienyltitanium dimethyl methoxide, cyclo Pentadienyltitanium dimethyl chloride, pentamethylcyclopentadienyltitanium trimethyl, indenyltitanium trimethyl, indenyltitanium triethyl, indenyltitanium tripropyl, indenyltitanium triphenyl, tetrahydroindenyltitanium tribenzyl, pentamethylcyclopentadienyltitanium triisopropyl, pentamethylcyclopentadienyltitanium tribenzyl, pentamethylcyclopentadienyltitanium dimethyl methoxide, pentamethylcyclopentadienyltitanium dimethyl chloride, bis(η 5 -2,4-dimethylpentadienyl)titanium, bis(η 5 -2,4-dimethylpentadienyl)titanium·trimethylphosphine, bis(η 5 -2,4-dimethylpentadienyl)titanium·triethylphosphine, Octahydrofluorenyltitanium trimethyl, Tetrahydroindenyltitanium trimethyl, Tetrahydrofluorenyltitanium trimethyl, (tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitanium dimethyl, (tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalenyl)dimethylsilanetitanium dimethyl, (tert-butylamido)(tetramethyl-η 5 -Cyclopentadienyl)dimethylsilanetitanium dibenzyl, (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium dimethyl, (tert-butylamido)(tetramethyl-η 5-cyclopentadienyl)-1,2-ethanediyltitanium dimethyl, (tert-butylamido)(tetramethyl-η 5 -indenyl)dimethylsilanetitanium dimethyl, (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(III) 2-(dimethylamino)benzyl, (tert-butylamido)(tetramethyl-η 5 -Cyclopentadienyl)dimethylsilanetitanium(III) allyl, (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(III) 2,4-dimethylpentadienyl, (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene,

[0086] (tert-butylamido)(tetramethyl-η 5-cyclopentadienyl)dimethylsilanetitanium(II) 1,3-pentadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(II) 2,4-hexadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV) 2,3-dimethyl-1,3-butadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV) isoprene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV) 1,3-butadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV) 2,3-dimethyl-1,3-butadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV) isoprene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV) dimethyl, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilane Titanium(IV) dibenzyl, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(IV) 1,3-butadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(II) 1,3-pentadiene, (tert-butylamido)(2,3-dimethylindenyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(II) 1,3-pentadiene, (tert-butylamido)(2 -methylindenyl)dimethylsilanetitanium(IV) dimethyl, (tert-butylamido)(2-methylindenyl)dimethylsilanetitanium(IV) dibenzyl, (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene, (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 1,3-pentadiene, (tert-butylamido)(2-methyl-4-phenylindenyl)dimethylsilanetitanium(II) 2,4-Hexadiene, (tert-butylamido)(tetramethyl-η, 5 -cyclopentadienyl)dimethyl-silanetitanium(IV) 1,3-butadiene, (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(IV) 2,3-dimethyl-1,3-butadiene, (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(IV) isoprene, (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethyl-silanetitanium(II) 1,4-dibenzyl-1,3-butadiene, (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethylsilanetitanium(II) 2,4-hexadiene, (tert-butylamido)(tetramethyl-η 5 -cyclopentadienyl)dimethyl-silanetitanium(II) 3-methyl-1,3-pentadiene, (tert-butylamido)(2,4-dimethylpentadien-3-yl)dimethylsilanetitanium dimethyl, (tert-butylamido)(6,6-dimethylcyclohexadienyl)dimethylsilanetitanium dimethyl, (tert-butylamido)(1,1-dimethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitanium dimethyl, (tert-butylamido)(1,1,2,3-tetramethyl-2,3,4,9,10-η-1,4,5,6,7,8-hexahydronaphthalen-4-yl)dimethylsilanetitanium dimethyl, (tert-butylamido)(tetramethyl-η 5 -Cyclopentadienylmethylphenylsilanetitanium(IV) dimethyl, (tert-butylamido)(tetramethyl-η 5 -Cyclopentadienylmethylphenylsilanetitanium(II) 1,4-diphenyl-1,3-butadiene, 1-(tert-butylamido)-2-(tetramethyl-η 5 -cyclopentadienyl)ethanediyltitanium(IV) dimethyl, 1-(tert-butylamido)-2-(tetramethyl-η 5-cyclopentadienyl)ethanediyl-titanium(II) 1,4-diphenyl-1,3-butadiene.

[0087] Each of the exemplary cyclopentadienyl procatalysts may include zirconium or hafnium in place of the titanium metal center of the cyclopentadienyl procatalyst.

[0088] Other procatalysts, particularly those containing other Group IV metal-ligand complexes, will be apparent to those skilled in the art.

[0089] Both heterogeneous and homogeneous catalysts can be used. Examples of heterogeneous catalysts include the well-known Ziegler-Natta compositions, particularly Group 2 metal halides or mixed halides and alkoxide-supported Group 4 metal halides, as well as the well-known chromium- or vanadium-based catalysts. Preferably, the catalysts for use herein are homogeneous catalysts comprising relatively pure organometallic compounds or metal complexes, particularly compounds or complexes based on metals selected from Groups 3-10 or the lanthanide series of the Periodic Table of the Elements.

[0090] Metal complexes for use herein may be selected from Groups 3-15 of the Periodic Table of the Elements containing one or more delocalized π-bonded or polyvalent Lewis base ligands. Examples include metallocenes, half-metallocenes, constrained geometry, and polyvalent pyridylamine or other polychelating base complexes. The complexes generally have the formula: MK k X x Z zwherein M is a metal selected from Groups 3 to 15, preferably Groups 3 to 10, more preferably Groups 4 to 10, and most preferably Group 4 of the Periodic Table of the Elements, or a dimer thereof. K, independently at each occurrence, is a group containing delocalized π electrons or one or more electron pairs, through which K is bonded to M, the K group containing up to 50 atoms, not counting hydrogen atoms, optionally, two or more K groups may be bonded together to form a bridged structure, and further optionally, one or more K groups may be bonded to Z, X, or both Z and X, and X, independently at each occurrence, is a monovalent anionic moiety having up to 40 non-hydrogen atoms, optionally, one or more X groups may be bonded together to thereby form a divalent or polyvalent anionic group, and further optionally, one or more X groups and one or more Z groups may be bonded together. and thereby form a moiety covalently bonded 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 are a conjugated diene having 4 to 30 non-hydrogen atoms bonded to M by delocalized π electrons, where M is in the +2 formula oxidation state; Z, independently at each occurrence, is a neutral Lewis base donor ligand of up to 50 non-hydrogen atoms containing at least one unshared electron pair through which Z coordinates to M; 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 k+x is equal to the formula oxidation state of M.

[0091] Suitable metal complexes include those containing one to three 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 diene and dienyl groups, allyl groups, boratabenzene groups, phospholes, and arene groups. The term "π-bonded" means that the ligand group is bonded to the transition metal by sharing electrons from a partially delocalized π bond.

[0092] Each atom in a delocalized π-bonded group may be independently substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, and hydrocarbyl-substituted heteroatom, where the heteroatom is selected from Groups 14-16 of the Periodic Table of the Elements, and such hydrocarbyl-substituted heteroatom radicals are further substituted with a moiety containing a Group 15 or 16 heteroatom. Furthermore, two or more such radicals may together form a fused ring system, including partially or fully hydrogenated fused ring systems, or they may together with a metal form a metallocycle. The term "hydrocarbyl" includes C 1~20 Straight-chain, branched-chain, and cyclic alkyl radicals, C 6~20 Aromatic radical, C 7~20 Alkyl-substituted aromatic radicals, and C 7~20 Aryl-substituted alkyl radicals are included. Suitable hydrocarbyl-substituted heteroatom radicals include mono-, di-, and tri-substituted radicals of boron, silicon, germanium, nitrogen, phosphorus, or oxygen, each hydrocarbyl group containing 1 to 20 carbon atoms. Examples include N,N-dimethylamino, pyrrolidinyl, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, methyldi(t-butyl)silyl, triphenylgermyl, and trimethylgermyl. Examples of moieties containing Group 15 or 16 heteroatoms include amino, phosphino, alkoxy, or alkylthio moieties, or divalent derivatives thereof, such as amido, phosphido, alkyleneoxy, or alkylenethio groups bonded to a transition metal or lanthanide metal and bonded to a hydrocarbyl group, π-bonded group, or hydrocarbyl-substituted heteroatom.

[0093] Examples of suitable anionic, delocalized π-bonded groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl groups, phosphole, and boratabenzyl groups, and inertly substituted derivatives thereof, especially those C 1-10 Hydrocarbyl-substituted or tris(C 1-10 and (hydrocarbyl)silyl-substituted derivatives. Preferred anionic delocalized π-bonded groups are cyclopentadienyl, pentamethylcyclopentadienyl, tetramethylcyclopentadienyl, tetramethylsilylcyclopentadienyl, indenyl, 2,3-dimethylindenyl, fluorenyl, 2-methylindenyl, 2-methyl-4-phenylindenyl, tetrahydrofluorenyl, octahydrofluorenyl, 1-indacenyl, 3-pyrrolidinoinden-1-yl, 3,4-(cyclopenta(1)phenanthren-1-yl), and tetrahydroindenyl.

[0094] More specifically, this class of Group 4 metal complexes for use in accordance with the present invention includes "constrained geometry catalysts" corresponding to the formula: [ka]

[0095] In the above formula, M is titanium or zirconium, preferably titanium in the +2, +3, or +4 formal oxidation state; K 1 optionally 1 to 5 R 2 is a delocalized π-bonded ligand group substituted with a group, R 2 is independently selected at each occurrence from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo, and combinations thereof; 2 has up to 20 non-hydrogen atoms or adjacent R 2wherein the groups together form a divalent derivative (i.e., a hydrocarbadiyl, siladiyl, or germadiyl group), thereby forming a fused ring system, and each X is a halo, hydrocarbyl, heterohydrocarbyl, hydrocarbyloxy, or silyl 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, and x is 1 or 2; Y is -O-, -S-, -NR'-, -PR'-; and X' is SiR'2, CR'2, SiR'2SiR'2, CR'2CR'2, CR'═CR', CR'2SiR'2, or GeR'2, where R' at each occurrence is independently hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy, and combinations thereof, and said R' having up to 30 carbon or silicon atoms.

