Telechelic polyolefins and methods for preparing telechelic polyolefins

Abstract

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

Description

[0001] Citation of Related Applications

[0002] This application claims the benefit of priority to U.S. Provisional Application No. 62 / 786,084, filed on December 28, 2018, which is incorporated herein by reference in its entirety. Technical Field

[0003] Embodiments relate to telechelic polyolefins and methods for making the same. Background Art

[0004] Polyolefins are among the most important and widely used polymer materials in the world. Due to the inherent chemical inertness of polyolefins, the introduction of reactive functional groups to form telechelic polyolefins with two reactive end groups has been actively sought for many years. However, there is a need in the art for a commercially viable process for preparing telechelic polyolefins. The present disclosure addresses this need and also relates to novel telechelic polyolefin compositions. Summary of the invention

[0005] The present disclosure relates to a composition comprising a telechelic polyolefin of formula (I):

[0006] A 1 L 1 L 2 A 2 (I) where:

[0007] L 1 It is a polyolefin;

[0008] A 1 Selected from the group consisting of: vinyl, formula CH2=C(Y 1 )-vinylidene group, formula Y 1 CH=CH-vinylene group, vinyl group and formula Y 1 A mixture of CH=CH-vinylene, vinyl and CH2=C(Y 1 )-vinylidene mixture, formula CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of CH=CH-vinylene and vinyl, CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of vinylene groups with CH=CH-;

[0009] Y 1 C1 to C independently at each occurrence 30 Hydrocarbon;

[0010] L2 It is C1 to C 32 alkylene; and

[0011] A 2 is a hydrocarbon group including a hindered double bond.

[0012] The present disclosure further relates to a method for preparing a composition comprising a telechelic polyolefin, the method comprising:

[0013] 1) combining starting materials including (A) a monomer component, (B) a chain transfer agent component, and (C) a catalyst component to form a solution, and polymerizing greater than 10 mol % to less than or equal to 99 mol % of the (A) monomer component in the solution;

[0014] 2) heating the solution; and

[0015] 3) recovering a product comprising said composition comprising said telechelic polyolefin, wherein:

[0016] The chain transfer agent component (B) comprises the formula Al(CH2CH(Y 2 )A 2 )3 organoaluminum compounds;

[0017] Y 2 is independently hydrogen or C1 to C 30 a hydrocarbon group; and

[0018] A 2 and R is independently at each occurrence a hydrocarbyl group including a hindered double bond. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1A and 1B 1H NMR and GC / MS spectra for the synthesis of CTA 1 are provided, respectively.

[0020] Figure 2 The 1H NMR spectrum for the synthesis of CTA 2 is provided.

[0021] Figure 3 1H NMR spectra for the synthesis of telechelic polyolefins using CTA 7 are provided.

[0022] Figure 4 1H NMR spectra for the synthesis of telechelic polyolefins using CTA 8 are provided. DETAILED DESCRIPTION

[0023] definition

[0024] All references to the periodic table herein shall refer to the periodic table published and copyrighted by CRC Press, Inc. in 2003. Moreover, any reference to one or more families shall be one or more families reflected in such periodic table using the IUPAC system for numbering families. Unless stated to the contrary, implied by the context, or customary in the art, all parts and percentages are by weight. For the purpose of U.S. patent practice, any patent, patent application, or publication mentioned herein is hereby incorporated by reference in its entirety (or its equivalent U.S. version is so incorporated by reference), especially for disclosures of synthesis techniques, definitions (in the case of inconsistency with any definition provided herein) and common knowledge in the art.

[0025] The numerical ranges disclosed herein include all values ​​from the lower limit and the upper limit and include the lower limit and the upper limit. For ranges containing exact values ​​(e.g., 1 or 2; or 3 to 5; or 6; or 7), any subranges between any two exact values ​​are included (e.g., 1 to 2; 2 to 6; 5 to 7; 3 to 7; 5 to 6, etc.). The numerical ranges disclosed herein further include fractions between any two exact values.

[0026] The terms "comprising," "including," "having," and derivatives thereof are not intended to exclude the presence of any additional components, steps, or procedures, whether or not the components, steps, or procedures are specifically disclosed. For the avoidance of any doubt, all compositions claimed through use of the term "comprising" may include any additional additives, adjuvants, components, or compounds, whether polymeric or otherwise, unless stated to the contrary. Conversely, the term "consisting essentially of excludes from the scope of any subsequent listing any other components, steps, or procedures, except those that are not essential to operability. The term "consisting of excludes any component, step, or procedure not specifically depicted or listed. Unless otherwise stated, the term "or" refers to the members of the list individually and in any combination.

[0027] The term "hindered double bond" refers to a carbon-carbon double bond that cannot easily participate in coordination polymerization. In other words, the reactivity of the hindered double bond in coordination polymerization is negligible. Examples of hindered double bonds include, but are not limited to, double bonds of vinylidene, double bonds of vinylidene, double bonds of trisubstituted olefins, and double bonds of vinyls connected to the alpha carbon of the branched chain. The term "hindered double bond" as defined herein excludes double bonds of strained cyclic olefins that can easily participate in coordination polymerization. As will be understood by those of ordinary skill in the art, examples of such strained cyclic olefins include, but are not limited to, norbornene, ethylidene norbornene (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-cyclohexylene-2-norbornene, and the like. The term "hindered double bond" as defined herein further excludes double bonds of vinyl groups attached to unbranched alpha carbons.

[0028] The term "composition" refers to a mixture of materials or components that comprise the composition. Thus, the term "composition comprising" and similar terms are not intended to exclude the presence of any additional components of the composition, whether or not the component is specifically disclosed.

[0029] The term "acyclic" refers to a series of atoms in a polymer or compound, wherein such series is linear or branched. Thus, the term "acyclic hydrocarbon group" refers to a linear or branched hydrocarbon group.

[0030] The term "cyclic" refers to a series of atoms in a polymer or compound, wherein such series comprises one or more rings. Thus, the term "cyclic hydrocarbon group" refers to a hydrocarbon group containing one or more rings. As used herein, a "cyclic hydrocarbon group" may contain a non-cyclic (straight or branched) portion in addition to one or more rings.

[0031] The term "substituted" means that one or more hydrogen atoms are replaced by, for example, an alkyl group. The term "unsubstituted" means that no such substitution is present.

[0032] As will be understood by one of ordinary skill in the art, 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 halogens.

[0033] As used herein, the terms "hydrocarbyl," "alkyl," and like terms refer to compounds composed entirely of hydrogen and carbon and include aliphatic, aromatic, acyclic, cyclic, polycyclic, branched, unbranched, saturated, and unsaturated compounds.

[0034] The terms "hydrocarbyl," "alkyl," "alkyl," "aryl," "aryl," "cycloalkene," and similar terms are intended to include every possible isomer, including every structural isomer or stereoisomer. 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.

[0035] The term "endocyclic double bond" refers to a double bond between two carbon atoms that are members of a ring. The term "exocyclic double bond" refers to a double bond between two carbon atoms, only one of which is a member of a ring.

[0036] "Active catalyst," "active catalyst composition," and similar terms refer to a transition metal compound that is capable of polymerizing unsaturated monomers with or without a co-catalyst. The active catalyst may be a "procatalyst" that becomes active in the absence of a co-catalyst to polymerize unsaturated monomers. Alternatively, the active catalyst may be a "procatalyst" that becomes active in combination with a co-catalyst to polymerize unsaturated monomers.

[0037] The term "procatalyst" may be used interchangeably with "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", "metal-ligand complex" and similar terms.

[0038] "Cocatalyst" refers to a compound that can activate certain primary catalysts to form an active catalyst capable of polymerizing unsaturated monomers. The term "cocatalyst" is used interchangeably with "activator" and similar terms.

[0039] "Polymer" refers to a compound prepared by polymerizing monomers, whether of the same or different type. The generic term "polymer" thus embraces the term "homopolymer" to refer to polymers 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 into and / or within the polymer.

[0040] "Interpolymer" or "copolymer" refers to polymers prepared by polymerizing at least two different types of monomers. These general terms include both polymers prepared from two different types of monomers and polymers prepared from more than two different types of monomers (e.g., terpolymers, tetrapolymers, etc.). These general terms include all forms of interpolymers or copolymers, such as random, block, homogeneous, heterogeneous, etc.

[0041] "Ethylene-based polymers" or "ethylene polymers" are polymers that contain a major amount (greater than 50 wt%) of polymerized ethylene, based on the weight of the polymer, and optionally may further contain polymerized units of at least one comonomer. "Ethylene-based interpolymers" are interpolymers that contain, in polymerized form, a major amount (greater than 50 wt%) of ethylene, based on the weight of the interpolymer, and further contain polymerized units of at least one comonomer. Preferably, the ethylene-based interpolymer is a random interpolymer (i.e., comprises a random distribution of its monomer components). "Ethylene homopolymers" are polymers that include repeating units derived from ethylene, but do not exclude residual amounts of other components.

[0042] "Propylene-based polymers" or "propylene polymers" are polymers that contain a major amount (greater than 50 wt%) of polymerized propylene, based on the weight of the polymer, and optionally may further contain polymerized units of at least one comonomer. "Propylene-based interpolymers" are interpolymers that contain, in polymerized form, a major amount (greater than 50 wt%) of propylene, based on the weight of the interpolymer, and further contain polymerized units of at least one comonomer. Preferably, the propylene-based interpolymer is a random interpolymer (i.e., comprises a random distribution of its monomer components). "Propylene homopolymers" are polymers that include repeating units derived from propylene, but do not exclude residual amounts of other components.

[0043] An "ethylene / α-olefin interpolymer" is an interpolymer that contains a major amount (greater than 50 wt%) of polymerized ethylene, based on the weight of the interpolymer, and further contains polymerized units of at least one α-olefin. Preferably, the ethylene / α-olefin interpolymer is a random interpolymer (i.e., comprising a random distribution of its monomer components). An "ethylene / α-olefin copolymer" is a copolymer that contains a major amount (greater than 50 wt%) of polymerized ethylene, based on the weight of the copolymer, and further contains polymerized units of an α-olefin. Preferably, the ethylene / α-olefin copolymer is a random copolymer (i.e., comprising a random distribution of its monomer components).

[0044] A "propylene / α-olefin interpolymer" is an interpolymer that contains a major amount (greater than 50 wt%) of polymerized propylene, based on the weight of the interpolymer, and further contains polymerized units of at least one α-olefin. Preferably, the propylene / α-olefin interpolymer is a random interpolymer (i.e., comprises a random distribution of its monomer components). A "propylene / α-olefin copolymer" is an interpolymer that contains a major amount (greater than 50 wt%) of polymerized propylene, based on the weight of the copolymer, and further contains polymerized units of an α-olefin. Preferably, the propylene / α-olefin copolymer is a random copolymer (i.e., comprises a random distribution of its monomer components).

[0045] "Polyolefin" refers to polymers produced from olefin monomers, wherein olefin monomers (also known as olefins) are linear, branched, or cyclic compounds of carbon and hydrogen having at least one double bond.

[0046] As used herein, the terms "chain transfer agent component" and "chain transfer agent" refer to a compound or mixture of compounds that is capable of causing reversible or irreversible polymer radical 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 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.

[0047] The term "olefin block copolymer" or "OBC" refers to an ethylene / α-olefin multi-block interpolymer and comprises ethylene and one or more copolymerizable α-olefin comonomers in polymerized form, characterized by multiple blocks or segments of two or more (preferably three or more) polymerized monomer units, said blocks or segments differing in chemical or physical properties. Specifically, the term "olefin block copolymer" refers to a polymer comprising two or more (preferably three or more) chemically distinct regions or segments (referred to as "blocks") joined in a linear manner rather than in a pendant or grafted manner, i.e., a polymer comprising chemically distinct units joined end-to-end (covalently bonded) with respect to polymerized functional groups. The blocks differ in the amount or type of comonomer incorporated therein, density, amount of crystallinity, type of crystallinity (e.g., polyethylene versus polypropylene), crystallite size attributable to polymers of such composition, type or degree of tacticity (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 unique distributions of both polymer polydispersity (PDI or Mw / Mn) and block length distribution, for example, based on the effect of using one or more shuttling agents in combination with a catalyst system. Non-limiting examples of the disclosed olefin block copolymers and methods for making the same 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 entirety.

[0048] The term "block composite" ("BC") refers to a polymer comprising three polymer components: (i) an ethylene-based polymer (EP) having an ethylene content of 10 mol% to 90 mol% (soft copolymer), based on the total moles of polymerized monomer units in the ethylene-based polymer (EP); (ii) an α-olefin-based polymer (AOP), having an α-olefin content of greater than 90 mol% (hard copolymer), based on the total moles of polymerized monomer units in the α-olefin-based polymer (AOP); and (iii) a block copolymer (diblock copolymer), the block copolymer having an ethylene block (EB) and an α-olefin block (AOB); wherein the ethylene block of the block copolymer has the same composition as the EP of component (i) of the block composite, and the α-olefin block of the block copolymer has the same composition as the AOP of component (ii) of the block composite. In addition, in the block composite, the composition split between the amounts of EP and AOP will be substantially the same as the composition split between the corresponding blocks in the block copolymer. Non-limiting examples of block composites of the present disclosure and methods for making the same are disclosed in U.S. Pat. Nos. 8,686,087 and 8,716,400, which are incorporated herein by reference in their entirety.

[0049] The term "specified block composite" ("SBC") refers to a polymer comprising three polymer components: (i) an ethylene-based polymer (EP) having an ethylene content of 78 mol% to 90 mol% (soft copolymer), based on the total moles of polymerized monomer units in the ethylene-based polymer (EP); (ii) an α-olefin-based polymer (AOP), having an α-olefin content of 61 mol% to 90 mol% (hard copolymer), based on the total moles of polymerized monomer units in the α-olefin-based polymer (AOP); and (iii) a block copolymer (diblock copolymer), the block copolymer having an ethylene block (EB) and an α-olefin block (AOB); wherein the ethylene block of the block copolymer has the same composition as the EP of component (i) of the specified block composite, and the α-olefin block of the block copolymer has the same composition as the AOP of component (ii) of the specified block composite. In addition, in the specified block composite, the composition split between the amounts of EP and AOP will be substantially the same as the composition split between the corresponding blocks in the block copolymer. Non-limiting examples of designated block composites of the present disclosure and methods for preparing the same are disclosed in WO 2017 / 044547, which is incorporated herein by reference in its entirety.

[0050] The term "crystalline block composite" ("CBC") refers to a polymer comprising three components: (i) a crystalline ethylene-based polymer (CEP) having an ethylene content greater than 90 mol%, based on the total moles of polymerized monomer units in the crystalline ethylene-based polymer (CEP); (ii) a crystalline α-olefin-based polymer (CAOP) having an α-olefin content greater than 90 mol%, based on the total moles of polymerized monomer units in the crystalline α-olefin-based polymer (CAOP); and (iii) a block copolymer comprising a crystalline ethylene block (CEB) and a crystalline α-olefin block (CAOB); wherein the CEB of the block copolymer 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, in the crystalline block composite, the composition split between the amounts of CEP and CAOP will be substantially the same as the composition split between the corresponding blocks in the block copolymer. Non-limiting examples of the crystalline block composites of the present disclosure and methods for preparing the same are disclosed in U.S. Pat. No. 8,822,598 B2 and WO 2016 / 01028961 A1, which are incorporated herein by reference in their entirety.

[0051] The term "crystalline" refers to a polymer having a first order transition or crystalline melting point (Tm) as determined by differential scanning calorimetry (DSC) or an equivalent technique. The term may be used interchangeably with the term "semi-crystalline." The term "amorphous" refers to a polymer lacking a crystalline melting point as determined by differential scanning calorimetry (DSC) or an equivalent technique.

[0052] Telechelic Polyolefin

[0053] The present disclosure relates to a formula A 1 L 1 L 2 A 2 A telechelic polyolefin and a composition comprising the telechelic polyolefin.

[0054] Specifically, the present disclosure relates to a telechelic polyolefin of formula (I) or a composition comprising a telechelic polyolefin of formula (I):

[0055] A 1 L 1 L 2 A 2 (I) where:

[0056] L 1 It is a polyolefin;

[0057] A 1 Selected from the group consisting of: vinyl, formula CH2=C(Y1 )-vinylidene, formula Y 1 CH=CH-vinylene, vinyl and formula Y 1 A mixture of CH=CH-vinylene, vinyl and CH2=C(Y 1 )-vinylidene mixture, formula CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of CH=CH-vinylene and vinyl, CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of vinylene groups with CH=CH-;

[0058] Y 1 C1 to C independently at each occurrence 30 Hydrocarbon;

[0059] L 2 It is C1 to C 32 alkylene; and

[0060] A 2 is a hydrocarbon group including a hindered double bond; and

[0061] The telechelic polyolefin of formula (I) has a weight average molecular weight of 1,000 g / mol to 10,000,000 g / mol.

[0062] In certain embodiments, L 2 is -CH2CH(Y 2 )-, such that the telechelic polyolefin of formula (I) is A 1 L 1 CH2CH(Y 2 )A 2 , where Y 2 is hydrogen or C1 to C 30 In certain embodiments, Y 2 In another embodiment, Y 2 The group is C1 to C 10 In another embodiment, Y 2 The group is ethyl.

[0063] As a person skilled in the art would know from formula A 1 L 1 L 2 A 2 Will understand, A 1 Through the carbon-carbon single bond 1 Covalent bonding, L 1 Through the carbon-carbon single bond 2 covalently bonded, and L2 A through a carbon-carbon single bond 2 Covalent bonding. Therefore, when the formula A is stated herein 1 L 1 L 2 A 2 L 1 When it is a polyolefin, it should be understood that L 1 It is connected to A through a carbon-carbon single bond 1 and L 2 Each covalently bonded divalent polyolefin group (a polyolefin lacking two hydrogen atoms) in the group. Similarly, when stating the formula A 1 L 1 L 2 A 2 L 1 When it is a polymer, it should be understood that L 1 It is connected to A through a carbon-carbon single bond 1 and L 2 Each covalently bonded divalent polymeric group (a polymer lacking two hydrogen atoms) in a group. For example, when stating that L 1 When it is an ethylene homopolymer, it should be understood that L 1 It is connected to A through a carbon-carbon single bond 1 and L 2 Each covalently bonded divalent ethylene homopolymer radical (ethylene homopolymer lacking two hydrogen atoms) in the group. As another example, when stating that L 1 When it is an ethylene / α-olefin copolymer, it should be understood that L 1 It is connected to A through a carbon-carbon single bond 1 and L 2 Each covalently bonded divalent ethylene / α-olefin interpolymer group (ethylene / α-olefin interpolymer lacking two hydrogen atoms) in the group.

[0064] In some embodiments, L of formula (I) 1It is a polyolefin produced by the coordination polymerization of unsaturated monomers (and comonomers). Examples of suitable monomers (and comonomers) include, but are not limited to, ethylene and α-olefins having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, such as propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 3,5,5-trimethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 5-ethyl-1-nonene, 1-octadecene and 1-eicosene; conjugated or unconjugated dienes such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene and 5-decadiene. ,9-dimethyl-1,4,8-decatriene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, and mixed isomers of dihydromyrcene and dihydroocimene; norbornene and alkenyl, alkylene, cycloalkenyl and cycloalkylene norbornenes, such as 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 5-methylene-2-norbornene, 5-propenyl-2-norbornene, 5 -isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene and norbornadiene; and aromatic vinyl compounds such as styrene, monoalkylstyrene or polyalkylstyrene (including styrene, o-methylstyrene, tert-methylstyrene, m-methylstyrene, p-methylstyrene, o-p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene).

[0065] L 1 Can be linear (unbranched), branched or cyclic. 1 The presence or absence of branching in L and the amount of branching (if any) can vary widely and can depend on the desired processing conditions and the desired polymer properties. 1 If there is branching in the chain, the branching may be short chain branching or long chain branching. 1 Exemplary types of long chain branching that may be present in include, but are not limited to, T-branching and H-branching. 1 Long chain branching may be included. In other words, in some embodiments, L 1One or more long chain branches may be included, wherein each long chain branch optionally includes A as defined herein for formula (I) 2 Group.

[0066] In some embodiments, the monomer and comonomer are used to form L 1 , A of formula (I) 1 The group is related to the last monomer or comonomer inserted. 1 The choice of monomers and comonomers for coordination polymerization will dictate the 1 Group and Y 1 What can the group be? In some embodiments, A 1 In some embodiments, A 1 The group is of the formula CH2=C(Y 1 )-vinylidene, wherein Y 1 It is C1 to C 30 In some embodiments, A 1 The group is of formula Y 1 CH=CH-vinylene, where Y 1 It is C1 to C 30 In some embodiments, A 1 The group is vinyl and the formula Y 1 A mixture of CH=CH-vinylene, wherein Y 1 It is C1 to C 30 In some embodiments, A 1 The group is vinyl and the formula is CH2=C(Y 1 )-vinylidene groups, wherein Y 1 It is C1 to C 30 In some embodiments, A 1 The group is of the formula CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of CH=CH-vinylene, wherein Y 1 It is C1 to C 30 In some embodiments, A 1 The group is vinyl, formula CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of CH=CH-vinylene, wherein Y 1 It is C1 to C 30 Hydrocarbon.

[0067] In another embodiment, A 1 The group is vinyl and the formula Y 1 A mixture of CH=CH-vinylene, wherein A 1The ratio of vinyl to Y is 0.99:0.01 to 0.01:0.99. 1 CH=CH-vinylene, and wherein Y 1 It is C1 to C 30 Hydrocarbon.

[0068] In another embodiment, A 1 The group is vinyl and the formula is CH2=C(Y 1 )-vinylidene mixture, wherein A 1 The ratio of 0.99:0.01 to 0.01:0.99 includes vinyl and CH2=C(Y 1 )-vinylidene, and wherein Y 1 It is C1 to C 30 Hydrocarbon.

[0069] In another embodiment, A 1 The group is of the formula CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of CH=CH-vinylene, wherein A 1 including the formula CH2=C(Y 1 )-vinylidene and formula Y 1 CH=CH-vinylene, and wherein Y 1 It is C1 to C 30 Hydrocarbon.

[0070] In another embodiment, A 1 The group is vinyl, formula CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of CH=CH-vinylene, wherein A 1 The ratio of vinyl to Y is 0.99:0.01 to 0.01:0.99. 1 CH=CH-ethylene, formula CH2=C(Y 1 )-vinylidene and vinyl groups, and wherein Y 1 It is C1 to C 30 Hydrocarbon.

[0071] In certain embodiments, L 1 is a homopolymer comprising units derived from one monomer. The monomer may be selected from any suitable monomer previously discussed. In another embodiment, L 1 is an ethylene homopolymer comprising units derived from ethylene. In further embodiments, L 1 is a propylene homopolymer comprising units derived from propylene.

[0072] In some embodiments, L 1 is an interpolymer comprising units derived from at least two different types of monomers (e.g., monomers and comonomers). Thus, in certain embodiments, L 1 is an interpolymer comprising units derived from a monomer and at least one comonomer different from the monomer. Each of the monomer and at least one comonomer different from the monomer can be selected from any suitable monomer discussed above.

[0073] In another embodiment, L 1 is a copolymer comprising units derived from two different types of monomers (e.g., 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 the comonomer may be selected from any suitable monomer previously discussed.

[0074] In certain embodiments, L 1 is an ethylene / α-olefin copolymer. In some embodiments, L 1 It includes derivatives from ethylene and C3 to C 30 An ethylene / α-olefin copolymer containing units of α-olefin, wherein the telechelic polyolefin of formula (I) comprises ethylene in an amount of greater than or equal to 50 wt %, or greater than or equal to 60 wt %, or greater than or equal to 70 wt %, or greater than or equal to 75 wt %, or greater than or equal to 80 wt %, or greater than or equal to 85 wt %, or greater than or equal to 88 wt %, or greater than or equal to 89 wt %, or greater than or equal to 90 wt %, based on the total weight of the telechelic polyolefin of formula (I). 30 The α-olefin may be selected from any suitable α-olefin previously discussed. 30 The α-olefin may be propylene, isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc. In some embodiments, L 1 It includes derivatives from ethylene and C3 to C 30 Ethylene / α-olefin copolymers containing α-olefin units, wherein C3 to C 30 The α-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.

[0075] In another embodiment, L 1 It is a propylene / α-olefin copolymer. 1 It may be derived from propylene and ethylene or C4 to C 30A propylene / α-olefin copolymer containing units of α-olefin, wherein the telechelic polyolefin of formula (I) comprises propylene in an amount greater than or equal to 50 wt %, or greater than or equal to 60 wt %, or greater than or equal to 70 wt %, or greater than or equal to 75 wt %, or greater than or equal to 80 wt %, or greater than or equal to 85 wt %, or greater than or equal to 88 wt %, or greater than or equal to 89 wt %, or greater than or equal to 90 wt %, based on the total weight of the telechelic polyolefin of formula (I). 30 The α-olefin can be any suitable α-olefin discussed above. 30 The α-olefin may be isobutylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-nonene, 1-decene, etc. In certain embodiments, L 1 It may be derived from propylene and ethylene or C4 to C 30 Propylene / α-olefin copolymers containing α-olefin units, wherein C4 to C 30 The α-olefin is selected from the group consisting of 1-butene, 1-hexene and 1-octene.

[0076] In certain embodiments, L 1 is a terpolymer comprising units derived from three different types of monomers, each of which can be selected from any suitable monomer discussed above. In further embodiments, L 1 It includes ethylene or propylene as the first monomer, C3 to C 30 A terpolymer of an α-olefin or styrene and a diene or a polar monomer as the third monomer.

[0077] In some embodiments, based on the total weight of the telechelic polyolefin of formula (I), L 1 The invention comprises 0 to 10 wt% of units derived from diene monomers. For example, based on the total weight of the telechelic polyolefin of formula (I), L 1 1 to 8 wt % or 1 to 5 wt % or 1 to 3 wt % of units derived from diene monomers may be included. In other embodiments, L 1 may be substantially free of units derived from diene monomers. For example, in certain embodiments, based on the total weight of the telechelic polyolefin of formula (I), L 1 Units derived from diene monomers may be included in an amount of 0 to 0.2 wt %, or 0 to 0.01 wt %, or 0 to 0.001 wt %, or 0 to 0.0001 wt %.

[0078] In certain embodiments, L 1 is an olefin block copolymer as defined herein. In further embodiments, L 1is a block composite, a specified block composite or a crystalline block composite as defined herein.

[0079] In some embodiments, A 2 is a hydrocarbon group including a hindered double bond. In another embodiment, A 2 is a hydrocarbon group including two or more hindered double bonds.

[0080] In certain embodiments, due to the hindered double bond, A 2 The group is used in the preparation of polyolefin L 1 The group that is not easily incorporated by the active catalyst under the process conditions makes A 2 Along L 1 The backbone of the invention is directly incorporated into less than or equal to 0.5 mol % or less than or equal to 0.1 mol %, or not detected, as described herein. 13 C NMR method or similar 13 Determined by C NMR method.

