CURABLE COMPOSITION COMPRISING UNSATURATED POLYOLEFIN - Patent application

Abstract

The present disclosure relates to unsaturated polyolefins and processes for preparing same. The present disclosure further relates to curable formulations comprising unsaturated polyolefins that exhibit improved crosslinking.

Description

[Technical field]

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS This application claims the benefit of priority to U.S. Provisional Application No. 62 / 786100, filed December 28, 2018, which is incorporated by reference in its entirety herein.

[0002] SUMMARY OF THE DISCLOSURE The present invention relates to curable compositions useful for improved crosslinking. [Background technology]

[0003] Crosslinking of elastomeric resins is frequently used to produce articles with good thermomechanical properties. For example, commercially available EPDM polymers are crosslinked and used in applications with a wide temperature range, including temperatures well above the melting point of the uncrosslinked resin. Generally, commercially available polyolefins that are crosslinked are of high molecular weight to allow efficient crosslinking. Alternatively, low molecular weight resins that can be crosslinked require a large number of unsaturations. This large number of unsaturations can result in crosslinked networks with low molecular weight between crosslinks and poor thermal and UV stability due to remaining backbone unsaturation. Furthermore, crosslinking of low molecular weight (low viscosity) resins requires very high peroxide levels and, in some cases, high gel fractions cannot be achieved, resulting in poor mechanical properties. Thus, there is a need for new low molecular weight unsaturated polyolefins that can be efficiently crosslinked and provide good mechanical properties, thermal and UV stability. Summary of the Invention

[0004] The present disclosure provides a curable composition comprising (A) a polyolefin component and (B) a curing component comprising a crosslinker, wherein the (A) polyolefin component is represented by Formula A 1 L 1 The unsaturated polyolefin comprises: L 1 is a polyolefin, A 1 is a vinyl group, formula CH2=C(Y 1 )-vinylidene group of the formula Y1 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 CH=CH- and vinyl groups of the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 and a mixture of CH=CH- and vinylene groups; Y 1 However, each occurrence is independent, C1~C 30 The present invention relates to a curable composition in which the hydrocarbyl group is

[0005] The present disclosure further provides a curable composition comprising (A) a polyolefin component and (B) a curing component comprising a crosslinker, wherein the polyolefin component is represented by Formula A 1 L 1 and an unsaturated polyolefin of formula A 1 L 1 L 2 A 2 The telechelic polyolefin comprises the formula: L 1 is, independently at each occurrence, a polyolefin; A 1 represents, independently at each occurrence, a vinyl group, of the 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 CH=CH- and vinyl groups of the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 and a mixture of CH=CH- and vinylene groups; Y 1 However, each occurrence is independent, C1~C 30 is a hydrocarbyl group, L 2 But, C1~C 32 is a hydrocarbylene group, A 2 is a hydrocarbyl group containing a sterically hindered double bond.

[0006] The curable compositions of the present disclosure may further comprise (C) an additive component. [Brief description of the drawings]

[0007] [Figure 1A] Provide 1H NMR and GC / MS spectra for the synthesis of CTA1. [Figure 1B] Provide 1H NMR and GC / MS spectra for the synthesis of CTA1. [Diagram 2] 1H NMR spectrum for synthesis of CTA2 is provided. [Diagram 3] 1H NMR spectra for the synthesis of telechelic polyolefins using CTA7 are provided. [Figure 4] 1H NMR spectra for the synthesis of telechelic polyolefins using CTA8 are provided. [Diagram 5] 1 provides torque versus time curves for specific examples. [Figure 6] 1 provides torque versus time curves for specific examples. [Figure 7] MH-ML vs. unsaturation / 1000C curves for specific examples are provided. [Figure 8] MH-ML vs. unsaturation / 1000C curves for specific examples are provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] definition All references herein to the Periodic Table of the Elements shall refer to the Periodic Table of the Elements, published and copyrighted in 2003 by CRC Press, Inc., and any references to groups shall be to the groups reflected in this Periodic Table of the Elements, using the IUPAC system for numbering the groups. Unless stated or suggested 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 referred to 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.

[0009] 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.

[0010] The terms "comprising," "including," "having," and their derivatives are not intended to exclude the presence of any additional component, step, or procedure, whether or not it is specifically disclosed. For the avoidance of any doubt, all compositions claimed through the use of the term "comprising" may include any additional additive, adjuvant, or compound, 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.

[0011] The term "sterically hindered double bond" refers to a carbon-carbon double bond that cannot readily participate in coordination polymerization. In other words, a sterically hindered double bond has only a small degree of reactivity to participate in coordination polymerization. Examples of sterically 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 alpha carbons. As defined herein, the term "sterically hindered double bond" does not include the double bonds of strained cyclic olefins that can readily participate in coordination polymerization. As one of ordinary skill in the art would appreciate, 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, a "sterically hindered double bond" further does not include the double bond of a vinyl group attached to an unbranched alpha carbon.

[0012] 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 component of the composition, whether or not it is specifically disclosed.

[0013] The term "acyclic" refers to a series of atoms in a polymer or compound, which series is linear or branched. Thus, the term "acyclic hydrocarbyl group" refers to a hydrocarbyl group that is linear or branched.

[0014] 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 contains one or more rings. As used herein, a "cyclic hydrocarbyl group" may contain acyclic (linear or branched) portions in addition to one or more rings.

[0015] The term "substituted" refers to one or more hydrogen atoms being replaced, for example, with an alkyl group. The term "unsubstituted" means the absence of such substitution.

[0016] As one of ordinary skill in the art would understand, the term "heteroatom" 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.

[0017] 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.

[0018] 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.

[0019] The term "endocyclic double bond" refers to a double bond between two carbon atoms that are ring members. The term "exocyclic double bond" refers to a double bond between two carbon atoms, only one of which is a ring member.

[0020] The terms "active catalyst", "active catalyst composition" and the like refer to a transition metal compound capable of polymerizing unsaturated monomers with or without a cocatalyst. An active catalyst may be a "procatalyst" that becomes active for polymerizing unsaturated monomers without a cocatalyst. Alternatively, an active catalyst may be a "procatalyst" that becomes active in combination with a cocatalyst for polymerizing unsaturated monomers.

[0021] 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.

[0022] "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 terms such as "activator."

[0023] "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.

[0024] "Interpolymer" or "copolymer" refers to a polymer prepared by polymerization of at least two different types of monomers. These generic terms include both polymers prepared from two different types of monomers and polymers prepared from three or more different types of monomers (e.g., terpolymers, tetrapolymers, etc.). These generic terms encompass all forms of interpolymers or copolymers, including random, block, uniform, heterogeneous, etc.

[0025] An "ethylene-based polymer" or "ethylene polymer" is a polymer that contains a majority amount (greater than 50% by weight) 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 amount (greater than 50% by weight) of polymerized ethylene, 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., composed of its monomeric constituents randomly distributed). An "ethylene homopolymer" is a polymer that contains repeat units derived from ethylene, but contains residual amounts of other components.

[0026] A "propylene-based polymer" or "propylene polymer" is a polymer that contains a majority amount (greater than 50% by weight) 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 amount (greater than 50% by weight) 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., composed of its monomeric constituents randomly distributed). A "propylene homopolymer" is a polymer that contains repeat units derived from propylene, but contains residual amounts of other components.

[0027] An "ethylene / alpha-olefin interpolymer" is an interpolymer that contains a majority (greater than 50% by weight) of polymerized ethylene, based on the weight of the interpolymer, and further contains polymerized units of at least one alpha-olefin. Preferably, the ethylene / alpha-olefin interpolymer is a random interpolymer (i.e., composed of randomly distributed monomer components). An "ethylene / alpha-olefin copolymer" is a copolymer that contains a majority (greater than 50% by weight) of polymerized ethylene, based on the weight of the copolymer, and further contains polymerized units of an alpha-olefin. Preferably, the ethylene / alpha-olefin copolymer is a random copolymer (i.e., composed of randomly distributed monomer components thereof).

[0028] A "propylene / alpha-olefin interpolymer" is an interpolymer that contains a majority (greater than 50% by weight) of polymerized propylene, based on the weight of the interpolymer, and further contains polymerized units of at least one alpha-olefin. Preferably, the propylene / alpha-olefin interpolymer is a random interpolymer (i.e., is composed of its monomeric constituents randomly distributed). A "propylene / alpha-olefin copolymer" is an interpolymer that contains a majority (greater than 50% by weight), based on the weight of the copolymer, of polymerized propylene, and further contains polymerized units of an alpha-olefin. Preferably, the propylene / alpha-olefin copolymer is a random copolymer (i.e., is composed of its monomeric constituents randomly distributed).

[0029] "Polyolefin" refers to 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.

[0030] The terms "chain transfer agent component" and "chain transfer agent" as used herein refer to a compound or mixture of compounds capable of causing reversible or irreversible polymeryl 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.

[0031] The term "olefin block copolymer" or "OBC" refers to an ethylene / alpha-olefin multi-block interpolymer, which comprises, in polymerized form, ethylene and one or more copolymerizable alpha-olefin comonomers characterized by multiple blocks or segments of two or more (preferably three or more) polymerized monomer units, the blocks or segments differing in chemical or physical properties. Specifically, the term "olefin block copolymer" refers to a polymer that contains two or more (preferably three or more) chemically distinct regions or segments (referred to as "blocks") linked in a linear fashion, i.e., chemically distinct units that are attached end-to-end (covalently bonded) to polymerized functional groups, rather than in a pendant or grafted fashion. The blocks differ in the amount or type of comonomer incorporated therein, density, amount of crystallinity, type of crystallinity (e.g., polyethylene vs. polypropylene), size of crystals resulting from polymers 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. Block copolymers are characterized by having unique distributions in both polymer molecular weight distribution (PDI or Mw / Mn) and block length distribution, based, for example, on the effect of the use of a shuttling agent in combination with the catalyst system. Non-limiting examples of olefin block copolymers of the present disclosure, as well as processes for preparing them, are disclosed in U.S. Pat. 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 entireties.

[0032] The term "block composite" ("BC") refers to a polymer that includes three polymeric components: (i) an ethylene-based polymer (EP) (soft copolymer) having an ethylene content of 10 mol% to 90 mol%, based on the total moles of polymerized monomer units in the ethylene-based polymer (EP), (ii) an alpha-olefin-based polymer (AOP) (hard copolymer) having an alpha-olefin content of more than 90 mol%, based on the total moles of polymerized monomer units in the alpha-olefin-based polymer (AOP), and (iii) a block copolymer (diblock copolymer) having an ethylene block (EB) and an alpha-olefin block (AOB), where the ethylene block of the block copolymer has the same composition as the EP of component (i) of the block composite, and the alpha-olefin block of the block copolymer has the same composition as the AOP of component (ii) of the block composite. In addition, the compositional distribution between the amount of EP and the amount of AOP in the block composite will be essentially the same as the compositional distribution between the corresponding blocks in the block copolymer. Non-limiting examples of block composites of the present disclosure, as well as processes for preparing the same, are disclosed in U.S. Pat. Nos. 8,686,087 and 8,716,400, which are incorporated by reference herein in their entireties.

[0033] The term "specific block composite" ("SBC") refers to a polymer comprising three polymeric 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 alpha-olefin-based polymer (AOP) (hard copolymer) having an alpha-olefin content of 61 mol% to 90 mol%, based on the total number of moles of polymerized monomer units in the alpha-olefin-based polymer (AOP); and (iii) a block copolymer (diblock copolymer) having an ethylene block (EB) and an alpha-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 alpha-olefin block of the block copolymer has the same composition as the AOP of component (ii) of the specific block composite. In addition, the compositional distribution between the amount of EP and the amount of AOP in the specific block composite will be essentially the same as the compositional distribution between the corresponding blocks in the block copolymer. Non-limiting examples of certain block conjugates of the present disclosure, as well as processes for preparing the same, are disclosed in WO2017 / 044547, which is incorporated herein by reference in its entirety.

[0034] The term "crystalline block composite" ("CBC") refers to a polymer that includes 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 alpha-olefin-based polymer (CAOP) having an alpha-olefin content of greater than 90 mol%, based on the total number of moles of polymerized monomer units in the crystalline alpha-olefin-based polymer (CAOP); and (iii) a block copolymer including an ethylene block (CEB) and a crystalline alpha-olefin block (CAOB), wherein the CEB of the block copolymer has the same composition as the CEP of component (i) of the crystalline block composite, and the CAOB of the block copolymer has the same composition as the CAOP of component (ii) of the crystalline block composite. In addition, the compositional distribution between the amount of CEP and the amount of CAOP in the crystalline block composite will be essentially the same as the compositional distribution between the corresponding blocks in the block copolymer. Non-limiting examples of crystalline block composite materials of the present disclosure, as well as processes for preparing the same, are disclosed in U.S. Pat. No. 8,822,598 B2 and WO2016 / 01028961 A1, which are incorporated by reference in their entireties.

[0035] 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.

[0036] (A) Polyolefin component In certain embodiments, the curable compositions of the present disclosure may comprise from 80% to 99.99% by weight of the (A) polyolefin component, based on the total weight of the curable composition.

[0037] In certain embodiments, the (A) polyolefin component has the formula A 1 L 1In a further embodiment, the (A) polyolefin component comprises an unsaturated polyolefin of formula A 1 L 1 and an unsaturated polyolefin of formula A 1 L 1 L 2 A 2 In a further embodiment, the (A) polyolefin component comprises a telechelic polyolefin of formula A 1 L 1 and an unsaturated polyolefin of formula A 1 L 1 L 2 A 2 The (A) polyolefin component is a telechelic polyolefin of the formula A in a ratio of 1:99 to 99:1, or 10:90 to 90:10, or 20:80 to 80:20, or 30:70 to 70:30, or 40:60 to 60:40, or 50:50. 1 L 1 of unsaturated polyolefin of formula A 1 L 1 L 2 A 2 The ratio of telechelic polyolelins is included.

[0038] The (A) polyolefin component is a polyolefin having the formula A, such as an ethylene-based polymer. 1 L 1 and an unsaturated polyolefin of formula A 1 L 1 L 2 A 2 Examples of ethylene-based polymers include, but are not limited to, ethylene / alpha-olefin copolymers, such as those available from The Dow Chemical Company under the trademark ENGAGE, and olefin block copolymers available from The Dow Chemical Company under the trademark INFUSE. These ethylene / alpha-olefin copolymers and olefin block copolymers have low or no unsaturation.