[0096] Specific examples of the aforementioned constrained geometry metal complexes include compounds corresponding to the following formulas: [ka]

[0097] In the above formula, Ar is an aryl group of 6 to 30 atoms, not counting hydrogen, and R 4is independently at each occurrence hydrogen, Ar, or hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy, trihydrocarbylsiloxy, bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino, hydrocarbylamino, hydrocarbylimino, di(hydrocarbyl)phosphino, hydrocarbadiylphosphino, hydrocarbylsulfide, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, trihydrocarbylsilyl-substituted hydrocarbyl a group other than Ar selected from the group consisting of bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl, di(hydrocarbyl)amino-substituted hydrocarbyl, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino-substituted hydrocarbyl, hydrocarbylenephosphino-substituted hydrocarbyl, or hydrocarbylsulfido-substituted hydrocarbyl, wherein the R group has up to 40 atoms, not counting hydrogen atoms, and optionally two adjacent R 4 The groups may be joined together to form a polycyclic fused ring group, where M is titanium and X' is SiR 6 2. CR 6 2. SiR 6 2SiR 6 2. CR 6 2CR 6 2. CR 6 =CR 6 , C.R. 6 2SiR 6 2.BR 6 , B.R. 6 L”, or GeR 6 2, and Y is -O-, -S-, or -NR 5 -,-PR 5 -, -NR 5 2, or -PR 5 2 and R 5 is independently at each occurrence hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, and R 5 has up to 20 atoms other than hydrogen, and optionally, two R 5 The group is or R 5together with Y or Z to form a ring system, and R 6 is independently at each occurrence hydrogen, or hydrocarbyl, hydrocarbyloxy, silyl, alkyl halide, aryl halide, -NR 5 2, and combinations thereof, wherein R 6 has up to 20 non-hydrogen atoms and optionally two R 6 The group is or R 6 forms a ring system together with Z, and Z is a neutral diene or optionally R 5 , R 6 or a monodentate or polydentate Lewis base bonded to X, where X is hydrogen, a monovalent anionic ligand group having up to 60 atoms not counting hydrogen, or two X groups bonded together thereby forming a divalent ligand group, where x is 1 or 2 and z is 0, 1, or 2.

[0098] Further examples of suitable metal complexes herein are polycyclic complexes corresponding to the formula: [ka]

[0099] where M is titanium in the +2, +3, or +4 formal oxidation state; R 7 is independently at each occurrence hydride, hydrocarbyl, silyl, germyl, halide, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino, hydrocarbylene-phosphino, hydrocarbylsulfide, halo-substituted hydrocarbyl, 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, hydrocarbylene-phosphino-substituted hydrocarbyl, or hydrocarbylsulfide-substituted hydrocarbyl;7 The group has up to 40 atoms, not counting hydrogen, and optionally two or more of the foregoing groups may together form a divalent derivative, R 8 is a divalent hydrocarbylene or substituted hydrocarbylene group that forms a condensed system with the remainder of the metal complex, and R 8 contains 1 to 30 atoms, not including the number of hydrogens, and X a is a divalent moiety or a moiety containing one π bond and two neutral electron pairs capable of forming a coordinate covalent bond with M, a contains boron or a member of Group 14 of the Periodic Table of the Elements and further contains nitrogen, phosphorus, sulfur, or oxygen; X is a monovalent anionic ligand group having up to 60 atoms excluding the class of ligands that are cyclic delocalized π-bonded ligand groups, optionally two X groups together form a divalent ligand group; Z is independently at each occurrence a neutral coordination compound having up to 20 atoms; x is 0, 1, or 2; and z is 0 or 1.

[0100] Further examples of metal complexes usefully employed as catalysts are complexes of polyvalent Lewis bases, such as compounds corresponding to the formula: [ka]

[0101] In the above formula, T b is preferably a bridging group containing two or more atoms other than hydrogen, and X b and Y b are each independently selected from the group consisting of nitrogen, sulfur, oxygen, and phosphorus, and more preferably, X b and Y b is nitrogen and R b and R b’ is independently at each occurrence hydrogen or C optionally containing one or more heteroatoms 1~50 A suitable R is a hydrocarbyl group, or an inertly substituted derivative thereof. b and R b’Non-limiting examples of groups include alkyl, alkenyl, aryl, aralkyl, (poly)alkylaryl, and cycloalkyl groups, as well as nitrogen-, phosphorus-, oxygen-, and halogen-substituted derivatives thereof. b and R b’ Specific examples of groups include methyl, ethyl, isopropyl, octyl, phenyl, 2,6-dimethylphenyl, 2,6-di(isopropyl)phenyl, 2,4,6-trimethylphenyl, pentafluorophenyl, 3,5-trifluoromethylphenyl, and benzyl; g and g' are each independently 0 or 1; M b is a metal element selected from groups 3 to 15 or the lanthanide series of the periodic table. b is a metal of Groups 3 to 13, and more preferably, M b is a group 4 to 10 metal, and L b is a monovalent, divalent, or trivalent anionic ligand containing 1 to 50 atoms, not counting hydrogen atoms. b Examples of groups include halide, hydride, hydrocarbyl, hydrocarbyloxy, di(hydrocarbyl)amide, hydrocarbyleneamide, di(hydrocarbyl)phosphide, hydrocarbyl sulfide, hydrocarbyloxy, tri(hydrocarbylsilyl)alkyl, and carboxylate. b The group is C1-20 alkyl, C 7-20 aralkyl, and chloride, h and h' are each independently an integer from 1 to 6, preferably from 1 to 4, more preferably from 1 to 3, j is 1 or 2, and the value of h×j is selected to provide charge balance; Z b is M b A neutral ligand group coordinated to the , containing up to 50 atoms, not including the number of hydrogen atoms. bGroups include aliphatic and aromatic amines, phosphines, and ethers, alkenes, alkadienes, and their inertly substituted derivatives. Suitable inert substituents include halogen, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, di(hydrocarbyl)amine, tri(hydrocarbyl)silyl, and nitrile groups. Preferred Z groups are b Examples of the group include triphenylphosphine, tetrahydrofuran, pyridine, and 1,4-diphenylbutadiene. f is an integer from 1 to 3, and T b , R b , and R b’ Two or three of these may be bonded together to form a single or multiple ring structure, and h is an integer of 1 to 6, preferably 1 to 4, more preferably 1 to 3.

[0102] In one embodiment, R b is X b In this embodiment, the most preferred R b The group is a linear alkyl group, a linear alkenyl group, or a group in which the nearest branch point is X b and their halo, dihydrocarbylamino, alkoxy, or trihydrocarbylsilyl substituted derivatives. Highly preferred R in this embodiment are b The group is a C1-8 straight chain alkyl group.

[0103] At the same time, in this embodiment, R b’ is preferably Y b The steric hindrance to R is relatively large. 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, dihydrocarbylamino, alkoxy, or trihydrocarbylsilyl substituted derivatives thereof. Preferred R groups in this embodiment are b’The group contains 3 to 40 atoms, not counting hydrogens, more preferably 3 to 30 atoms, and most preferably 4 to 20 atoms, and is branched or cyclic. b Examples of groups include the following formula: [ka] (In the formula, Each R d is a C hydrocarbyl group, preferably methyl, ethyl, n-propyl, i-propyl, t-butyl, phenyl, 2,6-dimethylphenyl, benzyl, or tolyl. e is a C hydrocarbyl, preferably methyl, ethyl, n-propyl, i-propyl, t-butyl, phenyl, 2,6-dimethylphenyl, benzyl, or tolyl. d group or R e The group, or mixtures of Rd and Re groups, may together form divalent or polyvalent derivatives of the hydrocarbyl group, such as 1,4-butylene, 1,5-pentylene, or cyclic or polycyclic groups, fused ring, polyvalent hydrocarbyl or heterohydrocarbyl groups, such as naphthalene-1,8-diyl.

[0104] Suitable examples of the polyvalent Lewis base complexes include the following: [ka] [ka]

[0105] In the above formula, R d’ are independently selected at each occurrence from the group consisting of hydrogen and C1-50 hydrocarbyl groups, optionally containing one or more heteroatoms, or inertly substituted derivatives thereof, or further optionally, two adjacent R d’ The groups may together form a divalent bridging group, d' is 4, and M b’is a Group 4 metal, preferably titanium or hafnium, or a Group 10 metal, preferably Ni or Pd, and L b’ is a monovalent ligand of up to 50 atoms, not counting hydrogens, preferably a halide or hydrocarbyl, or two L b’ The groups together form a divalent or neutral ligand group, preferably C 2~50 It may be a hydrocarbylene, hydrocarbadiyl, or diene group.

[0106] Polyvalent Lewis base complexes for use in the present invention include, in particular, Group 4 metal derivatives, especially hafnium derivatives of hydrocarbylamine-substituted heteroaryl compounds corresponding to the formula: [ka]

[0107] In the above formula, R 11 is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, and inertly substituted derivatives thereof, or divalent derivatives thereof, containing 1 to 30 atoms, not counting hydrogen; T 1 is a divalent bridging group of 1 to 41 atoms other than hydrogen, preferably 1 to 20 atoms other than hydrogen, most preferably a mono- or di-C1-20 hydrocarbyl-substituted methylene or silane group; R 12 C containing Lewis base functional groups 5~20 a heteroaryl group, in particular a pyridin-2-yl or substituted pyridin-2-yl group, or a divalent derivative thereof, M 1 is a Group 4 metal, preferably hafnium, and X 1 is an anionic, neutral or dianionic ligand group, and x' is such X 1 The number of groups is a number from 0 to 5, and bonds, optional bonds, and electron-donating interactions are represented by lines, dotted lines, and arrows, respectively.

[0108] Suitable complexes are those in which ligand formation involves hydrogen elimination from the amine group and, optionally, loss of one or more additional groups, particularly R 12Furthermore, electron donation from a Lewis base functional group, preferably an electron pair, provides additional stability to the metal center. Suitable metal complexes correspond to the formula: [ka]

[0109] In the above formula, M 1 , X 1 , x', R 11 , and T 1 is as already defined, and R 13 , R 14 , R 15 , and R 16 is hydrogen, halo, or an alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, or silyl group of up to 20 atoms, not counting hydrogen, or an adjacent R 13 , R 14 , R 15 , or R 16 Groups may be joined together to form fused ring derivatives, where bonds, optional bonds, and electron pair donating interactions are represented by lines, dotted lines, and arrows, respectively.