[0081] In some embodiments, A 2 is a hydrocarbon group including a hindered double bond, wherein the hindered double bond is selected from the group consisting of a double bond of a vinylidene group, a double bond of a vinylene group, a double bond of a trisubstituted olefin, and a double bond of a vinyl group attached to the alpha carbon of a branch.

[0082] In another embodiment, A 2 is a hydrocarbyl group including two or more hindered double bonds, wherein each hindered double bond is 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 olefin, and a double bond of a vinyl group attached to the alpha carbon of a branch.

[0083] In certain embodiments, A 2 is a hydrocarbon group comprising a functional group, wherein the functional group is selected from the group consisting of vinylidene, vinylene, trisubstituted olefins, and vinyl groups attached to the alpha carbon of a branch.

[0084] In another embodiment, A 2 is a hydrocarbon group comprising two or more functional groups, wherein each functional group is independently selected from the group consisting of vinylidene, vinylene, trisubstituted olefins, and vinyl attached to the alpha carbon of a branch.

[0085] A 2 The group may be a cyclic or acyclic (straight or branched) hydrocarbon group. 2 is a cyclic hydrocarbon group, then A 2 One or more rings may be included, wherein each ring may be monocyclic, bicyclic or polycyclic, and wherein each ring may include one or more hindered double bonds.

[0086] In addition, if A2 is a cyclic hydrocarbon group, each hindered double bond or functional group therein may be an endocyclic double bond, an exocyclic double bond, or an acyclic double bond. 2 A may be a cyclic hydrocarbon group including a vinylene group, wherein the double bond of the vinylene group may be an endocyclic double bond or an acyclic double bond. 2 A may be a cyclic hydrocarbon group including a vinylidene group, wherein the double bond of the vinylidene group may be an exocyclic double bond or an acyclic double bond. 2 A may be a cyclic hydrocarbon group including a trisubstituted olefin, wherein the double bond of the trisubstituted olefin may be an endocyclic double bond, an exocyclic double bond, or an acyclic double bond. 2 It may be a cyclic hydrocarbon group including a vinyl group attached to the alpha carbon of the branch, wherein the vinyl group attached to the alpha carbon of the branch is a non-cyclic double bond.

[0087] In any of the embodiments described herein, A 2 It may include 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.

[0088] In certain embodiments, A 2 is a C3 to C5 alkyl-substituted or unsubstituted cycloolefin. 30 In another embodiment, A 2 is an alkyl-substituted or unsubstituted cycloolefin comprising 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.

[0089] Exemplary unsubstituted cycloolefins include, but are not limited to, cyclohexene, cycloheptene, cyclooctene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, and 1,5-cyclooctadiene. Exemplary alkyl-substituted cycloolefins 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.

[0090] In some embodiments, A 2 A is a methyl-substituted or unsubstituted cycloolefin selected from the group consisting of methyl-substituted or unsubstituted cyclohexene, methyl-substituted or unsubstituted cycloheptene, and methyl-substituted or unsubstituted cyclooctene. 2It is a methyl-substituted or unsubstituted cyclohexene.

[0091] In some embodiments, A 2 It is C1 to C 10 Non-cyclic alkyl or C3 to C 10 Acyclic alkyl group or C4 to C8 acyclic alkyl group.

[0092] Exemplary A of the telechelic polyolefin of formula (I) 2 The groups include but are not limited to the following:

[0093]

[0094] With respect to each of (AA) to (AZ) and (AZ1), The symbol (wavy line symbol) represents the same as L in formula (I) 2 For example, in certain embodiments, the connection point of "Y" 2 ” and “A 1 L 1 The attachment point of the carbon to which CH2" is attached. In addition, with respect to each of (AA) to (AZ) and (AZ1), The symbol (wavy line symbol) represents the same chain transfer agent formula as discussed below: Al(CH2CH(Y 2 )A 2 )3 and Zn(CH2CH(Y 2 )A 2 )2 with hydrogen and Y 2 The connection point of the attached carbon.

[0095] With respect to each of (AA) to (AF), the endocyclic double bond may be located between any two adjacent carbon atoms that are ring members.

[0096] With respect to each of (AD) to (AF), the pendant methyl group may be attached to any carbon atom that is a ring member.

[0097] With respect to each of (AG) through (AL), the exocyclic double bond may be attached to any ring member carbon atom that is not already attached to more than two carbon atoms.

[0098] In some embodiments, the telechelic polyolefin of formula (I) 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 the GPC method described herein or a similar GPC method.

[0099] In some embodiments, the telechelic polyolefin of formula (I) 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 the GPC method described herein or a similar GPC method.

[0100] In some embodiments, the telechelic polyolefin of formula (I) 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 the GPC method described herein or a similar GPC method.

[0101] In some embodiments, the telechelic polyolefin of formula (I) 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.

[0102] In some embodiments, the telechelic polyolefin of formula (I) has a density 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 according to ASTM D-792, Method B.

[0103] In some embodiments, the telechelic polyolefin of formula (I) has a melt index (I2) of 0.01 to 2000 g / 10 min or 0.01 to 1,500 g / 10 min or 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 according to ASTM D-1238, Condition 190°C / 2.16 kg.

[0104] In some embodiments, the telechelic polyolefin of formula (I) has a T of mIn 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.

[0105] In some embodiments, the telechelic polyolefin of formula (I) has a Brookfield viscosity (as measured at 177° C.) of 10 to 10 8 cP or 10 to 10 7 cP or 10 to 10 6 cP or 10 to 750,000cP or 10 to 500,000cP or 10 to 250,000cP or 10 to 100,000cP or 10 to 75,000cP or 10 to 50,000cP or 10 to 40,000cP.

[0106] In some embodiments, the telechelic polyolefin of formula (I) has a melting enthalpy (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.

[0107] In some embodiments, the telechelic polyolefin of formula (I) has a crystallinity wt% of 0 to 80% or 0 to 60% or 5 to 50% or 7 to 40% based on a PEΔHm of 292 J / g according to the DSC method described herein or a similar DSC method.

[0108] In some embodiments, the telechelic polyolefin of formula (I) has a T of g It is -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.

[0109] In some embodiments, L 1 The telechelic polyolefin of formula (I) is substantially free of units derived from diene monomers and has a total number of unsaturations equal to or greater than 1.1 or equal to or greater than 1.2 or equal to or greater than 1.3 or equal to or greater than 1.4 or equal to or greater than 1.5 or equal to or greater than 1.6 or equal to or greater than 1.7 or equal to or greater than 1.8 or equal to or greater than 1.9. The total number of unsaturations can be defined as (unsaturations / 1000C)*(1000C / chain)=(unsaturations / 1000C)*(Mn / M CH2 / 1000), where unsaturation / 1000C is obtained by 1 H NMR, Mn as measured by GPC and for13 C NMR measured composition corrected number average molecular weight, M CH2 =14 g / mol. It is reported that the Mn measured by GPC is the number average molecular weight of the polymer backbone. The unsaturation / 1000C measured by 1H NMR is relative to the total carbon number in the polymer chain. For ethylene, propylene, octene and ethylidene norbornene, there are 2, 3, 8 and 9 total carbon atoms per 2 main chain carbon atoms, respectively. Therefore, the Mn corrected for composition is Mn(mol%C2 / 2+mol%C3 / 3+mol%C8 / 8+mol%ENB / 9) / 2 measured by GPC time. 13 C NMR, 1 H NMR and GPC herein refer to methods described herein or similar methods. As used herein, "substantially free" means L including, for example, 0 to 0.001 wt% of units derived from diene monomers, based on the total weight of the telechelic polyolefin of formula (I).

[0110] In some embodiments, based on the total weight of the telechelic polyolefin of formula (I), L 1 The telechelic polyolefin of formula (I) comprises 1 to 8 wt % or 1 to 5 wt % or 1 to 3 wt % of units derived from diene monomers, and the total number of unsaturations is equal to or greater than (X D +1.1), equal to or greater than (X D +1.2), equal to or greater than (X D +1.3), equal to or greater than (X D +1.4), equal to or greater than (X D +1.5), equal to or greater than (X D +1.6), equal to or greater than (X D +1.7), equal to or greater than (X D +1.8) or equal to or greater than (X D +1.9), where X D It is from L 1 The unsaturation in the units derived from diene monomers is the amount of unsaturation in the units derived from diene monomers, and wherein the unsaturation is measured as described in the previous paragraph.

[0111] In certain embodiments, the telechelic polyolefins of formula (I) contain unsaturation at the termini of the polymer chains, rather than randomly distributed along the polymer backbone (as in the case of EPDM or polybutadiene).

[0112] The telechelic polyolefin of formula (I) can be any embodiment or a combination of any of the above embodiments.

[0113] Method for preparing telechelic polyolefins

[0114] The present disclosure further relates to a method for preparing a telechelic polyolefin or a composition comprising a telechelic polyolefin, the method comprising:

[0115] 1) combining starting materials including (A) a monomer component, (B) a chain transfer agent component, and (C) a catalyst component including a main catalyst to form a solution, and polymerizing greater than 10 mol % to less than or equal to 99 mol % of the (A) monomer component in the solution;

[0116] 2) heating the solution to a temperature of at least 160° C. and maintaining the solution at the temperature of at least 160° C. for a period of at least 30 seconds; and

[0117] 3) recovering a product comprising said telechelic polyolefin or said composition comprising said telechelic polyolefin, wherein:

[0118] The chain transfer agent component (B) comprises the formula Al(CH2CH(Y 2 )A 2 )3 organoaluminum compounds;

[0119] Y 2 is independently hydrogen or C1 to C 30 a hydrocarbon group; and

[0120] A 2 and R is independently at each occurrence a hydrocarbyl group including a hindered double bond.

[0121] The present disclosure further relates to a process for preparing a telechelic polyolefin of formula (I) or a composition comprising a telechelic polyolefin of formula (I):

[0122] A 1 L 1 L 2 A 2 (I), the method comprising:

[0123] 1) combining starting materials including (A) a monomer component, (B) a chain transfer agent component, and (C) a catalyst component including a main catalyst to form a solution, and polymerizing greater than 10 mol % to less than or equal to 99 mol % of the (A) monomer component in the solution;

[0124] 2) heating the solution to a temperature of at least 160° C. and maintaining the solution at the temperature of at least 160° C. for a period of at least 30 seconds; and

[0125] 3) recovering a product comprising the telechelic polyolefin of formula (I) or a composition comprising the telechelic polyolefin of formula (I), wherein:

[0126] The chain transfer agent component (B) comprises the formula Al(CH2CH(Y 2 )A 2 )3 organoaluminum compounds;

[0127] L 1 It is a polyolefin;

[0128] L 2 It is C1 to C 32 alkylene;

[0129] A 1 Selected from the group consisting of: vinyl, formula CH2=C(Y 1 )-vinylidene, formula Y 1 CH=CH-vinylene, vinyl and formula Y 1 A mixture of CH=CH-vinylene, vinyl and CH2=C(Y 1 )-vinylidene mixture, formula CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of CH=CH-vinylene and vinyl, CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of vinylene groups with CH=CH-;

[0130] Y 1 C1 to C independently at each occurrence 30 Hydrocarbon;

[0131] Y 2 is independently hydrogen or C1 to C 30 a hydrocarbon group; and

[0132] A 2 is independently at each occurrence a hydrocarbyl group including a hindered double bond; and

[0133] The telechelic polyolefin of formula (I) has a weight average molecular weight of 1,000 g / mol to 10,000,000 g / mol.

[0134] L in formula (I) 1 , A 1 , Y 1 , L 2 , Y 2 and A 2 The previously described embodiments of each of the groups are applicable to the inventive methods disclosed herein. Similarly, the previously described embodiments of the telechelic polyolefins of formula (I) are applicable to the inventive methods disclosed herein.

[0135] The starting material in step 1) may further include (D) a solvent. The starting material (D) solvent may be any aromatic or aliphatic hydrocarbon. Suitable solvents include but are not limited to toluene, xylene, hexane, pentane, benzene, heptane, Isopar TM In addition, the starting material in step 1) may further include hydrogen, an adjuvant, a scavenger and / or a polymerization aid.

[0136] Step 1) is a coordination polymerization step for forming the backbone of the telechelic polyolefin of formula (I) from the monomers and comonomers of the (A) monomer component. During step 1), polymeric aluminum species may be formed by chain transfer between the (B) chain transfer agent component and the active catalyst from the (C) catalyst component. Subsequently, the polymeric aluminum species undergoes β-hydride elimination during step 2) to form a product including the telechelic polyolefin of formula (I), which is recovered during step 3).

[0137] Step 1) of the process for preparing a composition comprising a telechelic polyolefin of the present disclosure is preferably carried out as a solution polymerization step. Most preferably, step 1) is carried out as a continuous solution polymerization step, wherein the starting material is continuously supplied to the reaction zone, and the polymer product is continuously removed from the reaction zone. Within the scope of the term "continuous" as used in this context are those processes in which the reactants are intermittently added and the product is removed at regular or irregular intervals so that over time, the overall process is substantially continuous.

[0138] Step 1) can be performed 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) can be performed at a temperature of 60° C. to 150° C. or 80° C. to 140° C. or 100° C. to 130° C. or 110° C. to 120° C.

[0139] One of ordinary skill in the art will appreciate that the amount of each component of the starting materials, including components (A) through (D), may be varied in order to produce one or more polymers having different chemical or physical properties.

[0140] Without limiting the scope of the invention in any way, one way to carry out step 1) is as follows. In a stirred tank reactor, the monomers of the (A) monomer component are continuously introduced together with any solvent or diluent. The reactor contains a liquid phase consisting essentially of the monomers together with any solvent or diluent and dissolved polymer. Preferred solvents include C 4-10Hydrocarbon or its mixture, particularly alkane, such as hexane or alkane mixture, and one or more monomers in the monomer used in polymerization. (B) chain transfer agent component and (C) catalyst component are continuously or intermittently introduced into reactor liquid phase or any recycle part thereof. Reactor temperature and pressure can be controlled by adjusting solvent / monomer ratio, (C) addition rate of catalyst component and by cooling or heating coil, jacket or both. Polymerization rate is controlled by addition rate of (C) catalyst component. If (A) monomer component comprises ethylene and at least one comonomer, the ethylene content of polymer product is determined by the ratio of ethylene to comonomer in reactor, and the ratio is controlled by manipulating the corresponding feed rate of these components into reactor. Optionally, polymer product molecular weight is controlled by controlling other polymerization variables, such as temperature, monomer concentration or other variables known in the art. In continuous process, the average residence time of active catalyst and polymer in reactor is generally 5 minutes to 8 hours and preferably 10 minutes to 6 hours.

[0141] Alternatively, step 1) may be carried out in two or more reactors in series, operating under steady state polymerization conditions or in two or more zones of a reactor operating under plug flow polymerization conditions under different process conditions. Alternatively, step 1) may be carried out in one or more continuous loop reactors with or without a monomer, catalyst or chain transfer agent gradient established between its different zones, optionally with separate addition of catalyst and / or chain transfer agent, and operating under adiabatic or non-adiabatic solution polymerization conditions or a combination of the aforementioned reactor conditions.

[0142] After step 1), the polymer solution is heated according to step 2), as further described below. Such heating includes, but is not limited to, heating in a reactor post-heater. After step 2), the polymer product is recovered in step 3) by means known in the art. Such means include contacting the polymer solution with a catalyst killer, such as water, steam or alcohol, flashing off gaseous monomers and residual solvent or diluent under reduced pressure, and, if necessary, further devolatilization in a device such as a devolatilization extruder.

[0143] In some embodiments, the solution in step 2) is heated at 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.

[0144] In some embodiments, the solution in step 2) is heated at 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 period 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.

[0145] In some embodiments, the solution in step 2) is heated to a temperature of at least 160°C, or at least 180°C, or at least 200°C, or at least 210°C, or at least 220°C, or at least 230°C, or at least 240°C, or at least 250°C, or at least 260°C, or at least 270°C, or at least 280°C, or at least 290°C, or at least 300°C, and maintained at 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 period 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.

[0146] For example, in certain embodiments, the solution in step 2) is heated at a temperature of 160°C to 300°C or 180°C to 300°C or 200°C to 300°C or 210°C to 300°C or 220°C to 290°C or 230°C to 290°C or 240°C to 280°C.

[0147] In further embodiments, the solution in step 2) is heated at a temperature of 160°C to 300°C or 180°C to 300°C or 200°C to 300°C or 210°C to 300°C or 220°C to 290°C or 230°C to 290°C or 240°C to 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.

[0148] In another embodiment, the solution in step 2) is heated to a temperature of 160 to 300°C, or 180 to 300°C, or 200 to 300°C, or 210 to 300°C, or 220 to 290°C, or 230 to 290°C, or 240 to 280°C, and maintained at a temperature of 160 to 300°C, or 180 to 300°C, or 200 to 300°C, or 210 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.

[0149] (A) Monomer components

[0150] (A) The monomer component includes a monomer selected from the group consisting of L 1 Any monomer of the monomers and comonomers discussed. Examples of suitable monomers and comonomers include, but are not limited to, ethylene and α-olefins having 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-dimethyl-1-pentene. decaene; conjugated or unconjugated dienes such as butadiene, isoprene, 4-methyl-1,3-pentadiene, 1,3-pentadiene, 1,4-pentadiene, 1,5-hexadiene, 1,4-hexadiene, 1,3-hexadiene, 1,5-heptadiene, 1,6-heptadiene, 1,3-octadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 1,9-decadiene, 7-methyl-1,6-octadiene, 4-ethyl-8-methyl -1,7-nonadiene and 5,9-dimethyl-1,4,8-decatriene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, and mixed isomers of dihydromyrcene and dihydroocimene; norbornene and alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-ethylidene-2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 5-methylene-2-norbornene olefins, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene and norbornadiene; aromatic vinyl compounds such as styrene, monoalkylstyrene or polyalkylstyrene (including styrene, o-methylstyrene, tert-methylstyrene, m-methylstyrene, p-methylstyrene, o-, p-dimethylstyrene, o-ethylstyrene, m-ethylstyrene and p-ethylstyrene).

[0151] In some embodiments, (A) monomer components include ethylene monomers. In some embodiments, (A) monomer components include propylene monomers. In some embodiments, (A) monomer components include ethylene monomers and comonomers of C3 to C30 alpha olefins. C3 to C30 alpha olefins can 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, (A) monomer components include propylene monomers and comonomers of ethylene or C4 to C30 alpha olefins. The C4 to C30 α-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.

[0152] In certain embodiments, the (A) monomer component comprises ethylene monomer and a comonomer of a C3 to C30 alpha-olefin, wherein the C3 to C30 alpha-olefin is selected from propylene, 1-hexene, 1-butene, and 1-octene. In other embodiments, the (A) monomer component comprises ethylene monomer and a propylene comonomer. In other embodiments, the (A) monomer component comprises ethylene monomer and a 1-hexene comonomer. In other embodiments, the (A) monomer component comprises ethylene monomer and a 1-butene comonomer. In other embodiments, the (A) monomer component comprises ethylene monomer and a 1-octene comonomer.

[0153] In another embodiment, (A) monomer component comprises propylene monomer and ethylene or C4 to C30 alpha-olefin comonomer, wherein C4 to C30 alpha-olefin is selected from the group consisting of 1-hexene, 1-butene and 1-octene. In another embodiment, (A) monomer component comprises propylene monomer and ethylene comonomer. In another embodiment, (A) monomer component comprises propylene monomer and 1-hexene comonomer. In another embodiment, (A) monomer component comprises propylene monomer and 1-butene comonomer. In another embodiment, (A) monomer component comprises propylene monomer and 1-octene comonomer.

[0154] In certain embodiments, the (A) monomer component includes 50 wt% to 99 wt% or less (e.g., 60 wt% to 99 wt% or less, 70 wt% to 99 wt% or less, 75 wt% to 99 wt% or more, 80 wt% to 99 wt% or more, 85 wt% to 99 wt% or more, or 90 wt% to 99 wt% or less) of ethylene monomer and 1 wt% to 2 wt% of ethylene monomer. The invention relates to a copolymer of at least 50 wt% (e.g., from at least 1 wt% to at least 40 wt% or from at least 1 wt% to at least 30 wt% or from at least 1 wt% to at least 25 wt% or from at least 1 wt% to at least 20 wt% or from at least 1 wt% to at least 15 wt% or from at least 1 wt% to at least 10 wt%) of a C3 to C30 alpha-olefin selected from the group consisting of propylene, 1-hexene, 1-butene and 1-octene.

[0155] In certain embodiments, the (A) monomer component includes 50 wt% to 99 wt% or less (e.g., 60 wt% to 99 wt% or less, 70 wt% to 99 wt% or less, 75 wt% to 99 wt% or more, 80 wt% to 99 wt% or more, 85 wt% to 99 wt% or more, or 90 wt% to 99 wt% or less) of propylene monomer and 1 wt% to 2 wt% of propylene monomer. The invention relates to a copolymer of ethylene or a C4 to C30 alpha-olefin containing at least 50 wt% (e.g., from at least 1 wt% to at least 40 wt% or from at least 1 wt% to at least 30 wt% or from at least 1 wt% to at least 25 wt% or from at least 1 wt% to at least 20 wt% or from at least 1 wt% to at least 15 wt% or from at least 1 wt% to at least 10 wt%) of a comonomer of ethylene or a C4 to C30 alpha-olefin, wherein the C4 to C30 alpha-olefin is selected from the group consisting of 1-hexene, 1-butene and 1-octene.

[0156] In some embodiments, (A) monomer component includes 0 to 10 wt% of diene monomer. For example, (A) monomer component may include 0.5 to 8 wt% or 1 to 5 wt% or 1 to 3 wt% of diene monomer. In other embodiments, (A) monomer component may be substantially free of diene monomer. For example, in certain embodiments, (A) 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 diene monomer.

[0157] (B) Chain transfer agent

[0158] In certain embodiments, (B) the chain transfer agent component comprises the formula Al(CH2CH(Y 2 )A 2 )3 organic aluminum compound, wherein: Y 2 is independently hydrogen or C1 to C 30 A hydrocarbon group; and 2 is independently at each occurrence a hydrocarbon group including a hindered double bond. In another embodiment, the (B) chain transfer agent component is of the formula Al(CH2CH(Y 2 )A 2 )3 organic aluminum compound. 2 and A 2 may be Y with respect to the telechelic polyolefin of formula (I) 2 and A 2 In certain embodiments, the formula Al(CH2CH(Y 2 )A 2 )3 of the organoaluminum compound Y 2 Can be selected from the group consisting of hydrogen, methyl and ethyl. In certain embodiments, the formula Al(CH2CH(Y 2 )A 2 )3 of the organoaluminum compound A 2 Can be selected from (AA) to (AZ) and (AZ1) discussed previously. In another embodiment, the formula Al(CH2CH(Y 2 )A 2 )3 of the organoaluminum compound A 2 Selected from the group consisting of (AC), (AF), (AM), (AO), (AP), (AS) and (AZ1). The side methyl group of (AF) may be attached to any carbon atom that is a ring member.

[0159] Formula Al(CH2CH(Y 2 )A 2 The organoaluminum compound of the formula CH2=C(Y 2 )A 2(b) heating the organoaluminum solution to a temperature of 60 to 200°C, 80 to 180°C, 100 to 150°C, or 110 to 130°C, and maintaining the organoaluminum solution at a temperature of 60 to 200°C, 80 to 180°C, 100 to 150°C, or 110 to 130°C for 30 minutes to 200 hours, 30 minutes to 100 hours, 30 minutes to 50 hours, 30 minutes to 25 hours, 1 hour to 10 hours, 1 hour to 5 hours, or 3 hours to 5 hours; and (c) recovering a precipitate comprising the formula Al(CH2CH(Y 2 )A 2 )3, wherein: d is independently C1 to C 10 Alkyl; Y 2 is independently hydrogen or C1 to C 30 A hydrocarbon group; and 2 is independently a hydrocarbon group including a hindered double bond at each occurrence. In certain embodiments, the carbon of d connected to Al is a carbon connected to a tertiary carbon. For example, in certain embodiments, the alkylaluminum of formula Al(d)3 is triisobutylaluminum.

[0160] For the preparation of Al(CH2CH(Y 2 )A 2 )3 thermal process of organoaluminum compounds, Y 2 and A 2 may be Y with respect to the telechelic polyolefin of formula (I) 2 and A 2 The optional solvent may be any solvent discussed herein. The starting material in step (a) may include an alkyl aluminum of formula Al(d)3 and an alkyl aluminum of formula CH2=C(Y) in a ratio of 1:10 or 1:5 or 1:3. 2 )A 2 The starting material in step (a) may include a hydrocarbon of the formula CH2=C(Y 2 )A 2 One or more hydrocarbons, wherein: Y 2 Each hydrocarbon at each occurrence is independently hydrogen or a C1 to C 30 Hydrocarbon; A 2 Each hydrocarbon at each occurrence is independently a hydrocarbon group including a hindered double bond; and the starting material comprises an alkyl aluminum of formula Al(d)3 and a CH2=C(Y) in a ratio of 1:10 or 1:5 or 1:3 2 )A 2 In certain embodiments, Y 2 may be selected from the group consisting of hydrogen, methyl and ethyl, and A 2Can be selected from (AA) to (AZ) and (AZ1) discussed previously. In another embodiment, A 2 It can be selected from the group consisting of (AC), (AF), (AM), (AO), (AP), (AS) and (AZ1). The side methyl group of (AF) can be attached to any carbon atom as a ring member. 2 )A 2 )3, any excess of the organoaluminum compound of formula CH2=C(Y 2 )A 2 of hydrocarbons.

[0161] Alternatively, the formula Al(CH2CH(Y 2 )A 2 )3 can be prepared by a catalytic method, the catalytic method comprising: (a) comprising a compound of the formula CH2=CHA 2 Hydrocarbons of formula Al(Y 2 )3, a starting material combination of an alkyl aluminum, a primary catalyst, an optional co-catalyst and an optional solvent; and (b) recovering a catalyst comprising the formula Al(CH2CH(Y 2 )A 2 ) 3, wherein step (a) is carried out at a temperature of 1°C to 50°C, or 10°C to 40°C, or 20°C to 30°C, for a period of 1 to 50 hours, or 10 to 40 hours, or 15 to 25 hours, and wherein: Y 2 C1 to C independently at each occurrence 30 A hydrocarbon group; and 2 and R is independently at each occurrence a hydrocarbyl group including a hindered double bond.

