Telechelic polyolefins and methods for preparing same - Patents.com

Abstract

The present disclosure relates to novel telechelic polyolefins of formula (I) and methods for preparing the same. In at least one embodiment, the telechelic polyolefins of formula (I) contain unsaturation at both ends.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Application No. 62 / 786,084, filed December 28, 2018, which is incorporated by reference in its entirety.

[0002] SUMMARY OF THE DISCLOSURE The present invention relates to telechelic polyolefins and methods for preparing the same. [Background technology]

[0003] Polyolefins are one of the most important and widely used polymeric materials in the world. Due to their inherent chemical inertness, the introduction of reactive functional groups to form telechelic polyolefins with two reactive end groups has been actively pursued for many years. However, there is a need in the art for a commercially viable method for preparing telechelic polyolefins. The present disclosure addresses such a need and relates to a novel telechelic polyolefin composition. Summary of the Invention

[0004] The present disclosure provides a composition comprising a telechelic polyolefin of formula (I): A 1 L 1 L 2 A 2 (I), in the formula L 1 is a polyolefin, A 1 is a vinyl group, formula CH2=C(Y 1 )-vinylidene group of the formula Y 1 Vinylene group of CH=CH-, vinyl group and formula Y 1 A mixture of vinyl groups and vinylene groups of the formula CH2=C(Y 1 )- with vinylidene groups, the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1Mixtures of vinylene groups of the formula CH=CH- and vinyl groups of the formula CH2=C(Y 1 )- and a vinylidene group of the formula Y 1 and a mixture of CH=CH- and vinylene groups; Y 1 Each time it appears, it is assigned independently to C1~C 30 is a hydrocarbyl group, L 2 But, C1~C 32 is a hydrocarbylene group, and A 2 is a hydrocarbyl group containing a hindered double bond.

[0005] The present disclosure further provides a method for preparing a composition comprising a telechelic polyolefin, the method comprising: 1) combining starting materials including (A) a monomer component, (B) a chain transfer agent component, and (C) a catalyst component to form a solution, and polymerizing more than 10 mol % to 99 mol % or less of the (A) monomer component in the solution; 2) heating the solution; and 3) recovering a product comprising a composition comprising the telechelic polyolefin; (B) the chain transfer agent component is a compound represented by the formula Al(CHCH(Y 2 )A 2 ) 3 organoaluminum compounds, Y 2 Each occurrence is independently hydrogen or C1-C 30 is a hydrocarbyl group, and A 2 is, independently at each occurrence, a hydrocarbyl group that contains a hindered double bond. [Brief description of the drawings]

[0006] [Figure 1A-1B] 1H NMR and GC / MS spectra for the synthesis of CTA1 are provided, respectively. [Diagram 2] 1 provides the 1H NMR spectrum for the synthesis of CTA2. [Diagram 3] 1 provides 1H NMR spectra for the synthesis of telechelic polyolefins using CTA7. [Figure 4] 1 provides 1H NMR spectra for the synthesis of telechelic polyolefins using CTA8. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0007] definition All references herein to the Periodic Table of Elements shall refer to the Periodic Table of Elements, published and copyrighted in 2003 by CRC Press, Inc. Also, any reference to a group(s) shall be to the group(s) reflected in this Periodic Table of Elements, using the IUPAC system for numbering the groups. Unless stated or implied by context or customary in the art to the contrary, all parts and percentages are by weight. For purposes of U.S. patent practice, the contents of any patents, patent applications, or publications referenced herein are hereby incorporated by reference in their entirety (or their equivalent U.S. versions are so incorporated by reference), particularly with respect to synthetic techniques, definitions (to the extent not inconsistent with any definitions provided herein), and general knowledge in the art.

[0008] Numeric ranges disclosed herein include all values ​​from the lower limit to the upper limit, inclusive. For ranges containing explicit numerical values ​​(e.g., 1, or 2, or 3-5, or 6, or 7), any subrange between any two explicit numerical values ​​is included (e.g., 1-2, 2-6, 5-7, 3-7, 5-6, etc.). Numeric ranges disclosed herein further include fractions between any two explicit values.

[0009] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional components, steps, or procedures, whether specifically disclosed or not. For the avoidance of doubt, all compositions claimed through the use of the term "comprising" may include any additional additives, adjuvants, ingredients, or compounds, whether polymeric or not, unless stated to the contrary. In contrast, the term "consisting essentially of" excludes from the scope of any subsequent recitation any other component, step, or procedure, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure not specifically described or listed. The term "or" refers to the listed members individually and in any combination, unless otherwise stated.

[0010] The term "hindered double bond" refers to a carbon-carbon double bond that cannot readily participate in coordination polymerization. In other words, the hindered double bond has negligible reactivity to participate in coordination polymerization. Examples of hindered double bonds include, but are not limited to, the double bonds of vinylidene groups, the double bonds of vinylene groups, the double bonds of trisubstituted alkenes, and the double bonds of vinyl groups attached to branched α-carbons. As defined herein, the term "hindered double bond" excludes the double bonds of strained cyclic olefins that can readily participate in coordination polymerization. As will be appreciated by those skilled in the art, examples of such strained cyclic olefins include, but are not limited to, norbornene, ethylidenenorbornene (ENB), 5-vinyl-2-norbornene (VNB), dicyclopentadiene, norbornadiene, 5-methylene-2-norbornene (MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, etc. As defined herein, the term "hindered double bond" further excludes the double bond of a vinyl group attached to an unbranched α-carbon.

[0011] The term "composition" refers to a mixture of materials or components that make up the composition. Thus, the term "composition comprising" and similar terms are not intended to exclude the presence of any additional components of the composition, whether or not they are specifically disclosed.

[0012] The term "acyclic" refers to a series of atoms in a polymer or compound that is linear or branched. Thus, the term "acyclic hydrocarbyl group" refers to a hydrocarbyl group that is linear or branched.

[0013] The term "cyclic" refers to a series of atoms in a polymer or compound that includes one or more rings. Thus, the term "cyclic hydrocarbyl group" refers to a hydrocarbyl group that includes one or more rings. As used herein, a "cyclic hydrocarbyl group" can include acyclic (linear or branched) portions in addition to the one or more rings.

[0014] The term "substituted" refers to the replacement of one or more hydrogen atoms, for example by an alkyl group. The term "unsubstituted" refers to the absence of such substitution.

[0015] The term "heteroatom," as will be understood by one of ordinary skill in the art, refers to any main group atom that is not carbon or hydrogen. Suitable heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, phosphorus, and the halogens.

[0016] As used herein, the terms "hydrocarbyl," "hydrocarbyl group," and the like refer to compounds composed entirely of hydrogen and carbon, including aliphatic, aromatic, acyclic, cyclic, polycyclic, branched, unbranched, saturated, and unsaturated compounds.

[0017] Terms such as "hydrocarbyl," "hydrocarbyl group," "alkyl," "alkyl group," "aryl," "aryl group," "cycloalkene," and the like are intended to include all possible isomers, including all structural or stereoisomers. The same applies to similar terms, including, but not limited to, heterohydrocarbyl, hydrocarbylene, heterohydrocarbylene, alkylene, heteroalkyl, heteroalkylene, arylene, heteroaryl, heteroarylene, cycloalkyl, cycloalkylene, heterocycloalkyl, and heterocycloalkylene.

[0018] The term "endocyclic double bond" refers to a double bond between two carbon atoms that are members of a ring. The term "exocyclic double bond" refers to a double bond between two carbon atoms, only one of which is a member of a ring.

[0019] "Active catalyst," "active catalyst composition," and like terms refer to a transition metal compound capable of polymerizing unsaturated monomers with or without a cocatalyst. An active catalyst can be a "procatalyst" that is active and polymerizes unsaturated monomers without a cocatalyst. Alternatively, an active catalyst can be a "procatalyst" that is active and polymerizes unsaturated monomers in combination with a cocatalyst.

[0020] The term "procatalyst" is used interchangeably with terms such as "catalyst," "pre-catalyst," "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," "metal-ligand complex," and the like.

[0021] "Cocatalyst" refers to a compound capable of activating a particular procatalyst to form an active catalyst capable of polymerizing unsaturated monomers. The term "cocatalyst" is used interchangeably with "activator" and similar terms.

[0022] "Polymer" refers to a compound prepared by polymerizing monomers, whether of the same or different types. Thus, the generic term "polymer" encompasses the term "homopolymer," which refers to a polymer prepared from only one type of monomer, and the terms "interpolymer" or "copolymer," as defined herein. Trace amounts of impurities, such as catalyst residues, may be incorporated in and / or within the polymer.

[0023] "Interpolymer" or "copolymer" refers to a polymer prepared by polymerizing at least two different types of monomers. These generic terms include both polymers prepared from two different types of monomers and polymers prepared from more than two different types of monomers (e.g., terpolymers, tetrapolymers, etc.). These generic terms encompass all forms of interpolymers or copolymers, such as random, block, uniform, heterogeneous, etc.

[0024] An "ethylene-based polymer" or "ethylene polymer" is a polymer that contains a majority (greater than 50 wt%) of polymerized ethylene based on the weight of the polymer, and may optionally further contain polymerized units of at least one comonomer. An "ethylene-based interpolymer" is an interpolymer that contains a majority (greater than 50 wt%) of ethylene in polymerized form based on the weight of the interpolymer, and further contains polymerized units of at least one comonomer. Preferably, the ethylene-based interpolymer is a random interpolymer (i.e., contains its monomeric constituents randomly distributed). An "ethylene homopolymer" is a polymer that contains repeat units derived from ethylene but does not exclude residual amounts of other components.

[0025] A "propylene-based polymer" or "propylene polymer" is a polymer that contains a majority (greater than 50 wt%) of polymerized propylene based on the weight of the polymer, and may optionally further contain polymerized units of at least one comonomer. A "propylene-based interpolymer" is an interpolymer that contains a majority (greater than 50 wt%) of propylene in polymerized form based on the weight of the interpolymer, and further contains polymerized units of at least one comonomer. Preferably, the propylene-based interpolymer is a random interpolymer (i.e., contains its monomeric constituents randomly distributed). A "propylene homopolymer" is a polymer that contains repeat units derived from propylene but does not exclude residual amounts of other components.

[0026] An "ethylene / α-olefin interpolymer" is an interpolymer that contains a majority (greater than 50 wt%) of polymerized ethylene based on the weight of the interpolymer and further contains polymerized units of at least one α-olefin. Preferably, the ethylene / α-olefin interpolymer is a random interpolymer (i.e., contains its monomeric constituents randomly distributed). An "ethylene / α-olefin copolymer" is a copolymer that contains a majority (greater than 50 wt%) of polymerized ethylene based on the weight of the copolymer and further contains polymerized units of an α-olefin. Preferably, the ethylene / α-olefin copolymer is a random copolymer (i.e., contains its monomeric constituents randomly distributed).

[0027] A "propylene / α-olefin interpolymer" is an interpolymer that contains a majority (greater than 50 wt%) of polymerized propylene based on the weight of the interpolymer and further contains polymerized units of at least one α-olefin. Preferably, the propylene / α-olefin interpolymer is a random interpolymer (i.e., contains its monomeric constituents randomly distributed). A "propylene / α-olefin copolymer" is an interpolymer that contains a majority (greater than 50 wt%) of polymerized propylene based on the weight of the copolymer and further contains polymerized units of an α-olefin. Preferably, the propylene / α-olefin copolymer is a random copolymer (i.e., contains its monomeric constituents randomly distributed).

[0028] A "polyolefin" is a polymer made from olefin monomers, which are also called alkenes, linear, branched, or cyclic compounds of carbon and hydrogen with at least one double bond.

[0029] As used herein, the terms "chain transfer agent component" and "chain transfer agent" refer to a compound or mixture of compounds capable of undergoing reversible or irreversible polymer exchange with active catalyst sites. Irreversible chain transfer refers to the transfer of a growing polymer chain from an active catalyst to a chain transfer agent, resulting in the 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.

[0030] The term "olefin block copolymer" or "OBC" refers to an ethylene / α-olefin multiblock interpolymer, which comprises, in polymerized form, ethylene and one or more copolymerizable α-olefin comonomers characterized by multiple blocks or segments of two or more (preferably three or more) polymerized monomer units with different chemical or physical properties. Specifically, the term "olefin block copolymer" refers to a polymer that comprises two or more (preferably three or more) chemically distinct regions or segments (called "blocks") joined in a linear fashion, i.e., chemically distinct units that are joined end-to-end (covalently bonded) with respect to polymerized functional groups, rather than in a pendant or grafted manner. The blocks differ in the amount or type of comonomer incorporated therein, density, amount of crystallinity, type of crystallinity (e.g., polyethylene vs. polypropylene), crystallite size resulting from a polymer of such composition, type or degree of stereoregularity (isotactic or syndiotactic), regioregularity or regioirregularity, amount of branching, including long chain branching or hyperbranching, uniformity, and / or any other chemical or physical property. The block copolymers are characterized by unique distributions in both polymer molecular weight distribution (PDI or Mw / Mn) and block length distribution, for example, based on the effect of using a shuttling agent in combination with the catalyst system.Non-limiting examples of the olefin block copolymers of the present disclosure, as well as methods for preparing them, are disclosed in U.S. Patent Nos. 7,858,706 B2, 8,198,374 B2, 8,318,864 B2, 8,609,779 B2, 8,710,143 B2, 8,785,551 B2, and 9,243,090 B2, all of which are incorporated herein by reference in their entirety.

[0031] The term "block composite" ("BC") refers to a polymer comprising three polymer components: (i) an ethylene-based polymer (EP) (soft copolymer) having an ethylene content of 10 mol% to 90 mol% based on the total number of moles of polymerized monomer units in the ethylene-based polymer (EP); (ii) an α-olefin-based polymer (AOP) (hard copolymer) having an α-olefin content of more than 90 mol% based on the total number of moles of polymerized monomer units in the α-olefin-based polymer (AOP); and (iii) a block copolymer (diblock copolymer) having an ethylene block (EB) and an α-olefin block (AOB), wherein the ethylene block of the block copolymer has the same composition as the EP of component (i) of the block composite, and the α-olefin block of the block copolymer has the same composition as the AOP of component (ii) of the block composite. Moreover, in the block composite, the compositional division between the amount of EP and the amount of AOP will be essentially the same as the compositional division between the corresponding blocks in the block copolymer. Non-limiting examples of block conjugates of the present disclosure, as well as methods for preparing them, are disclosed in US Pat. Nos. 8,686,087 and 8,716,400, which are incorporated by reference herein in their entireties.

[0032] The term "specific block composite" ("SBC") refers to a polymer comprising three polymer components: (i) an ethylene-based polymer (EP) (soft copolymer) having an ethylene content of 78 mol% to 90 mol% based on the total number of moles of polymerized monomer units in the ethylene-based polymer (EP); (ii) an α-olefin-based polymer (AOP) (hard copolymer) having an α-olefin content of 61 mol% to 90 mol% based on the total number of moles of polymerized monomer units in the α-olefin-based polymer (AOP); and (iii) a block copolymer (diblock copolymer) having an ethylene block (EB) and an α-olefin block (AOB), wherein the ethylene block of the block copolymer has the same composition as the EP of component (i) of the specific block composite, and the α-olefin block of the block copolymer has the same composition as the AOP of component (ii) of the specific block composite. Moreover, in the specific block composite, the compositional division between the amount of EP and the amount of AOP will be essentially the same as the compositional division between the corresponding blocks in the block copolymer. Non-limiting examples of certain block conjugates of the present disclosure, as well as methods for preparing them, are disclosed in WO2017 / 044547, which is incorporated herein by reference in its entirety.

[0033] The term "crystalline block composite" ("CBC") refers to a polymer comprising three components: (i) a crystalline ethylene-based polymer (CEP) having an ethylene content of greater than 90 mol% based on the total number of moles of polymerized monomer units in the crystalline ethylene-based polymer (CEP); (ii) a crystalline α-olefin-based copolymer (CAOP) having an α-olefin content of greater than 90 mol% based on the total number of moles of polymerized monomer units in the crystalline α-olefin-based copolymer (CAOP); and (iii) a block copolymer comprising a crystalline ethylene block (CEB) and a crystalline α-olefin block (CAOB), wherein the CEB of the block copolymer is of the same composition as the CEP of component (i) of the crystalline block composite, and the CAOB of the block copolymer is of the same composition as the CAOP of component (ii) of the crystalline block composite. Furthermore, in the crystalline block composite, the compositional division between the amount of CEP and the amount of CAOP will be essentially the same as the compositional division between the corresponding blocks in the block copolymer. Non-limiting examples of crystalline block composites of the present disclosure, as well as methods for preparing them, are disclosed in U.S. Pat. No. 8,822,598 B2 and WO 2016 / 01028961 A1, which are incorporated by reference in their entireties.

[0034] The term "crystalline" refers to a polymer that has a first order transition or crystalline melting point (Tm) as determined by differential scanning calorimetry (DSC) or equivalent technique. This term may be used interchangeably with the term "semicrystalline." The term "amorphous" refers to a polymer that lacks a crystalline melting point as determined by differential scanning calorimetry (DSC) or equivalent technique.

[0035] Telechelic Polyolefin The present disclosure relates to a compound of formula A 1 L 1 L 2 A 2 The present invention relates to telechelic polyolefins of the present invention, as well as compositions containing such telechelic polyolefins.

[0036] Specifically, the present disclosure provides a telechelic polyolefin of formula (I) or a composition comprising a telechelic polyolefin of formula (I), A 1 L 1 L 2 A 2 (I), in the formula L 1 is a polyolefin, A 1 is a vinyl group, formula CH2=C(Y 1 )-vinylidene group of the formula Y 1 Vinylene group of CH=CH-, vinyl group and formula Y 1 A mixture of vinyl groups and vinylene groups of 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 of the formula CH=CH- and vinyl groups of the formula CH2=C(Y 1 )- and a vinylidene group of the formula Y 1 and a mixture of CH=CH- and vinylene groups; Y 1 Each time it appears, it is assigned independently to C1~C 30 is a hydrocarbyl group, L 2 But, C1~C 32 is a hydrocarbylene group, and A 2 is a hydrocarbyl group containing a hindered double bond, and The present invention relates to a telechelic polyolefin of formula (I) or a composition comprising a telechelic polyolefin of formula (I), wherein the telechelic polyolefin of formula (I) comprises a weight average molecular weight of 1,000 to 10,000,000 g / mol.

[0037] In certain embodiments, L 2 is -CH2CH(Y 2 )-, and therefore the telechelic polyolefin of formula (I) is 1 L 1 CH2CH(Y 2 )A 2 where Y 2is hydrogen or C1-C 30 In certain embodiments, Y is a hydrocarbyl group. 2 In a further embodiment, Y 2 The group is C1-C 10 In a further embodiment, Y is an alkyl group, or a C1-C6 alkyl group, or a C1-C3 alkyl group. 2 The group is an ethyl group.

[0038] Those skilled in the art will recognize that Formula A 1 L 1 L 2 A 2 Regarding A 1 is connected to L via a carbon-carbon single bond. 1 is covalently bonded to L 1 is connected to L via a carbon-carbon single bond. 2 is covalently bonded to L 2 is connected to A via a carbon-carbon single bond. 2 It will be understood that the compound of formula A is covalently bonded to the 1 L 1 L 2 A 2 L 1 If it is stated that is a polyolefin, L 1 is connected to A via a carbon-carbon single bond. 1 and L 2 It is understood that the divalent polyolefin radical (polyolefin lacking two hydrogens) is covalently bonded to each of the groups of formula A. 1 L 1 L 2 A 2 L 1 If it is stated that is a polymer, L 1 is connected to A via a carbon-carbon single bond. 1 and L 2 It is understood that the divalent polymer radical (a polymer lacking two hydrogens) is covalently bonded to each of the groups. For example, L 1 is stated to be an ethylene homopolymer, L 1 is connected to A via a carbon-carbon single bond. 1 and L 2It is understood that the divalent ethylene homopolymer group (ethylene homopolymer lacking two hydrogens) is covalently bonded to each of the groups. 1 is stated to be an ethylene / α-olefin copolymer, L 1 is connected to A via a carbon-carbon single bond. 1 and L 2 It is understood that each of the groups has a divalent ethylene / α-olefin copolymer group (an ethylene / α-olefin copolymer lacking two hydrogens) covalently bonded thereto.

[0039] In some embodiments, L of formula (I) 1are polyolefins resulting from the coordination polymerization of unsaturated monomers (and comonomers). Examples of suitable monomers (and comonomers) include ethylene and α-olefins of 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,5,5-trimethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 5-ethyl-1-nonene, 1-octadecene and 1-eicosene; conjugated or non-conjugated. Dienes such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene and 5,9-dimethyl norbornene and alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 5-methylene-2-norbornene, 5-propenyl-2-norbornene, 5-methyl-1,4,8-decatriene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyrcene and dihydroocimene; norbornene and alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 5-methylene-2-norbornene, 5-propenyl-2-norbornene, 5 -isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene and norbornadiene; and aromatic vinyl compounds such as, but not limited to, styrene, mono- or polyalkylstyrenes (including styrene, o-methylstyrene, t-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene).

[0040] L1 L can be linear (unbranched), branched, or cyclic. 1 The presence or absence of branching and the degree of branching (if branching is present) in L can vary widely and depend on the desired processing conditions and the desired polymer properties. 1 When present in, the branches may be short chain branches or long chain branches. 1 Exemplary types of long chain branches that may be present in include, but are not limited to, T-type branches and H-type branches. Thus, in some embodiments, L 1 may contain long chain branches. In other words, in some embodiments, L 1 may contain one or more long chain branches, each long chain branch being A as defined herein for formula (I). 2 The group optionally includes

[0041] In some embodiments, A of formula (I) 1 The group is L 1 is based on the coordination polymerization of a monomer and a comonomer to form a monomer or comonomer that is inserted last. Therefore, L 1 The selection of monomers and comonomers for the coordination polymerization of 1 Group and Y 1 In some embodiments, A 1 In some embodiments, the A group is a vinyl group. 1 The group has the formula CH2=C(Y 1 )-vinylidene group, 1 is C1~C 30 In some embodiments, A is a hydrocarbyl group. 1 The group has the formula Y 1 is a vinylene group of the formula CH=CH-, 1 is C1~C 30 In some embodiments, A is a hydrocarbyl group. 1 The group is a vinyl group and a group of formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 is C1~C 30In some embodiments, A is a hydrocarbyl group. 1 The group is a vinyl group and a cyclic alkyl group of the formula CH2=C(Y 1 )- and vinylidene groups, 1 is C1~C 30 In some embodiments, A is a hydrocarbyl group. 1 The group has the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 is C1~C 30 In some embodiments, A is a hydrocarbyl group. 1 The group is a vinyl group and a group of the formula CH2=C(Y 1 )- and a vinylidene group of the formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 is C1~C 30 It is a hydrocarbyl group.

[0042] In a further embodiment, A 1 The group is a vinyl group and a group of formula Y 1 A is a mixture of CH=CH- and vinylene groups, 1 is a vinyl group and a formula Y 1 The ratio of CH═CH— to vinylene groups, wherein Y 1 is C1~C 30 It is a hydrocarbyl group.

[0043] In a further embodiment, A 1 The group is a vinyl group and a cyclic alkyl group of the formula CH2=C(Y 1 )- and vinylidene groups, 1 is a 0.99:0.01 to 0.01:0.99 ratio of vinyl groups to the formula CH2=C(Y 1 )-vinylidene groups, wherein Y 1 is C1~C 30 It is a hydrocarbyl group.

[0044] In a further embodiment, A 1 The group has the formula CH2=C(Y 1)- and the vinylidene group of formula Y 1 A is a mixture of CH=CH- and vinylene groups, 1 is 0.99:0.01 to 0.01:0.99, the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 The ratio of CH═CH— to vinylene groups, wherein Y 1 is C1~C 30 It is a hydrocarbyl group.

[0045] In a further embodiment, A 1 The group is a vinyl group and a group of the formula CH2=C(Y 1 )- and a vinylidene group of the formula Y 1 A is a mixture of CH=CH- and vinylene groups, 1 is a 0.99:0.01 to 0.01:0.99 ratio of vinyl group to a compound represented by the formula Y 1 Vinylene group of the formula CH=CH-, CH2=C(Y 1 )- to the sum of vinylidene groups and vinyl groups, wherein Y 1 is C1~C 30 It is a hydrocarbyl group.

[0046] In certain embodiments, L 1 is a homopolymer comprising units derived from one monomer. The monomer may be selected from any of the suitable monomers listed above. In a further embodiment, L 1 is an ethylene homopolymer comprising units derived from ethylene. In a further embodiment, L 1 is a propylene homopolymer containing units derived from propylene.

[0047] In some embodiments, L 1 is an interpolymer that includes units derived from at least two different types of monomers, such as a monomer and a comonomer. Thus, in certain embodiments, L 1is an interpolymer comprising units derived from a monomer and at least one comonomer different from the monomer. Each of the monomer and the at least one comonomer different from the monomer may be selected from any of the suitable monomers described above.

[0048] In a further embodiment, L 1 is a copolymer that includes units derived from two different types of monomers, such as a monomer and a comonomer. Thus, in certain embodiments, L 1 is a copolymer comprising units derived from a monomer and a comonomer different from the monomer. The monomer and comonomer may each be selected from any of the suitable monomers described above.

[0049] In certain embodiments, L 1 is an ethylene / α-olefin copolymer. In some embodiments, L 1 Ethylene and C3-C 30 and an α-olefin, wherein the telechelic polyolefin of formula (I) comprises ethylene in an amount of 50% by weight or more, or 60% by weight or more, or 70% by weight or more, or 75% by weight or more, or 80% by weight or more, or 85% by weight or more, or 88% by weight or more, or 89% by weight or more, or 90% by weight or more, based on the total weight of the telechelic polyolefin of formula (I). 30 The α-olefin may be selected from any of the suitable α-olefins described above. In certain embodiments, C3-C 30 The α-olefin can be propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. In some embodiments, L 1 Ethylene and C3-C 30 An ethylene / α-olefin copolymer containing units derived from an α-olefin, 30The ethylene / α-olefin copolymer is an ethylene / α-olefin copolymer, where the α-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene.

[0050] In a further embodiment, L 1 is a propylene / α-olefin copolymer. 1 Propylene and ethylene or C4-C 30 and any of the α-olefins, wherein the telechelic polyolefin of formula (I) contains propylene in an amount of 50% by weight or more, or 60% by weight or more, or 70% by weight or more, or 75% by weight or more, or 80% by weight or more, or 85% by weight or more, or 88% by weight or more, or 89% by weight or more, or 90% by weight or more, based on the total weight of the telechelic polyolefin of formula (I). 30 The α-olefin may be any of the suitable α-olefins discussed above. In certain embodiments, 30 The α-olefin may be isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, and the like. 1 Propylene and ethylene or C4-C 30 Propylene / α-olefin copolymers containing units derived from any of the C4 to C6 α-olefins 30 The propylene / α-olefin copolymer may be one in which the α-olefin is selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

[0051] In certain embodiments, L 1 is a terpolymer comprising units derived from three different types of monomers, each of which may be selected from any of the suitable monomers discussed above. 1 is composed of ethylene or propylene as the first monomer and C3-C 30It is a terpolymer that includes an α-olefin or styrene and a diene or polar monomer as the third monomer.