[0110] Suitable examples of the aforementioned metal complexes correspond to the following formula: [ka]

[0111] In the above formula, M 1 , X 1 , and x' are as previously defined, and R 13 , R 14 , R 15 , and R 16 is as previously defined, preferably R 13 , R 14 , and R 15 is hydrogen or C1-4 alkyl, and R 16 is C 6~20 aryl, most preferably naphthalenyl; R a independently for each occurrence, C1-4 alkyl, a is 1 to 5, and most preferably R a is isopropyl or t-butyl, and R 17 and R 18 is independently at each occurrence hydrogen, halogen, or C 1-20 alkyl or aryl groups, most preferably R 17 and R 18 is hydrogen and the other is a C aryl group, particularly a 2-isopropyl, phenyl or fused polycyclic aryl group, most preferably an anthracenyl group, and bonds, optional bonds and electron pair donating interactions are represented by lines, dotted lines and arrows, respectively.

[0112] Exemplary metal complexes for use herein as catalysts correspond to the formula: [ka]

[0113] In the formula, X 1 is, at each occurrence, a halide, N,N-dimethylamide, or C 1~4 alkyl, and preferably, at each occurrence, X 1 is methyl and R f is independently at each occurrence hydrogen, halogen, C1-20 alkyl, or C6-20 aryl, or two adjacent R f groups are joined together to form a ring, f is 1 to 5, and R c are independently hydrogen, halogen, and C 1~20 Alkyl or C 6~20 aryl or two adjacent R c The groups are joined together to form a ring, and c is 1 to 5.

[0114] Suitable examples of metal complexes for use as catalysts include those of the formula: [ka]

[0115] In the above formula, R x is C1-4 alkyl or cycloalkyl, preferably methyl, isopropyl, t-butyl, or cyclohexyl; X 1 At each occurrence, is a halide, N,N-dimethylamide, or C1-4 alkyl, preferably methyl.

[0116] Examples of metal complexes useful as catalysts in accordance with the present invention include: [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]dimethylhafnium, [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium di(N,N-dimethylamide), [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium dichloride, [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]dimethylhafnium, [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium di(N,N-dimethylamide), [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium dichloride, [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]dimethylhafhium, [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafium(di(N,N-dimethylamido), and [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium dichloride.

[0117] Under the reaction conditions used to prepare the metal complexes used in this disclosure, the hydrogen at the 2-position of the α-naphthalene group substituted at the 6-position of the pyridin-2-yl group is eliminated, thereby uniquely forming a metal complex in which the metal is covalently bonded to both the resulting amide group and the 2-position of the α-naphthalenyl group and stabilized by coordination to the pyridinyl nitrogen atom through the nitrogen atom's electron pair.

[0118] Additional suitable procatalysts include imidazole amine compounds corresponding to those disclosed in WO 2007 / 130307 A2, WO 2007 / 130306 A2, and U.S. Patent Application No. 20090306318 A1, which are incorporated herein by reference in their entireties. Such imidazole-amine compounds include those corresponding to the following formula: [ka]

[0119] In the imidazole-amine compounds, X, independently at each occurrence, is an anionic ligand, or two X groups together form a dianionic ligand group or a neutral diene; T is an alicyclic or aromatic group containing one or more rings; and R 1 is independently at each occurrence hydrogen, halogen, or a monovalent polyatomic anionic ligand, or two or more R 1 groups are joined together, thereby forming a polyvalent fused ring system, and R 2is independently at each occurrence hydrogen, halogen, or a monovalent polyatomic anionic ligand, or two or more R 2 groups are joined together, thereby forming a polyvalent fused ring system, and R 4 is hydrogen, alkyl, aryl, aralkyl, trihydrocarbylsilyl, or trihydrocarbylsilylmethyl having 1 to 20 carbon atoms.

[0120] Further examples of such imidazole-amine compounds include, but are not limited to: [ka] [ka]

[0121] In the imidazole-amine compound, R 1 represents independently at each occurrence a C in which the carbon attached to the phenyl ring is secondary or tertiary substituted. 3~12 is an alkyl group, and R 2 is independently at each occurrence hydrogen or C 1~2 is an alkyl group, and R 4 is methyl or isopropyl, and R 5 is hydrogen or C 1~6 alkyl, and R 6 is hydrogen, C 1~6 alkyl or cycloalkyl, or two adjacent R 6 The groups together form a fused aromatic ring, and T' is oxygen, sulfur, or C 1~20 A hydrocarbyl-substituted nitrogen or phosphorus group, T″ is nitrogen or phosphorus, and X is methyl or benzyl.

[0122] The catalyst system of the present disclosure may include a cocatalyst or activator in addition to the ionic metal activator complex having the anion and countercation of Formula (I). Such additional cocatalysts may include, for example, tri(hydrocarbyl)aluminum compounds having 1 to 10 carbons in each hydrocarbyl group, oligomeric or polymeric alumoxane compounds, di(hydrocarbyl)(hydrocarbyloxy)aluminum compounds having 1 to 20 carbons in each hydrocarbyl or hydrocarbyloxy group, or mixtures of the foregoing compounds. It is typically useful to employ these aluminum compounds due to their beneficial ability to scavenge impurities such as oxygen, water, and aldehydes from the polymerization mixture.

[0123] Di(hydrocarbyl)(hydrocarbyloxy)aluminum compounds that may be used in conjunction with the activators described in this disclosure are represented by the formula T 1 2AlOT 2 or T 1 1Al(OT 2 )2(where, T 1 is a secondary or tertiary (C3-C6) alkyl, for example, isopropyl, isobutyl, or tert-butyl, and T 2 is alkyl-substituted (C6-C 30 ) aryl radical or aryl-substituted (C1-C 30 ) alkyl radical, for example, 2,6-di(tert-butyl)-4-methylphenyl, 2,6-di(tert-butyl)-4-methylphenyl, 2,6-di(tert-butyl)-4-methyltolyl, or 4-(3',5'-di-tert-butyltolyl)-2,6-di-tert-butylphenyl).

[0124] Additional examples of aluminum compounds include [C6]trialkylaluminum compounds, specifically those in which the alkyl group is ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl, neopentyl, or isopentyl; dialkyl(aryloxy)aluminum compounds containing 1 to 6 carbons in the alkyl group and 6 to 18 carbons in the aryl group (specifically, (3,5-di(t-butyl)-4-methylphenoxy)diisobutylaluminum); methylalumoxane, modified methylalumoxane, and diisobutylalumoxane.

[0125] In catalyst systems according to embodiments of the present disclosure, the molar ratio of ionic metal activator complex to Group IV metal-ligand complex can be, for example, 1:10,000 to 1000:1, e.g., 1:5000 to 100:1, 1:100 to 100:1, 1:10 to 10:1, 1:5 to 1:1, or 1.25:1 to 1:1. The catalyst system can include a combination of one or more ionic metal activator complexes described herein.

[0126] Polyolefin The catalyst system described in the previous paragraph is utilized in the polymerization of olefins, primarily ethylene and propylene. In some embodiments, only a single type of olefin, or α-olefin, is present in the polymerization scheme to produce a homopolymer. However, additional α-olefins may be incorporated into the polymerization procedure. The additional α-olefin comonomer typically has 20 or fewer carbon atoms. For example, the α-olefin comonomer may have 3 to 10 carbon atoms, or 3 to 8 carbon atoms. Exemplary α-olefin comonomers include, but are not limited to, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 5-ethylidene-2-norbornene, and 5-vinyl-2-norbornene. For example, the one or more α-olefin comonomers may be selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene, or alternatively, from the group consisting of 1-hexene and 1-octene.

[0127] An ethylene-based polymer, e.g., a homopolymer and / or interpolymer (including copolymer) of ethylene and, optionally, one or more comonomers such as α-olefins, can comprise at least 50 mole percent (mol%) of monomer units derived from ethylene. All individual values ​​and subranges encompassed by "from at least 50 mol%" are disclosed herein as separate embodiments; for example, an ethylene-based polymer, a homopolymer and / or interpolymer (including copolymer) of ethylene, and, optionally, one or more comonomers such as α-olefins, can comprise at least 60 mol% of monomer units derived from ethylene, at least 70 mol% of monomer units derived from ethylene, at least 80 mol% of monomer units derived from ethylene, or 50 to 100 mol% of monomer units derived from ethylene, or 80 to 100 mol% of units derived from ethylene.

[0128] In some embodiments, the ethylene-based polymer can comprise at least 90 mole percent units derived from ethylene. All individual values ​​and subranges from at least 90 mole percent are included herein and disclosed herein as separate embodiments. For example, the ethylene-based polymer can comprise at least 93 mole percent units derived from ethylene, at least 96 mole percent units, at least 97 mole percent units derived from ethylene, or alternatively, 90 to 100 mole percent units derived from ethylene, 90 to 99.5 mole percent units derived from ethylene, or 97 to 99.5 mole percent units derived from ethylene.

[0129] In some embodiments of the ethylene-based polymer, the ethylene-based polymer may comprise an amount of (C3-C 20 ) α-olefins (C3 to C 20 In some embodiments, the ethylene-based polymer comprises at least 0.5 mol % to 25 mol % (C to C) α-olefins. 20In further embodiments, the ethylene-based polymer may comprise at least 5 mol % to 10 mol % of an α-olefin, in some embodiments, the additional α-olefin is 1-octene.

[0130] Any conventional polymerization process in combination with a catalyst system according to an embodiment of the present disclosure can be used to produce ethylene-based polymers, including, but not limited to, solution polymerization processes, gas phase polymerization processes, slurry phase polymerization processes, and combinations thereof, using one or more conventional reactors such as loop reactors, isothermal reactors, fluidized bed gas phase reactors, stirred tank reactors, batch reactors, etc., in parallel, series, or any combination thereof.

[0131] In one embodiment, an ethylene-based polymer can be produced via solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system described herein and, optionally, one or more cocatalysts. In another embodiment, an ethylene-based polymer can be produced via solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in the presence of a catalyst system described herein and herein, and, optionally, one or more other catalysts. The catalyst system described herein, optionally in combination with one or more other catalysts, can be used in the first reactor or the second reactor. In one embodiment, an ethylene-based polymer can be produced via solution polymerization in a dual reactor system, e.g., a dual loop reactor system, where ethylene and, optionally, one or more α-olefins are polymerized in both reactors in the presence of a catalyst system described herein.

[0132] In another embodiment, the ethylene-based polymer can be produced via solution polymerization in a single reactor system, for example, a single loop reactor system, where ethylene and optionally one or more α-olefins are polymerized in the presence of a catalyst system described within this disclosure.