[0162] For the preparation of Al(CH2CH(Y 2 )A 2 )3 of the catalytic method of the organoaluminum compound, Y 2 will be C1 to C 30 Hydrocarbon, and A 2 Any of the previously described embodiments of the telechelic polyolefin of formula (I) may be used. Each of the primary catalyst, the optional cocatalyst, and the optional solvent may be any of those disclosed herein. The starting material in step (a) may include a 1:10, 1:5, or 1:3 ratio of formula Al(Y 2 )3 alkyl aluminum and formula CH2=CHA 2 The starting material in step (a) may include a hydrocarbon of the formula CH2=CHA 2 One or more hydrocarbons, wherein: A 2Each hydrocarbon at each occurrence is independently a hydrocarbon group including a hindered double bond; and the starting material comprises compounds of the formula Al(Y 2 )3 alkyl aluminum and formula CH2=C(Y 2 )A 2 In certain embodiments, Y 2 Can be C1 to C 10 Alkyl, and A 2 Can be selected from (AA) to (AZ) and (AZ1) discussed previously. In another embodiment, A 2 It may be selected from the group consisting of (AC), (AF), (AM), (AO), (AP), (AS) and (AZ1). The side methyl group of (AF) may be attached to any carbon atom that is a ring member.

[0163] In another embodiment, (B) the chain transfer agent component comprises the formula Al(CH2CH(Y 2 )A 2 )3 and an alkyl zinc of formula Zn(d)2, wherein: Y 2 is independently hydrogen or C1 to C 30 Hydrocarbon; A 2 is independently a hydrocarbon group including a hindered double bond at each occurrence; and d is independently C1 to C 10 In other embodiments, the (B) chain transfer agent component comprises 65 mol% to 99 mol% of the formula Al(CH2CH(Y 2 )A 2 )3 and 1 mol% to 35 mol% of an alkyl zinc of the formula Zn(d)2. 2 and A 2 may be Y with respect to the telechelic polyolefin of formula (I) 2 and A 2 Any of the previously described embodiments. 2 may be selected from the group consisting of hydrogen, methyl and ethyl, and A 2 can be selected from (AA) to (AZ) and (AZ1) discussed previously. Further, A 2 Can be selected from the group consisting of: (AC), (AF), (AM), (AO), (AP), (AS) and (AZ1). The side methyl group of (AF) can be attached to any carbon atom that is a ring member. Without being bound by any particular theory, the addition of alkyl zinc of formula Zn(d)2 can increase the rate of chain transfer reaction. The alkyl zinc of formula Zn(d)2 can be di(C 1-8Non-limiting examples of alkylzincs of formula Zn(d)2 are diethylzinc, diisopropylzinc, diisobutylzinc, di(n-hexyl)zinc and di(n-octyl)zinc.

[0164] In certain embodiments, (B) the chain transfer agent component comprises the formula Al(CH2CH(Y 2 )A 2 )3 organic aluminum compound and formula Zn(CH2CH(Y 2 )A 2 )2, wherein: Y 2 is independently hydrogen or C1 to C 30 A hydrocarbon group; and 2 is independently at each occurrence a hydrocarbon group comprising a hindered double bond. 2 )A 2 )3 organic aluminum compound and formula Zn(CH2CH(Y 2 )A 2 The (B) chain transfer agent component of the organozinc compound of formula (A1(CH2CH(Y 2 )A 2 )3 organic aluminum compound and formula Zn(CH2CH(Y 2 )A 2 )2, and then the two compounds are mixed in a formula Zn(CH2CH(Y 2 )A 2 )2 organic zinc compound with formula Al(CH2CH(Y 2 )A 2 )3 organic aluminum compounds are mixed together in a ratio of .

[0165] For this purpose, the formula Zn(CH2CH(Y 2 )A 2 )2 can be prepared by a catalytic method, the catalytic method comprising: (a) comprising a compound of the formula CH2=CHA 2 Hydrocarbons of formula Zn(Y 2 )2, a starting material combination of an alkyl zinc, a primary catalyst, an optional co-catalyst and an optional solvent; and (b) recovering a catalyst comprising a Zn(CH2CH(Y 2 )A 2 ) 2, wherein step (a) is carried out at a temperature of 1°C to 50°C, or 10°C to 40°C, or 20°C to 30°C, for a period of 1 to 50 hours, or 10 to 40 hours, or 15 to 25 hours, and wherein: Y 2C1 to C independently at each occurrence 30 A hydrocarbon group; and 2 and R is independently at each occurrence a hydrocarbyl group including a hindered double bond.

[0166] For the preparation formula Zn(CH2CH(Y 2 )A 2 )2 catalytic method of the organozinc compound, Y 2 will be C1 to C 30 Hydrocarbon, and A 2 Any of the previously described embodiments of the telechelic polyolefin of formula (I) may be used. Each of the primary catalyst, the optional cocatalyst, and the optional solvent may be any of those disclosed herein. The starting material in step (a) may include a 1:10, 1:5, or 1:2 ratio of the formula Zn(Y 2 )2 alkyl zinc with formula CH2=CHA 2 The starting material in step (a) may include a hydrocarbon of the formula CH2=CHA 2 One or more hydrocarbons, wherein: A 2 Each hydrocarbon at each occurrence is independently a hydrocarbon group including a hindered double bond; and the starting material comprises a ratio of 1:10 or 1:5 or 1:2 of the formula Zn(Y 2 )2 alkyl zinc formula CH2=C(Y 2 )A 2 In certain embodiments, Y 2 Can be C1 to C 10 Alkyl, and A 2 Can be selected from (AA) to (AZ) and (AZ1) discussed previously. In another embodiment, A 2 It may be selected from the group consisting of (AC), (AF), (AM), (AO), (AP), (AS) and (AZ1). The side methyl group of (AF) may be attached to any carbon atom that is a ring member.

[0167] Alternatively, the formula Al(CH2CH(Y 2 )A 2 )3 organic aluminum compound and formula Zn(CH2CH(Y 2 )A 2 The (B) chain transfer agent component of the organic zinc compound of formula Al(CH2CH(Y 2 )A 2 )3 organic aluminum compound and formula Zn(CH2CH(Y 2 )A 2 The chain transfer agent component (B) of the organic zinc compound of the formula CH2=CHA2 Hydrocarbons of formula Al(Y 2 )3 alkyl aluminum, formula Zn(Y 2 )2, a starting material combination of an alkyl zinc, a primary catalyst, an optional co-catalyst, and an optional solvent; and (b) recovering a product including (B) a chain transfer agent component, the chain transfer agent component comprising the formula Al(CH2CH(Y 2 )A 2 )3 organic aluminum compound and formula Zn(CH2CH(Y 2 )A 2 )2, wherein step (a) is carried out at a temperature of 1°C to 50°C, or 10°C to 40°C, or 20°C to 30°C, for a period of 1 to 50 hours, or 10 to 40 hours, or 15 to 25 hours, and wherein: Y 2 C1 to C independently at each occurrence 30 A hydrocarbon group; and 2 and R is independently at each occurrence a hydrocarbyl group including a hindered double bond.

[0168] For the preparation of the formula Al(CH2CH(Y 2 )A 2 )3 organic aluminum compound and formula Zn(CH2CH(Y 2 )A 2 )2 organic zinc compound (B) chain transfer agent catalytic method, Y 2 will be C1 to C 30 Hydrocarbon, and A 2 Any of the previously described embodiments of the telechelic polyolefin of formula (I) may be used. Each of the primary catalyst, the optional cocatalyst, and the optional solvent may be any of those disclosed herein. The starting material in step (a) may include a 1:1 ratio of formula Al(Y 2 )3 alkyl aluminum and Zn(Y 2 )2 alkyl zinc with formula CH2=CHA 2 The starting material in step (a) may further include a hydrocarbon of the formula Zn(Y) in a ratio of 1:99 to 80:20 or 10:90 to 60:40 or 20:80 to 40:60. 2 )2 alkyl zinc and formula Al(Y 2 )3. The starting material in step (a) may include the formula CH2=CHA 2 One or more hydrocarbons, wherein: A 2 Each hydrocarbon at each occurrence is independently a hydrocarbon group including a hindered double bond; and the starting material comprises a 1:1 ratio of the formula Al(Y 2 )3 alkyl aluminum and Zn(Y 2 )2 alkyl zinc with formula CH2=CHA 2and one or more hydrocarbons of the formula Zn(Y) in a ratio of 1:99 to 80:20 or 10:90 to 60:40 or 20:80 to 40:60 2 )2 alkyl zinc and formula Al(Y 2 )3. In certain embodiments, Y 2 Can be C1 to C 10 Alkyl, and A 2 Can be selected from (AA) to (AZ) and (AZ1) discussed previously. In another embodiment, A 2 It may be selected from the group consisting of (AC), (AF), (AM), (AO), (AP), (AS) and (AZ1). The side methyl group of (AF) may be attached to any carbon atom that is a ring member.

[0169] In another embodiment, the formula Al(CH2CH(Y 2 )A 2 )3 organic aluminum compound and formula Zn(CH2CH(Y 2 )A 2 The (B) chain transfer agent component of the organozinc compound of )2 can be prepared by a thermal process. This process is demonstrated by, but not limited to, the synthesis of CTA 6 in the examples.

[0170] In another embodiment, (B) the chain transfer agent can be a formula (d) 2AlCH2CH(Y 2 )A 2 An organoaluminum compound, wherein: Y 2 is independently hydrogen or C1 to C 30 A hydrocarbon group; and 2 is independently at each occurrence a hydrocarbon group including a hindered double bond. 2 )A 2 The organoaluminum compound can be prepared by the following method: (a) comprising a compound of the formula CH2=C(Y 2 )A 2 (b) heating the organoaluminum solution to a temperature of 10 to 200° C., 20 to 150° C., 30 to 100° C., or 40 to 80° C., and maintaining the organoaluminum solution at a temperature of 10 to 200° C., 20 to 150° C., 30 to 100° C., or 40 to 80° C. for a period of 30 minutes to 200 hours, 1 to 100 hours, 5 to 75 hours, 10 to 50 hours, or 15 to 30 hours; and (c) recovering the 2AlCHCH(Y) 2 )A 2 The product of an organoaluminum compound wherein d is C1 to C10 Alkyl, Y 2 is independently hydrogen or C1 to C 30 Hydrocarbon, A 2 is independently a hydrocarbon group comprising a hindered double bond at each occurrence. The starting material in step (a) may comprise an alkylaluminum of formula AlH(d)2 and an alkylaluminum of formula CH2=C(Y) in a ratio of 1:1. 2 )A 2 The starting material in step (a) may include a hydrocarbon of the formula CH2=C(Y 2 )A 2 One or more hydrocarbons, and the alkylaluminum of formula AlH(d)2 and the alkylaluminum of formula CH2=C(Y 2 )A 2 One or more hydrocarbons. 2 and A 2 may be Y with respect to the telechelic polyolefin of formula (I) 2 and A 2 Any of the previously described embodiments. In certain embodiments, Y 2 Can be selected from the group consisting of hydrogen, methyl and ethyl. 2 Can be selected from (AA) to (AZ) and (AZ1) discussed previously. In another embodiment, A 2 The side methyl group selected from the group consisting of (AC), (AF), (AM), (AO), (AP), (AS) and (AZ1) (AF) may be attached to any carbon atom which is a ring member.

[0171] (C) Catalyst component

[0172] In certain embodiments, (C) catalyst component comprises a main catalyst. In these embodiments, the main catalyst becomes an active catalyst to polymerize unsaturated monomers without a co-catalyst. In other embodiments, (C) catalyst component comprises a main catalyst and a co-catalyst, thereby forming an active catalyst by a combination of the main catalyst and the co-catalyst. In these embodiments, (C) active catalyst component may include a main catalyst and a co-catalyst in a ratio of 1:2 or 1:1.5 or 1:1.2.

[0173] Suitable procatalysts include, but are not limited to, procatalysts disclosed in WO 2005 / 090426, WO 2005 / 090427, WO 2007 / 035485, WO 2009 / 012215, WO 2014 / 105411, WO 2017 / 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 the terms "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" and similar terms.

[0174] Both heterogeneous and homogeneous catalysts can be used. Examples of heterogeneous catalysts include the well-known Ziegler-Natta compositions, especially Group 4 metal halides supported on Group 2 metal halides or mixed halides and alkoxides, and well-known chromium or vanadium based catalysts. Preferably, the catalyst used herein is a homogeneous catalyst comprising a relatively pure organometallic compound or metal complex, especially a compound or complex of a metal selected from Groups 3-10 or the lanthanide series of the Periodic Table of the Elements.

[0175] The metal complexes used herein may be selected from Groups 3 to 15 of the Periodic Table of Elements containing one or more delocalized, π-bonded ligands or multivalent Lewis base ligands. Examples include metallocene, semi-metallocene, constrained geometry and multivalent pyridylamine or other multi-chelate base complexes. The complexes are generally of the formula: MK k X x Z z , or a dimer thereof, wherein

[0176] M is a metal selected from Groups 3-15, preferably Groups 3-10, more preferably Groups 4-10 and most preferably Group 4 of the Periodic Table of the Elements;

[0177] K is independently at each occurrence a group containing a delocalized π electron or one or more electron pairs, K is bonded to M via said delocalized π electron or one or more electron pairs, said K group contains up to 50 atoms not counting hydrogen atoms, optionally two or more K groups may be joined together to form a bridged structure, and further optionally one or more K groups may be bonded to Z, X, or both Z and X;

[0178] X is independently at each occurrence a monovalent anionic moiety having up to 40 non-hydrogen atoms, optionally one or more X groups may be bonded together to form a divalent or multivalent anionic group, and further optionally one or more X groups and one or more Z groups may be bonded together to form a moiety covalently bonded to and coordinated to M; or two X groups together form a divalent anionic ligand group having up to 40 non-hydrogen atoms or together are a conjugated diene having 4 to 30 non-hydrogen atoms bonded to M via delocalized π electrons, wherein M is in the +2 formal oxidation state, and

[0179] Z, independently at each occurrence, is a neutral, Lewis base donor ligand having up to 50 non-hydrogen atoms with at least one unshared electron pair, Z being coordinated to M through said at least one unshared electron pair;

[0180] 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

[0181] The sum of k+x equals the formal oxidation state of M.

[0182] Suitable metal complexes include metal complexes containing 1 to 3 π-bonded anionic ligand groups or neutral ligand groups, which can be cyclic or acyclic delocalized π-bonded anionic ligand groups. Exemplary such π-bonded groups are conjugated or non-conjugated, cyclic or acyclic dienes and diene groups, allyl groups, boratabenzene groups, phospholes, and aromatic hydrocarbon 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.

[0183] Each atom in the delocalized π-bonded group may be independently substituted with a group selected from the group consisting of hydrogen, halogen, hydrocarbyl, halogenated hydrocarbyl, hydrocarbyl-substituted heteroatom, wherein the heteroatom is selected from Groups 14-16 of the Periodic Table of Elements, and such hydrocarbyl-substituted heteroatom groups are further substituted with moieties containing heteroatoms from Groups 15 or 16. In addition, two or more such groups may together form a fused ring system, including partially or fully hydrogenated fused ring systems, or the two or more such groups may form a metal ring with a metal. Included within the term "hydrocarbyl" is C 1-20 Straight chain, branched chain and cyclic alkyl groups, C 6-20 Aromatic groups, C 7-20 Alkyl-substituted aromatic groups and C 7-20Aryl substituted alkyl. Suitable hydrocarbyl substituted heteroatom groups include mono-, di- and tri-substituted groups of boron, silicon, germanium, nitrogen, phosphorus or oxygen, wherein each of the hydrocarbyl groups contains 1 to 20 carbon atoms. Examples include N,N-dimethylamino, pyrrolidinyl, trimethylsilyl, triethylsilyl, tert-butyldimethylsilyl, methyldi(tert-butyl)silyl, triphenylgermyl and trimethylgermyl. Examples of moieties containing heteroatoms of Groups 15 or 16 include amino, phosphino, alkoxy or alkylthio moieties or divalent derivatives thereof, such as amides, phosphides, alkyleneoxy or alkylenethio groups bonded to transition metals or lanthanide metals and bonded to hydrocarbyl, π-bonded groups or hydrocarbyl substituted heteroatoms.

[0184] Examples of suitable anion-delocalized π-bonded groups include cyclopentadienyl, indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, octahydrofluorenyl, pentadienyl, cyclohexadienyl, dihydroanthracenyl, hexahydroanthracenyl, decahydroanthracenyl, phosphazolyl and boratabenzyl groups, and inertly substituted derivatives thereof, especially C-substituted derivatives thereof. 1-10 Hydrocarbon-substituted or tri(C 1-10 Preferred anionically 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-pyrrolidininden-1-yl, 3,4-(cyclopenta(1)phenanthren-1-yl) and tetrahydroindenyl.

[0185] Borabenzyl ligands are anionic ligands that are boron-containing analogs of benzene. The borabenzyl ligands are previously known in the art and have been described by G. Herberich et al. in Organometallics, 14, 1, 471-480 (1995). Preferred borabenzyl ligands correspond to the formula:

[0186]

[0187] Where R 1 is an inert substituent, preferably selected from the group consisting of hydrogen, hydrocarbon, silyl, halogen or germyl, wherein R 1 having up to 20 atoms not counting hydrogen, and optionally two adjacent R 1 The groups may be joined together. In complexes involving divalent derivatives of such delocalized π-bonded groups, one atom thereof is bonded to another atom of the complex by means of a covalent bond or a covalently bonded divalent group bonding, thereby forming a bridged system.

[0188] Phosphorols are anionic ligands which are phosphorus-containing analogs of cyclopentadienyl. Such phosphorols are previously known in the art and have been described in WO 98 / 50392 and elsewhere. Preferred phosphorol ligands correspond to the formula:

[0189]

[0190] Where R 1 As defined previously.

[0191] Suitable transition metal complexes for use herein correspond to the formula: MK k X x Z z , or a dimer thereof, wherein:

[0192] M is a Group 4 metal;

[0193] K is a group containing delocalized π-electrons, K is bonded to M via the delocalized π-electrons, the K group contains up to 50 atoms excluding hydrogen atoms, optionally two K groups may be joined together to form a bridged structure, and further optionally one K may be bonded to X or Z;

[0194] X at each occurrence is a monovalent anionic moiety having up to 40 non-hydrogen atoms, optionally one or more X and one or more K groups are bonded together to form a metallacycle, and further optionally one or more X and one or more Z groups are bonded together to form a moiety covalently bonded to and coordinated to M;

[0195] Z, independently at each occurrence, is a neutral, Lewis base donor ligand having up to 50 non-hydrogen atoms with at least one unshared electron pair, Z being coordinated to M through said at least one unshared electron pair;

[0196] k is an integer from 0 to 3; x is an integer from 1 to 4; z is a number from 0 to 3; and the sum of k+x is equal to the formal oxidation state of M.

[0197] Suitable complexes include complexes containing one or two K groups. The latter complexes include complexes containing a bridging group connecting two K groups. Suitable bridging groups are those corresponding to formula (ER'2) e wherein E is silicon, germanium, tin or carbon, R' at each occurrence is independently hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy and combinations thereof, said R' having up to 30 carbon atoms or silicon atoms, and e is 1 to 8. Illustratively, R' at each occurrence is independently methyl, ethyl, propyl, benzyl, tert-butyl, phenyl, methoxy, ethoxy or phenoxy.

[0198] An example of a complex containing two K groups is a compound corresponding to the formula:

[0199]

[0200] in:

[0201] M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the +2 or +4 formal oxidation state; R 3 is independently selected at each occurrence from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halide, and combinations thereof, wherein R 3 With up to 20 non-hydrogen atoms, or adjacent R 3 The groups together form a divalent derivative (i.e., a hydrocarbyl group, a silyl group, or a germyl group), thereby forming a fused ring system, and

[0202] X" is independently at each occurrence an anionic ligand group having up to 40 non-hydrogen atoms, or two X" groups together form a divalent anionic ligand group having up to 40 non-hydrogen atoms or together are a conjugated diene having 4 to 30 non-hydrogen atoms bonded to M via delocalized π-electrons, such that M is in the +2 formal oxidation state, and

[0203] R', E and e are as defined previously.

[0204] Exemplary bridging ligands containing two π-bonded groups are: dimethylbis(cyclopentadienyl)silane, dimethylbis(tetramethylcyclopentadienyl)silane, dimethylbis(2-ethylcyclopentadien-1-yl)silane, dimethylbis(2-tert-butylcyclopentadien-1-yl)silane, 2,2-bis(tetramethylcyclopentadienyl)propane, dimethylbis(inden-1-yl)silane, dimethylbis(tetrahydroinden-1-yl)silane, dimethylbis(fluoren-1-yl)silane, dimethylbis(tetrahydrofluoren-1-yl)silane, dimethylbis(tetrahydrofluoren-1-yl)silane, dimethylbis(tetrahydrofluoren-1-yl)silane, dimethylbis(cyclopentadi ... Methylbis(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.

[0205] Suitable X" groups are selected from hydride, hydrocarbyl, silyl, germyl, halohydrocarbyl, halosilyl, silylhydrocarbyl and aminohydrocarbyl, or two X" groups together form a divalent derivative of a conjugated diene or together form a neutral, π-bonded conjugated diene. An exemplary X" group is a C1-20 hydrocarbyl.

[0206] Another class of metal complexes utilized in the present disclosure corresponds to the preceding formula: MKZ z X x , or a dimer thereof, wherein 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 form a metallacycle with M.

[0207] Suitable Z substituents include groups containing up to 30 non-hydrogen atoms including at least one atom which is oxygen, sulfur, boron or a member of Group 14 of the Periodic Table of the Elements directly attached to K and a different atom selected from the group consisting of nitrogen, phosphorus, oxygen or sulfur covalently bonded to M.

[0208] More specifically, such Group 4 metal complexes used in accordance with the present invention comprise a "constrained geometry catalyst" corresponding to the formula:

[0209]

[0210] wherein: M is titanium or zirconium, preferably titanium in the +2, +3 or +4 formal oxidation state;

[0211] K 1 is optionally replaced by 1 to 5 R 2 a group-substituted delocalized, π-bonded ligand group,

[0212] R 2 is independently selected at each occurrence from the group consisting of hydrogen, hydrocarbyl, silyl, germyl, cyano, halide, and combinations thereof, wherein R 2 With up to 20 non-hydrogen atoms, or adjacent R 2 The groups are taken together to form a divalent derivative (i.e., a hydrocarbyl group, a silyl group, or a germyl group), thereby forming a fused ring system,

[0213] Each X is a halogen, a hydrocarbyl, a heterohydrocarbyl, a hydrocarbyloxy or a silyl group, the group having up to 20 non-hydrogen atoms, or two X groups together form a neutral C5-30 conjugated diene or a divalent derivative thereof;

[0214] x is 1 or 2;

[0215] Y is -O-, -S-, -NR'-, -PR'-;

[0216] and X' is SiR'2, CR'2, SiR'2SiR'2, CR'2CR'2, CR'=CR', CR'2SiR'2 or GeR'2, wherein

[0217] R' at each occurrence is independently hydrogen or a group selected from silyl, hydrocarbyl, hydrocarbyloxy, and combinations thereof, said R' having up to 30 carbon atoms or silicon atoms.

[0218] Specific examples of the aforementioned constrained geometry metal complexes include compounds corresponding to the following formula:

[0219]

[0220] in,

[0221] Ar is an aromatic radical of 6 to 30 atoms not counting hydrogen;

[0222] R 4 is independently at each occurrence hydrogen, Ar, or a group other than Ar selected from the group consisting of hydrocarbyl, trihydrocarbylsilyl, trihydrocarbylgermyl, halide, hydrocarbyloxy, trihydrocarbylsilyloxy, bis(trihydrocarbylsilyl)amino, di(hydrocarbyl)amino, hydrocarbylamido, hydrocarbylimino, di(hydrocarbyl)phosphino, hydrocarbylphosphino, hydrocarbylsulfide, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, trihydrocarbylsilyl-substituted hydrocarbyl, trihydrocarbylsilyloxy-substituted hydrocarbyl, bis(trihydrocarbylsilyl)amino-substituted hydrocarbyl, di(hydrocarbyl)amino-substituted hydrocarbyl, hydrocarbyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino-substituted hydrocarbyl, hydrocarbylenephosphino-substituted hydrocarbyl, or hydrocarbylsulfide-substituted hydrocarbyl, the R group having up to 40 atoms not counting hydrogen atoms, and optionally two adjacent R 4 The groups can be joined together to form polycyclic fused ring groups;

[0223] M is titanium;

[0224] X' is SiR 6 2.CR 6 2. SiR 6 2SiR 6 2.CR 6 2CR 6 2.CR 6 =CR 6 , CR 6 2SiR 6 2. BR 6 , BR 6 L" or GeR 6 2;

[0225] Y is -O-, -S-, or -NR 5 -、-PR 5 -;-NR 5 2 or -PR 5 2;

[0226] R 5 is independently at each occurrence hydrocarbyl, trihydrocarbylsilyl or trihydrocarbylsilylhydrocarbyl, said R 5having up to 20 atoms other than hydrogen, and optionally two R 5 Group or R 5 Together with Y or Z, it forms a ring system;

[0227] R 6 is independently hydrogen at each occurrence or is selected from the group consisting of hydrocarbyl, hydrocarbyloxy, silyl, haloalkyl, haloaryl, -NR 5 2 and combinations thereof, the R 6 having up to 20 non-hydrogen atoms, and optionally two R 6 Group or R 6 Together with Z, it forms a ring system;

[0228] Z is optionally 5 , R 6 or an X-bonded neutral diene or a monodentate or polydentate Lewis base;

[0229] X is hydrogen, a monovalent anionic ligand group having up to 60 atoms not counting hydrogen, or two X groups joined together to form a divalent ligand group;

[0230] x is 1 or 2; and

[0231] z is 0, 1 or 2.

[0232] Further examples of suitable metal complexes in this context are polycyclic complexes corresponding to the following formula:

[0233]

[0234] wherein M is titanium in the +2, +3 or +4 formal oxidation state;

[0235] R 7 is independently at each occurrence hydride, hydrocarbyl, silyl, germyl, halide, hydrocarbyloxy, hydrocarbylsiloxy, hydrocarbylsilylamino, di(hydrocarbyl)amino, hydrocarbyleneamino, di(hydrocarbyl)phosphino, hydrocarbylene-phosphino, hydrocarbylsulfide, halogen-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, silyl-substituted hydrocarbyl, hydrocarbylsiloxy-substituted hydrocarbyl, hydrocarbylsilylamino-substituted hydrocarbyl, di(hydrocarbyl)amino-substituted hydrocarbyl, hydrocarbylyleneamino-substituted hydrocarbyl, di(hydrocarbyl)phosphino, hydrocarbylene-phosphino, or hydrocarbylsulfide-substituted hydrocarbyl, said R 7 The group has up to 40 atoms not counting hydrogen, and optionally two or more of the aforementioned groups may together form a divalent derivative;

[0236] R 8 is a divalent alkylene group or a substituted alkylene group which forms a condensed system with the rest of the metal complex, wherein R8 Containing from 1 to 30 atoms, not counting hydrogen;

[0237] X a is a divalent moiety, or a moiety comprising a π-bond and a neutral two-electron pair capable of forming a coordinate covalent bond with M, wherein X a comprising boron or a member of Group 14 of the Periodic Table of Elements and further comprising nitrogen, phosphorus, sulfur or oxygen;

[0238] X is a monovalent anionic ligand group having up to 60 atoms, a ligand class that does not include cyclic, delocalized, π-bonded ligand groups, and optionally two X groups together form a divalent ligand group;

[0239] Z, at each occurrence, is independently a neutral linked compound having up to 20 atoms;

[0240] x is 0, 1, or 2; and

[0241] z is zero or 1.