[0052] In some embodiments, L 1 contains 0 to 10% by weight of units derived from diene monomers based on the total weight of the telechelic polyolefin of formula (I). For example, L 1 may contain 1 to 8 wt. %, or 1 to 5 wt. %, or 1 to 3 wt. %, of units derived from diene monomers, based on the total weight of the telechelic polyolefin of formula (I). 1 may be substantially free of units derived from diene monomers. For example, in certain embodiments, L 1 may contain from 0 to 0.2 wt. %, or from 0 to 0.01 wt. %, or from 0 to 0.001 wt. %, or from 0 to 0.0001 wt. %, based on the total weight of the telechelic polyolefin of formula (I), of units derived from diene monomers.

[0053] In certain embodiments, L 1 is an olefin block copolymer as defined herein. In a further embodiment, L 1 is a block complex, a specific block complex, or a crystalline block complex, as defined herein.

[0054] In some embodiments, A 2 is a hydrocarbyl group containing a hindered double bond. 2 is a hydrocarbyl group containing two or more hindered double bonds.

[0055] In certain embodiments, due to the hindered double bond, A 2 The group is polyolefin L 1 is not readily incorporated by active catalysts under the process conditions used to make L 1 A along the backbone chain of 2 Direct incorporation of the 13 C NMR or similar13 less than or equal to 0.5 mol %, or less than or equal to 0.1 mol %, or not detectable as determined by C NMR methods.

[0056] In some embodiments, A 2 is a hydrocarbyl group containing a hindered double bond, the hindered double bond being selected from the group consisting of a double bond of a vinylidene group, a double bond of a vinylene group, a double bond of a trisubstituted alkene, and a double bond of a vinyl group attached to a branched α-carbon.

[0057] In a further embodiment, A 2 is a hydrocarbyl group containing two or more hindered double bonds, each hindered double bond being independently selected from the group consisting of a double bond of a vinylidene group, a double bond of a vinylene group, a double bond of a trisubstituted alkene, and a double bond of a vinyl group attached to a branched α-carbon.

[0058] In certain embodiments, A 2 is a hydrocarbyl group containing a functional group selected from the group consisting of vinylidene groups, vinylene groups, trisubstituted alkenes, and vinyl groups attached to a branched α-carbon.

[0059] In a further embodiment, A 2 is a hydrocarbyl group containing two or more functional groups, each functional group being independently selected from the group consisting of vinylidene groups, vinylene groups, trisubstituted alkenes, and vinyl groups attached to a branched α-carbon.

[0060] A 2 The group may be a cyclic or acyclic (linear or branched) hydrocarbyl group. 2 When A is a cyclic hydrocarbyl group, 2 may contain one or more rings, each of which may be a monocyclic, bicyclic, or polycyclic ring, and each of which may contain one or more hindered double bonds.

[0061] Furthermore, A 2 When A is a cyclic hydrocarbyl group, each hindered double bond or functional group therein can be an endocyclic double bond, an exocyclic double bond, or an acyclic double bond. For example, A 2 may be a cyclic hydrocarbyl group, including a vinylene group, where the double bond of the vinylene group may be an endocyclic double bond or an acyclic double bond. 2 may be a cyclic hydrocarbyl group comprising a vinylidene group, the double bond of which may be an exocyclic double bond or an acyclic double bond. 2 may be a cyclic hydrocarbyl group comprising a trisubstituted alkene, where the double bond of the trisubstituted alkene may be an endocyclic double bond, an exocyclic double bond, or an acyclic double bond. 2 may be a cyclic hydrocarbyl group comprising a vinyl group attached to a branched α-carbon, where the vinyl group attached to the branched α-carbon is an acyclic double bond.

[0062] In any of the embodiments described herein, A 2 may contain 3 to 30 carbon atoms, or 3 to 25 carbon atoms, or 3 to 20 carbon atoms, or 3 to 15 carbon atoms, or 3 to 10 carbon atoms, or 3 to 9 carbon atoms, or 3 to 8 carbon atoms, or 3 to 7 carbon atoms, or 3 to 6 carbon atoms, or 3 to 5 carbon atoms, or 3 to 4 carbon atoms, or 3 carbon atoms.

[0063] In certain embodiments, A 2 is a C3-C alkyl group containing alkyl substituted or unsubstituted cycloalkenes. 30 In a further embodiment, A is a cyclic hydrocarbyl group. 2is an alkyl substituted or unsubstituted cycloalkene containing 3 to 30 carbon atoms, or 3 to 25 carbon atoms, or 3 to 20 carbon atoms, or 3 to 15 carbon atoms, or 3 to 10 carbon atoms, or 3 to 9 carbon atoms, or 3 to 8 carbon atoms, or 3 to 7 carbon atoms, or 3 to 6 carbon atoms.

[0064] Exemplary unsubstituted cycloalkenes include, but are not limited to, cyclohexene, cycloheptene, cyclooctene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, and 1,5-cyclooctadiene. Exemplary alkyl-substituted cycloalkenes include, but are not limited to, alkyl-substituted cyclohexene, alkyl-substituted cycloheptene, alkyl-substituted cyclooctene, alkyl-substituted 1,3-cyclohexadiene, alkyl-substituted 1,4-cyclohexadiene, and alkyl-substituted 1,5-cyclooctadiene.

[0065] In some embodiments, A 2 is a methyl-substituted or unsubstituted cycloalkene selected from the group consisting of methyl-substituted or unsubstituted cyclohexene, methyl-substituted or unsubstituted cycloheptene, and methyl-substituted or unsubstituted cyclooctene. In some embodiments, A 2 is a methyl substituted or unsubstituted cyclohexene.

[0066] In some embodiments, A 2 is C1~C 10 Acyclic alkyl groups or C3-C 10 It is an acyclic alkyl group, or a C4 to C8 acyclic alkyl group.

[0067] Exemplary telechelic polyolefins of formula (I) 2 Groups include, but are not limited to, the following: [ka] [ka]

[0068] For each of (AA)~(AZ) and (AZ1),

number

number

[0069] For each of (AA) through (AF), the endocyclic double bond may be between any two adjacent carbon atoms that are ring members.

[0070] For each of (AD) through (AF), the pendant methyl group may be attached to any carbon atom that is a ring member.

[0071] For each of (AG)-(AL), the exocyclic double bond may be attached to any ring carbon atom that is not already attached to more than two carbon atoms.

[0072] In some embodiments, the telechelic polyolefin of Formula (I) comprises or has a weight average molecular weight (Mw) of 1,000 to 10,000,000 g / mol, or 1,000 to 5,000,000 g / mol, or 1,000 to 1,000,000 g / mol, or 1,000 to 750,000 g / mol, or 1,000 to 500,000 g / mol, or 1,000 to 250,000 g / mol according to a GPC method described herein or a similar GPC method.

[0073] In some embodiments, the telechelic polyolefin of Formula (I) comprises or has a number average molecular weight (Mn) of 1,000 to 10,000,000 g / mol, or 1,000 to 5,000,000 g / mol, or 1,000 to 1,000,000 g / mol, or 1,000 to 750,000 g / mol, or 1,000 to 500,000 g / mol, or 1,000 to 250,000 g / mol, according to a GPC method described herein or a similar GPC method.

[0074] In some embodiments, the telechelic polyolefin of formula (I) comprises or has an average molar mass (Mz) of from 1,000 to 10,000,000 g / mol, or from 1,000 to 5,000,000 g / mol, or from 1,000 to 1,000,000 g / mol, or from 1,000 to 750,000 g / mol, or from 1,000 to 500,000 g / mol, or from 5,000 to 500,000 g / mol, or from 10,000 to 500,000 g / mol, according to a GPC method described herein or a similar GPC method.

[0075] In some embodiments, the telechelic polyolefin of formula (I) comprises or has a Mw / Mn (PDI) of 1 to 10, or 1 to 7, or 1 to 5, or 1.5 to 4, or 2 to 4, according to the GPC method described herein or a similar GPC method.

[0076] In some embodiments, the telechelic polyolefin of Formula (I) comprises or has a density according to ASTM D-792, Method B, of 0.850 to 0.965 g / cc, or 0.854 to 0.950 g / cc, or 0.854 to 0.935 g / cc, or 0.854 to 0.925 g / cc, or 0.854 to 0.910 g / cc, or 0.854 to 0.900 g / cc, or 0.854 to 0.885 g / cc, or 0.854 to 0.880 g / cc, or 0.854 to 0.875 g / cc.

[0077] In some embodiments, the telechelic polyolefin of Formula (I) comprises or has a melt index (I2) according to ASTM D-1238, condition 190° C. / 2.16 kg, from 0.01 to 2000 g / 10 min, or from 0.01 to 1,500 g / 10 min, or from 0.01 to 1,000 g / 10 min, or from 0.01 to 500 g / 10 min, or from 0.01 to 100 g / 10 min, or from 0.5 to 50 g / 10 min, or from 0.5 to 30 g / 10 min.

[0078] In some embodiments, the telechelic polyolefin of formula (I) has a T ranging from -25°C to 165°C, or 25°C to 150°C, or -25°C to 125°C, or -25°C to 100°C, or 0°C to 80°C, or 10°C to 60°C according to the DSC method described herein or a similar DSC method. m Contains or has this.

[0079] In some embodiments, the telechelic polyolefin of formula (I) has a molecular weight of 10 to 10 8 cP, or 10-10 7 cP, or 10-10 6 cP, or 10 to 750,000 cP, or 10 to 500,000 cP, or 10 to 250,000 cP, or 10 to 100,000 cP, or 10 to 75,000 cP, or 10 to 50,000 cP, or 10 to 40,000 cP.

[0080] In some embodiments, the telechelic polyolefin of formula (I) comprises or has an enthalpy of fusion (ΔHm) of 0 to 235 J / g, or 0 to 200 J / g, or 10 to 175 J / g, or 10 to 150 J / g, or 10 to 125 J / g, or 20 to 117 J / g, according to a DSC method described herein or a similar DSC method.

[0081] In some embodiments, the telechelic polyolefin of Formula (I) comprises or has a weight percent crystallinity of 0-80%, or 0-60%, or 5-50%, or 7-40%, based on a PEΔHm of 292 J / g, according to the DSC method described herein or a similar DSC method.

[0082] In some embodiments, the telechelic polyolefin of formula (I) has a T of −80 to 100° C., or −80 to 75° C., or −80 to 50° C., or −80 to 25° C., or −80 to 0° C., or −80 to −15° C., or −70 to −30° C. according to a DSC method described herein or a similar DSC method. g Contains or has this.

[0083] In some embodiments, L 1 is substantially free of units derived from diene monomers, and the telechelic polyolefin of formula (I) comprises a total degree of unsaturation of 1.1 or more, or 1.2 or more, or 1.3 or more, or 1.4 or more, or 1.5 or more, or 1.6 or more, or 1.7 or more, or 1.8 or more, or 1.9 or more. The total degree of unsaturation is (degree of unsaturation / 1000C) * (1000C / chain)=(unsaturation degree / 1000C) * (Mn / M CH2 / 1000), where Unsaturation / 1000C is 1 H NMR, Mn is the number average molecular weight measured by GPC, 13 The composition is corrected for that measured by C NMR. CH2= 14 g / mol. As reported, Mn measured by GPC is the number average molecular weight of the polymer backbone. Unsaturation / 1000C measured by 1H NMR is based on the total number of carbons in the polymer chain. For ethylene, propylene, octene, and ethylidene norbornene, there are 2, 3, 8, and 9 total carbon atoms per 2 backbone carbon atoms, respectively. Thus, Mn corrected for composition is Mn measured by GPC time (mol% C2 / 2+mol% C3 / 3+mol% C8 / 8+mol% ENB / 9) / 2, where: 13 C NMR, 1 H NMR, and GPC refer to methods described herein or similar methods. As used herein, "substantially free" refers to L containing, for example, 0 to 0.001 wt. % of units derived from diene monomers, based on the total weight of the telechelic polyolefin of formula (I).

[0084] In some embodiments, L 1 comprises 1 to 8 wt. %, or 1 to 5 wt. %, or 1 to 3 wt. %, based on the total weight of the telechelic polyolefin of formula (I), of units derived from diene monomers, and the telechelic polyolefin of formula (I) is D +1.1) or more, (X D +1.2) or more, (X D +1.3) or more, (X D +1.4) or more, (X D +1.5) or more, (X D +1.6) or more, (X D +1.7), (X D +1.8) or more, or (X D +1.9) or more of total unsaturation, D , L 1 is the number of degrees of unsaturation from units derived from diene monomers in the copolymer, the degree of unsaturation being measured as described in the previous paragraph.

[0085] In certain embodiments, the telechelic polyolefins of formula (I) contain unsaturation at the ends of the polymer chains, rather than randomly distributed along the polymer backbone (as in EPDM or polybutadiene).

[0086] The telechelic polyolefin of formula (I) can be any embodiment or any combination of the embodiments described above.

[0087] Process for preparing telechelic polyolefins The present disclosure further provides a method for preparing a telechelic polyolefin or a composition comprising a telechelic polyolefin, the method comprising: 1) combining starting materials including (A) a monomer component, (B) a chain transfer agent component, and (C) a catalyst component including a procatalyst to form a solution, and polymerizing from greater than 10 mol% to less than or equal to 99 mol% of the (A) monomer component in the solution; 2) heating the solution to a temperature of at least 160° C. and holding the solution at a temperature of at least 160° C. for a time of at least 30 seconds; 3) recovering a product comprising the telechelic polyolefin or a composition comprising the telechelic polyolefin; (B) the chain transfer agent component is a compound represented by the formula Al(CHCH(Y 2 )A 2 ) 3 organoaluminum compounds, Y 2 Each occurrence is independently hydrogen or C1-C 30 is a hydrocarbyl group, and A 2 is, independently at each occurrence, a hydrocarbyl group that contains a hindered double bond.

[0088] The present disclosure further provides a method for preparing a telechelic polyolefin of formula (I) or a composition comprising a telechelic polyolefin of formula (I), comprising the steps of: A 1 L 1 L 2 A 2 (I) The method, 1) combining starting materials including (A) a monomer component, (B) a chain transfer agent component, and (C) a catalyst component including a procatalyst to form a solution, and polymerizing from greater than 10 mol% to less than or equal to 99 mol% of the (A) monomer component in the solution; 2) heating the solution to a temperature of at least 160° C. and holding the solution at a temperature of at least 160° C. for a time of at least 30 seconds; 3) recovering a product comprising the telechelic polyolefin of formula (I) or a composition comprising the telechelic polyolefin of formula (I), (B) the chain transfer agent component is a compound represented by the formula Al(CHCH(Y 2 )A 2 ) 3 organoaluminum compounds, L 1 is a polyolefin, L 2 But, C1~C 32 is a hydrocarbylene group, A 1 is a vinyl group, formula CH2=C(Y 1 )-vinylidene group of the formula Y 1 Vinylene group of CH=CH-, vinyl group and formula Y 1 A mixture of vinyl groups and vinylene groups of 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 of the formula CH=CH- and vinyl groups of the formula CH2=C(Y 1 )- and a vinylidene group of the formula Y 1 and a mixture of CH=CH- and vinylene groups; Y 1 Each time it appears, it is assigned independently to C1~C 30 is a hydrocarbyl group, Y 2 Each occurrence is independently hydrogen or C1-C 30 is a hydrocarbyl group, and A 2 is, independently at each occurrence, a hydrocarbyl group that contains a hindered double bond; and The telechelic polyolefin of formula (I) comprises a weight average molecular weight of 1,000 to 10,000,000 g / mol.

[0089] L in formula (I) 1 , A 1 , Y 1 , L 2 , Y 2 , and A 2 The embodiments described above for each of the groups apply with respect to the method disclosed herein.Similarly, the embodiments described above for the telechelic polyolefin of formula (I) apply with respect to the method disclosed herein.

[0090] The starting material of step 1) may further include a (D) solvent. The starting material (D) solvent may be any aromatic or aliphatic hydrocarbon. Suitable solvents include, but are not limited to, toluene, xylene, hexane, pentane, benzene, heptane, Isopar™, and combinations thereof. In addition, the starting material of step 1) may further include hydrogen, an adjuvant, a scavenger, and / or a polymerization aid.

[0091] Step 1) is a coordination polymerization step to form the backbone chain of the telechelic polyolefin of formula (I) from the monomers and comonomers of the (A) monomer component. During step 1), polymeric aluminum species may form via chain transfer between the (B) chain transfer agent component and the active catalyst from the (C) catalyst component. The polymeric aluminum species subsequently undergoes β-hydride elimination during step 2) to form a product comprising the telechelic polyolefin of formula (I), which is recovered during step 3).

[0092] Step 1) of the process for preparing a composition comprising telechelic polyolefins of the present disclosure is preferably carried out as a solution polymerization step. Most preferably, step 1) is carried out as a continuous solution polymerization step in which starting materials are continuously fed to a reaction zone and polymer product is continuously removed therefrom. As used in this context, within the scope of the terms "continuous" and "continuously" are processes in which there is intermittent addition of reactants and removal of products at regular or irregular intervals such that the overall process is substantially continuous over time.

[0093] Step 1) may be carried out at a temperature of 60° C., or 80° C., or 100° C., or 110° C., or 115° C. to 120° C., or 130° C., or 140° C., or 150° C. For example, in certain embodiments, step 1) may be carried out at a temperature of 60 to 150° C., or 80 to 140° C., or 100 to 130° C., or 110 to 120° C.

[0094] Those skilled in the art will appreciate that the amount of each component of the starting materials, including components (A) through (D), can be varied to produce polymers having one or more different chemical or physical properties.

[0095] Without limiting the scope of the invention in any way, one means for carrying out step 1) is as follows: In a stirred tank reactor, the monomers of the (A) monomer component are continuously introduced together with an optional solvent or diluent. The reactor contains a liquid phase consisting essentially of the monomers together with any solvent or diluent and dissolved polymer. Preferred solvents include C 4~10The solvents may be a hydrocarbon or mixture thereof, particularly an alkane or mixture of alkanes such as hexane, and one or more of the monomers used in the polymerization. (B) Chain transfer agent component and (C) catalyst component are continuously or intermittently introduced into the liquid phase of the reactor or any recycled portion thereof. The temperature and pressure of the reactor may be controlled by adjusting the solvent / monomer ratio, the rate of addition of the (C) catalyst component, and by cooling or heating coils, jackets, or both. The polymerization rate is controlled by the rate of addition of the (C) catalyst component. When the (A) monomer component includes ethylene and at least one comonomer, the ethylene content of the polymer product is determined by the ratio of ethylene to comonomer in the reactor, which ratio is controlled by manipulating the respective feed rates of these components to the reactor. The molecular weight of the polymer product is optionally controlled by controlling other polymerization variables such as temperature, monomer concentration, or others known in the art. In a continuous process, the average residence time of the active catalyst and polymer in the reactor is generally from 5 minutes to 8 hours, preferably from 10 minutes to 6 hours.

[0096] Alternatively, step 1) may be carried out under different process conditions in two or more reactors connected in series operating under steady-state polymerization conditions or in two or more sections of a reactor operating under plug-flow polymerization conditions. Alternatively, step 1) may be carried out in one or more continuous loop reactors, optionally with separate addition of catalyst and / or chain transfer agent, and operating under adiabatic or non-adiabatic solution polymerization conditions or a combination of the aforementioned reactor conditions, with or without monomer, catalyst or chain transfer agent gradients established between the different zones thereof.

[0097] After step 1), the polymer solution is heated according to step 2), as further described below. Such heating includes, but is not limited to, heating in a post-reactor heater. After step 2), the polymer product is recovered in step 3) by means known in the art. Such means include contacting the polymer solution with a catalyst killing agent such as water, steam, or alcohol, flashing off gaseous monomer and residual solvent or diluent under reduced pressure, and, if necessary, performing further devolatilization in an apparatus such as a devolatilizing extruder.

[0098] In some embodiments, the solution in step 2) is heated to a temperature of at least 160°C, or at least 180°C, or at least 200°C, or at least 210°C, or at least 220°C, or at least 230°C, or at least 240°C, or at least 250°C, or at least 260°C, or at least 270°C, or at least 280°C, or at least 290°C, or at least 300°C.

[0099] In some embodiments, the solution of step 2) is heated to a temperature of at least 160° C., or at least 180° C., or at least 200° C., or at least 210° C., or at least 220° C., or at least 230° C., or at least 240° C., or at least 250° C., or at least 260° C., or at least 270° C., or at least 280° C., or at least 290° C., or at least 300° C., for a time of at least 30 seconds, or at least 1 minute, or at least 5 minutes, or at least 10 minutes, or at least 15 minutes, or at least 20 minutes, or at least 30 minutes, or at least 45 minutes, or at least 1 hour, or at least 6 hours, or at least 12 hours, or at least 18 hours, or at least 24 hours.

[0100] In some embodiments, the solution of step 2) is heated to a temperature of at least 160° C., or at least 180° C., or at least 200° C., or at least 210° C., or at least 220° C., or at least 230° C., or at least 240° C., or at least 250° C., or at least 260° C., or at least 270° C., or at least 280° C., or at least 290° C., or at least 300° C., Heating at a temperature of 230°C, or at least 240°C, or at least 250°C, or at least 260°C, or at least 270°C, or at least 280°C, or at least 290°C, or at least 300°C for a time of at least 30 seconds, or at least 1 minute, or at least 5 minutes, or at least 10 minutes, or at least 15 minutes, or at least 20 minutes, or at least 30 minutes, or at least 45 minutes, or at least 1 hour, or at least 6 hours, or at least 12 hours, or at least 18 hours, or at least 24 hours.

[0101] For example, in certain embodiments, the solution in step 2) is heated to a temperature of 160-300°C, or 180-300°C, or 200-300°C, or 210-300°C, or 220-290°C, or 230-290°C, or 240-280°C.

[0102] In further embodiments, the solution of step 2) is heated at a temperature of 160-300°C, or 180-300°C, or 200-300°C, or 210-300°C, or 220-290°C, or 230-290°C, or 240-280°C, for a time of 30 seconds to 24 hours, or 30 seconds to 18 hours, or 30 seconds to 12 hours, or 30 seconds to 6 hours, or 30 seconds to 1 hour, or 30 seconds to 45 minutes, or 30 seconds to 30 minutes, or 30 seconds to 20 minutes, or 1 minute to 20 minutes, or 5 minutes to 20 minutes.

[0103] In a further embodiment, the solution of step 2) is heated to a temperature of 160-300°C, or 180-300°C, or 200-300°C, or 210-300°C, or 220-290°C, or 230-290°C, or 240-280°C, and heated at a temperature of 160-300°C, or 180-300°C, or 200-300°C, or 210-300°C, or 220-290°C, or 230-290°C, or 240-280°C for a time of 30 seconds to 24 hours, or 30 seconds to 18 hours, or 30 seconds to 12 hours, or 30 seconds to 6 hours, or 30 seconds to 1 hour, or 30 seconds to 45 minutes, or 30 seconds to 30 minutes, or 30 seconds to 20 minutes, or 1 minute to 20 minutes, or 5 minutes to 20 minutes.

[0104] (A) Monomer component (A) The monomer component is L 1Examples of suitable monomers and comonomers include any monomer selected from the monomers and comonomers discussed herein with respect to. Examples of suitable monomers and comonomers include ethylene and α-olefins of 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,5,5-trimethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 5-ethyl-1-nonene, 1-octadecene, and 1-eicosene; conjugated or non-conjugated. Dienes, such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene and 5,9-dimethylene. ethyl-1,4,8-decatriene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene and mixed isomers of dihydromyrcene and dihydroocimene; norbornene and alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 5-methylene-2-norbornene, 5-propenyl-2-norbornene , 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene, and norbornadiene; aromatic vinyl compounds, such as, but not limited to, styrene, mono- or polyalkylstyrenes, including styrene, o-methylstyrene, t-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene.

[0105] In some embodiments, the (A) monomer component includes an ethylene monomer. In some embodiments, the (A) monomer component includes a propylene monomer. In some embodiments, the (A) monomer component includes an ethylene monomer and a C3-C30 α-olefin comonomer. The C3-C30 α-olefin may be selected from propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,5,5-trimethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 5-ethyl-1-nonene, 1-octadecene, and 1-eicosene. In some embodiments, the (A) monomer component includes a propylene monomer and an ethylene or C4-C30 α-olefin comonomer. The C4 to C30 α-olefin may be selected from 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,5,5-trimethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 5-ethyl-1-nonene, 1-octadecene, and 1-eicosene.

[0106] In certain embodiments, the (A) monomer component comprises an ethylene monomer and a C3-C30 α-olefin comonomer, the C3-C30 α-olefin being selected from the group consisting of propylene, 1-hexene, 1-butene, and 1-octene. In further embodiments, the (A) monomer component comprises an ethylene monomer and a propylene comonomer. In further embodiments, the (A) monomer component comprises an ethylene monomer and a 1-hexene comonomer. In further embodiments, the (A) monomer component comprises an ethylene monomer and a 1-butene comonomer. In further embodiments, the (A) monomer component comprises an ethylene monomer and a 1-octene comonomer.

[0107] In a further embodiment, the (A) monomer component comprises a propylene monomer and an ethylene or C4-C30 α-olefin comonomer, the C4-C30 α-olefin being selected from the group consisting of 1-hexene, 1-butene, and 1-octene. In a further embodiment, the (A) monomer component comprises a propylene monomer and an ethylene comonomer. In a further embodiment, the (A) monomer component comprises a propylene monomer and a 1-hexene comonomer. In a further embodiment, the (A) monomer component comprises a propylene monomer and a 1-butene comonomer. In a further embodiment, the (A) monomer component comprises a propylene monomer and a 1-octene comonomer.

[0108] In a specific embodiment, the (A) monomer component includes 50% by weight or more and 99% by weight or less (e.g., 60% by weight or more and 99% by weight or less, or 70% by weight or more and 99% by weight or less, or 75% by weight or more and 99% by weight or less, or 80% by weight or more and 99% by weight or less, or 85% by weight or more and 99% by weight or less, or 90% by weight or more and 99% by weight or less) of an ethylene monomer and 1% by weight or more and 50% by weight or less (e.g., 1% by weight or more and 40% by weight or less, or 1% by weight or more and 30% by weight or less, or 1% by weight or more and 25% by weight or less, or 1% by weight or more and 20% by weight or less, or 1% by weight or more and 15% by weight or less, or 1% by weight or more and 10% by weight or less) of a C3-C30 α-olefin comonomer, the C3-C30 α-olefin being selected from the group consisting of propylene, 1-hexene, 1-butene, and 1-octene.