[0039] Those skilled in the art will recognize Formula A 1 L1 L 2 A 2 As will be understood in light of the above, 1 is connected to L through a carbon-carbon single bond. 1 Covalently bonded to L 1 is connected to L through a carbon-carbon single bond. 2 Covalently bonded to L 2 A is connected to A through a carbon-carbon single bond. 2 Thus, as used herein, the formula A 1 L 1 L 2 A 2 L 1 When it is stated that is a polyolefin, L 1 is connected to A through a carbon-carbon single bond. 1 and L 2 It is understood that a divalent polyolefinyl group (a polyolefin lacking two hydrogens) is covalently bonded to each of the groups. Similarly, 1 L 1 L 2 A 2 L 1 When it is said to be a polymer, L 1 is connected to A through a carbon-carbon single bond. 1 and L 2 It is understood that a divalent polymeric group (a polymer lacking two hydrogens) is covalently bonded to each of the groups. For example, L 1 is said to be an ethylene homopolymer, L 1 is connected to A through a carbon-carbon single bond. 1 and L 2 It is understood that the divalent ethylene homopolymer group (ethylene homopolymer lacking two hydrogens) is covalently bonded to each of the groups. 1 When it is stated that the copolymer is an ethylene / alpha-olefin copolymer, L 1 is connected to A through a carbon-carbon single bond. 1 and L 2 It is understood that there is a divalent ethylene / alpha-olefin copolymer group (an ethylene / alpha-olefin copolymer lacking two hydrogens) covalently bonded to each of the radicals.

[0040] Similarly, one skilled in the art can 1 L 1 As will be understood in light of the above, 1 is connected to L through a carbon-carbon single bond. 1 Thus, as used herein, the formula A 1 L 1 L 1 When it is stated that is a polyolefin, L 1 A is connected to A through a carbon-carbon single bond. 1 It is understood that the term is a polyolefin group (a polyolefin lacking one hydrogen) covalently bonded to a group.

[0041] L 1are polyolefins resulting from the coordination polymerization of unsaturated monomers (and comonomers), independently at each occurrence. Examples of suitable monomers (and comonomers) include ethylene and alpha-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; butadiene; ethylenediene, 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-1,4,8-decadiene. conjugated or non-conjugated dienes such as dihydromyrcene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, and the mixed isomers of dihydromyrcene and dihydroocimene; 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-cyclohexene ... These include, but are not limited to, norbornene and alkenyl, alkylidene, cycloalkenyl, and cycloalkylene norbornenes, such as xylidene-2-norbornene, and norbornadiene; and aromatic vinyl compounds, such as styrenes, mono- or polyalkylstyrenes (including styrene, o-methylstyrene, t-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene).

[0042] L 1 L can be linear (unbranched), branched, or cyclic. 1 The presence or absence of branching in L and the amount of branching (if branching is present) can vary widely and can depend on the desired processing conditions and the desired polymer properties. 1 When present, 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 selected from the group consisting of A, A 2 The group optionally includes

[0043] In some embodiments, the compound of formula A 1 L 1 and A 1 L 1 L 2 A 2 Each of A 1 The group is L 1 Based on the coordination polymerization of monomers and comonomers, L is correlated with the last inserted monomer or comonomer to form L. 1 By selecting monomers and comonomers for the coordination polymerization of 1 Group and Y 1 It will be shown what groups A can be. In some embodiments, 1 In some embodiments, the A group is a vinyl group. 1 The group has the formula CH2=C(Y 1 )-vinylidene group, 1 But, 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 But, C1~C 30 In some embodiments, A is a hydrocarbyl group. 1The group is a vinyl group and a group of formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 But, C1~C 30 In 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 But, 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 But, C1~C 30 In 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 the vinylidene group of formula Y 1 A mixture of CH=CH- and vinylene groups, wherein Y 1 But, C1~C 30 It is a hydrocarbyl group.

[0044] 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 However, the vinyl group to formula Y is 0.99:0.01 to 0.01:0.99. 1 The ratio of vinylene groups of CH=CH- is included, and Y 1 But, C1~C 30 It is a hydrocarbyl group.

[0045] 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 The vinyl group pair formula CH2=C(Y 1 )-vinylidene group ratio, Y 1 But, C1~C 30 It is a hydrocarbyl group.

[0046] 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 However, the formula CH2=C(Y 1 )-vinylidene group formula 1 The ratio of vinylene groups of CH=CH- is included, and Y 1 But, C1~C 30 It is a hydrocarbyl group.

[0047] 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 the vinylidene group of formula Y 1 A is a mixture of CH=CH- and vinylene groups, 1 However, the vinyl group to formula Y is 0.99:0.01 to 0.01:0.99. 1 Vinylene group of the formula CH=CH- and CH2=C(Y 1 )-, including the ratio of the total vinylidene groups to the total vinyl groups, Y 1 But, C1~C 30 It is a hydrocarbyl group.

[0048] 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.

[0049] In some embodiments, L 1 is an interpolymer that includes units derived from at least two different types of monomers, such as monomers and comonomers. 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 can be selected from any of the suitable monomers described above.

[0050] 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. Each of the monomer and comonomer may be selected from any of the suitable monomers described above.

[0051] In certain embodiments, L 1 is an ethylene / alpha-olefin copolymer. In some embodiments, L 1 is a unit derived from ethylene and C3-C 30 An ethylene / alpha-olefin copolymer comprising an alpha-olefin, the copolymer having the formula A 1 L 1 and A 1 L 1 L 2 A 2 Each of the polyolefins of formula A 1 L 1 and A 1 L 1 L 2 A 2 Based on the total weight of each of the polyolefins, C3 to C4 contain an amount of ethylene that is 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. 30 The alpha-olefin may be selected from any of the suitable alpha-olefins described above. In certain embodiments, C3-C 30The alpha-olefin may 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 is a unit derived from ethylene and C3-C 30 Ethylene / alpha-olefin copolymers containing alpha-olefins, C3-C 30 The alpha-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene.

[0052] In a further embodiment, L 1 is a propylene / alpha-olefin copolymer. 1 is propylene, and ethylene or C4-C 30 The propylene / alpha-olefin copolymer may be a propylene / alpha-olefin copolymer containing units derived from any of the alpha-olefins represented by the formula A 1 L 1 and A 1 L 1 L 2 A 2 Each of the polyolefins of formula A 1 L 1 and A 1 L 1 L 2 A 2 Based on the total weight of each of the polyolefins, C4 to C5 contain an amount of propylene that is 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. 30 The alpha-olefin may be any of the suitable alpha-olefins described above. In certain embodiments, the alpha-olefin may be any of the C4-C 30 The alpha-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 is propylene, and ethylene or C4-C 30It may be a propylene / alpha-olefin copolymer containing units derived from any of the alpha-olefins, C4 to C 30 The alpha-olefin is selected from the group consisting of 1-butene, 1-hexene, and 1-octene.

[0053] 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 described above. 1 The first monomer is ethylene or propylene, and the second monomer is C3-C 30 It is a terpolymer that includes an alpha-olefin or styrene and a diene or polar monomer as the third monomer.

[0054] In some embodiments, L 1 contains 0 to 10% by weight of units derived from diene monomers. 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. In further embodiments, L 1 may be substantially free of units derived from diene monomers. For example, in certain embodiments, L 1 may contain 0 to 0.2 wt %, or 0 to 0.01 wt %, or 0 to 0.001 wt %, or 0 to 0.0001 wt % of units derived from diene monomers.

[0055] In certain embodiments, L 1 is an olefin block copolymer as defined herein. In a further embodiment, L 1 is a block complex, a particular block complex, or a crystalline block complex as defined herein.

[0056] In certain embodiments, L 2 The telechelic polyolefin is A 1 L 1 CH2CH(Y 2)A 2 where Y 2 is hydrogen or C1-C 30 Hydrocarbyl groups such as -CHCH(Y 2 In certain embodiments, Y 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.

[0057] In some embodiments, A 2 is a hydrocarbyl group containing a sterically hindered double bond. 2 is a hydrocarbyl group containing two or more double bonds which are sterically hindered.

[0058] In certain embodiments, due to a sterically hindered double bond, A 2 The group is polyolefin L 1 Since L is a group that is not readily incorporated by the active catalyst under the process conditions used to make 1 A is directly integrated along the backbone of 2 However, 13 C NMR or similar 13 % or less, or 0.5 mol % or less, or 0.1 mol % or less, or not detectable, as determined by C NMR.

[0059] In some embodiments, A 2 is a hydrocarbyl group containing a sterically hindered double bond, the sterically 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 alpha carbon.

[0060] In a further embodiment, A 2is a hydrocarbyl group containing two or more sterically hindered double bonds, each sterically 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 alpha carbon.

[0061] In certain embodiments, A 2 is a hydrocarbyl group containing a functional group, the functional group being selected from the group consisting of vinylidene groups, vinylene groups, trisubstituted alkenes, and vinyl groups attached to a branched alpha carbon.

[0062] 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 a vinylidene group, a vinylene group, a trisubstituted alkene, and a vinyl group attached to a branched alpha carbon.

[0063] 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 monocyclic, bicyclic, or polycyclic, and each of which may contain one or more sterically hindered double bonds.

[0064] Furthermore, A 2 When A is a cyclic hydrocarbyl group, each sterically hindered double bond or functional group therein may be an endocyclic double bond, an exocyclic double bond, or an acyclic double bond. For example, A 2 may be a cyclic hydrocarbyl group comprising a vinylene group, the double bond of which may be an endocyclic double bond or an acyclic double bond. 2 may be a cyclic hydrocarbyl group that includes a vinylidene group, and the double bond of the vinylidene group may be an exocyclic double bond or an acyclic double bond. 2may be a cyclic hydrocarbyl group comprising a trisubstituted alkene, the double bond of which may be an endocyclic double bond, an exocyclic double bond, or an acyclic double bond. 2 can be a cyclic hydrocarbyl group comprising a vinyl group attached to a branched alpha carbon, the vinyl group attached to the branched alpha carbon being an acyclic double bond.

[0065] 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.

[0066] 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. 2 is 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.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] Exemplary A 2 Groups include, but are not limited to, the following: [ka]

[0071] With respect to each of (AA) to (AZ) and (AZ1), [ka] The symbol (wavy line symbol) is the formula A 1 L 1 L 2 A 2 L 2 For example, the point of attachment to the 1 L 1 CH2CH(Y 2 )A 2 The carbon bonded to the hydrogen of "Y 2 " and "A 1 L 1 In addition, for each of (AA) to (AZ) and (AZ1), [ka] The symbol (wavy line symbol) represents the formula Al(CHCH(Y 2 )A2 )3 and Zn(CH2CH(Y 2 )A 2 )2, the carbon bonded to the hydrogen of the chain transfer agent and Y 2 Represents the connection point with.

[0072] For each of (AA) through (AF), the endocyclic double bond may be between any two adjacent carbon atoms that are ring members.

[0073] For each of (AD) through (AF), the pendant methyl group may be attached to any carbon atom that is a ring member.

[0074] For each of (AG)-(AL), the exocyclic double bond may be attached to any ring carbon atom that is not already attached to three or more carbon atoms.

[0075] In some embodiments, (A) a polyolefin component (or formula A 1 L 1 and A 1 L 1 L 2 A 2 Each of the polyolefins) 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.

[0076] In some embodiments, (A) a polyolefin component (or formula A 1 L 1 and A 1 L 1 L 2 A 2Each of the polyolefins) 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.

[0077] In some embodiments, (A) a polyolefin component (or formula A 1 L 1 and A 1 L 1 L 2 A 2 Each of the polyolefins) comprises or has an average molar mass (Mz) 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 5,000 to 500,000 g / mol, or 10,000 to 500,000 g / mol, according to a GPC method described herein or a similar GPC method.

[0078] In some embodiments, (A) a polyolefin component (or formula A 1 L 1 and A 1 L 1 L 2 A 2 Each of the polyolefins) 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.

[0079] In some embodiments, (A) a polyolefin component (or formula A 1 L 1 and A 1 L 1 L 2 A 2each of the polyolefins 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.

[0080] In some embodiments, (A) a polyolefin component (or formula A 1 L 1 and A 1 L 1 L 2 A 2 Each of the polyolefins comprises or has a melt index (I2) according to ASTM D-1238, condition 190°C / 2.16 kg, of 0.01 to 2000 g / 10 min, 0.01 to 1,500 g / 10 min, 0.01 to 1,000 g / 10 min, or 0.01 to 500 g / 10 min, or 0.01 to 100 g / 10 min, or 0.5 to 50 g / 10 min, or 0.5 to 30 g / 10 min.

[0081] In some embodiments, (A) a polyolefin component (or formula A 1 L 1 and A 1 L 1 L 2 A 2 Each of the polyolefins has a T in the range of -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.

[0082] In some embodiments, (A) a polyolefin component (or formula A 1 L 1 and A 1 L 1 L 2 A 2Each of the polyolefins) is 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.

[0083] In some embodiments, (A) a polyolefin component (or formula A 1 L 1 and A 1 L 1 L 2 A 2 Each of the polyolefins 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 the DSC method described herein or a similar DSC method.

[0084] In some embodiments, (A) a polyolefin component (or formula A 1 L 1 and A 1 L 1 L 2 A 2 Each of the polyolefins (a) and (b) 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.

[0085] In some embodiments, (A) a polyolefin component (or formula A 1 L 1 and A 1 L 1 L 2 A 2Each of the polyolefins 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 the DSC method described herein or a similar DSC method. g Contains or has.

[0086] In some embodiments, L 1 is substantially free of units derived from diene monomers and has the formula A 1 L 1 The polyolefin of formula A has a total number of unsaturations of 0.6 or more, or 0.7 or more, or 0.8 or more, or 0.9 or more, or 1.0 or more, or 1.1 or more, or 1.2 or more, or 1.3 or more, 1 L 1 L 2 A 2 The polyolefins of formula (I) contain a total number of unsaturations 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 number of unsaturations is (unsaturations / 1000C)*(1000C / chain)=(unsaturations / 1000C)*(Mn / M CH2 / 1000), where the degree of unsaturation / 1000C is: 1 H NMR, Mn was measured by GPC, 13 is the number average molecular weight corrected for composition as measured by C NMR, M 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 two backbone carbon atoms, respectively. Thus, Mn corrected for composition is the Mn measured by GPC multiplied by (mol % C2 / 2 + mol % C3 / 3 + mol % C8 / 8 + mol % ENB / 9) / 2. Here, 13 C NMR, 1H NMR, and GPC refer to the methods described herein or similar methods. As used herein, "substantially free" refers to, for example, L 1 But, formula A 1 L 1 and A 1 L 1 L 2 A 2 This means that the polyolefin contains 0 to 0.001% by weight of units derived from a diene monomer, based on the total weight of each of the polyolefins.