[0242] Further examples of metal complexes useful as catalysts are complexes of polyvalent Lewis bases, such as compounds corresponding to the formula:

[0243]

[0244] Where T b is a bridging group, preferably containing 2 or more atoms other than hydrogen,

[0245] X b and Y b Each is independently selected from the group consisting of nitrogen, sulfur, oxygen and phosphorus; more preferably, X b and Y b Both are nitrogen,

[0246] R b and R b ' is independently hydrogen at each occurrence or C optionally containing one or more heteroatoms 1-50 A hydrocarbon group or an inertly substituted derivative thereof. Suitable R b and R b Non-limiting examples of R groups include alkyl, alkenyl, aryl, aralkyl, (poly)alkylaryl and cycloalkyl, as well as nitrogen, phosphorus, oxygen and halogen substituted derivatives thereof. Suitable R b and R b Specific examples of the ' group include methyl, ethyl, isopropyl, octyl, phenyl, 2,6-dimethylphenyl, 2,6-di(isopropyl)phenyl, 2,4,6-trimethylphenyl, pentafluorophenyl, 3,5-trifluoromethylphenyl and benzyl;

[0247] g and g' are each independently 0 or 1;

[0248] M b is a metal element selected from Groups 3 to 15 or the lanthanide series of the Periodic Table of Elements. b is a Group 3-13 metal, more preferably M b It is a Group 4-10 metal;

[0249] L b is a monovalent, divalent or trivalent anionic ligand containing 1 to 50 atoms, not counting hydrogen. Suitable L b Examples of the group include halides; hydrides; hydrocarbon groups, hydrocarbonoxy groups; di(hydrocarbyl)acylamino groups, hydrocarbylene amido groups, di(hydrocarbyl)phosphino groups; hydrocarbyl sulfide groups; hydrocarbonoxy groups, tri(hydrocarbylsilyl)alkyl groups; and carboxylates. More preferred L b The group is C1-20 alkyl, C 7-20 Aralkyl and chloride;

[0250] h and h' are each independently an integer from 1 to 6, preferably from 1 to 4, more preferably from 1 to 3, and j is 1 or 2, wherein the values ​​of h x j are selected to provide charge balance;

[0251] Z b It is with M b The preferred Z is a coordinating neutral ligand group and contains up to 50 atoms not counting hydrogen. b The group includes aliphatic and aromatic amines, phosphines and ethers, olefins, dienes and their inert substituted derivatives. Suitable inert substituents include halogen, alkoxy, aryloxy, alkoxycarbonyl, aryloxycarbonyl, di(hydrocarbyl)amine, tri(hydrocarbyl)silyl and nitrile groups. Preferred Z b The group includes triphenylphosphine, tetrahydrofuran, pyridine, and 1,4-diphenylbutadiene;

[0252] f is an integer from 1 to 3;

[0253] T b , R b and R b 'Two or three of them may be joined together to form a single or multiple ring structures;

[0254] h is an integer from 1 to 6, preferably from 1 to 4, more preferably from 1 to 3;

[0255] In one embodiment, it is preferred that R b Relative to X b In this embodiment, the most preferred Rb group is a straight chain alkyl, a straight chain alkenyl, a branched chain alkyl, wherein the closest branching point is from X bAt least 3 atoms removed and their halogen, dialkylamino, alkoxy or trialkylsilyl substituted derivatives. In this embodiment, highly preferred R b The group is a C1-8 straight chain alkyl group.

[0256] At the same time, in this embodiment, R b’ Preferably relative to Y b Has relatively high steric hindrance. Suitable R for this embodiment b Non-limiting examples of groups include alkyl or alkenyl groups, cycloalkyl, aryl, alkaryl, aliphatic or aromatic heterocyclic groups, organic or inorganic oligomeric, polymeric or cyclic groups and their halogen, dialkylamino, alkoxy or trialkylsilyl substituted derivatives containing one or more secondary or tertiary carbon centers. In this embodiment, preferred R b The group contains 3 to 40, more preferably 3 to 30 and most preferably 4 to 20 atoms, not counting hydrogen, and is branched or cyclic. Preferred T b Examples of groups are structures corresponding to the following formula:

[0257]

[0258] in

[0259] Each R d is a C1-10 hydrocarbon group, preferably methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, 2,6-dimethylphenyl, benzyl or tolyl. e is a C1-10 hydrocarbon group, preferably methyl, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, 2,6-dimethylphenyl, benzyl or tolyl. d or R e The group or mixture of Rd and Re groups may together form a divalent or polyvalent derivative of a hydrocarbyl group, such as 1,4-butene, 1,5-pentadiene, or a cyclic or polycyclic fused ring, polyvalent hydrocarbyl or heterohydrocarbyl group, such as naphthalene-1,8-diyl.

[0260] Suitable examples of the aforementioned multivalent Lewis base complexes include:

[0261]

[0262]

[0263] Where R d ' is independently selected at each occurrence from the group consisting of hydrogen and a C1-50 hydrocarbon group or an inertly substituted derivative thereof optionally containing one or more heteroatoms, or further optionally, two adjacent R d 'The groups may together form a divalent bridging group;

[0264] d' is 4;

[0265] M b ' is a Group 4 metal, preferably titanium or hafnium, or a Group 10 metal, preferably Ni or Pd;

[0266] L b ' is a monovalent ligand having up to 50 atoms not counting hydrogen, preferably a halide or a hydrocarbon group, or two L b ' groups together are divalent or neutral ligand groups, preferably C 2-50 alkylene, alkyl or diene.

[0267] The polyvalent Lewis base complexes used in the present invention particularly comprise Group 4 metal derivatives, particularly hafnium derivatives corresponding to the hydrocarbylamine-substituted heteroaryl compounds of the formula:

[0268]

[0269] in:

[0270] R 11 is selected from alkyl, cycloalkyl, heteroalkyl, cycloheteroalkyl, aryl and inertly substituted derivatives thereof containing 1 to 30 atoms not counting hydrogen or divalent derivatives thereof;

[0271] T 1 is a divalent bridging group having 1 to 41 atoms other than hydrogen, preferably 1 to 20 atoms other than hydrogen and most preferably a mono- or di-C1-20 hydrocarbon-substituted methylene or silyl group; and

[0272] R 12 It is a C containing Lewis base functional group 5-20 Heteroaryl, in particular pyridin-2-yl or substituted pyridin-2-yl or a divalent derivative thereof;

[0273] M 1 is a Group 4 metal, preferably hafnium;

[0274] X 1 is an anionic, neutral or dianionic ligand group;

[0275] x' is a number from 0 to 5 indicating the type of X 1 The number of groups; and bonds, optional bonds, and electron donating interactions are represented by lines, dashed lines, and arrows, respectively.

[0276] Suitable complexes are those in which the ligand is formed due to elimination of hydrogen from an amine group and optionally due to loss of one or more further groups, in particular R 12In addition, the electron donation, preferably the electron pair, from the Lewis base functional group provides additional stability to the metal center. Suitable metal complexes correspond to the following formula:

[0277]

[0278] Among them, M 1 , X 1 , x', R 11 and T 1 As defined previously,

[0279] R 13 , R 14 , R 15 and R 16 is hydrogen, a halide or an alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl or silyl group having up to 20 atoms not counting hydrogen, or an adjacent R 13 , R 14 , R 15 or R 16 The groups may be joined together to form fused ring derivatives, and bonds, optional bonds and electron-donating pair interactions are represented by lines, dashed lines and arrows, respectively. Suitable examples of the foregoing metal complexes correspond to the following formula:

[0280]

[0281] in

[0282] M 1 , X 1 and x' as defined previously,

[0283] R 13 , R 14 , R 15 and R 16 As defined previously, preferably R 13 , R 14 and R 15 is hydrogen or C1-4 alkyl, and R 16 It is C 6-20 Aryl, most preferably naphthyl;

[0284] R a C independently at each occurrence 1-4 alkyl, and a is 1-5, most preferably, R at the two ortho positions of nitrogen a is isopropyl or tert-butyl;

[0285] R 17 and R 18 is independently hydrogen, halogen or C 1-20 Alkyl or aryl, most preferably, R 17 and R18 One of is hydrogen and the other is C6-20 aryl, especially 2-isopropyl, phenyl or fused polycyclic aryl, most preferably anthracenyl, and bonds, optional bonds and electron-donating pair interactions are represented by lines, dashed lines and arrows, respectively.

[0286] Exemplary metal complexes useful as catalysts herein correspond to the following formula:

[0287]

[0288] Where X 1 Each occurrence is a halide, N,N-dimethylamino, or C 1-4 alkyl, and preferably at each occurrence X 1 It is methyl;

[0289] R f R is independently hydrogen, halogen, C1-20 alkyl or C6-20 aryl at each occurrence, or two adjacent R f The groups are joined together to form a ring, and f is 1-5; and

[0290] R c is independently at each occurrence hydrogen, halogen, 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.

[0291] Suitable examples of metal complexes for use as catalysts according to the invention are complexes having the following formula:

[0292]

[0293] Where R x is C1-4 alkyl or cycloalkyl, preferably methyl, isopropyl, tert-butyl or cyclohexyl; and

[0294] X 1 At each occurrence is halide, N,N-dimethylamino or C1-4 alkyl, preferably methyl.

[0295] Examples of metal complexes useful as catalysts according to the present invention include:

[0296] [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]dimethylhafnium;

[0297] [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium di(N,N-dimethylamido);

[0298] [N-(2,6-di(1-methylethyl)phenyl)amido)(o-tolyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium dichloride;

[0299] [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]dimethylhafnium;

[0300] [N-(2,6-bis(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium bis(N,N-dimethylamino);

[0301] [N-(2,6-di(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium dichloride;

[0302] [N-(2,6-di(1-methylethyl)phenyl)amido)(phenanthrene-5-yl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]dimethylhafnium;

[0303] [N-(2,6-bis(1-methylethyl)phenyl)amido)(phenanthrene-5-yl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]hafnium bis(N,N-dimethylamino); and

[0304] [N-(2,6-bis(1-methylethyl)phenyl)amido)(phenanthrene-5-yl)(α-naphthalene-2-diyl(6-pyridine-2-diyl)methane)]hafnium dichloride.

[0305] Under the reaction conditions used to prepare the metal complexes used in the present disclosure, the hydrogen at the 2-position of the α-naphthyl group substituted at the 6-position of the pyridin-2-yl group undergoes elimination, thereby uniquely forming a metal complex in which the metal is covalently bonded to both the resulting amide group and the 2-position of the α-naphthyl group, as well as being stabilized by coordination of the nitrogen atom's electron pair to the pyridinyl nitrogen atom.

[0306] Suitable additional procatalysts include imidazole-amine compounds corresponding to those disclosed in WO 2007 / 130307A2, WO 2007 / 130306A2 and U.S. Patent Application Publication No. 20090306318A1, which are incorporated herein by reference in their entirety. Such imidazole-amine compounds include imidazole-amine compounds corresponding to the following formula:

[0307] in

[0308] X is independently an anionic ligand at each occurrence, or two X groups together form a di-anionic ligand group, or a neutral diene; T is an alicyclic or aromatic group containing one or more rings; R 1 is independently hydrogen, halogen, or a monovalent polyatomic anionic ligand, or two or more R 1 The groups are joined together to form a multivalent fused ring system; R 2 is independently hydrogen, halogen, or a monovalent polyatomic anionic ligand, or two or more R 2 The groups are joined together to form a multivalent fused ring system; and R 4 is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, a trihydrocarbylsilyl group or a trihydrocarbylsilylmethyl group.

[0309] Additional examples of such imidazole-amine compounds include, but are not limited to, the following:

[0310] in:

[0311] R 1 C independently at each occurrence 3-12 Alkyl, wherein the carbon attached to the benzene ring is secondary or tertiary substituted; R 2 is independently hydrogen or C 1-2 Alkyl; R 4 is methyl or isopropyl; R 5 is hydrogen or C 1-6 Alkyl; R 6 It is hydrogen, C 1-6 Alkyl or cycloalkyl, or two adjacent R 6 The groups together form a fused aromatic ring; T' is oxygen, sulfur or C 1-20 A hydrocarbon-substituted nitrogen or phosphorus group; T" is nitrogen or phosphorus; and X is methyl or benzyl.

[0312] Additional suitable metal complexes of polyvalent Lewis bases for use herein include compounds corresponding to the formula:

[0313] in:

[0314] R 20 is an aromatic or inertly substituted aromatic group containing 5 to 20 atoms, not counting hydrogen, or a polyvalent derivative thereof;

[0315] T 3is a hydrocarbylene or hydrocarbylsilane group having 1 to 20 atoms, not counting hydrogen, or an inertly substituted derivative thereof;

[0316] M 3 is a Group 4 metal, preferably zirconium or hafnium;

[0317] G is an anionic, neutral or dianionic ligand group; preferably a halide, hydrocarbyl, silane, trihydrocarbylsilylhydrocarbyl, trihydrocarbylsilyl or dihydrocarbonylamide group having up to 20 atoms not counting hydrogen;

[0318] 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.

[0319] Illustratively, such complexes correspond to the formula:

[0320] in:

[0321] T 3 is a divalent bridging group having 2 to 20 atoms excluding hydrogen, preferably a substituted or unsubstituted C3-6 alkylene group;

[0322] And Ar 2 is independently at each occurrence arylene or alkyl or aryl substituted arylene having 6 to 20 atoms, not counting hydrogen;

[0323] M 3 is a Group 4 metal, preferably hafnium or zirconium;

[0324] G, at each occurrence, is independently an anionic, neutral, or dianionic ligand group;

[0325] g is a number from 1 to 5 indicating the number of such X groups; and electron donating interactions are represented by arrows.

[0326] Suitable examples of the metal complex having the aforementioned formula include the following compounds:

[0327]

[0328] Among them, M 3 is Hf or Zr;

[0329] Ar 4 It is C 6-20 aryl or an inertly substituted derivative thereof, in particular 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl or anthracen-5-yl, and

[0330] T 4 Include C independently at each occurrence 3-6Alkylene, C 3-6 Cycloalkylene or its inertly substituted derivative;

[0331] R 21 is independently at each occurrence hydrogen, halogen, hydrocarbyl having up to 50 atoms not counting hydrogen, trihydrocarbylsilyl, or trihydrocarbylsilylhydrocarbyl; and

[0332] G at each occurrence is independently a halo or hydrocarbyl or trihydrocarbylsilyl group having up to 20 atoms not counting hydrogen, or the two G groups together are a divalent derivative of the foregoing hydrocarbyl or trihydrocarbylsilyl groups.

[0333] Suitable compounds are compounds of the formula:

[0334]

[0335] Among them, Ar 4 is 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl or anthracene-5-yl,

[0336] R 21 is hydrogen, halogen or C1-4 alkyl, especially methyl,

[0337] T 4 is propane-1,3-diyl or butane-1,4-diyl, and

[0338] G is chloro, methyl or benzyl.

[0339] An exemplary metal complex having the above formula is:

[0340]

[0341] Suitable metal complexes for use in accordance with the present disclosure further include compounds corresponding to the following formula:

[0342] in:

[0343] M is zirconium or hafnium;

[0344] R 20 is independently at each occurrence a divalent aromatic or inertly substituted aromatic group containing from 5 to 20 atoms, not counting hydrogen;

[0345] T 3 is a divalent hydrocarbon or silane radical having 3 to 20 atoms, not counting hydrogen, or an inertly substituted derivative thereof; and

[0346] R D is independently at each occurrence a monovalent ligand group having from 1 to 20 atoms not counting hydrogen, or two RD The groups together are divalent ligand groups having from 1 to 20 atoms not counting hydrogen.

[0347] Such complexes may correspond to the following formula:

[0348] in:

[0349] Ar 2 is independently at each occurrence arylene or alkyl, aryl, alkoxy, or amino substituted arylene having from 6 to 20 atoms not counting hydrogen or any atoms of any substituent;

[0350] T 3 is a divalent hydrocarbon bridging group having 3 to 20 atoms not counting hydrogen, preferably a divalent substituted or unsubstituted C 3-6 an aliphatic, alicyclic or bis(alkylene)-substituted alicyclic group; and

[0351] R D is independently at each occurrence a monovalent ligand group having from 1 to 20 atoms not counting hydrogen, or two R D The groups together are divalent ligand groups having from 1 to 40 atoms not counting hydrogen.

[0352] Additional examples of metal complexes suitable for use herein include compounds having the formula:

[0353] in

[0354] Ar 4 C independently at each occurrence 6-20 Aryl or its inert substituted derivatives, in particular 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl, naphthyl, anthracen-5-yl, 1,2,3,4,6,7,8,9-octahydroanthracen-5-yl;

[0355] T 4 is independently at each occurrence propylene-1,3-diyl, bis(alkylene)cyclohexane-1,2-diyl or an inert substituted derivative thereof substituted with 1 to 5 alkyl, aryl or aralkyl substituents each having up to 20 carbons;

[0356] R 21 is independently at each occurrence hydrogen, halogen, hydrocarbyl having up to 50 atoms not counting hydrogen, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy, or amino; and

[0357] R Dis independently at each occurrence a halo or hydrocarbyl or trihydrocarbylsilyl group having up to 20 atoms not counting hydrogen, or 2 R D The groups together are divalent hydrocarbylene, hydrocarbyl or trihydrocarbylsilyl groups having up to 40 atoms not counting hydrogen.

[0358] Exemplary metal complexes are compounds having the formula:

[0359]

[0360] Among them, Ar 4 is independently at each occurrence 3,5-di(isopropyl)phenyl, 3,5-di(isobutyl)phenyl, dibenzo-1H-pyrrol-1-yl or anthracen-5-yl,

[0361] R 21 is independently at each occurrence hydrogen, halogen, hydrocarbyl having up to 50 atoms not counting hydrogen, trihydrocarbylsilyl, trihydrocarbylsilylhydrocarbyl, alkoxy, or amino;

[0362] T 4 is propane-1,3-diyl or bis(methylene)cyclohexane-1,2-diyl; and

[0363] R D is independently at each occurrence a halo or hydrocarbyl or trihydrocarbylsilyl group having up to 20 atoms not counting hydrogen, or 2 R D The groups together are hydrocarbylene, hydrocarbyl or hydrocarbylsilanediyl having up to 40 atoms not counting hydrogen.

[0364] Suitable metal complexes according to the present disclosure correspond to the following formula:

[0365]

[0366] Among them, R D is independently at each occurrence chloro, methyl or benzyl.

[0367] Specific examples of suitable metal complexes are the following compounds:

[0368] A) Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV) dimethyl, Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV) dichloride, Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-1 ,3-propanediylhafnium(IV)dibenzyl,bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV)dimethyl,bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV)dichloride,bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-1,3-propanediylhafnium(IV)dibenzyl;

[0369] B) Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV) dimethyl, bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV) dichloride, bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)- 1,4-Butanediylhafnium(IV) dibenzyl, bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV) dimethyl, bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV) dichloride, bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-1,4-butanediylhafnium(IV) dibenzyl;

[0370] C) Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV) dimethyl, Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV) dichloride, Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxy)- 2,4-pentanediylhafnium(IV) dibenzyl, bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV) dimethyl, bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV) dichloride, bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxy)-2,4-pentanediylhafnium(IV) dibenzyl;

[0371] D) Bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl hafnium(IV) dimethyl, bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl hafnium(IV) dichloride, bis((2-oxo-3-(1,2,3,4,6,7,8,9-octahydroanthracen-5-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediyl hafnium(IV) dichloride 2-cyclohexanediylhafnium(IV) dibenzyl, bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediylhafnium(IV) dimethyl, bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediylhafnium(IV) dichloride and bis((2-oxo-3-(dibenzo-1H-pyrrol-1-yl)-5-(methyl)phenyl)-2-phenoxymethyl)-methylene trans-1,2-cyclohexanediylhafnium(IV) dibenzyl.

[0372] The foregoing metal complexes can be conveniently prepared by standard metallation and ligand exchange procedures involving a transition metal source and a neutral multifunctional ligand source. The techniques used are the same or similar to those disclosed in USP 6,827,976 and US2004 / 0010103 and elsewhere.

[0373] The aforementioned multivalent Lewis base complexes are conveniently prepared by standard metalation and ligand exchange procedures involving a Group 4 metal source and a neutral multifunctional ligand source. Alternatively, the complexes may also be prepared starting from the corresponding Group 4 metal tetraamide and a hydrocarbylating agent such as trimethylaluminum by amide elimination and hydrocarbylation methods. Other techniques may also be used. These complexes are known from the disclosures of U.S. Patents 6,320,005, 6,103,657, WO 02 / 38628, WO 03 / 40195 and US 04 / 0220050.

[0374] It is also known that catalysts with high comonomer incorporation properties occasionally reincorporate long chain olefins prepared in situ during polymerization through β-hydride elimination and chain termination of growing polymers or other processes. The concentration of such long chain olefins is particularly enhanced by using continuous solution polymerization conditions at high conversions, especially 95% or higher ethylene conversions, more preferably 97% or higher ethylene conversions. Under such conditions, a small but detectable amount of olefin-terminated polymer can be reincorporated into the growing polymer chain, resulting in the formation of long chain branches, i.e., branches with carbon lengths greater than those produced by other intentionally added comonomers. In addition, these chains reflect the presence of other comonomers present in the reaction mixture. That is, depending on the comonomer composition of the reaction mixture, the chain may also contain short or long chain branching. Long chain branching of olefin polymers is further described in USPs 5,272,236, 5,278,272 and 5,665,800.

[0375] Alternatively, branching, including hyperbranching, can be induced in specific segments of the multi-block copolymers of the present invention by using specific catalysts known to cause "chain-walking" in the resulting polymer. For example, certain homogeneously bridged bis-indenyl- or partially hydrogenated bis-indenyl-zirconium catalysts disclosed by Kaminski et al., Journal of Molecular Catalysis A Editor: Chemical Catalysis (J.Mol.Catal.A:Chemical) , 102 (1995) 59-65; Zambelli et al., Macromolecules ( Macromolecules )”, 1988, 21, 617-622; or Dias et al., Journal of Molecular Catalysis Series A: Chemical Catalysis 》, 185(2002) 57-64 can be used to prepare branched copolymers from a single monomer containing ethylene.

[0376] Additional complexes suitable for use include Group 4-10 derivatives corresponding to the following formula:

[0377]

[0378] in

[0379] M 2 is a metal of Groups 4 to 10 of the Periodic Table of Elements, preferably a Group 4 metal, Ni(II) or Pd(II), most preferably zirconium;

[0380] T 2 is a group containing nitrogen, oxygen or phosphorus;

[0381] X 2 is a halogen, a hydrocarbon group or a hydrocarbonoxy group;

[0382] t is one or two;

[0383] x" is a number chosen to provide charge balance;

[0384] And T2 and N are connected through a bridging ligand.

[0385] Such catalysts have previously been described in Journal of the American Chemical Society ( J.Am.Chem.Soc. )》,118,267-268(1996); Journal of the American Chemical Society ,117,6414-6415(1995) and Organometallic 》,16,1514-1516,(1997) and disclosed in other publications.

[0386] Suitable examples of the aforementioned metal complexes for use as catalysts are aromatic diimine or aromatic dioxyamine complexes of Group 4 metals, especially zirconium, corresponding to the formula:

[0387]

[0388] in:

[0389] M 2 , X 2 and T 2 As previously defined;

[0390] R d is independently hydrogen, halogen or R e ;and

[0391] R e is independently C1-20 hydrocarbyl or heteroatom-, especially F, N, S or P-substituted derivatives thereof, more preferably C1-20 hydrocarbyl or F or N-substituted derivatives thereof, most preferably alkyl, dialkylaminoalkyl, pyrrolyl, piperidinyl, perfluorophenyl, cycloalkyl, (poly)alkylaryl or aralkyl.

[0392] A suitable example of the aforementioned metal complex used as a catalyst is an aromatic dioxyamine complex of zirconium corresponding to the formula:

[0393]

[0394] in:

[0395] X 2 As defined previously, preferably C1-10 hydrocarbon group, most preferably methyl or benzyl; and

[0396] R e ' is methyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, 2-methylcyclohexyl, 2,4-dimethylcyclohexyl, 2-pyrrolyl, N-methyl-2-pyrrolyl, 2-piperidinyl, N-methyl-2-piperidinyl, benzyl, o-tolyl, 2,6-dimethylphenyl, perfluorophenyl, 2,6-di(isopropyl)phenyl or 2,4,6-trimethylphenyl.

[0397] The aforementioned complexes used also include certain phosphinimine complexes disclosed in EP-A-890581. These complexes correspond to the formula: [(R f )3-P=N] f M(K 2 )(R f ) 3-f , where: R f is a monovalent ligand, or two R f The groups together are divalent ligands, preferably R f is hydrogen or C1-4 alkyl;

[0398] M is a Group 4 metal,

[0399] K 2 It is a group containing delocalized π-electrons, K 2 The K 2 The radical contains up to 50 atoms not counting hydrogen atoms, and f is 1 or 2.

[0400] Other suitable procatalysts include those disclosed in WO 2017 / 173080 A1, which is incorporated by reference in its entirety. Such procatalysts include a metal-ligand complex of formula (i):

[0401]

[0402] wherein M is titanium, zirconium or hafnium;

[0403] wherein each Z1 is independently a neutral, monoanionic or dianionic monodentate or polydentate ligand, wherein nn is an integer, and wherein Z1 and nn are selected in such a way that the metal-ligand complex of formula (i) is overall neutral;

[0404] Each Q 1 and Q 10Independently selected from the group consisting of: (C6-C 40 ) aryl, substituted (C6-C 40 ) aryl, (C3-C 40 ) heteroaryl and substituted (C3-C 40 ) heteroaryl;

[0405] Each Q 2 , Q 3 , Q 4 , Q 7 , Q 8 and Q 9 are independently selected from the group consisting of: hydrogen, (C1-C 40 ) alkyl, substituted (C1-C 40 ) hydrocarbon group, (C1-C 40 ) heteroalkyl, substituted (C1-C 40 ) heteroalkyl, halogen and nitro (NO2);

[0406] Each Q 5 and Q 6 Independently selected from (C1-C 40 ) alkyl, substituted (C1-C 40 )alkyl and [(Si)1-(C+Si) 40 ] a group consisting of an organosilyl group substituted with silyl;

[0407] wherein each N is independently nitrogen;

[0408] Optionally, Q 1-5 Two or more of the groups may be combined together to form a ring structure, wherein such ring structure has from 5 to 16 atoms in the ring excluding any hydrogen atoms; and

[0409] Optionally, Q 6-10 Two or more of the groups may be combined together to form a ring structure, wherein such ring structure has from 5 to 16 atoms in the ring excluding any hydrogen atoms.

[0410] The metal-ligand complex of formula (i) above and all specific examples thereof herein are intended to include every possible stereoisomer thereof, including coordination isomers.