[0109] In a particular embodiment, the (A) monomer component comprises 50% to 99% by weight (e.g., 60% to 99% by weight, or 70% to 99% by weight, or 75% to 99% by weight, or 80% to 99% by weight, or 85% to 99% by weight, or 90% to 99% by weight) of a propylene monomer and 1% to 50% by weight (e.g., 1% to 40% by weight, or 1% to 30% by weight, or 1% to 25% by weight, or 1% to 20% by weight, or 1% to 15% by weight, or 1% to 10% by weight) of an ethylene or C4 to C30 α-olefin comonomer, the C4 to C30 α-olefin being selected from the group consisting of 1-hexene, 1-butene, and 1-octene.

[0110] In some embodiments, the (A) monomer component includes 0 to 10 weight percent of a diene monomer. For example, the (A) monomer component may include 0.5 to 8 weight percent, or 1 to 5 weight percent, or 1 to 3 weight percent of a diene monomer. In further embodiments, the (A) monomer component may be substantially free of a diene monomer. For example, in certain embodiments, the (A) monomer component may include 0 to 0.2 weight percent, or 0 to 0.01 weight percent, or 0 to 0.001 weight percent, or 0 to 0.0001 weight percent of a diene monomer.

[0111] (B) Chain transfer agent In certain embodiments, the (B) chain transfer agent component has the formula Al(CHCH(Y 2 )A 2 )3, wherein Y 2 Each occurrence is independently hydrogen or C1-C 30 A is a hydrocarbyl group, 2 is, each occurrence independently, a hydrocarbyl group containing a hindered double bond. In a further embodiment, the (B) chain transfer agent component is represented by the formula Al(CHCH(Y 2 )A 2 )3 is an organoaluminum compound. 2 and A2 is, with respect to the telechelic polyolefin of formula (I), Y 2 and A 2 In certain embodiments, the formula Al(CHCH(Y 2 )A 2 )3 of the organoaluminum compound Y 2 may be selected from the group consisting of hydrogen, methyl, and ethyl. In certain embodiments, the formula Al(CHCH(Y 2 )A 2 )3 of the organoaluminum compound A 2 may be selected from among (AA) to (AZ) and (AZ1) above. In a further embodiment, the formula Al(CHCH(Y 2 )A 2 )3 of the organoaluminum compound A 2 is selected from the group consisting of (AC), (AF), (AM), (AO), (AP), (AS), and (AZ1). The pendant methyl group of (AF) may be attached to any carbon atom that is a ring member.

[0112] Formula Al(CHCH(Y 2 )A 2 )3 is an organoaluminum compound of the formula (a) CH2=C(Y 2 )A 2 (b) combining starting materials including a hydrocarbon of formula Al(CHCH(Y)), an alkylaluminum of formula Al(d), and an optional solvent to form an organoaluminum solution; (b) heating the organoaluminum solution to a temperature of 60-200° C., or 80-180° C., or 100-150° C., or 110-130° C., and holding the organoaluminum solution at a temperature of 60-200° C., or 80-180° C., or 100-150° C., or 110-130° C. for a time period of 30 minutes to 200 hours, or 30 minutes to 100 hours, or 30 minutes to 50 hours, or 30 minutes to 25 hours, or 1 hour to 10 hours, or 1 hour to 5 hours, or 3 hours to 5 hours; and (c) forming an organoaluminum solution of formula Al(CHCH(Y)), 2 )A 2 d for each occurrence independently represents one of C1 to C310 is an alkyl group, Y 2 Each occurrence is independently hydrogen or C1-C 30 A is a hydrocarbyl group, 2 is independently a hydrocarbyl group containing a hindered double bond at each occurrence. In certain embodiments, the carbon of d that is bonded to Al is a carbon that is connected to a tertiary carbon. For example, in certain embodiments, the alkylaluminum of formula Al(d)3 is triisobutylaluminum.

[0113] Formula Al(CHCH(Y 2 )A 2 For the thermal process of preparing organoaluminum compounds of formula 3, Y 2 and A 2 is, with respect to the telechelic polyolefin of formula (I), Y 2 and A 2 The optional solvent may be any of those discussed herein. The starting material for step (a) is a 1:10, or 1:5, or 1:3 mixture of an alkylaluminum of formula Al(d)3 and an alkylaluminum of formula CH2=C(Y 2 )A 2 The starting material for step (a) may comprise a ratio of a hydrocarbon of formula CH2=C(Y 2 )A 2 wherein Y 2 is independently hydrogen or C1-C 30 A is a hydrocarbon group. 2 is, independently for each occurrence of hydrocarbon, a hydrocarbyl group containing a hindered double bond, and the starting materials are a 1:10, or 1:5, or 1:3 mixture of an alkylaluminum of the formula Al(d)3 and an alkylaluminum of the formula CH2=C(Y 2 )A 2 In certain embodiments, the ratio of Y 2 may be selected from the group consisting of hydrogen, methyl and ethyl groups, and A 2may be selected from among (AA) to (AZ) and (AZ1) above. In a further embodiment, A 2 may be selected from the group consisting of (AC), (AF), (AM), (AO), (AP), (AS), and (AZ1). The pendant methyl group of (AF) may be attached to any carbon atom that is a ring member. 2 )A 2 In this process for preparing organoaluminum compounds of the formula CH2=C(Y 2 )A 2 The excess hydrocarbons can be removed by using vacuum and optional heating.

[0114] Alternatively, the formula Al(CHCH(Y 2 )A 2 )3 Organoaluminum compounds of the formula (a) CH2=CHA 2 Hydrocarbons of the formula Al(Y 2 (b) combining starting materials including an alkylaluminum of the formula Al(CHCH(Y 2 )A 2 and recovering a product comprising the organoaluminum compound of formula (3), wherein step (a) is carried out at a temperature between 1° C. and 50° C., or between 10° C. and 40° C., or between 20° C. and 30° C., for a period between 1 and 50 hours, or between 10 and 40 hours, or between 15 and 25 hours, and wherein Y 2 Each time it appears, it is assigned independently to C1~C 30 A is a hydrocarbon group, 2 is, independently at each occurrence, a hydrocarbyl group that contains a hindered double bond, and may be prepared by a catalytic process.

[0115] Formula Al(CHCH(Y 2 )A 2 ) 3. A catalytic process for preparing organoaluminum compounds of formula Y 2 is C1~C 30 A is a hydrocarbyl group. 2can be any of the embodiments described above for the telechelic polyolefin of formula (I). The procatalyst, optional cocatalyst, and optional solvent can each be any of those disclosed herein. The starting material for step (a) is a 1:10, or 1:5, or 1:3 mixture of a 1:10, or 1:5, or 1:3 mixture of a 1:10, or 1:3, ... 2 )3 alkylaluminum with the formula CH2=CHA 2 The starting material for step (a) may comprise a ratio of a hydrocarbon of formula CH2=CHA 2 and wherein A is a cyclic or cyclic hydrocarbon having a structure of the formula: 2 is, independently for each occurrence of each hydrocarbon, a hydrocarbyl group containing a hindered double bond, and the starting material is a 1:10, or 1:5, or 1:3 ratio of a compound of the formula Al(Y 2 )3 and alkylaluminum of the formula CH2=C(Y 2 )A 2 In certain embodiments, the ratio of Y 2 is C1~C 10 and A may be an alkyl group of the formula: 2 may be selected from among (AA) to (AZ) and (AZ1) above. In a further embodiment, A 2 may be selected from the group consisting of (AC), (AF), (AM), (AO), (AP), (AS), and (AZ1). The pendant methyl group of (AF) may be attached to any carbon atom that is a ring member.

[0116] In a further embodiment, the (B) chain transfer agent component has the formula Al(CHCH(Y 2 )A 2 )3 and an alkyl zinc of formula Zn(d)2, wherein Y 2 Each occurrence is independently hydrogen or C1-C 30 is a hydrocarbyl group, 2 is, independently at each occurrence, a hydrocarbyl group containing a hindered double bond, and d is, independently at each occurrence, C1 to C 10 In a further embodiment, the (B) chain transfer agent component is 65 mol % to 99 mol % of a group of the formula Al(CHCH(Y 2)A 2 )3 and 1 mol% to 35 mol% of an alkyl zinc of the formula Zn(d)2. 2 and A 2 is, with respect to the telechelic polyolefin of formula (I), Y 2 and A 2 Y may be any of the above-mentioned embodiments. 2 may be selected from the group consisting of hydrogen, methyl and ethyl groups, and A 2 can be selected from the above (AA) to (AZ) and (AZ1). 2 may be selected from the group consisting of (AC), (AF), (AM), (AO), (AP), (AS), and (AZ1). The pendant methyl group of (AF) may be attached to any carbon atom that is a ring member. Without being bound to a particular theory, the addition of an alkyl zinc of formula Zn(d)2 may enhance the rate of the chain transfer reaction. The alkyl zinc of formula Zn(d)2 is a di(C 1~8 ) alkyl zinc. Non-limiting examples of alkyl zinc of formula Zn(d)2 are diethyl zinc, diisopropyl zinc, diisobutyl zinc, di(n-hexyl) zinc, and di(n-octyl) zinc.

[0117] In certain embodiments, the (B) chain transfer agent component has the formula Al(CHCH(Y 2 )A 2 )3 and organoaluminum compounds of the formula Zn(CHCH(Y 2 )A 2 )2, wherein Y 2 Each occurrence is independently hydrogen or C1-C 30 A is a hydrocarbyl group, 2 Each occurrence is independently a hydrocarbyl group containing a hindered double bond. 2 )A 2 )3 and organoaluminum compounds of the formula Zn(CHCH(Y 2 )A 2 and (B) an organozinc compound of the formula Al(CHCH(Y 2 )A 2)3 and organoaluminum compounds of the formula Zn(CHCH(Y 2 )A 2 )2 are prepared independently, and then the two are mixed in a ratio of 1:99 to 80:20, or 10:90 to 60:40, or 20:80 to 40:60 of an organozinc compound of the formula Zn(CHCH(Y 2 )A 2 )2 and organozinc compounds of the formula Al(CH2CH(Y 2 )A 2 ) 3 in a ratio with an organoaluminum compound.

[0118] For this purpose, a compound of the formula Zn(CHCH(Y 2 )A 2 )2 is an organozinc compound of the formula (a) CH2=CHA 2 Hydrocarbons of the formula Zn(Y 2 (b) combining starting materials including a zinc alkyl of the formula Zn(CHCH(Y 2 )A 2 and recovering a product comprising the organozinc compound of formula (a) and (b), wherein step (a) is carried out at a temperature between 1° C. and 50° C., or between 10° C. and 40° C., or between 20° C. and 30° C., for a period between 1 and 50 hours, or between 10 and 40 hours, or between 15 and 25 hours, and 2 Each time it appears, it is assigned independently to C1~C 30 A is a hydrocarbon group, 2 is, independently at each occurrence, a hydrocarbyl group that contains a hindered double bond, and may be prepared by a catalytic process.

[0119] Formula Zn(CHCH(Y 2 )A 2 ) A catalytic process for preparing organozinc compounds of formula 2, 2 is C1~C 30 A is a hydrocarbyl group. 2may be any of the embodiments described above for the telechelic polyolefin of formula (I). The procatalyst, optional cocatalyst, and optional solvent may each be any of those disclosed herein. The starting material for step (a) is a 1:10, or 1:5, or 1:2 mixture of Zn(Y 2 )2 zinc alkyl with the formula CH2=CHA 2 The starting material for step (a) may comprise a ratio of a hydrocarbon of formula CH2=CHA 2 and wherein A is a cyclic or cyclic hydrocarbon having a structure of the formula: 2 is, independently for each occurrence of each hydrocarbon, a hydrocarbyl group containing a hindered double bond, and the starting material is a 1:10, or 1:5, or 1:2 ratio of Zn(Y 2 )2 zinc alkyl with the formula CH2=C(Y 2 )A 2 In certain embodiments, the ratio of Y 2 is C1~C 10 and A may be an alkyl group of the formula: 2 may be selected from among (AA) to (AZ) and (AZ1) above. In a further embodiment, A 2 may be selected from the group consisting of (AC), (AF), (AM), (AO), (AP), (AS), and (AZ1). The pendant methyl group of (AF) may be attached to any carbon atom that is a ring member.

[0120] Alternatively, the formula Al(CHCH(Y 2 )A 2 )3 and organoaluminum compounds of the formula Zn(CHCH(Y 2 )A 2 (B) the chain transfer agent component comprising an organozinc compound of the formula Al(CHCH(Y 2 )A 2 )3 and organoaluminum compounds of the formula Zn(CHCH(Y 2 )A 2 (B) a chain transfer agent component comprising an organozinc compound of the formula (a) CH2=CHA 2 Hydrocarbons of the formula Al(Y 2)3, alkylaluminum of the formula Zn(Y 2 (b) combining starting materials including a zinc alkyl of the formula Al(CHCH(Y 2 )A 2 )3 and organoaluminum compounds of the formula Zn(CHCH(Y 2 )A 2 and (B) recovering a product comprising a chain transfer agent component comprising an organozinc compound of formula (I) and (B) an organozinc compound of formula (I), wherein step (a) is carried out at a temperature of 1° C. to 50° C., or 10° C. to 40° C., or 20° C. to 30° C., for a period of 1 to 50 hours, or 10 to 40 hours, or 15 to 25 hours, and wherein Y 2 Each time it appears, it is assigned independently to C1~C 30 A is a hydrocarbon group, 2 is, independently at each occurrence, a hydrocarbyl group that contains a hindered double bond.

[0121] Formula Al(CHCH(Y 2 )A 2 )3 and organoaluminum compounds of the formula Zn(CHCH(Y 2 )A 2 ) 2 organozinc compounds and (B) a catalyst process for producing a chain transfer agent component comprising Y 2 is C1~C 30 A is a hydrocarbyl group. 2 can be any of the embodiments described above for the telechelic polyolefin of formula (I). The procatalyst, optional cocatalyst, and optional solvent can each be any of those disclosed herein. The starting material for step (a) is a 1:1 mixture of a 1:1 procatalyst and a 1:1 cocatalyst of formula Al(Y 2 )3 and alkylaluminum of the formula Zn(Y 2 )2 alkyl zinc with the formula CH2=CHA 2 The starting material of step (a) may further comprise a ratio of 1:99 to 80:20, or 10:90 to 60:40, or 20:80 to 40:60 of a hydrocarbon of formula Zn(Y 2 )2 and alkylzinc of the formula Al(Y 2The starting material for step (a) may be an aluminum alkyl of the formula CH2=CHA 2 and wherein A is a cyclic or cyclic hydrocarbon having a structure of the formula: 2 is independently for each occurrence of a hydrocarbon group containing a hindered double bond, and the starting material is a 1:1 mixture of the formula Al(Y 2 )3 and alkylaluminum of the formula Zn(Y 2 )2 alkyl zinc with the formula CH2=CHA 2 and having a ratio of 1:99 to 80:20, or 10:90 to 60:40, or 20:80 to 40:60, of the formula Zn(Y 2 )2 and alkylzinc of the formula Al(Y 2 In certain embodiments, Y 2 is C1~C 10 and A may be an alkyl group of the formula: 2 may be selected from among (AA) to (AZ) and (AZ1) above. In a further embodiment, A 2 may be selected from the group consisting of (AC), (AF), (AM), (AO), (AP), (AS), and (AZ1). The pendant methyl group of (AF) may be attached to any carbon atom that is a ring member.

[0122] In a further embodiment, the formula Al(CHCH(Y 2 )A 2 )3 and organoaluminum compounds of the formula Zn(CHCH(Y 2 )A 2 (B) The chain transfer agent component, which comprises the organozinc compound of (A) and (B) the organozinc compound of (C) and (C) can be prepared by a thermal process, which is illustrated by, but not limited to, the synthesis of CTA6 in the examples.

[0123] In a further embodiment, the (B) chain transfer agent has the formula (d) AlCHCH(Y 2 )A 2 wherein Y is an organoaluminum compound of the formula 2 Each occurrence is independently hydrogen or C1-C 30 A is a hydrocarbyl group,2 Each occurrence is independently a hydrocarbyl group containing a hindered double bond. 2 )A 2 The organoaluminum compounds of the formula (a) are 2 )A 2 (b) combining starting materials including a hydrocarbon of formula (d)2AlCH2CH(Y)2, an alkylaluminum of formula (d), and an optional solvent to form an organoaluminum solution; (b) heating the organoaluminum solution to a temperature of 10-200°C, or 20-150°C, or 30-100°C, or 40-80°C, and holding the organoaluminum solution at a temperature of 10-200°C, or 20-150°C, or 30-100°C, or 40-80°C for a time period of 30 minutes to 200 hours, or 1-100 hours, or 5-75 hours, or 10-50 hours, or 15-30 hours; and (c) reacting a hydrocarbon of formula (d)2AlCH2CH(Y)2 with an alkylaluminum of formula (d), to form an organoaluminum solution. 2 )A 2 and recovering a product containing an organoaluminum compound of the formula: 10 is an alkyl group, Y 2 Each occurrence is independently hydrogen or C1-C 30 is a hydrocarbyl group, 2 is, independently at each occurrence, a hydrocarbyl group containing a hindered double bond. The starting material for step (a) can be prepared by a process comprising a 1:1 mixture of an alkylaluminum of formula AlH(d) and an alkylaluminum of formula CH=C(Y 2 )A 2 The starting material for step (a) may comprise a ratio of a hydrocarbon of formula CH2=C(Y 2 )A 2 and a 1:1 ratio of an alkylaluminum of the formula AlH(d)2 to a hydrocarbon of the formula CH2=C(Y 2 )A 2 The ratio of the hydrocarbons to one or more of the hydrocarbons Y 2 and A 2 is, with respect to the telechelic polyolefin of formula (I), Y 2 and A 2 In certain embodiments, Y2 may be selected from the group consisting of hydrogen, methyl, and ethyl. 2 may be selected from among (AA) to (AZ) and (AZ1) above. In a further embodiment, A 2 is selected from the group consisting of (AC), (AF), (AM), (AO), (AP), (AS), and (AZ1). The pendant methyl group of (AF) may be attached to any carbon atom that is a ring member.

[0124] (C) Catalyst component In certain embodiments, the (C) catalyst component comprises a procatalyst. In these embodiments, the procatalyst becomes an active catalyst for polymerizing unsaturated monomers without a cocatalyst. In further embodiments, the (C) catalyst component comprises a procatalyst and a cocatalyst, such that an active catalyst is formed by the combination of the procatalyst and the cocatalyst. In these embodiments, the (C) active catalyst component may comprise a ratio of procatalyst to cocatalyst of 1:2, or 1:1.5, or 1:1.2.

[0125] Suitable procatalysts include, but are not limited to, those disclosed in WO2005 / 090426, WO2005 / 090427, WO2007 / 035485, WO2009 / 012215, WO2014 / 105411, WO2017 / 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. With reference 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."

[0126] Both heterogeneous and homogeneous catalysts may be used. Examples of heterogeneous catalysts include the well-known Ziegler-Natta compositions, particularly Group 4 metal halides supported on Group 2 metal halides or mixed halides, and alkoxides, 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.

[0127] Metal complexes for use herein may be selected from Groups 3-15 of the Periodic Table of the Elements that contain one or more delocalized pi-bonded or polyvalent Lewis base ligands. Examples include metallocene, half-metallocene, constrained geometry, and polyvalent pyridylamine, or other polychelated base complexes. The complexes generally have the formula: MK k X x Z z or a dimer thereof, wherein 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; K, for each occurrence, is independently 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 joined 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; X, at each occurrence, is independently a monovalent anionic moiety having up to 40 non-hydrogen atoms, optionally one or more X groups may be bonded together to form a divalent or polyvalent anionic group, further optionally one or more X groups and one or more Z groups may be bonded together to form a moiety that is 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 a conjugated diene having 4 to 30 non-hydrogen atoms bonded to M by delocalized π electrons, wherein M is in a +2 formal oxidation state; Z, for each occurrence, is independently a neutral Lewis base donor ligand of up to 50 non-hydrogen atoms containing at least one unshared electron pair coordinated to M; k is an integer from 0 to 3, x is an integer from 1 to 4, and z is a number from 0 to 3; The sum of k+x is equal to the formal oxidation state of M.

[0128] 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.

[0129] Each atom in a delocalized pi-bonded group may be independently substituted with a radical selected from the group consisting of hydrogen, halogen, hydrocarbyl, halohydrocarbyl, hydrocarbyl-substituted heteroatoms selected from Groups 14-16 of the Periodic Table, with such hydrocarbyl-substituted heteroatoms being further substituted with Group 15 or Group 16 heteroatom-containing moieties. In addition, two or more such radicals may together form fused ring systems, including partially or fully hydrogenated fused ring systems, or they may form a metal ring with a metal. Included in the term "hydrocarbyl" are radicals such as C 1~20 Linear, branched and cyclic alkyl radicals, C 6~20 Aromatic radical, C 7~20 Alkyl-substituted aromatic radicals, and C 7~20 Aryl-substituted alkyl radicals. Suitable hydrocarbyl-substituted heteroatom radicals include mono-, di- and tri-substituted radicals of boron, silicon, germanium, nitrogen, phosphorus or oxygen, each hydrocarbyl group containing from 1 to 20 carbon atoms. Examples include N,N-dimethylamino, pyrrolidinyl, trimethylsilyl, triethylsilyl, t-butyldimethylsilyl, methyldi(t-butyl)silyl, triphenylgermyl, and trimethylgermyl groups. Examples of Group 15 or Group 16 heteroatom-containing moieties 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, pi-bonded group, or hydrocarbyl-substituted heteroatom.

[0130] 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, as well as inertly substituted derivatives thereof, particularly their C1~10 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.

[0131] Boratabenzenyl ligands are anionic ligands that are boron-containing analogues to benzene. They have been known in the art for some time, having been described in G. Herberich, et al., Organometallics, 14, 1, 471-480 (1995). Preferred boratabenzenyl ligands correspond to the formula: [ka] In the formula, R 1 is preferably an inert substituent selected from the group consisting of hydrogen, hydrocarbyl, silyl, halo, or germyl, and R 1 has up to 20 atoms, not counting hydrogen, and optionally two adjacent R 1 In complexes containing divalent derivatives of such delocalized π-bonded groups, one atom thereof is bonded to another atom of the complex by a covalent bond or a covalently bonded divalent group, thereby forming a bridged system.

[0132] Phospholes are anionic ligands that are phosphorus-containing analogs to the cyclopentadienyl group. They have been known in the art for some time, as described in WO 98 / 50392 and elsewhere. Preferred phosphole ligands correspond to the formula: [ka] In the formula, R 1 is as defined above.

[0133] Suitable transition metal complexes for use herein have the formula: MK k X x Z z or a dimer thereof, wherein M is a Group 4 metal; K is a group containing delocalized π electrons, K being bonded to M, said K group containing up to 50 atoms, not counting hydrogen atoms, optionally two K groups may be joined together to form a bridged structure, further optionally one K group may be bonded to X or Z; X, each occurrence, is a monovalent anionic moiety having up to 40 non-hydrogen atoms, optionally one or more X and one or more K groups are bonded together to form a metallocycle, and further optionally one or more X and one or more Z groups are bonded together to form a moiety that is covalently bonded to and coordinated to M; Z, for each occurrence, is independently a neutral Lewis base donor ligand of up to 50 non-hydrogen atoms containing at least one unshared electron pair coordinated 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 of k+x is equal to the formal oxidation state of M.

[0134] Suitable complexes include those containing one or two K groups. The latter complexes include those that include a bridging group linking the two K groups. Suitable bridging groups are of the formula (ER'2): ewhere E is silicon, germanium, tin, or carbon, R' at each occurrence is independently hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy, and combinations thereof, R' having up to 30 carbon or silicon atoms, and e is 1 to 8. Illustratively, R' at each occurrence is independently methyl, ethyl, propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy, or phenoxy.

[0135] Examples of complexes containing two K groups are compounds corresponding to the formula: [ka] During the ceremony, M is titanium, zirconium, or hafnium in the formal oxidation state +2 or +4, preferably zirconium or hafnium; R 3 Each occurrence of R is independently selected from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo, and combinations thereof; 3 has 20 non-hydrogen atoms or adjacent R 3 the groups taken together form a divalent derivative (i.e., a hydrocarbadiyl, siladiyl, or germadiyl group), thereby forming a fused ring system; X″, in each occurrence, is independently an anionic ligand group of up to 40 non-hydrogen atoms, 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, M being in a +2 formal oxidation state; R', E, and e are as defined above.

[0136] Exemplary bridging ligands containing two π-bonding groups include dimethylbis(cyclopentadienyl)silane, dimethylbis(tetramethylcyclopentadienyl)silane, dimethylbis(2-ethylcyclopentadien-1-yl)silane, dimethylbis(2-t-butylcyclopentadien-1-yl)silane, 2,2-bis(tetramethylcyclopentadienyl)propane, dimethylbis(inden-1-yl)silane, dimethylbis(tetrahydroinden-1-yl)silane, dimethylbis(fluoren-1-yl)silane, dimethylbis(tetrahydrofluoren-1-yl)silane, dimethyl These are bis(2-methyl-4-phenylinden-1-yl)-silane, dimethylbis(2-methylinden-1-yl)silane, dimethyl(cyclopentadienyl)(fluoren-1-yl)silane, dimethyl(cyclopentadienyl)(octahydrofluoren-1-yl)silane, dimethyl(cyclopentadienyl)(tetrahydrofluoren-1-yl)silane, (1,1,2,2-tetramethyl)-1,2-bis(cyclopentadienyl)disilane, (1,2-bis(cyclopentadienyl)ethane, and dimethyl(cyclopentadienyl)-1-(fluoren-1-yl)methane.

[0137] Suitable X" groups are selected from hydride, hydrocarbyl, silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl, and aminohydrocarbyl groups, or two X" groups taken together form a divalent derivative of a conjugated diene, or else they take together to form a neutral pi-bonded conjugated diene. Exemplary X" groups are C1-20 hydrocarbyl groups.

[0138] A further class of metal complexes utilized in the present disclosure is represented by the formula MKZ z X x or a dimer thereof, where M, K, X, x, and z are as defined above, and Z is a substituent of up to 50 non-hydrogen atoms that together with K form a metallocycle with M.

[0139] Suitable Z substituents include groups containing up to 30 non-hydrogen atoms, including at least one atom that is a member of Group 14 of the Periodic Table of the Elements bonded directly to oxygen, sulfur, boron, or K, and a different atom selected from the group consisting of nitrogen, phosphorus, oxygen, or sulfur covalently bonded to M.

[0140] 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] where M is titanium or zirconium, preferably titanium in the +2, +3, or +4 formal oxidation state; K 1 is 1 to 5 R 2 is a delocalized π-bonded ligand group optionally substituted with a group; R 2 Each occurrence of R is independently selected 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 2 the groups taken together form a divalent derivative (i.e., a hydrocarbadiyl, siladiyl, or germadiyl group), thereby forming a fused ring system; 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; x is 1 or 2; Y is -O-, -S-, -NR'-, -PR'-, X' is SiR'2, CR'2, SiR'2SiR'2, CR'2CR'2, CR'=CR', CR'2SiR'2, or GeR'2, in which R' at each occurrence is independently hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy, and combinations thereof, said R' having up to 30 carbon or silicon atoms.