[0087] In some embodiments, L 1 is the formula A 1 L 1 and A 1 L 1 L 2 A 2 and each of the polyolefins of formula A contains 1 to 8 wt. %, or 1 to 5 wt. %, or 1 to 3 wt. % of units derived from a diene monomer, based on the total weight of each of the polyolefins of formula A. 1 L 1 The polyolefin of (X D +0.6) or more, (X D +0.7) or more, (X D +0.8) or more, (X D +0.9) or more, (X D +1) or more, (X D +1.1) or more, (X D +1.2) or more, or (X D +1.3) or more of unsaturation, 1 L 1 L 2 A 2 The polyolefin of (X 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) or more, (X D +1.8) or more, or (X D +1.9) or more, wherein X D But, L 1is the degree of unsaturation from units derived from diene monomers, the degree of unsaturation being measured as described in the previous paragraph.

[0088] (A) Preparation of polyolefin component The present disclosure further provides a compound of formula A 1 L 1 1. A process for preparing a polyolefin component comprising an unsaturated polyolefin of 1) combining starting materials including (a1) a monomer component, (b1) a chain transfer agent component, and (c1) 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 (a1) 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) Formula A 1 L 1 and recovering a product comprising a polyolefin component comprising an unsaturated polyolefin of (b1) the chain transfer agent component comprises an alkylaluminum of the formula Al(d)3; d is independent for each occurrence, C1 to C 10 is an alkyl group, 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 CH=CH- and vinyl groups of the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 and a mixture of CH=CH- and vinylene groups; Y 1 However, each occurrence is independent, C1~C 30 is a hydrocarbyl group, Formula A 1 L 1 wherein the unsaturated polyolefin comprises a weight average molecular weight of 1,000 to 10,000,000 g / mol.

[0089] The present disclosure further provides a compound of formula A 1 L 1 and polyolefins of formula A 1 L 1 L 2 A 2 1. A process for preparing a polyolefin component comprising a telechelic polyolefin of 1) combining starting materials including (a1) a monomer component, (b1) a chain transfer agent component, and (c1) 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 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) Formula A 1 L 1 and polyolefins of formula A 1 L 1 L 2 A 2 and recovering a product comprising a polyolefin component comprising the telechelic polyolefin of (b1) The chain transfer agent component is an alkylaluminum of the formula Al(d)3 and an alkylaluminum of the formula Al(CHCH(Y 2 )A 2 ) 3 organoaluminum compounds, d is C1 to C 10 is an alkyl group, L 1 is, independently at each occurrence, a polyolefin; A 1 represents, independently at each occurrence, a vinyl group, of the 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 CH=CH- and vinyl groups of the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 and a mixture of CH=CH- and vinylene groups; Y 1 However, each occurrence is independent, C1~C 30 is a hydrocarbyl group, L 2 But, C1~C 32 is a hydrocarbylene group, Y 2 is independently hydrogen or C1-C 30 is a hydrocarbyl group, A 2 is, independently at each occurrence, a hydrocarbyl group containing a sterically hindered double bond; Formula A 1 L 1 and an unsaturated polyolefin of formula A 1 L 1 L 2 A 2 wherein each of the telechelic polyolefins comprises a weight average molecular weight of 1,000 to 10,000,000 g / mol.

[0090] Formula A 1 L 1 and an unsaturated polyolefin of formula A 1 L 1 L 2 A 2 In the process for preparing a polyolefin component comprising a telechelic polyolefin of formula (b1), the chain transfer agent component is a 1:99 to 99:1, or 10:90 to 90:10, or 20:80 to 80:20, or 30:70 to 70:30, or 40:60 to 60:40, or 50:50 alkylaluminum of formula Al(d) to formula Al(CHCH(Y 2 )A 2 The organoaluminum compound of formula A prepared by the above process may include a ratio of 1:1 to 1:1. 1 L 1and an unsaturated polyolefin of formula A 1 L 1 L 2 A 2 Each of the telechelic polyolefins of formula A may have a weight average molecular weight 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. 1 L 1 and an unsaturated polyolefin of formula A 1 L 1 L 2 A 2 A polymer other than the telechelic polyolefin of formula A is prepared independently from the above process and then 1 L 1 and / or an unsaturated polyolefin of formula A 1 L 1 L 2 A 2 The present invention can be blended with telechelic polyolefins.

[0091] L 1 , A 1 , Y 1 , L 2 , Y 2 , and A 2 The embodiments described above for each of the groups apply to the present processes disclosed herein. 1 L 1 and an unsaturated polyolefin of formula A 1 L 1 L 2 A 2 The embodiments described above for the telechelic polyolefins apply to the present process disclosed herein.

[0092] The starting material of step 1) of any of the above processes may further include (d1) a solvent. The starting material (d1) 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.

[0093] Step 1) of any of the above processes may comprise: (a1) converting monomers and comonomers of the monomer component into L 1 During step 1), the polymeric aluminum species can be formed via chain transfer between (b1) the chain transfer agent component and the active catalyst from (c1) the catalyst component. The polymeric aluminum species then undergoes beta-hydride elimination during step 2) to form the (A) polyolefin component of formula A 1 L 1 and / or an unsaturated polyolefin of formula A 1 L 1 L 2 A 2 A product comprising a telechelic polyolefin of is formed, which is recovered during step 3).

[0094] Step 1) of any of the above processes 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 the reaction zone and polymer product is continuously removed from the reaction zone. As used in this context, within the scope of the terms "continuous" and "continuously" are those processes in which there is intermittent addition of reactants and removal of products at regular or irregular intervals, such that over time the overall process is substantially continuous.

[0095] Step 1) of any of the above processes 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.

[0096] One skilled in the art will understand that the amount of each component of the starting materials, including components (a1)-(d1), may be varied to produce polymers differing in one or more chemical or physical properties.

[0097] Without limiting the scope of the invention in any way, one means for carrying out step 1) is as follows: Monomers of (a1) monomer component are continuously introduced into a stirred tank reactor together with any solvent or diluent. The reactor contains a liquid phase consisting essentially of monomers together with any solvent or diluent and dissolved polymer. Preferred solvents include C 4~10or mixtures thereof, particularly an alkane or mixtures of alkanes such as hexane, and one or more of the monomers used in the polymerization. (b1) Chain transfer agent component and (c1) catalyst component are continuously or intermittently introduced into the reactor liquid phase or any recycle portion thereof. The reactor temperature and pressure can be controlled by adjusting the solvent / monomer ratio, the rate of addition of the (c1) catalyst component, as well as by cooling or heating coils, jackets, or both. The polymerization rate is controlled by the rate of addition of the (c1) catalyst component. When the (a1) monomer component includes ethylene and at least one comonomer, the ethylene content in the polymer product is determined by the ratio of ethylene to comonomer in the reactor, which 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.

[0098] Alternatively, step 1) of any of the above processes may be carried out under different process conditions in two or more reactors connected in series and operating under steady-state polymerization conditions, or in two or more zones of a reactor operating under plug-flow polymerization conditions. Alternatively, step 1) of any of the above processes may be carried out in one or more continuous loop reactors operating under adiabatic or non-adiabatic solution polymerization conditions, or a combination of the aforementioned reactor conditions, optionally with separate addition of catalyst and / or chain transfer agent, with or without monomer, catalyst or chain transfer agent gradients established between the different zones.

[0099] Following step 1), the polymer solution is heated according to step 2), which is further described below. Such heating includes, but is not limited to, heating in a post-reactor heater. Following 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 kill agent, such as water, steam, or alcohol, and degassing and separating the gaseous monomer and residual solvent or diluent under reduced pressure, and, if necessary, further degassing in an apparatus such as a degassing extruder.

[0100] In some embodiments, the solution of step 2) of any of the above processes 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.

[0101] In some embodiments, the solution of step 2) of any of the above processes 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.

[0102] In some embodiments, the solution of step 2) of any of the above processes 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., , 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.

[0103] For example, in certain embodiments, the solution of step 2) of any of the above processes 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.

[0104] In a further embodiment, the solution of step 2) of any of the above processes 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.

[0105] In a further embodiment, the solution of step 2) of any of the above processes 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 is then cooled 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. The temperature is maintained at 0 to 300°C, or 220 to 290°C, or 230 to 290°C, or 240 to 280°C for a period 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.

[0106] (a1) Monomer component (a1) The monomer component is L 1Examples of suitable monomers and comonomers include any monomer selected from those discussed herein with respect to. Examples of suitable monomers and comonomers include ethylene and alpha-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; 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-1,4,8-decadiene. conjugated or non-conjugated dienes such as 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, and the mixed isomers of dihydromyrcene and dihydroocimene; 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-cyclopentenyl ... These include, but are not limited to, norbornene and alkenyl, alkylidene, cycloalkenyl, and cycloalkylene norbornenes, such as cyclohexylidene-2-norbornene, and norbornadiene; aromatic vinyl compounds, such as styrenes, mono- or polyalkylstyrenes (including styrene, o-methylstyrene, t-methylstyrene, m-methylstyrene, p-methylstyrene, o,p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene, and p-ethylstyrene).

[0107] In some embodiments, the (a1) monomer component includes an ethylene monomer. In some embodiments, the (a1) monomer component includes a propylene monomer. In some embodiments, the (a1) monomer component includes an ethylene monomer and a C3-C30 alpha-olefin comonomer. The C3-C30 alpha-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 (a1) monomer component includes a propylene monomer and an ethylene or C4-C30 alpha-olefin comonomer. The C4 to C30 alpha-olefins 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.

[0108] In certain embodiments, the (a1) monomer component comprises an ethylene monomer and a C3-C30 alpha-olefin comonomer, the C3-C30 alpha-olefin being selected from the group consisting of propylene, 1-hexene, 1-butene, and 1-octene. In further embodiments, the (a1) monomer component comprises an ethylene monomer and a propylene comonomer. In further embodiments, the (a1) monomer component comprises an ethylene monomer and a 1-hexene comonomer. In further embodiments, the (a1) monomer component comprises an ethylene monomer and a 1-butene comonomer. In further embodiments, the (a1) monomer component comprises an ethylene monomer and a 1-octene comonomer.

[0109] In a further embodiment, the (a1) monomer component comprises a propylene monomer and an ethylene or C4-C30 alpha-olefin comonomer, the C4-C30 alpha-olefin being selected from the group consisting of 1-hexene, 1-butene, and 1-octene. In a further embodiment, the (a1) monomer component comprises a propylene monomer and an ethylene comonomer. In a further embodiment, the (a1) monomer component comprises a propylene monomer and a 1-hexene comonomer. In a further embodiment, the (a1) monomer component comprises a propylene monomer and a 1-butene comonomer. In a further embodiment, the (a1) monomer component comprises a propylene monomer and a 1-octene comonomer.

[0110] In certain embodiments, the (a1) 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 ethylene 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 a C3 to C30 alpha-olefin comonomer, wherein the C3 to C30 alpha-olefin is selected from the group consisting of propylene, 1-hexene, 1-butene, and 1-octene.

[0111] In certain embodiments, the (a1) 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 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 ethylene or C4 to C30 alpha-olefin comonomer, wherein the C4 to C30 alpha-olefin is selected from the group consisting of 1-hexene, 1-butene, and 1-octene.

[0112] In some embodiments, the (a1) monomer component includes 0 to 10 wt % of a diene monomer. For example, the (a1) monomer component may include 0.5 to 8 wt %, or 1 to 5 wt %, or 1 to 3 wt % of a diene monomer. In further embodiments, the (a1) monomer component may be substantially free of a diene monomer. For example, in certain embodiments, the (a1) monomer component may include 0 to 0.2 wt %, or 0 to 0.01 wt %, or 0 to 0.001 wt %, or 0 to 0.0001 wt % of a diene monomer.

[0113] (b1) Chain transfer agent (b1) The chain transfer agent component may include any chain transfer agent described herein or disclosed in U.S. Provisional Application Nos. 62 / 786084, 62 / 786100, 62 / 786119, and 62 / 786110.

[0114] The alkylaluminum of formula Al(d)3 is tri(C 1-8) alkylaluminum. Non-limiting examples of alkylaluminum of formula Al(d)3 are triethylaluminum, tri(i-propyl)aluminum, tri(i-butyl)aluminum, tri(n-hexyl)aluminum, and tri(n-octyl)aluminum.

[0115] Without being bound to any particular theory, the alkylaluminum of formula Al(d) is represented by the formula A 1 L 1 contributes to the formation of unsaturated polyolefins of the formula Al(CHCH(Y 2 )A 2 The organoaluminum compounds of formula A 1 L 1 L 2 A 2 This contributes to the formation of telechelic polyolefins.

[0116] In certain embodiments, the (b1) chain transfer agent component has the formula Al(CHCH(Y 2 )A 2 )3, wherein Y 2 is independently hydrogen or C1-C 30 is a hydrocarbyl group, 2 is, independently at each occurrence, a hydrocarbyl group containing a sterically hindered double bond. In a further embodiment, the (b1) chain transfer agent component is represented by the formula Al(CHCH(Y 2 )A 2 )3 is an organoaluminum compound. 2 and A 2 can be any of the above embodiments. 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(Y2 )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.

[0117] 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 an alkylaluminum of formula Al(d), an alkylaluminum of formula Al(e), 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) reacting an alkylaluminum of formula Al(CHCH(Y 2 )A 2 and recovering a product comprising an organoaluminum compound of formula (I) 3, wherein d is, independently at each occurrence, C1 to C6 10 is an alkyl group, Y 2 However, each occurrence is independent of hydrogen and C1-C 30 is a hydrocarbyl group, 2is, independently at each occurrence, a hydrocarbyl group containing a sterically hindered double bond. In certain embodiments, the carbon of d bonded to Al is a carbon bonded to a tertiary carbon. For example, in certain embodiments, the alkylaluminum of formula Al(d)3 is triisobutylaluminum. In certain embodiments, in step (b), the organoaluminum solution is heated at a temperature of 60-200° C., or 80-180° C., or 100-150° C., or 110-130° C. In further embodiments, in step (b), the organoaluminum solution is heated 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.

[0118] Formula Al(CHCH(Y 2 )A 2 In the thermal process for preparing the organoaluminum compound of formula 3, Y 2 and A 2 may be any of the embodiments described above. 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 to an alkylaluminum of formula CH2=C(Y 2 )A 2 The starting material for step (a) may comprise a ratio of hydrocarbons of the formula CH2=C(Y 2 )A 2 wherein each Y 2 independently for each occurrence hydrogen or C1-C 30 A is a hydrocarbyl group, and each hydrocarbon A 2 is, independently at each occurrence, a hydrocarbyl group containing a sterically hindered double bond, and the starting materials are a 1:10, or 1:5, or 1:3 mixture of alkylaluminum of the formula Al(d)3 to alkylaluminum of the formula CH2=C(Y 2 )A 2 In certain embodiments, the ratio of one or more hydrocarbons of Y2 may be selected from the group consisting of hydrogen, methyl and ethyl groups; A 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. 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 through the use of vacuum and optional heat.