[0133] The polymer process may further include incorporating one or more additives. Such additives include, but are not limited to, antistatic agents, color enhancers, dyes, lubricants, pigments, primary antioxidants, secondary antioxidants, processing aids, UV stabilizers, and combinations thereof. The ethylene-based polymer may include any amount of additives. The ethylene-based polymer may include a total amount of such additives of about 0 to about 10 weight percent, based on the weight of the ethylene-based polymer and the one or more additives. The ethylene-based polymer may further include a filler, which may include, but is not limited to, organic or inorganic fillers. The ethylene-based polymer may contain about 0 to about 20 weight percent of a filler, such as calcium carbonate, talc, or Mg(OH)2, based on the total weight of the ethylene-based polymer and all additives or fillers. The ethylene-based polymer may be further blended with one or more polymers to form a blend.

[0134] In some embodiments, a polymerization process for producing an ethylene-based polymer can include polymerizing ethylene and at least one additional α-olefin in the presence of a catalyst system incorporating at least one metal-ligand complex, an ionic metal activator complex, and optionally a scavenger. Polymers obtained from such catalyst systems incorporating a metal-ligand complex and an ionic metal activator complex can have a molecular weight of, for example, 0.850 g / cm according to ASTM D792, which is incorporated herein by reference in its entirety. 3 ~0.950g / cm 3 , 0.870g / cm 3 ~0.920g / cm 3 , 0.870g / cm 3 ~0.910g / cm 3 , or 0.870 g / cm 3 ~0.900g / cm 3 The density may be

[0135] In another embodiment, the polymers obtained from the catalyst system comprising a metal-ligand complex and an ionic metal activator complex have a melt flow ratio (I) of 5 to 15. 10 / I2), where the melt index I2 is measured at 190°C and a load of 2.16 kg according to ASTM D1238 (incorporated herein by reference in its entirety), and the melt index I 10 is measured according to ASTM D1238 at 190°C and a load of 10 kg. In other embodiments, the melt flow ratio (I 10 / I2) is 5-10, and in other embodiments the melt flow ratio is 5-9.

[0136] In some embodiments, the polymer obtained from the catalyst system comprising the metal-ligand complex and the ionic metal activator complex has a molecular weight distribution (MWD) of 1 to 25, wherein the MWD is w / M n is defined as M w is the weight average molecular weight, and M n is the number average molecular weight. In another embodiment, the polymer resulting from the catalyst system has an MWD of 1 to 6. Another embodiment has an MWD of 1 to 3, and another embodiment has an MWD of 1.5 to 2.5.

[0137] Batch Reactor Procedure A 2 L Parr reactor was used for all polymerization experiments. The reactor was heated by an electric heating mantle and cooled by an internal serpentine cooling coil filled with water. Both the reactor and the heating / cooling system were controlled and monitored by a Camile TG process computer. All chemicals used in polymerization or catalyst construction were passed through purification columns. 1-octene, toluene, and Isopar-E (a mixed alkane solvent available from ExxonMobil, Inc.) were passed through two columns: the first column containing A2 alumina and the second column containing Q5 reactant (available from Engelhard Chemicals Inc.). Ethylene gas was passed through two columns: the first column containing A204 alumina and activated 4 Å molecular sieves, and the second column containing Q5 reactant. Hydrogen gas was passed through the Q5 reactant and A2 alumina. Nitrogen gas was passed through a column containing A204 alumina, activated 4 Å molecular sieves, and Q5 reactant. Catalyst and cocatalyst (also called activator) solutions were handled in a nitrogen-filled glovebox.

[0138] Using an Ashcroft differential pressure cell, the load column was filled with Isopar-E to the fill set point, and the material was transferred to the reactor. 1-Octene was measured via syringe and added via a shot tank due to low usage. Immediately upon completion, reactor heating was initiated toward the reaction set point. A scavenger (MMAO-3A, ​​20 μmol) solution was added to the reactor via a shot tank after reaching 25°C before the set point. Next, a chain transfer agent (typically tri-n-octylaluminum) was added to the reactor via a shot tank. At 10°C before the set point, ethylene was added to the specified pressure while monitoring with a micromotion flow meter. Finally, simultaneously, a dilute toluene solution of catalyst and cocatalyst (as specified) was mixed, transferred to a shot tank, and added to the reactor to initiate the polymerization reaction. Polymerization conditions were maintained by adding additional ethylene on demand to maintain the specified pressure until an ethylene uptake of 20 g was typically achieved. Exotherm was continuously removed from the reactor via an internal cooling coil. After the desired ethylene uptake was reached, the reactor was heated to 200°C, a process that took approximately 20 minutes. At this temperature, the reactor was held at 200°C for an additional 20 minutes to remove the polymeryl chains from the in situ-generated polymeryl aluminum, resulting in a solution of vinyl-terminated ethylene / 1-octene copolymer. The resulting solution was removed from the reactor without the addition of a typical antioxidant package (Irganox 1010 and Irgafos 168). The polymer was recovered by evaporating overnight in a hood and then drying for approximately 12 hours in a temperature gradient vacuum oven with a final set point of 140°C.

[0139] At least one cleaning cycle was performed between polymerization runs, during which Isopar-E (850 g) was added and the reactor heated to a set point of 160-190° C. The reactor was then emptied of heated solvent just before starting a new polymerization run. The present specification includes the following aspects. Section 1: 1. A method for preparing a non-polar-polar diblock copolymer, comprising: polymerizing one or more olefin monomers in the presence of an alkylaluminum chain transfer agent to form a polymerylaluminum species, which is then heated to form a vinyl-terminated polyolefin; reacting a thiol compound with said vinyl-terminated polyolefin to form a sulfide-containing polyolefin intermediate, said thiol compound comprising a terminal hydroxyl or a protected terminal amine; forming a macroinitiator by reacting said sulfide-containing polyolefin intermediate with a linker, said linker comprising an acyl halide and a halogen atom attached to the alpha carbon to said acyl halide; The macroinitiator, radical reagent, and CH═CH—(X) monomer (wherein X is —C(O)OR, —CN, or —C(O)NHR, and R is —H, linear (C1-C 18 ) alkyl, or branched chain (C1-C 18 ) alkyl) via a reversible deactivation radical polymerization reaction to form the non-polar-polar diblock copolymer; A method comprising: Section 2: The CH═CH—(X) monomer is CH═CHC(O)(OR), where each R is —H, a straight chain (C1-C 18 ) alkyl, or branched chain (C1-C 18 ) alkyl), glycidyl acrylate, or a combination thereof. Section 3: Item 10. The method of claim 1, wherein the CH═CH—(X) monomer comprises at least one t-butyl acrylate. Section 4: Item 4. The method of item 3, further comprising reacting the non-polar-polar diblock copolymer under thermal or acidic conditions to form a non-polar-polar acid diblock copolymer, wherein the thermal conditions comprise a temperature greater than 20°C. Section 5: The thiol compound has the structure: [ka] (wherein x is 2 to 12, and Y is -NHR B or -OH, and R B 5. The method according to any one of items 1 to 4, wherein Item 6: Y is -NHR B Item 6. The method according to Item 5, Section 7: Item 6. The method according to item 5, further comprising deprotecting the protected terminal amine. Section 8: Item 8. The method according to any one of Items 5 to 7, wherein during the reaction of the thiol compound with the vinyl-terminated polyolefin, the —SH group of the thiol compound reacts with a terminal vinyl group of the vinyl-terminated polyolefin to produce the sulfide-containing polyolefin intermediate. Section 9: The polyolefin comprises a monomer derived from ethylene, and optionally one or more (C3 to C 12 Item 9. The method according to any one of Items 1 to 8, further comprising an α-olefin monomer. Section 10: Item 10. The method according to any one of Items 1 to 9, wherein the halogen atom bonded to the alpha carbon of the linker is bromine or iodine. Section 11: Item 11. The method according to any one of items 1 to 10, wherein the radical reagent comprises a copper(I) halide selected from CuBr, CuCl, or CuI. Section 12: Item 12. The method according to any one of Items 1 to 11, wherein the radical reagent is CuBr. Section 13: the radical reagent is CuX, Fe(III)X3, or Ru(III)X3 (wherein X is 2,2':6',2"-terpyridine (tpy), 2,2'-bipyridine (bpy), 4,4'-di(5-nonyl)-2,2'-bipyridine (dNbpy), N,N,N',N'-tetramethylethylenediamine (TMEDA), N-propyl(2-pyridyl)methanimine (NPrPMI), 4,4',4"-tris(5-nonyl)-2,2':6',2"-terpyridine (tNtpy), N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA), N,N- Item 12. The method according to any one of items 1 to 11, wherein the ligand is selected from the group consisting of bis(2-pyridylmethyl)octylamine (BPMOA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA), tris[2-(dimethylamino)ethyl]amine (MeTREN), tris[(2-pyridyl)methyl]amine (TPMA), 1,4,8,11-tetraaza-1,4,8,11-tetramethylcyclotetradecane (MeCYCLAM), and N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN). Section 14: The chain transfer agent is AlR3, where each R is independently (C1 to C 12 14. The method according to any one of items 1 to 13, wherein the aryl group is aryl, aryl, or aryl. Section 15: Item 15. The method according to any one of Items 1 to 14, wherein the vinyl-terminated polyolefin is produced by heating the polymeryl aluminum species via a β-elimination reaction. Section 16: The linker has a structure according to formula (II): [ka] (wherein X1 is a halogen atom, X2 is chlorine, bromine, or iodine, and R 1 and R 2 are independently (C1~C 20 16. The method according to any one of items 1 to 15, wherein the aryl group is a aryl group, and the aryl group is a aryl group. Section 17: Item 17. The method according to any one of items 1 to 16, wherein the non-polar-polar diblock copolymer is a polyolefin-polyacrylate diblock copolymer. Section 18: Item 18. The method according to any one of items 1 to 17, wherein the non-polar-polar diblock copolymer is a polyethylene-polyacrylate diblock copolymer. [Example]

[0140] Reaction Sequences A-H are illustrative synthetic procedures for the polymerization process shown in Scheme 1. In each reaction sequence, a different vinyl-terminated polyolefin was produced. Each vinyl-terminated polyolefin varied based on molecular weight and units derived from comonomer incorporation. One or more features of the present disclosure will be illustrated in light of the following examples.

[0141] In Reaction Sequences A through C, the vinyl-terminated polyolefin had a low molecular weight. In Reaction Sequence D, the vinyl-terminated polyolefin had an ultra-low molecular weight. In Reaction Sequences E through G, the vinyl-terminated polyolefin had a high molecular weight. In Reaction Sequence H, the thiol compound was 2-(BOC-amino)ethanethiol.