[0141] Specific examples of the aforementioned constrained geometry metal complexes include compounds corresponding to the following formulas: [ka] During the ceremony, Ar is an aryl group of 6 to 30 atoms, not counting hydrogen; R 4 is independently at each occurrence hydrogen, Ar, or a group other than Ar selected from hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy, trihydrocarbylsiloxy, bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino, hydrocarbadiylamino, hydrocarbylimino, di(hydrocarbyl)phosphino, hydrocarbadiylphosphino, hydrocarbylsulfide, halo-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, trihydrocarbylsilyl-substituted hydrocarbyl, bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl, di(hydrocarbyl)amino-substituted hydrocarbyl, hydrocarbyleneamino-substituted hydrocarbyl, hydrocarbylenephosphino-substituted hydrocarbyl, or hydrocarbylsulfide-substituted hydrocarbyl, the R group having 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; M is titanium; 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. BR6 , B.R. 6 L'', or GeR 6 2, Y is -O-, -S, -NR 5 -, -PR 5 -, -NR 5 2, or -PR 5 2, R 5 is independently at each occurrence hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl, 5 has up to 20 atoms other than hydrogen, and optionally two R 5 Group or R 5 and Y or Z together form a ring system, R 6 each occurrence independently represents hydrogen, or hydrocarbyl, hydrocarbyloxy, silyl, alkyl halide, aryl halide, -NR 5 2, and combinations thereof, 6 has up to 20 non-hydrogen atoms and optionally two R 6 Group or R 6 and Z together form a ring system, Z is optionally R 5 , R 6 or a neutral diene or monodentate or polydentate Lewis base bonded to X, X is a hydrogen atom, a monovalent anionic ligand group having up to 60 atoms not including hydrogen atoms, or two X groups joined together to form a divalent ligand group; x is 1 or 2; z is 0, 1, or 2.

[0142] Further examples of suitable metal complexes herein are polycyclic complexes corresponding to the formula: [ka] where M is titanium in the +2, +3, or +4 formal oxidation state; R 7is 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 aforementioned groups may be joined together to form a divalent derivative; R 8 is a divalent hydrocarbylene or substituted hydrocarbylene group that forms a condensation system with the remainder of the metal complex, 8 contains 1 to 30 atoms, not counting hydrogen, 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 to M, a contains boron or a member of group 14 of the periodic table of the elements and also contains nitrogen, phosphorus, sulfur, or oxygen; X is a monovalent anionic ligand group having up to 60 atoms excluding the class of ligands which are cyclic, delocalized, π-bonded ligand groups, optionally two X groups taken together form a divalent ligand group; Z, in each occurrence, is independently a neutral coordination compound having up to 20 atoms; x is 0, 1, or 2; z is zero or one.

[0143] Further examples of metal complexes usefully employed as catalysts are complexes of polyvalent Lewis bases, such as compounds corresponding to the formula: [ka] In the formula, T b is a bridging group, preferably containing two or more atoms other than hydrogen, X b and Y b are each independently selected from the group consisting of nitrogen, sulfur, oxygen, and phosphorus, more preferably X b and Y b are both nitrogen R b and R b Each occurrence of ' is independently hydrogen or C optionally containing one or more heteroatoms. 1~50 A hydrocarbyl group or an inertly substituted derivative thereof. b and R b Non-limiting examples of R' groups include alkyl, alkenyl, aryl, aralkyl, (poly)alkylaryl, and cycloalkyl groups, as well as nitrogen, phosphorus, oxygen, and halogen substituted derivatives thereof. Specific examples of suitable Rb and Rb' 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 of the Periodic Table or the Lanthanide series. b is a metal of Groups 3 to 13, and more preferably, M b is a Group 4 to 10 metal, L b is a monovalent, divalent, or trivalent anionic ligand containing 1 to 50 atoms, not counting hydrogen. bExemplary groups include halides; hydrides; hydrocarbyl, hydrocarbyloxy, di(hydrocarbyl)amide, hydrocarbyleneamide, di(hydrocarbyl)phosphide, hydrocarbylsulfide; hydrocarbyloxy, tri(hydrocarbylsilyl)alkyl; and carboxylate. More preferred L 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 x j is selected to provide charge balance; Z b is M b A neutral ligand group coordinated to Z, containing up to 50 atoms, not including hydrogen. b Groups include aliphatic and aromatic amines, phosphines, as well as ethers, alkenes, alkadienes, and inertly substituted derivatives thereof. Suitable inertly substituted groups include halogen, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, di(hydrocarbyl)amine, tri(hydrocarbyl)silyl, and nitrile groups. Preferred Z b Groups include triphenylphosphine, tetrahydrofuran, pyridine, and 1,4-diphenylbutadiene; f is an integer from 1 to 3; T b , R b , and R b two or three of 'may be joined together to form a single or multiple ring structure, h is an integer of 1 to 6, preferably 1 to 4, more preferably 1 to 3;

[0144] In one embodiment, R b X b In this embodiment, the most preferred R b The group is a linear alkyl group, a linear alkenyl group, or a group with the nearest branch point being X band their halo, dihydrocarbylamino, alkoxy or trihydrocarbylsilyl substituted derivatives. Highly preferred in this embodiment are R b The group is a C1-8 linear alkyl group.

[0145] At the same time, in this embodiment, R b ' is preferably Y b R b Non-limiting examples of R' 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 T' group contains 3 to 40 atoms, not counting hydrogen, more preferably 3 to 30 atoms, and most preferably 4 to 20 atoms, and is branched or cyclic. b Examples of groups are structures corresponding to the formula: [ka] During the ceremony, Each R d is a C1-10 hydrocarbyl group, preferably methyl, ethyl, n-propyl, i-propyl, t-butyl, phenyl, 2,6-dimethylphenyl, benzyl, or tolyl. e is C1-10 hydrocarbyl, preferably methyl, ethyl, n-propyl, i-propyl, t-butyl, phenyl, 2,6-dimethylphenyl, benzyl, or tolyl. d Group or R eGroups, or mixtures of Rd and Re groups, may together form divalent or polyvalent derivatives of hydrocarbyl groups, e.g., 1,4-butylene, 1,5-pentylene, or monocyclic or polycyclic fused ring, polyvalent hydrocarbyl or heterohydrocarbyl groups, e.g., naphthalene-1,8-diyl.

[0146] Suitable examples of the polyvalent Lewis base complexes include the following: [ka] In the formula, R d is independently selected from the group consisting of hydrogen and a C1-50 hydrocarbyl group, optionally containing one or more heteroatoms, or an inertly substituted derivative thereof, at each occurrence, or further optionally, two adjacent R d’ the groups may together form a divalent bridging group, d' is 4, M b’ is a Group 4 metal, preferably titanium or hafnium, or a Group 10 metal, preferably Ni or Pd; L b’ is a monovalent ligand of up to 50 atoms, not counting hydrogen, preferably a halide or hydrocarbyl, or two L b’ The groups taken together form a divalent or neutral ligand group, preferably C 2~50 It is a hydrocarbylene, hydrocarbadiyl, or diene group.

[0147] 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] During the ceremony, R 11is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, and inertly substituted derivatives thereof containing 1 to 30 atoms, not counting hydrogen, or divalent derivatives thereof; 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; X 1 is an anionic, neutral or dianionic ligand group, x' is such an X 1 A number from 0 to 5 indicates the number of groups, and bonds, optional bonds and electron donating interactions are represented by lines, dotted lines and arrows, respectively.

[0148] Suitable complexes are those in which the ligand formation occurs from the amine group and optionally one or more further groups, in particular R 12 In addition, 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] In the formula, M 1 , X 1 , x', R 11 and T 1 is as previously defined, R 13 , R 14 , R 15 , and R 16is 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, with bonds, optional bonds, and electron pair donating interactions represented by lines, dotted lines, and arrows, respectively. [ka] During the ceremony, M 1 , X 1 and x' are as defined above; R 13 , R 14 , R 15 , and R 16 is as defined above, preferably R 13 , R 14 , and R 15 is hydrogen or C1-4 alkyl, R 16 is C 6~20 aryl, most preferably naphthalenyl; R a Each occurrence of is independently 1~4 alkyl, a is 1 to 5, and most preferably R a is isopropyl or t-butyl, R 17 and R 18 Each occurrence is independently hydrogen, halogen, or C 1~20 is an alkyl or aryl group, most preferably R 17 and R 18 is hydrogen and the other is a C6-20 aryl group, particularly a 2-isopropyl, phenyl or fused polycyclic aryl group, most preferably an anthracenyl group, and bonds, optional bonds and electron pair donative interactions are represented by lines, dotted lines and arrows, respectively.

[0149] Exemplary metal complexes for use herein as catalysts correspond to the formula: [ka] In the formula, X 1 Each occurrence of X is a halide, N,N-dimethylamide, or C1-4 alkyl, preferably each occurrence of X is 1 is methyl, R f is independently at each occurrence hydrogen, halogen, C1-20 alkyl, or C6-20 aryl, or two adjacent R f the groups are joined together to form a ring, and f is 1 to 5; R c Each occurrence independently represents hydrogen, halogen, or C 1~20 Alkyl or C 6~20 Aryl or two adjacent R c the groups join together to form a ring and c is 1-5.

[0150] Suitable examples of metal complexes for use as catalysts according to the present invention are complexes of the formula: [ka] In the formula, R x is C1-4 alkyl or cycloalkyl, preferably methyl, isopropyl, t-butyl, or cyclohexyl; X 1 Each occurrence is a halide, N,N-dimethylamide, or C1-4 alkyl, preferably methyl.

[0151] Examples of metal complexes usefully employed as catalysts in accordance with the present invention include the following: [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium dimethyl; [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)]hafnium dimethyl; [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)]hafnium dimethyl; [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium di(N,N-dimethylamide); and [N-(2,6-di(l-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium dichloride.

[0152] Under the reaction conditions used to prepare the metal complexes used in the present disclosure, the hydrogen at the 2-position of the α-naphthalene group substituted at the 6-position of the pyridin-2-yl group undergoes elimination, thereby forming a metal complex in which the metal is covalently bonded to both the resulting amide group and to the 2-position of the α-naphthalenyl group, and stabilized by coordination to the pyridinyl nitrogen atom via the electron pair of the nitrogen atom.

[0153] Additional suitable procatalysts include imidazole amine compounds corresponding to those disclosed in WO2007 / 130307A2, WO2007 / 130306A2, and U.S. Patent Application Publication No. 2009 / 0306318A1, the entireties of which are incorporated herein by reference. Such imidazole amine compounds include those corresponding to the formula: [ka] During the ceremony, X, independently at each occurrence, is an anionic ligand, or two X groups taken together form a dianionic ligand group or a neutral diene; T is an alicyclic or aromatic group containing one or more rings; R 1 is independently, at each occurrence, a hydrogen, a halogen, or a monovalent polyatomic anionic ligand, or two or more R 1 The groups are joined together to thereby form a polyvalent fused ring system, R 2 is independently, at each occurrence, a hydrogen, a halogen, or a monovalent polyatomic anionic ligand, or two or more R 2 The groups, when joined together, form a polyvalent fused ring system, R 4 is hydrogen, alkyl of 1 to 20 carbons, aryl, aralkyl, trihydrocarbylsilyl, or trihydrocarbylsilylmethyl.

[0154] Further examples of such imidazole amine compounds include, but are not limited to, the following: [ka] During the ceremony, R 1 Each occurrence of 3~12 is an alkyl group, the carbon attached to the phenyl ring is substituted so as to be secondary or tertiary, R 2 is independently, each occurrence, hydrogen or C 1~2 is an alkyl group, R 4 is methyl or isopropyl, R 5 is hydrogen or C 1~6 is alkyl, R 6 is hydrogen, C 1~6 alkyl, or cycloalkyl, and two adjacent R 6 The groups taken together form a fused aromatic ring and T' is oxygen, sulfur, or C. 1~20 is a hydrocarbyl substituted nitrogen or phosphorus group, T'' is nitrogen or phosphorus, and X is methyl or benzyl.

[0155] Further suitable metal complexes of polyvalent Lewis bases for use herein include compounds according to the formula: [ka] During the ceremony, R 20 is an aromatic or inertly substituted aromatic group containing 5 to 20 atoms, not counting hydrogen, or a polyvalent derivative thereof; T 3 is a hydrocarbylene or hydrocarbylsilane group having 1 to 20 atoms, not counting hydrogen, or an inertly substituted derivative thereof; M 3 is a Group 4 metal, preferably zirconium or hafnium; G is an anionic, neutral or dianionic coordinating group; preferably a halide, hydrocarbyl, silane, trihydrocarbylsilylhydrocarbyl, trihydrocarbylsilyl, or dihydrocarbylamide group having up to 20 atoms, not counting hydrogen; g is a number from 1 to 5 indicating the number of such G groups, and bonds and electron donating interactions are represented by lines and arrows, respectively.

[0156] Exemplarily, such a complex corresponds to the formula: [ka] During the ceremony T 3 is a divalent bridging group of 2 to 20 atoms, not counting hydrogen, preferably a substituted or unsubstituted C3-6 alkylene group; Ar 2 is independently, at each occurrence, an arylene or alkyl- or aryl-substituted arylene group of 6 to 20 atoms, not counting hydrogens; M 3 is a Group 4 metal, preferably hafnium or zirconium; G is independently at each occurrence an anionic, neutral, or dianionic coordinating group; g is a number from 1 to 5 indicating the number of such X groups, and the electron donating interactions are represented by arrows.

[0157] Suitable examples of metal complexes of the above formula include the following compounds: [ka] In the formula, M 3 is Hf or Zr, Ar 4 is C 6~20 aryl or an inertly substituted derivative thereof, in particular 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl or anthracen-5-yl, T 4 Each occurrence of is independently 3~6 Alkylene group, C 3~6 cycloalkylene groups, or inertly substituted derivatives thereof, R 21is independently at each occurrence hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl of up to 50 atoms, not counting hydrogen; G in each occurrence is independently halo, or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms, not counting hydrogen, or two G groups together are a divalent derivative of the aforementioned hydrocarbyl or trihydrocarbylsilyl groups.

[0158] A suitable compound is of the formula: [ka] In the formula, Ar 4 is 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl, or anthracen-5-yl; R 21 is hydrogen, halo, or C1-4 alkyl, especially methyl; T 4 is propane-1,3-diyl or butane-1,4-diyl, G is chloro, methyl, or benzyl.

[0159] Exemplary metal complexes of the above formula are: [ka]

[0160] Suitable metal complexes for use according to the present disclosure further include compounds corresponding to the formula: [ka] , During the ceremony, M is zirconium or hafnium; R 20is independently at each occurrence a divalent aromatic or inertly substituted aromatic radical containing 5 to 20 atoms, not counting hydrogen; T 3 is a divalent hydrocarbon or silane group having 3 to 20 atoms, not counting hydrogen, or an inertly substituted derivative thereof; R D Each occurrence is independently a monovalent ligand radical of 1 to 20 atoms, not counting hydrogen, or two R D The groups taken together are a divalent ligand group of 1 to 20 atoms, not counting hydrogen.

[0161] Such a complex may correspond to the formula: [ka] , During the ceremony, Ar 2 each occurrence is independently an arylene, or an alkyl-, aryl-, alkoxy-, or amino-substituted arylene group of 6 to 20 atoms, not counting hydrogen or any atoms of any substituent; T 3 is a divalent hydrocarbon bridging group of 3 to 20 atoms, not counting hydrogen, preferably a divalent substituted or unsubstituted C 3~6 is an aliphatic, alicyclic, or bis(alkylene)-substituted alicyclic group; R D Each occurrence is independently a monovalent ligand radical of 1 to 20 atoms, not counting hydrogen, or two R D The groups taken together are a divalent ligand group of 1 to 40 atoms, not counting hydrogen.

[0162] Further examples of metal complexes suitable for use herein include compounds of the formula: [ka] , During the ceremony, Ar4 Each occurrence of is independently 6~20 Aryl or an inertly substituted derivative thereof, in particular 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl, naphthyl, anthracen-5-yl, 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl, T 4 is independently at each occurrence a propylene-1,3-diyl group, a bis(alkylene)cyclohexane-1,2-diyl group, or an inertly substituted derivative thereof, each substituted with 1 to 5 alkyl, aryl, or aralkyl substituents having up to 20 carbons; R 21 is independently hydrogen, halo, hydrocarbyl of up to 50 atoms not counting hydrogen, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy, or amino; R D Each occurrence is independently halo, or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms, not counting hydrogen, or two R D The groups taken together are divalent hydrocarbylene, hydrocarbadiyl, or trihydrocarbylsilyl groups of up to 40 atoms, not including hydrogen.

[0163] An exemplary metal complex is a compound of the formula: [ka] , In the formula, Ar 4 is independently at each occurrence 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl, or anthracen-5-yl; R 21is independently hydrogen, halo, hydrocarbyl of up to 50 atoms not counting hydrogen, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy, or amino; T 4 is propane-1,3-diyl or bis(methylene)cyclohexane-1,2-diyl, R D Each occurrence is independently halo, or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms, not counting hydrogen, or two R D The groups taken together are hydrocarbylene, hydrocarbadiyl, or hydrocarbylsilanediyl groups of up to 40 atoms, not counting hydrogen.

[0164] Suitable metal complexes according to the present disclosure correspond to the formula: [ka] In the formula, R D Each occurrence is independently chloro, methyl, or benzyl.

[0165] Specific examples of suitable metal complexes are the following compounds: A) bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV) dimethyl, Bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV) dichloride, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV) dibenzyl, Bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV) dimethyl, Bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV) dichloride, Bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV) dibenzyl, B) bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV) dimethyl, Bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV) dichloride, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV) dibenzyl, Bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV) dimethyl, Bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV) dichloride, Bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV) dibenzyl, C) bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV) dimethyl, Bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV) dichloride, bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV) dibenzyl, Bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV) dimethyl, Bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV) dichloride, Bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV) dibenzyl, D) bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediylhafnium(IV) dimethyl, Bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediylhafnium(IV) dichloride, Bis((2-oxoyl-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediylhafnium(IV) dibenzyl, Bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediylhafnium(IV) dimethyl, Bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediylhafnium(IV) dichloride, and Bis((2-oxoyl-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediylhafnium(IV) dibenzyl.

[0166] The aforementioned metal complexes can be conveniently prepared by standard metallation and ligand exchange procedures involving a transition metal source and a neutral polyfunctional ligand source. The techniques used are the same as or similar to those disclosed in USP 6,827,976 and US 2004 / 0010103, and elsewhere.

[0167] The aforementioned polyvalent Lewis base complexes can be conveniently prepared by standard metallation and ligand exchange procedures involving a Group 4 metal source (of the periodic table) and a neutral polyfunctional ligand source. In addition, the complexes can also be prepared by amide removal and hydrocarbylation processes starting from the corresponding Group 4 metal tetraamide and a hydrocarbylating agent such as trimethylaluminum. Other techniques can be used as well. These complexes are known from the disclosures of, inter alia, U.S. Pat. Nos. 6,320,005, 6,103,657, WO02 / 38628, WO03 / 40195, and US04 / 0220050.

[0168] Catalysts with high comonomer incorporation properties are also known to reincorporate in situ prepared long chain olefins that arise accidentally during polymerization via β-hydride removal and chain termination of the growing polymer, or otherwise. The concentration of such long chain olefins is particularly enhanced by the use of continuous solution polymerization conditions at high conversions, particularly ethylene conversions of 95% or more, more preferably ethylene conversions of 97% or more. Under such conditions, small but detectable amounts of olefin terminated polymers are reincorporated into the growing polymer chains, resulting in the formation of long chain branches, i.e., branches with longer carbon lengths than arise from other intentionally added comonomers. Moreover, such chains reflect the presence of other comonomers present in the reaction mixture. That is, the chains may contain short or long chain branches as well, depending on the comonomer composition of the reaction mixture. Long chain branching of olefin polymers is further described in USP 5,272,236, 5,278,272, and 5,665,800.

[0169] Alternatively, branching, including hyperbranching, can be induced in certain segments of the multiblock copolymer by using certain catalysts known to induce "chain-walking" in the resulting polymer.For example, branched copolymers can be prepared from a single monomer, including ethylene, using certain homogeneously bridged bisindenyl- or partially hydrogenated bisindenyl-zirconium catalysts disclosed by Kaminski, et al., J.Mol.Catal.A:Chemical, 102(1995)59-65, Zambelli, et al., Macromolecules, 1988,21,617-622, or Dias, et al., J.Mol.Catal.A:Chemical, 185(2002)57-64.

[0170] Further complexes suitable for use include Group 4-10 derivatives corresponding to the formula: [ka] During the ceremony, M2 is a metal of Groups 4 to 10 of the Periodic Table of the Elements, preferably a metal of Group 4, Ni(II), or Pd(II), most preferably zirconium; T 2 is a nitrogen-, oxygen-, or phosphorus-containing group; X 2 is halo, hydrocarbyl, or hydrocarbyloxy; t is 1 or 2; x'' is a number selected to provide charge balance; T 2 and N are linked by a bridging ligand. Such catalysts have been previously disclosed, among other things, in J. Am. Chem. Soc., 118, 267-268 (1996), J. Am. Chem. Soc., 117, 6414-6415 (1995), and Organometallics, 16, 1514-1516, (1997).

[0171] Suitable examples of the aforementioned metal complexes for use as catalysts are the aromatic diimine or aromatic dioximine complexes of Group 4 metals, particularly zirconium, corresponding to the formula: [ka] During the ceremony, M 2 , X 2 , and T 2 is as previously defined, R d Each occurrence is independently hydrogen, halogen, or R e and R e is independently at each occurrence C1-20 hydrocarbyl or a heteroatom, particularly an F, N, S, or P substituted derivative thereof, more preferably C1-20 hydrocarbyl or an F or N substituted derivative thereof, most preferably alkyl, dialkylaminoalkyl, pyrrolyl, piperidinyl, perfluorophenyl, cycloalkyl, (poly)alkylaryl, or aralkyl.

[0172] Suitable examples of the aforementioned metal complexes for use as catalysts are the aromatic dioxyimine complexes of zirconium corresponding to the formula: [ka] During the ceremony, X 2 is as defined above, preferably C1-10 hydrocarbyl, most preferably methyl or benzyl; R e ' is methyl, isopropyl, t-butyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,4-dimethylcyclohexyl, 2-pyrrolyl, N-methyl-2-pyrrolyl, 2-piperidenyl, N-methyl-2-piperidenyl, benzyl, o-tolyl, 2,6-dimethylphenyl, perfluorophenyl, 2,6-di(isopropyl)phenyl, or 2,4,6-trimethylphenyl.

[0173] The aforementioned complexes for use, including also certain phosphinimine complexes, are disclosed in EP-A-890581. These complexes have the formula: [(R f )3-P=N] f M(K 2 )(R f )3- f Wherein R f is a monovalent ligand, or two R f The groups taken together are a divalent ligand, preferably R f is hydrogen or C1-4 alkyl, M is a Group 4 metal; K 2 through it 2 is a group containing delocalized π electrons bonded to M, 2 The group contains up to 50 atoms, not counting hydrogen atoms, and f is 1 or 2.

[0174] Further suitable procatalysts include those disclosed in WO2017 / 173080A1, which is incorporated by reference in its entirety. Such procatalysts include metal-ligand complexes of formula (i): [ka] , where M is titanium, zirconium, or hafnium; each Z1 is independently a neutral, monoanionic, or dianionic, monodentate or polydentate ligand and nn is an integer, Z1 and nn being selected such that the metal-ligand complex of formula (i) is, overall, neutral; Each Q 1 and Q 10 are independently (C6~C 40 )Aryl, Substituted (C6-C 40 )Aryl, (C3-C 40 ) Heteroaryl, and substituted (C3-C 40 ) heteroaryl; Each Q 2 , Q 3 , Q 4 , Q 7 , Q 8 , and Q 9 are independently hydrogen, (C1-C 40 ) Hydrocarbyl, substituted (C1-C 40 ) hydrocarbyl, (C1-C 40 ) Heterohydrocarbyl, substituted (C1-C 40 ) selected from the group consisting of heterohydrocarbyl, halogen, and nitro (NO2); Each Q 5 and Q 6 are independently 40 ) Alkyl, Substituted (C1-C 40 ) alkyl, and [(Si)1-(C+Si) 40 ]-substituted organosilyl; each N is independently nitrogen; Optionally, Q 1~5Two or more of the groups can combine together to form a ring structure, such ring structure having 5 to 16 atoms in the ring, excluding any hydrogen atoms; Optionally, Q 6~10 Two or more of the groups can be combined together to form a ring structure, such ring structure having from 5 to 16 atoms in the ring, excluding any hydrogen atoms.

[0175] The metal-ligand complexes of formula (i) above and all specific embodiments thereof herein are intended to include all possible stereoisomers, including coordination isomers thereof.

[0176] The metal ligands of formula (i) above provide homoleptic and heteroleptic procatalyst components.

[0177] In an alternative embodiment, Q 1 , Q 2 , Q 3 , Q 4 , Q 5 , Q 6 , Q 7 , Q 8 , Q 9 , and Q 10 Any one or more of (C1~C 40 ) hydrocarbyl and (C1-C 40 ) each heterohydrocarbyl is independently unsubstituted or one or more R S Each R S are independently a halogen atom, a polyfluoro-substituted, a perfluoro-substituted, an unsubstituted (C1-C 18 ) Alkyl, (C6-C 18 )aryl, F3C, FCHO, F2HCO, F3CO, (R C1 )Si, (R C1 )3Ge, (R C1 )O, (R C1 )S, (R C1 )S(O), (R C1 )S(O)2, (R C1 )2P, (R C1 )2N, (R C1)2C=N, NC, NO2, (R C1 )C(O)O, (R C1 )OC(O), (R C1 )C(O)N(R C1 ), or (R C1 )2NC(O) or R S Two of them, taken together, are unsubstituted (C1-C 18 ) alkylene, and each R S are independently unsubstituted (C1 to C 18 ) alkyl, and independently, each R C1 is hydrogen, unsubstituted (C1-C 18 ) hydrocarbyl, or unsubstituted (C1-C 18 ) heterohydrocarbyl or absent (e.g., absent when N comprises -N=). In certain embodiments, Q 5 and Q 6 each independently represents a group consisting of (C1-C 40 ) is a primary or secondary alkyl group. The terms primary and secondary alkyl group have their normal accustomed meanings herein, i.e., primary indicates that the carbon atom directly attached to the ligand nitrogen bears at least two hydrogen atoms, and secondary indicates that the carbon atom directly attached to the ligand nitrogen bears only one hydrogen atom.