[0411] The metal-ligand complex of formula (i) above provides homoleptic as well as heteroleptic procatalyst components.

[0412] In an alternative embodiment, Q 1 , Q 2 , Q 3 , Q 4 , Q 5 , Q 6 , Q7 , Q 8 , Q 9 and Q 10 Any one or more of (C1-C 40 ) alkyl and (C1-C 40 ) Each of the heteroalkyl groups is independently unsubstituted or substituted with one or more R S is substituted with a substituent, and each R S are independently halogen atoms, polyfluorinated, perfluorinated, unsubstituted (C1-C 18 ) alkyl, (C6-C 18 )aryl, F3C, FCH2O, F2HCO, F3CO, (R C1 )3Si、(R C1 )3Ge、(R C1 )O、(R C1 )S、(R C1 )S(O),(R C1 )S(O)2、(R C1 )2P、(R C1 )2N、(R C1 )2C=N、NC、NO2、(R C1 )C(O)O、(R C1 )OC(O),(R C1 )C(O)N(R C1 ) or (R C1 )2NC(O), or R S The two of them together form an unsubstituted (C1-C 18 ) alkylene, wherein each R S are independently unsubstituted (C1-C 18 )alkyl, and each R C1 are independently hydrogen, unsubstituted (C1-C 18 ) alkyl or unsubstituted (C1-C 18 ) heteroalkyl, or is absent (eg, absent when N includes -N=). In certain embodiments, Q 5 and Q 6 Each independently (C1-C 40 ) primary alkyl or secondary alkyl. The terms primary alkyl and secondary alkyl are given their usual and customary meanings herein; that is, primary means that the carbon atom directly attached to the ligand nitrogen bears at least two hydrogen atoms, and secondary means that the carbon atom directly attached to the ligand nitrogen bears only one hydrogen atom.

[0413] Optionally, two or more Q 1-5 Group or two or more Q 6-10The groups each independently can be combined together to form ring structures, wherein such ring structures have from 5 to 16 atoms in the ring excluding any hydrogen atoms.

[0414] In a preferred embodiment, Q 5 and Q 6 Each independently is (C1-C 40 ) a primary or secondary alkyl group, and most preferably, Q 5 and Q 6 Each is independently propyl, isopropyl, neopentyl, hexyl, isobutyl and benzyl.

[0415] In a specific embodiment, the olefin polymerization procatalyst of formula (i) has a Q 1 and Q 10 is a substituted phenyl group; as shown in formula (ii),

[0416]

[0417] Among them J 1 -J 10 Each independently selected from R S a substituent and hydrogen; and wherein each R S are independently halogen atoms, polyfluorinated, perfluorinated, unsubstituted (C1-C 18 ) alkyl, (C6-C 18 )aryl, F3C, FCH2O, F2HCO, F3CO, (R C1 )3Si、(R C1 )3Ge、(R C1 )O、(R C1 )S、(R C1 )S(O),(R C1 )S(O)2、(R C1 )2P、(R C1 )2N、(R C1 )2C=N、NC、NO2、(R C1 )C(O)O、(R C1 )OC(O),(R C1 )C(O)N(R C1 ) or (R C1 )2NC(O), or R S The two of them together form an unsubstituted (C1-C 18 ) alkylene, wherein each R S are independently unsubstituted (C1-C 18 )alkyl, and each R C1 are independently hydrogen, unsubstituted (C1-C 18 ) alkyl or unsubstituted (C1-C18 ) heteroalkyl, or is absent (for example, absent when N includes -N=). More preferably, J of formula (ii) 1 , J 5 , J 6 and J 10 are each independently selected from the group consisting of a halogen atom, a (C1-C8) alkyl group and a (C1-C8) alkoxy group. Most preferably, J of formula (ii) 1 , J 5 , J 6 and J 10 Each is independently methyl; ethyl or isopropyl.

[0418] The term "[(Si)1-(C+Si) 40 ] substituted organosilyl group" refers to a substituted silyl group having 1 to 40 silicon atoms and 0 to 39 carbon atoms, such that the total number of carbon plus silicon atoms is between 1 and 40. [(Si)1-(C+Si) 40 Examples of the substituted organosilyl group include a trimethylsilyl group, a triisopropylsilyl group, a dimethylphenylsilyl group, a diphenylmethylsilyl group, a triphenylsilyl group, and a triethylsilyl group.

[0419] Preferably, in the metal-ligand complex of formula (i), except the OS bond in the S(O) or S(O)2 diradical functional group, there is no OO, SS or OS bond. More preferably, in the metal-ligand complex of formula (i), except the OS bond in the S(O) or S(O)2 diradical functional group, there is no OO, PP, SS or OS bond.

[0420] M is titanium, zirconium or hafnium. In one embodiment, M is titanium. In another embodiment, M is zirconium. In another embodiment, M is hafnium. In some embodiments, M is in a formal oxidation state of +2, +3 or +4. Each Z1 is independently a neutral, monoanionic or dianionic monodentate or multidentate ligand. Z1 and nn are selected in such a way that the metal-ligand complex of formula (i) is neutral overall. In some embodiments, each Z1 is independently a monodentate ligand. In one embodiment, when there are two or more Z1 monodentate ligands, each Z1 is the same. In some embodiments, the monodentate ligand is a monoanionic ligand. The net formal oxidation state of the monoanionic ligand is -1. Each monoanionic ligand can independently be a hydride, (C1-C 40 ) Hydrocarbyl carbon anion, (C1-C 40 ) heteroalkyl carbanions, halides, nitrates, carbonates, phosphates, borates, borohydrides, sulfates, HC(O)O-, alkoxides or aromatic oxides (RO - )、(C1-C40 ) hydrocarbon group C(O)O-, HC(O)N(H)-, (C1-C 40 )C(O)N(H)-, (C1-C 40 )alkylC(O)N((C1-C 20 )alkyl)-, R K R L B-, R K R L N-, R K O-、R K S-, R K R L P- or R M R K R L Si-, where each R K , R L and R M are independently hydrogen, (C1-C 40 )alkyl or (C1-C 40 ) heteroalkyl, or R K and R L Together they form (C2-C 40 )alkylene or (C1-C 40 )heteroalkylene, and R M As defined above.

[0421] In some embodiments, at least one monodentate ligand of Z1 is independently a neutral ligand. In some embodiments, the neutral ligand is a neutral Lewis base group, which is R X1 NR K R L , R K OR L , R K SR L or R X1 PR K R L , where each R X1 are independently hydrogen, (C1-C 40 )alkyl, [(C1-C 10 )alkyl]3Si, [(C1-C 10 )alkyl]3Si(C1-C 10 )alkyl or (C1-C 40 ) heteroalkyl, and each R K and R L are independently as defined above.

[0422] In some embodiments, each Z1 is a monodentate ligand which is independently a halogen atom, an unsubstituted (C1-C 20 ) alkyl, unsubstituted (C1-C20 )C(O)O- or R K R L N-, where R K and R L Each of which is independently unsubstituted (C1-C 20 In some embodiments, each monodentate ligand Z1 is a chlorine atom, (C1-C 10 )alkyl (e.g., (C1-C6)alkyl or benzyl), unsubstituted (C1-C 10 )C(O)O- or R K R L N-, where R K and R L Each of which is independently unsubstituted (C1-C 10 ) hydrocarbon group.

[0423] In some embodiments, there are at least two Z1, and the two Z1 together form a bidentate ligand. In some embodiments, the bidentate ligand is a neutral bidentate ligand. In one embodiment, the neutral bidentate ligand is of formula (R D1 )2C=C(R D1 )-C(R D1 )=C(R D1 )2, wherein each R D1 R is independently H, unsubstituted (C1-C6) alkyl, phenyl or naphthyl. In some embodiments, the bidentate ligand is a monoanionic-mono(Lewis base) ligand. The monoanionic-mono(Lewis base) ligand can be a 1,3-diketonate of formula (D): R E1 -C(O-)=CH-C(=O)-R E1 (D), where each R E1 is independently H, unsubstituted (C1-C6) alkyl, phenyl or naphthyl. In some embodiments, the bidentate ligand is a dianionic ligand. The net formal oxidation state of the dianionic ligand is -2. In one embodiment, each dianionic ligand is independently carbonate, oxalate (i.e., -O2CC(O)O-), (C2-C 40 )alkylene dicarbon anion, (C1-C 40 )heteroalkylene dicarbonium anion, phosphate or sulfate.

[0424] As mentioned previously, the number and charge (neutral, monoanionic, dianionic) of Z1 are selected according to the formal oxidation state of M such that the metal-ligand complex of formula (i) is overall neutral.

[0425] In some embodiments, each Z1 is the same, wherein each Z1 is methyl; isobutyl; neopentyl; neopentane; trimethylsilylmethyl; phenyl; benzyl; or chloro. In some embodiments, nn is 2, and each Z1 is the same.

[0426] In some embodiments, at least two Z1 are different. In some embodiments, each Z1 is a different group from the following: methyl; isobutyl; neopentyl; neopentane; trimethylsilylmethyl; phenyl; benzyl; and chloro.

[0427] In one embodiment, the metal-ligand complex of formula (i) is a mononuclear metal complex.

[0428] Other suitable procatalysts include those disclosed in Acc. Chem. Res., 2015, 48(8), pp. 2209-2220, including but not limited to those of the following structures:

[0429]

[0430] Suitable main catalysts further include "single component catalysts" that can catalyze olefin polymerization without the use of a co-catalyst. Such simple component catalysts include the main catalysts disclosed in the following documents: Watson, PL "Journal of the American Chemical Society" 1982, 104, 337-339; Yasuda, H., Ihara, E. "Adv. Polym. Sci." 1997, 133, 53-101; Ihara, E., Nodono, M., Katsura, K., Adachi, Y., Yasuda, H., Yamagashira, M., Hashimoto, H., Kanehisa, N. and Kai, Y. "Organometallic" 1997, 133, 53-101. 998, 17, 3945-3956; Long, DP, Bianconi, PA, Journal of the American Chemical Society, 1996, 118, 12453-12454; Gilchrist, JH, Bercaw, JE, Journal of the American Chemical Society, 1996, 118, 12021-12028; Mitchell, JP, Hajela, S., Brookhart, SK, Hardcastle, KI, Henling, LM, Bercaw, JE, Journal of the American Chemical Society, 1996, 118, 1045-1053; Evans ,WJ, DeCoster,DM, Greaves,J. Organometallics, 1996,15,3210-3221; Evans,WJ, DeCoster,DM, Greaves,J. Organometallics, 1995,28,7929-7936; Shapiro,PJ, Cotter,WD, Schaefer,WP, Labinger,JA, Bercaw,JE, Journal of the American Chemical Society, 1994,116,4623-4640; Schaverien,CJ Organometallics, 1994,13,69-82; C oughlin, EB, Journal of the American Chemical Society, 1992, 114, 7606-7607; Piers, WE, Bercaw, JE, Journal of the American Chemical Society, 1990, 112, 9406-9407; Burger, BJ, Thompson, ME, Cotter, WD, Bercaw, JE, Journal of the American Chemical Society, 1990, 112, 1566-1577; Shapiro, PJ, Bunel, E., Schaefer, WP, Organometallics, 1990, 9, 867-869; Jeske, G., Lauke, H.、Mauermann, H.、Swepston, PN、Schumann, H.、Marks, TJ "Journal of the American Chemical Society" 1985, 107, 8091-8103; Jeske, G.、Schock, LE、Swepston, PN、Schumann, H.、Marks, TJ "Journal of the American Chemical Society" 1985, 107, 8103-8110; and "Organometallics", 2001, 20(9), pp. 1752-1761. Exemplary non-limiting formulas of such simple component catalysts include:.

[0431] in:

[0432] M is Sm or Y; and R is a monovalent ligand having up to 50 atoms not counting hydrogen, preferably a halide or a hydrocarbon group, or two L b ' groups together are divalent or neutral ligand groups, preferably C 2-50 alkylene, alkyl or diene.

[0433] Suitable procatalysts include, but are not limited to, the procatalysts designated below as (Cat 1) to (Cat 17).

[0434] (Cat 1) can be prepared according to the teachings of WO 03 / 40195 and U.S. Pat. No. 6,953,764 B2 and has the following structure:

[0435]

[0436] (Cat 2) can be prepared according to the teachings of WO 03 / 40195 and WO 04 / 24740 and has the following structure:

[0437]

[0438] (Cat 3) can be prepared according to methods known in the art and has the following structure:

[0439]

[0440] (Cat 4) can be prepared according to the teachings of U.S. Patent Application Publication No. 2004 / 0010103 and has the following structure:

[0441]

[0442] (Cat 5) can be prepared according to the teaching of U.S. Pat. No. 7,858,706 B2 and has the following structure:

[0443]

[0444] (Cat 6) can be prepared according to the teaching of U.S. Pat. No. 7,858,706 B2 and has the following structure:

[0445]

[0446] (Cat 7) can be prepared according to the teachings of U.S. Pat. No. 6,268,444 and has the following structure:

[0447]

[0448] (Cat 8) can be prepared according to the teachings of U.S. Patent Publication No. 2003 / 004286 and has the following structure:

[0449]

[0450] (Cat 9) can be prepared according to the teachings of U.S. Patent Publication No. 2003 / 004286 and has the following structure:

[0451]

[0452] (Cat 10) is commercially available from Sigma-Aldrich and has the following structure:

[0453]

[0454] (Cat 11) can be prepared according to the teaching of WO 2017 / 173080 A1 and has the following structure:

[0455]

[0456] (Cat 12) can be prepared according to the teaching of WO 2017 / 173080 A1 and has the following structure:

[0457]

[0458] (Cat 13) can be prepared according to the teaching of Macromolecules (Washington, DC, United States), 43(19), 7903-7904 (2010) and has the following structure:

[0459]

[0460] (Cat 14) can be prepared according to the teaching of WO 2011 / 102989 A1 and has the following structure:

[0461]

[0462] (Cat 15) can be prepared according to the teaching of U.S. Pat. No. 8,101,696 B2 and has the following structure:

[0463]

[0464] (Cat 16) can be prepared according to the teaching of WO 2018 / 170138 A1 and has the following structure:

[0465]

[0466] (Cat 17) can be prepared according to the teaching of WO 2018 / 170138 A1 and has the following structure:

[0467]

[0468] In certain embodiments, the (C) catalyst component includes a primary catalyst and a co-catalyst. In these embodiments, the primary catalyst can be activated to form an active catalyst by combining with a co-catalyst (activator), preferably a cation-forming co-catalyst, a strong Lewis acid, or a combination thereof.

[0469] Suitable cation-forming cocatalysts include those previously known in the art for use in metal olefin polymerization complexes. Examples include neutral Lewis acids such as C 1-30Hydrocarbyl-substituted Group 13 compounds, especially tri(hydrocarbyl)boron compounds and halogenated (including perhalogenated) derivatives thereof having from 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, more especially perfluorinated tri(aryl)boron compounds and most especially tri(pentafluorophenyl)borane; non-polymeric, compatible, non-coordinating ion-forming compounds (including the use of such compounds under oxidizing conditions), especially the use of ammonium, phosphonium, oxonium, carbonium, silylonium 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 co-catalysts and techniques. The foregoing activating cocatalysts and activation techniques have been previously taught in the following references regarding different 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.

[0470] Combinations of neutral Lewis acids, especially trialkylaluminum compounds having 1 to 4 carbons in each alkyl group and halogenated tri(hydrocarbyl)boron compounds having 1 to 20 carbons in each hydrocarbyl group, especially tri(pentafluorophenyl)borane, additional combinations of such neutral Lewis acid mixtures with polymeric or oligomeric aluminoxanes, and combinations of single neutral Lewis acids (especially tri(pentafluorophenyl)borane) with polymeric or oligomeric aluminoxanes can be used as activating cocatalysts. Exemplary molar ratios of metal complex:tri(pentafluorophenyl)borane:aluminoxane are 1:1:1 to 1:5:20, such as 1:1:1.5 to 1:5:10.

[0471] Suitable ion-forming compounds that may be used as co-catalysts in one embodiment of the present disclosure include Bronsted acids capable of donating protons. cation, and a compatible non-coordinating anion A - As used herein, the term "non-coordinating" refers to anions or species that do not coordinate to the 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 a cationic metal complex, do not transfer anionic substituents or fragments thereof to the cation to form a neutral complex. "Compatible anions" are anions that do not degrade to neutrality when the initially formed complex decomposes, and do not interfere with the desired subsequent polymerization or other uses of the complex.

[0472] Suitable anions are anions containing single coordination complexes, and the single coordination complexes include metal or metalloid cores with electric charge, and the anions can balance the charge of the active catalyst species (metal cation) that may be formed when the two components are combined. Moreover, the anions should be sufficiently unstable to be replaced by olefinic, diene and acetylenic unsaturated compounds or other neutral Lewis bases, such as ether or nitrile. Suitable metals include but are not limited to aluminum, gold and platinum. Suitable metalloids include but are not limited to boron, phosphorus and silicon. Of course, compounds containing anions (which include coordination complexes containing monometallic or metalloid atoms) are well known, and many, particularly such compounds containing single boron atoms in the anion part are commercially available.

[0473] In one aspect, suitable co-catalysts can be represented by the following general formula:

[0474] (L*-H) g + (A) g- ,in:

[0475] L* is a neutral Lewis base;

[0476] (L*-H) + is the conjugated Bronsted acid of L*;

[0477] A g- is a non-coordinating, compatible anion having a g-charge, and g is an integer from 1 to 3.

[0478] More specifically, A g- Corresponding to the formula: [M'Q4] - ;in:

[0479] M' is boron or aluminum in the +3 formal oxidation state; and

[0480] Q is independently selected at each occurrence from hydride, dialkylamido, halide, hydrocarbyl, hydrocarbyloxy, halo-substituted hydrocarbyl, halo-substituted hydrocarbyloxy, and halo-substituted silyl hydrocarbyl (including perhalogenated hydrocarbyl-perhalogenated hydrocarbyloxy and perhalogenated silyl hydrocarbyl), each Q having up to 20 carbons, provided that Q is a halide at no more than one occurrence. Examples of suitable hydrocarbyloxy Q groups are disclosed in U.S. Pat. No. 5,296,433.

[0481] In an exemplary embodiment, g is one, i.e., the counterion has a single negative charge and is A - An activating cocatalyst comprising boron that is particularly useful in the preparation of the catalysts of the present disclosure can be represented by the following general formula: (L*-H) + (BQ4) - ;in:

[0482] L* is as defined previously;

[0483] B is boron in the formal oxidation state 3; and

[0484] Q is a hydrocarbyl, hydrocarbyloxy, fluorinated hydrocarbyl, fluorinated hydrocarbyloxy, or fluorinated silyl hydrocarbyl group having up to 20 non-hydrogen atoms, provided that in no more than one instance Q is a hydrocarbyl group.

[0485] Particularly useful Lewis base salts are ammonium salts, more preferably containing one or more C 12-40 In this regard, for example, Q at each occurrence may be a fluorinated aryl group, especially a pentafluorophenyl group.

[0486] Illustrative but non-limiting examples of boron compounds that can be used as activating co-catalysts in the preparation of the improved catalysts of the present disclosure include tri-substituted ammonium salts such as:

[0487] Trimethylammonium tetrakis(pentafluorophenyl)borate,

[0488] Triethylammonium tetrakis(pentafluorophenyl)borate,

[0489] Tripropylammonium tetrakis(pentafluorophenyl)borate,

[0490] Tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,

[0491] Tri(sec-butyl)ammonium tetrakis(pentafluorophenyl)borate,

[0492] Tetrakis(pentafluorophenyl)borate N,N-dimethylaniline,

[0493] n-Butyltri(pentafluorophenyl)boric acid N,N-dimethylaniline,

[0494] Benzyltris(pentafluorophenyl)boronic acid N,N-dimethylaniline,

[0495] N,N-dimethylanilinium tetrakis(4-(tert-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl)borate,

[0496] N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2,3,5,6-tetrafluorophenyl)borate,

[0497] Pentafluorophenoxy tris(pentafluorophenyl)boronic acid N,N-dimethylaniline,

[0498] Tetrakis(pentafluorophenyl)borate N,N-diethylaniline,

[0499] Tetrakis(pentafluorophenyl)boric acid N,N-dimethyl-2,4,6-trimethylaniline,

[0500] Dimethyloctadecylammonium tetrakis(pentafluorophenyl)borate,

[0501] Dioctadecylmethylammonium tetrakis(pentafluorophenyl)borate;

[0502] Various dialkylammonium salts, such as:

[0503] Di-(isopropyl)ammonium tetrakis(pentafluorophenyl)borate,

[0504] Methyloctadecylammonium tetrakis(pentafluorophenyl)borate,

[0505] octadecyl methyl ammonium tetrakis(pentafluorophenyl)borate, and

[0506] Dioctadecylammonium tetrakis(pentafluorophenyl)borate;

[0507] Various trisubstituted phosphonium salts, such as:

[0508] triphenylphosphonium tetrakis(pentafluorophenyl)borate,

[0509] tetrakis(pentafluorophenyl)borate methyl dioctadecylphosphonium salt, and

[0510] Tris(2,6-dimethylphenyl)tetrakis(pentafluorophenyl)borate phosphonium salt;

[0511] Disubstituted oxonium salts, such as:

[0512] Tetrakis(pentafluorophenyl)borate diphenyloxonium salt,

[0513] di(o-tolyl)oxonium tetrakis(pentafluorophenyl)borate, and

[0514] Dioctadecyloxonium tetrakis(pentafluorophenyl)borate; and

[0515] Disubstituted sulfonium salts, such as:

[0516] di(o-tolyl)sulfoniumtetrakis(pentafluorophenyl)borate, and

[0517] Methyldodecylsulfonium tetrakis(pentafluorophenyl)borate.

[0518] Further with respect to this aspect of the disclosure, useful (L*-H) + Examples of cations include, but are not limited to, methyldioctadecylammonium cations, dimethyloctadecylammonium cations, and cations derived from 14-18 The ammonium cation is a mixture of alkyl and trialkyl amines.

[0519] Another suitable ion-forming activating co-catalyst comprises a salt of a cationic oxidant and a non-coordinating, compatible anion represented by the formula: (Ox h+ ) g (A g- )h ,in:

[0520] Ox h+ It is a cationic oxidant with an h+ charge;

[0521] h is an integer from 1 to 3; and

[0522] A g- and g are as defined previously.

[0523] Examples of cationic oxidants include ferrocenium, hydrocarbyl-substituted ferrocenium, Ag + or Pb +2 . A g- Particularly useful examples are those anions previously defined with respect to containing Bronsted acids containing activating cocatalysts, especially tetrakis(pentafluorophenyl)borate.

[0524] Another suitable ion-forming activating cocatalyst may be a compound which is a salt of a carbonium ion and a non-coordinating, compatible anion represented by the formula: [C] + A -

[0525] in:

[0526] [C] + It is C 1-20 a carbonium ion; and

[0527] is a non-coordinating, compatible anion with a charge of -1. For example, a carbonium ion that works well is the trityl cation, ie, tritylium.

[0528] Additional suitable ion-forming activating cocatalysts include a compound which is a salt of a silyl ion and a non-coordinating, compatible anion represented by the formula: 1 3Si) + A -

[0529] in:

[0530] Q 1 It is C 1-10 Hydrocarbon, and A - As defined previously.

[0531] Suitable silyl onium salt activating cocatalysts include trimethylsilyl onium tetrapentafluorophenyl borate, triethylsilyl onium tetrapentafluorophenyl borate and ether-substituted adducts thereof. Silyl onium salts have previously been generally disclosed in J. Chem. Soc. Chem. Comm. 1993, 383-384 and in Lambert, JB et al., Organometallics 1994, 13, 2430-2443. The use of the above-mentioned silyl onium salts as activating cocatalysts for addition polymerization catalysts is also described in U.S. Pat. No. 5,625,087.

[0532] Certain complexes of alcohols, thiols, 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. Pat. No. 5,296,433.

[0533] Suitable activating cocatalysts for use herein also include polymeric or oligomeric aluminoxanes (also referred to as aluminoxanes), especially methylaluminoxane (MAO), triisobutylaluminum-modified methylaluminoxane (MMAO) or isobutylaluminoxane; Lewis acid-modified aluminoxanes, especially perhalogenated tri(hydrocarbyl)aluminum- or perhalogenated tri(hydrocarbyl)boron-modified aluminoxanes having 1 to 10 carbons in each hydrocarbyl or halogenated hydrocarbyl group, and most especially tri(pentafluorophenyl)borane-modified aluminoxanes. Such cocatalysts have previously been disclosed in U.S. Pat. Nos. 6,214,760, 6,160,146, 6,140,521, and 6,696,379.

[0534] A class of cocatalysts including non-coordinating anions (generally referred to as swelling anions, further disclosed in U.S. Pat. No. 6,395,671) can be suitably used to activate the metal complexes of the present disclosure for olefin polymerization. Generally, these cocatalysts (illustrated by cocatalysts having imidazole, substituted imidazole, imidazoline, substituted imidazoline, benzimidazole or substituted benzimidazole anions) can be depicted as follows:

[0535]

[0536] in:

[0537] A* + A cation, especially one containing a proton, and may be one containing one or two C 10-40 Alkyl trialkylammonium cations, especially methyl di(C 14-20 alkyl)ammonium cation,

[0538] Q 3is independently at each occurrence hydrogen or a halo, hydrocarbyl, halocarbonyl, halohydrocarbyl, silylhydrocarbyl, or silyl (including, for example, mono-, di- and tri(hydrocarbyl)silyl) group having up to 30 atoms not counting hydrogen, such as C 1-20 Alkyl, and

[0539] Q 2 It is tris(pentafluorophenyl)borane or tris(pentafluorophenyl)aluminane.