[0119] 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 However, each occurrence is independent, C1~C 30 A is a hydrocarbyl group of the formula: 2 is, independently at each occurrence, a hydrocarbyl group that contains a sterically hindered double bond, and may be prepared by a catalytic process. Formula Al(CHCH(Y 2 )A 2 In the catalytic process for preparing organoaluminum compounds of formula 3, Y 2 is C1~C 30 is a hydrocarbyl group, 2may be any of the embodiments described above. Each of the procatalyst, optional cocatalyst, and optional solvent may be any of those disclosed herein. The starting material for step (a) is a 1:10, or 1:5, or 1:3 mixture of Al(Y 2 )3 alkylaluminum pair of the formula CH2=CHA 2 The starting material for step (a) may comprise a ratio of hydrocarbons of the formula CH2=CHA 2 wherein each A of the hydrocarbons may include one or more of the following: 2 is, independently at each occurrence, a hydrocarbyl group containing a sterically hindered double bond, and the starting materials are a 1:10, or 1:5, or 1:3 mixture of the formula Al(Y 2 )3 alkylaluminum pair of the formula CH2=C(Y 2 )A 2 In certain embodiments, the ratio of one or more hydrocarbons of Y 2 is C1~C 10 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] (c1) Catalyst component In certain embodiments, the (c1) catalyst component comprises a procatalyst. In these embodiments, the procatalyst becomes an active catalyst for polymerizing unsaturated monomers without the use of a cocatalyst. In further embodiments, the (c1) catalyst component comprises a procatalyst and a cocatalyst, whereby an active catalyst is formed by the combination of the procatalyst and the cocatalyst. In these embodiments, the (c1) active catalyst component may comprise a ratio of procatalyst to cocatalyst of 1:2, or 1:1.5, or 1:1.2.

[0121] 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 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."

[0122] 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.

[0123] 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 polychelating 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 is, independently at each occurrence, a group containing delocalized π electrons or one or more electron pairs through which K is bonded to M, said K group containing up to 50 atoms not including 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 is, independently at each occurrence, a monovalent anionic moiety having up to 40 non-hydrogen atoms, optionally one or more X groups may be joined together to form a divalent or polyvalent anionic group, further optionally one or more X groups and one or more Z groups may be joined 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 formal oxidation state of +2; Z is, independently at each occurrence, 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, k+x, is equal to the formal oxidation state of M.

[0124] 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.

[0125] 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 heteroatom, where the heteroatom is selected from Groups 14-16 of the Periodic Table, and such hydrocarbyl-substituted heteroatom radicals are 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 together 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.

[0126] 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 C 1~10Hydrocarbyl-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.

[0127] Boratabenzenyl ligands are anionic ligands that are boron-containing analogues to benzene. They have been previously known in the art, 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 including 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.

[0128] 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 previously defined.

[0129] 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, by which K is bonded to M, said K group containing up to 50 atoms not including 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, for 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 is, independently at each occurrence, 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, k+x, is equal to the formal oxidation state of M.

[0130] 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): e where E is silicon, germanium, tin, or carbon, R' is, independently at each occurrence, 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' is, independently at each occurrence, methyl, ethyl, propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy, or phenoxy.

[0131] 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 is independently selected at each occurrence 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″ is, independently at each occurrence, an anionic ligand group of up to 40 non-hydrogen atoms, or two X″ groups taken together form a divalent anionic ligand group of up to 40 non-hydrogen atoms, or taken together is 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 previously defined.

[0132] 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.

[0133] Suitable X" groups are selected from hydrido, 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.

[0134] 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 previously defined, and Z is a substituent of up to 50 non-hydrogen atoms that together with K forms a metallocycle with M.

[0135] 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.

[0136] 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 is independently selected at each occurrence from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halo, and combinations thereof; 2 has up to 20 non-hydrogen atoms, or adjacent R 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' is independently at each occurrence hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy, and combinations thereof, said R' having up to 30 carbon or silicon atoms.

[0137] 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 containing no 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, said R group having up to 40 atoms not including hydrogen atoms and optionally having 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. BR 6 , 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 represents, independently at each occurrence, 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.

[0138] Additional 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 including 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 including 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 with M, a contains boron, or a member of group 14 of the periodic table of 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 is, independently at each occurrence, a neutral coordination compound having up to 20 atoms; x is 0, 1, or 2; z is zero or one.

[0139] Additional 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 ' is, independently at each occurrence, a C 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. b and R b’ Illustrative 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 metallic element selected from Groups 3 to 15 of the Periodic Table or the Lanthanide series. b is a Group 3 to 13 metal, 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 including hydrogen. bExemplary groups include halides; hydrides; hydrocarbyl, hydrocarbyloxy, di(hydrocarbyl)amide, hydrocarbyleneamide, di(hydrocarbyl)phosphide; hydrocarbyl sulfide; 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 inert substituents include halogen, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, di(hydrocarbyl)amine, tri(hydrocarbyl)silyl, and nitrile groups. Preferred Z groups are 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;

[0140] 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 R b The group is a C1-8 straight chain alkyl group.

[0141] 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, more preferably 3 to 30, and most preferably 4 to 20, atoms not including hydrogen, 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 e Groups, or mixtures of Rd and Re groups, may together form divalent or polyvalent derivatives of hydrocarbyl groups such as 1,4-butylene, 1,5-pentylene, or cyclic rings, or polycyclic fused rings, polyvalent hydrocarbyl or heterohydrocarbyl groups such as naphthalene-1,8-diyl.

[0142] Suitable examples of the polyvalent Lewis base complexes include the following: [ka] In the formula, R d’ is independently selected at each occurrence from the group consisting of hydrogen and a C1-50 hydrocarbyl group, optionally containing one or more heteroatoms, or an inertly substituted derivative thereof, 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 containing no 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.

[0143] 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 11 is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl, and inertly substituted derivatives thereof containing 1 to 30 atoms not including 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; R12 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 The numbers range from 0 to 5 indicating the number of groups, and bonds, optional bonds and electron donating interactions are represented by lines, dotted lines and arrows, respectively.

[0144] Suitable complexes are those in which the ligand formation is from the amine group and optionally one or more additional 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 16 is hydrogen, halo, or an alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, or silyl group of up to 20 atoms not including hydrogen, or an adjacent R 13 , R 14 , R 15 , or R 16 The groups may be joined together to form fused ring derivatives, with the 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 previously defined; R 13 , R 14 , R 15 and R 16 is as previously defined, preferably R 13 , R 14 , and R 15 is hydrogen or C1-4 alkyl, and R 16 is C 6~20 aryl, most preferably naphthalenyl; R a independently for each occurrence, C 1~4 alkyl, a is 1 to 5, and most preferably R a is isopropyl or t-butyl, R 17 and R 18 is independently hydrogen, halogen, or C 1~20 is an alkyl or aryl group, most preferably R 17 and R 18 one of which 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.

[0145] Exemplary metal complexes for use herein as catalysts correspond to the formula: [ka] In the formula, X 1 is, at each occurrence, a halide, an N,N-dimethylamide, or a C1-4 alkyl, preferably at each occurrence, X 1 is methyl, R f is independently at each occurrence hydrogen, halogen, C1-20 alkyl, or C6-20 aryl, or two adjacent Rf groups are joined together to form a ring, and f is 1 to 5; R c are independently defined for each occurrence as hydrogen, halogen, or C 1~20 Alkyl or C 6~20 Aryl or two adjacent R c the groups are joined together to form a ring and c is 1-5.

[0146] 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.

[0147] 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)]dimethylhafnium, [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium di(N,N-dimethylamide), [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium dichloride, [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]dimethylhafnium, [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium di(N,N-dimethylamide), [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium dichloride, [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]dimethylhafhium, [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafhium(di(N,N-dimethylamido), and [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthren-5-yl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium dichloride.

[0148] 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.

[0149] Additional suitable procatalysts include imidazole-amine compounds corresponding to those disclosed in WO2007 / 130307A2, WO2007 / 130306A2, and U.S. Patent Application Publication No. 20090306318A1, which are incorporated by reference in their entireties. Such imidazole-amine compounds include those corresponding to the formula: [ka] wherein X is, independently at each occurrence, 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, hydrogen, halogen, or a monovalent polyatomic anionic ligand, or two or more R 1 groups are linked together, thereby forming a polyvalent fused ring system, R 2 is, independently at each occurrence, hydrogen, halogen, or a monovalent polyatomic anionic ligand, or two or more R 2 groups are linked together, thereby forming a polyvalent fused ring system, R 4 is hydrogen, alkyl, aryl, aralkyl, trihydrocarbylsilyl, or trihydrocarbylsilylmethyl of 1 to 20 carbons.

[0150] Further examples of such imidazole-amine compounds include, but are not limited to, the following: [ka] In the formula, R 1 But for each occurrence, C 3~12 is an alkyl group, the carbon attached to the phenyl ring is secondary or tertiary substituted, R 2 is independently for 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 or C 1~6 alkyl or cycloalkyl, or 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.

[0151] Additional suitable metal complexes of polyvalent Lewis bases for use herein include compounds according to the formula: [ka] , In the formula, R 20 is an aromatic or inertly substituted aromatic group containing 5 to 20 atoms not including hydrogen, or a polyvalent derivative thereof; T 3 is a hydrocarbylene or hydrocarbylsilane group having 1 to 20 atoms, not including 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 including 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.

[0152] 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 containing 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 containing no hydrogen; 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.

[0153] 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 But, 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 But for each occurrence, C 3~6 Alkylene group, C 3~6 cycloalkylene groups, or inertly substituted derivatives thereof, R 21 is independently at each occurrence hydrogen, halo, hydrocarbyl, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl of up to 50 atoms containing no hydrogen; G is, independently at each occurrence, a halo, or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not including hydrogen, or two G groups together are a divalent derivative of the aforementioned hydrocarbyl or trihydrocarbylsilyl groups.

[0154] 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, in particular methyl; T 4is propane-1,3-diyl or butane-1,4-diyl; G is chloro, methyl, or benzyl.

[0155] Exemplary metal complexes of the above formula are: [ka]

[0156] Suitable metal complexes for use in accordance with the present disclosure further include compounds corresponding to the formula: [ka] , During the ceremony, M is zirconium or hafnium; R 20 is, independently at each occurrence, a divalent aromatic or inertly substituted aromatic radical containing 5 to 20 atoms not containing hydrogen; T 3 is a divalent hydrocarbon or silane group having 3 to 20 atoms not containing hydrogen, or an inertly substituted derivative thereof; R D is, independently for each occurrence, a monovalent ligand group of 1 to 20 atoms containing no hydrogen, or two R D The groups taken together are a divalent ligand group of 1 to 20 atoms containing no hydrogen.

[0157] Such complexes may correspond to the formula: [ka] During the ceremony, Ar 2 is independently at each occurrence an arylene, or an alkyl-, aryl-, alkoxy-, or amino-substituted arylene group of 6 to 20 atoms, or any atom of any substituent, not including hydrogen; T 3is a divalent hydrocarbon bridging group of 3 to 20 atoms not containing hydrogen, preferably a divalent substituted or unsubstituted C 3~6 is an aliphatic, alicyclic, or bis(alkylene)-substituted alicyclic group; R D is, independently for each occurrence, a monovalent ligand group of 1 to 20 atoms containing no hydrogen, or two R D The groups taken together are a divalent ligand group of 1 to 40 atoms containing no hydrogen.

[0158] Further examples of metal complexes suitable for use herein include compounds of the formula: [ka] , During the ceremony, Ar 4 But for each occurrence, 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, 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 at each occurrence hydrogen, halo, hydrocarbyl of up to 50 atoms not including hydrogen, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy, or amino; R D is independently at each occurrence halo, or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms not containing hydrogen, or two R DThe groups taken together are divalent hydrocarbylene, hydrocarbadiyl, or trihydrocarbylsilyl groups of up to 40 atoms, including no hydrogen.

[0159] 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 21 is independently at each occurrence hydrogen, halo, hydrocarbyl of up to 50 atoms not including hydrogen, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy, or amino; T 4 is propane-1,3-diyl or bis(methylene)cyclohexane-1,2-diyl, R D is independently at each occurrence a halo, or a hydrocarbyl or trihydrocarbylsilyl group of up to 20 atoms containing no hydrogen, or two R D The groups taken together are hydrocarbylene, hydrocarbadiyl, or hydrocarbylsilanediyl groups of up to 40 atoms not including hydrogen.

[0160] Suitable metal complexes according to the present disclosure correspond to the formula: [ka] In the formula, R D is independently at each occurrence chloro, methyl, or benzyl.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] Catalysts with high comonomer incorporation properties are also known to reincorporate in situ prepared long chain olefins that occur 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 chain, 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.

[0165] 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, 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 can be used to prepare branched copolymers from a single monomer, including ethylene.

[0166] Further complexes suitable for use include Group 4-10 derivatives corresponding to the formula: [ka] During the ceremony, M 2 is a metal from Groups 4 to 10 of the Periodic Table of the Elements, preferably a Group 4 metal, 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 in, among other disclosures, J. Am. Chem. Soc., 118, 267-268 (1996), J. Am. Chem. Soc., 117, 6414-6415 (1995), and Organometallics, 16, 1514-1516, (1997).

[0167] 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 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.

[0168] 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 previously defined, 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.

[0169] 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 has 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 including hydrogen atoms, and f is 1 or 2.

[0170] Further suitable procatalysts include those disclosed in WO2017 / 173080 A1, 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 1~5 Two 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 having from 5 to 16 atoms in the ring, excluding any hydrogen atoms.

[0171] 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.

[0172] The metal ligands of formula (i) above provide homoleptic and heteroleptic procatalyst components.

[0173] 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, with respect to its connection to the amine nitrogen of the parent ligand structure, (C1-C 40 ) are primary or secondary alkyl groups. The terms primary and secondary alkyl groups have their usual 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.

[0174] Optionally, two or more Q 1~5 Group or two or more Q 6~10 The groups are each independently combined together to form a ring structure having from 5 to 16 atoms in the ring, excluding any hydrogen atoms.

[0175] In a preferred embodiment, Q 5 and Q 6 are each independently, (C1~C 40 ), most preferably a primary or secondary alkyl group of Q 5 and Q 6 are each independently propyl, isopropyl, neopentyl, hexyl, isobutyl, and benzyl.

[0176] 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 Each independently, R s each R is selected from the group consisting of a substituent and hydrogen; S are independently selected from halogen atoms, polyfluoro-substituted, perfluoro-substituted, 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(RC1 ), or (R C1 )2NC(O) or R S Two of them, together, are unsubstituted (C1-C 18 ) alkylene, and each R S are independently unsubstituted (C1 to C 18 ) alkyl, and each R C1 are independently 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. 10 are 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.