[0142] Example 1 - Synthesis of Vinyl-Terminated Polyolefins (Vinyl-Terminated Polyolefins 1, 2, 3, 4, 5, 6, and 7) via Trialkylaluminum Chain Transfer Agents [ka]

[0143] To synthesize vinyl-terminated polyolefins, ethylene and optionally octene were polymerized in the presence of Al(octyl)3 and procatalyst 1 or procatalyst 2. The alkylaluminum functioned as a chain transfer agent, leading to the formation of polymerylaluminum species. After the olefin polymerization step, the reaction mixture was heated in the presence of excess ethylene and octene to yield primarily vinyl-terminated polymers and trialkylaluminums in equilibrium. [ka]

[0144] The results, summarized in Table 1, 1 Determined by H NMR, M n、有効 The molecular weight of the vinyl-terminated polyolefin produced is given as M n有効 To obtain M, the number of vinyl groups was normalized to 1 and the molecular weight contributions from vinyl groups (27 g / mol), aliphatic / polyolefin protons (2H = 14 g / mol), and any other distinguishable functional groups were summed. It was assumed that all vinyl groups were attached to the polymer and that all polymers had exactly one vinyl group. n、有効 The use of M allows for a single value to represent the molecular weight while providing the correct concentration of functional groups for the purposes of reaction stoichiometry. In Table 1, M is used for higher MW polymers when the chain end functionality is lower. n,有効 and GPC M n There is only a significant discrepancy between [Table 1]

[0145] a1 The M of the polymer when all chains are terminated with exactly one vinyl group, as determined by H NMR. n (See text for discussion). b The percentage of chains with one saturated (methyl) end group and one unsaturated (olefin) end group. c The percentage of unsaturated chain ends that are vinyl.

[0146] Reaction Sequence A [ka]

[0147] Synthesis of low MW hydroxyl-terminated polyolefin (compound A2)

[0148] In a glove box, vinyl-terminated polyolefin 3 (M n ABCN (248 mg, 1.0 mmol, 0.5 equiv.) in 2 mL of toluene was added. The reaction was stirred at 110°C for 4 hours, after which the reaction was removed from the glovebox. The product was precipitated in 500 mL of MeOH, filtered, and washed with additional MeOH. The product was then dried overnight at 70°C under a stream of N2 to give a white polymer (14.4 g, 94% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 3.68(q br,J=6.1Hz,2H,a),2.55(m br,4H,c),1.92-0.74(br overlap,1125H,Polyolefin+other aliphatic+PE Me ). [ka]

[0149] Synthesis of low MW macroinitiator [Compound A3]

[0150] In a glove box, hydroxyl-terminated polyethylene (compound A2, M n =8.0 kDa, 14.0 g, 1.75 mmol-OH) was dissolved in 48 mL of toluene in a jar under reflux. Triethylamine (1.22 mL, 8.80 mmol, 5 equiv.) was added, followed by the dropwise addition of 2-bromo-2-methylpropionyl bromide (0.87 mL, 7.0 mmol, 4 equiv.) diluted with 2 mL of toluene. The reaction was refluxed for 75 minutes, then removed from the glovebox, precipitated in 800 mL of MeOH, filtered, and then triturated with an additional 600 mL of MeOH and filtered again. The product was dried overnight at 70 °C under a stream of N to give a brown polymer (13.7 g, 96% yield). 1H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 4.25(t br,2H,a),2.58(m,4H,c),2.01(s,6H,d),1.78(m,2H,b),1.67(m,4H,e),1.92-0.74(br Duplicate, 1143H, polyolefin + other aliphatic + PE Me ). [ka]

[0151] Synthesis of low MW polyolefin-b-poly(tBA) [Compound A4]

[0152] In a glove box, compound A3 (M n CuBr (8.4 kDa, 12.5 g, 1.5 mmol) was dissolved in 25 mL of toluene at 110 °C. tert-Butyl acrylate (5.5 mL, 38 mmol, 25 equiv.) was added and the solution was stirred until homogeneous. CuBr (214 mg, 1.50 mmol, 1 equiv.) and PMDETA (0.312 mL, 1.50 mmol, 1 equiv.) were added as a stock solution in benzonitrile (1.29 mL), and the reaction was allowed to proceed for 1 h. The reaction was quenched by removing from the glovebox and exposing to air. The solution was diluted to 200 mL with hot toluene, washed with water, then with 0.5 M EDTA solution until the washings were nearly colorless, then precipitated twice into 800 mL of MeOH and filtered. The product was dried overnight at 70 °C under a stream of N to give a brown polymer (14 g, 88% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 4.09(t br,J=5.3,2H,a),2.55(t br,J=7.4Hz,4H,c),2.40-2.20(br,13H,f),2.00-1.57(br Overlap,35H,d+g / g'),1.51(s br,165H,e),1.47-1.11(br,1193H,Polyolefin+other aliphatic),0.96(t,J=6.7Hz,13H,PE Me ).

[0153] NMR showed that the acrylate resonances were associated with larger molecules, with no evidence of lower molecular weight acrylates. The diffusion coefficients were reduced in PE compared to the parent polymer, consistent with a polymer of approximately 10 kDa molecular weight (polyolefin equivalent). The acrylates had slightly larger diffusion coefficients than PE, with M w Not M n This was consistent with functionalization being proportional to the diffusion signal (the diffusion signal is proportional to the mass). [ka]

[0154] Synthesis of low MW polyolefin-b-poly(AA) [Compound A5]

[0155] In a glove box, compound A4 (M n = 10.7 kDa, 13.5 g, 23.2 mmol tert-butyl groups) was dissolved in 50 mL of toluene at 110 °C. Trifluoroacetic acid (8.16 mL, 106 mmol, 4.6 equiv.) was added and the solution was stirred at reflux for 10 minutes. The reaction mixture was then removed from the glovebox, precipitated into 600 mL of MeOH, and filtered. The solid / gel was washed with an additional 400 mL of MeOH and filtered again. The product was then dried overnight at 70 °C under a stream of N to give a brown polymer (11.4 g, 90% yield). 1 H NMR (500 MHz, 110 °C, d = 70 s, TCE-d:DMSO-d 10:1 v / v) δ 9.75-8.60 (br, 13H, COOH), 1.55-0.40 (br overlap, 1193H, polyolefin + other aliphatic + PE) Me ). [ka]

[0156] Reaction Sequence B [ka]

[0157] Synthesis of low MW hydroxyl-terminated polyolefin (compound B2)

[0158] In a glove box, vinyl-terminated polyolefin 4 (M n ABCN (414 mg, 1.7 mmol, 0.5 equiv.) in 2 mL of toluene was added. The reaction was stirred at 110 °C for 2 h, then removed from the glovebox, precipitated in 800 mL of MeOH, filtered, and washed with additional MeOH. The product was then dried overnight at 70 °C under a stream of N to give a white polymer in quantitative yield. 1 H NMR (500 MHz, 110 °C, d1 = 70 s, TCE-d2) δ 3.68 (q br, J = 6.1 Hz, 2H, a), 2.55 (m br, 4H, c), 1.92-0.74 (br overlap, 1098H, polyolefin + other aliphatic + PE) Me ). [ka]

[0159] Synthesis of a low MW macroinitiator (compound B3)

[0160] In a glove box, compound B2 (M n = 7.7 kDa, 23.0 g, 3.0 mmol-OH) was dissolved in 90 mL of toluene in a jar under reflux. Triethylamine (2.06 mL, 14.9 mmol, 5 equiv.) was added, followed by the dropwise addition of 2-bromo-2-methylpropionyl bromide (1.47 mL, 11.9 mmol, 4 equiv.) diluted with 5 mL of toluene. The reaction was refluxed for 75 minutes, then removed from the glovebox, precipitated in 800 mL of MeOH, filtered, and then triturated with an additional 600 mL of MeOH and filtered again. The product was dried overnight at 70 °C under a stream of N2 to give a brown polymer in quantitative yield. 1H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 4.25(t br,2H,a),2.58(m,4H,c),2.01(s,6H,d),1.78(m,2H,b),1.67(m,5H,e),1.92-0.74(br Duplicate, 1146H, polyolefin + other aliphatic + PE Me ). [ka]

[0161] Synthesis of low MW polyolefin-b-poly(tBA)-r-poly(nBA) (compound B4)

[0162] In a glove box, compound B3 (M n CuBr (=8.0 kDa, 10.0 g, 1.21 mmol) was dissolved in 28 mL of toluene at 110 °C. tert-Butyl acrylate (4.42 mL, 30.2 mmol, 25 equiv.) and n-butyl acrylate (4.32 mL, 30.2 mmol, 25 equiv.) were added and the solution stirred until homogeneous. CuBr (173 mg, 1.21 mmol, 1 equiv.) and PMDETA (209 mL, 1.21 mmol, 1 equiv.) were added as a stock solution in benzonitrile (1.04 mL), and the reaction was allowed to proceed for 1 h. The reaction was quenched by removing from the glovebox and exposing to air. The solution was diluted to 200 mL with hot toluene, washed with water, then with 0.5 M EDTA solution until the washings were nearly colorless, and then precipitated twice into 800 mL of MeOH and filtered. The product was dried under a stream of N2 at 70°C overnight to give a brown polymer (12.6g, 82% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 4.10(br,32H,a+h),2.50-2.40(br,17H,i+c),2.40-2.20(br,17H,f),2.00-1.57(br Overlap,88H,d+g / g'+j / j'+k),1.54-1.43(br,194H,e+l),1.47-1.11(br,1118H,Polyolefin+other aliphatic),1.04-0.92(t,J=6.7Hz,59H,PEMe +nBu Me ).