[0178] Optionally, two or more Q 1~5 Group or two or more Q 6~10 The groups may each independently be combined together to form a ring structure, such ring structure having from 5 to 16 atoms in the ring, excluding any hydrogen atoms.

[0179] In a preferred embodiment, Q 5 and Q 6 are each independently, (C1~C 40 ), most preferably Q 5 and Q 6 are each independently propyl, isopropyl, neopentyl, hexyl, isobutyl, and benzyl.

[0180] In certain embodiments, the Q of the olefin polymerization procatalyst of formula (i) 1 and Q 10 is a substituted phenyl group as shown in formula (ii), [ka] During the ceremony, J. 1 ~J 10 are each independently R s each R is selected from the group consisting of a substituent and hydrogen; S are independently a halogen atom, a polyfluoro-substituted, a perfluoro-substituted, an unsubstituted (C1-C 18 ) Alkyl, (C6-C 18 )aryl, F3C, FCHO, F2HCO, F3CO, (R C1 )Si, (R C1 )3Ge, (R C1 )O, (R C1 )S, (R C1 )S(O), (R C1 )S(O)2, (R C1 )2P, (R C1 )2N, (R C1 )2C=N, NC, NO2, (R C1 )C(O)O, (R C1 )OC(O), (R C1 )C(O)N(R C1 ), or (R C1 )2NC(O) or R S Two of them, taken together, are unsubstituted (C1-C 18 ) alkylene, and each R S are independently unsubstituted (C1 to C 18 ) alkyl, and independently, each R C1 Hydrogen, unsubstituted (C1-C 18 ) hydrocarbyl or unsubstituted (C1-C 18 ) heterohydrocarbyl or absent (e.g., absent when N comprises -N=). More preferably, J in formula (ii) 1 , J 5 , J 6 , and J. 10are each independently selected from the group consisting of a halogen atom, a (C1-C8) alkyl group, and a (C1-C8) alkoxyl group. 1 , J 5 , J 6 , and J. 10 are each independently methyl, ethyl, or isopropyl.

[0181] "[(Si)1-(C+Si) 40 The term "substituted organosilyl" refers to a substituted silyl radical having 1 to 40 silicon atoms and 0 to 39 carbon atoms, such that the total number of carbon and silicon atoms is 1 to 40. [(Si)1-(C+Si) 40 ]Examples of substituted organosilyls include trimethylsilyl, triisopropylsilyl, dimethylphenylsilyl, diphenylmethylsilyl, triphenylsilyl, and triethylsilyl.

[0182] Preferably, in the metal-ligand complex of formula (i), there are no OO, SS, or OS bonds other than the OS bonds in the S(O) or S(O)2 diradical functional groups. More preferably, in the metal-ligand complex of formula (i), there are no OO, PP, SS, or OS bonds other than the OS bonds in the S(O) or S(O)2 diradical functional groups.

[0183] M is titanium, zirconium, or hafnium. In one embodiment, M is titanium. In another embodiment, M is zirconium. In another embodiment, M is hafnium. In some embodiments, M is in a formal oxidation state of +2, +3, or +4. Each Z1 is independently a neutral, monoanionic, or dianionic monodentate or polydentate ligand. Z1 and nn are selected such that the metal-ligand complex of formula (i) is neutral overall. In some embodiments, each Z1 is independently a monodentate ligand. In one embodiment, when there are two or more Z1 monodentate ligands, each Z1 is the same. In some embodiments, the monodentate ligand is a monoanionic ligand. The monoanionic ligand has a net formal oxidation state of -1. Each monoanionic ligand is independently a hydride, (C1-C 40 ) Hydrocarbyl carbanion, (C1-C 40 ) Heterohydrocarbyl carbanions, halides, nitrates, carbonates, phosphates, borates, borohydrides, sulfates, HC(O)O - , alkoxide or aryloxide (RO - ), (C1~C 40 ) Hydrocarbyl C(O)O - , HC(O)N(H) - , (C1~C 40 ) Hydrocarbyl C(O)N(H) - , (C1~C 40 ) Hydrocarbyl C(O)N((C1-C 20 )hydrocarbyl) - , R K R L B - , R K R L N - , R K O - , R K S - , R K R L P - , or R M R K R L S - Each R may be K , R L , and RM are independently hydrogen, (C1-C 40 ) hydrocarbyl, or (C1-C 40 ) heterohydrocarbyl, or R K and R L Together (C2~C 40 ) hydrocarbylene or (C1-C 40 ) forms a heterohydrocarbylene, R M is as defined above.

[0184] In some embodiments, at least one monodentate ligand of Z is independently a neutral ligand. In one embodiment, the neutral ligand is R X1 NR K R L , R K OR L , R K S.R. L , or R X1 PR K R L is a neutral Lewis base group, and each R X1 are independently hydrogen, (C1-C 40 ) hydrocarbyl, [(C1-C 10 )hydrocarbyl]3Si, [(C1-C 10 )hydrocarbyl]3Si(C1-C 10 ) hydrocarbyl, or (C1-C 40 ) heterohydrocarbyl, each R K and R L are, independently, as defined above.

[0185] In some embodiments, each Z is independently a halogen atom, an unsubstituted (C 20 ) Hydrocarbyl, unsubstituted (C1-C 20 ) hydrocarbylC(O)O-, or R K R L N- is a monodentate ligand, and R K and R L are each independently unsubstituted (C1 to C 20 In some embodiments, each monodentate ligand Z1 is a chlorine atom, (C1-C10 ) hydrocarbyl (e.g., (C1-C6) alkyl or benzyl), unsubstituted (C1-C 10 ) hydrocarbylC(O)O-, or R K R L N- and R K and R L are each independently unsubstituted (C1 to C 10 ) hydrocarbyl.

[0186] In some embodiments, at least two Z1s are present, and the two Z1s together form a bidentate ligand. In some embodiments, the bidentate ligand is a neutral bidentate ligand. In one embodiment, the neutral bidentate ligand has the formula (R D1 )2C=C(R D1 )-C(R D1 )=C(R D1 )2 dienes, wherein each R D1 is independently H, unsubstituted (C1-C6) alkyl, phenyl, or naphthyl. In some embodiments, the bidentate ligand is a monoanionic-mono(Lewis base) ligand. The monoanionic mono(Lewis base) ligand has the formula (D): R E1 -C(O - )=CH-C(=O)-R E1 (D) may be a 1,3-dionate of E1 is independently H, unsubstituted (C1-C6) alkyl, phenyl, or naphthyl. In some embodiments, the bidentate ligand is a dianionic ligand. The dianionic ligand has a net formal oxidation state of -2. In one embodiment, each dianionic ligand is independently a carbonate, an oxalate (i.e., - O2CC(O)O - ), (C2~C 40 ) Hydrocarbylene dicarbanion, (C1-C 40 ) heterohydrocarbylene dicarbanion, phosphate, or sulfate.

[0187] As stated above, the number and charge (neutral, monoanionic, dianionic) of Z1 are selected depending on the formal oxidation state of M, such that the metal-ligand complex of formula (i) is overall neutral.

[0188] In some embodiments, each Z is the same and each Z is methyl, isobutyl, neopentyl, neophyl, trimethylsilylmethyl, phenyl, benzyl, or chloro. In some embodiments, nn is 2 and each Z is the same.

[0189] In some embodiments, at least two Z1 are different. In some embodiments, each Z1 is different from methyl, isobutyl, neopentyl, neophyl, trimethylsilylmethyl, phenyl, benzyl, and chloro.

[0190] In one embodiment, the metal-ligand complex of formula (i) is a mononuclear metal complex.

[0191] Further suitable procatalysts include those disclosed in Acc. Chem. Res., 2015, 48(8), pp2209-2220, but are not limited to those of the following structure: [ka]

[0192] Suitable procatalysts further include "single component catalysts" that can catalyze olefin polymerization without the use of a cocatalyst. Such single component catalysts are described in Watson, PLJ Am. Chem. Soc. 1982, 104, 337-339; Yasuda, H.; Ihara, E. Adv. Polym. Sci. 1997, 133, 53-101; Ihara, E.; Nodono, M.; Katsura, K.; Adachi, Y.; Yasuda, H.; Yamagashira, M.; Hashimoto, H.; Kanehisa, N.; and Kai, Y. Organometallics 1998,17,3945-3956, Long,DP;Bianconi,PAJAm.Chem.Soc.1996,118,12453-12454,Gilchrist,JH;Bercaw,JEJAm.Chem.Soc.1996,118,12021-12028,Mitchell,J P;Hajela,S.;Brookhart,SK;Hardcastle,KI;Henling,LM;Bercaw,JEJAm.Chem.Soc.1996,118,1045-1053;Evans,WJ;DeCoster,DM;Greaves,J.Organometallics 1996,15,3210-3221, Evans, WJ; DeCoster, DM; Greaves, J. Macromolecules 1995,28,7929-7936, Shapiro,PJ;Cotter,WD;Schaefer,WP;Labinger,JA;Bercaw,JEJAm.Chem.Soc.1994,116,4623-4640,Schaverien,CJOrganometallics 1994,13,69-82, Coughlin,EBJAm.Chem.Soc.1992,114,7606-7607, Piers,WE;Bercaw,JEJAm.Chem.Soc.1990,11 2,9406-9407, Burger,BJ;Thompson,ME,Cotter,WD;Bercaw,JEJAm.Chem.Soc.1990,112,1566-1577,Shapiro,PJ;Bunel, E.;Schaefer, WPOrganometallics 1990,9, 867-869, Jeske, G.;Lauke, H.;Mauermann, H.;Swepston, PN;Schumann, H.;Marks, TJJAm.Chem.Soc. 1985,107,8091-8103, Jeske, G.;Schock, LE;Swepston, PN;Schumann, H.;Marks, TJJAm.Chem.Soc. 1985,107,8103-8110, and Organometallics, 2001,20(9),pp1752-1761. Exemplary non-limiting formulas of such simple component catalysts include: [ka] During the ceremony, M is Sm or Y, R is a monovalent ligand of up to 50 atoms, not counting hydrogen, preferably a halide or hydrocarbyl, or two L b’ The groups taken together form a divalent or neutral ligand group, preferably C 2~50 It is a hydrocarbylene, hydrocarbadiyl, or diene group.

[0193] Suitable procatalysts include, but are not limited to, the following, designated (Cat 1) through (Cat 17):

[0194] (Cat1) can be prepared according to the teachings of WO03 / 40195 and U.S. Pat. No. 6,953,764 B2 and has the following structure: [ka] .

[0195] (Cat2) can be prepared according to the teachings of WO03 / 40195 and WO04 / 24740 and has the following structure: [ka] .

[0196] (Cat3) can be prepared according to methods known in the art and has the following structure: [ka] .

[0197] (Cat 4) can be prepared according to the teachings of U.S. Patent Application Publication No. 2004 / 0010103 and has the following structure: [ka] .

[0198] (Cat 5) can be prepared according to the teachings of U.S. Pat. No. 7,858,706 B2 and has the following structure: [ka] .

[0199] (Cat 6) can be prepared according to the teachings of U.S. Pat. No. 7,858,706 B2 and has the following structure: [ka] .

[0200] (Cat 7) can be prepared according to the teachings of U.S. Pat. No. 6,268,444 and has the following structure: [ka] .

[0201] (Cat 8) can be prepared according to the teachings of U.S. Patent Application Publication No. 2003 / 004286 and has the following structure: [ka] .

[0202] (Cat 9) can be prepared according to the teachings of U.S. Patent Application Publication No. 2003 / 004286 and has the following structure: [ka] .

[0203] (Cat10) is commercially available from Sigma-Aldrich and has the following structure: [ka] .

[0204] (Cat11) can be prepared according to the teachings of WO2017 / 173080A1 and has the following structure: [ka] .

[0205] (Cat12) can be prepared according to the teachings of WO2017 / 173080A1 and has the following structure: [ka] .

[0206] (Cat13) can be prepared according to the teachings of Macromolecules (Washington, DC, USA), 43(19), 7903-7904 (2010) and has the following structure: [ka] .

[0207] (Cat 14) can be prepared according to the teachings of WO2011 / 102989A1 and has the following structure: [ka] .

[0208] (Cat 15) can be prepared according to the teachings of U.S. Pat. No. 8,101,696 B2 and has the following structure: [ka] .

[0209] (Cat16) can be prepared according to the teachings of WO2018 / 170138A1 and has the following structure: [ka] .

[0210] (Cat17) can be prepared according to the teachings of WO2018 / 170138A1 and has the following structure: [ka] .

[0211] In certain embodiments, the (C) catalyst component comprises a procatalyst and a cocatalyst. In these embodiments, the procatalyst can be activated to form an active catalyst by combining with a cocatalyst (activator), preferably a cation-forming cocatalyst, a strong Lewis acid, or a combination thereof.

[0212] Suitable cation-forming cocatalysts include those previously known in the art for metal olefin polymerization complexes. Examples include neutral Lewis acids, e.g., C 1~30Hydrocarbyl-substituted Group 13 compounds, particularly tri(hydrocarbyl)boron compounds and their halogenated (including perhalogenated) derivatives having 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more particularly perfluorinated tri(aryl)boron compounds, most particularly tris(pentafluorophenyl)borane; non-polymeric, compatible, non-coordinating, ion-forming compounds (including the use of such compounds under oxidizing conditions), particularly the use of ammonium, phosphonium, oxonium, carbonium, silylium or sulfonium salts of compatible non-coordinating anions, or the use of ferrocenium, lead or silver salts of compatible non-coordinating anions; and combinations of the foregoing cation-forming cocatalysts and techniques. The aforementioned activating cocatalysts and activation techniques have been previously taught for various metal complexes for olefin polymerization in the following references: EP-A-277,003, U.S. Pat. Nos. 5,153,157, 5,064,802, 5,321,106, 5,721,185, 5,350,723, 5,425,872, 5,625,087, 5,883,204, 5,919,983, 5,783,512, WO 99 / 15534, and WO 99 / 42467.

[0213] Combinations of neutral Lewis acids, particularly trialkylaluminum compounds having 1-4 carbons in each alkyl group and halogenated tri(hydrocarbyl)boron compounds having 1-20 carbons in each hydrocarbyl group, particularly tris(pentafluorophenyl)borane, further combinations of such neutral Lewis acid mixtures with polymeric or oligomeric alumoxanes, and single neutral Lewis acids, particularly tris(pentafluorophenyl)borane with polymeric or oligomeric alumoxanes, can be used as activating cocatalysts. Exemplary molar ratios of metal complex:tris(pentafluorophenyl-borane:alumoxane) are 1:1:1 to 1:5:20, for example 1:1:1.5 to 1:5:10.

[0214] Suitable ion-forming compounds useful as cocatalysts in one embodiment of the present disclosure comprise a cation that is a Bronsted acid capable of donating a proton, and a compatible non-coordinating anion A - As used herein, the term "non-coordinating" refers to anions or substances that do not coordinate to Group 4 metal-containing precursor complexes and catalytic derivatives derived therefrom, or that only weakly coordinate to such complexes, thereby remaining sufficiently unstable to be displaced by a neutral Lewis base. Non-coordinating anions specifically refer to anions that, when functioning as charge-balancing anions in cationic metal complexes, do not transfer anionic substituents or fragments thereof to the cation, thereby forming a neutral complex. "Compatible anions" are anions that do not decompose to neutrality when the initially formed complex decomposes, and do not interfere with the desired subsequent polymerization or other uses of the complex.

[0215] Suitable anions are those that contain a single coordination complex containing a charge-bearing metal or metalloid core that can balance the charge of the active catalytic species (metal cation) that can be formed when the two components are combined. The anion should also be sufficiently labile to be displaced by olefinic, diolefinic and acetylenic unsaturated compounds, or other neutral Lewis bases, such as ethers or nitriles. Suitable metals include, but are not limited to, aluminum, gold, and platinum. Suitable metalloids include, but are not limited to, boron, phosphorus, and silicon. Compounds containing anions that contain coordination complexes containing a single metal or metalloid atom are, of course, well known, and many such compounds are commercially available, especially those containing a single boron atom in the anion portion.

[0216] In one embodiment, a suitable cocatalyst has the general formula: (L * -H) g +(A) g- In the formula: L * is a neutral Lewis base, (L * -H) + , L * is a conjugated Brønsted acid of A g- is a non-coordinating, compatible anion having a charge of g-, where g is an integer from 1 to 3.

[0217] More specifically, A g- is the formula: [M'Q4] - where: M' is boron or aluminum in the +3 formal oxidation state; Each occurrence of Q is independently selected from hydride, dialkylamide, halide, hydrocarbyl, hydrocarbyl oxide, halo-substituted hydrocarbyl, halo-substituted hydrocarbyloxy, and halo-substituted silyl hydrocarbyl radicals (including perhalogenated hydrocarbyl-perhalogenated hydrocarbyloxy- and perhalogenated silyl hydrocarbyl radicals), with each Q having up to 20 carbons, provided that in no more than one occurrence Q is a halide. Examples of suitable hydrocarbyl oxide Q groups are disclosed in U.S. Patent No. 5,296,433.

[0218] In an exemplary embodiment, g is 1, i.e., the counterion has a single negative charge and A - Boron-containing activating cocatalysts that are particularly useful in preparing the catalysts of the present disclosure have the general formula: (L * -H) + (BQ4) - In the formula: L * is as previously defined, B is boron in the formal oxidation state of 3; Q is a hydrocarbyl, hydrocarbyloxy, fluorinated hydrocarbyl, fluorinated hydrocarbyloxy, or fluorinated silylhydrocarbyl group of up to 20 non-hydrogen atoms, provided that in no more than one occurrence, Q is hydrocarbyl.

[0219] Particularly useful Lewis base salts are ammonium salts, more preferably containing one or more C 12~40 In this embodiment, for example, each occurrence of Q can be a fluorinated aryl group, particularly a pentafluorophenyl group.

[0220] Illustrative, but non-limiting examples of boron compounds that may be used as activating cocatalysts in the preparation of the improved catalysts of the present disclosure include trisubstituted ammonium salts, e.g., trimethylammonium tetrakis(pentafluorophenyl)borate, triethylammonium tetrakis(pentafluorophenyl)borate, tripropylammonium tetrakis(pentafluorophenyl)borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl)borate, N,N-dimethylanilinium benzyltris(pentafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl)borate, N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl)borate, N,N-diethylanilinium tetrakis(pentafluorophenyl)borate, N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl)borate, dimethyloctadecylammonium tetrakis(pentafluorophenyl)borate, methyldioctadecylammonium tetrakis(pentafluorophenyl)borate, Many dialkylammonium salts, e.g. di-(i-propyl)ammonium tetrakis(pentafluorophenyl)borate, methyloctadecylammonium tetrakis(pentafluorophenyl)borate, Methyloctadecylammonium tetrakis(pentafluorophenyl)borate, and dioctadecylammonium tetrakis(pentafluorophenyl)borate, Various trisubstituted phosphonium salts, e.g. triphenylphosphonium tetrakis(pentafluorophenyl)borate, Methyldioctadecylphosphonium tetrakis(pentafluorophenyl)borate, and tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl)borate, Disubstituted oxonium salts, for example diphenyloxonium tetrakis(pentafluorophenyl)borate, di(o-tolyl)oxonium tetrakis(pentafluorophenyl)borate, Di(octadecyl)oxonium tetrakis(pentafluorophenyl)borate, and Disubstituted sulfonium salts, for example Di(o-tolyl)sulfonium tetrakis(pentafluorophenyl)borate, and Methylcotadecylsulfonium tetrakis(pentafluorophenyl)borate is an example.

[0221] In addition to this aspect of the disclosure, useful (L * -H) + Examples of cations include methyldioctadecylammonium cation, dimethyloctadecylammonium cation, and cations with one or two C14~18 These include, but are not limited to, ammonium cations derived from a mixture of trialkylamines containing alkyl groups.

[0222] Another suitable ion-forming activating cocatalyst is a cationically oxidizing agent and a compound of the formula: (Ox h+ ) g (A g- ) h In one embodiment, the salt includes a salt with a non-coordinating compatible anion represented by the formula: Ox h+ is a cationic oxidant having an h+ charge, h is an integer from 1 to 3; A g- and g is as defined above.

[0223] Examples of cationic oxidizing agents include ferrocenium, hydrocarbyl-substituted ferrocenium, Ag + , or Pb +2 Examples include: A g- Particularly useful examples are the anions defined above for the Bronsted acid-containing activating cocatalyst, especially tetrakis(pentafluorophenyl)borate.

[0224] Other suitable ion-forming activating cocatalysts include a carbenium ion and a cation-forming cocatalyst of the formula: [C] + A - and a compound which is a salt with a non-coordinating compatible anion represented by During the ceremony, [C] + is C 1~20 is a carbenium ion, It is a non-coordinating, compatible anion having a charge of −1. For example, one carbenium ion that works well is the trityl cation, or triphenylmethylium.

[0225] Further suitable ion-forming activating cocatalysts include those having a silylium ion and the following formula: (Q 1 3Si) +A - The compound includes a compound which is a salt with a non-coordinating compatible anion represented by During the ceremony, Q 1 is C 1~10 A is a hydrocarbyl. - is as defined above.

[0226] Suitable silylium salt activating cocatalysts include trimethylsilyl tetrakis pentafluorophenyl borate, triethylsilylium tetrakis pentafluorophenyl borate, and their ether-substituted adducts.Silylium salts have been previously disclosed in general in J.Chem.Soc.Chem.Comm.1993,383-384 and Lambert,JB,et al.,Organometallics 1994,13,2430-2443.The use of the above silylium salts as activating cocatalysts for addition polymerization catalysts is also described in U.S. Patent No. 5,625,087.

[0227] Certain complexes of alcohols, mercaptans, silanols, and oximes with tris(pentafluorophenyl)borane are also effective catalyst activators and may be used in accordance with the present disclosure. Such cocatalysts are disclosed in U.S. Patent No. 5,296,433.

[0228] Activating cocatalysts suitable for use herein also include polymeric or oligomeric alumoxanes (also called aluminoxanes), particularly methylalumoxane (MAO), triisobutylaluminum-modified methylalumoxane (MMAO), or isobutylalumoxane; Lewis acid-modified alumoxanes, particularly perhalogenated tri(hydrocarbyl)aluminum- or perhalogenated tri(hydrocarbyl)boron-modified alumoxanes having 1 to 10 carbons in each hydrocarbyl or hydrocarbyl halide group, most particularly tris(pentafluorophenyl)borane-modified alumoxanes. Such cocatalysts have been previously disclosed in U.S. Patent Nos. 6,214,760, 6,160,146, 6,140,521, and 6,696,379.

[0229] The class of cocatalysts containing non-coordinating anions, commonly referred to as expanding anions, further disclosed in U.S. Patent No. 6,395,671, may be suitably used to activate the metal complexes of the present disclosure for olefin polymerization. In general, these cocatalysts (exemplified by those having an imidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide, or substituted benzimidazolide anion) can be represented as follows: [ka] During the ceremony, A *+ is a cation, particularly a proton-containing cation, and also contains one or two C 10~40 Trihydrocarbyl ammonium cations containing alkyl groups, especially methyldi(C 14~20 alkyl)ammonium cation, Q 3 each occurrence independently represents hydrogen, or a halo, hydrocarbyl, halocarbyl, halohydrocarbyl, silylhydrocarbyl, or silyl (e.g., mono-, di-, and tri(hydrocarbyl)silyl) group of up to 30 atoms, not counting hydrogen, such as C 1~20 is alkyl, Q 2 is tris(pentafluorophenyl)borane, or tris(pentafluorophenyl)almane.

[0230] Examples of these catalyst activators include trihydrocarbyl ammonium salts, in particular the methyl di(C 14~20 Alkyl)ammonium salts include: Bis(tris(pentafluorophenyl)borane)imidazolide, Bis(tris(pentafluorophenyl)borane)-2-undecylimidazolide, Bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolide, Bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolide, Bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolide, Bis(tris(pentafluorophenyl)borane)imidazolinide, Bis(tris(pentafluorophenyl)borane)-2-undecylimidazolinide, Bis(tris(pentafluorophenyl)borane)-2-heptadecylimidazolinide, Bis(tris(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazolinide, Bis(tris(pentafluorophenyl)borane)-4,5-bis(heptadecyl)imidazolinide, Bis(tris(pentafluorophenyl)borane)-5,6-dimethylbenzimidazolide, Bis(tris(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazolide, Bis(tris(pentafluorophenyl)almane)imidazolide, Bis(tris(pentafluorophenyl)almane)-2-undecylimidazolide, Bis(tris(pentafluorophenyl)alumane)-2-heptadecylimidazolide, Bis(tris(pentafluorophenyl)almane)-4,5-bis(undecyl)imidazolide, Bis(tris(pentafluorophenyl)almane)-4,5-bis(heptadecyl)imidazolide, Bis(tris(pentafluorophenyl)almane)imidazolinide, Bis(tris(pentafluorophenyl)alumane)-2-undecylimidazolinide, Bis(tris(pentafluorophenyl)almane)-2-heptadecylimidazolinide, Bis(tris(pentafluorophenyl)almane)-4,5-bis(undecyl)imidazolinide, Bis(tris(pentafluorophenyl)almane)-4,5-bis(heptadecyl)imidazolinide, Bis(tris(pentafluorophenyl)almane)-5,6-dimethylbenzimidazolide, and Bis(tris(pentafluorophenyl)alumane)-5,6-bis(undecyl)benzimidazolide.

[0231] Other activators include those described in PCT Publication WO 98 / 07515, such as tris(2,2',2''-nonafluorobiphenyl)fluoroaluminate. Combinations of activators, such as alumoxanes and ionizing activators, are also contemplated by the present disclosure, see, for example, EP-A-0573120, PCT Publications WO 94 / 07928 and WO 95 / 14044, and U.S. Pat. Nos. 5,153,157 and 5,453,410. For example, and in general terms, WO 98 / 09996 describes the use of perchlorates, periodates, and iodates (including their hydrates) to activate catalyst compounds. WO 99 / 18135 describes the use of organoboron aluminum activators. WO 03 / 10171 discloses catalyst activators that are adducts of Bronsted and Lewis acids. Other activators or methods for activating catalyst compounds are described, for example, in U.S. Patent Nos. 5,849,852, 5,859,653, and 5,869,723, EP-A-615981, and PCT Publication WO98 / 32775.According to the present disclosure, all of the above catalyst activators as well as any other known activators for transition metal complex catalysts can be used alone or in combination.However, in one embodiment, the cocatalyst may not include alumoxane.In another embodiment, for example, the cocatalyst may not include any specifically named activator or class of activators as disclosed herein.

[0232] In further embodiments, the molar ratio of procatalyst / cocatalyst used is generally in the range of 1:10,000 to 100:1, such as 1:5000 to 10:1 or 1:1000 to 1:1. When used by itself as an activating cocatalyst, alumoxanes can be used in large amounts, generally at least 100 times the amount of metal complex on a molar basis.