[0177] "[(Si)1-(C+Si) 40 "(Si)1-(C+Si)" means a substituted silyl radical having 1-40 silicon atoms and 0-39 carbon atoms, such that the total number of carbon and silicon atoms is 1-40. 40 ]Examples of substituted organosilyls include trimethylsilyl, triisopropylsilyl, dimethylphenylsilyl, diphenylmethylsilyl, triphenylsilyl, and triethylsilyl.

[0178] 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.

[0179] 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) - , (C 1- C 40 ) HydrocarbylC(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 K , R L , and R M 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.

[0180] 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 where 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.

[0181] 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 Each of is independently unsubstituted (C1 to C 20In some embodiments, each monodentate ligand Z1 is a chlorine atom, (C1-C 10 ) 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 Each of is independently unsubstituted (C1 to C 10 ) hydrocarbyl.

[0182] 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 are 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., -OCC(O)O-), a (C2-C 40 ) Hydrocarbylene dicarbanion, (C1-C 40 ) heterohydrocarbylene dicarbanion, phosphate, or sulfate.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] In one embodiment, the metal-ligand complex of formula (i) is a mononuclear metal complex.

[0187] Further suitable procatalysts include those disclosed in Acc. Chem. Res., 2015, 48(8), pp2209-2220, including, but not limited to, those of the following structure: [ka]

[0188] If you want to have a snack, you can also snack on a snake There is a lot of snowflakes in it The chemical reactions include Watson,PLJAm.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.; Kai,Y.Organometallics 1998,17,3945-3956;Long,DP;Bianconi,PAJAm.Chem.Soc.1996,118,12453-124 54. 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.Macroモルecules 1995,28,7929–7936; 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 for such simple component catalysts include: [ka] During the ceremony, M is Sm or Y and R is a monovalent ligand of up to 50 atoms, not counting hydrogen, preferably a halide or hydrocarbyl.

[0189] Suitable procatalysts include, but are not limited to, the following, designated (Catalyst 1) through (Catalyst 17).

[0190] (Catalyst 1) 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] .

[0191] (Catalyst 2) can be prepared according to the teachings of WO03 / 40195 and WO04 / 24740 and has the following structure: [ka] .

[0192] (Catalyst 3) can be prepared according to methods known in the art and has the following structure: [ka] .

[0193] (Catalyst 4) can be prepared according to the teachings of U.S. Patent Application Publication No. 2004 / 0010103 and has the following structure: [ka] .

[0194] (Catalyst 5) can be prepared according to the teachings of U.S. Pat. No. 7,858,706 (B2) and has the following structure: [ka] .

[0195] (Catalyst 6) can be prepared according to the teachings of U.S. Pat. No. 7,858,706 (B2) and has the following structure: [ka] .

[0196] (Catalyst 7) ​​can be prepared according to the teachings of U.S. Pat. No. 6,268,444 and has the following structure: [ka] .

[0197] (Catalyst 8) can be prepared according to the teachings of U.S. Patent Publication No. 2003 / 004286 and has the following structure: [ka] .

[0198] (Catalyst 9) can be prepared according to the teachings of U.S. Patent Publication No. 2003 / 004286 and has the following structure: [ka] .

[0199] (Catalyst 10) is commercially available from Sigma-Aldrich and has the following structure: [ka] .

[0200] (Catalyst 11) can be prepared according to the teachings of WO2017 / 173080(A1) and has the following structure: [ka] .

[0201] (Catalyst 12) can be prepared according to the teachings of WO2017 / 173080(A1) and has the following structure: [ka] .

[0202] (Catalyst 13) can be prepared according to the teachings of Macromolecules (Washington, DC, United States), 43(19), 7903-7904 (2010) and has the following structure: [ka] .

[0203] (Catalyst 14) can be prepared according to the teachings of WO2011 / 102989(A1) and has the following structure: [ka] .

[0204] (Catalyst 15) can be prepared according to the teachings of U.S. Pat. No. 8,101,696 (B2) and has the following structure: [ka] .

[0205] (Catalyst 16) can be prepared according to the teachings of WO2018 / 170138(A1) and has the following structure: [ka] .

[0206] (Catalyst 17) can be prepared according to the teachings of WO2018 / 170138(A1) and has the following structure: [ka] .

[0207] In certain embodiments, the (c1) catalyst component comprises a procatalyst and a cocatalyst. In these embodiments, the procatalyst can be activated by combining with a cocatalyst (activator), preferably a cation-forming cocatalyst, a strong Lewis acid, or a combination thereof, to form an active catalyst composition.

[0208] 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 hydrocarbyl halide, more particularly perfluorinated tri(aryl)boron compounds, and especially tris(pentafluoro-phenyl)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 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 in the following references for various metal complexes for olefin polymerization: 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.

[0209] 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.

[0210] 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.

[0211] 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 may 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, especially those containing a single boron atom in the anion portion, are commercially available.

[0212] 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) +is the conjugated Bronsted acid of L*, A g- is a non-coordinating, compatible anion having a charge of g-, where g is an integer from 1 to 3.

[0213] More specifically, A g- corresponds to the formula: [M'Q4]-, where: M' is boron or aluminum in the +3 formal oxidation state; 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), 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.

[0214] 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) - where: 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 each instance, Q is hydrocarbyl).

[0215] Particularly useful Lewis base salts are ammonium salts, more preferably containing one or more C 12~40In this embodiment, for example, Q at each occurrence can be a fluorinated aryl group, particularly a pentafluorophenyl group.

[0216] 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.

[0217] In addition to this aspect of the disclosure, useful (L*-H) + Examples of cations include methyldioctadecylammonium cation, dimethyloctadecylammonium cation, and cations containing one or two C 14~18 These include, but are not limited to, ammonium cations derived from a mixture of trialkylamines containing alkyl groups.

[0218] Other suitable ion-forming activating cocatalysts include salts of cationic oxidizing agents and the following formula: (Ox h+ ) g (A g- ) h and 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.

[0219] Examples of cationic oxidizing agents include ferrocenium, hydrocarbyl-substituted ferrocenium, Ag + , or Pb +2 Examples include: A g- Particularly useful examples of are the anions previously defined for the Bronsted acid-containing activating cocatalyst, especially tetrakis(pentafluorophenyl)borate.

[0220] Other suitable ion-forming activating cocatalysts include those which combine a carbenium ion with the following 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 with a charge of -1. For example, one carbenium ion that works well is the trityl cation, or triphenylmethylium.

[0221] Further suitable ion-forming activating cocatalysts include silylium ions and the following formula: (Q 1 3Si) + A - During the ceremony, Q 1 is C1~10 A is a hydrocarbyl. - is as defined above.

[0222] Suitable silylium salt activating cocatalysts include trimethylsilyl tetrakis pentafluorophenyl borate, triethylsilylium tetrakis pentafluorophenyl borate, and their ether-substituted adducts.Silylium salts have been generally disclosed previously 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.

[0223] 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.

[0224] 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, and especially 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.

[0225] 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 imidazolide, substituted imidazolide, imidazolinide, substituted imidazolinide, benzimidazolide, or substituted benzimidazolide anions) can be represented as follows: [ka] During the ceremony, A* + is a cation, particularly a proton-containing cation, with one or two C 10~40 Trihydrocarbyl ammonium cations containing alkyl groups, especially methyldi(C 14~20 alkyl)ammonium cation, Q 3 is independently for each occurrence 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 including hydrogen, such as C 1~20 Alkyl, etc. Q 2 is tris(pentafluorophenyl)borane, or tris(pentafluorophenyl)almane.

[0226] Examples of these catalyst activators include the trihydrocarbyl ammonium salts of the following, especially the methyldi(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.

[0227] 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. WO03 / 10171 discloses a catalyst activator that is an adduct of a Bronsted acid and a Lewis acid. Other activators or methods for activating catalyst compounds are described, for example, in U.S. Pat. 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 aforementioned 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 an alumoxane. In another embodiment, for example, the cocatalyst may not include any specifically named activator or class of activators as disclosed herein.

[0228] In further embodiments, the molar ratio of procatalyst / cocatalyst employed generally ranges from 1:10,000 to 100:1, such as 1:5000 to 10:1, or 1:1000 to 1:1. Alumoxanes, when used by themselves as activating cocatalysts, can be used in large amounts, generally at least 100 times the amount of metal complex on a molar basis.

[0229] When used as an activating cocatalyst, tris(pentafluorophenyl)borane may 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 may generally be used in about equimolar amounts to the metal complex.

[0230] In an exemplary embodiment of the present disclosure, the cocatalyst is [(C 16~18 H 33~37 )2CH3NH]tetrakis(pentafluorophenyl)borate salt.

[0231] Suitable cocatalysts also include those disclosed in U.S. Provisional Patent Applications Nos. 62650423, 62650412, and 62650453, which are incorporated herein by reference in their entireties. Such cocatalysts include those that are ionic complexes comprising an anion and a countercation, wherein 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 radicals (II) and radicals (III); [ka] Each Y is independently carbon or silicon; 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , and R 25 However, independently (C1~C40 ) Alkyl, (C6-C 40 ) Aryl, -OR C , -O-, -SR C , -H, or -F, and when R is a radical according to radical (III), the halogen-substituted R 21~25 At least one of (C1~C 40 ) Alkyl, halogen-substituted (C6-C 40 ) aryl, or -F, with the proviso that when each R is a radical (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, n is 4, each R is a radical (II) and each Y is carbon, each R 11 , R 12 , and R 13 However, halogen substitution (C1-C 40 ) Alkyl, halogen-substituted (C6-C 40 ) aryl, or -F, or R 11 , R 12 , and R 13 provided that the total number of halogen atoms in is at least 6, and each X is a halogen substitute (C1-C 20 ) Alkyl, (C1-C 20 ) Alkyl, halogen-substituted (C6-C 40 )Aryl, (C6-C 40 ) a monodentate ligand independently selected from aryl, triflate, or -S(O)3, and optionally two R groups are covalently linked, and each R N and R C However, independently, (C1~C 30 ) hydrocarbyl or -H.

[0232] Such cocatalysts further include bimetallic activator complexes comprising an anion and a countercation, wherein the anion has 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, and when n is 0, Q is absent; x is 0, 1, or 2, and when x is 0, Q is absent; and each R is independently selected from the group consisting of radicals (II) and radicals (III); [ka] Each Y is independently carbon or silicon; 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , and R 25 However, independently, (C1~C 40 ) Alkyl, (C6-C 40 ) Aryl, -H, -NR N 2, -OR C , -SR C or halogen, and when R is a radical (II), R 11~13 At least one of the following is perhalogenated (C1-C 40 ) Alkyl, Perhalogenated (C6-C 40 ) aryl, or -F, and when R is a radical (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 linked, and R N or R C However, independently, (C1~C 30 ) hydrocarbyl or -H.

[0233] Such cocatalysts further include metallic activator complexes comprising an anion and a counter cation, wherein the anion has the structure: [ka] wherein n is 0 or 1, and each R is independently selected from the group consisting of radicals (II) and radicals (III); [ka] Each Y is independently carbon or silicon; 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , and R 25 However, 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 the halogen-substituted (C1-C 40 ) Alkyl, halogen-substituted (C6-C 40 ) aryl, or -F, and each X is a halogen-substituted (C 20 ) Alkyl or halogen substituted (C6-C 40 ) a monodentate ligand independently selected from aryl, optionally wherein 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 + with the proviso that the anion is Al(C6F5)4.

[0234] (B) Curing component In certain embodiments, the curable compositions of the present disclosure may comprise from 0.01% to 20% by weight (or from 0.05% to 20% by weight, or from 1% to 20% by weight, or from 5% to 15% by weight, or from 5% to 10% by weight, etc.) of a curing component comprising a (B) crosslinker, based on the total weight of the curable composition.

[0235] In certain embodiments, the (B) curing component further comprises a coagent, a cure additive, an accelerator, and / or a scorch inhibitor. In certain embodiments, the (B) curing component comprises a crosslinker and a coagent. In further embodiments, the (B) curing component contains only a crosslinker.

[0236] 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, thiuram disulfides, paraquinone dioxime, dibenzoparaquinone dioxime, sulfur, imidazoles, silanes, metal oxides such as zinc, magnesium, and lead oxides, dinitroso compounds such as p-quinone-dioxime and p,p'-dibenzoylquinone-dioxime, and phenol-formaldehyde resins containing hydroxymethyl or halomethyl functional groups, and combinations thereof. The suitability of any of these crosslinking agents is largely governed by the choice of polymer, as is well known to those skilled in the art of formulation.

[0237] The crosslinking agent may include one or more organic peroxides, including but not limited to alkyl peroxides, aryl peroxides, ester peroxides, carbonate peroxides, diacyl peroxides, ketal peroxides, cyclic peroxides, dialkyl peroxides, ester peroxides, dicarbonates, 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-butyl-cumyl peroxide, 2,5-dimethyl-2,5-di(tert-butyl-peroxy)hexane, 1,3-bis(tert-butyl-peroxyl-isopropyl)benzene, or combinations thereof. An exemplary crosslinking agent is dicumyl peroxide, commercially available under the trade name LUPEROX® from Arkema, or TRIGONOX® from Akzo Nobel. 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, can also be used.

[0238] When a peroxide curing agent is used, a co-activator, or co-agent, may be used in combination with the peroxide curing agent. 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).

[0239] Suitable coagents further include, but are not limited to, the 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-, R1a is H or methyl, the subscript m is an integer equal to 1-4, 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-trivinyl-cyclotrisiloxane, or combinations thereof.

[0240] A scorch inhibitor / retarder is a molecule, or a collection 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 alpha-methylstyrene dimer or AMSD), and allyl-containing compounds as described in US 6,277,925 (B1), column 2, line 62 to column 3, line 46.

[0241] Suitable crosslinkers include those based on sulfur, such as elemental sulfur. When sulfur-based curing agents are used, the following curing agents may be used: amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates, xanthates, 4,4'-dithiodimorpholine, thiuram di- and polysulfides, alkylphenol disulfides, and 2-morpholino-dithiobenzothiazole, tetramethylthiuram disulfide (TMTD), dipentamethylenethiuram tetrasulfide (DPTT), 2-mercapto ... Accelerators and cure activators such as zinc 2-mercaptobenzothiazolate disulfide (MBT), 2-mercaptobenzothiazolate disulfide (MBTS), zinc 2-mercaptobenzothiazolate (ZMBT), zinc diethyldithiocarbamate zinc (ZDEC), zinc dibutyldithiocarbamate (ZDBC), dipentamethylene thiuram tetrasulfide (DPTT), Nt-butylbenzothiazole-2-sulfanamide (TBBS), and mixtures thereof may be used as well.

[0242] Additional 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 may 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"). Common industrial catalysts are "Speier's catalyst", which is HPtCl6, and Karstedt's catalyst, which is an alkene-stabilized platinum(0) catalyst.