[0163] NMR showed that the acrylate monomers were linked to larger molecules, with no evidence of smaller acrylates. [ka]

[0164] Synthesis of low MW polyolefin-b-poly(AA)-r-poly(nBA) (compound B5)

[0165] In a glove box, compound B4 (M n = 12.0 kDa (17 wt% tBA), 12.0 g, 16 mmol tert-butyl groups) was dissolved in 50 mL of toluene at 110 °C. Trifluoroacetic acid (5.58 mL, 73.0 mmol, 4.6 equiv) was added and the solution was stirred at reflux for 10 min, then precipitated into 600 mL of MeOH and filtered. The solid / gel was washed with an additional 400 mL of MeOH and filtered again. The product was then dried overnight at 70 °C under a stream of N to give a brown polymer (10.3 g, 90% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2:DMSO-d610:1 v / v)δ 7.74-6.63(br,14H,COOH),4.02(br,29H,h),2.60-2.18(DMSO),2.02-1.33(br Duplicate, 81H), 1.33-0.99 (br Duplicate, 1118H), 0.99-0.78 (br, 54H, PE Me +nBu Me ). [ka]

[0166] Reaction Sequence C [ka]

[0167] Synthesis of low MW polyolefin-b-poly(tBA)-r-poly(nBA) (compound C4)

[0168] In a glovebox, compound C3 (M) was produced using the same sequence as used to synthesize compound B2. n CuBr (=8.0 kDa, 10.0 g, 1.21 mmol) was dissolved in 28 mL of toluene at 110 °C. tert-Butyl acrylate (4.42 mL, 30.2 mmol, 25 equiv.) and n-butyl acrylate (10.1 mL, 70.5 mmol, 58 equiv.) were added and the solution stirred until homogeneous. CuBr (173 mg, 1.21 mmol, 1 equiv.) and PMDETA (209 mL, 1.21 mmol, 1 equiv.) were added as a stock solution in benzonitrile (1.04 mL), and the reaction was allowed to proceed for 1 h. The reaction was quenched by removing from the glovebox and exposing to air. The solution was diluted to 200 mL with hot toluene, washed with water, then with 0.5 M EDTA solution until the washings were nearly colorless, and then precipitated twice into 800 mL of MeOH and filtered. The product was dried under a stream of N2 at 70°C overnight to give a brown polymer (17.0 g, 89% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 4.10(br,79H),2.50-2.40(br,39H),2.40-2.20(br,20H),2.00-1.57(br overlap, 175H), 1.54-1.43 (br, 271H), 1.47-1.11 (br overlap, 1118H, polyolefin + other aliphatic), 1.04-0.92 (t, J = 6.7Hz, 128H, PE Me +nBu Me ).

[0169] NMR showed that the acrylate resonances were attached to large molecules, and there was no evidence of small acrylates. [ka]

[0170] Synthesis of low MW polyolefin-b-poly(AA)-r-poly(nBA) (compound C5)

[0171] In a glove box, compound C4 (M n = 15.5 kDa (16 wt% tBA), 13.0 g, 16 mmol tert-butyl groups) was dissolved in 60 mL of toluene at 110 °C. Trifluoroacetic acid (5.0 mL, 73.0 mmol, 4.0 equiv) was added and the solution was stirred at reflux for 10 min, then precipitated into 600 mL of MeOH and filtered. The solid / gel was washed with an additional 400 mL of MeOH and filtered again. The product was then dried overnight at 70 °C under a stream of N to give a brown polymer (11.0 g, 88% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2:DMSO-d610:1 v / v)δ 9.50-8.20(br,11H,COOH),4.02(br,77H,),2.45-2.18(br,62H,),2.02-1.33(br Duplicate,379H,),1.33-0.99(br Duplicate,1118H,),0.99-0.78(br,116H). [ka]

[0172] Reaction Order D [ka]

[0173] Synthesis of ultra-low MW hydroxyl-terminated polyolefin (compound D2)

[0174] In a glove box, vinyl-terminated polyolefin 5 (M n= 1.5 kDa, 25.3 g, 16.6 mmol) was dissolved in 80 mL of toluene in an evacuated glass jar at 110 °C. 6-Mercaptohexanol (6.80 mL, 47.8 mmol, 3 equiv.) was added in one portion, followed by ABCN (2.02 g, 8.3 mmol, 0.5 equiv.) in 10 mL of toluene. The reaction was stirred at 110 °C for 2 h, then removed from the glovebox, precipitated into 800 mL of MeOH, filtered, and washed with additional MeOH. The product was then dried overnight at 70 °C under a stream of N to yield a white polymer (26.5 g, 96% yield). 1 H NMR (500 MHz, 110 °C, d1 = 70 s, TCE-d2) δ 3.68 (q br, 2H, a), 2.55 (m br, 4H, c), 1.92-0.74 (br overlap, 205H, polyolefin + other aliphatic + PE) Me ). [ka]

[0175] Synthesis of an ultra-low MW macroinitiator (compound D3)

[0176] In a glove box, compound D2 (M n = 1.5 kDa, 26.0 g, 17.6 mmol -OH) was dissolved in 120 mL of toluene in a jar under reflux. Triethylamine (7.30 mL, 52.7 mmol, 3 equiv.) was added, followed by the dropwise addition of 2-bromo-2-methylpropionyl bromide (4.35 mL, 35.1 mmol, 2 equiv.) diluted with 10 mL of toluene. The reaction was refluxed for 30 minutes, then removed from the glovebox, precipitated in 800 mL of MeOH, filtered, and then triturated with an additional 600 mL of MeOH and filtered again. The product was dried overnight at 70 °C under a stream of N to give a brown polymer (27.8 g, 97% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 4.25(t br,2H)2.58(m,4H),2.01(s,6H),1.92-0.74(br overlap,208H). [ka]

[0177] Synthesis of ultra-low MW polyolefin-b-poly(tBA)-r-poly(nBA) (compound D4)

[0178] In a glove box, compound D3 (M n CuBr (=1.7 kDa, 26.0 g, 15.6 mmol) was dissolved in 180 mL of toluene at 110 °C in a 500 mL round-bottom flask equipped with a stir bar. tert-Butyl acrylate (11.4 mL, 77.8 mmol, 5 equiv.) and n-butyl acrylate (33.4 mL, 234 mmol, 15 equiv.) were added and the solution stirred until homogeneous. CuBr (2.23 g, 15.6 mmol, 1 equiv.) and PMDETA (2.70 g, 15.6 mmol, 1 equiv.) were added as a neat solution in benzonitrile (13.4 mL), and the reaction was allowed to proceed for 30 min. The reaction was quenched by removal from the glovebox and exposure to air, then precipitated twice into 800 mL of MeOH and filtered. The product was dried overnight at 70°C under a stream of N2 to give a brown polymer (18.6g, 35% yield) [*Conversion was good, but most of the product was lost in the washout]. 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 4.10(br,25H,a+h),2.50-2.40(br,13H,i+c),2.40-2.20(br,6H,f),2.00-1.57(br Overlap, 53H), 1.54-1.43 (br, 63H, e+l), 1.47-1.11 (br, 208H, polyolefin + other aliphatic), 1.04-0.92 (t, J=6.7Hz, 38H). [ka]

[0179] Synthesis of ultra-low MW polyolefin-b-poly(AA)-r-poly(nBA) (compound D5)

[0180] Compound D4(Mn A solution of 18.1 g of methyltrifluoroacetic acid (=3.6 kDa (15 wt% tBA), 18.1 g, 16 mmol tert-butyl groups) was added to a 500 mL round-bottom flask containing 200 mL of toluene and stirred with an overhead stirrer equipped with a reflux condenser and a heating mantle set at 115 °C. The mantle temperature was reduced to 105 °C, and trifluoroacetic acid (16.1 mL, 211 mmol, 10 equiv.) was added, and the solution was stirred for 1 h. The heating mantle was then removed, and the reaction was cooled to room temperature and then precipitated in portions into four 500 mL jars, each containing 300 mL of MeOH. The combined portions were isolated by filtration, and the resulting solid was washed with methanol, filtered, and dried in a vacuum oven at 50 °C for 18 h to yield a light brown powder (13.77 g, 81% yield). An additional portion (0.90 g, 5.3% yield) was obtained by settling the solid from the supernatant and isolating it in the same manner. The total yield is 14.67 g (87%). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2:DMSO-d610:1 v / v)δ 11.2-9.5(br,2H,COOH),4.02(br,23H),2.60-2.18(br,19H),2.02-1.33(br Overlap, 87H), 1.33-0.99 (br Overlap, 208H), 0.99-0.78 (br, 36H). [ka]

[0181] Reaction Order E [ka]

[0182] Synthesis of a high MW hydroxyl-terminated polyolefin (compound E2)

[0183] In a glove box, vinyl-terminated polyolefin 7 (M nA solution of 6-mercaptohexanol (1.20 mL, 9.0 mmol, 10 equiv.) and ABCN (218 mg, 0.89 mmol, 1 equiv.) in 5 mL of toluene was dissolved in 125 mL of toluene under reflux in an evacuated round-bottom flask. 6-Mercaptohexanol (1.20 mL, 9.0 mmol, 10 equiv.) was added in one portion, followed by ABCN (218 mg, 0.89 mmol, 1 equiv.) in 5 mL of toluene. The reaction was stirred for 2 h, at which point additional portions of 6-mercaptohexanol (1.20 mL, 9.0 mmol, 10 equiv.) and ABCN (218 mg, 0.89 mmol, 1 equiv.) were added. After an additional 2 h, the reaction was removed from the glovebox, precipitated in 800 mL of MeOH, filtered, and washed with additional MeOH. The product was then dried overnight at 70 °C under a stream of N to yield a white polymer (22.6 g, 97% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 3.68(m br,2H),2.55(m br,4H),1.92-0.74(br overlap,4433H). [ka]

[0184] Synthesis of a high MW macroinitiator (compound E3)

[0185] In a glove box, compound E2 (M n = 31.0 kDa, 22.5 g, 0.73 mmol-OH) was dissolved in 135 mL of toluene in a round-bottom flask under reflux. Triethylamine (1.56 mL, 11.3 mmol, 15.6 equiv.) was added, followed by the dropwise addition of 2-bromo-2-methylpropionyl bromide (0.84 mL, 0.68 mmol, 9.4 equiv.) diluted with 10 mL of toluene. The reaction was refluxed for 30 minutes, then removed from the glovebox, precipitated in 800 mL of MeOH, filtered, and then triturated with an additional 600 mL of MeOH and filtered again. The product was dried overnight at 70 °C under a stream of N2 to give a brown mass in quantitative yield. 1H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 4.25(t br,2H),2.58(m,4H),2.01(s,6H),1.78-1.74(br overlap,4265H,). [ka]

[0186] Synthesis of high MW polyolefin-b-poly(tBA) (compound E4)