[0540] Examples of these catalyst activators include trialkylammonium salts, especially the following methyl di(C 14-20 Alkyl) ammonium salt:

[0541] Bis(tri(pentafluorophenyl)borane)imidazole,

[0542] Bis(tri(pentafluorophenyl)borane)-2-undecylimidazole,

[0543] Bis(tri(pentafluorophenyl)borane)-2-heptadecylimidazole,

[0544] Bis(tri(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazole,

[0545] Bis(tri(pentafluorophenyl)borane)-4,5-bis(heptadecanyl)imidazole,

[0546] Bis(tris(pentafluorophenyl)borane)imidazoline,

[0547] Bis(tri(pentafluorophenyl)borane)-2-undecylimidazoline,

[0548] Bis(tri(pentafluorophenyl)borane)-2-heptadecylimidazoline,

[0549] Bis(tri(pentafluorophenyl)borane)-4,5-bis(undecyl)imidazoline,

[0550] Bis(tri(pentafluorophenyl)borane)-4,5-bis(heptadecanyl)imidazoline,

[0551] Bis(tri(pentafluorophenyl)borane)-5,6-dimethylbenzimidazole,

[0552] Bis(tri(pentafluorophenyl)borane)-5,6-bis(undecyl)benzimidazole,

[0553] Bis(tris(pentafluorophenyl)aluminum)imidazole,

[0554] Bis(tris(pentafluorophenyl)aluminum)-2-undecyl imidazole,

[0555] Bis(tris(pentafluorophenyl)aluminum)-2-heptadecylimidazole,

[0556] Bis(tris(pentafluorophenyl)aluminum)-4,5-bis(undecyl)imidazole,

[0557] Bis(tris(pentafluorophenyl)aluminum)-4,5-bis(heptadecanyl)imidazole,

[0558] Bis(tris(pentafluorophenyl)aluminum)imidazoline,

[0559] Bis(tri(pentafluorophenyl)aluminum)-2-undecyl imidazoline,

[0560] Bis(tri(pentafluorophenyl)aluminum)-2-heptadecylimidazoline,

[0561] Bis(tri(pentafluorophenyl)aluminum)-4,5-bis(undecyl)imidazoline,

[0562] Bis(tris(pentafluorophenyl)aluminum)-4,5-bis(heptadecanyl)imidazoline,

[0563] Bis(tris(pentafluorophenyl)alumina)-5,6-dimethylbenzimidazole, and

[0564] Bis(tris(pentafluorophenyl)alumina)-5,6-bis(undecyl)benzimidazolidine.

[0565] Other activators include those described in PCT Publication WO 98 / 07515, such as tris(2,2',2"-nonafluorobiphenyl)fluoroaluminate. Combinations of activators, such as aluminoxanes and ionizing activators, are also contemplated by the present disclosure, see, for example, EP-A-0 573120, 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, WO 98 / 09996 describes activation of catalyst compounds with perchlorates, periodates, and iodates (including hydrates thereof). WO 99 / 18135 describes the use of organoboroaluminum activators. WO 03 / 10171 discloses catalyst activators that are adducts of Bronsted acids and Lewis acids. 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; in EP-A-615981, and in PCT Publication WO 98 / 32775. All of the aforementioned catalyst activators and any other known activators for transition metal complex catalysts can be used alone or in combination according to the present disclosure. However, on the one hand, the cocatalyst may not contain aluminoxane. On the other hand, for example, the cocatalyst may not contain any specifically named activator or class of activators as disclosed herein.

[0566] In other aspects, the molar ratio of procatalyst / cocatalyst used is generally in the range of 1:10,000 to 100:1, such as 1:5000 to 10:1 or 1:1000 to 1:1. Aluminoxane, when used alone as an activating cocatalyst, can be used in large amounts, generally at least 100 times the amount of metal complex on a molar basis.

[0567] Tris(pentafluorophenyl)borane, when used as an activating cocatalyst, can generally be used in a molar ratio to the metal complex of 0.5:1 to 10:1, such as 1:1 to 6:1 and 1:1 to 5:1. The remaining activating cocatalyst is generally used in an amount approximately equimolar to the metal complex.

[0568] In an exemplary embodiment of the present disclosure, the co-catalyst is [(C 16-18 H 33-37 )2CH3NH]tetrakis(pentafluorophenyl)borate.

[0569] Suitable co-catalysts also include co-catalysts disclosed in U.S. Provisional Patent Application Nos. 62650423, 62650412, and 62650453, which are incorporated herein by reference in their entirety. Such co-catalysts include co-catalysts comprising an ionic complex of an anion and a counter cation, the anion having the following structure:

[0570]

[0571] Wherein: M is aluminum, boron or gallium; N is 2, 3 or 4; each R is independently selected from the group consisting of: group (II) and group (III):

[0572]

[0573] Each Y is independently carbon or silicon; each R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 and R 25 Independently selected from (C1-C 40 ) alkyl, (C6-C 40 ) aryl, -OR C 、-O-、-SR C , -H or -F, wherein when R is a group according to group (III), R 21-25 At least one of them is substituted with halogen (C1-C 40 ) alkyl, halogen-substituted (C6-C 40) aryl or -F; and provided that: when each R is group (II) and Y is carbon, R 11-13 At least one of them is substituted with halogen (C1-C 40 ) alkyl, halogen-substituted (C6-C 40 ) aryl or -F; or when M is aluminum and n is 4 and each R is group (II), and each Y is carbon: each R 11 , R 12 and R 13 Each is halogen-substituted (C1-C 40 ) alkyl, halogen-substituted (C6-C 40 )aryl or –F; or for each R 11 , R 12 and R 13 The total number of halogen atoms in the halogen atom is at least six; each X is independently selected from the following monodentate ligands: halogen-substituted (C1-C 20 )alkyl, (C1-C 20 ) alkyl, halogen-substituted (C6-C 40 ) aryl, (C6-C 40 )aryl, triflate or -S(O)3; optionally, two groups R are covalently linked; each R N and R C Independently (C1-C 30 )alkyl or –H.

[0574] Such co-catalysts further comprise a bimetallic activator complex comprising an anion and a counter cation, the anion having the following structure:

[0575]

[0576] wherein: each M is independently aluminum, boron or gallium; L is selected from species having at least two Lewis basic sites; each Q is independently a monodentate ligand; n is 0, 1 or 2, wherein when n is 0, Q is absent; x is 0, 1 or 2, wherein when x is 0, Q is absent; each R is independently selected from the group consisting of: group (II) and group (III):

[0577]

[0578] Each Y is independently carbon or silicon; each R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 and R 25 Independently selected from (C1-C 40) alkyl, (C6-C 40 )Aryl, –H, -NR N 2. -OR C ,–SR C or halogen, wherein when R is group (II), R 11-13 At least one of them is a fully halogenated (C1-C 40 ) alkyl, perhalogenated (C6-C 40 ) aryl or -F; and when R is group (III), R 21-25 At least one of them is a fully halogenated (C1-C 40 ) alkyl, perhalogenated (C6-C 40 ) aryl or -F; optionally, when n is 0 or 1, two R groups are covalently linked; and each R N or R C Independently (C1-C 30 )alkyl or –H.

[0579] Such co-catalysts further comprise a metal activator comprising an anion and a counter cation, the anion having the structure:

[0580]

[0581] wherein: n is 0 or 1; each R is independently selected from the group consisting of: group (II) and group (III):

[0582]

[0583] Each Y is independently carbon or silicon; each R 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 and R 25 Independently selected from (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, where R 11-13 At least one of R 21-25 One of them is substituted by halogen (C1-C 40 ) alkyl, halogen-substituted (C6-C 40 )aryl or -F; and each X is independently selected from (C1-C 20)alkyl or halogen-substituted (C6-C 40 ) is a monodentate ligand of an aromatic group; optionally, two X groups are covalently linked; each R C are independently halogen-substituted (C1-C 30 ) hydrocarbon group; provided that when the counter cation is (Ph)3C + And the anion is Al(C6F5)4.

[0584] Applications and end uses

[0585] The telechelic polyolefins of the present disclosure can be used in a variety of conventional manufacturing processes to produce useful articles, including objects prepared by casting, blowing, calendering or extrusion processes; molded articles, such as blow-, injection- or rotomolded articles; extrusions; fibers; and woven or nonwoven fabrics. The composition including the telechelic polyolefin of the present disclosure may further include, but is not limited to, other natural or synthetic polymers, oils, UV stabilizers, pigments, tackifiers, fillers (such as talc, calcium carbonate, glass fiber, carbon fiber), additives, reinforcing agents (such as calcium carbonate or magnesium carbonate, fatty acids and their salts), flame retardant additives, scorch inhibitors, antioxidants, stabilizers, colorants, extenders, carbon black, crosslinking agents, blowing agents, activators (such as zinc oxide or zinc stearate, silicon dioxide, aluminum silicate), plasticizers (such as dialkyl esters of dicarboxylic acids), antidegradants, softeners, waxes, (poly)alcohols, (poly)alcohol ethers, polyesters, metal salts, scavengers, nucleating agents, stability control agents, flame retardants, lubricants, processing aids, extrusion aids, and chemical protectants.

[0586] Particularly useful are curable formulations comprising telechelic polyolefins of formula (I). In some embodiments, curable formulations comprising telechelic polyolefins of formula (I) can be cured by ebeaming (electron beam) without the need for a crosslinking agent. In other embodiments, the curable formulation further comprises a crosslinking agent, and may also include coagents, curing additives, scorch inhibitors and / or accelerators. Curable formulations further comprising a crosslinking agent can be rheologically modified by curing via ebeaming.

[0587] 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, thiurams disulfide, p-quinone dioxime, dibenzo-p-quinone 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 will depend largely on the choice of polymer, as is well known to those skilled in the art of compounding.

[0588] The crosslinking agent may include one or more organic peroxides, including but not limited to alkyl peroxides, aryl peroxides, peroxyesters, peroxycarbonates, diacyl peroxides, peroxyketals, cyclic peroxides, dialkyl peroxides, peroxyesters, peroxydicarbonates, or a combination 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, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, di(sec-butyl)peroxydicarbonate, tert-amyl peroxyneodecanoate, 1,1-di-tert-butylperoxy-3,3,5-trimethylcyclohexane, tert-butyl-cumyl peroxide, 2,5-dimethyl-2,5-di(tert-butyl-peroxy)hexane, 1,3-bis(tert-butyl-peroxy-isopropyl)benzene, or a combination thereof. Exemplary crosslinking agents are available from Arkema under the trade name or from Akzo Nobel under the trade name Commercially available dicumyl peroxide. Additional exemplary crosslinking agents are DBPH-50. When the crosslinking agent is a peroxide, certain processing aids and cure activators such as stearic acid and ZnO may also be used.

[0589] When a peroxide-based curing agent is used, a co-activator or co-agent may be used in combination therewith. Suitable co-agents include, but are not limited to, trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), triallyl cyanurate (TAC), triallyl isocyanurate (TAIC), and 1,4-phenylenedimaleimide (available from TCI Chemicals).

[0590] Suitable coagents further include, but are not limited to, alkenyl-functional monocyclic organosiloxanes disclosed in WO 2019 / 000311 and WO 2019 / 000654, which are incorporated herein by reference in their entirety. For example, the coagent may be a monocyclic organosiloxane of formula [R1, R2SiO2 / 2]n, wherein subscript n is an integer greater than or equal to 3; each R1 is independently (C2-C4) alkenyl or H2C=C(R1a)-C(=O)-O-(CH2)m-, wherein R1a is H or methyl, and subscript m is an integer from 1 to 4; and each R2 is independently H, (C1-C4) alkyl, phenyl or R1. Examples of such monocyclic organosiloxanes include, but are not limited to, 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane, 2,4,6-trimethyl-2,4,6-trivinyl-cyclotrisiloxane, or combinations thereof.

[0591] Scorch inhibitors / retarders are molecules or collections of such molecules that inhibit 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 described in US 6277925B1, column 2, line 62 to column 3, line 46.

[0592] Suitable crosslinking agents include sulfur-based crosslinking agents such as elemental sulfur. When sulfur-based curing agents are used, accelerators and curing activators may also be used, such as amines, disulfides, guanidines, thioureas, thiazoles, thiurams, sulfenamides, dithiocarbamates, xanthates, 4,4'-dithiodimorpholine, thiuram disulfides and polysulfides, alkylphenol disulfides and 2-morpholino-dithiobenzothiazole, tetramethylthiuram disulfide (T M TD), dipentamethylenethiuram tetrasulfide (DPTT), 2-mercaptobenzothiazole (MBT), 2-mercaptobenzothiazole disulfide (MBTS), zinc 2-mercaptobenzothiazole (ZMBT), zinc diethyldithiocarbamate (ZDEC), zinc dibutyldithiocarbamate (ZDBC), dipentamethylenethiuram tetrasulfide (DPTT), N-tert-butylbenzothiazole-2-sulfonamide (TBBS) and mixtures thereof.

[0593] Additional crosslinking agents include, but are not limited to, phenolic resins, azides, aldehyde-amine reaction products, vinyl silanes, hydrosilylation agents, substituted ureas, substituted guanidines, substituted xanthates, substituted dithiocarbamates, and combinations thereof. The crosslinking agent may be a phenolic curing agent or a peroxide curing agent, with an optional coagent, or a hydrosilylation crosslinking agent with a hydrosilylation catalyst, or dibutyltin dilaurate ("DBTDL"), with an optional coagent alumina trihydrate ("ATH"). Popular industrial catalysts are "Speier's catalyst", H2PtCl6, and Karstedt's catalyst, an olefin-stabilized platinum (0) catalyst.

[0594] 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 of ordinary skill in the art based on the selected polymer and curing component.

[0595] Alternatively, the crosslinking agent can be activated by exposing it to radiation causing the generation of free radicals from the crosslinking agent. Non-limiting examples of suitable radiation include UV or visible radiation, electron beams or beta rays, gamma rays, X-rays or neutron rays. It is believed that radiation activates crosslinking by generating free radicals in polymers, which can then be combined and crosslinked. The radiation dose depends on many factors and can be determined by those skilled in the art. When the crosslinking agent is a peroxide photoinitiator, such as dibenzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, diacetyl peroxide, hydrogen peroxide, peroxodisulfate and 2,2-bis (tert-butyl peroxy) -2,5- dimethylhexane, UV or visible radiation activation can occur.

[0596] In some embodiments, a dual cure system comprising at least two activation methods may be effectively used, such as a combination selected from heat, moisture cure, and radiation. 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 characteristics of the polymer, such as molecular weight, molecular weight distribution, comonomer content, the presence of crosslinking enhancing coagents, other additives, etc.

[0597] When the composition containing the telechelic polyolefin is at least partially crosslinked, the degree of crosslinking can be measured by dissolving the composition in a solvent for a specified duration and calculating the percentage of gel or non-extractable components. The gel percentage generally increases with increasing levels of crosslinking. For cured articles according to the present invention, the gel percentage content is desirably in the range of 0 to 100%, or 5 to 100%, or 10 to 95%, or 20 to 90%, or 30 to 85%, or 40 to 80%.

[0598] Fibers can be prepared from the telechelic polyolefins of the present invention. The fibers that can be prepared include staple fibers, tows, multicomponents, sheath / core, twisted and monofilaments. Suitable fiber forming processes include spunbonding, meltblowing technology as disclosed in U.S. Pat. Nos. 4,430,563, 4,663,220, 4,668,566 and 4,322,027, gel spun fibers as disclosed in U.S. Pat. No. 4,413,110, woven and nonwoven fabrics as disclosed in U.S. Pat. No. 3,485,706, or structures made from these fibers, including blends with other fibers such as polyester, nylon or cotton, thermoformed articles, extruded profiles, including profile extrusion and coextrusion, calendered articles, and stretched, twisted or curled yarns or fibers. The novel polymers described herein can also be used in wire and cable coating operations, as well as sheet extrusion for vacuum forming operations and forming molded articles, including using injection molding, blow molding processes or rotational molding processes. The compositions comprising telechelic polyolefins can also be formed into fabricated articles, such as the previously mentioned articles, using conventional polyolefin processing techniques well known to those skilled in the art of polyolefin processing.

[0599] Dispersions (both aqueous and non-aqueous) may also be formed using the telechelic polyolefins of the present invention or formulations comprising the same.

[0600] Additives and adjuvants may be included in any formulation comprising the telechelic polyolefins of the present invention. Suitable additives include fillers such as organic or inorganic particles, including clay, talc, titanium dioxide, zeolites, powdered metals, organic or inorganic fibers, including carbon fibers, silicon nitride fibers, steel wires or meshes and nylon or polyester ropes, nano-sized particles, clays, etc.; tackifiers, oil extenders, including paraffinic or naphthenic oils; and other natural and synthetic polymers, including other polymers according to the present invention.

[0601] Suitable polymers for blending with the telechelic polyolefins of the present disclosure 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 / α-olefin interpolymers), other elastomers (SBC, PVC, EVA, ionomers, etc.), and other engineered thermoplastics (styrene, polyamide, polyester, etc.). Exemplary polymers for blending include polypropylene (both impact modified polypropylene, isotactic polypropylene, atactic polypropylene, and random ethylene / propylene copolymers), various types of polyethylene, including high pressure, free radical LDPE, Ziegler-Natta LLDPE, metallocene PE, including multiple reactor PE ("in-reactor" blends of Ziegler-Natta PE and metallocene PE, such as the products disclosed in U.S. Pat. Nos. 6,545,088, 6,538,070, 6,566,446, 5,844,045, 5,869,575, and 6,448,341), ethylene vinyl acetate (EVA), ethylene / vinyl alcohol copolymers, polystyrene, impact modified polystyrene, ABS, styrene / butadiene block copolymers and hydrogenated derivatives thereof (SBS and SEBS), ethylene-based olefin block copolymers (such as those available from The Dow Chemical Company under the trade name INFUSE TM vinyl olefin block copolymers obtained from the Dow Chemical Company), propylene-based olefin block copolymers (such as those available from the Dow Chemical Company under the trade name INTUNE TM Homogeneous polymers such as olefin plastomers and elastomers such as ethylene / α-olefin copolymers and propylene-based copolymers with low or no unsaturation (e.g., available from The Dow Chemical Company under the trade name VERSIFY TM Available from The Dow Chemical Company as ENGAGE TM Available from Mitsui Chemicals as TAFMER TM ExxonMobil TM and available from ExxonMobil as VISTAMAXX TM The polymers obtained) can also be used as a component in blends comprising the polymers of the invention.

[0602] Suitable end uses include crosslinkable or non-crosslinkable formulations for: films; fibers; soft touch items such as toothbrush handles and appliance handles; gaskets and profiles; adhesives (functional adhesives, crosslinking adhesives, hot melt adhesives); footwear (including soles and shoe linings); automotive interior parts and profiles; foam items (both open-cell and closed-cell); impact modifiers for other thermoplastic polymers such as high-density polyethylene, isotactic polypropylene or other olefin polymers; coated fabrics; hoses; pipes; weather stripping (weather stripping); stripping); cover linings; flooring; building or architectural parts; carpentry; coatings (powder coatings, water-based coatings for beverage and food linings, solvent-based coatings for industrial metal coatings); waterproofing; photovoltaic applications; wire and cable applications; thermoplastic vulcanizate (TPV) applications; EPDM thermosets; seals, belts, conveyor belts, automotive timing belts, etc., gaskets, dampers; tire compounds; highly filled compounds, sidewall and tread compounds; coagents for thermoset rubbers; cross-linked pipes; liquid (low viscosity) reaction injection molding; injection molded skins; 3D printing; and tubing.

[0603] The composition may also contain antiozonants or antioxidants known to rubber chemists in the general technical field. Antiozonants may be physical protectants, such as waxy materials that reach the surface and protect the parts from oxygen or ozone, or antiozonants may be chemical protectants that react with oxygen or ozone. Suitable chemical protectants include styrenated phenols, butylated octylated phenols, butylated di(dimethylbenzyl)phenol, p-phenylenediamine, butylated reaction products of p-cresol and dicyclopentadiene (DCPD), polyphenol antioxidants, hydroquinone derivatives, quinolines, diphenylene antioxidants, thioester antioxidants, and mixtures thereof. Some representative trade names of such products are Wingstay TM S Antioxidant, Polystay TM 100 Antioxidants, Polystay TM 100AZ Antioxidant, Polystay TM 200 Antioxidants, Wingstay TM L Antioxidant, Wingstay TM LHLS antioxidant, Wingstay TM K antioxidant, Wingstay TM 29 Antioxidants, Wingstay TM SN-1 Antioxidant and Irganox TM Antioxidants. In some applications, the antioxidants and antiozonants used will preferably be non-staining and non-migrating.

[0604] To provide additional stability against UV radiation, hindered amine light stabilizers (HALS) and UV absorbers may also be used. Suitable examples include Tinuvin available from Ciba Specialty Chemicals. TM 123. Tinuvin TM 144. Tinuvin TM 622. Tinuvin TM 765. Tinuvin TM 770 and Tinuvin TM 780, and Chemisorb available from Cytex Plastics, Houston, Texas, USA TM T944. A Lewis acid may additionally be included with the HALS compound in order to achieve excellent surface quality as disclosed in US Pat. No. 6,051,681.

[0605] For some compositions, an additional mixing process may be used to pre-disperse antioxidants, antiozonants, carbon black, UV absorbers, and / or light stabilizers to form a masterbatch, and subsequently form a polymer blend therefrom.

[0606] The composition according to the invention may also contain organic or inorganic fillers or other additives, such as starch, talc, calcium carbonate, glass fibers, polymer fibers (including nylon, rayon, cotton, polyester and polyaramid), metal fibers, flakes or particles, expandable layered silicates, phosphates or carbonates, such as clay, mica, silica, alumina, aluminosilicates or aluminophosphates, carbon whiskers, carbon fibers, nanoparticles (including nanotubes), wollastonite, graphite, zeolites and ceramics, such as silicon carbide, silicon nitride or titanium dioxide. Silane-based or other coupling agents may also be used for better filler bonding.

[0607] Suitable blowing agent includes but is not limited to inorganic blowing agent, organic blowing agent, chemical blowing agent and combination thereof.The limiting examples of suitable inorganic blowing agent include carbon dioxide, nitrogen, argon, water, air, nitrogen and helium.The limiting examples of suitable organic blowing agent include aliphatic hydrocarbons with 1-6 carbon atom, aliphatic alcohols with 1-3 carbon atom and aliphatic hydrocarbons with complete and partial halogenation of 1-4 carbon atom.The limiting examples of suitable aliphatic hydrocarbons include methane, ethane, propane, normal butane, isobutane, normal pentane, isopentane, neopentane etc.The limiting examples of suitable aliphatic alcohols include methyl alcohol, ethanol, n-propyl alcohol and isopropyl alcohol.The limiting examples of suitable complete and partial halogenation of aliphatic hydrocarbons include fluorocarbons, chlorocarbons and chlorofluoro compounds. Non-limiting examples of suitable fluorocarbons include methyl fluoride, perfluoromethane, ethyl fluoride, 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), pentafluoroethane, difluoromethane, perfluoroethane, 2,2-difluoropropane, 1,1,1-trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, and perfluorocyclobutane. The non-limiting examples of suitable partially halogenated chlorocarbons and chlorofluoro compounds include methyl chloride, methylene chloride, ethyl chloride, 1,1,1-trichloroethane, 1,1-dichloro-1-fluoroethane (HCFC-141b), 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). The non-limiting examples of suitable fully halogenated chlorofluoro compounds 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, azobisisobutyronitrile, benzenesulfonylhydrazide, 4,4-hydroxybenzenesulfonylsemicarbazide, p-toluenesulfonylsemicarbazide, barium azodicarboxylate, N,N'-dimethyl-N,N'-dinitrosoterephthalamide and trihydrazinotriazine. In some embodiments, the blowing agent is azodicarbonamide isobutane, CO2 or a mixture thereof.

[0608] The telechelic polyolefins of the present disclosure may also be chemically modified, for example, by grafting (eg, by using maleic anhydride (MAH), silanes, glycidyl methacrylate, or other grafting agents), halogenation, amination, sulfonation, or other chemical modifications. Specific embodiments

[0610] The following are non-limiting examples that illustrate the invention and provide detailed disclosure for any claims in this application.Unless otherwise stated, any measured properties or characterizations in the following examples are consistent with the test methods disclosed herein.

[0611] 1. A composition comprising a telechelic polyolefin of formula (I):

[0612] A 1 L 1 L 2 A 2 (I) where:

[0613] L 1 It is a polyolefin;

[0614] A 1 Selected from the group consisting of: vinyl, formula CH2=C(Y 1 )-vinylidene, formula Y 1 CH=CH-vinylene, vinyl and formula Y 1 A mixture of CH=CH-vinylene, vinyl and CH2=C(Y 1 )-vinylidene mixture, formula CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of CH=CH-vinylene and vinyl, CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of vinylene groups with CH=CH-;

[0615] Y 1 C1 to C independently at each occurrence 30 Hydrocarbon;

[0616] L 2 It is C1 to C 32 alkylene; and

[0617] A 2 is a hydrocarbon group including a hindered double bond.

[0618] 2. The composition according to embodiment 1, wherein L 2 is -CH2CH(Y 2 )-, and where Y 2 is hydrogen or C1 to C 30 Hydrocarbon.

[0619] 3. The composition according to embodiment 1 or 2, wherein L 1 is an ethylene homopolymer comprising units derived from ethylene.

[0620] 4. The composition according to embodiment 3, wherein A1 It's vinyl.

[0621] 5. The composition according to embodiment 3, wherein A 1 It is formula Y 1 CH=CH-vinylene, and wherein Y 1 It is C1 to C 30 alkyl.

[0622] 6. The composition according to embodiment 5, wherein Y 1 It's methyl.

[0623] 7. The composition according to embodiment 3, wherein A 1 It is vinyl and style Y 1 A mixture of CH=CH-vinylene groups, wherein Y 1 It is C1 to C 30 alkyl.

[0624] 8. The composition according to embodiment 7, wherein Y 1 It's methyl.

[0625] 9. The composition according to embodiment 7 or 8, wherein A 1 comprising vinyl and formula Y in a ratio of 0.99:0.1 to 0.1:0.99 1 Vinylene group: CH=CH-.

[0626] 10. The composition according to embodiment 1 or 2, wherein L 1 is a propylene homopolymer comprising units derived from propylene.

[0627] 11. The composition according to embodiment 10, wherein A 1 The formula is CH2=C(Y 1 )-vinylidene, and wherein Y 1 It's methyl.

[0628] 12. The composition according to embodiment 10, wherein A 1 It is the formula Y 1 CH=CH-vinylene, and wherein Y 1 It's methyl.

[0629] 13. The composition according to embodiment 10, wherein A 1 The formula is CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of CH=CH-vinylene groups, wherein Y 1 is independently at each occurrence methyl.

[0630] 14. The composition according to embodiment 13, wherein A 1 including the formula CH2=C(Y 1 )-vinylidene and formula Y 1 Vinylene group: CH=CH-.

[0631] 15. The composition according to embodiment 1 or 2, wherein L 1 It includes derivatives from ethylene and C3 to C 30 Ethylene / α-olefin copolymers containing α-olefin units.

[0632] 16. The composition according to embodiment 15, wherein the C3 to C 30 The α-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.

[0633] 17. The composition according to embodiment 16, wherein the C3 to C 30 The α-olefin is propylene, and L 1 It is an ethylene / propylene copolymer.

[0634] 18. The composition according to embodiment 17, wherein A 1 It's vinyl.

[0635] 19. The composition according to embodiment 17, wherein A 1 The formula is CH2=C(Y 1 )-vinylidene, and wherein Y 1 It's methyl.

[0636] 20. The composition of embodiment 17, wherein A 1 It is the formula Y 1 CH=CH-vinylene, and wherein Y 1 It's methyl.

[0637] 21. The composition of embodiment 17, wherein A 1 It is vinyl and style Y 1 A mixture of CH=CH-vinylene groups, wherein Y 1 It's methyl.

[0638] 22. The composition according to embodiment 21, wherein A 1 comprising vinyl and formula Y in a ratio of 0.99:0.1 to 0.1:0.99 1 Vinylene group: CH=CH-.