[0243] When 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 range is 50°C to 300°C, such as 80°C to 275°C. The time can be determined by one skilled in the art depending on the polymer and curing components selected.

[0244] Alternatively, the crosslinking agent can be activated by exposing it to radiation that causes the production of free radicals from the crosslinking agent. Non-limiting examples of suitable radiation include UV or visible light, electron beam, or beta, gamma, X-ray, or neutron radiation. Radiation is believed to activate crosslinking by generating 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. UV or visible light activation can occur when 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(terbutylperoxy)-2,5-dimethylhexane.

[0245] In some embodiments, a dual cure system comprising at least two activation methods, such as a combination selected from heat, moisture cure, and radiation, may 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. One skilled in the art will be able to readily select the amount of crosslinker based on the desired level of crosslinking, the properties of the polymer, such as molecular weight, molecular weight distribution, comonomer content, the presence of crosslinking promoters, other additives, etc.

[0246] When the (A) polyolefin component 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 unextractable components. The percentage of gel typically increases with increasing crosslinking levels. In cured articles according to the present invention, the percentage gel content can be 5 to 100 percent, or 10 to 95 percent, or 20 to 90 percent, or 30 to 85 percent, or 40 to 80 percent.

[0247] Intended and End Use The compositions 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; molded articles such as blow molded, injection molded, or rotational molded articles; extrudates; fibers; and woven or nonwoven fabrics. The compositions of the present disclosure can further include, 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 or magnesium carbonate, fatty acids and salts thereof, flame retardant additives, scorch inhibitors, antioxidants, stabilizers, colorants, extenders, carbon black, crosslinking agents, foaming agents, activators such as zinc oxide or zinc stearate, plasticizers such as silica, aluminum silicate, dialkyl esters of dicarboxylic acids, anti-aging agents, 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 protection agents.

[0248] Particularly useful are curable formulations that include (A) a polyolefin component. In some embodiments, the curable formulations that include (A) a polyolefin component can be cured via e-beam radiation (electron beam radiation) 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 modify the rheology by curing via e-beam radiation.

[0249] Fibers can be prepared from the composition. Fibers that can be prepared include staple fiber, coarse linen, multicomponent fiber, sheath / core, twisted, and monofilament. Suitable fiber-forming processes include spin-bonding, melt-blowing techniques, 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, extrusion profiles, including profile extrusions or coextrusions, calendared articles, and structures made from such fibers, including drawn, twisted, or crimped yarns or fibers. The new polymers described herein are also useful for forming shaped articles, including wire and cable coating operations, sheet extrusion for vacuum forming operations, and using injection molding, blow molding processes, or rotational molding processes. The compositions can also be formed into processed articles such as those mentioned above using conventional polyolefin processing techniques well known to those skilled in the art of polyolefin processing.

[0250] Dispersions, both aqueous and non-aqueous, can also be formed using the present formulations containing the compositions.

[0251] Additives and adjuvants can be included in any formulation.Suitable additives include organic or inorganic particles, including clay, talc, titanium dioxide, zeolite, powdered metals, organic or inorganic fibers, including carbon fiber, silicon nitride fiber, steel wire or mesh, and nylon or polyester coating, nano-sized particles, clay, etc.; tackifiers, oil extenders, including paraffinic or naphthenic oils; and fillers, such as synthetic polymers, including other natural polymers and other polymers according to the present invention.

[0252] Suitable polymers for blending (and for inclusion in the (A) polyolefin component) include thermoplastic and non-thermoplastic polymers, including natural and synthetic polymers. Such polymers include unsaturated polyolefin thermoplastics (EPDM, polybutadiene, etc.), polyolefin thermoplastics with low or no unsaturation (PE, PP, ethylene / alpha-olefin interpolymers), other elastomers (SBC, PVC, EVA, ionomers, etc.), and other engineering thermoplastics (styrenics, 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, multi-reactor PE 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 "in-reactor" blends of Ziegler-Natta PE and metallocene PE), 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 (Dow Chemical Company under the trade name INFUSE™), propylene-based olefin block copolymers (such as 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 / alpha-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™ from The Dow Chemical Company, TAFMER™ from Mitsui Chemicals, Exact™ from ExxonMobil, and VISTAMAXX™ available from ExxonMobil) may also be useful as components of blends comprising the present polymers.

[0253] Suitable end uses include films; fibers; soft touch articles such as toothbrush handles and instrument handles; gaskets and profiles; adhesives (functional, crosslinked, hot melt); footwear (including soles and insoles); 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; ducting; weatherstripping; cap liners; 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; sealants, belts, conveyor belts, automotive timing belts, gaskets, shock absorbers; 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 crosslinked or non-crosslinked formulations for piping.

[0254] The composition may also contain antiozonants or antioxidants known to those skilled in the art of rubber chemistry. Antiozonants may be physical protectants, such as wax-like materials that come to the surface and protect the part from oxygen or ozone, or may be 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 are 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-migrating.

[0255] Hindered amine light stabilizers (HALS) and UV absorbers can also be used to provide additional stability against UV light. 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 Tex., USA). In addition to the HALS compound, Lewis acids can be included to achieve superior surface quality, as disclosed in U.S. Patent No. 6,051,681.

[0256] In some compositions, an additional mixing process may be used to pre-disperse antioxidants, anti-ozonants, carbon black, UV absorbers, and / or light stabilizers to form a masterbatch, and then form the polymer blend from the masterbatch.

[0257] The composition according to the present 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. Silane-based or other coupling agents may also be used for better filler bonding. Non-limiting examples of suitable silane coupling agents include gamma-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl-tris-(β-methoxy)silane, allyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, β-(3,4-ethoxy-cyclohexyl)ethyltrimethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, gamma-aminopropyltrimethoxysilane, N-β-(aminoethyl)-gamma-aminopropyltrimethoxysilane, and 3-(trimethoxysilyl)propyl methacrylate, vinyltriacetoxysilane, gamma-(meth)acryloxy, propyltrimethoxysilane, and combinations thereof.

[0258] Suitable foams 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 fluorinated methyl, perfluoromethane, fluorinated ethyl, 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoro-ethane (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-tricliloroethane, 1,1-dichloro-1-fluoroethane (HCFC-14 Ib), 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, azodiisobutyro-nitrile, benzenesulfonhydrazide, 4,4-oxybenzenesulfonyl-semicarbazide, p-toluenesulfonyl semi-carbazide, barium azodicarboxylate, N,N'-dimethyl-N,N'-dinitrosoterephthalamide, and trihydrazinotriazine. In some embodiments, the blowing agent is azodicarbonamide isobutane, CO2, or a mixture thereof. The (A) polyolefin component 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 modification.

[0259] 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.

[0260] 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 sample pressing using ASTM D-792, Method B, which is incorporated herein by reference in its entirety.

[0261] 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.

[0262] GPC Sample polymers were tested for their properties via GPC according to the following:

[0263] A high temperature gel permeation chromatography system (GPC IR) 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 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 for 2 h at 160 °C. The injection volume was 200 μL and the flow rate was 1.0 mL / min.

[0264] 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.

[0265] 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 580-8,400,000 grams per mole (g / mol), and the standards were contained in six "cocktail" mixtures. There was at least one order of magnitude separation between the individual molecular weights in each standard mixture. The standard mixtures were purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards were prepared at 0.025 g in 50 mL of solvent for molecular weights equal to or greater than 1,000,000 g / mol, and 0.05 g in 50 mL of solvent for molecular weights less than 1,000,000 g / mol. The polystyrene standards were dissolved at 80° C. with gentle agitation for 30 minutes. To minimize degradation, the narrow standard mixtures were run first, and in descending order from the highest molecular weight (Mw) component. 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.

[0266] 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)

[0267] Here, B has a value of 1.0 and the experimentally determined value of A is approximately 0.41.

[0268] 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.

[0269] The number average, weight average, and z average molecular weights were calculated according to the following formulas:

number

[0270] 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.

[0271] MWD was expressed as the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn).

[0272] 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.

[0273] The GPC system consisted of a 150°C high temperature chromatograph equipped with an on-board differential refractometer (RI) from Waters (Milford, Massachusetts) (other suitable high temperature GPC instruments include Polymer Laboratories (Shropshire, UK) Model 210 and Model 220). Additional detectors could include an IR4 infrared detector from Polymer ChAR (Valencia, Spain), a two-angle laser light scattering detector model 2040 from Precision Detectors (Amherst, Mass.), 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.

[0274] 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 (MixA LS, Polymer Lab) column such as four 30 cm long Shodex HT803 13 micron columns or four 30 cm long Polymer Lab columns with 20 micron mixed pore size packings could be used. 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.

[0275] 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 (relaxation agent). The sample was capped and sealed with Teflon tape. The sample was dissolved and homogenized by heating the tube and its contents to 135 °C-140 °C.

[0276] Sample preparation: 1Samples were prepared for H NMR 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 through a pipette inserted into the tube for approximately 5 minutes, capped, and sealed with Teflon tape. Samples were heated at 115°C and vortexed to ensure homogeneity.

[0277] Data acquisition parameters: A Bruker 400 / 600 MHz spectrometer equipped with a Bruker high-temperature CryoProbe was used. 13 Data was collected for C NMR (see reference 1 below). Data were acquired using 256-8000 transients per data file, a pulse repetition delay of 7.3 seconds (6 second delay + 1.3 second acquisition time), a flip angle of 90 degrees, and a reverse-gated decoupling correction 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 the heated (125 °C) NMR sample exchanger and thermally equilibrated in the probe for 7 minutes prior to data acquisition.

[0278] Data acquisition parameters: Bruker AVANCE 400 / 600 MHz spectrometer equipped with a Bruker high temperature CryoProbe, and a sample temperature of 120 °C. 1 H NMR was performed. Two experiments were performed to obtain spectra, a control spectrum to quantify total polymer protons, and a double presaturation experiment, which suppresses strong polymer backbone peaks and allows high sensitivity spectra for end group quantification. The control was performed with a ZG pulse, 4 scans, SWH 10,000 Hz, AQ 1.64s, D 114s. The double saturation experiment was performed with a modified pulse sequence, lc1prf2.zz1, TD 32768, 100 scans, DS 4, SWH 10,000 Hz, AQ 1.64s, D 11s, D 13 This was carried out using 13s.

[0279] Data Analysis: Comonomer content was analyzed using corresponding matrix or algebraic methods. Unsaturation was analyzed using the method of Reference 3 below.

[0280] 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.

[0281] 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.

[0282] Reference 3: Z. Zhou, R. Cong, Y. He, M. Paradkar, M. Demirors, M. Cheatham, W. deGroot, Macromolecule Symposia, 2012, 312, 88.

[0283] 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.

[0284] GC / MS Tandem gas chromatography / low resolution mass spectrometry with 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 x 0.25 mm, 0.25 micron) at 70 eV for: Programmed Method: Oven equilibration time of 0.5 min at 50°C Then 25°C / min to 200°C and hold for 5 min Run time 11 minutes

[0285] 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 rate of 50 mL / min was used. High molecular weight samples (melt index <50 dg / min at 190°C) were pressed into thin films in a Carver Hydraulic press at 190°C and 20,000 psi for a time period of 4 minutes, followed by cooling at a temperature of 23°C and 20,000 psi for a time period of 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 packet, weighed, placed in a light aluminum pan, and crimped shut. The thermal behavior of the samples was investigated using the following temperature profile: Samples were rapidly heated to 180°C and held isothermal for 5 minutes. 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 cool 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. The percent crystallinity was calculated 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). Where the examples contain mostly propylene, the theoretical heat of fusion of PP of 165 J / g is used.

[0286] 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 min, then cooled at 23 °C and 20,000 psi for 1 min. The samples were placed on the lower plate and allowed to melt for 5 min. The plates were then closed to a gap of 2.0 mm, and the samples were trimmed to 25 mm diameter. Samples were allowed to equilibrate at 190 °C for 5 min 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).

[0287] Rubber Process Analyzer 180 with Alpha Technology RPA-2000 or MDR-2000 equipment oThe cure kinetics profile (also known as cure curve) of each formulation at 180°C was measured. A 4 gram sample of the resin was placed between two polyester Melinex S films. Alternatively, approximately 4 grams of material was punched from a compressed patty prepared using a Carver press at 20°C and 200 psi, following the Haake blending procedure detailed below, and then placed between two polyester Melinex S films. Testing was performed at a frequency of 1.67 Hz and an angle of 0.5 degrees at 180°C for a period of 30 minutes. The rheology or torque curve as a function of time for each formulation was measured from uncured blanket samples that were then cured during the analysis. Viscoelastic properties such as minimum S' torque (ML), maximum S' torque (MH), tan delta at ML, tan delta at MH, and time to reach a certain percentage of cure (e.g., t90, which corresponds to the time (in minutes) to reach a 90% cure state) were measured during the cure cycle. Immediately after curing, the instrument was set to cool to 70°C, and then the rheological properties of several formulations were evaluated at a frequency of 1.67Hz, an angle of 0.2 degrees, and at 70, 55, 40, and 25°C. Viscoelastic properties such as G”, G', tangent of phase angle (TanD), and S” torque were measured. Immediately after the temperature sweep, rheological properties at room temperature such as G”, G', tangent of phase angle (TanD), and S” torque were recorded at a 16-step frequency sweep from 0.02Hz to 15.92Hz (0.02, 0.03, 0.04, 0.06, 0.10, 0.16, 0.25, 0.40, 0.63, 1.00, 1.5, 2.52, 4.00, 6.34, 10.04, 15.92Hz), 25°C, and an angle of 0.2 degrees.

[0288] Gel Content The gel content of the sample polymers was measured according to ASTM D-2765 Procedure A using xylene as the solvent.

[0289] Compression set Compression set was measured at 23°C and 100°C according to ASTM D395. Disks with diameters of 29 mm (±0.5 mm) and thicknesses of 12.7 mm (±0.5 mm) were prepared as described in the compression molding section found in the Examples below. Each button specimen was inspected for notches, uneven thickness and non-uniformity, and selected buttons (without these defects) were tested. Compression set was performed on two specimens of each specimen at the specified temperature, and the average result of the two specimens was reported. The button specimens were placed in a compression device that had two metal plates that could be pressed together and locked into place at 75% of the original height of the button specimen. The compression device with the compressed specimen was then placed in an oven and equilibrated at the appropriate temperature for a specified time (22 hours at 23°C or 100°C). In this test, the stress was released at the test temperature, and the thickness of the specimen was measured after a 30 minute equilibration period at room temperature. Compression set is a measure of the recovery of a sample after compression and is calculated according to the formula CS=(H0-H2) / (H0-H1), where H0 is the original thickness of the sample, H1 is the thickness of the spacer bar used, and H2 is the final thickness of the sample after the compression force is removed.