[0187] In a glove box, compound E3 (M n = 30.0 kDa, 10.0 g, 0.33 mmol-Br) was dissolved in 50 mL of toluene at 110 °C. tert-Butyl acrylate (10.6 mL, 72.7 mmol, 218 equiv.) was added and the solution was stirred until homogeneous. CuBr (48 mg, 0.33 mmol, 1 equiv.) and PMDETA (0.069 mL, 0.33 mmol, 1 equiv.) were added as a stock solution in benzonitrile (0.29 mL), and the reaction was allowed to proceed for 5 h. The reaction was quenched by removing from the glovebox and exposing to air. The solution was then precipitated twice into 800 mL of MeOH, filtered, and washed with two additional 500 mL portions of MeOH until the polymer was colorless. The product was dried overnight at 70 °C under a stream of N2 to give a white polymer in quantitative yield. 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 4.09(t br,J=5.3,2H),2.55(t br,J=7.4,5H),2.40-2.20(br,48H),2.00-1.57(br overlap,93H),1.51(s br,486H),1.47-1.11(br,4234H),0.96(t,J=6.7,39H). [ka]

[0188] Synthesis of low MW polyolefin-b-poly(AA) (compound E5)

[0189] Compound E4(M n A 500 mL round-bottom flask equipped with a reflux condenser and mechanical stirrer was charged with toluene (200 mL). The mixture was stirred at reflux (heating mantle set at 115 °C) until a clear, viscous solution was obtained (approximately 20 min). The heating mantle temperature was reduced to 105 °C, and trifluoroacetic acid (12.3 mL, 160 mmol, 10 equiv.) was added rapidly to the mixture. The reaction was stirred at 105 °C for 1 h. The heating mantle was removed, and the reaction was allowed to cool to room temperature. The resulting gel / paste was precipitated into rapidly stirring jars (3 jars, each 350 mL) containing methanol, forming a milky white suspension. The suspensions were combined, filtered, washed with methanol, and dried in a vacuum oven at 50° C. for 18 hours to give a white powder (9.61 g, 97% yield). 1 H NMR (500 MHz, 110 °C, d = 70 s, TCE-d:DMSO-d 10:1 v / v) δ 11.50-10.50 (br, 43H, COOH), 1.28-0.99 (br, 423H, polyolefin), 0.89-0.84 (br, 52H, PE) Me ) [ka]

[0190] Reaction Order F [ka]

[0191] Synthesis of high MW hydroxyl-terminated polyolefin (compound F2)

[0192] In a glove box, vinyl-terminated polyolefin 6 (M nA solution of 1,2-dimethyl-2,4-trimethyl-1,2-trimethyl ... The product was then dried under a stream of N2 at 70°C overnight to give a white polymer (24.7g, 96% yield). 1 H NMR (500 MHz, 110 °C, d1 = 70 s, TCE-d2) δ 3.68 (br, 2H, a), 2.55 (m br, 4H, c), 1.92-0.74 (br, 4H, polyolefin, overlapping methylene s, PE Me ). [ka]

[0193] Synthesis of a high MW macroinitiator (compound F3)

[0194] In a glove box, compound F2 (M n= 29.8 kDa, 24.7 g, 0.83 mmol-OH) was dissolved in 145 mL of toluene in a 500 mL round-bottom flask under reflux. Triethylamine (1.71 mL, 12.4 mmol, 15 equiv.) was added dropwise, followed by 2-bromo-2-methylpropionyl bromide (0.92 mL, 7.4 mmol, 9 equiv.) diluted with 5 mL of toluene. The reaction was refluxed for 75 minutes, then removed from the glovebox, precipitated in 800 mL of MeOH, filtered, and then triturated with an additional 600 mL of MeOH and filtered again. The product was dried overnight at 70 °C under a stream of N2 to give a brown polymer (24.7 g, 99% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 4.25(t br,2H),2.58(br,4H),2.01(s,6H),1.78 -1.74(br overlap,4638H). [ka]

[0195] Synthesis of high MW polyolefin-b-poly(tBA)-r-poly(nBA) (compound F4)

[0196] In a glove box, compound F3 (M nCuBr (=32.3 kDa, 10.0 g, 0.31 mmol) was dissolved in 50 mL of toluene at 110 °C in a 250 mL glass jar equipped with a stir bar. tert-Butyl acrylate (10.8 mL, 74 mmol, 250 equiv.) and n-butyl acrylate (10.6 mL, 74 mmol, 250 equiv.) were added and the solution stirred until homogeneous. CuBr (42 mg, 0.3 mmol, 1 equiv.) and PMDETA (51 mg, 0.3 mmol, 1 equiv.) were added as a stock solution in benzonitrile (0.255 mL), and the reaction was allowed to proceed for 5 h. The reaction was quenched by removal from the glovebox and exposure to air. The slurry was then precipitated into 800 mL of MeOH, filtered, and rinsed with excess MeOH. The product was dried under a stream of N2 at 70°C overnight to give a white polymer (15.5g, 98% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 4.10(br,149H),2.50-2.40(br,75H),2.40-2.20(br,80H),2.00-1.57(br Duplication, 434H), 1.54-1.43 (br, 934H), 1.47-1.11 (br, 4621H), 1.04-0.92 (t,J=6.7,268H). [ka]

[0197] Synthesis of high MW polyolefin-b-poly(AA)-r-poly(nBA) (compound F5)

[0198] Compound F4(M nA 500 mL round-bottom flask equipped with a reflux condenser and mechanical stirrer was charged with 14.0 g of tBA (=51.2 kDa, 14.0 g, 18 wt % tBA, 19.7 mmol tert-butyl group) and toluene (200 mL) was added. The mixture was stirred at reflux (heating mantle set at 115 °C) until a clear, viscous solution was obtained (approximately 20 min). The heating mantle temperature was reduced to 105 °C, and trifluoroacetic acid (15.0 mL, 196 mmol, 10 equiv) was added rapidly to the mixture. The reaction was stirred at 105 °C for 1 h. The heating mantle was removed, and the reaction was allowed to cool to room temperature. The resulting suspension was precipitated into rapidly stirring jars (3 jars, each 350 mL) containing methanol, forming a milky white suspension. The suspensions were combined, filtered, washed with methanol, and dried in a vacuum oven at 50° C. for 18 hours to give a white powder (12.2 g, 95% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2:DMSO-d610:1 v / v)δ 11.37-9(br,47H,COOH),4.02(br,144H,h),2.45-2.18(br,133H),2.02-1.33(br Duplication, 678H), 1.33-0.99 (br, 4621H), 0.99-0.78 (br, 259H). [ka]

[0199] Reaction Sequence G [ka]

[0200] Synthesis of high MW polyolefin-b-poly(tBA)-r-poly(nBA) (compound G4)

[0201] In a glovebox, compound G3 (M) was produced using the same sequence as used to synthesize compound F2. nCuBr (=32.3 kDa, 10.0 g, 0.31 mmol) was dissolved in 50 mL of toluene at 110 °C in a 250 mL glass jar equipped with a stir bar. tert-Butyl acrylate (10.8 mL, 74 mmol, 250 equiv.) and n-butyl acrylate (24.7 mL, 173 mmol, 583 equiv.) were added and the solution stirred until homogeneous. CuBr (42 mg, 0.3 mmol, 1 equiv.) and PMDETA (51 mg, 0.3 mmol, 1 equiv.) were added as a stock solution in benzonitrile (0.255 mL), and the reaction was allowed to proceed for 5 h. The reaction was quenched by removal from the glovebox and exposure to air. The slurry was then precipitated into 800 mL of MeOH, filtered, and washed with excess MeOH. The product was dried under a stream of N2 at 70°C overnight to give a white polymer (17.2g, 97% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 4.10(br,311H),2.50-2.40(br,127H),2.40-2.20(br,85H),2.00-1.57(br Duplicate,702H),1.54-1.43(br,1075H,e+l),1.47-1.11(br,4621H),1.04-0.92(t,J=6.7,502H) [ka]

[0202] Synthesis of high MW polyolefin-b-poly(AA)-r-poly(nBA) (compound G5)

[0203] Compound G4(M nA 500 mL round-bottom flask equipped with a reflux condenser and mechanical stirrer was charged with 16.7 g of a (=60.8 kDa, 14 wt. % tBA, 18.1 mmol tert-butyl groups) block copolymer, and toluene (200 mL) was added. The mixture was stirred at reflux (heating mantle set at 115 °C for 50 min, then at 125 °C for 30 min) until a clear, viscous solution was obtained. The heating mantle temperature was reduced to 105 °C, and trifluoroacetic acid (13.9 mL, 181 mmol, 10 equiv.) was rapidly added to the mixture. The reaction was stirred at 105 °C for 1 h. The heating mantle was removed, and the reaction was allowed to cool to room temperature. The resulting paste / gel was precipitated into rapidly stirring jars (four jars, each 350 mL) of methanol, forming a milky white suspension. The suspensions were combined, filtered, washed with methanol, and dried in a vacuum oven at 50° C. for 18 hours to give a white powder (14.8 g, 95% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2:DMSO-d610:1 v / v)δ 11.37-9.20(br,38H,COOH),4.02(br,286H,h),2.45-2.18(br,189H,i+f),2.02-1.33(br Overlapping,1062H,g / g'+j / j'+k+l),1.33-0.99(br,4621H,Polyolefin),0.99-0.78(br,471H,PE Me +nBu Me ) [ka]

[0204] Reaction Order H [ka]

[0205] Synthesis of low MW NH-Boc-terminated polyolefins (compounds H2-BOC)

[0206] In a glove box, vinyl-terminated polyolefin 2 (M n= 4.2 kDa, 20.4 g, 5.1 mmol) was dissolved in 60 mL of toluene in an evacuated glass jar. 2-(Boc-amino)ethanethiol (4.06 mL, 24 mmol, 4.7 equiv) was added in one portion, followed by ABCN (588 mg, 2.40 mmol, 0.47 equiv) in 2 mL of toluene. The reaction was stirred at 110 °C for 4 h, then removed from the glovebox, precipitated in 600 mL of MeOH, filtered, and washed with an additional 400 mL of MeOH. The product was then dried overnight at 70 °C under a stream of N to give a white polymer (20.8 g, 98% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 4.76(br,1H,NH),3.34(q,J=6.5Hz,2H,a),2.69(t,J=6.6Hz,2H,b),2.58(t,J=7.3Hz,2H,c),1.78(m,2H,d),1.65(s,9H,e),1.49-0.89(br,691H). [ka]