[0639] 23. The composition of embodiment 17, wherein A 1 It is vinyl and the formula is CH2=C(Y1 )-vinylidene groups, and wherein Y 1 It's methyl.

[0640] 24. The composition of embodiment 23, wherein A 1 The ratio of 0.99:0.1 to 0.1:0.99 of vinyl and CH2=C(Y 1 )-vinylidene.

[0641] 25. The composition of embodiment 17, wherein A 1 It is vinyl, formula CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of CH=CH-vinylene groups, wherein Y 1 is independently at each occurrence methyl.

[0642] 26. The composition of embodiment 25, wherein A 1 The ratio of vinyl to Y is 0.99:0.01 to 0.01:0.99. 1 CH=CH-ethylene, formula CH2=C(Y 1 )- is the sum of the vinylidene and vinyl groups.

[0643] 27. The composition according to embodiment 16, wherein C3 to C 30 The α-olefin is 1-butene, and L 1 It is an ethylene / 1-butene copolymer.

[0644] 28. The composition of embodiment 27, wherein A 1 It's vinyl.

[0645] 29. The composition of embodiment 27, wherein A 1 The formula is CH2=C(Y 1 )-vinylidene, and wherein Y 1 Ethyl.

[0646] 30. The composition of embodiment 27, wherein A 1 It is the formula Y 1 CH=CH-vinylene, and wherein Y 1 It is ethyl.

[0647] 31. The composition of embodiment 27, wherein A 1 It is vinyl and style Y 1 A mixture of CH=CH-vinylene groups, wherein Y 1 It is ethyl.

[0648] 32. The composition of embodiment 31, wherein A 1 comprising vinyl and formula Y in a ratio of 0.99:0.1 to 0.1:0.99 1 Vinylene group: CH=CH-.

[0649] 33. The composition of embodiment 27, wherein A 1 It is vinyl and the formula is CH2=C(Y 1 )-vinylidene groups, and wherein Y 1 It is ethyl.

[0650] 34. The composition of embodiment 33, wherein A 1 The ratio of 0.99:0.1 to 0.1:0.99 of vinyl and CH2=C(Y 1 )-vinylidene.

[0651] 35. The composition of embodiment 27, wherein A 1 It is vinyl, formula CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of CH=CH-vinylene groups, wherein Y 1 is independently ethyl at each occurrence.

[0652] 36. The composition of embodiment 35, wherein A 1 The ratio of vinyl to Y is 0.99:0.01 to 0.01:0.99. 1 CH=CH-ethylene, formula CH2=C(Y 1 )- is the sum of the vinylidene and vinyl groups.

[0653] 37. The composition according to embodiment 16, wherein C3 to C 30 The α-olefin is 1-hexene, and L 1 It is an ethylene / 1-hexene copolymer.

[0654] 38. The composition of embodiment 37, wherein A 1 It's vinyl.

[0655] 39. The composition of embodiment 37, wherein A 1 The formula is CH2=C(Y 1 )-vinylidene, and wherein Y 1 It's butyl.

[0656] 40. The composition of embodiment 37, wherein A 1 It is the formula Y 1 CH=CH-vinylene, and wherein Y1 It's butyl.

[0657] 41. The composition of embodiment 37, wherein A 1 It is vinyl and style Y 1 A mixture of CH=CH-vinylene groups, wherein Y 1 It's butyl.

[0658] 42. The composition of embodiment 41, wherein A 1 comprising vinyl and formula Y in a ratio of 0.99:0.1 to 0.1:0.99 1 Vinylene group: CH=CH-.

[0659] 43. The composition of embodiment 37, wherein A 1 It is vinyl and the formula is CH2=C(Y 1 )-vinylidene groups, and wherein Y 1 It's butyl.

[0660] 44. The composition of embodiment 43, wherein A 1 The ratio of 0.99:0.1 to 0.1:0.99 of vinyl and CH2=C(Y 1 )-vinylidene.

[0661] 45. The composition of embodiment 37, wherein A 1 It is vinyl, formula CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of CH=CH-vinylene groups, wherein Y 1 is independently butyl at each occurrence.

[0662] 46. ​​The composition of embodiment 45, wherein A 1 The ratio of vinyl to Y is 0.99:0.01 to 0.01:0.99. 1 CH=CH-ethylene, formula CH2=C(Y 1 )- is the sum of the vinylidene and vinyl groups.

[0663] 47. The composition according to embodiment 16, wherein C3 to C 30 The α-olefin is 1-octene, and L 1 It is an ethylene / 1-octene copolymer.

[0664] 48. The composition of embodiment 47, wherein A 1 It's vinyl.

[0665] 49. The composition of embodiment 47, wherein A1 The formula is CH2=C(Y 1 )-vinylidene, and wherein Y 1 It is a C6 alkyl group.

[0666] 50. The composition of embodiment 47, wherein A 1 It is the formula Y 1 CH=CH-vinylene, and wherein Y 1 It is a C6 alkyl group.

[0667] 51. The composition of embodiment 47, wherein A 1 It is vinyl and style Y 1 A mixture of CH=CH-vinylene groups, wherein Y 1 It is a C6 alkyl group.

[0668] 52. The composition of embodiment 51, wherein A 1 comprising vinyl and formula Y in a ratio of 0.99:0.1 to 0.1:0.99 1 Vinylene group: CH=CH-.

[0669] 53. The composition of embodiment 47, wherein A 1 It is vinyl and the formula is CH2=C(Y 1 )-vinylidene groups, and wherein Y 1 It is a C6 alkyl group.

[0670] 54. The composition of embodiment 53, wherein A 1 The ratio of 0.99:0.1 to 0.1:0.99 of vinyl and CH2=C(Y 1 )-vinylidene.

[0671] 55. The composition of embodiment 47, wherein A 1 It is vinyl, formula CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of CH=CH-vinylene groups, wherein Y 1 is independently at each occurrence C6 alkyl.

[0672] 56. The composition of embodiment 55, wherein A 1 The ratio of vinyl to Y is 0.99:0.01 to 0.01:0.99. 1 CH=CH-ethylene, formula CH2=C(Y 1 )- is the sum of the vinylidene and vinyl groups.

[0673] 57. The composition of embodiment 1 or 2, wherein L1 It includes propylene and ethylene or C4 to C 30 Propylene / α-olefin copolymers containing α-olefin units.

[0674] 58. The composition according to embodiment 57, wherein the C4 to C 30 The α-olefin is selected from the group consisting of 1-butene, 1-hexene and 1-octene.

[0675] 59. The composition of embodiment 57, wherein L 1 It is a propylene / ethylene copolymer.

[0676] 60. The composition of embodiment 59, wherein A 1 It's vinyl.

[0677] 61. The composition of embodiment 59, wherein A 1 The formula is CH2=C(Y 1 )-vinylidene, and wherein Y 1 It's methyl.

[0678] 62. The composition of embodiment 59, wherein A 1 It is the formula Y 1 CH=CH-vinylene, and wherein Y 1 It's methyl.

[0679] 63. The composition of embodiment 59, wherein A 1 It is vinyl and style Y 1 A mixture of CH=CH-vinylene groups, wherein Y 1 It's methyl.

[0680] 64. The composition of embodiment 63, wherein A 1 comprising vinyl and formula Y in a ratio of 0.99:0.1 to 0.1:0.99 1 Vinylene group: CH=CH-.

[0681] 65. The composition of embodiment 59, wherein A 1 It is vinyl and the formula is CH2=C(Y 1 )-vinylidene groups, and wherein Y 1 It's methyl.

[0682] 66. The composition of embodiment 65, wherein A 1 The ratio of 0.99:0.1 to 0.1:0.99 of vinyl and CH2=C(Y 1 )-vinylidene.

[0683] 67. The composition of embodiment 59, wherein A 1 It is vinyl, formula CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of CH=CH-vinylene groups, wherein Y 1 is independently at each occurrence methyl.

[0684] 68. The composition of embodiment 67, wherein A 1 The ratio of vinyl to Y is 0.99:0.01 to 0.01:0.99. 1 CH=CH-ethylene, formula CH2=C(Y 1 )- is the sum of the vinylidene and vinyl groups.

[0685] 69. The composition according to any of embodiments 2 to 68, wherein Y 2 It's hydrogen.

[0686] 70. A composition according to any one of embodiments 2 to 68, wherein Y 2 It is a C1 to C10 alkyl group.

[0687] 71. The composition of embodiment 70, wherein Y 2 It is ethyl.

[0688] 72. The composition of any one of the preceding embodiments, wherein the hindered double bond is selected from the group consisting of a vinylidene double bond, a vinylene double bond, a trisubstituted olefin double bond, and a vinyl double bond attached to a branched alpha carbon.

[0689] 73. A composition according to any one of the preceding embodiments, wherein A 2 It is C3 to C 30 Cyclic hydrocarbon or C3 to C 30 Acyclic hydrocarbon groups.

[0690] 74. A composition according to any one of the preceding embodiments, wherein A 2 Selected from the group consisting of unsubstituted cycloolefins, alkyl-substituted cycloolefins and non-cyclic alkyl groups.

[0691] 75. A composition according to any one of the preceding embodiments, wherein A 2 Selected from the group consisting of:

[0692]

[0693] 76. A composition according to any one of the preceding embodiments, wherein A 2Selected from the group consisting of (AC), (AF), (AM), (AO), (AP), (AS) and (AZ1).

[0694] 77. The composition of any preceding embodiment, wherein the telechelic polyolefin of formula (I) has a weight average molecular weight (Mw) range selected from the group consisting of 1,000 to 10,000,000 g / mol, 1,000 to 5,000,000 g / mol, 1,000 to 1,000,000 g / mol, 1,000 to 750,000 g / mol, 1,000 to 500,000 g / mol, and 1,000 to 250,000 g / mol.

[0695] 78. The composition of any preceding embodiment, wherein the telechelic polyolefin of formula (I) has a number average molecular weight (Mn) range selected from the group consisting of 1,000 to 10,000,000 g / mol, 1,000 to 5,000,000 g / mol, 1,000 to 1,000,000 g / mol, 1,000 to 750,000 g / mol, 1,000 to 500,000 g / mol, and 1,000 to 250,000 g / mol.

[0696] 79. The composition of any preceding embodiment, wherein the telechelic polyolefin of formula (I) has an average molar mass (Mz) range selected from the group consisting of 1,000 to 10,000,000 g / mol, 1,000 to 5,000,000 g / mol, 1,000 to 1,000,000 g / mol, 1,000 to 750,000 g / mol, 1,000 to 500,000 g / mol, 5,000 to 500,000 g / mol, and 10,000 to 500,000 g / mol.

[0697] 80. The composition of any preceding embodiment wherein the telechelic polyolefin of formula (I) has a Mw / Mn(PDI) range selected from the group consisting of 1 to 10, 1 to 7, 1 to 5, 1.5 to 4, and 2 to 4.

[0698] 81. A composition according to any of the preceding embodiments, wherein the telechelic polyolefin of formula (I) is as described by AST MThe density range measured by D-792, Method B is selected from the group consisting of 0.850 to 0.965 g / cc, 0.854 to 0.950 g / cc, 0.854 to 0.935 g / cc, 0.854 to 0.925 g / cc, 0.854 to 0.910 g / cc, 0.854 to 0.900 g / cc, 0.854 to 0.885 g / cc, 0.854 to 0.880 g / cc and 0.854 to 0.875 g / cc.

[0699] 82. The composition of any preceding embodiment, wherein the telechelic polyolefin of formula (I) has a melt index (I2) range as measured by ASTM D-1238, Condition 190°C / 2.16 kg selected from the group consisting of 0.01 to 2000 g / 10 min, 0.01 to 1,500 g / 10 min, 0.01 to 1,000 g / 10 min, 0.01 to 500 g / 10 min, 0.01 to 100 g / 10 min, 0.5 to 50 g / 10 min, and 0.5 to 30 g / 10 min.

[0700] 83. A composition according to any one of the preceding embodiments, wherein the telechelic polyolefin of formula (I) has a T m The range is selected from the group consisting of -25°C to 165°C, -25°C to 150°C, -25°C to 125°C, -25°C to 100°C, 0°C to 80°C, and 10°C to 60°C.

[0701] 84. The composition of any of the preceding embodiments, wherein the telechelic polyolefin of formula (I) has a Brookfield viscosity range as measured by ASTM D-3236 at 177°C selected from the group consisting of: 10 to 10 8 cP, 10 to 10 7 cP, 10 to 10 6 cP, 10 to 750,000cP, 10 to 500,000cP, 10 to 250,000cP, 10 to 100,000cP, 10 to 75,000cP, 10 to 50,000cP and 10 to 40,000cP.

[0702] 85. The composition of any preceding embodiment, wherein the telechelic polyolefin of formula (I) has a melting enthalpy (ΔHm) range selected from the group consisting of 0 to 235 J / g, 0 to 200 J / g, 10 to 175 J / g, 10 to 150 J / g, 10 to 125 J / g, and 20 to 117 J / g.

[0703] 86. A composition according to any one of the preceding embodiments, wherein the telechelic polyolefin of formula (I) has a T gThe range is selected from the group consisting of -80 to 100°C, -80 to 75°C, -80 to 50°C, -80 to 25°C, -80 to 0°C, -80 to -15°C, and -70 to -30°C.

[0704] 87. The composition of any preceding embodiment wherein the telechelic polyolefin of formula (I) comprises 0 wt% to 0.001 wt% of units derived from diene monomers.

[0705] 88. The composition of embodiment 88, wherein the telechelic polyolefin of formula (I) has a total number of unsaturations in a range selected from the group consisting of: equal to or greater than 1.1, equal to or greater than 1.2, equal to or greater than 1.3, equal to or greater than 1.4, equal to or greater than 1.5, equal to or greater than 1.6, equal to or greater than 1.7, equal to or greater than 1.8, and equal to or greater than 1.9.

[0706] 89. The composition of any of embodiments 3 to 9, 15 to 56 and 69 to 88, wherein the telechelic polyolefin of formula (I) has a crystallinity wt% range selected from the group consisting of 0 to 80%, 0 to 60%, 5 to 50% and 7 to 40% based on a PEΔHm of 292 J / g.

[0707] 90. A composition according to any one of the preceding embodiments, wherein L 1 A through a carbon-carbon single bond 1 and L 2 Each of the covalent bonds, and where L 2 A through a carbon-carbon single bond 2 Covalent bonding.

[0708] 91. A composition according to any one of the preceding embodiments, wherein L 1 is missing two hydrogens and is 1 and L 2 Each of the covalently bonded polyolefins.

[0709] 92. The telechelic polyolefin of formula (I) according to any one of the preceding embodiments.

[0710] 1a. A method for preparing a telechelic polyolefin or a composition comprising a telechelic polyolefin, the method comprising:

[0711] 1) combining starting materials including (A) a monomer component, (B) a chain transfer agent component, and (C) a catalyst component including a main catalyst to form a solution, and polymerizing greater than 10 mol % to less than or equal to 99 mol % of the (A) monomer component in the solution;

[0712] 2) heating the solution; and

[0713] 3) recovering a product comprising said telechelic polyolefin or said composition comprising said telechelic polyolefin, wherein:

[0714] The chain transfer agent component (B) comprises the formula Al(CH2CH(Y 2 )A 2 )3 organoaluminum compounds;

[0715] Y 2 is independently hydrogen or C1 to C 30 a hydrocarbon group; and

[0716] A 2 and R is independently at each occurrence a hydrocarbyl group including a hindered double bond.

[0717] 2a. The method of embodiment 1a, wherein the starting material further comprises (D) a solvent.

[0718] 3a. The method of embodiment 1a or 2a, wherein step 2) is heating the solution to a temperature of at least 160°C or at least 180°C or at least 200°C or at least 220°C and maintaining the solution at a temperature of at least 160°C or at least 180°C or at least 200°C or at least 220°C for a period of at least 30 seconds or at least 1 minute or at least 5 minutes.

[0719] 4a. The method of any one of embodiments 1a to 3a, wherein step 2) is heating the solution at a temperature of at least 160°C or at least 180°C or at least 200°C or at least 220°C for a period of at least 30 seconds or at least 1 minute or at least 5 minutes.

[0720] 5a. The method according to any one of embodiments 1a to 4a, wherein step 2) is heating the solution at a temperature of 220°C to 290°C for a period of 5 minutes to 20 minutes.

[0721] 6a. The method according to any one of embodiments 1a to 5a, wherein step 2) heats the solution to a temperature of 220°C to 290°C and maintains the solution at a temperature of 220°C to 290°C for a period of 5 minutes to 20 minutes.

[0722] 7a. The method of any one of embodiments 1a to 6a, wherein the procatalyst is selected from the group consisting of (Cat 1) to (Cat 17) as described above.

[0723] 8a. The method according to embodiment 7a, wherein the main catalyst is (Cat 1), (Cat 13) (Cat 14) or (Cat 17) as described above.

[0724] 9a. The method of any one of embodiments 1a to 8a, wherein the catalyst component further comprises a co-catalyst.

[0725] 10a. The method according to any one of embodiments 1a to 9a, wherein the co-catalyst is [(C 16-18 H 33-37 )2CH3NH]tetrakis(pentafluorophenyl)borate.

[0726] 11a. The method of any one of embodiments 1a to 10a, wherein the (B) chain transfer agent component further comprises an alkyl zinc of formula Zn(d)2, wherein d is independently at each occurrence a C1 to C10 alkyl group.

[0727] 12a. The method according to embodiment 11a, wherein the (B) chain transfer agent component comprises 65 mol% to 99 mol% of the formula Al(CH2CH(Y 2 )A 2 )3 and 1 mol% to 35 mol% of an alkyl zinc of formula Zn(d)2.

[0728] 13a. The method according to any one of embodiments 1a to 10a, wherein the (B) chain transfer agent component comprises a component of the formula Al(CH2CH(Y 2 )A 2 )3 organic aluminum compound and formula Zn(CH2CH(Y 2 )A 2 )2, wherein: Y 2 is independently hydrogen or C1 to C 30 A hydrocarbon group; and 2 and R is independently at each occurrence a hydrocarbyl group including a hindered double bond.

[0729] 14a. The method according to embodiment 13a, wherein the (B) chain transfer agent component comprises a compound of formula Al(CH2CH(Y 2 )A 2 )3 organic aluminum compound and formula Zn(CH2CH(Y 2 )A 2 )2.

[0730] 15a. The method of any one of embodiments 1a to 14a, wherein the composition comprising the telechelic polyolefin is the composition of any one of embodiments 1 to 91.

[0731] 16a. The method of any one of embodiments 1a to 15a, wherein the telechelic polyolefin is the telechelic polyolefin of embodiment 92.

[0732] Test Method

[0733] Unless otherwise stated, the measurable properties discussed in the foregoing disclosure and the following examples are according to the following analytical methods.

[0734] density

[0735] Samples for density measurement were prepared according to ASTM D-1928, which is incorporated herein by reference in its entirety. Measurements were made within one hour of sample compression using ASTM D-792, Method B, which is incorporated herein by reference in its entirety.

[0736] Melt Index / Melt Flow Rate

[0737] Melt index (I2) was measured according to ASTM D-1238, Condition 190°C / 2.16 kg, and is reported in grams eluted per 10 minutes, ASTM-D 1238 being incorporated herein by reference in its entirety. Melt flow rate (I2) was measured according to ASTM D-1238, Condition 190°C / 10 kg, and is reported in grams eluted per 10 minutes. 10 ) and reported as grams eluted per 10 minutes.

[0738] GPC

[0739] The properties of the sample polymers were tested by GPC as follows.

[0740] Molecular weight (MW) and molecular weight distribution (MWD) were determined using a high temperature gel permeation chromatography system (GPC IR) consisting of an infrared concentration detector (IR-5) from PolymerChar Inc (Valencia, Spain). The carrier solvent was 1,2,4-trichlorobenzene (TCB). The autosampler chamber was operated at 160°C, and the column chamber was operated at 150°C. The columns used were four Polymer Laboratories Mixed A LS, 20 micron columns. The chromatographic solvent (TCB) and the sample preparation solvent were from the same solvent source, with 250ppm of butylated hydroxytoluene (BHT) and nitrogen sparge. The samples were prepared in TCB at a concentration of 2mg / mL. The polymer samples were gently shaken at 160°C for 2 hours. The injection volume was 200μl, and the flow rate was 1.0 ml / min.

[0741] Calibration of the GPC column set was performed with 21 narrow molecular weight distribution polystyrene standards. The molecular weights of the standards ranged from 580 to 8,400,000 g / mol and were arranged in 6 "cocktail" mixtures with at least one decade between the individual molecular weights.

[0742] The GPC column set was calibrated prior to running the example by running twenty-one narrow molecular weight distribution polystyrene standards. The molecular weight (Mw) range of the standards was from 580 to 8,400,000 grams per mole (g / mol), and the standards were contained in 6 "cocktail" mixtures. Each standard mixture was separated by at least one decade between individual molecular weights. The standard mixtures were purchased from Polymer Laboratories (Shropshire, UK). The polystyrene standards were prepared as follows: 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 stirring for 30 minutes. The narrow standard mixtures were run first, and were run in the order of decreasing the highest molecular weight (Mw) component to minimize degradation. The polystyrene standard peak molecular weight was converted to polyethylene Mw using the Mark-Houwink constants. Once the constants were obtained, these two values ​​were used to construct two linear reference routine calibration values ​​for polyethylene molecular weight and polyethylene intrinsic viscosity as a function of the eluting column.

[0743] Polystyrene standard peak molecular weights were converted to polyethylene molecular weights using the following equation (as described in Williams and Ward, J. Polym. Sci., Polym. Let., 6, 621 (1968)):

[0744] M 聚乙烯 =A(M 聚苯乙烯 ) B (1)

[0745] Here the value of B is 1.0, and the experimentally determined value of A is about 0.41.

[0746] The corresponding polyethylene-equivalent calibration points obtained from equation (1) were fit to their observed elution volumes of the polystyrene standards using a third order polynomial.

[0747] The number average molecular weight, weight average molecular weight and z average molecular weight were calculated according to the following equations:

[0748]

[0749]

[0750] Among them, Wf i is the weight fraction of the ith component, and M i is the molecular weight of the ith component.

[0751] MWD is expressed as the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn).

[0752] The exact value of A is determined by adjusting the value of A in equation (1) until the Mw and corresponding retention volume polynomial calculated using equation (3) agrees with the known Mw value of 120,000 g / mol for a standard linear polyethylene homopolymer reference.

[0753] The GPC system consisted of a Waters (Milford, Mass.) 150°C high temperature chromatograph equipped with an organic-borne differential refractometer (RI) (other suitable high temperature GPC instruments include Polymer Laboratories (Shropshire, U.K.) Model 210 and Model 220). Additional detectors may include an IR4 infrared detector from Polymer ChAR (Valencia, Spain), a 2-angle laser light scattering detector Model 2040 from Precision Detectors (Amherst, Mass.), and a 150R 4 capillary solution viscometer from Viscotek (Houston, Texas). A GPC with the last two independent detectors and at least one of the first detectors is sometimes referred to as a "3D-GPC," while the term "GPC" alone generally refers to a conventional GPC. Depending on the sample, either a 15-degree angle or a 90-degree angle of the light scattering detector is used for calculation purposes.

[0754] Data collection was performed using Viscotek TriSEC software version 3 and 4-channel Viscotek data manager DM400. The system is equipped with an online solvent degasser from Polymer Labs (Shropshire, UK). Suitable high temperature GPC columns can be used, such as four 30cm long Shodex HT803 13 micron columns or four 30cm Polymer Labs columns (MixA LS, Polymer Labs) of 20 micron mixed pore size fillers. The sample turntable chamber is operated at 140°C, and the column chamber is operated at 150°C. The sample is prepared with a concentration of 0.1 gram of polymer in 50 milliliters of solvent. Chromatographic solvent and sample preparation solvent contain 200ppm butylated hydroxytoluene (BHT). Both solvents are sprayed with nitrogen. The polyethylene sample is gently stirred for four hours (4 hours) at 160°C. The injection volume is 200 microliters (μL). The flow rate through GPC is set to 1 ml / min.

[0755] NMR 13 C and 1 H)

[0756] Sample preparation :for 13 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 was tetrachloroethane-d2 containing 0.025 M chromium acetylacetonate (relaxant). The sample was capped and sealed with Teflon tape. The sample was dissolved and homogenized by heating the tube and its contents at 135-140°C.

[0757] Sample preparation :for 1 H NMR, samples were prepared by adding 130 mg of sample to 3.25 g of 50 / 50 by weight tetrachloroethane-d2 / perchloroethylene with 0.001 M Cr(AcAc)3 in a 10 mm NMR tube. The sample was purged by bubbling N2 through the solvent for approximately 5 minutes via a pipette inserted into the tube to prevent oxidation, capped, and sealed with Teflon tape. The sample was heated and vortexed at 115°C to ensure homogeneity.

[0758] Data collection parameters :for 13 C NMR, using a Bruker 400 / 600MHz spectrometer equipped with a Bruker high temperature CryoProbe to collect data (see reference 1 mentioned below). Use 256-8000 transients per data file, 7.3 seconds pulse repetition delay (6 seconds delay + 1.3 seconds acquisition time), 90 degrees of tip angle and improved reverse gated decoupling to collect data at a sample temperature of 120°C (see reference 2 mentioned below). All measurements are performed on non-rotating samples in locked mode. Before being inserted into a heated (125°C) NMR sample converter, the sample is immediately homogenized and allowed to thermally equilibrate in the probe for 7 minutes before data acquisition.

[0759] Data collection parameters : The spectrometer was operated on a Bruker AVANCE 400 / 600 MHz spectrometer equipped with a Bruker high temperature CryoProbe and a sample temperature of 120 °C. 1H NMR. Two experiments were performed to obtain the spectrum, a control spectrum for quantification of total polymer protons, and a double presaturation experiment, which suppresses the strong polymer backbone peaks and enables high sensitivity spectra for quantification of end groups. The control was run with ZG pulse, 4 scans, SWH 10,000 Hz, AQ 1.64 s, D1 14 s. The modified pulse sequence lc1prf2.zz1, TD 32768, 100 scans, DS 4, SWH 10,000 Hz, AQ 1.64 s, D1 1 s, D 13 Double presaturation experiments were performed for 13 s.

[0760] Data analysis : Comonomer content was analyzed using the corresponding matrix or algebraic method. Unsaturation was analyzed using the method of reference 3 mentioned below.

[0761] Reference 1 : Z. Zhou, R. Kuemmerle, J. C. Stevens, D. Redwine, Y. He, X. Qiu, R. Cong, J. Klosin, N. G. Roof, Journal of Magnetic Resonance, 2009, 200, 328.

[0762] Reference 2 : Z. Zhou, R. Kümmerle, X. Qiu, D. Redwine, R. Cong, A. Taha, D. Baugh, B. Winniford, Journal of Magnetic Resonance: 187 (2007) 225.

[0763] Reference 3 : Z. Zhou, R. Cong, Y. He, M. Paradkar, M. Demirors, M. Cheatham, W. deGroot, Macromolecular Symposia, 2012, 312, 88.