[0290] Tensile strain-stress characteristics Tensile properties were measured using die cut specimens using a small "dog bone" shaped micro tensile die having dimensions as described in ASTM D-1708. Die cut specimens were cut from compression molded plaques prepared as described in the Compression Molding section. Tensile properties (50% modulus, 100% modulus, strain at break, and stress at break) were measured at room temperature according to method ASTM D-412 on an INSTRON Model 1122 from INSTRU-MET.

[0291] Shore A hardness Sample specimens were cut from compression molded plaques prepared as described in the Compression Molding section. Shore A hardness was measured in accordance with ASTM D2240 on an INSTRON Shore A Durometer Model 2000 with a Durometer Stand Model 902. This method allows for hardness measurements based on initial indentation, indentation after a specified period of time, or both. As used herein, indentation was measured at a specified time of 10 seconds.

[0292] Tear The tear strength of the sample polymers was measured under ambient conditions according to ASTM D-624 Type C, or ASTM D-1938, Trouser Tear (T-Tear). Test specimens were cut from compression molded plaques using a die and punch press. EXAMPLES

[0293] Preparation of chain transfer agents (CTA) Unless otherwise stated, all starting reagents and materials were obtained from Sigma-Aldrich. Procatalysts (catalyst 1), (catalyst 13), (catalyst 14), and (catalyst 17), as well as any others used in the following examples, are the same as those described above and are prepared according to the methods described above. Procatalyst (catalyst 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)]dimethylhafnium. "Procatalyst A" is the procatalyst used in the following examples and is bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine.

[0294] Synthesis of tris(2-(cyclohex-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, 1 A sample was dissolved in benzene-d6 for 1 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 clear peak at m / z of 110, consistent with the molecular weight of ethylcyclohexene (Figure 1B). Thus, 1 H NMR and GC / MS confirmed the synthesis of tris(2-(cyclohex-3-en-1-yl)ethyl)aluminum ("CTA1") via non-limiting Scheme 1. [ka]

[0295] Synthesis of tris(3,7-dimethyloct-6-en-1-yl)aluminum ("CTA2"): In a nitrogen-filled drybox, a 40 ml vial was equipped with a stir bar and 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 on a heating block and a vent needle was inserted into the headspace. The solution was allowed to stand at 110-112°C. o C for 9 hours to obtain a colorless, transparent solution ([Al] = 0.88M). 1 The desired product was determined via H NMR of the aliquot dissolved in C6D6 and by GC / MS of the hydrolyzed aliquot (M / Z=140) (FIG. 2). 1H NMR and GC / MS confirmed the synthesis of tris(3,7-(dimethyloct-6-en-1-yl)aluminum (“CTA2”) via non-limiting Scheme 2. [ka]

[0296] 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 for 25 min at 37°C for 1 h. o C for 14 hours. The hydrolyzed sample (see hydrolysis procedure below) 1 H NMR analysis showed no reaction. The solution was stirred for 22 hours at 60°C. o The vial was heated at 25°C. o After cooling to 0°C, an aliquot was hydrolyzed and analyzed. Complete reaction was observed, as indicated by the disappearance of the starting diene and the appearance of signals consistent with the hydrolysis products: isobutane and 2-hexene. 1 The analytical hydrolysis was performed by diluting ca. 0.1 mL of sample to ca. 2 mL with C6D6 in a vial, removing the sample from the glove box, and adding ca. 0.1 mL of nitrogen-purged water via syringe. After shaking the vial, the mixture was passed through a 0.45 μm syringe filter. Since the organic phase passes through more easily than the aqueous phase, it is possible to quickly isolate the organic phase for analysis. The sample was then mixed with a small amount of silica gel and filtered again. This helps remove any residual Al species that may cause gelation. Thus, 1 H NMR confirmed the synthesis of hex-4-en-1-yldiisobutylaluminum ("CTA3") via non-limiting Scheme 3. [ka]

[0297] Synthesis of bis(-2-ethylhex-4-en-1-yl)zinc ("CTA4"): In a nitrogen-filled drybox, 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(C6F5)4] (1.40 ml, 0.09 mmol, 0.064 M in methylcyclohexane) were mixed in a vial. (Catalyst 13) (0.045 g, 0.08 mmol) was added as a solid and the reaction mixture was stirred for 25 o C for 20 hours. The hydrolyzed sample (see hydrolysis procedure below) 1 1 H NMR and GC / MS analysis indicated incomplete reaction. 1 H NMR showed 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 products. Therefore, 1 H NMR and GC / MS confirmed the synthesis of bis(-2-ethylhex-4-en-1-yl)zinc ("CTA4") via non-limiting Scheme 4. [ka]

[0298] Synthesis of "CTA5": Diethylzinc (0.66 ml, 0.97 mmol, 1.47 M solution in toluene) in methylcyclohexane (0.60 ml, 0.039 mmol, 0.0644 M) and triethylaluminum (0.53 ml, 3.88 mmol, neat, 93%), 4-vinylcyclohexene (1.77 ml, 13.58 mmol, d 0.832), activator ([HNMe(C 18 H 37 A solution of [B(C6F5)4]) was dissolved in toluene (~10 ml). Catalyst 13 (0.023 g, 0.039 mmol) was added as a solid and the reaction mixture was stirred for 25o The mixture was stirred at RT for 14 h. An aliquot was dissolved in C6D6 and quenched with water. GC / MS and 1 H NMR confirmed consumption of 4-vinylcyclohexene and formation of the desired product (m / z=138), thus confirming that CTA5 was prepared via non-limiting Scheme 5. [ka]

[0299] 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, 10% of the diisobutylzinc was removed from the vial. 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. 1 For 1 H NMR analysis, an aliquot (0.1 ml) of this mixture was diluted with C6D6 (0.5 ml) and hydrolyzed. 1 H NMR analysis confirmed that the CTA was synthesized via non-limiting Scheme 6. [ka]

[0300] Synthesis of "CTA7": The synthesis of CTA7 is illustrated in the non-limiting Scheme 7 and described below. It was carried out in two steps. In the first step, trivinylcyclohexane (TVCH) was converted to a diene via 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, d 0.836). The mixture was stirred for 160 min at 4°C for 1 h. o The mixture was heated at 130° C. and stirred for 2 h 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 cooled to 130° C. and stirred for 2 h to form the cyclized TVCH. o C for 2 hours to obtain an Al-TVCH solution. [ka]

[0301] Synthesis of "CTA8": The synthesis of CTA8 is exemplified in the non-limiting Scheme 8 and described below. In a nitrogen-filled drybox, a 20 ml vial was equipped with a stir bar and 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 on a heating block and a vent needle was inserted through the septum cap to allow the solution to evaporate from 110 to 112°C. o The solvent and excess limonene were removed under vacuum at 50° C. for 11 hours. o C overnight to give the desired product as a colorless viscous oil (0.870 g, 83%). [ka]

[0302] Synthesis of "CTA9": The synthesis of CTA9 is exemplified in non-limiting Scheme 9 and described below. In a nitrogen-filled drybox, a 40 ml vial was equipped with a stir bar and 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 (with some bubbling) was observed. The vial was placed on a heating block and a vent needle was inserted through the septum cap, and the solution was heated to 110-112°C. o C for 3 hours. After 3 hours 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 hours. The reaction was driven to near completion. A small amount of dimer formation was observed from the alkene reagent. The reaction was continued for an additional 16 hours. Analysis of an aliquot showed no significant changes. [ka]

[0303] 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 via a batch reactor as follows.

[0304] Set 1 With reference to Tables 1A-1C, Set 1 includes telechelic polymers of the invention made in Runs BR1-BR12, which were prepared as follows. For each run, a 1 gallon stirred autoclave reactor is charged with Isopar™ E mixed alkane solvent (~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). In an inert atmosphere drybox, an active catalyst solution (the active catalyst solution has a ratio of procatalyst to cocatalyst A of 1:1.2) is prepared by mixing the procatalyst with an activator mixture (a mixture of 1.2 equivalents of cocatalyst A and 10 equivalents of modified methylaluminoxane (MMAO-3A)). 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 necessary. After 10 minutes, the reactor is heated to 200°C and held at that temperature for 20 minutes. The ethylene feed is shut off and the polymer solution is 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) is added to obtain a total additive content of approximately 0.1% in the polymer. The polymer is thoroughly dried in a vacuum oven. [Table 1] [Table 2] [Table 3]

[0305] Set 2 Referring to Table 2, Set 2 includes telechelic polymers of the present invention made in runs B1-B7 via a similar procedure as Set 1. Run B1 used scavenger MMAO-3A with a (catalyst 1):cocatalyst A:scavenger ratio of 1:1.2:10. Runs B2-B7 used a procatalyst to cocatalyst ratio of 1:1.2. All runs in Table 2 were run without hydrogen. All runs had the following conditions: 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 used 120 o C for 10 min. Experiments B3, B5, and B7 were performed at 200 o C for 20 minutes (120-200 o An additional heating step of 10 min was included (excluding the transition time to C). [Table 4]

[0306] Set 3 Set 3 includes the following examples for synthesizing telechelic polyethylene polymers of the present invention.

[0307] In a nitrogen-filled drybox, a vial equipped with a stir bar is charged with octene (10 mL), cocatalyst 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. Catalyst 13 (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. This polymer solution is transferred to a 600 mL Parr reactor and sealed. The reactor is heated to 200 degrees Celsius 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 synthesis occurred via the non-limiting reaction scheme shown below. [ka]

[0308] In a nitrogen-filled drybox, a vial equipped with a stir bar is charged with octene (10 ml), cocatalyst 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. Catalyst 13 (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. This polymer solution is transferred to a 600 mL Parr reactor and sealed. The reactor is heated to 200 degrees Celsius 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]

[0309] Continuous Solution Polymerization Non-limiting Example Formula A 1 L 1 L 2 A 2 and telechelic polyolefins of formula A 1 L 1 of unsaturated polyolefin was prepared via the following sequential solution polymerization.

[0310] 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 outlet, a side stream is taken to provide a steep flow 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, 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 beta-H removal of the polymer-Al takes place. A small amount of isopropyl alcohol is added either before the degassing separation, before the PRH (in the comparative examples) or after the PRH (in the inventive examples) along with any stabilizers or other additives. The polymer product is recovered by extrusion using a devolatilizing extruder.

[0311] The polymerization process conditions and results before post-reaction heating (PRH) for the present invention and comparative examples are listed in Tables A1-B2. 1 L 1 The unsaturated polyolefins of the present invention are named Inv.MP1 to MP4. 1 L 1 L 2 A 2The telechelic polyolefins of the present invention are designated Inv. TP1 to TP10. The comparative polymers are designated Comp. A and B. Additional abbreviations in the table are explained as follows: "Co." stands for comonomer, and "sccm" stands for standard cm 3 / min, "T" refers to temperature, "Cat" is short for procatalyst, "Cat 1" is short for procatalyst (catalyst 1), "Cat 17" is short for procatalyst (catalyst 17), "Cocatalyst" is short for Cocatalyst A, "Al CTA" is short for aluminum chain transfer agent, "TEA" is short for triethylaluminum, "TOA" is short for trioctylaluminum, "Poly Rate" is short for polymer production rate, "Conv" is short for ethylene conversion in the reactor, and "Eff" is short for efficiency, kg polymer / g catalyst metal.

[0312] Additionally, [CTA] / [C2H4] refers to the molar ratio in the reactor, Al / C2*1000=(Al feed rate*Al concentration / 1000000 / Mw of Al) / (total ethylene feed rate*(1-partial ethylene conversion) / Mw of ethylene)*1000. The "Al" in "Al / C2*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.

[0313] The properties of the inventive and comparative polymers after post-reactor heating and recovery are provided in Tables C1-E2. [Table 5] [Table 6] [Table 7] [Table 8] [Table 9] [Table 10] [Table 11] [Table 12] [Table 13] [Table 14]

[0314] 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 process of the present disclosure. Specifically, as will be appreciated by those skilled in the art, 1 H NMR and 13 C NMR analysis confirms the formation of new telechelic polyolefins, TP1 to TP10, in which such polyolefins have unsaturation at both ends. 1 A with a group (vinyl, vinylene, vinylidene) and a sterically hindered double bond at the other end (cyclohexene or trisubstituted alkene) 2 In contrast, Comparative Polymers A and B, which were not prepared according to the inventive process of the present disclosure, have 1 H NMR and 13 It is a polymer with low unsaturation as seen via C NMR analysis.

[0315] In Inv. TP5, the sterically hindered double bond of the A2 group is tri-substituted unsaturated, resulting in a high number of tri-substituted unsaturations / 1000000C, as reported in the table above. The number of tri-substituted unsaturations in TP5 is higher than that of Comparative B, which was produced using the same catalyst under similar reactor conditions, but with hydrogen to control the molecular weight. A small number of tri-substituted unsaturations may be formed via beta-hydride removal and subsequent rearrangement of ethylene / alpha-olefin unsaturation. The number of tri-substituted unsaturations formed by this thermal termination mechanism depends on the catalyst and process conditions used. A small number of tri-substituted unsaturations from this thermal termination mechanism is present in all comparative examples and inventive examples, but at lower levels than vinyl and vinylidene, except for TP5, where the majority of the tri-substituted unsaturation is from the A2 group.

[0316] 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 at 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 provide good thermal and UV degradation stability, since less unsaturation is required to form a crosslinked network with good 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.

[0317] In addition, the telechelic polyolefins of the present disclosure are produced by low-cost solution polymerization from ethylene and alpha-olefins, which is unique compared to telechelic polyolefins that have been produced in the literature through much more expensive and complicated synthetic routes. Furthermore, telechelic polyolefins also allow the opportunity to control chain extension to high molecular weight thermoplastics, unlike random copolymers with unsaturation. Since 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, etc.

[0318] Curing Example Inventive curable formulations (Inv. 1A-13A) were prepared containing inventive polyolefins MP1-MP4 and TP1. Comparative formulations (Comp. A-W) were also prepared containing the comparative polymers A and B described above, as well as comparative polymers "0ENB", "1ENB", "2.4ENB", "8.8ENB", "8100", "8200", and "8407".

[0319] Comparative polymers 0ENB, 1ENB, 2.4ENB, and 8.8ENB are EPDM polymers containing increasing amounts of ethylidene norbornene monomer and prepared according to the process conditions in Table 3. For the process conditions in Table 3, "Catalyst B" is a titanium procatalyst, [N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,3a,8a-eta.)-1,5,6,7-tetrahydro-2-methyl-s-indacen-1-yl]cyanoaminato(2-)-.kappa.N][(1,2,3,4-eta.)-1,3-pentadiene], "Cocatalyst" is Cocatalyst A from above, and "Cocatalyst 2" is modified methylalumoxane (MMAO) type 3A from Akzo Nobel, Inc. (no further purification was performed). For the comparative polymers 0ENB, 1ENB, 2.4ENB, and 8.8ENB, these polymers were determined to have approximately 0, 1, 2.4, and 8.8 units derived from ENB monomer per chain, respectively.