[0233] When used as an activating cocatalyst, tris(pentafluorophenyl)borane can generally be used in a molar ratio to the metal complex of 0.5:1 to 10:1, such as 1:1 to 6:1 and 1:1 to 5:1. The remaining activating cocatalyst is generally used in about equimolar amounts to the metal complex.

[0234] In an exemplary embodiment of the present disclosure, the cocatalyst is [(C 16-18 H 33-37 )-2CH3NH]tetrakis(pentafluorophenyl)borate salt.

[0235] Suitable cocatalysts also include those disclosed in U.S. Provisional Patent Applications Nos. 62650423, 62650412, and 62650453, which are incorporated by reference in their entireties. Such cocatalysts include ionic complexes comprising an anion and a countercation, where the anion has the structure: [ka] wherein M is aluminum, boron, or gallium; n is 2, 3, or 4; and each R is independently selected from the group consisting of groups (II) and (III); [ka] Each Y is independently carbon or silicon, and each R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , and R 25are independently 40 ) Alkyl, (C6-C 40 ) Aryl, -OR C , -O-, -SR C , -H, or -F, where R is a group according to group (III), R 21~25 At least one of the following is halogen-substituted (C1-C 40 ) Alkyl, halogen-substituted (C6-C 40 ) aryl, or -F, provided that when each R is a group (II) and Y is carbon, then R 11~13 At least one of the following is halogen-substituted (C1-C 40 ) Alkyl, halogen-substituted (C6-C 40 ) aryl, or -F; or when M is aluminum and n is 4 and each R is a group (II) and each Y is carbon, each R of each R 11 , R 12 , and R 13 is halogen-substituted (C1-C 40 ) Alkyl, halogen-substituted (C6-C 40 ) aryl, or -F; or R 11 , R 12 , and R 13 The total number of halogen atoms in is at least 6, and each X is independently a halogen substitution (C1 to C 20 ) Alkyl, (C1-C 20 ) Alkyl, halogen-substituted (C6-C 40 )Aryl, (C6-C 40 ) a monodentate ligand selected from aryl, triflate, or -S(O)3, optionally with two groups R covalently bonded, and each R N and R C are independently 30 ) hydrocarbyl or -H.

[0236] Such cocatalysts further include bimetallic activator complexes comprising an anion and a countercation, the anion having the structure: [ka] wherein each M is independently aluminum, boron, or gallium; L is selected from a species having at least two Lewis basic sites; each Q is independently a monodentate ligand; n is 0, 1, or 2, where when n is 0, Q is not present; x is 0, 1, or 2, where when x is 0, Q is not present; and each R is independently selected from the group consisting of groups (II) and (III); [ka] Each Y is independently carbon or silicon, and each R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , and R 25 are independently 40 ) Alkyl, (C6-C 40 ) Aryl, -H, -NR N 2, -OR C , -SR C or halogen, wherein when R is group (II), R 11~13 At least one of the following is perhalogenated (C1-C 40 ) Alkyl, Perhalogenated (C6-C 40 ) aryl, or -F, and where R is group (III), R 21~25 At least one of the following is perhalogenated (C1-C 40 ) Alkyl, Perhalogenated (C6-C 40 ) aryl, or -F, and optionally when n is 0 or 1, the two R groups are covalently bonded, and each R N or R C are independently 30 ) hydrocarbyl or -H.

[0237] Such cocatalysts further include metal activators comprising an anion and a counter cation, the anion having the structure: [ka] wherein n is 0 or 1, and each R is independently selected from the group consisting of groups (II) and (III); [ka] Each Y is independently carbon or silicon, and each R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , and R 25 are independently (C1~C 40 ) Alkyl, halogen-substituted (C1-C 40 ) Alkyl, (C6-C 40 )Aryl, halogen-substituted (C6-C 40 ) Aryl, -OR C , -SR C , -H, -F, or Cl; R 11~13 At least one of and R 21~25 One of them is halogen-substituted (C1-C 40 ) Alkyl, halogen-substituted (C6-C 40 ) aryl, or -F, and each X is independently a halogen substituted (C 20 ) Alkyl or halogen substituted (C6-C 40 ) aryl; and optionally, the two X groups are covalently linked, and each R C are independently halogen-substituted (C1-C 30 ) hydrocarbyl, provided that the counter cation is (Ph)C + where the anion is Al(C6F5)4.

[0238] Intended and end use The telechelic polyolefins of the present disclosure can be used in a variety of conventional manufacturing processes to produce useful articles, including objects prepared by casting, blowing, calendaring, or extrusion processes, such as blow-molded, injection-molded, or rotational molded articles, extrudates, fibers, and woven or nonwoven fabrics. Compositions comprising the telechelic polyesters of the present disclosure may further comprise, but are not limited to, other natural or synthetic polymers, oils, UV stabilizers, pigments, tackifiers, fillers (such as talc, calcium carbonate, glass fiber, carbon fiber, etc.), additives, reinforcing agents such as calcium carbonate or magnesium carbonate, fatty acids and their salts, ignition resistance additives, scorch inhibitors, antioxidants, stabilizers, colorants, extenders, carbon black, crosslinking agents, foaming agents, activators such as zinc oxide or zinc stearate, silica, aluminum silicate, plasticizers such as dialkyl esters of dicarboxylic acids, antidegradants, softeners, waxes, (poly)alcohols, (poly)alcohol ethers, polyesters, metal salts, scavengers, nucleating agents, stability control agents, flame retardants, lubricants, processing aids, extrusion aids, and chemical protectants.

[0239] Particularly useful are curable formulations that include telechelic polyolefins of formula (I). In some embodiments, the curable formulations that include telechelic polyolefins of formula (I) can be cured by E-beam (electron beam) without the need for a crosslinker. In further embodiments, the curable formulations further include a crosslinker and may also include coagents, curing additives, scorch inhibitors, and / or accelerators. The curable formulations that further include a crosslinker can have their rheology modified by E-beam curing.

[0240] Non-limiting examples of suitable crosslinking agents include peroxides, phenols, azides, aldehyde-amine reaction products, substituted ureas, substituted guanidines, substituted xanthates, substituted dithiocarbamates, sulfur-containing compounds such as thiazoles, sulfenamides, thiuramidisulfides, paraquinonedioxime, dibenzoparaquinonedioxime, sulfur, imidazoles, silanes, metal oxides such as zinc oxide, magnesium oxide, lead oxide, dinitroso compounds such as p-quinonedioxime and p,p'-dibenzoylquinonedioxime, phenol-formaldehyde resins containing hydroxymethyl or halomethyl functional groups, and combinations thereof. The suitability of any of these crosslinking agents will be largely governed by the choice of polymer, as is well known to those skilled in the art of compounding.

[0241] Crosslinking agents may include one or more organic peroxides, including but not limited to alkyl peroxides, aryl peroxides, peroxyesters, peroxycarbonates, diacyl peroxides, peroxyketals, cyclic peroxides, dialkyl peroxides, peroxyesters, peroxydicarbonates, or combinations of two or more thereof. Examples of peroxides include, but are not limited to, di-tert-butyl peroxide, dicumyl peroxide, di(3,3,5-trimethylhexanoyl)peroxide, t-butyl peroxypivalate, t-butyl peroxyneodecanoate, di(sec-butyl) peroxydicarbonate, t-amyl peroxyneodecanoate, 1,1-di-t-butylperoxy-3,3,5-trimethylcyclohexane, t-butylcumyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxyl)hexane, 1,3-bis(tert-butyl-peroxyl-isopropyl)benzene, or combinations thereof. An exemplary crosslinking agent is dicumyl peroxide, available from Arkema under the trade name LUPEROX® or from Akzo Nobel under the trade name TRIGONOX®. A further exemplary crosslinking agent is VAROX® DBPH-50 from Vanderbilt Chemicals. When the crosslinking agent is a peroxide, certain processing aids and cure activators such as stearic acid and ZnO may also be used.

[0242] When peroxide-based curing agents are used, co-activators or co-agents may be used in combination therewith. Suitable co-agents include, but are not limited to, trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), and 1,4-phenylenedimaleimide (available from TCI Chemicals).

[0243] Suitable coagents further include, but are not limited to, alkenyl-functional monocyclic organosiloxanes disclosed in WO2019 / 000311 and WO2019 / 000654, the entireties of which are incorporated herein by reference. For example, the coagent may be a monocyclic organosiloxane of the formula [R1,R2SiO2 / 2]n, where the subscript n is an integer equal to or greater than 3, each R1 is independently (C2-C4)alkenyl or H2C=C(R1a)-C(=O)-O-(CH2)m-, where R1a is H or methyl, the subscript m is an integer from 1 to 4, and each R2 is independently H, (C1-C4)alkyl, phenyl, or R1. Examples of such monocyclic organosiloxanes include, but are not limited to, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6-trimethyl-2,4,6-trivinylcyclotrisiloxane, or combinations thereof.

[0244] A scorch inhibitor / retarder is a molecule or group of such molecules that inhibits premature curing. Examples of scorch inhibitors / retarders are hindered phenols, semi-hindered phenols, TEMPO, TEMPO derivatives, 1,1-diphenylethylene, 2,4-diphenyl-4-methyl-1-pentene (also known as α-methylstyrene dimer or AMSD), and allyl-containing compounds as described in US6277925B1, column 2, line 62 to column 3, line 46.

[0245] Suitable crosslinkers include those based on sulfur, such as elemental sulfur. When sulfur-based curing agents are used, they may be amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates, xanthates, 4,4'-dithiodimorpholine, thiuram di- and polysulfides, alkylphenol disulfides and 2-morpholino-dithiobenzothiazoles, tetramethylthiuram disulfide (TMTD), dipentamethylenethiuram tetrasulfide (DPTT), 2-mercapto ... Accelerators and cure activators such as mercaptobenzothiazolate disulfide (MBT), 2-mercaptobenzothiazolate disulfide (MBTS), zinc-2-mercaptobenzothiazolate (ZMBT), zinc diethyldithiocarbamate (ZDEC), zinc dibutyldithiocarbamate (ZDBC), dipentamethylene thiuram tetrasulfide (DPTT), Nt-butylbenzothiazole-2-sulfenamide (TBBS), and mixtures thereof may be used as well.

[0246] Further crosslinkers include, but are not limited to, phenolic resins, azides, aldehyde-amine reaction products, vinyl silanes, hydrosilylating agents, substituted ureas, substituted guanidines, substituted xanthates, substituted dithiocarbamates, and combinations thereof. The crosslinker can be a phenolic or peroxide curing agent with an optional coagent, or a hydrosilation crosslinking agent with a hydrosilation catalyst, or dibutyltin dilaurate ("DBTDL") with an optional coagent alumina trihydrate ("ATH"). Popular industrial catalysts are "Speier's catalyst", HPtCl, and Karstedt's catalyst, which is an alkene-stabilized platinum(0) catalyst.

[0247] If a crosslinking agent is used, crosslinking can be induced by activating the crosslinking agent in the curable formulation. The crosslinking agent can be activated by exposing it to a temperature above its decomposition temperature. The temperature ranges from 50° C. to 300° C., for example, from 80° C. to 275° C. The time can be determined by one skilled in the art depending on the polymer and curing components selected.

[0248] Alternatively, the crosslinking agent can be activated by exposing it to radiation that causes the crosslinking agent to produce free radicals. Non-limiting examples of suitable radiation include UV or visible radiation, electron beam, or beta, gamma, X-ray, or neutron radiation. Radiation is believed to activate crosslinking by producing radicals in the polymer, which can subsequently bond and crosslink. The radiation dose depends on many factors and can be determined by those skilled in the art. If the crosslinking agent is a peroxide photoinitiator, such as dibenzoyl peroxide, cumene hydroperoxide, di-t-butyl peroxide, diacetyl peroxide, hydrogen peroxide, peroxy disulfate, and 2,2-bis(tert-butylperoxy)-2,5-dimethylhexane, UV or visible radiation activation can be performed.

[0249] In some embodiments, a dual cure system comprising at least two activation methods, such as a combination selected from heat, moisture cure, and radiation, can be effectively used. For example, it may be desirable to use a peroxide crosslinker in combination with a silane crosslinker, a peroxide crosslinker in combination with radiation, a sulfur-containing crosslinker in combination with a silane crosslinker, etc. Those skilled in the art will be able to easily select the amount of crosslinker based on the desired crosslinking level, the properties of the polymer, such as molecular weight, molecular weight distribution, comonomer content, the presence of crosslinking promoters, other additives, etc.

[0250] When the telechelic polyolefin-containing composition is at least partially crosslinked, the degree of crosslinking can be measured by dissolving the composition in a solvent for a specified period of time and calculating the percentage of gel or non-extractable components. The percentage of gel typically increases with increasing crosslinking levels. For cured articles according to the present invention, the percentage gel content desirably ranges from 0 to 100 percent, or from 5 to 100 percent, or from 10 to 95 percent, or from 20 to 90 percent, or from 30 to 85 percent, or from 40 to 80 percent.

[0251] Fibers can be prepared from the telechelic polyolefins. Fibers that can be prepared include staple fibers, coarse linen, multicomponent, sheath / core, twisted, and monofilament. Suitable fiber-forming processes include spin-bonded melt-blowing technology as disclosed in U.S. Pat. Nos. 4,430,563, 4,663,220, 4,668,566, and 4,322,027, gel-spun fibers as disclosed in U.S. Pat. No. 4,413,110, woven and nonwoven fabrics as disclosed in U.S. Pat. No. 3,485,706, or blends with other fibers such as polyester, nylon, or cotton, thermoformed articles, extruded shapes including profile extrusions or coextrusions, calendered articles, and structures made from such fibers, including drawn, twisted, or crimped yarns or fibers. The new polymers described herein are also useful in wire and cable coating operations, in sheet extrusion for vacuum forming operations, and in forming molded articles, including using injection molding, blow molding processes, or rotational molding processes. Compositions containing telechelic polyolefins can also be formed into articles such as those mentioned above using conventional polyolefin processing techniques well known to those skilled in the art of polyolefin processing.

[0252] The telechelic polyolefins or formulations containing same can also be used to form dispersions (both aqueous and non-aqueous).

[0253] Any formulation containing this telechelic polyolefin can contain additives and adjuvants.Suitable additives include fillers, such as clay, talc, titanium dioxide, zeolite, organic or inorganic particles, including powdered metals, carbon fibers, silicon nitride fibers, steel wire or mesh, and organic or inorganic fibers, including nylon or polyester cords, nano-sized particles, clay, etc.; tackifiers, oil extenders, including paraffin oil or naphthenic oil; and other natural and synthetic polymers, including other polymers according to the present invention.

[0254] Suitable polymers for blending with the telechelic polyolefins of the present disclosure include thermoplastic and non-thermoplastic polymers, including natural and synthetic polymers, including unsaturated polyolefin thermoplastics (EPDM, polybutadiene, etc.), polyolefin thermoplastics with low or no unsaturation (PE, PP, ethylene / α-olefin interpolymers), other elastomers (SBC, PVC, EVA, ionomers, etc.), and other engineering thermoplastics (styrenes, polyamides, polyesters, etc.). Exemplary polymers for blends include polypropylene (both impact modified, isotactic, atactic, and random ethylene / propylene copolymers), various types of polyethylene (including high pressure free radical LDPE, Ziegler-Natta LLDPE, metallocene PE, including multiple reactor PE ("in reactor" blends of Ziegler-Natta PE and metallocene PE, such as the products disclosed in U.S. Pat. Nos. 6,545,088, 6,538,070, 6,566,446, 5,844,045, 5,869,575, and 6,448,341), ethylene-vinyl acetate (EVA), ethylene / vinyl alcohol copolymers, polystyrene, impact modified polystyrene, ABS, styrene / butadiene block copolymers and their hydrogenated derivatives (SBS and SEBS), ethylene-based olefin block copolymers (e.g., the Dow Chemical Examples of suitable polyurethanes include those available under the trade name INFUSE™ available from The Dow Chemical Company, propylene-based olefin block copolymers (e.g., those available under the trade name INTUNE™ available from The Dow Chemical Company), and thermoplastic polyurethanes.Homogeneous polymers such as olefin plastomers, and elastomers such as ethylene / α-olefin copolymers and propylene-based copolymers with low or no unsaturation (e.g., polymers available under the trade names VERSIFY™ available from The Dow Chemical Company, ENGAGE™ available from The Dow Chemical Company, TAFMER™ from Mitsui Chemicals, Exact™ from ExxonMobil, and VISTAMAXX™ from ExxonMobil) may also be useful as components of blends comprising the present polymer.

[0255] Suitable end uses include crosslinkable or non-crosslinkable formulations for films; fibers; soft touch articles such as toothbrush handles and appliance handles; gaskets and profiles; adhesives (functional, crosslinkable, hot melt adhesives); footwear (including soles and shoe liners); automotive interior parts and profiles; foam articles (both open and closed cell); impact modifiers for other thermoplastic polymers such as high density polyethylene, isotactic polypropylene, or other olefin polymers; coated fabrics; hoses; tubing; weather stripping; cap lines. applications include: painters; flooring; construction or building components; woodworking; coatings (powder coatings, water-based coatings for beverage and food liners, solvent-based coatings for industrial metal coatings); waterproofing; photovoltaic applications; wire and cable applications; thermoplastic vulcanizate (TPV) applications; EPDM thermosets; seals, belts, conveyor belts, automotive timing belts, etc., gaskets, dampers; tire compounds; highly filled compounds, sidewall and tread compounds; auxiliary agents for thermoset rubber; crosslinked tubing; liquid (low viscosity) reaction injection molding; injection molded skins; 3D printing; and piping.

[0256] The composition may also contain antiozonants or antioxidants known to a rubber chemist of ordinary skill. Antiozonants may be physical protectants, such as wax-like materials that come to the surface and protect the part from oxygen or ozone, or chemical protectants that react with oxygen or ozone. Suitable chemical protectants include styrenated phenol, butylated octylated phenol, butylated di(dimethylbenzyl)phenol, p-phenylenediamine, butylated reaction products of p-cresol with dicyclopentadiene (DCPD), polyphenolic antioxidants, hydroquinone derivatives, quinolines, diphenylene antioxidants, thioester antioxidants, and blends thereof. Some representative trade names for such products include Wingstay™ S Antioxidant, Polystay™ 100 Antioxidant, Polystay™ 100AZ Antioxidant, Polystay™ 200 Antioxidant, Wingstay™ L Antioxidant, Wingstay™ LHLS Antioxidant, Wingstay™ K Antioxidant, Wingstay™ 29 Antioxidant, Wingstay™ SN-1 Antioxidant, and Irganox™ Antioxidant. In some applications, the antioxidants and antiozonants used will preferably be non-staining and non-migratory.

[0257] Hindered amine light stabilizers (HALS) and UV absorbers can also be used to provide additional stability against UV radiation.Suitable examples include Tinuvin 123, Tinuvin 144, Tinuvin 622, Tinuvin 765, Tinuvin 770, and Tinuvin 780 available from Ciba Specialty Chemicals, and Chemisorb T944 available from Cytex Plastics, Houston, Texas, USA.As disclosed in U.S. Patent No. 6,051,681, Lewis acids can be included together with HALS compounds to achieve superior surface quality.

[0258] For some compositions, a further mixing process can be used to pre-disperse antioxidants, antiozonants, carbon black, UV absorbers, and / or light stabilizers to form a masterbatch from which the polymer blend is subsequently formed.

[0259] The composition according to the invention may also contain organic or inorganic fillers or other additives, such as starch, talc, calcium carbonate, glass fibers, polymeric fibers (including nylon, rayon, cotton, polyester, and polyaramid), metal fibers, flakes or particles, clay, mica, silica, alumina, expandable layered silicates such as aluminosilicates or aluminophosphates, phosphates or carbonates, carbon whiskers, carbon fibers, nanoparticles including nanotubes, wollastonite, graphite, zeolites, and ceramics such as silicon carbide, silicon nitride, or titania. For better filler bonding, silane-based or other coupling agents may also be used.

[0260] Suitable blowing agents include, but are not limited to, inorganic blowing agents, organic blowing agents, chemical blowing agents, and combinations thereof. Non-limiting examples of suitable inorganic blowing agents include carbon dioxide, nitrogen, argon, water, air, nitrogen, and helium. Non-limiting examples of suitable organic blowing agents include aliphatic hydrocarbons having 1-6 carbon atoms, aliphatic alcohols having 1-3 carbon atoms, and fully and partially halogenated aliphatic hydrocarbons having 1-4 carbon atoms. Non-limiting examples of suitable aliphatic hydrocarbons include methane, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, and the like. Non-limiting examples of suitable aliphatic alcohols include methanol, ethanol, n-propanol, and isopropanol. Non-limiting examples of suitable fully and partially halogenated aliphatic hydrocarbons include fluorocarbons, chlorocarbons, and chlorofluorocarbons. Non-limiting examples of suitable fluorocarbons include methyl fluoride, perfluoromethane, ethyl fluoride, 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), pentafluoroethane, difluoromethane, perfluoroethane, 2,2-difluoropropane, 1,1,1-trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, and perfluorocyclobutane. Non-limiting examples of suitable partially halogenated chlorocarbons and chlorofluorocarbons include methyl chloride, methylene chloride, ethyl chloride, 1,1,1-trichloroethane, 1,1-dichloro-1-fluoroethane (HCFC-14Ib), 1-chloro-1,1-difluoroethane (HCFC-142b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), and 1-chloro-1,2,2,2-tetrafluoroethane (HCFC-124).Non-limiting examples of suitable fully halogenated chlorofluorocarbons include trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1,1-trifluoroethane, pentafluoroethane, dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane, and dichlorohexafluoropropane. Non-limiting examples of suitable chemical blowing agents include azodicarbonamide, azodiisobutyronitrile, benzenesulfonhydrazide, 4,4-oxybenzenesulfonyl-semicarbazide, p-toluenesulfonylsemicarbazide, barium azodicarboxylate, N,N'-dimethyl-N,N'-dinitrosoterephthalamide, and trihydrazinotriazine. In some embodiments, the blowing agent is azodicarbonamide isobutane, CO2, or a mixture thereof.

[0261] The telechelic polyolefins of the present disclosure may also be chemically modified, such as by grafting (e.g., by use of maleic anhydride (MAH), silanes, glycidyl methacrylate, or other grafting agents), halogenation, amination, sulfonation, or other chemical modifications.