[0207] Low MW NH3-TFA terminated polyolefin (compound H2-H + ) synthesis

[0208] In a glove box, the compound H2-BOC(M n = 4.8 kDa, 20.0 g, 4.17 mmol) was dissolved in 40 mL of toluene at 110 °C. Trifluoroacetic acid (3.0 mL, 39 mmol, 9.5 equiv.) was added and the solution was stirred at reflux for 30 minutes, then precipitated into 500 mL of MeOH and filtered. The solid was washed with an additional 300 mL of MeOH and filtered again. The product was then dried overnight at 70 °C under a stream of N to give a brown polymer in quantitative yield. 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 5.00(br,3H,NH3 +),3.23(br,2H,a),2.90(t,J=7.4Hz,2H),2.60(t,J=7.4Hz,2H),1.66(m,2H,d),1.56-0.85(br,772H). [ka]

[0209] Synthesis of low MW amine-terminated polyolefin (compound H3)

[0210] In a glove box, compound H2-H + (M n = 5.1 kDa, 17.0 g, 3.33 mmol) was dissolved in 80 mL of toluene at 110 °C. 1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU) (0.94 mL, 6.3 mmol, 1.9 equiv.) was added, and the solution was stirred at reflux for 20 min, then precipitated into 800 mL of MeOH, filtered, and washed with an additional 500 mL of MeOH. The product was then dried overnight at 70 °C under a stream of N to give a brown polymer in quantitative yield. 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 2.99(br,2H,a),2.71(br,2H,b),2.60(t,J=7.2Hz,2H,c),1.68(m,2H,d),1.61-0.89(br,713H,Polyolefin+PE Me ). [ka]

[0211] Synthesis of a low MW amide-linked macroinitiator (compound H3)

[0212] In a glove box, compound H2(M n= 5.0 kDa, 16.0 g, 3.2 mmol NH2) was dissolved in 48 mL of toluene in a jar under reflux. Triethylamine (2.63 mL, 19.0 mmol, 5.9 equiv.) was added, followed by the dropwise addition of 2-bromo-2-methylpropionyl bromide (1.57 mL, 12.7 mmol, 4 equiv.) diluted with 5 mL of toluene. The reaction was refluxed for 75 minutes, then removed from the glovebox, precipitated in 800 mL of MeOH, filtered, and then triturated with an additional 600 mL of MeOH and filtered again. The product was dried overnight at 70 °C under a stream of N2 to give a brown polymer in quantitative yield. 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 6.90(br,1H,NH),3.50(td,J=6.4,6.2Hz,2H,a),2.74(t,J=6.6Hz,2H,b),2. 61(t,J=7.3Hz,2H,c),2.01(s,6H,e),1.66(m,2H,d),1.59-0.84(br,750H). [ka]

[0213] Synthesis of low MW amide-linked polyolefin-b-poly(tBA) (compound H4)

[0214] In a glove box, compound H3(M nCuBr (=5.3 kDa, 15.0 g, 2.8 mmol) was dissolved in 60 mL of toluene at 110 °C. tert-Butyl acrylate (19.5 mL, 133 mmol, 47 equiv.) was added and the solution was stirred until homogeneous. CuBr (384 mg, 2.7 mmol, 0.95 equiv.), CuBr2 (32 mg, 0.14 mmol, 0.05 equiv.), and PMDETA (0.590 mL, 2.8 mmol, 1 equiv.) were added as a stock solution in benzonitrile (2.3 mL), and the reaction was allowed to proceed for 75 min. The reaction was quenched by removing from the glovebox and exposing to air. The solution was diluted to 200 mL with hot toluene, washed with water, then with 0.5 M EDTA solution until the washings were nearly colorless, and then precipitated twice into 800 mL of MeOH and filtered. The product was dried under a stream of N2 at 70°C overnight to give a brown polymer (21.4g, 80% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2)δ 3.44(br,2H,a),2.69(br,2H,b),2.57(br,2H,c),2.32(br,24H,g),2.00-1.58(br overlap 48H,h / h'+e),1.51(br s,260H),1.51-0.86(br,750H). [ka]

[0215] Synthesis of low MW amide-linked polyolefin-b-poly(AA)-r-poly(nBA) (compound H5)

[0216] In a glove box, compound H4 (M n= 5.3 kDa, 41 wt% tBA, 21.0 g, 67 mmol tert-butyl groups) was dissolved in 120 mL of toluene at 110 °C. Trifluoroacetic acid (26.0 mL, 336 mmol, 5 equiv.) was added and the solution was stirred at reflux for 10 min, then precipitated into 600 mL of MeOH and filtered. The solid / gel was washed with an additional 400 mL of MeOH and filtered again. The product was then dried overnight at 70 °C under a stream of N to give a brown polymer (16.2 g, 94% yield). 1 H NMR(500MHz,110℃,d1=70s,TCE-d2:DMSO-d610:1 v / v)δ 10.00-8.10(br,25H,COOH),1.46-0.75(br,750H). [ka]

[0217] For each of the reaction sequences A to H, the amount of end-functionalized polymer (specifically, vinyl-terminated polyolefin) was quantitatively determined. 13 C NMR was used to determine the

[0218] Figure 2A shows the gradient 2 Proton NMR ( ) of tert-butyl resonances from the polar block or methylene (CH ) resonances from the non-polar block as a function of / 1000 1 Figure 2A is a graph of the natural logarithm of the integral of the H NMR signal. In Figure 2A, two lines are present: one corresponds to the methylene in the polyethylene, and the other to the tert-butyl resonance in the polar block. Both lines have approximately the same slope, thus indicating a controlled mechanism of polymerization of the acrylate monomer from the macroinitiator. Thus, Figure 2 shows that the nonpolar (polyethylene) block and the polar (polyacrylate) block are linked.

[0219] Some examples include octene-derived units in the non-polar block, however the amount of octene-derived methylene in the non-polar block is small enough to be considered negligible.

[0220] The results of the graph shown in Figure 2 were calculated using the procedure described in "Molecular mass estimation by PFG NMR spectroscopy" by Crutchfield, CA, and Harris, DJ Journal of Magnetic Resonance, 185 (2007) 179-182.

[0221] Example 7 - Polymerization Results [Table 2] [Table 3] [Table 4] [Table 5]

Claims

1. 1. A method for preparing a non-polar-polar diblock copolymer, comprising: polymerizing one or more olefin monomers in the presence of an alkylaluminum chain transfer agent to form a polymerylaluminum species, which is then heated to form a vinyl-terminated polyolefin; reacting a thiol compound with said vinyl-terminated polyolefin to form a sulfide-containing polyolefin intermediate, said thiol compound comprising a terminal hydroxyl or a protected terminal amine; forming a macroinitiator by reacting said sulfide-containing polyolefin intermediate with a linker, said linker comprising an acyl halide and a halogen atom attached to the alpha carbon to said acyl halide; The macroinitiator, radical reagent, and CH ２ ═CH—(X) monomers, where X is —C(O)OR, —CN, or —C(O)NHR, and R is —H, linear (C １ ~C １８ ) alkyl, or branched chain (C １ ~C １８ ) alkyl) via a reversible deactivation radical polymerization reaction to form the non-polar-polar diblock copolymer; A method comprising:

2. The CH ２ =CH-(X) monomer is CH ２ =CHC(O)(OR) (wherein, each R is -H, straight chain (C １ ~C １８ ) alkyl, or branched chain (C １ ~C １８ ) alkyl), glycidyl acrylate, or a combination thereof.

3. The CH ２ The method of claim 1 , wherein the =CH-(X) monomer comprises at least one t-butyl acrylate.

4. 4. The method of claim 3, further comprising reacting the non-polar-polar diblock copolymer under acidic conditions or thermal conditions at a temperature above 20° C. to form a non-polar-polar acid diblock copolymer.

5. 10. The method of claim 1, wherein the thiol compound has the structure: 【Chemistry 1】 (wherein x is 2 to 12 and Y is —NHR Ｂ or —OH, and R Ｂ The method of any one of claims 1 to 4, wherein

6. Y is -NHR Ｂ The method of claim 5, wherein

7. 6. The method of claim 5, further comprising deprotecting the protected terminal amine.

8. 8. The method of any one of claims 5 to 7, wherein during the reaction of the thiol compound with the vinyl-terminated polyolefin, the -SH group of the thiol compound reacts with a terminal vinyl group of the vinyl-terminated polyolefin to produce the sulfide-containing polyolefin intermediate.

9. The olefin monomers include ethylene monomers, and optionally one or more (C ３ ~C １２ The method of any one of claims 1 to 8, further comprising:

10. 10. The method of any one of claims 1 to 9, wherein the halogen atom attached to the alpha carbon of the linker is bromine or iodine.

11. 11. The method of any one of claims 1 to 10, wherein the radical reagent comprises a copper(I) halide selected from CuBr, CuCl, or CuI.

12. The method of any one of claims 1 to 11, wherein the radical reagent is CuBr.

13. The radical reagent is CuX, Fe(III)X ３ , or Ru(III)X ３ (wherein X is 2,2':6',2"-terpyridine (tpy), 2,2'-bipyridine (bpy), 4,4'-di(5-nonyl)-2,2'-bipyridine (dNbpy), N,N,N',N'-tetramethylethylenediamine (TMEDA), N-propyl(2-pyridyl)methanimine (NPrPMI), 4,4',4"-tris(5-nonyl)-2,2':6',2"-terpyridine (tNtpy), N,N,N',N",N"-pentamethyldiethylenetriamine (PMDETA), N,N-bis(2-pyridylmethyl)octylamine (BPMOA), 1,1,4,7,10,10-hexamethyltriethylenetetramine (HMTETA), tris[2-(dimethylamino)ethyl]amine (Me ６ 12. The method of any one of claims 1 to 11, wherein the ligand is selected from the group consisting of N,N,N',N'-tetrakis(2-pyridylmethyl)ethylenediamine (TPEN), N,N,N'-tetrakis(2-pyridylmethyl)ethylenediamine (N ...

14. The chain transfer agent is AlR ３ wherein each R is independently (C １ ~C １２ 14. The method of claim 1, wherein:

15. The method of any one of claims 1 to 14, wherein the vinyl-terminated polyolefin is produced via a beta-elimination reaction by heating the polymeryl aluminum species.

16. The linker has a structure according to formula (II): 【Chemistry 2】 (In the formula, X １ is a halogen atom, and X ２ is chlorine, bromine, or iodine, and R １ and R ２ are independently (C １ ~C ２０ 16. The method of any one of claims 1 to 15, wherein:

17. The method of any one of claims 1 to 16, wherein the non-polar-polar diblock copolymer is a polyolefin-polyacrylate diblock copolymer.

18. The method of any one of claims 1 to 17, wherein the non-polar-polar diblock copolymer is a polyethylene-polyacrylate diblock copolymer.

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