[0320] Comparative polymers "8100", "8200", and "8407" are polymers available as ENGAGE™ 8100, ENGAGE™ 8200, and ENGAGE™ 8407 available from Dow Chemical Company. ENGAGE™ 8100 has a viscosity of 0.870 g / cm 3 (ASTM D792) and a melt index of 1.0 g / 10 min (ASTM D1238, 190° C. / 2.16 kg). ENGAGE™ 8200 has a density of 0.870 g / cm 3 (ASTM D792) and a melt index of 5.0 g / 10 min (ASTM D1238, 190° C. / 2.16 kg). ENGAGE™ 8407 has a density of 0.870 g / cm 3 (ASTM D792) and a melt index of 30 g / 10 min (ASTM D1238, 190° C. / 2.16 kg).

[0321] Formulations Inv. 1A, 3A, 4A, and 5A, and Comp. A-K were prepared according to the following procedure, according to the amounts listed in Tables 4 and 5. The polymer was weighed into a 250 mL wide-mouth glass jar, and then zinc oxide (ZnO) solids were added. The jar was placed in a heating block set at 110° C. (resulting in an internal temperature of approximately 100° C.). The mixture of polymer and ZnO was kept in the heating block for at least 45 minutes to soften the polymer. After this, a pre-weighed mixture of stearic acid, 1,4-dimaleimidobenzene (1,4-DMB), or 1,3-dimaleimidobenzene (1,3-DMB; VANAX MBM) coagent, and VAROX DBPH-50 peroxide was added to the polymer, taking care to avoid solids sticking to the walls of the jar. The contents of the jar were then mixed using an overhead stirrer equipped with a 4-blade 1.5 inch pitch blade turbine agitator. Mixing speeds and times were 25 rpm for 2 minutes, 100 rpm for 4 minutes, and 175-200 rpm for 6 minutes. If there appeared to be unmixed solids on the jar walls or the stirrer shaft, the jar was manually turned up and down to encourage incorporation of the solids. Heat-resistant gloves were used during this step, as the glass jar was hot. After mixing, the jar was lowered and any polymer remaining on the stirrer blade was allowed to drip back into the jar. The jar was removed using heat-resistant gloves, then placed upside down in a clamp, and the polymer was collected on a sheet of silicon-treated paper. After minimizing the flow rate of polymer from the jar, a silicon spatula was used to isolate the remaining polymer from the jar. Typical recoveries were about 90%. A portion of the polymer (about 4 grams) was then tested on a Rubber Process Analyzer (RPA, see above for procedure). If testing could not be completed on the same day, the polymer was stored in a double-stacked ziplock bag in a freezer set at -13°C or below.

[0322] Formulations Inv. 2A and 6A-13A and Comp. L-W were prepared according to the amounts in Tables 4, 5, and 10, following the Haake blending procedure. The peroxide was VAROX DBPH-50 and the coagent was 1,4-dimaleimidobenzene (1,4-DMB) or 1,3-dimaleimidobenzene (1,3-DMB; VANAX MBM). The blends were prepared using a Rheomix 600 Haake mixing bowl and an RS5000 torque rheometer equipped with a standard roller blade. The blends were mixed at 100°C and 50 rpm for 5 minutes, during which the melt torque was monitored to ensure that the torque reached a steady state after the components melted. The samples were immediately removed and pressed into patties using a Carver press set at 20°C and 200 psi for a period of 3 minutes. A portion of the polymer (approximately 4 grams) was then tested on a Rubber Process Analyzer (RPA, see above for procedure). If testing could not be completed on the same day, the polymer was stored in a double-stacked 127iploc bag in a freezer set at -13°C or below.

[0323] Following their preparation, the inventive and comparative formulations were cured via heating at 180° C. for 30 minutes, with cure rates measured according to the Rubber Process Analyzer method described above. Such cure rates, calculated as (MH-ML) / (t90-t10), are provided in Tables 6, 7, and 11.

[0324] Additionally, the physical properties of the inventive and comparative formulations were measured according to the methods described above and are presented in Tables 8, 9, and 11. The physical properties of the formulations were measured from the cured plaques in a compression molding machine (for tensile, compression set test, C-tear, temperature shrinkage). The samples were compression molded according to ASTM D3182 using a PHI (100 ton press). The desired molds (2" x 4", or compression buttons) were placed on the platens. The samples (uncured patties) were cut slightly smaller than the dimensions of the individual mold spaces. The molds were spray brushed with a dilute solution of silicone. The platens were closed. The "normal" operating pressure was 100 tons, and the gauge reads 200,000 pounds. At the end of the cure time, the bottom platen automatically opened. The samples were removed and immediately placed in water to stop the cure. The samples were conditioned at room temperature for 24 hours before testing. To cure the samples, the samples were conditioned at 180° C. using t95 data plus 3 minutes for the plaques and t95 data plus 15 minutes for the compression set buttons. [Table 15] [Table 16] [Table 17] [Table 18] [Table 19] [Table 20] [Table 21] [Table 22] [Table 23] [Table 24] [Table 25] [Table 26] [Table 27] [Table 28] [Table 29]

[0325] As can be seen in the table, the formulations of the present invention exhibited improved crosslinking performance (such as increased MH-ML and faster cure speed) while also maintaining or improving physical properties compared to the relevant comparative examples. The following description with reference to the figures provides further explanation.

[0326] In Table 11, with the inventive examples, a higher degree of cure was achieved at lower peroxide levels, as indicated by the higher MH-ML. Less peroxide is beneficial, for example, to reduce the cost of the formulation and to reduce the level of peroxide by-products (volatile organic compounds, odorous species). Using less peroxide with the inventive resins also provides scorch resistance, as indicated by the longer t10. Comparative Examples O-U are based on ENGAGE 8407. Comparative W is uncured MP3 polymer. Inventive Examples 8A-13A are peroxide cured compositions based on MP3. The overall peroxide range used was the same (0.5-9.5 PHR). These examples show that inventive examples can achieve similar MH-ML using lower peroxide levels. For example, the highest MH-ML with 8407 was 7.21 dNm for Comp U with 9.5 PHR peroxide, while similar MH-ML was achieved with MP3 and Inv12A using 3 PHR peroxide. Higher peroxide levels resulted in higher MH-ML (Inv. 8A and 13A) that could not be achieved with 8407, which used up to 9.5 PHR peroxide. Such high levels of peroxide can result in significant gassing due to peroxide by-products, causing defects in the molded cured parts. Comp U with similar MH-ML compared to Inv12A has better scorch resistance (higher t10) but faster cure (lower t95), and higher tensile strength, elongation at break, and tear strength. Comp T compared to Inv11A has higher MH-ML, faster cure rate, higher stress at break, higher tear strength, lower tan delta, and similar compression set while using less peroxide. On the other hand, Inv12A (3 PHR peroxide), Inv8A (6 PHR peroxide), and Inv13A (9.5 PHR peroxide) have lower compression set and tan delta than Comp T (3 PHR peroxide), Comp O (6 PHR peroxide), and Comp U (9.5 PHR peroxide), respectively, when compared at the same peroxide levels.

[0327] FIG. 5 shows that the ethylene / propylene unsaturated polymers of the present invention compared to saturated ethylene / propylene polymers enable significantly better crosslinking performance when both polymers have approximately the same melt index, are used in the same cure package, and are cured under the same conditions.

[0328] FIG. 6 shows that the ethylene / 1-octene unsaturated polymers of the present invention compared to saturated ethylene / 1-octene polymers enable significantly better crosslinking performance when both polymers have approximately the same melt index, are used in the same cure package, and are cured under the same conditions.

[0329] FIG. 7 surprisingly shows that the ethylene / propylene unsaturated polymers of the present invention allow better crosslinking performance when the same cure package and the same cure conditions are used compared to some EPDM polymers with unsaturation. Meanwhile, Inv.1A did not cure as well as the 8.8ENB comparison, and cured slightly better than the 2.4ENB comparison. It is surprising that the unsaturated polymers of the present invention, which have unsaturation only at the terminals, rather than along the polymer backbone, show a higher degree of cure, higher crosslink density, and faster cure speed compared to EPDM polymers with about twice the degree of unsaturation. In other words, the unsaturated polymers of the present invention show better crosslinking performance compared to EPDM polymers with more unsaturation per 1000 carbons derived from pendant dienes.

[0330] FIG. 8 shows that the ethylene / 1-octene telechelic polymers of the present invention enable better crosslinking performance compared to saturated ethylene / 1-octene polymers.

[0331] Thus, the present disclosure provides novel low molecular weight unsaturated polyolefins that can be efficiently crosslinked and provide good mechanical properties, thermal and UV stability. The present invention includes the following aspects. Section 1. A curable composition comprising (A) a polyolefin component and (B) a curing component comprising a crosslinking agent, wherein the (A) polyolefin component is represented by the formula A 1 L 1 The unsaturated polyolefin comprises: 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 CH=CH- and vinyl groups of the formula CH2=C(Y 1 )- and the vinylidene group of formula Y 1 and a mixture of CH=CH- and vinylene groups; Y 1 However, each occurrence is independent, C1~C 30 The curable composition, wherein the hydrocarbyl group. Section 2. The (A) polyolefin component is represented by the formula A 1 L 1 L 2 A 2 The present invention further comprises a telechelic polyolefin of the formula: L 2 But, C1~C 32 is a hydrocarbylene group, A 2 is a hydrocarbyl group containing a sterically hindered double bond. Section 3. Item 3. The composition according to any one of items 1 and 2, wherein the blend comprises 80% by weight to 99.99% by weight of the (A) polyolefin component and 0.01% by weight to 20% by weight of the (B) curing component including the crosslinker. Section 4. L 1However, units derived from ethylene and C3-C 30 Item 4. The composition according to any one of items 1 to 3, which is an ethylene / alpha-olefin copolymer containing an alpha-olefin. Section 5. Said C3~C 30 5. The composition according to any one of items 1 to 4, wherein the alpha-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene, and 1-octene. Section 6. The composition according to any one of items 1 to 5, wherein the sterically 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 alpha carbon. Section 7. A 2 , C3~C 30 Cyclic hydrocarbyl group or C3-C 30 The composition according to any one of items 1 to 6, wherein the acyclic hydrocarbyl group is a cyclic hydrocarbyl group. Section 8. A 2 is selected from the group consisting of unsubstituted cycloalkene, alkyl-substituted cycloalkene, and acyclic alkyl group. Section 9. A 2 is selected from the group consisting of: [ka] In the formula, the endocyclic double bond of (AC) and (AF) may be between any two adjacent carbon atoms that are ring members, and the pendant methyl group of (AF) may be bonded to any carbon atom that is a ring member. The composition according to any of items 1 to 8. Section 10. The (A) polyolefin component represented by formula A 1 L 1 and the unsaturated polyolefin of formula A 1 L 1 L 2 A 2Item 10. The composition according to any one of items 1 to 9, wherein each of the telechelic polyolefins has a weight average molecular weight (Mw) in the range of 1,000 to 1,000,000 g / mol. Section 11. Formula A 1 L 1 The unsaturated polyolefin L 1 through a carbon-carbon single bond 1 11. The curable composition according to any one of items 1 to 10, wherein the compound is covalently bonded to Section 12. Formula A 1 L 1 L 2 A 2 The telechelic polyolefin L 1 through a carbon-carbon single bond 1 and L 2 and a compound of formula A 1 L 1 L 2 A 2 The telechelic polyolefin L 2 through a carbon-carbon single bond 2 Item 12. The curable composition according to any one of items 2 to 11, wherein the compound is covalently bonded to Section 13. Item 13. The composition according to any one of items 1 to 12, wherein the (b) curing component further contains an auxiliary. Section 14. Item 14. The composition according to any one of items 1 to 13, further comprising 0 to 10% by weight of an additive component (C). Section 15. Item 15. The composition according to any one of items 1 to 14, wherein the additive component (C) includes zinc oxide and / or stearic acid.

Claims

1. A curable composition comprising (A) a polyolefin component and (B) a curing component comprising a crosslinking agent, wherein the (A) polyolefin component is represented by the formula A １ L １ and an unsaturated polyolefin of formula A １ L １ L ２ A ２ The telechelic polyolefin comprises the formula: 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 Vinylene group of CH=CH-, vinyl group and formula Y １ A mixture of vinyl groups and vinylene groups of the formula CH ２ = C(Y １ )- with vinylidene groups, ２ = C(Y １ )- and a vinylidene group of formula Y １ Mixtures of vinylene groups of the formula CH=CH- and vinyl groups and groups of the formula CH ２ = C(Y １ )- and a vinylidene group of formula Y １ CH═CH— and a mixture of vinylene groups; Y １ However, for each occurrence, C １ ~C ３０ is a hydrocarbyl group, L ２ But, C １ ~C ３２ is a hydrocarbylene group, A ２ is a hydrocarbyl group containing a sterically hindered double bond; 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 alpha carbon;

2. 2. The curable composition of claim 1, comprising 80% to 99.99% by weight of said (A) polyolefin component, and 0.01% to 20% by weight of said (B) curing component.

3. L １ is a unit derived from ethylene and C ３ ~C ３０ The curable composition of claim 1 or 2, which is an ethylene / alpha-olefin copolymer comprising an alpha-olefin.

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

5. A ２ is selected from the group consisting of unsubstituted cycloalkenyl groups, alkyl substituted cycloalkenyl groups, and acyclic alkenyl groups containing a sterically hindered double bond.

6. A ２ is selected from the group consisting of: 【Chemistry 1】 6. The curable composition of any 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. The curable composition of any of claims 1 to 6, wherein said unsaturated polyolefin and said telechelic polyolefin each comprise a weight average molecular weight (Mw) in the range of 1,000 to 1,000,000 g / mol.

8. The unsaturated polyolefin L １ is connected to A through a carbon-carbon single bond. １ The curable composition according to any one of claims 1 to 7, wherein the compound is covalently bonded to

9. The telechelic polyolefin L １ is connected to A through a carbon-carbon single bond. １ and L ２ and L of said telechelic polyolefin is covalently bonded to each of ２ is connected to A through a carbon-carbon single bond. ２ The curable composition according to any one of claims 1 to 8, wherein the compound is covalently bonded to

10. The curable composition according to any one of claims 1 to 9, wherein the (B) curing component further comprises an auxiliary.

11. The curable composition according to any one of claims 1 to 10, further comprising 0 to 10 wt% of an additive component (C).

12. The curable composition according to claim 11 , wherein the (C) additive component comprises zinc oxide and / or stearic acid.

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