[0262] Specific embodiments The following are non-limiting embodiments that illustrate the present invention and provide detailed disclosure for any claims in this application. Unless otherwise stated, the properties or characterizations measured in the following embodiments are in accordance with the test methods disclosed herein. 1. A composition comprising a telechelic polyolefin of formula (I), A 1 L 1 L 2 A 2 (I), in the formula L 1 is a polyolefin, A 1 is a vinyl group, formula CH2=C(Y 1 )-vinylidene group of the formula Y 1Vinylene group of CH=CH-, vinyl group and formula Y 1 A mixture of vinyl groups and vinylene groups of 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 of the formula CH=CH- and vinyl groups of the formula CH2=C(Y 1 )- and a vinylidene group of the formula Y 1 and a mixture of CH=CH- and vinylene groups; Y 1 Each time it appears, it is assigned independently to C1~C 30 is a hydrocarbyl group, L 2 But, C1~C 32 is a hydrocarbylene group, and A 2 is a hydrocarbyl group containing a hindered double bond. 2.L 2 -CH2CH(Y 2 )-, wherein Y 2 is hydrogen or C1-C 30 The composition of embodiment 1, wherein the R is a hydrocarbyl group. 3.L 1 The composition of embodiment 1 or 2, wherein is an ethylene homopolymer comprising units derived from ethylene. 4.A 1 is a vinyl group. 5.A 1 is the formula Y 1 is a vinylene group of the formula CH=CH-, 1 C1~C 30 The composition of embodiment 3, wherein the group is an alkyl group. 6.Y 1 is a methyl group. 7.A 1 is a vinyl group and the formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 C1~C 30 The composition of embodiment 3, wherein the group is an alkyl group. 8.Y1 is a methyl group. 9.A 1 is 0.99:0.1 to 0.1:0.99, vinyl group and formula Y 1 The composition of embodiment 7 or 8, comprising a ratio of CH═CH— to vinylene groups. 10.L 1 The composition of any one of the preceding claims, wherein is a propylene homopolymer comprising units derived from propylene. 11.A 1 The formula is CH2=C(Y 1 )-vinylidene group, 1 is a methyl group. 12.A 1 is the formula Y 1 is a vinylene group of the formula CH=CH-, 1 is a methyl group. 13.A 1 But the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 is, each occurrence, independently, a methyl group. 14.A 1 The formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 The composition of embodiment 13, comprising a ratio of CH═CH— to vinylene groups. 15.L 1 However, ethylene and C3-C 30 The composition of any one of the preceding embodiments, wherein the composition is an ethylene / α-olefin copolymer comprising units derived from an α-olefin and an α-olefin. 16. C3~C 30 The composition of embodiment 15, wherein the α-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene. 17. C3~C 30 The α-olefin is propylene, and L 1The composition of embodiment 16, wherein is an ethylene / propylene copolymer. 18.A 1 is a vinyl group. 19.A 1 The formula is CH2=C(Y 1 )-vinylidene group, 1 is a methyl group. 20.A 1 is the formula Y 1 is a vinylene group of the formula CH=CH-, 1 is a methyl group. 21.A 1 is a vinyl group and the formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 is a methyl group. 22.A 1 is 0.99:0.1 to 0.1:0.99, vinyl group and formula Y 1 22. The composition of embodiment 21, comprising a ratio of CH═CH— to vinylene groups. 23.A 1 is a vinyl group and the formula CH2=C(Y 1 )- and vinylidene groups, 1 is a methyl group. 24.A 1 is 0.99:0.1 to 0.1:0.99, vinyl group and formula CH2=C(Y 1 24. The composition of embodiment 23, comprising a ratio of 1 to 1 vinylidene groups. 25.A 1 is a vinyl group and a compound of the formula CH2=C(Y 1 )- and a vinylidene group of the formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 is, each occurrence, independently, a methyl group. 26.A 1 is 0.99:0.01 to 0.01:0.99, and a vinyl group and a compound represented by the formula Y 1 Vinylene group of the formula CH=CH-, CH2=C(Y 126. The composition of embodiment 25, comprising a ratio of vinylidene groups to the sum of vinyl groups of -. 27. C3~C 30 The α-olefin is 1-butene, and L 1 The composition of embodiment 16, wherein is an ethylene / 1-butene copolymer. 28.A 1 is a vinyl group. 29.A 1 The formula is CH2=C(Y 1 )-vinylidene group, 1 is an ethyl group. 30.A 1 is the formula Y 1 is a vinylene group of the formula CH=CH-, 1 is an ethyl group. 31.A 1 is a vinyl group and the formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 is an ethyl group. 32.A 1 is 0.99:0.1 to 0.1:0.99, vinyl group and formula Y 1 The composition of embodiment 31, comprising a ratio of CH═CH— to vinylene groups. 33.A 1 is a vinyl group and the formula CH2=C(Y 1 )- and vinylidene groups, 1 is an ethyl group. 34.A 1 is 0.99:0.1 to 0.1:0.99, vinyl group and formula CH2=C(Y 1 34. The composition of embodiment 33, comprising a ratio of 1 to 10 vinylidene groups. 35.A 1 is a vinyl group and a compound of the formula CH2=C(Y 1 )- and a vinylidene group of the formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 is, each occurrence, independently, an ethyl group. 36.A 1 is 0.99:0.01 to 0.01:0.99, and a vinyl group and a compound represented by the formula Y 1 Vinylene group of the formula CH=CH-, CH2=C(Y 1 36. The composition of embodiment 35, comprising a ratio of vinylidene groups to the sum of vinyl groups of -. 37. C3~C 30 The α-olefin is 1-hexene, and L 1 The composition of embodiment 16, wherein is an ethylene / 1-hexene copolymer. 38.A 1 is a vinyl group. 39.A 1 The formula is CH2=C(Y 1 )-vinylidene group, 1 is a butyl group. 40.A 1 is the formula Y 1 is a vinylene group of the formula CH=CH-, 1 is a butyl group. 41.A 1 is a vinyl group and the formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 is a butyl group. 42.A 1 is 0.99:0.1 to 0.1:0.99, vinyl group and formula Y 1 The composition of embodiment 41, comprising a ratio of CH═CH— to vinylene groups. 43.A 1 is a vinyl group and the formula CH2=C(Y 1 )- and vinylidene groups, 1 is a butyl group. 44.A 1 is 0.99:0.1 to 0.1:0.99, vinyl group and formula CH2=C(Y 1 The composition of embodiment 43, comprising a ratio of 1 to 10 vinylidene groups. 45.A 1 is a vinyl group and a compound of the formula CH2=C(Y1 )- and a vinylidene group of the formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 is, independently at each occurrence, a butyl group. 46.A 1 is 0.99:0.01 to 0.01:0.99, and a vinyl group and a compound represented by the formula Y 1 Vinylene group of the formula CH=CH-, CH2=C(Y 1 46. ​​The composition of embodiment 45, comprising a ratio of vinylidene groups to the sum of vinyl groups of -. 47. C3~C 30 The α-olefin is 1-octene, and L 1 The composition of embodiment 16, wherein is an ethylene / 1-octene copolymer. 48.A 1 is a vinyl group. 49.A 1 The formula is CH2=C(Y 1 )-vinylidene group, 1 is a C6 alkyl group. 50.A 1 is the formula Y 1 is a vinylene group of the formula CH=CH-, 1 is a C6 alkyl group. 51.A 1 is a vinyl group and the formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 is a C6 alkyl group. 52.A 1 is 0.99:0.1 to 0.1:0.99, vinyl group and formula Y 1 The composition of embodiment 51, comprising a ratio of CH═CH— to vinylene groups. 53.A 1 is a vinyl group and the formula CH2=C(Y 1 )- and vinylidene groups, 1 is a C6 alkyl group. 54.A 1is 0.99:0.1 to 0.1:0.99, vinyl group and formula CH2=C(Y 1 54. The composition of embodiment 53, comprising a ratio of 1 to 10 vinylidene groups. 55.A 1 is a vinyl group and a compound of the formula CH2=C(Y 1 )- and a vinylidene group of the formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 is, at each occurrence, independently a C alkyl group. 56.A 1 is 0.99:0.01 to 0.01:0.99, and a vinyl group and a compound represented by the formula Y 1 Vinylene group of the formula CH=CH-, CH2=C(Y 1 56. The composition of embodiment 55, comprising a ratio of vinylidene groups to the sum of vinyl groups of -. 57.L 1 However, propylene and ethylene or C4 to C 30 The composition of any one of the preceding embodiments, which is a propylene / α-olefin copolymer comprising units derived from either an α-olefin or an α-olefin. 58. C4~C 30 The composition of embodiment 57, wherein the α-olefin is selected from the group consisting of 1-butene, 1-hexene, and 1-octene. 59.L 1 The composition of embodiment 57, wherein is a propylene / ethylene copolymer. 60.A 1 is a vinyl group. 61.A 1 The formula is CH2=C(Y 1 )-vinylidene group, 1 is a methyl group. 62.A 1 is the formula Y 1 is a vinylene group of the formula CH=CH-, 1 is a methyl group. 63.A 1 is a vinyl group and the formula Y 1A mixture of CH=CH- and vinylene groups, wherein Y 1 is a methyl group. 64.A 1 is 0.99:0.1 to 0.1:0.99, vinyl group and formula Y 1 The composition of embodiment 63, comprising a ratio of CH═CH— to vinylene groups. 65.A 1 is a vinyl group and the formula CH2=C(Y 1 )- and vinylidene groups, 1 is a methyl group. 66.A 1 is 0.99:0.1 to 0.1:0.99, vinyl group and formula CH2=C(Y 1 The composition of embodiment 65, comprising a ratio of 1 to 10 vinylidene groups. 67.A 1 is a vinyl group and a compound of the formula CH2=C(Y 1 )- and a vinylidene group of the formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 is, independently at each occurrence, a methyl group. 68.A 1 is 0.99:0.01 to 0.01:0.99, and a vinyl group and a compound represented by the formula Y 1 Vinylene group of the formula CH=CH-, CH2=C(Y 1 68. The composition of embodiment 67, comprising a ratio of vinylidene groups to the sum of vinyl groups of -. 69.Y 2 The composition of any one of embodiments 2-68, wherein is hydrogen. 70.Y 2 The composition of any one of embodiments 2-68, wherein is a C1-C10 alkyl group. 71.Y 2 is an ethyl group. 72. The composition of any one of the preceding embodiments, wherein the hindered double bond is selected from the group consisting of a double bond of a vinylidene group, a double bond of a vinylene group, a double bond of a trisubstituted alkene, and a double bond of a vinyl group attached to a branched α-carbon. 73.A 2 C3~C 30 Cyclic hydrocarbyl group or C3-C 30 The composition of any one of embodiments 1-72, wherein the hydrocarbyl group is an acyclic hydrocarbyl group. 74.A 2 is selected from the group consisting of unsubstituted cycloalkene, alkyl substituted cycloalkene, and acyclic alkyl group. 75.A 2 The composition of any one of embodiments 1-74, wherein is selected from the group consisting of: [ka] [ka] 76.A 2 The composition of any one of the preceding embodiments, wherein is selected from the group consisting of (AC), (AF), (AM), (AO), (AP), (AS), and (AZ1). 77. The composition of any one of the preceding embodiments, wherein the telechelic polyolefin of formula (I) comprises or has a weight average molecular weight (Mw) range selected from the group consisting of 1,000-10,000,000 g / mol, 1,000-5,000,000 g / mol, 1,000-1,000,000 g / mol, 1,000-750,000 g / mol, 1,000-500,000 g / mol, and 1,000-250,000 g / mol. 78. The composition of any one of the preceding embodiments, wherein the telechelic polyolefin of formula (I) comprises or has a number average molecular weight (Mn) range selected from the group consisting of 1,000-10,000,000 g / mol, 1,000-5,000,000 g / mol, 1,000-1,000,000 g / mol, 1,000-750,000 g / mol, 1,000-500,000 g / mol, and 1,000-250,000 g / mol. 79. The composition of any one of the preceding embodiments, wherein the telechelic polyolefin of formula (I) comprises or has an average molar mass (Mz) range selected from the group consisting of 1,000-10,000,000 g / mol, 1,000-5,000,000 g / mol, 1,000-1,000,000 g / mol, 1,000-750,000 g / mol, 1,000-500,000 g / mol, 5,000-500,000 g / mol, and 10,000-500,000 g / mol. 80. The composition of any one of the preceding embodiments, wherein the telechelic polyolefin of formula (I) comprises or has a Mw / Mn (PDI) range selected from the group consisting of 1-10, 1-7, 1-5, 1.5-4, and 2-4. 81. The composition of any one of the preceding embodiments, wherein the telechelic polyolefin of formula (I) comprises or has a density range selected from the group consisting of 0.850-0.965 g / cc, 0.854-0.950 g / cc, 0.854-0.935 g / cc, 0.854-0.925 g / cc, 0.854-0.910 g / cc, 0.854-0.900 g / cc, 0.854-0.885 g / cc, 0.854-0.880 g / cc, and 0.854-0.875 g / cc, as measured by ASTM D-792, Method B. 82. The composition of any one of the preceding embodiments, wherein the telechelic polyolefin of formula (I) comprises or has a melt index (I2) range selected from the group consisting of 0.01 to 2000 g / 10 min, 0.01 to 1,500 g / 10 min, 0.01 to 1,000 g / 10 min, 0.01 to 500 g / 10 min, 0.01 to 100 g / 10 min, 0.5 to 50 g / 10 min, and 0.5 to 30 g / 10 min, as measured by ASTM D-1238, condition 190° C. / 2.16 kg. 83. The telechelic polyolefin of formula (I) is heated to a temperature selected from the group consisting of -25°C to 165°C, -25°C to 150°C, -25°C to 125°C, -25°C to 100°C, 0°C to 80°C, and 10°C to 60°C. mThe composition of any one of embodiments 1 to 82, including or having a range. 84. The telechelic polyolefin of formula (I) has a viscosity of 10 to 100 MPa when measured by ASTM D-3236 at 177 °C. 8 cP, 10-10 7 cP, 10-10 6 84. The composition of any one of the preceding embodiments, comprising or having a Brookfield viscosity range selected from the group consisting of 10 to 750,000 cP, 10 to 500,000 cP, 10 to 250,000 cP, 10 to 100,000 cP, 10 to 75,000 cP, 10 to 50,000 cP, and 10 to 40,000 cP. 85. The composition of any one of the preceding embodiments, wherein the telechelic polyolefin of formula (I) comprises a melting enthalpy (ΔHm) range selected from the group consisting of 0-235 J / g, 0-200 J / g, 10-175 J / g, 10-150 J / g, 10-125 J / g, and 20-117 J / g. 86. The telechelic polyolefin of formula (I) is heated to a temperature selected from the group consisting of -80 to 100°C, -80 to 75°C, -80 to 50°C, -80 to 25°C, -80 to 0°C, -80 to -15°C, and -70 to -30°C. g The composition of any one of embodiments 1 to 85, including or having a range. 87. The composition of any one of the preceding embodiments, wherein the telechelic polyolefin of formula (I) comprises 0% to 0.001% by weight of units derived from diene monomers. 88. The composition of embodiment 88, wherein the telechelic polyolefin of formula (I) comprises or has a total degree of unsaturation in a range selected from the group consisting of 1.1 or more, 1.2 or more, 1.3 or more, 1.4 or more, 1.5 or more, 1.6 or more, 1.7 or more, 1.8 or more, and 1.9 or more. 89. The composition of any one of embodiments 3-9, 15-56, and 69-88, wherein the telechelic polyolefin of formula (I) comprises or has a weight percent crystallinity range selected from the group consisting of 0-80%, 0-60%, 5-50%, and 7-40%, based on a PEΔHm of 292 J / g. 90.L 1 is connected to A via a carbon-carbon single bond. 1 and L 2 Each is covalently bonded to L 2 is connected to A via a carbon-carbon single bond. 2 90. The composition of any one of embodiments 1-89, wherein the compound is covalently attached to 91.L 1 is missing two hydrogens and A 1 and L 2 91. The composition of any one of the preceding embodiments, wherein each of the polyolefins is covalently bonded to the other of the preceding embodiments. 92. A telechelic polyolefin of formula (I) according to any one of embodiments 1 to 91. 1a. A method for preparing a telechelic polyolefin or a composition comprising a telechelic polyolefin, the method comprising: 1) combining starting materials including (A) a monomer component, (B) a chain transfer agent component, and (C) a catalyst component including a procatalyst to form a solution, and polymerizing from greater than 10 mol% to less than or equal to 99 mol% of the (A) monomer component in the solution; 2) heating the solution; and 3) recovering a product comprising the telechelic polyolefin or a composition comprising the telechelic polyolefin; (B) the chain transfer agent component is a compound represented by the formula Al(CHCH(Y 2 )A 2 ) 3 organoaluminum compounds, Y 2 Each occurrence is independently hydrogen or C1-C 30 is a hydrocarbyl group, and A 2 is, independently at each occurrence, a hydrocarbyl group containing a hindered double bond. 2a. The method of embodiment 1a, wherein the starting material further comprises (D) a solvent. 3a. The method of embodiment 1a or 2a, wherein step 2) is heating the solution to a temperature of at least 160° C., or at least 180° C., or at least 200° C., or at least 220° C., and holding the solution at a temperature of at least 160° C., or at least 180° C., or at least 200° C., or at least 220° C. for a period of at least 30 seconds, or at least 1 minute, or at least 5 minutes. 4a. The method of any one of embodiments 1a-3a, wherein step 2) is heating the solution at a temperature of at least 160° C., or at least 180° C., or at least 200° C., or at least 220° C., for a period of at least 30 seconds, or at least 1 minute, or at least 5 minutes. 5a. The method of any one of embodiments 1a-4a, wherein step 2) is heating the solution at a temperature between 220° C. and 290° C. for a time period between 5 minutes and 20 minutes. 6a. The method of any one of embodiments 1a-5a, wherein step 2) is heating the solution to a temperature of 220° C.-290° C. and holding the solution at a temperature of 220° C.-290° C. for a time period of 5 minutes-20 minutes. 7a. The method of any one of embodiments 1a to 6a, wherein the procatalyst is selected from the group consisting of (Cat 1) to (Cat 17), as described above. 8a. The method of embodiment 7a, wherein the procatalyst is (Cat 1), (Cat 13), (Cat 14), or (Cat 17), as described above. 9a. The method of any one of embodiments 1a-8a, wherein the catalyst component further comprises a cocatalyst. 10a. The cocatalyst is [(C 16~18 H 33~37 ) -2 The method of any one of embodiments 1a-9a, wherein the tetrakis(pentafluorophenyl)borate salt is CH3NH]tetrakis(pentafluorophenyl)borate salt. 11a. The method of any one of embodiments 1a-10a, wherein (B) the chain transfer agent component further comprises an alkyl zinc of formula Zn(d)2, where each occurrence of d is independently a C1-C10 alkyl group. 12a.(B) The chain transfer agent component is 65 mol% to 99 mol% of the formula Al(CHCH(Y 2 )A 2 The method according to embodiment 11a, comprising an organoaluminum compound of formula Zn(d)3 and 1 mol % to 35 mol % of an alkyl zinc of formula Zn(d)2. 13a. (B) The chain transfer agent component has the formula Al(CHCH(Y 2 )A 2 )3 and organoaluminum compounds of the formula Zn(CHCH(Y 2 )A 2 )2, wherein Y 2 Each occurrence is independently hydrogen or C1-C 30 A is a hydrocarbyl group, 2 The method of any one of embodiments 1a-10a, wherein each occurrence is independently a hydrocarbyl group that contains a hindered double bond. 14a.(B) The chain transfer agent component is a 20:80 to 40:60 mixture of the formula Al(CHCH(Y 2 )A 2 )3 and organoaluminum compounds of the formula Zn(CHCH(Y 2 )A 2 The method of embodiment 13a, comprising a ratio of 2 to the organozinc compound. 15a. The method of any one of embodiments 1a-14a, wherein the composition comprising a telechelic polyolefin is a composition according to any one of embodiments 1-91. 16a. The method of any one of embodiments 1a-15a, wherein the telechelic polyolefin is the telechelic polyolefin of embodiment 92.

[0263] Test Method Unless otherwise stated, the measurable properties discussed in the foregoing disclosure and in the examples below are in accordance with the following analytical methods.

[0264] density The samples whose density was measured were prepared according to ASTM D-1928, which is incorporated herein by reference in its entirety. Measurements were taken within 1 hour of the sample press using Method B of ASTM D-792, which is incorporated herein by reference in its entirety.

[0265] Melt Index / Melt Flow Rate Melt index (I2) was measured in accordance with ASTM D-1238, condition 190° C. / 2.16 kg, which is incorporated herein by reference in its entirety, and reported in grams dissolved per 10 minutes. 10 ) was measured according to ASTM D-1238, condition 190° C. / 10 kg, and reported in grams dissolved per 10 minutes.

[0266] GPC The sample polymers were tested for their properties by GPC according to the following.

[0267] A high temperature gel permeation chromatography system (GPCIR) consisting of an infrared concentration detector (IR-5) from PolymerChar Inc (Valencia, Spain) was used for the determination of molecular weight (MW) and molecular weight distribution (MWD). The carrier solvent was 1,2,4-trichlorobenzene (TCB). The autosampler compartment was operated at 160 °C and the column compartment was operated at 150 °C. The columns used were four Polymer Laboratories Mixed A LS, 20 micron columns. The chromatography solvent (TCB) and sample preparation solvent were from the same solvent source with 250 ppm butylated hydroxytoluene (BHT) and sparged with nitrogen. Samples were prepared at a concentration of 2 mg / mL in TCB. The polymer samples were gently shaken at 160 °C for 2 h. The injection volume was 200 μl and the flow rate was 1.0 ml / min.

[0268] Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards ranging from 580 to 8,400,000 g / mol, with individual molecular weights spaced at least one decade apart in six "cocktail" mixtures.

[0269] Prior to running the examples, the GPC column set was calibrated by running 21 narrow molecular weight distribution polystyrene standards. The molecular weights (Mw) of the standards ranged from 580 to 8,400,000 grams per mole (g / mol) and the standards were contained in six "cocktail" mixtures. Each standard mixture had at least one order of magnitude separation between the individual molecular weights. The standard mixtures were purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards were prepared at 0.025 grams in 50 mL of solvent for molecular weights equal to or greater than 1,000,000 g / mol and 0.05 grams in 50 mL of solvent for molecular weights less than 1,000,000 g / mol. The polystyrene standards were dissolved at 80°C for 30 minutes with gentle agitation. The narrow standard mixtures were run first and in order of decreasing highest molecular weight (Mw) components to minimize degradation. The polystyrene standard peak molecular weights were converted to polyethylene Mw using the Mark-Houwink constants. Once the constants were obtained, the two values ​​were used to construct a two-linear standard calibration for polyethylene molecular weight and polyethylene intrinsic viscosity as a function of elution column.

[0270] Polystyrene standard peak molecular weights were converted to polyethylene molecular weights using the following equation (Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)): M ポリエチレン =A(M ポリスチレン ) B (1)

[0271] Here, the value of B is 1.0 and the experimentally determined value of A is approximately 0.41.

[0272] A third order polynomial was used to fit each of the polyethylene equivalent calibration points obtained from equation (1) to their observed elution deposits of the polystyrene standards.

[0273] The number average, weight average, and z average molecular weights were calculated according to the following formulas:

number

[0274] In the formula, Wf i is the weight fraction of the i-th component, and M i is the molecular weight of the i-th component.

[0275] MWD was expressed as the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn).

[0276] The exact A value was determined by adjusting the A value in equation (1) until the Mw and corresponding retention deposition polynomial calculated using equation (3) matched the known Mw value of a standard linear polyethylene homopolymer reference, 120,000 g / mol.

[0277] The GPC system consisted of a 150°C high temperature chromatograph from Waters (Milford, Massachusetts) (other suitable high temperature GPC instruments include Polymer Laboratories (Shropshire, UK) Model 210 and Model 220) with an on-board differential refractometer (RI). Additional detectors may include an IR4 infrared detector from Polymer ChAR (Valencia, Spain), a two-angle laser light scattering detector model 2040 from Precision Detector (Amherst, Massachusetts), and a 150R4-capillary solution viscometer from Viscotek (Houston, Texas). GPC with the last two independent detectors and at least one first detector is sometimes referred to as "3D-GPC", although the term "GPC" alone generally refers to conventional GPC. Depending on the sample, either the 15 degree or 90 degree of the light scattering detector was used for the calculation.

[0278] Data collection was performed using Viscotek TriSEC software, Version 3 and a 4-channel Viscotek Data Manager DM400. The system was also equipped with an online solvent degassing device from Polymer Laboratories (Shropshire, UK). A suitable high temperature GPC column such as four 30 cm long Shodex HT803 13 micron columns or four 30 cm Polymer Labs columns packed with 20 micron mixed pore size could be used (MixA LS, Polymer Labs). The sample carousel compartment was operated at 140°C and the column compartment was operated at 150°C. Samples were prepared at a concentration of 0.1 grams of polymer in 50 milliliters of solvent. The chromatographic solvent and sample preparation solvent contain 200 ppm butylated hydroxytoluene (BHT). Both solvents were sparged with nitrogen. The polyethylene samples were gently stirred at 160°C for four hours (4h). The injection volume was 200 microliters (μL). The flow rate through the GPC was set at 1 ml / min.

[0279] NMR( 13 C and 1 H) Sample preparation: 13 For C NMR, samples were prepared by adding approximately 2.7 g of stock solvent to 0.20-0.40 g of sample in a 10 mm NMR tube. The stock solvent is tetrachloroethane-d2 containing 0.025 M chromium acetylacetonate (a relaxation agent). The samples were capped and sealed with Teflon tape. The samples were dissolved and homogenized by heating the tube and its contents at 135 °C-140 °C.

[0280] Sample preparation: 1 For H NMR, samples were prepared by adding 130 mg of sample to 3.25 g of 50 / 50 by weight tetrachloroethane-d2 / perchloroethylene containing 0.001 M Cr(AcAc)3 in a 10 mm NMR tube. To prevent oxidation, the sample was purged by bubbling N2 through the solvent via a pipette inserted into the tube for approximately 5 min, capped, and sealed with Teflon tape. Samples were heated at 115 °C and vortexed to ensure homogeneity.

[0281] Data acquisition parameters: 13 For C NMR, data were collected using a Bruker 400 / 600 MHz spectrometer equipped with a Bruker high temperature CryoProbe (see reference 1 below). Data were acquired using 256-8000 transients per data file, a pulse repetition delay of 7.3 seconds (6 seconds delay + 1.3 seconds acquisition time), a flip angle of 90 degrees, and modified inverse gated decoupling at a sample temperature of 120 °C (see reference 2 below). All measurements were performed on non-spinning samples in a stationary fashion. Samples were homogenized immediately prior to insertion into a heated (125 °C) NMR sample exchanger and allowed to thermally equilibrate in the probe for 7 minutes before data acquisition.

[0282] Data acquisition parameters:1 H NMR was performed on a Bruker AVANCE 400 / 600 MHz spectrometer equipped with a Bruker high temperature CryoProbe at a sample temperature of 120 °C. Two experiments were performed to obtain spectra, a control spectrum to quantify total polymer protons, and a double presaturation experiment, thereby suppressing the intense polymer backbone peaks and allowing high sensitivity spectra for quantification of end groups. The control was performed with a ZG pulse, 4 scans, SWH10,000Hz, AQ1.64s, D114s. The double presaturation experiment was performed with a modified pulse sequence, lc1prf2.zz1, TD32768, 100 scans, DS4, SWH10,000Hz, AQ1.64s, D11s, D 13 This was carried out in 13s.

[0283] Data Analysis: Comonomer content was analyzed by corresponding matrix or algebraic methods. Unsaturation was analyzed by the method of Reference 3 below.

[0284] Reference 1: Z. Zhou, R. Kuemmerle, JC Stevens, D. Redwine, Y. He, X. Qiu, R. Cong, J. Klosin, N. Montanez, G. Roof, Journal of Magnetic Resonance, 2009, 200, 328.

[0285] Reference 2: Z. Zhou, R. Kummerle, X. Qiu, D. Redwine, R. Cong, A. Taha, D. Baugh, B. Winniford, Journal of Magnetic Resonance: 187 (2007) 225.

[0286] Reference 3: Z. Zhou, R. Cong, Y. He, M. Paradkar, M. Demirors, M. Cheatham, W. deGroot, Macromolecular Symposia, 2012, 312, 88.

[0287] Brookfield Viscosity Brookfield viscosity was measured at 177° C. according to ASTM D-3236 using a Brookfield RV-DV-II-Pro viscometer and spindle SC-31.

[0288] GC / MS Tandem gas chromatography / low resolution mass spectrometry using electron impact ionization (EI) is performed on an Agilent Technologies 6890N series gas chromatograph equipped with an Agilent Technologies 5975 inert XL mass selective detector and an Agilent Technologies capillary column (HP1MS, 15 m×0.25 mm, 0.25 micron) at 70 eV as follows: Programmed Method: Oven equilibration time of 0.5 min at 50°C Then, increase to 200°C at 25°C / min and hold for 5 min. Duration: 11 minutes

[0289] DSC Differential scanning calorimetry (DSC) was performed using a TA Instruments Discovery DSC equipped with an RCS cooling unit and autosampler. A nitrogen purge gas flow of 50 mL / min was used. High molecular weight samples (melt index <50 dg / min at 190°C) were pressed into thin films at 190°C in a Carver hydraulic press at 20,000 psi for 4 minutes, followed by cooling at a temperature of 23°C at 20,000 psi for 1 minute. Approximately 3-10 mg of material was cut from the pressed film, weighed, placed in a light aluminum pan, and crimped shut. For low molecular weight samples (melt index >50 dg / min at 190°C), approximately 3-10 mg of material was cut from the as-received bales, weighed, placed in a light aluminum pan, and crimped shut. The thermal behavior of the samples was investigated using the following temperature profile: The sample was rapidly heated to 180°C and held isothermally for 5 min. The sample was then cooled to -90°C at 10°C / min and held isothermally for 5 min. The sample was then heated to 150°C at 10°C / min. The cooling curve and the second heating curve were used for analysis. The glass transition temperature (Tg), melting temperature (Tm), and enthalpy heat (ΔHm) were obtained from the second heat data. The crystallization temperature (Tc) was obtained from the first cooling data. Tg was determined using the half-height method. Tm and Tc were determined as the peaks of the melting endotherm and crystallization exotherm, respectively. Calculate percent crystallinity by dividing the heat of fusion (Hf) determined from the second heat curve by the theoretical heat of fusion of 292 J / g for PE and multiplying this amount by 100 (e.g., % crystallinity = (Hf / 292 J / g) x 100 for PE). If the example contains mostly propylene, use the theoretical heat of fusion of 165 J / g for PP.

[0290] DMS Rheology was measured with an Advanced Rheometric Expansion System (ARES) equipped with 25 mm stainless steel parallel plates. Constant temperature dynamic frequency sweeps in the frequency range of 0.1-100 rad / s were performed under nitrogen purge at 190 °C. Samples of approximately 25.4 mm diameter and 3.2 mm thickness were compression molded in a Carver hydraulic hot press at 190 °C and 20,000 psi for 4 minutes, then cooled at 23 °C and 20,000 psi for 1 minute. The samples were placed on the lower plate and allowed to melt for 5 minutes. The plates were then closed to a gap of 2.0 mm, and the samples were trimmed to 25 mm diameter. The samples were allowed to equilibrate at 190 °C for 5 minutes before testing began. Complex viscosity was measured at a constant strain amplitude of 10%. The viscosities at 0.1 rad / s (V0.1) and 100 rad / s (V100) are reported, as well as the ratio of the two viscosity values ​​(V0.1 / V100). EXAMPLES

[0291] Preparation of materials All starting reagents and materials were obtained from Sigma-Aldrich unless otherwise stated. Procatalysts (Cat 1), (Cat 13), (Cat 14), and (Cat 17), as well as others used in the following examples, are the same as those described above and are prepared according to the methods described above. Procatalyst (Cat 1) can also be identified as [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)]methane)]hafnium dimethyl. "Cocat A" is the cocatalyst used in the following examples and is bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine.