[0764] Brookfield Viscosity

[0765] Brookfield viscosity was measured at 177°C according to ASTM D-3236 using a Brookfield RV-DV-II-Pro viscometer and spindle SC-31.

[0766] GC / MS

[0767] Tandem gas chromatography / low resolution mass spectrometry using electron impact ionization (EI) was performed at 70 eV 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) for the following:

[0768] Programmatic approach:

[0769] Oven equilibration time of 0.5 min at 50 °C

[0770] Then 25℃ / min to 200℃ and hold for 5 minutes

[0771] Running time: 11 minutes

[0772] DSC

[0773] Differential Scanning Calorimetry (DSC) was performed using a TA Instruments Discovery DSC equipped with an RCS cooling unit and an autosampler. A nitrogen purge gas flow of 50 ml / min was used. The higher molecular weight samples (melt index <50 dg / min at 190°C) were pressed into films under the following conditions: at 190°C, on a Carver hydraulic press, at a pressure of 20,000 psi and for a period of 4 minutes, followed by cooling at a temperature of 23°C, at a pressure of 20,000 psi, for a period of 1 minute. About 3-10 mg of material was cut from the pressed film, weighed, placed in a light aluminum pan, and crimped closed. For low molecular weight samples (melt index >50 dg / min at 190°C), about 3-10 mg of material was cut from the bundle as received, weighed, placed in a light aluminum pan, and crimped closed. The thermal behavior of the samples was studied using the following temperature profile: the samples were rapidly heated to 180°C and held isothermally for 5 minutes. The sample is then cooled to -90°C at 10°C / min and held isothermally for 5 minutes. The sample is then heated to 150°C at 10°C / min. The cooling curve and the second heating curve are used for analysis. The glass transition temperature (Tg), melting temperature (Tm) and enthalpy heat (ΔHm) are obtained from the second heating data. The crystallization temperature (Tc) is obtained from the first cooling data. Tg is determined using the half-height method. Tm and Tc are determined as the peaks of the melting endotherm and crystallization exotherm, respectively. The percentage of crystallinity is calculated by dividing the heat of fusion (Hf) determined by the second heating curve by the theoretical heat of fusion of 292J / g for PE and multiplying this number by 100 (e.g., crystallinity %=(Hf / 292J / g)×100 (for PE)). If the example contains a large portion of propylene, the theoretical heat of fusion of 165J / g for PP is used.

[0774] DMS

[0775] Rheology was measured on an Advanced Rheological Dilatation System (ARES) equipped with "25mm" stainless steel parallel plates. Constant temperature dynamic frequency sweeps were performed in a frequency range of 0.1 to 100rad / s under a nitrogen purge at 190°C. Samples of approximately "25.4mm diameter" and "3.2mm thickness" were compression molded on a Carver hydraulic hot press at a temperature of 190°C under a pressure of 20,000psi for a period of four minutes, followed by cooling at a temperature of 23°C under a pressure of 20,000psi for a period of one minute. The sample was placed on the lower plate and allowed to melt for five minutes. The plate was then closed to a gap of 2.0mm, and the sample was trimmed to "25mm diameter". The sample was balanced at 190°C for five minutes before starting the test. 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, along with the ratio of these two viscosity values ​​(V0.1 / V100).

[0776] Examples

[0777] Preparation of materials

[0778] Unless otherwise noted, all starting reagents and materials were obtained from Sigma-Aldrich. The procatalysts (Cat 1), (Cat 13), (Cat 14) and (Cat 17) and any other materials used in the following examples are the same as the procatalysts and any other materials discussed previously and are prepared according to the methods discussed previously. The procatalyst (Cat 1) can also be identified as [N-(2,6-bis(1-methylethyl)phenyl)amido)(2-isopropylphenyl)(α-naphthalene-2-diyl(6-pyridin-2-diyl)methane)]dimethylhafnium. "Cocat A" is the cocatalyst used in the following examples and is bis(hydrogenated tallow alkyl)methyl, tetrakis(pentafluorophenyl)borate(1-)amine.

[0779] three (2-(Cyclohex-3-en-1-yl)ethyl)aluminum ("CTA 1”) : An exemplary chain transfer agent of the present disclosure was prepared as follows. In a dry box, 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 stirring bar and a capped vent needle. The mixture was heated at 120° C. for 3 hours with stirring. After 3 hours, the sample was dissolved in benzene-d6 and subjected to HPLC. 1 H NMR analysis, and another aliquot was hydrolyzed with water and analyzed by GC / MS. 1H NMR showed that all vinyl groups reacted and internal double bonds were retained ( Figure 1A GC / MS showed a clean peak at m / z 110, consistent with the molecular weight of ethylcyclohexene ( Figure 1B ).therefore, 1 The synthesis of tri(2-(cyclohex-3-en-1-yl)ethyl)aluminum ("CTA 1") was confirmed by H NMR and GC / MS via non-limiting Scheme 1.

[0780]

[0781] Tri(3,7-dimethyloct-6-en-1-yl)aluminum ("CTA 2”) : In a nitrogen-filled dry box, a 40 mL vial was equipped with a stirring bar and charged with DIBAL-H (8.10 mL, 9.64 mmol; 20 wt% in toluene) and citronellal (4.00 g, 28.93 mmol; mixture of isomers). The vial was placed in a heating block and a vent needle was inserted into the headspace. The solution was heated at 110-112°C for 9 hours to give a colorless, transparent solution ([Al] = 0.88 M). The aliquot of 1 HNMR Figure 2 ) and GC / MS (m / z=140) of a hydrolyzed aliquot confirmed that the material was the desired product. 1 The synthesis of tris(3,7-dimethyloct-6-en-1-yl)aluminum ("CTA 2") was confirmed by H NMR and GC / MS via non-limiting Scheme 2.

[0782]

[0783] Hex-4-en-1-yl diisobutylaluminum ("CTA 3”) : An exemplary chain transfer agent of the present disclosure was prepared as follows. 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 in a nitrogen-filled dry box. The reaction mixture was stirred at 25° C. for 14 hours. The hydrolyzed sample 1 H NMR analysis (see hydrolysis procedure below) showed no reaction. The solution was heated at 60°C for 22 hours with stirring. After allowing the vial to cool to 25°C, an aliquot was hydrolyzed and analyzed. The presence of a signal consistent with the hydrolysis products: isobutane and 2-hexene was indicated by the disappearance of the starting diene and the appearance of signals consistent with the hydrolysis products: isobutane and 2-hexene. 1Complete reaction was observed by H NMR. Analytical hydrolysis was performed by diluting approximately 0.1 mL of sample to approximately 2 mL with C6D6 in a vial, removing the sample from the glove box, and adding approximately 0.1 mL of nitrogen-purged water via syringe. After shaking the vial, the mixture was passed through a 0.45 μm syringe filter. The organic phase passes more easily than the aqueous phase, allowing for rapid separation of the organic phase for analysis. The sample was then mixed with a small amount of silica gel and filtered again. This helps to remove residual Al species that may cause gelation. Therefore, 1 The synthesis of hex-4-en-1-yl diisobutylaluminum ("CTA 3") was confirmed by H NMR via non-limiting Scheme 3.

[0784]

[0785] Synthesis of bis(-2-ethylhex-4-en-1-yl)zinc ("CTA 4") In a nitrogen-filled dry box, diethylzinc (3.40 mL, 5.00 mmol, 20 wt% in toluene), 1,4-hexadiene (1.16 mL, 10.00 mmol, d 0.710; mixture of cis and trans isomers) and an activating agent [HNMe(C 18 H 37 )2][B(C6F5)4](1.40 mL, 0.09 mmol, 0.064 M in methylcyclohexane). (Cat 13) (0.045 g, 0.08 mmol) was added as a solid and the reaction mixture was stirred at 25°C for 20 hours. 1 H NMR and GC / MS analysis (see hydrolysis procedure below) showed complete reaction. 1 H NMR was indicated by the disappearance of the starting diene and the appearance of a signal consistent with the hydrolysis product 5-methylhept-2-ene. GC / MS showed the same expected hydrolysis product. Therefore, 1 H NMR and GC / MS confirmed the synthesis of bis(-2-ethylhex-4-en-1-yl)zinc ("CTA 4") via non-limiting Scheme 4.

[0786]

[0787] "CTA 5" Synthesis : Diethylzinc (0.66 mL, 0.97 mmol; 1.47 M in toluene), 4-vinylcyclohexene (1.77 mL, 13.58 mmol; d 0.832), methylcyclohexane (0.60 mL, 0.039 mmol; 0.0644 M) and an activating agent ([HNMe(C 18 H 37)2][B(C6F5)4]) solution and triethylaluminum (0.53 mL, 3.88 mmol; pure, 93%) were dissolved in toluene (about 10 mL). (Cat 13) (0.023 g, 0.039 mmol) was added as a solid and the reaction mixture was stirred at 25°C for 14 hours. An aliquot was dissolved in C6D6 and quenched with water. GC / MS and 1 H NMR confirmed the consumption of 4-vinylcyclohexene and the formation of the desired product (m / z = 138). Thus, this confirmed that CTA 5 was prepared via non-limiting Scheme 5.

[0788]

[0789] Synthesis of "CTA 6" A toluene solution of tri(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 hours while a vent needle was inserted through the septum cap of the vial to allow isobutylene to escape. During this treatment, the DIBZ i Transfer of the Bu group to Al and thermal elimination of isobutylene followed by 4-vinylcyclohexene insertion ensured that all alkyl groups on Al and Zn were cyclohexenylethyl. An aliquot (0.1 mL) of this mixture was diluted with C6D6 (0.5 mL) and hydrolyzed. 1 H NMR analysis. 1 H NMR analysis confirmed that CTA was synthesized via non-limiting Scheme 6.

[0790]

[0791] "CTA 7” SynthesisThe synthesis of CTA 7 is illustrated in non-limiting scheme 7 and is described as follows. The synthesis is carried out in two steps. In the first step, trivinylcyclohexane (TVCH) is converted into diene by intramolecular cyclization in the presence of a catalytic amount of DIBAL-H, and additional DIBAL-H is added in the second step to form CTA. Therefore, in a nitrogen-filled drying oven, DIBAL-H (0.30 g, 2.11 mmol) is added to TVCH (4.09 mL, 21.1 mmol; d 0.836). The mixture is heated and stirred at 160 ° C for 2 hours to form cyclized TVCH. In a separate vial, additional DIBAL-H (0.35 g, 2.46 mmol) is dissolved in decane (5 mL), followed by a portion of the cyclized TVCH obtained above (2.05 mL, 10.5 mmol). The solution is maintained at 130 ° C for 2 hours to obtain an Al-TVCH solution.

[0792]

[0793] "CTA 8” Synthesis The synthesis of CTA 8 is illustrated in non-limiting Scheme 8 and described below. In a nitrogen-filled dry box, a 20 mL vial was equipped with a stirring bar and charged with DIBAL-H (2.00 mL, 2.39 mmol; 20 wt % toluene (1.196 M)) and (R)-(+)-limonene (2.32 mL, 14.35 mmol; d 0.842). The vial was placed in a heating block, a vent needle was inserted through the septum cap, and the solution was heated at 110-112° C. for 11 hours. The solvent and excess limonene were removed overnight at 50° C. under vacuum to obtain the desired product (0.870 g, 83%) as a colorless viscous oil.

[0794]

[0795] "CTA 9” SynthesisThe synthesis of CTA 9 is illustrated in non-limiting Scheme 9 and described as follows. In a nitrogen-filled drying oven, a 40 mL vial was equipped with a stirring bar and loaded 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 in a heating block, a vent needle was inserted through the septum cap, and the solution was heated at 110-112 ° C for 3 hours. After 3 hours of reaction time, aliquots showed the progress of the reaction. The solution contained a small amount of suspended white solid particles. The reaction was continued for another 22 hours. The reaction was almost complete. A small amount of dimer formation from the olefin reagent was observed. The reaction was continued for another 16 hours. Analysis of the aliquots showed no significant changes.

[0796]

[0797] Synthesis of Telechelic Polyolefins in Batch Reactors

[0798] Formula A was synthesized by batch reactor as follows 1 L 1 L 2 A 2 Three groups of non-limiting examples of telechelic polyolefins.

[0799] Group 1

[0800] Referring to Tables 1A-1C, Group 1 contains the telechelic polymers of the present invention made in Runs BR1 through BR12 prepared as follows. In each run, a one gallon stirred autoclave reactor was charged with Isopar TM E mixed alkane solvent (about 1.3kg), desired mass of propylene or octene and / or ethylidene norbornene (ENB) (60g) and CTA. The reactor is heated to 120°C and loaded with ethylene (20g). An active catalyst solution is prepared in a drying oven under an inert atmosphere by mixing a main catalyst and an activator mixture (a mixture of 1.2 equivalents of Cocat A and 10 equivalents of modified methylaluminoxane (MMAO-3A)), wherein the ratio of the main catalyst of the active catalyst solution to Cocat A is 1:1.2. The active catalyst solution is injected into the reactor to initiate polymerization. The pressure and temperature of the reactor are kept constant by feeding ethylene during the polymerization and cooling the reactor as needed. After 10 minutes, the reactor is heated to 200°C and maintained at the temperature for 20 minutes. The ethylene feed is turned off and the polymer solution is transferred to a resin pot purged with nitrogen. Add a phosphorus stabilizer and a phenolic antioxidant (a weight ratio of 2:1 in toluene) and add a 1:1 ratio of ... 168 and 1010) to give a total additive content of about 0.1% in the polymer. The polymer was thoroughly dried in a vacuum oven.

[0801] Table 1A

[0802]

[0803] Table 1B

[0804]

[0805] *Cat A=Zirconium,[2,2"'-[1,3-propanediylbis(oxy-κO)bis[3",5,5"-tris(1,1-dimethylethyl)-5'-methyl[1,1':3',1"-terphenyl]-2'-olato-κO]]dimethyl-,(OC-6-33)-

[0806] Table 1C

[0807]

[0808] **EXCLUDING ENB

[0809] Group 2

[0810] Referring to Table 2, Group 2 contains telechelic polymers of the present invention prepared in Experiments B1-B7 by a procedure similar to that of Group 1. Experiment B1 uses a scavenger MMAO-3A in which the ratio of (Cat 1): Cocat A: scavenger is 1:1.2:10. Experiments B2 to B7 use a primary catalyst to a cocatalyst in a ratio of 1:1.2. All experiments in Table 2 were conducted in the absence of hydrogen. All runs had the following conditions: ethylene (g): 20, 1-octene (g): 60, pressure (psi): 55, solvent (Isopar E, g): 1325. The CTA 5 loading is based on the number of transferable groups. Experiments B1, B2, B4 and B6 were maintained at 120°C for 10 minutes. Experiments B3, B5 and B7 included an additional heating step at 200°C for 20 minutes (excluding the transition time from 120 to 200°C).

[0811] Table 2

[0812]

[0813] Group 3

[0814] Group 3 comprises the following examples used to synthesize the telechelic polyethylene polymers of the present invention.

[0815] In a nitrogen-filled drying oven, octene (10 mL), Cocat A (0.023 mL of a 0.075 M solution, 0.0017 mmol) and CTA 7 (0.402 mL of a 0.5 M solution, 0.2 mmol) were loaded into a vial equipped with a stirring rod. The vial was sealed with a septum cap and placed in a heating block set at 100 ° C. An ethylene line (from a small cylinder) was connected and the vial head space was slowly purged through a needle. Cat 13 (0.067 mL of a 0.02 M solution, 0.0013 mmol) was injected, and the cleaning needle was removed to maintain the total pressure at 20 psig. The polymerization was maintained for 20 minutes, the ethylene line was then removed, and the polymer solution was cooled down. This polymer solution was transferred to a 600 mL Parr reactor and sealed. The reactor was heated to 200 ° C under an ethylene pressure of 200 psig for 30 minutes. The polymer was quenched with a large amount of methanol, filtered and dried overnight under vacuum. 1HNMR( Figure 3 ) demonstrated that the synthesis was carried out via the non-limiting reaction scheme shown below.

[0816]

[0817] In a nitrogen-filled drying oven, octene (10 mL), Cocat A (0.023 mL of a 0.075 M solution, 0.0017 mmol) and CTA 8 (0.088 g, 0.2 mmol) were loaded into a vial equipped with a stirring bar. The vial was sealed with a septum cap and placed in a heating block set at 100°C. An ethylene line (from a small cylinder) was connected and the vial head space was slowly purged through a needle. Cat 13 (0.067 mL of a 0.02 M solution, 0.0013 mmol) was injected, and the cleaning needle was removed to maintain the total pressure at 20 psig. The polymerization was maintained for 20 minutes, the ethylene line was then removed, and the polymer solution was cooled down. This polymer solution was transferred to a 600 mL Parr reactor and sealed. The reactor was heated to 200°C under an ethylene pressure of 200 psig for 30 minutes. The polymer was quenched with a large amount of methanol, filtered and dried overnight under vacuum. 1H NMR ( Figure 4 ) Analysis confirmed that the synthesis was carried out via the following non-limiting reaction scheme.

[0818]

[0819] Continuous Solution Polymerization of Telechelic Polyolefins

[0820] Formula A was prepared by continuous solution polymerization as follows 1 L 1 L 2 A 2 Non-limiting examples of telechelic polyolefins.

[0821] Continuous solution polymerization was carried out in a computer-controlled autoclave reactor equipped with an internal stirrer. Purified mixed alkane solvent (Isopar available from ExxonMobil) was added to the TM E), monomers and molecular weight regulators (hydrogen or chain transfer agents) are supplied to a 3.8L 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 of the reactor. At the discharge port of the pump, a side stream is used to provide a flushing flow for the main catalyst, activator and chain transfer agent (catalyst component solution) injection pipeline. These flows are measured by a micro-motion mass flow meter and controlled by a control valve. The remaining solvent is combined with monomers and hydrogen and fed into the reactor. The temperature of the solvent / monomer solution is controlled by using a heat exchanger before entering the reactor. This stream enters the bottom of the reactor. The catalyst component solution is measured using a pump and a mass flow meter, and the solution is combined with a catalyst flushing solvent and introduced into the bottom of the reactor. Under vigorous stirring, the reactor is filled with liquid at 500psig. The polymer is removed through the outlet pipeline at the top of the reactor. All outlet pipelines from the reactor are steam traced and insulated. The product stream was then heated at 230°C by passing through a post-reactor heater (PRH) where β-H elimination of the polymer-based-Al occurred. Prior to devolatilization, either before the PRH (for comparative examples) or after the PRH (for inventive examples), a small amount of isopropanol was added along with any stabilizers or other additives. The polymer product was recovered by extrusion using a devolatilizing extruder.

[0822] Tables 3 and 4 list the polymerization process conditions and results of the inventive examples and comparative examples before post reactor heating (PRH). 1 L 1 L 2 A 2 The telechelic polyolefins of the present invention are designated as TP1 to TP10 of the present invention. The comparative polymers are designated as Comparative A and B. The other abbreviations in the table are explained as follows: "Co." stands for comonomer; "sccm" stands for standard cm 3 / minute; "T" refers to temperature; "Cat" stands for primary catalyst; "Cat 1" stands for primary catalyst (Cat 1); "Cat 17" stands for primary catalyst (Cat 17), "Cocat" stands for Cocat A; "Al CTA" stands for aluminum chain transfer agent"; "TEA" stands for triethylaluminum; "TOA" stands for trioctylaluminum, "Poly Rate" stands for polymer production rate; "Conv" stands for the percentage of ethylene conversion in the reactor; and "Eff." stands for efficiency, kg polymer / g catalyst metal.

[0823] In addition, [CTA] / [C2H4] refers to the molar ratio in the reactor; Al / C2*1000=(Al feed flow rate*Al concentration / 1000000 / Mw of Al) / (total ethylene feed flow rate*(1-ethylene conversion fraction) / Mw of ethylene)*1000. "Al" in "Al / C2*1000" refers to the amount of Al in CTA used in the polymerization process, and "C2" refers to the amount of ethylene used in the polymerization process.

[0824] The properties of the inventive and comparative polymers after post-reactor heating and recovery are provided in Tables 5-8.

[0825] Table 3

[0826]

[0827] Table 4.

[0828]

[0829] Table 5

[0830]

[0831] Table 6

[0832]

[0833] Table 7

[0834]

[0835] Table 8

[0836]

[0837] As can be seen in the table above, 1 H NMR and 13 C NMR analysis confirmed the synthesis of novel telechelic polyolefins TP1 to TP10 by the inventive method disclosed herein. Specifically, as will be appreciated by one of ordinary skill in the art, 1 H NMR and 13 C NMR analysis confirmed the formation of novel telechelic polyolefins of TP1 to TP10, wherein such polyolefins have unsaturation at both ends. Specifically, such polyolefins have A 1 group (vinyl, vinylidene, vinylidene), and at the other end has A 2 Group, the A 2 The groups have hindered double bonds (cyclohexene or trisubstituted olefins). In contrast, comparative polymers A and B, which were not prepared according to the inventive process of the present disclosure, were prepared as described by 1 H NMR and13 C NMR analysis revealed a polymer with low unsaturation.

[0838] In TP5 of the present invention, the hindered double bond of the A2 group is a trisubstituted unsaturation, resulting in a high number of trisubstituted unsaturations / 1000000C, as reported in the table above. The number of trisubstituted unsaturations in TP5 is higher than in Comparative B, which is produced with the same catalyst under similar reactor conditions but with hydrogen to control the molecular weight. A small amount of trisubstituted unsaturations can be formed by β-hydride elimination and subsequent rearrangement of unsaturations in ethylene / α-olefins. The number of trisubstituted unsaturations formed by this thermal termination mechanism depends on the catalyst and process conditions used. A small amount of trisubstituted unsaturations from this thermal termination mechanism is present in all comparative examples and examples of the present invention, but its level is lower than that of vinyl and vinylidene, except for TP5, in which most of the trisubstituted unsaturations come from the A2 group.

[0839] As described 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 can be suitable for curable formulations and can improve crosslinking. By controlling the location of the unsaturation at the end of the polymer chain, a more controlled network structure is formed (uniform Mw between crosslinks), and the unsaturation on the polymer chain is used more efficiently. This should provide better thermal and UV aging stability because for a given molecular weight, less unsaturation is required to form a crosslinked network with good mechanical properties. Unlike high Mw EPDM, the low viscosity of the low Mw telechelic polyolefins of the present disclosure will provide excellent processing performance and flow before crosslinking.

[0840] In addition, the telechelic polyolefins of the present disclosure are produced from ethylene and α-olefins in a low-cost solution polymerization, unlike telechelic polyolefins that have been produced in the literature by more expensive and complex synthetic routes. Further, unlike random copolymers with unsaturation, telechelic polyolefins also enable the opportunity for controlled chain extension to higher molecular weight thermoplastics. Because the unsaturation is located at the chain end, the telechelic polyolefins can be chain extended to form high molecular weight thermoplastic resins. Suitable crosslinking and chain extension chemistries include, but are not limited to, peroxide, thiol-ene, sulfur cure, phenolic cure, and the like.

Claims

1. A telechelic polyolefin of formula (I): A 1 L 1 L 2 A 2 (I), in which: L 1 It includes derivatives from ethylene and C3 to C 30 Ethylene / α-olefin copolymers containing α-olefin units; A 1 Selected from the group consisting of: vinyl, formula CH2=C(Y 1 )-vinylidene, formula Y 1 CH=CH-vinylene, vinyl and formula Y 1 A mixture of CH=CH-vinylene, vinyl and CH2=C(Y 1 )-vinylidene mixture, formula CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of CH=CH-vinylene and vinyl, CH2=C(Y 1 )-vinylidene and formula Y 1 A mixture of vinylene groups with CH=CH-; Y 1 C1 to C independently at each occurrence 30 Hydrocarbon; L 2 It is C1 to C 32 alkylene; A 2 is a hydrocarbyl group comprising a hindered double bond, wherein the hindered double bond is selected from the group consisting of a double bond of a vinylidene group, a double bond of a vinylene group, a double bond of a trisubstituted olefin, and a double bond of a vinyl group attached to the alpha carbon of a branch; and wherein the telechelic polyolefin of formula (I) has an Mw / Mn of 1 to 4 and a total number of unsaturations greater than 1.9, and wherein the telechelic polyolefin of formula (I) contains unsaturations at the ends of the polymer chains rather than randomly distributed along the polymer backbone.

2. The telechelic polyolefin according to claim 1, wherein the C3 to C 30 The α-olefin is selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene.

3. The telechelic polyolefin according to any one of claims 1 to 2, wherein A 2 It is C3 to C 30 Cyclic hydrocarbon or C3 to C 30 Acyclic hydrocarbon groups.

4. The telechelic polyolefin according to any one of claims 1 to 2, wherein A 2 Selected from the group consisting of unsubstituted cycloolefins and alkyl-substituted cycloolefins.

5. The telechelic polyolefin according to any one of claims 1 to 2, wherein A 2 Selected from the group consisting of: wherein the endocyclic double bond in (AC) and (AF) may be between any two adjacent carbon atoms as ring members, and wherein the pendant methyl group of (AF) may be attached to any carbon atom as a ring member.

6. The telechelic polyolefin according to any one of claims 1-2, wherein the telechelic polyolefin of formula (I) has a weight average molecular weight (Mw) ranging from 1,000 g / mol to 1,000,000 g / mol.

7. The telechelic polyolefin according to any one of claims 1 to 2, wherein L 1 A through a carbon-carbon single bond 1 and L 2 Each of the covalent bonds, and where L 2 A through a carbon-carbon single bond 2 Covalent bonding.

8. A composition comprising a telechelic polyolefin according to any one of the preceding claims.

9. A method for preparing a telechelic polyolefin, the method comprising: 1) combining starting materials including (A) a monomer component, (B) a chain transfer agent component, and (C) a catalyst component including a main catalyst to form a solution, and polymerizing greater than 10 mol% to less than or equal to 99 mol% of the (A) monomer component in the solution at 60 to 150° C.; 2) heating the solution to a temperature of at least 160° C.; and 3) recovering a product comprising the telechelic polyolefin, wherein: The chain transfer agent component (B) comprises the formula Al(CH2CH(Y 2 )A 2 )3 organoaluminum compounds; Y 2 is independently hydrogen or C1 to C 30 a hydrocarbon group; and A 2 is independently at each occurrence a hydrocarbyl group comprising a hindered double bond, wherein the hindered double bond is selected from the group consisting of a double bond of a vinylidene group, a double bond of a vinylene group, a double bond of a trisubstituted olefin, and a double bond of a vinyl group attached to the alpha carbon of a branch, The main catalyst is selected from: The telechelic polyolefins contain unsaturation at the ends of the polymer chains rather than being randomly distributed along the polymer backbone.

10. The method according to claim 9, wherein the starting material further comprises (D) a solvent.

11. The method according to claim 9 or 10, wherein step 2) is heating the solution to a temperature of at least 180°C and maintaining the solution at the temperature of at least 180°C for a period of at least 30 seconds.

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