[0292] Synthesis of tris(2-(cyclohexen-3-en-1-yl)ethyl)aluminum ("CTA1"). An exemplary chain transfer agent of the present disclosure was prepared as follows. In a drybox, 4-vinyl-1-cyclohexene (3.2 mL, 24.6 mmol) and triisobutylaluminum (2.0 ml, 7.92 mmol) were added to 5 mL of decane in a vial equipped with a stir bar and vent needle in the cap. The mixture was heated at 120° C. with stirring for 3 hours. After 3 hours, the sample was 1 It was dissolved in benzene-d6 for H NMR analysis, and another aliquot was hydrolyzed with water and analyzed by GC / MS. 1 H NMR showed that all the vinyl groups had reacted, leaving only an internal double bond (Figure 1A). GC / MS showed a clean peak at m / z of 110, consistent with the molecular weight of ethylcyclohexene (Figure 1B). Thus, 1 The synthesis of tris(2-(cyclohex-3-en-1-yl)ethyl)aluminum (“CTA1”) via non-limiting Scheme 1 was confirmed by 1 H NMR and GC / MS. [ka]

[0293] Synthesis of tris(3,7-dimethyloct-6-en-1-yl)aluminum ("CTA2"): In a nitrogen-filled drybox, a 40 mL vial equipped with a stir bar was charged with DIBAL-H (8.10 mL, 9.64 mmol; 20 wt % solution in toluene) and citronellene (4.00 g, 28.93 mmol; mixture of isomers). The vial was placed in a heating block and a vent needle was inserted into the headspace. The solution was heated to 110-112 °C for 9 h to give a clear, colorless solution ([Al] = 0.88 M). The material was prepared by the steps of: 1 The desired product was determined via H NMR as well as GC / MS (m / z=140) of a hydrolyzed aliquot ( FIG. 2 ). 1The synthesis of tris(3,7-dimethyloct-6-en-1-yl)aluminum ("CTA2") via non-limiting Scheme 2 was confirmed by 1 H NMR and GC / MS. [ka]

[0294] Synthesis of hex-4-en-1-yldiisobutylaluminum ("CTA3"): An exemplary chain transfer agent of the present disclosure was prepared as follows. In a nitrogen-filled drybox, DIBAL-H (0.800 g, 5.63 mmol) and 1,4-hexadiene (0.65 mL, 5.63 mmol, d 0.710; mixture of cis and trans isomers) were added to 3 mL of dry, degassed toluene. The reaction mixture was stirred at 25°C for 14 hours. The hydrolyzed sample (see Hydrolysis Procedure below) 1 H NMR analysis showed no reaction. The solution was heated at 60° C. with stirring for 22 h. After cooling the vial to 25° C., an aliquot was hydrolyzed and analyzed. Completion of the reaction was indicated by the disappearance of the starting diene and the appearance of signals consistent with the hydrolysis products isobutane and 2-hexene. 1 The hydrolysis for analysis was performed by diluting about 0.1 mL of sample with about 2 mL of C6D6 in a vial, removing the sample from the glove box, and adding about 0.1 mL of nitrogen-purged water with a syringe. After shaking the vial, the mixture was passed through a 0.45 μm syringe filter. The organic phase passes through easier than the aqueous phase, allowing the organic phase to be quickly separated for analysis. The sample was then mixed with a small amount of silica gel and filtered again. This helps to remove any residual Al species that may cause gelation. Thus, 1 The synthesis of hex-4-en-1-yldiisobutylaluminum ("CTA3") via non-limiting Scheme 3 was confirmed by 1 H NMR. [ka]

[0295] Synthesis of bis(-2-ethylhex-4-en-1-yl)zinc ("CTA4"): In a nitrogen-filled dry box, diethylzinc (3.40 mL, 5.00 mmol, 20 wt % in toluene), 1,4-hexadiene (1.16 mL, 10.00 mmol, d 0.710; mixture of cis and trans isomers), and activator [HNMe(C 18 H 37 )2][B(CF)4] (1.40 mL, 0.09 mmol, 0.064 M in methylcyclohexane) were mixed in a vial. (Cat13) (0.045 g, 0.08 mmol)) was added as a solid and the reaction mixture was stirred at 25 °C for 20 h. The hydrolyzed sample (see hydrolysis procedure below) 1 1 H NMR and GC / MS analysis indicated a complete reaction. 1 H NMR was evidenced by the disappearance of the starting diene and the appearance of signals consistent with the hydrolysis product 5-methylhept-2-ene. GC / MS showed the same expected hydrolysis product. Therefore, 1 The synthesis of bis(-2-ethylhex-4-en-1-yl)zinc ("CTA4") via non-limiting Scheme 4 was confirmed by 1 H NMR and GC / MS. [ka]

[0296] Synthesis of "CTA5": Diethylzinc (0.66 mL, 0.97 mmol; 1.47 M solution in toluene), 4-vinylcyclohexene (1.77 mL, 13.58 mmol; d 0.832), activator ([HNMe(C 18 H 37A solution of [B(CF)] and triethylaluminum (0.53 mL, 3.88 mmol; neat, 93%) was dissolved in toluene (ca. 10 mL). (Cat13) (0.023 g, 0.039 mmol) was added as a solid and the reaction mixture was stirred at 25 °C for 14 h. An aliquot was dissolved in C6D6 and quenched with water. GC / MS and 1 H NMR confirmed the consumption of 4-vinylcyclohexene and the formation of the desired product (m / z=138), thus confirming that CTA5 was prepared via non-limiting Scheme 5. [ka]

[0297] Synthesis of "CTA6": A toluene solution of tris(2-(cyclohex-3-en-1-yl)ethyl)aluminum (10 mL, [Al] = 0.424 M) was mixed with diisobutylzinc (0.286 g, 1.59 mmol) and 4-vinylcyclohexene (0.416 mL, 3.19 mmol; d 0.830). The solution was heated at 110 °C for 4 h and a vent needle was inserted through the septum cap of the vial to allow the escape of isobutylene. During this process, the toluene from DIBZ was removed. i The Bu group was transferred to Al, and thermal elimination of isobutylene followed by insertion of 4-vinylcyclohexene ensured that all alkyl groups on Al and Zn were cyclohexenylethyl groups. An aliquot (0.1 mL) of this mixture was diluted with C6D6 (0.5 mL) and 1 It was hydrolyzed for 1 H NMR analysis. 1 H NMR analysis confirmed that the CTA was synthesized via non-limiting Scheme 6. [ka]

[0298] Synthesis of "CTA7": The synthesis of CTA7 is illustrated in the non-limiting scheme 7 and described as follows. It was carried out in two steps. In the first step, trivinylcyclohexane (TVCH) was converted to a diene by intramolecular cyclization in the presence of a catalytic amount of DIBAL-H, and in the second step, additional DIBAL-H was added to form the CTA. Thus, in a nitrogen-filled dry box, DIBAL-H (0.30 g, 2.11 mmol) was added to TVCH (4.09 mL, 21.1 mmol; d0.836). The mixture was heated at 160°C and stirred for 2 hours to form the cyclized TVCH. In a separate vial, additional DIBAL-H (0.35 g, 2.46 mmol) was dissolved in decane (5 mL), followed by the addition of a portion of the cyclized TVCH (2.05 mL, 10.5 mmol) obtained above. The solution was maintained at 130° C. for 2 hours to obtain an Al-TVCH solution. [ka]

[0299] Synthesis of "CTA8": The synthesis of CTA8 is exemplified in the non-limiting Scheme 8 and described as follows: In a nitrogen-filled drybox, a 20 mL vial equipped with a stir bar was charged with DIBAL-H (2.00 mL, 2.39 mmol; 20 wt % in toluene (1.196 M)) and (R)-(+)-limonene (2.32 mL, 14.35 mmol; d 0.842). The vial was placed in a heating block, a vent needle was inserted through the septum cap, and the solution was heated at 110-112 °C for 11 h. The solvent and excess limonene were removed under vacuum at 50 °C overnight to give the desired product as a colorless viscous oil (0.870 g, 83%). [ka]

[0300] Synthesis of "CTA9": The synthesis of CTA9 is exemplified in the non-limiting Scheme 9 and described as follows: In a nitrogen-filled drybox, a 40 mL vial equipped with a stir bar was charged with DIBAL-H (2.00 g, 14.06 mmol), toluene (9.2 mL), and 7-methyl-1,6-octadiene (5.24 g, 42.19 mmol). An immediate exotherm (accompanied by some bubbling) was observed. The vial was placed in a heating block, a vent needle was inserted through the septum cap, and the solution was heated at 110-112 °C for 3 h. After 3 h of reaction time, an aliquot showed progress of the reaction. The solution contained a small amount of suspended white solid particles. The reaction was continued for an additional 22 h. The reaction was nearly complete. A small amount of dimer formation from the alkene reagent was observed. The reaction was continued for an additional 16 h. Analysis of the aliquot showed no significant changes. [ka]

[0301] Batch reactor synthesis of telechelic polyolefins. Formula A 1 L 1 L 2 A 2 Three sets of non-limiting examples of telechelic polyolefins were synthesized in a batch reactor as follows.

[0302] Set 1 With reference to Tables 1A-1C, Set 1 includes telechelic polymers of the present invention made in runs BR1-BR12, which were prepared as follows: In each run, a 1-gallon stirred autoclave reactor is charged with Isopar™ E mixed alkane solvent (approximately 1.3 kg), the desired mass of propylene or octene, and / or ethylidene norbornene (ENB) (60 g), and CTA. The reactor is heated to 120° C. and charged with ethylene (20 g). An active catalyst solution is prepared in a dry box under an inert atmosphere by mixing the procatalyst with an activator mixture (a mixture of 1.2 equivalents of Cocat A and 10 equivalents of modified methylaluminoxane (MMAO-3A)), where the active catalyst solution has a ratio of procatalyst to Cocat A of 1:1.2. The active catalyst solution is injected into the reactor to initiate polymerization. The reactor pressure and temperature are kept constant during polymerization by feeding ethylene and cooling the reactor as needed. After 10 minutes, the reactor was heated to 200°C and held at that temperature for 20 minutes. The ethylene supply was shut off and the polymer solution was transferred to a nitrogen purged resin kettle. An additive solution containing phosphorus stabilizer and phenolic antioxidant (Irgafos® 168 and Irganox® 1010 in toluene at a weight ratio of 2:1) was added to bring the total additive content in the polymer to about 0.1%. The polymer was thoroughly dried in a vacuum oven. [Table 1] [Table 2] [Table 3]

[0303] Set 2 Referring to Table 2, set 2 includes telechelic polymers of the invention made in runs B1-B7 by a procedure similar to set 1. Run B1 used scavenger MMAO-3A in a ratio of (Cat1):Cocat A:scavenger of 1:1.2:10. Runs B2-B7 used a procatalyst to cocatalyst ratio of 1:1.2. All runs in Table 2 were performed without hydrogen. Conditions for all runs were as follows: ethylene (g):20, 1-octene (g):60, pressure (psi):55, solvent (Isopar E, g):1325. The loading of CTA5 was based on the number of transferable groups. Runs B1, B2, B4, and B6 were at 120° C. for 10 min. Runs B3, B5, and B7 included an additional heating step at 200° C. for 20 min (excluding the transition time from 120 to 200° C.). [Table 4]

[0304] Set 3 Set 3 includes the following examples for synthesizing telechelic polyethylene polymers of the present invention.

[0305] In a nitrogen-filled drybox, a vial equipped with a stir bar is charged with octene (10 mL), Cocat A (0.023 mL of a 0.075 M solution, 0.0017 mmol), and CTA7 (0.402 mL of a 0.5 M solution, 0.2 mmol). The vial is sealed with a septum cap and placed in a heating block set at 100° C. An ethylene line (from a small cylinder) is connected and the headspace of the vial is slowly purged through a needle. Cat13 (0.067 mL of a 0.02 M solution, 0.0013 mmol) is injected and the purge needle is removed to maintain a total pressure of 20 psig. The polymerization is maintained for 20 minutes, then the ethylene line is removed and the polymer solution is cooled. The polymer solution is transferred to a 600 mL Parr reactor and sealed. The reactor is heated to 200° C. under 200 psig ethylene pressure for 30 minutes. The polymer was quenched with copious amounts of methanol, filtered, and dried under vacuum overnight. 1H NMR (Figure 3) confirmed that the synthesis occurred via the non-limiting reaction scheme shown below. [ka]

[0306] In a nitrogen-filled drybox, a vial equipped with a stir bar is charged with octene (10 mL), Cocat A (0.023 mL of a 0.075 M solution, 0.0017 mmol), and CTA8 (0.088 g, 0.2 mmol). The vial is sealed with a septum cap and placed in a heating block set at 100° C. An ethylene line (from a small cylinder) is connected and the headspace of the vial is slowly purged through a needle. Cat13 (0.067 mL of a 0.02 M solution, 0.0013 mmol) is injected and the purge needle is removed to maintain a total pressure of 20 psig. The polymerization is maintained for 20 minutes, then the ethylene line is removed and the polymer solution is cooled. The polymer solution is transferred to a 600 mL Parr reactor and sealed. The reactor is heated to 200° C. under 200 psig ethylene pressure for 30 minutes. The polymer was quenched with copious amounts of methanol, filtered, and dried under vacuum overnight. 1H NMR (FIG. 4) analysis confirmed that the synthesis occurred via the following non-limiting reaction scheme: [ka]

[0307] Continuous solution polymerization of telechelic polyolefins. Formula A 1 L 1 L 2 A 2 A non-limiting example of a telechelic polyolefin was prepared by continuous solution polymerization as follows.

[0308] A continuous solution polymerization is carried out in a computer-controlled autoclave reactor equipped with an internal stirrer. Purified mixed alkanes solvent (Isopar™ E available from ExxonMobil), monomer, and molecular weight regulator (hydrogen or chain transfer agent) are fed into a 3.8 L reactor equipped with a jacket for temperature control. The solvent feed to the reactor is measured by a mass flow controller. A variable speed diaphragm pump controls the solvent flow rate and pressure to the reactor. At the pump discharge, a side stream is taken to provide flush flows to the procatalyst, activator, and chain transfer agent (catalyst component solution) injection lines. These streams are measured by Micro-Motion mass flow meters and controlled by control valves. The remaining solvent is mixed with monomer and hydrogen and fed to the reactor. The temperature of the solvent / monomer solution is controlled by the use of a heat exchanger before entering the reactor. This stream enters the bottom of the reactor. The catalyst component solution is metered using pumps and mass flow meters and is combined with the catalyst flush solvent and introduced into the bottom of the reactor. The reactor is liquid full at 500 psig with vigorous stirring. Polymer is removed through an exit line at the top of the reactor. All exit lines from the reactor are steam traced and insulated. The product stream is then heated at 230°C by passing through a post reactor heater (PRH) where β-hydrogen desorption of the polymer Al occurs. A small amount of isopropyl alcohol, along with any stabilizers or other additives, is added either before the PRH (for comparative examples) or after the PRH (for inventive examples) before devolatilization. The polymer product is recovered by extrusion using a devolatilizing extruder.

[0309] The polymerization process conditions and results before post-reactor heating (PRH) for the inventive and comparative examples are listed in Tables 3 and 4. 1 L 1 L 2 A 2 The telechelic polyolefins of the present invention are designated Inventive TP1 to TP10. The comparative polymers are designated Comparative A and B. Additional abbreviations in the table are explained as follows: "Co" stands for comonomer, "sccm" stands for standard cm3 / min, "T" stands for temperature, "Cat" stands for procatalyst, "Cat1" stands for procatalyst (Cat1), "Cat17" stands for procatalyst (Cat17), "Cocat" stands for Cocat A, "Al CTA" stands for aluminum chain transfer agent, "TEA" stands for triethylaluminum, "TOA" stands for trioctylaluminum, "Poly Rate" stands for polymer production rate, "Conv" stands for percent ethylene conversion in the reactor, and "Eff" stands for efficiency, kg polymer / g catalyst metal.

[0310] Furthermore, [CTA] / [C2H4] refers to the molar ratio in the reactor; Al / C2 * 1000=(Al supply flow rate * Al concentration / 1,000,000 / Mw of Al) / (total ethylene supply flow rate * (1-fractional ethylene conversion rate) / Mw of ethylene) * 1000. "Al / C2 * The "Al" in "1000" refers to the amount of Al in the CTA used in the polymerization process, and "C2" refers to the amount of ethylene used in the polymerization process.

[0311] The properties of the inventive and comparative polymers after post-reactor heating and recovery are listed in Tables 5-8. [Table 5] [Table 6] [Table 7] [Table 8] [Table 9] [Table 10]

[0312] As seen in the table above, 1 H NMR and 13 C NMR analysis confirms the synthesis of new telechelic polyolefins TP1-TP10 via the inventive method of the present disclosure. Specifically, as will be appreciated by those skilled in the art, 1 H NMR and 13 C NMR analysis confirmed the formation of new telechelic polyolefins for TP1-TP10, where such polyolefins have unsaturation at both ends. 1 A having a group (vinyl, vinylene, vinylidene) and a hindered double bond at the other end 2 In contrast, Comparative Polymers A and B, which were not prepared according to the inventive method of the present disclosure, have 1 H NMR and 13 It is a polymer with low unsaturation as seen by C NMR analysis.

[0313] In TP5 of the present invention, the hindered double bond of the A2 group is tri-unsaturated, resulting in a high number of tri-unsaturations / 1000000C, as reported in the table above. The number of tri-unsaturations in TP5 is higher than Comparative B, which was produced under similar reactor conditions with the same catalyst, but with hydrogen to control the molecular weight. A small number of tri-unsaturations may be formed by β-hydride elimination followed by rearrangement of ethylene / α-olefin unsaturation. The number of tri-unsaturations formed by this thermal termination mechanism depends on the catalyst and process conditions used. A small number of tri-unsaturations from this thermal termination mechanism is present in all comparative examples and inventive examples, but at a lower level than vinyl and vinylidene, except for TP5, where the majority of the tri-unsaturation is from the A2 group.

[0314] As mentioned above, the novel telechelic polyolefins of the present disclosure contain unsaturation at the end of the chain, rather than randomly distributed along the polymer backbone. Such telechelic polyolefins may be suitable for curable formulations and may improve crosslinking. By controlling the location of the unsaturation relative to the polymer chain end, a more controlled network structure is formed (uniform Mw between crosslinks) and the unsaturation of the polymer chain is used more efficiently. This should result in better heat and UV aging stability, since less unsaturation is required to form a crosslinked network with excellent mechanical properties for a given molecular weight. The low viscosity of the low Mw telechelic polyolefins of the present disclosure will provide excellent processability and flowability before crosslinking, unlike high Mw EPDM.

[0315] Furthermore, the telechelic polyolefins of the present disclosure are produced by low-cost solution polymerization from ethylene and α-olefins, making them unique in the literature for telechelic polyolefins that have been produced via much more expensive and complex synthetic routes. Furthermore, telechelic polyolefins, unlike random copolymers with unsaturation, also allow for controlled chain extension to high molecular weight thermoplastics. Because the unsaturation is at the end of the chain, telechelic polyolefins can be chain extended to form high molecular weight thermoplastics. Suitable crosslinking and chain extension chemistries include, but are not limited to, peroxide, thiolene, sulfur cure, phenol cure, and the like. The present invention includes the following aspects. Section 1. A telechelic polyolefin of formula (I), A 1 L 1 L 2 A 2 (I), in the formula L 1 is a polyolefin, A 1 is a vinyl group, formula CH2=C(Y 1 )-vinylidene group of the formula Y 1 Vinylene group of CH=CH-, vinyl group and formula Y1 A mixture of vinyl groups and vinylene groups of 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 of the formula CH=CH- and vinyl groups of the formula CH2=C(Y 1 )- and a vinylidene group of the formula Y 1 and a mixture of CH=CH- and vinylene groups; Y 1 Each time it appears, it is assigned independently to C1~C 30 is a hydrocarbyl group, L 2 But, C1~C 32 is a hydrocarbylene group, and A 2 is a hydrocarbyl group containing a hindered double bond. Section 2. L 1 Item 2. The telechelic polyolefin according to item 1, wherein the telechelic polyolefin is an ethylene-based polymer. Section 3. L 1 is an ethylene homopolymer or a C3-C 30 Item 3. The telechelic polyolefin according to item 1 or 2, which is an ethylene / α-olefin copolymer containing units derived from an α-olefin. Section 4. Said C3~C 30 Item 4. The telechelic polyolefin according to item 3, wherein the α-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene. Section 5. Item 5. The telechelic polyolefin according to any one of items 1 to 4, wherein the hindered double bond is selected from the group consisting of a double bond of a vinylidene group, a double bond of a vinylene group, a double bond of a trisubstituted alkene, and a double bond of a vinyl group bonded to a branched α-carbon. Section 6. A 2 C3~C 30 Cyclic hydrocarbyl group or C3-C 30Item 6. The telechelic polyolefin according to any one of items 1 to 5, wherein the group is an acyclic hydrocarbyl group. Section 7. A 2 is selected from the group consisting of unsubstituted cycloalkenes, alkyl-substituted cycloalkenes, and acyclic alkyl groups. Section 8. A 2 but, [ka] wherein the endocyclic double bond of (AC) and (AF) can be between any two adjacent carbon atoms that are ring members, and the pendant methyl group of (AF) can be attached to any carbon atom that is a ring member. Section 9. Item 9. The telechelic polyolefin according to any one of items 1 to 8, wherein the telechelic polyolefin of formula (I) has a weight average molecular weight (Mw) in the range of 1,000 to 1,000,000 g / mol. Section 10. L 1 is connected to A via a carbon-carbon single bond. 1 and L 2 Each is covalently bonded to L 2 is connected to A via a carbon-carbon single bond. 2 Item 10. The telechelic polyolefin according to any one of items 1 to 9, wherein the telechelic polyolefin is covalently bonded to Section 11. Item 11. A composition comprising the telechelic polyolefin according to any one of items 1 to 10. Section 12. 1. A process for preparing a telechelic polyolefin, the process comprising: 1) combining starting materials including (A) a monomer component, (B) a chain transfer agent component, and (C) a catalyst component including a procatalyst to form a solution, and polymerizing from greater than 10 mol % to 99 mol % or less of the (A) monomer component in the solution; 2) heating the solution; and 3) recovering a product comprising the telechelic polyolefin; The (B) chain transfer agent component is represented by the formula Al(CHCH(Y 2 )A 2 ) 3 organoaluminum compounds, Y 2 Each occurrence is independently hydrogen or C1-C 30 is a hydrocarbyl group, and A 2 is, independently at each occurrence, a hydrocarbyl group containing a hindered double bond. Section 13. Item 13. The method of item 12, wherein the starting material further comprises (D) a solvent. Section 14. Item 14. The method of item 12 or 13, wherein step 2) is heating the solution to a temperature of at least 160° C. and holding the solution at said temperature of at least 160° C. for a period of at least 30 seconds.

Claims

1. A telechelic polyolefin of formula (I), A １ L １ L ２ A ２ (I), where L １ is a polyolefin, A １ is a vinyl group, of the formula CH ２ = C(Y １ )-vinylidene group of the formula Y １ CH═CH—, vinylene groups, and combinations of at least two thereof; Y １ But for each occurrence, C １ ~C ３０ is a hydrocarbyl group, L ２ But, C １ ~C ３２ is a hydrocarbylene group, and A ２ is a hydrocarbyl group containing a hindered double bond; A telechelic polyolefin, wherein the hindered double bond is selected from the group consisting of a cyclic double bond of a vinylidene group, a cyclic double bond of a vinylene group, a double bond of a trisubstituted alkene, and a double bond of a vinyl group attached to a branched α-carbon.

2. L １ The telechelic polyolefin of claim 1 , wherein is an ethylene-based polymer.

3. L １ is an ethylene homopolymer or a copolymer of ethylene and C ３ ~C ３０ 3. The telechelic polyolefin of claim 1, which is an ethylene / α-olefin copolymer comprising units derived from an α-olefin.

4. Said C ３ ~C ３０ The telechelic polyolefin of claim 3, wherein the α-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene.

5. A ２ The telechelic polyolefin of any one of claims 1 to 4, wherein is selected from the group consisting of unsubstituted cycloalkenes, alkyl-substituted cycloalkenes, and acyclic alkyl groups.

6. A ２ is selected from the group consisting of: 【Chemistry 1】 6. The telechelic polyolefin of any one of claims 1 to 5, wherein the endocyclic double bond of (AA) through (AF) may be between any two adjacent carbon atoms that are ring members, the pendant methyl groups of (AD) through (AF) may be attached to any carbon atom that is a ring member, and the exocyclic double bond of (AG) through (AL) may be attached to any ring member carbon atom that is not already attached to three or more carbon atoms.

7. 7. The telechelic polyolefin of any one of claims 1 to 6, wherein the telechelic polyolefin comprises a weight average molecular weight (Mw) in the range of 1,000 to 1,000,000 g / mol.

8. L １ is connected to A via a carbon-carbon single bond １ and L ２ Each is covalently bonded to L ２ is connected to A via a carbon-carbon single bond ２ The telechelic polyolefin of any one of claims 1 to 7, wherein the

9. A composition comprising the telechelic polyolefin of any one of claims 1 to 8.

10. 1. A process for preparing a telechelic polyolefin, the process comprising: 1) combining starting materials including (A) a monomer component, (B) a chain transfer agent component, and (C) a catalyst component including a procatalyst to form a solution, and polymerizing from greater than 10 mol % to up to 99 mol % of the (A) monomer component in the solution; 2) heating the solution; and 3) recovering a product comprising the telechelic polyolefin; The (B) chain transfer agent component is represented by the formula Al(CH ２ CH (Y ２ ) A ２ ) ３ The organoaluminum compound includes Y ２ is independently at each occurrence hydrogen or C １ ~C ３０ is a hydrocarbyl group, and A ２ is, independently at each occurrence, a hydrocarbyl group containing a hindered double bond; The method of claim 1, wherein the hindered double bond is selected from the group consisting of a cyclic double bond of a vinylidene group, a cyclic double bond of a vinylene group, a double bond of a trisubstituted alkene, and a double bond of a vinyl group attached to a branched α-carbon.

11. The method of claim 10 , wherein the starting material further comprises (D) a solvent.

12. 12. The method of claim 10 or 11, wherein step 2) is heating the solution to a temperature of at least 160° C. and holding the solution at said temperature of at least 160° C. for a time of at least 30 seconds.

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